TWI620805B - 金屬箔與樹脂薄膜之層合用黏著劑、層合體、電池外裝用包裝材以及電池外殼、及其製造方法 - Google Patents

金屬箔與樹脂薄膜之層合用黏著劑、層合體、電池外裝用包裝材以及電池外殼、及其製造方法 Download PDF

Info

Publication number
TWI620805B
TWI620805B TW105141842A TW105141842A TWI620805B TW I620805 B TWI620805 B TW I620805B TW 105141842 A TW105141842 A TW 105141842A TW 105141842 A TW105141842 A TW 105141842A TW I620805 B TWI620805 B TW I620805B
Authority
TW
Taiwan
Prior art keywords
adhesive
resin film
metal foil
laminating
metal
Prior art date
Application number
TW105141842A
Other languages
English (en)
Other versions
TW201736558A (zh
Inventor
Hiroto Kouka
Kazunari Fukase
Yasuhiro Nakagawa
Original Assignee
Showa Denko Kk
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 Showa Denko Kk filed Critical Showa Denko Kk
Publication of TW201736558A publication Critical patent/TW201736558A/zh
Application granted granted Critical
Publication of TWI620805B publication Critical patent/TWI620805B/zh

Links

Classifications

    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • B32B15/082—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 vinyl resins; comprising acrylic resins
    • 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
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/24—Layered products comprising a layer of synthetic resin characterised by the use of special additives using solvents or swelling agents
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • 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
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • 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
    • 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
    • B32B27/36—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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6204—Polymers of olefins
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • 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
    • 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
    • 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
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H01M50/133—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/154—Coating solid articles, i.e. non-hollow articles
    • B29C48/155—Partial coating thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/08—Deep drawing or matched-mould forming, i.e. using mechanical means only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0097—Glues or adhesives, e.g. hot melts or thermofusible adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2305/00—Use of metals, their alloys or their compounds, as reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7146—Battery-cases
    • 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
    • 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
    • B32B2250/04—4 layers
    • 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
    • B32B2250/05—5 or more layers
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2274/00—Thermoplastic elastomer material
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • 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
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/752—Corrosion inhibitor
    • 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
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • 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
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • 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
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本發明係具有多元醇(A)、聚異氰酸酯的多聚物(B)、以及作為7族及12族中的至少1種金屬的化合物之金屬化合物(C)的金屬箔與樹脂薄膜之層合用黏著劑，聚異氰酸酯的多聚物(B)包含飽和脂肪族聚異氰酸酯的多聚物及飽和脂環式聚異氰酸酯的多聚物。本發明之層合體係隔著由本發明的層合用黏著劑所得之黏著劑層而層合金屬箔與樹脂薄膜。本發明之電池外裝用包裝材係使用本發明之層合體而得到。本發明之電池外殼係使用本發明之電池外裝用包裝材而得到。本發明的外殼之製造方法係將本發明之電池外裝用包裝材進行深拉成形或拉伸成形。藉由本發明，可提供具有優異的黏著力，耐熱性、耐電解液性優異的金屬箔與樹脂薄膜之層合用黏著劑等。

