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WO2025070386A1 - Séparateur, composition durcissable et procédé de production de séparateur - Google Patents

Séparateur, composition durcissable et procédé de production de séparateur Download PDF

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Publication number
WO2025070386A1
WO2025070386A1 PCT/JP2024/033927 JP2024033927W WO2025070386A1 WO 2025070386 A1 WO2025070386 A1 WO 2025070386A1 JP 2024033927 W JP2024033927 W JP 2024033927W WO 2025070386 A1 WO2025070386 A1 WO 2025070386A1
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WO
WIPO (PCT)
Prior art keywords
group
formula
compound
separator
compound represented
Prior art date
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Pending
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PCT/JP2024/033927
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English (en)
Japanese (ja)
Inventor
幸治 弘中
寛 野副
竜太 竹上
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Fujifilm Corp
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Fujifilm Corp
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Publication of WO2025070386A1 publication Critical patent/WO2025070386A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials

Definitions

  • the present invention relates to a separator, a curable composition suitable for producing a separator, and a method for producing a separator.
  • Hydrogen is a clean energy source that does not emit carbon dioxide, and is used, for example, as fuel for fuel cell vehicles and household fuel cells.
  • Water electrolysis (water electrolysis) is a known method for producing hydrogen. If water electrolysis is performed using renewable energy as electricity, hydrogen can be produced without emitting carbon dioxide, so hydrogen is attracting increasing attention as a fundamental energy source for a sustainable society.
  • alkaline water electrolysis using a high-concentration alkaline aqueous solution as an electrolyte is known.
  • a gas barrier separator diaphragm is disposed between the cathode and the anode to prevent the movement of bubbly hydrogen (2H 2 O+2e ⁇ ⁇ H 2 +2OH ⁇ ) generated at the cathode (negative electrode) to the anode side and to prevent the movement of bubbly oxygen (4OH ⁇ ⁇ O 2 +2H 2 O+4e ⁇ ) generated at the anode (positive electrode) to the cathode side.
  • Anion exchange membrane water electrolysis (AEMWE) using an anion exchange membrane that improves the efficiency of the movement of OH ⁇ from the cathode side to the anode side has also been proposed as this separator.
  • AEMWE hydroxy ions can be highly efficiently conducted from the cathode side to the anode side without using a high-concentration alkaline aqueous solution as an electrolyte.
  • Water electrolysis technology is also known that uses a cation (proton) exchange membrane as a separator that also serves as an electrolyte.
  • a cation (proton) exchange membrane as a separator that also serves as an electrolyte.
  • the reaction 2H 2 O ⁇ O 2 +4H + +4e - occurs at the anode
  • the reaction 2H + +2e - ⁇ H 2 occurs at the cathode.
  • H + moves between the electrodes, connecting the anode reaction and the cathode reaction.
  • Patent Document 1 describes an invention for an ion exchange membrane for water electrolysis in which ion exchange resin is filled into the pores of a laminated porous substrate film made of multiple laminated porous substrate films with a porosity of 30 to 50% and an average pore diameter of less than 0.01 to 0.1 ⁇ m, the total thickness of the porous substrate films being 50 to 200 ⁇ m, and the difference in porosity between adjacent porous substrate films being 10% or less.
  • the technology described in Patent Document 1 is said to be able to provide an ion exchange membrane for water electrolysis that has high gas barrier properties and low membrane resistance.
  • the separator In alkaline water electrolysis and the like, the separator is required to have high ion permeability (low ion resistance) and low water permeability.
  • An object of the present invention is to provide a separator having high ion permeability and low water permeability.
  • Another object of the present invention is to provide a curable composition suitable for forming the separator.
  • Another object of the present invention is to provide a method for producing a separator using the curable composition.
  • a separator comprising a crosslinked product obtained by a curing reaction of any one of the following (a) to (d):
  • X1 and Y represent groups having at least one of an epoxy group and an oxetanyl group
  • n is a number of 2 or more.
  • X2 represents a hydrogen atom or a non-chain polymerizable organic group
  • Y and n have the same meanings as Y and n in formula (I-1), respectively.
  • the content of the constituent component derived from the compound represented by the above formula (I-1) in the crosslinked product is 50 mass% or more
  • the content of the constituent component derived from the compound represented by the above formula (I-2) in the crosslinked product is 50 mass% or more
  • the content of the constituent component derived from the compound represented by the above formula (II-1) in the crosslinked product is 50 mass% or more
  • the content of the constituent component derived from the compound represented by the above formula (II-2) in the crosslinked product is 50% by mass or more.
  • a curable composition comprising the following (a) or (b) and a photoacid generator or a thermal acid generator: (a) A compound represented by the following formula (I-1): In the above formula (I-1), X1 and Y represent groups having at least one of an epoxy group and an oxetanyl group, and n is a number of 2 or more.
  • R 1 and R 2 each represent an alkyl group.
  • a method for producing a separator comprising subjecting the curable composition according to [12] or [13] to a curing reaction to obtain a crosslinked product.
  • an epoxy compound means a compound having at least one epoxy group (oxiranyl group) in one molecule.
  • the term “epoxy compound” includes both a monofunctional epoxy compound having one epoxy group in one molecule and a multifunctional epoxy compound having multiple epoxy groups in one molecule. Unless otherwise specified, the "epoxy compound” does not have an oxetanyl group or an allyl group.
  • the oxetane compound means a compound having at least one oxetanyl group in one molecule.
  • oxetane compound includes both a monofunctional oxetane compound having one oxetanyl group in one molecule and a polyfunctional oxetane compound having multiple oxetanyl groups in one molecule.
  • the "oxetane compound” does not have an epoxy group or an allyl group.
  • an allyl compound means a compound having at least one allyl group in one molecule. That is, the term “allyl compound” includes both a monofunctional allyl compound having one allyl group in one molecule and a polyfunctional allyl compound having multiple allyl groups in one molecule.
