WO2011144406A1 - Polysiloxan blockcopolymere und deren verwendung in kosmetischen formulierungen - Google Patents
Polysiloxan blockcopolymere und deren verwendung in kosmetischen formulierungen Download PDFInfo
- Publication number
- WO2011144406A1 WO2011144406A1 PCT/EP2011/056203 EP2011056203W WO2011144406A1 WO 2011144406 A1 WO2011144406 A1 WO 2011144406A1 EP 2011056203 W EP2011056203 W EP 2011056203W WO 2011144406 A1 WO2011144406 A1 WO 2011144406A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- radical
- formula
- radicals
- methacrylate
- substituted
- Prior art date
Links
- 0 C*C(CC(*)(*)*)C(NC)=O Chemical compound C*C(CC(*)(*)*)C(NC)=O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
-
- 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
Definitions
- the invention relates to specific polyorganosiloxane compounds, in particular polysiloxane alkoxyamines and polysiloxane block copolymers prepared therefrom, in particular those suitable for use in cosmetic formulations and personal care formulations, a process for preparing the polysiloxane alkoxyamines and preparation of the polysiloxane block copolymers by nitroxide-based controlled free-radical Polymerization, and compositions containing the polysiloxane
- Block copolymers as well as their use in cosmetic and personal care applications.
- Cosmetic and personal care formulations e.g. Hair styling sprays, hair conditioners, foams, gels and shampoos often contain resins, gums and adhesives to provide a variety of beneficial effects, such as hair conditioning.
- beneficial effects such as hair conditioning.
- film-forming properties, thickening properties, tactile properties, such as improved grip and hair shaping properties to produce are particularly desirable.
- Polymers used in such formulations include, but are not limited to, organic or silicone-containing linear or grafted copolymers which may be composed of a variety of different monomers.
- the polymer blocks may be alternating, random, block-structured, branched or hyperbranched or homopolymer blocks.
- Grafted polymers are known as film-forming polymers in cosmetic formulations for the treatment of hair or skin. These grafted polymers typically comprise a polymeric backbone and one or more macromonomers grafted onto the backbone, allowing the physical and chemical properties, such as glass transition temperature and water solubility, to be independently set for the polymeric backbone and grafted macromonomers to be as desired To adjust the overall properties of the complete polymer.
- WO 95/01383 and WO 95/01384 disclose the use of water and alcohol soluble or dispersible graft copolymers in hair and skin care compositions in which the copolymer has a backbone and one or more polymeric side chains prepared by the random copolymerization of Monomer A and monomer B.
- Monomer A is selected to have a hydrophobic character and macromonomer B has a long hydrophilic portion.
- EP 0 412 704, EP 0 408 313 and EP 0 412 707 disclose the use of silicone-grafted acrylate copolymers in US Pat
- WO 02/053111 describes the use of silicone polyether block copolymers with (AB) n structures in aqueous, surface-active body cleansing compositions which have good cosmetic properties especially for the volume
- Block copolymers have the advantage over grafted copolymers that the polymer construction can be better controlled. This is particularly important and important if you want to tailor polymers with areas that For example, alternating "hard” and “soft” segments in a polymer for hairspray applications provide improved hold and feel to specific physical and chemical properties.
- US 5,468,477 discloses cosmetic compositions containing a vinyl-silicone grafted copolymer or a block copolymer characterized in that the copolymer contains a silicone segment and a vinyl polymer segment.
- the block or grafted copolymer is prepared by free radical polymerization of a mercapto-functionalized silicone which functions as a chain transfer agent with a vinylic monomer. Copolymers made by this method typically have low molecular weights and low silicone content due to the early chain termination reactions.
- organopolysiloxane macroinitiators are organopolysiloxanes containing groups that can form radicals. Such compounds are described in US 5,523,365.
- the use for the preparation of copolymers is disclosed in WO 98/48771 and US 6,074,628.
- a disadvantage of this method is the handling of dangerous, prone to explosive decomposition, organosiloxane macroinitiators, which must be used in significant amounts, since the end product otherwise contains too few silicone units.
- the large-scale production of macroinitiators is extremely difficult and associated with a considerable amount of security.
- the reaction is inefficient because of large amounts of unreacted silicone oil must be separated by means of a time-consuming extraction. This process is very difficult upscalebar.
- WO 00/71606 describes a process for the preparation of polysiloxane block copolymers in which an organopolysiloxane macroinitiator in an atom transfer radical polymerization (ATRP) with copper salts as a catalyst for the preparation of controlled architecture block copolymers is used.
- ATRP atom transfer radical polymerization
- the document does not disclose anything about the copper content of the polymers produced.
- the polymers produced are terminated with bromine atoms, which is disadvantageous for use in cosmetic formulations.
- WO 2009043629 relates to polysiloxane block copolymers of the formula A [LB (S) Q] m , where A is a polyoxyalkane, L is a divalent organic linker, B is a polymer block composed of free-radically polymerizable monomers, S is a sulfur atom and Q is a monovalent organic radical and m is an integer from 1 to 50, a process for their preparation and their use in cosmetics or personal care.
- the process for producing polysiloxane block copolymers disclosed in WO 2009043629 is characterized in that it comprises the steps A) of reacting an atom transfer radical initiator which is a polysiloxane macroinitiator of the formula A [LX] m which contains at least one organically bonded halogen atom X.
- A is a polysiloxane block
- L is a divalent organic radical
- m is an integer of 1 to 50
- B addition of a compound Q-SH with Q is a monovalent organic radical to the polymerization mixture of step A).
- adversely in this method is that halogen-containing initiators and copper are used and that these must then be removed in an additional process step again.
- US 2008/0312377 also discloses reacting a macroinitiator with methyl methacrylate to form an AB block copolymer.
- a disadvantage of this method is that very mild reaction conditions, which are technically only with great effort to produce, are used for esterification because iBA-DEPN decomposes at temperatures> 30 ° C.
- monoalkoxyamine siloxanes which are obtainable from monofunctionalized siloxanes are described. Such simply functionalized siloxanes are very difficult and expensive to produce and continue to limit the type of silicones used very strong.
- US2008 / 0312377 does not disclose use of the described polymers in cosmetic formulations.
- EP 1 464 648 discloses the preparation of alkoxyamines of the following general formula (III):
- R H or CH 3 and M is a sequence of free-radically polymerizable vinylic monomers, n is an integer which may also be zero, X is greater than or equal to 1 and Z is a mono- or polyfunctional structural unit which may also be a silicone can.
