WO2018101176A1 - Feuille de transfert pour transfert de couche et feuille dotée d'une couche de catalyseur d'électrode - Google Patents

Feuille de transfert pour transfert de couche et feuille dotée d'une couche de catalyseur d'électrode Download PDF

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Publication number
WO2018101176A1
WO2018101176A1 PCT/JP2017/042286 JP2017042286W WO2018101176A1 WO 2018101176 A1 WO2018101176 A1 WO 2018101176A1 JP 2017042286 W JP2017042286 W JP 2017042286W WO 2018101176 A1 WO2018101176 A1 WO 2018101176A1
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Prior art keywords
layer
sheet
transfer
electrode catalyst
porous
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PCT/JP2017/042286
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English (en)
Japanese (ja)
Inventor
裕太 黒木
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日東電工株式会社
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Priority to KR1020187030727A priority Critical patent/KR102255814B1/ko
Priority to KR1020187010777A priority patent/KR101921876B1/ko
Publication of WO2018101176A1 publication Critical patent/WO2018101176A1/fr

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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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • 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]
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a transfer sheet for transferring a layer, and more specifically to a transfer sheet that can be used for supporting and transferring an electrode catalyst layer of an electrochemical element such as a fuel cell.
  • the present invention also relates to a sheet with an electrode catalyst layer.
  • a transfer sheet according to the present invention includes a thermoplastic resin layer and a pair of fluororesin porous layers that are bonded to the thermoplastic resin layer and sandwich the thermoplastic resin layer. It is a sheet.
  • the sheet with an electrode catalyst layer of the present invention comprises a thermoplastic resin layer, and a pair of fluororesin porous layers that are joined to the thermoplastic resin layer and sandwich the thermoplastic resin layer; and an electrode catalyst; And a layer.
  • the electrode catalyst layer is disposed on at least one of the fluororesin porous layers of the sheet.
  • a transfer sheet includes a thermoplastic resin layer, and a pair of fluororesin porous layers that are bonded to the thermoplastic resin layer and sandwich the thermoplastic resin layer. This is a transfer sheet.
  • the layer transferred by the transfer sheet is an electrode catalyst layer.
  • the curl height at the end when the transfer sheet of the first or second aspect is allowed to stand in an atmosphere at 120 ° C. for 5 minutes is 10 mm or less.
  • thermoplastic resin layer and the pair of fluororesin porous layers are joined by fusion bonding.
  • the melting point of the thermoplastic resin constituting the thermoplastic resin layer is 280 ° C. or less.
  • thermoplastic resin constituting the thermoplastic resin layer is made of polyester, polyacetal, polyethylene, ultrahigh molecular weight polyethylene, and polypropylene. At least one selected from the group.
  • the fluororesin constituting the fluororesin porous layer is polytetrafluoroethylene.
  • the fluororesin porous layer has a thickness of 3 ⁇ m to 200 ⁇ m.
  • the thickness of the transfer sheet is 15 ⁇ m to 400 ⁇ m.
  • An eleventh aspect of the present disclosure is a sheet comprising: a thermoplastic resin layer; and a pair of fluororesin porous layers that are joined to the thermoplastic resin layer and sandwich the thermoplastic resin layer; An electrode catalyst layer; Provided is a sheet with an electrode catalyst layer, wherein the electrode catalyst layer is disposed on at least one of the fluororesin porous layers of the sheet.
  • FIG. 1 shows a transfer sheet 10 of the present embodiment.
  • the sheet 10 includes a thermoplastic resin layer (hereinafter simply “resin layer”) 1 and a pair of fluororesin porous layers (hereinafter simply “porous layers”) 2 that sandwich the resin layer 1.
  • the sheet 10 is a transfer sheet for transferring a layer formed and supported thereon to another member.
  • the carrying surface of the sheet 10 carrying the layer to be transferred (transfer layer) is the main surface of at least one porous layer 2 (the main surface 22 opposite to the main surface 21 on the side in contact with the resin layer 1). It is. That is, the carrying surface of the sheet 10 is made of a fluororesin, and high releasability with respect to the transfer layer formed thereon is ensured.
  • the support surface of the sheet 10 is porous, for example, a material applied to the support surface, as a more specific example, even when the viscosity and / or solid content concentration of the paste that becomes the electrode catalyst layer after drying is low, The material is less likely to be repelled compared to a transfer sheet that is a simple fluororesin sheet, particularly a non-porous fluororesin sheet.
