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WO2016152161A1 - Adhesive composition, layered body, packaging material for power storage device, container for power storage device, and power storage device - Google Patents

Adhesive composition, layered body, packaging material for power storage device, container for power storage device, and power storage device Download PDF

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Publication number
WO2016152161A1
WO2016152161A1 PCT/JP2016/001692 JP2016001692W WO2016152161A1 WO 2016152161 A1 WO2016152161 A1 WO 2016152161A1 JP 2016001692 W JP2016001692 W JP 2016001692W WO 2016152161 A1 WO2016152161 A1 WO 2016152161A1
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WO
WIPO (PCT)
Prior art keywords
storage device
adhesive
layer
adhesive composition
acid
Prior art date
Application number
PCT/JP2016/001692
Other languages
French (fr)
Japanese (ja)
Inventor
睦 中里
Original Assignee
東洋インキＳｃホールディングス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋インキＳｃホールディングス株式会社 filed Critical 東洋インキＳｃホールディングス株式会社
Priority to CN201680017172.7A priority Critical patent/CN107429133B/en
Priority to KR1020177029945A priority patent/KR102005491B1/en
Publication of WO2016152161A1 publication Critical patent/WO2016152161A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
    • C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1472—Fatty acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
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    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • 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
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    • 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 an adhesive composition. Moreover, this invention relates to the laminated body which laminated
  • a secondary battery is a typical power storage device. Due to the rapid growth of electronic devices such as mobile phones and portable personal computers, the demand for secondary batteries such as lightweight and small lithium-ion batteries has increased. Conventionally, metal cans have been used as outer bodies of secondary batteries, but packaging materials in which plastic films, metal foils, and the like are laminated are becoming mainstream from the viewpoints of weight reduction and productivity. As the simplest packaging material, a laminate composed of a resin film layer (11), a metal foil layer (12), an adhesive layer (13) and a heat seal layer (14) in order from the outer layer side as shown in FIG. It is done. As shown in FIG.
  • the container for an electricity storage device is formed by molding the packaging material so that the resin film layer (11) forms a convex surface and the heat seal layer (14) forms a concave surface (deep drawing molding process, overhanging). Molding process, etc.).
  • the battery is manufactured by enclosing and sealing an electrode, electrolyte solution, etc. to the concave surface side of the container for electrical storage devices.
  • Capacitors are also one of power storage devices, and lithium ion capacitors are an area in which market growth is expected in the future.
  • Patent Document 1 an aqueous emulsion and / or an aqueous solution containing a water-soluble polymer aqueous solution as a main component is blended with a compound having an epoxy group and a compound having at least two isocyanate groups in the molecule or a polymer thereof.
  • An adhesive composition is disclosed.
  • Patent Document 2 discloses (A) a polyolefin resin having at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group, and a carboxylic acid metal salt, and (B) two epoxy groups.
  • An adhesive resin composition containing the epoxidized vegetable oil having a molecular weight of 3000 or less in a specific ratio is disclosed.
  • Patent Document 3 an acid-modified polypropylene resin containing 70% by mass or more of a propylene component and 0.1 to 10% by mass of an acid component and a crosslinking agent containing at least one of an oxazoline compound and an epoxy compound are specified.
  • a battery case having an adhesive layer contained in a proportion is disclosed.
  • Patent Document 4 contains an acid-modified polyolefin resin (A) and an epoxy resin compound (B) having two or more epoxy groups in one molecule and 10 or more hydroxyl groups in one molecule.
  • An adhesive resin composition is disclosed.
  • Patent Document 5 discloses a laminate adhesive composition containing a polyolefin resin (A) having a hydroxyl group and / or an acid group, a phosphoric acid-modified compound (B), and an epoxy resin (C) having an epoxy equivalent of 160 to 1000.
  • a product is disclosed (see claims 4 and 9). And the application to the laminated body for secondary batteries is disclosed.
  • JP-A-55-005937 Japanese Patent No. 3184725 JP 2012-216364 A JP 2013-91702 A International Publication No. 2014/050686
  • the adhesive layer for bonding the metal foil layer and the heat seal layer among the packaging materials for the electricity storage device.
  • the adhesive strength between the metal foil layer and the heat seal layer is large.
  • the adhesive layer has electrolyte solution resistance. That is, the adhesive strength between the metal foil and the heat seal layer can be maintained even if the electrolyte solution is sealed in the battery container.
  • the electrolyte solution of a lithium battery includes a lithium salt (electrolyte) such as lithium hexafluorophosphate and a solvent such as propylene carbonate, ethylene carbonate, diethyl carbonate, and dimethyl carbonate.
  • the electrolyte solution When the electrolyte solution is put into the container for the electricity storage device, the electrolyte solution passes through the heat seal layer, reaches the adhesive layer, and causes a decrease in the adhesive strength between the heat seal layer and the metal foil. Further, when moisture enters the electrolyte solution from the outside of the battery container, a lithium salt such as lithium hexafluorophosphate reacts with water to generate hydrofluoric acid. The generated hydrofluoric acid passes through the heat seal layer and the adhesive layer, reaches the metal foil, and corrodes the metal foil. This corrosion significantly reduces the adhesive strength between the heat seal layer and the metal foil.
  • a lithium salt such as lithium hexafluorophosphate reacts with water to generate hydrofluoric acid.
  • the generated hydrofluoric acid passes through the heat seal layer and the adhesive layer, reaches the metal foil, and corrodes the metal foil. This corrosion significantly reduces the adhesive strength between the heat seal layer and the metal foil.
  • the adhesive layer that bonds the heat seal layer and the metal foil layer is required to have resistance to a substance generated by an intruder from the outside of the electricity storage device acting on the electrolyte solution in addition to resistance to the electrolyte solution itself.
  • power storage devices have been required to have a large capacity and long-term durability. Therefore, more excellent electrolyte solution resistance is required particularly for in-vehicle applications.
  • Patent Document 1 describes that an adhesive composition is used to join between a lauan sawing material and a stone-grown slate plate by a cold-pressing method, and there is some adhesive force even after repeated boiling.
  • Patent Document 1 does not disclose or suggest a battery packaging material.
  • the moisture resistance of the adhesive strength as described above and the electrolyte solution resistance are completely different.
  • Patent Document 2 the adhesive strength between an adhesive resin composition layer formed by melt-extruding an adhesive resin composition on a polyester film or a polyamide film and each film has a temperature of 60 ° C. and a relative humidity of 90%. It is stated that it can be maintained to some extent even after being left in a constant temperature bath for 48 hours.
  • Patent Document 2 does not disclose or suggest a battery packaging material.
  • Patent Document 3 discloses a battery exterior material as described above. However, the electrolyte solution resistance is only about 24 hours at 85 ° C. or 100 ° C.
  • Patent Document 4 does not disclose or suggest a battery packaging material. Although the initial adhesive strength is described, there is no mention of the durability of the adhesive strength. Needless to say, no electrolyte solution resistance is suggested.
  • Patent document 5 discloses the application to the laminated body for secondary batteries as mentioned above, and mentions "electrolyte resistance".
  • electrolyte resistance is merely a level of immersion in a solvent (ethylene carbonate, propyl carbonate) not containing an electrolyte such as a lithium salt at 40 ° C. for 30 days. That is, “electrolyte resistance” in the cited document 4 is merely solvent resistance. Resistance to an electrolyte solution containing an electrolyte is completely different from mere solvent resistance.
  • the present invention has been made in view of the above background, and in the case of an aging time of about 40 ° C. for about 3 days, a laminate capable of maintaining a high level of adhesive strength even when immersed in an electrolyte solution at 85 ° C. for 2 weeks. It is an object of the present invention to provide an adhesive composition that can form a film. Moreover, this invention makes it a subject to provide the packaging material for electrical storage devices, the container for electrical storage devices, and an electrical storage device which are more excellent in electrolyte solution tolerance than before.
  • the present inventor found that the epoxy compound (B) obtained by the reaction of the unsaturated fatty acid polymer (B1) and the compound (B2) having two or more epoxy groups is excellent in compatibility with the polyolefin and has a curing reaction.
  • the present invention has been completed. That is, the present invention is an adhesive composition for laminating a metal foil layer and a heat seal layer via an adhesive layer, and comprises a polyolefin resin (A) having a carboxyl group or an acid anhydride group, The present invention relates to an adhesive composition comprising a saturated fatty acid polymer (B1) and an epoxy compound (B) obtained by a reaction of a compound (B2) having two or more epoxy groups.
  • the epoxy compound (B) is an epoxy compound obtained by further hydrogenating a reaction product of a polymer (B1) of an unsaturated fatty acid and a compound (B2) having two or more epoxy groups.
  • the polymer (B1) of the unsaturated fatty acid is at least one of a compound (dimer acid) obtained by dimerizing an unsaturated fatty acid having 12 to 24 carbon atoms and a compound (trimer acid) obtained by trimerization.
  • the compound (B2) having two or more epoxy groups is preferably at least one selected from a bisphenol A type epoxy compound and a bisphenol F type epoxy compound.
  • the epoxy equivalent of the epoxy compound (B) is preferably 200 to 7000.
  • the polyolefin resin (A) preferably has a mass average molecular weight of 50,000 to 500,000.
  • the polyolefin resin (A) is preferably obtained by further acid-modifying a copolymer obtained from 1-butene and another olefin.
  • the content of carboxyl groups per gram of the polyolefin resin (A) is X mmol and the content of acid anhydride groups is Y mmol
  • X + 2Y is 0.05 to 0. .6 is preferred.
  • the content of the polyolefin resin (A) is P grams and the epoxy group in the epoxy compound (B) is Z mmol
  • Z / [(X + 2Y) P] is 0. 3 to 10 is preferable.
  • the present invention relates to a laminate in which a metal foil layer and a heat seal layer are laminated via an adhesive layer formed from the above adhesive composition.
  • the present invention is an electricity storage device packaging material in which a resin film layer, a metal foil layer, an adhesive layer, and a heat seal layer are essential from the outer layer, and the adhesive layer is formed from the adhesive composition.
  • the present invention relates to a packaging material for an electricity storage device.
  • the present invention also relates to a container for an electricity storage device formed from the packaging material for an electricity storage device, wherein a heat seal layer constitutes the inner surface. Furthermore, this invention relates to the electrical storage device formed using the said container for electrical storage devices.
  • the adhesive composition of the present invention in the case of aging at 40 ° C. for about 3 days, it is possible to form a laminate capable of maintaining the adhesive strength at a high level even when immersed in an electrolyte solution at 85 ° C. for 2 weeks.
  • the packaging material for an electricity storage device of the present invention includes at least a resin film layer (11), a metal foil layer (12), an adhesive layer (13), and a heat seal layer (14) that are sequentially laminated. Become.
  • the adhesive layer (13) plays a role of bonding the metal foil layer (12) and the heat seal layer (14) together.
  • the container for an electricity storage device of the present invention is formed using the packaging material for an electricity storage device of the present invention, and the form thereof is not particularly limited.
  • the heat seal layer (14) is arranged inside the tray, that is, on the concave side forming a space for accommodating the electrode, the electrolyte solution, etc., and the resin on the outer layer side outside the tray, that is, on the convex side.
  • a film layer (11) is arranged.
  • cylindrical (cylindrical, square, elliptical, etc.) modes can be exemplified.
  • These electric storage device containers are usually obtained by molding a flat storage device for an electric storage device.
  • the inside of the electricity storage device container that is, the surface in contact with the electrolyte solution or the like is a heat seal layer (14).
  • the heat seal layer (14) of the flange portion and the heat seal layer (14) constituting another packaging material for the electricity storage device or the heat seal layer (14) of the flange portion of the container for another electricity storage device are opposed to and in contact with each other. By heating, the heat seal layers (14) are fused together to enclose an electricity storage device member such as an electrolyte solution and electrodes.
  • the container for an electricity storage device of the present invention includes a bag-like container (pouch type) in addition to a tray shape.
  • the adhesive composition of this invention is used suitably for formation of an adhesive bond layer (13).
  • the adhesive composition of the present invention contains a polyolefin resin (A) having a carboxyl group or an acid anhydride group and an epoxy compound (B) modified with a polymer of an unsaturated fatty acid.
  • a polyolefin resin (A) having a carboxyl group or an acid anhydride group is simply abbreviated as a polyolefin resin (A), and is reacted with a polymer (B1) of an unsaturated fatty acid and a compound (B2) having two or more epoxy groups.
  • the resulting epoxy compound (B) may simply be abbreviated as epoxy compound (B).
  • the acid anhydride group is reacted with the epoxy group in the epoxy compound (B).
  • a strong cross-linked structure is formed, sufficient adhesive strength can be exhibited, and the adhesive strength can be maintained at a high level even when immersed in a higher temperature electrolyte solution for a long period of time.
  • the polyolefin resin (A) preferably has an amorphous part.
  • the reason is that it is excellent in the solubility with respect to the solvent used for the adhesive composition, and is excellent in storage stability in which the dissolved solution can be stably stored without precipitation.
  • the polyolefin resin (A) used in the present invention preferably has a mass average molecular weight of 50,000 to 500,000, a melting point of 60 to 110 ° C., and a melting energy ( ⁇ E) of 15 to 50 (mJ / mg). .
  • the polyolefin resin (A) has a mass average molecular weight (Mw) of 50,000 to 500,000, the storage stability of the polyolefin resin (A) constituting the adhesive composition as a solution, and a packaging material for an electricity storage device As a result, it is easy to achieve both electrolyte solution resistance, heat sealability, and coating properties. More preferably, the Mw of the polyolefin resin (A) is 100,000 to 400,000. In other words, if the Mw of the polyolefin resin (A) is less than 50,000, the entanglement of the polymer chain of the polyolefin resin (A) is insufficient, so that the film strength of the adhesive layer is lowered and the electrolyte solution resistance may be insufficient.
  • Mw mass average molecular weight
  • the polyolefin resin (A) has a melting point of 60 to 110 ° C. and a melting energy ( ⁇ E) of 15 to 50 (mJ / mg), so that the adhesive strength as an energy storage device packaging material (initially, after immersion in an electrolyte solution) And heat sealability can be satisfied in a well-balanced manner.
  • ⁇ E melting energy
  • the melting point of the polyolefin resin (A) is 60 to 90 ° C. Further, when the melting energy ( ⁇ E) of the polyolefin resin (A) is less than 15 mJ / mg, the adhesive strength and heat sealability after immersion in the electrolyte solution are lowered, and when it exceeds 50 mJ / mg, the crystallinity is high. A) Storage stability as a solution may decrease. More preferably, the melting energy ( ⁇ E) of the polyolefin resin (A) is 20 to 50 mJ / mg, more preferably 20 to 40 mJ / mg.
  • the packaging material for power storage devices is further heat-sealed. It is also required to have excellent properties.
  • the heat seal layer (14) constituting the packaging material for the electricity storage device is fused with the heat seal layer (14) by heat, and an electricity storage device member such as an electrolyte solution or an electrode in the electricity storage device container.
  • an electricity storage device member such as an electrolyte solution or an electrode in the electricity storage device container.
  • the adhesive layer (13) that has bonded the heat seal layer (14) and the metal foil layer (12) melts or deforms due to heat and pressure during heat sealing, the electrode terminal and the metal foil There is a possibility that the layer (12) is electrically connected. When conducting, it does not function as an electricity storage device. Therefore, it is required that the adhesive layer (13) is not melted or deformed by heat and pressure during heat sealing so that the insulation between the electrode terminal and the metal foil layer (12) is not impaired by heat sealing. It is done.
  • the polyolefin resin (A) whose melting point and melting energy ( ⁇ E) are within the above ranges, melting and deformation of the adhesive layer (13) during heat sealing can be effectively suppressed / prevented.
  • “storage stability” means that 10 g of resin is added to 90 g of toluene, the resin is heated and dissolved to obtain a transparent solution, and then cooled to 25 ° C. for one week at the same temperature. A thing that does not cause precipitation upon standing.
  • the polyolefin resin (A) in the present invention only needs to have a carboxyl group or an acid anhydride group.
  • the polyolefin resin (A-1) having no carboxyl group or acid anhydride group has no ethylenic group.
  • examples thereof include a modified polyolefin resin obtained by graft polymerization of a saturated carboxyl group or its acid anhydride, and a copolymer of an olefin monomer and an ethylenically unsaturated carboxylic acid or its acid anhydride.
  • the polyolefin which has a carboxyl group can also be obtained by making it react with the acid anhydride group of polyolefin which has an acid anhydride group, and water or alcohol.
  • a modified polyolefin resin obtained by graft-polymerizing an ethylenically unsaturated carboxyl group or an acid anhydride thereof to a polyolefin resin (A-1) having no carboxyl group or acid anhydride group is preferable.
  • the polyolefin resin (A) may be used alone or in combination of two or more kinds. The amount of the carboxyl group or acid anhydride group in the polyolefin resin (A) will be described later.
  • the method for graft polymerization of polyolefin is not particularly limited.
  • the polyolefin resin (A) is not particularly limited.
  • a homopolymer of olefin monomers such as ethylene, propylene, 1-butene, butadiene, isoprene, 1-hexene and 1-octene, Or a copolymer with other monomers, and a polymer mainly composed of a hydrocarbon skeleton, such as a hydride or a halide of the obtained polymer.
  • the polyolefin resin (A) is preferably a copolymer of olefin monomers.
  • the copolymer of olefin monomers is preferably a copolymer of 1-butene and other olefin monomers.
  • Other olefins are preferably ethylene and propylene, and copolymers of 1-butene and other olefin monomers are binary copolymers of ethylene and 1-butene, and binary of propylene and 1-butene.
  • Examples of the copolymer include a terpolymer of ethylene, propylene and 1-butene, and a binary copolymer of propylene and 1-butene is more preferable.
  • the melting point may be lower than 60 ° C. when propylene is less than 10 mol%, and the melting point may be higher than 110 ° C. when it is higher than 80 mol%.
  • Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene and indene; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, Alkyl (meth) acrylate compounds such as behenyl (meth) acrylate; (Meth) acrylate compounds having an alicyclic structure such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; (Meth) acrylate compounds having an aromatic ring such as benzyl (meth) acryl
  • the ethylenically unsaturated carboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, and itaconic acid. These ethylenically unsaturated carboxylic acids or acid anhydrides thereof may be used alone or in combination of two or more.
  • the polymerization method of the olefin monomer is not particularly limited.
  • the polymerization can be performed by adding a metal catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.
  • a metal catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.
  • promoters such as (methyl) aluminoxane, as needed.
  • Mw of polyolefin resin (A) is calculated
  • the melting point and melting energy ( ⁇ E) can be determined by DSC measurement according to JIS K7121. Specifically, it is obtained as follows. When the diameter or each side of the polyolefin resin (A) of about 10 mg is 0.5 mm or less, it is used as it is, and if it exceeds 0.5 mm, it is cut into 0.5 mm or less and put into a container.
  • the melting point is determined by changing a provisional value of melting point predicted from the olefin composition (hereinafter referred to as provisional melting point) or measurement conditions. It is then heated at 10 ° C. per minute to a temperature about 30 ° C. above the provisional melting point and then cooled to 10 ° C. per minute to a temperature about 50 ° C.
  • polyolefin resin A
  • Sumifit CK1D (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Unistor P-401, P-802, P-902 (trade name), Umex 1001, 1010, 2000 (trade name, manufactured by Sanyo Chemical Co., Ltd.), Auroren 350S, 351S, 359S, S-5247S, S-5248S, S-5297S, S-5349S, S-5350S, and the like.
  • a polyolefin resin having no carboxyl group or acid anhydride group may be used in combination with the polyolefin resin (A) having a carboxyl group or acid anhydride group, as long as the effects of the invention are not impaired. .
  • Examples of the polyolefin resin having no carboxyl group or acid anhydride group used in the present invention include Tough selenium T3712, T3722, T3522 (propylene elastomer), Sumitomo Nobrene (polypropylene), Mitsui Chemicals, manufactured by Sumitomo Chemical Co., Ltd.
  • Tafmer DF & A Tafmer H, Tafmer XM, Tafmer BL, Tafmer M ( ⁇ -olefin copolymer), Kuraray LIR-30 (isoprene polymer), LIR-200 (hydrogenated isoprene polymer), LBR -300 (butadiene polymer), Kuraray Septon 2002, 2004 (more hydrogenated styrene-isoprene-styrene copolymer), 2104, 4033, HG252 (more hydrogenated styrene-isoprene / butadiene-styrene copolymer) Coalescence), Asahi Kasei Chemical Asaprene T-432 and T-437 manufactured by Clayton Polymer Japan, Clayton D1155 manufactured by Clayton Polymer Japan (above, styrene-butadiene-styrene copolymer), Tuftec P1500, P2000 and MP10 manufactured by Asahi Kasei Chemicals
  • the epoxy compound (B) obtained by the reaction of the unsaturated fatty acid polymer (B1) used in the present invention with the compound (B2) having two or more epoxy groups will be described. Due to the strong cross-linked structure obtained by reacting the epoxy group in the epoxy compound (B) with the carboxyl group or acid anhydride group in the polyolefin resin (A), sufficient adhesive strength can be expressed, and a higher temperature electrolyte solution can be obtained. Even if it is immersed for a long time, its adhesive strength can be maintained at a high level.
  • the epoxy compound (B) used in the present invention is not limited to the following, but is a compound (B2) having a carboxyl group and two or more epoxy groups in the polymer (B1) of unsaturated fatty acid. ) Or a hydrogenated compound thereof obtained by an esterification reaction with an epoxy group.
  • the epoxy compound (B) modified with the unsaturated fatty acid polymer (B1) the compatibility with the polyolefin resin (A) is remarkably improved, and the carboxyl group or acid anhydride group in the polyolefin resin (A) is improved. Reaction is promoted, and productivity can be improved.