- EP 1 464 648 does not disclose the nature of the silicone, nor is an example given.
- A is an OH radical or a chlorine atom or TO radical
- T alkali metal such as Li, Na, K, NH 4
- R H or CH 3
- M is a sequence of free-radically polymerizable vinylic monomers
- n is an integer which may also be zero, with a mono- or polyfunctional structural unit Z to form an ester functionality.
- EP 1 526 138 Bl discloses the preparation of polyalkoxyamines of the formula (V)
- R 1 is a linear or branched alkyl radical having 1 to 3 carbon atoms
- R 2 is a hydrogen atom, a linear or branched alkyl radical having 1 to 8 carbon atoms, a phenyl radical, an alkali metal such as Li, Na or K or an ammonium such as NH 4 +, NBu 4 + or NHBu 3 + represents and preferably R 1 is CH 3 and R 2 is H; optionally in the presence of one or more solvents, at a reaction temperature of preferably between 0 and 90 ° C with a polyunsaturated compound of formula (VII).
- -CH CH 2
- Z is an aryl group or is a formula ZI- [X-C (O)] n , wherein ZI is a polyfunctional structure derived, for example, from a polyol-type compound, X is an oxygen atom, a nitrogen atom is one carbon-containing group or also a hydrogen atom, where X can also be a sulfur atom and n is a number greater than or equal to two.
- EP 1 526 138 B1 makes no statement as to whether Z or ZI can also be a siloxane-containing polyfunctional structure or about the use of the polymers described in cosmetic formulations.
- the object of the present invention was to provide a process for the preparation of polysiloxane block copolymers which does not have one or more disadvantages of the prior art.
- the present invention therefore relates to polyorganosiloxane compounds of the formula (VIII):
- A is a polysiloxane block
- L is a divalent organic radical
- G -O-, -S-, -CR 3 (OH) -CH (R 3 ) -O-, -NR 3 -, with R 3 independently of one another hydrogen or a monovalent substituted or unsubstituted, linear or branched 1 to 18 Containing carbon atoms,
- R 1 is identical or different and is a linear or branched alkyl radical having 1 to 3 carbon atoms, preferably CH 3
- R 2 is a hydrogen atom, a linear or branched alkyl radical having 1 to 8 carbon atoms, a phenyl radical, an alkali metal such as Li, Na or K or Ammonium such as NH 4 + , NR 5 R 6 R 7 R 8+ with R 5 , R 6 R 7 and R 8 independently of one another denote H or C 1 -C 40 -alkyl radical, and preferably R 2 represents H,
- B is a polymer block composed of free-radically polymerized monomers
- n 1 to 50
- R 2 is H, and optional
- the siloxane content can be varied widely and the resulting products can be widely used z. B. in the field of cosmetic and personal care formulations, especially in hair care, find.
- the polysiloxane block copolymers according to the invention, a process for their preparation and their use are described below by way of example, without the invention being restricted to these exemplary embodiments. Given below, ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their contents are intended to form part of the disclosure content of the present invention. If the following information is given as a percentage, this is by weight unless otherwise stated. If mean values are indicated below, these are, unless stated otherwise, by number average.
- A is an m-linked polyorganosiloxane radical
- L is a divalent organic radical
- R 1 is identical or different and is a linear or branched alkyl radical having 1 to 3 carbon atoms, preferably CH 3
- R 2 is a hydrogen atom or a linear or branched alkyl radical having 1 to 8 carbon atoms, a phenyl radical, an alkali metal cation such as Li + , Na + or K. +, or an ammonium, such as NH 4 +, NR 5 R 6 R 7 R 8 + R 5, R 6 R 7 and R 8 are independently H or Ci-C 40 alkyl radical, preferably a hydrogen atom,
- SGI is a radical of the formula (II)
- B is a polymer block composed of free-radically polymerizable or polymerized monomers
- n is an integer from 1 to 50, preferably 2 to 10 and preferably 2, 3 or 4.
- the unit A is preferably a polysiloxane radical of the formula (IX) is with
- j is a number from 0 to 10, preferably ⁇ 5 and particularly preferably 0,
- k is a number from 1 to 500, preferably 1 to 250 and particularly preferably 1 to 100,
- R f is the same or different radicals R 9 or a bond to the building block L, with the proviso that m radicals R f are a bond to the building block L,
- R 9 is substituted or unsubstituted alkyl radicals having 1 to 18 C atoms, preferably 1 to 6 C atoms, more preferably methyl or an aryl radical, preferably a phenyl radical.
- polysiloxane compounds are in the form of a mixture having a distribution substantially governed by statistical law.
- the values for the indices j and k therefore represent mean values.
- Residue L ' can be interrupted by divalent radicals attached on both sides to carbon atoms, such as -0-, -C (0) 0-, C0NR p, NR P C (0), or -C (0) -, wherein R p is a monovalent substituted or unsubstituted, linear or branched 1 to 18 carbon atoms containing radical.
- Particularly preferred polyorganosiloxane compounds are those in which L is a linear unbranched hydrocarbon radical having 3-10 C atoms, preferably a -CH 2 -CH 2 -CH 2 - or -CH 2 - (CH 2 ) 4 -CH 2 - radical.
- polyorganosiloxane compounds according to the invention are to be used as macroinitiators, it may be advantageous if b is 0.
- b is 0.
- b is 1
- the free-radically polymerizable monomers for the construction of the block B can be selected from all known free-radically polymerizable monomers M.
- the polymer block B is preferably from radically polymerized monomers M selected from substituted or unsubstituted (meth) acrylic acids and their derivatives built up .
- Preferably used monomers M include acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, n-butylacrylate, iso-o-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate,
- Me thoxyethy 1 ethacry 1 at, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, maleic acid, the monoesters of maleic acid, the diesters of maleic acid, Ma 1 one anhydro anhydr id, Ma 1 one ime re imi de, fumaric acid, itaconic acid , the monoesters of itaconic acid, the diesters of itaconic acid, itaconic anhydride, crotonic acid, angelic acid, diallyldimethylammonium chloride, vinyl in pyrrole, Vi ny 1 i mi da zo 1, Me t hy 1 iny 1 et r, Me thy 1 iny 1 ke tone, vinylpyridine, vinylfuran, styrene, styrenesulfonate,
- suitable monomers M are hydrocarbons having at least one unsaturated carbon-carbon double bond, preferably selected from styrene, alpha-methylstyrene, t-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene, para-methylstyrene, and mixtures thereof.
