WO2015178191A1 - 樹脂フィルム、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

樹脂フィルム、積層体及びその製造方法並びに燃料電池の製造方法 Download PDF

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WO2015178191A1
WO2015178191A1 PCT/JP2015/063038 JP2015063038W WO2015178191A1 WO 2015178191 A1 WO2015178191 A1 WO 2015178191A1 JP 2015063038 W JP2015063038 W JP 2015063038W WO 2015178191 A1 WO2015178191 A1 WO 2015178191A1
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resin
film
layer
film according
ion exchange
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PCT/JP2015/063038
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English (en)
French (fr)
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岡田　和之
西村　協
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ダイセルバリューコーティング株式会社
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Priority to CN201580026037.4A priority Critical patent/CN106414600B/zh
Priority to EP15795404.1A priority patent/EP3147325B1/en
Priority to US15/308,703 priority patent/US10355298B2/en
Priority to KR1020167034996A priority patent/KR20170010316A/ko
Publication of WO2015178191A1 publication Critical patent/WO2015178191A1/ja

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    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • 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
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    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
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    • C—CHEMISTRY; METALLURGY
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Definitions

  • the present invention relates to a resin film used for production of a polymer electrolyte fuel cell, a laminate (laminated film) including the resin film, a method for producing the same, and a method for producing a membrane electrode assembly using the laminate. About.
  • 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.
  • the layers formed on the support are brought into contact with each other, the temperature is about 130 to 150 ° C. (depending on the material used, about 150 to 200 ° C.), and the pressure is 1 to 10 MPa.
  • a method is used in which the support is peeled after it is brought into close contact by thermocompression bonding at a degree. Therefore, a release film is used as the support, but the release film is required to have appropriate release properties (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 release property and a side chain containing a sulfonic acid group having a low release property. It is difficult to predict behavior related to moldability, and it is difficult to balance releasability and adhesion.
  • release films are often used by being laminated with a base film with high mechanical properties in order to improve handleability and productivity, but they are general-purpose base materials that do not have reactive groups. It is difficult to improve the adhesion to the film.
  • 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.
  • a release film a fluorine-based film is generally used.
  • it is excellent in heat resistance, release property, and non-contamination property, it is expensive and is disposed of after incineration after use. It is difficult to combust in and it is easy to generate toxic gas.
  • 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 formed release film is also described.
  • 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 is excellent in releasability to electrolyte membranes and electrode membranes containing an ion exchange resin, but has low adhesion to the polyethylene terephthalate film, and the base film is easy to peel off. MEA productivity decreases. Further, the release film is not sufficiently releasable from the electrolyte membrane and the electrode membrane in the high temperature MEA manufacturing process.
  • Patent Document 2 discloses a first layer laminated on a plastic substrate and made of a chlorine-containing resin, and laminated on the first layer and made of a cyclic polyolefin resin.
  • the laminated film can be used for industrial materials such as industrial release films, packaging films such as foods, pharmaceuticals or chemicals, and optical members such as polarizing plates for liquid crystals.
  • a preferable cyclic polyolefin resin a copolymer of a cyclic olefin and a chain olefin is described.
  • Patent Document 3 discloses that the first component made of a transparent plastic material is not thermodynamically miscible with the first component and the temperature dependence of the refractive index is also different.
  • a thermally reversible molding material having a second component made of a non-liquid crystal plastic material is disclosed.
  • cycloolefin is exemplified as an example of the first component
  • vinylidene chloride is exemplified as an example of the monomer constituting the second component.
  • a molding material in which a copolyamide and a terpolymer containing a styrene monomer are combined is prepared.
  • the use of molding materials describes thermally reversible plastic molding materials such as shielding systems that regulate the amount of light and temperature, for example glazing, such as buildings, greenhouses, automobiles and solar concentrating systems. Yes.
  • JP 2010-234570 A (Claims, Example 2) JP 2009-102558 A (Claim 1, paragraphs [0052] [0079]) JP 2000-95957 A (claims, paragraph [0001], examples)
  • an object of the present invention is to provide a general-purpose substrate without interposing an adhesive layer such as an easy-adhesive layer, while having appropriate release properties and adhesion to the electrolyte membrane and electrode membrane of the solid polymer fuel cell. It is providing the resin film which can be closely_contact
  • Another object of the present invention is a resin film that is excellent in heat resistance and handleability, and that can improve the productivity of a membrane / electrode assembly (electrolyte membrane and / or electrode membrane) of a polymer electrolyte fuel cell, including the resin film It is providing the laminated film, its manufacturing method, and the method of manufacturing the said membrane electrode assembly using the said laminated film.
  • Still another object of the present invention is to provide a resin film that can be easily thinned by coating, a laminated film including the resin film, a method for producing the same, and a method for producing the membrane electrode assembly using the laminated film. It is in.
  • the present inventors have formed a resin film by combining a cyclic olefin-based resin and a chlorine-containing resin, thereby providing an electrolyte membrane and an electrode membrane for a polymer electrolyte fuel cell.
  • the present invention has been completed by finding that it has appropriate releasability and adhesion, and can be adhered to a general-purpose substrate film without interposing an adhesive layer such as an easy adhesion layer.
  • the resin film of the present invention is formed of a resin composition containing a cyclic olefin resin (A) and a chlorine-containing resin (B).
  • the chlorine-containing resin (B) may be a vinylidene chloride polymer.
  • the cyclic olefin resin (A) may be a cyclic olefin copolymer (particularly a copolymer of norbornenes and ⁇ -chain C 2-4 olefin).
  • the cyclic olefin resin (A) may be a cyclic olefin resin not containing an olefin unit having an alkyl group having 3 to 10 carbon atoms in the side chain.
  • the ratio of the chlorine-containing resin (B) may be about 0.5 to 60 parts by weight with respect to 100 parts by weight of the cyclic olefin resin (A).
  • the film of the present invention may be a release film for producing a membrane electrode assembly of a polymer electrolyte fuel cell.
  • the present invention includes a laminated film in which the film is laminated as a release layer on at least one surface of the base material layer.
  • the base material layer may be formed of at least one selected from the group consisting of polyolefin, polyvinyl alcohol polymer, polyester, polyamide, polyimide, and cellulose derivative.
  • the base material layer is formed of polyester and may not have an adhesive layer or an easy-adhesion layer.
  • the release layer may be a layer formed by coating and having an average thickness of about 0.01 to 20 ⁇ m.
  • an ion exchange layer containing an ion exchange resin may be laminated on the release layer.
  • the ion exchange resin may be a fluororesin having a sulfonic acid group in the side chain, and the ion exchange layer may be an electrolyte membrane and / or an electrode membrane.
  • the present invention also includes a method for producing the laminated film including a laminating step in which a release layer is formed by coating a solution containing the resin composition on the base material layer.
  • the present invention also includes a method for producing a membrane / electrode assembly of a polymer electrolyte fuel cell including a peeling step of peeling an ion exchange layer containing an ion exchange resin from the laminated film.
  • 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, and an electrode membrane containing an ion exchange resin and a catalyst is also an ion exchange layer. include.
  • a resin film is formed by combining a cyclic olefin resin containing a cyclic olefin unit and a chain olefin unit and a chlorine-containing resin, it is suitable for an electrolyte membrane and an electrode membrane of a polymer electrolyte fuel cell. While having releasability (peelability) and adhesiveness, it can adhere to a general-purpose substrate film without interposing an adhesive layer such as an easy adhesion layer.
  • the membrane / electrode assembly (electrolyte membrane and / or electrode membrane) of the polymer electrolyte fuel cell can be improved. Furthermore, it can be easily thinned by coating. Therefore, winding with a roll is possible, it can manufacture continuously by a roll-to-roll (roll to roll) system, and the productivity of a laminated film can also be improved.
  • the resin film of the present invention is formed of a resin composition containing a cyclic olefin resin (A) and a chlorine-containing resin (B).
  • the cyclic olefin resin (A) only needs to contain at least a cyclic olefin unit (A1) as a repeating unit.
  • the cyclic olefin resin (A) is an olefin resin having no long-chain alkyl group in the side chain, and in particular, an olefin unit having a C 3-10 alkyl group in the side chain (ie, C 3-10 It may be a cyclic olefin resin not containing a chain olefin unit having an alkyl group and / or a cyclic olefin unit having a C 3-10 alkyl group.
  • the polymerization component (monomer) for forming the cyclic olefin unit (A1) is a polymerizable cyclic olefin having an ethylenic double bond in the ring, and is a monocyclic olefin, a bicyclic olefin, a tricyclic or higher ring. It can be classified into 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 thereof; adducts of cyclopentadiene with tetrahydroindene and the like;
  • cyclic olefins can be used alone or in combination of two or more.
  • bicyclic olefins are preferred because they are excellent in the balance between the releasability and flexibility of the resin film.
  • the ratio of bicyclic olefins (particularly norbornenes) to the whole cyclic olefin (cyclic olefin for forming the cyclic olefin unit (A1)) may be 10 mol% or more, for example, 30 mol% or more, Preferably it is 50 mol% or more, More preferably, it is 80 mol% or more (especially 90 mol% or more), and bicyclic olefin independent (100 mol%) may be sufficient.
  • the ratio of the tricyclic or higher polycyclic olefin is increased, it becomes difficult to use for production in a roll-to-roll system.
  • Typical bicyclic olefins include, for example, norbornene (2-norbornene) which may have a substituent, octaline (octahydronaphthalene) which may have a substituent, and the like.
  • substituents include a methyl group, an ethyl group, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a cyano group, an amide group, and a 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 because it does not impair the releasability of the resin film.
  • norbornenes such as norbornene and norbornene having a C 1-2 alkyl group (particularly norbornene) are particularly preferable.
  • the cyclic olefin resin (A) may contain at least the cyclic olefin unit (A1) as a repeating unit. From the viewpoint of adhesion between the resin film and the base film and mechanical properties, the cyclic olefin resin A coalescence (cycloolefin copolymer) is preferred.
