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WO2018066671A1 - Matériau d'enveloppe pour batterie ainsi que procédé de fabrication de celui-ci, et batterie - Google Patents

Matériau d'enveloppe pour batterie ainsi que procédé de fabrication de celui-ci, et batterie Download PDF

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Publication number
WO2018066671A1
WO2018066671A1 PCT/JP2017/036385 JP2017036385W WO2018066671A1 WO 2018066671 A1 WO2018066671 A1 WO 2018066671A1 JP 2017036385 W JP2017036385 W JP 2017036385W WO 2018066671 A1 WO2018066671 A1 WO 2018066671A1
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WO
WIPO (PCT)
Prior art keywords
layer
packaging material
probe
battery
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/JP2017/036385
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English (en)
Japanese (ja)
Inventor
かおる 津森
山下　力也
山下　孝典
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
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Priority to CN201780006100.7A priority Critical patent/CN108431987B/zh
Priority to JP2018543975A priority patent/JP7238403B2/ja
Publication of WO2018066671A1 publication Critical patent/WO2018066671A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • H01M50/30—Arrangements for facilitating escape of gases
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a packaging material for a battery, a manufacturing method thereof, and a battery.
  • the battery may continuously increase the temperature in the battery due to charging due to overvoltage or discharging with an excessive current, causing a battery reaction runaway.
  • the battery packaging material is sealed without sealing until reaching a certain temperature.
  • it is required to design so as to gradually release the gas in the battery packaging material by gently opening the wrapping material while suppressing ignition and the like due to a sudden ejection of the combustible gas.
  • An object of the present invention is to provide a battery packaging material that can suppress excessive expansion and ignition of the battery packaging material.
  • a battery comprising a laminate including at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order.
  • the probe is set on the surface of the adhesive layer in the cross section of the battery packaging material, and the deflection setting value of the probe at the start of measurement is ⁇
  • the battery packaging material whose temperature is lower than the initial value is 130 ° C. or less.
  • the battery element can be kept sealed until the pressure or temperature in the battery rises to a certain level, and when the pressure or temperature rises in the battery is advanced, it leads to a gentle opening. It is possible It was found that.
  • the present inventors are composed of a laminate including at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order, and in a thermomechanical analysis for measuring the displacement of the probe
  • the probe is placed on the surface of the adhesive layer in the cross section of the packaging material for the battery, and the probe deflection setting value at the start of measurement is ⁇ 4 V and the temperature rise rate is 5 ° C./min.
  • the packaging material for batteries whose temperature is 100 ° C. or less is at a certain level where the pressure and temperature in the battery are increased.
  • the battery element can be maintained in a sealed state, and can be led to a gentle opening when the pressure and temperature in the battery are continuously increased.
  • Item 1 It is composed of a laminate comprising at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order,
  • the probe is set on the surface of the adhesive layer in the cross section of the laminate, and the set value of the deflection of the probe at the start of measurement is ⁇ 4 V and the heating rate is 5 ° C.
  • a battery packaging material in which, when the probe is heated from 40 ° C. to 220 ° C.
  • a temperature at which the position of the probe decreases from an initial value is 130 ° C. or less.
  • Item 2. It is composed of a laminate comprising at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order, In the thermomechanical analysis for measuring the displacement of the probe, the probe is set on the surface of the adhesive layer in the cross section of the laminate, and the set value of the deflection of the probe at the start of measurement is ⁇ 4 V and the heating rate is 5 ° C.
  • a packaging material for a battery wherein a temperature at which the position of the probe reaches the highest point is 100 ° C. or lower when the probe is heated from 40 ° C. to 220 ° C.
  • Item 5 The battery packaging material according to any one of Items 1 to 4, wherein the base material layer includes at least a polyester film layer and a polyamide film layer.
  • Item 7. Item 7.
  • Item 8. Item 8.
  • Item 9. Item 9.
  • Item 10. Item 10.
  • a packaging material for a battery according to claim 1. Item 14.
  • Item 1 is a cured product of a resin composition containing a curing agent having at least one selected from the group consisting of an oxygen atom, a heterocyclic ring, a C ⁇ N bond, and a C—O—C bond.
  • the battery packaging material according to any one of 12 to 12.
  • Item 16. The battery packaging material according to any one of Items 1 to 15, wherein the adhesive layer has a thickness of 5 ⁇ m or less.
