Composite membranes of specially reinforced fluorine-containing proton or ion exchange membranes, composite membrane electrodes, specially reinforced fluorine-chlorine-containing alkaline battery membranes, special release membranes, and methods for manufacturing the same.

Abstract

To provide a composite membrane of a special highly-enhanced fluorine-containing proton or ion exchange membrane, a composite membrane electrode, and a fluorine-containing chlor-alkali battery membrane which are not contaminated by a release agent, and have heat resistance, improved tensile strength, and improved dimensional stability, and also to provide a preparation method of the membranes which reduces production cost and uses no release agent.SOLUTION: A composite membrane of a special highly-enhanced fluorine-containing proton or ion exchange membrane comprises at least two microporous enhancement membranes, wherein both sides of each microporous enhancement membrane are filled with a fluorine-containing proton or ion exchange resin, the composite membrane has tensile strength in both directions >40 MPa, room-temperature ionic conductivity >0.007 S / cm, and extremely low air permeability, and it is measured using a Gurley permeability tester that the time required for 100 ml of air to penetrate through the composite membrane is >5 minutes.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to composite membranes of special highly reinforced fluorine-containing proton or ion exchange membranes, composite membrane electrodes, special highly reinforced fluorine-chlorine-containing alkaline battery membranes, special release membranes, and methods for manufacturing the same. [Background technology]

[0002] As a highly efficient power generation device that directly converts fuel and chemical energy into electrical energy, proton exchange membrane fuel cells (PEMFCs) are attracting attention in various industries due to their higher energy conversion efficiency compared to conventional batteries, environmental friendliness, low-temperature starting capabilities, and low noise levels. The core component is the proton exchange membrane, located at the very center of the fuel cell, which provides a channel for transporting protons generated at the cathode to the anode. Currently, the most widely available proton exchange membranes remain the Nafion perfluorosulfonate series (thickness >25 μm) from DuPont, the earliest commercialized manufacturer, primarily obtained by melt extrusion, rolling, and tensile processes. In recent years, Gore's Gore-Select series of membranes has emerged, consisting of ultra-thin (thickness <25 μm) single-layer microporous PTFE-reinforced membranes, primarily cast-coated single-layer microporous PTFE-reinforced membranes (see US Patent Nos. US5547551A, US5599614A), which are being imitated by a small number of companies in China.

[0003] Fluorine-containing sulfonic acid resins have a molecular structure consisting of a fluorocarbon main chain with low polarizability and hydrophilic sulfonic acid or carboxylic acid groups in the side chains that can adsorb water molecules, and side chains with sulfonic acid groups at their ends. The strong difference in polarity between the hydrophobic main chain and the hydrophilic side chains forms a microscopic phase separation structure within the membrane, which plays an important role in its mechanical and transport properties. For this reason, perfluorosulfonic acid resin membranes have excellent proton conductivity, low gas permeability, good mechanical properties and dimensional stability, and low contact resistance with the catalyst layer, thus meeting the requirements for use as proton exchange membranes. There are many methods for manufacturing proton exchange membranes from sulfonic acid resin solutions, such as the casting method, immersion method, and spray method. Currently, the manufacturing process for proton exchange membranes and various reinforced composite proton exchange membranes is complex, and continuous production is difficult.

[0004] Patent CN101771159B (Patent No. ZL201010104002.7) discloses a method for producing a proton exchange membrane, which involves blending sulfonated polyether ether ketone and sulfonated polyether sulfone to form a membrane solution, placing this membrane solution in a mold, evaporating the solvent to form a membrane, and then obtaining a proton exchange membrane through vacuum drying and acid treatment. However, the production of the product membrane is carried out in units, resulting in low production efficiency and high costs.

[0005] Patent CN100513460 (Patent No. ZL200710011141.3) discloses a novel method for forming a proton exchange membrane, using a single-layer stretched polytetrafluoroethylene microporous membrane as a base film, first immersing it in a low-concentration resin solution, and then repeatedly immersing it in a high-concentration resin solution until it reaches a suitable film thickness. However, this method has a complex manufacturing process, low efficiency, high production and usage costs for fuel cells, and limits the commercialization of fuel cells.

[0006] Patent CN106968110B (ZL201710251603.2) discloses a fluorine-chlorine-containing conductive polymer double-sided filled composite film, but the film manufacturing method uses release paper, and when producing high-quality films, dandruff contamination due to the quality of the release paper is likely to occur.

[0007] A release film is a film with a detachable surface that, after contact with a specific material under limited conditions, has no tackiness or only slight tackiness. Typically, to increase the release force of a plastic film, the plastic film is subjected to surface modification treatment by corona or plasma treatment, followed by the application of a release agent. More commonly, silicone-containing or fluorine-containing release agents are applied to the surface of the film material to achieve very light and stable release force against various organic adhesives. Currently, silicone release paper (film) is commonly found on the market, and all of these use silicone as a release agent. The biggest drawback is that silicone may remain on the product surface during peeling.

[0008] Polycarbonate insulating release films are a common type of release film. Their main component is 2,2'-bis(4-hydroxyphenyl)propane polycarbonate, commonly known as polycarbonate. It is a high-molecular polymer containing carbonate groups formed by the condensation polymerization of bisphenol A in its molecular chains. It is an amorphous, odorless, non-toxic, highly transparent, colorless or slightly yellowish thermoplastic engineering plastic with excellent physical and mechanical properties, particularly superior impact resistance, high tensile strength, flexural strength, and compressive strength, low creep, and dimensional stability. Therefore, it is widely used in various fields. However, polycarbonate insulating release films function by adding other additives or applying a release agent.

[0009] Patent CN105440641A discloses a polycarbonate insulating release film that requires the addition of other additives, which are prone to being released during the casting process and contaminating the film surface.

[0010] Patent CN1840324A discloses a method for manufacturing a release film, which involves a complex process, requires the application of a release agent, and is prone to contamination of the film surface during the casting process.

[0011] Furthermore, as in the technologies disclosed in patents CN100588676C (patent number 200710013624.7), US7259208B, CN101350415B, CN101780376B, CN104018181A, CN101320818B, CN201546122U, CN103187549A, CN1298890C, etc., the fluorine-containing polymer microfibers are not continuous phases and cannot be linked to form a film.

[0012] With the development of a low-carbon, clean economy, the demand for and applications of fluorine-containing proton exchange membranes or ion exchange membranes, and their counterparts, release membranes, are increasing. In practical terms, release membranes need to have not only isolation and filling functions, but also protective functions, prevent the release agent from contaminating the cast paint, and dissipate heat. Therefore, the requirements for cleanliness, mechanical strength, and service life of fluorine-containing proton exchange membranes or ion exchange membranes are becoming increasingly important. [Overview of the project] [Problems that the invention aims to solve]

[0013] The present invention has been made in view of the problems of the prior art described above, and its purpose is to provide a composite membrane of a special highly reinforced fluorine-containing proton or ion exchange membrane, a composite membrane electrode, or a special highly reinforced fluorine-chlorine-containing membrane for alkaline batteries, in order to solve the problems of the prior art, such as the complexity of the manufacturing process of the exchange membrane, the susceptibility to contamination by release agents, and the difficulty of continuous manufacturing. [Means for solving the problem]

[0014] To achieve the above technical objectives, the present invention employs the following technical embodiments.

[0015] <First Embodiment of the Invention> In a first aspect of the present invention, there is provided a special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane comprising at least two layers of microporous reinforcing membranes, wherein both sides of each layer of the microporous reinforcing membrane are filled with a fluorine-containing proton or ion exchange resin, and the weight ratio of the microporous reinforcing membrane to the fluorine-containing proton or ion exchange resin is 5:95 to 40:60. The thickness of the composite membrane is 1 to 300 µm. The composite membrane has a tensile strength of >40 MPa in both directions, a room temperature ionic conductivity of >0.007 S / cm, an extremely low air permeability, and the time required for 100 ml of air to permeate through the composite membrane measured by a Gurley air permeability tester is >5 minutes.

[0016] Preferably, the weight ratio of the microporous reinforcing membrane to the fluorine-containing proton or ion exchange resin is 10:90 to 30:70, and the composite membrane further comprises a special release membrane attached to the lowermost layer of the composite membrane. The component of the special release membrane is selected from engineering plastics containing bisphenol A as a main component, or engineering plastics containing hexafluorodimethylbisphenol A as a main component, provided that the engineering plastic containing bisphenol A as a main component is a polymer obtained by polymerizing or copolymerizing bisphenol A, and the weight ratio thereof exceeds 50%; the engineering plastic containing hexafluorodimethylbisphenol A as a main component is a polymer obtained by polymerizing or copolymerizing hexafluorodimethylbisphenol A, and the weight ratio thereof exceeds 50%.

[0017] Preferably, the number of layers of the microporous reinforcing membrane is 2 to 50.

[0018] Preferably, the number of layers of the microporous reinforcing membrane is 2 to 30.

[0019] Preferably, the polymer obtained by polymerizing or copolymerizing bisphenol A is any of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

[0020] Preferably, the microporous reinforcement film has a dry weight of 0.5 to 30 g / m². 2 The material has an open porosity of 40% to 95%, a thickness of 0.5 to 30 μm, and a tensile strength of >40 MPa in both directions.

[0021] Preferably, the method for producing the microporous reinforced film involves processes such as spinning by melt spinning, wet spinning, wet phase change method, temperature difference phase change method, dry solvent method, electrospinning method, or ultra-high speed centrifugal spinning method to uniformly converge nano or micro-sized fibers to form a random mesh-like microporous structure, and then forming a microporous film after heat fixing. The resin used is a thermoplastic fluorine-containing or chlorine-containing resin, a carbon fiber precursor, or a resin that can be converted into carbon fibers. The method involves extruding the microporous film into a paste and biaxially stretching it.

[0022] Preferably, one or more of the following are mixed into a solution of the fluorine-containing proton exchange resin or ion exchange resin: metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, and rare metal powder, the total weight of which does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin.

[0023] Preferably, the metal nanopowder comprises one of silver, platinum, or palladium, or a platinum / carbon composite material, and the metal oxide powder comprises one of zirconia or ceria.

[0024] Preferably, the total amount of the composite film is 2 to 500 g / m². 2 That is the case.

