Classifications

• • 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
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
  • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F220/56—Acrylamide; Methacrylamide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/36—Amides or imides
  • C08F222/38—Amides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/24—Homopolymers or copolymers of amides or imides
  • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • 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
  • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
• • 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
• • 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
• • 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
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/42—Acrylic resins
• • 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
  • H01M50/423—Polyamide resins
• • 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
  • H01M50/431—Inorganic material
• • 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
  • H01M50/431—Inorganic material
  • H01M50/434—Ceramics
• • 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
• • 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
  • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
• • 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
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
• • 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
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
  • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
• • 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
  • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • 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 raw material for a coating material for a secondary battery separator, a coating material for a secondary battery separator, a method for manufacturing a secondary battery separator, a secondary battery separator, and a secondary battery.
• the secondary battery is provided with a separator for separating the positive electrode and the negative electrode and allowing ions in the electrolytic solution to pass through.
• a separator for example, a polyolefin porous membrane is known.
• a heat-resistant coat layer may be provided on the separator.
• the heat-resistant coating layer formed on the separator for example, a coating layer obtained by applying a coating slurry containing a binder resin and a filler to a porous film and drying it is known. More specifically, a heat-resistant layer obtained by applying and drying a coating slurry containing sodium carboxymethyl cellulose (CMC) and alumina to a base material porous film obtained from a polyolefin resin composition has been proposed. (See, for example, Patent Document 1 (Example).).
• the separator of the secondary battery is required to have air permeability because it is necessary for ions to pass through for power generation.
• the heat-resistant layer described above has a problem of reducing the air permeability of the separator.
• the present invention provides a coating material raw material for a secondary battery separator capable of obtaining a secondary battery separator having both excellent heat resistance and air permeability, and a coating material for a secondary battery separator including the coating material raw material for the secondary battery separator. It is an object of the present invention to provide a secondary battery separator provided with a coating film of a coating material for the secondary battery separator, a method for manufacturing the secondary battery separator, and a secondary battery provided with the secondary battery separator.
• the present invention [1] contains a water-soluble polymer having a repeating unit derived from methacrylamide and a repeating unit derived from a carboxy group-containing vinyl monomer, and is derived from the methacrylamide with respect to the total amount of the water-soluble polymer.
• the content of the repeating unit is 60% by mass or more and 97% by mass or less
• the content of the repeating unit derived from the carboxy group-containing vinyl monomer is 3% by mass or more and 40% by mass or less
• the water-soluble polymer is used.
• the present invention [2] includes a coating material for a secondary battery separator, which includes a coating material for a secondary battery separator according to the above [1].
• the present invention [3] further includes the coating material for a secondary battery separator according to the above [3], which contains an inorganic filler and a dispersant.
• the present invention [4] comprises a secondary battery separator including a porous film and a coating film for a coating material for a secondary battery separator according to the above [2] or [3], which is arranged on at least one surface of the porous film. including.
• the present invention [5] comprises a step of preparing a porous film and a step of applying a coating material for a secondary battery separator according to claim 2 or 3 to at least one surface of the porous film. Including the manufacturing method of.
• the present invention [6] includes a secondary battery including a positive electrode, a negative electrode, and a secondary battery separator according to the above [4], which is arranged between the positive electrode and the negative electrode.
• the coating material raw material for a secondary battery separator of the present invention contains a water-soluble polymer having a repeating unit derived from methacrylamide and a repeating unit derived from a carboxy group-containing vinyl monomer in a predetermined ratio, and the weight of the water-soluble polymer.
• the average molecular weight and the glass transition temperature are adjusted within a predetermined range. Therefore, according to the raw material for the coating material for the secondary battery separator of the present invention, a secondary battery separator having excellent heat resistance and air permeability can be obtained.
• the coating material for the secondary battery separator of the present invention contains the above-mentioned raw material for the coating material for the secondary battery separator, a secondary battery separator having excellent heat resistance and air permeability can be obtained.
• the secondary battery separator of the present invention includes the coating film of the coating material for the secondary battery separator described above, it is excellent in heat resistance and air permeability.
• a secondary battery separator having excellent heat resistance and air permeability can be efficiently manufactured.
• the secondary battery of the present invention is provided with the above-mentioned secondary battery separator, it is excellent in heat resistance and air permeability, and as a result, is excellent in durability and power generation efficiency.
