WO2005068520A1 - Acrylat-polymerisate auf basis von tert.-butylacrylat zur verwendung in sprayformulierungen - Google Patents
Acrylat-polymerisate auf basis von tert.-butylacrylat zur verwendung in sprayformulierungen Download PDFInfo
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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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/22—Peroxides; Oxygen; Ozone
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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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
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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
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
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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
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
- A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
Definitions
- the present invention relates to polymers obtainable by radical polymerization of a) 30 to 99% by weight of tert-butyl acrylate and / or tert-butyl methacrylate as monomer b) 1 to 70% by weight of acrylic acid and / or methacrylic acid as monomer B and c) 0 to 12% by weight of a free-radically copolymerizable monomer or a free-radically copolymerizable monomer mixture as monomer C, at least one of the monomers C providing a homopolymer with a glass transition temperature below 30 ° C., with the proviso that the weight Add% to 100, the K value of the polymers being between 27 and 38 and the polymerization being carried out in the presence of a regulator if the K value of the polymers is less than or equal to 35, and the use of these polymers in preparations for in particular cosmetics and oral and dental care.
- Polymers with film-forming properties are used in cosmetics for cosmetic, dermatological, hygienic and / or pharmaceutical formulations and are particularly suitable as additives for hair and skin cosmetics.
- EP-A 379 082 describes hair fixatives containing, as film formers, copolymers based on tert-butyl acrylate and / or tert-butyl methacrylate with a K value of 10 to 50, which are obtained by radical polymerization of
- the polymers are preferably obtained by solution polymerization.
- EP-A 696916 describes hair fixatives containing, as film formers, copolymers based on tert-butyl acrylate or tert-butyl methacrylate with a K value of 10 to 50, obtainable by radical polymerization of A) 30 to 72% by weight tert.
- WO 02/38638 describes polymers which are obtainable by free-radical polymerization of from 30 to 99% by weight of tert-butyl acrylate and / or tert-butyl methacrylate as monomer A,
- VOC volatile organic compounds
- the object of the present invention was to provide polymers for in particular cosmetic preparations and preparations for oral and dental care which can be formulated in solvents or solvent mixtures with an increased water content and whose formulations have better sprayability with good mechanical properties of the films formed.
- the polymers should give the hair good strengthening and longer hold, good have washability and can be formulated as optically clear VOC-55 aerosols (ie with a VOC content of at most 55% by weight).
- the object is achieved by the polymers described at the outset.
- the object is further achieved in particular by polymers obtainable by free-radical polymerization of a) 60 to 80% by weight of tert-butyl acrylate and / or tert-butyl methacrylate as monomer A, b) 20 to 40% by weight of acrylic acid and / or Methacrylic acid as monomer B and c) 0 to 12% by weight of a free-radically copolymerizable monomer or a free-radically copolymerizable monomer mixture as monomer C, at least one of the monomers C providing a homopolymer with a glass transition temperature below 30 ° C., with the proviso that the% by weight add up to 100, the K value of the polymers being between 27 and 38.
- the polymerization is carried out in the presence of regulators. If the K value of the polymers according to the invention is in the range between 35 and 38, it is optionally possible to work in the presence of regulators.
- At least one further monomer C may optionally be copolymerized. This monomer or at least one of these monomers is said to be a homopolymer with one
- these are monomers selected from the group consisting of C ⁇ -C ⁇ 8 -alkyl, CrC 8 alkyl methacrylates, NdC - ⁇ - alkyl acrylamides and N-CrC ⁇ -Alkylmethacryl- amides.
- Particularly preferred are C 4 NC alkylacrylamides or -methacrylamides, or mixtures of two or more of these monomers, particularly preferred are unbranched C ⁇ - to C 4 alkyl acrylates alone or in admixture with branched NC 3 - to -C -alkylacrylamides.
- Suitable CrC ⁇ alkyl radicals in the (meth) acrylates and (meth) acrylamides mentioned are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
- Particularly preferred monomers C are ethyl acrylate or a mixture of ethyl acrylate and N-tert-butyl acrylamide.
- Preferred polymers according to the invention are polymers for the preparation of which the amount of monomer C provided is less than 10% by weight, preferably less than 5% by weight, particularly preferably less than 3% by weight, of the total amount of monomers.
- the proportion of component C is particularly preferably in the range from 0.01 to 3% by weight.
- polymers whose components A and B are polymerized, but not C.
- the polymers according to the invention are distinguished by a significantly improved sprayability of the formulations containing up to a maximum of 55% by weight of organic volatile components and at the same time good mechanical properties of the films.
- the polymers according to the invention show good compatibility with customary cosmetic ingredients, good washability from, for example, hair and formulation in clear VOC-55 aerosols.
- monomer A is tert-butyl acrylate
- monomer B is methacrylic acid
- monomer C is ethyl acrylate.
- Particularly preferred embodiments are polymers obtainable by radical polymerization of 75 to 80% by weight of tert-butyl acrylate, 20 to 25% by weight of methacrylic acid and 0 to 2% by weight of ethyl acrylate, with the proviso that the
- the acrylate polymers are prepared in a known manner by free-radical polymerization of the monomers A, B and, if appropriate, C.
- the usual polymerization techniques are used here, for example the methods of suspension, emulsion or solution polymerization.
- the acrylate polymers are preferably prepared in a known manner by free-radically initiated aqueous emulsion polymerization of the monomers A, B and, if appropriate, C.
- the free-radically initiated aqueous emulsion polymerization usually takes place in such a way that the monomers, usually with the help of Use of dispersants, dispersed in an aqueous medium and polymerized by means of at least one radical polymerization initiator.
- Free radical polymerization initiators for the free radical aqueous emulsion polymerization according to the invention are all those which are capable of initiating a free radical aqueous emulsion polymerization. In principle, these can be both peroxides and azo compounds. Of course, redox initiator systems can also be used.
- inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric acid, such as, for example, their mono- and di-sodium, potassium or ammonium salts, or organic peroxides, such as alkyl hydroperoxides, can be used as peroxides , for example tert-butyl, p-menthyl or cumyl hydroperoxide, tert-butyl perpivalate and dialkyl or diaryl peroxides, such as di-tert-butyl or di-cumyl peroxide, 2,5-dimethyl-2,5-di- (t) butyl peroxy (hexane) or dibenzoyl peroxide can be used.
- organic peroxides such as alkyl hydroperoxides
- the azo compound found is essentially 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (amidinopropyl) dihydrochloride (AIBA, corresponds to V-50 TM from Wako Chemicals ), 1,1'-azo-bis- (1-cyclohexane carbonitrile), 2,2'-azobis (2-amidinopropane) salts, 4,4'-azobis (4-cyanovaleric acid) or 2- (carbamoylazo) - isobutyronitrile ,
- the above-mentioned peroxides are essentially suitable as oxidizing agents for redox initiator systems.
- Sulfur compounds with a low oxidation level such as alkali sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium hydrogen sulfite, alkali metal sulfites, for example potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / or Sodium formaldehyde sulfoxylate, alkali salts, especially potassium and / or sodium salts of aliphatic sulfinic acids and alkali metal hydrogen sulfides, such as, for example, potassium and / or sodium hydrogen sulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II) - Ammonium sulfate, iron (II) phosphate, end
- Alkanthiols are preferably used as regulators. Mixtures of several controllers can also be used. 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 12 to C ⁇ , in particular of C 12 to C 18 .