Description

金屬箔與樹脂薄膜之層合用黏著劑、層合體、電池外裝用包裝材以及電池外殼、及其製造方法
本發明關於適合鋰離子電池等二次電池之外裝材用的黏著劑之金屬箔與樹脂薄膜之層合用黏著劑、使用該金屬箔與樹脂薄膜之層合用黏著劑所製造的層合體、使用該層合體之電池外裝用包裝材、將該電池外裝用包裝材予以成形而得到的電池外殼、及該電池外殼之製造方法。
近年來，筆記型個人電腦、行動電話等的電子機器係進行小型化、輕量化、薄型化。因此，對於電子機器用的二次蓄電池，亦要求高能量密度化、輕量化，代替以往之鉛蓄電池或鎳氫電池，具有高能量密度的鋰離子電池之開發係旺盛地進行。再者，對於電動汽車或混合動力車之電源亦可使用的鋰離子電池係實用化。
於鋰離子電池中，使用包含鋰的化合物作為正極材料，使用石墨或焦炭等的碳材料作為負極材料。再者，於正極及負極之間，具備在碳酸伸乙酯、碳酸伸丙 酯、碳酸二乙酯等之具有浸透力的非質子性溶劑中溶解有LiPF6、LiBF4等的鋰鹽作為電解質之電解液，或由含浸有該電解液的聚合物凝膠所成之電解質層。
自以往以來，作為電池外殼用包裝材，已知依順序層合有作為外側層的耐熱性樹脂延伸薄膜層、鋁箔層與作為內側層的熱塑性樹脂未延伸薄膜層之層合體。使用如此構造的電池外殼用包裝材而得到電池外殼時，如電解液之具有浸透力的溶劑若通過電池之外裝所用的層合體中之成為密封劑的薄膜層，則鋁箔層與樹脂薄膜層間之層合強度降低，很可能成為電解液漏出之原因。因此，開發出於鋁箔層與內側層之間，隔著黏著劑層而黏著之電池外殼用包材，該黏著劑層含有：含有酸酐基或羧基、羥基等之與異氰酸酯有反應性的官能基之樹脂、與多官能異氰酸酯化合物。
例如，專利文獻1~3中記載使用使改性聚烯烴樹脂與多官能異氰酸酯化合物溶解或分散於有機溶劑中之溶劑型黏著劑，形成黏著劑層之方法，該改性聚烯烴樹脂係對於丙烯的均聚物或丙烯與乙烯之共聚物，接枝聚合有乙烯性不飽和羧酸或其酐者。
然而，專利文獻1~3之改性聚烯烴樹脂係強烈受到塗佈‧熟化時的濕度或層合體的基材之厚度等左右黏著劑層中所含有的水分量之要素的影響，有在其黏著力發生偏差而耐電解液性差之問題。
[先前術文獻] [專利文獻]
[專利文獻1]日本特開2010-92703號公報
[專利文獻2]日本特開2014-89985號公報
[專利文獻3]WO2013/114934號
本發明係在如此的先前技術之下完成者，其目的在於提供一種層合用金屬箔與樹脂薄膜之層合用黏著劑，其具有優異的黏著力，其黏著力係早期且安定地展現，耐電解液性優異。又，本發明之另一目的在於提供一種金屬箔與樹脂薄膜之層合體，其係耐電解液性優異，適合電池外裝用包裝材。再者，本發明之其他目的在於提供使用由該層合體所成之電池外裝用包裝材而形成的耐電解液性優異之電池外殼及其製造方法。
即，本發明關於以下之[1]~[15]。
[1]一種金屬箔與樹脂薄膜之層合用黏著劑，其係具有：具有羧基的聚烯烴樹脂(A)、與多官能異氰酸酯化合物(B)、以及作為7族及12族中的至少1種金屬的化合物的金屬化合物(C)。
[2]如上述[1]記載之金屬箔與樹脂薄膜之層合用黏著劑，其中，前述具有羧基的聚烯烴樹脂(A)包含改性聚烯烴樹脂，該改性聚烯烴樹脂係包含丙烯或丙烯與乙烯、及乙烯性不飽和羧酸或其酸酐來作為單體單元。
[3]如上述[1]或[2]記載之金屬箔與樹脂薄膜之層合用黏著劑，其中，前述具有羧基的聚烯烴樹脂(A)包含在130℃下測得的MFR為5g/10分~42g/10分的具有羧基的聚烯烴樹脂。
[4]如上述[1]~[3]中任一項記載之金屬箔與樹脂薄膜之層合用黏著劑，其中，前述多官能異氰酸酯化合物(B)包含聚異氰酸酯的多聚物。
[5]如上述[1]~[4]中任一項記載之金屬箔與樹脂薄膜之層合用黏著劑，其中，前述聚異氰酸酯的多聚物包含聚異氰酸酯的異三聚氰酸酯物。
[6]如上述[1]~[5]中任一項記載之金屬箔與樹脂薄膜之層合用黏著劑，其中，相對於前述具有羧基的聚烯烴樹脂(A)中所包含的羧基數而言，多官能異氰酸酯化合物(B)中所包含的異氰酸基數之比率為0.5~13。
[7]如上述[1]~[6]中任一項記載之金屬箔與樹脂薄膜之層合用黏著劑，其中，前述金屬化合物(C)包含7族及12族中的至少1種金屬的羧酸鹽至少1種以上。
[8]如上述[1]~[7]中任一項記載之金屬箔與樹脂薄膜之層合用黏著劑，其中，前述金屬化合物(C)包含鋅或錳的羧酸鹽。
[9]如上述[1]~[8]中任一項記載之金屬箔與樹脂薄膜之層合用黏著劑，其中，進而包含溶劑(D)。
[10]一種層合體，其係金屬箔與樹脂薄膜隔著黏著劑層並經層合而成，該黏著劑層係由上述[1]~[9]中任一項記載金屬箔與樹脂薄膜之層合用黏著劑而得到。
[11]如上述[10]記載之層合體，其中，前述金屬箔為鋁箔，前述樹脂薄膜含有熱熔著性樹脂薄膜。
[12]如上述[10]或[11]記載之層合體，其中，前述金屬箔之厚度為10~100μm，前述樹脂薄膜之厚度為9~100μm。
[13]一種電池外裝用包裝材，其係使用上述[10]~[12]中任一項記載之層合體而得到。
[14]一種電池外殼，其係使用上述[13]記載之電池外裝用包裝材而得到。
[15]一種電池外殼之製造方法，其係將上述[13]記載之電池外裝用包裝材進行深拉成形或拉伸成形。
本發明之金屬箔與樹脂薄膜之層合用黏著劑係黏著力優異，使用該金屬箔與樹脂薄膜之層合用黏著劑所形成之金屬箔與樹脂薄膜之層合體，由於耐電解液性優異，而適合作為鋰離子電池等的二次電池之製作所用的電池外裝用包裝材之材料。又，使用本發明之電池外裝用包裝材所形成的電池外殼，係耐電解液性優異，藉由使用 其，可提供壽命長的安全之二次電池。
[實施發明的形態] [金屬箔與樹脂薄膜之層合用黏著劑]
本實施形態的金屬箔與樹脂薄膜之層合用黏著劑係具有：具有羧基的聚烯烴樹脂(A)、與多官能異氰酸酯化合物(B)、以及作為7族及12族中的至少1種金屬的化合物的金屬化合物(C)。
於本實施形態的金屬箔與樹脂薄膜之層合用黏著劑中，前述具有羧基的聚烯烴樹脂(A)係相當於主劑，多官能異氰酸酯化合物(B)係相當於硬化劑，金屬化合物(C)係相當於反應促進劑。
本實施形態的金屬箔與樹脂薄膜之層合用黏著劑係可適用於金屬箔與樹脂薄膜之黏著，特別有用作為金屬箔與樹脂薄膜之層合用的黏著劑，其層合體係可適用作為電池外裝用包裝材。