  • the surface of the barrier layer has an acid-resistant film, When the acid-resistant film is analyzed using time-of-flight secondary ion mass spectrometry, at least one selected from the group consisting of Ce 2 PO 4 + , CePO 4 ⁇ , CrPO 2 + , and CrPO 4 ⁇ is used. Item 17.
  • the acid barrier film comprising at least one selected from the group consisting of a phosphorus compound, a chromium compound, a fluoride, and a triazine thiol compound on the surface of the barrier layer.
  • a battery wherein a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte is accommodated in a package formed of the battery packaging material according to any one of items 1 to 19.
  • Item 21 At least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer are provided so as to be laminated in this order, and a step of obtaining a laminate is provided.
  • thermomechanical analysis for measuring the displacement of the probe as the adhesive layer the probe is set on the surface of the adhesive layer in the cross section of the laminate, and the deflection setting value of the probe at the start of measurement is ⁇ 4V, A battery for which a temperature at which the position of the probe is lowered from the initial value when the probe is heated from 40 ° C. to 220 ° C. at a temperature increase rate of 5 ° C./min is 130 ° C. or less is used.
  • Manufacturing method of packaging material Item 22. At least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer are provided so as to be laminated in this order, and a step of obtaining a laminate is provided.
  • thermomechanical analysis for measuring the displacement of the probe as the adhesive layer the probe is set on the surface of the adhesive layer in the cross section of the laminate, and the deflection setting value of the probe at the start of measurement is ⁇ 4V, A battery packaging material that uses a probe whose temperature reaches a maximum of 100 ° C. or less when the probe is heated from 40 ° C. to 220 ° C. at a heating rate of 5 ° C./min. Manufacturing method.
  • the first battery packaging material of the present invention is a battery packaging material composed of a laminate comprising at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order,
  • the probe is set on the surface of the adhesive layer in the cross section of the battery packaging material, and the set value of the deflection of the probe at the start of measurement is ⁇ 4 V, and the heating rate is 5 ° C.
  • the temperature at which the position of the probe decreases from the initial value is 130 ° C. or less.
  • the second battery packaging material of the present invention is composed of a laminate including at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order.
  • a probe is set on the surface of the adhesive layer in the cross section of the battery packaging material, and the setting value of the deflection of the probe at the start of measurement is ⁇ 4 V and the temperature rising rate is 5 ° C./min.
  • the temperature at which the probe position becomes the highest point is 100 ° C. or less.
  • the battery packaging material of the present invention the battery packaging material can be gently opened even when the pressure or temperature in the battery continuously increases, and the battery packaging material is excessive. Safe expansion can be suppressed.
  • FIG. 5 is an example of a cross-sectional structure of a battery packaging material, and is a diagram for illustrating a position where a probe is installed (an adhesive layer surface of a cross section of the battery packaging material) in a thermomechanical analysis for measuring a displacement amount of the probe. It is a conceptual diagram of the position change of the probe in the thermomechanical analysis which measures the displacement amount of a probe.
  • the graph which shows the relationship between the heating temperature at the time of setting a probe in the adhesive layer surface of the cross section of the battery packaging material obtained in Example 1, and heating a probe from 40 degreeC to predetermined temperature, and the position of a probe. It is.
  • the graph which shows the relationship between the heating temperature at the time of setting a probe in the adhesive layer surface of the cross section of the battery packaging material obtained in Example 2, and heating a probe from 40 degreeC to predetermined temperature, and the position of a probe. It is.
  • the graph which shows the relationship between the heating temperature at the time of setting a probe in the adhesive layer surface of the cross section of the battery packaging material obtained in Example 3, and heating a probe from 40 degreeC to predetermined temperature, and the position of a probe. It is.
  • the graph which shows the relationship between the heating temperature at the time of setting a probe in the adhesive layer surface of the cross section of the battery packaging material obtained by the comparative example 2 and heating a probe from 40 degreeC to predetermined temperature, and the position of a probe. It is.
  • One side surface of a state (A) in which two battery packaging materials of the present invention are heat-sealed to form a sealed space (A), a state in which peeling is formed after the temperature rise (B), and a state at the time of opening (C) Is a schematic cross-sectional view (the left end is heat-sealed, and the right-hand side is omitted).
