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WO2016159190A1 - Matériau d'emballage de pile, son procédé de fabrication, et pile - Google Patents

Matériau d'emballage de pile, son procédé de fabrication, et pile Download PDF

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Publication number
WO2016159190A1
WO2016159190A1 PCT/JP2016/060575 JP2016060575W WO2016159190A1 WO 2016159190 A1 WO2016159190 A1 WO 2016159190A1 JP 2016060575 W JP2016060575 W JP 2016060575W WO 2016159190 A1 WO2016159190 A1 WO 2016159190A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
packaging material
battery packaging
heat
adhesive layer
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2016/060575
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English (en)
Japanese (ja)
Inventor
かおる 宮崎
宏年 坂元
陽祐 早川
山下　力也
山下　孝典
鈴木　剛
望月　洋一
一彦 横田
哲也 小尻
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dai Nippon Printing Co Ltd
Original Assignee
Dai Nippon Printing Co Ltd
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
Priority claimed from JP2016056037A external-priority patent/JP6686587B2/ja
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Priority to HK18105028.5A priority Critical patent/HK1246003B/zh
Priority to CN201680019778.4A priority patent/CN107431152B/zh
Priority to US15/561,704 priority patent/US10886506B2/en
Priority claimed from JP2016069528A external-priority patent/JP6686634B2/ja
Publication of WO2016159190A1 publication Critical patent/WO2016159190A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/141—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against humidity
    • 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
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • 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
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/145—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against corrosion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/62—Hybrid vehicles

Definitions

  • the present invention relates to a battery packaging material, a method for producing the same, and a battery.
  • Patent Document 1 discloses a battery case including a biaxially stretched polyamide film layer as an outer layer, an unstretched thermoplastic resin film layer as an inner layer, and an aluminum foil layer disposed between the two film layers.
  • a packaging material is disclosed.
  • Patent Document 2 discloses a base material layer, an adhesive layer, an aluminum foil layer provided with a corrosion prevention treatment layer, an adhesive resin layer, and a sealant provided on the opposite side of the adhesive resin layer to the base material layer.
  • An exterior material for a lithium ion battery in which layers are sequentially laminated and an adhesive resin layer includes an acid-modified polyolefin resin and an elastomer is disclosed.
  • minute foreign matters such as electrode active material and electrode tab fragments have electrical conductivity.
  • conductive foreign matter exists between the electrode tab and the heat-fusible resin layer, if the foreign matter penetrates the heat-fusible resin layer due to heat and pressure during heat sealing, the electrode tab and battery There is a possibility that the metal layer of the packaging material is electrically connected to cause a short circuit.
  • a minute foreign matter such as an electrode active material or an electrode tab fragment is a heat-sealed portion such as an interface between the heat-fusible resin layers or between the electrode tab and the heat-fusible resin layer.
  • the main object is to provide a battery packaging material having high insulation and durability.
  • the battery packaging material is a laminate including at least a base material layer, a metal layer, an adhesive layer, and a heat-fusible resin layer in this order, and the adhesive layer has a melting point of 50 to 120 ° C. It has been found that a battery packaging material having high insulation and durability can be obtained by having a resin composition containing the acid-modified polyolefin and an epoxy resin having a weight average molecular weight of 50 to 2,000.
  • the present inventor made the battery packaging material a laminate including at least a base material layer, a metal layer, an adhesive layer, and a heat-fusible resin layer in this order, and the adhesive layer was an acid-modified polyolefin.
  • the first invention of the present invention is an invention that has been completed through further studies based on these findings.
  • 1st invention provides the packaging material for batteries of the aspect hung up below, its manufacturing method, and a battery.
  • Item 1A At least a laminate comprising a base material layer, a metal layer, an adhesive layer, and a heat-fusible resin layer in this order,
  • the adhesive layer has an acid-modified polyolefin and a resin composition containing an epoxy resin,
  • the probe is placed on the surface of the adhesive layer at the end of the battery packaging material, and the probe is heated from 40 ° C. to 220 ° C.
  • a battery packaging material in which the position of the battery does not fall below the initial value.
  • the probe When measuring the amount of displacement of the probe using a thermomechanical analyzer, the probe is placed on the surface of the adhesive layer at the end of the battery packaging material, and when the probe is heated from 40 ° C. to 220 ° C., 140 ° C.
  • Item 1A The battery packaging material according to Item 1A, wherein the amount of increase in the position of the probe when heated from 220 ° C to 220 ° C is larger than the amount of increase in the position of the probe when heated from 80 ° C to 120 ° C.
  • Item 3A The packaging material for a battery according to Item 1A or 2A, wherein the adhesive layer has a resin composition containing an acid-modified polyolefin having a melting point of 50 ° C. or more and 120 ° C.
  • Item 4A At least a base material layer, a metal layer, an adhesive layer, and a heat-fusible resin layer are composed of a laminate provided in this order, The battery packaging material, wherein the adhesive layer has a resin composition containing an acid-modified polyolefin having a melting point of 50 ° C or higher and 120 ° C or lower and an epoxy resin having a weight average molecular weight of 50 or higher and 2000 or lower.
  • the adhesive layer has a resin composition containing an acid-modified polyolefin having a melting point of 50 ° C or higher and 120 ° C or lower and an epoxy resin having a weight average molecular weight of 50 or higher and 2000 or lower.
  • Item 8A Item 8.
  • Item 12A. At least a layering step for obtaining a laminate including a base material layer, a metal layer, an adhesive layer, and a heat-fusible resin layer in this order,
  • the adhesive layer using a resin composition containing an acid-modified polyolefin and an epoxy resin, In measuring the displacement of the probe using a thermomechanical analyzer, the probe is placed on the surface of the adhesive layer at the end of the battery packaging material, and the probe is heated from 40 ° C. to 220 ° C.
  • the present inventor conducted further intensive studies in order to solve the above problems.
  • the battery packaging material is a laminate including at least a base material layer, a metal layer, a first insulating layer, a second insulating layer, and a heat-fusible resin layer in this order. It has been found that a battery packaging material having high insulation and durability can be obtained by setting the melting temperature of the layer to 200 ° C. or higher and setting the melting temperature of the second insulating layer lower than the melting temperature of the first insulating layer. It was.
  • the second invention of the present invention is an invention that has been completed by further studies based on these findings.
  • 2nd invention provides the packaging material for batteries of the aspect hung up below, its manufacturing method, and a battery.
  • Item 1B At least a base material layer, a metal layer, a first insulating layer, a second insulating layer, and a laminate including a heat-fusible resin layer in this order, The melting temperature of the first insulating layer is 200 ° C. or higher; The battery packaging material, wherein a melting temperature of the second insulating layer is lower than a melting temperature of the first insulating layer.
  • Item 2B The battery packaging material according to Item 1B, wherein the first insulating layer is formed of an acid-modified polyolefin and an epoxy resin.
  • Item 3B The battery packaging material according to Item 1B, wherein the first insulating layer is formed of an acid-modified polyolefin and an epoxy resin.
  • Item 4. The battery packaging material according to any one of Items 1B to 3B, wherein a melting temperature of the heat-fusible resin layer is lower than a melting temperature of the second insulating layer.
  • Item 5. The battery packaging material according to any one of Items 1B to 4B, wherein the first insulating layer and the second insulating layer are bonded via an adhesive layer.
  • Item 6 The battery packaging material according to any one of Items 1B to 6B, wherein the thickness of the second insulating layer is 10 ⁇ m or more and 50 ⁇ m or less.
  • Item 8B The battery packaging material according to any one of Items 5B to 7B, wherein the adhesive layer has a thickness of 20 ⁇ m or less.
  • Item 9B The battery packaging material according to any one of Items 1B to 8B, wherein the heat-fusible resin layer is formed of polyolefin.
  • Item 10B Item 10. The battery packaging material according to any one of Items 1B to 9B, wherein the surface of the heat-fusible resin layer has fine irregularities.
  • Item 11B The battery packaging material according to any one of Items 1B to 6B, wherein the thickness of the second insulating layer is 10 ⁇ m or more and 50 ⁇ m or less.
  • Item 8B The battery packaging material according to any one of Items 5B to 7B, wherein the adhesive layer has a thickness of 20 ⁇ m or less
  • the heat-fusible resin layer is formed of a plurality of layers, Item 10.
  • Item 12B. A battery in which a battery element including a positive electrode, a negative electrode, and an electrolyte is sealed with a package formed of the battery packaging material according to any one of Items 1B to 11B.
  • Item 13B A battery in which a battery element including a positive electrode, a negative electrode, and an electrolyte is sealed with a package formed of the battery packaging material according to any one of Items 1B to 11B.
  • the melting temperature of the first insulating layer is 200 ° C. or higher
  • a method for producing a battery packaging material wherein a melting temperature of the second insulating layer is set lower than a melting temperature of the first insulating layer.
  • a minute foreign matter such as an electrode active material or electrode tab debris is present at the interface between the heat-fusible resin layers or between the electrode tab and the heat-fusible resin layer. Even when present in the heat-sealed portion, a battery packaging material having high insulation and durability can be provided. That is, by sealing the battery element with the battery packaging material of the present invention, the insulation and durability of the battery can be enhanced.