  • Examples of the unsaturated fatty acid polymer (B1) include unsaturated fatty acid dimers, trimers and oligomers of tetramers or more. Dimers (dimer acid), trimers (trimer acid) ) Is preferable, and a mixture of the two may be used.
  • unsaturated fatty acids include fatty acids having one unsaturated group such as oleic acid, elaidic acid, vaccenic acid, ricinolenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid; Fatty acids having two unsaturated groups such as linoleic acid, icosadienoic acid, docosadienoic acid; Fatty acids having three unsaturated groups such as icosatrienoic acid, eleostearic acid, dihomo- ⁇ -linolenic acid, pinolenic acid, mead acid, linolenic acid; Examples include fatty acids having four unsaturated groups such as stearidonic acid, adachidonic acid, eicosatetraenoic acid, and adrenic acid.
  • Examples of commercially available products of these polymerized fatty acids include “Pripol 1004”, “Plipol 1006”, “Plipol 1009”, “Plipol 1013”, “Plipol 1015”, “Plipol 1017”, and “Plipol 1022” manufactured by Croda Japan. , “Prepole 1025”, “Prepole 1040”, “Empole 1008”, “Empole 1012”, “Empole 1016”, “Empole 1026”, “Empole 1028”, “Empole 1043”, “Empole 1061” manufactured by BASF Japan And “Empole 1062”. Of these, unsaturated fatty acids having 12 to 24 carbon atoms, which have good compatibility with the polyolefin resin (A) and are easily obtained industrially, are preferable.
  • the compound (B2) having two or more epoxy groups may be a compound having two or more epoxy groups in one molecule.
  • a commercial product for example, trade name “Epicoat” manufactured by Mitsubishi Chemical Corporation 828 ”,“ Epicoat 834 ”,“ Epicoat 1001 ”,“ Epicoat 1004 ”, trade names“ Epicron 840 ”,“ Epicron 850 ”,“ Epicron 1050 ”,“ Epicron 2055 ”manufactured by Dainippon Ink and Chemicals, NS Bisphenol A type epoxy compounds such as “Epototo 128” manufactured by Kagaku Co .; Product name “Epicron 830S” manufactured by Dainippon Ink & Chemicals, Inc.
  • Epicron EXA1514 Bisphenol fluorene type epoxy compounds such as “BPFG” manufactured by Osaka Gas Co., Ltd., “YL-6056”, “YL-6021”, “YX-4000”, “YX-4000H” manufactured by Mitsubishi Chemical Corporation, etc.
  • Epicron N-690 Epicron N-695
  • Epicron N-730 Epicron N-770
  • Epicron N-865 trade names “Epototo YDCN” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. -701 ”,“ Epototo YDCN-704 ”, trade names“ EPPN-201 ”,“ EOCN-1025 ”,“ EOCN-1020 ”,“ EOCN-104S ”,“ RE-306 ”manufactured by Nippon Kayaku Co., Ltd.
  • Novolac epoxy compounds Product name “Epicoat YL-903” manufactured by Mitsubishi Chemical Corporation, product names “Epicron 152” and “Epicron 165” manufactured by Dainippon Ink and Chemicals, Inc.
  • Epoxy compounds having a dicyclopentadiene skeleton such as trade names “HP-7200” and “HP-7200H” manufactured by Dainippon Ink & Chemicals, Inc .
  • Trishydroxyphenylmethane type epoxy compounds such as trade names “YL-933” manufactured by Mitsubishi Chemical Corporation and trade names “EPPN-501” and “EPPN-502” manufactured by Nippon Kayaku Co., Ltd .
  • Heterocyclic epoxy compounds such as Nissan Chemical's trade name “TEPIC” and Mitsubishi Gas Chemical's trade name “TGI”
  • Glycidylamine type epoxy compounds such as trade names “jER604” and “jER630” manufactured by Mitsubishi Chemical Corporation, “Epototo YH-434” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and “Araldite MY720” manufactured by Asahi Kasei Corporation
  • Alicyclic epoxy compounds such as “Celoxide 2011” manufactured by Daicel Chemical Industries, “Araldite CY175
  • the epoxy equivalent of the epoxy compound (B) obtained by the reaction of the unsaturated fatty acid polymer (B1) and the compound (B2) having two or more epoxy groups used in the present invention is pot life, adhesive strength, Also, from the reason of excellent chemical resistance, it is preferably 200 to 7000. It is preferable that the epoxy equivalent is 200 or more from the viewpoint of improving the initial adhesive force due to the length of the pot life of the adhesive composition and the appropriate crosslinking density of the adhesive layer. Moreover, when the epoxy equivalent is 7000 or less, the crosslinking density of the adhesive layer can be increased, the initial adhesive force can be improved, and the chemical resistance can also be improved.
  • the epoxy equivalent is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and was calculated by potentiometric titration based on JIS K7236.
  • the esterification reaction for producing the epoxy compound (B) obtained by the reaction of the unsaturated fatty acid polymer (B1) used in the present invention with the compound (B2) having two or more epoxy groups is known.
  • the reaction can be performed. That is, the production method is not particularly limited, and for example, it is synthesized by a reaction between a carboxyl group and an epoxy group using a catalyst.
  • the reaction can be easily carried out by contacting them in the presence of a catalyst at a temperature of 50 to 200 ° C., preferably 120 to 180 ° C. for 30 minutes to 20 hours.
  • the acid value of the reaction product is 5 mgKOH / g.
  • the end point of the reaction is preferably the time when 1 mgKOH / g or less is reached.
  • Catalysts such as halides such as zinc chloride and lithium chloride; Tertiary amines such as N, N-dimethylaniline, pyridine, triethylamine, hexamethylenediamine, diazabicycloundecene and their basic acids or odorates; Quaternary ammonium salts such as tetramethylammonium chloride and trimethyldodecylbenzylammonium chloride; Sulfonic acids such as paratoluenesulfonic acid are used.
  • the epoxy compound (B) obtained by the reaction of the unsaturated fatty acid polymer (B1) and the compound (B2) having two or more epoxy groups is also available as a commercial product.
  • “Epicoat 871”, “Epicoat 872”, “Epicoat 872-X-75” manufactured by Mitsubishi Chemical Corporation, “YD-172”, “YD-172X75” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. may be used.
  • the content of carboxyl groups per gram of polyolefin resin (A) is X mmol
  • the content of acid anhydride groups is In the case of Y mmol
  • X + 2Y is preferably 0.05 to 0.6.
  • X + 2Y is less than 0.05, there are few acidic groups that serve as crosslinking points, crosslinking is not sufficient, and sufficient adhesive strength and electrolyte solution resistance may not be obtained. If it is larger than 0.6, the crosslinking strength of the coating film is large, so that the adhesive strength may be insufficient, or the solubility in a solvent may be reduced.
  • Z / (X + 2Y) P is within a range of 0.3 to 10. More preferably, the epoxy compound (B) is included in the range of 0.5 to 7.
  • Z / (X + 2Y) P is preferably 0.3 or more so that a sufficient cross-linked structure can be formed to improve cohesion. From the viewpoint of electrolyte solution resistance, Z / (X + 2Y) P is preferably 10 or less so that no unreacted epoxy compound (B) remains.
  • the adhesive of the present invention can further contain a silane coupling agent in order to increase the adhesive strength with the metal foil.
  • a silane coupling agent include trialkoxysilanes having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane.
  • glycidyl group such as trialkoxysilane having an amino group such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane
  • examples include trialkoxysilane.
  • the addition amount of the silane coupling agent is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass based on the solid content of the adhesive.
  • the adhesive of the present invention can contain catechol or a derivative thereof in order to increase the adhesive strength with the metal foil.
  • catechol or a derivative thereof in order to increase the adhesive strength with the metal foil.
  • Specific examples include catechol, t-butylcatechol, adrenaline, noradrenaline, dopamine, nordihydroguaiaretic acid and the like.
  • the adhesive composition of the present invention can contain an organic solvent.
  • An epoxy compound (B) which can dissolve a material used in the present adhesive composition alone or as a mixed solvent, and which is obtained by reacting an unsaturated fatty acid polymer (B1) with a compound (B2) having two or more epoxy groups. ) Is inactive and is not particularly limited as long as it can be volatilized and removed by heating in the drying step during adhesive coating.
  • solvents include aromatic organic solvents such as toluene and xylene; aliphatic organic solvents such as n-hexane and n-heptane; Cycloaliphatic organic solvents such as cyclohexane and methylcyclohexane; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ester solvents such as ethyl acetate and butyl acetate; Alcohol solvents such as ethanol, methanol, n-propanol, 2-propanol, butanol, hexanol; Ether solvents such as diisopropyl ether, butyl cellosolve, tetrahydrofuran, dioxane, butyl carbitol; Glycol ether solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether;
  • a combination of an aromatic organic solvent and a ketone solvent, a combination of an aromatic organic solvent and an alcohol solvent, an alicyclic organic solvent from the viewpoint of the storage stability of the solution of the polyolefin resin (A), a combination of an aromatic organic solvent and a ketone solvent, a combination of an aromatic organic solvent and an alcohol solvent, an alicyclic organic solvent, The combined use of a ketone solvent and the combined use of an alicyclic organic solvent and an alcohol solvent are preferred.
  • tackifiers that can be used in the present invention include polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, styrene resins, and hydrogenated petroleum resins. Used for the purpose of improving strength. These may be used alone or in any combination of two or more.
  • plasticizer used in the present invention include liquid rubber such as polyisoprene and polybutene, process oil, and the like.
  • the adhesive composition of the present invention is suitably used for laminating the metal foil layer (12) and the heat seal layer (14).
  • the metal of the metal foil layer (12) include aluminum, copper, and nickel. These metal foils may be subjected to various surface treatments. Examples of the surface treatment include physical treatment such as sand blast treatment and polishing treatment, degreasing treatment by vapor deposition, etching treatment, and surface treatment such as primer treatment for applying a coupling agent or a coating agent.
  • the treatment agent for forming the surface treatment layer preferably contains a functional group that reacts with an epoxy group, and more preferably contains at least one functional group selected from the group consisting of a carboxylic acid, a hydroxyl group and an amino group. .
  • the amino group here is a primary amine, a secondary amine, or an imino group.
  • the heat seal layer (14) is not particularly limited, but is preferably a polyolefin film, and at least selected from the group consisting of polyethylene, polypropylene, olefin copolymers, acid-modified products thereof, and ionomers.
  • An unstretched film made of one kind of thermoplastic resin is preferable.
  • the thickness of the heat seal layer is not particularly limited, but is preferably 20 to 150 ⁇ m.
  • a laminate using the adhesive composition of the present invention can be obtained, for example, as follows. On one side of the metal foil layer (12) (or heat seal layer (14)), the adhesive composition of the present invention is applied, and the solvent is stripped (dried) to form an uncured adhesive layer. After the heat seal layer (14) (or the metal foil layer (12)) is stacked on the surface of the uncured adhesive layer under pressure at 60 to 150 ° C., it is 3 to 10 days at 40 to 80 ° C.
  • the laminate can be obtained by allowing to stand to a certain degree, sufficiently curing the adhesive layer (also referred to as aging), and bonding the metal foil and the heat seal layer together.
  • a general coating machine such as a comma coater can be used for coating of the adhesive composition.
  • the thickness (amount) of the cured adhesive layer at the time of dry curing is preferably about 0.5 to 10 g / m 2 .
  • the packaging material for an electricity storage device of the present invention is the outer layer side adhesive on the other surface of the metal foil layer (12) (the surface where the adhesive layer (13) formed from the adhesive composition of the present invention is not in contact).
  • a resin film layer (11) can be provided through the layer.
  • the resin film layer (11) is previously laminated on the metal foil layer (12) using an adhesive composition (which may be the same as or different from the adhesive composition of the present invention).
  • an outer layer side adhesive bond layer is attached to a metal foil layer (12).
  • the resin film layer (11) can also be laminated.
  • the resin film layer (11) used examples include stretched films such as a polyester resin and a polyamide resin (nylon), and the resin film layer (11) uses a laminate as a packaging material for an electricity storage device and is used for an electricity storage device.
  • stretched films such as a polyester resin and a polyamide resin (nylon)
  • the resin film layer (11) uses a laminate as a packaging material for an electricity storage device and is used for an electricity storage device.
  • the container is located outside the electrolyte solution.
  • the container for an electricity storage device of the present invention is molded using the aforementioned packaging material for an electricity storage device so that the resin film layer (11) on the outer layer side forms a convex surface and the heat seal layer (14) forms a concave surface.
  • the “concave surface” as used in the present invention is a surface having a dent that can accommodate the electrolyte solution when the flat packaging material for an electricity storage device is molded into a tray shape as shown in FIG.
  • the term “convex surface” as used in the present invention refers to the self-back surface (opposite surface, back surface) of the surface having the depression.
  • An electricity storage device such as a secondary battery includes a battery body, a plurality of terminals respectively joined to a positive electrode and a negative electrode of the battery body, a battery container, and an electrolyte solution.
  • the battery container is obtained from a laminate in which a metal foil layer (12) and a heat seal layer (14) are laminated via an adhesive layer (13) formed from the adhesive composition of the present invention. The heat seal layer is in contact with the electrolyte solution.
  • the electrolyte solution starts to penetrate from the heat seal layer (14) toward the metal foil layer (12), but the adhesive layer (13) formed from the adhesive composition of the present invention has excellent resistance to the electrolyte solution. Therefore, the adhesive strength between the heat seal layer and the metal foil does not decrease, and problems such as liquid leakage do not occur.
  • X 0.1 * b / a ⁇ Quantification of acid anhydride group>
  • a weighed sample of c grams was dissolved in refluxed xylene, cooled to room temperature, and d mmol of octylamine equal to or greater than the acid anhydride group of the sample was added.
  • the copolymer composition ratio of the polyolefin was determined by 13 C measurement using NMR (JNM-LA400) manufactured by JEOL. A 20 mg sample was dissolved in 1 mL deuterated chloroform and measured. The methylene group derived from ethylene has a peak at 40-50 ppm, the methine group derived from propylene has a peak at 25-30 ppm, and the methine group derived from 1-butene has a peak at 30-35 ppm. The copolymer composition ratio was determined from the integration ratio of each peak.
  • ⁇ Synthesis Example 9> 280 g of propylene-ethylene copolymer (propylene / ethylene 82/18% by mass, mass average molecular weight 85000) was melted by heating in a four-necked flask under a nitrogen atmosphere, and then the system temperature was maintained at 180 ° C. with stirring. Then, 35.0 g of maleic anhydride as an acid component and 6.0 g of di-t-butyl peroxide as a radical generator were added over 2 hours, and then reacted for 1 hour. After completion of the reaction, the obtained reaction product was put into a large amount of acetone to precipitate a resin.
  • This resin was further washed several times with acetone to remove unreacted maleic anhydride, and then dried under reduced pressure in a vacuum dryer to obtain an acid-modified polypropylene resin (mass average molecular weight 40000).
  • a stirrer equipped with a hermetically sealed 1 liter glass container with a heater, 60.0 g of the acid-modified polypropylene resin, 60.0 g of tetrahydrofuran, 6.9 g of N, N-dimethylethanolamine (acid When 1.03.1 equivalent to the carboxyl group of the acid component in the modified polypropylene resin) and 173.1 g of distilled water were charged into a glass container and stirred at a rotation speed of 300 rpm, the resin was placed at the bottom of the container.
  • Pripol 1013 C18 unsaturated fatty acid dimer acid, acid value 196 mg KOH / g
  • jER1001 Mitsubishi Chemical Corporation, bisphenol A type epoxy compound, epoxy equivalent: 475
  • triphenylphosphine 4 parts After 160 parts of toluene and 40 parts of isopropyl alcohol were heated and dissolved in a four-necked flask under a nitrogen atmosphere, the system temperature was maintained at 100 ° C. while stirring. The reaction was carried out until the acid value became 1.0 mgKOH / g or less, followed by cooling to obtain an epoxy compound (B-1) having a solid content of 50% and an epoxy equivalent of 1236.
  • MEK methyl ethyl ketone
  • an unstretched polypropylene film (hereinafter referred to as CPP) having a thickness of 40 ⁇ m was superposed on the adhesive layer and passed between two rolls set at 80 ° C. to obtain a laminate. Thereafter, the obtained laminate was cured (aging) at 40 ° C. for 3 days or 5 days.
  • the aluminum foil / CPP laminate film thus obtained is hereinafter referred to as “Al / CPP laminate film”.
  • the initial adhesive strength, solvent resistance, and electrolyte solution resistance were evaluated according to the methods described below. The results are shown in Table 2.
  • Examples 2 to 22> ⁇ Comparative Examples 1 to 6> With the compositions shown in Tables 2 and 3, an adhesive solution and an Al / CPP laminated film were obtained in the same manner as in Example 1 and evaluated in the same manner.
  • P-401 “Unistor P-401”, manufactured by Mitsui Chemicals, acid-modified polyolefin resin, solid content acid value 55 mgKOH / g, heating residue 8%
  • P-902 “Unistor P-902”, manufactured by Mitsui Chemicals, acid-modified polyolefin resin, solid content acid value 55 mgKOH / g, heating residue 22%
  • jER871 Dimer acid-modified epoxy compound manufactured by Mitsubishi Chemical Corporation (epoxy equivalent 430 g / eq)
  • YD172 Nippon Steel & Sumikin Chemical Co., Ltd.
  • the adhesive solution was applied to a 100 ⁇ m PET film with a bar coater and dried at 100 ° C. for 1 minute to obtain an adhesive layer having a coating amount after drying of about 2 g / m 2 .
  • the compatibility was determined according to the following criteria. A: Less than 3 B: 3 or more and less than 5 C: 5 or more
  • the temperature was 85 ° C.
  • an adhesive having good adhesive strength (initially, after immersion in an organic solvent and an electrolyte solution) can be provided even if the aging period is short.
  • the adhesives of Comparative Examples 1 and 5 are epoxy compounds that do not contain a polymerized fatty acid-modified site, and have poorer compatibility with polyolefins than the epoxy compound (B) of the present invention, so that adhesive strength is manifested in aging in a short period of time.
  • the adhesion strength is significantly reduced after immersion in an organic solvent or electrolyte solution.
  • Comparative Example 2 uses an isocyanate compound having low solvent resistance as a curing agent in addition to the bisphenol A type epoxy resin, the solvent resistance is further deteriorated compared to Comparative Example 1. Since the adhesives of Comparative Examples 3 and 4 use phosphoric acid epoxy, the solvent resistance is improved as compared with Comparative Example 5, but the adhesive strength is not sufficiently exhibited by short-term aging. Even if the adhesive of Comparative Examples 4 and 6 uses an epoxy compound having an acid anhydride or a carboxyl group and a triphenylphosphine or an amino group as a catalyst for the reaction of the epoxy group, the adhesive strength is low when aging is performed for a short period of time. Not fully expressed.
  • the adhesive composition according to the present invention can be suitably used for a packaging material (laminate) for forming a container for an electricity storage device such as a lithium ion battery, an electric double layer capacitor, or a lithium ion capacitor.
  • the adhesive composition according to the present invention is a packaging material for forming a container for an electricity storage device, as well as various industrial fields that require high adhesive strength and chemical resistance, such as architecture, chemistry, medicine, and automobiles. It is used suitably for formation of the laminated body in.

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Abstract

Provided is an adhesive composition whereby a layered body can be formed in which adhesive strength can be maintained at a high level even when the layered body is immersed for two weeks or more in an electrolytic solution at a temperature of 85°C when aged for about 3 days at a temperature of 40°C. Provided are a layered body having excellent resistance to an electrolytic solution relative to the prior art, a packaging material for a power storage device, a container for a power storage device, and a power storage device. This adhesive composition is an adhesive composition for layering a metal foil layer and a heat seal layer via an adhesive layer, and is characterized by containing a polyolefin resin (A) having a carboxyl group or an acid anhydride group, and an epoxy compound (B) obtained by reacting a polymer (B1) of an unsaturated fatty acid and a compound (B2) having two or more epoxy groups.

Description

接着剤組成物、積層体、蓄電デバイス用包装材、蓄電デバイス用容器および蓄電デバイスAdhesive composition, laminate, storage device packaging, storage device container, and storage device
　本発明は接着剤組成物に関する。また、本発明は金属箔層とヒートシール層とを前記接着剤組成物を用いて積層した積層体および蓄電デバイス用包装材に関する。さらに本発明は、前記ヒートシール層が内面となるように前記蓄電デバイス用包装材を加工してなる蓄電デバイス用容器、および前記蓄電デバイス用容器を用いてなる蓄電デバイスに関する。 The present invention relates to an adhesive composition. Moreover, this invention relates to the laminated body which laminated | stacked the metal foil layer and the heat seal layer using the said adhesive composition, and the packaging material for electrical storage devices. Furthermore, the present invention relates to a power storage device container obtained by processing the power storage device packaging material so that the heat seal layer is an inner surface, and a power storage device using the power storage device container.
　二次電池は代表的な蓄電デバイスである。携帯電話、携帯型パソコン等の電子機器の急速な成長により、軽量かつ小型のリチウムイオン電池などの二次電池の需要が増大してきた。二次電池の外装体としては、従来、金属製缶が用いられてきたが、軽量化や生産性の観点よりプラスチックフィルムや金属箔などを積層した包装材が主流となりつつある。
　最もシンプルな包装材としては、図１のような外層側から順に樹脂フィルム層（１１）、金属箔層（１２）、接着剤層（１３）およびヒートシール層（１４）からなる積層体が挙げられる。蓄電デバイス用容器は、図２に示すように、樹脂フィルム層（１１）が凸面を構成し、ヒートシール層（１４）が凹面を構成するように前記包装材を成型（深絞り成型加工、張出し成型加工等）したものである。そして、蓄電デバイス用容器の凹面側に、電極や電解質溶液等を封入してシールすることにより電池を製造している。
　また、キャパシタも蓄電デバイスの１つであり、中でもリチウムイオンキャパシタは今後市場の成長が見込まれる分野である。 A secondary battery is a typical power storage device. Due to the rapid growth of electronic devices such as mobile phones and portable personal computers, the demand for secondary batteries such as lightweight and small lithium-ion batteries has increased. Conventionally, metal cans have been used as outer bodies of secondary batteries, but packaging materials in which plastic films, metal foils, and the like are laminated are becoming mainstream from the viewpoints of weight reduction and productivity.
