WO2008140123A1 - 多孔質フィルムの製造方法 - Google Patents
多孔質フィルムの製造方法 Download PDFInfo
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- WO2008140123A1 WO2008140123A1 PCT/JP2008/058986 JP2008058986W WO2008140123A1 WO 2008140123 A1 WO2008140123 A1 WO 2008140123A1 JP 2008058986 W JP2008058986 W JP 2008058986W WO 2008140123 A1 WO2008140123 A1 WO 2008140123A1
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- porous film
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
- C08J2201/0442—Elimination of an inorganic solid phase the inorganic phase being a metal, its oxide or hydroxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/12—Polyester-amides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a method for producing a porous film. Specifically, the present invention relates to a method for producing a liquid crystal polyester-containing porous film.
- Porous films are used in non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries and lithium polymer secondary batteries as a separate event.
- a separate evening consists of a porous film with fine pores.
- the separator is required to have high heat resistance.
- a porous film for solving this problem a porous film made of liquid crystal polyester can be cited.
- Japanese Patent Application Laid-Open No. 2000-001-2 4 8 2 discloses that a composition comprising a liquid crystal polyester and an inorganic compound is melt-kneaded and stretched to produce a film.
- a method for producing a porous film by eluting is disclosed.
- An object of the present invention is to provide a production method capable of producing a porous film having high heat resistance at a low cost by a simpler operation. Disclosure of the invention
- the present invention provides the following inventions.
- a method for producing a liquid crystal polyester-containing porous film comprising the following steps (a), (b) and (c) in this order.
- (a) A slurry-like coating solution is prepared by dispersing 1 to 1500 parts by weight of a filler in 100 parts by weight of the liquid crystal polyester in a solution in which 100 parts by weight of the liquid crystal polyester is dissolved in a solvent.
- the coating solution is applied to at least one side of the substrate to form a coating film.
- the base material is a porous film made of a thermoplastic resin (wherein the thermoplastic resin is a resin different from liquid crystal polyester).
- Fig. 1 is a schematic diagram of a shutdown temperature measurement device. Explanation of symbols
- the present invention provides a method for producing a liquid crystal polyester-containing porous film characterized by including the following steps (a), (b) and (c) in this order.
- (a) A slurry-like coating solution is prepared in which 1 to 1500 parts by weight of filler is dispersed in 100 parts by weight of the liquid crystal polyester in a solution in which 100 parts by weight of the liquid crystal polyester is dissolved in a solvent.
- the coating solution is applied to at least one side of the substrate to form a coating film.
- liquid crystalline polyester for example,
- the obtained liquid crystal polyester-containing porous film is more excellent in heat resistance and preferable.
- aromatic dicarboxylic acids aromatic diols, and aromatic amines having phenolic hydroxyl groups
- derivatives for forming esters or derivatives for forming amides May be used.
- a derivative for forming an ester of a carboxylic acid or a derivative for forming an amide for example, an acid chloride or acid anhydride in which a strong lpoxyl group promotes a polyester formation reaction or a polyamide formation reaction
- Such as those that are highly reactive derivatives such as carboxyl groups that form polyesters or polyamides by transesterification or amide exchange reactions, such as alcohols that form esters or amides with ethylene glycol, amines, etc. And the like.
- Derivatives for forming an ester of a phenolic hydroxyl group include, for example, those in which a phenolic hydroxyl group forms an ester with a carboxylic acid so that a polyester is formed by a transesterification reaction. .
- examples of the derivative for forming an amide of an amino group include those that form an amide with a carboxylic acid that forms a polyamide by an amide exchange reaction.
- aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic amines having phenolic hydroxyl groups, and aromatic diamines are chlorine atoms as long as they do not inhibit ester formation or amide formation. It may be substituted with a halogen atom such as a fluorine atom, an alkyl group such as a methyl group or an ethyl group, or an aryl group such as a phenyl group.
