WO2023167052A1 - 熱硬化型接着シートおよび燃料電池用サブガスケット - Google Patents

熱硬化型接着シートおよび燃料電池用サブガスケット Download PDF

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Publication number
WO2023167052A1
WO2023167052A1 PCT/JP2023/006160 JP2023006160W WO2023167052A1 WO 2023167052 A1 WO2023167052 A1 WO 2023167052A1 JP 2023006160 W JP2023006160 W JP 2023006160W WO 2023167052 A1 WO2023167052 A1 WO 2023167052A1
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WIPO (PCT)
Prior art keywords
adhesive sheet
adhesive layer
resin
thermosetting adhesive
base film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/006160
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English (en)
French (fr)
Japanese (ja)
Inventor
章 片倉
智史 青木
琢磨 山脇
優 小田
聡 寺田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honda Motor Co Ltd
Higashiyama Film Co Ltd
Original Assignee
Honda Motor Co Ltd
Higashiyama Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Honda Motor Co Ltd, Higashiyama Film Co Ltd filed Critical Honda Motor Co Ltd
Priority to US18/281,656 priority Critical patent/US12612537B2/en
Priority to CN202380010668.1A priority patent/CN117083738A/zh
Priority to JP2023544075A priority patent/JP7606717B2/ja
Publication of WO2023167052A1 publication Critical patent/WO2023167052A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0276—Sealing means characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0284—Organic resins; Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0286—Processes for forming seals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2896—Adhesive compositions including nitrogen containing condensation polymer [e.g., polyurethane, polyisocyanate, etc.]

Definitions

  • the present invention relates to a thermosetting adhesive sheet used for sealing around a membrane-electrode assembly (MEA) in which electrodes are arranged on both sides of a solid polymer electrolyte membrane of a fuel cell, and such a subgasket.
  • MEA membrane-electrode assembly
  • Fuel cells generate energy through an electrochemical reaction between hydrogen and oxygen. Examples include phosphoric acid fuel cells, molten carbonate fuel cells, solid electrolyte fuel cells, solid polymer fuel cells, and the like. can be mentioned.
  • polymer electrolyte fuel cells are attracting attention as electric power sources for automobiles (two-wheeled and four-wheeled vehicles) and portable power sources, because they can be started at room temperature, are compact, and have high output.
  • the fuel gas supplied to the anode side electrode for example, a gas mainly containing hydrogen (hereinafter also referred to as a hydrogen-containing gas), hydrogen is ionized on the electrode catalyst, and the hydrogen is It migrates to the cathode side electrode through the solid polymer electrolyte membrane. At that time, electrons generated at the anode side electrode are taken out to an external circuit and used as DC electric energy.
  • the cathode-side electrode is supplied with an oxidant gas, for example, a gas containing mainly oxygen or air (hereinafter also referred to as an oxygen-containing gas), and hydrogen ions react with oxygen molecules that have received electrons. water is produced.
  • a fuel cell has a stack structure in which a large number of cells are stacked.
  • the cell stack comprises an electrode assembly (MEA) having an electrolyte membrane and electrodes, separators sandwiching the MEA, and sealing materials (gaskets, subgaskets) for sealing around the electrode members and between adjacent separators.
  • MEA electrode assembly
  • sealing materials gaskets, subgaskets
  • Hot-melt adhesives such as those disclosed in Patent Document 1, for example, are known as such sealing materials.
  • Patent Document 2 discloses an adhesive sheet using an adhesive resin composition containing a crystalline polyester resin and an amorphous polyester resin.
  • the sealing material such as the adhesive sheet When using the fuel cell, the sealing material such as the adhesive sheet is exposed to a high-temperature and high-humidity environment. It is desirable to maintain high sealing performance even in such an environment. Further, when forming a cell stack while sealing predetermined portions of the MEA with an adhesive sheet, it is preferable that the handling and adhesion of the adhesive sheet can be performed easily.
  • the sealing material of Patent Document 1 is a hot-melt adhesive and needs to be pressed at a high temperature for a long time in the bonding process with the MEA.
  • Patent Document 2 may cause heat damage to the adhesive sheet of Patent Document 2
  • the adhesive sheet of Patent Document 2 can be adhered at a low temperature, in order to maintain an uncured or semi-cured state until the bonding step after sheet formation, it is usually necessary to store or transport the sheet at a low temperature.
  • a hardening treatment process such as heat treatment or aging is required.
  • the problem of the present invention is that it can be stored at room temperature, after heat-pressing, adhesion is completed without going through a curing treatment process, and after adhesion, even if it is placed in a high-temperature and high-humidity environment, adhesion such as floating, peeling, and voids.