  • the cyclic olefin copolymer may be a copolymer of cyclic olefin units (A1) containing different types of cyclic olefin units, or a copolymer of cyclic olefin units (A1) and other copolymerizable units. It may be.
  • a copolymer of the cyclic olefin unit (A1) and other copolymerizable units is preferable from the viewpoint of excellent balance between the adhesion and mechanical properties, and the cyclic olefin unit ( A copolymer comprising A1) and a chain olefin unit (A2) is particularly preferred.
  • the copolymer includes a random copolymer, a block copolymer, or a graft copolymer.
  • the chain olefin unit (A2) may be a chain olefin unit generated by ring-opening of a cyclic olefin, but from the viewpoint of easy control of the ratio between the cyclic olefin unit and the chain olefin unit, A unit as a polymerization component is preferred.
  • chain olefins examples include chain C 2-4 olefins such as ethylene, propylene, 1-butene and isobutene. These chain olefins can be used alone or in combination of two or more. Of these chain olefins, ⁇ -chain C 2-3 olefins are preferable, and ethylene is more preferable.
  • the ratio of the cyclic olefin unit (A1) is too small, the heat resistance of the resin film is lowered, and when it is too much, the mechanical properties of the resin film are also easily lowered.
  • the cyclic olefin resin (A) may contain other copolymerizable units in addition to the cyclic olefin unit (A1) and the chain olefin unit (A2).
  • polymerization components (copolymerizable monomers) for forming other copolymerizable units include vinyl ester monomers such as vinyl acetate and vinyl propionate; diene monomers such as butadiene and isoprene; (meth) acrylic Ethyl unsaturated carboxylic acids such as acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid and angelic acid; methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl esters such as butyl acrylate, (meth) acrylic acid hydroxyalkyl esters, (meth) acrylic acid esters such as glycid
  • the ratio of the other copolymerizable units is preferably in a range that does not impair the releasability (peelability) of the resin film with respect to the ion exchange layer.
  • the total of olefin units for example, cyclic olefin units (A1) and chain-like) For example, it is 10 mol% or less, preferably 5 mol% or less, and more preferably 1 mol% or less, based on the total of olefin units (A2).
  • the number average molecular weight of the cyclic olefin resin (A) is, for example, 10,000 to 100,000, preferably 20,000 to 80,000 in terms of polystyrene in gel permeation chromatography (GPC) (solvent: toluene). Degree. 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 glass transition temperature (Tg) of the cyclic olefin-based resin (A) is, for example, 50 to 350 ° C. (for example, 100 to 340 ° C.), preferably 120 to 320 ° C. (for example, for example) in the method according to JIS K7121-1087. 160 to 300 ° C.), more preferably 160 to 250 ° C. (especially 170 to 200 ° C.). If the glass transition temperature is too low, the heat resistance is low, so that the resin film tends to fail to release from the ion exchange layer (peeling failure), and if it is too high, the production of the resin film becomes difficult. In the present specification, the glass transition temperature can be measured using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • a differential scanning calorimeter (“DSC6200” manufactured by SII NanoTechnology Co., Ltd.) may be used and measured in accordance with JIS K7121 under a nitrogen stream at a heating rate of 10 ° C./min.
  • the cyclic olefin-based resin (A) may be a resin obtained by addition polymerization or 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 resin (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, Japanese Patent Application Laid-Open Nos. 2004-107442, 2007-119660, 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, for example, a catalyst synthesized by the method described in these documents, Macromolecules, 31, 3184 (1988), Journal ⁇ of Organometallic Chemistry, 2006, 691, 193. Etc. can be used.
  • the chlorine-containing resin (B) may be a chlorinated resin such as chlorinated polyethylene or chlorinated polypropylene, but is usually a polymer having a chlorine-containing monomer as a polymerization component.
  • an adhesive layer such as an easy-adhesive layer is interposed while maintaining appropriate adhesion (releasing properties) to the ion exchange layer.
  • the resin film can be in close contact with a general-purpose substrate film such as a polyethylene terephthalate (PET) film.
  • PET polyethylene terephthalate
  • chlorine-containing monomers examples include vinyl chloride monomers and vinylidene chloride monomers. These chlorine-containing monomers can be used alone or in combination of two or more. Of these, vinylidene chloride monomer is preferred from the viewpoint of the adhesion of the resin film to the base film.
  • the chlorine-containing resin may contain a copolymerizable unit other than the chlorine-containing monomer unit.
  • the polymerization component for forming other copolymerizable units include the copolymerizable monomers exemplified in the section of the cyclic olefin resin (A).
  • the copolymerizable monomers can be used alone or in combination of two or more.
  • vinyl acetate, (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, glycidyl (meth) acrylate, (meth) acrylonitrile and the like are generally used.
  • the proportion of the other copolymerizable units may be such that it does not impair the properties of the chlorine-containing resin, and is usually 0.1 to 50% by weight (for example, 0.3 to 25% by weight), preferably 0.5 to 20% by weight, more preferably about 1 to 15% by weight (for example, 3 to 10% by weight).
  • chlorine-containing resin (B) examples include vinyl chloride polymers [vinyl chloride monomer homopolymer (polyvinyl chloride), vinyl chloride copolymers (vinyl chloride-vinyl acetate copolymer, vinyl chloride- ( Meta) acrylic acid ester copolymers, etc.], vinylidene chloride polymers [vinylidene chloride homopolymer (polyvinylidene chloride), vinylidene chloride copolymers (vinylidene chloride-vinyl chloride copolymer, vinylidene chloride- Vinyl acetate copolymer, vinylidene chloride- (meth) acrylic acid copolymer, vinylidene chloride- (meth) acrylic acid ester copolymer, vinylidene chloride- (meth) acrylonitrile copolymer, etc.). These chlorine-containing resins can be used alone or in combination of two or more.
  • a vinylidene chloride polymer (particularly, a vinylidene chloride copolymer such as a vinylidene chloride-vinyl chloride copolymer) is preferable from the viewpoint that adhesion with a base film can be improved.
  • the vinylidene chloride polymer may not contain an emulsifier, a surfactant and the like contained in the aqueous emulsion.
  • the number average molecular weight of the chlorine-containing resin (B) is, for example, 10,000 to 500,000, preferably 20,000 to 250,000, more preferably 25, in terms of polystyrene in gel permeation chromatography (GPC). It may be about 000 to 100,000.
  • the proportion of the chlorine-containing resin (B) may be more than 0.2 parts by weight and less than 100 parts by weight with respect to 100 parts by weight of the cyclic olefin resin (A). Parts by weight (eg 0.5-60 parts by weight), preferably 0.8-70 parts by weight (eg 1-60 parts by weight), more preferably 1.2-50 parts by weight (especially 1.5-30 parts by weight). Part by weight). Even if the ratio of the chlorine-containing resin (B) is small, the adhesion to the base film can be improved. Therefore, the ratio of the chlorine-containing resin (B) is, for example, 100 parts by weight of the cyclic olefin resin (A).
  • 0.5 to 30 parts by weight preferably 0.8 to 10 parts by weight (eg 1 to 5 parts by weight), more preferably 1.2 to 3 parts by weight (especially 1.5 to 2.5 parts by weight) It may be.
  • the ratio of the chlorine-containing resin is too small, it becomes difficult to improve the adhesion to the base film, and when it is too large, the releasability with respect to the ion exchange layer is lowered.
  • the resin film may further contain other resins and conventional additives.
  • other resins include chain olefin resins (polyethylene, polypropylene, etc.).
  • 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 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 the silicone compound is substantially contained. Preferably not.
  • the average thickness of the resin film (release layer) can be selected from the range of about 0.01 to 100 ⁇ m, for example, but a thin film with a smooth surface can be formed by coating, for example, 0.01 to 20 ⁇ m, preferably Is about 0.03 to 15 ⁇ m, more preferably about 0.05 to 10 ⁇ m (particularly 0.1 to 5 ⁇ m). If the film is thin, it is easy to handle, suitable for a roll-to-roll method, etc., and also economical. In the case of a coating film, the average thickness can be calculated based on the coating amount (solid content (active ingredient) weight per unit area) and density of the resin film.
  • the resin film of the present invention is excellent in releasability and heat resistance, it can be used for industrial release films and the like, and has appropriate adhesion and releasability (peelability) to the ion exchange layer.
  • a MEA membrane electrode assembly
  • a polymer electrolyte fuel cell in particular, an electrolyte membrane and / or an electrode membrane containing an ion exchange resin. It can be preferably used for a film for peeling from the MEA.
  • the resin film of the present invention is excellent in releasability and heat resistance, it may be used alone (single layer) as a release film, but it can improve the productivity of a fuel cell, and is a thin film with a uniform thickness. It is preferable to laminate the resin film as a release layer on at least one surface of the base material layer (base material film).
  • 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. If the elastic modulus is too small, the dimensional stability of the laminated film will be reduced, and the release layer will be peeled off from the electrolyte membrane or electrode film in the roll-to-roll manufacturing, resulting in lower fuel cell productivity. There is a risk of doing.
  • 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.
  • the thermoplastic resin include polyolefin (polypropylene resin, cyclic polyolefin, etc.), polyvinyl alcohol polymer, polyester, polyamide, polyimide, polycarbonate, polyphenylene ether, polyphenylene sulfide, cellulose derivatives (cellulose ester such as cellulose acetate). Etc. These thermoplastic resins can be used alone or in combination of two or more.
  • thermoplastic resins are formed with reactive groups and polar groups (reactive groups) for improving adhesion. It is preferably substantially free of side chains and the like.
  • these thermoplastic resins at least one selected from the group consisting of polyolefins, polyvinyl alcohol polymers, polyesters, polyamides, polyimides and cellulose derivatives (particularly selected from the group consisting of polyolefins, polyesters, polyimides and cellulose esters). At least one kind) is preferred, and polyester and polyimide are particularly preferred from the viewpoint of excellent balance between heat resistance and flexibility.
  • poly C 2-4 alkylene arylate resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) can be preferably used.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • polyimide include thermoplastic polyimide, polyetherimide, and polyamideimide.