• the raw material for the coating material for the secondary battery separator of the present invention contains a water-soluble polymer.
• the water-soluble polymer is a polymer obtained by polymerizing a water-soluble polymer raw material (monomer composition).
• the water-soluble polymer is defined as a polymer having a residual solid content of 0.1% or less when 1 g of the polymer is stirred and dissolved in 100 ml of water for 24 hours and then filtered through a wire mesh of 300 mesh.
• the water-soluble polymer raw material contains methacrylamide and a carboxy group-containing vinyl monomer as essential components.
• the water-soluble polymer raw material does not contain the (meth) acrylic acid alkyl ester described later, but contains methacrylamide and a carboxy group-containing vinyl monomer.
• Methacrylamide may be used in combination with acrylamide, or methacrylamide may be used alone without being used in combination with acrylamide.
• Methacrylamide is preferably used alone, not in combination with acrylamide, from the viewpoint of improving heat resistance.
• the content ratio of methacrylamide to the water-soluble polymer raw material will be described later.
• the carboxy group-containing vinyl monomer is a copolymerizable monomer copolymerizable with methacrylamide and contains a carboxy group.
• Examples of the carboxy group-containing vinyl monomer include monocarboxylic acids, dicarboxylic acids, and salts thereof.
• Examples of the monocarboxylic acid include (meth) acrylic acid.
• Examples of the dicarboxylic acid include itaconic acid, maleic acid, fumaric acid, itaconic anhydride, maleic anhydride, fumaric anhydride and the like.
• (meth) acrylic includes acrylic and methacryl (the same applies hereinafter).
• carboxy group-containing vinyl monomers can be used alone or in combination of two or more.
• the secondary battery separator obtained by using the secondary battery separator coating material (described later) containing the secondary battery separator coating material raw material can be used. , Excellent heat resistance.
• the carboxy group-containing vinyl monomer is preferably a monocarboxylic acid, more preferably a (meth) acrylic acid, and even more preferably a methacrylic acid.
• the secondary battery separator (described later) obtained by using the secondary battery separator coating material (described later) containing the secondary battery separator coating material raw material will have even higher heat resistance. Excellent in sex.
• the content ratio of the carboxy group-containing vinyl monomer to the water-soluble polymer raw material will be described later.
• the water-soluble polymer raw material may contain, as an optional component, a copolymerizable monomer copolymerizable with a methacrylamide and / or a carboxy group-containing vinyl monomer (hereinafter, referred to as a water-soluble-copolymerizable monomer).
• a copolymerizable monomer copolymerizable with a methacrylamide and / or a carboxy group-containing vinyl monomer hereinafter, referred to as a water-soluble-copolymerizable monomer.
• water-soluble-copolymerizable monomer examples include (meth) acrylic acid alkyl ester, functional group-containing vinyl monomer (excluding carboxy group-containing vinyl monomer), vinyl esters, aromatic vinyl monomer, and N-substituted unsaturated monomer.
• examples thereof include carboxylic acid amides, heterocyclic vinyl compounds, vinylidene halide compounds, ⁇ -olefins, dienes, and crosslinkable vinyl monomers.
• Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth).
• Alkyl (meth) acrylates having an alkyl moiety having 1 to 4 carbon atoms such as acrylate, for example, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate.
• Examples of the functional group-containing vinyl monomer include a hydroxyl group-containing vinyl monomer, an amino group-containing vinyl monomer, a glycidyl group-containing vinyl monomer, a cyano group-containing vinyl monomer, a sulfonic acid group-containing vinyl monomer, and the like.
• Examples thereof include the salt, an acetoacetoxy group-containing vinyl monomer, and a phosphoric acid group-containing compound.
• hydroxyl group-containing vinyl monomer examples include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
• amino group-containing vinyl monomer examples include 2-aminoethyl (meth) acrylate, 2- (N-methylamino) ethyl (meth) acrylate, and 2- (N, N-dimethylamino) (meth) acrylate. Ethyl and the like can be mentioned.
• Examples of the glycidyl group-containing vinyl monomer include glycidyl (meth) acrylate.
• Examples of the cyano group-containing vinyl monomer include (meth) acrylonitrile.
• Examples of the sulfonic acid group-containing vinyl monomer include allyl sulfonic acid, metallic sulfonic acid, and acrylamide t-butyl sulfonic acid.