- Preferred alkanethiols are n-decanethiol, n-dodecanethiol, tert-dodecanethiol, n-tetradecanethiol, n-pentadecanethiol, n-hexadecanethiol, n-heptadecanethiol, n-octadecanethiol, n-nonadecanethiol, n-eicosanethiol and 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.
- alkanethiols with a C chain length of C 10 to C 13 are used in the polymerization, a subsequent hydrogen peroxide treatment is necessary in order to obtain odorlessly neutral polymers.
- this hydrogen peroxide treatment following the polymerization usually 0.01 to 2.0% by weight, in particular 0.02 to 1.0% by weight, preferably 0.3 to 0.8% by weight, are further preferred 0.03 to 0.15% by weight of hydrogen peroxide, based on the monomers to be polymerized. It has proven to be 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 carried out for a period of 30 minutes to 240 minutes, in particular 45 minutes to 90 minutes.
- hydrogen peroxide treatment can be omitted. In a further embodiment of the invention, however, hydrogen peroxide treatment can also be used when using alkanethiols with a chain length of C 4 to C 22 .
- the polymers according to the invention have K values between 27 and 38.
- the K value of the polymers according to the invention is in the range from 29 to 35, particularly preferably in the range from 30 to 34 and very particularly preferably in the range from 30 to 32.
- the K value desired in each case can be selected by choosing the polymerization conditions , for example the polymerization temperature and the initiator concentration.
- regulators are used to adjust the K value, in particular when using emulsion and suspension polymerization.
- the K value can be set by selecting the type and / or the quantity of the controller. In a preferred embodiment, lower K values are set by larger amounts of regulator based on the total amount of monomer.
- the monomers C which are optionally used to prepare the polymers according to the invention, are selected so that at least one of the monomers C provides a homopolymer with a glass transition temperature below 30 ° C.
- the polymers according to the invention usually have glass transition temperatures T g between 50 and 130 ° C., in particular between 60 and 100 ° C.
- the glass transition temperature T g means the limit value of the glass transition temperature which, according to G. Kanig (Colloid Journal & Journal for Polymers, Vol. 190, page 1, equation 1), strives with increasing molecular weight.
- the glass transition temperature is determined using the DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53 765).
- Tg values for the homopolymers of the abovementioned monomers are known and are listed, for example, in Ullmann's Ecyclopedia of Industrial Chemistry, Verlag Chemie, Weinheim, 1992, Vol. 5, Vol. A21, page 169; Further sources for glass transition temperatures of homopolymers are, for example, J. Brandrup, EH Immergut, Polymer Handbook, Ist Ed., J. Wiley, New York 1966, 2nd Ed. J. Wiley, New York 1975, and 3 rd Ed. J. Wiley, New York 1989).
- x1, x2, .... xn are the mass fractions of the monomers 1, 2 n and T g 1, T g 2 T g n are the glass transition temperatures of the build-up of only one of the monomers 1, 2, .... n Polymer in degrees Kelvin mean.
- the emulsion polymerization is usually carried out with the exclusion of oxygen, for example under a nitrogen or argon atmosphere, at temperatures in the range from 20 to 200.degree. Polymerization temperatures in the range from 50 to 130, in particular 70 to 95 ° C. are advantageous. In the case of free-radically initiated emulsion polymerization, care must be taken, in particular at higher temperatures, to avoid the formation of coagulum that the polymerization mixture does not boil. This can be avoided, for example, by the polymerization reaction being carried out at an inert gas pressure which is higher than the vapor pressure of the polymerization mixture, for example 1.2 bar, 1.5 bar, 2 bar, 3 bar, 5 bar, 10 bar or even higher ( absolute values).
- the polymerization can be carried out batchwise, semi-continuously or continuously.
- the polymerization or the monomer and regulator metering are frequently carried out semi-continuously by the feed process.
- the amounts of monomers and dispersants are expediently chosen so that they contain a 30 to 80% by weight dispersion of the copolymers.
- at least some of the monomers, initiators and optionally regulators are metered uniformly into the reaction vessel during the polymerization.
- the monomers and the initiator can also be placed in the reactor and polymerized, with cooling possibly being necessary.
- the polymerization is carried out using a seed latex.
- the seed latex is expediently prepared from the polymers to be polymerized in the first polymerization phase in a conventional manner.
- the remaining part of the monomer mixture is then added, preferably by the feed process.
- the polymerization reaction advantageously takes place up to a monomer conversion> 95% by weight, preferably> 98% by weight or> 99% by weight.
- aqueous polymer dispersion obtained is subjected to a post-polymerization step in order to further reduce the amount of unreacted monomer.
- This measure is known to the person skilled in the art (for example EP-B 3957, EP-B 28348, EP-B 563726, EP-A 764699, EP-A 767180, DE-A 3718 520, DE-A 3834734, DE-A 4232194, DE -A 19529599, DE-A 19741187, DE-A 19839199, DE-A 19840586, WO 95/33775 or US 4529753).
- aqueous polymer dispersions obtainable according to the invention can be dried in a simple manner to give redispersible polymer powders.
- the polymer is prepared by emulsion polymerization, the one obtained can
- Dispersion can either be incorporated directly into an aqueous, aqueous-alcoholic or alcoholic cosmetic preparation, for example a hair-setting preparation, or the dispersion is dried, for example spray drying or freeze-drying, so that the polymer can be used and processed as a powder.
- aqueous polymer dispersion obtained it is also possible to subject the aqueous polymer dispersion obtained to an inert gas and / or steam stripping which is also known to the person skilled in the art before or after the postpolymerization step. This stripping process preferably takes place after the post-polymerization step.
- partial neutralization of the dispersion to a pH in the range from 5 to 7, preferably to a pH in the range from 5.5 to 6.5 is advantageous before the physical deodorization.
- the polymers present in the aqueous dispersion before or after the aftertreatment can be partially or completely neutralized. Partial or complete neutralization of the polymer dispersions is advantageous, in particular for the use of the polymers in hair cosmetic preparations.
- the neutralization of the polymers is usually carried out partially or completely with an alkali metal hydroxide or preferably with an amine, advantageously to 5 to 100%, or frequently to 30 to 95%.
- the polymers are partially neutralized, in a particularly preferred embodiment completely.
- the neutralization is advantageously carried out using a mono-, di- or trialkanolamine having 2 to 5 carbon atoms in the alkanol radical, which is optionally present in etherified form, for example mono-, di- and triethanolamine, mono-, di- and tri-n-propanolamine , Mono-, di- and tri-so-propanolamine, 2-amino-2-methylpropanol and di (2-methoxyethyl) amine, an alkanediolamine with 2 to 5 carbon atoms, for example 2-amino-2-methylpropane-1, 3- diol and 2-amino-2-ethylpropane-1,3-diol, or a primary, secondary or tertiary alkylamine with a total of 5 to 10 carbon atoms, for example N, N-diethylpropylamine or 3-diethyI-amino-1-propylamine.