- repeating structural unit (A) of the liquid crystalline polyester examples include the following, but are not limited thereto.
- the above repeating structural unit may be substituted with a halogen atom, an alkyl group or an aryl group.
- the above repeating structural unit may be substituted with a halogen atom, an alkyl group or an aryl group.
- the above repeating structural unit may be substituted with a halogen atom, an alkyl group or an aryl group.
- Repeating structural units derived from aromatic amines having phenolic hydroxyl groups may be substituted with a halogen atom, an alkyl group or an aryl group.
- the above repeating structural unit may be substituted with a halogen atom, an alkyl group or an aryl group.
- alkyl group which may be substituted on the repeating structural unit for example, an alkyl group having 1 to 10 carbon atoms is usually used, and among them, a methyl group, an ethyl group, a propyl group or a butyl group is preferable.
- aryl group which may be substituted with the repeating structural unit for example, an aryl group having 6 to 20 carbon atoms is usually used, and among them, a phenyl group is preferable.
- the liquid crystalline polyester is the above ( ⁇ , ( ⁇ 3 ), ( ⁇ ,), ( ⁇ 2 ) or ( ⁇ 3 ) It preferably includes a repeating unit represented by the formula.
- examples of a preferable combination of the structural units including the repeating unit include the following (a) to (d).
- (d) A combination in which (D,) is partially or wholly replaced with ( ⁇ ,) or ( ⁇ 5 ) in each of the combinations of (a). More preferable combinations include 30 to 80 mol% of repeating structural units derived from at least one compound selected from the group consisting of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, and 4-hydroxydilin.
- At least one compound selected from the group consisting of 10 to 35 mol% of repeating structural units derived from at least one compound selected from the group consisting of 4,4′-diaminodiphenyl ether, terephthalic acid and isophthalic acid It is more preferable that the repeating structural unit is derived from 10 to 35 mol%, and further, the repeating structural unit derived from 2-hydroxymono6-naphthoic acid is 30 to 80 mol% and the repeating is derived from 4-hydroxyaniline. It is especially composed of 10 to 35 mol% of structural units and 10 to 35 mol% of repeating structural units derived from isofuric acid. preferable.
- the weight average molecular weight of the liquid crystal polyester is not particularly limited, but is usually about 500,000 to 500,000, preferably about 100,000 to 500,000.
- the production method of the liquid crystalline polyester is not particularly limited.
- the amount of fatty acid anhydride added is preferably 1.0 to 1.2 times equivalent to the total of phenolic hydroxyl groups and amino groups, more preferably 1.05 to 1.1 times equivalents. It is. If the amount of fatty acid anhydride added is small, the acylated product, aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, etc., sublimate during polymerization by transesterification / amide exchange, and the reactor piping tends to be clogged. In addition, if the amount of the fatty acid anhydride added is too large, the resulting liquid crystal polyester may be remarkably colored.
- the acylation reaction is preferably performed at 130 to 180 for 5 minutes to 10 hours, more preferably at 140 to 160 ⁇ for 10 minutes to 3 hours.
- the fatty acid anhydride used for the acylation reaction is not particularly limited, but for example, anhydrous acetic acid, anhydrous propionic acid, anhydrous butyric acid, anhydrous isobutyric acid, anhydrous valeric acid, anhydrous pivalic acid, anhydrous 2-ethylhexanoic acid, anhydrous Monochloroacetic acid, dichloroacetic anhydride, trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, daltaric anhydride, maleic anhydride, succinic anhydride, anhydrous ) 3_Bromopropionic acid,
- the acyl group of the acylated product is 0.8 to 1.2 times the equivalent of the strong lpoxyl group.
- the polymerization temperature is preferably 40 O t: or less, more preferably 35 0 or less.
- the rate of temperature increase during the temperature increase is preferably 0.1 to 50 Z minutes, and more preferably 0.3 to 5 / min.
