WO2024195459A1 - イオン交換膜、ポリオレフィン系多孔質膜、膜電極接合体、水電解装置、および、ポリオレフィン系多孔質膜の製造方法 - Google Patents

イオン交換膜、ポリオレフィン系多孔質膜、膜電極接合体、水電解装置、および、ポリオレフィン系多孔質膜の製造方法 Download PDF

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WO2024195459A1
WO2024195459A1 PCT/JP2024/007331 JP2024007331W WO2024195459A1 WO 2024195459 A1 WO2024195459 A1 WO 2024195459A1 JP 2024007331 W JP2024007331 W JP 2024007331W WO 2024195459 A1 WO2024195459 A1 WO 2024195459A1
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Prior art keywords
ion exchange
membrane
polyolefin
exchange membrane
resin
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PCT/JP2024/007331
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English (en)
French (fr)
Japanese (ja)
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まさみ 菅田
祐 三嶋
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Tokuyama Corp
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Tokuyama Corp
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Priority to JP2024539886A priority Critical patent/JP7644314B2/ja
Priority to CN202480019689.4A priority patent/CN120917087A/zh
Priority to EP24774604.3A priority patent/EP4506397A4/en
Publication of WO2024195459A1 publication Critical patent/WO2024195459A1/ja
Priority to JP2025030530A priority patent/JP2025078675A/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • 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
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • 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
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention relates to an ion exchange membrane, a polyolefin-based porous membrane, a membrane electrode assembly, a water electrolysis device, and a method for producing a polyolefin-based porous membrane.
  • Porous membranes formed from thermoplastic resins are widely used as separation membranes, selective permeable membranes, support membranes, and isolation membranes for substances.
  • Applications include, for example, battery separators used in lithium ion secondary batteries, nickel-hydrogen batteries, nickel-cadmium batteries, and polymer batteries, separators for electric double-layer capacitors, various filters such as reverse osmosis filtration membranes, ultrafiltration membranes, and microfiltration membranes, moisture-permeable waterproof clothing, medical materials, and supports for ion exchange membranes.
  • an ion exchange membrane having a porous membrane as a support and pores filled with an ion exchange resin can be used as a membrane for a polymer electrolyte fuel cell or a membrane for water electrolysis.
  • Water electrolysis is a method for producing hydrogen, in which water is electrolyzed to generate hydrogen gas and oxygen gas. Hydrogen produced using energy obtained in a way that suppresses the generation of carbon dioxide as electricity is called CO2 - free hydrogen, or green hydrogen, and is expected to be the next generation of clean energy to replace fossil fuels.
  • anion exchange membrane (AEM) water electrolysis using an AEM does not require the use of expensive noble metals as a catalyst and has attracted attention.
  • AEM water electrolysis method an alkaline aqueous solution may be used in the operating environment.
  • anion exchange membrane used in the AEM water electrolysis method it has been disclosed that a highly chemically resistant olefin-based porous membrane or nonwoven fabric is used as the support.
  • Patent Document 1 discloses an anion exchange membrane using an ultra-high molecular weight polyethylene porous membrane (Hipore (registered trademark) manufactured by Asahi Kasei Chemicals Corporation, Setira (registered trademark) manufactured by Tonen Kagaku Nasu Corporation, etc.) as a substrate.
  • Anion exchange membranes using such supports have characteristics such as low membrane resistance and excellent mechanical strength due to the presence of the support.
  • other olefin porous membranes disclosed include a dry process polypropylene porous film (Patent Document 2) and a wet process polypropylene microporous membrane (Patent Document 3), which can be suitably used as a separator for a lithium ion battery.
  • Patent Document 4 discloses an anion exchange membrane that is a porous membrane using a silane-modified polyolefin.
  • the anion exchange membrane described in Patent Document 4 has high membrane resistance and is expected to lose its toughness during use, so there is a demand for a membrane that functions adequately as an anion exchange membrane and has sufficient toughness.
  • the present invention solves the problems of the conventional techniques described above, and provides an ion exchange membrane that has high toughness and is unlikely to break even when incorporated into a water electrolysis device, and has low membrane resistance, a polyolefin-based porous membrane that can be used as a support for the ion exchange membrane, and a method for producing the polyolefin porous membrane.
  • the inventors discovered that by setting the tear characteristics of an ion exchange membrane of a specified structure within a specific range, it is possible to improve the toughness of the ion exchange membrane while reducing the membrane resistance of the ion exchange membrane, thereby improving the life of the water electrolysis device when the ion exchange membrane is installed in the device and used repeatedly.
  • the inventors also discovered that by constructing an ion exchange membrane using a polyolefin porous membrane as a support, with a toughness and (F40-F30) value of at least a predetermined value, it is possible to improve the toughness of the ion exchange membrane while reducing the membrane resistance of the ion exchange membrane, thereby improving the life of the water electrolysis device when it is installed in the device and used repeatedly.
  • the inventors also discovered that by constructing an ion exchange membrane using a polyolefin-based porous membrane manufactured by a method including a specified process as a support, it is possible to reduce the membrane resistance of the ion exchange membrane while improving the toughness of the ion exchange membrane, thereby improving the life of the water electrolysis device when the ion exchange membrane is installed in the device and used repeatedly.
  • ion exchange resins have ion exchange groups, they tend to swell when water is present. On the other hand, when water is reduced (water is no longer present), the ion exchange resins shrink. Therefore, when the ion exchange membrane is fixed with a gasket or the like, a local load may be applied at the boundary between the part fixed with the gasket and the part not fixed, due to the dimensional change caused by the swelling and shrinkage of the ion exchange membrane.
  • the ion exchange membrane of the present invention using the polyolefin porous membrane of the present invention as a support is unlikely to break even if it is repeatedly swollen and dried over a long period of time, which is thought to contribute to improving the life of the water electrolysis device.
  • the ion exchange membrane having the polyolefin porous membrane of the present invention as a support, the ion exchange membrane of the present invention, or the ion exchange membrane having the porous membrane produced by the method of the present invention as a support exhibits its effects more effectively, particularly when used as anion exchange membranes in AEM water electrolysis devices.
  • the present invention comprises the following:
  • An ion exchange membrane comprising a porous support and an ion exchange resin filled in the pores of the porous support, the ion exchange membrane having a tear strength of 3.5 N or more in each of the MD and TD directions.
  • An ion exchange membrane comprising a porous support and an ion exchange resin filled in the pores of the porous support, the ion exchange membrane having a toughness of 0.25 J or more in each of the MD and TD directions.
  • the polyolefin resin comprises a polypropylene resin.
  • An ion exchange membrane comprising the polyolefin-based porous membrane according to any one of [12] to [17] as a support, and an ion exchange resin filled in the pores of the support.
  • a membrane electrode assembly comprising the ion exchange membrane according to any one of [1] to [11] and [18] and an electrode.
  • a water electrolysis device comprising the ion exchange membrane according to any one of [1] to [11] and [18].
  • a water electrolysis device comprising the membrane electrode assembly according to [19].
  • a method for producing a polyolefin-based porous membrane comprising the following steps (a) to (d): (a) a step of melt-kneading a resin composition containing a polyolefin resin and an olefin-based elastomer, the content of the olefin-based elastomer in the resin composition being 5% by mass or more and less than 50% by mass based on the resin composition, with a plasticizer to obtain a gel-like solution; (b) cooling the gel-like solution to obtain a gel-like sheet; (c) biaxially stretching the gel-like sheet at area stretch ratios in MD and TD of 10 to 35 times to obtain a biaxially stretched gel-like film; and (d) washing the gel-like film with a solvent and drying the washed film to obtain a polyolefin-based porous membrane.