- the monomers M are mixtures of monomers which contain from 50 to 99% by weight, preferably 75 to 95% by weight, of (meth) acrylic acid or derivatives thereof, in particular monomers selected from the group Methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, N, N-
- the indices o and p greater than 0, and mixtures thereof are particularly preferred, and from 1 to 50 wt .-%, preferably 5 to 25 wt .-% hydrocarbons having at least one unsaturated carbon-carbon double bond, preferably selected from styrene, alpha-methylstyrene, t-butylstyrene, butadiene, Isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene, para-methylstyrene and mixtures thereof.
- the polymer block B preferably has a number-average molecular weight of from 1000 g / mol to 200000 g / mol, preferably a number-average molecular weight of 4000 g / mol to 120000 g / mol and more preferably from 4000 g / mol to 75000 g / mol.
- the polymer block B is particularly preferably a poly (meth) acrylate block, preferably having a number average molecular weight of from 1000 g / mol to 200000 g / mol, preferably having a number average molecular weight of 4000 g / mol to 120000 g / mol and more preferably a number average molecular weight of 4000 g / mol to 75000 g / mol.
- the polyorganosiloxane compound according to the invention preferably has a number-average molecular weight of from 1 to 2,000 g / mol to 1,000,000 g / mol, preferably from 5,000 g / mol to 500,000 g / mol and most preferably from 10,000 g / mol to 250,000 g / mol.
- the polyorganosiloxane compounds of the invention can be prepared in various ways.
- the polyorganosiloxane compounds according to the invention are preferably obtainable by the process according to the invention described below.
- B. be obtained by first a suitable vinylically unsaturated compound V with the / the reactive groups of a polysiloxane, for. B. is reacted in a nucleophilic substitution reaction.
- the polysiloxane used is preferably a polysiloxane which has at least one functional group which has a 0, N or S atom and is suitable for nucleophilic attack on these atoms.
- polysiloxanes are used which are selected from polysiloxanes of the formula (IXa), With
- b is a number from 0 to 10, preferably ⁇ 5 and preferably 0, a is a number from 1 to 500, preferably 1 to 250 and preferably 1 to 100,
- R r is the same or different radicals R m or R n , with the proviso that at least one radical R f is a radical R n ,
- R m is alkyl having 1 to 18 C atoms, preferably 1 to 6 C atoms, or an aryl radical, preferably phenyl, where R m may be substituted or unsubstituted,
- R 1 is a radical of the general formula (X)
- L ' is a divalent optionally branched substituted or unsubstituted hydrocarbon radical having 1 to 60 C atoms, preferably 1 to 20 C atoms and particularly preferably 3 to 10 C atoms, and
- R 3 is independent of one another is a monovalent substituted or unsubstituted, linear or branched radical containing 1 to 18 carbon atoms.
- the divalent radical L ' may be interrupted by divalent radicals which are bonded to carbon atoms on both sides, for example -O-, -C (O) O-, CONR 4 , NR 4 C (O), or -C ( 0) -, wherein R 4 is a monovalent substituted or unsubstituted, linear or branched 1 to 18 carbon atoms containing radical.
- a suitable vinylic unsaturated compound V is preferably used a compound containing at least one group C (0) X ', in which X' is a leaving group, which is in a nucleophilic attack by the 0, N or S atom of the functional group of Polysiloxane can be substituted and containing at least one vinylic double bond, to which an alkoyxamine of the formula (VIII) can be added in a radical addition.
- Preferred suitable vinylic unsaturated compounds are compounds of the formula (XI):
- CH 2 CH-C (O) X '(XI) where X' is the leaving group.
- the leaving group is a halogen atom (F, Cl, Br, or I) or an OH group or a R '0 group, wherein R' represents an alkyl radical.
- X ' is an OH group
- the nucleophilic substitution reaction between functional polysiloxane and suitable vinylic unsaturated compound can be carried out under the reaction conditions typical of such reactions, which are known to those skilled in the art.
- R 1 is a linear or branched alkyl radical 1 to 3 carbon atoms
- R 2 is a hydrogen atom,
- the solvent is preferably selected from the group comprising water, alcohols, such as, for example, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert. Butanol, pentanol, hexanol, heptanol, octanol, Cycl ohexano 1, aromatic solvents, chlorinated and or fluorinated solvents, ethers, such.
- alcohols such as, for example, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert.
- Butanol pentanol, hexanol, heptanol, octanol, Cycl ohexano 1, aromatic solvents, chlorinated and or fluorinated solvents, ethers, such.
- the reaction after step A) can be carried out at atmospheric pressure, underpressure or overpressure, preferably at atmospheric pressure.
- the reaction after step A) is preferably carried out at a temperature of 0 ° C to 90 ° C, preferably from 0 ° C to 80 ° C, more preferably from 25 ° C to less than 80 ° C.
- the reaction according to step A) is preferably carried out under a protective gas selected from the group comprising nitrogen, noble gases, C0 2 or gaseous hydrocarbons, such as methane, or mixtures thereof. Particularly preferred is the implementation under nitrogen as a protective gas.
- the solvent can be removed by distillation or by another method known to the person skilled in the art before the optional process step B), the temperature for removing the solvent or the solvent mixture being 90 ° C, preferably 80 ° C, does not exceed. This can e.g. be achieved by a corresponding adjustment of the pressure in a distillation.
- radically polymerizable monomers M all suitable monomers can be used in step B).
- ethylenically unsaturated monomers are used in step B).
- polymerizable is meant monomers which, as described in the present invention, are polymerizable using nitroxide-based controlled radical polymerisation
- the polymer chain length and the polymer chain length can be polymerized
- Polymer architecture can be controlled in a known manner and it can polydispersity of the
- Molar mass distribution (ratio of weight average molecular weight to number average molecular weight) narrowly distributed polymers can be obtained.
- ethylenically unsaturated monomers monomers having at least one polymerizable carbon-carbon double bond, which double bond may be mono-, di-, tri-or tetra-substituted, either single monomers or mixtures of monomers selected to meet the desired physical and chemical properties of the polysiloxane block copolymer.
- Preferred ethylenically unsaturated monomers M which can be used for the polymerization are those of the formula (XII)
- radicals R 9 and R 10 can be selected independently of one another from the group consisting of hydrogen, unbranched or branched C 1 - to C 10 - Alkyl radicals, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethyl and 2-ethoxyethyl radicals.
