Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D171/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
• • 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/22—Esters containing halogen
• • 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
  • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
  • C08G65/2633—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen the other compounds containing amide groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
  • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
  • C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/12—Chemical modification
  • C08J7/16—Chemical modification with polymerisable compounds
  • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation

Definitions

• the invention relates to LCST polymers, their preparation and use.
• LCST polymers based on polyalkylene oxides are known.
• a LCST (Lower Critical Solution Temperature) polymer is understood as meaning a polymer which, although soluble at a lower temperature in a liquid medium, is above a certain temperature, namely the cloud point, or the LCST temperature, from the liquid medium fails. This process is reversible, so that the system becomes homogeneous again during cooling.
• the temperature at which the solution becomes clear on cooling is called the cloud point (see German standard DIN EN 1890 of September 2006). This temperature is characteristic of a particular substance.
• WO 01/60926 A1 discloses a process for coating particles with LCST polymers, in which the LCST polymer is dissolved in a solvent below the LCST, the resulting solution is mixed with the particles to be coated, and then the temperature of the obtained mixture is raised to a temperature above the LCST with precipitation of the LCST polymers on the particle surfaces.
• LCST polymers based on polyalkylene oxides are known, which are terminally substituted with an optionally substituted acrylate. It is further known from WO 2004/046258 A2 to use these LCST polymers for coating particle-free and non-particulate substrate surfaces, the polymers being contacted with the particles or surfaces in a liquid medium below the LCST temperature , the temperature increases above the LCST temperature and polymerize the polymers via the double bonds at this or a higher temperature on the surface of the particles, or the surfaces.
• the invention relates to formula I.
• R 1 and R 2 are hydrogen or an alkyl radical, in particular with 1
• A is a radical containing the radicals A1 and A2, in which mean
• R 3 to R 6 are identical or different, H, C 1 - to C 5 -alkyl, in particular methyl, ethyl, propyl or aryl, in particular phenyl,
• A1 is one of the following radicals
• A2 is in particular one of the following radicals: PO - ⁇ CH 2 - CH
• n and q are as defined above.
• A preferably consists of the radicals A1 and A2 and in particular represents the group - A2-A1 -A2-.
• the repeating units in residues A1 and A2 can be randomly distributed or in blocks. If the radical A 2 has both propylene glycol radicals and polytetrahydrofuran units, in a preferred embodiment the polytetrahydrofuran units are terminally attached.
• the radicals A1 and A2 can be substituted, in particular with an alkyl radical having 1-4 C atoms or an aryl radical, in particular phenyl.
• An example of a substituted repeating radical is the phenyl-substituted ethylene glycol radical (styrene oxide).
• a particularly preferred embodiment is characterized in that A has the structure - (PO) x- (EO) y- (PO) z -, in which mean
• x, z are the same or different, a number from 1 to 100, in particular 1 to 20
• y is a number from 1 to 100, in particular 1 to 90
• x, z, the same or different are from 5 to 10
• y is a number from 60 to 80, in particular from 65 to 75.
• the structure - (PO) x - (EO) y - (PO) z preferably has an EO content by weight of 5 to 85 wt .-% and a number average molecular weight (Mn) of 200 to 50,000 g / mol.
• Mn number average molecular weight
• x, z are a number, identical or different, of from 0.1 to 200, in particular from 5 to 20 y, a number, identical or different, of from 1 to 100, in particular from 60 to 80.
• the compounds according to the invention are outstandingly suitable A method for producing coatings by applying the compounds to the surface of substrates and polymerization.
• the invention therefore furthermore relates to a process for the preparation of coatings based on a compound of the formula I on the surface of a molded article of a fusible substrate S, in particular on fibers, in a melt spinning process or films after extrusion, wherein a) the substrate is provided in molten form becomes,
• the molten substrate is formed via a suitable device V, preferably a nozzle or a gap, to a molded article, in particular to a fiber or a film, wherein
• the molded article at the outlet from the device V has a temperature above the cloud point of the compound of formula I
• the surface of the molded article above the cloud point with the compound of formula I is brought under deposition of the compound of formula I in contact, characterized in that after deposition on the surface, the polymerization of the double bonds of the compound of formula I is initiated to form a preferably crosslinked coating of the surface.
• a preferred embodiment is characterized in that after leaving the device V, the molded article is passed into a preferably aqueous bath B which contains the compound of the formula I and, if appropriate, a polymerization initiator, the mold article entering the bath of the molded article has a temperature above the cloud point, the compound of formula I is deposited on the molded article and
• the bath has a temperature below the cloud point and the polymerization is carried out at a temperature below the cloud point.