As the simplest packaging material, a laminate composed of a resin film layer (11), a metal foil layer (12), an adhesive layer (13) and a heat seal layer (14) in order from the outer layer side as shown in FIG. It is done. As shown in FIG. 2, the container for an electricity storage device is formed by molding the packaging material so that the resin film layer (11) forms a convex surface and the heat seal layer (14) forms a concave surface (deep drawing molding process, overhanging). Molding process, etc.). And the battery is manufactured by enclosing and sealing an electrode, electrolyte solution, etc. to the concave surface side of the container for electrical storage devices.
Capacitors are also one of power storage devices, and lithium ion capacitors are an area in which market growth is expected in the future.
　特許文献１には、水性エマルジョンおよび／または水溶性高分子水溶液を主体成分とする水溶液に、エポキシ基を有する化合物および少なくともその分子中にイソシアネート基を２個以上有する化合物またはその重合物を配合してなる接着剤組成物が開示されている。また、特許文献２には、（Ａ）酸無水物基、カルボキシル基およびカルボン酸金属塩からなる群から選ばれた少なくとも１種の官能基を有するポリオレフィン系樹脂および（Ｂ）エポキシ基を２個以上有し、かつ分子量が３０００以下であるエポキシ化植物油を、特定割合で含有する接着性樹脂組成物が開示されている。 In Patent Document 1, an aqueous emulsion and / or an aqueous solution containing a water-soluble polymer aqueous solution as a main component is blended with a compound having an epoxy group and a compound having at least two isocyanate groups in the molecule or a polymer thereof. An adhesive composition is disclosed. Patent Document 2 discloses (A) a polyolefin resin having at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group, and a carboxylic acid metal salt, and (B) two epoxy groups. An adhesive resin composition containing the epoxidized vegetable oil having a molecular weight of 3000 or less in a specific ratio is disclosed.
　特許文献３には、プロピレン成分を７０質量％以上含有すると共に酸成分を０．１～１０質量％含有する酸変性ポリプロピレン樹脂と、オキサゾリン化合物及びエポキシ化合物の少なくとも一方を含む架橋剤とを特定の割合で含有する接着層を有する電池用外装体が開示されている。 In Patent Document 3, an acid-modified polypropylene resin containing 70% by mass or more of a propylene component and 0.1 to 10% by mass of an acid component and a crosslinking agent containing at least one of an oxazoline compound and an epoxy compound are specified. A battery case having an adhesive layer contained in a proportion is disclosed.
　特許文献４には、酸変性ポリオレフィン樹脂（Ａ）と、エポキシ基を１分子中に２つ以上有し、且つ、水酸基を１分子中に１０以上有するエポキシ樹脂系化合物（Ｂ）とを含有する接着性樹脂組成物が開示されている。 Patent Document 4 contains an acid-modified polyolefin resin (A) and an epoxy resin compound (B) having two or more epoxy groups in one molecule and 10 or more hydroxyl groups in one molecule. An adhesive resin composition is disclosed.
　特許文献５には、水酸基及び／又は酸基を有するポリオレフィン樹脂（Ａ）、リン酸変性化合物（Ｂ）、およびエポキシ当量が１６０～１０００であるエポキシ樹脂（Ｃ）を含有するラミネート用接着剤組成物が開示されている（請求項４、９参照）。そして、二次電池用の積層体への適用が開示されている。 Patent Document 5 discloses a laminate adhesive composition containing a polyolefin resin (A) having a hydroxyl group and / or an acid group, a phosphoric acid-modified compound (B), and an epoxy resin (C) having an epoxy equivalent of 160 to 1000. A product is disclosed (see claims 4 and 9). And the application to the laminated body for secondary batteries is disclosed.
特開昭５５－００５９３７号公報JP-A-55-005937 特許第３１８４７２５号公報Japanese Patent No. 3184725 特開２０１２－２１６３６４号公報JP 2012-216364 A 特開２０１３－９１７０２号公報JP 2013-91702 A 国際公開第２０１４／０５０６８６号International Publication No. 2014/050686
　蓄電デバイス用包装材のうち、金属箔層とヒートシール層とを貼り合わせるための接着剤層には、主に以下の性能が要求される。
（１）　金属箔層とヒートシール層との接着強度が大きいこと。
（２）　上記の接着剤層が電解質溶液耐性を有していること。即ち、電解質溶液を電池容器内に密封しても、金属箔とヒートシール層との接着強度が維持できること。
　例えば、リチウム電池の電解質溶液は、六フッ化リン酸リチウムのようなリチウム塩（電解質）と、プロピレンカーボネート、エチレンカーボネート、ジエチルカーボネート、ジメチルカーボネート等の溶剤とを含む。
　蓄電デバイス用容器に電解質溶液を入れると、電解質溶液がヒートシール層を通り抜け、接着剤層に達し、ヒートシール層と金属箔との接着強度低下を引き起こす。また、電池容器外部から電解質溶液に水分が浸入すると、六フッ化リン酸リチウムのようなリチウム塩と水とが反応し、フッ酸が発生する。発生したフッ酸はヒートシール層及び接着剤層を通り抜け、金属箔にまで到達し、金属箔を腐食させ、この腐食がヒートシール層と金属箔との接着強度を著しく低下させる。
　そこで、ヒートシール層と金属箔層とを貼りあわせる接着剤層には、電解質溶液そのものに対する耐性の他、蓄電デバイス外部からの侵入物が電解質溶液に作用し生じる物質に対する耐性も求められる。
　ところで、近年、車載や家庭蓄電など用途が拡大するに伴い、蓄電デバイスには大容量化、長期の耐久性が求められるようになった。そのため特に車載用途においてはより優れた電解質溶液耐性が求められる。 The following performance is mainly required for the adhesive layer for bonding the metal foil layer and the heat seal layer among the packaging materials for the electricity storage device.
(1) The adhesive strength between the metal foil layer and the heat seal layer is large.
(2) The adhesive layer has electrolyte solution resistance. That is, the adhesive strength between the metal foil and the heat seal layer can be maintained even if the electrolyte solution is sealed in the battery container.
For example, the electrolyte solution of a lithium battery includes a lithium salt (electrolyte) such as lithium hexafluorophosphate and a solvent such as propylene carbonate, ethylene carbonate, diethyl carbonate, and dimethyl carbonate.
When the electrolyte solution is put into the container for the electricity storage device, the electrolyte solution passes through the heat seal layer, reaches the adhesive layer, and causes a decrease in the adhesive strength between the heat seal layer and the metal foil. Further, when moisture enters the electrolyte solution from the outside of the battery container, a lithium salt such as lithium hexafluorophosphate reacts with water to generate hydrofluoric acid. The generated hydrofluoric acid passes through the heat seal layer and the adhesive layer, reaches the metal foil, and corrodes the metal foil. This corrosion significantly reduces the adhesive strength between the heat seal layer and the metal foil.
Therefore, the adhesive layer that bonds the heat seal layer and the metal foil layer is required to have resistance to a substance generated by an intruder from the outside of the electricity storage device acting on the electrolyte solution in addition to resistance to the electrolyte solution itself.
Incidentally, in recent years, with the expansion of applications such as in-vehicle and household power storage, power storage devices have been required to have a large capacity and long-term durability. Therefore, more excellent electrolyte solution resistance is required particularly for in-vehicle applications.
　特許文献１には、接着剤組成物を用いて、ラワンひき材および石渡スレート板の間に、冷圧締方式により接合し、煮沸繰り返し後もある程度接着力がある旨、記載する。しかし、特許文献１は電池用包装材を開示しないし、示唆もしない。上記のような接着強度の耐湿性と電解質溶液耐性とは全く異なる。
　特許文献２は、接着性樹脂組成物をポリエステルフィルム上もしくはポリアミドフィルム上に溶融押し出して形成した接着性樹脂組成物層と、各フィルムとの間の接着強度が、温度６０℃、相対湿度９０％の恒温槽に４８時間放置後も、ある程度維持できる旨、記載する。しかし、特許文献２は電池用包装材を開示しないし、示唆もしない。上記のような接着強度の耐湿性と電解質溶液耐性とは全く異なる。
　特許文献３は、前述の通り電池外装材を開示する。しかし、その電解質溶液耐性は、８５℃または１００℃で２４時間程度のレベルに過ぎない。
　特許文献４は電池用包装材を開示しないし、示唆もしない。そして、初期の接着強度は記載されているが、接着強度の耐久性に対する言及は一切ない。当然、電解質溶液耐性は一言も示唆されていない。
　特許文献５は、前述の通り二次電池用の積層体への適用を開示し、「耐電解質性」に言及する。しかし、その「耐電解質性」は、リチウム塩のような電解質を含まない単なる溶剤（エチレンカーボネート、プロピルカーボネート）に４０℃で３０日間浸漬するレベルに過ぎない。すなわち、引用文献４における「耐電解質性」は単なる耐溶剤性である。電解質を含む電解質溶液に対する耐性と、単なる耐溶剤性とは全く異なる。 Patent Document 1 describes that an adhesive composition is used to join between a lauan sawing material and a stone-grown slate plate by a cold-pressing method, and there is some adhesive force even after repeated boiling. However, Patent Document 1 does not disclose or suggest a battery packaging material. The moisture resistance of the adhesive strength as described above and the electrolyte solution resistance are completely different.
In Patent Document 2, the adhesive strength between an adhesive resin composition layer formed by melt-extruding an adhesive resin composition on a polyester film or a polyamide film and each film has a temperature of 60 ° C. and a relative humidity of 90%. It is stated that it can be maintained to some extent even after being left in a constant temperature bath for 48 hours. However, Patent Document 2 does not disclose or suggest a battery packaging material. The moisture resistance of the adhesive strength as described above and the electrolyte solution resistance are completely different.
Patent Document 3 discloses a battery exterior material as described above. However, the electrolyte solution resistance is only about 24 hours at 85 ° C. or 100 ° C.
Patent Document 4 does not disclose or suggest a battery packaging material. Although the initial adhesive strength is described, there is no mention of the durability of the adhesive strength. Needless to say, no electrolyte solution resistance is suggested.
Patent document 5 discloses the application to the laminated body for secondary batteries as mentioned above, and mentions "electrolyte resistance". However, the “electrolyte resistance” is merely a level of immersion in a solvent (ethylene carbonate, propyl carbonate) not containing an electrolyte such as a lithium salt at 40 ° C. for 30 days. That is, “electrolyte resistance” in the cited document 4 is merely solvent resistance. Resistance to an electrolyte solution containing an electrolyte is completely different from mere solvent resistance.
　本発明は、上記背景を鑑みてなされたものであり、４０℃、３日間程度のエージング時間の場合に、８５℃の電解質溶液に２週間浸漬されても接着強度を高レベルで維持できる積層体を形成できる接着剤組成物を提供することを課題とする。また、本発明は、従来よりも電解質溶液耐性に優れる蓄電デバイス用包装材、蓄電デバイス用容器および蓄電デバイスを提供することを課題とする。 The present invention has been made in view of the above background, and in the case of an aging time of about 40 ° C. for about 3 days, a laminate capable of maintaining a high level of adhesive strength even when immersed in an electrolyte solution at 85 ° C. for 2 weeks. It is an object of the present invention to provide an adhesive composition that can form a film. Moreover, this invention makes it a subject to provide the packaging material for electrical storage devices, the container for electrical storage devices, and an electrical storage device which are more excellent in electrolyte solution tolerance than before.
　本発明者は、不飽和脂肪酸の重合体（Ｂ１）と２つ以上のエポキシ基を有する化合物（Ｂ２）との反応により得られるエポキシ化合物（Ｂ）が、ポリオレフィンとの相溶性に優れ、硬化反応を早くすることを見出し、本発明を完成した。
　即ち、本発明は、金属箔層とヒートシール層とを接着剤層を介して積層するための接着剤組成物であって、カルボキシル基もしくは酸無水物基を有するポリオレフィン樹脂（Ａ）と、不飽和脂肪酸の重合体（Ｂ１）と２つ以上のエポキシ基を有する化合物（Ｂ２）との反応により得られるエポキシ化合物（Ｂ）とを含有することを特徴とする接着剤組成物に関する。 The present inventor found that the epoxy compound (B) obtained by the reaction of the unsaturated fatty acid polymer (B1) and the compound (B2) having two or more epoxy groups is excellent in compatibility with the polyolefin and has a curing reaction. The present invention has been completed.
That is, the present invention is an adhesive composition for laminating a metal foil layer and a heat seal layer via an adhesive layer, and comprises a polyolefin resin (A) having a carboxyl group or an acid anhydride group, The present invention relates to an adhesive composition comprising a saturated fatty acid polymer (B1) and an epoxy compound (B) obtained by a reaction of a compound (B2) having two or more epoxy groups.
　前記エポキシ化合物（Ｂ）は、不飽和脂肪酸の重合体（Ｂ１）と２つ以上のエポキシ基を有する化合物（Ｂ２）との反応生成物を、さらに水添することにより得られるエポキシ化合物であることが好ましい。
　前記不飽和脂肪酸の重合体（Ｂ１）は、炭素数が１２～２４個の不飽和脂肪酸を２量化させた化合物（ダイマー酸）および３量化させた化合物（トリマー酸）の少なくとも一方であることが好ましい。
　２つ以上のエポキシ基を有する前記の化合物（Ｂ２）は、ビスフェノールＡ型エポキシ化合物およびビスフェノールＦ型エポキシ化合物から選ばれる少なくとも一方とすることが好ましい。
　前記エポキシ化合物（Ｂ）のエポキシ当量は、２００～７０００であることが好ましい。 The epoxy compound (B) is an epoxy compound obtained by further hydrogenating a reaction product of a polymer (B1) of an unsaturated fatty acid and a compound (B2) having two or more epoxy groups. Is preferred.
The polymer (B1) of the unsaturated fatty acid is at least one of a compound (dimer acid) obtained by dimerizing an unsaturated fatty acid having 12 to 24 carbon atoms and a compound (trimer acid) obtained by trimerization. preferable.
The compound (B2) having two or more epoxy groups is preferably at least one selected from a bisphenol A type epoxy compound and a bisphenol F type epoxy compound.
The epoxy equivalent of the epoxy compound (B) is preferably 200 to 7000.
　前記ポリオレフィン樹脂（Ａ）の質量平均分子量は５万～５０万であることが好ましい。
　前記ポリオレフィン樹脂（Ａ）は、１－ブテンと他のオレフィンとから得られる共重合体を、さらに酸変性することにより得たものであることが好ましい。 The polyolefin resin (A) preferably has a mass average molecular weight of 50,000 to 500,000.
The polyolefin resin (A) is preferably obtained by further acid-modifying a copolymer obtained from 1-butene and another olefin.
　本発明の接着剤組成物は、前記ポリオレフィン樹脂（Ａ）１グラム当たりのカルボキシル基の含有量をＸミリモル、酸無水物基の含有量をＹミリモルとした場合に、Ｘ＋２Ｙが０．０５～０．６であることが好ましい。
　本発明の接着剤組成物は、前記ポリオレフィン樹脂（Ａ）の含有量をＰグラム、前記エポキシ化合物（Ｂ）中のエポキシ基をＺミリモルとした場合に、Ｚ／［（Ｘ＋２Ｙ）Ｐ］が０．３～１０であることが好ましい。 In the adhesive composition of the present invention, when the content of carboxyl groups per gram of the polyolefin resin (A) is X mmol and the content of acid anhydride groups is Y mmol, X + 2Y is 0.05 to 0. .6 is preferred.
In the adhesive composition of the present invention, when the content of the polyolefin resin (A) is P grams and the epoxy group in the epoxy compound (B) is Z mmol, Z / [(X + 2Y) P] is 0. 3 to 10 is preferable.
　また、本発明は、前記の接着剤組成物から形成される接着剤層を介して、金属箔層とヒートシール層とが積層されてなる積層体に関する。 Also, the present invention relates to a laminate in which a metal foil layer and a heat seal layer are laminated via an adhesive layer formed from the above adhesive composition.
　さらに、本発明は、外層から順に、樹脂フィルム層、金属箔層、接着剤層、ヒートシール層を必須とする蓄電デバイス用包装材において、前記接着剤層が前記の接着剤組成物から形成されることを特徴とする蓄電デバイス用包装材に関する。 Furthermore, the present invention is an electricity storage device packaging material in which a resin film layer, a metal foil layer, an adhesive layer, and a heat seal layer are essential from the outer layer, and the adhesive layer is formed from the adhesive composition. The present invention relates to a packaging material for an electricity storage device.
　また、本発明は、前記の蓄電デバイス用包装材から形成されてなる蓄電デバイス用容器であって、ヒートシール層が内面を構成している、蓄電デバイス用容器に関する。
　さらに、本発明は、前記の蓄電デバイス用容器を使用してなる蓄電デバイスに関する。 The present invention also relates to a container for an electricity storage device formed from the packaging material for an electricity storage device, wherein a heat seal layer constitutes the inner surface.
Furthermore, this invention relates to the electrical storage device formed using the said container for electrical storage devices.
　本発明の接着剤組成物により、４０℃、３日間程度のエージングの場合に、８５℃の電解質溶液に２週間浸漬されても接着強度を高レベルで維持できる積層体を形成できる。 With the adhesive composition of the present invention, in the case of aging at 40 ° C. for about 3 days, it is possible to form a laminate capable of maintaining the adhesive strength at a high level even when immersed in an electrolyte solution at 85 ° C. for 2 weeks.
本発明の蓄電デバイス用包装材の一態様の模式的断面図である。It is typical sectional drawing of the one aspect | mode of the packaging material for electrical storage devices of this invention. 本発明の蓄電デバイス用容器の一態様（トレイ状）の模式的斜視図である。It is a typical perspective view of one mode (tray form) of the container for electrical storage devices of the present invention.
　以下、本発明の実施の形態を、詳細に説明する。なお、本明細書において「任意の数Ａ～任意の数Ｂ」なる記載は、数Ａおよび数Ａより大きい範囲であって、数Ｂおよび数Ｂより小さい範囲を意味する。
　本発明の蓄電デバイス用包装材は、図１に示すように、少なくとも樹脂フィルム層（１１）、金属箔層（１２）、接着剤層（１３）およびヒートシール層（１４）が順次積層されてなる。接着剤層（１３）は、金属箔層（１２）とヒートシール層（１４）とを貼りあわせる役割を担う。 Hereinafter, embodiments of the present invention will be described in detail. In the present specification, the description “any number A to any number B” means a range larger than the numbers A and A but smaller than the numbers B and B.
As shown in FIG. 1, the packaging material for an electricity storage device of the present invention includes at least a resin film layer (11), a metal foil layer (12), an adhesive layer (13), and a heat seal layer (14) that are sequentially laminated. Become. The adhesive layer (13) plays a role of bonding the metal foil layer (12) and the heat seal layer (14) together.
　本発明の蓄電デバイス用容器は、本発明の蓄電デバイス用包装材を用いて形成されたものであり、その形態は特に制限されない。好適な例として、図２に示すようなトレイ状の態様が挙げられる。この例において、トレイの内部、即ち、電極や電解質溶液等を収容するための空間を形成する凹面側にヒートシール層（１４）が配置され、トレイの外側、即ち、凸面側に外層側の樹脂フィルム層（１１）が配置される。トレイ状の他、筒状（円筒、四角筒、楕円筒等）の態様が例示できる。これらの蓄電デバイス用容器は、通常、平たい状態の蓄電デバイス用包装材を成型加工して得られる。蓄電デバイス用容器の内側、即ち電解質溶液等と接する面は、ヒートシール層（１４）である。フランジ部のヒートシール層（１４）と、別の蓄電デバイス用包装材を構成するヒートシール層（１４）または別の蓄電デバイス用容器のフランジ部のヒートシール層（１４）とを対向・接触させ、加熱することにより、ヒートシール層（１４）同士を融着させ、電解質溶液および電極等の蓄電デバイス部材を封入する。
　本発明の蓄電デバイス用の容器には、トレイ状の他、袋状用の容器（パウチタイプ）もある。 The container for an electricity storage device of the present invention is formed using the packaging material for an electricity storage device of the present invention, and the form thereof is not particularly limited. As a suitable example, a tray-like embodiment as shown in FIG. In this example, the heat seal layer (14) is arranged inside the tray, that is, on the concave side forming a space for accommodating the electrode, the electrolyte solution, etc., and the resin on the outer layer side outside the tray, that is, on the convex side. A film layer (11) is arranged. In addition to the tray shape, cylindrical (cylindrical, square, elliptical, etc.) modes can be exemplified. These electric storage device containers are usually obtained by molding a flat storage device for an electric storage device. The inside of the electricity storage device container, that is, the surface in contact with the electrolyte solution or the like is a heat seal layer (14). The heat seal layer (14) of the flange portion and the heat seal layer (14) constituting another packaging material for the electricity storage device or the heat seal layer (14) of the flange portion of the container for another electricity storage device are opposed to and in contact with each other. By heating, the heat seal layers (14) are fused together to enclose an electricity storage device member such as an electrolyte solution and electrodes.
The container for an electricity storage device of the present invention includes a bag-like container (pouch type) in addition to a tray shape.