[0025] <Second embodiment of the present invention> In a second embodiment of the present invention, a special highly reinforced fluorine-containing proton or ion exchange membrane composite membrane for use in a battery separator is provided, comprising at least two layers of microporous reinforcement membranes, wherein both sides of each layer of microporous reinforcement membrane are filled with a fluorine-containing proton or ion exchange resin, and the weight ratio of the microporous reinforcement membrane to the fluorine-containing proton or ion exchange resin is 5:95 to 40:60. In the case where the weight ratio of the microporous reinforcement membrane to the fluorine-containing proton or ion exchange resin is 10:90 to 30:70, the composite membrane electrode of the special highly reinforced fluorine-containing proton or ion exchange membrane has a total weight of 2 to 500 g / m². 2 The thickness is 1 μm to 300 μm. The composite membrane electrode of the special highly reinforced fluorine-containing proton or ion exchange membrane has a tensile strength of >40 MPa in both directions, an ionic conductivity at room temperature of >0.007 S / cm, and extremely low air permeability, with a Gurley air permeability meter measuring >5 minutes for 100 ml of air to pass through the composite membrane electrode.

[0026] Preferably, the composite film includes a special release film attached to the bottom layer, the components of which are selected from an engineering plastic mainly containing bisphenol A or an engineering plastic mainly containing hexafluorodimethylbisphenol A, wherein the engineering plastic mainly containing bisphenol A is a polymer obtained by polymerizing or copolymerizing bisphenol A and its weight ratio exceeds 50%, and the engineering plastic mainly containing hexafluorodimethylphenol A is a polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A and its weight ratio exceeds 50%.

[0027] Preferably, the weight ratio of the microporous reinforcement film to the fluorine-containing proton or ion exchange resin is 10:90 to 30:70.

[0028] Preferably, the microporous reinforcement film consists of 2 to 50 layers.

[0029] Preferably, the microporous reinforcement film consists of 2 to 30 layers.

[0030] Preferably, the polymer obtained by polymerizing or copolymerizing bisphenol A is any of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

[0031] Preferably, the microporous reinforcement film has a dry weight of 0.5 to 30 g / m². 2 The material has an open porosity of 40% to 95%, a thickness of 0.5 to 30 μm, and a tensile strength of >40 MPa in both directions.

[0032] Preferably, the method for producing the microporous reinforced film involves processes such as spinning by melt spinning, wet spinning, wet phase change method, temperature difference phase change method, dry solvent method, electrospinning method, or ultra-high speed centrifugal spinning method to uniformly converge nano or micro-sized fibers to form a random mesh-like microporous structure, and then forming a microporous film after heat fixing. The resin used is a thermoplastic fluorine-containing or chlorine-containing resin, a carbon fiber precursor, or a resin that can be converted into carbon fibers. The method involves extruding the microporous film into a paste and biaxially stretching it.

[0033] Preferably, one or more of the following are mixed into a solution of the fluorine-containing proton exchange resin or ion exchange resin: metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, and rare metal powder, the total weight of which does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin.

[0034] Preferably, the metal nanopowder comprises one of silver, platinum, or palladium, or a platinum / carbon composite material, and the metal oxide powder comprises one of zirconia or ceria.

[0035] Preferably, the microporous reinforcement film consists of 2 to 20 layers.

[0036] <Third Embodiment of the Invention> A third embodiment of the present invention provides a special highly reinforced fluorine-chlorine-containing alkaline battery film comprising at least two layers of microporous reinforcement films, wherein both sides of each layer of microporous reinforcement film are filled with a fluorine-containing proton exchange resin or ion exchange resin, and the weight ratio of the microporous reinforcement film to the fluorine-containing proton exchange resin or ion exchange resin is 5:95 to 40:60. The highly reinforced fluorine-chlorine-containing alkaline battery film has a total weight of 20 to 500 g / m². 2 The thickness is 10 μm to 260 μm. The tensile strength of the highly reinforced fluorine-chlorine-containing alkaline battery film is >40 MPa in both directions, the room-temperature ionic conductivity of the highly reinforced fluorine-chlorine-containing alkaline battery film is >0.007 S / cm, and the air permeability of the highly reinforced fluorine-chlorine-containing alkaline battery film is >5 minutes, as measured by a Gurley air permeability meter, for 100 ml of air to pass through the composite film.

[0037] Preferably, the weight ratio of the microporous reinforcement film to the fluorine-containing proton or ion exchange resin is 10:90 to 30:70.

[0038] Preferably, the microporous reinforcement film consists of 2 to 50 layers.

[0039] Preferably, the microporous reinforcement film consists of 2 to 30 layers.

[0040] Preferably, the product further includes a special release film that does not contain a release agent, the components of which are selected from an engineering plastic mainly containing bisphenol A or an engineering plastic mainly containing hexafluorodimethylbisphenol A, wherein the engineering plastic mainly containing bisphenol A is a polymer obtained by polymerizing or copolymerizing bisphenol A and its weight ratio exceeds 50%, and the engineering plastic mainly containing hexafluorodimethylphenol A is a polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A and its weight ratio exceeds 50%.

[0041] Preferably, the polymer obtained by polymerizing or copolymerizing bisphenol A is any of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

[0042] Preferably, the microporous reinforcement film has a dry weight of 0.5 to 30 g / m². 2 The material has an open porosity of 40% to 95%, a thickness of 0.5 to 30 μm, and a tensile strength of >40 MPa in both directions.

[0043] Preferably, the method for manufacturing the microporous reinforcement film and the material are selected from the following:

[0044] (1) Spinning processes such as melt spinning, wet spinning, wet phase change method, temperature difference phase change method, dry solvent method, electrospinning method, or ultra-high speed centrifugal spinning method are carried out to uniformly converge nano or μm sized fibers into a random mesh-like microporous structure, and after heat fixation a microporous film is formed. The resin used is a thermoplastic fluorine-containing or chlorine-containing resin, a carbon fiber precursor, or a resin that can be converted into carbon fibers.

[0045] (2) The stretched microporous polytetrafluoroethylene film, or microporous polyolefin film, or modified polyolefin film, is obtained by extruding the microporous film into a paste and biaxially stretching it.

[0046] Preferably, one or more of the following are mixed into a solution of the fluorine-containing proton exchange resin or ion exchange resin: metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, and rare metal powder, the total weight of which does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin.

[0047] Preferably, the acid equivalent of the fluorine-containing proton exchange resin or ion exchange resin is 400 to 1500, and the selectable fluorine-containing proton exchange resin or ion exchange resin includes a fluorine-containing sulfonic acid resin and a fluorine-containing carboxylic acid resin, and the perfluorocarboxylic acid resin:perfluorosulfonic acid resin is filled into the special highly reinforced fluorine-chlorine-containing alkaline battery film in a dry weight ratio of 1:9 to 5:5.

[0048] <Fourth Embodiment of the Invention> A fourth embodiment of the present invention provides a manufacturing method for a composite membrane of a special highly reinforced fluorine-containing proton or ion exchange membrane described in the first embodiment of the present invention, a composite membrane electrode described in the second embodiment, or a fluorine-chlorine-containing alkaline battery membrane described in the third embodiment, comprising the following steps.

[0049] Step 1: Cast-coat one side of the special release film with a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution and allow it to adhere.

[0050] Step 2: The coated resin solution is covered with a microporous reinforcement film, and the resin solution coated on the release film and the covered microporous reinforcement film are thoroughly mixed to obtain a composite film.

[0051] Step 3: The composite film obtained in Step 2 is dried.

[0052] Step 4 The upper surface of the micropore-reinforced film of the composite film is further cast coated with a resin solution, and the cast-coated resin solution and the coated micropore-reinforced film are thoroughly blended to obtain a composite film.

[0053] Step 5: The composite film obtained in Step 4 is dried.

[0054] Preferably, the microporous reinforcement film of the composite film obtained in step 2 is further coated with the resin solution, and the resin solution is thoroughly mixed and filled into both the upper and lower surfaces of the microporous reinforcement film to form a composite film, and then all the materials are dried together.

[0055] Preferably, the void volume in which the microporous reinforcement film is filled in the fluorine-containing proton exchange resin solution or fluorine-containing ion exchange resin solution is at least 60% to 90%.

[0056] Preferably, the void volume in which the microporous reinforcement film is filled in the fluorine-containing proton exchange resin solution or fluorine-containing ion exchange resin solution is at least 80%.

[0057] Preferably, the dry weight ratio of the microporous reinforcement film to the fluorine-containing proton exchange resin or ion exchange resin is 5:95 to 40:60.

[0058] Preferably, the dry weight ratio of the microporous reinforcement film to the fluorine-containing proton exchange resin or ion exchange resin is 10:90 to 30:70.

[0059] Preferably, the components of the special release film are selected from engineering plastics containing bisphenol A as the main component, or engineering plastics containing hexafluorodimethylbisphenol A as the main component, provided that the engineering plastic containing bisphenol A as the main component is a polymer obtained by polymerizing or copolymerizing bisphenol A and its weight ratio exceeds 50%, and the engineering plastic containing hexafluorodimethylphenol A as the main component is a polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A and its weight ratio exceeds 50%.

[0060] Preferably, the polymer obtained by polymerizing or copolymerizing bisphenol A is any of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

[0061] Preferably, one or more of the following are mixed with the fluorine-containing proton exchange resin solution or fluorine-containing ion exchange resin solution: metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, and rare metal powder, the total weight of which does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin.

[0062] <Fifth Embodiment of the Invention> A fifth embodiment of the present invention provides a special release film free of mold release agents for manufacturing a battery separator by a cast coating method. The components of the special release film free of mold release agents are selected from an engineering plastic mainly containing bisphenol A, or an engineering plastic mainly containing hexafluorodimethylbisphenol A, wherein the engineering plastic mainly containing bisphenol A is a polymer obtained by polymerizing or copolymerizing bisphenol A and its weight ratio exceeds 50%, and the engineering plastic mainly containing hexafluorodimethylphenol A is a polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A and its weight ratio exceeds 50%.

[0063] Preferably, the polymer obtained by polymerizing or copolymerizing bisphenol A is any of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing hexafluorodimethylphenol A is any of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

[0064] Preferably, the special release film, which does not contain the release agent, has a thickness of 10 to 500 μm, a width of at least 100 mm, and does not deform at a heat resistance of 100°C.

[0065] Preferably, the thickness of the special crystalline film, which does not contain a mold release agent, is 25 to 300 μm.

[0066] Furthermore, the special release film that does not contain the aforementioned release agent is used to manufacture battery separators by a cast coating method.