• Examples of the salt of the sulfonic acid group-containing vinyl monomer include alkali metal salts such as sodium salt and potassium salt, for example, ammonium salt and the like. Specific examples thereof include sodium allyl sulfonate, sodium methallyl sulfonate, ammonium metharyl sulfonate and the like.
• acetoxy group-containing vinyl monomer examples include acetoxyethyl (meth) acrylate.
• Examples of the phosphoric acid group-containing compound include 2-methacryloxyethyl acid phosphate and the like.
• vinyl esters examples include vinyl acetate and vinyl propionate.
• aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene and the like.
• N-substituted unsaturated carboxylic acid amide examples include N-methylol (meth) acrylamide.
• heterocyclic vinyl compound examples include vinylpyrrolidone.
• halogenated vinylidene compound examples include vinylidene chloride and vinylidene fluoride.
• ⁇ -olefins examples include ethylene and propylene.
• diene examples include butadiene.
• crosslinkable vinyl monomer examples include two or more such as methylenebis (meth) acrylamide, divinylbenzene, polyethylene glycol chain-containing di (meth) acrylate, trimethylolpropane tetraacrylate, pentaeristol triacrylate, and pentaeristol tetraacrylate.
• examples include vinyl monomers containing the vinyl group of.
• These water-soluble-copolymerizable monomers can be used alone or in combination of two or more.
• the water-soluble-copolymerizable monomer preferably includes a copolymerizable monomer containing a hydrophilic group, and more specifically, a hydroxyl group-containing vinyl monomer, a sulfonic acid group-containing vinyl monomer, and a phosphoric acid group-containing vinyl monomer. Examples thereof include, more preferably, a hydroxyl group-containing vinyl monomer.
• the content ratio of methacrylicamide is, for example, 60 from the viewpoint of improving the adsorptivity to the inorganic filler described later and obtaining excellent heat resistance with respect to 100 parts by mass of the total amount of the water-soluble polymer raw material. It is by mass or more, preferably 70 parts by mass or more, more preferably 75 parts by mass or more, still more preferably 80 parts by mass or more, and also improves the adsorptivity to the inorganic filler described later and has excellent heat resistance. From the viewpoint of obtaining, for example, 97 parts by mass or less, preferably 96 parts by mass or less, more preferably 95 parts by mass or less.
• the content ratio of the carboxy group-containing vinyl monomer is from the viewpoint of improving the adsorptivity to the inorganic filler described later with respect to 100 parts by mass of the total amount of the water-soluble polymer raw material and obtaining excellent heat resistance. Therefore, for example, it is 3 parts by mass or more, preferably 4 parts by mass or more, more preferably 5 parts by mass or more, and from the viewpoint of suppressing adsorption to the substrate described later and obtaining excellent air permeability, for example, 40. It is less than or equal to parts by mass, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less.
• the content ratio of the water-soluble-copolymerizable monomer is within the range in which the water-soluble property of the water-soluble polymer is maintained, for example, with respect to 100 parts by mass of the total amount of the water-soluble polymer raw material.
• it is 37 parts by mass or less, preferably 15 parts by mass or less, 0 parts by mass or more, and particularly preferably 0 parts by mass.
• the water-soluble polymer raw material may be a composition composed of methacrylamide and a carboxy group-containing vinyl monomer without containing a water-soluble-copolymerizable monomer, or may be composed of methacrylamide and a carboxy group-containing vinyl monomer. It may be a composition composed of a water-soluble-copolymerizable monomer.
• the water-soluble polymer raw material is a composition composed of methacrylamide and a carboxy group-containing vinyl monomer.
• the water-soluble polymer can be obtained by polymerizing the above-mentioned water-soluble polymer raw material by a known method.
• a water-soluble polymer raw material and a polymerization initiator are mixed with water, the water-soluble polymer raw material is polymerized, and then aged as necessary.
• the polymerization initiator is not particularly limited, but for example, persulfate (ammonium persulfate, potassium persulfate, etc.), hydrogen peroxide, organic hydroperoxide, 4,4'-azobis (4-cyanovaleric acid) acid, etc.
• persulfate ammonium persulfate, potassium persulfate, etc.
• hydrogen peroxide organic hydroperoxide
• 4,4'-azobis (4-cyanovaleric acid) acid etc.
• water-soluble initiator of the above include oil-soluble initiators such as benzoyl peroxide and azobisisobutyronitrile, and redox-based initiators.