  • the "allyl compound” does not have an epoxy group or an oxetanyl group.
  • the polyethyleneoxy group means a structure in which two or more ethyleneoxy groups are repeated in a linear chain.
  • the separator of the present invention has high ion permeability and low water permeability.
  • the curable composition of the present invention is suitable for forming this separator. Furthermore, the method for producing the separator of the present invention makes it possible to obtain a separator with high ion permeability and low water permeability.
  • the separator of the present invention can be widely used as a separator in water electrolysis, such as alkaline water electrolysis, anion exchange membrane water electrolysis, and proton exchange membrane water electrolysis, and is suitable as a diaphragm separating an anode and a cathode in water splitting.
  • the basic function of this diaphragm is to prevent the transfer of gas generated at each electrode to the other electrode.
  • the separator of the present invention has this basic function, and has excellent ion permeability and low water permeability. The configuration of the separator of the present invention will be described.
  • the separator of the present invention contains a crosslinked body obtained by a curing reaction of any of the following (a) to (d):
  • the crosslinked product obtained by the curing reaction of the above (a) has a content of the constituent component derived from the compound represented by the above formula (I-1) in this crosslinked product of 50% by mass or more.
  • X2 represents a hydrogen atom or a non-chain polymerizable organic group (a group which is non-chain polymerizable and has a carbon atom).
  • Y and n are respectively defined as Y and n in formula (I-1), and the preferred ranges are also the same.
  • the crosslinked product obtained by the curing reaction of the above (b) has a content of the constituent component derived from the compound represented by the above formula (I-2) in this crosslinked product of 50 mass % or more.
  • the crosslinked product obtained by the curing reaction of the above (c) has a content of the constituent component derived from the compound represented by the above formula (II-1) in this crosslinked product of 50 mass % or more.
  • the crosslinked product obtained by the curing reaction of the above (d) has a content of the constituent component derived from the compound represented by the above formula (II-2) in this crosslinked product of 50 mass % or more.
  • the crosslinked material constituting the separator of the present invention has a high affinity with water due to the action of the polyethyleneoxy group, but is difficult to dissolve in water due to the crosslinked structure. It can also be made in a water-insoluble form. In addition, because it is a crosslinked material, the mechanical strength is also increased to a desired level. Furthermore, due to its structure, it tends to have excellent heat resistance and alkali resistance.
  • the curing reaction for obtaining the crosslinked product is preferably a cationic polymerization reaction or a radical polymerization reaction.
  • the crosslinked product obtained by curing (a) or (b) is usually a crosslinked product obtained by a cationic polymerization reaction
  • the crosslinked product obtained by curing (c) or (d) is usually a crosslinked product obtained by a radical polymerization reaction. Therefore, the curing reaction is carried out by mixing each of the compounds specified in (a) to (d) with a polymerization initiator. If necessary, a sensitizer may be mixed.
  • reactive monomers other than each of the compounds specified in (a) to (d) may be mixed and cured.
  • the crosslinked material does not have a hydrolyzable structural portion such as an ester bond, an amide bond, a urethane bond, a urea bond, etc. This can further improve the alkali resistance of the resulting separator.
  • the separator of the present invention preferably contains a crosslinked material obtained by a curing reaction of (a).
  • the separator of the present invention can be in the form of a film formed of a crosslinked body obtained by a curing reaction of any of (a) to (d).
  • the separator of the present invention can also be in the form of a film containing a porous support and the crosslinked body.
  • the separator can be in the form of a laminate of a film of a crosslinked body obtained by a curing reaction of any of (a) to (d) and a porous support.
  • the separator can also be in the form of a laminate of a film of a crosslinked body obtained by a curing reaction of any of (a) to (d) and a porous support.
  • the separator can be in the form of a composite in which a crosslinked body obtained by a curing reaction of any of (a) to (d) is formed at least in the pores of the porous support by a curing reaction of any of (a) to (d).
  • the compound represented by the above formula (I-1) has a polyethyleneoxy group, and also has a group selected from an epoxy group and an oxetanyl group in both X1 and Y. That is, X1 and Y each represent a group having at least one of an epoxy group (oxiranyl group) and an oxetanyl group. X1 and Y each preferably represent a group having an epoxy group (oxiranyl group).
  • the epoxy group and the oxetanyl group may have an alkyl group as a substituent, and the alkyl group preferably has 1 to 3 carbon atoms.
  • X1 may have only one group selected from an epoxy group and an oxetanyl group, or may have two or more groups selected from the epoxy group and the oxetanyl group.
  • Y may have only one group selected from an epoxy group and an oxetanyl group, or may have two or more groups selected from the group consisting of an epoxy group and an oxetanyl group, and preferably has only one of an epoxy group and an oxetanyl group.
  • Both X1 and Y are preferably a structure having an epoxy group and no oxetanyl group, or a structure having an oxetanyl group and no epoxy group, and more preferably a structure having an epoxy group and no oxetanyl group.
  • the compound represented by the above formula (I-1) is preferably a structure having an epoxy group and no oxetanyl group, or a structure having an oxetanyl group and no epoxy group, and more preferably a structure having an epoxy group and no oxetanyl group.
  • Both X1 and Y are preferably free of an allyl group.
  • X 1 is preferably a monovalent saturated group which has one or more of at least one of an epoxy group and an oxetanyl group and is composed only of atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms. It is preferable that X1 does not have an active hydrogen (a hydrogen atom bonded to an oxygen atom, a nitrogen atom, or a sulfur atom).
  • the chemical formula weight of X 1 is preferably 55 to 50,000, more preferably 55 to 10,000, and even more preferably 55 to 5,000.
  • X1 has only one group selected from an epoxy group and an oxetanyl group
  • This alkylene group is preferably an unsubstituted alkylene group.