  • An object of the present invention is to provide a thermosetting adhesive sheet capable of suppressing defects and such a fuel cell subgasket.
  • thermosetting adhesive sheet is a thermosetting adhesive used for sealing around an electrolyte membrane/electrode structure in which electrodes are arranged on both sides of a solid polymer electrolyte membrane of a fuel cell.
  • a sheet comprising an adhesive layer formed from a cured adhesive composition containing a polyurethane resin having a reactive functional group and a cross-linking agent, wherein the adhesive layer has a gel fraction of 60.
  • the storage elastic modulus (G' 100 ) at 100°C is 5.0 ⁇ 10 4 Pa or more and 1.0 ⁇ 10 8 Pa or less, and the storage elastic modulus (G' 100 ) at 100°C is The decrease rate of the storage elastic modulus (G' 120 ) at 120°C is 0.5 or less.
  • the glass transition temperature of the adhesive layer is preferably -10°C or higher and 100°C or lower. Furthermore, it is preferable that the glass transition temperature of the adhesive layer is 50° C. or higher.
  • the reactive functional group may contain a carboxyl group
  • the cross-linking agent may contain a polyfunctional epoxy cross-linking agent.
  • the ratio (b/a) of the molar amount (a) of the carboxy groups in the polyurethane-based resin to the molar amount (b) of the epoxy groups in the epoxy-based cross-linking agent is preferably 1.0 or more and 10.0 or less. .
  • the adhesive layer is formed on one surface of a substrate film, and the substrate film is made of polyarylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyphenylene sulfide, polysulfone, polyethersulfone,
  • the film is preferably composed of at least one resin material selected from the group consisting of polyetheretherketone and polyarylate.
  • thermosetting adhesive sheet further has a second base film on the side of the adhesive layer opposite to the side on which the base film is provided, and the second base film is a film composed of at least one resin material selected from the group consisting of polyarylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, and polyarylate. Good to have.
  • a fuel cell subgasket according to the present invention includes a thermosetting adhesive sheet in which the adhesive layer described above is formed on one surface of a base film.
  • thermosetting adhesive sheet according to the present invention has an adhesive layer having the above-described predetermined material composition and physical properties, so that it has excellent storage stability, and can complete adhesion without going through a curing treatment step after thermocompression bonding. Even in a high-humidity environment, adhesion defects such as lifting, peeling, and voids can be suppressed. Therefore, the thermosetting adhesive sheet can be suitably used as a sealing material for fuel cells.
  • the glass transition temperature of the adhesive layer is ⁇ 10° C. or higher and 100° C. or lower, the adhesiveness of the adhesive layer is good, and furthermore, floating, peeling, voids, etc. in a high-temperature and high-humidity environment are prevented. Adhesion failure can be effectively suppressed. In addition, it becomes easy to remove foreign matter attached to the adhesive layer. Furthermore, when the adhesive layer has a glass transition temperature of 50° C. or higher, it is easy to maintain high adhesiveness even when the adhesive layer is placed under high temperature and high humidity conditions.
  • the reactive functional group contains a carboxyl group and the cross-linking agent contains a polyfunctional epoxy cross-linking agent, the reactivity between the polyurethane-based resin and the cross-linking agent increases.
  • the ratio (b/a) of the molar amount (a) of the carboxy groups in the polyurethane resin to the molar amount (b) of the epoxy groups in the epoxy-based cross-linking agent is 1.0 or more and 10.0 or less, A high crosslink density is obtained in the adhesive layer, making it easier to achieve a suitable storage modulus. Also, the adhesion of the adhesive layer to the adherend is enhanced.
  • thermosetting adhesive sheet is easy to handle. , placement on the MEA, and the like.
  • thermosetting adhesive sheet further has a second base film on the side of the adhesive layer opposite to the side on which the base film is provided, and the second base film has the predetermined
  • both sides of the adhesive sheet are covered with the base film and the second base film, so the thermosetting adhesive sheet is particularly easy to handle. Even if foreign matter adheres to the sheet, it can be easily removed.
  • a fuel cell subgasket according to the present invention includes a thermosetting adhesive sheet in which the adhesive layer described above is formed on one surface of a base film.
  • the adhesive layer constituting the thermosetting adhesive sheet has a predetermined material composition and physical properties, so that the fuel cell subgasket has excellent storage stability and undergoes a curing treatment step after thermocompression bonding. It is possible to complete the adhesion without any damage, and to suppress adhesion defects such as floating, peeling, and voids even in a high-temperature and high-humidity environment.