• These polymerization initiators can be used alone or in combination of two or more.
• polymerization initiator examples include a water-soluble initiator, more preferably persulfate, and even more preferably ammonium persulfate.
• the blending ratio of the polymerization initiator is, for example, 0.01 part by mass or more, preferably 0.% by mass, based on 100 parts by mass of the water-soluble polymer raw material, from the viewpoint of adjusting the weight average molecular weight of the water-soluble polymer to the range described later. It is 1 part by mass or more, more preferably 0.2 part by mass or more, further preferably 0.25 part by mass or more, and for example, 3 parts by mass or less, preferably 2 parts by mass or less.
• the polymerization conditions and aging conditions are appropriately set so that the weight average molecular weight of the obtained water-soluble polymer is in the range described later.
• the polymerization temperature is, for example, 30 ° C. or higher, preferably 50 ° C. or higher, and for example, 95 ° C. or lower, preferably 85 ° C. or lower.
• the polymerization time is, for example, 0.5 hours or more, preferably 1.5 hours or more, and for example, 20 hours or less, preferably 10 hours or less.
• the aging time is, for example, 0.5 hours or more, preferably 1.5 hours or more, and for example, 6 hours or less, preferably 3 hours or less.
• a pH adjuster for example, a metal ion encapsulant such as ethylenediaminetetraacetic acid and a salt thereof, for example, mercaptans, low molecular weight halogen compounds and the like.
• Known additives such as a molecular weight regulator (chain transfer agent) can be added in an appropriate ratio.
• the pH can be adjusted in the range of 7 or more and 11 or less by blending a neutralizing agent such as ammonia before or after the above-mentioned polymerization.
• a neutralizing agent such as ammonia
• a water-soluble polymer can be obtained as a polymer of the water-soluble polymer raw material.
• an aqueous solution containing a water-soluble polymer and a water-soluble polymer (raw material for a coating material for a secondary battery separator) can be obtained.
• the water-soluble polymer has a repeating unit derived from methacrylamide and a repeating unit derived from a carboxy group-containing vinyl monomer, the water-soluble polymer is relatively relative to the water-insoluble polymer described later. It has hydrophilicity.
• the content of the repeating unit derived from methacrylamide in the water-soluble polymer is the same as the content of methacrylamide in the water-soluble polymer raw material.
• the content of the repeating unit derived from methacrylamide is 60% by mass or more from the viewpoint of improving the adsorptivity to the inorganic filler described later and obtaining excellent heat resistance with respect to the total amount of the water-soluble polymer. It is preferably 70% by mass or more, more preferably 75% by mass or more, further preferably 80% by mass or more, 97% by mass or less, preferably 96% by mass or less, and more preferably 95% by mass or less. be.
• the content of the repeating unit derived from the carboxy group-containing vinyl monomer in the water-soluble polymer is the same as the content of the carboxy group-containing vinyl monomer in the water-soluble polymer raw material.
• the content of the repeating unit derived from the carboxy group-containing vinyl monomer is 3% by mass from the viewpoint of improving the adsorptivity to the inorganic filler described later and obtaining excellent heat resistance with respect to the total amount of the water-soluble polymer.
• the above is preferably 4% by mass or more, more preferably 5% by mass or more, and from the viewpoint of suppressing adsorption to the substrate described later and obtaining excellent heat resistance, 40% by mass or less, preferably 30% by mass. % Or less, more preferably 25% by mass or less, still more preferably 20% by mass or less.
• the water-soluble polymer can contain a repeating unit derived from the above-mentioned water-soluble-copolymerizable monomer.
• the content of the repeating unit derived from the water-soluble-copolymerizable monomer in the water-soluble polymer is the same as the content of the water-soluble-copolymerizable monomer in the water-soluble polymer raw material.
• the content of the repeating unit derived from the water-soluble-copolymerizable monomer is, for example, 0% by mass or more, for example, 27% by mass or less, preferably 15% by mass, based on the total amount of the water-soluble polymer.
• the following is particularly preferable, and it is 0% by mass.
• the weight average molecular weight of the water-soluble polymer is 20,000 or more, preferably 30,000 or more, more preferably 40,000 or more, from the viewpoint of suppressing permeation into the pores of the porous membrane described later and obtaining excellent air permeability. From the viewpoint of obtaining excellent heat resistance, the amount is 200,000 or less, preferably 180,000 or less, and more preferably 150,000 or less.