  • One side surface of a state (A) in which two battery packaging materials of the present invention are heat-sealed to form a sealed space (A), a state in which peeling is formed after the temperature rise (B), and a state at the time of opening (C) Is a schematic cross-sectional view (the left end is heat-sealed, and the right-hand side is omitted).
  • thermomechanical analysis which measures the displacement amount of a probe, it is a schematic perspective view for showing the position (5 places) where a probe is installed.
  • the first battery packaging material of the present invention is composed of a laminate including at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order, and measures the displacement of the probe.
  • a probe is placed on the surface of the adhesive layer in the cross section of the laminate, and the probe deflection setting at the start of measurement is ⁇ 4 V, the temperature rise rate is 5 ° C./min, and the probe is 40 ° C.
  • the temperature at which the probe position is lowered from the initial value when heated to 220 ° C. is 130 ° C. or less.
  • the second battery packaging material of the present invention is composed of a laminate including at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer in this order.
  • a probe is set on the surface of the adhesive layer in the cross section of the laminate, and the probe deflection setting value at the start of measurement is ⁇ 4 V, and the temperature rise rate is 5 ° C./min.
  • the temperature at which the position of the probe reaches the highest point when heated from 40 ° C. to 220 ° C. is 100 ° C. or less.
  • the battery packaging material of the present invention can maintain the sealed state of the battery element until the pressure or temperature in the battery rises to a certain level.
  • the pressure or temperature rises continuously it can lead to a gentle opening.
  • the internal pressure can be gently lowered by releasing the combustible gas generated inside the battery to the outside after the pressure and temperature inside the battery reach a certain level.
  • the internal pressure inside the battery it is possible to suppress the release of the electrolytic solution to the outside of the battery cell.
  • the concentration of the combustible gas generated inside the battery is reduced, and the ignition of the battery can be suppressed.
  • the ignition of the battery can be suppressed also by the fact that the electrolyte in the battery is easily dried by the inflow of air.
  • the separator inside the battery is likely to shrink, so the battery is deformed with an increase in internal pressure, and there is an increased risk of ignition due to a short circuit, but by using the battery packaging material of the present invention, Since the concentration of the flammable gas that causes ignition can be reduced by the release of the flammable gas generated inside the battery and the inflow of air from the outside, ignition due to a short circuit can be effectively suppressed.
  • the battery packaging material of the present invention will be described in detail.
  • the numerical range indicated by “to” means “above” or “below”.
  • the notation of 2 to 15 mm means 2 mm or more and 15 mm or less.
  • the battery packaging material 10 of the present invention includes a base layer 1, a barrier layer 3, an adhesive layer 4, and a heat-fusible resin layer 5 in this order, for example, as shown in FIG. It is composed of a laminate.
  • 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 of the present invention has an adhesive layer 2 between the base material layer 1 and the barrier layer 3 for the purpose of enhancing the adhesion between them. It may be.
  • the surface coating layer 6 etc. may be provided in the outer side of the base material layer 1 (opposite side to the heat-fusible resin layer 5) as needed.
  • the thickness of the laminate constituting the battery packaging material of the present invention is not particularly limited, but is preferably about 160 ⁇ m or less from the viewpoint of exhibiting high insulation while reducing the thickness of the laminate as much as possible. More preferred is about 35 to 155 ⁇ m, still more preferred is about 45 to 120 ⁇ m. Even when the thickness of the laminate constituting the battery packaging material of the present invention is as thin as 160 ⁇ m or less, for example, the present invention can exhibit excellent insulation. For this reason, the packaging material for batteries of this invention can contribute to the improvement of the energy density of a battery.
  • each layer forming the battery packaging material [base material layer 1]
  • 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.
  • Examples of the material for forming the base material layer 1 include polyester, polyamide, epoxy resin, acrylic resin, fluorine resin, polyurethane, silicon resin, phenol resin, polyetherimide, polyimide, and a mixture or copolymer thereof. Resin. As the base material layer 1, a resin film may be used or a resin may be applied and formed.
  • the base material layer 1 may have a single-layer structure formed of these resins, or may have a multilayer structure in order to improve pinhole resistance and insulation when used as a battery package. Good.
  • Specific examples of the multilayer structure 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, and a multilayer structure in which a plurality of polyester films are laminated.