  • the base material layer may be formed of a stretched film from the viewpoint of improving the film strength of the laminated film.
  • 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 base material layer may also contain conventional additives exemplified in the section of the resin film.
  • the ratio of the synthetic resin in the base material 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 whole base material layer. Also good.
  • the surface smoothness of the base material layer is not particularly limited as long as the release layer can be formed by coating, but the arithmetic average roughness Ra based on JIS B0601 may be 1 ⁇ m or less, preferably 100 nm or less (for example, 10 to 100 nm).
  • the surface of the base material layer may be subjected to a surface treatment in order to improve the adhesion with the release layer.
  • a surface treatment include conventional surface treatments such as corona discharge treatment, flame treatment, plasma treatment, ozone and ultraviolet irradiation treatment. Of these, corona discharge treatment is preferred.
  • the base material layer is an easy-adhesion layer formed of a conventional adhesive resin (for example, when the base material layer is a polyester resin, an adhesive property such as a low molecular weight polyester resin, an aliphatic polyester resin, or an amorphous polyester resin). It may have an easy-adhesion layer formed of a resin, etc., or may not substantially have an easy-adhesion layer.
  • the release layer (resin film) is excellent in adhesion to the base material layer, and even if the base material layer does not have an easy-adhesion layer, it has the adhesion necessary for the production of the fuel cell, A base material layer having no easy adhesion layer is particularly preferred. Therefore, in this invention, the layer structure of a laminated body can be simplified and it can also reduce in thickness by using the base material layer which does not have an easily bonding layer.
  • 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, it will be difficult to produce by roll-to-roll method, and if it is too thin, dimensional stability and transportability by roll-to-roll method will deteriorate and wrinkles will be mixed. There is a fear.
  • the laminate film (laminate) of the present invention may be a release film for producing a polymer electrolyte fuel cell.
  • the laminate film (release film) An ion exchange layer (electrolyte membrane, electrode membrane, membrane electrode assembly) containing an ion exchange resin is adhered onto the release layer. Therefore, in the laminated film of the present invention, the ion exchange layer containing the ion exchange resin is laminated on the release layer of the release film (the release layer formed of the resin film alone or the release layer of the laminated film). It may be a laminate (a laminate of a release film and an ion exchange layer).
  • 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.
  • polystyrene-graft-polyethylenetetrafluoroethylene copolymer having a sulfonic acid group 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 resin film, for example, inorganic materials such as inorganic particles and inorganic fibers (carbonaceous material, glass, ceramics, etc.). Good.
  • inorganic materials such as inorganic particles and inorganic fibers (carbonaceous material, glass, ceramics, etc.). 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 resin film of the present invention can be produced by a method of coating a coating material containing a resin composition and a solvent (for example, a solution coating agent) on a substrate because it is easy to form a thin and smooth film.
  • a coating material containing a resin composition and a solvent (for example, a solution coating agent)
  • it can be produced by a method of coating (or casting) a coating agent containing a cyclic olefin-based resin, a chlorine-containing resin and a solvent on a base material layer and then drying.
  • 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. Oils, ethers such as tetrahydrofuran and dioxane can be used. These solvents may be used alone or in combination of two or more. Of these, aromatic hydrocarbons such as toluene, aromatic oils such as solvent naphtha, and cyclic ethers such as tetrahydrofuran are preferred, and mixed solvents of aromatic hydrocarbons and cyclic ethers are particularly preferred.
  • the solid content concentration (resin composition concentration or active ingredient concentration) in the coating agent is, for example, 0.1 to 50% by weight, preferably 0.3 to 30% by weight, more preferably 0.5 to 20% by weight ( In particular, it is about 0.8 to 15% by weight).
  • 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.
  • a laminated film (a laminate of a release film and an ion exchange layer) in which an ion exchange layer is formed, on a release layer (a release layer formed of a resin film alone or a release layer of a laminated film),
  • An ion exchange layer may be laminated.
  • the laminated film may be formed by coating an ion exchange layer (an electrolyte membrane containing an ion exchange resin and / or an electrode membrane containing an ion exchange resin) on the release layer.
  • an ion exchange layer an electrolyte membrane containing an ion exchange resin and / or an electrode membrane containing an ion exchange resin
  • the first film release film
  • an electrode film may be laminated by coating to produce a laminate in which the electrode film is laminated on the second release film.
  • the electrolyte membrane and the electrode membrane are used for coating in the state of a solution or dispersion in which an ion exchange resin (and catalyst particles) are dissolved or dispersed in a solvent. Is done.
  • 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.
  • sulfoxides and the like.
  • concentration of the solute or solid content (ion exchange resin, catalyst particles) in the solution or dispersion is, for example, about 1 to 80% by weight, preferably 2 to 60% by weight, and more
  • 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 resin film or the laminated 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 the dimensional stability of the laminated film, elongation due to the tension of the laminated film is suppressed 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 obtained laminate may be subjected to an adhesion process.
  • 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 adhered in the adhesion step (laminated body in which the electrolyte layer and the electrode film are in close contact) is subjected to a separation step of peeling the release film from the ion exchange layer (electrolyte membrane and / or electrode film), and is a solid polymer.
  • Type membrane fuel cell membrane electrode assembly is obtained.
  • 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 needs to 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 (particularly the release step).
  • the peel strength of the laminate is, for example, about 0.1 to 100 mN / mm, preferably about 0.5 to 80 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 laminate in which the electrode film for the cathode electrode) is adhered is peeled off to release the release film, and the fuel gas is supplied onto each electrode film by a conventional method.
  • a membrane electrode assembly (MEA) is obtained by laminating a layer and an air supply layer.
  • Ion exchange resin solution a solution of a perfluoropolymer having a sulfonic acid group in the side chain, “Nafion (registered trademark) DE2021CS” manufactured by DuPont, solid content of 20% by weight PET film: “Polyester film Emblet (registered trademark) S50” manufactured by Unitika Ltd., thickness 50 ⁇ m, no easy-adhesion layer OPP film: “P3018” manufactured by Toyoshina Film Co., Ltd., thickness 30 ⁇ m, no easy-adhesion layer TAC film: “Z-TAC” manufactured by FUJIFILM Corporation, thickness 60 ⁇ m, no easy adhesion layer Nb / Et: 2-norbornene-ethylene copolymer, “TOPAS (registered trademark) 6017S-04” manufactured by TOPAS Advanced Polymers GmbH, glass Transition temperature 178 ° C PVDC: Vinylidene chloride copolymer, “PVDC Resin R204”
  • the cellophane tape (“CT405AP-15” manufactured by Nichiban Co., Ltd.) was strongly pressure-bonded on the ion exchange layer of the obtained laminate, and the tape was peeled off and evaluated according to the following criteria.
  • Comparative Example 2 A release film was obtained in the same manner as in Comparative Example 1 except that an OPP film was used instead of the PET film.
  • Comparative Example 3 A release film was obtained in the same manner as in Comparative Example 1 except that a TAC film was used instead of the PET film.
  • Example 2 A release film was obtained in the same manner as in Example 1 except that the ratio of PVDC was changed to 1.2 parts by weight.
  • Example 3 A release film was obtained in the same manner as in Example 1 except that the ratio of PVDC was changed to 2 parts by weight.
  • Example 4 A release film was obtained in the same manner as in Example 3 except that the solid concentration (resin component concentration) was changed to 0.5% by weight and the thickness of the release layer after drying was 0.01 ⁇ m.
  • Example 5 A release film was obtained in the same manner as in Example 1 except that the ratio of PVDC was changed to 60 parts by weight.
  • Table 1 shows the results of evaluating the release films obtained in the examples and comparative examples.
  • the resin film of the present invention is excellent in releasability and heat resistance, it can be used for various industrial release films and the like, and in particular, suitable releasability (peelability) and adhesion to the ion exchange layer. Therefore, it is suitable for a release film for producing a membrane electrode assembly of a polymer electrolyte fuel cell.