[0067] By adopting the above technical configuration, the composite film, composite electrode, and fluorine-chlorine-containing alkaline battery film of the present invention, which are special highly reinforced fluorine-containing proton or ion exchange membranes, are not susceptible to contamination by release agents, can withstand multiple heat treatments, and have heat resistance of at least 100°C. The multilayer microporous reinforced film can conceal the defect of bubbles that may occur from a single coating film, significantly improving productivity, greatly improving the tensile strength of the composite film, composite electrode, and fluorine-chlorine-containing alkaline battery film, improving the dimensional stability of the composite film, composite electrode, and fluorine-chlorine-containing alkaline battery film, which is extremely important for service life, enabling high-speed continuous production, meeting the requirements of commercial mass production, and resulting in high cleanliness and stability of the resulting product film.

[0068] The present invention provides a method for manufacturing composite films, composite film electrodes, and fluorine-chlorine-containing alkaline battery films that is simple in process, reduces production costs, and, more importantly, avoids the problem of release films containing trace amounts of release agent, thereby significantly improving the yield of the final product. The special release film of the present invention, which does not contain release agents, can have a release function without corona treatment or coating with release agents, can be used in continuous production, simplifies the production process, and reduces manufacturing costs.

[0069] <Modes for carrying out the invention> The present invention will be described further below. While this embodiment provides detailed embodiments and specific operating procedures based on the technical aspects of the present invention, the scope of protection of the present invention is not limited to this embodiment.

[0070] (1) The composite membrane, composite membrane electrode, or fluorine-chlorine-containing alkaline battery membrane of the special highly reinforced fluorine-containing proton or ion exchange membrane includes at least two layers of microporous reinforcement membrane, and both sides of the microporous reinforcement membrane (continuous phase) of each layer are filled with fluorine-containing proton exchange resin or ion exchange resin. (2) A special release film is attached to the lower surface of the composite membrane, composite membrane electrode, or fluorine-chlorine-containing alkaline battery membrane of the special highly reinforced fluorine-containing proton or ion exchange membrane.

[0071] The fluorine-containing proton exchange resin or ion exchange resin may be a commercially available product from, for example, Nafion, 3M, or Solvay, or it may be manufactured by referring to the method for manufacturing a fluorine-containing chlorine-containing conductive polymer resin disclosed in Patent CN106947027B (Patent No. ZL201710251598.5).

[0072] The reinforced composite film, composite film electrode, or fluorine-chlorine-containing alkaline battery film comprises at least two layers of microporous reinforced film, with both sides of each layer of the microporous reinforced film filled with a fluorine-containing proton exchange resin or ion exchange resin, and the overall manufacturing method comprises the following steps.

[0073] <Method for manufacturing microporous reinforced film> The processes and materials used to manufacture the microporous reinforced film can be selected from the following two groups.

[0074] (1) A method is used in which nano or μm sized fibers are uniformly converged to form a random mesh-like microporous structure by processes such as melt spinning, wet spinning, wet phase change method, temperature difference phase change method, dry solvent method, electrostatic spinning, and ultra-high speed centrifugal spinning, and a microporous film is formed after heat fixing. Preferred resins used are heat-meltable fluorine-containing resins or chlorine-containing resins, carbon fiber precursors, or resins that can be converted into carbon fibers such as polyacrylonitrile (PAN) or its copolymers, polyimide, polyamide (nylon), polyester (PET), aramid, and polyetherketone (PEEK). (2) Microporous reinforced films (for example, stretched microporous polytetrafluoroethylene films, or microporous polyolefin films (polyethylene, polypropylene, etc.), modified polyolefin films) can be obtained by paste extrusion + biaxial stretching.

[0075] The microporous reinforced film has a tensile strength (TD, MD) (see ASTM D882 test method) of >40 MPa in both directions, preferably >50 MPa, most preferably >80 MPa, and an open porosity of 40% to 95%. The microporous reinforced film has a mesh-like microporous structure, and this mesh-like microporous structure can form a continuous phase microporous reinforced film after thermal setting. The dry weight of the microporous reinforced film is 0.5 to 30 g / m². 2 Preferably 1 to 10 g / m 2 The open porosity is 40-95%, preferably 50-90%, and the thickness is 0.5-30 μm, preferably 1-15 μm.

[0076] <Method for manufacturing highly reinforced composite films, composite film electrodes, or special highly reinforced fluorine-chlorine-containing alkaline battery films> A release film that does not contain the aforementioned release agent and can withstand drying at least 100°C may be cast-coated with a fluorine-containing proton exchange resin or ion exchange resin solution to cover at least two layers of micropore-reinforced films. The fluorine-containing proton exchange resin solution or ion exchange resin solution is filled as completely as possible into the pores on both sides of the micropore-reinforced films by multiple cast-coating or immersion methods, where the fluorine-containing proton exchange resin or ion exchange resin has an acid equivalent number (meq / g) of sulfonic acid or carboxylic acid of 400 to 1500, preferably 500 to 1100, and more preferably 600 to 950. The solvent is removed from the composite material by drying to produce a composite film of a special high-enhancement fluorine-containing proton or ion exchange film, a composite film electrode, or a special high-enhancement fluorine-chlorine-containing alkaline battery film.

[0077] The method for producing a specially reinforced fluorine-containing composite film or membrane electrode of the present invention includes the following steps.

[0078] Step 1: Cast-coat one side of a release film that does not contain a special release agent with a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution and allow it to adhere.

[0079] Step 2: Cover the coated resin solution with a microporous reinforcing membrane, and sufficiently blend the resin solution coated on the release film with the covered microporous reinforcing membrane to obtain a composite membrane.

[0080] Step 3: Dry the composite membrane obtained in Step 2.

[0081] Step 4: Further cast-coat a resin solution on the upper surface of the microporous reinforcing membrane of the composite membrane, and dry twice to obtain a finished product.

[0082] However, the components of the special release film will be described in detail later.

[0083] The method for manufacturing a special reinforced fluorine-containing composite membrane or film electrode of the present invention has a simple process and can reduce production cost. More importantly, it avoids the problem that the release membrane contains a release agent that is released in a trace amount, and greatly improves the yield of the final product. More than 60%, preferably more than 80%, most preferably more than 90% of the void volume on both sides of the dried microporous reinforcing membrane is filled with a fluorine-containing proton exchange resin. The dry weight ratio of the microporous reinforcing membrane to the fluorine-containing proton exchange resin or ion exchange resin is (5:95) to (40:60), preferably (10:90) to (30:70), and the total weight of the reinforced fluorine-containing composite membrane is 3 to 60 g / m 2 , the thickness is 2 μm to 30 μm, the tensile strength (TD, MD) of the highly reinforced composite membrane is >40 MPa in both directions, preferably >50 MPa, most preferably >80 MPa, the room temperature ionic conductivity of the reinforced composite membrane is >0.007 S / cm, preferably >0.013 S / cm, more preferably >0.018 S / cm, the air permeability of the reinforced composite membrane is extremely low, and the time required for 100 ml of air measured by a Gurley air permeability tester to permeate through the composite membrane is >5 minutes, preferably >15 minutes.

[0084] Furthermore, the resin solution is applied to the micropore-reinforced film of the composite film obtained in step 2, and the resin solution is thoroughly mixed and filled into both the upper and lower surfaces of the micropore-reinforced film to form a composite film, and then all the materials are dried together.

[0085] Alternatively, step 2 is repeated after step 3 to coat with an N-layer microporous reinforcement film, but the microporous reinforcement film may consist of 2 to 50 layers, preferably a highly reinforced fluorine-containing composite film with 2 to 30 layers of microporous reinforcement films, provided that the total dry weight ratio of the microporous reinforcement film to the fluorine-containing proton exchange resin or ion exchange resin is (5:95) to (40:60). The highly reinforced fluorine-containing composite film comprises 2 to 50 layers of microporous reinforcement films, preferably 2 to 30 layers of microporous reinforcement films, and both sides of each layer of microporous reinforcement film are filled with a fluorine-containing proton exchange resin or ion exchange resin, and the total weight of the highly reinforced fluorine-containing composite film is 3 to 500 g / m². 2 Preferably 5-300 g / m 2 Most preferably 10-250 g / m² 2 The thickness of the highly reinforced fluorine-containing composite film is 2 μm to 250 μm, preferably 3 μm to 150 μm, most preferably 5 μm to 130 μm; the tensile strength (TD, MD) of the highly reinforced fluorine-containing composite film is >40 MPa in both directions, preferably >50 MPa, most preferably >80 MPa; the ionic conductivity at room temperature of the highly reinforced fluorine-containing composite film is >0.007 (S / cm), preferably >0.013 (S / cm), more preferably >0.018 (S / cm); the air permeability of the highly reinforced fluorine-containing composite film is very low, and the time required for 100 ml of air to pass through this composite film, as measured by a Gurley air permeability meter, is >5 minutes, preferably >15 minutes.

[0086] The dry weight ratio of the microporous reinforcement film to the fluorine-containing proton exchange resin or ion exchange resin is 10:90 to 30:70.

[0087] The fluorine-containing proton exchange resin or ion exchange resin has an acid equivalent (g / equivalent wt.) of 400 to 1500, preferably 600 to 1200, and the fluorine-containing proton exchange resin or ion exchange resin includes, but is not limited to, selectable fluorine-containing sulfonic acid resins and fluorine-containing carboxylic acid resins. One or more of the following are mixed into the fluorine-containing proton exchange resin solution or fluorine-containing ion exchange resin solution: metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, and rare metal powder, the total weight of which does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin. The metal nanopowder includes, but is not limited to, silver, platinum alloy, or palladium, or platinum / carbon composites. The metal oxide powder includes, but is not limited to, zirconia and ceria.

[0088] The advantages of the material of the present invention are that, since such a release film does not contain any coating release agent, the risk of the release agent contaminating the product film electrode can be eliminated. By casting and coating the multilayer microporous reinforced film multiple times, bubble defects that may be formed by a single coating layer can be concealed and significantly reduced, greatly improving the yield. Unexpectedly, the multilayer microporous composite film also contributes to improving the tensile strength of the composite film, improving the dimensional stability of the composite film, which is extremely important for the service life. High-speed continuous production can be realized, meeting the requirements of commercial mass production, and the cleanliness and stability of the resulting product film are found to be high.