  • the ion exchange membrane having the polyolefin porous membrane of the present invention as a support, the ion exchange membrane of the present invention, or the ion exchange membrane having the porous membrane produced by the method of the present invention as a support can provide an ion exchange membrane with excellent toughness while maintaining low membrane resistance, that is, an ion exchange membrane with high toughness that is less likely to break even when incorporated into a water electrolysis device.
  • an ion exchange membrane with high toughness that is less likely to break even when incorporated into a water electrolysis device.
  • FIG. 1 is a schematic diagram of a water electrolysis device using an ion exchange membrane having the polyolefin porous membrane of the present invention as a support, an anion exchange membrane which is one embodiment of an ion exchange membrane having the ion exchange membrane of the present invention or a porous membrane produced by the method of the present invention as a support.
  • 1 is a graph showing stress-strain curves of the porous films obtained in Example 13 and Comparative Example 3.
  • the ion exchange membrane of the present invention comprises a porous support and an ion exchange resin filled in the pores of the porous support.
  • the polyolefin-based porous membrane of the present invention can be used as a porous support that serves as the base material of the ion exchange membrane.
  • the polyolefin-based porous membrane of the present invention is mainly composed of polyolefin resin.
  • the polyolefin resin constituting the polyolefin-based porous membrane includes polymers obtained by polymerizing monomers such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, and 5-methyl-1-heptene. These polymers can be used alone or in combination of two or more. Among these, polypropylene is preferably used as the main component because of its excellent heat resistance and moldability.
  • the above-mentioned main component means that the resin composition containing the above-mentioned polyolefin resin and the polyolefin-based elastomer described later is taken as the standard (100 mass%) and contains the above-mentioned polyolefin resin in an amount of 50 mass% or more, more preferably 60 mass% or more, and even more preferably 70 mass% or more.
  • the operating temperature is about 60°C to 80°C. Therefore, when used as a support for an ion exchange membrane, it is preferable that crystal relaxation does not occur at that temperature, because the physical properties of the support do not change over long-term use. From this viewpoint, it is preferable that the melting point of the polyolefin resin is 140°C or higher and 290°C or lower. The lower limit is more preferably 145°C or higher, more preferably 150°C or higher, and even more preferably 160°C or higher.
  • the upper limit is preferably 280°C or lower, more preferably 270°C or lower, and even more preferably 200°C or lower.
  • the melting point herein refers to a value measured by DSC (differential scanning calorimetry) based on JIS K7121 (1987), and all the following descriptions refer to values obtained by the above measurement.
  • the polypropylene may be a copolymer with other olefins, but from the viewpoint of mechanical strength, it is preferable that the polypropylene is a homopolymer, which is a single polymer of propylene.
  • Examples of comonomers contained as copolymers with other olefins include ethylene and ⁇ -olefins such as 1-butene, 1-pentene, 4-methylpentene-1, and 1-octene.
  • the content of these comonomers in the polypropylene is preferably 10% by mass or less, more preferably 5% by mass or less.
  • the weight average molecular weight of the polypropylene resin is preferably 1 ⁇ 10 5 or more and 5 ⁇ 10 6 or less, more preferably 5 ⁇ 10 5 or more and 2.5 ⁇ 10 6 or less, and even more preferably 9 ⁇ 10 5 or more and 2 ⁇ 10 6 or less. If the weight average molecular weight is less than 1 ⁇ 10 5 , the entanglement between the molecules cannot be sufficiently ensured, so that the film may break during film formation or the strength of the porous film may be insufficient. If the weight average molecular weight is 5 ⁇ 10 6 or more, the viscosity may be too high, so that the thickness uniformity may be deteriorated or the moldability may be deteriorated.
  • the weight average molecular weight is too high, the internal pressure of the extruder is likely to be high during melt kneading, so that the size of the extruder must be excessively large relative to the discharge amount, which is not preferable because it leads to an increase in cost.
  • the molecular weight distribution of the polypropylene resin is preferably about 5 or more and 10 or less. When the molecular weight distribution is within the above range, the workability is improved when melt-kneading with a plasticizer and extruding in the wet method for producing a porous membrane described later.
  • the melt flow rate (MFR) of the polypropylene resin is preferably 0.3 g/10 min or more and less than 1.0 g/10 min. If the MFR is within the above range, the workability when melt-kneading with the plasticizer and extruding is good, as is the molecular weight distribution.
  • the resin composition constituting the polyolefin-based porous membrane of the present invention preferably contains an olefin-based elastomer in order to improve the toughness as a substrate.
  • the olefin-based elastomer include ethylene- ⁇ -olefin copolymer, propylene- ⁇ -olefin copolymer, 1-butene- ⁇ -olefin copolymer, etc.
  • the polyolefin resin is polypropylene, it is preferable to use a propylene- ⁇ -olefin copolymer from the viewpoint of compatibility.
  • the propylene- ⁇ -olefin copolymer may be a binary copolymer such as a propylene-ethylene copolymer, or a ternary copolymer such as a propylene-ethylene-butene copolymer.
  • the arrangement of the monomers may be a random copolymer or a block copolymer.
  • the resin is plasticized by the plasticizer, which accelerates molecular diffusion of the polyolefin resin, and in the case of a polyolefin resin with high crystallinity, this may result in the formation of coarse crystals with a high-order structure. If the high-order structure of the crystals becomes coarse, unevenness will occur between sufficiently oriented and not oriented parts in the subsequent stretching process, which may result in embrittlement when filled with ion exchange resin.
  • the inventors have found that by adding a certain amount of olefin-based elastomer to polyolefin resin, not only can the toughness of the porous film be improved, but the crystal structure of the main component polyolefin resin can be refined, and the coarse high-order structure that is likely to occur in wet porous film production can be suppressed.
  • the proportion of the olefin-based elastomer is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less.
  • the content of the olefin-based elastomer is less than 5% by mass, the effect of improving the toughness of the substrate cannot be sufficiently obtained, and the membrane may become brittle in the mechanical property evaluation of the ion exchange membrane using the produced porous membrane as a substrate. If the content exceeds 50% by mass, the pores of the porous membrane may be blocked because the properties of the elastomer are too strong. If the pores are blocked, the porosity of the porous membrane is low and the air resistance is too high, so that the ion exchange capacity of the final ion exchange membrane may decrease and the membrane resistance may increase.
  • a porous membrane with excellent toughness and toughness can be obtained by combining with the membrane production method described later.
  • the melting point of the olefin-based elastomer is not particularly limited, but from the viewpoint of preventing clogging of pores during film formation, it is preferable that the melting point of the polyolefin resin, which is the main component, is not less than (melting point of polyolefin resin - 15) °C and not more than (melting point of polyolefin resin + 5) °C.
  • additives can be blended into the resin composition as necessary.
  • additives include antioxidants such as phenol-based, phosphorus-based, and sulfur-based, nucleating agents such as aromatic phosphate metal salt-based, benzoic acid metal salt-based, and sorbitol-based, light stabilizers, and antistatic agents.
  • antioxidants such as phenol-based, phosphorus-based, and sulfur-based
  • nucleating agents such as aromatic phosphate metal salt-based, benzoic acid metal salt-based, and sorbitol-based, light stabilizers, and antistatic agents.