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Abstract

　環状オレフィン系樹脂（Ａ）と塩素含有樹脂（Ｂ）とを含む樹脂組成物で樹脂フィルムを形成する。前記塩素含有樹脂（Ｂ）は塩化ビニリデン系重合体であってもよい。前記環状オレフィン系樹脂（Ａ）は環状オレフィン系共重合体であってもよい。前記塩素含有樹脂（Ｂ）の割合は、環状オレフィン系樹脂（Ａ）１００重量部に対して、０．５～６０重量部であってもよい。このフィルムは、固体高分子型燃料電池の電解質膜及び電極膜に対する適度な離型性と密着性とを有すると共に、易接着層などの接着層を介在させることなく、汎用の基材フィルムに密着できるため、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に適している。

Description

樹脂フィルム、積層体及びその製造方法並びに燃料電池の製造方法
　本発明は、固体高分子型燃料電池の製造などに使用される樹脂フィルム、この樹脂フィルムを含む積層体（積層フィルム）及びその製造方法並びに前記積層体を用いて膜電極接合体を製造する方法に関する。
　固体高分子型燃料電池は、膜電極接合体（Ｍｅｍｂｒａｎｅ　Ｅｌｅｃｔｒｏｄｅ　Ａｓｓｅｍｂｌｙ：ＭＥＡ）と称される基本構成を有している。ＭＥＡは、イオン交換膜である固体高分子電解質膜の両面に、白金族金属触媒を担持したカーボン粉末を主成分とする電極膜（触媒層又は電極触媒膜）を積層し、得られた積層体を導電性の多孔膜である燃料ガス供給層と空気供給層とでさらに挟み込んで得られる。このＭＥＡにおいて、電解質膜及び電極膜のいずれにもイオン交換樹脂が含まれているが、通常、電解質膜及び電極膜はキャスト法及び／又はコーティング法などにより形成される。電解質膜と電極膜との積層方法としては、通常、支持体にそれぞれ形成された両層を接触させて、温度１３０～１５０℃程度（使用材料によっては１５０～２００℃程度）、圧力１～１０ＭＰａ程度で加熱圧着することにより密着した後、支持体を剥離する方法が用いられる。そのため、支持体としては離型フィルムが用いられるが、離型フィルムには、電解質膜及び電極膜に対する適度な離型性（剥離性）と密着性とが要求される。電解質膜及び電極膜に含まれるイオン交換樹脂は、離型性の高いフッ素樹脂の主鎖と、離型性の低いスルホン酸基を含む側鎖とを有する特異な構造を有する樹脂であり、離型性に関する挙動を予測するのは困難であり、離型性と密着性とのバランスをとるのが困難である。また、離型フィルムは、取り扱い性や生産性を向上させるために、機械的特性の高い基材フィルムと積層して使用されることが多いが、反応性基などを有さない汎用の基材フィルムに対する密着性を向上させるのは困難である。さらに、燃料電池製造用離型フィルムには、製造工程上、耐熱性が要求される上に、生産性の点から、ロール・ツー・ロール方式で製造されるため、柔軟性も要求される。離型フィルムとしては、一般的には、フッ素系フィルムが汎用されているが、耐熱性、離型性、非汚染性には優れているものの、高価である上に、使用後の廃棄焼却処理において燃焼し難く、有毒ガスを発生し易い。さらに、弾性率が低いため、ロール・ツー・ロール方式での製造が困難である。そこで、フッ素系フィルムに代わる離型フィルムとして、環状オレフィン系樹脂で形成された離型フィルムも提案されている。
　特開２０１０－２３４５７０号公報（特許文献１）には、シクロオレフィン系コポリマーからなる離型フィルムが開示されており、ポリエチレンテレフタレートフィルムなどの基材フィルムの上にシクロオレフィン系コポリマー溶液をコーティングして形成された離型フィルムも記載されている。また、実施例では、ポリエチレンテレフタレートフィルムの上に、流延装置を用いて、エチレンとノルボルネンとの共重合体を含む溶液をキャストし、厚さ０．５μｍの離型フィルムを形成している。
　しかし、この離型フィルムは、イオン交換樹脂を含む電解質膜や電極膜に対する離型性は優れているものの、ポリエチレンテレフタレートフィルムとの密着性が低く、基材フィルムが剥離し易いため、取り扱い性やＭＥＡの生産性が低下する。また、この離型フィルムは、高温でのＭＥＡの製造工程では電解質膜や電極膜に対する離型性が十分でない。
　特開２００９－１０２５５８号公報（特許文献２）には、プラスチック基材に積層され、塩素含有樹脂で構成された第一層と、この第一層に積層され、環状ポリオレフィン系樹脂で構成された第二層とで構成された積層フィルムであって、前記第一層及び前記第二層がそれぞれコーティングにより形成された積層フィルムが開示されている。この文献には、積層フィルムが、工業用離型フィルムなどの工業材料、食品、医薬品又は化学品などの包装フィルム、液晶用偏光板などの光学部材に利用できることが記載されている。また、好ましい環状ポリオレフィン系樹脂として、環状オレフィンと鎖状オレフィンとの共重合体が記載されている。
　しかし、この文献には、燃料電池については記載されていない。また、このフィルムを燃料電池製造用離型フィルムに用いても、層構造が複雑であるため、生産性や取り扱い性も低い。なお、この文献には、環状ポリオレフィン系樹脂のうち、環状オレフィンと鎖状オレフィンとの共重合体が好ましい理由は記載されていない。
　また、特開２０００－９５９５７号公報（特許文献３）には、透明プラスチック材料からなる第１の成分と、第１の成分と熱力学的に混和性でなく、屈折率の温度依存性も異なる非液晶プラスチック材料からなる第２の成分とを有する熱的に可逆な成形材料が開示されている。この文献では、第１の成分の一例として、シクロオレフィンが例示され、第２の成分を構成するモノマーの一例として、塩化ビニリデンが例示されている。実施例では、コポリアミドとスチレン系モノマーなどを含むターポリマーとを組み合わせた成形材料が調製されている。さらに、成形材料の用途としては、光と温度の量を調節する遮蔽システムなどの熱的に可逆なプラスチック成形材料、例えば、建物、温室、自動車及び太陽熱集光システムなどのグレイジングが記載されている。
　しかし、この文献にも、燃料電池については記載されていない。また、この文献では、環状オレフィン系樹脂と塩素含有樹脂との組み合わせの意義も記載されていない。
特開２０１０－２３４５７０号公報（特許請求の範囲、実施例２） 特開２００９－１０２５５８号公報（請求項１、段落［００５２］［００７９］） 特開２０００－９５９５７号公報（特許請求の範囲、段落［０００１］、実施例）
　従って、本発明の目的は、固体高分子型燃料電池の電解質膜及び電極膜に対する適度な離型性と密着性とを有すると共に、易接着層などの接着層を介在させることなく、汎用の基材フィルムに密着できる樹脂フィルム、この樹脂フィルムを含む積層フィルム及びその製造方法並びに前記積層フィルムを用いて前記膜電極接合体を製造する方法を提供することにある。
　本発明の他の目的は、耐熱性や取り扱い性に優れ、固体高分子型燃料電池の膜電極接合体（電解質膜及び／又は電極膜）の生産性を向上できる樹脂フィルム、この樹脂フィルムを含む積層フィルム及びその製造方法並びに前記積層フィルムを用いて前記膜電極接合体を製造する方法を提供することにある。
　本発明のさらに他の目的は、コーティングにより容易に薄肉化できる樹脂フィルム、この樹脂フィルムを含む積層フィルム及びその製造方法並びに前記積層フィルムを用いて前記膜電極接合体を製造する方法を提供することにある。
　本発明者らは、前記課題を達成するため鋭意検討した結果、環状オレフィン系樹脂と塩素含有樹脂とを組み合わせて樹脂フィルムを形成することにより、固体高分子型燃料電池の電解質膜及び電極膜に対する適度な離型性と密着性とを有すると共に、易接着層などの接着層を介在させることなく、汎用の基材フィルムに密着できることを見出し、本発明を完成した。
　すなわち、本発明の樹脂フィルムは、環状オレフィン系樹脂（Ａ）と塩素含有樹脂（Ｂ）とを含む樹脂組成物で形成されている。前記塩素含有樹脂（Ｂ）は塩化ビニリデン系重合体であってもよい。前記環状オレフィン系樹脂（Ａ）は、環状オレフィン系共重合体（特にノルボルネン類とα－鎖状Ｃ２－４オレフィンとの共重合体）であってもよい。前記環状オレフィン系樹脂（Ａ）は、繰り返し単位として環状オレフィン単位（Ａ１）及び鎖状オレフィン単位（Ａ２）を含んでいてもよく、前記環状オレフィン単位（Ａ１）と鎖状オレフィン単位（Ａ２）との割合（モル比）は、前者／後者＝５０／５０～９０／１０程度であってもよい。前記環状オレフィン系樹脂（Ａ）は、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まない環状オレフィン系樹脂であってもよい。前記塩素含有樹脂（Ｂ）の割合は、環状オレフィン系樹脂（Ａ）１００重量部に対して、０．５～６０重量部程度であってもよい。本発明のフィルムは、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もよい。
　本発明には、基材層の少なくとも一方の面に、前記フィルムが離型層として積層されている積層フィルムも含まれる。前記基材層は、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、ポリイ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種で形成されていてもよい。前記基材層は、ポリエステルで形成され、かつ接着層又は易接着層を有していてなくてもよい。前記離型層はコーティングで形成された平均厚み０．０１～２０μｍ程度の層であってもよい。本発明の積層フィルムは、前記離型層の上にイオン交換樹脂を含むイオン交換層が積層されていてもよい。前記イオン交換樹脂は、側鎖にスルホン酸基を有するフッ素樹脂であり、かつ前記イオン交換層は、電解質膜及び／又は電極膜であってもよい。
　本発明には、基材層の上に樹脂組成物を含む溶液をコーティングして離型層を形成する積層工程を含む前記積層フィルムの製造方法も含まれる。
　本発明には、前記積層フィルムからイオン交換樹脂を含むイオン交換層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も含まれる。
　なお、本明細書では、「イオン交換層」とは、イオン交換樹脂を含む層を意味し、イオン交換膜である電解質膜に限定されず、イオン交換樹脂及び触媒を含む電極膜もイオン交換層に含まれる。