  • 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 base material layer 1 is formed from two resin films, 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 thickness of each layer is preferably 3 to 25 ⁇ m.
  • each layer may be bonded through an adhesive, or may be directly laminated without using an adhesive.
  • a method of bonding in a hot-melt state such as a co-extrusion method, a sandwich lamination method, or a thermal lamination method can be used.
  • the adhesive agent to be used may be a two-component curable adhesive, or a one-component curable adhesive.
  • the adhesive 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, an electron beam curable type, an ultraviolet curable type, and the like. Specific examples of the adhesive include those similar to the adhesive exemplified in the adhesive layer 2. Further, the thickness of the adhesive can be the same as that of the adhesive layer 2.
  • the base material layer 1 preferably includes at least one of a polyester film layer and a polyamide film layer, and more preferably includes at least a polyester film layer and a polyamide film layer.
  • the polyester constituting the polyester film layer is a copolymer mainly composed of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and ethylene terephthalate.
  • Examples thereof include a polyester and a copolyester having butylene terephthalate as a main repeating unit.
  • the copolymer polyester mainly composed of ethylene terephthalate is a copolymer polyester that polymerizes with ethylene isophthalate mainly composed of ethylene terephthalate (hereinafter, polyethylene (terephthalate / isophthalate)).
  • polyethylene terephthalate / isophthalate
  • polyethylene terephthalate / adipate
  • polyethylene terephthalate / sodium sulfoisophthalate
  • polyethylene terephthalate / sodium isophthalate
  • polyethylene terephthalate / phenyl-dicarboxylate
  • polyethylene terephthalate / decanedicarboxylate
  • polyester mainly composed of butylene terephthalate as a repeating unit
  • a copolymer polyester that polymerizes with butylene isophthalate having butylene terephthalate as a repeating unit hereinafter referred to as polybutylene (terephthalate / isophthalate).
  • polybutylene (terephthalate / adipate) polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene naphthalate and the like.
  • These polyesters may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Polyester has the advantage of being excellent in electrolytic solution resistance and less likely to cause whitening due to the adhesion of the electrolytic solution, and is suitably used as a material for forming the base material layer 1.
  • the polyester film layer is preferably composed of a biaxially stretched polyester film, particularly a biaxially stretched polyethylene terephthalate film.
  • the thickness of the polyester film layer is not particularly limited, but is preferably about 20 ⁇ m or less, more preferably about 1 to 15 ⁇ m, and still more preferably from the viewpoint of exhibiting excellent moldability while thinning the battery packaging material.
  • An example is about 3 to 12 ⁇ m.
  • polyamide constituting the polyamide film layer examples include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and a copolymer of nylon 6 and nylon 66.
  • Hexamethylenediamine-isophthalic acid-terephthalic acid such as nylon 6I, nylon 6T, nylon 6IT, nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) containing structural units derived from terephthalic acid and / or isophthalic acid
  • Polyamides containing aromatics such as copolymerized polyamides and polymetaxylylene adipamide (MXD6); Alicyclic polyamides such as polyaminomethylcyclohexyl adipamide (PACM6); and lactam components and 4,4′-diphenylmethane-diisocyanate Isocyanates such as Min copolymerized allowed polyamide, copolyamide and a polyester and polyalkylene ether glycol with
  • polyamides may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the stretched polyamide film is excellent in stretchability, can prevent whitening due to resin cracking of the base material layer 1 during molding, and is suitably used as a material for forming the base material layer 1.
  • the polyamide film layer is preferably composed of a biaxially stretched polyamide film, particularly a biaxially stretched nylon film.
  • the thickness of the polyamide film layer is not particularly limited, but is preferably about 30 ⁇ m or less, more preferably about 1 to 25 ⁇ m, and still more preferably from the viewpoint of exhibiting excellent moldability while thinning the battery packaging material.
  • An example is about 10 to 25 ⁇ m.
  • the ratio of the thickness of the polyester film layer to the thickness of the polyamide film layer (the thickness of the polyester film layer: the thickness of the polyamide film layer) in the base material layer 1 is 1: 1 to 1. Is preferably in the range of 1: 5, more preferably in the range of 1: 1.2 to 1: 4. When the ratio of the thickness is within such a range, it is easy to balance the stress at the time of forming the battery packaging material, and the battery packaging material can be suitably thinned.