- the by-product fatty acid and the unreacted fatty acid anhydride are distilled out of the system, for example, by evaporation.
- the polymerization by the acylation reaction, transesterification / amide exchange may be carried out in the presence of a catalyst.
- a catalyst conventionally known catalysts for polyester polymerization can be used.
- magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, anti-trioxide examples thereof include metal salt catalysts such as mon, and organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole.
- the catalyst is usually present during the acylation reaction and it is not always necessary to remove it after the acylation reaction.
- the next treatment (polymerization by transesterification / amide exchange) can be carried out as it is. Moreover, when performing the said process, you may further add the above catalysts.
- Polymerization by transesterification / amide exchange is usually carried out by melt polymerization, but melt polymerization and solid phase polymerization may be used in combination.
- the solid phase polymerization can be performed by a known solid phase polymerization method after the polymer is extracted from the melt polymerization step, solidified, and pulverized into powder or flakes. Specifically, for example, a method of heat treatment in a solid state at 20 to 3500 t: for 1 to 30 hours in an inert atmosphere such as nitrogen can be given.
- the solid phase polymerization may be performed while stirring or in a state of standing without stirring.
- the melt polymerization tank and the solid phase polymerization tank can be made the same reaction tank.
- the obtained liquid crystal polyester may be pelletized by a known method.
- the liquid crystal polyester can be produced using, for example, a batch apparatus, a continuous apparatus or the like, and the liquid crystal polyester can be produced as described above.
- the liquid crystalline polyester when the liquid crystalline polyester contains a nitrogen atom, it is preferable to use a polar amide solvent or a polar urea solvent as the solvent.
- a polar amide solvent or a polar urea solvent As the solvent.
- N, N-dimethylformamide examples thereof include N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NM P), and tetramethylurea.
- NM P N-methyl-2-pyrrolidone
- a protic solvent as the solvent.
- A represents a halogen atom or a trihalogenated methyl group
- i represents an integer value of 1 or more and 5 or less
- a plurality of A's may be the same or different. May be.
- examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Since the liquid crystal polyester is easily dissolved, A chlorine atom is preferred, and in this case, examples of the halogen-substituted phenol compound include pentafluorophenol, tetrafluorophenol, o-chlorophenol, and p-chlorophenol. Further, o_black-mouth phenol and p-black-mouth phenol are preferred, and particularly preferred is -chlorophenol.
- the amount of the solvent to be used for the liquid crystal polyester can be appropriately selected.
- the liquid crystal polyester is used in an amount of 0.001 to 100 parts by weight with respect to 100 parts by weight of the solvent. . If the liquid crystal polyester is less than 0.1 part by weight, the thickness of the liquid crystal polyester-containing porous film tends not to be uniform. If the liquid crystal polyester exceeds 100 parts by weight, it may be difficult to dissolve. From the viewpoint of operability and economy, the liquid crystalline polyester is preferably 0.5 to 50 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the solvent. .
- a liquid crystal polyester is dissolved using a solvent to obtain a solution.
- the filler may be selected from organic powder, inorganic powder or a mixture thereof as the material.
- organic powder examples include styrene, vinyl ketone, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, methyl acrylate alone, or a copolymer of two or more kinds, polytetra Fluoro-based resins such as fluoroethylene, tetrafluoroethylene-1, hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride; melamine resin; urea resin; polyolefin; polymethacrylate, etc. And powders made of organic materials. These organic powders may be used alone or in combination of two or more. Among these organic powders, polytetrafluoroethylene powder is preferable from the viewpoint of chemical stability.
- the inorganic powder examples include powders made of inorganic substances such as metal oxides, metal nitrides, metal carbides, metal hydroxides, carbonates and sulfates.
- the powder examples include alumina, silica, titanium dioxide, or calcium carbonate.
- the inorganic powder may be used alone or in combination of two or more.