  • a probe of a thermomechanical analyzer is installed on the surface of the adhesive layer at the end of the battery packaging material obtained in Example 10A, and the heating temperature and the displacement of the probe position when the probe is heated from 40 ° C. to 250 ° C. It is a graph which shows the relationship.
  • a probe of a thermomechanical analyzer is installed on the surface of the adhesive layer at the end of the battery packaging material obtained in Comparative Example 11A, and the heating temperature and the displacement of the probe position when the probe is heated from 40 ° C. to 250 ° C. It is a graph which shows the relationship.
  • the battery packaging material comprises at least a base material layer, a metal layer, an adhesive layer, and a heat-fusible resin layer in this order
  • the adhesive layer has a resin composition containing an acid-modified polyolefin having a melting point of 50 to 120 ° C. and an epoxy resin having a weight average molecular weight of 50 to 2000.
  • the battery packaging material is a laminate including at least a base material layer, a metal layer, an adhesive layer, and a heat-fusible resin layer in this order.
  • the adhesive layer has a resin composition containing an acid-modified polyolefin and an epoxy resin, and in measuring the displacement of the probe using a thermomechanical analyzer, the end of the battery packaging material is When the probe is installed on the surface of the adhesive layer and the probe is heated from 40 ° C. to 220 ° C., the position of the probe does not decrease from the initial value.
  • the battery packaging material of the present invention, the manufacturing method thereof, and the battery of the present invention in which the battery element is sealed with the battery packaging material of the present invention will be described in detail with reference to FIGS. 1 to 3.
  • contents that are not common between the first embodiment and the second embodiment are clearly indicated, and unless otherwise noted, the contents are common.
  • the battery packaging material of the second invention is composed of a laminate comprising at least a base material layer, a metal layer, a first insulating layer, a second insulating layer, and a heat-fusible resin layer in this order,
  • the melting temperature of the first insulating layer is 200 ° C. or higher, and the melting temperature of the second insulating layer is lower than the melting temperature of the first insulating layer.
  • the battery packaging material of the present invention, the manufacturing method thereof, and the battery of the second invention in which the battery element is sealed with the battery packaging material of the second invention will be described in detail with reference to FIGS. Describe.
  • contents that are not common between the first invention and the second invention are clearly indicated, and unless otherwise specified, the contents are common.
  • the base material layer 1, the adhesive layer 2, the metal layer 3, and the surface coating layer are common.
  • the battery packaging material of the first invention comprises at least a base material layer 1, a metal layer 3, an adhesive layer 4 and a heat-fusible resin layer 5 as shown in FIG. It consists of the laminated body prepared in order.
  • the base material layer 1 is the outermost layer side
  • the heat-fusible resin layer 5 is the innermost layer. That is, at the time of battery assembly, the heat sealing resin layers 5 positioned at the periphery of the battery element are thermally fused together to seal the battery element, thereby sealing the battery element.
  • the battery packaging material according to the first aspect of the invention has an adhesive layer 2 between the base material layer 1 and the metal layer 3 as necessary for the purpose of enhancing the adhesion between them. May be provided.
  • the battery packaging material of the second invention comprises at least a base material layer 1, a metal layer 3, a first insulating layer 51, a second insulating layer 52, and a heat-fusible resin layer 41. It consists of a laminated body provided in this order.
  • the base material layer 1 is the outermost layer and the heat-fusible resin layer 41 is the innermost layer. That is, at the time of battery assembly, the heat-fusible resin layers 41 positioned at the periphery of the battery element are thermally welded to seal the battery element, thereby sealing the battery element.
  • the battery packaging material of the second invention is provided with an adhesive layer 2 between the base material layer 1 and the metal layer 3 as necessary for the purpose of improving the adhesion. It may be done. Further, as shown in FIGS. 11 and 12, the battery packaging material of the second invention is provided between the first insulating layer 51 and the second insulating layer 52 as needed for the purpose of enhancing the adhesion between them.
  • the adhesive layer 6 may be provided. Furthermore, as shown in FIG. 12, an adhesive layer 7 may be provided between the metal layer 3 and the first insulating layer 51 as necessary for the purpose of improving the adhesion.
  • the base material layer 1 is a layer located on the outermost layer side.
  • the material for forming the base material layer 1 is not particularly limited as long as it has insulating properties.
  • the material for forming the base material layer 1 include resin films such as polyester resin, polyamide resin, epoxy resin, acrylic resin, fluorine resin, polyurethane resin, silicon resin, phenol resin, and mixtures and copolymers thereof.
  • a polyester resin and a polyamide resin are mentioned, More preferably, a biaxially stretched polyester resin and a biaxially stretched polyamide resin are mentioned.
  • polyester resin examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolyester, and polycarbonate.
  • polyamide resin examples include nylon 6, nylon 6,6, a copolymer of nylon 6 and nylon 6,6, nylon 6,10, polymetaxylylene adipamide (MXD6), and the like. It is done.
  • the base material layer 1 may be formed of a single resin film, but may be formed of two or more resin films in order to improve pinhole resistance and insulation. Specific examples include a multilayer structure in which a polyester film and a nylon film are laminated, a multilayer structure in which a plurality of nylon films are laminated, a multilayer structure in which a plurality of polyester films are laminated, and the like.
  • the base material layer 1 has a multilayer structure, a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film, a laminate of a plurality of biaxially stretched nylon films, and a laminate of a plurality of biaxially stretched polyester films The body is preferred.
  • the polyester resin and the polyester resin are laminated, the polyamide resin and the polyamide resin are laminated, or the polyester resin and the polyamide resin are laminated. It is preferable to use a structure in which polyethylene terephthalate and polyethylene terephthalate are laminated, a structure in which nylon and nylon are laminated, or a structure in which polyethylene terephthalate and nylon are laminated.
  • the polyester resin is difficult to discolor when, for example, the electrolytic solution adheres to the surface, it is preferable to laminate the base material layer 1 so that the polyester resin is located in the outermost layer in the laminated configuration.
  • the thickness of each layer is preferably 2 ⁇ m or more and 25 ⁇ m or less.
  • the base material layer 1 is formed of a multilayer resin film
  • two or more resin films may be laminated via an adhesive component such as an adhesive or an adhesive resin, and the type and amount of the adhesive component used. Is the same as that of the adhesive layer 2 described later.
  • an adhesive component such as an adhesive or an adhesive resin
  • stacking two or more resin films A well-known method can be employ
  • the dry lamination method is mentioned.
  • the thickness of the adhesive layer is, for example, about 2 ⁇ m to 5 ⁇ m.
  • the thickness of the base material layer 1 is not particularly limited as long as it exhibits a function as a base material layer, and examples thereof include about 4 ⁇ m to 50 ⁇ m, preferably about 10 ⁇ m to 35 ⁇ m.
  • the adhesive layer 2 is a layer provided between the base material layer 1 and the metal layer 3 as necessary in order to firmly bond the base material layer 1 and the metal layer 3.
  • the adhesive layer 2 is formed of an adhesive capable of bonding the base material layer 1 and the metal layer 3 together.
  • the adhesive used for forming the adhesive layer 2 may be a two-component curable adhesive or a one-component curable adhesive.
  • the bonding mechanism of the adhesive used for forming the adhesive layer 2 is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, and the like.
  • adhesive components that can be used to form the adhesive layer 2 include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and copolyester; Polyether adhesive; Polyurethane adhesive; Epoxy resin; Phenol resin resin; Polyamide resin such as nylon 6, nylon 66, nylon 12, copolymer polyamide; polyolefin, carboxylic acid modified polyolefin, metal modified polyolefin, etc.
  • Polyolefin resins polyvinyl acetate resins, cellulose adhesives, (meth) acrylic resins, polyimide resins, urea resins, melamine resins and other amino resins, chloroprene rubber, nitrile rubber, - Len rubbers such as butadiene rubber, silicone-based resins.
  • These adhesive components may be used individually by 1 type, and may be used in combination of 2 or more type. Among these adhesive components, a polyurethane adhesive is preferable.
  • the thickness of the adhesive layer 2 is not particularly limited as long as it exhibits a function as an adhesive layer.
  • the thickness is about 1 ⁇ m to 10 ⁇ m, preferably about 2 ⁇ m to 5 ⁇ m.
  • the metal layer 3 is a layer that functions as a barrier layer for preventing water vapor, oxygen, light, and the like from entering the battery, in addition to improving the strength of the battery packaging material.
  • Specific examples of the metal constituting the metal layer 3 include aluminum, stainless steel, and titanium, and preferably aluminum.
  • the metal layer 3 can be formed by metal foil, metal vapor deposition, or the like, preferably by metal foil, and more preferably by aluminum foil.
  • annealed aluminum JIS H4160 A8021H-O, JIS H4160 A8079H-O, JIS H4000: It is more preferable to use soft aluminum foil such as 2014 A8021P-O, JIS H4000: 2014 A8079P-O).
  • the thickness of the metal layer 3 is not particularly limited as long as it functions as a barrier layer such as water vapor, but can be, for example, about 10 ⁇ m to 50 ⁇ m, preferably about 10 ⁇ m to 35 ⁇ m.
  • the metal layer 3 is preferably subjected to chemical conversion treatment on at least one side, preferably both sides, in order to stabilize adhesion, prevent dissolution and corrosion, and the like.