  • the order of lamination of the polyester film layer and the polyamide film layer is not particularly limited.
  • the polyester resin is difficult to discolor when, for example, the electrolyte solution adheres to the surface, the electrolyte solution of the battery packaging material From the viewpoint of improving the properties, it is preferable that a polyamide film layer and a polyester film layer are provided in this order from the barrier layer 3 side described later.
  • a layer containing at least one of polyester and polyolefin may be provided between the polyester film layer and the polyamide film layer.
  • the polyolefin preferably includes a resin composition containing a modified thermoplastic resin graft-modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative component.
  • the modified thermoplastic resin preferably includes a resin obtained by modifying a polyolefin resin, a styrene elastomer, a polyester elastomer or the like with an unsaturated carboxylic acid derivative component.
  • the said resin may be used individually by 1 type, and may be used in combination of 2 or more types.
  • unsaturated carboxylic acid derivative component unsaturated carboxylic acid, an acid anhydride of unsaturated carboxylic acid, ester of unsaturated carboxylic acid, etc. are mentioned.
  • unsaturated carboxylic acid derivative component one kind may be used alone, or two or more kinds may be used in combination.
  • polyolefin resin in the modified thermoplastic resin examples include low density polyethylene, medium density polyethylene, high density polyethylene; ethylene- ⁇ olefin copolymer; homo, block or random polypropylene; propylene- ⁇ olefin copolymer; Examples include copolymers obtained by copolymerizing polar molecules such as acrylic acid and methacrylic acid; polymers such as crosslinked polyolefins, and the like.
  • One type of polyolefin resin may be used alone, or two or more types of combinations may be used.
  • styrenic elastomer in the modified thermoplastic resin examples include a copolymer of styrene (hard segment) and butadiene or isoprene or a hydrogenated product (soft segment) thereof.
  • One type of polyolefin resin may be used alone, or two or more types of combinations may be used.
  • polyester elastomer in the modified thermoplastic resin examples include a copolymer of crystalline polyester (hard segment) and polyalkylene ether glycol (soft segment).
  • hard segment crystalline polyester
  • soft segment polyalkylene ether glycol
  • One type of polyolefin resin may be used alone, or two or more types of combinations may be used.
  • Examples of the unsaturated carboxylic acid in the modified thermoplastic resin include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo [2,2,1] hept-2-ene- Examples include 5,6-dicarboxylic acid.
  • Examples of unsaturated carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6- And dicarboxylic acid anhydride.
  • Examples of the unsaturated carboxylic acid ester include methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, tetrahydro And esters of unsaturated carboxylic acids such as dimethyl phthalic anhydride and dimethyl bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylate.
  • modified thermoplastic resin with respect to 100 parts by mass of a base thermoplastic resin, 0.2 to 100 parts by mass of the unsaturated carboxylic acid derivative component is heated and reacted in the presence of a radical initiator. It is obtained with.
  • the reaction temperature is preferably about 50 to 250 ° C, more preferably about 60 to 200 ° C.
  • the reaction time depends on the production method, in the case of a melt graft reaction by a twin screw extruder, it is preferably about 2 to 30 minutes, more preferably about 5 to 10 minutes, which is within the residence time of the extruder.
  • the denaturation reaction can be carried out under both normal pressure and pressurized conditions.
  • the radical initiator used in the modification reaction includes organic peroxides.
  • Various materials can be selected as the organic peroxide depending on temperature conditions and reaction time.
  • alkyl peroxides aryl peroxides, acyl peroxides, ketone peroxides, peroxyketals, peroxycarbonates, peroxides. Examples thereof include oxyesters and hydroperoxides.
  • alkyl peroxides, peroxyketals and peroxyesters are preferable, and di-t-butyl peroxide, 2,5-dimethyl-2,5-di-t- It is more preferable to use butylperoxy-hexyne-3, dicumyl peroxide.
  • the thickness of the adhesive positioned between the polyester film layer and the polyamide film layer is preferably about 0.1 to 5 ⁇ m, more preferably about 0.5 to 3 ⁇ m.
  • the adhesive layer 13 may contain the same colorant as that of the adhesive layer 2 described later.
  • a lubricant is present on the surface of the base material layer 1 (surface opposite to the barrier layer).
