WO2015072372A1 - 離型フィルム、積層体及びその製造方法並びに燃料電池の製造方法 - Google Patents
離型フィルム、積層体及びその製造方法並びに燃料電池の製造方法 Download PDFInfo
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- WO2015072372A1 WO2015072372A1 PCT/JP2014/079256 JP2014079256W WO2015072372A1 WO 2015072372 A1 WO2015072372 A1 WO 2015072372A1 JP 2014079256 W JP2014079256 W JP 2014079256W WO 2015072372 A1 WO2015072372 A1 WO 2015072372A1
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- release film
- release
- cyclic olefin
- ion exchange
- layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/68—Release sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/0046—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by constructional aspects of the apparatus
- B32B37/0053—Constructional details of laminating machines comprising rollers; Constructional features of the rollers
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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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
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- 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
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- 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
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- 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
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8814—Temporary supports, e.g. decal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1093—After-treatment of the membrane other than by polymerisation mechanical, e.g. pressing, puncturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/18—Fuel cells
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- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- 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
- C08J2427/00—Characterised by the use 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 halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use 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 halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use 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 halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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- 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
- C08J2427/00—Characterised by the use 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 halogen; Derivatives of such polymers
- C08J2427/22—Characterised by the use 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 halogen; Derivatives of such polymers modified by chemical after-treatment
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- 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
- C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a release film used when a membrane electrode assembly, which is a constituent member of a polymer electrolyte fuel cell, is produced (film formation), a laminate including the release film (lamination film), and production thereof.
- the present invention relates to a method and a method for producing the membrane electrode assembly using the release film.
- the polymer electrolyte fuel cell has a basic structure called a membrane electrode assembly (MEA).
- MEA is a laminate obtained by laminating an electrode membrane (catalyst layer or electrode catalyst membrane) mainly composed of carbon powder carrying a platinum group metal catalyst on both surfaces of a solid polymer electrolyte membrane which is an ion exchange membrane. Is further sandwiched between a fuel gas supply layer and an air supply layer which are conductive porous membranes.
- both the electrolyte membrane and the electrode membrane contain an ion exchange resin, but the electrolyte membrane and the electrode membrane are usually formed by a casting method and / or a coating method.
- both layers formed on a support are brought into contact with each other, about 130 to 150 ° C. (about 150 to 200 ° C. depending on the material used), and a pressure of about 1 to 10 MPa.
- a method is used in which the support is peeled off after it is brought into close contact by thermocompression. For this reason, a release film is used as the support, but the release film is required to have appropriate peelability and adhesion to the electrolyte membrane and the electrode membrane.
- the ion exchange resin contained in the electrolyte membrane and the electrode membrane is a resin having a unique structure having a main chain of a fluororesin having a high releasability and a side chain containing a sulfonic acid group having a low releasability. It is difficult to predict the behavior related to the property, and it is difficult to balance the peelability and the adhesion. Furthermore, the release film for manufacturing a fuel cell is required to have heat resistance in the manufacturing process, and is also required to be flexible because it is manufactured by a roll-to-roll method from the viewpoint of productivity.
- fluorine-based films are widely used as mold release films, but they are excellent in heat resistance, mold release, and non-contamination, are expensive, and are incinerated after disposal. It is difficult to combust in and it is easy to generate toxic gas. Furthermore, since the elastic modulus is low, it is difficult to manufacture by a roll-to-roll method. Therefore, a release film formed of a cyclic olefin resin has been proposed as a release film that replaces the fluorine film.
- Patent Document 1 discloses a release film made of a cycloolefin copolymer, and a cycloolefin copolymer solution is coated on a base film such as a polyethylene terephthalate film. A release film formed in this way is also described.
- the glass transition temperature of a cycloolefin copolymer is usually 50 ° C. or more, most preferably 160 ° C. or more, and the upper limit of Tg of a general cycloolefin copolymer is about 250 ° C. ing.
- a solution containing a copolymer of ethylene and norbornene is cast on a polyethylene terephthalate film using a casting apparatus to form a release film having a thickness of 0.5 ⁇ m.
- this release film has low heat resistance, is not sufficiently peelable in the high temperature manufacturing process, and does not have sufficient toughness. Therefore, in the roll-to-roll manufacturing, cracks and cracks are likely to occur.
- Patent Document 2 discloses (A) a structural unit derived from propylene and (B) 6 to 6 carbon atoms as a copolymer for forming a polarizing film of a liquid crystal display device.
- a copolymer comprising 12 structural units derived from ⁇ -olefin and (C) a structural unit derived from norbornene, wherein 10 to 69 mol% of the structural unit (A) is contained in the structural unit ( A copolymer containing 1 to 50 mol% of B), 30 to 89 mol% of the structural unit (C) and having a weight average molecular weight of 50,000 to 1,000,000 is disclosed.
- the glass transition temperature of the copolymer is described as 50 to 250 ° C. (especially 80 to 200 ° C.). In the examples, copolymers having a glass transition temperature of 92 to 168 ° C. are prepared.
- Patent Document 3 discloses a cyclic olefin addition copolymer obtained from a cyclic olefin (A) monomer unit and an ⁇ -olefin (B) monomer unit having 5 or more carbon atoms.
- the proportion of the structural unit (A) is 80 to 99 mol% and the proportion of the structural unit (B) is 1 to 20 mol in a total of 100 mol% of the structural unit (A) and the structural unit (B).
- % Optical film is disclosed.
- the cyclic olefin addition copolymer is excellent in heat resistance, transparency, low water absorption, moldability and toughness, and has a small coefficient of linear expansion, and is used for applications such as optical substrates for displays. It is described as preferred.
- the glass transition temperature of the cyclic olefin addition copolymer is described as 200 to 400 ° C. (especially 245 to 300 ° C.), and in the examples, copolymers having a glass transition temperature of 245 to 262 ° C. are prepared.
- JP 2010-234570 A (claims, paragraphs [0024] [0025], Example 2) Japanese Patent No. 5017222 (claims, paragraph [0030], Examples) JP 2009-298999 A (claims, paragraphs [0019] [0028] [0044], Examples)
- an object of the present invention is to provide a release film capable of improving the productivity of a membrane / electrode assembly (electrolyte membrane and / or electrode membrane) of a polymer electrolyte fuel cell, a laminated film including this release film, and a method for producing the same
- Another object of the present invention is to provide a method for producing the membrane electrode assembly using the release film.
- Another object of the present invention is to have moderate peelability and adhesion to the electrolyte membrane and electrode membrane, as well as high heat resistance and toughness, and heat-treat in a roll-to-roll manner.
- a release film capable of manufacturing the membrane electrode assembly with high productivity a laminated film including the release film, a manufacturing method thereof, and a method of manufacturing the membrane electrode assembly using the release film are provided. There is.
- Still another object of the present invention is to provide a release film that is excellent in solubility in a solvent and can be easily produced by coating, a laminated film including the release film, a method for producing the release film, and the membrane electrode bonding using the release film.
- the object is to provide a method of manufacturing a body.
- the present inventors first pay attention to the fact that the heat resistance of the release film in Patent Document 1 is not sufficient, and adjust the glass transition temperature of the ethylene-norbornene copolymer of Patent Document 1. Study was carried out. However, in the case of ethylene-norbornene copolymer, the glass transition temperature is increased by increasing the norbornene content, and if the releasability at high temperature is improved, the toughness is lowered, or the release film is damaged (cracked or cracked). The membrane electrode assembly (MEA) of the polymer electrolyte fuel cell could not be efficiently produced by the roll-to-roll method.
- MAA membrane electrode assembly
- the release layer of the release film for producing MEA is a cyclic olefin resin containing an olefin unit having an alkyl group having 3 to 10 carbon atoms in the side chain. It has been found that the productivity of MEA can be improved by forming the above, and the present invention has been completed.
- the release film of the present invention is a release film for producing a membrane electrode assembly of a polymer electrolyte fuel cell, and includes an olefin unit having an alkyl group having 3 to 10 carbon atoms in the side chain.
- a release layer formed of a cyclic olefin resin is included.
- the release layer may have a glass transition temperature of about 210 to 350 ° C.