此處，本說明書中的「~」係意指「~」記載的前方之值以上且「~」記載的後方之值以下。
<具有羧基的聚烯烴樹脂(A)>
本實施形態所用之具有羧基的聚烯烴樹脂(以下亦稱為「(A)成分」或「(A)」)只要是在分子構造中含 有羧基者，則沒有特別的限制。再者，此處所言的羧基，就是除了來自羧酸的構成單元，還包含來自羧酸酐的構成單元。作為如此的樹脂，例如可舉出將具有羧基的單體接枝聚合於聚烯烴者，將具有羧基的單體與烯烴共聚合者，或組合彼等而共聚合者等。
作為具有羧基的單體，例如可舉出丙烯酸、甲基丙烯酸等之乙烯性不飽和羧酸、馬來酸酐、檸康酸酐、伊康酸酐等之乙烯性不飽和羧酸酐、(甲基)丙烯酸β-羧基乙酯等之含有羧基的乙烯性不飽和羧酸酯等，其中較佳為馬來酸酐。
又，亦可包含不具有羧基的乙烯性不飽和羧酸酯作為單體單元。作為不具有羧基的乙烯性不飽和羧酸酯，例如可舉出丙烯酸或甲基丙烯酸與碳數1~20之不具有羧基的醇之酯化物，可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十八酯等。亦可使用此等的混合物。再者，本說明書中所謂的「具有羧基的聚烯烴樹脂(A)包含~作為單體單元」，就是指「包含~作為將具有羧基的聚烯烴樹脂(A)聚合時的原料單體」。
作為聚烯烴樹脂，可舉出包含乙烯、丙烯、丁烯、戊烯、己烯、庚烯、辛烯、4-甲基-1-戊烯等的單烯烴作為單體單元者，再者可舉出包含環戊烯、環己烯等的 脂環族烯烴、1,4-己二烯、1,5-己二烯、二乙烯基苯、1,3-環戊二烯、1,3-環己二烯、5-乙烯基-2-降莰烯等的鏈狀或環狀的多烯、苯乙烯、取代苯乙烯等的芳香族乙烯系化合物作為單體單元者等。其中，從對於聚烯烴基材的密著性之觀點來看，較佳為包含丙烯、或乙烯與丙烯作為單體單元者。
具有羧基的聚烯烴樹脂(A)較佳為包含在130℃下測得的MFR(熔體質量流速)為5g/10分~42g/10分的具有羧基的聚烯烴樹脂。若MFR為5g/10分以上，則由本實施形態的金屬箔與樹脂薄膜之層合用黏著劑所得之黏著劑層的黏著力即使接觸電解液也難以降低，若MFR為42g/10分以下，則本實施形態的金屬箔與樹脂薄膜之層合用黏著劑的塗佈時之操作性良好。再者，本說明書中的MFR係以JIS K 7210中記載之方法，在溫度130℃、荷重2160g之條件下而得到之值。具有羧基的聚烯烴樹脂(A)在130℃下測得的MFR更佳為8g/10分~40g/10分，尤佳為12g/10分~40g/10分。
具有羧基的聚烯烴樹脂(A)之酸價較佳為3~60mgKOH/g，更佳為5~50mgKOH/g，尤佳為5~45mgKOH/g。若酸價為3mgKOH/g以上，則由本實施形態的金屬箔與樹脂薄膜之層合用黏著劑所得的黏著劑層之黏著力係即使接觸電解液也難以降低，若為60mgKOH/g以下，則本實施形態的金屬箔與樹脂薄膜之層合用黏著劑的塗佈時之操作性良好。再者，本說明書中的酸價係以 JIS 0070中記載之方法而得到之值。
<多官能異氰酸酯化合物(B)>
作為本實施形態中使用的多官能異氰酸酯化合物(B)(以下亦稱為「(B)成分」或「(B)」)，只要是含有2個以上的異氰酸基之聚異氰酸酯或其多聚物，則沒有特別的限制。本實施形態中的多官能異氰酸酯化合物(B)係作為硬化劑摻合於本實施形態的金屬箔與樹脂薄膜之層合用黏著劑中。
作為多官能異氰酸酯化合物(B)，例如可舉出1,4-環己烷二異氰酸酯、異佛爾酮二異氰酸酯、亞甲基雙(4-環己基異氰酸酯)、1,3-雙(異氰酸根甲基)環己烷、1,4-雙(異氰酸根甲基)環己烷、降莰烷二異氰酸酯等之飽和脂環式二異氰酸酯；2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、二苯基甲烷-4,4’-二異氰酸酯、1,3-苯二甲基二異氰酸酯、1,4-苯二甲基二異氰酸酯等之芳香族二異氰酸酯；六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯等之脂肪族二異氰酸酯、或此等的脲基甲酸酯化多聚物；異三聚氰酸酯物；及縮二脲改性物等。此等係可單獨或2種以上混合使用。更佳為脲基甲酸酯化多聚物、異三聚氰酸酯物、縮二脲改性物等之聚異氰酸酯的多聚物。藉由使聚異氰酸酯成為多聚物，金屬箔與樹脂薄膜之層合用黏著劑係成為耐電解液性優異。其理由雖然未明，但推測因為異三聚氰 酸酯物及脲基甲酸酯化多聚物等之構造係耐電解液性優異。於此等聚異氰酸酯的多聚物之中，聚異氰酸酯的異三聚氰酸酯物尤其耐電解液性優異而較佳。
相對於具有羧基的聚烯烴樹脂(A)中所包含的羧基數而言，多官能異氰酸酯化合物(B)中所包含的異氰酸基數之比率(以下亦稱為NCO/COOH比)較佳為0.3~15，更佳為0.5~10，尤佳為0.8~10。若NCO/COOH比為0.3以上，則由本實施形態的金屬箔與樹脂薄膜之層合用黏著劑所得之黏著劑層尤其對於樹脂薄膜的黏著力變良好，若NCO/COOH比為15以下，則由本實施形態的金屬箔與樹脂薄膜之層合用黏著劑所得之黏著劑層的黏著力，係即使接觸電解液也難以降低。再者，於NCO/COOH比的算出之際，當羧基為來自羧酸酐的構成單元時，將1莫耳當作相當於來自羧酸的構成單元之羧基2莫耳者計算。
<作為7族及12族中的至少1種金屬的化合物的金屬化合物(C)>
本實施形態之作為週期表之7族及12族中的至少1種金屬的化合物的金屬化合物(C)(以下，亦稱為「7族及/或12族的金屬化合物(C)」或「金屬化合物(C)」或「(C)成分」或「(C)」)，係作為促進本實施形態的金屬箔與樹脂薄膜之層合用黏著劑中之具有羧基的聚烯烴樹脂(A)及多官能異氰酸酯化合物(B)之 反應用的反應促進劑而摻合者。
本實施形態中使用之作為7族及12族中的至少1種金屬的化合物的金屬化合物(C)，係可單獨或併用包含由錳、鎝、錸所選出的7族、由鋅、鎘、汞所選出的12族之各金屬元素的化合物。
作為7族及12族中的至少1種金屬的化合物的金屬化合物(C)，例如可舉出金屬己酸鹽、金屬辛酸鹽(2-乙基己酸鹽)、金屬新癸酸鹽、金屬硬脂酸鹽、金屬油酸鹽等的金屬羧酸鹽、金屬乙醯丙酮化物等。其中，從長期電解液浸漬後的黏著強度之觀點來看，金屬化合物(C)較佳為包含7族及12族中的至少1種金屬的羧酸鹽至少1種以上，更佳為包含由鋅及錳所選出之金屬的羧酸鹽至少1種以上，更佳為包含鋅的羧酸鹽。