  • the amount of the lubricant is not particularly limited, but is preferably about 3 mg / m 2 or more, more preferably 4 to 15 mg / m 2 in a temperature 24 ° C. and humidity 60% environment.
  • about m 2 more preferably about 5 to 14 mg / m 2 is mentioned.
  • the lubricant is not particularly limited, but preferably an amide lubricant.
  • Specific examples of the lubricant include saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylol amide, saturated fatty acid bisamide, unsaturated fatty acid bisamide and the like.
  • Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide and the like.
  • Specific examples of the unsaturated fatty acid amide include oleic acid amide and erucic acid amide.
  • substituted amide examples include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide and the like.
  • methylolamide examples include methylol stearamide.
  • saturated fatty acid bisamides include methylene bis stearamide, ethylene biscapric amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bisbehenic acid amide, hexamethylene bis stearic acid amide.
  • acid amide hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sebacic acid amide, and the like.
  • unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide Etc.
  • Specific examples of the fatty acid ester amide include stearoamidoethyl stearate.
  • aromatic bisamide examples include m-xylylene bis stearic acid amide, m-xylylene bishydroxy stearic acid amide, N, N′-distearyl isophthalic acid amide and the like.
  • One type of lubricant may be used alone, or two or more types may be used in combination.
  • the base material layer 1 may contain a lubricant. Further, the lubricant present on the surface of the base material layer 1 may be obtained by leaching the lubricant contained in the resin constituting the base material layer 1 or by applying a lubricant to the surface of the base material layer 1. It may be.
  • the thickness of the base material layer 1 is preferably about 4 ⁇ m or more, more preferably about 10 to 75 ⁇ m from the viewpoint of making the battery packaging material excellent in moldability while reducing the thickness of the battery packaging material. Preferably, the thickness is about 10 to 50 ⁇ m.
  • the adhesive layer 2 is a layer provided between the base material layer 1 and the barrier layer 3 as necessary in order to firmly bond them.
  • the adhesive layer 2 is formed of an adhesive capable of bonding the base material layer 1 and the barrier 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, and copolyester; polyethers Polyurethane adhesive; epoxy resin; phenolic resin; polyamide resin such as nylon 6, nylon 66, nylon 12, copolymer polyamide; polyolefin resin such as polyolefin, carboxylic acid modified polyolefin, metal modified polyolefin , Polyvinyl acetate resin; cellulose adhesive; (meth) acrylic resin; polyimide resin; polycarbonate; amino resin such as urea resin and melamine resin; chloroprene rubber, nitrile rubber, styrene - 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
  • the polyurethane adhesive is a polyurethane adhesive containing a main component containing a polyol component (A) and a curing agent containing a polyisocyanate component (B), and the polyol component (A) is a polyester polyol ( A1), the polyester polyol (A1) is a polyester polyol having a number average molecular weight of 5,000 to 50,000 and comprising a polybasic acid component and a polyhydric alcohol component, and is aromatic in 100 mol% of the polybasic acid component. Examples include those containing 45 to 95 mol% of a polybasic acid component and having a tensile stress of 100 kg / cm 2 or more and 500 kg / cm 2 or less when the adhesive layer is 100% elongated.
  • An equivalent ratio [NCO] / ([OH] + [COOH]) of isocyanate groups contained in the agent is 1 to 30.
  • the adhesive agent containing resin containing ((A) or (B)) is also mentioned.
  • the adhesive layer 2 may contain a colorant.
  • the battery packaging material can be colored.
  • the colorant known ones such as pigments and dyes can be used.
  • 1 type may be used for a coloring agent, and 2 or more types may be mixed and used for it.
  • inorganic pigments preferably include carbon black and titanium oxide.
  • organic pigments preferably include azo pigments, phthalocyanine pigments, and condensed polycyclic pigments.
  • azo pigments include soluble pigments such as watching red and force-min 6C; insoluble azo pigments such as monoazo yellow, disazo yellow, pyrazolone orange, pyrazolone red, and permanent red, and phthalocyanine pigments include copper phthalocyanine pigments.
  • blue pigments and green pigments as metal-free phthalocyanine pigments, and condensed polycyclic pigments include dioxazine violet and quinacridone violet.
  • a pearl pigment, a fluorescent pigment, or the like can be used.
  • carbon black is preferable in order to make the appearance of the battery packaging material black.