[0089] <Composite membranes of special high-enhancement fluorine-containing proton or ion exchange membranes, composite membrane electrodes, and special high-enhancement fluorine-chlorine-containing alkaline battery membranes> The highly reinforced composite film and composite film electrode of the present invention include at least two layers of microporous reinforcement film, each layer of which is filled on both sides with a fluorine-containing proton exchange resin or ion exchange resin. The weight ratio of the microporous reinforcement film to the fluorine-containing proton exchange resin or ion exchange resin is (5:95) to (40:60), preferably (10:90) to (30:70). The total weight of the reinforced composite film and composite film electrode is 2 to 500 g / m². 2 Preferably 5-300 g / m2 Most preferably 5-200 g / m 2 The thickness of the composite membrane is 1 μm to 300 μm, preferably 2 μm to 200 μm, most preferably 3 μm to 100 μm; the tensile strength of the reinforcing composite membrane and composite membrane electrode (see ASTM D882 test method) (TD, MD) is >40 MPa in both directions, preferably >50 MPa, most preferably >80 MPa; the room temperature proton / ion conductivity (Ionic Conductivity, GB / T20042.3-2009 Part 3 of Proton Exchange Membrane Fuel Cells: Proton Exchange Membrane Test Method) of the reinforcing composite membrane is >0.007 (S / cm), preferably >0.013 (S / cm), more preferably >0.018 (S / cm); and the air permeability of the reinforcing composite membrane and composite membrane electrode is extremely low, with the time required for 100 ml of air to pass through the composite membrane and composite membrane electrode, as measured by a Gurley air permeability meter, being >5 minutes, preferably >15 minutes.

[0090] The special highly reinforced fluorine-chlorine-containing alkaline battery film according to the present invention comprises at least two layers of microporous reinforcement films, each microporous reinforcement film being filled on both sides with a fluorine-containing proton exchange resin or ion exchange resin, the weight ratio of the microporous reinforcement film to the fluorine-containing proton exchange resin or ion exchange resin being 5:95 to 40:60, and the total weight of the highly reinforced fluorine-chlorine-containing alkaline battery film being 20 to 500 g / m² 2 The thickness of the highly reinforced fluorine-chlorine-containing alkaline battery film is 10 μm to 260 μm, the tensile strength of the highly reinforced fluorine-chlorine-containing alkaline battery film is >40 MPa in both directions, the room-temperature ionic conductivity of the highly reinforced fluorine-chlorine-containing alkaline battery film is >0.007 S / cm, and the air permeability of the highly reinforced fluorine-chlorine-containing alkaline battery film is >5 minutes, measured by a Gurley air permeability meter, which is the time required for 100 ml of air to pass through the composite film.

[0091] The fluorine-containing proton exchange resin or ion exchange resin solution may be mixed with one or more types of metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, rare metal powder, etc., and the mixture may be collectively filled into the pores on both sides of the microporous membrane.

[0092] The total weight of the aforementioned metal nanopowder, metal oxide nanopowder, carbon powder, graphite powder, graphene, rare metal powder, etc., does not exceed 80% of the dry weight of the fluorine-containing proton exchange resin or ion exchange resin. The aforementioned rare metal nanopowder includes, but is not limited to, silver, platinum, or palladium, or platinum / carbon composites. The aforementioned metal oxide powder includes, but is not limited to, zirconia or ceria.

[0093] In some embodiments of the present invention, the resulting special highly reinforced fluorine-containing proton or ion exchange membrane composite film comprises at least two layers of microporous reinforcement film, each layer of microporous reinforcement film being filled on both sides with a fluorine-containing proton exchange resin or ion exchange resin, and the total weight of the reinforced composite film is 2 to 500 g / m². 2 Preferably 5-300 g / m 2 Most preferably 5-200 g / m 2 The thickness (see ASTM D756) is 1 μm to 300 μm, preferably 2 μm to 200 μm, most preferably 3 μm to 100 μm; the tensile strength (see ASTM D882 test method) (TD, MD) of the highly reinforced composite membrane is >40 MPa in both directions, preferably >50 MPa, most preferably >80 MPa; the room temperature proton / ion conductivity (Ionic Conductivity, see GB / T20042.3-2009 Part 3 of Proton Exchange Membrane Fuel Cells: Proton Exchange Membrane Measurement Method) of the highly reinforced composite membrane is >0.007 (S / cm), preferably >0.013 (S / cm), more preferably >0.018 (S / cm); the highly reinforced composite membrane has extremely low air permeability, with a time required to pass 100 ml of air through the composite membrane, as measured by a Gurley air permeability meter, being >5 minutes, preferably >15 minutes.

[0094] In some embodiments of the present invention, the resulting special highly reinforced fluorine-containing proton or ion exchange membrane composite electrode includes at least two layers of microporous reinforcement membranes, each layer of microporous reinforcement membrane being filled on both sides with a fluorine-containing proton exchange resin or ion exchange resin, with 2 to 30 layers of microporous reinforcement membranes being preferred, and most preferably 2 to 15 layers. The total weight of the reinforced composite membrane electrode is 3 to 80 g / m². 2 Preferably 8-50 g / m 2 Most preferably 10-30 g / m 2 The thickness (see ASTM D756) is 3 μm to 35 μm, preferably 5 μm to 25 μm, most preferably 7 μm to 18 μm; the tensile strength (TD, MD) of the highly reinforced composite film electrode is >40 MPa in both directions, preferably >50 MPa, most preferably >80 MPa; the ionic conductivity at room temperature of the highly reinforced composite film electrode is >0.007 (S / cm), preferably >0.013 (S / cm), more preferably >0.018 (S / cm); the air permeability of the highly reinforced composite film is very low, with the time required for 100 ml of air to pass through the composite film, as measured by a Gurley air permeability meter, being >5 minutes, preferably >15 minutes.

[0095] In another embodiment of the present invention, the special highly reinforced fluorine-containing proton or ion exchange membrane composite electrode comprises at least two layers of microporous reinforcement membranes, preferably 2 to 45 layers, most preferably 2 to 20 layers, with both sides of the microporous reinforcement membranes filled with a fluorine-containing proton exchange resin or ion exchange resin, the weight ratio of the microporous reinforcement membranes to the fluorine-containing proton exchange resin or ion exchange resin being (5:95) to (40:60), preferably (10:90) to (30:70), and the total weight of this highly reinforced composite membrane electrode being 70 to 500 g / m² 2 Preferably 80-300 g / m 2 Most preferably 100-200 g / m² 2The thickness of the composite film electrode is 30 μm to 300 μm, preferably 50 μm to 200 μm, most preferably 60 μm to 120 μm. The tensile strength (TD, MD) of the highly reinforced composite film electrode is >40 MPa in both directions, preferably >50 MPa, most preferably >80 MPa. The ionic conductivity at room temperature of the highly reinforced composite film electrode is >0.007 (S / cm), preferably >0.013 (S / cm), more preferably >0.018 (S / cm). The air permeability of the highly reinforced composite film electrode is very low, with the time required for 100 ml of air to pass through this composite film, as measured by a Gurley air permeability meter, being >5 minutes, preferably >15 minutes.

[0096] In yet another embodiment of the present invention, the specially reinforced fluorinated chlorine-containing alkaline battery film comprises three layers of microporous reinforcement films, each layer of microporous reinforcement films being filled on both sides with a fluorine-containing proton exchange resin or ion exchange resin, the weight ratio of the microporous reinforcement film to the fluorine-containing proton exchange resin or ion exchange resin being (5:95) to (40:60), preferably (10:90) to (30:70), and the total weight of the highly reinforced fluorinated chlorine-containing alkaline battery film being 2 to 500 g / m² 2 Preferably 5-300 g / m 2 Most preferably 5-200 g / m 2 The thickness of the microporous reinforcement film is 1 μm to 300 μm, preferably 2 μm to 200 μm, most preferably 3 μm to 100 μm; the tensile strength (see ASTM D882 test method) (TD, MD) of the highly reinforced fluorine-chlorine-containing film is >40 MPa in both directions, preferably >50 MPa, most preferably >80 MPa; the room-temperature proton / ion conductivity (Ionic Conductivity, GB / T20042.3-2009 Part 3 of Proton Exchange Membrane Fuel Cells: Proton Exchange Membrane Measurement Method) of the reinforced composite film is >0.007 (S / cm), preferably >0.013 (S / cm), more preferably >0.018 (S / cm); and the air permeability of the reinforced composite film is extremely low, with the time required for 100 ml of air to pass through the composite film, as measured by a Gurley air permeability meter, being >5 minutes, preferably >15 minutes.

[0097] In yet another embodiment of the present invention, the special highly reinforced fluorinated chlorine-containing alkaline battery film comprises 3 to 30 layers of microporous reinforcement film, each layer of microporous reinforcement film being filled on both sides with a fluorine-containing proton exchange resin or ion exchange resin, the highly reinforced fluorinated chlorine-containing alkaline battery composite film having one entire surface coated with a perfluorocarboxylic acid resin and the other entire surface coated with a perfluorosulfonic acid resin, the total weight ratio of the microporous reinforcement film to the fluorine-containing proton exchange resin or ion exchange resin being (5:95) to (40:60), preferably (10:90) to (30:70), and the total weight of the highly reinforced chlorine-containing alkaline battery composite film being 20 to 450 g / m² 2 Preferably 50-300 g / m 2 Most preferably 100-250 g / m 2 The composite film has a thickness of 10 μm to 230 μm, preferably 25 μm to 150 μm, most preferably 50 μm to 130 μm, a tensile strength (TD, MD) of the highly reinforced fluorine-chlorine-containing alkaline battery composite film is >40 MPa in both directions, preferably >50 MPa, most preferably >80 MPa, an ionic conductivity at room temperature of the highly reinforced fluorine-chlorine-containing alkaline battery composite film is >0.007 (S / cm), preferably >0.013 (S / cm), more preferably >0.018 (S / cm), and the air permeability of the reinforced fluorine-chlorine-containing alkaline battery composite film is extremely low, with a time required for 100 ml of air to pass through the composite film, as measured by a Gurley air permeability meter, being >5 minutes, preferably >15 minutes.

[0098] The total dry weight ratio in which the perfluorocarboxylic acid resin is filled into the special highly reinforced fluorine-chlorine-containing alkaline battery film is (1:9) to (5:5), preferably (2:8) to (4:6).

[0099] The special high-reinforcement fluorine-chlorine-containing alkaline battery film of the present invention is free from contamination by release agents, can withstand multiple heat treatments, and has heat resistance of at least 100°C. The multilayer microporous reinforcement film can conceal air bubble defects that may occur from a single coating film, significantly improving productivity. It also contributes to improving the tensile strength of the special high-strength fluorine-chlorine-containing alkaline battery film, improving its dimensional stability, which is extremely important for its service life, enabling high-speed continuous production, meeting the requirements of commercial mass production, and resulting in a product film with high cleanliness and stability.