具體而言，作為7族及12族中的至少1種金屬的化合物的金屬化合物(C)，較佳為新癸酸鋅(C20H38O4Zn)、2-乙基己酸鋅(辛酸鋅、己酸鹽(hexoate)鋅、(C16H30O4Zn)、硬脂酸鋅(C36H70O4Zn)、乙醯丙酮化鋅(C10H14O4Zn)、2-乙基己酸錳(辛酸錳、己酸鹽錳、C16H30O4Mn)，更佳為新癸酸鋅(C20H38O4Zn)、2-乙基己酸鋅(辛酸鋅、己酸鹽鋅、C16H30O4Zn)。
作為(C)成分以外之反應促進劑，亦可併用作為有機錫化合物的二月桂酸二丁錫、二月桂酸二辛錫、二乙酸二辛錫、或作為三級胺的2,4,6-三(二甲基胺基甲基)苯酚、二甲基苯胺、二甲基對甲苯胺、N,N-二(β-羥 基乙基)-p-甲苯胺等。
相對於具有羧基的聚烯烴樹脂(A)100質量份而言，作為7族及12族中的至少1種金屬的化合物的金屬化合物(C)之比率係沒有特別的限制，但相對於具有羧基的聚烯烴樹脂(A)100質量份而言，金屬化合物(C)之含量以金屬的質量換算，較佳為0.0001質量份~5質量份，更佳為0.0005質量份~5質量份，尤佳為0.001質量份~5質量份。若為0.0001質量份以上，則由本發明的金屬箔與樹脂薄膜之層合用黏著劑所得的黏著劑層之黏著力係即使長期間浸漬於電解後也充分地高，若為5質量份以下，則常態的黏著強度變高。再者，7族及/或12族的金屬化合物(C)係可在具有羧基的聚烯烴樹脂(A)之製造時添加，也可在黏著劑之調製時添加。
<溶劑(D)>
本實施形態的金屬箔與樹脂薄膜之層合用黏著劑亦可包含溶劑(D)(以下，亦稱為「(D)成分」或「(D)」)。
溶劑(D)只要是能溶解或分散具有羧基的聚烯烴樹脂(A)、多官能異氰酸酯化合物(B)及作為7族及12族中的至少1種金屬的化合物的金屬化合物(C)，則沒有特別的限制。例如，可舉出甲苯、二甲苯等之芳香族系有機溶劑，環己烷、甲基環己烷、乙基環己烷等之脂環式系有機溶劑，正己烷、正庚烷等之脂肪族系有機溶劑，醋 酸乙酯、醋酸丙酯、醋酸丁酯等之酯系有機溶劑，丙酮、甲基乙基酮、甲基丁基酮等之酮系有機溶劑等。此等係可單獨或2種以上混合使用。
於此等之中，特別地從具有羧基的聚烯烴樹脂(A)之溶解性的觀點來看，較佳為醋酸乙酯、醋酸丙酯、醋酸丁酯、甲苯、甲基環己烷、甲基乙基酮，更佳為醋酸乙酯、甲苯、甲基環己烷。
於本實施形態的金屬箔與樹脂薄膜之層合用黏著劑中，溶劑(D)之含量較佳為30~95質量%，更佳為40~90質量%，尤佳為50~80質量%。若為30質量%以上，則本實施形態的金屬箔與樹脂薄膜之層合用黏著劑之塗佈時的操作性變良好，若為95質量%以下，則將本實施形態的金屬箔與樹脂薄膜之層合用黏著劑予以塗佈‧硬化而得到的層合體之厚度控制性係變良好。
<其他成分>
本實施形態的金屬箔與樹脂薄膜之層合用黏著劑係視需要亦可含有增黏劑、可塑劑等之添加劑。
作為前述增黏劑，並沒有特別的限定。例如，於天然系中可舉出聚萜烯系樹脂、松香系樹脂等，於石油系中可舉出由石腦油的分解油餾份所得之脂肪族(C5)系樹脂、芳香族(C9)系樹脂、共聚合(C5/C9)系樹脂、脂環族系樹脂等。又，可舉出將此等樹脂之雙鍵部分予以氫化後之氫化樹脂。此增黏劑係可僅使用1種， 也可併用2種以上。作為前述可塑劑，並沒有特別的限定，例如可舉出聚異戊二烯、聚丁烯等之液狀橡膠、加工油等。
又，只要是不妨礙本實施形態的效果之範圍，則亦可含有具有羧基的聚烯烴樹脂(A)以外之熱塑性樹脂或熱塑性彈性體。作為可摻合的熱塑性樹脂及熱塑性彈性體，例如可舉出乙烯-醋酸乙烯酯共聚合樹脂、乙烯-丙烯酸乙酯共聚合樹脂、SEBS(苯乙烯-乙烯-丁烯-苯乙烯)、SEPS(苯乙烯-乙烯-丙烯-苯乙烯)等。
於本實施形態的金屬箔與樹脂薄膜之層合用黏著劑中，(A)、(B)、(C)及(D)成分之合計含量較佳為80質量%以上，更佳為90質量%以上，尤佳為95質量%以上，尤更佳為98質量%以上。
[層合體]
本實施形態之層合體係金屬箔與樹脂薄膜隔著黏著劑層並經層合而成，該黏著劑層係由本實施形態的金屬箔與樹脂薄膜之層合用黏著劑(以下，亦僅稱「本實施形態之層合用黏著劑」)而得到，又，於本實施形態之層合體中，只要是包含隔著由本實施形態之層合用黏著劑所得之黏著劑層來接合金屬箔與樹脂薄膜而成之層，則另外亦可包含隔著由本實施形態之層合用黏著劑所得之黏著劑層來接合金屬箔彼此及/或樹脂薄膜彼此而成之層。此接合方法係可使用熱層合方式或 乾層合方式等之眾所周知的方法。於本實施形態中，所謂的熱層合方式，就是藉由將不含溶劑(D)的本實施形態之層合用黏著劑，在相接於黏著劑層的層表面上加熱熔融，或與相接於黏著劑層的層一起加熱擠出，使其介於層合體之層間存在，而形成黏著劑層之方式。又，於本實施形態中，所謂的乾層合方式，就是藉由將含有溶劑(D)的本實施形態之層合用黏著劑塗佈在相接於黏著劑層的層表面上，使其乾燥後，與另一層疊合而進行壓黏，使其介於層合體之層間存在，而形成黏著劑層之方式。
金屬箔係在材質上一般使用純鋁系或鋁-鐵系合金的O材(軟質材)等之鋁箔且為較佳。作為鋁箔之厚度，為了確保加工性及確保能防止層合體的氧或水分穿透的阻隔性，較佳為10~100μm左右。鋁箔之厚度未達10μm時，有於成形時發生鋁箔的斷裂，或發生針孔，以致氧或水分穿透層合體之虞。另一方面，鋁箔之厚度超過100μm時，成形時的斷裂改善效果或針孔發生防止效果並沒有特別地提高，只有層合體的總厚度變厚，質量增加。鋁箔一般使用30~50μm左右的厚度者，較佳使用40~50μm的厚度者。再者，對於鋁箔，為了與樹脂薄膜的黏著性提高或耐蝕性提高，較佳預先進行矽烷偶合劑或鈦偶合劑等的底漆處理、鉻酸鹽處理等的化成處理。
作為樹脂薄膜，較佳為聚丙烯、聚乙烯、馬來酸改性聚丙烯、乙烯-丙烯酸酯共聚物或離子聚合物樹脂等之熱熔著性樹脂薄膜。此等樹脂係具有熱封性，擔任 使耐藥品性升高之角色者。此等之薄膜厚度較佳為9~100μm，更佳為20~80μm，尤佳為40~80μm。若樹脂薄膜之厚度為9μm以上，則得到充分的熱封強度，耐蝕性良好。若樹脂薄膜之厚度為100μm以下，則強度充分，而且成形性良好。