  • FIG. 1 is a perspective view of a thermosetting adhesive sheet according to a first embodiment of the invention
  • FIG. 4 is a perspective view of a thermosetting adhesive sheet according to a second embodiment of the invention
  • thermosetting adhesive sheet and a fuel cell subgasket according to embodiments of the present invention will be described below.
  • various physical property values are values measured at room temperature (about 23° C.) in the atmosphere.
  • FIG. 1 is a perspective view of a thermosetting adhesive sheet (hereinafter sometimes simply referred to as an adhesive sheet) 10 according to the first embodiment of the present invention.
  • an adhesive sheet 10 according to the first embodiment of the present invention has a base film 12 and an adhesive layer 14 formed on the surface of the base film 12.
  • the adhesive layer 14 is exposed on the outermost surface of the adhesive sheet 10 as a whole.
  • An opening W1 is provided in the central portion of the adhesive sheet 10 as a through-hole region.
  • the adhesive sheet 10 is used together with an electrolyte membrane-electrode assembly (MEA) in which electrodes are arranged on both sides of an electrolyte membrane, and is used as a sealing material for sealing the periphery of the MEA.
  • MEA electrolyte membrane-electrode assembly
  • a specific configuration of the base film 12 is not particularly limited.
  • the base film 12 include polymer films and glass films.
  • the thickness of the base film 12 is not particularly limited, it is preferably in the range of 12 ⁇ m or more and 500 ⁇ m or less from the viewpoint of handleability. More preferably, the thickness of the base film 12 is 38 ⁇ m or more, or 50 ⁇ m or more, and on the other hand, it is preferably 200 ⁇ m or less, or 100 ⁇ m or less.
  • film generally refers to a film having a thickness of less than 0.25 mm. shall be included.
  • the polymer material constituting the base film 12 includes polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyester resin such as liquid crystal polyester, polycarbonate resin, Polyolefin resins such as poly(meth)acrylate resins, polystyrene resins, polyamide resins, polyphthalamide resins, polyimide resins, polyacrylonitrile resins, polypropylene resins, polyethylene resins, polycycloolefin resins, cycloolefin copolymer resins, polyphenylene sulfide resins, poly Vinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polyvinylidene fluoride resin, fluorine resin, silicone resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyarylate resin, and the like.
  • the polymer material of the base film 12 may be composed of only one of these materials, or may be composed of a combination of two or more materials by lamination or the like.
  • these resins polyarylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, and polyarylate are selected from the viewpoint of heat resistance and mechanical properties.
  • the base film 12 is composed of at least one resin material selected from the group consisting of these resins.
  • the substrate film 12 may be composed of a single layer composed of a layer containing one or more of the above polymer materials, or a layer containing one or more of the above polymer materials and a layer containing this polymer material. It may be composed of two or more layers, such as a layer containing one or more polymeric materials different from the layer.
  • the adhesive layer 14 is formed from a cured adhesive composition containing a polyurethane resin having a reactive functional group and a cross-linking agent.
  • the adhesive composition has thermosetting properties, and the adhesive sheet 10 having the adhesive layer 14 functions as a thermosetting adhesive sheet.
  • the adhesive sheet 10 before use the adhesive layer 14 is left partially uncured and cured (semi-cured state). By further curing, it can be used as a thermosetting adhesive sheet.
  • the concept of adhesiveness is intended to include forms having stickiness, ie, pressure-sensitive adhesiveness.
  • the thickness of the adhesive layer 14 is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, from the viewpoint of ensuring adhesiveness. On the other hand, from the viewpoint of reducing the size of the fuel cell, the thickness of the adhesive layer 14 is preferably 50 ⁇ m or less, more preferably 25 ⁇ m or less.
  • the gel fraction of the adhesive layer 14 is 60% by mass or more.
  • the adhesion can be completed without going through the curing treatment step after thermocompression bonding in the adhesion step with the MEA.
  • the storage stability is excellent, and adhesion failures such as lifting, peeling, and voids can be suppressed even in a high-temperature and high-humidity environment.
  • it can be stably stored at room temperature without low-temperature storage to maintain the uncured or semi-cured state until the bonding step.
  • the gel fraction is preferably 65% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and the upper limit is 100% by mass.