- the radical G ' may be selected from the group comprising - hydroxy, -O (M) 1 / v , -O-R 11 , -NH 2 , -NHR 11 and -N (R 11 ) (R 12 ); where M is a counterion of valence v selected from the group the metal ions, such as alkali metal ions,
- Ammonium ions such as, mono-, di-, tri- or tetraalkylammonium ions, and each radical R 11 and R 12 may be independently selected from the group consisting of hydrogen, Ci - C 40 straight or branched alkyl chains, polyether radicals, polyetheramine optionally substituted with one or more substituents selected from the group consisting of hydroxy, amino, Ci - C 3 alkoxy, Ci - C 3 alkylamino and di (Ci - C 3 alkyl) amino, z. N, -dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl.
- monomers also include protected or unprotected acrylic acid and methacrylic acid, as well as salts and esters and amides of these acids.
- the salts can be derived from any metal, ammonium or substituted ammonium counterion.
- the esters can be derived from C 1 -C 40 straight-chain, C 3 -C 40 branched alkyl chains or C 3 -C 40 carbocyclic alcohols, from polyfunctional alcohols containing from 2 to 8 carbon atoms and from 2 to 8 hydroxyl groups, from amino alcohols and from polyethylene glycols or
- Polypropylene glycols or other polyether radicals and hydroxy groups functionalized polyethers include ethylene glycol,
- Propylene glycol, butyleneglycol, hexyleneglycol, glycerol and 1,2,6-hexanetriol), of aminoalcohols include aminoethanol, dimethylaminoethanol, diethylaminoethanol and their quaternized products) or of ether alcohols, such as e.g. As methoxyethanol or ethoxyethanol.
- the amides can be unsubstituted, N-alkyl or N-alkylamino mono-substituted or dis, ⁇ -dialkyl, or N, -dialkylamino disubstituted, wherein the alkyl or alkylamino groups are derived from Ci - C 0 straight-chain or C 3 -C 0 branched, or C 3 - C 40 cyclic units.
- the alkylamino group may be quaternized.
- Also usable monomers are protected or unprotected acrylic and / or methacrylic acids, their salts, esters and amides, wherein the second or third carbon position of the acrylic acids and / or methacrylic acids may be substituted independently of one another.
- the substituents may be selected from the group comprising C 1 -C 4 -alkyl radicals, hydroxyl, -CN, and -COOH, for example methacrylic acid, ethacrylic acid and 3-cyanoacrylic acid.
- the salts, esters and amides of these substituted aryl and methacrylic acids as described above can also be used.
- Other useful monomers M include: vinyl and allyl ethers of straight chain 3 to 40 carbon atom containing, branched or 3 to 40 carbon atoms containing carbocyclic carboxylic acids, pyridines substituted with at least one vinyl or allyl group (eg vinylpyridine or allylpyridine), Hydrocarbons having at least one unsaturated carbon-carbon double bond (eg styrene, alpha-methylstyrene, t-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene, para-methylstyrene) and mixtures from that.
- vinyl and allyl ethers of straight chain 3 to 40 carbon atom containing, branched or 3 to 40 carbon atoms containing carbocyclic carboxylic acids pyridines substituted with at least one vinyl or allyl group (eg vinylpyridine or allylpyridine
- Preferably used as free-radically polymerizable monomers M substituted or unsubstituted (meth) acrylic acid or derivatives thereof.
- Preferably used monomers M include acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl
- Glyceryl monoacrylate glyceryl monomethacrylate
- Maleic acid the monoesters of maleic acid, the diesters of maleic acid, maleic anhydride, maleic imides, fumaric acid, itaconic acid, itaconic acid monoesters, itaconic acid diesters, itaconic anhydride, crotonic acid, angelic acid, diallyldimethylammonium chloride, vinylpyrrolidones, vinylimidazole, methyl vinyl ether,
- R s is H, alkyl, preferably C 1 to C 3 alkyl, preferably methyl
- monomers selected from the group comprising methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate,
- mixtures of monomers which contain from 50 to 99% by weight, preferably 75 to 95% by weight, of (meth) acrylic acid or derivatives thereof, in particular monomers selected from the group comprising methyl acrylate, Methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, N, N-
- indices o and p greater than 0, and mixtures thereof are particularly preferred, and from 1 to 50 wt .-%, preferably 5 to 25 wt .-% hydrocarbons having at least one unsaturated carbon-carbon double bond, preferably selected from styrene, alpha-methylstyrene, t-butylstyrene, butadiene, Isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene, para-methylstyrene and mixtures thereof.
- the polymerization in step B) can be carried out in bulk or in solution.
- the polymerization in step B) may, for. B.
- a solvent is preferably selected from the group comprising water, alcohols, such as, for example, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert. Butanol, pentanol, hexanol, heptanol, octanol, cyclohexanol, aromatic solvents, chlorinated and or fluorinated solvents, ethers, such as.
- alcohols such as, for example, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert.
- tetrahydrofuran, 1,4-dioxane organic esters such as butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone; ether; Aliphaten, preferably pentane, hexane and further polar aprotic Lieremitten used.
- the list is only exemplary and not exhaustive.
- the amount of solvent or solvent mixture is 5 to 95 wt .-% based on the amount of monomers M and macroinitiator (Villa), preferably 10 to 75 wt .-% and most preferably 20 to 50 wt .-%.
- the reaction after step B) can be carried out at normal pressure, lower or lower pressure
- Overpressure preferably at atmospheric pressure to be performed.
- the temperature in optional step B) of the process according to the invention is preferably greater than or equal to 70 ° C. and particularly preferably greater than or equal to 80 ° C.
- the reaction of step B) is preferably selected from a group consisting of nitrogen, noble gases, CO 2 or gaseous hydrocarbons, e.g. Methane, or mixtures thereof are carried out. Particularly preferred is the implementation under nitrogen as a protective gas.
- the polyorganosiloxane compounds of the formula (VIII) according to the invention can be used grisseitg.
- the polyorganosiloxane compounds of the formula (VIII) according to the invention for the preparation of cosmetic or pharmaceutical compositions or of
- compositions according to the invention comprise at least one polyorganosiloxane compound of the formula (VIII) according to the invention and at least one component other than this compound, eg. B. one for cosmetic or pharmaceutical compositions or
- compositions suitable vehicle may, for. As cosmetic or pharmaceutical compositions or
- compositions according to the invention preferably contain from 0.01% by mass to 20% by mass, preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 3% by mass of at least one organopolysiloxane compound according to formula (VIII) based on the total weight of the formulation.
- compositions of the invention may, for.
- As for the treatment of hair as Kondi t ioniermi tel for hair treatment agents, used as a hair aftertreatment agent and to improve the hair structure.