- alumina powder is preferred from the viewpoint of chemical stability.
- it is more preferable that all of the particles constituting the filler are alumina particles, and even more preferable that all of the particles constituting the filler are alumina particles, and some or all of them are substantially spherical.
- the substantially spherical alumina particles include true spherical particles.
- Examples of the shape of the filler in the present invention include a substantially spherical shape, a plate shape, a columnar shape, a needle shape, a whisker shape, and a fiber shape. Any particle can be used, but it is easy to form uniform pores. It is preferably a substantially spherical particle.
- the average particle diameter of the particles constituting the filler is preferably from 0.01 m to 1 m.
- the value measured from the scanning electron micrograph is used as the average particle diameter. Specifically, 50 particles are arbitrarily extracted from the particles photographed in the photograph, each particle diameter is measured, and the average value is used.
- a pressure disperser (Gorin homogenizer, Nanomizer 1) or the like may be used as an apparatus for obtaining a slurry-like coating liquid by dispersing a filler in a solution.
- examples of the method of applying the slurry-like coating liquid to the base material include coating methods such as knives, blades, bars, gravure, and dies. Coating is simple, but industrially, die coating having a structure in which the solution does not come into contact with outside air is preferable. In addition, the coating may be performed more than once. Coating is performed continuously by the coating apparatus described in Japanese Patent Application Laid-Open No. 2 00 1-3 1 6 0 06 and the method described in Japanese Patent Application Laid-Open No. 2 0 1-2 3 6 0 2 Is preferred.
- the solvent is usually removed by a method of evaporating the solvent.
- Methods for evaporating the solvent include heating, decompression, and ventilation. Among them, heating and evaporation are preferable from the viewpoint of production efficiency and operability, and heating and evaporation while ventilating are more preferable.
- Examples of the solvent that does not dissolve the liquid crystal polyester in step (c) include water and alcohol. This dipping may also serve as washing of the obtained liquid crystalline polyester-containing porous film. Further, after this immersion, drying is performed by a method such as heating, decompression, and ventilation to obtain a liquid crystal polyester-containing porous film.
- examples of the substrate include those that do not dissolve or swell in a solvent that does not dissolve the liquid crystalline polyester.
- a resin film an polyolefin resin made of polyethylene, polypropylene, polymethylpentene, or the like.
- Film Polyester film such as polyethylene terephthalate (PET), Polyethylene naphthaate (PEN), Super engineering plastic film such as polyimide and PPS, Polytetrafluoroethylene (PTFE), Ethylene-tetrafluoro Fluorine resin film such as polyethylene copolymer film (ETFE) can be used.
- metal plate such as copper plate and stainless steel plate and ceramic plate such as glass can be used.
- the porous film may be any, for example, the liquid crystal polyester-containing porous film of the present invention.
- the porous film is a thermoplastic resin (here, a thermoplastic resin). Is a resin different from liquid crystal polyester), a laminated type porous film having a shirt down function can be obtained, such as a lithium ion secondary battery, a lithium polymer secondary battery, etc. This is particularly useful as a separator for non-aqueous electrolyte secondary batteries.
- thermoplastic resin (here, the thermoplastic resin is a resin different from the liquid crystalline polyester) is preferably one that is deformed and softened at 80 to 180 ° C.
- non-aqueous electrolyte secondary batteries that do not dissolve in the electrolyte can be selected.
- polyolefins such as polyethylene and polypropylene, and thermoplastic polyurethanes, and a mixture of two or more of these may be used.
- Polyethylene is preferred because it softens and shuts down at lower temperatures.
- polyethylene include polyethylene such as low density polyethylene, high density polyethylene, and linear polyethylene, and ultrahigh molecular weight polyethylene can also be mentioned.
- the thermoplastic resin preferably contains at least an ultrahigh molecular weight polyethylene. Further, in the production of a porous film made of a thermoplastic resin, the thermoplastic resin may preferably contain a wax made of polyolefin having a low molecular weight (weight average molecular weight of 10,000 or less).