[0100] <Release film that does not contain release agents> One of the objectives of the present invention is to overcome the shortcomings of conventional production processes. Conventional release films contain trace amounts of free release agents, particularly silicon-containing release agents, which are easily adsorbed onto the cast coating material, contaminating the final product and making cleaning difficult. This is extremely disadvantageous for producing high-quality, highly clean proton exchange films. The present invention provides a release film that does not contain release agents (i.e., the film itself has a release function due to its physical properties, and does not require the application of corona or release agents), which can be used in continuous production. A fluorine-containing proton exchange resin solution or ion exchange resin solution can be applied to such a release film by a casting method, and it will not deform even when dried at least 100°C, enabling the production of high-quality fluorine-containing proton exchange films or fluorine-containing ion exchange films. Furthermore, by applying such a modified film that does not contain release agents to the surface with one or more cast coatings, and a micropore-reinforced film can be further coated onto the coating solution. By drying and repeatedly processing the applied fluorine-containing sulfonic acid or carboxylic acid resin solution, the mass production of fluorine-containing proton exchange films can be made more convenient and production costs can be further reduced.

[0101] The present invention discloses a special release film that does not contain any coating release agents, does not require corona treatment, has a thickness of 10 to 500 μm, preferably 25 to 300 μm, a width of at least 100 mm, can withstand heat at at least 100°C without deformation, preferably 120°C without deformation, can be used to manufacture fluorine-containing proton exchange films or fluorine-containing ion exchange films, and is applicable to battery separators. The manufacturing process for battery separators involves using a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution with excellent film-forming properties, casting a release film onto such a film, drying it to form a film, and winding it onto a roll.

[0102] The release film component is selected from (1) a polymer obtained by polymerizing or copolymerizing bisphenol A with engineering plastics containing bisphenol A as the main component (weight ratio > 50%), such as polycarbonate, polyphenylene ether, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, or (2) a polymer obtained by polymerizing or copolymerizing hexafluorodimethylbisphenol A with engineering plastics containing hexafluorodimethylbisphenol A as the main component (weight ratio > 50%), such as polycarbonate, polyphenylene ether, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

[0103] We have discovered that the film surface contains no additional coating release agents, does not require corona treatment, the coating film can be cast once or multiple times, the strength of the composite film can be improved by coating with a microporous reinforcement film during the casting process, and a proton exchange film or ion exchange film can be formed that is unexpectedly easy to peel off after casting and drying, and free from residual solvent and release agent contamination. The advantages of the material of the present invention are that since such a release film does not contain a coated release agent, there is no risk of the release agent contaminating the product film, multiple casting coatings of multilayer microporous reinforcement films can hide and significantly reduce the defects of air bubbles that may occur from a single coating film, significantly improve productivity, enable continuous production, meet the requirements of commercial mass production, the resulting product film has high cleanliness and stability, and waste recovery is convenient.

[0104] When manufacturing a battery separator using a special release film that does not contain a mold release agent by a cast coating method, the manufacturing process may be as follows: 1. Apply a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution to one side of the special release film and allow it to adhere, then coat the applied resin solution with a microporous reinforcement film, allow the resin solution applied to the special release film and the coated microporous reinforcement film to adhere well, and then dry. 2. The composite film obtained in step 1 (placed on the special engineering plastic film) is subjected to a second cast coating of resin solution on the coated first layer of microporous reinforcement film, then coat the second layer of microporous reinforcement film on the resin solution that was cast coated for the second time, allow the resin solution applied to the special release film to adhere well with the coated microporous reinforcement film, then dry, and after drying, the void volume on both sides of each layer of microporous reinforcement film is filled with fluorine-containing proton exchange resin to more than 60%, preferably more than 80%, and most preferably more than 90%. 3. Repeat step 2 at least 0 to 48 times, preferably 0 to 28 times, and finally apply the resin solution to the coated microporous reinforcement layer and dry it to obtain a highly reinforced proton exchange membrane, ion exchange membrane, or membrane electrode having at least two layers (2 to 50 layers, preferably 2 to 30 layers) of microporous reinforcement. [Example 1]

[0105] (Release film that does not contain release agents) (1A) A carbonate resin obtained by polycondensation of bisphenol A (without the addition of any auxiliary agents or mold release agents) is melt-extruded and biaxially stretched to obtain transparent films with thicknesses of approximately 300 μm, 150 μm, and 25 μm (used as is without corona treatment).

[0106] (1B) A polycarbonate resin obtained by polycondensation of hexafluorodimethylphenol A (without the addition of any additives or mold release agents) is melt-extruded and biaxially stretched to obtain transparent films with thicknesses of approximately 300 μm, 150 μm, and 25 μm (used as is without corona treatment).

[0107] (1C) A release film of the thickness described above is manufactured, using polyphenylene ether-p-bisphenol A type epoxy resin (EHPPO type, used as is without any additives or release agents, and without corona treatment), and the resin manufacturing process is superbranched polyphenylene JPEG0007912243000001.jpg5170 Fuji, Li Xiaoyu, Wang Haiqiao, Key Laboratory of the Department of Carbon Fiber and Functional Polymers, School of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, Abstract: Reactive terminal epoxy superbranched polyphenylene ether (EHPPO) was prepared, added to bisphenol A type epoxy resin for modification, cured with an acid anhydride curing agent, and the thermal, mechanical, and dielectric properties of the cured samples were characterized. Comparative modification studies were also conducted using superbranched polyphenylene ether (CHPPO) with the same molecular main chain structure but non-reactive benzyl end groups. From these results, it was found that the two different modifying agents each had superior modification effects on bisphenol A type epoxy resin. The epoxy resin modified with EHPPO had better thermal performance and tensile strength, while the epoxy resin modified with CHPPO had a lower dielectric constant. The films obtained as described in (1A) to (1C) above have a high release effect and leave no residue, even without corona treatment or the application of a release agent. [Example 2]

[0108] (Formulation of proton exchange resin solution, ion exchange resin solution, or mixture) S1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 830%], 40% ethanol, and 40% water).

[0109] S2 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 790], 40% ethanol, and 40% water).

[0110] L1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 1000], 40% n-propanol, and 40% water).

[0111] L2 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 950], 40% ethanol, and 40% water).

[0112] L3 (weight ratio: 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 1100], 40% n-propanol, and 40% water).

[0113] L4 (Weight ratio: Contains approximately 10% platinum black powder, 10% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 1100], 40% n-propanol, and 40% water.)

[0114] L5 (weight ratio: contains approximately 5% ZrO2 zirconia nanopowder, approximately 15% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 1100], 40% n-propanol, and 40% water).

[0115] LC6 (weight ratio: contains approximately 5% ZrO2 zirconia nanopowder, approximately 15% [tetrafluoroethylene and CF2=CF-O-CF2CF2CF2-COOH fluorine-containing proton exchange resin copolymer, with an acid equivalent (meq / g) of approximately 1000], 40% n-propanol, and 40% water).

[0116] LC7 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-COOH fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 950], 40% n-propanol, and 40% water).

[0117] L8 (weight ratio: contains approximately 10% platinum / carbon black powder, 10% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 1100], 40% n-propanol, and 40% water). [Example 3]

[0118] (For comparison) (Release film 1A, a microporous reinforced film with a thickness of 10 μm per layer)

[0119] A proton exchange resin solution S1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 830], 40% ethanol, and 40% water) is applied to a release film 1A with a thickness of approximately 25 μm, and then covered with a microporous polytetrafluoroethylene reinforced film with a thickness of approximately 10 μm. This film is dried with a blower, and then the same proton exchange resin solution is applied again to the microporous polytetrafluoroethylene reinforced film. The film was then dried with a blower, and finally baked in an oven at 120 degrees Celsius for 5 minutes before being removed and cooled. The fluorine-containing proton exchange film could be smoothly peeled off the release film 1A, with no visible residue on the release film. The thickness of the peeled fluorine-containing proton exchange film was approximately 16-18 μm on a flat surface, the density was approximately 2.20, the acid equivalent number (meq / g) of the composite film was approximately 1000, the tensile strengths TD and MD were both 40-50 MPa, the room temperature proton / ion conductivity (Ionic Conductivity) was >0.012 (S / cm), and the time required for 100 ml of air to pass through this composite film, as measured by a Gurley air permeability meter, was >15 minutes. [Example 4]

[0120] (Release film 1A, a two-layer microporous reinforcement film with a thickness of 5 μm) A proton exchange resin solution S1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, acid equivalent number (meq / g) approximately 830%, containing 40% ethanol and 40% water]) is applied to a release film 1A with a thickness of approximately 25 μm, and then a thin microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of approximately 5 μm is applied and dried with a blower. Subsequently, the same proton exchange resin solution is applied to the microporous polytetrafluoroethylene reinforced film, and then the same thin microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of approximately 5 μm is applied and dried with a blower. The same proton exchange resin solution was applied to the olioethylene-reinforced film, dried with a blower, and finally baked in an oven at 120 degrees Celsius for 5 minutes before being removed and cooled. The fluorine-containing proton exchange film could be smoothly peeled off the release film 1A, with no visible residue on the release film. The thickness of the peeled fluorine-containing proton exchange film was approximately 16-18 μm on a flat surface, the density was approximately 2.19, the acid equivalent number (meq / g) of the composite film was approximately 1020, and the tensile strengths TD and MD were both 60-70 MPa. Unexpectedly, the tensile strength was superior to that of the single-layer microporous reinforced film with a thickness of 10 μm used in Example 3. The room-temperature proton / ion conductivity (Ionic Conductivity) was >0.012 (S / cm), and it was found that the time required for 100 ml of air to pass through this composite film, as measured by a Gurley air permeability meter, was >15 minutes. [Example 5]

[0121] (Release film 1A, a 3-layer microporous reinforced film with a thickness of 3 μm) A proton exchange resin solution S1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 830], 40% ethanol, and 40% water) is applied to a release film 1A with a thickness of approximately 25 μm, and then a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of approximately 3 μm is applied and dried with a blower. Subsequently, the same proton exchange resin solution is applied to the microporous polytetrafluoroethylene reinforced film, and then a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of approximately 3 μm is applied and dried with a blower. Subsequently, the same proton exchange resin solution is applied to the microporous polytetrafluoroethylene reinforced film, and then a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of approximately 3 μm is applied and dried with a blower. A polytetrafluoroethylene-reinforced film (continuous phase) was coated and dried with a blower. Then, the same proton exchange resin solution was applied to the microporous polytetrafluoroethylene-reinforced film and dried again with a blower. Finally, it was heated in an oven at 120 degrees Celsius, baked for 5 minutes, removed, and cooled. The fluorine-containing proton exchange film could be smoothly peeled off the release film 1A, with no visible residue on the release film. The thickness of the peeled fluorine-containing proton exchange film was approximately 16-18 μm on a flat surface, the density was approximately 2.18, the acid equivalent number (meq / g) of the composite film was approximately 1040, and the tensile strengths TD and MD were both 80-90 MPa. Unexpectedly, its strength was superior to that of the single-layer microporous reinforced film with a thickness of 10 μm used in Example 3. Room temperature proton / ionic conductivity (Ionic We found that the Conductivity was >0.012 (S / cm), and that the time required for 100 ml of air to pass through this composite membrane, as measured by a Gurley air permeability meter, was >15 minutes. [Example 6]