  • the shear storage modulus (G' 100 ) of the adhesive layer 14 at 100° C. is 5.0 ⁇ 10 4 Pa or more. If the pressure is 5.0 ⁇ 10 4 Pa or more, the adhesive layer 14 is moderately hardened even before thermocompression bonding, so bonding can be completed in a short period of time. From the viewpoint of further enhancing this effect, G′ 100 is preferably 7.0 ⁇ 10 4 Pa or more, more preferably 1.0 ⁇ 10 5 Pa or more. Also, G' 100 is 1.0 ⁇ 10 8 Pa or less. If the pressure is 1.0 ⁇ 10 8 Pa or less, the adhesive layer 14 can maintain its elasticity even at high temperatures, and thus good adhesion can be obtained. G′ 100 is preferably 1.0 ⁇ 10 7 Pa or less, more preferably 5.0 ⁇ 10 6 Pa or less.
  • the decrease rate of the storage elastic modulus (G' 120 ) at 120° C. with respect to the storage elastic modulus (G′ 100 ) at 100° C. of the adhesive layer 14 is 0.5 or less. If the reduction rate is 0.5 or less, even if the adhesive layer 14 is placed in a high-temperature and high-humidity environment, adhesion failures such as lifting, peeling, and voids can be suppressed. From the viewpoint of further enhancing this effect, the rate of decrease is preferably 0.48 or less, more preferably 0.45 or less, and even more preferably 0.3 or less. Although there is no particular lower limit for the lowering rate, it is usually -0.1 or more, preferably 0 or more. The rate of decrease is obtained by the formula (G' 100 -G' 120 )/G' 100 .
  • the shear storage modulus (G' 120 ) of the adhesive layer 14 at 120° C. is preferably 5.0 ⁇ 10 4 Pa or more. If it is 5.0 ⁇ 10 4 Pa or more, the adhesive strength can be easily maintained even in a high-temperature environment, so that the wet heat resistance can be improved. From the viewpoint of further enhancing this effect, G' 120 is more preferably 7.0 ⁇ 10 4 Pa or more, and still more preferably 1.0 ⁇ 10 5 Pa or more. Also, G' 120 is preferably 1.0 ⁇ 10 8 Pa or less. If the pressure is 1.0 ⁇ 10 8 Pa or less, the adhesive layer 14 can maintain its elasticity even at high temperatures, and thus good adhesion can be obtained. G′ 120 is more preferably 1.0 ⁇ 10 7 Pa or less, still more preferably 5.0 ⁇ 10 6 Pa or less.
  • the glass transition temperature of the adhesive layer 14 is preferably -10°C or higher. If the glass transition temperature is ⁇ 10° C. or higher, it is possible to effectively suppress adhesion defects such as floating, peeling, and voids even in a high-temperature and high-humidity environment, and the adhesion to the adhesive layer 14 can be prevented. Foreign matter can be easily removed. From this point of view, the glass transition temperature is more preferably ⁇ 8° C. or higher, more preferably ⁇ 5° C. or higher. °C or higher. On the other hand, the glass transition temperature is preferably 100° C. or lower. When the glass transition temperature is 100° C. or lower, the adhesiveness to the MEA can be particularly good. Also, from this point of view, the glass transition temperature is more preferably 95° C. or lower, more preferably 90° C. or lower.
  • the adhesive strength of the adhesive layer 14 to the base film 12 and MEA at 23°C is preferably 1 N/25 mm or more, more preferably 1.2 N/25 mm or more, and still more preferably 2 N/25 mm or more. If the adhesive strength is 1 N/25 mm or more, lifting and peeling of the adhesive layer 14 can be suitably suppressed. Although the upper limit of the adhesive strength is not particularly limited, it is usually 50 N/25 mm or less and 40 N/25 mm or less.
  • the evaluation of the adhesive strength of the adhesive layer 14 may be performed by the same method as the measurement of the "initial peel strength" in the examples below.
  • the adhesive composition forming the adhesive layer 14 contains a polyurethane-based resin having a reactive functional group, as described above. By using a polyurethane-based resin, the adhesive layer 14 has appropriate flexibility and resistance to moist heat, and bonding can be completed by thermocompression bonding for a short period of time.
  • Polyurethane-based resin is a general term for compounds containing two or more urethane bonds in one molecule.
  • a polyurethane-based resin has a structure in which a polyisocyanate and a polyol are polymerized.
  • the polyisocyanate may have two or more isocyanate groups in one molecule, and from the physical properties of the adhesive layer 14, diisocyanate or triisocyanate is preferable, and diisocyanate is more preferable.
  • diisocyanate an aliphatic diisocyanate such as hexamethylene diisocyanate and an aromatic diisocyanate such as benzene-1,3-diisocyanate can be appropriately selected and used in consideration of the physical properties of the adhesive layer 14. .
  • Polyisocyanate can be used individually by 1 type or in combination of 2 or more types.
  • an isocyanate group-terminated prepolymer obtained by reacting a polyol with an excess amount of polyisocyanate may be used as an intermediate for the polyurethane resin.