- thermoplastic resin wherein the thermoplastic resin is a resin different from liquid crystal polyester
- the pore size is usually 3 m or less.
- the porosity is usually 30 to 80% by volume, preferably 40 to 70% by volume.
- the thickness of the obtained liquid crystal polyester-containing porous film is 1 zm or more and 30 / m or less, and further 1 / m It can be made as thin as 10 m or less.
- the pore size (diameter) of the obtained liquid crystalline polyester-containing porous film can be reduced to 3 m or less, and further to 1 m or less.
- the porosity of the obtained liquid crystalline polyester-containing porous film is usually 30 to 80% by volume, preferably 40 to 70% by volume.
- thermoplastic resin is a resin different from the liquid crystalline polyester
- JP-A-7-295 As described in JP-A No.
- JP-A-7-3 0 4 1 10 a method of removing a plasticizer with an appropriate solvent after adding a plasticizer to a thermoplastic resin to form a film, or JP-A-7-3 0 4 1 10
- a film made of a thermoplastic resin produced by a known method is used, and a microscopic pore is formed by selectively stretching a structurally weak amorphous portion of the film.
- a porous film made of a thermoplastic resin is formed from a polyolefin resin containing an ultrahigh molecular weight polyethylene and a low molecular weight polyolefin having a weight average molecular weight of 10,000 or less, from the viewpoint of production cost, the following is shown. It is preferable to manufacture by such a method. That is,
- a method comprising a step of stretching the sheet obtained in step (3) to form a shutdown layer, or
- Step (3) Step of removing the inorganic filler (C) from the stretched sheet obtained in step (3) to obtain a porous film made of a thermoplastic resin.
- the thickness of the liquid crystalline polyester-containing porous film was measured in accordance with J IS standard (K7130-1992).
- J IS standard K7130-1992
- a value obtained by subtracting the thickness of the polyethylene porous film from the thickness of the laminated porous film was used.
- the air permeability of the film was measured with a digital evening image type Gurley type densometer manufactured by Yasuda Seiki Seisakusho Co., Ltd. based on JISP 8117.
- a film sample was cut into a 10 cm long square and the weight W (g) and thickness D (cm) were measured. Find the weight (Wi (g)) of each layer in the sample, find the true specific gravity (true specific gravity i (gZcm 3 )) and force ⁇ of the material of Wi and each layer, and find the volume of each layer, The porosity (volume%) was obtained from the following equation.
- Porosity (volume%) 100 X ⁇ 1-(W 1 Z true specific gravity 1 + W 2 Z true specific gravity 2 + ⁇ ⁇ + WnZ true specific gravity n) / (10X 10 XD) ⁇
- the electrolyte (9) contains ethylene carbonate 30 V o 1%: dimethyl carbonate 35 V o 1%: ethylmethyl carbonate 35 V o 1% mixed solution, lmo 1ZL Li PF What dissolved 6 was used.
- the terminal of the impedance analyzer (7) was connected to both poles (10) and (10) of the assembled cell, and the resistance value at l kHz was measured.
- a thermocouple (14) was installed directly under the separation overnight so that the temperature could be measured at the same time, and the impedance and temperature were measured while the temperature was raised at a rate of 2 ° CZ of the rate of temperature rise. .
- the temperature when the impedance at 1 kHz reached 100 00 ⁇ was defined as the shutdown temperature (SD temperature).
- SD temperature the temperature at which the film was torn and the internal resistance began to decrease was measured as the thermal film breaking temperature.
- Carpoxymethylcellulose, polytetrafluoroethylene, acetylene black, lithium cobaltate powder which is a positive electrode active material, and water were dispersed and kneaded to obtain a positive electrode mixture paste.