  • the chemical conversion treatment refers to a treatment for forming an acid-resistant film on the surface of the metal layer.
  • chromic acid compounds such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromic acetyl acetate, chromium chloride, potassium sulfate chromium, etc.
  • X represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group.
  • R 1 and R 2 are the same or different and each represents a hydroxyl group, an alkyl group, or a hydroxyalkyl group.
  • examples of the alkyl group represented by X, R 1 and R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms such as a tert-butyl group.
  • Examples of the hydroxyalkyl group represented by X, R 1 and R 2 include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 3- A linear or branched chain having 1 to 4 carbon atoms substituted with one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group An alkyl group is mentioned.
  • the alkyl group and hydroxyalkyl group represented by X, R 1 and R 2 may be the same or different.
  • X is preferably a hydrogen atom, a hydroxyl group or a hydroxyalkyl group.
  • the number average molecular weight of the aminated phenol polymer having the repeating units represented by the general formulas (1) to (4) is preferably, for example, from 500 to 1,000,000, and from about 1,000 to 20,000. Is more preferable.
  • a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate fine particles dispersed in phosphoric acid is coated.
  • a method of forming a corrosion-resistant treatment layer on the surface of the metal layer 3 by performing a baking treatment at 150 ° C. or higher can be mentioned.
  • a resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be further formed on the corrosion-resistant treatment layer.
  • examples of the cationic polymer include polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine graft acrylic resin obtained by graft polymerization of a primary amine on an acrylic main skeleton, and polyallylamine. Or the derivative, aminophenol, etc. are mentioned.
  • these cationic polymers only one type may be used, or two or more types may be used in combination.
  • examples of the crosslinking agent include a compound having at least one functional group selected from the group consisting of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.
  • chemical conversion treatment only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion processing may be performed in combination. Furthermore, these chemical conversion treatments may be carried out using one kind of compound alone, or may be carried out using a combination of two or more kinds of compounds.
  • chemical conversion treatments chromic acid chromate treatment, chromate treatment combining a chromic acid compound, a phosphoric acid compound, and an aminated phenol polymer are preferable.
  • the amount of the acid-resistant film formed on the surface of the metal layer 3 in the chemical conversion treatment is not particularly limited.
  • a chromic acid compound is present per 1 m 2 of the surface of the metal layer 3.
  • a solution containing a compound used for forming an acid-resistant film is applied to the surface of the metal layer by a bar coating method, a roll coating method, a gravure coating method, an immersion method, or the like, and then the temperature of the metal layer is 70. It is performed by heating so that the temperature is about 200 ° C. or higher.
  • the metal layer may be previously subjected to a degreasing treatment by an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or the like. By performing the degreasing treatment in this way, it becomes possible to more efficiently perform the chemical conversion treatment on the surface of the metal layer.
  • the adhesive layer 4 is a layer provided between the metal layer 3 and the heat-fusible resin layer 5 in order to enhance the insulation and durability of the battery packaging material.
  • the adhesive layer 4 has a resin composition containing an acid-modified polyolefin having a melting point of 50 ° C. or more and 120 ° C. or less and an epoxy resin having a weight average molecular weight of 50 or more and 2000 or less. is doing.
  • the adhesive layer 4 is preferably formed of the resin composition.
  • the adhesive layer 4 may contain an additive such as an anti-blocking agent (such as silica), and the additive or the like may be contained in the resin composition.
  • the resin composition is a cured product.
  • the adhesive layer 4 has a resin composition containing an acid-modified polyolefin and an epoxy resin.
  • the acid-modified polyolefin functions as a main agent and the epoxy resin functions as a curing agent.
  • the resin composition becomes a cured product.
  • the melting point of the acid-modified polyolefin is preferably 50 ° C. or higher and 120 ° C. or lower
  • the weight average molecular weight of the epoxy resin is preferably 50 or higher and 2000 or lower.
  • the probe 10 of the thermomechanical analyzer is installed on the surface of the adhesive layer 4 at the end of the battery packaging material.
  • the edge part at this time is a part where the cross section of the adhesive layer 4 obtained by cutting in the thickness direction so as to pass through the central part of the battery packaging material is exposed. Cutting can be performed using a commercially available rotary microtome or the like.
  • the portion where the heat-welding resin layers of the battery packaging material are heat-sealed with each other Measure.
  • thermomechanical analyzer an atomic force microscope to which a cantilever with a heating mechanism can be attached can be used.
  • the tip radius of the probe 10 is 30 nm or less
  • the load applied to the probe 10 is a deviation (Defection) ⁇ 4 V
  • the rate is 5 ° C / min.
  • the probe 10 is pushed up, and the position of the probe 10 is set to the initial value (probe temperature). Is higher than the position when the temperature is 40 ° C.).
  • the adhesive layer 4 is softened, pierces the probe 10 adhesive layer 4 as shown in FIG. 4C, and the position of the probe 10 is lowered.
  • the battery packaging material to be measured is at room temperature (25 ° C.), and a probe heated to 40 ° C. is placed on the surface of the adhesive layer 4. To start measurement.
  • the probe is heated from 40 ° C. to 220 ° C. (more preferably from 40 ° C. to 250 ° C.) from the viewpoint of further improving the insulation and durability. It is preferable that the position of the probe 10 placed on the surface of the adhesive layer 4 does not fall below the initial value (position when the probe temperature is 40 ° C.), and is heated from 160 ° C. to 200 ° C. More preferably, the position of the probe 10 installed on the surface of the adhesive layer 4 does not decrease.
  • the step of heat-sealing the heat-fusible resin layers of the battery packaging material to seal the battery element is usually performed by heating at about 160 ° C. to 200 ° C. For this reason, when the probe is heated from 160 ° C. to 200 ° C., the battery packaging material in which the position of the probe 10 placed on the surface of the adhesive layer 4 does not decrease can exhibit particularly high insulation and durability.
  • the probe 10 in measuring the displacement of the probe 10 using a thermomechanical analyzer, the probe 10 is placed on the surface of the adhesive layer 4 at the end of the battery packaging material, and the probe is heated from 40 ° C. to 220 ° C. (More preferably, when heated from 40 ° C. to 250 ° C.)
  • the amount of increase in the position of the probe 10 when heated from 140 ° C. to 220 ° C. is the position of the probe 10 when heated from 80 ° C. to 120 ° C. It is preferable that it is larger than the rising amount.
  • the adhesive layer 4 for bonding the metal layer 3 and the heat-fusible resin layer 5 is a resin composition having the above specific composition.
  • a minute foreign matter such as an electrode active material or electrode tab debris may cause heat sealing such as the interface between the heat-fusible resin layers or between the electrode tab and the heat-fusible resin layer. Even when it is present in the portion to be provided, the insulation and durability of the battery packaging material are enhanced.
  • the adhesive layer 4 has a resin composition containing an acid-modified polyolefin and an epoxy resin, and a thermomechanical analyzer is used.
  • a thermomechanical analyzer is used.
  • the acid-modified polyolefin may be further modified with a (meth) acrylic acid ester.
  • the modified polyolefin further modified with (meth) acrylic acid ester is obtained by acid-modifying polyolefin by using unsaturated carboxylic acid or its acid anhydride and (meth) acrylic acid ester in combination. is there.
  • “(meth) acrylic acid ester” means “acrylic acid ester” or “methacrylic acid ester”.
  • One type of acid-modified polyolefin may be used alone, or two or more types may be used in combination.
  • the polyolefin to be acid-modified is not particularly limited as long as it is a resin containing an olefin as at least a monomer unit.
  • the polyolefin can be composed of, for example, at least one of polyethylene and polypropylene, and is preferably composed of polypropylene.
  • the polyethylene can be composed of, for example, at least one of homopolyethylene and ethylene copolymer.
  • Polypropylene can be composed of, for example, at least one of homopolypropylene and propylene copolymer.
  • propylene copolymer examples include copolymers of propylene and other olefins such as ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-propylene-butene copolymer.
  • the proportion of the propylene unit contained in the polypropylene is preferably about 50 mol% or more and 100 mol% or less, more preferably about 80 mol% or more and 100 mol% or less, from the viewpoint of further improving the insulation and durability of the battery packaging material. More preferably.
  • the proportion of the ethylene unit contained in the polyethylene is preferably about 50 mol% or more and 100 mol% or less, and more preferably 80 mol% or more and 100 mol% from the viewpoint of further improving the insulation and durability of the battery packaging material. More preferably, it is about the following.
  • Each of the ethylene copolymer and the propylene copolymer may be a random copolymer or a block copolymer.
  • the ethylene copolymer and the propylene copolymer may each be crystalline or amorphous, and may be a copolymer or a mixture thereof.
  • the polyolefin may be formed of one type of homopolymer or copolymer, or may be formed of two or more types of homopolymer or copolymer.
  • the unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and crotonic acid.
  • an acid anhydride the acid anhydride of the unsaturated carboxylic acid illustrated above is preferable, and maleic anhydride and itaconic anhydride are more preferable.
  • the acid-modified polyolefin may be one modified with one type of unsaturated carboxylic acid or its acid anhydride, or one modified with two or more types of unsaturated carboxylic acid or its acid anhydride. Also good.