- the dynamic storage elastic modulus E ′ of the release layer may have a transition point in the range of ⁇ 50 to 100 ° C.
- the cyclic olefin-based resin may contain a chain olefin unit having an alkyl group having 3 to 10 carbon atoms and / or a cyclic olefin unit having an alkyl group having 3 to 10 carbon atoms as a repeating unit. It may be a copolymer comprising a cyclic olefin unit (A) having no alkyl group having 3 to 10 carbon atoms and a chain or cyclic olefin unit (B) having an alkyl group having 3 to 10 carbon atoms. .
- the cyclic olefin unit (B) may be an ethylene or norbornene unit having a linear alkyl group having 4 to 8 carbon atoms.
- the average thickness of the release layer may be about 0.2 to 5 ⁇ m.
- the release film of the present invention further includes a base material layer, the release layer is laminated on at least one surface of the base material layer, and the base material layer is polyolefin, polyvinyl alcohol polymer, polyester, polyamide, and cellulose derivative. It may be formed of at least one selected from the group consisting of
- the release film of the present invention may be a film formed by coating.
- the present invention provides a laminate for producing a polymer electrolyte fuel cell, the release film, and an ion exchange layer laminated on the release layer of the release film and containing an ion exchange resin. And a laminate formed by the above.
- the ion exchange resin may be a fluororesin having a sulfonic acid group in the side chain.
- the ion exchange layer containing the ion exchange resin may be an electrolyte membrane and / or an electrode membrane.
- the laminate of the present invention may be a laminate produced by a roll-to-roll method.
- the present invention includes a method for producing the laminate including a lamination step of laminating an ion exchange layer containing an ion exchange resin on a release layer of a release film.
- lamination may be performed by a roll-to-roll method.
- the present invention includes a method for producing a membrane / electrode assembly of a polymer electrolyte fuel cell including a peeling step of peeling a release film from the laminate.
- the “ion exchange layer” means a layer containing an ion exchange resin, and is not limited to an electrolyte membrane that is an ion exchange membrane.
- An electrode membrane containing a catalyst in addition to an ion exchange resin is also an ion membrane. Included in the exchange layer.
- the release layer of the release film for producing MEA is formed of a cyclic olefin resin containing an olefin unit having an alkyl group having 3 to 10 carbon atoms in the side chain.
- the release film of the present invention has appropriate elasticity, it can be wound up by a roll, can be continuously produced by a roll-to-roll system, and can be manufactured by a roll-to-roll system. Even if it manufactures by heat-processing (for example, heat processing to 140 degreeC or more), a peeling defect and a release layer damage (a crack, a crack, etc.) can be suppressed, it can manufacture stably and productivity can be improved. Furthermore, it has excellent solubility in solvents and can be easily manufactured by coating.
- the release film of the present invention is a release film for producing a membrane electrode assembly (MEA) of a polymer electrolyte fuel cell, and has an olefin unit having an alkyl group having 3 to 10 carbon atoms in a side chain.
- a release layer formed of the cyclic olefin-based resin is included.
- the release film of the present invention may be a film for peeling an MEA after laminating an electrolyte membrane and / or an electrode membrane containing an ion exchange resin on the membrane.
- the release layer of the present invention contains a cyclic olefin resin, and since this cyclic olefin resin contains an olefin unit having an alkyl group having 3 to 10 carbon atoms in the side chain, it has a predetermined viscoelastic property. It is.
- the glass transition temperature (Tg) of the release layer (cyclic olefin resin) can be selected from a range of about 210 to 350 ° C., and is preferably 220 to 350 ° C., for example, from the viewpoint of the balance between heat resistance and mechanical properties. Is about 230 to 340 ° C. (for example, 250 to 320 ° C.), more preferably about 260 to 300 ° C. (especially 265 to 280 ° C.). For applications requiring high heat resistance, for example, 270 to 350 ° C., Preferably, it may be about 280 to 340 ° C. (particularly 300 to 335 ° C.). If the glass transition temperature is too low, the heat resistance is low, so that peeling failure is likely to occur, and if it is too high, production becomes difficult. In the present specification, the glass transition temperature can be measured using a differential scanning calorimeter (DSC).
- DSC differential scanning calorimeter
- the dynamic storage elastic modulus E ′ of the release layer is a temperature range lower than the glass transition temperature in a dynamic viscoelasticity test measured from ⁇ 50 ° C. to 250 ° C. under conditions of a temperature rising rate of 5 ° C./min and a frequency of 10 Hz. It preferably has a transition point (for example, about ⁇ 50 to 100 ° C.). When there is no transition point, toughness decreases, and when the side chain is too long or the proportion of units having side chains is too large, the glass transition temperature decreases and the heat resistance decreases.
- the dynamic storage elastic modulus can be measured by the method described in the examples. In the test, the mechanical loss tangent tan ⁇ , which is the ratio of the dynamic storage elastic modulus E ′ and the dynamic loss elastic modulus E ′′, is a maximum. It can be evaluated from taking points.
- the cyclic olefin-based resin having such characteristics may contain an olefin unit having an alkyl group having 3 to 10 carbon atoms (C 3-10 alkyl group) in the side chain, and the C 3-10 alkyl group is Because the main chain of the cyclic olefin resin is present as a side chain with a high degree of freedom, the energy generated by deformation can be converted to thermal energy, or the glass transition temperature of the cyclic olefin resin is increased to increase heat resistance. Even if it improves, elasticity and toughness can be maintained.
- the carbon number of the terminal alkyl group is 3 or more, it becomes liquid at room temperature.
- the carbon number of the side chain alkyl group is 3 or more, the above-described effects are exhibited. . On the other hand, if the carbon number exceeds 10, the glass transition temperature is too low.
- Examples of the C 3-10 alkyl group include propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, Examples thereof include linear or branched alkyl groups such as 2-ethylhexyl group, nonyl group, and decanyl group. These C 3-10 alkyl groups can be used alone or in combination of two or more.
- a linear C 4-9 alkyl group (for example, n-butyl group, n-hexyl group, n-octyl group, etc.) is preferable from the viewpoint of excellent balance between heat resistance, elasticity, and toughness. Further preferred are linear C 4-8 alkyl groups (particularly linear C 5-7 alkyl groups such as n-hexyl group).
- the cyclic olefin-based resin includes a chain olefin unit having a C 3-10 alkyl group and / or a cyclic olefin having a C 3-10 alkyl group as a repeating unit. It may contain a unit and may be a homopolymer. However, from the viewpoint of easy adjustment of desired properties, the chain olefin unit and / or the cyclic olefin unit and other copolymerizable units.
- copolymers are preferred, and cyclic olefin units having no C 3-10 alkyl group (a), a copolymer particularly preferably contains a linear or cyclic olefin units having a C 3-10 alkyl group (B) .
- the polymerization component (monomer) for forming the cyclic olefin unit (A) is a polymerizable cyclic olefin having an ethylenic double bond in the ring, and includes a monocyclic olefin, a bicyclic olefin, and a tricyclic ring. It can be classified into the above polycyclic olefins.
- monocyclic olefins examples include cyclic C 4-12 cycloolefins such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene.
- bicyclic olefin examples include 2-norbornene; norbornenes having a C 1-2 alkyl group such as 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, and 5-ethyl-2-norbornene.
- polycyclic olefin examples include dicyclopentadiene; 2,3-dihydrodicyclopentadiene, methanooctahydrofluorene, dimethanooctahydronaphthalene, dimethanocyclopentadienonaphthalene, methanooctahydrocyclopentadienaphthalene, etc.
- Derivatives having a substituent such as 6-ethyl-octahydronaphthalene; adducts of cyclopentadiene and tetrahydroindene, tripentamers of cyclopentadiene, and the like.
- cyclic olefins can be used alone or in combination of two or more.
- bicyclic olefins are preferred because they have a good balance between peelability and flexibility.
- the proportion of bicyclic olefins (particularly norbornenes) is 10 mol% or more with respect to the total cyclic olefins having no C 3-10 alkyl group (cyclic olefins for forming cyclic olefin units (A)).