[0122] (Release film 1B, two-layer microporous reinforcement film) A proton exchange resin solution S2 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 790], 40% ethanol, and 40% water) is applied to a release film 1B with a thickness of approximately 25 μm, and then a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of approximately ~2 μm is applied and dried with a blower. After that, the same proton exchange resin solution is applied to the microporous polytetrafluoroethylene reinforced film again, and then a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of approximately ~2 μm is applied. The film is then dried with a blower, and the same proton exchange resin solution is applied to the microporous polytetrafluoroethylene reinforced film, dried with a blower, and finally heated in an oven to 120 degrees Celsius and baked for 5 minutes before being removed and cooled. The fluorine-containing proton exchange film can be smoothly peeled off the release film 1B, no residue is visible on the release film, the thickness of the peeled fluorine-containing proton exchange film is approximately 8-9 μm on a flat surface, the density is approximately 2.20, the acid equivalent number (meq / g) of the composite film is approximately 10¹⁰, the tensile strength TD and MD are both >100 MPa, the room temperature proton / ion conductivity (Ionic Conductivity) is >0.013 (S / cm), and the time required for 100 ml of air to pass through this composite film, as measured by a Gurley air permeability meter, is >15 minutes. [Example 7]

[0123] (Release film 1C, 2 layers of microporous reinforcement film) A proton exchange resin solution S1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 830], 40% ethanol, and 40% water) is applied to a release film 1C with a thickness of approximately 25 μm, and then a thinner microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of approximately ~1 μm is applied and dried with a blower. After that, the same proton exchange resin solution is applied again to the microporous polytetrafluoroethylene reinforced film, and then a thin microporous polytetrafluoroethylene reinforced film (continuous phase) with a thickness of approximately ~1 μm is applied and covered. The film was dried with a blower, then the same proton exchange resin solution was applied to the microporous polytetrafluoroethylene reinforced film, dried again with a blower, and finally heated in an oven at 120 degrees Celsius for 5 minutes before being removed and cooled. The fluorine-containing proton exchange film could be smoothly peeled off the release film 1C, with no visible residue on the release film. The thickness of the peeled fluorine-containing proton exchange film was approximately 5-6 μm on a flat surface, the density was approximately 2.20, the acid equivalent number (meq / g) of the composite film was approximately 990, the tensile strength TD and MD were both >120 MPa, the room temperature proton / ion conductivity (Ionic Conductivity) was >0.015 (S / cm), and the time required for 100 ml of air to pass through this composite film, as measured by a Gurley air permeability meter, was >15 minutes. [Example 8]

[0124] (Release film 1A, 5-layer microporous reinforcement film, 2 layers of polytetrafluoroethylene on the front and back, 3 layers of polypropylene in the middle) A proton exchange resin solution S1 (weight ratio: approximately 20% tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, acid equivalent (meq / g) approximately 830, containing 40% ethanol and 40% water) is cast-coated onto a release film 1A with a thickness of approximately 150 μm, and then a thin microporous polytetrafluoroethylene reinforced film with a thickness of approximately ~3 μm is coated over it and dried with a blower. Subsequently, the same proton exchange resin solution is applied again to the microporous polytetrafluoroethylene reinforced film, and then a thin microporous polypropylene reinforced film with a thickness of approximately ~4 μm is coated over it and dried with a blower. Subsequently, the same proton exchange resin solution is applied again to the microporous polypropylene reinforced film, and then a thin microporous polypropylene reinforced film with a thickness of approximately ~4 μm is coated over it and dried with a blower. Subsequently, the same proton exchange resin solution is applied again to the microporous polypropylene reinforced film, and so A thin, microporous polypropylene reinforced film with a thickness of approximately 4 μm is coated and dried with a blower. Then, the same proton exchange resin solution is applied again to the microporous polypropylene reinforced film, and a thin, microporous polytetrafluoroethylene reinforced film with a thickness of approximately 3 μm is coated and dried with a blower. Then, the same proton exchange resin solution is applied again to the microporous polytetrafluoroethylene reinforced film and dried again with a blower. Finally, it is heated in an oven at 120 degrees Celsius, baked for 5 minutes, removed and cooled, and the fluorine-containing proton exchange film can be smoothly peeled off the release film 1A. No residue is visible on the release film, the thickness of the peeled fluorine-containing proton exchange film is approximately 28-30 μm on a flat surface, the density is approximately 2.1, the acid equivalent number (meq / g) of the composite film is approximately 1050, the tensile strength TD and MD are both >70 MPa, and the room temperature proton / ion conductivity (Ionic The conductivity is > 0.011 (S / cm), and the time required for 100 ml of air to pass through this composite membrane, as measured by a Gurley air permeability meter, is > 15 minutes. [Example 9]

[0125] (Release film 1A, 10 layers of microporous reinforcement film, 2 layers of polytetrafluoroethylene on the front and back, 8 layers of polyacrylonitrile PAN in the middle) A proton exchange resin solution L1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 1000], 40% n-propanol, and 40% water) is cast-coated onto a release film 1A with a thickness of approximately 150 μm, and then a microporous polytetrafluoroethylene reinforced film with a thickness of approximately ~3 μm is coated over it and dried with a blower. After that, a proton exchange resin solution L2 (weight ratio: approximately 20% [tetrafluoroethylene]) is applied to the microporous polytetrafluoroethylene reinforced film. A solution of ethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H (fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 950, containing 40% ethanol and 40% water) is applied, and then a thin polyacrylonitrile PAN-reinforced film with a thickness of approximately 3-4 μm is coated and dried with a blower. Subsequently, the same proton exchange resin solution L2 is applied to the microporous polyacrylonitrile PAN-reinforced film, and then a thin polyacrylonitrile PAN-reinforced film with a thickness of approximately 3-4 μm is coated and dried with a blower. Subsequently, the microporous polyacrylonitrile PAN-reinforced film The same proton exchange resin solution L2 is applied, and then a thin polyacrylonitrile PAN reinforced film with a thickness of approximately 3-4 μm is covered and dried with a blower. Then, the same proton exchange resin solution L2 is applied to the microporous polyacrylonitrile PAN reinforced film, and then a thin polyacrylonitrile PAN reinforced film with a thickness of approximately 3-4 μm is covered and dried with a blower. Then, the same proton exchange resin solution L2 is applied to the microporous polyacrylonitrile PAN reinforced film, and then a thin polyacrylonitrile PAN reinforced film with a thickness of approximately 3-4 μm is covered and dried with a blower. Then, the microporous polyacrylonitrile The same proton exchange resin solution L2 is applied to the polyacrylonitrile PAN-reinforced film, and then a thin polyacrylonitrile PAN-reinforced film with a thickness of approximately 3-4 μm is covered and dried with a blower. Subsequently, the same proton exchange resin solution L2 is applied to the microporous polyacrylonitrile PAN-reinforced film, and then a thin polyacrylonitrile PAN-reinforced film with a thickness of approximately 3-4 μm is covered and dried with a blower. Subsequently, the same proton exchange resin solution L2 is applied to the microporous polyacrylonitrile PAN-reinforced film, and then a thin polyacrylonitrile PAN-reinforced film with a thickness of approximately 3-4 μm is covered and dried with a blower.The same proton exchange resin solution L2 was applied to a microporous polyacrylonitrile PAN-reinforced film, and then a thin polytetrafluoroethylene-reinforced film approximately 3 μm thick was coated over it. It was dried with a blower, and finally baked in an oven at 130°C for 10 minutes before being removed and cooled. The fluorine-containing proton exchange film could be smoothly peeled off the release film 1A, with no visible residue on the release film. The peeled fluorine-containing proton exchange film had a flat thickness of approximately 58-60 μm, a density of approximately 2.1, an acid equivalent number (meq / g) of approximately 1050, tensile strengths TD and MD both >50 MPa, room temperature proton / ion conductivity (Ionic Conductivity) >0.01 (S / cm), and the time required for 100 ml of air to pass through this composite film, as measured by a Gurley air permeability meter, was >15 minutes. [Example 10]

[0126] (Release film 1B and 15-layer microporous reinforcement film are both made of stretched polytetrafluoroethylene.) Proton exchange membrane electrodes containing platinum black on both sides: Because the ultra-fine powder of metallic platinum is black, it is called "platinum black," with an apparent density of 15.8-17.6 and a specific surface area of ​​40-60 m². 2The particle size is <10 nm. Platinum black powder and proton exchange resin solution L4 (weight ratio: approximately 10% platinum black powder, 10% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, acid equivalent number (meq / g) approximately 1100], 40% n-propanol, 40% water) are cast-coated onto a release film 1B with a thickness of approximately 150 μm, and then a thin microporous polytetrafluoroethylene reinforced film with a thickness of approximately ~3 μm is coated over it and dried with a blower. After that, proton exchange resin solution L1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer]) is applied to the microporous polytetrafluoroethylene reinforced film. A proton exchange resin copolymer (containing an acid equivalent number (meq / g) of approximately 1000, 40% n-propanol, and 40% water) is further applied, and a thin, microporous polytetrafluoroethylene reinforced film with a thickness of approximately 3 μm is covered and dried with a blower. Then, a proton exchange resin solution L2 (by weight: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, containing an acid equivalent number (meq / g) of approximately 950], 40% ethanol, and 40% water) is further applied to the microporous polytetrafluoroethylene reinforced film, and a thin, microporous polytetrafluoroethylene reinforced film with a thickness of approximately 3 μm is covered and dried with a blower. [Then, the following steps are repeated 10 times.]A proton exchange resin solution L2 is further applied to the microporous polytetrafluoroethylene reinforced film, and then a thin microporous polytetrafluoroethylene reinforced film with a thickness of approximately 3 μm is covered and dried with a blower. Subsequently, a proton exchange resin solution L1 is further applied to the microporous polytetrafluoroethylene reinforced film, and then a thin microporous polytetrafluoroethylene reinforced film with a thickness of approximately 3 μm is covered and dried with a blower. Finally, a proton exchange resin solution L4 containing platinum black is applied to the microporous polytetrafluoroethylene reinforced film. The material was then applied, dried with a blower, and finally baked in an oven at 130 degrees Celsius for 10 minutes before being removed and cooled. The fluorine-containing proton exchange film containing platinum black on both sides could be smoothly peeled off the release film 1B, with no visible residue on the release film. The thickness of the peeled fluorine-containing proton exchange film containing platinum black on both sides was approximately 87-90 μm on a flat surface, the density was approximately 2.2, the tensile strength TD and MD were both >50 MPa, the room temperature proton / ion conductivity (Ionic Conductivity) was >0.08 (S / cm), and the time required for 100 ml of air to pass through this composite film, as measured by a Gurley air permeability meter, was >15 minutes. [Example 11]