  • the number of carbon atoms in this alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
  • a part of the alkylene group may form an alicyclic ring together with the epoxy group.
  • X1 has two or more groups selected from an epoxy group and an oxetanyl group
  • X1 is preferably a branched alkyl group having a group selected from an epoxy group and an oxetanyl group as a substituent, i.e., a branched alkyl group having groups having a group selected from an epoxy group and an oxetanyl group bonded to at least two branch ends of a branched alkyl chain (saturated hydrocarbon chain).
  • the group having a group selected from an epoxy group and an oxetanyl group bonded to at least two branched ends preferably has a chemical formula weight of 250 to 50,000, more preferably 300 to 50,000, and even more preferably 500 to 30,000.
  • a polyethyleneoxy structure is present between at least two branched ends of the branched alkyl chain and the group selected from an epoxy group and an oxetanyl group. It is more preferable that the group having a group selected from an epoxy group and an oxetanyl group bonded to at least two branched ends has the same structure as -O(C 2 H 4 O) n -Y in the above formula (I-1).
  • the branched alkyl chain may contain an oxygen atom in the chain.
  • the branched alkyl group having a group selected from an epoxy group and an oxetanyl group as a substituent has, as a structure of the branched alkyl chain portion (branched saturated hydrocarbon structure), preferably 2 to 5 branched ends to which a group having a group selected from an epoxy group and an oxetanyl group is bonded, more preferably 2 to 4 branched ends, and even more preferably 2 to 3 branched ends. Note that the number of branched ends does not include the end bonded to the oxygen atom bonded to X1 shown in the above formula (I-1).
  • Y is preferably a monovalent saturated group having at least one of an epoxy group and an oxetanyl group, and composed only of atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms. It is preferable that Y does not have active hydrogen (a hydrogen atom bonded to an oxygen atom, a nitrogen atom, or a sulfur atom).
  • Y has at least one of an epoxy group and an oxetanyl group.
  • the chemical formula weight of Y is preferably 55 to 300, more preferably 55 to 200, and even more preferably 55 to 150.
  • the epoxy group or the oxetanyl group is bonded to the oxygen atom bonded to Y in formula (I-1) via an alkylene group.
  • This alkylene group is preferably an unsubstituted alkylene group.
  • the number of carbon atoms in this alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
  • a part of the alkylene group may form an alicyclic ring together with the epoxy group.
  • n represents an integer of 2 or more, preferably 2 to 1000, more preferably 3 to 500, even more preferably 4 to 300, and even more preferably 5 to 200.
  • the above (a) may contain one or more compounds represented by formula (I-1).
  • the crosslinked body obtained by the curing reaction of (a) if the content of the component derived from the compound represented by the above formula (I-1) is 50 mass% or more, the crosslinked body may contain a component derived from at least one of the compounds represented by formula (I-2), (II-1), and (II-2).
  • the curing reaction (a) may be carried out in the presence of at least one of an oxetane compound not having a polyethyleneoxy group and an epoxy compound not having a polyethyleneoxy group, and is preferably carried out in the presence of an oxetane compound not having a polyethyleneoxy group.
  • the compound represented by the above formula (I-1) is preferably an epoxy compound (a compound having an epoxy group and not having an oxetanyl group).
  • the compound represented by the above formula (I-1) is preferably an oxetane compound (a compound having an oxetanyl group and not having an epoxy group).
  • the oxetane compound having no polyethyleneoxy group is preferably an oxetane compound having no polyethyleneoxy group and composed only of atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms.
  • the oxetane compound having no polyethyleneoxy group is preferably free of a hydrolyzable structural part such as an ester bond in its molecular structure.
  • the oxetane compound having no polyethyleneoxy group may be a monofunctional oxetane compound or a polyfunctional oxetane compound.
  • the number of oxetanyl groups in the polyfunctional oxetane compound is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 to 3, and even more preferably 2.
  • the molecular weight of the oxetane compound that does not have a polyethyleneoxy group is preferably 80 to 1000, more preferably 100 to 1000, more preferably 100 to 500, and even more preferably 100 to 250.
  • Epoxy compound not having a polyethyleneoxy group is preferably an epoxy compound having no polyethyleneoxy group and composed only of atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms.
  • the epoxy compound having no polyethyleneoxy group is preferably free of a hydrolyzable structural part such as an ester bond in its molecular structure.
  • the epoxy compound having no polyethyleneoxy group may be a monofunctional epoxy compound or a polyfunctional epoxy compound. In the case of a polyfunctional epoxy compound, the number of epoxy groups in the polyfunctional epoxy compound is preferably 2 to 6, more preferably 2 to 5, and even more preferably 3 to 4.
  • the epoxy compound having no polyethyleneoxy group may have a vinyl group.
  • the molecular weight of the epoxy compound that does not have a polyethyleneoxy group is preferably 150 to 1,000, more preferably 150 to 600, and particularly preferably 200 to 400.
  • the content of the component derived from the compound represented by formula (I-1) in the crosslinked product is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the content of the component derived from the compound represented by formula (I-1) in the crosslinked product may be 100% by mass (i.e., a form in which all of the reactive monomers have been cured as the compound represented by formula (I-1)).
  • the total amount of the components derived from the oxetane compound having no polyethyleneoxy group and the components derived from the compound having no polyethyleneoxy group in this crosslinked body is 50 mass% or less, preferably 5 to 40 mass%, more preferably 10 to 40 mass%, and more preferably 10 to 30 mass%.
  • total means the components derived from the epoxy compound having no polyethyleneoxy group when the crosslinked body does not have a component derived from the oxetane compound having no polyethyleneoxy group, and means the components derived from the oxetane compound having no polyethyleneoxy group when the crosslinked body does not have a component derived from the epoxy compound having no polyethyleneoxy group.
  • X2 represents a hydrogen atom or a non-chain polymerizable organic group.