　本発明では、環状オレフィン単位及び鎖状オレフィン単位を含む環状オレフィン系樹脂と塩素含有樹脂とを組み合わせて樹脂フィルムが形成されているため、固体高分子型燃料電池の電解質膜及び電極膜に対する適度な離型性（剥離性）と密着性とを有すると共に、易接着層などの接着層を介在させることなく、汎用の基材フィルムに密着できる。また、特定の環状オレフィン系樹脂を含むため、耐熱性や取り扱い性に優れ、固体高分子型燃料電池の膜電極接合体（電解質膜及び／又は電極膜）の生産性を向上できる。さらに、コーティングにより容易に薄肉化できる。そのため、ロールでの巻き取りが可能であり、ロール・ツー・ロール（ｒｏｌｌ　ｔｏ　ｒｏｌｌ）方式で連続的に製造でき、積層フィルムの生産性も向上できる。
　［樹脂フィルム］
　本発明の樹脂フィルムは、環状オレフィン系樹脂（Ａ）と塩素含有樹脂（Ｂ）とを含む樹脂組成物で形成されている。
　（Ａ）環状オレフィン系樹脂
　環状オレフィン系樹脂（Ａ）は、少なくとも繰り返し単位として環状オレフィン単位（Ａ１）を含んでいればよい。環状オレフィン系樹脂（Ａ）は、側鎖に長鎖アルキル基を有さないオレフィン系樹脂であり、特に、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（すなわち、Ｃ３－１０アルキル基を有する鎖状オレフィン単位及び／又はＣ３－１０アルキル基を有する環状オレフィン単位）を含まない環状オレフィン系樹脂であってもよい。
　環状オレフィン単位（Ａ１）を形成するための重合成分（モノマー）は、環内にエチレン性二重結合を有する重合性の環状オレフィンであり、単環式オレフィン、二環式オレフィン、三環以上の多環式オレフィンなどに分類できる。
　単環式オレフィンとしては、例えば、シクロブテン、シクロペンテン、シクロヘプテン、シクロオクテンなどの環状Ｃ４－１２シクロオレフィン類などが挙げられる。
　二環式オレフィンとしては、例えば、２－ノルボルネン；５－メチル－２－ノルボルネン、５，５－ジメチル－２－ノルボルネン、５－エチル－２－ノルボルネンなどのＣ１―２アルキル基を有するノルボルネン類；５－エチリデン－２－ノルボルネンなどのアルケニル基を有するノルボルネン類；５－メトキシカルボニル－２－ノルボルネン、５－メチル－５－メトキシカルボニル－２－ノルボルネンなどのアルコキシカルボニル基を有するノルボルネン類；５－シアノ－２－ノルボルネンなどのシアノ基を有するノルボルネン類；５－フェニル－２－ノルボルネン、５－フェニル－５－メチル－２－ノルボルネンなどのアリール基を有するノルボルネン類；オクタリン；６－エチル－オクタヒドロナフタレンなどのＣ１－２アルキル基を有するオクタリンなどが例示できる。
　多環式オレフィンとしては、例えば、ジシクロペンタジエン；２，３－ジヒドロジシクロペンタジエン、メタノオクタヒドロフルオレン、ジメタノオクタヒドロナフタレン、ジメタノシクロペンタジエノナフタレン、メタノオクタヒドロシクロペンタジエノナフタレンなどの誘導体；シクロペンタジエンとテトラヒドロインデンなどとの付加物；シクロペンタジエンの３～４量体などが挙げられる。
　これらの環状オレフィンは、単独で又は二種以上組み合わせて使用できる。これらの環状オレフィンのうち、樹脂フィルムの離型性と柔軟性とのバランスに優れる点から、二環式オレフィンが好ましい。環状オレフィン（環状オレフィン単位（Ａ１）を形成するための環状オレフィン）全体に対して二環式オレフィン（特にノルボルネン類）の割合は１０モル％以上であってもよく、例えば、３０モル％以上、好ましくは５０モル％以上、さらに好ましくは８０モル％以上（特に９０モル％以上）であり、二環式オレフィン単独（１００モル％）であってもよい。特に、三環以上の多環式オレフィンの割合が大きくなると、ロール・ツー・ロール方式での製造に用いることが困難となる。
　代表的な二環式オレフィンとしては、例えば、置換基を有していてもよいノルボルネン（２－ノルボルネン）、置換基を有していてもよいオクタリン（オクタヒドロナフタレン）などが例示できる。前記置換基としては、メチル基、エチル基、アルケニル基、アリール基、ヒドロキシル基、アルコキシ基、カルボキシル基、アルコキシカルボニル基、アシル基、シアノ基、アミド基、ハロゲン原子などが例示できる。これらの置換基は、単独で又は二種以上組み合わせてもよい。これらの置換基のうち、樹脂フィルムの離型性を損なわない点から、メチル基やエチル基などの非極性基が好ましい。これらの二環式オレフィンのうち、ノルボルネンやＣ１－２アルキル基を有するノルボルネンなどのノルボルネン類（特にノルボルネン）が特に好ましい。
　環状オレフィン系樹脂（Ａ）は、少なくとも繰り返し単位として環状オレフィン単位（Ａ１）を含んでいればよいが、樹脂フィルムと基材フィルムとの密着性や機械的特性の点から、環状オレフィン系共重合体（シクロオレフィンコポリマー）が好ましい。環状オレフィン系共重合体は、異なる種類の環状オレフィン単位を含む環状オレフィン単位（Ａ１）の共重合体であってもよく、環状オレフィン単位（Ａ１）と他の共重合性単位との共重合体であってもよい。これらの共重合体のうち、前記密着性及び機械的特性のバランスに優れる点から、環状オレフィン単位（Ａ１）と他の共重合性単位との共重合体が好ましく、繰り返し単位として環状オレフィン単位（Ａ１）及び鎖状オレフィン単位（Ａ２）を含む共重合体が特に好ましい。共重合体には、ランダム共重合体、ブロック共重合体、又はグラフト共重合体が含まれる。
　鎖状オレフィン単位（Ａ２）は、環状オレフィンの開環により生じた鎖状オレフィン単位であってもよいが、環状オレフィン単位と鎖状オレフィン単位との割合を制御し易い点から、鎖状オレフィンを重合成分とする単位が好ましい。
　鎖状オレフィンとしては、例えば、エチレン、プロピレン、１－ブテン、イソブテンなどの鎖状Ｃ２－４オレフィン類などが挙げられる。これらの鎖状オレフィンは、単独で又は二種以上組み合わせて使用できる。これらの鎖状オレフィンのうち、好ましくはα－鎖状Ｃ２－３オレフィン類であり、さらに好ましくはエチレンである。
　環状オレフィン単位（Ａ１）と鎖状オレフィン単位（Ａ２）との割合（モル比）は、例えば、前者／後者＝１／９９～９９／１程度の範囲から選択でき、例えば、前者／後者＝３０／７０～９５／５、好ましくは５０／５０～９０／１０（例えば、５５／４５～８０／２０）、さらに好ましくは６０／４０～７５／２５（特に６５／３５～７０／３０）程度である。環状オレフィン単位（Ａ１）の割合が少なすぎると、樹脂フィルムの耐熱性が低下し、多すぎると、樹脂フィルムの機械的特性も低下し易い。
　環状オレフィン系樹脂（Ａ）は、環状オレフィン単位（Ａ１）及び鎖状オレフィン単位（Ａ２）以外に他の共重合性単位を含んでいてもよい。他の共重合性単位を形成するための重合成分（共重合性モノマー）としては、例えば、酢酸ビニル、プロピオン酸ビニルなどのビニルエステル系モノマー；ブタジエン、イソプレンなどのジエン系モノマー；（メタ）アクリル酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸、クロトン酸、イソクロトン酸、メサコン酸、アンゲリカ酸などのエチレン系不飽和カルボン酸；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチルなどの（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸ヒドロキシアルキルエステル、グリシジル（メタ）アクリレートなどの（メタ）アクリル酸エステル；（メタ）アクリロニトリルなどのシアン化ビニル系モノマーなどが挙げられる。これらの共重合性モノマーは、単独で又は二種以上組み合わせて使用できる。
　他の共重合性単位の割合は、樹脂フィルムのイオン交換層に対する離型性（剥離性）を損なわない範囲であるのが好ましく、オレフィン単位の合計（例えば、環状オレフィン単位（Ａ１）及び鎖状オレフィン単位（Ａ２）の合計）に対して、例えば、１０モル％以下、好ましくは５モル％以下、さらに好ましくは１モル％以下である。
　環状オレフィン系樹脂（Ａ）の数平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）において（溶媒：トルエン）、ポリスチレン換算で、例えば、１０，０００～１００，０００、好ましくは２０，０００～８０，０００程度である。分子量が小さすぎると、製膜性が低下し易く、大きすぎると、粘度が高くなるため、取り扱い性が低下し易い。
　環状オレフィン系樹脂（Ａ）のガラス転移温度（Ｔｇ）は、ＪＩＳ　Ｋ７１２１－１０８７に準拠した方法において、例えば、５０～３５０℃（例えば、１００～３４０℃）、好ましくは１２０～３２０℃（例えば、１６０～３００℃）、さらに好ましくは１６０～２５０℃（特に１７０～２００℃）程度である。ガラス転移温度が低すぎると、耐熱性が低いため、樹脂フィルムのイオン交換層との離型不良（剥離不良）が起こり易く、高すぎると、樹脂フィルムの生産が困難となる。なお、本明細書において、ガラス転移温度は、示差走査熱量計（ＤＳＣ）を用いて測定できる。例えば、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℃／分で測定してもよい。
　環状オレフィン系樹脂（Ａ）は、付加重合により得られた樹脂であってもよく、開環重合（開環メタセシス重合など）により得られた樹脂であってもよい。また、開環メタセシス重合により得られた重合体は、水素添加された樹脂（水添樹脂）であってもよい。環状オレフィン系樹脂の重合方法は、慣用の方法、例えば、メタセシス重合触媒を用いた開環メタセシス重合、チーグラー型触媒を用いた付加重合、メタロセン系触媒を用いた付加重合（通常、メタセシス重合触媒を用いた開環メタセシス重合）などを利用できる。具体的な重合方法としては、例えば、特開２００４－１０７４４２号公報、特開２００７－１１９６６０号公報、特開２００８－２５５３４１号公報、Macromolecules, 43, 4527(2010)、Polyhedron, 24, 1269(2005), J. Appl. Polym. Sci, 128(1), 216(2013), Polymer Journal, 43, 331(2011)に記載の方法などを利用できる。また、重合に用いる触媒も、慣用の触媒、例えば、これらの文献や、Macromolecules, 31, 3184(1988)、Journal of Organometallic Chemistry, 2006年, 691巻, 193頁に記載の方法で合成された触媒などを利用できる。