• the weight average molecular weight is the polystyrene-equivalent molecular weight according to the gel permeation chromatogram.
• the weight average molecular weight is measured according to the examples described later.
• the glass transition temperature of the water-soluble polymer is 200 ° C. or higher, preferably 210 ° C. or higher, more preferably 220 ° C. or higher, still more preferably 230 ° C. or higher, still more preferably 230 ° C. or higher, from the viewpoint of obtaining excellent heat resistance.
• 240 ° C. or higher usually 400 ° C. or lower, preferably 300 ° C. or lower, more preferably 280 ° C. or lower.
• the glass transition temperature is calculated by the FOX formula (the same applies hereinafter).
• the content (solid content concentration) of the water-soluble polymer is, for example, 3% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, and also. For example, it is 50% by mass or less, preferably 30% by mass or less.
• the pH value of the aqueous solution is, for example, 5 or more, and 9 or less, for example.
• the raw material for the coating material for the secondary battery separator can contain a water-insoluble polymer as an optional component.
• the water-insoluble polymer is a polymer obtained by polymerizing a water-insoluble polymer raw material (monomer composition).
• the water-insoluble polymer is defined as a polymer having a residual solid content of 90% or more when 1 g of the polymer is stirred and dissolved in 100 ml of water for 24 hours and then filtered through a 300 mesh wire mesh.
• the water-insoluble polymer raw material contains, for example, (meth) acrylic acid alkyl ester.
• Examples of the (meth) acrylic acid alkyl ester include the above-mentioned (meth) acrylic acid alkyl ester.
• the water-insoluble polymer raw material can contain a copolymerizable monomer (hereinafter, referred to as a water-insoluble-copolymerizable monomer) copolymerizable with the (meth) acrylic acid alkyl ester.
• a copolymerizable monomer hereinafter, referred to as a water-insoluble-copolymerizable monomer
• water-insoluble-copolymerizable monomer examples include a functional group-containing vinyl monomer.
• Examples of the functional group-containing vinyl monomer include the above-mentioned carboxy group-containing vinyl monomer, the above-mentioned hydroxyl group-containing vinyl monomer, the above-mentioned amino group-containing vinyl monomer, the above-mentioned glycidyl group-containing vinyl monomer, the above-mentioned cyano group-containing vinyl monomer, and the above-mentioned.
• Examples thereof include the above-mentioned sulfonic acid group-containing vinyl monomer and its salt, the above-mentioned acetoacetoxy group-containing vinyl monomer, and a phosphoric acid group-containing compound.
• the water-insoluble-copolymerizable monomer the above-mentioned vinyl esters, the above-mentioned aromatic vinyl monomer, the above-mentioned N-substituted unsaturated carboxylic acid amide, acrylamide and / or methacrylamide, and the above-mentioned heterocyclic vinyl compound.
• the above-mentioned vinylidene halide compound, the above-mentioned ⁇ -olefins, the above-mentioned dienes, and the above-mentioned crosslinkable vinyl monomer the above-mentioned vinyl esters, the above-mentioned aromatic vinyl monomer, the above-mentioned N-substituted unsaturated carboxylic acid amide, acrylamide and / or methacrylamide, and the above-mentioned heterocyclic vinyl compound.
• These water-insoluble-copolymerizable monomers can be used alone or in combination of two or more.
• the content ratio of the water-insoluble-copolymerizable monomer is appropriately set according to the purpose and application.
• the water-insoluble polymer has hydrophobicity relative to the above-mentioned water-soluble polymer.
• the glass transition temperature of the water-insoluble polymer is, for example, ⁇ 30 ° C. or higher, preferably ⁇ 20 ° C. or higher, preferably ⁇ 15 ° C. or higher, and for example, 80 ° C. or lower, preferably 50 ° C. or lower. be.
• the coating raw material for the secondary battery separator contains a water-insoluble polymer
• the coating raw material for the secondary battery separator is a composite resin (for example, resin particles) containing the water-soluble polymer and the water-insoluble polymer. It may be a dispersion obtained by polymerizing a water-soluble polymer raw material in the presence of a water-insoluble polymer, and further, it may be obtained by polymerizing a water-insoluble polymer raw material in the presence of a water-soluble polymer. It may be a dispersion liquid to be obtained. Further, the raw material for the coating material for the secondary battery separator may be, for example, a mixed solution of an aqueous solution of the water-soluble polymer obtained individually and a dispersion liquid of the water-insoluble polymer.