  • the "non-chain polymerizable organic group” refers to an organic group that does not undergo chain polymerization, i.e., an organic group that does not have an organic group that undergoes chain polymerization (for example, groups having a carbon-carbon double bond such as a vinyl group, a vinyl ether group, a vinyl thioether group, a styryl group, an acryloyl group, a methacryloyl group, and derivatives thereof; and cyclic ether groups such as an epoxy group and an oxetanyl group). It is preferable that X2 does not have an active hydrogen (a hydrogen atom bonded to an oxygen atom, a nitrogen atom, or a sulfur atom).
  • the chemical formula weight of X2 is preferably 1-500, more preferably 1-300, further preferably 1-100, and particularly preferably 1-50.
  • Examples of the non-chain polymerizable organic group that can be taken as X2 include an alkyl group, an aryl group, an aralkyl group, etc., and an unsubstituted alkyl group is preferable.
  • the number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
  • X2 is preferably a hydrogen atom or an unsubstituted alkyl group.
  • Y and n have the same meanings as Y and n in formula (I-1), and the preferred ranges are also the same.
  • Y is preferably a group having at least one of an epoxy group and an oxetanyl group. Therefore, the compound represented by the above formula (I-2) is preferably a structure having an epoxy group and no oxetanyl group, or a structure having an oxetanyl group and no epoxy group, and more preferably a structure having an epoxy group and no oxetanyl group.
  • the above (b) may contain one or more compounds represented by formula (I-2).
  • n is an integer of 2 or more.
  • Polyfunctional epoxy compound not having polyethyleneoxy group As the polyfunctional epoxy compound having no polyethyleneoxy group in (b), a polyfunctional epoxy compound having no polyethyleneoxy group among the epoxy compounds having no polyethyleneoxy group explained in (a) above can be used.
  • Polyfunctional oxetane compound not having a polyethyleneoxy group As the polyfunctional oxetane compound not having a polyethyleneoxy group in (b), a polyfunctional oxetane compound not having a polyethyleneoxy group among the oxetane compounds not having a polyethyleneoxy group explained in (a) above can be used.
  • the polyfunctional epoxy compound having no polyethyleneoxy groups and the polyfunctional oxetane compound having no polyethyleneoxy groups do not have a hydrolyzable structural part such as an ester bond in their molecular structure.
  • the content of the component derived from the compound represented by formula (I-2) in the crosslinked product is 50% by mass or more, preferably 55 to 98% by mass, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass.
  • the total amount of the components derived from the polyfunctional epoxy compound having no polyethyleneoxy group and the components derived from the polyfunctional oxetane compound having no polyethyleneoxy group in this crosslinked body is 50 mass% or less, preferably 2 to 45 mass%, more preferably 5 to 40 mass%, and even more preferably 10 to 35 mass%.
  • total means the components derived from the polyfunctional epoxy compound having no polyethyleneoxy group when the crosslinked body does not have a component derived from the polyfunctional oxetane compound having no polyethyleneoxy group, and means the components derived from the polyfunctional oxetane compound having no polyethyleneoxy group when the crosslinked body does not have a component derived from the polyfunctional epoxy compound having no polyethyleneoxy group. It is also preferable that the crosslinked body contains, in the remainder excluding the above-mentioned components, a component derived from a monofunctional oxetane compound having no polyethyleneoxy group.
  • At least one of a monofunctional epoxy compound having no polyethyleneoxy group and a monofunctional oxetane compound having no polyethyleneoxy group may be further used.
  • the monofunctional epoxy compound having no polyethyleneoxy group and the monofunctional oxetane compound having no polyethyleneoxy group preferably do not have a hydrolyzable structural part such as an ester bond in their molecular structure.
  • the curing reaction may be carried out with at least one of the compounds represented by formula (I-1), (II-1), and (II-2), but it is preferable not to carry out the curing reaction with these compounds.
  • the allyl group may have an alkyl group as a substituent, and the alkyl group preferably has 1 to 3 carbon atoms.
  • X3 may have only one allyl group or may have two or more allyl groups.
  • Z may have only one allyl group or may have two or more allyl groups, and preferably has only one allyl group.
  • X3 and Z preferably do not have an epoxy group or an oxetanyl group.
  • X3 is preferably a monovalent group having one or more allyl groups and composed only of atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms.
  • the chemical formula weight of X 3 is preferably 40-100, more preferably 40-80, and even more preferably 40-60.
  • X3 has only one allyl group, it is preferable that the allyl group is bonded to the oxygen atom bonded to X3 in formula (II-1) directly or through an alkylene group.
  • This alkylene group is preferably an unsubstituted alkylene group.
  • the number of carbon atoms in this alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
  • X3 is particularly preferably an allyl group.
  • X3 is preferably a branched alkyl group having an allyl group as a substituent, i.e., a branched alkyl group having groups having allyl groups bonded to at least two branch ends of a branched alkyl chain.
  • the group having an allyl group bonded to the at least two branched ends preferably has a chemical formula weight of 40 to 50,000, more preferably 40 to 20,000.
  • a polyethyleneoxy structure is present between the at least two branched ends of the branched alkyl chain and the allyl group.
  • the group having an allyl group bonded to the at least two branched ends has the same structure as -O(C 2 H 4 O) n -Z in formula (II-1).
  • the branched alkyl chain may contain an oxygen atom in the chain.
  • the branched alkyl group having an allyl group as a substituent has, as a structure of the branched alkyl chain portion (branched saturated hydrocarbon structure), preferably 2 to 6 branched ends to which groups having an allyl group are bonded, more preferably 2 to 5, and even more preferably 3 to 4. Note that the number of branched ends does not include the end bonded to the oxygen atom bonded to X3 in the above formula (II-1).