　本発明の接着剤組成物は、接着剤層（１３）の形成に好適に用いられる。
　本発明の接着剤組成物は、カルボキシル基もしくは酸無水物基を有するポリオレフィン樹脂（Ａ）と、不飽和脂肪酸の重合体により変性されたエポキシ化合物（Ｂ）とを含有する。カルボキシル基もしくは酸無水物基を有するポリオレフィン樹脂（Ａ）を単にポリオレフィン樹脂（Ａ）と略し、不飽和脂肪酸の重合体（Ｂ１）と２つ以上のエポキシ基を有する化合物（Ｂ２）との反応により得られるエポキシ化合物（Ｂ）を単にエポキシ化合物（Ｂ）と略すこともある。
　硬化前の乾燥した層の形態を成す本発明の接着剤組成物を、金属箔層（１２）とヒートシール層（１４）との間に挟んだ状態で、ポリオレフィン樹脂（Ａ）中のカルボキシル基もしくは酸無水物基と、エポキシ化合物（Ｂ）中のエポキシ基とを反応させる。その結果、強固な架橋構造を形成し、充分な接着強度を発現でき、より高温の電解質溶液に長期間浸漬されても、その接着強度を高レベルで維持できる。 The adhesive composition of this invention is used suitably for formation of an adhesive bond layer (13).
The adhesive composition of the present invention contains a polyolefin resin (A) having a carboxyl group or an acid anhydride group and an epoxy compound (B) modified with a polymer of an unsaturated fatty acid. A polyolefin resin (A) having a carboxyl group or an acid anhydride group is simply abbreviated as a polyolefin resin (A), and is reacted with a polymer (B1) of an unsaturated fatty acid and a compound (B2) having two or more epoxy groups. The resulting epoxy compound (B) may simply be abbreviated as epoxy compound (B).
The carboxyl group in the polyolefin resin (A) in a state where the adhesive composition of the present invention in the form of a dried layer before curing is sandwiched between the metal foil layer (12) and the heat seal layer (14). Alternatively, the acid anhydride group is reacted with the epoxy group in the epoxy compound (B). As a result, a strong cross-linked structure is formed, sufficient adhesive strength can be exhibited, and the adhesive strength can be maintained at a high level even when immersed in a higher temperature electrolyte solution for a long period of time.
＜カルボキシル基もしくは酸無水物基を有するポリオレフィン樹脂（Ａ）＞
　ポリオレフィン樹脂（Ａ）は、非結晶性部位を有することが好ましい。その理由は、接着剤組成物に使用する溶剤に対する溶解性に優れ、また、その溶解した溶液が沈殿せず安定に保管できる保存安定性に優れるためである。一方、積層体における接着剤層としての電解質溶液耐性を向上するためには、結晶性部位も有すことが好ましい。即ち、非結晶性部位と結晶性部位のバランスが重要となる。本発明で使用するポリオレフィン樹脂（Ａ）は、質量平均分子量が５万～５０万、融点が６０～１１０℃であり、融解エネルギー（ΔＥ）が１５～５０（ｍＪ/ｍｇ）であることが好ましい。 <Polyolefin resin (A) having carboxyl group or acid anhydride group>
The polyolefin resin (A) preferably has an amorphous part. The reason is that it is excellent in the solubility with respect to the solvent used for the adhesive composition, and is excellent in storage stability in which the dissolved solution can be stably stored without precipitation. On the other hand, in order to improve the electrolyte solution resistance as an adhesive layer in the laminate, it is preferable to have a crystalline part. That is, the balance between the non-crystalline part and the crystalline part is important. The polyolefin resin (A) used in the present invention preferably has a mass average molecular weight of 50,000 to 500,000, a melting point of 60 to 110 ° C., and a melting energy (ΔE) of 15 to 50 (mJ / mg). .
　ポリオレフィン樹脂（Ａ）は、質量平均分子量（Ｍｗ）が５万～５０万であることによって、接着剤組成物を構成するポリオレフィン樹脂（Ａ）の溶液としての保存安定性と、蓄電デバイス用包装材としての電解質溶液耐性、ヒートシール性、塗工性を両立しやすくなる。より好ましくは、ポリオレフィン樹脂（Ａ）のＭｗは１０万～４０万である。
　言い換えると、ポリオレフィン樹脂（Ａ）のＭｗが５万未満であると、ポリオレフィン樹脂（Ａ）のポリマー鎖の絡み合いが不足するため、接着剤層の膜強度が低くなり電解質溶液耐性が不足する恐れがある。また、Ｍｗが５０万より大きいとポリオレフィン樹脂（Ａ）溶液としての２５℃での保存安定性が低下したり、接着剤溶液の粘度が高すぎて塗工性が悪化したりする恐れがある。 Since the polyolefin resin (A) has a mass average molecular weight (Mw) of 50,000 to 500,000, the storage stability of the polyolefin resin (A) constituting the adhesive composition as a solution, and a packaging material for an electricity storage device As a result, it is easy to achieve both electrolyte solution resistance, heat sealability, and coating properties. More preferably, the Mw of the polyolefin resin (A) is 100,000 to 400,000.
In other words, if the Mw of the polyolefin resin (A) is less than 50,000, the entanglement of the polymer chain of the polyolefin resin (A) is insufficient, so that the film strength of the adhesive layer is lowered and the electrolyte solution resistance may be insufficient. is there. On the other hand, if Mw is larger than 500,000, the storage stability at 25 ° C. as the polyolefin resin (A) solution may be lowered, or the viscosity of the adhesive solution may be too high to deteriorate the coatability.
　ポリオレフィン樹脂（Ａ）は、融点が６０～１１０℃、融解エネルギー（ΔＥ）が１５～５０（ｍＪ/ｍｇ）であることによって、蓄電デバイス用包装材としての接着強度（初期、電解質溶液浸漬後）やヒートシール性をバランスよく満足することができる。
　言い換えると、ポリオレフィン樹脂（Ａ）の融点が６０℃未満であると、電解質溶液浸漬後の接着強度やヒートシール性が低下する恐れがある。融点が１１０℃より大きくなると接着強度（初期、電解質溶液浸漬後）が低下する恐れがある。より好ましくはポリオレフィン樹脂（Ａ）の融点は６０～９０℃である。
　また、ポリオレフィン樹脂（Ａ）の融解エネルギー（ΔＥ）が１５ｍＪ/ｍｇ未満であると電解質溶液浸漬後の接着強度やヒートシール性が低下し、５０ｍＪ/ｍｇより大きくなると結晶性が高く、ポリオレフィン樹脂（Ａ）溶液としての保存安定性が低下する場合がある。より好ましくは、ポリオレフィン樹脂（Ａ）の融解エネルギー（ΔＥ）は、２０～５０ｍＪ/ｍｇであり、さらに好ましくは２０～４０ｍＪ/ｍｇである。 The polyolefin resin (A) has a melting point of 60 to 110 ° C. and a melting energy (ΔE) of 15 to 50 (mJ / mg), so that the adhesive strength as an energy storage device packaging material (initially, after immersion in an electrolyte solution) And heat sealability can be satisfied in a well-balanced manner.
In other words, when the melting point of the polyolefin resin (A) is less than 60 ° C., the adhesive strength and the heat sealability after immersion in the electrolyte solution may be lowered. If the melting point is higher than 110 ° C., the adhesive strength (initially, after immersion in the electrolyte solution) may be reduced. More preferably, the melting point of the polyolefin resin (A) is 60 to 90 ° C.
Further, when the melting energy (ΔE) of the polyolefin resin (A) is less than 15 mJ / mg, the adhesive strength and heat sealability after immersion in the electrolyte solution are lowered, and when it exceeds 50 mJ / mg, the crystallinity is high. A) Storage stability as a solution may decrease. More preferably, the melting energy (ΔE) of the polyolefin resin (A) is 20 to 50 mJ / mg, more preferably 20 to 40 mJ / mg.
　ここで、ヒートシール性について説明する。
　蓄電デバイス用包装材には、上述した［発明が解決しようとする課題］の項の冒頭で述べた２つの性能（接着強度が大きいこと、電解質溶液耐性に優れること）の他に、さらにヒートシール性に優れることも求められる。
　蓄電デバイス用包装材を構成するヒートシール層（１４）は、前述の通り、熱により、ヒートシール層（１４）同士を融着させ、蓄電デバイス用容器内に電解質溶液や電極等の蓄電デバイス部材を封入する機能を担う。大きなヒートシール強度（ヒートシール層（１４）同士の剥離強度）を確保するという観点からは、高温・高圧でのヒートシールが好ましいと考えられる。
　しかし、ヒートシール時の熱と圧力により、ヒートシール層（１４）と金属箔層（１２）とを貼り合わせていた接着剤層（１３）が溶融したり変形したりすると、電極端子と金属箔層（１２）とが導通してしまうおそれがある。導通してしまうと、蓄電デバイスとして機能しない。そこで、電極端子と金属箔層（１２）との絶縁性がヒートシールによって損なわれないよう、ヒートシール時の熱と圧力により、接着剤層（１３）が溶融したり変形したりしないことが求められる。
　融点および融解エネルギー（ΔＥ）が上記範囲内のポリオレフィン樹脂（Ａ）を用いることにより、ヒートシール時の接着剤層（１３）の溶融や変形を効果的に抑制・防止できる。 Here, the heat sealability will be described.
In addition to the two performances (high adhesive strength and excellent resistance to electrolyte solution) described at the beginning of the above-mentioned section [Problems to be Solved by the Invention], the packaging material for power storage devices is further heat-sealed. It is also required to have excellent properties.
As described above, the heat seal layer (14) constituting the packaging material for the electricity storage device is fused with the heat seal layer (14) by heat, and an electricity storage device member such as an electrolyte solution or an electrode in the electricity storage device container. Responsible for the function of sealing. From the viewpoint of securing a large heat seal strength (peel strength between heat seal layers (14)), it is considered that heat seal at high temperature and high pressure is preferable.
However, when the adhesive layer (13) that has bonded the heat seal layer (14) and the metal foil layer (12) melts or deforms due to heat and pressure during heat sealing, the electrode terminal and the metal foil There is a possibility that the layer (12) is electrically connected. When conducting, it does not function as an electricity storage device. Therefore, it is required that the adhesive layer (13) is not melted or deformed by heat and pressure during heat sealing so that the insulation between the electrode terminal and the metal foil layer (12) is not impaired by heat sealing. It is done.
By using the polyolefin resin (A) whose melting point and melting energy (ΔE) are within the above ranges, melting and deformation of the adhesive layer (13) during heat sealing can be effectively suppressed / prevented.
　なお、本発明において「保存安定性がある」とは、トルエン：９０ｇに樹脂：１０ｇを加え、樹脂を加熱溶解し、透明な溶液を得た後、２５℃に冷却し、同温で一週間静置して沈殿を生じないものを言う。 In the present invention, “storage stability” means that 10 g of resin is added to 90 g of toluene, the resin is heated and dissolved to obtain a transparent solution, and then cooled to 25 ° C. for one week at the same temperature. A thing that does not cause precipitation upon standing.
　本発明におけるポリオレフィン樹脂（Ａ）は、カルボキシル基または酸無水物基を有していればよく、例えば、カルボキシル基または酸無水物基を有していないポリオレフィン樹脂（Ａ－１）にエチレン性不飽和カルボキシル基またはその酸無水物をグラフト重合させた変性ポリオレフィン樹脂や、オレフィンモノマーとエチレン性不飽和カルボン酸またはその酸無水物との共重合体等が挙げられる。また、酸無水物基を有するポリオレフィンの酸無水物基と、水やアルコールと反応させることによりカルボキシル基を有するポリオレフィンを得ることもできる。カルボキシル基または酸無水物基を有していないポリオレフィン樹脂（Ａ－１）にエチレン性不飽和カルボキシル基またはその酸無水物をグラフト重合させた変性ポリオレフィン樹脂が好ましい。ポリオレフィン樹脂（Ａ）は単独で使用してもよいし、２種以上を任意に組み合わせて使用してもよい。
　ポリオレフィン樹脂（Ａ）中のカルボキシル基または酸無水物基の量については、後述する。 The polyolefin resin (A) in the present invention only needs to have a carboxyl group or an acid anhydride group. For example, the polyolefin resin (A-1) having no carboxyl group or acid anhydride group has no ethylenic group. Examples thereof include a modified polyolefin resin obtained by graft polymerization of a saturated carboxyl group or its acid anhydride, and a copolymer of an olefin monomer and an ethylenically unsaturated carboxylic acid or its acid anhydride. Moreover, the polyolefin which has a carboxyl group can also be obtained by making it react with the acid anhydride group of polyolefin which has an acid anhydride group, and water or alcohol. A modified polyolefin resin obtained by graft-polymerizing an ethylenically unsaturated carboxyl group or an acid anhydride thereof to a polyolefin resin (A-1) having no carboxyl group or acid anhydride group is preferable. The polyolefin resin (A) may be used alone or in combination of two or more kinds.
The amount of the carboxyl group or acid anhydride group in the polyolefin resin (A) will be described later.
　ポリオレフィンのグラフト重合方法は、特に限定されないが、例えば特開平１１－２９３２１６に開示されている方法を用いることができる。
　ポリオレフィン樹脂（Ａ）としては、特に限定されるものではないが、例えば、エチレン、プロピレン、１－ブテン、ブタジエン、イソプレン、１－ヘキセン、１－オクテン等のオレフィンモノマーの単独重合体、オレフィンモノマー同士の共重合体、もしくはその他のモノマーとの共重合体、および得られた重合体の水素化物やハロゲン化物など、炭化水素骨格を主体とする重合体を指す。ポリオレフィン樹脂（Ａ）は、オレフィンモノマー同士の共重合体が好ましい。 The method for graft polymerization of polyolefin is not particularly limited. For example, the method disclosed in JP-A-11-293216 can be used.
The polyolefin resin (A) is not particularly limited. For example, a homopolymer of olefin monomers such as ethylene, propylene, 1-butene, butadiene, isoprene, 1-hexene and 1-octene, Or a copolymer with other monomers, and a polymer mainly composed of a hydrocarbon skeleton, such as a hydride or a halide of the obtained polymer. The polyolefin resin (A) is preferably a copolymer of olefin monomers.
　オレフィンモノマー同士の共重合体としては、１－ブテンと他のオレフィンモノマーとの共重合体が好ましい。他のオレフィンとしては、エチレン、プロピレンが好ましく、１－ブテンと他のオレフィンモノマーとの共重合体としては、エチレンと１－ブテンとの二元共重合体、プロピレンと１－ブテンとの二元共重合体、エチレンとプロピレンと１－ブテンとの三元共重合体が挙げられ、プロピレンと１－ブテンとの二元共重合体がより好ましい。共重合比は、モル比においてプロピレン：１－ブテン＝１０：９０～８０：２０であることが好ましく、４０：６０～８０：２０であることがより好ましい。プロピレンと１－ブテンの共重合体において、プロピレンが１０モル％未満の場合は融点が６０℃より低い場合があり、８０モル％より多い場合は融点が１１０℃より高くなる場合がある。 The copolymer of olefin monomers is preferably a copolymer of 1-butene and other olefin monomers. Other olefins are preferably ethylene and propylene, and copolymers of 1-butene and other olefin monomers are binary copolymers of ethylene and 1-butene, and binary of propylene and 1-butene. Examples of the copolymer include a terpolymer of ethylene, propylene and 1-butene, and a binary copolymer of propylene and 1-butene is more preferable. The copolymerization ratio in terms of molar ratio is preferably propylene: 1-butene = 10: 90 to 80:20, and more preferably 40:60 to 80:20. In the copolymer of propylene and 1-butene, the melting point may be lower than 60 ° C. when propylene is less than 10 mol%, and the melting point may be higher than 110 ° C. when it is higher than 80 mol%.
　オレフィンモノマーに共重合してもよいその他のモノマーとしては、特に限定されず、例えば、
　スチレン、α－メチルスチレン、インデン等の芳香族ビニル化合物；
　メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレート等のアルキル（メタ）アクリレート化合物；
　シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等の脂環構造を有する（メタ）アクリレート化合物；
　ベンジル（メタ）アクリレート等の芳香環を有する（メタ）アクリレート化合物；
　２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等の水酸基含有（メタ）アクリレート化合物；
　ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ｔ－ブチルアミノエチル（メタ）アクリレート等のアミノ基を有する（メタ）アクリレート化合物；
　（メタ）アクリルアミド、ジメチル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、イソプロピル（メタ）アクリルアミド、ジエチル（メタ）アクリルアミド、ヒドロキシエチル（メタ）アクリルアミド等のアクリルアミド類；
　（メタ）アクリロニトリル、アクリロイルモルホリン等が挙げられる。
　グラフト重合性の点およびポリオレフィンとの相溶性の点から、スチレン、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレートが好ましい。
　前記エチレン性不飽和カルボン酸としては、特に限定されるものではないが、例えば、アクリル酸、メタクリル酸、マレイン酸、フマル酸、クロトン酸、イタコン酸等が挙げられる。これらエチレン性不飽和カルボン酸またはその酸無水物は、１種のみを用いてもよいし、２種以上を併用してもよい。 Other monomers that may be copolymerized with the olefin monomer are not particularly limited, for example,
Aromatic vinyl compounds such as styrene, α-methylstyrene and indene;
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, Alkyl (meth) acrylate compounds such as behenyl (meth) acrylate;
(Meth) acrylate compounds having an alicyclic structure such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate;
(Meth) acrylate compounds having an aromatic ring such as benzyl (meth) acrylate;
Hydroxyl group-containing (meth) acrylate compounds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;
(Meth) acrylate compounds having an amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate;
Acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, isopropyl (meth) acrylamide, diethyl (meth) acrylamide, hydroxyethyl (meth) acrylamide;
(Meth) acrylonitrile, acryloylmorpholine, etc. are mentioned.
Styrene, dodecyl (meth) acrylate, and stearyl (meth) acrylate are preferable from the viewpoint of graft polymerization and compatibility with polyolefin.
The ethylenically unsaturated carboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, and itaconic acid. These ethylenically unsaturated carboxylic acids or acid anhydrides thereof may be used alone or in combination of two or more.
　オレフィンモノマーの重合方法は、特に限定されないが、例えば、特公平０７－０８０９４８号に開示されているように、チーグラー・ナッタ触媒やメタロセン触媒などの金属触媒を添加して重合できる。また、必要に応じて（メチル）アルミノキサン等の助触媒を添加して重合できる。 The polymerization method of the olefin monomer is not particularly limited. For example, as disclosed in JP-B-07-080948, the polymerization can be performed by adding a metal catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Moreover, it can superpose | polymerize by adding promoters, such as (methyl) aluminoxane, as needed.
　なお、ポリオレフィン樹脂（Ａ）のＭｗは、以下のようにして求める。
　ＴＳＫｇｅｌ　ｓｕｐｅｒＨＺＭ－Ｎのカラムを２本接続した東ソー社製ＨＬＣ－８２２０ＧＰＣシステムにより、カラム温度４０℃、溶離液にテトラヒドロフラン、流量毎分０．３５ｍＬの条件にて測定した。サンプルは、２ｍｇのポリオレフィン樹脂（Ａ）を、５ｍＬのテトラヒドロフランに溶解して調製した。また、Ｍｗは標準ポリスチレン換算で算出した。
　ポリオレフィン樹脂（Ａ）を２種以上併用した場合は、その混合物全体の質量平均分子量を意味する。 In addition, Mw of polyolefin resin (A) is calculated | required as follows.
Measurement was performed with a column temperature of 40 ° C., tetrahydrofuran as an eluent, and a flow rate of 0.35 mL per minute using a Tosoh HLC-8220GPC system in which two TSKgel superHZM-N columns were connected. A sample was prepared by dissolving 2 mg of polyolefin resin (A) in 5 mL of tetrahydrofuran. Mw was calculated in terms of standard polystyrene.
When two or more types of polyolefin resins (A) are used in combination, it means the mass average molecular weight of the entire mixture.
　また融点、融解エネルギー（ΔＥ）は、ＪＩＳ　Ｋ７１２１に準じてＤＳＣ測定により求めることができる。具体的には以下のようにして求める。
　約１０ｍｇのポリオレフィン樹脂（Ａ）の直径または各辺が０．５ｍｍ以下の場合はそのまま使用し、０．５ｍｍを超えるものは０．５ｍｍ以下に切断して容器に入れる。
　融点は、オレフィン組成から予測される融点の暫定値（以下、暫定融点という）または測定条件を振って、暫定融点を求める。次いで、毎分１０℃で暫定融点より約３０℃高い温度まで加熱し、その後毎分１０℃でＴｇより約５０℃低い温度まで冷却する。明確なＴｇが観測されない場合は、暫定融点より約５０℃低い温度まで冷却する。その後、毎分１０℃で暫定融点より約３０℃高い温度まで加熱した際に表れる融解に対応するピークのピークトップを融点とした。また、ΔＥは、融解に対応するピークが、ベースラインから離れてから再度ベースラインに戻るまでの部分の面積より求める。
　ポリオレフィン樹脂（Ａ）を２種以上併用する場合は、融点は高温側のピークのピークトップより求め、ΔＥは融解により得られる全てのピーク面積の合計から算出する。 The melting point and melting energy (ΔE) can be determined by DSC measurement according to JIS K7121. Specifically, it is obtained as follows.
When the diameter or each side of the polyolefin resin (A) of about 10 mg is 0.5 mm or less, it is used as it is, and if it exceeds 0.5 mm, it is cut into 0.5 mm or less and put into a container.
The melting point is determined by changing a provisional value of melting point predicted from the olefin composition (hereinafter referred to as provisional melting point) or measurement conditions. It is then heated at 10 ° C. per minute to a temperature about 30 ° C. above the provisional melting point and then cooled to 10 ° C. per minute to a temperature about 50 ° C. below Tg. If no clear Tg is observed, cool to about 50 ° C. below the provisional melting point. Then, the peak top of the peak corresponding to the melting that appears when heated to about 30 ° C. higher than the temporary melting point at 10 ° C. per minute was taken as the melting point. Further, ΔE is obtained from the area of the portion from when the peak corresponding to melting is separated from the baseline until it returns to the baseline again.