- it is 30 mol% or more, preferably 50 mol% or more, more preferably 80 mol% or more (particularly 90 mol% or more), and may be a bicyclic olefin alone (100 mol%).
- the ratio of the tricyclic or higher polycyclic olefin is increased, it becomes difficult to use for production in a roll-to-roll system.
- Exemplary bicyclic olefins e.g., C 3-10 alkyl which may norbornene have a substituent group other than group (2-norbornene), have a substituent other than C 3-10 alkyl group
- An example is octalin (octahydronaphthalene).
- the substituent include methyl, ethyl group, alkenyl group, aryl group, hydroxyl group, alkoxy group, carboxyl group, alkoxycarbonyl group, acyl group, cyano group, amide group and halogen atom. These substituents may be used alone or in combination of two or more.
- a nonpolar group such as a methyl group or an ethyl group is preferable from the viewpoint that the peelability is not impaired.
- norbornenes such as norbornene and norbornene having a C 1-2 alkyl group (particularly norbornene) are particularly preferable.
- the polymerization component (monomer) for forming the chain or cyclic olefin unit (B) can form a C 3-10 alkyl group as a side chain with respect to the main chain of the cyclic olefin resin, and ethylene.
- a polymerizable olefins having sex double bond can be classified into a cyclic olefin having a chain olefins, C 3-10 alkyl group having a C 3-10 alkyl group.
- the chain olefin unit may be a chain olefin unit generated by ring-opening of a cyclic olefin, but a unit having a chain olefin as a polymerization component is preferable from the viewpoint of easily controlling the ratio of both units.
- Examples of the chain olefin having a C 3-10 alkyl group include, for example, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-nonene, And ⁇ -chain C 5-13 olefins such as decene, 1-undecene and 1-dodecene. These chain olefins can be used alone or in combination of two or more.
- chain olefins ⁇ -chain C 6-12 olefins are preferable, and ⁇ -chain C 6-10 olefins (particularly ⁇ -chain C 7-9 olefins such as 1-octene) are more preferable. ).
- the cyclic olefin having a C 3-10 alkyl group may be a cyclic olefin in which a C 3-10 alkyl group is substituted on the cyclic olefin skeleton exemplified in the section of the cyclic olefin unit (A).
- a bicyclic olefin particularly norbornene is preferable.
- Preferred cyclic olefins having a C 3-10 alkyl group include, for example, 5-propyl-2-norbornene, 5-butyl-2-norbornene, 5-pentyl-2-norbornene, 5-hexyl-2-norbornene, 5- Examples thereof include linear or branched C 3-10 alkyl norbornene such as octyl-2-norbornene and 5-decyl-2-norbornene. These cyclic olefins can be used alone or in combination of two or more.
- linear C was 4-9 alkyl norbornene, still preferably linear C such as linear C 4-8 alkyl norbornene (particularly 5-hexyl-2-norbornene 5- 7 alkyl norbornene).
- the ratio of the cyclic olefin unit (A) is too small, the heat resistance is lowered, and when it is too much, the toughness is easily lowered.
- the cyclic olefin resin may contain other copolymerizable units in addition to the cyclic olefin unit (A) and the chain or cyclic olefin unit (B).
- polymerization components (monomers) for forming other copolymerizable units include ⁇ -chain C 1-4 olefins (ethylene, propylene, 1-butene, isobutene, etc.), vinyl ester monomers Body (for example, vinyl acetate, vinyl propionate, etc.), diene monomer (for example, butadiene, isoprene, etc.), (meth) acrylic monomer [for example, (meth) acrylic acid, or derivatives thereof (( Meth) acrylic acid ester, etc.)] and the like.
- polymerization components can be used alone or in combination of two or more.
- monomers that do not substantially contain a unit having a polar group such as a carboxyl group, a hydroxy group, and an amino group are preferable from the viewpoint of not deteriorating the peelability, and ⁇ -chain C 1 such as ethylene and propylene is preferable.
- -4 olefins are widely used.
- the ratio of the other copolymerizable unit is, for example, 10 mol% or less, preferably 5 mol% or less, more preferably 1%, based on the total of the cyclic olefin unit (A) and the chain or cyclic olefin unit (B). It is less than mol%.
- the number average molecular weight of the cyclic olefin-based resin is, for example, 10,000 to 300,000, preferably 50,000 to 250,000, and more preferably about 80,000 to 200,000 (particularly 100,000 to 150,000) in terms of polystyrene in gel permeation chromatography (GPC). . If the molecular weight is too small, the film-forming property is liable to be lowered, and if it is too large, the viscosity is increased, so that the handleability is liable to be lowered.
- the cyclic olefin-based resin may be a resin obtained by addition polymerization, or may be a resin obtained by ring-opening polymerization (ring-opening metathesis polymerization or the like).
- the polymer obtained by ring-opening metathesis polymerization may be a hydrogenated hydrogenated resin.
- the polymerization method of the cyclic olefin resin is a conventional method, for example, ring-opening metathesis polymerization using a metathesis polymerization catalyst, addition polymerization using a Ziegler type catalyst, addition polymerization using a metallocene catalyst (usually a metathesis polymerization catalyst).
- the ring-opening metathesis polymerization used can be used.
- Specific polymerization methods include, for example, JP-A No. 2004-197442, JP-A No. 2007-119660, JP-A No. 2008-255341, Macromolecules, 43, 4527 (2010), Polyhedron, 24, 1269 (2005). ), J. Appl. Polym. Sci, 128 (1), 216 (2013), Polymer Journal, 43, 331 (2011).
- the catalyst used for the polymerization is also a conventional catalyst such as a catalyst synthesized by the method described in Macromolecules, 1988, Vol. 31, 313184, Journal of Organometallic Chemistry, 2006, 691, 1193. Available.
- the release layer may further contain a conventional additive.
- conventional additives include fillers, lubricants (waxes, fatty acid esters, fatty acid amides, etc.), antistatic agents, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), flame retardants, viscosity adjustments Agents, thickeners, antifoaming agents and the like may be included.
- organic or inorganic particles particularly, anti-blocking agents such as zeolite may be included as long as the surface smoothness is not impaired.
- the ratio of the cyclic olefin-based resin in the release layer is, for example, 80% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more (for example, 95 to 100% by weight) with respect to the entire release layer. It may be.
- the releasability can be improved without containing a low molecular weight release agent such as a silicone compound that easily contaminates the electrolyte membrane or the electrode membrane, and it is preferable that the silicone compound is not substantially contained. .
- the average thickness of the release layer is, for example, about 0.1 to 100 ⁇ m, preferably about 0.3 to 80 ⁇ m, and more preferably about 0.5 to 50 ⁇ m.
- the release layer when it is a coating film, it may be thin, for example, 0.2 to 5 ⁇ m, preferably 0.5 to 3 ⁇ m, and more preferably about 0.8 to 2 ⁇ m.
- the average thickness can be calculated based on the coating amount (solid content weight per unit area) and density of the release layer.
- the release film of the present invention is not particularly limited as long as it includes the release layer, and is a single-layer release film (for example, a release film formed by extrusion molding) formed by the release layer alone. It may be a release film having a laminated structure in which the release layer is laminated on at least one surface of the base material layer. Among these, a release film having a laminated structure is preferable because productivity of the fuel cell can be improved and a thin release layer having a uniform thickness can be easily manufactured.
- the base material layer can improve the dimensional stability of the release film in the manufacturing process of the fuel cell. In particular, even when tension is applied in the roll-to-roll method, it can suppress the elongation, and further, the drying process and thermocompression bonding. Even when exposed to high temperatures due to processing, etc., it is preferable that it is formed of a material having high heat resistance and high dimensional stability from the viewpoint of maintaining high dimensional stability and suppressing peeling from the electrolyte membrane and electrode membrane, Specifically, it may be formed of a synthetic resin having an elastic modulus at 150 ° C. of 100 to 1000 MPa.
- the elastic modulus may be, for example, about 120 to 1000 MPa, preferably about 150 to 1000 MPa, and more preferably about 200 to 1000 MPa. When the elastic modulus is too small, the dimensional stability is lowered, and peeling from the electrolyte membrane and the electrode membrane occurs in the production by the roll-to-roll method, and the productivity of the fuel cell is lowered.