  • Z is preferably a monovalent group having one or two allyl groups and composed only of atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms, and is preferably an allyl group or a monovalent group formed by combining an allyl group with an alkyl group. It is preferable that Z has only one allyl group. When Z has only one allyl group, the chemical formula weight of Z is preferably 40 to 100, more preferably 40 to 80, and even more preferably 40 to 60. When Z has only one allyl group, it is preferable that the allyl group is bonded to the oxygen atom bonded to Z in formula (II-1) directly or via an alkyl group.
  • This alkyl group is preferably an unsubstituted alkyl group, and the number of carbon atoms of this alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
  • n has the same meaning as n in formula (I-1), and the preferred range is also the same.
  • the above (c) may contain one or more compounds represented by formula (II-1).
  • n is an integer of 2 or more.
  • the crosslinked body obtained by the curing reaction of (c) if the content of the component derived from the compound represented by the above formula (II-1) is 50 mass% or more, the crosslinked body may contain components derived from at least one of the compounds represented by formula (I-I), (I-2), and (II-2), but it is preferable that the crosslinked body does not contain components derived from these compounds.
  • an allyl compound that does not have a polyethyleneoxy group (a compound that has an allyl group) may be used as a reactive monomer.
  • the allyl compound having no polyethyleneoxy group is preferably a monofunctional allyl compound or a polyfunctional allyl compound having no polyethyleneoxy group and composed of atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms.
  • the number of allyl groups possessed by the polyfunctional allyl compound is preferably 2 to 6, more preferably 2 to 5, and even more preferably 3 to 4.
  • the allyl compound having no polyethyleneoxy group preferably does not have a hydrolyzable structural portion such as an ester bond in its molecular structure.
  • the molecular weight of the allyl compound that does not have a polyethyleneoxy group is preferably 90 to 1000, more preferably 150 to 600, and particularly preferably 250 to 300.
  • the content of the component derived from the compound represented by formula (II-1) in the crosslinked body is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the content of the component derived from the compound represented by formula (II-1) in the crosslinked body may be 100% by mass.
  • the content of the component derived from the allyl compound that does not have a polyethyleneoxy group in the crosslinked body obtained by the curing reaction of (c) is 50 mass% or less, preferably 5 to 40 mass%, and more preferably 10 to 40 mass%.
  • the above (d) may contain one or more compounds represented by formula (II-2).
  • n is an integer of 2 or more.
  • polyfunctional allyl compound having no polyethyleneoxy group among the allyl compounds having no polyethyleneoxy group described in (c) above, a polyfunctional allyl compound having no polyethyleneoxy group can be used.
  • a monofunctional allyl compound having no polyethyleneoxy group may be further used.
  • the monofunctional allyl compound having no polyethyleneoxy group among the allyl compounds having no polyethyleneoxy group explained in the above (c), a monofunctional allyl compound having no polyethyleneoxy group can be used.
  • the content of the component derived from the compound represented by formula (II-2) in the crosslinked product is 50% by mass or more, preferably 55 to 98% by mass, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass.
  • the content of the component derived from the polyfunctional allyl compound having no polyethyleneoxy group in this crosslinked body is 50 mass % or less, preferably 2 to 45 mass %, more preferably 5 to 40 mass %, and further preferably 10 to 35 mass %.
  • the crosslinked product may contain, in the remainder excluding the above-mentioned components, a component derived from a monofunctional allyl compound having no polyethyleneoxy group.
  • the curing reaction may be carried out with at least one of the compounds represented by formula (I-1), (I-2), and (II-1), but it is preferable not to carry out the curing reaction with these compounds.
  • the crosslinked body obtained by the curing reaction of any of (a) to (d) may contain other components in addition to the components described above.
  • it may contain a component derived from an acid generator, a component derived from a polymerization initiator, and/or a photosensitizer, etc., as described below.
  • the curing reaction for obtaining a crosslinked body by curing (a) or (b) is preferably a cationic polymerization reaction.
  • This cationic polymerization reaction is preferably a reaction using an acid generator (a photoacid generator or a thermal acid generator) as a polymerization initiator, and more preferably a reaction using at least one of a sulfonium salt and an iodonium salt as an acid generator.
  • This cationic polymerization reaction is preferably a reaction using a photosensitizer.
  • any ordinary compound used in the ring-opening reaction of epoxy groups and oxetanyl groups can be used without any particular limitation.
  • sulfonium salts or iodonium salts can be preferably used.
  • Nonionic acid generators and ferrocene-based (having a ferrocene structure) acid generators can also be used.
  • the description in the Journal of the Adhesion Society of Japan, Vol. 56, No. 10 (2020) pp. 403-414 can be referred to.
  • the amount of the photoacid generator or thermal acid generator used is preferably 0.5 to 15 parts by mass, more preferably 1 to 12 parts by mass, and even more preferably 1.5 to 9 parts by mass, per 100 parts by mass of the total reactive monomers used in the curing reaction of (a) or (b) above (the total of all polymerizable monomers that undergo polymerization in the polymerization reaction to obtain the crosslinked body of the present invention).
  • a photosensitizer can be further used for the purpose of controlling the exposure sensitivity and/or the photosensitive wavelength.
  • the photosensitizer is not particularly limited, and any conventional photosensitizer can be used. Among them, an anthracene compound represented by the following formula (1) can be preferably used.
  • R 1 and R 2 each represent an alkyl group.
  • the alkyl group which can be taken as R 1 and R 2 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
  • the amount of photosensitizer used is preferably 0.5 to 15 parts by mass, more preferably 1 to 12 parts by mass, and even more preferably 1.5 to 9 parts by mass, per 100 parts by mass of the total reactive monomers used in the curing reaction (a) or (b).
  • the curing reaction for obtaining a crosslinked body by curing (c) or (d) above is preferably a radical polymerization reaction.
  • This radical polymerization reaction can be carried out using a conventional polymerization initiator such as an organic peroxide.