When two or more polyolefin resins (A) are used in combination, the melting point is determined from the peak top of the peak on the high temperature side, and ΔE is calculated from the sum of all peak areas obtained by melting.
　ポリオレフィン樹脂（Ａ）としては、市販品を用いることもでき、例えば、スミフィットＣＫ１Ｄ（商品名、住友化学社製）、ユニストールＰ－４０１、Ｐ－８０２、Ｐ－９０２（商品名）、ユーメックス１００１、１０１０、２０００（商品名、三洋化成社製）、アウローレン３５０Ｓ、３５１Ｓ、３５９Ｓ、Ｓ－５２４７Ｓ、Ｓ－５２４８Ｓ、Ｓ－５２９７Ｓ、Ｓ－５３４９Ｓ、Ｓ－５３５０Ｓなどが挙げられる。 Commercially available products can also be used as the polyolefin resin (A). For example, Sumifit CK1D (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Unistor P-401, P-802, P-902 (trade name), Umex 1001, 1010, 2000 (trade name, manufactured by Sanyo Chemical Co., Ltd.), Auroren 350S, 351S, 359S, S-5247S, S-5248S, S-5297S, S-5349S, S-5350S, and the like.
　本発明では、発明の効果を損なわない範囲で、カルボキシル基または酸無水物基を有するポリオレフィン樹脂（Ａ）の他に、カルボキシル基または酸無水物基を有さないポリオレフィン樹脂を併用してもよい。 In the present invention, a polyolefin resin having no carboxyl group or acid anhydride group may be used in combination with the polyolefin resin (A) having a carboxyl group or acid anhydride group, as long as the effects of the invention are not impaired. .
　本発明で使用されるカルボキシル基または酸無水物基を有さないポリオレフィン樹脂としては、例えば、住友化学社製のタフセレンＴ３７１２、Ｔ３７２２、Ｔ３５２２（プロピレン系エラストマー）、住友ノーブレン（ポリプロピレン）、三井化学社製タフマーＤＦ＆Ａ、タフマーＨ、タフマーＸＭ、タフマーＢＬ、タフマーＭ（α－オレフィン共重合体）、クラレ社製のクラプレンＬＩＲ－３０（イソプレン重合体）、ＬＩＲ－２００（水素化イソプレン重合体）、ＬＢＲ－３００（ブタジエン重合体）、クラレ社製のセプトン２００２、２００４（以上、水素化スチレン－イソプレン－スチレン共重合体）、２１０４、４０３３、ＨＧ２５２（以上、水素化スチレン－イソプレン／ブタジエン－スチレン共重合体）、旭化成ケミカルズ社製のアサプレンＴ－４３２、Ｔ－４３７、クレイトンポリマージャパン社製のクレイトンＤ１１５５（以上、スチレン－ブタジエン－スチレン共重合体）、旭化成ケミカルズ社製のタフテックＰ１５００、Ｐ２０００、ＭＰ１０（部分水素化スチレン－ブタジエン－スチレン共重合体）、Ｈ１０５２、Ｈ１０４３（以上、水素化スチレン－ブタジエン－スチレン共重合体）、日本製紙ケミカル社製のスーパークロンＣ（プロピレン重合体の塩素化物）、日本ポリエチレン社製のレクスパールＥＭＡ（エチレン－アクリル酸メチル共重合体）、レクスパールＥＥＡ（エチレン－アクリル酸エチル共重合体）、三井・デュポンポリケミカル社製エバフレックス（エチレン－酢酸ビニル共重合体）、住友化学社製ボンドファースト（エチレン－グリシジルメタクリレート共重合体）等が挙げられる。これらは単独で使用してもよいし、２種以上を任意に組み合わせて使用してもよい。 Examples of the polyolefin resin having no carboxyl group or acid anhydride group used in the present invention include Tough selenium T3712, T3722, T3522 (propylene elastomer), Sumitomo Nobrene (polypropylene), Mitsui Chemicals, manufactured by Sumitomo Chemical Co., Ltd. Tafmer DF & A, Tafmer H, Tafmer XM, Tafmer BL, Tafmer M (α-olefin copolymer), Kuraray LIR-30 (isoprene polymer), LIR-200 (hydrogenated isoprene polymer), LBR -300 (butadiene polymer), Kuraray Septon 2002, 2004 (more hydrogenated styrene-isoprene-styrene copolymer), 2104, 4033, HG252 (more hydrogenated styrene-isoprene / butadiene-styrene copolymer) Coalescence), Asahi Kasei Chemical Asaprene T-432 and T-437 manufactured by Clayton Polymer Japan, Clayton D1155 manufactured by Clayton Polymer Japan (above, styrene-butadiene-styrene copolymer), Tuftec P1500, P2000 and MP10 manufactured by Asahi Kasei Chemicals (partially hydrogenated styrene- Butadiene-Styrene Copolymer), H1052, H1043 (Hydrogenated Styrene-Butadiene-Styrene Copolymer), Nippon Paper Chemicals Super Clon C (propylene polymer chlorinated product), Nippon Polyethylene Lex Pearl EMA (ethylene-methyl acrylate copolymer), Lexpearl EEA (ethylene-ethyl acrylate copolymer), Everflex (ethylene-vinyl acetate copolymer) manufactured by Mitsui DuPont Polychemical Co., Ltd., Sumitomo Chemical Co., Ltd. Bond First (ethylene-g Lysidyl methacrylate copolymer). These may be used alone or in any combination of two or more.
　次に本発明で使用される不飽和脂肪酸の重合体（Ｂ１）と２つ以上のエポキシ基を有する化合物（Ｂ２）との反応により得られるエポキシ化合物（Ｂ）について説明する。
　エポキシ化合物（Ｂ）中のエポキシ基と、ポリオレフィン樹脂（Ａ）中のカルボキシル基または酸無水物基とを反応させた強固な架橋構造により、充分な接着強度を発現でき、より高温の電解質溶液に長期間浸漬されてもその接着強度を高レベルで維持できる。 Next, the epoxy compound (B) obtained by the reaction of the unsaturated fatty acid polymer (B1) used in the present invention with the compound (B2) having two or more epoxy groups will be described.
Due to the strong cross-linked structure obtained by reacting the epoxy group in the epoxy compound (B) with the carboxyl group or acid anhydride group in the polyolefin resin (A), sufficient adhesive strength can be expressed, and a higher temperature electrolyte solution can be obtained. Even if it is immersed for a long time, its adhesive strength can be maintained at a high level.
　本発明で使用されるエポキシ化合物（Ｂ）としては、以下に限定されるものではないが、不飽和脂肪酸の重合体（Ｂ１）中のカルボキシル基と、２つ以上のエポキシ基を有する化合物（Ｂ２）中のエポキシ基とのエステル化反応により得られる樹脂またはその水添化合物が挙げられる。
　不飽和脂肪酸の重合体（Ｂ１）で変性したエポキシ化合物（Ｂ）を用いることにより、ポリオレフィン樹脂（Ａ）との相溶性を著しく改善し、ポリオレフィン樹脂（Ａ）中のカルボキシル基または酸無水物基との反応が促進され、生産性を向上させることができる。 The epoxy compound (B) used in the present invention is not limited to the following, but is a compound (B2) having a carboxyl group and two or more epoxy groups in the polymer (B1) of unsaturated fatty acid. ) Or a hydrogenated compound thereof obtained by an esterification reaction with an epoxy group.
By using the epoxy compound (B) modified with the unsaturated fatty acid polymer (B1), the compatibility with the polyolefin resin (A) is remarkably improved, and the carboxyl group or acid anhydride group in the polyolefin resin (A) is improved. Reaction is promoted, and productivity can be improved.
　不飽和脂肪酸の重合体（Ｂ１）としては、例えば、不飽和脂肪酸の２量体、３量体や４量体以上のオリゴマーが挙げられ、２量体（ダイマー酸）、３量体(トリマー酸)が好ましく、両者の混合物であってもよい。
　不飽和脂肪酸としては、例えばオレイン酸、エライジン酸、バクセン酸、リシノレン酸、ガドレイン酸、エイコセン酸、エルカ酸、ネルボン酸などの１つの不飽和基を有する脂肪酸；
　リノール酸、イコサジエン酸、ドコサジエン酸などの２つの不飽和基を有する脂肪酸；
　イコサトリエン酸、エレオステアリン酸、ジホモ－γ－リノレン酸、ピノレン酸、ミード酸、リノレン酸などの３つの不飽和基を有する脂肪酸；
　ステアリドン酸、アダキドン酸、エイコサテトラエン酸、アドレン酸などの４つの不飽和基を有する脂肪酸が挙げられる。
　これら重合脂肪酸の市販品としては、例えば、クローダジャパン社製の「プリポール１００４」、「プリポール１００６」、「プリポール１００９」、「プリポール１０１３」、「プリポール１０１５」、「プリポール１０１７」、「プリポール１０２２」、「プリポール１０２５」、「プリポール１０４０」や、ＢＡＳＦジャパン社製の「エンポール１００８」、「エンポール１０１２」、「エンポール１０１６」、「エンポール１０２６」、「エンポール１０２８」、「エンポール１０４３」、「エンポール１０６１」、「エンポール１０６２」等が挙げられる。
　中でも、ポリオレフィン樹脂（Ａ）との相溶性がよく、工業的に得られやすい炭素数が１２～２４個の不飽和脂肪酸が好ましい。 Examples of the unsaturated fatty acid polymer (B1) include unsaturated fatty acid dimers, trimers and oligomers of tetramers or more. Dimers (dimer acid), trimers (trimer acid) ) Is preferable, and a mixture of the two may be used.
Examples of unsaturated fatty acids include fatty acids having one unsaturated group such as oleic acid, elaidic acid, vaccenic acid, ricinolenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid;
Fatty acids having two unsaturated groups such as linoleic acid, icosadienoic acid, docosadienoic acid;
Fatty acids having three unsaturated groups such as icosatrienoic acid, eleostearic acid, dihomo-γ-linolenic acid, pinolenic acid, mead acid, linolenic acid;
Examples include fatty acids having four unsaturated groups such as stearidonic acid, adachidonic acid, eicosatetraenoic acid, and adrenic acid.
Examples of commercially available products of these polymerized fatty acids include “Pripol 1004”, “Plipol 1006”, “Plipol 1009”, “Plipol 1013”, “Plipol 1015”, “Plipol 1017”, and “Plipol 1022” manufactured by Croda Japan. , "Prepole 1025", "Prepole 1040", "Empole 1008", "Empole 1012", "Empole 1016", "Empole 1026", "Empole 1028", "Empole 1043", "Empole 1061" manufactured by BASF Japan And “Empole 1062”.
Of these, unsaturated fatty acids having 12 to 24 carbon atoms, which have good compatibility with the polyolefin resin (A) and are easily obtained industrially, are preferable.
　２つ以上のエポキシ基を有する化合物（Ｂ２）は、１分子中に２つ以上のエポキシ基を有する化合物であればよく、例えば、市販品としては、例えば、三菱化学社製の商品名「エピコート８２８」、「エピコート８３４」、「エピコート１００１」、「エピコート１００４」、大日本インキ化学工業社製の商品名「エピクロン８４０」、「エピクロン８５０」、「エピクロン１０５０」、「エピクロン２０５５」、新日鉄住金化学社製の商品名「エポトート１２８」等のビスフェノールＡ型エポキシ化合物；
　大日本インキ化学工業社製の商品名「エピクロン８３０Ｓ」、三菱化学社製の商品名「エピコート８０７」、新日鉄住金化学社製の商品名エポトートＹＤＦ－１７０」、「エポトートＹＤＦ－１７５」、「エポトートＹＤＦ－２００４」等のビスフェノールＦ型エポキシ化合物；
　日本化薬製の商品名「ＥＢＰＳ－２００」、旭電化工業社製の商品名「ＥＰＸ－３０」、大日本インキ化学工業社製の商品名「エピクロンＥＸＡ１５１４」等のビスフェノールＳ型エポキシ化合物；
　大阪ガス社製の商品名「ＢＰＦＧ」等のビスフェノールフルオレン型エポキシ化合物、三菱化学社製の商品名「ＹＬ－６０５６」、「ＹＬ－６０２１」、「ＹＸ－４０００」、「ＹＸ－４０００Ｈ」等のビキシレノール型、或いはビフェニル型エポキシ化合物、又はそれらの混合物；
　新日鉄住金化学社製の商品名「エポトートＳＴ－２００４」、「ＳＴ－２００７」、「ＳＴ－３０００」等の水添ビスフェノールＡ型エポキシ化合物；
　三菱化学社製の商品名「エピコート１５２」、「エピコート１５４」、ダウケミカル社製の商品名「Ｄ．Ｅ．Ｎ．４３１」、「Ｄ．Ｅ．Ｎ．４３８」、大日本インキ化学工業社製の商品名「エピクロンＮ－６９０」、「エピクロンＮ－６９５」、「エピクロンＮ－７３０」、「エピクロンＮ－７７０」、「エピクロンＮ－８６５」、新日鉄住金化学社製の商品名「エポトートＹＤＣＮ－７０１」、「エポトートＹＤＣＮ－７０４」、日本化薬社製の商品名「ＥＰＰＮ－２０１」、「ＥＯＣＮ－１０２５」、「ＥＯＣＮ－１０２０」、「ＥＯＣＮ－１０４Ｓ」、「ＲＥ－３０６」等のノボラック型エポキシ化合物；
　三菱化学社製の商品名「エピコートＹＬ－９０３」、大日本インキ化学工業社製の商品名「エピクロン１５２」、「エピクロン１６５」、新日鉄住金化学社製の商品名「エポトートＹＤＢ－４００」、「エポトートＹＤＢ－５００」等の臭素化ビスフェノールＡ型エポキシ化合物；
　新日鉄化学社製の商品名「ＥＳＮ－１９０」、「ＥＳＮ－３６０」、大日本インキ化学工業社製の商品名「ＨＰ－４０３２」、「ＥＸＡ－４７００」、「ＥＸＡ－４７５０」等のナフタレン骨格を有するエポキシ化合物；
　大日本インキ化学工業社製の商品名「ＨＰ－７２００」、「ＨＰ－７２００Ｈ」等のジシクロペンタジエン骨格を有するエポキシ化合物；
　三菱化学社製の商品名「ＹＬ－９３３」、日本化薬社製の商品名「ＥＰＰＮ－５０１」「ＥＰＰＮ－５０２」等のトリスヒドロキシフェニルメタン型エポキシ化合物；
　日産化学社製の商品名「ＴＥＰＩＣ」、三菱ガス化学社製の商品名「ＴＧＩ」等の複素環式エポキシ化合物；
　三菱化学社製の商品名「ｊＥＲ６０４」、「ｊＥＲ６３０」、新日鉄住金化学社製の商品名「エポトートＹＨ－４３４」、旭化成工業社製の商品名「アラルダイトＭＹ７２０」、等のグリシジルアミン型エポキシ化合物；
　ダイセル化学工業社製の商品名「セロキサイド２０１１」、旭化成工業社製の商品名「アラルダイトＣＹ１７５」、「アラルダイトＣＹ１７９」、新日本理化社製の商品名「ＨＢＥ－１００」等の脂環式エポキシ化合物等が挙げられるが、これらに限定されるものではない。これらエポキシ化合物は単独又は２種以上を組み合わせて使用することができる。
　中でも接着力の点から、ビスフェノールＡ型エポキシ化合物またはビスフェノールＦ型エポキシ化合物であることが好ましい。 The compound (B2) having two or more epoxy groups may be a compound having two or more epoxy groups in one molecule. For example, as a commercial product, for example, trade name “Epicoat” manufactured by Mitsubishi Chemical Corporation 828 ”,“ Epicoat 834 ”,“ Epicoat 1001 ”,“ Epicoat 1004 ”, trade names“ Epicron 840 ”,“ Epicron 850 ”,“ Epicron 1050 ”,“ Epicron 2055 ”manufactured by Dainippon Ink and Chemicals, NS Bisphenol A type epoxy compounds such as “Epototo 128” manufactured by Kagaku Co .;
Product name “Epicron 830S” manufactured by Dainippon Ink & Chemicals, Inc. Product name “Epicoat 807” manufactured by Mitsubishi Chemical Corporation, product names “Epototo YDF-170”, “Epototo YDF-175”, “Epototo” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Bisphenol F type epoxy compounds such as “YDF-2004”;
Bisphenol S type epoxy compounds such as Nippon Kayaku brand name “EBPS-200”, Asahi Denka Kogyo Co., Ltd. trade name “EPX-30”, Dainippon Ink Chemical Co., Ltd. trade name “Epicron EXA1514”;
Bisphenol fluorene type epoxy compounds such as “BPFG” manufactured by Osaka Gas Co., Ltd., “YL-6056”, “YL-6021”, “YX-4000”, “YX-4000H” manufactured by Mitsubishi Chemical Corporation, etc. Bixylenol type or biphenyl type epoxy compounds, or mixtures thereof;
Hydrogenated bisphenol A type epoxy compounds such as “Epototo ST-2004”, “ST-2007”, “ST-3000” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .;
Product names “Epicoat 152” and “Epicoat 154” manufactured by Mitsubishi Chemical Corporation, product names “DEN 431” and “DEN 438” manufactured by Dow Chemical Company, Dainippon Ink and Chemicals, Inc. “Epicron N-690”, “Epicron N-695”, “Epicron N-730”, “Epicron N-770”, “Epicron N-865”, trade names “Epototo YDCN” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. -701 ”,“ Epototo YDCN-704 ”, trade names“ EPPN-201 ”,“ EOCN-1025 ”,“ EOCN-1020 ”,“ EOCN-104S ”,“ RE-306 ”manufactured by Nippon Kayaku Co., Ltd. Novolac epoxy compounds;
Product name “Epicoat YL-903” manufactured by Mitsubishi Chemical Corporation, product names “Epicron 152” and “Epicron 165” manufactured by Dainippon Ink and Chemicals, Inc. Product names “Epototo YDB-400” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Brominated bisphenol A type epoxy compounds such as “Epototo YDB-500”;
Naphthalene skeletons such as trade names “ESN-190” and “ESN-360” manufactured by Nippon Steel Chemical Co., Ltd., trade names “HP-4032”, “EXA-4700”, “EXA-4750” manufactured by Dainippon Ink & Chemicals, Inc. An epoxy compound having:
Epoxy compounds having a dicyclopentadiene skeleton such as trade names “HP-7200” and “HP-7200H” manufactured by Dainippon Ink & Chemicals, Inc .;
Trishydroxyphenylmethane type epoxy compounds such as trade names “YL-933” manufactured by Mitsubishi Chemical Corporation and trade names “EPPN-501” and “EPPN-502” manufactured by Nippon Kayaku Co., Ltd .;
Heterocyclic epoxy compounds such as Nissan Chemical's trade name “TEPIC” and Mitsubishi Gas Chemical's trade name “TGI”;
Glycidylamine type epoxy compounds such as trade names “jER604” and “jER630” manufactured by Mitsubishi Chemical Corporation, “Epototo YH-434” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and “Araldite MY720” manufactured by Asahi Kasei Corporation;
Alicyclic epoxy compounds such as “Celoxide 2011” manufactured by Daicel Chemical Industries, “Araldite CY175”, “Araldite CY179” manufactured by Asahi Kasei Kogyo, and “HBE-100” manufactured by Shin Nippon Chemical Co., Ltd. However, it is not limited to these. These epoxy compounds can be used alone or in combination of two or more.
Among these, bisphenol A type epoxy compounds or bisphenol F type epoxy compounds are preferable from the viewpoint of adhesive strength.
　本発明で使用される不飽和脂肪酸の重合体（Ｂ１）と２つ以上のエポキシ基を有する化合物（Ｂ２）との反応により得られるエポキシ化合物（Ｂ）のエポキシ当量は、ポットライフ、接着強度、および薬品耐性に優れるという理由から、２００～７０００であることが好ましい。接着剤組成物のポットライフの長さと、接着剤層の適度な架橋密度による初期接着力の向上の点から、エポキシ当量は２００以上であることが好ましい。またエポキシ当量が７０００以下であることにより、接着剤層の架橋密度を高め、初期接着力を向上でき、薬品耐性も向上できる。なお、エポキシ当量は、1グラム当量のエポキシ基を含む樹脂のグラム数(g/eq)であり、ＪＩＳ　Ｋ７２３６に基づき、電位差滴定法により算出した。 The epoxy equivalent of the epoxy compound (B) obtained by the reaction of the unsaturated fatty acid polymer (B1) and the compound (B2) having two or more epoxy groups used in the present invention is pot life, adhesive strength, Also, from the reason of excellent chemical resistance, it is preferably 200 to 7000. It is preferable that the epoxy equivalent is 200 or more from the viewpoint of improving the initial adhesive force due to the length of the pot life of the adhesive composition and the appropriate crosslinking density of the adhesive layer. Moreover, when the epoxy equivalent is 7000 or less, the crosslinking density of the adhesive layer can be increased, the initial adhesive force can be improved, and the chemical resistance can also be improved. The epoxy equivalent is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and was calculated by potentiometric titration based on JIS K7236.