　（Ｂ）塩素含有樹脂
　塩素含有樹脂（Ｂ）は、塩素化ポリエチレン、塩素化ポリプロピレンなどの塩素化された樹脂であってもよいが、通常、塩素含有モノマーを重合成分とする重合体である。本発明では、環状オレフィン系樹脂（Ａ）に塩素含有樹脂（Ｂ）を配合すると、イオン交換層に対する適度な密着性（離型性）を維持しつつ、易接着層などの接着層を介在させることなく、ポリエチレンテレフタレート（ＰＥＴ）フィルムなどの汎用の基材フィルムに樹脂フィルムを密着できる。
　塩素含有モノマーとしては、例えば、塩化ビニルモノマー、塩化ビニリデンモノマーなどが挙げられる。これらの塩素含有モノマーは、単独で又は二種以上組み合わせて使用できる。これらのうち、樹脂フィルムの基材フィルムに対する密着性の点から、塩化ビニリデンモノマーが好ましい。
　塩素含有樹脂は、塩素含有モノマー単位以外の他の共重合性単位を含んでいてもよい。他の共重合性単位を形成するための重合成分としては、例えば、前記環状オレフィン系樹脂（Ａ）の項で例示された共重合性モノマーなどが挙げられる。前記共重合性モノマーは単独で又は二種以上組み合わせて使用できる。前記共重合性モノマーのうち、酢酸ビニル、（メタ）アクリル酸、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸ヒドロキシアルキルエステル、グリシジル（メタ）アクリレート、（メタ）アクリロニトリルなどが汎用される。
　他の共重合性単位（共重合性モノマー）の割合は、塩素含有樹脂の特性を損なわない程度であればよく、塩素含有樹脂全体に対して、通常、０．１～５０重量％（例えば、０．３～２５重量％）、好ましくは０．５～２０重量％、さらに好ましくは１～１５重量％（例えば、３～１０重量％）程度であってもよい。
　塩素含有樹脂（Ｂ）としては、例えば、塩化ビニル系重合体［塩化ビニルモノマーの単独重合体（ポリ塩化ビニル）、塩化ビニル系共重合体（塩化ビニル－酢酸ビニル共重合体、塩化ビニル－（メタ）アクリル酸エステル共重合体など）など］、塩化ビニリデン系重合体［塩化ビニリデンの単独重合体（ポリ塩化ビニリデン）、塩化ビニリデン系共重合体（塩化ビニリデン－塩化ビニル共重合体、塩化ビニリデン－酢酸ビニル共重合体、塩化ビニリデン－（メタ）アクリル酸共重合体、塩化ビニリデン－（メタ）アクリル酸エステル共重合体、塩化ビニリデン－（メタ）アクリロニトリル共重合体など）など］などが挙げられる。これらの塩素含有樹脂は、単独で又は二種以上組み合わせて使用できる。
　これらの塩素含有樹脂のうち、基材フィルムとの密着性を向上できる点から、塩化ビニリデン系重合体（特に、塩化ビニリデン－塩化ビニル共重合体などの塩化ビニリデン系共重合体）が好ましい。塩化ビニリデン－塩化ビニル共重合体において、塩化ビニリデン単位と塩化ビニル単位の割合（モル比）は、例えば、前者／後者＝９９／１～５／９５、好ましくは９７／３～１０／９０、さらに好ましくは９５／５～５０／５０程度である。塩化ビニリデン系重合体は、水性エマルジョンに含有される乳化剤、界面活性剤などを含んでいなくてもよい。
　塩素含有樹脂（Ｂ）の数平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）において、ポリスチレン換算で、例えば、１０,０００～５００,０００、好ましくは２０,０００～２５０,０００、さらに好ましくは２５,０００～１００,０００程度であってもよい。
　塩素含有樹脂（Ｂ）の割合は、環状オレフィン系樹脂（Ａ）１００重量部に対して、０．２重量部を超え、かつ１００重量部未満であってもよく、例えば、０．５～９０重量部（例えば、０．５～６０重量部）、好ましくは０．８～７０重量部（例えば、１～６０重量部）、さらに好ましくは１．２～５０重量部（特に１．５～３０重量部）程度である。塩素含有樹脂（Ｂ）の割合が少なくても、基材フィルムに対する密着性を向上できるため、塩素含有樹脂（Ｂ）の割合は、環状オレフィン系樹脂（Ａ）１００重量部に対して、例えば、０．５～３０重量部、好ましくは０．８～１０重量部（例えば、１～５重量部）、さらに好ましくは１．２～３重量部（特に１．５～２．５重量部）程度であってもよい。塩素含有樹脂の割合が少なすぎると、基材フィルムに対する密着力を向上させるのが困難となり、多すぎると、イオン交換層に対する離型性が低下する。
　樹脂フィルムには、さらに他の樹脂や慣用の添加剤が含まれていてもよい。他の樹脂としては、例えば、鎖状オレフィン系樹脂（ポリエチレンやポリプロピレンなど）などが挙げられる。慣用の添加剤としては、例えば、充填剤、滑剤（ワックス、脂肪酸エステル、脂肪酸アミドなど）、帯電防止剤、安定剤（酸化防止剤、熱安定剤、光安定剤など）、難燃剤、粘度調整剤、増粘剤、消泡剤などが含まれていてもよい。また、表面平滑性を損なわない範囲で、有機又は無機粒子（特にゼオライトなどのアンチブロッキング剤）を含んでいてもよい。
　特に、本発明では、電解質膜や電極膜を汚染し易いシリコーン化合物などの低分子量の離型剤を含んでいなくても離型性（剥離性）を向上でき、シリコーン化合物を実質的に含んでいないのが好ましい。
　樹脂フィルム（離型層）の平均厚みは、例えば、０．０１～１００μｍ程度の範囲から選択できるが、コーティングにより、表面が平滑で薄肉なフィルムも形成でき、例えば、０．０１～２０μｍ、好ましくは０．０３～１５μｍ、さらに好ましくは０．０５～１０μｍ（特に０．１～５μｍ）程度である。フィルムが薄肉であると、取り扱い性に優れ、ロール・ツー・ロール方式などに適するとともに、経済性も向上する。なお、平均厚みは、コーティング膜の場合、樹脂フィルムの塗工量（単位面積当たりの固形分（有効成分）重量）及び密度に基づいて算出できる。
　本発明の樹脂フィルムは、離型性及び耐熱性に優れるため、工業用の離型フィルムなどに利用でき、イオン交換層に対して適度な密着性と離型性（剥離性）とを有するため、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、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に好ましく利用できる。
　［積層フィルム］
　本発明の樹脂フィルムは、離型性及び耐熱性に優れるため、単独（単層）で離型フィルムとして使用してもよいが、燃料電池の生産性を向上でき、薄肉で厚みの均一なフィルムを形成し易い点から、基材層（基材フィルム）の少なくとも一方の面に、前記樹脂フィルムを離型層として積層するのが好ましい。
　（基材層）
　基材層は、燃料電池の製造工程において、離型フィルムの寸法安定性を向上でき、特に、ロール・ツー・ロール方式において張力が負荷されても、伸びを抑制でき、さらに乾燥工程や加熱圧着処理などによって高温に晒されても、高い寸法安定性を維持し、電解質膜や電極膜との剥離を抑制できる点から、耐熱性及び寸法安定性の高い材質で形成されているのが好ましく、具体的には、１５０℃における弾性率が１００～１０００ＭＰａの合成樹脂で形成されていてもよい。前記弾性率は、例えば、１２０～１０００ＭＰａ、好ましくは１５０～１０００ＭＰａ、さらに好ましくは２００～１０００ＭＰａ程度であってもよい。弾性率が小さすぎると、積層フィルムの寸法安定性が低下し、ロール・ツー・ロール方式での製造において離型層と電解質膜や電極膜との剥離が発生し、燃料電池の生産性が低下する虞がある。
　このような合成樹脂としては、例えば、各種の熱可塑性樹脂や熱硬化性樹脂が使用できるが、ロール・ツー・ロール方式で製造できる柔軟性を有する点から、熱可塑性樹脂が好ましい。熱可塑性樹脂としては、例えば、ポリオレフィン（ポリプロピレン系樹脂、環状ポリオレフィンなど）、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、ポリイミド、ポリカーボネート、ポリフェニレンエーテル、ポリフェニレンスルフィド、セルロース誘導体（セルロースアセテートなどのセルロースエステルなど）などが挙げられる。これらの熱可塑性樹脂は、単独で又は二種以上組み合わせて使用できる。本発明では、離型層（樹脂フィルム）が基材層に対する密着性に優れるため、これらの熱可塑性樹脂は、密着性を向上させるための反応性基や極性基（反応性基で形成された側鎖など）を実質的に有さないのが好ましい。これらの熱可塑性樹脂のうち、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、ポリイ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（特に、ポリオレフィン、ポリエステル、ポリイミド及びセルロースエステルからなる群より選択された少なくとも１種）が好ましく、耐熱性と柔軟性とのバランスに優れる点から、ポリエステル、ポリイミドが特に好ましい。さらに、ポリエステルとしては、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）などのポリＣ２－４アルキレンアリレート系樹脂が好ましく使用できる。ポリイミドとしては、熱可塑性ポリイミド、ポリエーテルイミド、ポリアミドイミドなどが挙げられる。
　基材層は、積層フィルムのフィルム強度を向上させる点から、延伸フィルムで形成されていてもよい。延伸は、一軸延伸であってもよいが、フィルム強度を向上できる点から、二軸延伸が好ましい。延伸倍率は、縦及び横方向において、それぞれ、例えば、１．５倍以上（例えば、１．５～６倍）であってもよく、好ましくは２～５倍、さらに好ましくは３～４倍程度である。延伸倍率が低すぎると、フィルム強度が不十分となり易い。
　基材層も、前記樹脂フィルムの項で例示された慣用の添加剤を含んでいてもよい。基材層中の合成樹脂の割合は、例えば、基材層全体に対して８０重量％以上、好ましくは９０重量％以上、さらに好ましくは９５重量％以上（例えば９５～１００重量％）であってもよい。