• the pH value is, for example, 5 or more, and 9 or less, for example.
• the resin content (solid content concentration) is, for example, 5% by mass or more, and for example, 50% by mass or less.
• the above-mentioned raw material for a coating material for a secondary battery separator contains a water-soluble polymer having a repeating unit derived from methacrylamide and a repeating unit derived from a carboxy group-containing vinyl monomer in a predetermined ratio, and the weight average of the water-soluble polymer.
• the molecular weight and the glass transition temperature are adjusted within a predetermined range. Therefore, according to the above-mentioned raw material for the coating material for the secondary battery separator, a secondary battery separator having excellent heat resistance and air permeability can be obtained.
• the water-soluble polymer is adsorbed to the inorganic filler (described later), and the water-soluble polymer binds the inorganic filler (described later) to obtain heat resistance. Improvement is planned.
• the heat resistance of the separator decreases.
• the water-soluble polymer permeates into the pores of the porous membrane described later and reduces the air permeability of the separator.
• the thickening reduces the coating workability of the water-soluble polymer and makes the coating film non-uniform, so that the heat resistance of the separator is lowered. do.
• the content of the repeating unit derived from methacrylamide, the content of the repeating unit derived from the carboxy group-containing vinyl monomer, the weight average molecular weight and the glass transition temperature are adjusted to predetermined ranges, respectively. Excellent heat resistance and air permeability can be obtained in a well-balanced manner.
• the coating material for the secondary battery separator of the present invention contains the above-mentioned raw material for the coating material for the secondary battery separator, and if necessary, an inorganic filler and a dispersant.
• the mixing ratio of the coating material raw material for the secondary battery separator is the total amount of the coating material raw material for the secondary battery separator, the inorganic filler, and the dispersant (hereinafter referred to as the coating material component for the secondary battery separator).
• solid content For 100 parts by mass (solid content), for example, it is 0.1 part by mass or more (solid content), and for example, 10 parts by mass or less (solid content).
• the inorganic filler examples include oxides such as alumina, silica, titania, zirconia, magnesia, ceria, itria, zinc oxide and iron oxide, and nitrides such as silicon nitride, titanium nitride and boron nitride, for example, silicon.
• Carbide carbides such as calcium carbonate, eg, sulfates such as magnesium sulfate, aluminum sulfate, hydroxides such as aluminum hydroxide, aluminum hydroxide, eg talc, kaolinite, decite, nacrite, halloysite, pyro Phyllite, montmorillonite, cericite, mica, amesite, bentonite, asbestos, zeolite, calcium silicate, magnesium silicate, diatomaceous soil, silica sand, glass and other siliceous substances, such as potassium titanate.
• oxides and hydroxides and more preferably aluminum oxide and aluminum hydroxide.
• the blending ratio of the inorganic filler is, for example, 50 parts by mass or more (solid content) with respect to 100 parts by mass (solid content) of the coating material component for the secondary battery separator, and for example, 99.7 parts by mass or less. (Solid content).
• Examples of the dispersant include ammonium polycarboxylic acid and sodium polycarboxylic acid.
• the dispersant is ammonium polycarboxylic acid
• the above-mentioned coating material raw material for a secondary battery separator and an inorganic filler can be uniformly dispersed, and a coating film having a uniform thickness (described later) can be obtained.
• the mixing ratio of the dispersant is, for example, 0.1 part by mass or more (solid content) with respect to 100 parts by mass (solid content) of the coating material component for the secondary battery separator, and for example, 5 parts by mass or less (solid content). Solid content).
• an inorganic filler and a dispersant are mixed with water in the above proportions to prepare an inorganic filler dispersion liquid.
• the inorganic filler dispersion liquid is mixed with the coating material raw material for the secondary battery separator (or the dispersion liquid containing the coating material raw material for the secondary battery separator) in the above ratio and stirred.
• the stirring method is not particularly limited, and for example, a ball mill, a bead mill, a planetary ball mill, a vibrating ball mill, a sand mill, a colloid mill, an attritor, a roll mill, a high-speed impeller dispersion, a disperser, a homogenizer, a high-speed impact mill, an ultrasonic dispersion, and a stirring blade.