• a further preferred embodiment is characterized in that the molded article is passed immediately after exiting the device V at a temperature above the cloud point in a spray and sprayed there with the compound of formula I, preferably in the form of an aqueous solution, wherein the temperature of the sprayed polymer is below the cloud point, depositing the compound of formula I on the surface of the substrate.
• Particularly preferred substrates are polyamides, polyesters, polypropylene or polyurethanes.
• the substrate is a glass, steel or wood.
• the polymerization of the double bonds can be carried out in the bath B or subsequent to the treatment in the bath B.
• a polymerization initiator is preferably added.
• the polymerization of the acrylate groups of the compounds of the formula I according to the invention preferably takes place free-radically, in particular from aqueous or alcoholic solution.
• the polymerization preferably takes place in the presence of radical formers, in particular inorganic or organic peroxides, azo compounds or metals or organometallic compounds.
• radical formers in particular inorganic or organic peroxides, azo compounds or metals or organometallic compounds.
• suitable polymerization regulators in particular mercaptans, organic halogen compounds, aldehydes or xanthates or nitroxyl radical formers may be added.
• the polymerization is preferably carried out at temperatures of 50 to 100 ° C, in particular at 60 to 80 ° C.
• the polymerization of the acrylate groups of the compounds of the formula I according to the invention can also be initiated by means of a photoinitiator.
• Photoinitiators are generally present in amounts of 0.01 to 10 and especially 0.01 to 3 wt .-%, based on the compound of formula I. Suitable photoinitiators are those compounds which are capable of forming free radicals upon exposure to actinic light and which provide rapid photopolymerization. sation of the compound of formula I trigger.
• photoinitiators come z. For example, acyloins and acyloin ethers, aromatic diketones and their derivatives and polynuclear quinones.
• photoinitiators and thermal polymerization inhibitors such as hydroquinone, p-methoxyphenol, dinitrobenzene, p-quinone, methylene blue, beta-naphthol, N-nitrosamines such as N-nitrosodiphenylamine, phenothiazine, phosphorous acid esters such as triphenyl phosphite or the salts and in particular the alkali and aluminum salts of N-nitroso-cyclohexylhydroxylamine be used.
• the inhibitors may be used in amounts of 0.001 to 3, preferably 0.01 to 1 wt .-%, based on the compound of formula I.
• the acrylate end groups in the compounds of the formula I to be used according to the invention can be replaced in an amount of 0.1 to 99 mol%, in particular 20 to 50 mol%, by radicals of: a) maleic acid or maleic acid derivatives (in particular esters)
• X is hydroxyl, halogen, preferably chlorine, an acid group, an alkyl group or an alkoxy group having 1 to 100 carbon atoms, in a molar ratio of at least 1: 1 to 1: 4, in particular 1: 2.
• the reaction is preferably carried out in a solvent such as tertiary monools, preferably tert-butanol, tert-amyl alcohol, pyridine, poly-C 1 -C 4 -alkylene glycol-C 1 -C 4 -alkyl ethers, preferably polyethylene glycol-C 1 -C 4 -alkyl ethers, such as z. B.
• a solvent such as tertiary monools, preferably tert-butanol, tert-amyl alcohol, pyridine, poly-C 1 -C 4 -alkylene glycol-C 1 -C 4 -alkyl ethers, preferably polyethylene glycol-C 1 -C 4 -alkyl ethers, such as z. B.
• Preferred compounds of the formula I according to the invention can be prepared by 1. direct implementation of the preformed compounds HO - A ⁇ with (meth) acrylic acid, or (meth) acrylic acid derivatives
• Aryl (meth) acrylates for example benzyl (meth) acrylate or phenyl (meth) acrylate, which may each be unsubstituted or have 1-4-substituted aryl radicals; other aromatic substituted (meth) acrylates such as naphthyl (meth) acrylate;
• Amount of catalyst 0.1-10% by weight (preferably 0.5-5% by weight) with respect to starting materials
• Reaction time 1 - 10 hours, preferably 1 - 6 hours
• an entraining agent eg, cyclohexane or toluene
• the esterification can be carried out without pressure, with overpressure or underpressure both continuously and discontinuously.
• Catalyst quantity 0.01 to 10% by weight of catalyst, preferably from 0.1 to 5% by weight, more preferably from 0.2 to 2% by weight of catalyst, based on the total reaction mixture.
• Catalysts organylmetal oxides, organylmetal halides such as diorganyltin oxides,
• Diorganyltin halides alkali metal salts of inorganic acid, in particular of phosphoric acid, transition metal alcoholates such as titanium alkoxides, alkali metal amides such as lithium amide, alkali metal and alkaline earth metal alkoxides such as potassium tert-butylate, acids such as sulfuric acid, alkyl- or arylsulfonic acids, e.g.