  • the amount of polymerization initiator used is preferably 0.5 to 15 parts by mass, more preferably 1 to 12 parts by mass, and even more preferably 1.5 to 9 parts by mass, per 100 parts by mass of the total of the reactive monomers used in the curing reaction of (c) or (d).
  • the conditions for the curing reaction to obtain a crosslinked product by curing any one of the above (a) to (d) can be appropriately set by referring to the usual curing reaction conditions for epoxy compounds, oxetane compounds, and vinyl compounds.
  • the illuminance of the light used for irradiation is preferably 1 to 100 mW/cm 2 , more preferably 5 to 50 mW/cm 2 , as a value at 365 nm.
  • the exposure dose is preferably 50 to 5000 mJ/cm 2 , more preferably 100 to 1000 mJ/cm 2 .
  • the photocuring reaction can also be carried out using electron beams (EB) at a dose of 100 to 2000 kGy.
  • EB electron beams
  • the heating temperature is preferably from 50 to 200° C., more preferably from 60 to 150° C., and even more preferably from 70 to 100° C.
  • the heating time is preferably from 0.5 to 60 minutes, and more preferably from 1 to 30 minutes.
  • the porous support is not particularly limited as long as it has pores that can transmit water and ions.
  • the porous support is preferably formed with a large number of fine pores that penetrate from the front surface to the back surface.
  • a porous support used in a separator for water splitting can be used.
  • the material of the porous support is preferably a resin, for example, polyphenylene sulfide, polysulfone, polypropylene, polyethylene, polymethylpentene, polyvinylidene fluoride, polytetrafluoroethylene, or the like.
  • the porous support may be any type so long as it has a porous structure, and may be a membrane in which pores are formed by forming a resin into a film and stretching it, or may be a woven fabric or a nonwoven fabric.
  • the porous support may further have an inorganic particle layer applied thereto, or may have inorganic particles composited therein. Examples of inorganic particles include zirconium oxide and magnesium hydroxide.
  • the porous support is preferably a polypropylene/polyethylene nonwoven fabric, a polyphenylene sulfide nonwoven fabric, or a polysulfone-zirconium oxide composite porous membrane.
  • the thickness of the porous support is preferably 1 to 500 ⁇ m, more preferably 5 to 400 ⁇ m, even more preferably 10 to 300 ⁇ m, and particularly preferably 20 to 200 ⁇ m.
  • the porosity of the porous support is preferably from 10 to 99%, more preferably from 20 to 95%, further preferably from 30 to 90%, and particularly preferably from 40 to 80%.
  • the porosity can be determined by calculation from the apparent volume and the theoretical volume, and specifically, it can be determined as follows.
  • Porosity (%) [1-(Y/X)] x 100
  • porous supports As examples of porous supports, reference can be made to the "porous substrate film” and “laminated porous substrate film” described in paragraphs [0018] to [0023] of JP 2018-127506 A, and the "microporous membrane” described in paragraph [0022] of JP 2022-181107 A.
  • the separator of the present invention is made of a film (a self-supporting film) formed of a crosslinked product obtained by a curing reaction of any one of (a) to (d), the thickness of this film is preferably 10 to 500 ⁇ m, more preferably 20 to 400 ⁇ m, further preferably 30 to 300 ⁇ m, and particularly preferably 40 to 200 ⁇ m.
  • the separator of the present invention is in the form of a laminate of a membrane (crosslinked membrane) formed of a crosslinked product obtained by a curing reaction of any one of (a) to (d) and a porous support
  • the thickness of the crosslinked membrane is preferably 1 to 500 ⁇ m, more preferably 2 to 400 ⁇ m, further preferably 3 to 300 ⁇ m, and particularly preferably 4 to 200 ⁇ m.
  • the thickness of the porous support is as described above.
  • the thickness of this composite is preferably 1 to 500 ⁇ m, more preferably 2 to 400 ⁇ m, even more preferably 3 to 300 ⁇ m, and particularly preferably 4 to 200 ⁇ m.
  • the thickness of the separator of the present invention can be determined by measuring the thickness at five random locations and calculating the arithmetic average using a constant pressure thickness gauge (e.g., DG-525H manufactured by Ono Sokki Co., Ltd.)
  • the thickness of the porous support described above is also determined in the same manner.
  • the thickness of the separator of the present invention is measured after drying the separator to remove moisture.
  • the ionic resistance of the separator of the present invention is preferably less than 1.00 ⁇ cm 2 , more preferably less than 0.50 ⁇ cm 2, and even more preferably less than 0.20 ⁇ cm 2 , when a 30 mass % potassium hydroxide solution is used at 80° C.
  • the ionic resistance of the separator of the present invention is usually 0.01 ⁇ cm 2 or more.
  • the ionic resistance of the separator can be measured by the method described in the Examples.
  • the water permeability of the separator of the present invention is preferably less than 300 mL/min ⁇ cm 2 ⁇ bar, more preferably less than 100 mL/min ⁇ cm 2 ⁇ bar, and even more preferably less than 20 mL/min ⁇ cm 2 ⁇ bar.
  • the water permeability of the separator can be measured by the method described in the Examples.
  • the separator of the present invention is suitable as a diaphragm separating an anode and a cathode in water electrolysis.
  • the separator can be used as a separator in alkaline water electrolysis (AWE), anion exchange membrane water electrolysis (AEMWE), and proton exchange membrane water electrolysis (PEMWE).
  • AWE alkaline water electrolysis
  • AEMWE anion exchange membrane water electrolysis
  • PEMWE proton exchange membrane water electrolysis
  • the separator of the present invention can be suitably used in alkaline water electrolysis and anion exchange membrane water electrolysis, and is particularly suitable for alkaline water electrolysis.
  • the separator of the present invention can also be formed into a form having excellent heat resistance, alkali resistance, and the like.