- thermoplastic resin As such a synthetic resin, for example, various thermoplastic resins and thermosetting resins can be used, but a thermoplastic resin is preferable from the viewpoint of flexibility that can be manufactured by a roll-to-roll method.
- thermoplastic resin include polyolefin (polypropylene resin, cyclic polyolefin, etc.), polyvinyl alcohol polymer, polyester, polyamide, polyimide, polycarbonate, polyphenylene ether, polyphenylene sulfide, and cellulose derivatives. These thermoplastic resins can be used alone or in combination of two or more.
- thermoplastic resins At least one selected from the group consisting of polyolefins, polyvinyl alcohol polymers, polyesters, polyamides, polyimides, and cellulose derivatives is preferred, from the point of excellent balance between heat resistance and flexibility, Polyester and polyimide are particularly preferable.
- polyester poly C 2-4 alkylene arylate resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) can be preferably used.
- polyimide examples include thermosetting polyimide (such as pyromellitic acid-based polyimide, bismaleimide-based polyimide, nadic acid-based polyimide, and acetylene-terminated polyimide), thermoplastic polyimide, polyetherimide, and polyamideimide.
- the base material layer may be formed of a stretched film from the viewpoint of improving the film strength.
- the stretching may be uniaxial stretching, but biaxial stretching is preferred from the viewpoint that the film strength can be improved.
- the stretching ratio may be, for example, 1.5 times or more (eg, 1.5 to 6 times), preferably 2 to 5 times, more preferably about 3 to 4 times in the longitudinal and transverse directions, respectively. It is. If the draw ratio is too low, the film strength tends to be insufficient.
- the average thickness of the base material layer is, for example, about 1 to 300 ⁇ m, preferably about 5 to 200 ⁇ m, more preferably about 10 to 100 ⁇ m (particularly about 20 to 80 ⁇ m). If the thickness of the base material layer is too large, production by the roll-to-roll method becomes difficult, and if it is too thin, the dimensional stability is lowered.
- the surface of the base material layer may be subjected to conventional surface treatment or easy adhesion treatment in order to improve adhesion with the release layer.
- the release film As a method for producing the release film, a conventional method can be used.
- the release film When the release film is formed of a single release layer, it may be formed by, for example, extrusion molding or coating, and may have a laminated structure with the base material layer.
- a method such as coating, co-extrusion or extrusion lamination, thermocompression bonding, or the like may be used, and lamination may be performed via an adhesive or an adhesive.
- the method of drying after coating (or casting) a solution containing a cyclic olefin-based resin on the base material layer is preferable from the viewpoint that a thin-walled and smooth surface release layer can be easily formed.
- the coating method conventional methods such as roll coater, air knife coater, blade coater, rod coater, reverse coater, bar coater, comma coater, die coater, gravure coater, screen coater method, spray method, spinner method and the like can be mentioned. It is done. Of these methods, the blade coater method, the bar coater method, the gravure coater method and the like are widely used.
- a nonpolar solvent can be used, for example, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, and aromatics such as solvent naphtha. Oil can be used. These solvents may be used alone or in combination of two or more. Of these, aromatic hydrocarbons such as toluene and aromatic oils such as solvent naphtha are preferred.
- the solid content concentration in the solution is, for example, about 0.1 to 50% by weight, preferably 0.3 to 30% by weight, more preferably 0.5 to 20% by weight (particularly 0.8 to 15% by weight). is there.
- Drying may be natural drying, or the solvent may be evaporated by heating and drying.
- the drying temperature may be 50 ° C. or higher, for example, 50 to 200 ° C., preferably 60 to 150 ° C., and more preferably about 80 to 120 ° C.
- the laminate of the present invention is a laminate for producing a polymer electrolyte fuel cell, and is an ion exchange layered on a release film and a release layer of the release film and containing an ion exchange resin.
- Layer electrophilyte membrane, electrode membrane, membrane electrode assembly.
- ion exchange resin a conventional ion exchange resin used in a fuel cell can be used, and among them, a cation exchange resin such as a strong acid cation exchange resin or a weak acid cation exchange resin is preferable.
- Ion exchange resin having sulfonic acid group, carboxyl group, phosphoric acid group, phosphonic acid group, etc. specifically, sulfonic acid group, carboxyl group, phosphoric acid group, phosphonic acid group, etc. have been introduced as electrolyte group having electrolyte function
- An ion exchange resin having a sulfonic acid group is particularly preferable.
- the ion exchange resin having a sulfonic acid group various resins having a sulfonic acid group can be used.
- the various resins include polyolefins such as polyethylene and polypropylene, (meth) acrylic resins, styrene resins, polyacetals, polyesters, polycarbonates, polyamides, polyamideimides, polyimides, polyethers, polyetherimides, polyether ketones, Examples include polyetheretherketone, polysulfone, polyethersulfone, polyphenylene sulfide, and fluororesin.
- ion exchange resins having a sulfonic acid group a fluorine resin having a sulfonic acid group, a sulfonated product of a crosslinked polystyrene, and the like are preferable.
- a polystyrene-graft-ethylenetetrafluoroethylene copolymer having a sulfonic acid group, a polystyrene-graft. -It may be a polytetrafluoroethylene copolymer or the like.
- a fluororesin having a sulfonic acid group (such as a fluorohydrocarbon resin in which at least some of the hydrogen atoms are substituted with fluorine atoms) is particularly preferable from the viewpoint of releasability.
- a fluororesin having a sulfonic acid group (or —CF 2 CF 2 SO 3 H group) in the side chain, such as [2- (2-sulfotetrafluoroethoxy) hexafluoropropoxy]
- a copolymer (such as a block copolymer) of trifluoroethylene and tetrafluoroethylene is preferably used.
- the ion exchange capacity of the ion exchange resin may be 0.1 meq / g or more, for example, 0.1 to 2.0 meq / g, preferably 0.2 to 1.8 meq / g, more preferably 0.3. It may be about ⁇ 1.5 meq / g (particularly 0.5 to 1.5 meq / g).
- an ion exchange resin a commercially available product such as “Registered trademark: Nafion” manufactured by DuPont can be used.
- an ion exchange resin described in JP 2010-234570 A may be used.
- the ion exchange layer may be an electrolyte membrane formed of the ion exchange resin, an electrode membrane including the ion exchange resin and catalyst particles.
- the catalyst particles include a metal component having a catalytic action (particularly, a noble metal element such as platinum (Pt) or an alloy containing a noble metal), and is usually an electrode film for a cathode electrode. Contains platinum, and the electrode film for the anode electrode contains a platinum-ruthenium alloy. Furthermore, the catalyst particles are usually used as composite particles in which the metal component is supported on a conductive material (carbon material such as carbon black).
- the ratio of the ion exchange resin is, for example, about 5 to 300 parts by weight, preferably about 10 to 250 parts by weight, and more preferably about 20 to 200 parts by weight with respect to 100 parts by weight of the catalyst particles.
- the ion exchange layer may also contain the conventional additives exemplified in the section of the release layer, for example, inorganic materials such as inorganic particles and inorganic fibers (carbonaceous material, glass, ceramics, etc.). Also good.
- inorganic materials such as inorganic particles and inorganic fibers (carbonaceous material, glass, ceramics, etc.). Also good.
- the ion exchange layer may be formed on at least one surface of the release layer, may be formed on both surfaces of the release layer, or may be formed only on one surface of the release layer.
- the average thickness of the ion exchange layer is, for example, about 1 to 500 ⁇ m, preferably about 1.5 to 300 ⁇ m, and more preferably about 2 to 200 ⁇ m.
- the average thickness of the electrolyte membrane is, for example, about 1 to 500 ⁇ m, preferably about 5 to 300 ⁇ m, and more preferably about 10 to 200 ⁇ m.
- the average thickness of the electrode film is, for example, about 1 to 100 ⁇ m, preferably about 2 to 80 ⁇ m, and more preferably about 2 to 50 ⁇ m.
- the manufacturing method of the laminated body of this invention includes the lamination process of laminating
- an ion exchange layer (an electrolyte membrane containing an ion exchange resin and / or an electrode membrane containing an ion exchange resin) may be formed on the release layer of the release film by coating.