  • the sheet 10 includes not only the porous layer 2 but also the resin layer 1 bonded thereto.
  • the porous layer 2 alone can easily extend as a sheet substrate, and the extension of the sheet causes deformation such as deformation or cracking of the transfer layer formed on the support surface, but in the sheet 10, the resin layer 1 serves as a reinforcing layer, Such deformation and damage of the transfer layer are suppressed.
  • This characteristic is particularly advantageous when the transfer layer is formed by the so-called roll-to-roll by using the belt-like sheet 10.
  • the resin layer 1 and the porous layer 2 are fused (bonded by fusion). Joining by fusing both layers is suitable for forming a sheet 10 having a uniform thickness and reducing the manufacturing cost of the sheet 10.
  • the fusion between the porous layer 2 and the resin layer 1 can be performed by, for example, thermal lamination or hot pressing.
  • the temperature of the hot roll is maintained at 130 to 290 ° C., for example, and is pressed with a linear pressure of 10 to 40 N / m, for example, to fuse the porous layer 2 and the resin layer 1 together.
  • the line speed at this time varies depending on the hot roll diameter and the heating temperature, but is preferably 3.0 to 20.0 m / min, for example.
  • the thickness of the sheet 10 is, for example, in the range of 15 ⁇ m to 400 ⁇ m, and preferably in the range of 50 ⁇ m to 300 ⁇ m.
  • the form of joining of the resin layer 1 and the porous layer 2 is not limited.
  • the resin layer 1 and the porous layer 2 may be joined by, for example, an adhesive or a pressure-sensitive adhesive.
  • the melting point of the thermoplastic resin constituting the resin layer 1 is preferably 280 ° C. or lower.
  • the thermoplastic resin constituting the resin layer 1 is preferably at least one selected from the group consisting of polyester, polyacetal (POM), polyethylene (PE), ultrahigh molecular weight polyethylene (UHMWPE), and polypropylene (PP).
  • the polyester include polyethylene terephthalate (PET) and polybutylene terephthalate.
  • PET polyethylene terephthalate
  • PET polybutylene terephthalate
  • a resin having a low softening temperature is preferable, and a resin that starts softening at a temperature lower than 233 ° C. is particularly preferable.
  • POM and PET are preferable thermoplastic resins from the viewpoint of resistance to alteration during heating, heat resistance, and chemical resistance.
  • the resin layer 1 composed of a thermoplastic resin having a melting point of 280 ° C. or lower can be satisfactorily fused with the porous layer 2. With the sheet 10 in which the porous layer 2 and the resin layer 1 are fused well, and the two layers are difficult to peel from each other, the transfer layer can be more favorably formed on the carrying surface. The fluororesin porous layer 2 is excluded from the resin layer 1.
  • the form of the resin layer 1 is not limited, and may be, for example, a woven fabric, a nonwoven fabric, a net, a stretched porous membrane, a fine particle fusion porous membrane, or the like, but is preferably a nonporous membrane.
  • the resin layer 1 is a non-porous film, the surface roughness of the main surface 11 of the resin layer 1 facing the porous layer 2 is reduced, so that the surface roughness of the support surface of the sheet 10 via the porous layer 2 is reduced.
  • the value of Rz can be reduced.
  • the transfer layer can be more stably held together with the porous layer 2.
  • fluororesin constituting the porous layer 2 examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP). is there.
  • a preferred fluororesin is PTFE.
  • the porous layer 2 may not contain a component other than the fluororesin, and may not contain a component other than the fluororesin substantially. In this specification, “substantially free” means that the content is less than 0.1% by weight, preferably less than 0.01% by weight.
  • the thickness of the porous layer 2 is, for example, in the range of 3 to 200 ⁇ m, preferably in the range of 4 to 150 ⁇ m, more preferably in the range of 5 to 90 ⁇ m, and further preferably in the range of 7 to 80 ⁇ m. . Within these ranges, partial loss of the porous membrane 2 due to cohesive failure or the like is unlikely to occur, and the handling properties of the sheet 10 become better.
  • the contact angle of the carrying surface of the sheet 10 with water is preferably 100 degrees or more, 120 degrees or more, and further 130 degrees or more.