  • the separator in this form can be suitably used in an environment of 80 to 90°C or for alkaline water electrolysis using a high-concentration alkaline aqueous solution.
  • the separator of the present invention does not usually have a cationic group or anionic group, it can also be used in alkaline water electrolysis, anion exchange membrane water electrolysis, and proton exchange membrane water electrolysis, because the highly hydrophilic polyethyleneoxy structure can incorporate and conduct hydroxy ions and protons together with water into the separator.
  • the curable composition of the present invention is a curable composition suitable for forming a crosslinked product by a curing reaction of either the above (a) or (b).
  • the curable composition of the present invention contains (a) or (b) and an acid generator (a photoacid generator or a thermal acid generator).
  • an acid generator a photoacid generator or a thermal acid generator.
  • the content of the compound represented by formula (I-1) in the solid content of the curable composition is 50 mass% or more.
  • the content of the compound represented by formula (I-2) in the solid content of the curable composition is 50 mass% or more.
  • the (a) and (b) in the curable composition of the present invention are the same as the (a) and (b) in the separator of the present invention described above.
  • the reactive monomers that can be used in combination (in the case of (a), at least one of the compounds represented by formula (I-2), the compounds represented by formula (II-1), and the compounds represented by formula (II-2), oxetane compounds having no polyethyleneoxy groups, epoxy compounds having no polyethyleneoxy groups, etc.; in the case of (b), at least one of the monofunctional epoxy compounds having no polyethyleneoxy groups and monofunctional oxetane compounds having no polyethyleneoxy groups, and at least one of the compounds represented by formula (I-1), the compounds represented by formula (II-1), and the compounds represented by formula (II-2)).
  • the curable composition of the present invention contains a photoacid generator, it may further contain a photosensitizer.
  • Preferred aspects, contents, etc. of (a) and (b), the reactive monomer that can be used in combination, the acid generator, and the photosensitizer in the curable composition of the present invention are the same as the preferred aspects, contents, etc. of (a) and (b), the acid generator, and the photosensitizer that can be used in combination with the curable composition of the present invention explained in the separator of the present invention.
  • the curable composition of the present invention may contain a solvent, such as acetonitrile, 4-methyl-2-pentanone, methyl ethyl ketone, 1,2-dimethoxyethane, butyl acetate, or ethyl acetate.
  • a solvent such as acetonitrile, 4-methyl-2-pentanone, methyl ethyl ketone, 1,2-dimethoxyethane, butyl acetate, or ethyl acetate.
  • the solid content in the curable composition of the present invention is preferably from 1 mass % to 99 mass %, more preferably from 5 mass % to 95 mass %, and even more preferably from 10 mass % to 90 mass %.
  • the method for producing the separator of the present invention includes subjecting the above-mentioned curable composition of the present invention to a curing reaction to obtain a crosslinked product.
  • a preferred embodiment of the method for producing the separator of the present invention includes, for example, a step of subjecting a porous support body impregnated with the curable composition of the present invention to a curing reaction, thereby obtaining a composite body of the porous support body and a crosslinked body.
  • the conditions for the curing reaction are the same as those for the curing reaction of any one of the above-mentioned (a) to (d) to obtain a crosslinked product.
  • Mn is the number average molecular weight.
  • Example 1 As a porous support, a 7 cm x 7 cm polypropylene-polyethylene nonwoven fabric (manufactured by Freudengerg, film thickness about 100 ⁇ m) was prepared, and this nonwoven fabric was attached to a 10 cm x 10 cm glass plate using Kapton tape. 2 ml of the curable composition 1 in the above table was applied to the nonwoven fabric, and the nonwoven fabric was impregnated with the curable composition 1.
  • the nonwoven fabric was exposed to light using a mercury xenon lamp (product name: EXECURE-3000, manufactured by HOYA Corporation) at 10 mW/cm 2 (value at 365 nm) and an exposure dose of 500 mJ/cm 2 , and then post-baked at 90°C for 10 minutes using a hot plate. After post-baking, the glass plate was removed. In this way, the separator of Example 1 was obtained. The thickness of this separator was about 100 ⁇ m, the same as the thickness of the original nonwoven fabric.
  • a mercury xenon lamp product name: EXECURE-3000, manufactured by HOYA Corporation
  • Example 2 A separator of Example 2 was obtained in the same manner as in the production of the separator of Example 1, except that the curable composition 2 was used instead of the curable composition 1 in the production of the separator of Example 1.
  • Example 3 A separator of Example 3 was obtained in the same manner as in the production of the separator of Example 1, except that curable composition 3 was used instead of curable composition 1 in the production of the separator of Example 1.
  • Example 4 A separator of Example 4 was obtained in the same manner as in the production of the separator of Example 1, except that curable composition 4 was used instead of curable composition 1 in the production of the separator of Example 1.
  • Examples 5 to 7 Separators of Examples 5 to 7 were obtained in the same manner as in the production of the separator of Example 1, except that curable compositions 5 to 7 were used instead of curable composition 1.
  • Examples 8 to 9 In the production of the separator of Example 1, except that the curable compositions 8 to 9 were used instead of the curable composition 1, the nonwoven fabric was impregnated with the curable compositions 8 to 9 in the same manner as in the production of the separator of Example 1. Thereafter, the nonwoven fabric was irradiated with an electron beam (EB) at an acceleration voltage of 80 keV and a dose of 1000 kGy. In this manner, the separators of Examples 8 to 9 were obtained. The thickness of these separators was about 100 ⁇ m, which was the same as the thickness of the original nonwoven fabric.
  • EB electron beam
  • Comparative Example 2 The separator of Comparative Example 2 was made of only the polypropylene-polyethylene nonwoven fabric.
  • the separator of Comparative Example 1 is an anion exchange membrane and does not contain a crosslinked body obtained by a curing reaction of any of the above (a) to (d).