- Sodium, or potassium and ammonium hydroxide are particularly suitable as alkali metal hydroxides for neutralization.
- Aqueous buffer solutions such as buffers based on alkali or ammonium carbonate or bicarbonate, are also suitable for neutralization.
- the neutralizing agents are preferably added to the polymer dispersion as a dilute aqueous solution.
- the pH can optionally also be adjusted by adding a buffer solution, buffers based on alkali or ammonium carbonate or bicarbonate being preferred.
- the polymer particles present in aqueous dispersion generally have a weight-average particle diameter> 5 nm,> 10 nm,> 20 nm,> 30 nm,> 40 nm,> 50 nm,> 60 nm,> 70 nm,> 80 nm,> 90 nm or> 100 nm and all values in between and ⁇ 700 nm, ⁇ 500 nm, ⁇ 400 nm, ⁇ 350 nm, ⁇ 300 nm, ⁇ 250 nm,
- weight-average particle diameter is understood to mean the weight-average D w50 value determined by the analytical ultracentrifuge method (cf. SE Harding et al., Analytical Ultra-centrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cam-bridge, Great Britain 1992, Chapter 10, Analysis of Polymer Dispersions with an Eight-Cell-AUC-Multiplexer: High Resolution Particie Size Distribution and Density Gradient Techniques, W. Switzerland, pages 147 to 175).
- the polymer solids content of the aqueous polymer dispersions accessible according to the invention is frequently 5 to 70% by weight, often 20 to 60% by weight or 30 to 60% by weight.
- the (meth) acrylate polymers according to the invention are used in cosmetic, hygienic dermatological and / or pharmaceutical preparations, the preparation of which is carried out according to the usual rules familiar to the person skilled in the art.
- the (meth) acrylate polymers according to the invention are preferred in cosmetic
- Preparations particularly preferably used in hair cosmetic preparations.
- the (meth) acrylate polymers according to the invention are furthermore preferably used in preparations for oral and dental care.
- the (meth) acrylate polymers according to the invention are notable for excellent film-forming properties. Another object of the invention therefore relates to the use of the (meth) acrylate polymers as film formers.
- the (meth) acrylate polymers present in partial or completely neutralized form are particularly suitable for use in cosmetic preparations. Cosmetic preparations
- the (meth) acrylate polymers according to the invention can be used in cosmetic preparations as aqueous or aqueous-alcoholic solutions, O / W and W / O emulsions in the form of shampoos, creams, foams, sprays (pump spray or aerosol), gels, gel sprays, Lotions or mousse are present and can be formulated accordingly with the usual other auxiliaries.
- the (meth) acrylate polymers according to the invention are preferably formulated in cosmetic preparations as sprays (pump spray or aerosol). They are particularly preferably provided as VOC-55 formulations.
- the cosmetic, dermatological, hygienic and / or pharmaceutical preparations can also contain conventional additives such as emulsifiers and co-emulsifiers, surfactants, oil bodies, preservatives, perfume oils, cosmetic care products. and active ingredients such as AHA acids, fruit acids, cerarnides, phytantriol, collagen, vitamins and provitamins, for example vitamins A, E and C, retinol, bisabolol, panthenol, natural and synthetic light stabilizers, natural substances, opacifiers, solubilizers, repellents, bleaches, colorants, Tinting agents, browning agents (e.g.
- micropigments such as titanium oxide or zinc oxide, superfatting agents, pearlescent waxes, consistency agents, thickeners, solubilizers, complexing agents, fats, waxes, silicone compounds, hydrotropes, dyes, stabilizers, pH value regulators, reflectors, proteins and protein hydro Contain lysates (e.g. wheat, almond or pea proteins), ceramide, protein hydrolysates, salts, gelling agents, consistency agents, silicones, humectants, moisturizers and other common additives.
- further polymers can also be included to adjust the properties desired in each case.
- UV light stabilizers can also be present in the cosmetic preparations.
- the auxiliaries can be present during the polymerization and / or can be added after the polymerization. Examples of the respective classes of auxiliaries are given below, without restricting the possible auxiliaries to those mentioned by way of example.
- Another object of the invention accordingly relates to the use of the polymers according to the invention in cosmetic and / or pharmaceutical preparations.
- the purpose of the light protection filters used in cosmetic and pharmaceutical preparations is to prevent or at least to reduce the harmful effects of sunlight on human skin.
- these light protection filters also serve to protect other ingredients from destruction or degradation by UV radiation.
- damage to the keratin fiber by UV rays is to be reduced.
- the sunlight reaching the earth's surface has a share of UV-B (280 to 320 nm) and UV-A radiation (320 to 400 nm), which directly adjoin the range of visible light.
- the influence on human skin is particularly noticeable with UV-B radiation due to sunburn.
- the narrower range around 308 nm is given as a maximum of the erythema effectiveness of sunlight.
- UV-B radiation Numerous compounds are known for protection against UV-B radiation, which include are derivatives of 3-benzylidene camphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and 2-phenylbenzimidazole. It is also important to have filter substances available for the range between about 320 nm and about 400 nm, the so-called UV-A range, since their rays can cause reactions in light-sensitive skin. It has been proven that UV-A radiation leads to damage to the elastic and collagen fibers of the connective tissue, which causes the skin to age prematurely, and that it can be seen as the cause of numerous phototoxic and photoallergic reactions. The damaging influence of UV-B radiation can be intensified by UV-A radiation.
- Oil-soluble organic UV-A filters and / or UV-B filters and / or water-soluble organic UV-A filters and / or UV-B filters can be used as UV light protection filters.
- the total amount of UV light protection filters is generally 0.1% by weight to 30% by weight, preferably 0.5 to 15% by weight, in particular 1 to 10% by weight, based on the total weight of the preparations.
- the UV light protection filters are advantageously chosen so that the preparations protect the skin from the entire range of ultraviolet radiation.
- UV light protection filters are:
- combinable light stabilizers include the following compounds:
- UV light protection filters which can be used in combination with the polymers according to the invention, is of course not intended to be limiting.
- Germ inhibitors can also be used. These generally include all suitable preservatives with a specific effect against gram-positive bacteria, e.g. triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether), chlorhexidine (1,1 - hexamethylene bis [5- (4-chlorophenyl) biguanide) and 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 deoparfums.
- Clove oil (eugenol), mint oil (menthol) or thyme oil (thymol) show a pronounced antimicrobial activity.
- the antibacterial substances are generally used in concentrations of approx. 0.1 to 0.3% by weight.
- Cosmetic preparations include, for example, skin cosmetic preparations, in particular those for the care and / or cleaning of the skin. These are in particular available as W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-wrinkle creams, facial expression creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, care lotions and moisturizing lotions. Furthermore, they are suitable for skin cosmetic preparations such as facial tonic, face masks, deodorants and other cosmetic lotions and for use in decorative cosmetics, for example as concealer, theater paint, in mascara and eyeshadow, lipsticks, eye pencils, eyeliners, makeup, foundations, blushes and powders and eyebrow pencils.