本實施形態之層合體的用途係沒有特別的限定，但作為有用的用途，可舉出包裝用途。作為此層合體所包裝的內容物，可舉出包含酸、鹼、有機溶劑等的液狀物，例如油灰(厚塗油灰、薄塗油灰等)、塗料(油性塗料等)、清噴漆(透明漆等)、汽車用複合物等之溶劑系者等。又，此層合體由於亦適合包裝鋰離子電池的電解液，故可作為電池外裝用包裝材且係較佳。作為電池外裝用包裝材使用時，較佳係金屬箔為鋁箔，樹脂薄膜包含熱熔著性樹脂薄膜，而且於鋁箔之外側設置由耐熱性樹脂薄膜所成之外層。
[電池外裝用包裝材]
本實施形態之電池外裝用包裝材係使用本實施形態之層合體而得到。
本實施形態之電池外裝用包裝材較佳為在本實施形態之層合體的金屬箔之外側，設有由樹脂薄膜尤其耐熱性樹脂薄膜所成之外層者。又，視需要，為了提高機械強度或耐電解液性等之特性，亦可成為附加有第1中間樹脂層或/及第2中間樹脂層等之構成。作為較佳的形態，具體而 言可成為如以下之構成。再者，黏著劑層係意指「由本實施形態之層合用黏著劑所得之黏著劑層」，例示金屬箔層為鋁箔層。
(1)外層/鋁箔層/黏著劑層/樹脂薄膜層
(2)外層/第1中間樹脂層/鋁箔層/黏著劑層/樹脂薄膜層
(3)外層/鋁箔層/第2中間樹脂層/黏著劑層/樹脂薄膜層
(4)外層/第1中間樹脂層/鋁箔層/第2中間樹脂層/黏著劑層/樹脂薄膜層
(5)塗層/外層/鋁箔層/黏著劑層/樹脂薄膜層
(6)塗層/外層/第1中間樹脂層/鋁箔層/黏著劑層/樹脂薄膜層
(7)塗層/外層/鋁箔層/第2中間樹脂層/黏著劑層/樹脂薄膜層
(8)塗層/外層/第1中間樹脂層/鋁箔層/第2中間樹脂層/黏著劑層/樹脂薄膜層
(第1中間樹脂層、第2中間樹脂層)
於上述中，作為第1中間樹脂層，聚醯胺樹脂、聚酯樹脂或聚乙烯樹脂等係以提高電池外裝用包裝材的機械強度為目的而使用。作為第2中間樹脂層，與第1中間樹脂層同樣地，聚醯胺樹脂、聚酯樹脂或聚乙烯樹脂或聚丙烯等的熱黏著性擠出樹脂係主要以提高耐電解液性為目的而 使用。樹脂薄膜層係可使用單層的樹脂薄膜、複層的樹脂薄膜(藉由2層的共擠出或3層的共擠出等而製造)。又，第2中間樹脂層亦可使用單層的樹脂薄膜或複層的共擠出樹脂薄膜。第1中間樹脂層及第2中間樹脂層之厚度係沒有特別的限定，設置此等時，通常為0.1~30μm左右。
(外層)
使用於外層的樹脂薄膜係耐熱性、成形性、絕緣性等優異者，一般使用聚醯胺(尼龍)樹脂或聚酯樹脂之延伸薄膜。此外層薄膜之厚度為9~50μm左右，未達9μm時，則在進行包裝材的成形時延伸薄膜的伸展不足，在鋁箔發生頸縮，容易發生成形不良。另一方面，超過50μm的厚度時，成形性的效果也沒有特別地提高，反而使體積能量密度降低，同時只會造成成本上升。外層薄膜之厚度更佳為10~40μm左右，尤佳為20~30μm。
作為使用於此外層的樹脂薄膜，在將延伸薄膜的延伸方向當作0°之情況，以0°、45°、90°的3個方向各自成為拉伸方向之方式，將薄膜切出指定的大小，進行拉伸試驗時，使用其拉伸強度為150N/mm2以上，較佳為200N/mm2以上，更佳為250N/mm2以上，且3個方向的拉伸所致的伸長率為80%以上，較佳為100%以上，更佳為120%以上者，係在得到更銳利的形狀之點為較佳。由於拉伸強度為150N/mm2以上或拉伸所致的伸長率為80% 以上，而充分發揮上述效果。再者，拉伸強度及拉伸所致的伸長率之值係薄膜的拉伸試驗(試驗片的長度150mm×寬度15mm×厚度9~50μm，拉伸速度100mm/min)中到斷裂為止之值。試驗片係對於3個方向各自切出。
(金屬箔)
金屬箔由於擔任對於水蒸氣等的阻隔性之角色，作為材質，一般使用純鋁系或鋁-鐵系合金的O材(軟質材)且為較佳。作為鋁箔之厚度，為了確保加工性及確保能防止氧或水分滲入包裝內之阻隔性，較佳為10~100μm左右。鋁箔之厚度未達10μm時，有於成形時發生鋁箔的斷裂，或發生針孔，以致氧或水分的滲入之虞。另一方面，鋁箔之厚度超過100μm時，成形時的斷裂改善效果或針孔發生防止效果並沒有特別地提高，只有包裝材的總厚度變厚，質量增加，體積能量密度降低。鋁箔一般使用30~50μm左右的厚度者，較佳使用40~50μm的厚度者。再者，對於鋁箔，為了與樹脂薄膜的黏著性提高或耐蝕性提高，較佳預先進行矽烷偶合劑或鈦偶合劑等的底漆處理、鉻酸鹽處理等的化成處理。
(樹脂薄膜)
作為樹脂薄膜，較佳為聚丙烯、聚乙烯、馬來酸改性聚丙烯、乙烯-丙烯酸酯共聚物或離子聚合物樹脂等之熱熔著性樹脂薄膜。此等樹脂係具有熱封性，擔任使對於腐 蝕性強的鋰二次電池之電解液等的耐藥品性升高之角色者。此等之薄膜厚度較佳為9~100μm，更佳為20~80μm，尤佳為40~80μm。樹脂薄膜之厚度若為9μm以上，則得到充分的熱封強度，對於電解液等的耐蝕性變良好。若樹脂薄膜之厚度為100μm以下，則電池外裝用包裝材之強度充分，而且成形性良好。
(塗層)
本實施形態之電池外裝用包裝材亦可在外層之上設置塗層。作為塗層之形成法，有塗佈阻氣性的聚合物之方法，蒸鍍鋁金屬或氧化矽、氧化鋁等之無機氧化物，塗佈金屬及無機物的薄膜之方法等。藉由設置塗層，而得到阻隔水蒸氣及其他的氣體之性能更優異的層合體。
[電池外殼]
本實施形態之電池外殼係使用本實施形態之電池外裝用包裝材而得到。例如，藉由將電池外裝用包裝材予以成形而得到。
本實施形態之電池外裝用包裝材係耐電解液性或耐熱性、阻隔水蒸氣及其他的氣體之性能優異，適用作為二次電池尤其鋰離子電池用的電池外殼。又，本實施形態之電池外裝用包裝材由於成形性非常良好，故藉由依照眾所周知之方法進行成形，可簡便地得到本實施形態之電池外殼。成形之方法係沒有特別的限定，但若藉由深拉成形或 拉伸成形進行成形，則可製作複雜的形狀或尺寸精度高之電池外殼。
[實施例]
以下，藉由實施例及比較例，更具體地說明本發明，惟本發明完全不受此等的實施例所限制。
對於實施例1~11及比較例1~3的金屬箔與樹脂薄膜之層合用黏著劑之製造中所用之具有羧基的聚烯烴樹脂(A)，實施以下之評價。
<具有羧基的聚烯烴樹脂(A)之酸價測定>
具有羧基的聚烯烴樹脂(A)之酸價係根據JIS 0070測定。
<具有羧基的聚烯烴樹脂(A)之MFR測定>