　基材層の表面平滑性は、コーティングにより離型層を形成できればよく、特に限定されないが、ＪＩＳ　Ｂ０６０１に準拠した算術平均粗さＲａは１μｍ以下であってもよく、好ましくは１００ｎｍ以下（例えば、１０～１００ｎｍ）程度である。
　基材層の表面は、離型層との密着性を向上させるために、表面処理に供してもよい。表面処理としては、慣用の表面処理、例えば、コロナ放電処理、火炎処理、プラズマ処理、オゾンや紫外線照射処理などが挙げられる。これらのうち、コロナ放電処理が好ましい。
　基材層は、慣用の接着性樹脂で形成された易接着層（例えば、基材層がポリエステル樹脂である場合、低分子量のポリエステル樹脂、脂肪族ポリエステル樹脂、非晶性ポリエステル樹脂などの接着性樹脂で形成された易接着層など）を有していてもよく、易接着層を実質的に有していなくてもよい。これらのうち、離型層（樹脂フィルム）が基材層に対する密着性に優れ、基材層が易接着層を有していなくても、燃料電池の製造に必要な密着性を有する点から、易接着層を有さない基材層が特に好ましい。そのため、本発明では、易接着層を有さない基材層を用いることにより、積層体の層構造を簡略化でき、薄肉化することもできる。
　基材層の平均厚みは、例えば、１～３００μｍ、好ましくは５～２００μｍ、さらに好ましくは１０～１００μｍ（特に２０～８０μｍ）程度である。基材層の厚みが大きすぎると、ロール・ツー・ロール方式での生産が困難となり、薄すぎると、寸法安定性、ロール・ツー・ロール方式での搬送性が低下し、シワなどが混入する虞がある。
　（イオン交換層）
　本発明の積層フィルム（積層体）は、固体高分子型燃料電池を製造するための離型フィルムであってもよく、この離型フィルムとして利用される場合、前記積層フィルム（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（電解質膜、電極膜、膜電極接合体）を密着させる。そのため、本発明の積層フィルムは、離型フィルムの離型層（樹脂フィルム単独で形成された離型層又は積層フィルムの離型層）の上にイオン交換樹脂を含むイオン交換層が積層された積層体（離型フィルムとイオン交換層との積層体）であってもよい。
　前記イオン交換樹脂としては、燃料電池で利用される慣用のイオン交換樹脂を利用できるが、なかでも、強酸性陽イオン交換樹脂や弱酸性陽イオン交換樹脂などの陽イオン交換樹脂が好ましく、例えば、スルホン酸基、カルボキシル基、リン酸基、ホスホン酸基などを有するイオン交換樹脂（詳しくは、電解質機能を有する電解質基として、スルホン酸基、カルボキシル基、リン酸基、ホスホン酸基などが導入されたイオン交換樹脂）などが挙げられ、スルホン酸基を有するイオン交換樹脂（電解質基としてスルホン酸基が導入されたイオン交換樹脂）が特に好ましい。
　前記スルホン酸基を有するイオン交換樹脂としては、スルホン酸基を有する各種の樹脂を使用できる。各種の樹脂としては、例えば、ポリエチレンやポリプロピレンなどのポリオレフィン、（メタ）アクリル系樹脂、スチレン系樹脂、ポリアセタール、ポリエステル、ポリカーボネート、ポリアミド、ポリアミドイミド、ポリイミド、ポリエーテル、ポリエーテルイミド、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、フッ素樹脂などが挙げられる。
　前記スルホン酸基を有するイオン交換樹脂のなかでも、スルホン酸基を有するフッ素樹脂、架橋ポリスチレンのスルホン化物などが好ましく、スルホン酸基を有するポリスチレン－グラフト－ポリエチレンテトラフルオロエチレン共重合体、ポリスチレン－グラフト－ポリテトラフルオロエチレン共重合体などであってもよい。なかでも、離型性などの点から、スルホン酸基を有するフッ素樹脂（少なくとも一部の水素原子がフッ素原子に置換されたフルオロ炭化水素樹脂など）が特に好ましい。特に、固体高分子型燃料電池では、側鎖にスルホン酸基（又は－ＣＦ２ＣＦ２ＳＯ３Ｈ基）を有するフッ素樹脂、例えば、［２－（２－スルホテトラフルオロエトキシ）ヘキサフルオロプロポキシ］トリフルオロエチレンとテトラフルオロエチレンとの共重合体（ブロック共重合体など）などが好ましく利用される。
　イオン交換樹脂のイオン交換容量は０．１ｍｅｑ／ｇ以上であってもよく、例えば、０．１～２．０ｍｅｑ／ｇ、好ましくは０．２～１．８ｍｅｑ／ｇ、さらに好ましくは０．３～１．５ｍｅｑ／ｇ（特に０．５～１．５ｍｅｑ／ｇ）程度であってもよい。
　このようなイオン交換樹脂としては、デュポン社製「登録商標：ナフィオン（Ｎａｆｉｏｎ）」などの市販品を利用できる。なお、イオン交換樹脂としては、特開２０１０－２３４５７０号公報に記載のイオン交換樹脂などを用いてもよい。
　イオン交換層は、前記イオン交換樹脂で形成された電解質膜、前記イオン交換樹脂及び触媒粒子を含む電極膜であってもよい。
　電極膜（触媒層又は電極触媒膜）において、触媒粒子は触媒作用を有する金属成分（特に、白金（Ｐｔ）などの貴金属単体又は貴金属を含む合金）を含んでおり、通常、カソード電極用電極膜では白金を含み、アノード電極用電極膜では白金－ルテニウム合金を含む。さらに、触媒粒子は、通常、前記金属成分を、導電材料（カーボンブラックなどの炭素材料など）に担持させた複合粒子として使用される。電極膜において、イオン交換樹脂の割合は、例えば、触媒粒子１００重量部に対して、例えば、５～３００重量部、好ましくは１０～２５０重量部、さらに好ましくは２０～２００重量部程度である。
　イオン交換層も、樹脂フィルムの項で例示された慣用の添加剤を含んでいてもよく、例えば、無機粒子や無機繊維などの無機材料（炭素質材料、ガラス、セラミックスなど）を含んでいてもよい。
　イオン交換層は、離型層の少なくとも一方の面に形成されていればよく、離型層の両面に形成されていてもよく、離型層の一方の面のみに形成されていてもよい。
　イオン交換層の平均厚みは、例えば、１～５００μｍ、好ましくは１．５～３００μｍ、さらに好ましくは２～２００μｍ程度である。
　電解質膜の平均厚みは、例えば、１～５００μｍ、好ましくは５～３００μｍ、さらに好ましくは１０～２００μｍ程度である。
　電極膜の平均厚みは、例えば、１～１００μｍ、好ましくは２～８０μｍ、さらに好ましくは２～５０μｍ程度である。
　［樹脂フィルム、積層フィルム及び膜電極接合体の製造方法］
　本発明の樹脂フィルムは、薄肉で、表面平滑なフィルムを形成し易い点から、基材の上に樹脂組成物及び溶媒を含むコーティング剤（例えば、溶液状コーティング剤）をコーティングする方法により製造でき、具体的には、積層フィルムの場合、基材層の上に環状オレフィン系樹脂、塩素含有樹脂及び溶媒を含むコーティング剤をコーティング（又は流延）した後、乾燥する方法により製造できる。なお、樹脂フィルムを単層で製造する場合は、剥離可能な基材の上にコーティングしてもよい。
　コーティング方法としては、慣用の方法、例えば、ロールコーター、エアナイフコーター、ブレードコーター、ロッドコーター、リバースコーター、バーコーター、コンマコーター、ダイコーター、グラビアコーター、スクリーンコーター法、スプレー法、スピナー法などが挙げられる。これらの方法のうち、ブレードコーター法、バーコーター法、グラビアコーター法などが汎用される。
　溶媒としては、非極性溶媒を利用でき、例えば、ヘキサンなどの脂肪族炭化水素類、シクロヘキサンなどの脂環族炭化水素類、トルエンやキシレンなどの芳香族炭化水素類、ソルベントナフサなどの芳香族系油、テトラヒドロフランやジオキサンなどのエーテル類などを利用できる。これらの溶媒は単独で又は２種以上組み合わせてもよい。これらのうち、トルエンなどの芳香族炭化水素類、ソルベントナフサなどの芳香族系油、テトラヒドロフランなどの環状エーテルが好ましく、芳香族炭化水素類と環状エーテルとの混合溶媒が特に好ましい。
　コーティング剤中における固形分濃度（樹脂組成物濃度又は有効成分濃度）は、例えば、０．１～５０重量％、好ましくは０．３～３０重量％、さらに好ましくは０．５～２０重量％（特に０．８～１５重量％）程度である。
　乾燥は、自然乾燥であってもよいが、加熱して乾燥することにより溶媒を蒸発させてもよい。乾燥温度は、５０℃以上であってもよく、例えば、５０～２００℃、好ましくは６０～１５０℃、さらに好ましくは８０～１２０℃程度である。
　イオン交換層が形成された積層フィルム（離型フィルムとイオン交換層との積層体）では、離型層（樹脂フィルム単独で形成された離型層又は積層フィルムの離型層）の上に、イオン交換層を積層してもよい。
　この積層フィルムは、離型層の上に、イオン交換層（イオン交換樹脂を含む電解質膜及び／又はイオン交換樹脂を含む電極膜）をコーティングにより形成すればよく、例えば、第１のフィルム（離型フィルム）の離型層の上に電解質膜をコーティングにより積層し、第１の離型フィルムの上に電解質膜が積層された積層体を製造し、かつ第２のフィルムの離型層の上に電極膜をコーティングにより積層し、第２の離型フィルムの上に電極膜が積層された積層体を製造してもよい。
　電解質膜及び電極膜をコーティング（又は流延）により形成するために、電解質膜及び電極膜は、イオン交換樹脂（及び触媒粒子）を溶媒に溶解又は分散した溶液又は分散液の状態でコーティングに供される。
　溶媒としては、例えば、水、アルコール類（メタノール、エタノール、イソプロパノール、１－ブタノールなどのＣ１－４アルカノールなど）、ケトン類（アセトン、メチルエチルケトンなど）、エーテル類（ジオキサン、テトラヒドロフランなど）、スルホキシド類（ジメチルスルホキシドなど）などが挙げられる。これらの溶媒は、単独で又は二種以上組み合わせて使用できる。これらの溶媒のうち、取り扱い性などの点から、水や、水とＣ１－４アルカノールとの混合溶媒が汎用される。溶液又は分散液中の溶質又は固形分（イオン交換樹脂、触媒粒子）の濃度は、例えば、１～８０重量％、好ましくは２～６０重量％、さらに好ましくは３～５０重量％程度である。
　コーティング方法としては、前記離型フィルムの製造方法で例示された慣用の方法が挙げられる。これらの方法のうち、ブレードコーター法、バーコーター法などが汎用される。
　イオン交換樹脂（及び触媒粒子）を含む溶液をコーティングした後、加熱して乾燥することにより溶媒を蒸発させてもよい。乾燥温度は、５０℃以上であってもよく、電解質膜では、例えば、８０～２００℃（特に１００～１５０℃）程度であり、電極膜では、例えば、５０～１５０℃（特に６０～１２０℃）程度である。