　本発明で使用される不飽和脂肪酸の重合体（Ｂ１）と２つ以上のエポキシ基を有する化合物（Ｂ２）との反応により得られるエポキシ化合物（Ｂ）を製造するためのエステル化反応は、公知の反応で行うことができる。即ち、製造法には特に制限が無く、例えば、触媒を用いたカルボキシル基とエポキシ基の反応により合成される。触媒の存在下、５０～２００℃、好ましくは１２０～１８０℃の温度で３０分～２０時間両者を接触させることにより容易に行うことができるが、通常、反応生成物の酸価が５ｍｇＫＯＨ／ｇ、好ましくは１ｍｇＫＯＨ／ｇ以下になった時点を反応の終点とする。
　触媒としては塩化亜鉛、塩化リチウムなどのハロゲン化物；
　Ｎ，Ｎ－ジメチルアニリン、ピリジン、トリエチルアミン、ヘキサメチレンジアミン、ジアザビシクロウンデセンなどの３級アミン及びその塩基酸または臭酸塩；
　テトラメチルアンモニウムクロライド、トリメチルドデシルベンジルアンモニウムクロライドなどの４級アンモニウム塩；
　パラトルエンスルホン酸などのスルホン酸類などが用いられる。 The esterification reaction for producing the epoxy compound (B) obtained by the reaction of the unsaturated fatty acid polymer (B1) used in the present invention with the compound (B2) having two or more epoxy groups is known. The reaction can be performed. That is, the production method is not particularly limited, and for example, it is synthesized by a reaction between a carboxyl group and an epoxy group using a catalyst. The reaction can be easily carried out by contacting them in the presence of a catalyst at a temperature of 50 to 200 ° C., preferably 120 to 180 ° C. for 30 minutes to 20 hours. Usually, the acid value of the reaction product is 5 mgKOH / g. The end point of the reaction is preferably the time when 1 mgKOH / g or less is reached.
Catalysts such as halides such as zinc chloride and lithium chloride;
Tertiary amines such as N, N-dimethylaniline, pyridine, triethylamine, hexamethylenediamine, diazabicycloundecene and their basic acids or odorates;
Quaternary ammonium salts such as tetramethylammonium chloride and trimethyldodecylbenzylammonium chloride;
Sulfonic acids such as paratoluenesulfonic acid are used.
　不飽和脂肪酸の重合体（Ｂ１）と２つ以上のエポキシ基を有する化合物（Ｂ２）との反応により得られるエポキシ化合物（Ｂ）は、市販品としても入手できる。例えば、三菱化学社製「エピコート８７１」、「エピコート８７２」、「エピコート８７２－Ｘ－７５」、新日鉄住金化学社製「ＹＤ－１７２」、「ＹＤ－１７２Ｘ７５」などが挙げられる。 The epoxy compound (B) obtained by the reaction of the unsaturated fatty acid polymer (B1) and the compound (B2) having two or more epoxy groups is also available as a commercial product. For example, “Epicoat 871”, “Epicoat 872”, “Epicoat 872-X-75” manufactured by Mitsubishi Chemical Corporation, “YD-172”, “YD-172X75” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. may be used.
　本発明で使用されるポリオレフィン樹脂（Ａ）は、接着性および溶解性に優れるという観点から、ポリオレフィン樹脂（Ａ）１グラムあたりのカルボキシル基の含有量がＸミリモル、酸無水物基の含有量がＹミリモルとした場合に、Ｘ＋２Ｙが０．０５～０．６であることが好ましい。
　Ｘ＋２Ｙが０．０５未満であると、架橋点となる酸性基が少なく、架橋が充分でなく、充分な接着強度や電解質溶液耐性が得られない場合がある。０．６より大きいと、塗膜の架橋収縮が大きいために接着強度が不充分であったり、溶剤への溶解性が低下したりする場合がある。 From the viewpoint that the polyolefin resin (A) used in the present invention is excellent in adhesion and solubility, the content of carboxyl groups per gram of polyolefin resin (A) is X mmol, and the content of acid anhydride groups is In the case of Y mmol, X + 2Y is preferably 0.05 to 0.6.
When X + 2Y is less than 0.05, there are few acidic groups that serve as crosslinking points, crosslinking is not sufficient, and sufficient adhesive strength and electrolyte solution resistance may not be obtained. If it is larger than 0.6, the crosslinking strength of the coating film is large, so that the adhesive strength may be insufficient, or the solubility in a solvent may be reduced.
　接着剤組成物中に含まれるポリオレフィン樹脂（Ａ）をＰグラム、エポキシ化合物（Ｂ）由来のエポキシ基をＺミリモルとした場合に、Ｚ／（Ｘ＋２Ｙ）Ｐが０．３～１０となる範囲でエポキシ化合物（Ｂ）を含み、０．５～７の範囲で含むことがより好ましい。
　接着強度、電解質溶液耐性の向上のために、充分な架橋構造が形成により凝集力を向上できるよう、Ｚ／（Ｘ＋２Ｙ）Ｐが０．３以上であることが好ましい。電解質溶液耐性の点から未反応のエポキシ化合物（Ｂ）が残らないよう、Ｚ／（Ｘ＋２Ｙ）Ｐが１０以下であることが好まししい。 When the polyolefin resin (A) contained in the adhesive composition is P grams and the epoxy group derived from the epoxy compound (B) is Z mmol, Z / (X + 2Y) P is within a range of 0.3 to 10. More preferably, the epoxy compound (B) is included in the range of 0.5 to 7.
In order to improve adhesive strength and electrolyte solution resistance, Z / (X + 2Y) P is preferably 0.3 or more so that a sufficient cross-linked structure can be formed to improve cohesion. From the viewpoint of electrolyte solution resistance, Z / (X + 2Y) P is preferably 10 or less so that no unreacted epoxy compound (B) remains.
　本発明の接着剤には、金属箔との接着強度を高めるために、さらに、シランカップリング剤を含有させることができる。シランカップリング剤としては、例えばビニルトリメトキシシラン、ビニルトリエトキシシラン等のビニル基を有するトリアルコキシシラン、３－アミノプロピルトリエトキシシラン、Ｎ－（２－アミノエチル）３－アミノプロピルトリメトキシシラン等のアミノ基を有するトリアルコキシシラン、３－グリシドキシプロピルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン等のグリシジル基を有するトリアルコキシシラン等が挙げられる。シランカップリング剤の添加量は、接着剤の固形分を基準として０．１～５質量％であることが好ましく、０．５～３質量％であることがより好ましい。 The adhesive of the present invention can further contain a silane coupling agent in order to increase the adhesive strength with the metal foil. Examples of the silane coupling agent include trialkoxysilanes having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane. Having a glycidyl group such as trialkoxysilane having an amino group such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane Examples include trialkoxysilane. The addition amount of the silane coupling agent is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass based on the solid content of the adhesive.
　本発明の接着剤は、金属箔との接着強度を高めるため、カテコールまたはその誘導体を含有することができる。具体的には、カテコール、ｔ－ブチルカテコール、アドレナリン、ノルアドレナリン、ドーパミン、ノルジヒドログアヤレチック酸などが挙げられる。 The adhesive of the present invention can contain catechol or a derivative thereof in order to increase the adhesive strength with the metal foil. Specific examples include catechol, t-butylcatechol, adrenaline, noradrenaline, dopamine, nordihydroguaiaretic acid and the like.
　本発明の接着剤組成物は有機溶剤を含むことができる。単独もしくは混合溶剤として本接着剤組成物で使用する材料を溶解でき、不飽和脂肪酸の重合体（Ｂ１）と２つ以上のエポキシ基を有する化合物（Ｂ２）との反応により得られるエポキシ化合物（Ｂ）との反応性が不活性であり、接着剤塗工時の乾燥工程における加熱により揮発させて除去できるものであれば特に限定されない。これらの溶剤の具体例としては、例えば、トルエン、キシレン等の芳香族系有機溶剤；
　ｎ－ヘキサン、ｎ－ヘプタン等の脂肪族系有機溶剤；
　シクロヘキサン、メチルシクロヘキサン等の脂環族系有機溶剤；
　メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン系溶剤；
　酢酸エチル、酢酸ブチル等のエステル系溶剤；
　エタノール、メタノール、ｎ－プロパノール、２－プロパノール、ブタノール、ヘキサノール等のアルコール系溶剤；
　ジイソプロピルエーテル、ブチルセロソルブ、テトラヒドロフラン、ジオキサン、ブチルカルビトール等のエーテル系溶剤；
　ジエチレングリコールモノメチルエーテル、トリエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル等のグリコールエーテル系溶剤；
　エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート等のグリコールエステル系溶剤等が挙げられ、これらは単独で使用してもよいし、２種以上を併用してもよい。
　これらの中でも、ポリオレフィン樹脂（Ａ）の溶液の保存安定性の点から、芳香族系有機溶剤とケトン系溶剤の併用、芳香族系有機溶剤とアルコール系溶剤の併用、脂環族系有機溶剤とケトン系溶剤の併用、脂環族系有機溶剤とアルコール系溶剤の併用が好ましい。 The adhesive composition of the present invention can contain an organic solvent. An epoxy compound (B) which can dissolve a material used in the present adhesive composition alone or as a mixed solvent, and which is obtained by reacting an unsaturated fatty acid polymer (B1) with a compound (B2) having two or more epoxy groups. ) Is inactive and is not particularly limited as long as it can be volatilized and removed by heating in the drying step during adhesive coating. Specific examples of these solvents include aromatic organic solvents such as toluene and xylene;
aliphatic organic solvents such as n-hexane and n-heptane;
Cycloaliphatic organic solvents such as cyclohexane and methylcyclohexane;
Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone;
Ester solvents such as ethyl acetate and butyl acetate;
Alcohol solvents such as ethanol, methanol, n-propanol, 2-propanol, butanol, hexanol;
Ether solvents such as diisopropyl ether, butyl cellosolve, tetrahydrofuran, dioxane, butyl carbitol;
Glycol ether solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether;
Examples include glycol ester solvents such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate. These may be used alone or in combination of two or more.
Among these, from the viewpoint of the storage stability of the solution of the polyolefin resin (A), a combination of an aromatic organic solvent and a ketone solvent, a combination of an aromatic organic solvent and an alcohol solvent, an alicyclic organic solvent, The combined use of a ketone solvent and the combined use of an alicyclic organic solvent and an alcohol solvent are preferred.
　本発明の接着剤組成物において、発明の効果を損なわない範囲で、必要に応じて、粘着付与剤、可塑剤等の公知の添加剤を配合してもよい。
　本発明で使用できる粘着付与剤としては、ポリテルペン樹脂、ロジン系樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、共重合系石油樹脂、スチレン樹脂および水添石油樹脂等が挙げられ、接着強度を向上させる目的で用いられる。これらは単独で用いてもよいし、２種以上を任意に組み合わせて使用してもよい。
　また、本発明で使用される可塑剤としては、ポリイソプレン、ポリブテン等の液状ゴムやプロセスオイル等が挙げられる。 In the adhesive composition of the present invention, known additives such as a tackifier and a plasticizer may be blended as necessary within a range not impairing the effects of the invention.
Examples of tackifiers that can be used in the present invention include polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, styrene resins, and hydrogenated petroleum resins. Used for the purpose of improving strength. These may be used alone or in any combination of two or more.
Examples of the plasticizer used in the present invention include liquid rubber such as polyisoprene and polybutene, process oil, and the like.
　本発明の接着剤組成物は、金属箔層（１２）とヒートシール層（１４）との積層に好適に使用される。
　金属箔層（１２）の金属としては、アルミニウム、銅、ニッケル等が挙げられる。これらの金属箔は、各種表面処理を施したものであってもよい。表面処理の例としては、例えば、サンドブラスト処理、研磨処理などの物理的処理や蒸着による脱脂処理、エッチング処理、カップリング剤やコーティング剤を塗布するプライマー処理などの表面処理がある。　表面処理層を形成するための処理剤は、エポキシ基と反応する官能基を含むことが好ましく、カルボン酸、水酸基およびアミノ基からなる群より選ばれる少なくとも１種の官能基の含むことがより好ましい。ここでいうアミノ基とは１級アミン、２級アミン、およびイミノ基のことである。このような官能基を含む表面処理層を金属箔層（１２）表面に設けることにより、接着剤組成物を熱硬化する際、接着剤層中のエポキシ基と、表面処理層中の前記官能基とが反応することにより、初期接着強度が大きく、電解質溶液耐性に優れた積層体を得ることができる。 The adhesive composition of the present invention is suitably used for laminating the metal foil layer (12) and the heat seal layer (14).
Examples of the metal of the metal foil layer (12) include aluminum, copper, and nickel. These metal foils may be subjected to various surface treatments. Examples of the surface treatment include physical treatment such as sand blast treatment and polishing treatment, degreasing treatment by vapor deposition, etching treatment, and surface treatment such as primer treatment for applying a coupling agent or a coating agent. The treatment agent for forming the surface treatment layer preferably contains a functional group that reacts with an epoxy group, and more preferably contains at least one functional group selected from the group consisting of a carboxylic acid, a hydroxyl group and an amino group. . The amino group here is a primary amine, a secondary amine, or an imino group. By providing a surface treatment layer containing such a functional group on the surface of the metal foil layer (12), the epoxy group in the adhesive layer and the functional group in the surface treatment layer when the adhesive composition is thermally cured. , A laminate having high initial adhesive strength and excellent electrolyte solution resistance can be obtained.
　ヒートシール層（１４）は特に限定されるものではないが、ポリオレフィン系フィルムであることが好ましく、ポリエチレン、ポリプロピレン、オレフィン系共重合体、これらの酸変性物およびアイオノマーからなる群より選ばれた少なくとも１種類の熱可塑性樹脂からなる未延伸フィルムであることが好ましい。ヒートシール層の厚さは特に限定されるものではないが、２０～１５０μｍであることが好ましい。 The heat seal layer (14) is not particularly limited, but is preferably a polyolefin film, and at least selected from the group consisting of polyethylene, polypropylene, olefin copolymers, acid-modified products thereof, and ionomers. An unstretched film made of one kind of thermoplastic resin is preferable. The thickness of the heat seal layer is not particularly limited, but is preferably 20 to 150 μm.
　本発明の接着剤組成物を用いてなる積層体は、例えば、以下のようにして得ることができる。
　金属箔層（１２）（又はヒートシール層（１４））の一方の面に、本発明の接着剤組成物を塗工し、溶剤を揮散させ（乾燥させ）、未硬化の接着剤層を形成し、６０～１５０℃、加圧下に前記未硬化の接着剤層の表面に、ヒートシール層（１４）（又は金属箔層（１２））を重ねた後、４０～８０℃で３～１０日程度静置し、接着剤層を充分硬化させ（エージングとも称する）、金属箔とヒートシール層とを貼り合わせることで、積層体を得ることができる。
　接着剤組成物の塗工には、コンマコーター等の一般的な塗工機を用いることができる。また、乾燥硬化時の硬化接着剤層の厚み（量）は、０．５～１０ｇ／ｍ2程度であることが好ましい。 A laminate using the adhesive composition of the present invention can be obtained, for example, as follows.
On one side of the metal foil layer (12) (or heat seal layer (14)), the adhesive composition of the present invention is applied, and the solvent is stripped (dried) to form an uncured adhesive layer. After the heat seal layer (14) (or the metal foil layer (12)) is stacked on the surface of the uncured adhesive layer under pressure at 60 to 150 ° C., it is 3 to 10 days at 40 to 80 ° C. The laminate can be obtained by allowing to stand to a certain degree, sufficiently curing the adhesive layer (also referred to as aging), and bonding the metal foil and the heat seal layer together.
For coating of the adhesive composition, a general coating machine such as a comma coater can be used. The thickness (amount) of the cured adhesive layer at the time of dry curing is preferably about 0.5 to 10 g / m 2 .
　本発明の蓄電デバイス用包装材は、金属箔層（１２）の他方の面（本発明の接着剤組成物から形成される接着剤層（１３）が接していない面）に、外層側接着剤層を介して樹脂フィルム層（１１）を具備することができる。
　樹脂フィルム層（１１）は、予め接着剤組成物（本発明の接着剤組成物と同じであってもよいし、異なっていてもよい）を用いて、金属箔層（１２）に積層されていてもよいし、本発明の接着剤組成物を用いて金属箔層（１２）とヒートシール層（１４）との積層体を得た後、金属箔層（１２）に外層側接着剤層を介して樹脂フィルム層（１１）を積層することもできる。
　用いられる樹脂フィルム層（１１）としては、ポリエステル樹脂やポリアミド樹脂（ナイロン）等の延伸フィルム等が挙げられ、樹脂フィルム層（１１）は、積層体を蓄電デバイス用包装材として用い、蓄電デバイス用容器を形成する際、電解質溶液とは接触しない外側に位置するとなる。 The packaging material for an electricity storage device of the present invention is the outer layer side adhesive on the other surface of the metal foil layer (12) (the surface where the adhesive layer (13) formed from the adhesive composition of the present invention is not in contact). A resin film layer (11) can be provided through the layer.
The resin film layer (11) is previously laminated on the metal foil layer (12) using an adhesive composition (which may be the same as or different from the adhesive composition of the present invention). Or after obtaining the laminated body of a metal foil layer (12) and a heat seal layer (14) using the adhesive composition of this invention, an outer layer side adhesive bond layer is attached to a metal foil layer (12). The resin film layer (11) can also be laminated.
Examples of the resin film layer (11) used include stretched films such as a polyester resin and a polyamide resin (nylon), and the resin film layer (11) uses a laminate as a packaging material for an electricity storage device and is used for an electricity storage device. When forming the container, the container is located outside the electrolyte solution.
　本発明の蓄電デバイス用容器は、前述の蓄電デバイス用包装材を用い、外層側の樹脂フィルム層（１１）が凸面を構成し、ヒートシール層（１４）が凹面を構成するように成型して得ることができる。
　なお、本発明でいう「凹面」とは、平たい状態の蓄電デバイス用包装材を成型加工して図２に示すようなトレイ状とした場合に、電解質溶液を内部に収容し得る窪みを有する面という意であり、本発明でいう「凸面」とは、前記窪みを有する面の自背面（反対側の面、裏側の面）の意である。 The container for an electricity storage device of the present invention is molded using the aforementioned packaging material for an electricity storage device so that the resin film layer (11) on the outer layer side forms a convex surface and the heat seal layer (14) forms a concave surface. Obtainable.
The “concave surface” as used in the present invention is a surface having a dent that can accommodate the electrolyte solution when the flat packaging material for an electricity storage device is molded into a tray shape as shown in FIG. The term “convex surface” as used in the present invention refers to the self-back surface (opposite surface, back surface) of the surface having the depression.
　二次電池等の蓄電デバイスは、電池本体と、前記電池本体の正極と負極にそれぞれ接合されてなる複数の端子と、電池容器と、電解質溶液とを具備する。前記電池容器は、本発明の接着剤組成物から形成される接着剤層（１３）を介して、金属箔層（１２）とヒートシール層（１４）とが積層されてなる積層体から得られるものであり、前記ヒートシール層が前記電解質溶液に接する。 An electricity storage device such as a secondary battery includes a battery body, a plurality of terminals respectively joined to a positive electrode and a negative electrode of the battery body, a battery container, and an electrolyte solution. The battery container is obtained from a laminate in which a metal foil layer (12) and a heat seal layer (14) are laminated via an adhesive layer (13) formed from the adhesive composition of the present invention. The heat seal layer is in contact with the electrolyte solution.
　電解質溶液は、ヒートシール層（１４）から金属箔層（１２）に向かって浸透し始めるが、本発明の接着剤組成物から形成された接着剤層（１３）は、電解質溶液に対する耐性に優れているので、ヒートシール層と金属箔との間の接着強度は低下せず、液漏れ等の問題が発生しない。 The electrolyte solution starts to penetrate from the heat seal layer (14) toward the metal foil layer (12), but the adhesive layer (13) formed from the adhesive composition of the present invention has excellent resistance to the electrolyte solution. Therefore, the adhesive strength between the heat seal layer and the metal foil does not decrease, and problems such as liquid leakage do not occur.
　以下、実施例により、本発明をさらに詳細に説明するが、以下の実施例は本発明の権利範囲を何ら制限するものではない。なお、実施例中における各評価は下記の方法に従った。なお、実施例中、％は質量％を、部は質量部を示す。
　＜カルボキシル基の定量＞
　秤量した試料ａグラムを還流させたキシレン中に溶解させ、室温まで冷却後、フェノールフタレインを指示薬とし、０．１Ｍのエタノール性水酸化カリウムを用いて滴定することにより定量を行った。指示薬の呈色が１０秒間残留した時を滴定の終点とした。滴定量をｂミリリットルとすると、以下の式からＸを求めることができる。
　Ｘ＝０．１＊ｂ／ａ
　＜酸無水物基の定量＞
　秤量した試料ｃグラムを還流させたキシレン中に溶解させ、室温まで冷却後、試料の酸無水物基の当量以上のオクチルアミンｄミリモルを添加した。残存するオクチルアミンを、０．１Ｍエタノール性過塩素酸を用いて滴定することにより定量を行った。滴定量をｅミリリットルとすると、以下の式からＹを求めることができる。
　Ｙ＝（０．１*ｅ－ｄ）／ｃ EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, a following example does not restrict | limit the right range of this invention at all. In addition, each evaluation in an Example followed the following method. In the examples,% represents mass%, and part represents mass part.
<Quantification of carboxyl group>
The weighed sample a gram was dissolved in refluxed xylene, cooled to room temperature, and then titrated with 0.1M ethanolic potassium hydroxide using phenolphthalein as an indicator. The end point of the titration was when the color of the indicator remained for 10 seconds. If the titer is b milliliter, X can be obtained from the following equation.
X = 0.1 * b / a
<Quantification of acid anhydride group>
A weighed sample of c grams was dissolved in refluxed xylene, cooled to room temperature, and d mmol of octylamine equal to or greater than the acid anhydride group of the sample was added. The remaining octylamine was quantified by titrating with 0.1M ethanolic perchloric acid. If the titration amount is e milliliter, Y can be obtained from the following equation.