- the compositions according to the invention can be used for the treatment of hair, in particular for use as a hair conditioner.
- the organopolysiloxane compounds of the invention can also in wide ranges of different types of products such.
- compositions hair spray Compositions, hair styling compositions mousses, gels, lotions, sprays, shampoos, conditioners, hand and body lotions, facial moisturizers, sunscreen, anti-acne formulations, anti-aging formulations, topical analgesics, mascara and the like, the list being exemplary and not exhaustive is to be used.
- the vehicles and additional components needed to formulate such products vary with the type of product and can be readily selected by one skilled in the art. In the following, some possible carrier substances and additional components which may be contained in compositions according to the invention are described.
- compositions of the invention may, for. As a carrier or a mixture of different carriers, which are suitable for use in cosmetic or pharmaceutical compositions or in
- compositions in particular for use on hair.
- the content of carrier in the formulation is from 0.5% by weight to 99.5% by weight, preferably from 5.0% by weight to 99.5% by weight, particularly preferably 10.0 Wt .-% to 98 wt
- suitable for use on hair means that the wearer does not damage the hair, does not adversely affect the aesthetic appearance of the hair, or produce irritation to the underlying skin
- Suitable carriers for the use of hair care products in the present invention include, for example, those used in hair sprays, mousses, tonic, gels, shampoos, conditioners or rinses
- suitable carrier depends on the type of block copolymer used and whether the formulated product should remain on the surface to which it is added was applied (eg.
- Hair spray, mousse, tonic or gel or whether it is after Application is rinsed off again (eg shampoo, conditioner, rinses).
- the carriers used may comprise a wide range of compounds commonly used in compositions, especially hair care compositions.
- the carriers may comprise a solvent to dissolve or disperse the copolymer used, with water, C 1 -C 6 alcohols, alkyl acetates having alkyl groups comprising one to ten carbon atoms, and mixtures thereof being preferred.
- the carriers can halogenate a wide range of additional substances, such as acetone, hydrocarbons (for example: isobutane, pentane, hexane, decene)
- Hydrocarbons such as freons
- volatile silicone derivatives such as cyclomethicone.
- the preferred solvents include water, ethanol, volatile silicone derivatives and mixtures thereof.
- the solvents used in such mixtures may be miscible or immiscible with each other.
- Mousses and aerosol hair sprays may also contain any conventional propellant to apply the material as a foam (in the case of mousse) or as a fine, uniform spray (in the case of the aerosol hair spray).
- blowing agents include materials from the group comprising trichlorofluoromethane, dichlorodifluoromethane, difluoroethane, dimethyl ether, propane, n-butane or isobutane or mixtures thereof.
- a low viscosity tonic or hairspray product may also contain an emulsifier.
- suitable emulsifiers include nonionic, cationic, anionic surfactants or mixtures thereof. When such an emulsifier is used, the composition contains the emulsifier in a concentration of 0.01% to 7.5%.
- the content of propellant can be adjusted as needed, but is usually between 3% and 30% for Mousse compositions and from 15% to 50% in aerosol hair sprays.
- Suitable containers for spraying are well known to those skilled in the art and include conventional non-aerosol pump sprays, i. H. "Atomisers", aerosol cans or cans with propellant as described above, and also pump aerosol cans using compressed air as propellant
- the carrier can contain a wide variety of conditioning compounds
- the hair care compositions are shampoos, the vehicle may contain surfactants, suspending aids and thickeners.
- the wearer may include various appearances, e.g.
- the carrier may be an emulsion comprising e.g. As oil-in-water emulsions, water-in-oil emulsions, water-in-oil-in-water and oil-in-water-in-silicone emulsions.
- the viscosity of the emulsions can range from 100 cps to 200,000 cps.
- These emulsions can also be sprayed using either mechanical pumping containers or pressurized aerosol containers with the usual propellants.
- the carriers can also be applied in the form of mousse.
- suitable topical carriers include non-aqueous liquid solvents such as oils, alcohols and silicones (e.g., mineral oil, ethanol, isopropanol, dimethicones, cyclomethicones, and the like), water-based liquid monophase solvents (eg, water / alcohol solvent systems), and thickened variants of these t water-based and water-based liquid single-phase solvents (eg where the viscosity of the solvent has been increased to a solid or semi-solid by the addition of suitable gums, waxes, resins, polymers, salts and similar substances). Additional components:
- compositions of the present invention can be used in the compositions of the present invention, particularly in the cosmetic and personal care compositions of the present invention.
- An enumeration of possible components can, for.
- DE 10 2008 001 786 are taken.
- examples include, but are not limited to, sunscreen, such as: B. 2-ethylhexyl-p-methoxy cinnamate, 2-ethyl-N, -dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, Homomenthylsalycilate,
- Octyl salicylates 4,4'-methoxy-t-butyldibenzoylmethane, 4-isopropyldibenzoylmethane, 3-benzylidene camphor, 3
- Antidandruff active ingredients such as bis (2-pyridylthio) zinc ⁇ , ⁇ '-dioxide, piroctone, selenium disulphide, sulfur, coal tar and the like.
- the hydrocarbons can be unbranched or branched and have between 10 and 16 carbon atoms, preferably between 12 and 16
- Carbon atoms included.
- suitable hydrocarbons are decane, dodecane, tetradecane, tridecane and mixtures thereof.
- conditioning agents containing silicone include cyclic or linear polydimethylsiloxanes,
- Phenyl and alkyl phenyl silicones and silicone polyols are quaternary, even silicone-containing, ammonium salts or the salts of fatty acid amines.
- the content is surfactants preferably from 10% to 30% and more preferably from 12% to 25% of the composition.
- the preferred level of surfactants is from about 0.2% to about 3%.
- the surfactants useful in the compositions include anionic, nonionic, zwitterionic, cationic and amphoteric surfactants.
- Polymeric thickeners with carboxylic acid groups contain one or more derivatives of acrylic acid, substituted acrylic acid, salts and esters of these acrylic acids and substituted acrylic acids, in the case of crosslinked polymers, the crosslinking agent containing two or more carbon-carbon double bonds.
- polymeric thickeners are those selected from the group consisting of carbomers, acrylates / Cio-C 30 alkyl acrylates crosslinked copolymers, and mixtures thereof.
- Compositions of the present invention may contain from 0.025% to 1%, preferably from 0.05% to 0.75%, and more preferably from 0.10% to 0.50% of the polymeric thickeners having carboxylic acid groups.