- An electrolyte membrane is laminated on the mold release film by coating to produce a laminate in which the electrolyte film is laminated on the mold release film, and an electrode film is laminated on the second mold release film by coating.
- a laminate in which an electrode film is laminated on a release film may be manufactured.
- the electrolyte membrane and the electrode membrane are subjected to coating in the state of a solution in which an ion exchange resin (and catalyst particles) are dissolved in a solvent.
- the solvent examples include water, alcohols (C 1-4 alkanols such as methanol, ethanol, isopropanol, and 1-butanol), ketones (acetone, methyl ethyl ketone, etc.), ethers (dioxane, tetrahydrofuran, etc.), sulfoxides, and the like. (Such as dimethyl sulfoxide).
- alcohols C 1-4 alkanols such as methanol, ethanol, isopropanol, and 1-butanol
- ketones acetone, methyl ethyl ketone, etc.
- ethers dioxane, tetrahydrofuran, etc.
- sulfoxides and the like.
- concentration of the solute (ion exchange resin, catalyst particles) in the solution is, for example, about 1 to 80% by weight, preferably 2 to 60% by weight, and more preferably about 3 to 50% by weight.
- Examples of the coating method include conventional methods exemplified in the method for producing a release film. Of these methods, the blade coater method, the bar coater method and the like are widely used.
- the solvent may be evaporated by heating and drying.
- the drying temperature may be 50 ° C. or more, for example, about 80 to 200 ° C. (especially 100 to 150 ° C.) for an electrolyte membrane, and for example, 50 to 150 ° C. (especially 60 to 120 ° C.) for an electrode membrane. )
- the laminate obtained in the laminating step is usually subjected to an adhesion step, but when continuously manufactured, the laminate is transported to a place where the adhesion step is performed in the lamination step before the adhesion step.
- the release film is excellent in flexibility, a laminating process involving such conveyance can be performed by a roll-to-roll method, and productivity can be improved. Furthermore, since the combination of the release layer and the base material layer is excellent in dimensional stability, the release film can be prevented from being stretched by tension even in the roll-to-roll method. Therefore, the ion exchange layer can be wound up in a roll shape without peeling, and productivity can be improved.
- the laminate obtained in the lamination step may be subjected to an adhesion step.
- the membrane electrode assembly is prepared by closely adhering the electrolyte membrane and the electrode film respectively laminated on the release layers of the first and second release films.
- the adhesion between the electrolyte membrane and the electrode membrane is usually carried out by thermocompression bonding.
- the heating temperature is, for example, about 80 to 250 ° C., preferably 90 to 230 ° C., more preferably about 100 to 200 ° C.
- the pressure is, for example, about 0.1 to 20 MPa, preferably about 0.2 to 15 MPa, and more preferably about 0.3 to 10 MPa.
- the complex (the laminate in which the electrolyte layer and the electrode film are in close contact with each other) in the adhesion process is subjected to a separation process in which the release film is separated from the ion exchange layer (electrolyte film and / or electrode film).
- a membrane electrode assembly of a molecular fuel cell is obtained.
- even a laminate that has undergone the above-described drying process or thermocompression treatment has an appropriate peeling strength, so that the release film and the ion exchange layer do not peel off in the lamination process or the adhesion process, and the peeling process. Then, the release film can be easily peeled off and workability can be improved.
- the release layer of the release film must have a predetermined release property with respect to the ion exchange layer, and the peel strength between the release layer and the ion exchange layer of the release film (especially the lamination in the release step).
- the peel strength of the body is, for example, about 0.1 to 20 mN / mm, preferably about 0.5 to 18 mN / mm, more preferably about 1 to 15 mN / mm (particularly 2 to 12 mN / mm). If the peel strength is too high, the peeling work becomes difficult, and if it is too low, workability in the laminating step and the adhesion step is lowered.
- the peel strength can be measured by a method of leaving 180 ° at 300 mm / min after standing at 20 ° C. and 50% RH for 1 hour or more.
- an electrode film (second release film) is further formed on the release layer of the third release film, similarly to the adhesion step and the release step.
- the electrode film for the anode electrode is used, the electrode film of the cathode electrode film) is adhered and peeled off, and the fuel gas supply layer and the air supply are provided on each electrode film by a conventional method.
- a membrane electrode assembly (MEA) is obtained by laminating the layers.
- a film having a thickness of 50 to 100 ⁇ m was prepared by a hot press method or a solution cast method, cut into a width of 5 mm and a length of 50 mm, and a dynamic viscoelasticity measuring apparatus (TE Instruments Japan Co., Ltd.).
- the dynamic storage elastic modulus (E ′) was measured from ⁇ 100 ° C. to 250 ° C. under the conditions of a distance between chucks of 20 mm, a heating rate of 5 ° C./min and an angular frequency of 10 Hz.
- composition ratio of cyclic olefin resin The composition ratio of the cyclic olefin resin (copolymer) was measured by 13 C-NMR.
- the surface on the electrolyte membrane side of the obtained laminate and the surface on the electrode membrane side of the laminate including the electrode membrane obtained in Examples and Comparative Examples are pressure-bonded at a temperature and a pressure of 10 MPa shown in Table 1, and an electrode
- the base film on the membrane side was peeled off, and the releasability was evaluated according to the following criteria.
- a release film is set on a roll, the release film is sent out at a speed of 0.3 m / min, and the electrode film coating solution used in the examples is applied to the roll at a coating amount of Pt basis weight of 0.5 mg / cm 2.
- ⁇ Coating was done by the two-roll method and evaluated according to the following criteria.
- ⁇ Cracks and cracks do not occur in the release layer, and the coating can be performed without problems.
- ⁇ The release layer is cracked and cannot be applied.
- the obtained reaction mixture was released into a large amount of methanol adjusted to be acidic with hydrochloric acid to precipitate a precipitate, which was separated by filtration, washed and dried to obtain 2-norbornene / 1-octene copolymer A. 5.0 g was obtained.
- the obtained copolymer A has a number average molecular weight Mn of 30,000, a glass transition temperature Tg of 215 ° C., a dynamic storage elastic modulus (E ′) having a transition point in the vicinity of ⁇ 20 ° C., and 2-norbornene
- the obtained copolymer D has a Mn of 175,000, a Tg of 331 ° C., a dynamic storage elastic modulus (E ′) having a transition point in the vicinity of ⁇ 20 ° C., 2-norbornene and 5-hexyl-2-
- the polymerization reaction solution is poured into a large amount of acidic methanol in hydrochloric acid to completely precipitate the polymer, filtered, washed, and dried under reduced pressure at 70 ° C. for 3 hours or more to give 2-norbornene / 1-hexene copolymer E. 8.7g was obtained.
- the obtained copolymer E has a number average molecular weight Mn of 32,000, a glass transition temperature Tg of 300 ° C., a dynamic storage elastic modulus (E ′) having a transition point in the vicinity of ⁇ 20 ° C., and 2-norbornene
- a magnetic stirrer was placed in a 100 mL glass reactor with a rubbed glass stopper, and was sufficiently replaced with nitrogen gas.
- 0.464 g of the prepared dry aluminoxane was added, and then a predetermined amount of a 2-norbornene toluene solution (concentration 5.14 mol / L) was added.
- the whole was diluted with toluene until 29 mL, and the 2-norbornene concentration was adjusted to 1.5 mol / L.
- 1 atmosphere of ethylene was introduced and saturated.
- the dynamic storage elastic modulus (E ′) showed no transition point at ⁇ 50 to 100 ° C.
- a release film 2 (dry layer 1 ⁇ m dry thickness) was obtained in the same manner as in Production Example 1 except that 1 part by weight of 2-norbornene / 1-octene copolymer B was dissolved in 99 parts by weight of toluene. It was.
- a release film 4 (dry thickness of the release layer) was prepared in the same manner as in Production Example 1 except that 1 part by weight of 2-norbornene / 5-hexyl-2-norbornene copolymer D was dissolved in 99 parts by weight of toluene. 1 ⁇ m) was obtained.