Y = (0.1 * ed) / c
　＜質量平均分子量＞
　ＴＳＫｇｅｌ　ｓｕｐｅｒＨＺＭ－Ｎのカラムを２本接続した東ソー社製ＨＬＣ－８２２０ＧＰＣシステムにより、溶離液にテトラヒドロフラン、カラム温度を４０℃とし、流量毎分０．３５ｍＬの条件にて測定した。サンプルは、２ｍｇのポリオレフィン樹脂（Ａ）を、５ｍＬのテトラヒドロフランに溶解して調製した。また、質量平均分子量は標準ポリスチレン換算で算出した。 <Mass average molecular weight>
Using an HLC-8220GPC system manufactured by Tosoh Corporation, to which two TSKgel superHZM-N columns were connected, the eluent was tetrahydrofuran, the column temperature was 40 ° C., and the flow rate was 0.35 mL per minute. A sample was prepared by dissolving 2 mg of polyolefin resin (A) in 5 mL of tetrahydrofuran. The mass average molecular weight was calculated in terms of standard polystyrene.
　＜融点、融解エネルギー（ΔＥ）＞
　前述と同様の方法により求めた。 <Melting point, melting energy (ΔE)>
It calculated | required by the method similar to the above-mentioned.
＜共重合組成比＞
　ポリオレフィンの共重合組成比は、日本電子社製ＮＭＲ（ＪＮＭ－ＬＡ４００）を用いて、13Ｃの測定により求めた。
　サンプル２０ｍｇを１ｍＬの重クロロホルムに溶解して測定した。エチレン由来のメチレン基は４０－５０ｐｐｍに、プロピレン由来のメチン基は２５－３０ｐｐｍに、１－ブテン由来のメチン基は３０－３５ｐｐｍにピークがある。各ピークの積分比から共重合組成比を求めた。 <Copolymerization composition ratio>
The copolymer composition ratio of the polyolefin was determined by 13 C measurement using NMR (JNM-LA400) manufactured by JEOL.
A 20 mg sample was dissolved in 1 mL deuterated chloroform and measured. The methylene group derived from ethylene has a peak at 40-50 ppm, the methine group derived from propylene has a peak at 25-30 ppm, and the methine group derived from 1-butene has a peak at 30-35 ppm. The copolymer composition ratio was determined from the integration ratio of each peak.
　＜合成例１＞
　窒素置換した内容積５００ｍＬのガラス製オートクレーブに精製トルエン２５０ｍＬ、メチルアルミノキサンをＡｌ原子換算で０．５ｍｇ、ジメチルシリル－ビス－（４，５，６，７，８－ペンタヒドロアズレン－２－イル）ジルコニウムジクロライドをＺｒ原子換算で１．２５μｇ原子を投入し、４０℃に昇温した。続いてエチレンとプロピレンを、それぞれ５０Ｌ／ｈｒ、４０Ｌ／ｈｒの一定速度で供給しながら、４０℃で１．３２ＭＰａの一定圧力を維持するように１－ブテンモノマーを連続供給し、重合を開始した。４０℃、８時間、重合を行った後、イソプロパノールを添加して重合を停止した。得られたポリマー溶液を、多量のメタノールに添加し、ポリマーを析出させた。析出したポリマーをろ過、乾燥することにより、エチレン／プロピレン／１－ブテン＝４６／３３／１５（モル比）で共重合されたポリオレフィンを得た。
　得られたポリオレフィン２０ｇと、セロソルブアセテート２０ｇとを仕込み、窒素気流下、加熱溶解させ、溶液温度の１１０℃にした。無水マレイン酸４ｇ、ラウリルメタクリレート２ｇおよび過酸化ベンゾイル０．６ｇをセロソルブアセテート２３９．４ｇに溶解したものを２時間かけて滴下した。滴下終了後さらに１時間その温度で反応を続けた。得られたポリマー溶液を、多量のメタノールに添加し、ポリマーを析出させた。析出したポリマーをろ過、乾燥することにより、酸無水物基を有するポリオレフィン樹脂（Ａ１）を得た。
　ポリオレフィン樹脂（Ａ１）のＭｗ、融点、ΔＥは、それぞれ４７００、１０３℃、４５ｍＪ／ｍｇであった。 <Synthesis Example 1>
Nitrogen-substituted 500 mL glass autoclave with purified volume of 250 mL of toluene, methylaluminoxane 0.5 mg in terms of Al atom, dimethylsilyl-bis- (4,5,6,7,8-pentahydroazulen-2-yl) Zirconium dichloride was charged with 1.25 μg atoms in terms of Zr atoms and heated to 40 ° C. Subsequently, while supplying ethylene and propylene at a constant rate of 50 L / hr and 40 L / hr, respectively, 1-butene monomer was continuously supplied so as to maintain a constant pressure of 1.32 MPa at 40 ° C., and polymerization was started. . After polymerization at 40 ° C. for 8 hours, isopropanol was added to terminate the polymerization. The obtained polymer solution was added to a large amount of methanol to precipitate a polymer. The precipitated polymer was filtered and dried to obtain a polyolefin copolymerized with ethylene / propylene / 1-butene = 46/33/15 (molar ratio).
20 g of the obtained polyolefin and 20 g of cellosolve acetate were charged and dissolved by heating in a nitrogen stream to a solution temperature of 110 ° C. A solution prepared by dissolving 4 g of maleic anhydride, 2 g of lauryl methacrylate and 0.6 g of benzoyl peroxide in 239.4 g of cellosolve acetate was added dropwise over 2 hours. The reaction was continued at that temperature for an additional hour after the addition. The obtained polymer solution was added to a large amount of methanol to precipitate a polymer. The precipitated polymer was filtered and dried to obtain a polyolefin resin (A1) having an acid anhydride group.
Mw, melting | fusing point, and (DELTA) E of polyolefin resin (A1) were 4700, 103 degreeC, and 45 mJ / mg, respectively.
＜合成例２～４、６～１２＞
　表１に示すオレフィン重合時の混合ガスの流量比と重合温度、グラフト重合時のモノマー添加量以外は、合成例１と同様にして酸無水物基を有するポリオレフィン樹脂（Ａ２）～（Ａ４）、（Ａ６）～（Ａ８）を得た。 <Synthesis Examples 2 to 4, 6 to 12>
The polyolefin resins (A2) to (A4) having an acid anhydride group in the same manner as in Synthesis Example 1 except for the flow rate ratio and polymerization temperature of the mixed gas shown in Table 1 and the monomer addition amount during graft polymerization. (A6) to (A8) were obtained.
＜合成例５＞
　表１に示す混合ガスの流量比、グラフト重合時のモノマー添加量以外は、合成例１と同様にして酸無水物基を有するポリオレフィン樹脂を得た。得られたポリオレフィン樹脂を、８５℃、８５％ＲＨの環境下に３日間保存することにより、カルボキシル基を有するポリオレフィン樹脂（Ａ５）を得た。 <Synthesis Example 5>
A polyolefin resin having an acid anhydride group was obtained in the same manner as in Synthesis Example 1 except for the flow rate ratio of the mixed gas shown in Table 1 and the monomer addition amount during graft polymerization. The obtained polyolefin resin was stored in an environment of 85 ° C. and 85% RH for 3 days to obtain a polyolefin resin (A5) having a carboxyl group.
＜合成例９＞
　プロピレン－エチレン共重合体（プロピレン／エチレン＝８２／１８質量％、質量平均分子量８５０００）２８０ｇを４つ口フラスコ中、窒素雰囲気下で加熱溶融させた後、系内温度を１８０℃に保って攪拌下、酸成分として無水マレイン酸３５．０ｇ、ラジカル発生剤としてジ－t－ブチルパーオキサイド６．０ｇをそれぞれ２時間かけて加え、その後１時間反応させた。反応終了後、得られた反応物を多量のアセトン中に投入し、樹脂を析出させた。この樹脂をさらにアセトンで数回洗浄し、未反応の無水マレイン酸を除去した後、減圧乾燥機中で減圧乾燥して酸変性ポリプロピレン樹脂（質量平均分子量４００００）を得た。
　ヒーター付きの密閉できる耐圧１リットル容ガラス容器を備えた撹拌機を用いて、６０．０ｇの前記酸変性ポリプロピレン系樹脂、６０．０ｇのテトラヒドロフラン、６．９ｇのＮ，Ｎ－ジメチルエタノールアミン（酸変性ポリプロピレン樹脂中の酸成分のカルボキシル基に対して１．０倍当量）及び１７３．１ｇの蒸留水をガラス容器内に仕込み、撹拌翼の回転速度を３００ｒｐｍとして撹拌したところ、容器底部には樹脂粒状物の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、１０分後にヒーターの電源を入れ加熱した。そして系内温度を１４０℃に保ってさらに６０分間撹拌した後、ヒーターの電源を切り６０℃まで自然冷却した。冷却後６０℃に保持し、撹拌及び減圧下で脱溶剤を行い、必要に応じて水を添加し、媒体を水に置換することによりポリオレフィン樹脂（Ａ９）の水分散体を得た。 <Synthesis Example 9>
280 g of propylene-ethylene copolymer (propylene / ethylene = 82/18% by mass, mass average molecular weight 85000) was melted by heating in a four-necked flask under a nitrogen atmosphere, and then the system temperature was maintained at 180 ° C. with stirring. Then, 35.0 g of maleic anhydride as an acid component and 6.0 g of di-t-butyl peroxide as a radical generator were added over 2 hours, and then reacted for 1 hour. After completion of the reaction, the obtained reaction product was put into a large amount of acetone to precipitate a resin. This resin was further washed several times with acetone to remove unreacted maleic anhydride, and then dried under reduced pressure in a vacuum dryer to obtain an acid-modified polypropylene resin (mass average molecular weight 40000).
Using a stirrer equipped with a hermetically sealed 1 liter glass container with a heater, 60.0 g of the acid-modified polypropylene resin, 60.0 g of tetrahydrofuran, 6.9 g of N, N-dimethylethanolamine (acid When 1.03.1 equivalent to the carboxyl group of the acid component in the modified polypropylene resin) and 173.1 g of distilled water were charged into a glass container and stirred at a rotation speed of 300 rpm, the resin was placed at the bottom of the container. Precipitation of particulate matter was not recognized, and it was confirmed that it was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. The system temperature was maintained at 140 ° C. and stirring was continued for 60 minutes, and then the heater was turned off and naturally cooled to 60 ° C. After cooling, the temperature was maintained at 60 ° C., the solvent was removed under stirring and reduced pressure, water was added as necessary, and the medium was replaced with water to obtain an aqueous dispersion of polyolefin resin (A9).
Figure JPOXMLDOC01-appb-T000001

表１中、記号は以下の通り。
ＬＭＡ：ラウリルメタクリレート
Ｓｔ：スチレン
Figure JPOXMLDOC01-appb-T000001

In Table 1, the symbols are as follows.
LMA: Lauryl methacrylate St: Styrene
＜合成例１０＞
　クローダジャパン社製プリポール１０１３（Ｃ１８不飽和脂肪酸のダイマー酸、酸価１９６ｍｇＫＯＨ／ｇ）４６ｇ、ｊＥＲ１００１（三菱化学社製、ビスフェノールＡ型エポキシ化合物、エポキシ当量：４７５）１５４部、トリフェニルホスフィン４部、トルエン１６０部およびイソプロピルアルコール４０部を４つ口フラスコ中、窒素雰囲気下で加熱溶解させた後、攪拌しながら系内温度を１００℃に保った。酸価が１．０ｍｇＫＯＨ／ｇ以下となるまで反応させ、冷却させることにより固形分５０％、エポキシ当量１２３６のエポキシ化合物（Ｂ－１）を得た。 <Synthesis Example 10>
46 g of Pripol 1013 (C18 unsaturated fatty acid dimer acid, acid value 196 mg KOH / g), jER1001 (Mitsubishi Chemical Corporation, bisphenol A type epoxy compound, epoxy equivalent: 475), 154 parts, triphenylphosphine 4 parts, After 160 parts of toluene and 40 parts of isopropyl alcohol were heated and dissolved in a four-necked flask under a nitrogen atmosphere, the system temperature was maintained at 100 ° C. while stirring. The reaction was carried out until the acid value became 1.0 mgKOH / g or less, followed by cooling to obtain an epoxy compound (B-1) having a solid content of 50% and an epoxy equivalent of 1236.
＜合成例１１＞
　クローダジャパン社製プリポール１０１０（Ｃ１８不飽和脂肪酸のダイマー酸の水添物、酸価１９５ｍｇＫＯＨ／ｇ）１４ｇ、ｊＥＲ１００７（三菱化学社製、ビスフェノールＡ型エポキシ化合物、エポキシ当量１９７５ｇ/ｅｑ）１８６部、トリフェニルホスフィン４部、トルエン１６０部およびイソプロピルアルコール４０部を４つ口フラスコ中、窒素雰囲気下で加熱溶解させた後、攪拌しながら系内温度を１００℃に保った。酸価が１．０ｍｇＫＯＨ／ｇ以下となるまで反応させ、冷却させることにより固形分５０％、エポキシ当量４２３８のエポキシ化合物（Ｂ－２）を得た。 <Synthesis Example 11>
14 g of Pripol 1010 manufactured by Croda Japan (hydrogenated product of dimer acid of C18 unsaturated fatty acid, acid value 195 mgKOH / g), jER1007 (Mitsubishi Chemical Corporation, bisphenol A type epoxy compound, epoxy equivalent 1975 g / eq) 186 parts, tri After 4 parts of phenylphosphine, 160 parts of toluene and 40 parts of isopropyl alcohol were dissolved in a four-necked flask under heating in a nitrogen atmosphere, the system temperature was maintained at 100 ° C. with stirring. The reaction was carried out until the acid value became 1.0 mgKOH / g or less, followed by cooling to obtain an epoxy compound (B-2) having a solid content of 50% and an epoxy equivalent of 4238.
＜合成例１２＞
　クローダジャパン社製プリポール１０１０（Ｃ１８不飽和脂肪酸のダイマー酸の水添物、酸価１９５ｍｇＫＯＨ／ｇ）７ｇ、ｊＥＲ１０１０（三菱化学社製、ビスフェノールＡ型エポキシ化合物、エポキシ当量４０００ｇ/ｅｑ）１９３部、トリフェニルホスフィン４部、トルエン１６０部およびイソプロピルアルコール４０部を４つ口フラスコ中、窒素雰囲気下で加熱溶解させた後、攪拌しながら系内温度を１００℃に保った。酸価が１．０ｍｇＫＯＨ／ｇ以下となるまで反応させ、冷却させることにより固形分５０％、エポキシ当量８２８８のエポキシ化合物（Ｂ－３）を得た。 <Synthesis Example 12>
Cropol Japan Co., Ltd. Pripol 1010 (hydrogenated dimer acid of C18 unsaturated fatty acid, acid value 195 mg KOH / g), jER1010 (Mitsubishi Chemical Corporation, bisphenol A type epoxy compound, epoxy equivalent 4000 g / eq) 193 parts, tri After 4 parts of phenylphosphine, 160 parts of toluene and 40 parts of isopropyl alcohol were dissolved in a four-necked flask under heating in a nitrogen atmosphere, the system temperature was maintained at 100 ° C. with stirring. The reaction was carried out until the acid value became 1.0 mgKOH / g or less, followed by cooling to obtain an epoxy compound (B-3) having a solid content of 50% and an epoxy equivalent of 8288.
＜合成例１３＞
　クローダジャパン社製プリポール１００４（Ｃ２２不飽和脂肪酸のダイマー酸の水添物、酸価１６２ｍｇＫＯＨ／ｇ）１０９ｇ、ｊＥＲ６３０（三菱化学社製、グリシジルアミン型エポキシ化合物、エポキシ当量９６ｇ/ｅｑ）９１部、トリフェニルホスフィン４部、トルエン１６０部およびイソプロピルアルコール４０部を４つ口フラスコ中、窒素雰囲気下で加熱溶解させた後、攪拌しながら系内温度を１００℃に保った。酸価が１．０ｍｇＫＯＨ／ｇ以下となるまで反応させ、冷却させることにより固形分５０％、エポキシ当量３１７のエポキシ化合物（Ｂ－４）を得た。 <Synthesis Example 13>
109 parts of Tripol 1004 (dimer acid hydrogenated C22 unsaturated fatty acid, acid value 162 mgKOH / g), jER630 (Mitsubishi Chemical Co., Ltd., glycidylamine type epoxy compound, epoxy equivalent 96 g / eq) 91 parts, Trida After 4 parts of phenylphosphine, 160 parts of toluene and 40 parts of isopropyl alcohol were dissolved in a four-necked flask under heating in a nitrogen atmosphere, the system temperature was maintained at 100 ° C. with stirring. The reaction was continued until the acid value became 1.0 mgKOH / g or less, followed by cooling to obtain an epoxy compound (B-4) having a solid content of 50% and an epoxy equivalent of 317.
＜合成例１４＞
　クローダジャパン社製プリポール１０４０（Ｃ１８不飽和脂肪酸のトリマー酸、酸価１８９ｍｇＫＯＨ／ｇ）２２ｇ、ｊＥＲ４００５Ｐ（三菱化学社製、ビスフェノールＦ型エポキシ化合物、エポキシ当量１１７５ｇ/ｅｑ）１７８部、トリフェニルホスフィン４部、トルエン１６０部およびイソプロピルアルコール４０部を４つ口フラスコ中、窒素雰囲気下で加熱溶解させた後、攪拌しながら系内温度を１００℃に保った。酸価が１．０ｍｇＫＯＨ／ｇ以下となるまで反応させ、冷却させることにより固形分５０％、エポキシ当量３８２２のエポキシ化合物（Ｂ－５）を得た。 <Synthesis Example 14>
Cropol Japan Co., Ltd. Pripol 1040 (C18 unsaturated fatty acid trimer acid, acid value 189 mg KOH / g) 22 g, jER4005P (Mitsubishi Chemical Corporation, bisphenol F type epoxy compound, epoxy equivalent 1175 g / eq) 178 parts, triphenylphosphine 4 parts Then, 160 parts of toluene and 40 parts of isopropyl alcohol were heated and dissolved in a four-necked flask under a nitrogen atmosphere, and the system temperature was kept at 100 ° C. with stirring. The reaction was carried out until the acid value became 1.0 mgKOH / g or less, followed by cooling to obtain an epoxy compound (B-5) having a solid content of 50% and an epoxy equivalent of 3822.
＜合成例１５＞　ラウリン酸（酸価２００ｍｇＫＯＨ／ｇ）８７ｇ、三菱ガス化学社製ＴＥＴＲＡＤ－Ｃ（エポキシ当量９１ｇ/ｅｑ）１１３部、トリフェニルホスフィン４部、トルエン１６０部およびイソプロピルアルコール４０部を４つ口フラスコ中、窒素雰囲気下で加熱溶解させた後、攪拌しながら系内温度を１００℃に保った。酸価が１．０ｍｇＫＯＨ／ｇ以下となるまで反応させ、冷却させることにより固形分５０％、エポキシ当量６４５のエポキシ化合物（Ｂ－５）を得た。 <Synthesis Example 15> 87 g of lauric acid (acid value 200 mg KOH / g), 113 parts of TETRAD-C (epoxy equivalent 91 g / eq) manufactured by Mitsubishi Gas Chemical Company, 4 parts of triphenylphosphine, 160 parts of toluene and 40 parts of isopropyl alcohol In a three-necked flask, the solution was heated and dissolved in a nitrogen atmosphere, and the system temperature was kept at 100 ° C. while stirring. The reaction was carried out until the acid value became 1.0 mgKOH / g or less, followed by cooling to obtain an epoxy compound (B-5) having a solid content of 50% and an epoxy equivalent of 645.
＜添加剤の合成例＞
　攪拌機、温度計、還流冷却器および窒素ガス導入管を備えた反応容器にｊＥＲ１００１（三菱化学社製、ビスフェノールＡ型エポキシ化合物、エポキシ当量：４７５）５４５．５部と、ジエチレングリコールジメチルエーテル２５９．０部とを仕込んで、加熱溶解させながら、８０℃まで昇温した。溶解後、８０℃にてアクリル酸５９．７部を仕込み、続いてジブチルヒドロキシトルエン０．６部、トリフェニルホスフィン２．４部を仕込み、１１０℃まで１時間かけて昇温しながら撹拌した。１１０℃で３時間保持して反応を続行せしめて、酸価が１．０ｍｇＫＯＨ／ｇ以下となった所で、８０℃にまで下げて、８５％リン酸１２．１部およびジエチレングリコールジメチルエーテル７０．２部からなる混合物を、１時間かけて連続滴下した。滴下終了後も引き続いて、８０℃で４時間反応させ、次いで、ジエチレングリコールジメチルエーテル５０．５部仕込むことにより、不揮発分が６４．０％で、かつ、酸価が９．０なる、リン酸変性エポキシ化合物（Ｃ－１）の溶液を得た。 <Synthesis example of additive>
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 545.5 parts of jER1001 (Mitsubishi Chemical Corporation, bisphenol A type epoxy compound, epoxy equivalent: 475), 259.0 parts of diethylene glycol dimethyl ether, Was heated to 80 ° C. while being heated and dissolved. After dissolution, 59.7 parts of acrylic acid was charged at 80 ° C., followed by 0.6 parts of dibutylhydroxytoluene and 2.4 parts of triphenylphosphine, and stirred while heating to 110 ° C. over 1 hour. The reaction was continued by maintaining at 110 ° C. for 3 hours. When the acid value became 1.0 mgKOH / g or less, the temperature was lowered to 80 ° C., and 12.1 parts of 85% phosphoric acid and 70.2% diethylene glycol dimethyl ether were used. The mixture consisting of parts was continuously added dropwise over 1 hour. The phosphoric acid-modified epoxy having a non-volatile content of 64.0% and an acid value of 9.0 by continuously reacting at 80 ° C. for 4 hours after completion of the dropping and then charging 50.5 parts of diethylene glycol dimethyl ether. A solution of compound (C-1) was obtained.