- skin cosmetic preparations such as facial tonic, face masks, deodorants and other cosmetic lotions and for use in decorative cosmetics, for example as concealer, theater paint, in mascara and eyeshadow, lipsticks, eye pencils, eyeliners, makeup, foundations, blushes and powders and eyebrow pencils.
- the (meth) acrylate polymers according to the invention can be used in nose strips for pore cleaning, in anti-acne agents, repellents, shaving agents, hair removal agents, intimate hygiene products, foot care products and in baby care.
- the polymers according to the invention are used as or in coating compositions for keratin-containing and keratin-analog surfaces, such as hair, skin and nails.
- the polymers according to the invention are also used in cosmetic compositions for cleaning the skin.
- cosmetic cleaning agents are, for example, 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 bathing preparations, such as washing lotions, shower baths and gels, bubble baths, oil baths and scrub preparations, shaving foams, lotions, and creams.
- 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
- showering and bathing preparations such as washing lotions, shower baths and gels, bubble baths, oil baths and scrub
- the agents according to the invention can be applied in a form suitable for skin care, for example as a cream, foam, gel, stick, mousse, milk, spray or lotion.
- a form suitable for skin care for example as a cream, foam, gel, stick, mousse, milk, spray or lotion.
- the skin cosmetic preparations can also contain other active ingredients and auxiliaries customary in skin cosmetics, as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, natural and synthetic light stabilizers, bleaches, colorants, tinting agents, tanning agents, collagen, protein hydrolyzates, stabilizers, pH Value regulators, dyes, salts, thickeners, gelling agents, consistency agents, silicones, humectants, lipid replenishers and other common additives.
- active ingredients and auxiliaries customary in skin cosmetics as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, natural and synthetic light stabilizers, bleaches, colorants, tinting agents, tanning agents, collagen,
- Preferred oil and fat components of the skin cosmetic and dermatological agents are the aforementioned mineral and synthetic oils, such as paraffins, silicone oils and aliphatic hydrocarbons with more than 8 carbon atoms, animal and vegetable oils, such as sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as, for example, 6. triglycerides of C 6 -C 30 fatty acids, wax esters, such as, for example, jojoba oil, fatty alcohols, petroleum jelly, hydrogenated lanolin and acetylated lanolin and mixtures thereof.
- the polymers according to the invention can also be mixed with conventional polymers if special properties are to be set.
- the skin cosmetic and dermatological preparations can also contain conditioning substances based on silicone compounds in order to adjust certain properties, such as, for example, improving the feel, the spreading behavior, the water resistance and / or the binding of active ingredients and auxiliaries such as pigments.
- Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins.
- the cosmetic or dermatological preparations are produced by customary methods known to the person skilled in the art.
- the cosmetic and dermatological agents are preferably in the form of emulsions, in particular in the form of water-in-oil (W / O) or oil-in-water (O / W) emulsions.
- hydro-dispersions for example hydro-dispersions, gels, oils, oleogels, multiple emulsions, for example in the form of W / O / W or O / W / O emulsions, anhydrous ointments or ointment bases, etc.
- Emulsions are prepared by known methods.
- the emulsions generally contain customary constituents, such as fatty alcohols, fatty acid esters and in particular fatty acid triglycerides, acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.
- customary constituents such as fatty alcohols, fatty acid esters and in particular fatty acid triglycerides, acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.
- a suitable emulsion e.g. for a skin cream etc., generally contains an aqueous phase which is emulsified in an oil or fat phase by means of a suitable emulsifier system.
- the proportion of the emulsifier system in this type of emulsion is preferably about 4 to 35% by weight, based on the total weight of the emulsion.
- the proportion of the fat phase is preferably about 20 to 60% by weight.
- the proportion of the aqueous phase is preferably about 20 and 70%, in each case based on the total weight of the emulsion.
- the emulsifiers are those which are usually used in this type of emulsion.
- C 12 -C 18 sorbitan fatty acid esters esters of hydroxystearic acid and C 2 -C 30 fatty alcohols, mono- and diesters of C 12 -C 18 fatty acids and glycerol or polyglycerol, condensates of ethylene oxide and propylene glycols, oxypropylenated / oxyethylated C ⁇ 2 -C 18 fatty alcohols, polycyclic alcohols such as sterols, aliphatic alcohols with a high molecular weight such as lanolin, mixtures of oxypropylenated / polyglycerolated alcohols and magnesium isostearate; Succine esters of polyoxyethylene or polyoxypropylene fatty alcohols and mixtures of magnesium, calcium, lithium, zinc or aluminum lanolate and hydrogenated lanolin or lanolin alcohol.
- Preferred fat components which can be contained in the fat phase of the emulsions are hydrocarbon oils such as paraffin oil, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in these oils, animal or vegetable oils such as sweet almond oil, avocado oil, calophylum oil, lanolin and derivatives thereof, castor oil , Sesame oil, olive oil, jojoba oil, karite oil, hoplostethus oil, mineral oils whose distillation begins at atmospheric pressure at approx. 250 ° C and whose distillation end point is approx. 410 ° C, such as Vaseline oil, esters of saturated or unsaturated fatty acids such as alkyl myristates, e.g.
- the fat phase can also contain silicone oils soluble in other oils such as, for example, dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.
- oils such as, for example, B. carnauba wax, candililla wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.
- the water-in-oil emulsions are prepared by placing the fat phase and the emulsifier in a batch container.
- the agents according to the invention are a shower gel, a shampoo formulation or a bath preparation.
- shower gels are preferred, in particular clear shower gels.
- Such formulations contain at least one polymer according to the invention and usually anionic surfactants as base surfactants and amphoteric and / or nonionic surfactants as cosurfactants.
- Further suitable active substances and / or auxiliary substances are usually selected from lipids, perfume oils, dyes, organic acids, preservatives and antioxidants as well as thickeners / gel formers, skin conditioners and humectants.
- formulations preferably contain about 2 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 8 to 30% by weight, of surfactants, based on the total weight of the formulation.
- All anionic, neutral, amphoteric or cationic surfactants commonly used in personal cleansing agents can be used in the washing, showering and bathing preparations.
- 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 isothionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, in particular alkali metal alkali metal sulfates, for example alkali metal alkali metal sulfates Sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts.
- the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 and 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units, in the molecule.
- Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or propionates, alkylamphodiacetates or dipropionates.
- cocodimethylsulfopropylbetaine laurylbetaine, cocamidopropylbetaine or sodium 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 one mole of alcohol.
- Alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, alkylpolyglycosides or sorbitan ether esters are also suitable.
- washing, showering and bathing preparations can contain conventional cationic surfactants, such as e.g. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
- conventional cationic surfactants such as e.g. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
- cationic polymers can also be used, e.g. Copolymers of acrylamide and dimethyldiallylammonium chloride (polyquaternium-7), cationic cellulose derivatives (polyquaternium-4, polyquaternium-10), guar hydroxypropyltrimethylammonium chloride (INCI: hydroxylpropyl guar hydroxypropyltrimonium chloride), copolymers of N-vinylpyridoleminone 16, -44, -46), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Polyquaternium-11) and others.
- shower gel / shampoo formulations can include thickeners, e.g. Table salt, PEG-55, propylene glycol oleate, PEG-120 methyl glucose dioleate and others, as well as preservatives, other active and auxiliary substances and water.