  • the separator of Comparative Example 1 has a low water permeability due to a dense separator structure, but has an ionic resistance of 1.00 ⁇ cm2 or more. It is presumed that the alkali resistance at 80°C in the presence of a 30% by mass potassium hydroxide solution is insufficient.
  • the separator of Comparative Example 2 was made only of polypropylene-polyethylene nonwoven fabric, and did not contain a crosslinked body obtained by a curing reaction of any of the above (a) to (d).
  • the separator of Comparative Example 2 was made only of nonwoven fabric, and therefore was prone to absorb electrolyte, and had low ionic resistance, but in return had a water permeability of 300 mL/min cm2 bar or more.
  • the separator of Comparative Example 3 contains a compound represented by formula (I-1), but the content of the constituent component derived from the compound represented by formula (I-1) is 40 mass%, which does not satisfy the provisions of the present invention.
  • the separator of Comparative Example 3 had a water permeability of 300 mL/min ⁇ cm2 ⁇ bar or more.
  • the separator of Comparative Example 3 had a high increase in water permeability of 30% or more after 24 hours at 90°C, and was poor in heat resistance and alkali resistance.
  • the separator of the present invention exhibited low ionic resistance of less than 1.00 ⁇ cm2 and low water permeability of less than 300 mL/min ⁇ cm2 ⁇ bar. It is believed that the presence of a hydrophilic polyethyleneoxy structure in a dense structure allows both low water permeability and low ionic resistance to be achieved. Moreover, the separators of Examples 1 to 7 showed a low rate of increase in water permeability after being left at 90° C. for 24 hours, and were excellent in heat resistance and alkali resistance.

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Abstract

La présente invention concerne : un séparateur qui contient un corps réticulé qui est obtenu par une réaction de durcissement d'un élément quelconque parmi (a) un composé représenté par la formule (I-1), (b) une combinaison d'un composé représenté par la formule (I-2) et d'un composé époxy ou oxétane polyfonctionnel n'ayant pas de groupe polyéthylèneoxy, (c) un composé représenté par la formule (II -1), et (d) une combinaison d'un composé représenté par la formule (II -2) et d'un composé allyle polyfonctionnel n'ayant pas de groupe polyéthylèneoxy, le composant constitutif dérivé d'un composé représenté par chaque formule étant de 50 % en masse ou plus ; une composition durcissable ; et un procédé de production du séparateur. X1 et Y représentent un groupe qui a au moins un élément parmi un groupe époxy et un groupe oxétanyle. n représente un nombre égal ou supérieur à 2, X2 et X4 représentent un atome d'hydrogène ou un groupe organique non polymérisable en chaîne. X3 et Z représentent un groupe ayant un groupe allyle.
PCT/JP2024/033927 2023-09-25 2024-09-24 Séparateur, composition durcissable et procédé de production de séparateur Pending WO2025070386A1 (fr)

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JP2003297385A (ja) * 2002-04-03 2003-10-17 Nisshinbo Ind Inc 燃料電池セパレータの製造方法、燃料電池セパレータ、および固体高分子型燃料電池
JP2009010000A (ja) * 2007-06-26 2009-01-15 Shin Etsu Polymer Co Ltd コンデンサ及びその製造方法
JP2015132828A (ja) * 2015-02-06 2015-07-23 日東電工株式会社 偏光板、該偏光板の製造方法、光学フィルムおよび画像表示装置
JP2016219106A (ja) * 2015-05-14 2016-12-22 東海カーボン株式会社 燃料電池用セパレータの製造方法
WO2018084175A1 (fr) * 2016-11-01 2018-05-11 国立研究開発法人宇宙航空研究開発機構 Cellule pour la production d'énergie de pile à combustible/électrolyse de l'eau et corps d'empilement de cellules ayant une pluralité de cellules identiques empilées
US20190036162A1 (en) * 2017-07-28 2019-01-31 Lg Chem, Ltd. Composition for gel polymer electrolyte and lithium secondary battery comprising the gel polymer electrolyte formed therefrom
JP2019121438A (ja) * 2017-12-28 2019-07-22 株式会社日本触媒 電気化学素子用セパレータ
WO2021131355A1 (fr) * 2019-12-25 2021-07-01 富士フイルム株式会社 Composition de résine, produit durci, absorbeur uv, filtre bloquant les uv, lentille, matériau protecteur, composé et procédé de synthèse de composé

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003297385A (ja) * 2002-04-03 2003-10-17 Nisshinbo Ind Inc 燃料電池セパレータの製造方法、燃料電池セパレータ、および固体高分子型燃料電池
JP2009010000A (ja) * 2007-06-26 2009-01-15 Shin Etsu Polymer Co Ltd コンデンサ及びその製造方法
JP2015132828A (ja) * 2015-02-06 2015-07-23 日東電工株式会社 偏光板、該偏光板の製造方法、光学フィルムおよび画像表示装置
JP2016219106A (ja) * 2015-05-14 2016-12-22 東海カーボン株式会社 燃料電池用セパレータの製造方法
WO2018084175A1 (fr) * 2016-11-01 2018-05-11 国立研究開発法人宇宙航空研究開発機構 Cellule pour la production d'énergie de pile à combustible/électrolyse de l'eau et corps d'empilement de cellules ayant une pluralité de cellules identiques empilées
US20190036162A1 (en) * 2017-07-28 2019-01-31 Lg Chem, Ltd. Composition for gel polymer electrolyte and lithium secondary battery comprising the gel polymer electrolyte formed therefrom
JP2019121438A (ja) * 2017-12-28 2019-07-22 株式会社日本触媒 電気化学素子用セパレータ
WO2021131355A1 (fr) * 2019-12-25 2021-07-01 富士フイルム株式会社 Composition de résine, produit durci, absorbeur uv, filtre bloquant les uv, lentille, matériau protecteur, composé et procédé de synthèse de composé

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