  • the supporting surface showing a high contact angle with water is excellent in releasability from the transfer layer.
  • the contact angle with water is a value evaluated by the sessile drop method defined in JIS R3257.
  • JIS R3257 is a standard relating to a method for evaluating the contact angle on the surface of the substrate glass, but the contact angle with water on the carrying surface of the sheet 10 can be evaluated according to the test conditions defined in the standard.
  • the curl height at the end when the sheet is allowed to stand in an atmosphere of 120 ° C. for 5 minutes is, for example, 10 mm or less, preferably 7 mm or less, more preferably 5 mm or less.
  • the curl height at the end can be evaluated as follows. First, a sheet as an evaluation object is cut out to a width of 490 mm ⁇ 500 mm to obtain a test piece 31 ((a) in FIG. 2 and (a) in FIG. 3). FIG. 3 shows the test piece 31 shown in FIG. And the cross section which cut
  • “Width” is, for example, the TD direction of the sheet (in the case of a belt-like sheet, the width direction).
  • the “length” is, for example, the MD direction of the sheet (in the case of a belt-like sheet, the longitudinal direction).
  • the test piece 31 is accommodated in a drier maintained at 120 ° C. and allowed to stand for 5 minutes. At that time, the test piece 31 is placed on a flat surface 32 that does not cause deformation at 120 ° C. that affects the evaluation of the curl height.
  • the plane 32 is, for example, the surface of a metal plate. After leaving for 5 minutes, the test piece 31 together with the plane 32 is taken out of the dryer and cooled to room temperature.
  • the curl height of the end is determined by the above method using a sheet cut out with a smaller size as the test piece. Can be sought.
  • the measurement value is multiplied by a coefficient corresponding to the size of the test piece used for the measurement, and converted to a value when a test piece having a width of 490 mm ⁇ 500 mm is used for the measurement.
  • the curl height at the end can be set.
  • the sheet 10 is as described for the transfer sheet 10 of the present invention described above, including preferred examples thereof.
  • the transfer layer 3 is a layer having a thin and / or uniform thickness in which, for example, deformation and damage during the formation thereof are suppressed.
  • the sheet catalyst 15 can be used to transfer the electrode catalyst layer to the electrolyte membrane to form an MEA. As shown in FIG. 5, in the MEA 20, the transfer layer 3 transferred onto the electrolyte membrane 5 becomes an electrode catalyst layer 6.
  • the structure of the transfer layer 3 that is an electrode catalyst layer is as described for the electrode catalyst layer 6 below.
  • MEA electrochemical element
  • the MEA 20 includes an electrolyte membrane 5 that is typically a polymer electrolyte membrane, and a pair of electrode catalyst layers 6 that sandwich the electrolyte membrane 5.
  • the electrode catalyst layer 6 is, for example, a porous thin film having pores having a diameter of 1 ⁇ m or less, and mainly contains catalyst substance-supporting particles and a polymer electrolyte.
  • known polymer electrolytes such as a fluorine-based polymer electrolyte and a hydrocarbon-based polymer electrolyte can be used.
  • the MEA manufacturing method using the sheet 10 includes, for example, an electrode catalyst layer laminating step, an electrolyte membrane laminating step, a thermocompression bonding step, and a peeling step.
  • the electrode catalyst layer lamination step is a step of forming the transfer layer 3 as an electrode catalyst layer on the sheet 10.
  • the electrolyte membrane laminating step is a step of laminating the sheet 10 and the electrolyte membrane 5 so that the transfer layer 3 and the electrolyte membrane 5 are in contact with each other.
  • the thermocompression bonding process is a process in which the transfer layer 3 and the electrolyte membrane 5 are thermocompression bonded.
  • the peeling step is a step of peeling the sheet 10 and leaving the transfer layer 3 as the electrode catalyst layer 6 on the electrolyte membrane 5.
  • Electrode catalyst layer lamination process An example of an electrode catalyst layer lamination process is shown. First, a catalyst solution (electrode catalyst layer paste) in which catalyst substance-supporting particles and a polymer electrolyte are dispersed in a solvent is applied to the main surface (supporting surface) 22 of the sheet 10 where the porous layer 2 is exposed. A coating film is formed. Next, it is dried by heating at a temperature of about 30 to 180 ° C. to obtain a laminate (sheet 15 with an electrode catalyst layer) of the sheet 10 and the transfer layer 3 as an electrode catalyst layer.