具有羧基的聚烯烴樹脂(A)之MFR係以JIS K 7210中記載之方法，在溫度130℃、荷重2160g之條件下測定。
對於實施例1~11及比較例1~3的金屬箔與樹脂薄膜之層合用黏著劑，實施以下之評價。
<黏著劑的NCO/COOH比之算出>
根據JIS K 6806，測定實施例1~11及比較例1~3的金屬箔與樹脂薄膜之層合用黏著劑之製造中使用的多官 能異氰酸酯(B)中所包含的異氰酸基數。又，由經由上述所測定之具有羧基的聚烯烴樹脂(A)之酸價，算出聚烯烴樹脂(A)中所包含的羧基之羧基數。然後，使用此等的異氰酸基數及羧基數，算出異氰酸基數相對於羧基之比率，當作NCO/COOH比。
<適用期之判斷>
將黏著劑在30℃保存12小時、24小時、48小時後，塗佈於未延伸聚丙烯薄膜上，用以下之基準判斷塗佈性之良否。
◎‧‧‧48小時後，可塗佈。
○‧‧‧24小時後，可塗佈，但48小時後，增黏或凝膠化而無法塗佈。
△‧‧‧12小時後，可塗佈，但24小時後，增黏或凝膠化而無法塗佈。
×‧‧‧12小時後，增黏或凝膠化而無法塗佈。
對於使用實施例及比較例的金屬箔與樹脂薄膜之層合用黏著劑所製作的電池外殼用包裝材料，評價以下之剝離強度。自所得之電池外裝用包裝材，切出長度150mm×寬度15mm之尺寸，將其當作試驗片使用。
<剝離強度> (1)常態T字剝離強度
使用上述試驗片及Autograph AG-X(股份有限公司 島津製作所製)，於23℃×50%RH環境下以100mm/min的剝離速度使其剝離，測定鋁箔層與未延伸聚丙烯薄膜層間之90°剝離強度。
(2)電解液溶劑浸漬後之T字剝離強度
將上述試驗片浸漬於電解液溶劑(碳酸伸丙酯/碳酸二乙酯，質量比50/50)中，於85℃環境下放置1日後取出，使用該試驗片，與上述(1)同樣地測定鋁箔層與未延伸聚丙烯薄膜層間之90°剝離強度。
如以下製造實施例1~11及比較例1~3的金屬箔與樹脂薄膜之層合用黏著劑的製造中使用之具有羧基的聚烯烴樹脂(A)。
(合成例1)
使用機筒部的最高溫度經設定在170℃之雙軸擠壓機，將使用茂金屬觸媒作為聚合觸媒所製造之丙烯-乙烯無規共聚物(丙烯-乙烯莫耳比97：3，MFR10g/10分)100質量份、馬來酸酐2質量份、甲基丙烯酸月桂酯1質量份及二第三丁基過氧化物1.5質量份予以混煉及使其反應。然後，於擠壓機內進行減壓脫氣，去除殘留的未反應物而得到具有羧基的聚烯烴樹脂(a1)。
(合成例2~7)
除了使用如表1中所示的MFR不同之丙烯-乙烯無規 共聚物、丙烯聚合物或丙烯-乙烯-丁烯無規共聚物以外，以與合成例1同樣之方法，得到具有羧基的聚烯烴樹脂(a2)~(a7)。
如以下地調製實施例1~11及比較例1~3的金屬箔與樹脂薄膜之層合用黏著劑。
(實施例1)
使作為(A)成分之具有羧基的聚烯烴樹脂(a1)15g分散於作為溶劑(D)之甲苯/醋酸乙酯(質量比9/1)的混合溶劑85.0g中。接著，添加作為(B)成分之Duranate TKA-100(旭化成化學股份有限公司製，六亞甲基二異氰酸酯的異三聚氰酸酯物，異氰酸酯基含量21.7%)1.74g、作為(C)成分之「BiCAT Z」(Shepherd Chemical公司製，新癸酸鋅)0.50g，而調製金屬箔與樹脂薄膜之層合用黏著劑。
(實施例2~11、比較例1~3)
除了成為表2~3中所示的摻合以外，與實施例1同樣地，調製實施例2~11及比較例1~3的金屬箔與樹脂薄膜之層合用黏著劑。
使用實施例1~11及比較例1~3的金屬箔與樹脂薄膜之層合用黏著劑，如以下地以乾層合方式，製造具有外層/外層用黏著劑/鋁箔層/內層用黏著劑/內層之構造的電池外殼用包裝材料。
外層：PET/延伸聚醯胺層合薄膜(厚度27μm)
外層用黏著劑：胺基甲酸酯系乾層合用黏著劑(Toyo-Morton股份有限公司製：AD502/CAT10，塗佈量3g/m2(塗佈時))
鋁箔層：鋁-鐵系合金之鋁箔(AA規格8079-O材，厚度40μm)
內層用黏著劑：金屬箔與樹脂薄膜之層合用黏著劑(塗佈量：乾燥後之厚度為2μm)
內層：未延伸聚丙烯薄膜(厚度80μm)
黏著後熟化條件，期間：40℃、5%RH、24小時
[評價結果]
表1中顯示實施例1~11及比較例1~3的金屬箔與樹脂薄膜之層合用黏著劑的製造中使用之聚烯烴樹脂的評價結果。又，表2中顯示實施例1~11的金屬箔與樹脂薄膜之層合用黏著劑的評價結果，表4中顯示比較例1~3的金屬箔與樹脂薄膜之層合用黏著劑的評價結果。再者，表2中顯示使用實施例1~11的金屬箔與樹脂薄膜之層合用黏著劑所製作之電池外殼用包裝材料的評價結果，表3中顯示使用比較例1~3的金屬箔與樹脂薄膜之層合用黏著劑所製作之電池外殼用包裝材料的評價結果。
再者，表2中的各成分之詳細係如以下。
‧己酸鹽鋅：東榮化工股份有限公司製，2-乙基己酸鋅(65質量份)及礦油精(35質量份)之混合物
‧F-co-kem ZNS-P：股份有限公司ADEKA製，硬脂酸鋅
‧乙醯丙酮化鋅：東京化成工業股份有限公司製之試藥
‧己酸鹽錳：東榮化工股份有限公司製，辛酸錳(42質量份)及礦油精(58質量份)之混合物
‧KS-1260：堺化學工業股份有限公司製，二月桂酸丁錫
‧乙醯丙酮化鈦：東京化成工業股份有限公司製之試藥
‧BiCAT8210：Shepherd Chemical公司製，三(2-乙基己酸)鉍(鉍三(2-乙基己酸鹽))(89質量份)及2-乙基己酸(11質量份)之混合物
(考察)
由表2之結果可知，本發明的金屬箔與樹脂薄膜之層合用黏著劑(實施例1~11)係常態T字剝離強度、電解液溶劑浸漬後之T字剝離強度皆優異。
相對於其，如表3中所示，使用不含(C)成分的金屬箔與樹脂薄膜之層合用黏著劑時(比較例1~3)，可知常態T字剝離強度、電解液溶劑浸漬後之T字剝離強度皆不充分。
[產業上的利用可能性]
本發明的金屬箔與樹脂薄膜層合用金屬箔與樹脂薄膜之層合用黏著劑，係即使在電解液浸漬後也具有優異的黏著力，尤其適合鋁箔與熱熔著性樹脂薄膜之接合用。又，本發明之層合體由於耐電解液性優異，而適用於鋰離子電池等之二次電池的製作中所用之電池外裝用包裝材，藉由將此層合體予以成形，可製造耐電解液性優異之電池外殼。而且，藉由使用該電池外殼，壽命長之安全的二次電池之製造係成為可能。