- Example 1 7 parts by weight of Pt-supported carbon (“TEC10E50E” manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) and 35 parts by weight of the ion exchange resin solution (Nafion DE2020CS) were mixed by a ball mill to obtain a coating solution for an electrode film (electrode catalyst layer). . On the release layer of the release film 1, the electrode film coating solution is applied using a doctor blade, and then dried at 100 ° C. for 10 minutes, and the electrode film having a Pt weight per unit area of 0.5 mg / cm 2 is included. A laminate was obtained.
- Examples 2-6 and Comparative Examples 1-2 A laminate was obtained in the same manner as in Example 1 except that the release films 2 to 8 were used instead of the release film 1, respectively.
- Table 1 shows the results of evaluating the laminates obtained in Examples and Comparative Examples.
- the release films of the examples are excellent in toughness and release properties.
- the releasability tends to improve as the difference between the glass transition temperature and the processing temperature increases, and Examples 2 to 4 and 6 show excellent releasability.
- the release film of Comparative Example 1 since the release film of Comparative Example 1 has low heat resistance, it tends to cause defective release in the manufacturing process of the fuel cell, and the yield may be reduced. Since the release film of Comparative Example 2 has low toughness, it causes defective release from the ion exchange layer due to cracks or cracks in the release layer of the release film during the roll-to-roll manufacturing process. It is easy to cause a decrease in yield.
- the release film of the present invention is used for producing a membrane electrode assembly of a polymer electrolyte fuel cell.
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Abstract
Description
本発明の離型フィルムは、固体高分子型燃料電池の膜電極接合体(MEA)を製造するための離型フィルムであって、側鎖に炭素数3~10のアルキル基を有するオレフィン単位を含む環状オレフィン系樹脂で形成された離型層を含む。本発明の離型フィルムは、特に、イオン交換樹脂を含む電解質膜及び/又は電極膜をその上に積層し、MEAを製造した後、MEAから剥離するためのフィルムであってもよい。
本発明の離型層は、環状オレフィン系樹脂を含み、この環状オレフィン系樹脂が側鎖に炭素数3~10のアルキル基を有するオレフィン単位を含んでいるため、所定の粘弾特性を有していている。
本発明の離型フィルムは、前記離型層を含む限り、特に限定されず、前記離型層単独で形成された単層の離型フィルム(例えば、押出成形により形成された離型フィルム)であってもよく、基材層の少なくとも一方の面に前記離型層が積層された積層構造の離型フィルムであってもよい。これらのうち、燃料電池の生産性を向上でき、薄肉で厚みの均一な離型層を容易に製造できる点から、積層構造の離型フィルムが好ましい。
離型フィルムの製造方法としては、慣用の方法を利用でき、単独の離型層で形成されている場合は、例えば、押出成形やコーティングで形成してもよく、基材層との積層構造の場合は、例えば、コーティング、共押出や押出ラミネート、加熱圧着などの方法であってもよく、粘着剤や接着剤を介して積層してもよい。
本発明の積層体は、固体高分子型燃料電池を製造するための積層体であり、離型フィルムと、この離型フィルムの離型層の上に積層され、かつイオン交換樹脂を含むイオン交換層(電解質膜、電極膜、膜電極接合体)とで形成されている。
本発明の積層体の製造方法は、離型フィルムの離型層の上(離型層の少なくとも一方の面)にイオン交換樹脂を含むイオン交換層を積層する積層工程を含む。
示差走査熱量計(エスアイアイ・ナノテクノロジー(株)製「DSC6200」)を用い、JIS K7121に準じ、窒素気流下、昇温速度10℃/分で測定を行った。
試験片について、熱プレス法又は溶液キャスト法により厚み50~100μmのフィルムを作製し、幅5mm、長さ50mmに切り出し、動的粘弾性測定装置(ティー・エイ・インスツルメント・ジャパン(株)製、RSA-III)を用い、チャック間距離20mm、昇温速度5℃/分及び角周波数10Hzの条件で、-100℃から250℃まで動的貯蔵弾性率(E’)を測定した。
環状オレフィン系樹脂(共重合体)の組成比は、13C-NMRで測定した。
離型フィルムを構成する環状オレフィン系樹脂1重量部を、トルエン9重量部中に添加して攪拌し、室温での溶解状態を目視で観察し、以下の基準で評価した。
△:溶解に所定の時間を要する
×:溶解しない。
易接着性二軸延伸ポリエステルフィルム(東洋紡(株)製「コスモシャインA4100」、厚み50μm)、イオン交換樹脂溶液(デュポン社製「ナフィオン(登録商標)DE2020CS」、イオン交換樹脂の水-アルコール分散液、固形分濃度20重量%)を用意し、ドクターブレードを用いて、前記ポリエステルフィルムの易接着層面に前記イオン交換樹脂溶液をキャストし、その塗膜を130℃のオーブン内で乾燥させて、電解質膜であるイオン交換層(厚み20μm)を含む積層体を形成した。
△…離型層に電極膜が僅かに残存している
×…離型層に電極膜が残存している。
ロールに離型フィルムをセットし、0.3m/分の速度で離型フィルムを送り出し、Pt目付量0.5mg/cm2の塗布量で、実施例で使用した電極膜の塗布液を、ロール・ツー・ロール方式で塗工し、以下の基準で評価した。
×:離型層が割れて塗工できない。
乾燥した300mLの2口フラスコ内を窒素ガスで置換した後、ジメチルアニリウム テトラキス(ペンタフルオロフェニル)ボレート8.1mg、トルエン235.7mL、7.5モル/Lの濃度でノルボルネンを含有するトルエン溶液7.0mL、1-オクテン5.7mL、トリイソブチルアルミニウム2mLを添加して、反応溶液を25℃に保持した。この溶液とは別個に、グローブボックス中で、触媒として、92.9mgの(t-ブチルアミド)ジメチル-9-フルオレニルシランチタンジメチル[(t-BuNSiMe2Flu)TiMe2]をフラスコに入れ、5mLのトルエンに溶解させた。この触媒溶液2mLを300mLフラスコに加えて重合を開始した。2分後に2mLのメタノールを添加して反応を終了させた。次いで、得られた反応混合物を塩酸で酸性に調整した大量のメタノール中に放出して沈殿物を析出させ、濾別、洗浄後、乾燥して、2-ノルボルネン・1-オクテン共重合体Aを5.0g得た。得られた共重合体Aの数平均分子量Mnは30,000、ガラス転移温度Tgは215℃、動的貯蔵弾性率(E’)が-20℃付近に転移点を有し、2-ノルボルネンと1-オクテンとの組成(モル比)は、前者/後者=70/30であった。
1-オクテンの配合量を3.3mLに変更する以外は合成例1と同様にして、2-ノルボルネン・1-オクテン共重合体Bを5.0g得た。得られた共重合体BのMnは121,000、Tgは269℃、動的貯蔵弾性率(E’)が-20℃付近に転移点を有し、2-ノルボルネンと1-オクテンとの組成(モル比)は、前者/後者=83/17であった。
1-オクテンの配合量を1.7mLに変更する以外は合成例1と同様にして、2-ノルボルネン・1-オクテン共重合体Cを4.6g得た。得られた共重合体CのMnは123,000、Tgは325℃、動的貯蔵弾性率(E’)が-20℃付近に転移点を有し、2-ノルボルネンと1-オクテンとの組成(モル比)は、前者/後者=94/6であった。