  • Examples of (meth) acrylic acid esters include esterified products of (meth) acrylic acid and alcohols having 1 to 30 carbon atoms, preferably esterified products of (meth) acrylic acid and alcohols having 1 to 20 carbon atoms. Is mentioned. Specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) Examples include octyl acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. In modification of polyolefin, only one type of (meth) acrylic acid ester may be used, or two or more types may be used.
  • the ratio of the unsaturated carboxylic acid or its acid anhydride in the acid-modified polyolefin is preferably about 0.1% by mass to 30% by mass, and preferably about 0.1% by mass to 20% by mass. It is more preferable. By setting it as such a range, the insulation and durability of the packaging material for batteries can be improved more.
  • the proportion of (meth) acrylic acid ester in the acid-modified polyolefin is preferably about 0.1% by mass to 40% by mass, more preferably about 0.1% by mass to 30% by mass. preferable. By setting it as such a range, the insulation and durability of the packaging material for batteries can be improved more.
  • the weight average molecular weight of the acid-modified polyolefin is preferably about 6000 to 200000, and more preferably about 8000 to 150,000. In the present invention, the weight average molecular weight of the acid-modified polyolefin is a value measured by gel permeation chromatography (GPC) measured under conditions using polystyrene as a standard sample.
  • the melting point of the acid-modified polyolefin is preferably about 50 ° C. or higher and 120 ° C. or lower, and more preferably about 50 ° C. or higher and 100 ° C. or lower. In the present invention, the melting point of the acid-modified polyolefin refers to an endothermic peak temperature in differential scanning calorimetry.
  • the method for modifying the polyolefin is not particularly limited, and for example, an unsaturated carboxylic acid or an acid anhydride thereof or a (meth) acrylic acid ester may be copolymerized with the polyolefin.
  • examples of such copolymerization include random copolymerization, block copolymerization, graft copolymerization (graft modification), and the like, and preferably graft copolymerization.
  • the epoxy resin is not particularly limited as long as it is a resin capable of forming a crosslinked structure with an epoxy group present in the molecule, and a known epoxy resin can be used.
  • the weight average molecular weight of the epoxy resin may be in the range of 50 or more and 2000 or less.
  • the weight average molecular weight of the epoxy resin is preferably about 100 to 1000, more preferably 200 to 800. The following are mentioned.
  • the weight average molecular weight of the epoxy resin is a value measured by gel permeation chromatography (GPC) measured under conditions using polystyrene as a standard sample.
  • epoxy resin examples include bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether.
  • An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the proportion of the epoxy resin in the adhesive layer 4 is preferably in the range of 0.5 to 20 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin, and in the range of 1 to 10 parts by mass. More preferably. Thereby, the insulation and durability of the battery packaging material can be further improved.
  • the melting temperature of the adhesive layer 4 is preferably about 180 ° C. or higher and 260 ° C. or lower, more preferably about 200 ° C. or higher and 240 ° C. or lower.
  • the melting temperature of the adhesive layer 4 is a value measured by a method in accordance with the provisions of JIS K7196: 2012 “Softening temperature test method by thermomechanical analysis of thermoplastic film and sheet”, specifically, It is a value measured by the method described in the examples.
  • the penetration temperature was the melting temperature.
  • the solid content of the adhesive layer 4 is not particularly limited, but is preferably about 0.5 g / m 2 or more and 10 g / m 2 or less, more preferably 0.8 g / m 2 from the viewpoint of further improving the insulation and durability. the degree m 2 or more 5.2 g / m 2 or less and the like. From the same viewpoint, the thickness of the adhesive layer 4 is preferably 0.6 ⁇ m or more and 11 ⁇ m or less, more preferably 0.9 ⁇ m or more and 5.8 ⁇ m or less.
  • the heat-fusible resin layer 5 corresponds to the innermost layer and is a layer that heat-welds the heat-fusible resin layers together to seal the battery element when the battery is assembled. .
  • the resin component used in the heat-fusible resin layer 5 of the first invention is not particularly limited as long as it can be heat-welded, and examples thereof include polyolefin and acid-modified polyolefin.
  • polyolefins include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymers (for example, block copolymers of propylene and ethylene), polypropylene Polypropylenes such as random copolymers (for example, random copolymers of propylene and ethylene); ethylene-butene-propylene terpolymers; and the like.
  • polyethylene and polypropylene are preferable, and polypropylene is more preferable.
  • the polyolefin may be a cyclic polyolefin.
  • the cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin that is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, and isoprene. It is done.
  • examples of the cyclic monomer that is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene, and the like.
  • cyclic alkene is preferable, and norbornene is more preferable.
  • the acid-modified polyolefin is a polymer obtained by modifying the above polyolefin by block polymerization or graft polymerization with carboxylic acid or the like.
  • carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.
  • the acid-modified polyolefin may be an acid-modified cyclic polyolefin.
  • the acid-modified cyclic polyolefin is a copolymer obtained by copolymerizing a part of the monomer constituting the cyclic polyolefin in place of the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, or ⁇ , ⁇ -unsaturated with respect to the cyclic polyolefin. It is a polymer obtained by block polymerization or graft polymerization of a saturated carboxylic acid or its anhydride.
  • the cyclic polyolefin to be acid-modified is the same as described above.
  • the carboxylic acid used for modification is the same as that used for modification of the acid-modified cycloolefin copolymer.
  • polyolefins preferred are polyolefins, and more preferred are propylene copolymers.
  • propylene copolymer include copolymers of propylene and other olefins such as ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-propylene-butene copolymer.
  • the proportion of the propylene unit contained in the polypropylene is preferably about 50 mol% or more and 100 mol% or less, more preferably about 80 mol% or more and 100 mol% or less, from the viewpoint of further improving the insulation and durability of the battery packaging material. More preferably.
  • the proportion of the ethylene unit contained in the polyethylene is preferably about 50 mol% or more and 100 mol% or less, and more preferably 80 mol% or more and 100 mol% from the viewpoint of further improving the insulation and durability of the battery packaging material. More preferably, it is about the following.
  • Each of the ethylene copolymer and the propylene copolymer may be a random copolymer or a block copolymer, and a random propylene copolymer is preferred.
  • the heat-fusible resin layer 5 of the first invention preferably has polypropylene, and preferably has a layer formed of polypropylene.
  • the heat-fusible resin layer 5 may be formed of one kind of resin component alone or may be formed of a blend polymer in which two or more kinds of resin components are combined. Furthermore, the heat-fusible resin layer 5 may be formed of only one layer, but may be formed of two or more layers using the same or different resin components.
  • the innermost layer (the side opposite to the metal layer 3) of the heat-fusible resin layer 5 is formed by a dry laminating method or extrusion molding.
  • the formed layer is preferable. Thereby, insulation and a moldability can be improved further.
  • the heat-fusible resin layer 5 of the first invention preferably has fine irregularities on its surface (the innermost layer side surface). Thereby, a moldability can be improved further.
  • a method of forming fine irregularities on the surface of the heat-fusible resin layer 5 a method of adding a matting agent exemplified in the surface coating layer described later to the heat-fusible resin layer 5, and irregularities on the surface. For example, a method may be used in which the cooling roll is brought into contact with the mold.
  • the ten-point average roughness of the surface of the heat-fusible resin layer 5 is preferably 0.3 ⁇ m or more and 35 ⁇ m or less, more preferably 0.3 ⁇ m or more and 10 ⁇ m or less, and further preferably 0.5 ⁇ m or more. 2 micrometers or less are mentioned.
  • the ten-point average roughness is a value measured using a Keyence laser microscope VK-9710 under the measurement conditions of 50 times objective lens and no cutoff in a method in accordance with JIS B0601: 1994.
  • the thickness of the heat-fusible resin layer 5 of the first invention is not particularly limited as long as it exhibits the function as the heat-fusible resin layer, but from the viewpoint of further improving the insulation and durability, For example, 10 micrometers or more and 40 micrometers or less, Preferably 15 micrometers or more and 40 micrometers or less are mentioned.
  • the first insulating layer 51 is formed of the metal layer 3 and the heat-fusible resin layer 41 together with the second insulating layer 52 to be described later in order to enhance the insulation and durability of the battery packaging material. It is a layer provided between them.
  • the first insulating layer 51 is laminated on the metal layer 3 side, and the second insulating layer 52 is laminated on the heat-fusible resin layer 41 side.
  • the melting temperature of the first insulating layer 51 is 200 ° C. or higher.
  • the melting temperature of the first insulating layer 51 is 200 ° C. or higher.
  • the melting temperature of the first insulating layer 51 is not particularly limited as long as it is 200 ° C. or higher, but is preferably about 200 to 260 ° C., more preferably about 200 to 240 ° C.
  • the melting temperature is a value measured by a method compliant with the provisions of JIS K7196: 2012 “Softening temperature test method by thermomechanical analysis of thermoplastic film and sheet”, specifically Is a value measured by the method described in Examples. The penetration temperature was taken as the melting temperature.
  • the second insulating layer 52 having a melting temperature lower than the melting temperature is formed together with the first insulating layer 51 having a specific melting temperature. Therefore, it has high heat-resistant mechanical strength when heat such as heat sealing is applied, has high flexibility, and can effectively suppress generation of fine cracks due to stress such as bending.