- Emulsifiers for emulsifying a wide variety of excipients described in composition in this invention include polyethylene glycol 20 sorbitan monolaurate (polysorbate 20), polyethylene glycol 5 soybean sterol, steareth-20, ceteareth-20, PPG-2 methylglucose ether distearate, ceteth-10, polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, polysorbate 60, glyceryl stearate , PEG-100 stearate and mixtures thereof.
- the emulsifiers may be used singly or as a mixture of two or more emulsifiers.
- Personal care composition may comprise an emulsifier content of from 0.15% to 10%, preferably from 1% to 7% and most preferably from 1% to 5%.
- Vitamins and derivatives thereof eg ascorbic acid, vitamin E, tocopherol acetate, retinoic acid, retinol, retinoids and the like.
- Cationic polymers e.g., cationic guar derivatives such as guar hydroxypropyltrimonium chloride and
- Components such as perfume, fragrances, dyes, pigments, hair nutrients, and essential oils.
- corresponding SiH-group-containing siloxanes are used.
- 2 moles of 1-hexenol are reacted instead of 2 moles of allyl alcohol.
- Polydimethylsiloxane is then analogous to the description reacted further in Example 1 with 2 mol of acrylic acid and worked up as described.
- Dimethylaminoethylmethacrylat and 0.9 g of styrene was added dropwise and heated at 110 ° C for a further 8h. It was then cooled and bottled the product.
- a mixture of 10.4 g of dimethylaminoethyl methacrylate and 0.9 g of styrene and 15 g of the difunctional polydimethylsiloxanedialkoxyamine prepared above was initially charged in a multi-necked flask equipped with a stirrer, thermometer, backflow tube, nitrogen inlet tube and dropping funnel under N 2 atmosphere and after careful degassing heated to 110 ° C for 5 h.
- Dimethylaminoethylmethacrylat and 2.1 g of styrene was added dropwise and heated at 110 ° C for a further 6h. It was then cooled and bottled the product.
- hair tresses are used for sensory tests are damaged beforehand standardized manner by a permanent wave treatment ⁇ and a bleaching treatment.
- hairdressing customary products are used.
- the base materials used as well as the details of the evaluation criteria are described in DE 103 27 871.
- the polysiloxane copolymers were tested in a simple hair rinse having the composition given in Table 1.
- TEGI CILT C and TEG Alkanol 16 are available from Evonik Goldschmidt GmbH.
- conditioner refers to the polyorganosiloxane compounds described in Examples 1 to 5.
- the hair strands were wetted under running, warm water. The excess water was gently squeezed out by hand, then the rinse was applied and gently incorporated into the hair (1 ml / strand of hair (2 g)). After a residence time of 1 min, the hair was rinsed for 1 min. Before the sensory evaluation, the hair was dried in air at 50% humidity and 25 ° C for at least 12 hours.
- the formulation of the test formulation is deliberately simple in order to avoid affecting the test results by (normally present) formulation ingredients.
- Formulations according to the invention may contain, in addition to the ingredients mentioned and / or instead of the ingredients mentioned, further ingredients. In particular, the combination with other ingredients can lead to a synergistic improvement of the conditioning effect. Such ingredients are described above. assessment criteria
- Test criteria were scored on scores ranging from 1 to 5, with 1 being the worst and 5 being the best scores.
- the individual test criteria each receive their own rating.
- the test criteria are: Detangling, wet combability, wet grip, dry combability,
- the polysiloxane block copolymers have hair conditioning properties. They are significantly better than the control without control
- the polysiloxane block copolymer of Example 2 was incorporated into a formulation for a non-aerosol hairspray with 80% by mass of volatile organic compounds (so-called 80% VOC non-aerosol hairspray) according to the composition listed in Table 3.
- AMP-95 (INCI name: Aminomethyl Propanol) is a product of ANGUS Chemical Company.
- ABIL B 8843 (INCI name: PEG-14 Dimethicone) is a product of Goldschmidt GmbH.
- SD Alcohol 40 Ethanol.
- Table 3 when applied as a hair spray, showed improved flexibility of the treated hair and produced a noticeably improved feel than a formulation which was not according to the invention
- the polysiloxane block copolymer of Example 1 was incorporated into a formulation for a hair styling gel according to the composition listed in Table 4.
- AMP-95 (INCI name: Aminomethyl Propanol) is a product of Angus.
- Carbopol ETD 2020 (INCI Name: Acrylic C 10-30 Alkyl Acrylate Crosspolymer) is a product of Noveon.
- the formulation from Table 4 forms a gel with a pudding-like consistency which, when applied as a styling gel, leads to sufficient stability in the hair, while at the same time providing flexibility and a comfortable grip.