乾燥したガラス反応器に、トルエン199.3g、2-ノルボルネン33.9g、5-ヘキシル-2-ノルボルネン15.4g、及びMMAO-3A(Modified methyl aluminoxane type 3、東ソーファインケム(株)製、濃度2.23モル/L)3.1gを添加した。次に、トルエン0.87gに溶解させた(t-ブチルアミド)ジメチル-9-フルオレニルシランチタンジメチル0.0074g(20μモル)を、前記反応器に添加した。40℃で7時間攪拌して重合を継続した後、メタノール3gを添加して反応を終了させた。その後、重合反応液を多量の塩酸酸性メタノールに注いで重合体を完全に析出させ、濾別、洗浄後、70℃で3時間以上減圧乾燥して、2-ノルボルネン・5-ヘキシル-2-ノルボルネン共重合体Dを21.3g得た。得られた共重合体DのMnは175,000、Tgは331℃、動的貯蔵弾性率(E’)が-20℃付近に転移点を有し、2-ノルボルネンと5-ヘキシル-2-ノルボルネンとの組成(モル比)は、前者/後者=79/21であった。
乾燥したガラス反応器に、トルエン646.1mL、2-ノルボルネン117.5g、1-ヘキセン114.7mL、及びMMAO-3A(Modified methyl aluminoxane type 3、東ソーファインケム(株)製、濃度2.23モル/L)7.0mLを添加した。次に、トルエン2.6mLに溶解させた(t-ブチルアミド)ジメチル-9-フルオレニルシランチタンジメチル0.0074gを、前記反応器に添加した。40℃で3時間攪拌して重合を継続した後、メタノール3gを添加して反応を終了させた。その後、重合反応液を多量の塩酸酸性メタノールに注いで重合体を完全に析出させ、濾別、洗浄後、70℃で3時間以上減圧乾燥して、2-ノルボルネン・1-ヘキセン共重合体Eを8.7g得た。得られた共重合体Eの数平均分子量Mnは32,000、ガラス転移温度Tgは300℃、動的貯蔵弾性率(E’)が-20℃付近に転移点を有し、2-ノルボルネンと1-ヘキセンとの組成(モル比)は、前者/後者=88/12であった。
1-ヘキセンを1-デセンに変更し、配合量を174.7mLに変更する以外は合成例5と同様にして、2-ノルボルネン・1-デセン共重合体Fを8.5g得た。得られた共重合体Fの数平均分子量Mnは27,000、ガラス転移温度Tgは244℃、動的貯蔵弾性率(E’)が-20℃付近に転移点を有し、2-ノルボルネンと1-デセンとの組成(モル比)は、前者/後者=85/15であった。
メタロセン化合物として、(t-BuNSiMe2Flu)TiMe2を、「Macromolecules, 1998年, 第31巻, 3184頁」の記載に基づいて調製し、-20℃にてヘキサン中で再結晶して精製した。また、乾燥アルミノキサンを、「Macromolecules, 2001年, 第34巻, 3142頁」の記載に基づいて調製した。
2-ノルボルネン濃度を1.9モル/Lに変更する以外は合成例7と同様にして、2-ノルボルネン・エチレン共重合体Hを0.9g得た。得られた共重合体HのMnは55,000、Tgは212℃、2-ノルボルネンとエチレンとの組成(モル比)は、前者/後者=95/5であった。なお、動的貯蔵弾性率(E’)は、-50~100℃に転移点は認められなかった。
1重量部の2-ノルボルネン・1-オクテン共重合体Aを、9重量部のトルエンに溶解し、塗工液を調製した。基材フィルムとして、易接着性二軸延伸ポリエステルフィルム(コスモシャインA4100)を用い、塗工液をメイヤーバーコーティング法により基材のフィルムの片面にコーティングし、100℃の温度で1分間乾燥して離型層(乾燥厚み1μm)を形成し、離型フィルム1を得た。
1重量部の2-ノルボルネン・1-オクテン共重合体Bを、99重量部のトルエンに溶解する以外は製造例1と同様にして、離型フィルム2(離型層の乾燥厚み1μm)を得た。
1重量部の2-ノルボルネン・1-オクテン共重合体Cを、99重量部のトルエンに溶解する以外は製造例1と同様にして、離型フィルム3(離型層の乾燥厚み1μm)を得た。
1重量部の2-ノルボルネン・5-ヘキシル-2-ノルボルネン共重合体Dを、99重量部のトルエンに溶解する以外は製造例1と同様にして、離型フィルム4(離型層の乾燥厚み1μm)を得た。
2-ノルボルネン・1-オクテン共重合体Aの代わりに、2-ノルボルネン・1-ヘキセン共重合体Eを用いる以外は製造例1と同様にして、離型フィルム5(離型層の乾燥厚み1μm)を得た。
2-ノルボルネン・1-オクテン共重合体Aの代わりに、2-ノルボルネン・1-デセン共重合体Fを用いる以外は製造例1と同様にして、離型フィルム6(離型層の乾燥厚み1μm)を得た。
2-ノルボルネン・1-オクテン共重合体Aの代わりに、2-ノルボルネン・エチレン共重合体(Topas Advanced Polymers,GmbH社製「TOPAS(登録商標)6017S-04」、Tg178℃)を用いる以外は製造例1と同様にして、離型フィルム7(離型層の乾燥厚み1μm)を得た。
2-ノルボルネン・1-オクテン共重合体Aの代わりに、2-ノルボルネン・エチレン共重合体Gを用いる以外は製造例1と同様にして、離型フィルム8(離型層の乾燥厚み1μm)を得た。
2-ノルボルネン・1-オクテン共重合体Aの代わりに、2-ノルボルネン・エチレン共重合体Hをトルエンに溶解しようと試みたが、溶解しなかったため、離型フィルムを作製できなかった。
Pt担持カーボン(田中貴金属工業(株)製「TEC10E50E」)7重量部、前記イオン交換樹脂溶液(ナフィオンDE2020CS)35重量部をボールミルで混合し、電極膜(電極用触媒層)の塗布液とした。離型フィルム1の離型層の上に、ドクターブレードを用いて電極膜の塗布液を塗工後、100℃で10分乾燥し、Pt目付量が0.5mg/cm2の電極膜を含む積層体を得た。
離型フィルム1の代わりに、それぞれ離型フィルム2~8を用いる以外は実施例1と同様にして積層体を得た。
Claims (16)
- 固体高分子型燃料電池の膜電極接合体を製造するための離型フィルムであって、側鎖に炭素数3~10のアルキル基を有するオレフィン単位を含む環状オレフィン系樹脂で形成された離型層を含む離型フィルム。
- 離型層のガラス転移温度が210~350℃である請求項1記載の離型フィルム。
- 離型層の動的貯蔵弾性率E’が-50~100℃の範囲に転移点を有する請求項1又は2記載の離型フィルム。
- 環状オレフィン系樹脂が、繰り返し単位として、炭素数3~10のアルキル基を有する鎖状オレフィン単位及び/又は炭素数3~10のアルキル基を有する環状オレフィン単位を含む請求項1~3のいずれかに記載の離型フィルム。
- 環状オレフィン系樹脂が、繰り返し単位として、炭素数3~10のアルキル基を有さない環状オレフィン単位(A)と、炭素数3~10のアルキル基を有する鎖状又は環状オレフィン単位(B)とを含む共重合体である請求項1~4のいずれかに記載の離型フィルム。
- 鎖状又は環状オレフィン単位(B)が、炭素数4~8の直鎖状アルキル基を有するエチレン又はノルボルネン単位である請求項5記載の離型フィルム。
- 環状オレフィン単位(A)と鎖状又は環状オレフィン単位(B)との割合(モル比)が、前者/後者=50/50~99/1である請求項5又は6記載の離型フィルム。
- 離型層の平均厚みが0.2~5μmである請求項1~7のいずれかに記載の離型フィルム。
- さらに基材層を含み、離型層が基材層の少なくとも一方の面に積層され、かつ基材層がポリオレフィン、ポリビニルアルコール系重合体、ポリエステル、ポリアミド及びセルロース誘導体からなる群より選択された少なくとも1種で形成されている請求項1~8のいずれかに記載の離型フィルム。
- コーティングで形成されたフィルムである請求項1~9のいずれかに記載の離型フィルム。
- 固体高分子型燃料電池を製造するための積層体であり、請求項1~10のいずれかに記載の離型フィルムと、この離型フィルムの離型層の上に積層され、かつイオン交換樹脂を含むイオン交換層とで形成された積層体。
- イオン交換樹脂が側鎖にスルホン酸基を有するフッ素樹脂であり、かつイオン交換樹脂を含むイオン交換層が、電解質膜及び/又は電極膜である請求項11記載の積層体。
- ロール・ツー・ロール方式で製造される請求項11又は12記載の積層体。
- 離型フィルムの離型層の上にイオン交換樹脂を含むイオン交換層を積層する積層工程を含む請求項11~13のいずれかに記載の積層体の製造方法。
- 積層工程において、ロール・ツー・ロール方式で積層する請求項14記載の製造方法。
- 請求項11~13のいずれかに記載の積層体から離型フィルムを剥離する剥離工程を含む固体高分子型燃料電池の膜電極接合体の製造方法。
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JP2018045841A (ja) * | 2016-09-13 | 2018-03-22 | トヨタ自動車株式会社 | 膜電極ガス拡散接合体の製造方法 |
US11123967B2 (en) * | 2017-03-30 | 2021-09-21 | Nitto Denko Corporation | Heat resistant release sheet and method for manufacturing same |
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WO2019013219A1 (ja) * | 2017-07-12 | 2019-01-17 | 日本ゼオン株式会社 | 電気化学素子用積層体及び電気化学素子用部材の製造方法 |
US10971708B2 (en) * | 2018-04-23 | 2021-04-06 | International Business Machines Corporation | Release layer for preparation of ion conducting membranes |