- thickeners e.g. Table salt, PEG-55, propylene glycol oleate, PEG-120 methyl glucose dioleate and others, as well as preservatives, other active and auxiliary substances and water.
- 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 solutions, setting lotions, shampoos, hair waxes, pomades, hair foams, or hair colorants hairsprays. It is particularly preferred to use the (meth) acrylic polymers in hairstyle fixtures which are in the form of spray preparations and / or hair foams.
- the (meth) acrylate polymers according to the invention are distinguished in hair cosmetic preparations by their high compatibility with the non-polar blowing agents in spray preparations, in particular with hydrocarbons such as n-propane, isopropane, n-butane, iso-butane, n-pentane and mixtures thereof and in particular from the excellent sprayability as a pump spray or aerosol.
- Additives have a good hair-setting effect, form films with very good mechanical properties and are characterized by the fact that they practically do not stick the hair together.
- the (meth) acrylate polymers have outstanding 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. In particular, they can be clearly formulated in aqueous low-VOC preparations with a maximum of 55% by weight of volatile organic constituents (VOC-55).
- the hair fixatives according to the invention can be washed out of the hair perfectly. Hair treated with them has increased suppleness and a pleasant natural feel. At the same time, the strengthening effect is high, so that in principle it is possible to reduce the amount of film former required in the hair spray formulation. Due to the odorlessness of the
- (meth) acrylate polymers can be dispensed with the addition of odor-covering perfume oils.
- the (meth) acrylate polymers are particularly suitable as film formers in hair cosmetic preparations.
- the (meth) acrylate polymers are usually present in 0.1 to 20% by weight, preferably 0.5 to 10% by weight, in particular 2 to 10% by weight, of the partially or completely neutralized (meth) acrylate polymer based on the cosmetic preparation used.
- a customary organic solvent such as, above all, ethanol, isopropanol and dimethoxymethane and also acetone, n-propanol, n-butanol, 2-methoxypropan-1-ol, n-pentane, n-hexane, cyclohexane, n-heptane, n-octane or dichloromethane or mixtures thereof
- a conventional blowing agent such as n-propane, iso-propane, n-butane, sobutane, 2,2-dimethylbutane, n -Pentane, isopentane, dimethyl ether, difluoroethane, fluorotrichloromethane, dichlorodifluoromethane or dichlorotetrafluoroethane, HFC 152 A or mixtures thereof
- Alkanolamines are used to neutralize various types of acids and to adjust the pH of cosmetic products.
- Examples (INCI) are aminomethyl propanol, diethanolamine, diisopropanolamine, ethanolamine, methylethanolamine, N-lauryl diethanolamine, triethanolamine, triisoproanolamine, etc.
- alkali metal hydroxides eg NaOH, KOH
- other bases can be used for neutralization (eg histidine, arginine , Lysine or ethylenediamine, diethylene triamine, melamine, benzoguanamine). All of the stated bases can be used alone or as a mixture with other bases for neutralizing acidic cosmetic products.
- Propellant gases Propellant gases
- blowing agents used above all are the hydrocarbons, in particular propane, n-butane, n-pentane and mixtures thereof, and also dimethyl ether and difluoroethane. If appropriate, one or more of the chlorinated hydrocarbons mentioned are also used in blowing agent mixtures, but only in small amounts, approximately up to 20% by weight, based on the blowing agent mixture.
- 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 for example, has the following composition:
- anionic, cationic, amphoteric and neutral polymers are suitable as conventional polymers.
- Copolymers of acrylic acid, methyl methacrylate, octylacrylamide, butylaminoethyl methyl acrylate and hydroxypropyl methacrylate
- Copolymers of vinyl acetate and crotonic acid and / or (vinyl) neodecanoate
- Copolymers of tert-butyl acrylate, methacrylic acid and dimethicone copolyol are preferred.
- preparations which contain the polymers in combination with these other polymers have unexpected properties.
- the preparations according to the invention are superior in particular to the preparations of the prior art with regard to their skin and hair care properties. Furthermore, they have very good film-forming and strengthening properties.
- Copolymer are available, for example, as commercial products Luviflex TM Soft (BASF).
- Copolymers of N-tert-butylacrylamide, ethyl acrylate and acrylic acid are available, for example, as commercial products Ultrahold Strang TM, Ultrahold 8 TM (BASF).
- Polyvinylpyrrolidones (INCI name: PVP) are available, for example, under the trade names Luviskol K TM, Luviskol K 30 TM (BASF) and PVP K (ISP).
- Polyvinylcaprolactams (INCI: Polyvinylcaprolactame) are available, for example, under the trade name Luviskol Plus TM (BASF).
- Polyurethanes (INCI: Polyurethane -1) are, for example, under the trade name
- Luviset TM PUR available.
- Copolymers of acrylic acid, methyl methacrylate, octylacrylamide, butylaminoethyl methacrylate, hydroxypropyl methacrylate are known, for example, under the trade names Amphomer TM 28-4910 and Amphomer TM LV-71 (National Starch).
- Copolymers of vinyl acetate and crotonic acid are available, for example, under the trade names Luviset CA 66 TM (BASF), Resyn TM 28-1310 (National Starch) and Aristoflex TM A (Celanese).
- Copolymers of vinyl acetate, crotonic acid and (vinyl) neodecanoate are available, for example, under the trade names Resyn TM 28-2930 (National Starch) and Luviset TM CAN (BASF).
- Copolymers of vinyl acetate and N-vinylpyrrolidone are available, for example, under the trade names Luviskol VA TM (BASF) and PVP / VA (ISP).
- Carboxy-functional copolymers of vinyl pyrrolidone, t-butyl acrylate, methacrylic acid are available, for example, under the trade name Luviskol TM VBM (BASF).
- Copolymers of tert-butyl acrylate, methacrylic acid and dimethicone copolyol are available, for example, under the trade name Luviflex TM Silk (BASF).
- Anionic polymers are suitable as further polymers.
- Such anionic polymers are homopolymers and copolymers of acrylic acid and methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and their salts, sodium salts of polyhydroxycarboxylic acids, copolymers of acrylic acid and methacrylic acid with, for example, hydrophobic monomers, for example C 4 , from the (meth) acrylate polymers according to the invention -C 30 alkyl esters of (meth) acrylic acid, C -C 30 alkyl vinyl esters, C 4 -C 30 alkyl vinyl ethers and hyaluronic acid as well as others under the trade names Amerhold DR-25, Ultrahold TM, Luviset TM PUR, Acronal TM, Acu- dyne TM, Lovocryl TM, Versatyl TM, Amphomer TM (28-4910, LV-71), Placise TM L53, Gantrez
- additional polymers are water-soluble or water-dispersible polyesters, polyureas, co-polyurethaneureas, maleic anhydride copolymers which may have been reacted with alcohols or anionic polysiloxanes.
- Additional suitable polymers are, for example, cationic polymers with the INCI name Polyquaternium, for example
- Copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts available, for example, under the trade name Luviquat Hold TM
- copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate available, for example, under the trade name Luviquat TM
- Neutral polymers such as polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and copolymers with N-vinylpyrrolidone, cellulose derivatives, polyaspartic acid salts and derivatives are also suitable as further hair cosmetic polymers.