  • the heat-fusible resin layer 41 the heat-fusible resin layer generated when the heat-sealing resin layer 41 is heat-sealed with fine cracks that are likely to occur in a thin portion, through-holes due to foreign matter, and the like, and the electrolyte solution being bitten. Even when a void or the like is formed due to foaming of the electrolytic solution, the first insulating layer 51 and the second insulating layer 52 can prevent the electrolytic solution from directly contacting the metal layer and protect the metal layer 3.
  • the combination of the first insulating layer 51 and the second insulating layer 52 having both high heat resistance and high flexibility makes it possible to pack the battery packaging material due to foreign matter. It is possible to prevent a decrease in insulation.
  • the resin for forming the first insulating layer 51 is not particularly limited as long as it has the aforementioned melting temperature. From the viewpoint of further improving the insulating properties and durability by using the second insulating layer 52 together with the second insulating layer 52, the first insulating layer 51 is preferably formed of an acid-modified polyolefin and an epoxy resin.
  • the acid-modified polyolefin it is preferable to use a polyolefin modified with an unsaturated carboxylic acid or an acid anhydride thereof. Furthermore, the acid-modified polyolefin may be further modified with a (meth) acrylic acid ester.
  • the modified polyolefin further modified with (meth) acrylic acid ester is obtained by acid-modifying polyolefin by using unsaturated carboxylic acid or its acid anhydride and (meth) acrylic acid ester in combination. is there.
  • the polyolefin to be acid-modified is not particularly limited as long as it is a resin containing an olefin as at least a monomer unit.
  • the polyolefin can be composed of, for example, at least one of polyethylene and polypropylene, and is preferably composed of polypropylene.
  • the polyethylene can be composed of, for example, at least one of homopolyethylene and ethylene copolymer.
  • Polypropylene can be composed of, for example, at least one of homopolypropylene and propylene copolymer.
  • propylene copolymer examples include copolymers of propylene and other olefins such as ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-propylene-butene copolymer.
  • the proportion of the propylene unit contained in the polypropylene is preferably about 50 mol% or more and 100 mol% or less, more preferably about 80 mol% or more and 100 mol% or less, from the viewpoint of further improving the insulation and durability of the battery packaging material. More preferably.
  • the proportion of the ethylene unit contained in the polyethylene is preferably about 50 mol% or more and 100 mol% or less, and more preferably 80 mol% or more and 100 mol% from the viewpoint of further improving the insulation and durability of the battery packaging material. More preferably, it is about the following.
  • Each of the ethylene copolymer and the propylene copolymer may be a random copolymer or a block copolymer.
  • the ethylene copolymer and the propylene copolymer may each be crystalline or amorphous, and may be a copolymer or a mixture thereof.
  • the polyolefin may be formed of one type of homopolymer or copolymer, or may be formed of two or more types of homopolymer or copolymer.
  • the unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and crotonic acid.
  • an acid anhydride the acid anhydride of the unsaturated carboxylic acid illustrated above is preferable, and maleic anhydride and itaconic anhydride are more preferable.
  • the acid-modified polyolefin may be one modified with one type of unsaturated carboxylic acid or its acid anhydride, or one modified with two or more types of unsaturated carboxylic acid or its acid anhydride. Also good.
  • Examples of (meth) acrylic acid esters include esterification products of (meth) acrylic acid and alcohols having 1 to 30 carbon atoms, preferably esterification products of (meth) acrylic acid and alcohols having 1 to 20 carbon atoms. Is mentioned. Specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) Examples include octyl acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. In modification of polyolefin, only one type of (meth) acrylic acid ester may be used, or two or more types may be used.
  • the ratio of the unsaturated carboxylic acid or its acid anhydride in the acid-modified polyolefin is preferably about 0.1% by mass to 30% by mass, and preferably about 0.1% by mass to 20% by mass. It is more preferable. By setting it as such a range, the insulation and durability of the packaging material for batteries can be improved more.
  • the proportion of (meth) acrylic acid ester in the acid-modified polyolefin is preferably about 0.1% by mass to 40% by mass, more preferably about 0.1% by mass to 30% by mass. preferable. By setting it as such a range, the insulation and durability of the packaging material for batteries can be improved more.
  • the weight average molecular weight of the acid-modified polyolefin is preferably about 6000 to 200000, and more preferably about 8000 to 150,000.
  • the weight average molecular weight of the acid-modified polyolefin is a value measured by gel permeation chromatography (GPC) measured under conditions using polystyrene as a standard sample.
  • GPC gel permeation chromatography
  • the melting point of the acid-modified polyolefin is preferably about 50 ° C. or higher and 160 ° C. or lower, and more preferably about 50 ° C. or higher and 120 ° C. or lower.
  • the melting point of the acid-modified polyolefin refers to the endothermic peak temperature in differential scanning calorimetry.
  • the method for modifying the polyolefin is not particularly limited, and for example, an unsaturated carboxylic acid or an acid anhydride thereof or a (meth) acrylic acid ester may be copolymerized with the polyolefin.
  • examples of such copolymerization include random copolymerization, block copolymerization, graft copolymerization (graft modification), and the like, and preferably graft copolymerization.
  • the epoxy resin is not particularly limited as long as it is a resin capable of forming a crosslinked structure with an epoxy group present in the molecule, and a known epoxy resin can be used.
  • epoxy resin examples include bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether.
  • An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the proportion of the epoxy resin in the first insulating layer 51 is preferably in the range of 0.5 to 20 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin, and is 1 to 10 parts by mass. It is more preferable that it is in the range. Thereby, the insulation and durability of the battery packaging material can be further improved.
  • the thickness of the first insulating layer 51 is not particularly limited, but is preferably 10 ⁇ m or less, more preferably about 1 ⁇ m or more and 5 ⁇ m or less from the viewpoint of further enhancing the insulation and durability together with the second insulating layer 52. .
  • the second insulating layer 52 is formed of the metal layer 3 and the heat-fusible resin layer 41 together with the above-described first insulating layer 51 in order to improve the insulation and durability of the battery packaging material. It is a layer provided between them.
  • the second insulating layer 52 is laminated on the heat-fusible resin layer 41 side, and the first insulating layer 51 is laminated on the metal layer 3 side.
  • the melting temperature of the second insulating layer 52 is lower than the melting temperature of the first insulating layer 51. Since the melting temperature of the second insulating layer 52 is set lower than the melting temperature of the first insulating layer 51, the first insulating layer 51 and the second insulating layer 52 exhibit high durability and high flexibility. In addition, it is possible to effectively prevent a decrease in insulation properties of the battery packaging material due to foreign matter.
  • the melting temperature of the second insulating layer 52 is not particularly limited as long as it is lower than the melting temperature of the first insulating layer 51, but is preferably 150 ° C. or higher, more preferably about 150 ° C. or higher and 180 ° C. or lower.
  • the resin for forming the second insulating layer 52 is not particularly limited as long as it has the aforementioned melting temperature.
  • the second insulating layer 52 is preferably made of polyolefin from the viewpoint of further improving the insulating properties and durability when used together with the first insulating layer 51.
  • the polyolefin is not particularly limited as long as it is a resin containing at least an olefin as a monomer unit.
  • the polyolefin can be composed of, for example, at least one of polyethylene and polypropylene, and is preferably composed of polypropylene.
  • the polyethylene can be composed of, for example, at least one of homopolyethylene and ethylene copolymer.
  • Polypropylene can be composed of, for example, at least one of homopolypropylene and propylene copolymer.
  • propylene copolymer examples include copolymers of propylene and other olefins such as ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-propylene-butene copolymer.
  • the proportion of the propylene unit contained in the polypropylene is preferably about 50 mol% or more and 100 mol% or less, more preferably about 80 mol% or more and 100 mol% or less, from the viewpoint of further improving the insulation and durability of the battery packaging material. More preferably.
  • the proportion of the ethylene unit contained in the polyethylene is preferably about 50 mol% or more and 100 mol% or less, and more preferably 80 mol% or more and 100 mol% from the viewpoint of further improving the insulation and durability of the battery packaging material. More preferably, it is about the following.
  • Each of the ethylene copolymer and the propylene copolymer may be a random copolymer or a block copolymer, and a block propylene copolymer is preferred.
  • the ethylene copolymer and the propylene copolymer may each be crystalline or amorphous, and may be a copolymer or a mixture thereof.
  • the polyolefin may be formed of one type of homopolymer or copolymer, or may be formed of two or more types of homopolymer or copolymer.
  • the melting point of the polyolefin is preferably about 120 ° C. or higher and 180 ° C. or lower, more preferably 140 ° C. or higher and 180 ° C. or lower.
  • the melting point of polyolefin refers to the endothermic peak temperature in differential scanning calorimetry.
  • the thickness of the second insulating layer 52 is not particularly limited, but is preferably about 10 ⁇ m or more and 50 ⁇ m or less, more preferably about 15 ⁇ m or more and 40 ⁇ m or less from the viewpoint of further improving insulation and durability together with the first insulating layer 51. Is mentioned.