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Cosmetics (AREA)
- Polymerization Catalysts (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/642,323 US20130035452A1 (en) | 2010-05-19 | 2011-04-19 | Polysiloxane block copolymers and use thereof in cosmetic formulations |
JP2013510538A JP2013527286A (ja) | 2010-05-19 | 2011-04-19 | ポリシロキサンブロックコポリマーおよび化粧料配合物におけるその使用 |
BR112012029304A BR112012029304A2 (pt) | 2010-05-19 | 2011-04-19 | copolíme-ros em bloco de polissiloxano e seu uso em formulações cosmeticas |
EP11715232A EP2571911A1 (de) | 2010-05-19 | 2011-04-19 | Polysiloxan blockcopolymere und deren verwendung in kosmetischen formulierungen |
CN2011800211295A CN102858827A (zh) | 2010-05-19 | 2011-04-19 | 聚硅氧烷嵌段共聚物及其在化妆品配制物中的用途 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US34608310P | 2010-05-19 | 2010-05-19 | |
US61/346,083 | 2010-05-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011144406A1 true WO2011144406A1 (de) | 2011-11-24 |
Family
ID=44201058
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2011/056203 WO2011144406A1 (de) | 2010-05-19 | 2011-04-19 | Polysiloxan blockcopolymere und deren verwendung in kosmetischen formulierungen |
Country Status (6)
Country | Link |
---|---|
US (1) | US20130035452A1 (de) |
EP (1) | EP2571911A1 (de) |
JP (1) | JP2013527286A (de) |
CN (1) | CN102858827A (de) |
BR (1) | BR112012029304A2 (de) |
WO (1) | WO2011144406A1 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102011078382A1 (de) | 2011-06-30 | 2013-01-03 | Evonik Goldschmidt Gmbh | Mikroemulsion von quaternären Ammoniumgruppen enthaltenden Polysiloxanen, derenHerstellung und Verwendung |
DE102013206175A1 (de) | 2013-04-09 | 2014-10-09 | Evonik Industries Ag | Polysiloxan-Polyether-Copolymere mit Amino- und/oder quaternären Ammoniumgruppen im Polyetherteil und Verfahren zu deren Herstellung |
AU2016285815B2 (en) * | 2015-06-30 | 2019-02-28 | The Gillette Company Llc | Liquid compositions for hair removal devices |
EP3438158B1 (de) | 2017-08-01 | 2020-11-25 | Evonik Operations GmbH | Herstellung von sioc-verknüpften polyethersiloxanen |
EP3744764A1 (de) | 2019-05-28 | 2020-12-02 | Evonik Operations GmbH | Herstellung von sioc-verknüpften polyethersiloxanen |
EP3744752A1 (de) | 2019-05-28 | 2020-12-02 | Evonik Operations GmbH | Verfahren zur herstellung von nichtcyclischen alkoxyfunktionellen polysiloxanen |
JP7350253B2 (ja) * | 2019-07-23 | 2023-09-26 | 長瀬産業株式会社 | ビスハロアルキルシロキサン化合物及びその製造方法、並びに、両末端官能性のシロキサン化合物の製造方法 |
JP2021017424A (ja) * | 2019-07-23 | 2021-02-15 | 共栄社化学株式会社 | 有機ケイ素化合物及びエネルギー線硬化型樹脂組成物 |
Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3810140C1 (de) | 1988-03-25 | 1989-10-05 | Th. Goldschmidt Ag, 4300 Essen, De | |
EP0408313A1 (de) | 1989-07-10 | 1991-01-16 | Nkk Corporation | Legierung auf Titan-Basis und Verfahren zu deren Superplastischer Formgebung |
US4988506A (en) | 1989-08-07 | 1991-01-29 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer non-pressure sensitive topical binder composition and method of coating therewith |
EP0412707A1 (de) | 1989-08-07 | 1991-02-13 | The Procter & Gamble Company | Haarkonditionierungs- und Haarformmittel |
EP0412704A2 (de) | 1989-08-07 | 1991-02-13 | The Procter & Gamble Company | Haarpflege- und Fixierungsmittel |
WO1995001383A1 (en) | 1993-07-01 | 1995-01-12 | The Procter & Gamble Company | Thermoplastic elastomeric copolymers and hair and skin care, compositions containing the same |
WO1995001384A1 (en) | 1993-07-01 | 1995-01-12 | The Procter & Gamble Company | Thermoplastic elastomeric copolymers and hair and skin care compositions containing the same |
US5468477A (en) | 1992-05-12 | 1995-11-21 | Minnesota Mining And Manufacturing Company | Vinyl-silicone polymers in cosmetics and personal care products |
US5523365A (en) | 1993-11-10 | 1996-06-04 | Wacker-Chemie Gmbh | Graft copolymers of organopolysiloxanes as free radical macroinitiators |
WO1998048771A1 (en) | 1997-04-25 | 1998-11-05 | The Procter & Gamble Company | Hair spray compositions |
US6074628A (en) | 1997-04-25 | 2000-06-13 | Procter & Gamble | Hairspray compositions containing silicon block copolymers |
WO2000071606A1 (en) | 1999-05-24 | 2000-11-30 | Unilever Plc | Polysiloxane block copolymers in topical cosmetic and personal care compositions |
WO2002053111A2 (fr) | 2001-01-02 | 2002-07-11 | L'oreal | Compositions cosmetiques contenant une silicone bloc polyether et une silicone polyether et leurs utilisations |
EP1464648A1 (de) | 2003-04-01 | 2004-10-06 | Atofina | Beta-phosphorierte Alkoxyamine und ihre Verwendung zur Herstellung von Alpha-Omega funktionellen Polymeren |
DE10327871A1 (de) | 2003-06-18 | 2005-01-05 | Goldschmidt Ag | Verwendung von Alkylguanidin-Verbindungen zur Behandlung und Nachbehandlung von Haaren |
US20050107577A1 (en) * | 2003-10-24 | 2005-05-19 | Jean-Luc Couturier | Process for the preparation of polyalkoxyamines which can be used as initiators for the radical polymerization of polyfunctional living (CO)polymers |
WO2006096550A2 (en) * | 2005-03-07 | 2006-09-14 | Arkema Inc. | Conductive block copolymers |
WO2007078819A2 (en) * | 2005-12-16 | 2007-07-12 | Arkema Inc. | Low surface energy block co-polymer preparation methods and applications |
WO2009043629A1 (de) | 2007-09-27 | 2009-04-09 | Evonik Goldschmidt Gmbh | Polysiloxan blockcopolymere |
DE102008001786A1 (de) | 2008-05-15 | 2009-11-26 | Evonik Goldschmidt Gmbh | Verwendung organomodifizierter Siloxanblockcopolymere als Pflegewirkstoff zur Pflege von menschlichen oder tierischen Körperteilen |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6680362B1 (en) * | 2003-02-05 | 2004-01-20 | 3M Innovative Properties Company | Ring-opened azlactone initiators for nitroxide-mediated polymerization |
ATE535581T1 (de) * | 2008-02-22 | 2011-12-15 | Basf Se | Fluornivellierungsmittel |
-
2011
- 2011-04-19 JP JP2013510538A patent/JP2013527286A/ja active Pending
- 2011-04-19 EP EP11715232A patent/EP2571911A1/de not_active Withdrawn
- 2011-04-19 US US13/642,323 patent/US20130035452A1/en not_active Abandoned
- 2011-04-19 WO PCT/EP2011/056203 patent/WO2011144406A1/de active Application Filing
- 2011-04-19 CN CN2011800211295A patent/CN102858827A/zh active Pending
- 2011-04-19 BR BR112012029304A patent/BR112012029304A2/pt not_active IP Right Cessation