- These include the Luviskol TM (K, VA, Plus), PVP K, PVP / VA, Advantage TM HC and H 2 OLD EP-1 known under the trade names.
- biopolymers i.e. Polymers that are obtained from naturally renewable raw materials and are built up from natural monomer components, e.g. Cellulose derivatives, chitin, chitosan, DNA, hyaluronic acid and RNA derivatives.
- Suitable polymers are betaine polymers such as Yukaformer (R205, SM) and Diaformer.
- Suitable anionic surfactants include for example alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl aryl carboxylate, alkyl succinates, alkyl sulphosuccinates, N-AIkoylsarkosinate, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether, alpha-olefin sulfonates, especially the alkali metal and alkaline earth metal salts, eg sodium, potassium , Magnesium, calcium, and ammonium and triethanolamine salts.
- the alkyl ether sulfates, alkyl ether phosphates, alkyl glycol alkoxylates and - diglycol alkoxylates and alkyl ether carboxylates can be between 1 to 10 ethylene oxide or
- Propylene oxide units preferably 1 to 3 ethylene oxide units in the molecule.
- 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 dodecyl benzene sulfonate are suitable.
- Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or propionates, alkylamphodiacetates or dipropionates.
- cocodimethylsulfopropylbetaine laurylbetaine, cocamidopropylbetaine or sodium 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, alkylglycol alkoxylates and diglycol alkoxylates or sorbitan ether esters are also suitable.
- the agents can contain conventional cationic surfactants, e.g. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
- conventional cationic surfactants e.g. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
- the (meth) acrylate polymers according to the invention are used in shampoo formulations, they usually contain anionic surfactants as base surfactants and amphoteric and nonionic surfactants as cosurfactants.
- anionic surfactants as base surfactants
- amphoteric and nonionic surfactants as cosurfactants.
- relevant reviews such as J. Falbe (ed.), “Surfactants in Consumer Products”, Springer Verlag, Berlin, 1987, pp. 54-124 or J. Falbe (ed.), “Catalysts , Tenside und Mineralöladditive ", Thieme Verlag, Stuttgart, 1978, pp. 123-217.
- the cosmetic preparations usually contain 2 to 50% by weight of surfactants, preferably 5 to 40% by weight, particularly preferably 8 to 30% by weight.
- Suitable emulsifiers are, for example, 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
- polyol and in particular polyglycerol esters such as polyglycerol polyricin oleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate. Mixtures of compounds from several of these classes of substances are also suitable; (7) adducts of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;
- partial esters based on linear, branched, unsaturated or saturated C6 / 22 - fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, Butyl glucoside, lauryl glucoside) and polyglucosides (eg cellulose);
- the 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 Degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out.
- C 12 to C 18 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 2024051 as refatting agents for cosmetic preparations.
- C 8 to C 18 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.
- glycoside ester 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 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 carry at least one quaternary ammonium group and at least one carboxylate and / or one sulfonate group in the molecule.
- Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylamino propyl-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 cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
- fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred.
- Suitable emulsifiers are ampholytic surfactants.
- Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C 8 -C 18 -alkyl or -acyl group, contain at least one free amino group and at least one -COOH and / or -SO 3 H group in the molecule and for the formation of internal ones Salts are capable.
- ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylamino-butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylamino acetic acids, each with about 8 to 18 carbon atoms in the alkyl group.
- Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12 to C-
- 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 that can be used are, for example: 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 with 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; Fat- 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
- Suitable consistency agents are primarily fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxy fatty acids. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred.
- Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates (for example Carbopol TM from Goodrich or Synthalen TM from Sigma), polyacrylic amides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as, for example, pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with restricted homolog distribution or alkyl oligoglucosides, and electrolytes such as sodium chloride and ammonium chloride.
- polysaccharides in particular xanthan gum, guar gu
- 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, calcium, 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.
- 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 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; Methylol 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;
- Aminosugars such as glucamine.
- 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.
- Perfume oils include, for example, mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit shells (bergamot, Lemon, orange), roots (mace, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme ), Needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olivanum, opoponax).
- 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, 4-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phthalate nyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
- the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonate, the ketones, for example, the jonones, cc-isomethyl ions and methyl cedryl ketone the alcohols anethof, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terioneol, the hydrocarbons mainly include the terpenes and balsams.
- fragrance oils of lower volatility which are mostly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil.
- bergamot oil dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, a-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, Cyclovertal, lavandin oil, muscatel Sage oil, b-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillate, iroty
- the dyes which can be used are those 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 total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight, based on the composition.
- the polymers according to the invention are readily soluble in solvents and solvent mixtures with an increased water content. Because of the ability of the polymers according to the invention to form films with good mechanical properties, they can be used in preparations for dental care. Possible forms of provision are, for example, toothpastes, toothbrush jelly, chewing gum or mouthwash.
- the polymers according to the invention are provided in the non, partially or completely neutralized form, preferably in the non or partially neutralized form, for oral and dental care.
- the polymers according to the invention and the films made from these polymers are therefore preferably in an anionic charge state.
- the agents for oral and dental care contain customary constituents such as abrasives and polishes (for example chalk), humectants (for example sorbitol, glycerol, polyethylene glycols), surfactants (for example lauryl sulfate, betaines, alkyl polyglucosides), aroma components, consistency regulators, deodorant agents, swelling agents, binders (e.g. carboxymethyl cellulose, xanthan gum), agents against mouth or tooth diseases, water-soluble fluorine compounds (e.g. sodium fluoride).
- abrasives and polishes for example chalk
- humectants for example sorbitol, glycerol, polyethylene glycols
- surfactants for example lauryl sulfate, betaines, alkyl polyglucosides
- aroma components for example e.g., sorbitol, glycerol, polyethylene glycols
- surfactants for example lauryl sulf
- anionic surfactants are soaps, alkylbenzene sulfonates, alkane sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, glycerol ether sulfates, hydroxy mixed ether sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinic acid amides, sulfosuccinic acid amide, sulfosuccinic acid amide and sulfosuccinic acid amide their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids, such as, for example, acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates
- anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution.
- Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, glucoronic acid derivatives, fatty acid-N-alkylglucamides, wheat-based, protein hydrolysate products, especially protein hydrolysate products , Sorbitan esters, polysorbates and amine oxides.
- nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
- Typical examples of amphoteric or zwitterionic surfactants are aminopropionates, aminoglycinates.
- betaines, monoglyceride (ether) sulfates and alkyl and or alkenyl oligoglycosides, mono- and dialkyl sulfosuccinates and / or taurates are preferably added to the alkoxylated carboxylic acid esters.
- the surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example, J.
- the K values are measured according to Fikentscher, Cellulosechemie, vol. 13, pp. 58 to 64 (1932) at 25 ° C in aqueous / ethanolic or ethanolic solution and represent a measure of the molecular weight.
- the aqueous / Ethanolic or ethanolic solution of the polymer contains 1 g polymer in 100 ml solution.