  • the polyol may have two or more hydroxyl groups in one molecule, and from the physical properties of the adhesive layer 14, diols or triols are preferable, and diols are more preferable.
  • diol an aliphatic diol such as ethylene glycol or an aromatic diol such as benzenediol can be appropriately selected and used in consideration of the physical properties of the adhesive layer 14 .
  • a polyol can be used individually by 1 type or in combination of 2 or more types. Prepolymers such as polyether polyols, polyester polyols and polycarbonate polyols may also be used.
  • the polyurethane-based resin may be a polyurethane-urea-based resin further having a urea bond.
  • Polyurethane urea-based resins have, for example, a structure in which a polyamine is bound to a urethane-based resin having an isocyanate group at its end. Any polyamine may be used as long as it has two or more amino groups in one molecule. From the viewpoint of the physical properties of the adhesive layer 14, diamine or triamine is preferable, and diamine is more preferable. Considering the physical properties of the adhesive layer 14, the diamine can be appropriately selected and used from known aliphatic diamines such as ethylenediamine and known aromatic diamines such as phenylenediamine. A polyamine can be used individually by 1 type or in combination of 2 or more types.
  • the weight average molecular weight (Mw) of the polyurethane resin is preferably 5,000 or more, more preferably 10,000 or more, and still more preferably 50,000 or more.
  • Mw is preferably 1,000,000 or less, more preferably 500,000, and even more preferably 200,000 or less.
  • the reactive functional group possessed by the polyurethane-based resin is not particularly limited as long as it is a functional group capable of forming a bond by reacting with a cross-linking agent. , amino group, epoxy group, oxetanyl group, oxazoline group, oxazine group, aziridine group, thiol group, isocyanate group, blocked isocyanate group, blocked carboxyl group, silanol group and the like.
  • the polyurethane-based resin may contain these reactive functional groups singly or in combination of two or more.
  • the reactive functional group may be directly bonded to the polyurethane chain, such as a polyol moiety, or may be introduced into a side chain bonded to the polyurethane chain.
  • the acid value of the polyurethane-based resin is preferably 4.0 mgKOH/g or more and 40 mgKOH/g or less.
  • the acid value is more preferably 6.0 mgKOH/g or more, more preferably 8.0 mgKOH/g or more.
  • it is more preferably 30 mgKOH/g or less, or 20 mgKOH/g or less.
  • the adhesive composition forming the adhesive layer 14 contains a cross-linking agent in addition to the polyurethane-based resin.
  • the cross-linking agent is a compound having two or more reactive groups in one molecule that can react with the reactive functional groups of the polyurethane resin. to form a cross-link.
  • Examples of cross-linking agents include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, metal chelate-type cross-linking agents, melamine resin-based cross-linking agents, and urea resin-based cross-linking agents.
  • epoxy-based cross-linking agents are more preferable from the viewpoint of adhesiveness, heat resistance, and the like.
  • An epoxy-based cross-linking agent is a compound that has two or more epoxy groups as reactive groups in one molecule.
  • the epoxy-based cross-linking agents may be used alone or in combination of two or more.
  • Epoxy crosslinking agents include, for example, bisphenol A type epoxy resin, epichlorohydrin type epoxy resin, ethylene glycidyl ether, N,N,N',N'-tetrakis(2,3-epoxypropyl)-1,4- phenylenediamine, N,N,N',N'-tetrakis(oxiran-2-ylmethyl)-4,4'-methylenebisaniline, N,N-diglycidyl-4-(glycidyloxy)aniline, N,N,N ',N'-Tetraglycidyl-m-xylenediamine, 1,1,2,2-tetrakis(3-glycidyloxyphenyl)ethane, diglycidylaniline, diamineglycidylamine, 1,3-bis(N,N-di glycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, n
  • the cross-linking agent in the adhesive composition is preferably a liquid with a viscosity of 500 mPa ⁇ s or more at 25°C or a solid with a softening point of 100°C or less.
  • the molecular weight of the cross-linking agent in the adhesive composition is preferably 200 or more, more preferably 400 or more, still more preferably 600 or more.
  • the molecular weight is preferably 10,000 or less, more preferably 5,000 or less, even more preferably 1,000 or less.
  • the functional group equivalent of the reactive group of the cross-linking agent in the adhesive composition is preferably 50 g/eq or more, more preferably 100 g/eq or more, and still more preferably 150 g/eq or more. is.