  • the adhesive layer 6 is a layer provided between the first insulating layer 51 and the second insulating layer 52, if necessary, in order to enhance the adhesion between the first insulating layer 51 and the second insulating layer 52.
  • the adhesive layer 6 is formed of an adhesive capable of adhering the first insulating layer 51 and the second insulating layer 52. Although it does not restrict
  • the thickness of the adhesive layer 6 is not particularly limited as long as it exhibits a function as an adhesive layer, and may be, for example, 20 ⁇ m or less, preferably about 2 ⁇ m or more and 10 ⁇ m or less.
  • the adhesive layer 7 is a layer provided between these layers as necessary in order to firmly bond the metal layer 3 and the first insulating layer 51.
  • the adhesive layer 7 is formed of an adhesive capable of bonding the metal layer 3 and the first insulating layer 51.
  • the adhesive component used for the adhesive layer 7 is preferably acid-modified polyolefin, more preferably carboxylic acid-modified polyolefin, and particularly preferably carboxylic acid-modified polypropylene.
  • the thickness of the adhesive layer 7 is not particularly limited as long as it exhibits a function as an adhesive layer, and examples thereof include about 1 ⁇ m to 10 ⁇ m, preferably about 1 ⁇ m to 5 ⁇ m.
  • the heat-fusible resin layer 41 corresponds to the innermost layer, and is a layer that heat-welds the heat-fusible resin layers together to seal the battery element when the battery is assembled. .
  • the resin component used for the heat-fusible resin layer 41 is not particularly limited as long as it can be heat-welded, and examples thereof include polyolefin and acid-modified polyolefin.
  • polyolefins include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymers (for example, block copolymers of propylene and ethylene), polypropylene Polypropylenes such as random copolymers (for example, random copolymers of propylene and ethylene); ethylene-butene-propylene terpolymers; and the like.
  • polyethylene and polypropylene are preferable, and polypropylene is more preferable.
  • the polyolefin may be a cyclic polyolefin.
  • the cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin that is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, and isoprene. It is done.
  • examples of the cyclic monomer that is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene, and the like.
  • cyclic alkene is preferable, and norbornene is more preferable.
  • the acid-modified polyolefin is a polymer obtained by modifying the above polyolefin by block polymerization or graft polymerization with carboxylic acid or the like.
  • carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.
  • the acid-modified polyolefin may be an acid-modified cyclic polyolefin.
  • An acid-modified cyclic polyolefin is a copolymer in which a part of the monomer constituting the cyclic polyolefin is copolymerized in place of the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, or ⁇ , ⁇ -unsaturated with respect to the cyclic polyolefin. It is a polymer obtained by block polymerization or graft polymerization of a saturated carboxylic acid or its anhydride.
  • the cyclic polyolefin to be acid-modified is the same as described above.
  • the carboxylic acid used for modification is the same as that used for modification of the acid-modified cycloolefin copolymer.
  • polyolefins preferred are polyolefins, and more preferred are propylene copolymers.
  • propylene copolymer include copolymers of propylene and other olefins such as ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-propylene-butene copolymer.
  • the proportion of the propylene unit contained in the polypropylene is preferably about 50 mol% or more and 100 mol% or less, more preferably about 80 mol% or more and 100 mol% or less, from the viewpoint of further improving the insulation and durability of the battery packaging material. More preferably.
  • the proportion of the ethylene unit contained in the polyethylene is preferably about 50 mol% or more and 100 mol% or less, and more preferably 80 mol% or more and 100 mol% from the viewpoint of further improving the insulation and durability of the battery packaging material. More preferably, it is about the following.
  • Each of the ethylene copolymer and the propylene copolymer may be a random copolymer or a block copolymer, and a random propylene copolymer is preferred.
  • the heat-fusible resin layer 41 may be formed of one type of resin component alone, or may be formed of a blend polymer in which two or more types of resin components are combined. Furthermore, the heat-fusible resin layer 41 may be formed of only one layer, but may be formed of two or more layers using the same or different resin components.
  • the innermost layer (the side opposite to the metal layer 3) of the heat-fusible resin layer 41 is a layer formed by a dry lamination method or extrusion molding. Preferably there is. Thereby, insulation and a moldability can be improved further.
  • the melting temperature of the heat-fusible resin layer 41 is preferably lower than the melting temperature of the second insulating layer 52.
  • the melting temperature of the heat-fusible resin layer 41 is preferably about 80 ° C. or higher and 160 ° C. or lower, more preferably about 100 ° C. or higher and 140 ° C. or lower.
  • the heat-fusible resin layer 41 preferably has fine irregularities on its surface (the innermost layer side surface). Thereby, a moldability can be improved further.
  • a method of forming fine irregularities on the surface of the heat-fusible resin layer 41 a method of adding a matting agent exemplified in the surface coating layer described later to the heat-fusible resin layer 41, and irregularities on the surface. For example, a method may be used in which the cooling roll is brought into contact with the mold.
  • the thickness of the heat-fusible resin layer 41 is not particularly limited as long as it exhibits the function as the heat-fusible resin layer, and for example, it is about 10 ⁇ m to 40 ⁇ m, preferably about 15 ⁇ m to 40 ⁇ m. .
  • the base material layer 1 may be formed on the base material layer 1 as necessary (the metal layer of the base material layer 1). If necessary, a surface coating layer (not shown) may be provided on the side opposite to (3).
  • a surface coating layer is a layer located in the outermost layer when a battery is assembled.
  • the surface coating layer can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, or the like. Of these, the surface coating layer is preferably formed of a two-component curable resin. Examples of the two-component curable resin that forms the surface coating layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Moreover, you may mix
  • Examples of the matting agent include fine particles having a particle size of about 0.5 nm to 5 ⁇ m.
  • the material of the matting agent is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances.
  • the shape of the matting agent is not particularly limited, and examples thereof include a spherical shape, a fiber shape, a plate shape, an indeterminate shape, and a balloon shape.
  • Specific examples of the matting agent include talc, silica, graphite, kaolin, montmorilloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, and aluminum oxide.
  • These matting agents may be used individually by 1 type, and may be used in combination of 2 or more type. Among these matting agents, silica, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability and cost.
  • the matting agent may be subjected to various surface treatments such as insulation treatment and high dispersibility treatment on the surface.
  • the method for forming the surface coating layer is not particularly limited, and examples thereof include a method of applying a two-component curable resin for forming the surface coating layer on one surface of the base material layer 1.
  • the matting agent may be added to the two-component curable resin, mixed, and then applied.
  • the thickness of the surface coating layer is not particularly limited as long as it exhibits the above function as the surface coating layer, and examples thereof include about 0.5 ⁇ m or less and about 10 ⁇ m or less, preferably about 1 ⁇ m or less and about 5 ⁇ m or less.
  • the method for producing the battery packaging material of the first invention is not particularly limited as long as a laminate in which layers of a predetermined composition are laminated is obtained, and at least the base material layer 1 and And a lamination step for obtaining a laminate comprising the metal layer 3, the adhesive layer 4, and the heat-fusible resin layer 5 in this order, and the adhesive layer 4 is an acid-modified polyolefin having a melting point of 50 ° C. or higher and 120 ° C. or lower.
  • a method of forming a resin composition containing an epoxy resin having a weight average molecular weight of 50 to 2000 can be employed. That is, the battery packaging material of the present invention can be manufactured by laminating each layer using the adhesive layer 4 described in the section of “2. Each layer forming the battery packaging material”.
  • a laminate including the base material layer 1, the adhesive layer 2, and the metal layer 3 in this order (hereinafter also referred to as “laminate A”) is formed.
  • the laminate A is formed by extruding an adhesive used for forming the adhesive layer 2 on the base layer 1 or the metal layer 3 whose surface is subjected to a chemical conversion treatment, if necessary. It can be performed by a dry laminating method in which the metal layer 3 or the base material layer 1 is laminated and the adhesive layer 2 is cured after being applied and dried by a coating method such as a method or a roll coating method.
  • the adhesive layer 4 and the heat-fusible resin layer 5 are laminated on the metal layer 3 of the laminate A.
  • laminating the adhesive layer 4 and the heat-fusible resin layer 5 on the metal layer 3 for example, (1) the adhesive layer 4 and the heat-fusible resin layer 5 are formed on the metal layer 3 of the laminate A.
  • a method of laminating by coextrusion (coextrusion lamination method) (2) Separately, a laminated body in which the adhesive layer 4 and the heat-fusible resin layer 5 are laminated is formed on the metal layer 3 of the laminated body A.
  • the above resin composition for forming the adhesive layer 4 on the metal layer 3 of the laminate A is applied by a coating method such as a gravure coating method or a roll coating method.
  • the heat-sealable resin layer is laminated to dry the adhesive layer 4, and (4) the metal layer 3 of the laminate A and the heat-sealable resin layer previously formed into a sheet shape 5, while the molten adhesive layer 4 is poured in between the laminated body 5 and the laminated body via the adhesive layer 4.
  • Etc. be bonded method heat-welding resin layer 5 may be mentioned as.
  • the method (3) is preferable.
  • the above resin composition for forming the adhesive layer 4 is laminated on the metal layer 3 and then dried at a temperature of 60 ° C. or higher and 120 ° C. or lower.