- appropriate amounts of the dispersion are made up to 100 ml with ethanol, depending on the polymer content of the dispersion, so that the concentration of 1 g of polymer in 100 ml of solution is formed.
- the K value is measured in a Micro Ubbelohde capillary type M Ic from Schott.
- the setting of polymeric film formers is also measured physically as the bending stiffness of thin strands of hair that have been treated with the polymer solution and dried again.
- a force transducer determines the force required for bending, while the entire measurement takes place under standardized conditions in a climate room at 65% relative air humidity.
- bending stiffness 3.0% by weight solutions of the polymers according to the invention were prepared. The bending stiffness was measured on 5 to 10 strands of hair (approximately 3 g and 24 cm in length) at 20 ° C. and 65% relative humidity. The weighed, dry tresses of hair were immersed in the 3.0% by weight polymer solution, with an even distribution being ensured by immersion and removal three times. The excess film-forming solution was then wiped off between the thumb and forefinger and the strands of hair were then carefully squeezed out by squeezing between filter paper. The strands were then shaped by hand so that they had a round cross-section. At 20 ° C and 65% relative humidity it was dried overnight in a climatic room.
- the tests were carried out in a climate room at 20 ° C and 65% relative humidity using a tension / pressure tester.
- the lock of hair was placed symmetrically on two cylindrical rollers of the sample holder. Exactly in the middle, the strand was bent from above with a rounded punch 40 mm (breaking the polymer film).
- the force required for this was measured with a load cell (50 N) and given in Newtons.
- the particle sizes of the liquid aerosols were determined using the scattered light analysis method with a commercial Malvern TM Master Sizer X (Malvern Instruments Inc., Southborough MA, USA).
- the measuring system is based on laser light diffraction on the particle.
- this method is also suitable for determining the size of solids, suspensions and emulsions in the size range from 0.1 ⁇ m to 2000 ⁇ m.
- the aerosols were sprayed at a distance of 29.5 cm from the laser beam.
- the spray cone entered at right angles to the laser beam.
- the aerosol cans were fixed to a permanently installed holding device, so that it was achieved that all aerosols to be tested were measured at exactly the same distance.
- the evaluation contained a tabular representation over 32 class widths from 0.5 ⁇ m to 2000 ⁇ m and also a graphic representation of the particle size distribution.
- the mean diameter "D" (v, 0.5) was given.
- this value is dependent on the polymer content, valve, spray head geometry, solvent ratio and propellant gas - Quantities below 120 ⁇ m, preferably below 10 ⁇ m, particularly preferably in the range from 30 ⁇ m to 70 ⁇ m.
- valve A Seaquist Perfect; Cone 0.32 mm, 0.50 VPH 0.40 mm (239436) as spray head: SK1 (yellow); DU381
- feed II was metered in over the course of 3 hours with constant feed streams.
- reaction mixture was stirred for a further hour at 80 ° C. and then cooled to 60 ° C.
- Feed III was added while maintaining the temperature at 60.degree. It is then cooled to 35 ° C. and feed IV was added while maintaining the reaction temperature.
- Feed II is an aqueous monomer emulsion made from:
- TweenTM 80 for example, can be used as the nonionic emulsifier.
- Example FB1 hairspray as VOC 55 formulation
- Example FB 1 was repeated with the copolymers S1, S2, S4, S5, S6, S7.
- Example FB 2 hairspray with some additives as VOC 55 formulation
- Example FB 2 was repeated with the copolymers S1, S2, S4, S5, S6, S7.
- Example FB 3 hairspray with HF 152A as VOC 55 formulation
- Example FB 4 hairspray with HF 152A and DME as VOC 55 formulation
- Example FB 4 was repeated with the copolymers S1, S2, S4, S5, S6, S7.
- Example FB 5 hairspray with acrylates copolymer as VOC 55 formulation wt .-% INCI
- Example FB 5 was repeated with the copolymers S1, S2, S4, S5, S6, S7.
- Example FB 6 hairspray with octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer as VOC 55 formulation
- Example FB 6 was repeated with the copolymers S1, S2, S4, S5, S6, S7.
- Example FB 7 hairspray with acrylate / octylacrylamide copolymer as VOC 55 formulation
- Example FB 7 was repeated with the copolymers S1, S2, S4, S5, S6, S7.
- Example FB 8 hairspray with VA / Crotonates / Vinyl Neodecanoate as VOC 55 formulation
- Example FB 8 was repeated with the copolymers S1, S2, S4, S5, S6, S7.
- Example FB 9 aerosol hair spray as VOC80 formulation wt .-% INCI
- Example FB 9 was repeated with the copolymers S1, S2, S4, S5, S6, S7.
- Example FB 10 aerosol hair spray with Polyurethane-1 as VOC80 formulation
- Example FB 10 was repeated with the copolymers S1, S2, S4, S5, S6, S7.
- Example FB 11 aerosol hair spray with PEG / PPG-25/25 dimethicone / acrylates copolymer as VOC80 formulation
- Example FB 11 was repeated with the copolymers S1, S2, S4, S5, S6, S7.
- Example FB 12 aerosol hair spray as VOC95 formulation
- Example FB 12 was repeated with the copolymers S1, S2, S4, S5, S6, S7.
- Example FB 13 Pump hair spray wt .-% INCI:
- Example FB 13 was repeated with the copolymers S1, S2, S4, S5, S6, S7.