• the enzymatically catalyzed transesterification is preferably carried out under the following conditions: temperature: 10 ° -80 ° C., more preferably 20 ° -40 ° C.
• Catalyst lipases with and without solvent in excess of (meth) acrylic acid esters of from 1:50 to 1: 500 mol / mol, more preferably from 1: 100 to 1: 400, relative to the substrate.
• these have either a spraying device immediately following the exit of the fiber from the nozzle or a bath which preferably contains an aqueous solution of the polymer according to the invention.
• This bath may additionally contain a polymerization initiator for carrying out the polymerization.
• the plants known per se for the production of films for example based on an extruder, which promotes the melt of the substrate, or the substrate melts and extruded through a nozzle, in particular a slot die, to form a film.
• effect substances are deposited on the shaped body together with the compounds of the formula I according to the invention.
• effect substances are understood in particular compounds which improve the properties of the shaped body, in particular the films and fibers, such as UV stabilizers, pigments, nanoparticles, IR-absorbing compounds, etc.
• the effect substances together with the compound of formula I, preferably in the bath B be included.
• the molded articles according to the invention d. H. Films and fibers can be stretched in a manner known per se, in particular also after application and polymerization of the acrylate groups.
• diethylene glycol 53.05 g, 0.5 mol
• potassium t-butylate 10.2 g, 0.5 wt% of the final amount. It was made inert three times with nitrogen to 5 bar and dosed after reaching 120 ° C ethylene oxide mass controlled to (1364.0 g). The temperature was then increased to 130 ° C. and propylene oxide (638 g, 11 mol) was added over the course of 700 minutes. The mixture was allowed to react for 4 h and cooled to 80 ° C with stirring.
• the crude product was mixed with magnesium silicate (3 wt .-%) and pressure-filtered after 1 h stirring on a rotary evaporator over a 900 Seitz filter medium.
• PPG-PEG-PPG 250 g, 0.05 mol from example 1 .1, ethyl acrylate (1000 g, 10 mol), molecular sieve 5
• a powder (Fluka) 55.5 g (10 -fold amount based on theoretical amount of resulting alcohol).
• the stabilizers added were 4-methoxyphenol (MeHQ): 98.6 mg; (Aldrich) (99% [GC]) (400 ppm based on theoretical amount of product); Phenothiazine (PTZ): 3.0 mg (Fluka) (purum;> 98.0% [GC]) (10 ppm based on theoretical amount of product).
• Novozym 435 (33.71 g) (7.0% by weight, based on starting material) was added at about 30.degree. The mixture was allowed to stir for 48 h at 40 ° C (bath 46 ° C) and 150 rpm by means of glass PTFE intensive stirrer with the introduction of air.
• the mixture was then filtered off with suction through a 4 l glass filter chute G 2 filled with silica gel 60 (0.040-0.064 mm) at approx. 500-600 mbar, washed with 4 l acetone and at 60 ° C. with introduction of air to remove ethyl acrylate residues in Rotary evaporator dried.
• Example 2 Fiber Coating The fiber coating is tested using the example of a melt spinning process for polypropylene. For this purpose, an aqueous solution of the following components (% by weight) is used:
• adhesion promoter polyethyleneimine
• microfibers 120 dtexf32
• dtex is a unit of measure for the fineness of threads. Described is the weight in g at 10000 m fiber] obtained from a melt at a nozzle temperature of 295 ° C.
• the fiber is brought into contact with the LCST polymer solution by spraying at a temperature of 80-100 ° C. (about 100 cm after the exit of the fiber material from the spinneret).
• the resulting fiber-coated yarns are characterized by improved properties, in particular in terms of flexibility and Aufzieh App.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Toxicology (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Polyesters Or Polycarbonates (AREA)
• Polyethers (AREA)

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• 2012
  • 2012-04-11 RU RU2013150131/04A patent/RU2013150131A/ru not_active Application Discontinuation
  • 2012-04-11 AU AU2012241931A patent/AU2012241931A1/en not_active Abandoned
  • 2012-04-11 BR BR112013023946A patent/BR112013023946A2/pt not_active IP Right Cessation
  • 2012-04-11 JP JP2014504292A patent/JP2014511927A/ja active Pending
  • 2012-04-11 EP EP12712692.8A patent/EP2697284A1/de not_active Withdrawn
  • 2012-04-11 SG SG2013073010A patent/SG194002A1/en unknown
  • 2012-04-11 CN CN2012800179114A patent/CN103476830A/zh active Pending
  • 2012-04-11 KR KR1020137029540A patent/KR20140038403A/ko not_active Application Discontinuation
  • 2012-04-11 MX MX2013010424A patent/MX2013010424A/es not_active Application Discontinuation
  • 2012-04-11 WO PCT/EP2012/056548 patent/WO2012140059A1/de active Application Filing

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