  • the innermost layer of the heat-fusible resin layer is preferably a layer formed by a dry lamination method or extrusion molding.
  • the surface coating layer is laminated on the surface of the base material layer 1 opposite to the metal layer 3.
  • the surface coating layer can be formed, for example, by applying the above-described resin for forming the surface coating layer to the surface of the base material layer 1.
  • the order of the step of laminating the metal layer 3 on the surface of the base material layer 1 and the step of laminating the surface coating layer on the surface of the base material layer 1 are not particularly limited.
  • the metal layer 3 may be formed on the surface of the base material layer 1 opposite to the surface coating layer.
  • a heat roll contact type is further provided. It may be subjected to heat treatment such as hot air, near or far infrared. Examples of such heat treatment conditions include 150 to 250 ° C. and 1 to 5 minutes.
  • the method for producing the battery packaging material of the second invention is not particularly limited as long as a laminate in which layers of a predetermined composition are laminated is obtained. At least the base material layer, the metal layer, and the first insulation are provided. A step of laminating a layer, a second insulating layer, and a heat-fusible resin layer in this order to obtain a laminate, wherein the melting temperature of the first insulating layer is 200 ° C. or higher, A method of setting the melting temperature lower than the melting temperature of the first insulating layer can be employed. That is, as the first insulating layer 51 and the second insulating layer 52, by using the layers described in the section of “2. Each layer for forming a battery packaging material”, by laminating each layer, the battery of the second invention Packaging materials can be produced.
  • a laminate including the base material layer 1, the adhesive layer 2, and the metal layer 3 in this order (hereinafter may be referred to as “laminate A”) is formed.
  • the laminate A is formed by extruding an adhesive used for forming the adhesive layer 2 on the base layer 1 or the metal layer 3 whose surface is subjected to a chemical conversion treatment, if necessary. It can be performed by a dry laminating method in which the metal layer 3 or the base material layer 1 is laminated and the adhesive layer 2 is cured after being applied and dried by a coating method such as a method or a roll coating method.
  • the first insulating layer 51, the second insulating layer 52, and the heat-fusible resin layer 4 are stacked on the metal layer 3 of the stacked body A.
  • the method for laminating the first insulating layer 51 and the second insulating layer 52 on the metal layer 3 is not limited.
  • the resin and the second insulating layer that form the first insulating layer 51 on the metal layer 3 are used.
  • covers resin which comprises 52 in order is mentioned.
  • a resin film constituting the first insulating layer 51 or a resin film constituting the second insulating layer 52 may be laminated.
  • the second insulating layer 52 is laminated after applying the resin constituting the adhesive layer 6 on the first adhesive layer 51. do it. Further, a film in which the adhesive layer 6 is previously laminated on the second insulating layer 52 may be laminated on the first insulating layer 51.
  • a resin for forming the adhesive layer 7 is applied on the metal layer 3, and then the first insulating layer 51 and the like are laminated. do it.
  • the battery packaging material of the second invention is obtained.
  • the surface coating layer is laminated on the surface of the base material layer 1 opposite to the metal layer 3.
  • the surface coating layer can be formed, for example, by applying the above-described resin for forming the surface coating layer to the surface of the base material layer 1.
  • the order of the step of laminating the metal layer 3 on the surface of the base material layer 1 and the step of laminating the surface coating layer on the surface of the base material layer 1 are not particularly limited.
  • the metal layer 3 may be formed on the surface of the base material layer 1 opposite to the surface coating layer.
  • surface coating layer / base material layer 1 / adhesive layer 2 provided as needed / metal layer 3 whose surface is subjected to chemical conversion treatment as needed / adhesive layer 7 / provided as needed A laminate composed of the first insulating layer 51 / adhesive layer 6 / second insulating layer 52 / heat-fusible resin layer 4 provided as needed is formed, but the adhesive layer 2 and provided as needed.
  • heat treatment such as a hot roll contact type, a hot air type, a near or far infrared type. Examples of such heat treatment conditions include 150 ° C. or more and 250 ° C. or less and 1 minute or more and 5 minutes or less.
  • each layer constituting the laminate improves or stabilizes film forming properties, lamination processing, suitability for final processing (pouching, embossing), etc., as necessary. Therefore, surface activation treatment such as corona treatment, blast treatment, oxidation treatment, ozone treatment may be performed.
  • the battery packaging material of the present invention is used as a packaging material for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte.
  • a battery element including at least a positive electrode, a negative electrode, and an electrolyte is formed using the battery packaging material of the present invention, with the metal terminals connected to each of the positive electrode and the negative electrode protruding outward.
  • a flange portion region where the heat-fusible resin layers are in contact with each other
  • heat-sealing the heat-fusible resin layers of the flange portion to seal the battery
  • the battery packaging material of the present invention is used so that the heat-fusible resin portion is on the inner side (surface in contact with the battery element).
  • the battery packaging material of the present invention may be used for either a primary battery or a secondary battery, but is preferably a secondary battery.
  • the type of secondary battery to which the battery packaging material of the present invention is applied is not particularly limited.
  • a lithium ion battery, a lithium ion polymer battery, a lead battery, a nickel / hydrogen battery, a nickel / cadmium battery , Nickel / iron livestock batteries, nickel / zinc livestock batteries, silver oxide / zinc livestock batteries, metal-air batteries, polyvalent cation batteries, capacitors, capacitors and the like are suitable applications for the battery packaging material of the present invention.
  • the weight average molecular weight of the resin is a value measured by gel permeation chromatography (GPC) measured under conditions using polystyrene as a standard sample.
  • the melting temperature is a penetration temperature according to the TMA penetration mode according to JIS K7196: 2012, and EXSTAR6000 manufactured by Seiko Instruments Inc. was used as the apparatus.
  • the melting point of the main agent of the adhesive layer was measured using a differential scanning calorimeter in accordance with the provisions of JIS K7121: 2012.
  • Examples 1A to 12A and Comparative Examples 1A to 17A> On a nylon film (thickness 25 ⁇ m) as a base material layer, a metal layer made of aluminum foil (thickness 35 ⁇ m) subjected to chemical conversion treatment on both surfaces was laminated by a dry laminating method. Specifically, a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to one surface of the aluminum foil, and an adhesive layer (thickness 3 ⁇ m) was formed on the metal layer. Subsequently, after laminating the adhesive layer and the base material layer on the metal layer, an aging treatment was carried out at 40 ° C.
  • a two-component urethane adhesive polyol compound and aromatic isocyanate compound
  • the chemical conversion treatment of the aluminum foil used as the metal layer is performed by roll coating a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m 2 (dry mass).
  • the coating was performed on both surfaces of the aluminum foil by the method and baked for 20 seconds under the condition that the film temperature was 180 ° C. or higher.
  • Comparative Example 17 polypropylene was extruded on the metal layer to obtain a laminate including a base material layer, an adhesive layer, a metal layer, and a heat-fusible resin layer in this order. Each obtained laminate was aged at 70 ° C. for 24 hours to obtain battery packaging materials of Examples 1A to 12A and Comparative Examples 1A to 17A. Table 1A shows the thickness of the adhesive layer converted from the coating amount and density.
  • Each battery packaging material obtained above was cut into 60 mm (MD direction, vertical direction) ⁇ 150 mm (TD direction, horizontal direction) as shown in the schematic diagram of FIG. 5 (FIG. 5A). .
  • the cut battery packaging material was folded in two so that the heat-fusible resin layers face each other in the TD direction (FIG. 5B).
  • one side E facing in the TD direction and one side F in the MD direction are heat-welded (the width of the heat-welded portion S is 7 mm) to produce a bag-shaped battery packaging material in which one side in the TD direction opens. (FIG. 5C, opening G).
  • the heat welding conditions were a temperature of 190 ° C., a surface pressure of 1.0 MPa, and a heating / pressurization time of 3 seconds.
  • 3 g of the electrolytic solution H was injected from the opening G.
  • the opening G was 7 mm wide and heat-welded under the same conditions as above (FIG. 5E).
  • the portion where the opening G of the battery packaging material was located was faced up (state shown in FIG. 5 (e)), and was allowed to stand in an isothermal layer at 85 ° C. for 24 hours.
  • each battery packaging material is taken out from the thermostatic layer, and as shown in FIG. 5 (f), the side into which the electrolytic solution H has been injected is cut off (the position indicated by the broken line in FIG. 5 (f)). Was opened, and the electrolytic solution H was taken out (FIG. 5G).
  • a portion with a width W15 mm in the TD direction of the battery packaging material was cut into a strip shape (a broken line portion in FIG. 5H) to obtain a test piece T (FIG. 5I).
  • the heat-sealable resin layer and the metal layer of the obtained test piece T were peeled off, and the heat-sealable resin layer and the metal layer were separated by 50 mm using a tensile tester (trade name AGS-50D manufactured by Shimadzu Corporation).
  • the sample was pulled at a rate of / min and the peel strength (N / 15 mm) of the test piece was measured (peel strength after the durability test).
  • the peel strength was measured in the same manner for the test piece T obtained by cutting the battery packaging materials obtained in Examples 1A to 12A and Comparative Examples 1A to 17A to a width of 15 mm (peel strength before the durability test).
  • the results are shown in Table 1A.