- the weight ratio of each component contained in this paste is as follows: carboxymethylcellulose: polytetrafluoroethylene: acetylene black: lithium cobaltate powder: water by weight ratio of 0.75: 4.5: 2.7 : 92:45.
- Predetermined on both sides of the positive electrode current collector thickness 20 ⁇ mA 1 foil It was applied to the part, dried, roll-pressed, and slitted to obtain a positive electrode sheet. The length of the A 1 foil at the portion where the positive electrode mixture was not applied was 1.5 cm, and an aluminum lead was resistance welded to the portion where the positive electrode mixture was not applied.
- Carpoxymethylcellulose, natural graphite, artificial graphite and water were dispersed and mixed to obtain a negative electrode mixture paste.
- the weight ratio of each component contained in this paste was 2.0: 58.8: 39.2: 122.8 in the weight ratio of carboxymethylcellulose: natural graphite: artificial graphite: water.
- the paste was applied to predetermined portions on both sides of a 12 m-thick foil serving as a negative electrode current collector, followed by drying, roll pressing, and slitting to obtain a negative electrode sheet.
- the length of the Cu foil in the portion where the negative electrode mixture was not applied was 1.5 cm, and a nickel lead was resistance-welded to the portion where it was not applied.
- the film is used as a separator, and the positive electrode sheet, negative electrode sheet (negative electrode electrode mixture uncoated portion 30 cm) are arranged in the order of the positive electrode sheet, separator film, and negative electrode sheet, and the negative electrode mixture is not applied.
- the electrodes were laminated so that the outermost part was the outermost periphery, and wound up from one end to form an electrode group.
- the electrode group was inserted into a battery can, as an electrolytic solution, Echire Nkabone Bok dimethyl Capo sulfonates and E chill methyl carbonate in a volume ratio 1 to 6: 10: L i PF 6 becomes 1 mole Z liters to 74 mixture
- the battery was impregnated with the electrolyte solution as described above, and the battery lid also serving as the positive electrode terminal was sealed with a lid through a gasket to obtain an 18650 size cylindrical battery (non-aqueous electrolyte secondary battery).
- a laminated porous film is used as a separator, the liquid crystalline polyester-containing porous film is in contact with the positive electrode sheet, and the polyethylene porous film in the separator is in contact with the negative electrode sheet. Laminated.
- the cylindrical battery obtained as described above is fixed to a dedicated base, and a ⁇ 2.5 mm nail attached to a hydraulic press type nail penetration tester is lowered at a speed of 5 mmZ sec. The thermal behavior was observed when a nail was passed through the center of the cylinder.
- Example 1
- a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer and reflux condenser was charged with 94 lg (5.0 mol) of 2-hydroxy-6-naphthoic acid and 273 g of 2-aminophenol (2. 5 mol), 415.3 g (2.5 mol) of isophthalic acid and 1123 g (1 1 mol) of acetic anhydride. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 over 15 minutes under a nitrogen gas stream, and the temperature was maintained and refluxed for 3 hours.
- N_methyl-2-pyrrolidone was further added, stirred, and 100 g of a liquid crystal polyester concentration of 3 wt% was added to high purity alumina (average particle size: 0.013 m) manufactured by Aerosol. After adding 9 g, alumina was dispersed in the solution by high-speed stirring at 6000 rpm to obtain a slurry-like coating solution.
- a slurry-like coating solution was applied to the entire film, and a coating film was applied on the porous film.
- the glass plate was allowed to stand in a 70 oven for 30 minutes to evaporate the solvent.
- the film was removed from the glass plate and washed with water using a resin vat for 5 minutes.
- the obtained laminated porous film had a thickness of 20 m, a porosity of 45%, an air permeability of 4500 seconds Z 1 0 0 cc, and a free chlorine content of 60 ppm by weight.
- the shutdown temperature of the laminated porous film was 1 3 4, and even at 2 0 0, no thermal film breakage was observed, indicating that the heat resistance was high.