  • the functional group equivalent is preferably 1000 g/eq or less, more preferably 600 g/eq or less, still more preferably 400 g/eq or less, and particularly preferably 250 g/eq. If the molecular weight and reactive group content of the cross-linking agent are within the above ranges, good adhesion to MEA and resistance to moist heat can be obtained.
  • the content of the cross-linking agent in the adhesive composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 5 parts by mass or more, and particularly preferably 100 parts by mass of the polyurethane resin. is 10 parts by mass or more. On the other hand, the content thereof is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less. If the content of the cross-linking agent (B) is within the above range, good adhesion to MEA and resistance to moist heat can be obtained.
  • (b/a) is preferably 1.0 or more, more preferably 1.1 or more, and still more preferably 1.3 or more.
  • the molar ratio is preferably 10.0 or less, more preferably 8.0 or less, still more preferably 7.0 or less. If the molar ratio is 1.0 or more, a sufficient crosslink density can be obtained and a suitable storage elastic modulus can be obtained. If the molar ratio is 10.0 or less, the adhesion of the adhesive layer 14 to the adherend is increased, peeling is effectively suppressed, and durability is improved.
  • additives In addition to the polyurethane resin and the cross-linking agent, other additives may be added to the adhesive composition.
  • Other additives include cross-linking accelerators, cross-linking retarders, fillers, plasticizers, softeners, release aids, silane coupling agents, dyes, pigments, pigments, fluorescent brighteners, antistatic agents, wetting agents. , surfactant, thickener, antifungal agent, preservative, oxygen absorber, ultraviolet absorber, antioxidant, near-infrared absorber, water-soluble quencher, fragrance, metal deactivator, nucleating agent, alkyl modifiers, flame retardants, lubricants, processing aids, and the like. These are appropriately selected and blended according to the application and purpose of use of the adhesive sheet 10, that is, the specific type and structure of the MEA to which the adhesive sheet 10 is applied, the usage environment, and the like.
  • the filler is blended for the purpose of improving resistance to moist heat, adjusting the elastic modulus, making the adhesive sheet 10 tack-free and improving the ability to remove adhering foreign matter.
  • the filler may be either an inorganic filler or an organic filler.
  • inorganic fillers include inorganic particles such as silica, alumina, calcium carbonate, talc and clay.
  • resin fillers include (meth)acrylic resins, styrene resins, styrene-(meth)acrylic resins, urethane resins, polyamide resins, silicone resins, epoxy resins, phenolic resins, polyethylene resins, cellulose, and the like. and resin particles made of a resin.
  • the adhesive composition can be produced by mixing a polyurethane resin, a cross-linking agent, and other additives used as necessary.
  • the adhesive composition may be a solution diluted with a suitable solvent to a suitable viscosity for forming the adhesive layer 14 .
  • solvents include aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, Ketones such as isophorone and cyclohexanone; esters such as ethyl acetate, propyl acetate, isopropyl acetate and butyl acetate; cellosolve solvents such as ethyl cellosolve; ethanol, isopropyl alcohol, n-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether , propylene glycol monomethyl ether, and diethylene glycol monobutyl ether.
  • aliphatic hydrocarbons such as hexane and heptane
  • solvents may be used singly or in combination of two or more.
  • the amount of the solvent used may be appropriately adjusted so that the adhesive composition has a viscosity suitable for coating, and is not particularly limited. It is preferably 10% by mass to 80% by mass, and still more preferably 20% by mass to 70% by mass.
  • the adhesive sheet 10 of the present embodiment is prepared by: (1) applying an adhesive composition directly onto one surface of the base film 12, performing a drying and curing step by heat treatment, and optionally aging. (2) An adhesive composition is applied on the surface of the release film, heat-treated, transferred to one surface of the base film 12, and then cured as necessary. can be done. Among these, from the viewpoint of adhesion to the substrate, the method (1) in which the adhesive composition is directly applied to one surface of the substrate film 12 is preferable.
  • the adhesive composition for example, reverse gravure coating method, direct gravure coating method, die coating method, bar coating method, wire bar coating method, roll coating method, spin coating method, dip coating method, spray coating method, knife
  • Various coating methods such as coating method and kiss coating method, and various printing methods such as inkjet method, offset printing, screen printing and flexographic printing can be employed.
  • the surface of the base film 12 may be subjected to surface treatment such as corona treatment, plasma treatment, hot air treatment, ozone treatment, and ultraviolet treatment.
  • corona treatment such as corona treatment, plasma treatment, hot air treatment, ozone treatment, and ultraviolet treatment.
  • the drying and curing steps are not particularly limited as long as the solvent or the like used in the adhesive composition can be removed and the adhesive composition can be cured.
  • the drying temperature is preferably 120°C to 130°C.