Claims (14)

  1. 一種金屬箔與樹脂薄膜之層合用黏著劑，其係具有：具有羧基的聚烯烴樹脂(A)、與多官能異氰酸酯化合物(B)、以及作為7族及12族中的至少1種金屬的化合物的金屬化合物(C)，前述具有羧基的聚烯烴樹脂(A)在130℃下測得的MFR為5g/10分~42g/10分，相對於前述具有羧基的聚烯烴樹脂(A)中所包含的羧基數而言，多官能異氰酸酯化合物(B)中所包含的異氰酸基數之比率為0.5~15，相對於前述具有羧基的聚烯烴樹脂(A)100質量份而言，金屬化合物(C)之含量以金屬質量換算為0.0001質量份~5質量份。
  2. 如請求項1之金屬箔與樹脂薄膜之層合用黏著劑，其中，前述具有羧基的聚烯烴樹脂(A)包含改性聚烯烴樹脂，該改性聚烯烴樹脂係包含丙烯或丙烯與乙烯、及乙烯性不飽和羧酸或其酸酐來作為單體單元。
  3. 如請求項1之金屬箔與樹脂薄膜之層合用黏著劑，其中，前述多官能異氰酸酯化合物(B)包含聚異氰酸酯的多聚物。
  4. 如請求項3之金屬箔與樹脂薄膜之層合用黏著劑，其中，前述聚異氰酸酯的多聚物包含聚異氰酸酯的異三聚氰酸酯物。
  5. 如請求項1之金屬箔與樹脂薄膜之層合用黏著 劑，其中，相對於前述具有羧基的聚烯烴樹脂(A)中所包含的羧基數而言，多官能異氰酸酯化合物(B)中所包含的異氰酸基數之比率為0.5~13。
  6. 如請求項1之金屬箔與樹脂薄膜之層合用黏著劑，其中，前述金屬化合物(C)包含7族及12族中的至少1種金屬的羧酸鹽至少1種以上。
  7. 如請求項1之金屬箔與樹脂薄膜之層合用黏著劑，其中，前述金屬化合物(C)包含鋅或錳的羧酸鹽。
  8. 如請求項1之金屬箔與樹脂薄膜之層合用黏著劑，其中，進而包含溶劑(D)。
  9. 一種層合體，其係金屬箔與樹脂薄膜隔著黏著劑層並經層合而成，該黏著劑層係由請求項1~8中任一項之金屬箔與樹脂薄膜之層合用黏著劑而得到。
  10. 如請求項9之層合體，其中，前述金屬箔為鋁箔，前述樹脂薄膜含有熱熔著性樹脂薄膜。
  11. 如請求項9或10之層合體，其中，前述金屬箔之厚度為10~100μm，前述樹脂薄膜之厚度為9~100μm。
  12. 一種電池外裝用包裝材，其係使用請求項9~11中任一項之層合體而得到。
  13. 一種電池外殼，其係使用請求項12之電池外裝用包裝材而得到。
  14. 一種電池外殼之製造方法，其係將請求項12之電池外裝用包裝材進行深拉成形或拉伸成形。
TW105141842A 2016-02-03 2016-12-16 金屬箔與樹脂薄膜之層合用黏著劑、層合體、電池外裝用包裝材以及電池外殼、及其製造方法 TWI620805B (zh)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2016018933 2016-02-03