  • These additives may be blended directly into the resin composition, or may be blended as a master batch in which the additives are mixed in advance with the polyolefin resin.
  • the blending amount of each additive is not particularly limited, but is usually 0.01% by mass or more and 5.00% by mass or less with respect to the resin composition.
  • examples of the nucleating agent for polypropylene include ⁇ -crystal nucleating agents and ⁇ -crystal nucleating agents, but it is preferable not to include a ⁇ -crystal nucleating agent.
  • a ⁇ -crystal nucleating agent is used, needle-shaped crystals are formed, which may cause strong anisotropy in the initial high-order structure. Therefore, when polypropylene is used, it is better to use an ⁇ -crystal nucleating agent as the crystal nucleating agent.
  • the crystalline fusion heat peak derived from ⁇ crystals appears at a lower temperature than the crystalline fusion heat peak derived from ⁇ crystals. Specifically, in the case of homopolypropylene, it is found in the range of 120°C to 150°C.
  • the resin is first heated, melted, and mixed with a plasticizer.
  • the resulting resin solution is then extruded through a die and cooled to form a gel-like sheet.
  • the resulting gel-like sheet is stretched in at least one direction, after which the plasticizer is removed with a solvent and the sheet is dried to obtain a porous film.
  • the crystals are torn to open the holes, resulting in coarse pores and poor strength, but no cleaning process is required, making it less costly to manufacture.
  • the porous membrane made of polypropylene resin is manufactured by dry method, but the porous membrane of the present invention is preferably manufactured by wet method.
  • the manufacturing method of the polyolefin porous membrane of the present invention comprises the following steps (a) to (d).
  • steps such as heat treatment, aging, corona treatment, and hydrophilization treatment may be carried out as necessary.
  • the step of obtaining a gel-like solution is preferably a method in which a resin composition containing a polyolefin resin and an olefin-based elastomer, and various additives as necessary, are introduced into a kneader, and while heating and melting the mixture, a plasticizer is added up to a predetermined amount, and the mixture is further kneaded to mix uniformly.
  • the plasticizer is not particularly limited as long as it has sufficient compatibility with the resin composition.
  • plasticizers examples include stearyl alcohol, ceryl alcohol, paraffin wax, polyethylene oxide, etc.
  • aromatic carboxylic acid esters are preferably used because they are easy to form holes in the porous membrane, and are easy to mold with little bleeding out during the manufacturing process.
  • liquid paraffin or paraffin wax is used, it is difficult to open holes compared to when aromatic carboxylic acid esters are used, so a large amount of them is required, which may increase costs.
  • plasticizers can be used alone or in combination.
  • the amount of plasticizer to be added is preferably 40% by mass or more and 70% by mass or less, based on the gel solution (100% by mass) which is the sum of the resin composition and the plasticizer.
  • the lower limit is more preferably 50% by mass or more, and even more preferably 55% by mass or more. If the amount of plasticizer to be added is less than 40% by mass, a sufficient number of holes will not be formed, and the ion exchange capacity of the finally obtained ion exchange membrane may decrease and the membrane resistance may increase.
  • the upper limit is more preferably 65% by mass or less, and even more preferably 60% by mass or less.
  • the amount of plasticizer exceeds 70% by mass, the viscosity may be too low, which may deteriorate the workability during film formation, or the entanglement of the molecular chains may become weak, which may reduce the strength of the obtained porous membrane.
  • the amount of plasticizer to be added in the above preferred range, a membrane that has sufficient strength and pore formation to be used as a substrate for AEM can be obtained by the film formation method described below, without causing a decrease in extensibility during film formation.
  • the method and device for kneading the resin composition, plasticizer, and various additives as required are not particularly limited as long as they can be melt-kneaded uniformly.
  • Each raw material may be directly fed into the extruder, but to knead uniformly, the polyolefin resin, olefin-based elastomer, and solids of various additives may be premixed in advance using a Henschel mixer or the like and then fed into the kneader.
  • a Henschel mixer or the like As the kneader, for example, a small batch kneader such as the Labo Plastomill manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • a continuous kneader such as a twin-screw extruder may be used.
  • a method using a twin-screw extruder for example, the methods described in JP-B-06-104736 and Japanese Patent No. 3347835 may be used.
  • the resin composition is mixed with the plasticizer and various additives added as necessary at a temperature at which the resin composition is completely melted.
  • the melt-kneading temperature varies depending on the polyolefin resin used, but the lower limit is preferably (melting point of polyolefin resin + 5°C), and more preferably (melting point of polyolefin resin + 10°C).
  • the upper limit is preferably (melting point of polyolefin resin + 70°C), and more preferably (melting point of polyolefin resin + 60°C). Since the melting point of polypropylene in this invention is approximately 160°C to 180°C, the melt-kneading temperature is preferably 165°C to 250°C.
  • the lower the melt-kneading temperature the better; however, if the melt-kneading temperature is too low, unmelted resin will be generated, which may cause process defects such as film breakage and uneven stretching in the subsequent stretching process. Furthermore, unmelted resin may cause poor appearance and uneven thickness in the final porous film. If the melt-kneading temperature is too high, resin deterioration may reduce the mechanical strength of the final porous film.
  • the ratio (L/D) of the screw length (D) to the diameter (L) is preferably 25 or more and 80 or less.
  • the lower limit is preferably 30 or more, more preferably 35 or more.
  • the upper limit is preferably 70 or less, more preferably 60 or less.
  • the rotation speed (N) of the extruder is preferably 100 rpm or more and 400 rpm or less.
  • the rotation speed is too high, the resin may be deteriorated due to shearing of the screw, so a low rotation speed is preferable, but if the rotation speed is too low, unmelted material may be generated due to poor kneading, so it is sufficient to adjust it appropriately while checking the properties of the extruded resin.
  • step of obtaining a gel-like sheet the gel-like solution is formed into a sheet shape and then cooled to obtain a gel-like sheet.
  • the sheet can be obtained by cooling the gel liquid once at room temperature and then press-molding it again at a temperature equal to or higher than the melting point of the gel liquid, or by supplying the gel liquid from an extruder to a die and extruding the gel solution from the die.
  • the extrusion method may be either the T-die method or the inflation method, but from the viewpoint of achieving a uniform thickness, it is preferable to use the T-die method.
  • the gel-like sheet may be a single layer membrane, or may have a multi-layer structure of two or more layers.
  • Known methods for producing a multi-layer gel-like sheet include a method in which separate gel-like sheets are produced and then heat-sealed, and a co-extrusion method in which the resins of each layer are fed from separate extruders to a single die and extruded while being integrated.
  • a substrate for an ion exchange membrane it is preferable to use the co-extrusion method, from the viewpoints that the adhesive strength between the layers is high and that it is easy to form communicating holes between the layers.
  • the cooling method for forming the sheet can be any known method, such as direct contact with cooling air, cooling water, or other cooling medium, or contact with a roll cooled with a refrigerant.
  • a temperature between 0°C and 25°C is preferable from the standpoint of compatibility with workability, such as preventing condensation. Cooling must be performed until both sides reach a crystallization end temperature or lower.
  • the crystallization end temperature refers to the extrapolated crystallization end temperature measured in accordance with JIS K7121 (1987).
  • the thickness of the gel-like sheet is not particularly limited, but is set appropriately depending on the thickness of the desired porous membrane, and is preferably approximately 0.2 mm to 5 mm, more preferably 0.5 mm to 3 mm.