　前記積層工程で得られた積層体は、通常、密着工程に供されるが、連続的に製造する場合は、密着工程の前に、積層工程において、密着工程が行われる場所に搬送される。
　本発明では、前記樹脂フィルム又は前記積層フィルムが柔軟性に優れるため、このような搬送を伴う積層工程をロール・ツー・ロール方式で行うことができ、生産性を向上できる。さらに、離型層と基材層との組み合わせにより、積層フィルムの寸法安定性にも優れるため、ロール・ツー・ロール方式でも、積層フィルムの張力による伸びが抑制される。そのため、イオン交換層が剥離することなく、ロール状に巻き取ることができ、生産性を向上できる。
　得られた積層体は、密着工程に供してもよい。密着工程では、第１及び第２の離型フィルムの離型層の上にそれぞれ積層された電解質膜と電極膜とを密着させて膜電極接合体が調製される。
　電解質膜と電極膜との密着は、通常、加熱圧着により密着される。加熱温度は、例えば、８０～２５０℃、好ましくは９０～２３０℃、さらに好ましくは１００～２００℃程度である。圧力は、例えば、０．１～２０ＭＰａ、好ましくは０．２～１５ＭＰａ、さらに好ましくは０．３～１０ＭＰａ程度である。
　密着工程で密着した複合体（電解質層と電極膜とが密着した積層体）は、イオン交換層（電解質膜及び／又は電極膜）から離型フィルムを剥離する剥離工程に供され、固体高分子型燃料電池の膜電極接合体が得られる。本発明では、前述の乾燥工程や加熱圧着処理を経た積層体であっても適度な剥離強度を有するため、積層工程や密着工程では離型フィルムとイオン交換層とが剥離せずに、剥離工程では容易に離型フィルムを剥離でき、作業性を向上できる。
　離型フィルム（樹脂フィルム又は積層フィルム）の離型層は、イオン交換層に対して、所定の離型性を有する必要があり、離型層とイオン交換層との剥離強度（特に、剥離工程での積層体の剥離強度）は、例えば、０．１～１００ｍＮ／ｍｍ、好ましくは０．５～８０ｍＮ／ｍｍ程度である。剥離強度が大きすぎると、剥離作業が困難となり、小さすぎると、積層工程及び密着工程での作業性が低下する。
　本明細書では、剥離強度は、２０℃、５０％ＲＨで１時間以上静置した後、３００ｍｍ／分の条件で１８０°剥離する方法で測定できる。
　さらに、第１の離型フィルムを剥離した電解質膜に対して、前記密着工程及び剥離工程と同様に、さらに第３の離型フィルムの離型層の上に電極膜（第２の離型フィルムがアノード電極用電極膜である場合、カソード電極用電極膜）が積層された積層体の電極膜を密着させて離型フィルムを剥離し、慣用の方法で、各電極膜の上に燃料ガス供給層及び空気供給層をそれぞれ積層することにより膜電極接合体（ＭＥＡ）が得られる。
　以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。実施例及び比較例で得られた離型フィルムの特性は、以下の方法で評価した。
　［使用した原料］
　イオン交換樹脂溶液：側鎖にスルホン酸基を有するパーフルオロポリマーの溶液、デュポン社製「ナフィオン（登録商標）ＤＥ２０２１ＣＳ」、固形分２０重量％
　ＰＥＴフィルム：ユニチカ（株）製「ポリエステルフィルム　エンブレット（登録商標）　Ｓ５０」、厚み５０μｍ、易接着層なし
　ＯＰＰフィルム：豊科フイルム（株）製「Ｐ３０１８」、厚み３０μｍ、易接着層なし
　ＴＡＣフィルム：富士フイルム（株）製「Ｚ－ＴＡＣ」、厚み６０μｍ、易接着層なし
　Ｎｂ／Ｅｔ：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」、ガラス転移温度１７８℃
　ＰＶＤＣ：塩化ビニリデン系共重合体、旭化成ケミカルズ（株）製「ＰＶＤＣレジン　Ｒ２０４」。
　［密着性（離型層と基材層との密着性）］
　実施例及び比較例で得られた離型フィルムを２０℃、５０ＲＨ％で１時間以上静置後、離型層の上にセロハンテープ（ニチバン（株）製「ＣＴ４０５ＡＰ－１５」）を強く圧着させ、テープの端を４５°の角度で一気に引き剥がし、テープを剥がした面積に対して塗膜（離型層）が残存した面積（面積比）を求めて評価した。
　［離型性（離型層とイオン交換樹脂層との離型性）］
　実施例及び比較例で得られた離型フィルム、イオン交換樹脂溶液（デュポン社製「ナフィオン（登録商標）ＤＥ２０２１ＣＳ」、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、前記離型フィルムの離型層の上に前記イオン交換樹脂溶液をキャストし、その塗膜を１００℃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。
　得られた積層体のイオン交換層の上にセロハンテープ（ニチバン（株）製「ＣＴ４０５ＡＰ－１５」）を強く圧着させ、テープを剥がし、以下の基準で評価した。
　　○…イオン交換層が全て剥がれる。
　　×…イオン交換層が剥がれない。
　比較例１
　Ｎｂ／Ｅｔを、固形分濃度（樹脂成分の濃度）が５重量％となるように、トルエンに添加し、加温して溶解し、塗工液を調製した。得られた塗工液をメイヤーバーコーティング法によりＰＥＴ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０．３μｍ）を形成し、離型フィルムを得た。
　比較例２
　ＰＥＴフィルムの代わりにＯＰＰフィルムを用いる以外は比較例１と同様にして離型フィルムを得た。
　比較例３
　ＰＥＴフィルムの代わりにＴＡＣフィルムを用いる以外は比較例１と同様にして離型フィルムを得た。
　実施例１
　Ｎｂ／Ｅｔ１００重量部及びＰＶＤＣ１重量部を、固形分濃度（樹脂成分の濃度）が５重量％となるように、トルエン及びテトラヒドロフランの混合溶媒（トルエン／テトラヒドロフラン＝７０／３０（重量比））に添加し、加温して溶解し、塗工液を調製した。得られた塗工液を用いて比較例１と同様にして離型フィルムを得た。
　実施例２
　ＰＶＤＣの割合を１．２重量部に変更する以外は実施例１と同様にして離型フィルムを得た。
　実施例３
　ＰＶＤＣの割合を２重量部に変更する以外は実施例１と同様にして離型フィルムを得た。
　実施例４
　固形分濃度（樹脂成分の濃度）を０．５重量％に変更し、乾燥後の離型層の厚み０．０１μｍとした以外は実施例３と同様にして離型フィルムを得た。
　実施例５
　ＰＶＤＣの割合を６０重量部に変更する以外は実施例１と同様にして離型フィルムを得た。
　実施例及び比較例で得られた離型フィルムを評価した結果を表１に示す。
Figure JPOXMLDOC01-appb-T000001
　表１の結果から明らかなように、比較例１～３では、離型層と基材層との密着性が低かった。これに対して、実施例では、密着性、離型性のバランスに優れていた。
　本発明の樹脂フィルムは、離型性及び耐熱性に優れるため、各種の工業用離型フィルムなどに利用でき、特に、イオン交換層に対して適度な離型性（剥離性）と密着性とを有するため、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に好適である。

Claims (17)

  1. 　環状オレフィン系樹脂（Ａ）と塩素含有樹脂（Ｂ）とを含む樹脂組成物で形成された樹脂フィルム。
  2. 　塩素含有樹脂（Ｂ）が塩化ビニリデン系重合体である請求項１記載の樹脂フィルム。
  3. 　環状オレフィン系樹脂（Ａ）が、環状オレフィン系共重合体である請求項１又は２記載の樹脂フィルム。
  4. 　環状オレフィン系樹脂（Ａ）が、繰り返し単位として環状オレフィン単位（Ａ１）及び鎖状オレフィン単位（Ａ２）を含む請求項１～３のいずれかに記載の樹脂フィルム。
  5. 　環状オレフィン系樹脂（Ａ）がノルボルネン類とα－鎖状Ｃ２－４オレフィンとの共重合体である請求項１～４のいずれかに記載の樹脂フィルム。
  6. 　環状オレフィン単位（Ａ１）と鎖状オレフィン単位（Ａ２）との割合（モル比）が、前者／後者＝５０／５０～９０／１０である請求項４又は５記載の樹脂フィルム。
  7. 　環状オレフィン系樹脂（Ａ）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まない環状オレフィン系樹脂である請求項１～６のいずれかに記載の樹脂フィルム。
  8. 　塩素含有樹脂（Ｂ）の割合が、環状オレフィン系樹脂（Ａ）１００重量部に対して、０．５～６０重量部である請求項１～７のいずれかに記載の樹脂フィルム。
  9. 　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る請求項１～８のいずれかに記載の樹脂フィルム。
  10. 　基材層の少なくとも一方の面に、請求項１～９のいずれかに記載のフィルムが離型層として積層されている積層フィルム。
  11. 　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、ポリイ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１０記載の積層フィルム。
  12. 　基材層が、ポリエステルで形成され、かつ接着層又は易接着層を有していてない請求項１１記載の積層フィルム。
  13. 　離型層がコーティングで形成された平均厚み０．０１～２０μｍの層である請求項１０～１２のいずれかに記載の積層フィルム。
  14. 　離型層の上にイオン交換樹脂を含むイオン交換層が積層された請求項１０～１３のいずれかに記載の積層フィルム。
  15. 　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１４記載の積層フィルム。
  16. 　基材層の上に樹脂組成物を含む溶液をコーティングして離型層を形成する積層工程を含む請求項１０～１５のいずかに記載の積層フィルムの製造方法。
  17. 　請求項１４又は１５記載の積層フィルムからイオン交換樹脂を含むイオン交換層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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CN106414600A (zh) 2017-02-15
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