- Example FB 14 Pump hair spray with VP / methacrylamide / vinyl imidazole copolymer wt .-% INCI
- Example FB 14 was repeated with the copolymers S1, S2, S4, S5, S6, S7. Results of the application tests of aerosol formulations containing the polymers according to the invention
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- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002552231A CA2552231A1 (en) | 2004-01-16 | 2005-01-13 | Acrylate polymers based on tert.-butyl acrylate which are to be used in spray formulations |
US10/585,889 US20080312395A1 (en) | 2004-01-16 | 2005-01-13 | Acrylate Polymers Based on Tert.- Butyl Acrylate Which are to be Used in Spray Formulations |
JP2006548260A JP2007517950A (ja) | 2004-01-16 | 2005-01-13 | スプレー製剤で使用するためのtert−ブチルアクリレートベースのアクリレートポリマー |
EP05700874A EP1709093A1 (de) | 2004-01-16 | 2005-01-13 | Acrylat-polymerisate auf basis von tert.-butylacrylat zur verwendung in sprayformulierungen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004002650A DE102004002650A1 (de) | 2004-01-16 | 2004-01-16 | Acrylat-Polymerisate auf Basis von tert.-Butylacrylat zur Verwendung in Sprayformulierungen |
DE102004002650.5 | 2004-01-16 |
Publications (1)
Publication Number | Publication Date |
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WO2005068520A1 true WO2005068520A1 (de) | 2005-07-28 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2005/000258 WO2005068520A1 (de) | 2004-01-16 | 2005-01-13 | Acrylat-polymerisate auf basis von tert.-butylacrylat zur verwendung in sprayformulierungen |
Country Status (9)
Country | Link |
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US (1) | US20080312395A1 (de) |
EP (1) | EP1709093A1 (de) |
JP (1) | JP2007517950A (de) |
KR (1) | KR20070001132A (de) |
CN (1) | CN1910211A (de) |
CA (1) | CA2552231A1 (de) |
DE (1) | DE102004002650A1 (de) |
RU (1) | RU2006129559A (de) |
WO (1) | WO2005068520A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013103980A2 (en) * | 2012-01-06 | 2013-07-11 | Enamelite Llc | Acrylic spray |
JP5430149B2 (ja) * | 2006-04-17 | 2014-02-26 | 三菱鉛筆株式会社 | 水系液体メイクアップ化粧料 |
US20150157543A1 (en) * | 2009-04-27 | 2015-06-11 | Akzo Nobel Chemicals International B.V. | Film forming polymer compositions for boosting spf in sunscreens |
US11180665B2 (en) | 2020-02-21 | 2021-11-23 | Swimc Llc | Stain-blocking polymers, primers, kits, and methods |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5628031B2 (ja) | 2007-07-25 | 2014-11-19 | スリーエム イノベイティブ プロパティズ カンパニー | 治療用歯科用組成物及び関連する方法 |
EP2106784B1 (de) * | 2008-04-03 | 2015-04-22 | Rohm and Haas Company | Haarstylingzusammensetzung |
EP2322570A1 (de) * | 2009-11-16 | 2011-05-18 | DSM IP Assets B.V. | Acrylpolymer |
EP2646486A1 (de) * | 2010-12-02 | 2013-10-09 | DSM IP Assets B.V. | Acrylpolymer |
US8607803B2 (en) | 2011-09-29 | 2013-12-17 | The Procter & Gamble Company | Hair treatment process providing dispersed colors by light diffraction |
JP5840025B2 (ja) * | 2012-02-20 | 2016-01-06 | 株式会社マンダム | 整髪用エアゾールスプレー化粧料 |
IN2015DN03893A (de) | 2013-03-28 | 2015-10-02 | Procter & Gamble | |
CN104745125B (zh) * | 2013-12-27 | 2017-03-15 | 比亚迪精密制造有限公司 | 可喷涂胶液及其制备方法和带有嵌件的注塑产品的制备方法 |
US20200085716A1 (en) * | 2017-05-23 | 2020-03-19 | Basf Se | Use of specific polymers to bring about an anti-pollution effect |
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EP0379082A2 (de) * | 1989-01-18 | 1990-07-25 | BASF Aktiengesellschaft | Haarfestigungsmittel |
WO1994024986A1 (de) * | 1993-04-30 | 1994-11-10 | Basf Aktiengesellschaft | Haarfestigungsmittel |
WO2002038638A1 (de) * | 2000-11-10 | 2002-05-16 | Basf Aktiengesellschaft | Acrylatpolymerisate auf basis von tert.butylacrylat und/oder tert.-butylmethacrylat |
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US4529753A (en) * | 1984-04-10 | 1985-07-16 | Polysar Limited | Chemical/steam stripping |
DE3718520A1 (de) * | 1987-06-03 | 1988-12-15 | Bayer Ag | Emulsionspolymerisate |
DE4003422A1 (de) * | 1990-02-06 | 1991-08-08 | Basf Ag | Waessrige polyurethanzubereitungen |
DE4210208A1 (de) * | 1992-03-28 | 1993-09-30 | Hoechst Ag | Verfahren zur Verminderung des Restmonomerengehaltes in wäßrigen Kunststoffdispersionen auf Polyvinylesterbasis |
CN1120180C (zh) * | 1994-06-03 | 2003-09-03 | 巴斯福股份公司 | 聚合物水分散液的制备 |
DE19741187A1 (de) * | 1997-09-18 | 1999-03-25 | Basf Ag | Verfahren zur Verminderung des Restmonomerengehalts in wässrigen Polymerdispersionen |
DE19839199A1 (de) * | 1998-08-28 | 2000-03-02 | Basf Ag | Verfahren zur Verminderung der Restmonomerenmenge in wässrigen Polymerdispersionen |
DE19840586A1 (de) * | 1998-09-05 | 2000-03-09 | Basf Ag | Verfahren zur Verminderung der Restmonomerenmenge in wässrigen Polymerdispersionen |
-
2004
- 2004-01-16 DE DE102004002650A patent/DE102004002650A1/de not_active Withdrawn
-
2005
- 2005-01-13 CN CNA2005800022512A patent/CN1910211A/zh active Pending
- 2005-01-13 CA CA002552231A patent/CA2552231A1/en not_active Abandoned
- 2005-01-13 EP EP05700874A patent/EP1709093A1/de not_active Withdrawn
- 2005-01-13 US US10/585,889 patent/US20080312395A1/en not_active Abandoned
- 2005-01-13 KR KR1020067016313A patent/KR20070001132A/ko not_active Application Discontinuation
- 2005-01-13 WO PCT/EP2005/000258 patent/WO2005068520A1/de active Application Filing
- 2005-01-13 JP JP2006548260A patent/JP2007517950A/ja not_active Withdrawn
- 2005-01-13 RU RU2006129559/04A patent/RU2006129559A/ru not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0379082A2 (de) * | 1989-01-18 | 1990-07-25 | BASF Aktiengesellschaft | Haarfestigungsmittel |
WO1994024986A1 (de) * | 1993-04-30 | 1994-11-10 | Basf Aktiengesellschaft | Haarfestigungsmittel |
WO2002038638A1 (de) * | 2000-11-10 | 2002-05-16 | Basf Aktiengesellschaft | Acrylatpolymerisate auf basis von tert.butylacrylat und/oder tert.-butylmethacrylat |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5430149B2 (ja) * | 2006-04-17 | 2014-02-26 | 三菱鉛筆株式会社 | 水系液体メイクアップ化粧料 |
US8663666B2 (en) | 2006-04-17 | 2014-03-04 | Mitsubishi Pencil Company, Limited | Water based liquid makeup cosmetic |
US20150157543A1 (en) * | 2009-04-27 | 2015-06-11 | Akzo Nobel Chemicals International B.V. | Film forming polymer compositions for boosting spf in sunscreens |
US10039700B2 (en) | 2009-04-27 | 2018-08-07 | Bayer Healthcare Llc | Enhanced efficiency of sunscreen compositions |
WO2013103980A2 (en) * | 2012-01-06 | 2013-07-11 | Enamelite Llc | Acrylic spray |
WO2013103980A3 (en) * | 2012-01-06 | 2013-10-10 | Enamelite Llc | Acrylic spray |
US11180665B2 (en) | 2020-02-21 | 2021-11-23 | Swimc Llc | Stain-blocking polymers, primers, kits, and methods |
US11649361B2 (en) | 2020-02-21 | 2023-05-16 | Swimc Llc | Stain-blocking polymers, primers, kits, and methods |
Also Published As
Publication number | Publication date |
---|---|
KR20070001132A (ko) | 2007-01-03 |
CA2552231A1 (en) | 2005-07-28 |
DE102004002650A1 (de) | 2005-08-11 |
RU2006129559A (ru) | 2008-02-27 |
CN1910211A (zh) | 2007-02-07 |
JP2007517950A (ja) | 2007-07-05 |
EP1709093A1 (de) | 2006-10-11 |
US20080312395A1 (en) | 2008-12-18 |
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