  • the obtained gel-like sheet is stretched in biaxial directions.
  • the stretching method is performed by a tenter method or a roll method, or a combination of these.
  • biaxial stretching simultaneous biaxial stretching, sequential biaxial stretching, or a combination of these may be used.
  • the stretching may be one-stage stretching or multi-stage stretching.
  • tenter stretching may be performed in a batch manner.
  • the lower limit of the area stretching ratio (longitudinal ratio x lateral ratio), which is the sum of the longitudinal and lateral ratios in the stretching process, is preferably 10 times or more, more preferably 12 times or more, and even more preferably 16 times or more. If the lower limit is within the above preferred range, the initial crystal structure generated in the gel-like sheet can be sufficiently refined to improve the mechanical strength. If the lower limit is less than 10 times, the higher-order structure of the crystals that remain unrefined becomes the starting point, and when an ion exchange membrane is produced using the obtained porous membrane as a substrate, embrittlement is likely to occur.
  • the upper limit of the area stretching ratio is preferably 40 times or less, more preferably 35 times or less, even more preferably 30 times or less, and particularly preferably less than 25 times.
  • the higher the area stretching ratio the higher the strength of the porous membrane, but excessive orientation progresses and the entanglement of the molecular chains becomes weak, so that the elongation decreases when made into an ion exchange membrane, and as a result, the toughness may decrease.
  • Whether the area magnification is sufficient can be determined by the (F40 - F30) value described below.
  • the stretching temperature is preferably set to a temperature equal to or lower than the melting point of the polyolefin resin, which is the main component, and more preferably, is in the range of (polyolefin resin crystal dispersion temperature Tcd) to (polyolefin resin melting point -5°C), where Tcd is the crystal dispersion temperature of the polyolefin resin. If the temperature is equal to or lower than (polyolefin resin melting point -5°C), the resin can be prevented from fusing to the clips and stretching rolls that hold the sheet during stretching.
  • the crystal dispersion temperature Tcd of the polyolefin resin can be determined from the temperature characteristics of dynamic viscoelasticity measured according to ASTM D4065 using a sheet that is ice-cooled at 0°C after melt pressing the resin composition at melting point +50°C.
  • the stretching temperature is preferably 110° C. or higher and 175° C. or lower, more preferably higher than 115° C. and lower than 160° C., and even more preferably 120° C. or higher and 155° C. or lower.
  • the respective stretching temperatures may be the same or different.
  • the stretching is performed while the gel-like sheet contains a plasticizer.
  • the crystal structure can be uniformly crushed, and the toughness of the porous film can be improved.
  • the pores are formed uniformly and densely, making it less likely that embrittlement due to coarseness or density of the ion exchange resin will occur.
  • step (d) Step of washing and drying the gel film to obtain a porous film.
  • the gel film obtained in step (c) is washed with a solvent to extract the plasticizer.
  • the solvent for extracting the plasticizer is not particularly limited as long as it is a poor solvent for the resin composition and a good solvent for the plasticizer.
  • the solvent include hydrocarbons such as n-hexane and cyclohexane, fluorocarbons in which some or all of the hydrogen in the hydrocarbons are replaced with fluorine, alcohols such as ethanol and isopropanol, and ketones such as acetone and 2-butanone.
  • washing method a method of immersing the gel film in a solvent, a shower method, or a combination of these methods can be used.
  • the washing solvent after washing can be removed by air drying, heat drying, or the like. From the viewpoint of suppressing the blocking of the pores due to heating and the destruction of the pore structure due to the rapid evaporation of the washing solvent, it is preferable to dry at a low temperature of less than 50°C.
  • a heat treatment may be performed to stabilize the porous film.
  • Heat treatment stabilizes the crystal structure and relieves residual strain, stabilizing the dimensions and the crystal structure within the film.
  • the higher the heat treatment temperature the faster stabilization can be achieved, but a high temperature can cause sudden shrinkage or pore blockage due to melting of the crystals, so it should be adjusted appropriately to suit the desired porosity.
  • the polyolefin-based porous membrane of the present invention has high mechanical properties, so when it is used as the support of ion-exchange membrane, it can obtain the excellent ion-exchange membrane with excellent toughness and excellent effect of suppressing embrittlement.
  • the properties of the polyolefin-based porous membrane of the present invention are described below. The measuring method of each property will be described in detail in the embodiment.
  • the thickness of the polyolefin-based porous membrane of the present invention is not particularly limited. However, in order to exhibit suitable performance as a support for an ion exchange membrane, it is preferable that the thickness is 10 ⁇ m or more and 150 ⁇ m or less. From the viewpoint of reducing the membrane resistance when used as an ion exchange membrane, the thinner the thickness, the lower the gas barrier property and mechanical strength. In particular, in the AEM water electrolysis using an anion exchange membrane, a high pressure is applied to the membrane, so it is preferable that the membrane has a certain thickness from the viewpoint of mechanical strength and gas barrier property. Therefore, the thickness of the porous membrane is more preferably 15 ⁇ m or more and 120 ⁇ m or less, and even more preferably 25 ⁇ m or more and 100 ⁇ m or less.
  • the porosity of the polyolefin-based porous membrane of the present invention is preferably 10% or more and less than 50%.
  • the lower limit of the porosity is more preferably 15% or more, more preferably 20% or more, and particularly preferably 30% or more. If the porosity is less than 10%, when used as a support for an ion exchange membrane, the amount of ion exchange resin filled is reduced, so that the ion conductivity is likely to deteriorate and the membrane resistance is likely to increase.
  • the porosity is more than 50%, the expansion of the ion exchange resin due to water absorption in a wet state cannot be suppressed when used as an ion exchange membrane, and the shape of the ion exchange membrane may not be maintained.
  • the upper limit of the porosity is more preferably 45% or less.
  • the air resistance per 20 ⁇ m of the polyolefin-based porous membrane of the present invention is preferably 300s/100ccAir or more and 7000s/100ccAir.
  • the lower limit of the air resistance per 20 ⁇ m is preferably 400s/100ccAir or more, more preferably 500s/100ccAir. If the air resistance per 20 ⁇ m is lower than 300s/100ccAir, when it is used as the support of ion exchange membrane, it may have poor gas barrier properties.
  • the upper limit of the air resistance per 20 ⁇ m of polyolefin-based porous membrane is preferably 5000s/100ccAir or less, more preferably 2500s/100ccAir or less, and even more preferably 1350s/100ccAir or less.
  • the impregnation of the ion exchange resin may become slow, which may deteriorate the productivity, and the membrane resistance of the obtained ion exchange membrane may become high.
  • the lower limit of the tensile elastic modulus in the MD direction (length direction of the membrane surface, machine direction) and TD direction (direction perpendicular to the MD direction, width direction of the membrane surface) of the polyolefin-based porous membrane of the present invention is preferably 200 MPa or more, more preferably 300 MPa or more, and even more preferably 400 MPa or more.
  • the upper limit of the elastic modulus is preferably 1200 MPa or less, more preferably 1000 MPa or less.
  • the elastic modulus is in the preferred range, it is less likely to wrinkle when used as a support for an ion exchange membrane, and has excellent handling properties.
  • the elastic modulus of the ion exchange membrane finally obtained can also be increased.