  • a known method such as a doctor blade method, a screen printing method, a roll coating method, or a spray method can be employed.
  • the thermocompression bonding step can be carried out by hot pressing a laminated body of the electrolyte membrane 5 and the sheet 15 in a state where the electrolyte membrane 5 and the transfer layer 3 are in contact with each other or passing through a pair of hot rolls.
  • the temperature of the thermocompression bonding at this time is preferably about 80 to 150 ° C. depending on the type of the electrolyte membrane 5 and the like.
  • the transfer layer 3 may be simultaneously bonded to both surfaces of the electrolyte membrane 5 by passing a laminate in which both surfaces of the electrolyte membrane 5 are sandwiched between two sheets 15 with an electrode catalyst layer through a pair of heat rolls.
  • the peeling step can be performed by, for example, continuously peeling the sheet 10 from the pressure-bonded body of the electrolyte membrane 5 and the sheet 10 using a roll that winds the sheet 10.
  • the peeled sheet 10 can be reused.
  • FIG. 6 shows an example of an apparatus that performs the thermocompression bonding process and the peeling process as a series of processes.
  • the layer 3 of the electrode catalyst layer-attached sheet 15 fed from the feed roll 52 is brought into contact with the electrolyte membrane 5 and passed between the pair of heating rolls 54, thereby bringing them into close contact with each other. Thereafter, only the sheet 10 is peeled off and wound up by the collection roll 53, whereby the laminate 7 in which the electrode catalyst layer 6 is bonded to one surface of the electrolyte membrane 5 can be continuously produced.
  • Catalyst materials used for the catalyst material-supporting particles include, for example, platinum group elements such as platinum, palladium, ruthenium, iridium, rhodium and osmium; iron, lead, copper, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, Metals such as aluminum; alloys thereof; oxides and double oxides of these metals.
  • platinum group elements such as platinum, palladium, ruthenium, iridium, rhodium and osmium
  • the particle size of the catalyst is preferably 0.5 to 20 nm, more preferably 1 to 5 nm.
  • a catalyst that is a particle of one or more metals selected from the group consisting of platinum, gold, palladium, rhodium, ruthenium, and iridium is excellent in electrode reactivity, and the electrode reaction is efficiently stabilized by the catalyst. Done.
  • a polymer electrolyte fuel cell including an electrode catalyst layer containing such a catalyst exhibits high power generation characteristics.
  • a known material can be used for the polymer electrolyte regardless of the difference in cation conductivity and anion conductivity.
  • the cation conductivity is, for example, proton conductivity.
  • a fluorine-based polymer electrolyte or a hydrocarbon-based polymer electrolyte can be used as the polymer electrolyte having proton conductivity.
  • the fluorine-based polymer electrolyte is, for example, Nafion (registered trademark) manufactured by DuPont.
  • hydrocarbon polymer electrolyte examples include sulfonated polyether ketone, sulfonated polyethersulfone, sulfonated polyetherethersulfone, sulfonated polysulfide, and sulfonated polyphenylene.
  • the electrolyte constituting the electrolyte membrane and the electrolyte constituting the electrode catalyst layer are preferably the same.
  • the solvent used in the catalyst solution is not particularly limited as long as it does not erode the catalyst material-supporting particles and can dissolve or disperse the polymer electrolyte in a highly fluid state.
  • Solvents used in the catalyst solution include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, pentanol, etc.
  • Alcohols such as acetone, methyl ethyl ketone, pentanone, methyl isobutyl ketone, heptanone, cyclohexanone, methyl cyclohexanone, acetonyl acetone, diisobutyl ketone, and other ketone solvents; tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, anisole, methoxy toluene, dibutyl ether, and other ethers Solvents: dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, diethylene glycol, diacetone alcohol, 1-methoxy-2- It is a propanol.
  • the solvent used in the catalyst solution preferably includes a volatile organic solvent, and preferably includes a polar solvent.
  • the solvent used in the catalyst solution may be a mixture of two or more of these solvents.
  • the catalyst solution may contain a dispersant.
  • the dispersant is, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant.