  • the cured state of the adhesive composition it is preferable to leave a partially uncured material (in a semi-cured state).
  • Curing is, for example, at 40°C to 80°C for about 3 to 20 days, preferably at 60°C for about 4 to 7 days.
  • the adhesive sheet 10 may have a release sheet on the surface of the adhesive layer 14 before use.
  • the release sheet is used as a protective material for the adhesive layer 14 and is peeled off when the adhesive sheet of the present invention is attached to an adherend.
  • Examples of the release sheet include paper such as glassine paper, coated paper, laminated paper, and various plastic sheets coated with a release agent such as silicone resin.
  • a sheet having stickiness on at least one side may be used.
  • the plastic sheet used for the release sheet the one exemplified as the base film 12 can be appropriately used.
  • the thickness of the release sheet is not particularly limited, it is usually 10 ⁇ m to 150 ⁇ m.
  • the adhesive sheet 10 can be used as a subgasket for MEA.
  • the surface of the adhesive sheet 10 on which the adhesive layer 14 is formed is brought into contact with the MEA to laminate the adhesive sheet 10 and the MEA.
  • the opening W1 of the adhesive sheet 10 is aligned with the solid electrolyte membrane of the MEA.
  • the adhesive sheet 10 is heated while pressure is applied to the MEA to bond the adhesive layer 14 to the MEA.
  • the pressure can be 0.5 to 10 MPa
  • the heating temperature can be 130 to 170° C.
  • the pressurization/heating time can be 3 to 60 seconds.
  • After the thermocompression bonding process it can be used in subsequent processes such as lamination of power generation cells without undergoing a hardening treatment process such as heat treatment or aging.
  • FIG. 2 is a perspective view of an adhesive sheet 20 according to a second embodiment of the invention.
  • the adhesive sheet 20 according to the second embodiment of the present invention includes a substrate film 12, an adhesive layer 14 formed on the surface of the substrate film 12, and a second substrate. It has a film 16 .
  • the second base film 16 is provided on the side of the adhesive layer 14 opposite to the side on which the base film 12 is provided.
  • the second base film 16 covers the surface of the adhesive layer 14 at the portion of the adhesive layer 14 that is not in contact with the MEA. That is, the second base film 16 is provided with an exposure opening W2 as a through hole (including the entire opening W1 inside) that is larger than the opening W1 provided in the base film 12 and the adhesive layer 14.
  • the adhesive layer 14 is exposed in the portion surrounding the opening W1 inside the exposure opening W2.
  • the adhesive layer 14 exposed inside the exposure opening W2 comes into contact with the MEA overlaid on the adhesive sheet 20 and is adhered to the MEA.
  • the adhesive layer 14 is not exposed on the outermost surface in portions other than the portion inside the exposure opening W2 where the MEA is adhered, so adhesion of foreign matter to the adhesive layer 14 can be suppressed. At the same time, adhering foreign substances and the like can be easily removed.
  • configurations similar to those of the adhesive sheet 10 according to the first embodiment described above can be applied.
  • the second base film 16 is made of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyester resin such as liquid crystal polyester, polycarbonate resin, poly(meth)acrylate resin, polystyrene resin.
  • polyolefin resins such as polyamide resins, polyphthalamide resins, polyimide resins, polyacrylonitrile resins, polypropylene resins, polyethylene resins, polycycloolefin resins, cycloolefin copolymer resins, polyphenylene sulfide resins, polyvinyl chloride resins, polyvinylidene chloride resins, Polyvinyl alcohol resin, polyvinylidene fluoride resin, fluorine resin, silicone resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polyarylate resin and the like.
  • the polymeric material of the second base film 16 may be composed of only one of these, or may be composed of a combination of two or more by lamination or the like.
  • these resins polyarylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, and polyarylate are selected from the viewpoint of heat resistance and mechanical properties.
  • the second base film 16 is composed of at least one resin material selected from the group consisting of these resins.
  • the adhesive layer 14 (and the second base film 16) is provided only on one surface of the base film 12.
  • a configuration in which the adhesive layers 14 (and the second base film 16) are provided on both sides of the base film 12 may be employed.
  • the handleability of the adhesive sheet is improved, and operations such as lamination with the MEA are facilitated.
  • the adhesive sheet may be composed only of the adhesive layer 14 as a self-supporting adhesive film.
  • the adhesive sheets 10 and 20 are formed in a shape having an opening W1 and are in the form of a subgasket that is used by being laminated with the MEA. It does not have to be configured, and it can be used by being molded into a shape according to the application at a location where a seal is required in the fuel cell.