  • the ratio of the elastic modulus in the MD direction to the elastic modulus in the TD direction is preferably 0.5 or more and 1.5 or less. If the elastic modulus ratio is outside this range, the anisotropy will be so strong that when used as a support for an ion exchange membrane, the dimensional change when the ion exchange membrane swells will be anisotropic, and when the membrane is incorporated into a water electrolysis device and used, wrinkles and other defects may occur due to the difference in dimensional change.
  • the toughness of the polyolefin-based porous membrane of the present invention in the MD direction and the TD direction is preferably 0.35 J or more.
  • toughness is one of the parameters that indicate the tenacity of a material, and refers to the amount of energy that is required until the material breaks when it is pulled. Specifically, as described in L. E. Nielsen (Shigeharu Onogi); "Kinematic Properties of Polymers” 98-100, Kagaku Dojin (1965), it can be obtained from the area of the stress-strain curve obtained in tensile test.
  • the toughness of a polyolefin-based porous membrane is 0.35 J or more, when used as a support for an ion exchange membrane, it exhibits an excellent effect of suppressing embrittlement, and it is possible to obtain a strong ion exchange membrane that is not easily broken.
  • the lower limit of the toughness is more preferably 0.40 J or more. The higher the toughness, the better, but the practical upper limit is about 1.5 J.
  • the (F40-F30) in the MD and TD directions of the polyolefin-based porous membrane of the present invention is preferably 2.0 MPa or more.
  • the crystal structure in the porous membrane is sufficiently finely divided and oriented. If the structure is not finely oriented or oriented enough, even if the porous membrane has high mechanical properties, it may become significantly brittle when filled with ion-exchange resin.(F40-F30) is used as a parameter to determine this finely oriented and oriented.
  • the inventors have found that when the value of (F40-F30) is less than 2.0 MPa, even if the porous membrane has sufficient toughness, it tends to become brittle when used as a support for an ion exchange membrane.
  • the lower limit of (F40-F30) is preferably 2.0 MPa or more, more preferably 2.5 MPa or more, and even more preferably 3.0 MPa or more.
  • the polyolefin-based porous membrane of the present invention has the above-mentioned (F40-F30) characteristics in both the MD and TD directions.
  • the method of supporting the ion exchange resin is not particularly limited, but for example, the following four methods can be mentioned.
  • a polymerizable composition containing an ion-exchange group-containing monomer (or a solution of the polymerizable composition, if necessary) is brought into contact with a porous membrane to fill the pores of the porous membrane with the polymerizable composition.
  • the polymerizable composition that has filled the pores is then polymerized.
  • a polymerizable composition consisting of only the ion-exchange group-containing monomer may be used, or a polymerizable composition containing the ion-exchange group-containing monomer and other monomers that are blended as necessary may be used.
  • the other monomers may include a crosslinking agent that is multifunctional, such as divinylbenzene.
  • a polymerizable composition containing a monomer capable of introducing an ion exchange group (or a solution of the polymerizable composition, if necessary) is brought into contact with a porous membrane, and the pores of the porous membrane are filled with the polymerizable composition.
  • the polymerizable composition is then polymerized. Thereafter, an ion exchange group is introduced into the resulting precursor polymer in which the monomer capable of introducing an ion exchange group is polymerized. More detailed explanation is as follows.
  • the polymerizable composition is filled into the voids of the porous membrane, and then polymerized and cured to prepare a precursor of an ion exchange membrane filled with a resin having a halogenoalkyl group.
  • the halogenoalkyl group is converted into an ion exchange group to form an ion exchange membrane.
  • a polymerizable monomer having a halogenoalkyl group is exemplified, but it is also possible to prepare a precursor of the precursor before introducing the halogenoalkyl group using, for example, styrene, etc., and then introduce the halogenoalkyl group into the precursor. After the introduction of the halogenoalkyl group, the same operations as described above may be carried out.
  • polymerizable composition containing an ion-exchange group-containing monomer.
  • the resulting solution containing the ion-exchange group-containing polymer is brought into contact with the polyolefin-based porous membrane described above to produce an ion-exchange membrane in which the ion-exchange resin (the polymer) fills at least the pores.
  • the polymerizable composition can also contain other monomers containing crosslinking agents, but care must be taken because if the degree of crosslinking becomes too high, the solubility of the ion-exchange group-containing polymer tends to decrease.
  • a polymerizable composition containing a monomer capable of introducing an ion exchange group is polymerized.
  • a solution of the resulting polymer is brought into contact with a porous membrane, and the pores of the porous membrane are filled with the polymer (a precursor polymer formed by polymerizing a monomer capable of introducing an ion exchange group).
  • an ion exchange group is introduced into the precursor polymer formed by polymerizing a monomer capable of introducing an ion exchange group.
  • other monomers including a crosslinking agent can also be blended into the polymerizable composition, but care must be taken because if the degree of crosslinking becomes too high, the solubility of the precursor polymer tends to decrease.
  • method (1) or (2) it is preferable to adopt a method in which a monomer composition of polymerizable monomers is first impregnated into a porous membrane, then polymerized, and ion exchange groups are introduced as necessary.
  • This ion exchange resin is not particularly limited, but considering compatibility with the porous membrane, adhesion, etc., it is preferable that the resin portion excluding the ion exchange group is composed of a crosslinked hydrocarbon polymer.
  • the hydrocarbon polymer refers to a polymer that does not substantially contain carbon-fluorine bonds and the majority of the bonds in the main chain and side chain that constitute the polymer are composed of carbon-carbon bonds.
  • This hydrocarbon polymer may contain a small amount of other atoms such as oxygen, nitrogen, silicon, sulfur, boron, phosphorus, etc. between the carbon-carbon bonds through ether bonds, ester bonds, amide bonds, siloxane bonds, etc.
  • the atoms bonded to the main chain and side chains do not all need to be hydrogen atoms, and may be substituted with other atoms such as chlorine, bromine, fluorine, iodine, etc., or with a substituent containing other atoms, as long as the amount is small.
  • the amount of these elements other than carbon and hydrogen is preferably 40 mol % or less, preferably 10 mol % or less, of all elements that constitute the resin (polymer) excluding the ion exchange group.
  • the anion exchange group in the anion exchange membrane (the anion exchange group of the anion exchange resin filled in the voids of the porous membrane) is not particularly limited, but is preferably a quaternary ammonium base or a pyridinium base in consideration of ease of production, ease of availability, and the like.
  • the counter ion of the anion exchange group is often obtained as a halogen ion.
  • ion-exchange the counter ion of the anion exchange membrane having the halogen ion as the counter ion into the OH- type by, for example, immersing the anion exchange membrane having the halogen ion as the counter ion in an excess amount of an alkaline aqueous solution.
  • the ion exchange method there is no particular limitation on the ion exchange method, and it is possible to use a known method, for example, immersing the anion exchange type electrolyte membrane having the halogen ion as the counter ion in an aqueous solution of sodium hydroxide or potassium hydroxide for 2 to 10 hours.
  • the cation exchange groups in the cation exchange membrane are not particularly limited, but are preferably sulfonic acid or carboxylic acid types in consideration of ease of production, availability, etc.
  • the ion exchange membrane of the present invention uses a polyolefin-based porous membrane having high toughness and high (F40-F30) as a support, and therefore, when incorporated in a water electrolysis device, the membrane is unlikely to be damaged even after long-term use, which contributes to extending the life of the water electrolysis device.
  • the characteristics of the ion exchange membrane of the present invention are described below.