- the laminated porous film obtained above was allowed to stand at 25 t: 80% relative humidity for 12 hours, and then used as a separator.
- the secondary battery was fabricated and the thermal behavior was observed when the nail was penetrated through the battery, it was found that the temperature rise was slow and that the insulation under high humidity, that is, the weather resistance was excellent. .
- Example 2
- Liquid crystal polyester-containing porous film in the same manner as in Example 1 except that a PET film having a thickness of 100 m was used instead of the polyethylene porous film, and the clearance was adjusted to 0.2 mm.
- the PET film was peeled off to obtain a single layer porous film.
- the film had a thickness of 20 zm, a porosity of 50%, and an air permeability of 4600 seconds 1100 cc. In addition, even when the film was 20 0, no thermal film breakage was observed, indicating that the film had high heat resistance.
- a porous film having high heat resistance can be produced at a low cost by a simpler operation, and the porous film obtained by the present invention comprises a filtration membrane, a separation membrane, Alternatively, the present invention is extremely useful industrially because it can be used for a battery such as a non-aqueous electrolyte secondary battery or a separator for a capacitor.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Cell Separators (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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CN200880015772A CN101679665A (zh) | 2007-05-14 | 2008-05-09 | 多孔质薄膜的制造方法 |
US12/600,200 US20100239744A1 (en) | 2007-05-14 | 2008-05-09 | Process for producing porous film |
EP08752840A EP2157123A4 (en) | 2007-05-14 | 2008-05-09 | METHOD FOR MANUFACTURING POROUS FILM |
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JP2007-127703 | 2007-05-14 | ||
JP2007127703 | 2007-05-14 |
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WO2008140123A1 true WO2008140123A1 (ja) | 2008-11-20 |
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PCT/JP2008/058986 WO2008140123A1 (ja) | 2007-05-14 | 2008-05-09 | 多孔質フィルムの製造方法 |
Country Status (7)
Country | Link |
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US (1) | US20100239744A1 (ja) |
EP (1) | EP2157123A4 (ja) |
JP (1) | JP5109789B2 (ja) |
KR (1) | KR20100017779A (ja) |
CN (1) | CN101679665A (ja) |
TW (1) | TW200914511A (ja) |
WO (1) | WO2008140123A1 (ja) |
Families Citing this family (7)
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JP5853329B2 (ja) * | 2010-06-04 | 2016-02-09 | 国立大学法人 東京大学 | 複合半透膜 |
JP2015120867A (ja) * | 2013-01-28 | 2015-07-02 | 株式会社リコー | 多孔体、その製造方法、及びその連続製造装置 |
JP6842978B2 (ja) * | 2017-04-14 | 2021-03-17 | 住友化学株式会社 | 非水電解液二次電池用絶縁性多孔質層 |
US20210095386A1 (en) * | 2018-03-29 | 2021-04-01 | Toray Industries, Inc. | Composite electrolyte membrane |
CN115023466A (zh) * | 2020-02-21 | 2022-09-06 | 引能仕株式会社 | 复合物、浆料组合物、膜以及金属箔层叠板 |
CN114426750A (zh) * | 2020-10-29 | 2022-05-03 | 秀昌有限公司 | 液晶高分子组成物及绝缘膜 |
JP2022156865A (ja) | 2021-03-31 | 2022-10-14 | 日東電工株式会社 | 多孔質液晶ポリマーシートおよび配線回路基板 |
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Also Published As
Publication number | Publication date |
---|---|
JP2008308669A (ja) | 2008-12-25 |
US20100239744A1 (en) | 2010-09-23 |
TW200914511A (en) | 2009-04-01 |
CN101679665A (zh) | 2010-03-24 |
JP5109789B2 (ja) | 2012-12-26 |
EP2157123A4 (en) | 2011-08-31 |
EP2157123A1 (en) | 2010-02-24 |
KR20100017779A (ko) | 2010-02-16 |
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