＜実施例１＞
　ポリオレフィン樹脂（Ａ１）１５部をトルエン／メチルエチルケトン（以下、ＭＥＫという）＝７／３（重量比）１１７．９部に加熱溶解した。冷却後、ｊＥＲ８７１（三菱化学社製、エポキシ当量４３０のダイマー酸変性エポキシ化合物）を５．８部添加して攪拌することで、固形分１５％の接着剤溶液を得た。
　４０μｍのアルミニウム箔に、前記接着剤溶液をバーコーターにて塗布し、１００℃、１分間乾燥し、乾燥後の塗布量が約２ｇ／ｍ2の接着剤層を得た。次いで、前記接着剤層に厚み４０μｍの未延伸ポリプロピレンフィルム（以下ＣＰＰと呼ぶ）を重ね合わせ、８０℃に設定した２つのロール間を通過させ、積層体を得た。その後、得られた積層体を４０℃で３日間または５日間の硬化（エージング）を行った。こうして、得られたアルミニウム箔／ＣＰＰラミネートフィルムを、以下「Ａｌ／ＣＰＰ積層フィルム」と呼ぶ。
　後述する方法に従って、初期接着強度、耐溶剤性、電解質溶液耐性を評価した。結果を表２に示す。 <Example 1>
15 parts of polyolefin resin (A1) was heated and dissolved in 117.9 parts of toluene / methyl ethyl ketone (hereinafter referred to as MEK) = 7/3 (weight ratio). After cooling, 5.8 parts of jER871 (manufactured by Mitsubishi Chemical Corporation, dimer acid-modified epoxy compound having an epoxy equivalent of 430) was added and stirred to obtain an adhesive solution having a solid content of 15%.
The adhesive solution was applied to a 40 μm aluminum foil with a bar coater and dried at 100 ° C. for 1 minute to obtain an adhesive layer having a coating amount of about 2 g / m 2 after drying. Next, an unstretched polypropylene film (hereinafter referred to as CPP) having a thickness of 40 μm was superposed on the adhesive layer and passed between two rolls set at 80 ° C. to obtain a laminate. Thereafter, the obtained laminate was cured (aging) at 40 ° C. for 3 days or 5 days. The aluminum foil / CPP laminate film thus obtained is hereinafter referred to as “Al / CPP laminate film”.
The initial adhesive strength, solvent resistance, and electrolyte solution resistance were evaluated according to the methods described below. The results are shown in Table 2.
＜実施例２～２２＞、＜比較例１～６＞
　表２、３に示す組成にて、実施例１と同様にして接着剤溶液およびＡｌ／ＣＰＰ積層フィルムを得、同様に評価した。 <Examples 2 to 22>, <Comparative Examples 1 to 6>
With the compositions shown in Tables 2 and 3, an adhesive solution and an Al / CPP laminated film were obtained in the same manner as in Example 1 and evaluated in the same manner.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
表２、３中の記号は以下の通り。
Ｐ－４０１：「ユニストールＰ－４０１」、三井化学社製、酸変性ポリオレフィン樹脂、固形分酸価５５ｍｇＫＯＨ/ｇ、加熱残分８％
Ｐ－９０２：「ユニストールＰ－９０２」、三井化学社製、酸変性ポリオレフィン樹脂、固形分酸価５５ｍｇＫＯＨ/ｇ、加熱残分２２％
ｊＥＲ８７１：三菱化学社製ダイマー酸変性エポキシ化合物（エポキシ当量４３０ｇ／ｅｑ）
ＹＤ１７２：新日鉄住金化学社製ダイマー酸変性エポキシ化合物（エポキシ当量６５０ｇ／ｅｑ）
ｊＥＲ６３０：三菱化学社製、Ｎ，Ｎ－ビス（２，３－エポキシプロピル）－４－（２，３－エポキシプロポキシ）アニリン（エポキシ当量９６ｇ／ｅｑ）
ＴＥＴＲＡＤ－Ｃ：三菱ガス化学社製、1，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン（エポキシ当量９１ｇ／ｅｑ）
Ｂ－７：アデカレジンＥＭ－０５１７（アデカ社製、ビスフェノールＡ時グリシジルエーテル型エポキシ樹脂）を水で固形分濃度１０％に希釈したものＢ－８：バソナートＨＷ－１００（ＢＡＳＦ社製非ブロック型の多官能イソシアネート化合物、イソシアネート含有率約１７％）を水で固形分濃度１０％に希釈したもの
８６０：「ＥＰＩＣＬＯＮ８６０」、ＤＩＣ社製、エポキシ当量２４５ｇ／ｅｑのビスフェノールＡ型エポキシ樹脂
ＴＰＰ：トリフェニルホスフィン
混合溶剤１：トルエン／メチルエチルケトン＝７／３（質量比）
混合溶剤２：トルエン／イソプロピルアルコール＝８／２（質量比）
混合溶剤３：メチルシクロヘキサン／イソプロピルアルコール＝８／２（質量比） The symbols in Tables 2 and 3 are as follows.
P-401: “Unistor P-401”, manufactured by Mitsui Chemicals, acid-modified polyolefin resin, solid content acid value 55 mgKOH / g, heating residue 8%
P-902: “Unistor P-902”, manufactured by Mitsui Chemicals, acid-modified polyolefin resin, solid content acid value 55 mgKOH / g, heating residue 22%
jER871: Dimer acid-modified epoxy compound manufactured by Mitsubishi Chemical Corporation (epoxy equivalent 430 g / eq)
YD172: Nippon Steel & Sumikin Chemical Co., Ltd. dimer acid-modified epoxy compound (epoxy equivalent 650 g / eq)
jER630: Mitsubishi Chemical Corporation, N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) aniline (epoxy equivalent 96 g / eq)
TETRAD-C: manufactured by Mitsubishi Gas Chemical Company, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (epoxy equivalent 91 g / eq)
B-7: Adeka Resin EM-0517 (manufactured by Adeka, glycidyl ether type epoxy resin with bisphenol A) diluted with water to a solid content concentration of 10% B-8: Vasonate HW-100 (non-block type manufactured by BASF) Polyfunctional isocyanate compound, isocyanate content of about 17%) diluted with water to a solid content concentration of 10% 860: “EPICLON 860”, manufactured by DIC, bisphenol A type epoxy resin TPP with epoxy equivalent of 245 g / eq: triphenylphosphine Mixed solvent 1: toluene / methyl ethyl ketone = 7/3 (mass ratio)
Mixed solvent 2: toluene / isopropyl alcohol = 8/2 (mass ratio)
Mixed solvent 3: methylcyclohexane / isopropyl alcohol = 8/2 (mass ratio)
［相溶性］
　１００μｍのＰＥＴフィルムに、接着剤溶液をバーコーターにて塗布し、１００℃、１分間乾燥し、乾燥後の塗布量が約２ｇ／ｍ2の接着剤層を得た。この積層フィルムを、ＪＩＳ　Ｋ７１３６に準じ、ヘイズを測定することにより相溶性を、以下の基準にて判定した。
　Ａ　：３未満
　Ｂ　：３以上～５未満
　Ｃ　：５以上 [Compatibility]
The adhesive solution was applied to a 100 μm PET film with a bar coater and dried at 100 ° C. for 1 minute to obtain an adhesive layer having a coating amount after drying of about 2 g / m 2 . By measuring the haze of this laminated film according to JIS K7136, the compatibility was determined according to the following criteria.
A: Less than 3 B: 3 or more and less than 5 C: 5 or more
［初期接着強度］
　Ａｌ／ＣＰＰ積層フィルムを、２５℃、湿度６５％の環境下で６時間静置後、それぞれ２００ｍｍ×１５ｍｍの大きさに切断し、ＡＳＴＭ－Ｄ１８７６－６１の試験法に準じ、引張り試験機を用いて、２５℃、湿度６５％の環境下で、剥離速度１００ｍｍ／分でＴ型剥離試験を行った。アルミニウム箔／ＣＰＰ間の１５ｍｍ巾の剥離強度（Ｎ）を５個の試験片の平均値で示す。以下の基準にて判定した。
　Ａ　：１０Ｎ以上
　Ｂ　：５Ｎ以上～１０Ｎ未満
　Ｃ　：５Ｎ未満 [Initial bond strength]
The Al / CPP laminated film was allowed to stand for 6 hours in an environment of 25 ° C. and 65% humidity, then cut to a size of 200 mm × 15 mm, and a tensile tester was used according to the test method of ASTM-D1876-61. Then, a T-type peel test was performed at a peel rate of 100 mm / min in an environment of 25 ° C. and a humidity of 65%. The peel strength (N) of 15 mm width between the aluminum foil / CPP is shown as an average value of five test pieces. Judgment was made according to the following criteria.
A: 10N or more B: 5N or more to less than 10N C: less than 5N
［耐溶剤性、電解質溶液耐性（接着強度の変化）］
　初期接着強度試験に用いたのと同様の試験片を、下記の有機溶剤、電解質溶液にそれぞれ２週間浸漬した。その後、試験片を取り出し約１０分程度流水で洗浄し、ペーパーワイパーで水を充分に拭き取った後に試験片の接着強度を、浸漬試験前の接着強度測定と同様にして測定した。以下の基準にて判定した。
　Ａ　：初期接着強度に対して、変化率が±１０％未満
　Ｂ　：初期接着強度に対して、変化率が±３０％未満
　Ｃ　：初期接着強度に対して、変化率が±３０％以上
［有機溶剤］：４０℃のエチレンカーボネート。
［電解質溶液］：１．５ｍｏｌ／Ｌになるように６フッ化リン酸リチウムをエチレンカーボネート／ジエチルカーボネート／ジメチルカーボネート＝１／１／１（容積比）に溶解した溶液としたもの。温度は８５℃とした。 [Solvent resistance, electrolyte solution resistance (change in adhesive strength)]
Test pieces similar to those used in the initial adhesive strength test were immersed in the following organic solvent and electrolyte solution for 2 weeks, respectively. Thereafter, the test piece was taken out and washed with running water for about 10 minutes. After sufficiently wiping off the water with a paper wiper, the adhesive strength of the test piece was measured in the same manner as the adhesive strength measurement before the immersion test. Judgment was made according to the following criteria.
A: Change rate is less than ± 10% with respect to initial bond strength B: Change rate is less than ± 30% with respect to initial bond strength C: Change rate with respect to initial bond strength is ± 30% or more [organic Solvent]: 40 ° C. ethylene carbonate.
[Electrolyte solution]: A solution prepared by dissolving lithium hexafluorophosphate in ethylene carbonate / diethyl carbonate / dimethyl carbonate = 1/1/1 (volume ratio) so as to be 1.5 mol / L. The temperature was 85 ° C.
　表２の実施例１～１９に示すように、エージング期間が短くても接着強度（初期、有機溶剤及び電解質溶液浸漬後）が良好な接着剤を提供することができる。
　比較例１および５の接着剤は、重合脂肪酸変性部位を含有しないエポキシ化合物であり、本発明のエポキシ化合物（Ｂ）よりポリオレフィンとの相溶性が悪いために短期間でのエージングでは接着強度が発現しにくく、有機溶剤や電解質溶液に浸漬後、接着強度が著しく低下する。
　比較例２の接着剤は、ビスフェノールＡ型のエポキシ樹脂に加え、耐溶剤性の低いイソシアネート化合物を硬化剤に用いるので、比較例１よりさらに耐溶剤性が落ちている。
　比較例３および４の接着剤は、リン酸エポキシを用いるので、比較例５に比して耐溶剤性は向上するが、短期間のエージングでは接着強度が充分発現しない。
　比較例４および６の接着剤は、酸無水物またはカルボキシル基と、エポキシ基の反応の触媒になるトリフェニルホスフィンやアミノ基を有するエポキシ化合物を用いていても、短期間のエージングでは接着強度が充分発現しない。 As shown in Examples 1 to 19 in Table 2, an adhesive having good adhesive strength (initially, after immersion in an organic solvent and an electrolyte solution) can be provided even if the aging period is short.
The adhesives of Comparative Examples 1 and 5 are epoxy compounds that do not contain a polymerized fatty acid-modified site, and have poorer compatibility with polyolefins than the epoxy compound (B) of the present invention, so that adhesive strength is manifested in aging in a short period of time. The adhesion strength is significantly reduced after immersion in an organic solvent or electrolyte solution.
Since the adhesive of Comparative Example 2 uses an isocyanate compound having low solvent resistance as a curing agent in addition to the bisphenol A type epoxy resin, the solvent resistance is further deteriorated compared to Comparative Example 1.
Since the adhesives of Comparative Examples 3 and 4 use phosphoric acid epoxy, the solvent resistance is improved as compared with Comparative Example 5, but the adhesive strength is not sufficiently exhibited by short-term aging.
Even if the adhesive of Comparative Examples 4 and 6 uses an epoxy compound having an acid anhydride or a carboxyl group and a triphenylphosphine or an amino group as a catalyst for the reaction of the epoxy group, the adhesive strength is low when aging is performed for a short period of time. Not fully expressed.
　また、各実施例の積層体（長方形）２枚を用い、ＣＰＰが内面となるよう３辺をヒートシールし、パウチ（袋）を作成した。擬似電極端子としての２つアルミニウム片同士は相互には接触させずに、開放端における２枚の積層体で挟みヒートシールした場合、高温（１５０～２００℃）、高圧（０．５～３．０ｋｇ／ｃｍ2）でヒートシールしても、接着剤層が溶融したり著しく変形したりすることはなかった。
　しかし、硬化剤にイソシアネート化合物を併用した比較例２では、高温・高圧下でヒートシールした場合に接着剤が溶融して端部からはみ出した結果、擬似電極端子とアルミニウムが接触することにより、絶縁性を確保できない場合があった。 In addition, two laminates (rectangles) of each example were used, and three sides were heat-sealed so that the CPP became the inner surface, and a pouch (bag) was created. When two aluminum pieces as pseudo electrode terminals are not brought into contact with each other and are heat-sealed by sandwiching them between two laminates at the open end, high temperature (150 to 200 ° C.), high pressure (0.5 to 3. Even when heat-sealing at 0 kg / cm 2 ), the adhesive layer did not melt or deform significantly.
However, in Comparative Example 2 in which an isocyanate compound is used in combination with the curing agent, when the heat seal is performed under high temperature and high pressure, the adhesive melts and protrudes from the end portion. In some cases, the sex could not be secured.
　本発明に係る接着剤組成物は、リチウムイオン電池や電気二重層キャパシタ、リチウムイオンキャパシタ等の蓄電デバイスの容器を形成するための包材用（積層体）に好適に使用できる。
　その他、本発明に係る接着剤組成物は、蓄電デバイスの容器を形成するための包材の他、建築、化学、医療、自動車などのように高接着強度、耐薬品性が求められる各種産業分野における積層体の形成に好適に使用される。 The adhesive composition according to the present invention can be suitably used for a packaging material (laminate) for forming a container for an electricity storage device such as a lithium ion battery, an electric double layer capacitor, or a lithium ion capacitor.
In addition, the adhesive composition according to the present invention is a packaging material for forming a container for an electricity storage device, as well as various industrial fields that require high adhesive strength and chemical resistance, such as architecture, chemistry, medicine, and automobiles. It is used suitably for formation of the laminated body in.
　この出願は、２０１５年３月２５日に出願された日本出願特願２０１５－０６３１５０を基礎とする優先権を主張し、その開示の全てをここに取り込む。 This application claims priority based on Japanese Patent Application No. 2015-063150 filed on March 25, 2015, the entire disclosure of which is incorporated herein.
１１　　樹脂フィルム層
１２　　金属箔層
１３　　接着剤層
１４　　ヒートシール層 11 Resin film layer 12 Metal foil layer 13 Adhesive layer 14 Heat seal layer

Claims (13)

  1. 　金属箔層とヒートシール層とを接着剤層を介して積層するための接着剤組成物であって、
    　カルボキシル基もしくは酸無水物基を有するポリオレフィン樹脂（Ａ）と、不飽和脂肪酸の重合体（Ｂ１）と２つ以上のエポキシ基を有する化合物（Ｂ２）との反応により得られるエポキシ化合物（Ｂ）とを含有することを特徴とする接着剤組成物。     An adhesive composition for laminating a metal foil layer and a heat seal layer via an adhesive layer,
    An epoxy compound (B) obtained by a reaction between a polyolefin resin (A) having a carboxyl group or an acid anhydride group, a polymer (B1) of an unsaturated fatty acid and a compound (B2) having two or more epoxy groups; An adhesive composition comprising:
  2. 　エポキシ化合物（Ｂ）が、不飽和脂肪酸の重合体（Ｂ１）と２つ以上のエポキシ基を有する化合物（Ｂ２）との反応生成物を、さらに水添することにより得られるエポキシ化合物であることを特徴とする請求項１記載の接着剤組成物。 The epoxy compound (B) is an epoxy compound obtained by further hydrogenating a reaction product of a polymer (B1) of an unsaturated fatty acid and a compound (B2) having two or more epoxy groups. The adhesive composition according to claim 1.
  3. 　不飽和脂肪酸の重合体（Ｂ１）が、炭素数が１２～２４個の不飽和脂肪酸を２量化させた化合物および３量化させた化合物の少なくとも一方であることを特徴とする請求項１または２記載の接着剤組成物。 3. The unsaturated fatty acid polymer (B1) is at least one of a compound obtained by dimerizing and trimerizing an unsaturated fatty acid having 12 to 24 carbon atoms. Adhesive composition.
  4. 　２つ以上のエポキシ基を有する化合物（Ｂ２）が、ビスフェノールＡ型エポキシ化合物およびビスフェノールＦ型エポキシ化合物の少なくとも一方から選ばれることを特徴とする請求項１～３いずれか１項に記載の接着剤組成物。 The adhesive according to any one of claims 1 to 3, wherein the compound (B2) having two or more epoxy groups is selected from at least one of a bisphenol A type epoxy compound and a bisphenol F type epoxy compound. Composition.
  5. 　前記エポキシ化合物（Ｂ）のエポキシ当量が２００～７０００であることを特徴とする請求項１～４いずれか１項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 4, wherein an epoxy equivalent of the epoxy compound (B) is 200 to 7000.
  6. 　前記ポリオレフィン樹脂（Ａ）の質量平均分子量が５万～５０万であることを特徴とする請求項１～５いずれか１項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 5, wherein the polyolefin resin (A) has a mass average molecular weight of 50,000 to 500,000.
  7. 　前記ポリオレフィン樹脂（Ａ）が、１－ブテンと他のオレフィンとから得られる共重合体を、さらに酸変性することにより得られることを特徴とする請求項１～６いずれか１項に記載の接着剤組成物。 The adhesive according to any one of claims 1 to 6, wherein the polyolefin resin (A) is obtained by further acid-modifying a copolymer obtained from 1-butene and another olefin. Agent composition.
  8. 　前記ポリオレフィン樹脂（Ａ）１グラム当たりのカルボキシル基の含有量をＸミリモル、酸無水物基の含有量をＹミリモルとした場合に、Ｘ＋２Ｙが０．０５～０．６であることを特徴とする請求項１～７いずれか１項に記載の接着剤組成物。 When the content of carboxyl groups per gram of the polyolefin resin (A) is X mmol and the content of acid anhydride groups is Y mmol, X + 2Y is 0.05 to 0.6. The adhesive composition according to any one of claims 1 to 7.
  9. 　前記ポリオレフィン樹脂（Ａ）の含有量をＰグラム、前記エポキシ化合物（Ｂ）中のエポキシ基をＺミリモルとした場合に、Ｚ／［（Ｘ＋２Ｙ）Ｐ］が０．３～１０であることを特徴とする請求項８記載の接着剤組成物。 Z / [(X + 2Y) P] is 0.3 to 10 when the content of the polyolefin resin (A) is P grams and the epoxy group in the epoxy compound (B) is Z mmol. The adhesive composition according to claim 8.
  10. 　請求項１～９いずれか１項に記載の接着剤組成物から形成される接着剤層を介して、金属箔層とヒートシール層とが積層されてなる積層体。 A laminate comprising a metal foil layer and a heat seal layer laminated via an adhesive layer formed from the adhesive composition according to any one of claims 1 to 9.
  11. 　外層から順に、樹脂フィルム層、金属箔層、接着剤層、ヒートシール層を必須とする蓄電デバイス用包装材において、
    　前記接着剤層が請求項１～９いずれか１項に記載の接着剤組成物から形成されることを特徴とする蓄電デバイス用包装材。     In order from the outer layer, in a packaging material for an electricity storage device that requires a resin film layer, a metal foil layer, an adhesive layer, and a heat seal layer,
    A packaging material for an electricity storage device, wherein the adhesive layer is formed from the adhesive composition according to any one of claims 1 to 9.
  12. 　請求項１１記載の蓄電デバイス用包装材から形成されてなる蓄電デバイス用容器であって、ヒートシール層が内面を構成している、蓄電デバイス用容器。 An electrical storage device container formed from the electrical storage device packaging material according to claim 11, wherein the heat seal layer constitutes the inner surface.
  13. 　請求項１２記載の蓄電デバイス用容器を使用してなる蓄電デバイス。 An electrical storage device using the electrical storage device container according to claim 12.
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CN109423240B (en) * 2017-08-23 2020-12-29 藤森工业株式会社 Adhesive resin composition and laminate
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CN111133075A (en) * 2017-10-04 2020-05-08 Dic株式会社 Adhesive, laminate, battery member, and battery
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JP7254670B2 (en) 2019-09-26 2023-04-10 東洋紡株式会社 laminate

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JP5900680B1 (en) 2016-04-06
JP2016183223A (en) 2016-10-20
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TWI695870B (en) 2020-06-11
CN107429133B (en) 2019-07-02

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