  • Ion exchange capacity (meq./g)
  • the ion exchange capacity of the ion exchange membrane of the present invention is not particularly limited. However, in order to exhibit suitable performance as an ion exchange membrane, it is preferably 1.0 meq. /g or more, more preferably 1.2 meq. /g, and even more preferably 1.4 meq. /g.
  • the upper limit is preferably 6.0 meq. /g or less.
  • the membrane resistance of the ion exchange membrane of the present invention is not particularly limited. However, in order to exhibit suitable performance as an ion exchange membrane, the membrane resistance per 20 ⁇ m is 0.5 ⁇ cm 2 or less. When the membrane resistance per 20 ⁇ m is 0.5 ⁇ cm 2 or less, when the membrane is incorporated into, for example, a hydrogen production device, the device can be operated at a low voltage, and the energy consumption is excellent.
  • the tear strength (N) in the MD and TD directions of the ion exchange membrane of the present invention is preferably 3.5 N or more.
  • the lower limit of the tear strength is more preferably 4.0 N or more, and even more preferably 5.0 N or more.
  • the boundary portion may be torn. Since the ion exchange membrane of the present invention has high tear strength, the membrane is unlikely to be torn even during long-term use and has a long life. The higher the tear strength, the more preferable it is. However, the practical upper limit is about 15N.
  • the toughness in the MD direction and the TD direction of the ion exchange membrane of the present invention is preferably 0.25 J or more.
  • toughness is a parameter indicating the tenacity of a material. Since the ion exchange membrane of the present invention has high toughness, it is strong as a material, is not easily broken when handled, and has excellent handling properties. In addition, like the tear strength, it is not easily broken because of its toughness, and has excellent life.
  • the lower limit of the toughness is more preferably 0.30 J or more. The higher the toughness, the more preferable it is, but the practical upper limit is 1.00 J or less.
  • the elastic modulus of the ion exchange membrane of the present invention in the MD direction and the TD direction is not particularly limited, but is preferably 500 MPa or more.
  • the lower limit of the elastic modulus is more preferably 600 MPa or more, and even more preferably 1000 MPa or more. If the elastic modulus is high, for example, when the obtained ion exchange membrane is transported in the next process, it is less likely to wrinkle and has excellent handling properties. The higher the elastic modulus, the more preferable it is, but the substantial upper limit is 1800 MPa or less.
  • the thickness of the ion exchange membrane of the present invention is not particularly limited. However, in order to exhibit suitable performance as an ion exchange membrane, it is preferable that the thickness is 10 ⁇ m or more and 200 ⁇ m or less. From the viewpoint of reducing the membrane resistance of the ion exchange membrane, the thinner the thickness, the lower the gas barrier property and mechanical strength. In particular, in the AEM water electrolysis using an anion exchange membrane, the membrane is subjected to high pressure, so it is preferable that the membrane has a certain thickness from the viewpoint of handling property and gas barrier property. Therefore, the thickness of the ion exchange membrane is more preferably 15 ⁇ m or more and 170 ⁇ m or less, and even more preferably 25 ⁇ m or more and 150 ⁇ m or less.
  • a membrane electrode assembly (MEA) can be manufactured.
  • the MEA is a composite membrane in which an ion exchange membrane and an electrode are integrated.
  • the integrated electrodes may include a first electrode which is a cathode and a second electrode which is an anode.
  • the membrane electrode assembly may include only a catalyst electrode layer, or may include a gas diffusion layer.
  • the membrane electrode assembly may have an ion exchange membrane interposed between the first electrode and the second electrode.
  • the electrode may contain a metal catalyst and, optionally, an ion conductor, a conductive agent, and a binder.
  • the proportions of the metal catalyst, ion conductor, conductive agent, and binder in the electrode may be adjusted appropriately depending on the materials used.
  • the metal catalyst promotes an oxidation or reduction reaction.
  • the metal catalyst is typically in the form of particles.
  • the metal catalyst that can be used include platinum, gold, silver, palladium, iridium, rhodium, ruthenium, tin, iron, cobalt, nickel, manganese, molybdenum, tungsten, vanadium, chromium, tantalum, zirconium, aluminum, zinc, oxides or hydroxides thereof, or alloys thereof.
  • the metal catalyst for the anode preferably contains nickel.
  • the metal catalyst for the cathode preferably contains platinum, gold, silver, palladium, iridium, rhodium, ruthenium, tin, iron, cobalt, nickel, manganese, or alloys thereof.
  • the ion conductive agent enhances the ion conductivity of the electrode.
  • the ion conductive agent include perfluorocarbon polymers, aromatic polyether ether ketones, polysulfones, etc., each of which has an acidic functional group. Ion exchange resins may also be used as the ion conductive agent.
  • the conductive agent enhances the electronic conductivity of the electrode.
  • the conductive agent may be used as a support for a metal catalyst. Examples of the conductive agent include carbon black, activated carbon, graphite, fullerene, carbon nanotubes, and mixtures thereof.
  • the binder increases the rigidity of the electrode.
  • binders that can be used include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine-based rubber, polyacrylic acid compounds, imide compounds, or mixtures of these.
  • the method for producing the membrane electrode assembly is not particularly limited, and any known method may be used.
  • the following method may be used.
  • First, an ion exchange membrane is prepared.
  • the ion exchange membrane may be in a wet state, but is preferably in a dry state.
  • the metal catalyst is mixed with, optionally, an ion conductive agent, a conductive agent, a binder, and an organic solvent to prepare a first electrode forming composition and a second electrode forming composition, respectively.
  • These electrode forming compositions are, for example, applied onto a release paper to obtain a coating film.
  • the coating film is dried.
  • the dried coating film is peeled off from the release paper and laminated on one main surface and the other main surface of the ion exchange membrane, respectively.
  • An ion conductive agent may be applied in advance onto each main surface of the ion exchange membrane.
  • the first electrode forming composition and/or the second electrode forming composition may be directly applied onto each main surface of the ion exchange membrane to form a coating film.
  • the obtained laminate is heated, pressurized, or both to integrate the first and second coating films with the ion exchange membrane.
  • a membrane electrode assembly is obtained in which the first electrode, the ion exchange membrane, and the second electrode are laminated in this order. Note that either the first electrode or the second electrode may be omitted, and an electrode may be provided on only one side of the ion exchange membrane.
  • a water electrolysis device can be formed using the ion exchange membrane or membrane electrode assembly (MEA) of the present invention described above.
  • MEA ion exchange membrane or membrane electrode assembly
  • AEM anion exchange membrane
  • the configuration of the water electrolysis device is as shown in Figure 1.
  • the water electrolysis device may be a water electrolysis device that uses water or a low-concentration alkaline aqueous solution, or may be a device that uses a high-concentration alkaline aqueous solution of 5 mass % or more.
  • catalyst layers in which a catalyst is dispersed in an anion exchange resin are disposed on an anion exchange membrane 1, and each is provided with a gas diffusion layer 4.
  • the configuration of the gas diffusion layer 4 is not particularly limited, and a porous material such as graphite fiber that is generally used in AEM type water electrolysis devices can be used.
  • the above-mentioned MEA may be used instead of the anion exchange membrane 1, the anode 2, and the cathode 3.
  • the anode chamber 5 on the anode 2 side is provided with a water supply port 6 for supplying water and an oxygen outlet 7 for discharging oxygen.
  • the cathode chamber 8 on the cathode 3 side is provided with a hydrogen outlet 9 for discharging hydrogen.
  • hydrogen can be produced by water electrolysis.