US20220001581A1 (en) * | 2018-10-04 | 2022-01-06 | Nitto Denko Corporation | Heat-resistant release sheet and thermocompression bonding method |
US20210380771A1 (en) * | 2018-10-05 | 2021-12-09 | Rensselaer Polytechnic Institute | Preparation of ion exchange membranes from polyolefins and polycyclic olefins |
JP6967128B1 (ja) * | 2020-08-26 | 2021-11-17 | 株式会社ダイセル | 積層フィルムおよびその製造方法ならびに燃料電池の製造方法 |
JP2022040112A (ja) * | 2020-08-26 | 2022-03-10 | 株式会社ダイセル | 積層フィルムおよびその製造方法ならびに燃料電池の製造方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0517222B2 (ja) | 1983-07-15 | 1993-03-08 | Mitsui Toatsu Chemicals | |
JP2004197442A (ja) | 2002-12-19 | 2004-07-15 | Shiroki Corp | ワイヤ式ウィンドレギュレータ |
JP2007119660A (ja) | 2005-10-31 | 2007-05-17 | Nippon Zeon Co Ltd | 環状オレフィン付加共重合体、その製造方法、及び成形用材料 |
JP2008255341A (ja) | 2007-03-09 | 2008-10-23 | Nippon Zeon Co Ltd | 環状オレフィン付加重合体の製造方法、環状オレフィン付加重合用触媒、および遷移金属化合物 |
JP2009298999A (ja) | 2008-05-14 | 2009-12-24 | Kaneka Corp | 環状オレフィン付加共重合体、光学用フィルム及び液晶またはel表示素子用透明導電性フィルム |
JP2010080169A (ja) * | 2008-09-25 | 2010-04-08 | Dainippon Printing Co Ltd | 固体高分子形燃料電池用触媒転写フィルム並びにそれを用いて得られる触媒層−電解質膜積層体及び固体高分子形燃料電池 |
JP2010234570A (ja) | 2009-03-30 | 2010-10-21 | Japan Gore Tex Inc | 積層体およびその製造方法 |
JP2014154273A (ja) * | 2013-02-06 | 2014-08-25 | Daicel Corp | 燃料電池製造用離型フィルム及び積層体並びに燃料電池の製造方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5017222B2 (ja) | 1971-10-04 | 1975-06-19 | ||
DE69836911T2 (de) * | 1997-07-18 | 2007-10-31 | Nippon Zeon Co., Ltd. | Modifiziertes cycloolefin-additionspolymer und härtbare harzzusammensetzung die dieses enthält |
WO2002005371A1 (fr) * | 2000-07-06 | 2002-01-17 | Matsushita Electric Industrial Co., Ltd. | Procede pour produire un ensemble film-electrodes, et procede pour produire une pile a combustible du type polymere solide |
JP2006257399A (ja) * | 2005-02-21 | 2006-09-28 | Kureha Corp | 離型フィルム、積層離型フィルム及びそれらの製造方法 |
KR101041125B1 (ko) * | 2007-09-19 | 2011-06-13 | 삼성에스디아이 주식회사 | 연료 전지용 전극, 연료 전지용 막-전극 어셈블리, 및 이를포함하는 연료 전지 시스템 |
JP5017222B2 (ja) | 2007-09-25 | 2012-09-05 | 富士フイルム株式会社 | 環状オレフィン系共重合体、フィルム、これを用いた偏光板および液晶表示装置 |
JP5321181B2 (ja) * | 2009-03-24 | 2013-10-23 | 凸版印刷株式会社 | 燃料電池部材の触媒層と電解質膜の接合体の製造方法 |
KR101745038B1 (ko) * | 2010-02-09 | 2017-06-08 | 스미또모 베이크라이트 가부시키가이샤 | 적층 필름 |
WO2012132150A1 (ja) * | 2011-03-28 | 2012-10-04 | 日本ゼオン株式会社 | 熱硬化性架橋環状オレフィン樹脂組成物、熱硬化性架橋環状オレフィン樹脂フィルム、熱硬化性架橋環状オレフィン樹脂組成物の製造方法及び熱硬化性架橋環状オレフィン樹脂フィルムの製造方法 |
WO2012144644A1 (ja) * | 2011-04-21 | 2012-10-26 | 株式会社ダイセル | 環状オレフィン系樹脂の架橋体及びその製造方法 |
-
2014
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0517222B2 (ja) | 1983-07-15 | 1993-03-08 | Mitsui Toatsu Chemicals | |
JP2004197442A (ja) | 2002-12-19 | 2004-07-15 | Shiroki Corp | ワイヤ式ウィンドレギュレータ |
JP2007119660A (ja) | 2005-10-31 | 2007-05-17 | Nippon Zeon Co Ltd | 環状オレフィン付加共重合体、その製造方法、及び成形用材料 |
JP2008255341A (ja) | 2007-03-09 | 2008-10-23 | Nippon Zeon Co Ltd | 環状オレフィン付加重合体の製造方法、環状オレフィン付加重合用触媒、および遷移金属化合物 |
JP2009298999A (ja) | 2008-05-14 | 2009-12-24 | Kaneka Corp | 環状オレフィン付加共重合体、光学用フィルム及び液晶またはel表示素子用透明導電性フィルム |
JP2010080169A (ja) * | 2008-09-25 | 2010-04-08 | Dainippon Printing Co Ltd | 固体高分子形燃料電池用触媒転写フィルム並びにそれを用いて得られる触媒層−電解質膜積層体及び固体高分子形燃料電池 |
JP2010234570A (ja) | 2009-03-30 | 2010-10-21 | Japan Gore Tex Inc | 積層体およびその製造方法 |
JP2014154273A (ja) * | 2013-02-06 | 2014-08-25 | Daicel Corp | 燃料電池製造用離型フィルム及び積層体並びに燃料電池の製造方法 |
Non-Patent Citations (9)
Title |
---|
J. APPL. POLYM. SCI, vol. 128, no. 1, 2013, pages 216 |
JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 691, 2006, pages 193 |
MACROMOLECULES, vol. 31, 1988, pages 3184 |
MACROMOLECULES, vol. 31, 1998, pages 3184 |
MACROMOLECULES, vol. 34, 2001, pages 3142 |
MACROMOLECULES, vol. 43, 2010, pages 4527 |
POLYHEDRON, vol. 24, 2005, pages 1269 |
POLYMER JOURNAL, vol. 43, 2011, pages 331 |
See also references of EP3070770A4 |
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TW201535851A (zh) | 2015-09-16 |
EP3070770A1 (en) | 2016-09-21 |
JP6062407B2 (ja) | 2017-01-18 |
TWI641179B (zh) | 2018-11-11 |
KR102220134B1 (ko) | 2021-02-25 |
US10622658B2 (en) | 2020-04-14 |
EP3070770A4 (en) | 2017-05-24 |
CN105722654A (zh) | 2016-06-29 |
US20160276689A1 (en) | 2016-09-22 |
EP3070770B1 (en) | 2020-07-15 |
CN105722654B (zh) | 2018-02-02 |
KR20160085831A (ko) | 2016-07-18 |
JP2015118916A (ja) | 2015-06-25 |
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