  • sulfonic acid type surfactants such as alkylbenzene sulfonic acid, oil-soluble alkyl benzene sulfonic acid, ⁇ -olefin sulfonic acid, sodium alkyl benzene sulfonate, oil-soluble alkyl benzene sulfonate and ⁇ -olefin sulfonate are preferably used. .
  • Example 1 20 parts by weight of a liquid lubricant (n-dodecane, manufactured by Japan Energy Co., Ltd.) is uniformly mixed with 100 parts by weight of PTFE fine powder (Daikin Kogyo Co., Ltd., Polyflon F-104). It extruded with the extruder and obtained the sheet-like molded object extended in a longitudinal direction. This sheet-like molded body was passed through a metal rolling roll in a state containing a liquid lubricant, and rolled to a thickness of 0.2 mm. Then, the liquid lubricant was removed by heating the sheet-shaped molded body to 150 ° C., and the sheet-shaped molded body was dried.
  • a liquid lubricant n-dodecane, manufactured by Japan Energy Co., Ltd.
  • the sheet-like molded body was stretched at a magnification of 20 times in the longitudinal direction at 370 ° C.
  • the obtained sheet-like molded body stretched in the longitudinal direction was stretched at a magnification of 5 times in the width direction at 180 ° C. to obtain a PTFE porous membrane having a film thickness of 40 ⁇ m and an average pore diameter of 3.0 ⁇ m.
  • the obtained PTFE porous membrane was used as a porous layer, and a non-porous PET film (EMBLET SD-75, film thickness 75 ⁇ m, manufactured by Unitika Ltd.) was prepared as a resin layer. These layers are laminated so that both the front and back surfaces of the PET film are sandwiched between a pair of PTFE porous membranes, pressed at 20 kN for 60 seconds with a high-temperature press at 280 ° C., and the PET layer and a pair of sandwiching the PET layer A composite sheet fused with the PTFE porous layer was obtained.
  • EMBLET SD-75 film thickness 75 ⁇ m, manufactured by Unitika Ltd.
  • Example 2 Except for changing the thickness of the PTFE porous membrane to 80 ⁇ m and the average pore size to 2.5 ⁇ m (manufactured by Nitto Denko Corporation, NTF1133), the PET layer and a pair of PTFE sandwiching the PET layer are the same as in Example 1. A composite sheet fused with the porous layer was obtained.
  • Example 3 Except for changing the thickness of the PTFE porous membrane to 20 ⁇ m and the average pore size to 0.4 ⁇ m (NTF1026D manufactured by Nitto Denko Corporation), a PET layer and a pair of PTFE sandwiching the PET layer are the same as in Example 1. A composite sheet fused with the porous layer was obtained.
  • Example 4 A non-porous POM film (manufactured by Kurashiki Boseki Co., Ltd., PM-1500, film thickness 100 ⁇ m) was used as the resin layer, and the POM layer was the same as in Example 1 except that the temperature of the high-temperature press was 200 ° C. Thus, a composite sheet was obtained in which a pair of porous PTFE layers sandwiching it were fused.
  • Example 5 A non-porous PP film (Toray Industries, Inc., Trefan BO, film thickness 100 ⁇ m) was used as the resin layer, except that the temperature of the high-temperature press was 180 ° C. A composite sheet was obtained in which a pair of porous PTFE layers sandwiching this were fused.
  • Example 6 A non-porous UHMWPE film (manufactured by Nitto Denko Corporation, No. 440, film thickness: 100 ⁇ m) was used as the resin layer, and the PP layer was formed in the same manner as in Example 1 except that the temperature of the high-temperature press was 150 ° C. Thus, a composite sheet was obtained in which a pair of porous PTFE layers sandwiching it were fused.
  • Example 7 20 parts by weight of a liquid lubricant (n-dodecane, manufactured by Japan Energy Co., Ltd.) is uniformly mixed with 100 parts by weight of PTFE fine powder (Daikin Kogyo Co., Ltd., Polyflon F-104). It extruded with the extruder and obtained the sheet-like molded object extended in a longitudinal direction. This sheet-like molded body was passed through a metal rolling roll in a state containing a liquid lubricant, and rolled to a thickness of 0.2 mm. Then, the liquid lubricant was removed by heating the sheet-shaped molded body to 150 ° C., and the sheet-shaped molded body was dried.
  • a liquid lubricant n-dodecane, manufactured by Japan Energy Co., Ltd.