Patent Citations (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3810140C1 (de) | 1988-03-25 | 1989-10-05 | Th. Goldschmidt Ag, 4300 Essen, De | |
EP0408313A1 (de) | 1989-07-10 | 1991-01-16 | Nkk Corporation | Legierung auf Titan-Basis und Verfahren zu deren Superplastischer Formgebung |
US4988506A (en) | 1989-08-07 | 1991-01-29 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer non-pressure sensitive topical binder composition and method of coating therewith |
EP0412707A1 (de) | 1989-08-07 | 1991-02-13 | The Procter & Gamble Company | Haarkonditionierungs- und Haarformmittel |
EP0412704A2 (de) | 1989-08-07 | 1991-02-13 | The Procter & Gamble Company | Haarpflege- und Fixierungsmittel |
US5468477A (en) | 1992-05-12 | 1995-11-21 | Minnesota Mining And Manufacturing Company | Vinyl-silicone polymers in cosmetics and personal care products |
WO1995001383A1 (en) | 1993-07-01 | 1995-01-12 | The Procter & Gamble Company | Thermoplastic elastomeric copolymers and hair and skin care, compositions containing the same |
WO1995001384A1 (en) | 1993-07-01 | 1995-01-12 | The Procter & Gamble Company | Thermoplastic elastomeric copolymers and hair and skin care compositions containing the same |
US5523365A (en) | 1993-11-10 | 1996-06-04 | Wacker-Chemie Gmbh | Graft copolymers of organopolysiloxanes as free radical macroinitiators |
US6074628A (en) | 1997-04-25 | 2000-06-13 | Procter & Gamble | Hairspray compositions containing silicon block copolymers |
WO1998048771A1 (en) | 1997-04-25 | 1998-11-05 | The Procter & Gamble Company | Hair spray compositions |
WO2000071606A1 (en) | 1999-05-24 | 2000-11-30 | Unilever Plc | Polysiloxane block copolymers in topical cosmetic and personal care compositions |
WO2002053111A2 (fr) | 2001-01-02 | 2002-07-11 | L'oreal | Compositions cosmetiques contenant une silicone bloc polyether et une silicone polyether et leurs utilisations |
EP1464648A1 (de) | 2003-04-01 | 2004-10-06 | Atofina | Beta-phosphorierte Alkoxyamine und ihre Verwendung zur Herstellung von Alpha-Omega funktionellen Polymeren |
DE10327871A1 (de) | 2003-06-18 | 2005-01-05 | Goldschmidt Ag | Verwendung von Alkylguanidin-Verbindungen zur Behandlung und Nachbehandlung von Haaren |
US20050107577A1 (en) * | 2003-10-24 | 2005-05-19 | Jean-Luc Couturier | Process for the preparation of polyalkoxyamines which can be used as initiators for the radical polymerization of polyfunctional living (CO)polymers |
EP1526138B1 (de) | 2003-10-24 | 2008-03-26 | Arkema France | Verfahren zur Herstellung von Polyalkoxyaminen zur Verwendung als Initiatoren radikalischer Polymerisationen von polyfunktionellen lebenden Polymeren |
WO2006096550A2 (en) * | 2005-03-07 | 2006-09-14 | Arkema Inc. | Conductive block copolymers |
WO2007078819A2 (en) * | 2005-12-16 | 2007-07-12 | Arkema Inc. | Low surface energy block co-polymer preparation methods and applications |
US20080312377A1 (en) | 2005-12-16 | 2008-12-18 | Arkema, Inc. | Low Surface Energy Block Copolymer Preparation Methods and Applications |
WO2009043629A1 (de) | 2007-09-27 | 2009-04-09 | Evonik Goldschmidt Gmbh | Polysiloxan blockcopolymere |
DE102008001786A1 (de) | 2008-05-15 | 2009-11-26 | Evonik Goldschmidt Gmbh | Verwendung organomodifizierter Siloxanblockcopolymere als Pflegewirkstoff zur Pflege von menschlichen oder tierischen Körperteilen |
Also Published As
Publication number | Publication date |
---|---|
BR112012029304A2 (pt) | 2016-07-26 |
US20130035452A1 (en) | 2013-02-07 |
JP2013527286A (ja) | 2013-06-27 |
CN102858827A (zh) | 2013-01-02 |
EP2571911A1 (de) | 2013-03-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2011144406A1 (de) | Polysiloxan blockcopolymere und deren verwendung in kosmetischen formulierungen | |
EP2193159A1 (de) | Polysiloxan blockcopolymere | |
CZ20014208A3 (cs) | Způsob výroby polysiloxanového blokového kopolymeru | |
WO2006079632A1 (de) | Verwendung von wasser-in-wasser-emulsionspolymerisaten als verdicker in kosmetischen zubereitungen | |
EP1576945A1 (de) | Kosmetische oder pharmazeutische Mittel, enthaltend modifizierte Polyorganosiloxane | |
EP1694728A1 (de) | Copolymere auf basis von tert.-butyl(meth)acrylat und deren verwendung | |
EP1694725A1 (de) | Anionische ampholytische copolymere | |
EP1345575A2 (de) | Kosmetische und dermatologische haarbehandlungsmittel | |
EP1656111A1 (de) | Kosmetische und pharmazeutische mittel auf basis von polyelektrolyt-komplexen | |
WO2005068520A1 (de) | Acrylat-polymerisate auf basis von tert.-butylacrylat zur verwendung in sprayformulierungen | |
EP2066705A1 (de) | Kationische polymere als verdicker für wässrige und alkoholische zusammensetzungen | |
WO2005095479A1 (de) | Diallylamine enthaltende polymerisate | |
EP1847253A1 (de) | Wasserlösliche Polymere und ihre Verwendung in kosmetischen und pharmazeutischen Zubereitungen | |
RU2245347C2 (ru) | Полисилоксановые блок-сополимеры в локальных косметических и гигиенических композициях | |
EP1804920A1 (de) | Kosmetische zubereitungen enthaltend copolymere von ethylmethacrylat und mindestens einer monoethylenisch ungesättigten carbonsäure | |
WO2011144407A1 (de) | Polysiloxan blockcopolymere und deren verwendung in kosmetischen formulierungen | |
DE60302340T2 (de) | Triblock-copolymere für kosmetik- oder pflegezusammensetzungen | |
EP1117711B1 (de) | Kationische polymerisate und ihre verwendung | |
WO2015059084A1 (de) | Fällungspolymerisation in gegenwart eines tertiären amins und eines anhydrids | |
DE10163523A1 (de) | Verfahren zur Herstellung von Polymerisaten | |
WO2004078810A2 (de) | Polymere produkte | |
DE602004004252T2 (de) | Aba-blockcopolymere für eine haarstyling-zusammensetzung | |
DE10163118A1 (de) | Verfahren zur Herstellung von Polymerisaten | |
DE10311120A1 (de) | Polymere Produkte und ihre Verwendung in kosmetischen Zubereitungen | |
EP2913351A1 (de) | Verfahren zur Herstellung von Copolymeren der 2-Acrylamido-2-methylpropansulfonsäure |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180021129.5 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11715232 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13642323 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011715232 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2013510538 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012029304 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012029304 Country of ref document: BR Kind code of ref document: A2 Effective date: 20121116 |