  • the anion exchange membrane functions as a solid electrolyte membrane that transfers ions between the anode and the cathode, and also plays a role in suppressing the mixing of oxygen gas generated at the anode and hydrogen gas generated at the cathode.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyolefin resin and the olefin-based elastomer were determined by gel permeation chromatography (GPC) under the following conditions. Note that the molecular weights are relative to polystyrene and dibenzyl standards. From Mw and Mn, the molecular weight distribution was calculated as Mw/Mn.
  • Apparatus High-temperature GPC apparatus (Tosoh, HLC-8321GPC/HT) Detector: Differential refractive index detector RI Column: Shodex HT-G, Shodex HT-806M (Showa Denko) Solvent: 1,2,4-trichlorobenzene Flow rate: 1.0 mL/min Column temperature: 145° C. ⁇ Injection volume: 0.200mL Standard samples: Monodisperse polystyrene manufactured by Tosoh, dibenzyl manufactured by Tokyo Kasei
  • MFR Melting Point
  • the MFR of the polyolefin resin and the olefin-based elastomer were measured based on JIS K 7210-1: 2014.
  • the melting points of the polyolefin resin and the olefin-based elastomer were measured by DSC based on JIS K 7121 (1987).
  • ⁇ Thickness ( ⁇ m)> The thickness of a porous membrane cut to 120 mm x 120 mm was measured at a total of nine points at 30 mm intervals in both the width and length directions using a contact thickness meter (Mitutoyo Corporation, Digital Indicator ID-H0530), and the measured thickness was recorded as the membrane thickness.
  • ⁇ Porosity (%)> The volume V (cm 3 ) and mass M (g) of the porous membrane were measured, and the porosity P was calculated using the following formula, where ⁇ is the density (g/cm 3 ) of the resin composition forming the porous membrane. P 100 ⁇ (1-M/( ⁇ V))
  • the density of the resin composition was determined by melting the resin composition at its melting point + 50°C, pressing it to a thickness of about 0.1 mm using a compression molding machine, and quenching it in ice water at 0°C to obtain a sheet.
  • the obtained stress ⁇ was plotted on the vertical axis and the strain ⁇ on the horizontal axis to obtain a stress-strain curve. From this stress-strain curve, the following tensile properties (1) to (4) were obtained. Note that each value was measured in both the MD and TD directions.
  • a dried chloride ion type membrane was used, which was obtained by immersing the ion exchange membrane in a 0.5 mol/L NaCl aqueous solution for 10 hours or more, rinsing it with ion exchange water, and air-drying it at room temperature (25° C.) for 12 hours or more.
  • F40 (MPa) On the horizontal axis of the stress-strain curve, the stress (MPa) at the point where the strain was 0.4 was read, and this value was designated as F40 (MPa).
  • ⁇ Tear strength (N)> A tear test was carried out at a test speed of 200 mm/min based on JIS K7128-3 (1998), and the obtained maximum tear load (N) was taken as the tear strength (N). Measurements were carried out in both the MD and TD directions.
  • a dried chloride ion type membrane was used, which was obtained by immersing the ion exchange membrane in a 0.5 mol/L NaCl aqueous solution for 10 hours or more, rinsing it with ion exchange water, and air-drying it at room temperature (25° C.) for 12 hours or more.
  • IEC ⁇ Ion exchange capacity (IEC) (meq./g)>
  • the ion exchange membrane was immersed in a 0.5 mol/L NaCl aqueous solution for 10 hours or more to convert it to a chloride ion type.
  • the chloride ion type was then replaced with a 0.2 mol/L NaNO3 aqueous solution to convert it to a nitrate ion type.
  • the chloride ions liberated at this time were quantified using a silver nitrate aqueous solution with a potentiometric titrator (COMTITE-900, manufactured by Hiranuma Sangyo Co., Ltd.), and the obtained value was designated as A (mol).
  • ⁇ Membrane resistance ( ⁇ cm 2 )> The ion exchange membrane was immersed in a 0.5 mol/L NaCl aqueous solution for 10 hours or more to convert it to a chloride ion type.
  • the ion exchange membrane after the above treatment was placed in the center of a two-chamber cell equipped with a platinum electrode, and the Both sides of the ion exchange membrane were filled with a 0.5 mol ⁇ L ⁇ 1 -NaCl aqueous solution, and the resistance a ( ⁇ cm 2 ) between the electrodes at 25° C. was measured using an AC bridge (frequency 1000 cycles/sec). Similarly, the resistance b ( ⁇ cm 2 ) between the electrodes was measured without installing the ion exchange membrane.
  • the membrane resistance was calculated from the obtained measured value by the following formula.
  • Membrane resistance ( ⁇ cm 2 ) (a-b)
  • the obtained membrane resistance was divided by the membrane thickness ( ⁇ m) and then multiplied by 20 to calculate the membrane resistance per 20 ⁇ m.
  • the ion exchange membrane was removed from the frame and the appearance of the ion exchange membrane was confirmed. In the visual inspection of the appearance, those that were confirmed to have cracks were judged to be defective. The test was carried out by cutting out 10 test pieces from one ion exchange membrane, and the percentage of those found to be defective in appearance was evaluated. The evaluation results were expressed as follows. ⁇ : 0 to 1 defective sheet out of 10 sheets ⁇ : 2 to 3 defective sheets out of 10 sheets ⁇ : 4 or more defective sheets out of 10 sheets
  • Example 1 (Production of porous membrane)
  • a plasticizer 60% by mass of diisononyl phthalate was added from the side feeder of the twin-screw extruder, with the total of the resin composition and the plasticizer being 100% by mass, and the mixture was melt-kneaded at 180°C and 100 rpm to obtain a gel-like solution.
  • the obtained gel-like solution was extruded from a T-die attached to the tip of a twin-screw extruder and taken up with a cooling roll at 25° C. to form a gel-like sheet having a thickness of about 1 mm.
  • the obtained gel-like sheet is biaxially stretched to 4 times the length and 4 times the width at 130 ° C.
  • the porous membrane was taken out of the polymerizable monomer composition, and 100 ⁇ m polyester films were laminated on both sides of the taken-out porous membrane as release materials.
  • the laminate obtained was heated at 80° C. for 5 hours under nitrogen pressure of 0.3 MPa to polymerize the polymerizable monomer composition in the porous membrane.
  • the obtained membrane-like material was immersed in an aqueous solution containing 6% by mass of trimethylamine and 25% by mass of acetone at room temperature for 16 hours to aminated the chloromethylstyrene polymerized portion, washed with pure water, and then air-dried for 16 hours or more to obtain an ion exchange membrane.
  • the obtained ion exchange membrane was evaluated as described above. The results are shown in Table 2.
  • Examples 2 to 9, 20, Comparative Examples 1 to 9> A porous membrane and an ion exchange membrane were produced in the same manner as in Example 1, except that the mixing ratio of the polyolefin resin, the olefin-based elastomer, and the plasticizer, as well as the stretching temperature and the stretching ratio were changed as shown in Table 1. The obtained porous membrane and ion exchange membrane were evaluated as described above. The results are shown in Tables 1 and 2.
  • Example 10 The polyolefin resin, olefin-based elastomer, and plasticizer were the same as those used in Example 1.
  • a resin composition of 90% by mass of polyolefin resin and 10% by mass of olefin-based elastomer was mixed with 60% by mass of plasticizer in a Toyo Seiki Seisakusho Laboplastomill and melt-kneaded at 180°C and 50 rpm to obtain a gel-like solution.