• a ball mill a bead mill, a planetary ball mill, a vibrating ball mill, a sand mill, a colloid mill, an attritor, a roll mill, a high-speed impeller dispersion, a disperser, a homogenizer, a high-speed impact mill, an ultrasonic dispersion, and a stirring blade.
• a ball mill a bead mill, a planetary ball mill, a vibrating ball mill, a sand mill, a colloid mill, an attritor, a roll mill,
• Such a coating material for a secondary battery separator can be obtained as a dispersion liquid dispersed in water.
• additives such as a hydrophilic resin, a thickener, a wetting agent, an antifoaming agent, and a pH adjusting agent can be added to the coating material for the secondary battery separator in an appropriate ratio.
• additives can be used alone or in combination of two or more.
• the above-mentioned coating material for the secondary battery separator contains the above-mentioned raw material for the coating material for the secondary battery separator, a secondary battery separator having excellent heat resistance and air permeability can be obtained.
• this coating material for the secondary battery separator can be suitably used as the coating material for the secondary battery separator.
• the secondary battery separator of the present invention can be manufactured by a manufacturing method including a step of preparing a porous film and a step of applying the above-mentioned coating material for a separator to at least one surface of the porous film.
• porous membrane examples include a polyolefin porous membrane such as polyethylene and polypropylene, for example, an aromatic polyamide porous membrane, and preferably a polyolefin porous membrane.
• the porous membrane may be surface-treated, if necessary. Examples of the surface treatment include corona treatment and plasma treatment.
• the thickness of the porous membrane is, for example, 1 ⁇ m or more, preferably 5 ⁇ m or more, and for example, 40 ⁇ m or less, preferably 20 ⁇ m or less.
• the dispersion liquid of the above-mentioned separator coating material is applied to at least one side of the porous membrane, and then, if necessary, dried. To obtain a coating film.
• the coating method is not particularly limited, and for example, the gravure coater method, the small diameter gravure coater method, the reverse roll coater method, the transfer roll coater method, the kiss coater method, the dip coater method, the micro gravure coat method, the knife coater method, and the air doctor coater.
• Examples include the method, blade coater method, rod coater method, squeeze coater method, cast coater method, die coater method, screen printing method, and spray coating method.
• the drying temperature is, for example, 40 ° C. or higher, and for example, 80 ° C. or lower.
• the thickness of the coating film is, for example, 1 ⁇ m or more, preferably 3 ⁇ m or more, and for example, 10 ⁇ m or less, preferably 8 ⁇ m or less.
• the coating film of the coating material for the secondary battery separator is arranged on at least one side of the porous film, but the above coating film can also be arranged on both sides of the porous film.
• the above-mentioned secondary battery separator includes the coating film of the above-mentioned coating material for the secondary battery separator, it is excellent in heat resistance and air permeability.
• a secondary battery separator having excellent heat resistance and air permeability can be efficiently manufactured.
• this secondary battery separator can be suitably used as a separator for the secondary battery.
• the secondary battery of the present invention includes a positive electrode, a negative electrode, the above-mentioned secondary battery separator arranged between the positive electrode and the negative electrode, and an electrolyte impregnated in the positive electrode, the negative electrode and the above-mentioned secondary battery separator.
• the positive electrode for example, a known electrode including a positive electrode current collector and a positive electrode active material laminated on the positive electrode current collector is used.
• Examples of the current collector for the positive electrode include aluminum, titanium, stainless steel, nickel, calcined carbon, a conductive polymer, and a conductive material of conductive glass.
• the positive electrode active material is not particularly limited, and examples thereof include known positive positive active materials such as lithium-containing transition metal oxide, lithium-containing phosphate, and lithium-containing sulfate.
• These positive electrode active materials can be used alone or in combination of two or more.
• the negative electrode for example, a known electrode including a negative electrode current collector and a negative electrode active material laminated on the negative electrode current collector is used.
• Examples of the current collector for the negative electrode include conductive materials such as copper and nickel.
• the negative electrode active material is not particularly limited, and examples thereof include carbon active materials such as graphite, soft carbon, and hard carbon.
• These negative electrode active materials can be used alone or in combination of two or more.
• the lithium salt is dissolved in a carbonate compound such as ethylene carbonate (EC), propylene carbonate (PC), and ethyl methyl carbonate (EMC).