  • the adhesive layer located between these layers is laminated on either or both of the heat-fusible resin layer and the metal layer. It becomes.
  • each battery packaging material obtained above was cut into a size of 60 mm (horizontal direction) ⁇ 150 mm (vertical direction) to obtain a test piece (FIG. 6A).
  • this test piece was folded so that the short sides were opposed to each other, and the test pieces were arranged so that the surfaces of the heat-fusible resin layers of the test pieces were opposed to each other.
  • a wire M of 25 ⁇ m ⁇ was inserted between the surfaces of the heat-fusible resin layers facing each other (FIG. 6B).
  • the heat-fusible resin layers were heat-sealed with a heat-sealing machine composed of a flat plate-like hot plate 7 mm wide in the direction perpendicular to the length direction of the battery packaging material (FIG. 6 (c). ), Heat-welded portion S).
  • a heat-sealing machine composed of a flat plate-like hot plate 7 mm wide in the direction perpendicular to the length direction of the battery packaging material (FIG. 6 (c). ), Heat-welded portion S).
  • heat sealing was performed from above the portion where the wire M is located, and the heat-fusible resin layer was heat-sealed to the wire M.
  • the positive electrode of the tester was connected to the wire M, and the negative electrode was connected to the battery packaging material on one side.
  • the adhesive layer disposed between the metal layer and the heat-fusible resin layer is composed of an acid-modified polyolefin having a melting point of 50 ° C. to 120 ° C. and an epoxy having a weight average molecular weight of 50 to 2000. It can be seen that the battery packaging materials of Examples 1A to 12A formed of a resin composition containing a resin are excellent in durability and insulation.
  • Comparative Examples 9A to 12A not using acid Comparative Examples 13A to 16A not using acid-modified polyolefin, and Comparative Example 17 having no adhesive layer, compared to Examples 1A to 12A, respectively. Many have low insulation and low durability.
  • thermomechanical analyzer A probe was placed on the surface of the adhesive layer at the end of each battery packaging material obtained in Example 10A and Comparative Example 11A, and the probe was heated from 40 ° C. to 250 ° C. (temperature increase rate 5 ° C./min, tip of probe) The radius was 30 nm or less, the load applied to the probe was deviation (Defection-4V), and the displacement of the probe was measured. Graphs showing the relationship between the heating temperature and the displacement of the probe position are shown in FIG. 7 (Example 10A) and FIG. 8 (Comparative Example 11A), respectively. Details of the measurement conditions are as follows.
  • thermomechanical analyzer An afm plus system manufactured by ANALYSIS INSTRUMENTS was used as the thermomechanical analyzer, and a cantilever ThermaLever was used as the probe.
  • three kinds of attached samples polycaprolactam (melting point 55 ° C.), polyethylene (melting point 116 ° C.), polyethylene terephthalate (melting point 235 ° C.)) were used, applied voltage 0.1-10 V, speed 0.2 V / Second, Deviation-4V.
  • Example 10A As shown in FIG. 7, in the battery packaging material obtained in Example 10A, the probe position was measured when the probe was heated from 40 ° C. to 220 ° C. in the probe displacement measurement using the thermomechanical analyzer. It can be seen that is not lower than the initial value. Furthermore, in Example 10A, it can be seen that the amount of increase in the position of the probe when heated from 140 ° C. to 220 ° C. is larger than the amount of increase in the position of the probe when heated from 80 ° C. to 120 ° C. On the other hand, as shown in FIG. 8, in the battery packaging material obtained in Comparative Example 11A, when the probe displacement was measured from 40 ° C. to 220 ° C. in the probe displacement measurement using the thermomechanical analyzer, the probe It can be seen that the position of is lower than the initial value.
  • Examples 1B to 4B and Comparative Examples 1B to 4B> On a nylon film (thickness 25 ⁇ m) as a base material layer, a metal layer made of aluminum foil (thickness 35 ⁇ m) subjected to chemical conversion treatment on both surfaces was laminated by a dry laminating method. Specifically, a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of an aluminum foil, and an adhesive layer (thickness 3 ⁇ m) was formed on the metal layer. Subsequently, after laminating the adhesive layer and the base material layer on the metal layer, an aging treatment was performed at 40 ° C.
  • a two-component urethane adhesive a polyol compound and an aromatic isocyanate compound
  • the chemical conversion treatment of the aluminum foil used as the metal layer is performed by roll coating a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m 2 (dry mass).
  • the coating was performed on both surfaces of the aluminum foil by the method and baked for 20 seconds under the condition that the film temperature was 180 ° C. or higher.
  • Example 4B a laminated film of an adhesive layer, a second insulating layer, and a heat-fusible resin layer was laminated on the first insulating layer by a dry laminating method.
  • the resin constituting each layer, the thickness, and the melting temperature are as shown in Table 1B.
  • the base material layer / adhesive layer / metal layer / first insulating layer / second insulating layer / heat-fusible resin layer were laminated in this order. A laminate was obtained.
  • Example 4B the laminated body by which the base material layer / adhesive layer / metal layer / first insulating layer / adhesive layer / second insulating layer / heat-fusible resin layer was laminated in this order was obtained.
  • Comparative Example 1 a laminate was obtained in which the base material layer / adhesive layer / metal layer / first insulating layer / heat-sealable resin layer were laminated in this order.
  • Comparative Example 2 a laminate was obtained in which the base material layer / adhesive layer / metal layer / second insulating layer / heat-sealable resin layer were laminated in this order.
  • Each of the obtained laminates was aged at 70 ° C. for 24 hours to obtain battery packaging materials of Examples 1B to 4B and Comparative Examples 1B to 4B.
  • acid-modified PP means maleic anhydride-modified polypropylene
  • random PP means random propylene copolymer
  • block PP means block propylene copolymer
  • the battery packaging material is a laminate including at least a base material layer, a metal layer, a first insulating layer, a second insulating layer, and a heat-fusible resin layer in this order.
  • the battery packaging material of Examples 1B to 4B, wherein the melting temperature of the first insulating layer is 200 ° C. or higher and the melting temperature of the second insulating layer is set lower than the melting temperature of the first insulating layer It can be seen that is excellent in durability and insulation.
  • the battery packaging material of Comparative Example 1 in which the second insulating layer was not provided had poor insulation.
  • the battery packaging material of Comparative Example 2B in which the first insulating layer was not provided durability and insulation were inferior.
  • the 1st insulating layer and the 2nd insulating layer were provided, in the packaging material for batteries of Comparative Examples 3B and 4B whose melting temperature of the 1st insulating layer is less than 200 degreeC, durability and insulation were inferior. .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

L'invention concerne un matériau d'emballage de pile présentant de hautes performances d'isolation et une haute durabilité. Le matériau d'emballage de pile comprend un corps stratifié comportant au moins une couche de substrat, une couche métallique, une couche adhésive et une couche de résine thermofusible, dans l'ordre indiqué. La couche adhésive a une composition de résine qui contient une polyoléfine modifiée par un acide et une résine époxy. Dans des mesures de quantité de déplacement de sonde impliquant l'utilisation d'un analyseur thermomécanique, lorsqu'on place une sonde sur la surface de la couche adhésive au niveau d'une partie d'extrémité du matériau d'emballage de pile et on chauffe la sonde de 40 °C à 220 °C, la position de la sonde ne chute pas par rapport à la valeur initiale.
PCT/JP2016/060575 2015-03-30 2016-03-30 Matériau d'emballage de pile, son procédé de fabrication, et pile Ceased WO2016159190A1 (fr)

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HK18105028.5A HK1246003B (zh) 2015-03-30 2016-03-30 电池用包装材料、其制造方法和电池
CN201680019778.4A CN107431152B (zh) 2015-03-30 2016-03-30 电池用包装材料、其制造方法和电池
US15/561,704 US10886506B2 (en) 2015-03-30 2016-03-30 Cell packaging material, method for manufacturing same, and cell

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JP2016069528A JP6686634B2 (ja) 2015-03-30 2016-03-30 電池用包装材料、その製造方法及び電池
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CN111587495A (zh) * 2018-01-22 2020-08-25 大日本印刷株式会社 电池用包装材料、其制造方法和电池
CN111587495B (zh) * 2018-01-22 2022-10-04 大日本印刷株式会社 电池用包装材料、其制造方法和电池
WO2019142934A1 (fr) * 2018-01-22 2019-07-25 大日本印刷株式会社 Matériau de conditionnement de batterie et son procédé de production, et batterie
WO2020085461A1 (fr) * 2018-10-24 2020-04-30 大日本印刷株式会社 Matériau de conditionnement pour dispositif de stockage d'énergie, son procédé de production et dispositif de stockage d'énergie
JPWO2020085461A1 (ja) * 2018-10-24 2021-09-24 大日本印刷株式会社 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス
JP7447797B2 (ja) 2018-10-24 2024-03-12 大日本印刷株式会社 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス
JP2024075583A (ja) * 2018-10-24 2024-06-04 大日本印刷株式会社 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス
JP7740403B2 (ja) 2018-10-24 2025-09-17 大日本印刷株式会社 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス
CN114080725A (zh) * 2019-07-11 2022-02-22 株式会社自动网络技术研究所 配线模块、蓄电模块、汇流条及蓄电模块的制造方法

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