  • the obtained gel-like solution was solidified at room temperature to obtain a gel-like solid.
  • a certain amount was cut out from the obtained gel-like solid, pressed into a sheet using a compression molding machine heated to 180°C, and then introduced into ice water at 0°C to cool and solidify, obtaining a gel-like sheet with a thickness of about 0.5 mm.
  • the obtained gel-like sheet was biaxially stretched at 145°C to 4 times the length and 4 times the width using a small tenter batch stretching machine to obtain a gel-like film.
  • the obtained gel-like film was immersed in acetone to extract and remove diisononyl phthalate, and then the attached acetone was dried and removed to obtain a porous membrane.
  • the obtained porous membrane was used to obtain an ion exchange membrane in the same manner as in Example 1.
  • the obtained porous membrane and ion exchange membrane were evaluated as described above. The results are shown in Tables 1 and 2.
  • Example 11 to 18, Comparative Example 10> A porous membrane and an ion exchange membrane were produced in the same manner as in Example 10, except that the mixing ratio of the polyolefin resin, the olefin-based elastomer, and the plasticizer was changed as shown in Table 1. The obtained porous membrane and the ion exchange membrane were evaluated as described above. The results are shown in Tables 1 and 2.
  • Example 11 A porous membrane was produced in the same manner as in Example 1, except that the compounding ratio of the polyolefin resin, the olefin-based elastomer, and the plasticizer was as shown in Table 1. Since the amount of plasticizer was large and the composition was soft, the gel composition was torn when it was extruded from the T-die and taken up by a roll, and a gel sheet could not be obtained.
  • Example 12 Except for the blending ratio of polyolefin resin, olefin-based elastomer, and plasticizer, and the stretching temperature and ratio are as shown in Table 1, the same procedure as in Example 1 was used to try to manufacture a porous membrane. During stretching, the gel film was frequently torn due to the clip of the stretching machine coming off, and a porous membrane could not be obtained.
  • Example 13 Except for the blending ratio of polyolefin resin, olefin-based elastomer, plasticizer, and stretching temperature and ratio are as shown in Table 1, the same procedure as in Example 1 was used to try to manufacture porous membrane. During stretching, film breakage occurred, and porous membrane could not be obtained.
  • Example 21 As the olefin-based elastomer, Vistamaxx 3000, a propylene-based elastomer manufactured by ExxonMobil, was used, the initial gel-like sheet was molded to a thickness of about 1.0 mm, and the mixing ratio of the polyolefin resin, the olefin-based elastomer, and the plasticizer was changed as shown in Table 1.
  • a porous membrane and an ion exchange membrane were produced in the same manner as in Example 10. The obtained porous membrane and ion exchange membrane were evaluated as described above. The results are shown in Tables 1 and 2.
  • Example 23 A porous membrane and an ion exchange membrane were prepared in the same manner as in Example 21, except that Vistamaxx 3588FL, a propylene elastomer manufactured by ExxonMobil, was used as the olefin elastomer. The porous membrane and the ion exchange membrane obtained were evaluated as described above. The results are shown in Tables 1 and 2.
  • Examples 24 to 26> When producing a porous membrane, a roll-type longitudinal stretching machine and a tenter-type transverse stretching machine are used, A porous membrane and an ion exchange membrane were prepared in the same manner as in Example 1, except that the stretching was performed by the sequential stretching method of stretching in the MD direction and then in the TD direction, and the stretching ratio and stretching temperature were as shown in Table 1. The obtained porous membrane and ion exchange membrane were evaluated as described above. The results are shown in Tables 1 and 2.
  • the tear strength is 3.5 N or more in both MD and TD directions, and the toughness evaluation is ⁇ or ⁇ , which is good.
  • the porosity of the polyolefin-based porous membrane is too small, so the membrane resistance and ion exchange capacity of the obtained ion exchange membrane cannot be measured.
  • the ion exchange membranes of Comparative Examples 1 to 9 had a tear strength of less than 3.5 N in at least one of the MD and TD directions, and were evaluated as poor in toughness, i.e., X.
  • the amount of plasticizer added was outside the preferred range of the present invention, and in Comparative Examples 12 and 13, the stretching temperature was outside the preferred range of the present invention, so that a porous membrane could not be obtained.
  • the toughness is 0.35J or more in both MD and TD, and (F40-F30) is 2.0MPa or more.
  • the toughness evaluation of the obtained ion exchange membrane is ⁇ or ⁇ , which is good.
  • the porous membranes of Comparative Examples 1, 2, and 5 to 9 had a toughness of less than 0.35 J, and the porous membranes of Comparative Examples 3 and 4 had (F40-F30) of less than 2.0 MP in either the MD or TD direction, and the toughness evaluation of the obtained ion exchange membrane was x, which was poor.
  • Comparative Example 10 the content of the polyolefin-based elastomer in the resin composition constituting the gel solution was outside the preferred range of the present invention, so that the obtained membrane had a porosity of 0% as shown in Table 1, and no pores were formed, and the membrane was poor as a porous membrane. Since no pores were formed, the ion exchange resin could not be filled inside, and the membrane resistance of the obtained ion exchange membrane was extremely high as shown in Table 2, and the ion exchange capacity could not be measured, and the membrane was poor as an ion exchange membrane.
  • Example 1 in the polyolefin-based porous membrane production method of the present invention (Examples 1 to 20), the toughness evaluation of the ion exchange membrane obtained was ⁇ or ⁇ , as shown in Table 2, and was good.
  • the stretching ratio was outside the preferred range of the present invention, and therefore, as shown in Table 2, the toughness of the obtained ion exchange membranes was evaluated as x, which was poor.
  • the resin composition constituting the gel solution did not contain a polyolefin-based elastomer, and therefore, as shown in Table 2, the toughness evaluation of the obtained ion exchange membrane was poor, being rated as x.
  • the content of the polyolefin-based elastomer in the resin composition constituting the gel solution was outside the preferred range of the present invention, and therefore, as shown in Table 1, the obtained membrane had a porosity of 0% and no pores were formed, and was poor as a porous membrane. Since no pores were formed, the ion exchange resin could not be filled inside, and as shown in Table 2, the membrane resistance of the obtained ion exchange membrane was extremely high, the ion exchange capacity could not be measured, and it was poor as an ion exchange membrane.

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PCT/JP2024/007331 2023-03-20 2024-02-28 イオン交換膜、ポリオレフィン系多孔質膜、膜電極接合体、水電解装置、および、ポリオレフィン系多孔質膜の製造方法 Ceased WO2024195459A1 (ja)

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CN202480019689.4A CN120917087A (zh) 2023-03-20 2024-02-28 离子交换膜、聚烯烃系多孔质膜、膜电极接合体、水电解装置和聚烯烃系多孔质膜的制造方法
EP24774604.3A EP4506397A4 (en) 2023-03-20 2024-02-28 ION EXCHANGE MEMBRANE, POLYOLEFIN-BASED POROUS MEMBRANE, MEMBRANE-ELECTRODE ASSEMBLY, WATER ELECTROLYSIS DEVICE AND METHOD FOR PRODUCING POLYOLEFIN-BASED POROUS MEMBRANE
JP2025030530A JP2025078675A (ja) 2023-03-20 2025-02-27 イオン交換膜、ポリオレフィン系多孔質膜、膜電極接合体、水電解装置、および、ポリオレフィン系多孔質膜の製造方法

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