[0127] (Release film 1A, 20-layer microporous reinforcement film, both are made of stretched polytetrafluoroethylene) Reinforced chlorine-alkaline battery separator: Nanometallic zirconium oxide powder was mixed with a perfluorocarboxylic acid resin solution to obtain LC6 (weight ratio: approximately 5% ZrO2 zirconia nanopowder, 15% [tetrafluoroethylene and CF2=CF-O-CF2CF2CF2-COOH fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 1000], 40% n-propanol, and 40% water). This was cast-coated onto a release film 1A with a thickness of approximately 150 μm, and then coated with a thin microporous polytetrafluoroethylene reinforced film with a thickness of approximately ~3 μm. It was dried with a blower, and then the microporous polytetrafluoroethylene A fluoroethylene-reinforced film is coated with a perfluorocarboxylic acid resin solution LC7 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-COOH fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 950], 40% n-propanol, and 40% water), and then a thin, microporous polytetrafluoroethylene-reinforced film with a thickness of approximately 3 μm is coated over it and dried with a blower. After that, the microporous polytetrafluoroethylene-reinforced film is coated with a perfluorocarboxylic acid resin solution LC7 (weight ratio: approximately 20% [tetrafluoroethylene]). The process involves applying a fluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-COOH fluorine-containing proton exchange resin copolymer (with an acid equivalent number (meq / g) of approximately 950), 40% ethanol, and 40% water, then covering it with a thin, approximately 3 μm thick, microporous polytetrafluoroethylene reinforced film, drying it with a blower, and then applying the same perfluorocarboxylic acid resin solution LC7 to the microporous polytetrafluoroethylene reinforced film, covering it with another approximately 3 μm thick, and drying it with a blower (3 steps). [The process is repeated 13 times], [then, perfluorosulfonic acid resin solution L2 is applied to the microporous polytetrafluoroethylene reinforced film, and then a thin microporous polytetrafluoroethylene reinforced film with a thickness of approximately 3 μm is applied and dried with a blower], finally, nanozirconia powder-containing perfluorosulfonic acid resin solution L5 is applied to the microporous polytetrafluoroethylene reinforced film and dried with a blower, and finally, it is heated in an oven at 130 degrees Celsius, baked for 10 minutes, then removed and cooled, so that both sides contain zirconia and one side contains perfluorocarboxylic acid resin,The other side yields a reinforced composite film containing fluorine-containing sulfonic acid resin, which can be smoothly peeled off the release film 1A. No residue is visible on the release film, and both peeled surfaces contain zirconia. The thickness of the fluorine-chlorine-containing alkaline battery film is approximately 115-120 μm on a flat surface, with a density of approximately 2.2. The tensile strengths TD and MD are both >50 MPa, the room-temperature proton / ion conductivity (Ionic Conductivity) is >0.01 (S / cm), and the time required for 100 ml of air to pass through this composite film, as measured by a Gurley air permeability meter, is >15 minutes. [Example 12]

[0128] (Release film 1B, 30-layer microporous reinforcement film; both are stretched polytetrafluoroethylene films pre-filled with ceria CeO2.) Reinforced proton exchange membrane: L3 (weight ratio: 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent (meq / g) of approximately 1100], 40% n-propanol, and 40% water) is cast-coated onto a release film 1B with a thickness of approximately 300 μm, and then covered with a thin, microporous polytetrafluoroethylene reinforced film with a thickness of approximately 3 μm [pre-filled weight ratio (ceria CeO2: polytetrafluoroethylene) ~10%], dried with a blower, and then, A perfluorosulfonic acid resin solution L2 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, acid equivalent (meq / g) approximately 950], 40% ethanol, and 40% water) is applied to a microporous polytetrafluoroethylene reinforced film, and then a thin microporous polytetrafluoroethylene reinforced film (containing 10% ceria CeO2) with a thickness of approximately 3 μm is applied, dried with a blower, and then the microporous polytetrafluoroethylene The reinforcing film is coated with perfluorocarboxylic acid resin solution L2, and then a thin, approximately 3 μm thick, microporous polytetrafluoroethylene reinforcing film (containing 10% ceria CeO2) is applied and dried with a blower. [Then, the same perfluorosulfonic acid resin solution L2 is applied to the microporous polytetrafluoroethylene reinforcing film, and then a microporous polytetrafluoroethylene reinforcing film (containing 10% ceria CeO2) approximately 3 μm thick is applied and dried with a blower. This process is repeated 27 times.] Finally, the microporous polytetrafluoroethylene reinforcing film is coated with The fluorine-containing sulfonic acid resin solution L3 was applied, dried with a blower, and finally baked in an oven at 130 degrees Celsius for 10 minutes before being removed and cooled. The fluorine-containing sulfonic acid resin reinforced film containing ceria could be smoothly peeled off from the release film 1B, with no visible residue on the release film. The thickness of the peeled ceria-containing reinforced fluorine-containing proton exchange film was approximately 175-180 μm on a flat surface, the density was approximately 2.2, the tensile strengths TD and MD were both >50 MPa, the room temperature proton / ion conductivity (Ionic Conductivity) was >0.01 (S / cm), and the time required for 100 ml of air to pass through this composite film, as measured by a Gurley air permeability meter, was >15 minutes. [Example 13]

[0129] (Release film 1A, 45-layer microporous reinforcement film; both are stretched polytetrafluoroethylene films pre-filled with ceria CeO2.) Reinforced proton exchange membrane: L5 (weight ratio: 5% zirconia ZrO2, 15% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 1100], 40% n-propanol, 40% water) was cast-coated onto a release film 1A with a thickness of approximately 300 μm, and then a thin, microporous polytetrafluoroethylene reinforced film with a thickness of approximately ~3 μm [pre-filled weight ratio (ceria CeO2: polytetrafluoroethylene) ~10%] was dried with a blower, and then, A perfluorosulfonic acid resin solution L2 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 950], 40% ethanol, and 40% water) is applied to a microporous polytetrafluoroethylene reinforced film, and then a thin microporous polytetrafluoroethylene reinforced film (containing 10% ceria CeO2) with a thickness of approximately 3 μm is dried with a blower, and then perfluorocarbon acid is applied to the microporous polytetrafluoroethylene reinforced film. The perfluorosulfonic acid resin solution L2 is applied, and then a thin, approximately 3 μm thick, microporous polytetrafluoroethylene reinforced film (containing 10% ceria CeO2) is covered and dried with a blower. [Then, the process of applying the same perfluorosulfonic acid resin solution L2 to the microporous polytetrafluoroethylene reinforced film, and covering it with a microporous polytetrafluoroethylene reinforced film (containing 10% ceria CeO2) approximately 3 μm thick, and drying with a blower is repeated 37 times.] Finally, the microporous polytetrafluoroethylene reinforced film is coated with a fluorine-containing sulfonic acid resin solution L5. The material is applied, dried with a blower, and finally baked in an oven at 130 degrees Celsius for 10 minutes before being removed and cooled to obtain a fluorine-containing sulfonic acid resin reinforced film containing zirconia on both sides and ceria internally. This reinforced composite film can be smoothly peeled off the release film 1A, with no visible residue on the release film. The thickness of the peeled ceria-containing reinforced fluorine-containing proton exchange film is approximately 260-270 μm on a flat surface, with a density of approximately 2.2, tensile strengths TD and MD both >50 MPa, and ionic conductivity at room temperature >0.The air permeability is 0.01 (S / cm), and the time required for 100 ml of air to pass through this composite membrane, as measured by a Gurley air permeability meter, is >15 minutes. [Example 14]

[0130] (Release film 1B, 3-layer microporous reinforcement film) A proton exchange resin solution L8 (weight ratio: approximately 10% platinum / carbon black, 10% [tetrafluoroethylene and CF2=CF-O-CF2CFCF3-OCF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent (meq / g) of approximately 1100], 40% n-propanol, and 40% water) was cast-coated onto a release film 1B with a thickness of approximately 150 μm, and then covered with a thin, approximately 3 μm thick, microporous polytetrafluoroethylene reinforced film (containing 10% ceria CeO2), and dried with a blower. Subsequently, proton exchange resin solution L2 was applied to the microporous polytetrafluoroethylene reinforced film, and then covered with a thin, approximately 3 μm thick, microporous polytetrafluoroethylene reinforced film (containing 10% ceria CeO2), and dried with a blower. Next, the microporous polytetrafluoroethylene reinforced film was coated with proton exchange resin solution L2, and then covered with a thin microporous polytetrafluoroethylene reinforced film (containing 10% ceria CeO2) with a thickness of approximately 3 μm, and dried with a blower. Then, the microporous polytetrafluoroethylene reinforced film was coated with proton exchange resin solution L8, and dried with a blower. Finally, it was heated in an oven at 120 degrees Celsius, baked for 5 minutes, removed and cooled, and the fluorine-containing proton exchange film could be smoothly peeled off the release film 1B. No residue was visible on the release film, the thickness of the peeled fluorine-containing proton exchange film electrode was approximately 28 μm, the tensile strengths TD and MD of the film were both 80-90 MPa, the room temperature proton / ion conductivity (Ionic Conductivity) was >0.012 (S / cm), and the time required for 100 ml of air to pass through this composite film, as measured by a Gurley air permeability meter, was >15 minutes. It is suitable for use as a membrane electrode in fuel cells. <Comparative Example 1>