  • the sheet-like molded body was stretched at a magnification of 20 times in the longitudinal direction at 370 ° C., and further stretched at a magnification of 5 times at 370 ° C.
  • the obtained sheet-like molded body stretched in the longitudinal direction was stretched at a magnification of 4 times in the width direction at 150 ° C. to obtain a PTFE porous membrane having a film thickness of 10 ⁇ m and an average pore diameter of 10 ⁇ m.
  • the obtained PTFE porous membrane was used as a porous layer, and a non-porous PP film (manufactured by Toray Industries, Inc., Trefan BO, film thickness 100 ⁇ m) was prepared as a resin layer. These layers are laminated so that both the front and back surfaces of the PP film are sandwiched between a pair of PTFE porous membranes, and pressed at 4.5 kN for 30 seconds with a high-temperature press machine at 180 ° C. A composite sheet in which a pair of sandwiched PTFE porous layers were fused was obtained.
  • Example 8 A PP net and a pair of PTFE porous layers sandwiching the PP net are used in the same manner as in Example 1 except that a PP net (film thickness: 100 ⁇ m) is used as the resin layer and the temperature of the high-temperature press is 180 ° C. And a composite sheet fused to each other was obtained.
  • Nafion Solution DE1020 (trade name; manufactured by DuPont) and carbon black were weighed and mixed so that the value obtained by dividing the weight of Nafion contained in Nafion Solution by the weight of carbon black was 0.8. Furthermore, the pure water was mixed so that the alcohol ratio contained might be 25 mass%, and the liquid mixture was obtained.
  • the Nafion Solution DE1020 contained alcohol. The mixture is centrifuged for 5 minutes in a mixer (Sinky Co., Ltd., trade name “Awatori Netaro”), and then stirred with a homogenizer (HSIANGTAI, HG-200) to form an electrode catalyst layer. A paste for was obtained.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Fuel Cell (AREA)
  • Inert Electrodes (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une feuille de transfert pourvue d'une couche de résine thermoplastique, et d'une paire de couches de résine fluorée poreuses liées à ladite couche de résine thermoplastique et prenant en sandwich ladite couche de résine thermoplastique. Ladite feuille de transfert est une feuille de transfert dans laquelle une couche de transfert peut être favorablement formée sur une surface de support, en particulier, une feuille de transfert dans laquelle ladite couche peut être favorablement formée sur la surface de support même lorsqu'un chauffage est nécessaire pour former la couche de transfert. La couche transférée par ladite feuille de transfert est, par exemple, une couche de catalyseur d'électrode à utiliser dans un élément électrochimique tel qu'une pile à combustible.
PCT/JP2017/042286 2016-11-29 2017-11-24 Feuille de transfert pour transfert de couche et feuille dotée d'une couche de catalyseur d'électrode WO2018101176A1 (fr)

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KR1020187010777A KR101921876B1 (ko) 2016-11-29 2017-11-24 층을 전사하기 위한 전사 시트 및 전극 촉매층이 부착된 시트

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JP6553962B2 (ja) * 2015-07-06 2019-07-31 日東電工株式会社 層を転写するためのシート及びそれを用いた電極触媒層付きシート

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JPH07251438A (ja) * 1994-03-15 1995-10-03 Japan Gore Tex Inc 液晶ポリマーフィルム及びその製造方法
JP2005533884A (ja) * 2002-07-19 2005-11-10 エイイーエイ テクノロジー バッテリー システムズ リミテッド フッ化ビニリデンを含む多孔質高分子膜
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JP2015096325A (ja) * 2013-10-11 2015-05-21 日東電工株式会社 薄層転写用シート、電極触媒層付薄層転写用シート、薄層転写用シートの製造方法、および膜電極接合体の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019230610A1 (fr) * 2018-05-30 2019-12-05 日東電工株式会社 Feuille de transfert pour transfert de couche et feuille dotée d'une couche de catalyseur d'électrode
JP2019209687A (ja) * 2018-05-30 2019-12-12 日東電工株式会社 層を転写するための転写シート及び電極触媒層付きシート
JP7324615B2 (ja) 2018-05-30 2023-08-10 日東電工株式会社 層を転写するための転写シート及び電極触媒層付きシート

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KR102255814B1 (ko) 2021-05-24
KR101921876B1 (ko) 2018-11-23

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