Publications (2)

Publication Number Publication Date
TW201736558A TW201736558A (zh) 2017-10-16
TWI620805B true TWI620805B (zh) 2018-04-11

Family

ID=59499679

Family Applications (1)

Application Number Title Priority Date Filing Date
TW105141842A TWI620805B (zh) 2016-02-03 2016-12-16 金屬箔與樹脂薄膜之層合用黏著劑、層合體、電池外裝用包裝材以及電池外殼、及其製造方法

Country Status (5)

Country Link
US (1) US10703944B2 (zh)
JP (1) JP6583837B2 (zh)
CN (1) CN108495901A (zh)
TW (1) TWI620805B (zh)
WO (1) WO2017134931A1 (zh)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6621694B2 (ja) * 2016-03-25 2019-12-18 株式会社神戸製鋼所 ポリオレフィン系樹脂接着用表面処理鋼板及びそれを用いた複合部材
EP3492261A4 (en) 2016-07-27 2019-08-07 Mitsubishi Chemical Corporation MULTILAYER STRUCTURE, RESIN COMPOSITION FOR ADHESIVE RESIN LAYERS AND METHOD FOR PRODUCING A MULTILAYER STRUCTURE
JP6895992B2 (ja) 2016-12-22 2021-06-30 昭和電工株式会社 接着剤、これを用いた積層体、電池外装材、並びに電池ケース及びその製造方法
WO2019225254A1 (ja) * 2018-05-24 2019-11-28 三井化学株式会社 コーティング剤、フィルム、積層体および電池ケース用包材
WO2020203213A1 (ja) * 2019-03-29 2020-10-08 昭和電工株式会社 接着剤用組成物、蓄電装置用外装材及びその製造方法
JP7254670B2 (ja) * 2019-09-26 2023-04-10 東洋紡株式会社 積層体
US20220336935A1 (en) * 2019-10-03 2022-10-20 Nippon Steel Corporation Battery cell case and battery manufacturing method using same
WO2021131812A1 (ja) * 2019-12-23 2021-07-01 東亞合成株式会社 接着剤組成物、熱融着性部材、及び、二次電池包材
JP7272304B2 (ja) * 2020-03-18 2023-05-12 トヨタ自動車株式会社 全固体電池、および全固体電池の製造方法
KR20250121416A (ko) * 2023-01-16 2025-08-12 엠씨피피 이노베이션 고도가이샤 폴리올레핀 조성물, 실란 가교성 성형체, 그리고, 실란 가교 성형체 및 그 사용

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201437308A (zh) * 2013-02-07 2014-10-01 Mitsui Chemicals Inc 接著劑、積層體、電池外殼用包裝材、電池、強鹼溶液用包裝材、含醇溶液用包裝材及包裝體
TWI480354B (zh) * 2008-01-16 2015-04-11 Toagosei Co Ltd An adhesive composition, and a hot-melt adhesive member using the same
TWI507494B (zh) * 2010-12-28 2015-11-11 Toagosei Co Ltd An adhesive composition and a hot melt adhesive member using the composition
CN105238314A (zh) * 2015-11-13 2016-01-13 深圳先进技术研究院 一种耐湿热高可靠性环氧导电银胶及其制备方法与应用

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56155220A (en) * 1980-03-17 1981-12-01 Troy Chemical Corp Urethane reaction catalyst
JPH0784437A (ja) * 1993-09-10 1995-03-31 Ricoh Co Ltd 帯電用部材
DE10110437A1 (de) 2001-03-05 2002-09-19 Bayer Ag Verfahren zur Herstellung von Polyisocyanaten durch Umsetzung von Carbonsäuren mit Isocyanaten, die nach diesem Verfahren hergestellten Produkte und deren Verwendung in Polyurethankunststoffen
JP5177149B2 (ja) * 2008-01-10 2013-04-03 東亞合成株式会社 接着剤組成物及びそれを用いた熱融着性部材
JP5474329B2 (ja) * 2008-10-08 2014-04-16 昭和電工パッケージング株式会社 電池ケース用包材及び電池用ケース
DE102009046362A1 (de) * 2009-11-03 2011-05-05 Tesa Se Haftklebestoff aus einem vernetzbaren Polyolefin und einem Klebharz
US10239287B2 (en) 2012-02-01 2019-03-26 Showa Denko Packaging Co., Ltd. Molding packaging material and method for producing same
JP5815764B2 (ja) 2014-02-05 2015-11-17 昭和電工パッケージング株式会社 電池ケース用包材及び電池用ケース
US20180162100A1 (en) * 2015-06-10 2018-06-14 Showa Denko K.K. Adhesive for laminating metal foil and resin film, laminated body, packaging material for battery exterior, and battery case and method for manufacturing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI480354B (zh) * 2008-01-16 2015-04-11 Toagosei Co Ltd An adhesive composition, and a hot-melt adhesive member using the same
TWI507494B (zh) * 2010-12-28 2015-11-11 Toagosei Co Ltd An adhesive composition and a hot melt adhesive member using the composition
TW201437308A (zh) * 2013-02-07 2014-10-01 Mitsui Chemicals Inc 接著劑、積層體、電池外殼用包裝材、電池、強鹼溶液用包裝材、含醇溶液用包裝材及包裝體
CN105238314A (zh) * 2015-11-13 2016-01-13 深圳先进技术研究院 一种耐湿热高可靠性环氧导电银胶及其制备方法与应用

Also Published As

Publication number Publication date
CN108495901A (zh) 2018-09-04
US10703944B2 (en) 2020-07-07
TW201736558A (zh) 2017-10-16
JP6583837B2 (ja) 2019-10-02
JPWO2017134931A1 (ja) 2018-08-09
WO2017134931A1 (ja) 2017-08-10
US20190023954A1 (en) 2019-01-24

Similar Documents

Publication Publication Date Title
TWI620805B (zh) 金屬箔與樹脂薄膜之層合用黏著劑、層合體、電池外裝用包裝材以及電池外殼、及其製造方法
JP6895992B2 (ja) 接着剤、これを用いた積層体、電池外装材、並びに電池ケース及びその製造方法
CN103534085B (zh) 成型用包装材料和电池用外壳
JP5774139B2 (ja) 成形用包装材及びその製造方法
CN103918099B (zh) 蓄电装置用外包装材料
TWI642538B (zh) 金屬箔與樹脂薄膜之層合用接著劑、層合體、電池外裝用包裝材以及電池盒及其製造方法
TWI654215B (zh) 金屬箔與樹脂薄膜之疊層用接著劑、使用該組成物之層合體、電池外裝用包裝材料及電池外殼
CN108198965A (zh) 成型用包装材料和电池用外壳
JP7058465B2 (ja) 蓄電デバイス金属端子部密封用接着性フィルム
TW201342690A (zh) 電池外裝用積層體、使用此積層體之電池外殼及電池
JP2017079199A (ja) 電池用包装材料
HK1241143B (zh) 电池用包装材料