[0131] (PET base film, no release agent included, single-layer microporous reinforcement film) The PET (CAS: 25038-59-9) base film contains no mold release agent on its surface. A proton exchange resin solution S1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 830], 40% ethanol, and 40% water) was applied to a PET base film with a thickness of approximately 25 μm that did not contain a mold release agent. The cast slurry was flat, and a microporous polytetrafluoroethylene reinforced film with a thickness of approximately 8-9 μm was applied and dried with a blower. Then, the same proton exchange resin solution was applied to the microporous polytetrafluoroethylene reinforced film and dried with a blower. Finally, it was heated in an oven at 120 degrees Celsius, baked for 5 minutes, removed, and cooled. The fluorine-containing proton exchange film could not be peeled off the PET base film, and could not be peeled off smoothly even when immersed in water. PET is the most common commercially available release film material and, similarly, is a base film made from aromatic engineering plastics and contains no release agents. However, while PET base films are not suitable for producing fluorine-containing proton exchange films, the release films proposed in the above examples of the present invention, such as 1A, 1B, and 1C, exhibit excellent performance suitable for application, yielding unexpected results. <Comparative Example 2>

[0132] (PET base film, no release agent included, corona treated, single layer of microporous reinforcement film) The PET base film (CAS: 25038-59-9) contained no mold release agent on its surface, but was corona-treated. Proton exchange resin solution S1 (weight ratio: approximately 20% tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 830, 40% ethanol, and 40% water) was applied to the corona-treated PET base film, which was approximately 25 μm thick. The cast slurry was flat, and a microporous polytetrafluoroethylene reinforced film approximately 8-9 μm thick was applied to coat the film. It was dried with a blower, and then the same proton exchange resin solution was applied to the microporous polytetrafluoroethylene reinforced film. It was dried with a blower, and finally heated in an oven at 120 degrees Celsius for 5 minutes. After baking and cooling, the fluorine-containing proton exchange film could not be peeled off from the corona-treated PET base film, and could not be peeled off smoothly even when immersed in water. PET is the most common commercially available release film material and, similarly, is a base film made from aromatic engineering plastics and contains no release agents. However, while PET base films are not suitable for producing fluorine-containing proton exchange films, the release films proposed in the above examples of the present invention, such as 1A, 1B, and 1C, exhibit excellent performance suitable for application, yielding unexpected results. <Comparative Example 3>

[0133] (The PET release film contains a silicone release agent and is a single layer of microporous reinforcement film.) Conventional release films have often been made by corona-treating PET (CAS: 25038-59-9) and adding release agents, such as silicon-containing or fluorine-containing release agents. A proton exchange resin solution S1 (weight ratio: approximately 20% [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, with an acid equivalent number (meq / g) of approximately 830], 40% ethanol, and 40% water) was applied to a PET release film containing a silicone release agent with a thickness of approximately 25 μm. The flatness of the cast slurry was poor, and internal aggregation occurred. Then, a microporous polytetrafluoroethylene reinforced film with a thickness of approximately 8-9 μm was applied and dried with a blower. After that, the microporous polytetrafluoroethylene reinforced film... The same proton exchange resin solution was applied, dried with a blower, and finally heated in an oven at 120 degrees Celsius for 5 minutes before being removed and cooled. The fluorine-containing proton exchange membrane could be smoothly peeled off this (PET / silicone) release film, and no residue was visible on the release film. The thickness of the peeled fluorine-containing proton exchange membrane electrode was approximately 10-18 μm, and it had poor flatness. Infrared IR analysis revealed that silicon-containing contaminants remained on the film surface, and such a release film is not suitable for use in the production of high-quality proton exchange membranes. <Comparative Example 4>

[0134] (The PET release film contains a fluorine-containing release agent and is a single layer of microporous reinforced film.) A PET release film with a fluorine-containing release agent on its surface was used. A proton exchange resin solution S1 (weight ratio: approximately 20 [tetrafluoroethylene and CF2=CF-O-CF2CF2-SO3H fluorine-containing proton exchange resin copolymer, its acid equivalent (meq / g) approximately 830], 40% ethanol, and 40% water] was applied to a PET release film containing a fluorine release agent with a thickness of approximately 25 μm. The cast slurry was well flat, and a microporous polytetrafluoroethylene reinforced film with a thickness of approximately 8-9 μm was coated over it and dried with a blower. Then, the same proton exchange resin solution was applied to the microporous polytetrafluoroethylene reinforced film and dried with a blower. Finally, it was heated in an oven at 120 degrees Celsius, baked for 5 minutes, and then removed and cooled. The fluorine-containing proton exchange film could not be peeled off from the (PET / fluorine) release film, and could only be peeled off after being immersed in water. The thickness of the fluorine-containing proton exchange film was approximately 13-16 μm, and the surface was partially damaged. Such release films are also unsuitable for use in the production of high-quality proton exchange membranes.

[0135] As is clear from the above examples and comparative examples, the special release agent-free release film used in the present invention is used in composite films of special highly reinforced fluorine-containing proton or ion exchange films, composite film electrodes, or fluorine-chlorine-containing alkaline battery films, and has superior performance to composite films obtained from conventional release films containing release agents.

[0136] Those skilled in the art will understand that various modifications and variations are possible based on the above-described technical forms and concepts, and it is intended that all such modifications and variations fall within the scope of the claims of this invention.

Claims

1. A composite membrane of a special highly reinforced fluorine-containing proton or ion exchange membrane (hereinafter referred to as "this composite membrane") which is substantially free from contamination by release agents, This composite film includes at least two layers of microporous reinforcement films. Each layer of the microporous reinforcement film is filled on both sides with a fluorine-containing proton or ion exchange resin, and the weight ratio of the microporous reinforcement film to the fluorine-containing proton or ion exchange resin is 5:95 to 40:

60. The thickness of the composite film is 1 μm to 300 μm. The aforementioned composite film has a tensile strength exceeding 60 MPa in both the MD and TD directions, and a room-temperature ionic conductivity exceeding 0.007 S / cm. This composite membrane is characterized by having extremely low air permeability, and the time required for 100 ml of air to pass through the composite membrane, as measured by a Gurley air permeability meter, exceeds 5 minutes.

2. In the composite film according to claim 1, the weight ratio of the micropore-reinforced film to the fluorine-containing proton or ion exchange resin is 10:90 to 30:70, or the total weight of the composite film is 2 to 500 g / m². ２ This composite film is characterized by the following:

3. A composite film electrode using the composite film described in claim 1 or claim 2 as a battery separator, The total weight of the composite film electrodes is 2 to 500 g / m². ２ A special high-enhancement fluorine-containing proton or ion exchange membrane composite membrane electrode characterized by having a thickness of 1 μm to 300 μm, tensile strength exceeding 60 MPa in both the MD and TD directions, ionic conductivity exceeding 0.007 S / cm at room temperature, extremely low air permeability, and a time required for 100 ml of air to pass through the composite membrane electrode, as measured by a Gurley air permeability meter, exceeding 5 minutes.

4. A special highly reinforced fluorine-chlorine-containing alkaline battery film that is substantially free from contamination by release agents, It comprises at least two layers of microporous reinforcement film, each layer of microporous reinforcement film being filled on both sides with a fluorine-containing proton exchange resin or ion exchange resin, and the weight ratio of the microporous reinforcement film to the fluorine-containing proton exchange resin or ion exchange resin is 5:95 to 40:

60. Total weight: 20-500 g / m ２ The thickness is 10 μm to 260 μm. A special highly reinforced fluorinated chlorine-containing alkaline battery film characterized by tensile strength exceeding 60 MPa in both the MD and TD directions, ionic conductivity exceeding 0.007 S / cm at room temperature, and a time required for 100 ml of air to pass through it, as measured by a Gurley air permeability meter, exceeding 5 minutes.

5. The alkaline battery film according to claim 4, characterized in that the weight ratio of the micropore-reinforced film to the fluorine-containing proton or ion exchange resin is 10:90 to 30:

70.

6. A film or electrode according to any one of claims 1 to 5, further comprising a special release film attached to the bottom layer, wherein the special release film is made of an engineering plastic that does not contain a release agent, and the engineering plastic is selected from either an engineering plastic mainly containing bisphenol A or an engineering plastic mainly containing hexafluorodimethylbisphenol A, wherein the engineering plastic mainly containing bisphenol A is a polymer obtained by polymerizing or copolymerizing bisphenol A and its weight ratio exceeds 50%, or the engineering plastic mainly containing hexafluorodimethylbisphenol A is a polymer obtained by polymerizing or copolymerizing hexafluorodimethylbisphenol A and its weight ratio exceeds 50%.

7. The film or electrode according to any one of claims 1 to 5, characterized in that the microporous reinforcement film comprises 2 to 50 layers.

8. The film or electrode according to any one of claims 1 to 5, characterized in that the microporous reinforcement film consists of 2 to 30 layers.

9. The film or electrode according to claim 6, characterized in that the polymer obtained by polymerizing or copolymerizing the bisphenol A is any of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof, and the polymer obtained by polymerizing or copolymerizing the hexafluorodimethylbisphenol A is any of polycarbonate, polyphenylene oxide, polysulfone resin, polyepoxy resin, or a mixed copolymer thereof.

10. The aforementioned microporous reinforced film has a dry weight of 0.5 to 30 g / m². ２ The film or electrode according to any one of claims 1 to 5, characterized in that it has an open porosity of 40 to 95%, a thickness of 0.5 to 30 μm, and a tensile strength exceeding 40 MPa in both directions.

11. Step 1 involves casting a fluorine-containing proton exchange resin solution or a fluorine-containing ion exchange resin solution onto one side of a special release film and allowing it to adhere. Step 2 involves coating the coated resin solution with a microporous reinforcement film, and allowing the resin solution coated on the special release film and the coated microporous reinforcement film to blend thoroughly to obtain a composite film. Step 3 involves drying the composite film obtained in Step 2, Step 4 involves further casting a resin solution onto the upper surface of the micropore-reinforced film of the composite film, allowing the cast-coated resin solution and the coated micropore-reinforced film to blend thoroughly, thereby obtaining a composite film. Step 5 involves drying the composite film obtained in step 4. A method for manufacturing a film or electrode according to any one of claims 1 to 5, characterized by including the following:

12. The method according to 11, characterized in that the micropore-reinforced film of the composite film obtained in step 2 is further coated with the resin solution, the upper and lower surfaces of the micropore-reinforced film and the resin solution are thoroughly mixed and filled to form a composite film, and all materials are dried together.

13. The method according to 11 or 12, characterized in that the composite film obtained in step 4 is subjected to the steps 2 + 3 + 4 at least once.

14. The method according to any one of claims 11 to 13, characterized in that the void volume of the microporous reinforcement membrane filled in the fluorine-containing proton exchange resin solution or fluorine-containing ion exchange resin solution is 60% to 90%.

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