• EC ethylene carbonate
• PC propylene carbonate
• EMC ethyl methyl carbonate
• a separator of the secondary battery is sandwiched between a positive electrode and a negative electrode, these are housed in a battery housing (cell), and an electrolyte is injected into the battery housing. do.
• the above-mentioned secondary battery is provided with the above-mentioned secondary battery separator, it is excellent in heat resistance and air permeability, and as a result, is excellent in durability and power generation efficiency.
• the weight average molecular weight of the water-soluble polymer contained in the obtained aqueous solution was determined using a GPC device (device name: P KP-22, manufactured by Fromm Co., Ltd.).
• the measurement conditions were as follows, and the weight average molecular weight was determined by standard polyethylene glycol / polyethylene oxide conversion.
• glass transition temperature (Tg) of the water-soluble polymer contained in the obtained aqueous solution was calculated by the following FOX formula.
• Tg is the glass transition temperature of the copolymer (unit: K)
• the compounding formula was treated in the same manner as in Production Example 1 except that the formulation was changed according to the description in Table 1, to produce a coating material raw material for a separator. Further, in the same manner as in Production Example 1, the weight average molecular weight of the water-soluble polymer was measured, and the glass transition temperature of the water-soluble polymer was calculated.
• pigment 100 parts by mass of aluminum hydroxide oxide (manufactured by Daimei Chemical Co., Ltd., Boehmite Grade C06, particle size: 0.7 ⁇ m), and as a dispersant, an aqueous solution of ammonium polycarboxylic acid (manufactured by Sannopco Co., Ltd., SN Dispersant 5468) by 3.0 mass. Parts (in terms of solid content) were uniformly dispersed in 110 parts by mass of water to obtain a pigment dispersion liquid.
• aluminum hydroxide oxide manufactured by Daimei Chemical Co., Ltd., Boehmite Grade C06, particle size: 0.7 ⁇ m
• dispersant an aqueous solution of ammonium polycarboxylic acid (manufactured by Sannopco Co., Ltd., SN Dispersant 5468) by 3.0 mass. Parts (in terms of solid content) were uniformly dispersed in 110 parts by mass of water to obtain a pigment dispersion liquid.
• the aqueous solution produced in Production Example 1 was added to this pigment dispersion so as to have a solid content of 5 parts by mass, and water was further added to adjust the solid content to 40%, and the mixture was stirred for 15 minutes.
• the surface of the polyolefin resin porous membrane was corona-treated. More specifically, as a polyolefin resin porous membrane, product number SW509C + (film thickness 9.6 ⁇ m, porosity 40.6%, air permeability 158 g / 100 ml, surface density 5.5 g / m 2 , Changzhou star source new energy source material Co., Ltd.) prepared. Next, the surface of the polyolefin resin porous membrane is cut to A4 size, and then the surface of the polyolefin resin porous membrane is cut to an output of 0.15 KW and a transfer speed by a switchback automatic traveling type corona surface treatment device (manufactured by Wedge Co., Ltd.). Corona treatment was performed under the conditions of 3.0 m / s ⁇ 2 times and a corona discharge distance of 9 mm.
• the above-mentioned coating material for the secondary battery separator was applied to the surface of the corona-treated polyolefin resin porous film. After coating, it was dried at 50 ° C. to form a coating film of 5 ⁇ m on the surface of the porous polyolefin resin film.
• Example 1 Treatment is the same as in Example 1 except that the aqueous solutions produced in Production Example 2 to Production Example 5 and Production Comparative Examples 1 to 6 are used instead of the aqueous solution produced in Production Example 1. Then, a secondary battery separator was manufactured.
• Example 2 Treatment in the same manner as in Example 1 except that sodium carboxymethyl cellulose (CMC, trade name cellogen 3H manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., weight average molecular weight of about 110,000) was used instead of the aqueous solution produced in Production Example 1. Then, a secondary battery separator was manufactured.
• CMC carboxymethyl cellulose
• the heat shrinkage rate was 25% or more and less than 60%.
• the heat shrinkage rate was 60% or more.
• the air permeation resistance was less than 180 s / 100 mL.
• the air permeation resistance was 180 s / 100 mL or more and less than 220 s / 100 mL.
• the air permeation resistance was 220 s / 100 mL or more and less than 300 s / 100 mL.
• the air permeation resistance was 300 s / 100 mL or more.
• the coating material for a secondary battery separator of the present invention is suitably used in various industrial fields where a secondary battery is required.

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