  • Example 1 ⁇ Preparation of adhesive composition
  • the following epoxy-based cross-linking agent ⁇ 1>("HD-901" manufactured by Toyochem) is added to 100 parts by mass of the solid content of the following polyurethane resin ⁇ 1>("HD-9302" manufactured by Toyochem). 0 mass part (solid content) was added, and toluene was further added so that the solid content concentration was 19 mass %, to prepare an adhesive composition.
  • PEN film Polyethylene naphthalate (PEN) film ("Teonex Q51” manufactured by Toyobo) is coated with an adhesive composition using a baker-type film applicator so that the thickness after drying is 10 ⁇ m. and heated for 3 minutes at 150° C. After that, a release film (“HY-S10” manufactured by Higashiyama Film Co., Ltd., silicone-based PET release film, thickness 25 ⁇ m) was peeled off from the surface of the adhesive composition not covered with the PEN film. The surfaces were bonded together, and then aged at 60° C. for 6 days to prepare an adhesive sheet.
  • PEN Polyethylene naphthalate
  • HY-S10 manufactured by Higashiyama Film Co., Ltd., silicone-based PET release film, thickness 25 ⁇ m
  • Adhesive sheets were produced in the same manner as in Example 1, except that the composition of the adhesive composition and the aging conditions were as shown in Table 1.
  • the measurement conditions were shear mode, geometry: parallel plate with a diameter of 8 mm, axial force: 1.0 N, normal load: 1.0 N, frequency: 1 Hz, and heating rate: 5°C/min.
  • the loss elastic modulus (G′′) was also measured, and the loss tangent (tan ⁇ ) was taken as the glass transition temperature.
  • the release sheet of the adhesive sheet is peeled off from the adhesive layer, and a solid polymer electrolyte membrane (manufactured by DuPont, "Nafion PFSA NR-212", thickness: 50.8 ⁇ m) is superimposed on the surface of the adhesive layer.
  • a test sample was prepared by pressing using a press machine "H400-15”.
  • the peel force was measured under the conditions of a peel speed of 50 mm/min and a peel angle of 180°. If the peel force is about 1 N/25 mm, it can be said that the initial peel force is sufficiently large and the adhesion has been completed.
  • Lifting, peeling, and voids with a length of less than 1 mm are permissible as bonding conditions for MAE subgaskets in a high-temperature, high-humidity environment.
  • ⁇ 3 or more out of 5 samples have lift, peeling, or voids of less than 1 mm in length at the edges, but none of the samples have lift or peeling of 1 mm or more in length. None of the examples and comparative examples were classified into this stage.
  • ⁇ Lifting, peeling, or voids with a length of 1 mm or more were observed in one or more of the five samples.
  • Table 1 shows the composition of each sample and the results of the evaluation.
  • the content of each component is expressed in units of parts by mass.
  • the adhesive layer of the thermosetting adhesive sheet was formed from a cured product of an adhesive composition containing a polyurethane resin having a reactive functional group and a cross-linking agent.
  • the gel fraction of 60% by mass or more, the storage elastic modulus (G' 100 ) at 100°C of 5.0 ⁇ 10 4 Pa or more and 1.0 ⁇ 10 8 Pa or less, and the storage elastic modulus at 100°C is 0.5 or less.
  • the adhesive sheet has excellent storage stability, and as shown in the evaluation results of the initial peel strength, the adhesion can be completed in a short time by thermocompression bonding, and as shown in the evaluation results of the appearance after boiling.
  • adhesion defects such as lifting, peeling and voids can be suppressed even in a high-temperature and high-humidity environment.
  • the adhesive layer had a gel fraction of 90% by mass or more and a rate of decrease in storage elastic modulus of 0.2 or less, a particularly large initial peel force and a high humidity and high temperature environment were obtained.
  • Comparative Examples 1 and 2 peeling of the adhesive layer occurred in the boiling test corresponding to the rate of decrease in storage modulus exceeding 0.5.
  • Comparative Example 1 had a G' 100 of less than 5.0 ⁇ 10 4 Pa and a gel fraction of less than 60 mass %, and the adhesiveness was poor, so the initial peel strength was not measured.
  • G′ 100 exceeded 1.0 ⁇ 10 8 Pa, and the adhesiveness of the adhesive layer was so low that it could not adhere to the solid polymer electrolyte membrane.
  • Adhesive sheet 12 Base film 14 Adhesive layer 16 Second base film W1 Opening W2 Exposure opening

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PCT/JP2023/006160 2022-03-01 2023-02-21 熱硬化型接着シートおよび燃料電池用サブガスケット Ceased WO2023167052A1 (ja)

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