  • the average particle diameter of the pigment is not particularly limited, and examples thereof include about 0.05 to 5 ⁇ m, preferably about 0.08 to 2 ⁇ m.
  • the average particle diameter of a pigment be the median diameter measured with the laser diffraction / scattering type particle size distribution measuring apparatus.
  • the content of the pigment in the adhesive layer 2 is not particularly limited as long as the battery packaging material is colored, and examples thereof include about 5 to 60% by mass.
  • the thickness of the adhesive layer 2 is not particularly limited as long as it exhibits a function as an adhesive layer, and may be, for example, about 1 to 10 ⁇ m, preferably about 2 to 5 ⁇ m.
  • the colored layer is a layer provided as necessary between the base material layer 1 and the adhesive layer 2 (illustration is omitted). By providing the colored layer, the battery packaging material can be colored.
  • the colored layer can be formed, for example, by applying an ink containing a colorant to the surface of the base material layer 1 or the surface of the barrier layer 3.
  • a colorant known ones such as pigments and dyes can be used.
  • 1 type may be used for a coloring agent, and 2 or more types may be mixed and used for it.
  • colorant contained in the colored layer are the same as those exemplified in the column of [Adhesive layer 2].
  • the barrier 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.
  • the barrier layer 3 can be formed of a metal foil, a metal vapor-deposited film, an inorganic oxide vapor-deposited film, a carbon-containing inorganic oxide vapor-deposited film, a film provided with these vapor-deposited layers, or the like, and is a layer formed of metal.
  • the metal constituting the barrier layer 3 include aluminum, stainless steel, titanium steel, and preferably aluminum.
  • the barrier layer 3 can be formed by metal foil or metal vapor deposition, preferably by metal foil, and more preferably by aluminum foil or stainless steel foil. From the viewpoint of preventing generation of wrinkles and pinholes in the barrier layer 3 during the production of the battery packaging material, for example, annealed aluminum (JIS H4160: 1994 A8021H-O, JIS H4160: 1994 A8079H-O). JIS H4000: 2014 A8021P-O, JIS H4000: 2014 A8079P-O) and the like, and more preferably formed of a soft aluminum foil.
  • examples of the stainless steel foil include austenitic stainless steel foil and ferritic stainless steel foil.
  • the stainless steel foil is preferably made of austenitic stainless steel.
  • austenitic stainless steel constituting the stainless steel foil include SUS304, SUS301, SUS316L, and among these, SUS304 is particularly preferable.
  • the thickness of the barrier layer 3 is not particularly limited as long as it functions as a barrier layer such as water vapor, but the upper limit is preferably about 85 ⁇ m or less, more preferably about 50 ⁇ m or less, and still more preferably 40 ⁇ m or less.
  • the lower limit is preferably about 10 ⁇ m or more, and the thickness range is, for example, about 10 to 85 ⁇ m, preferably about 10 to 50 ⁇ m, and more preferably about 10 to 45 ⁇ m.
  • the thickness of the stainless steel foil is preferably about 85 ⁇ m or less, more preferably about 50 ⁇ m or less, still more preferably about 40 ⁇ m or less, and further preferably about 30 ⁇ m or less.
  • Particularly preferred is about 25 ⁇ m or less, and the lower limit is about 10 ⁇ m or more, and the preferred thickness range is about 10 to 85 ⁇ m, about 10 to 50 ⁇ m, more preferably about 10 to 40 ⁇ m, more preferably About 10 to 30 ⁇ m, more preferably about 15 to 25 ⁇ m.
  • the barrier 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 barrier layer.
  • the barrier layer 3 includes an acid resistant film.
  • chromate chromate using 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- C1-C4 straight or branched chain in which one hydroxyl group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group is substituted
  • 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 a repeating unit represented by the general formulas (1) to (4) is, for example, preferably 500 to 1,000,000, and more preferably 1,000 to 20,000. .
  • a phosphoric acid is coated with a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate fine particles dispersed therein.
  • a method of forming an acid-resistant film on the surface of the barrier 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 acid resistant film.
  • 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.
  • an acid-resistant film for example, as an example, at least the surface on the inner layer side of an aluminum foil (barrier layer) is first subjected to an alkali dipping method, electrolytic cleaning method, acid cleaning method, electrolytic A degreasing treatment is performed by a known treatment method such as an acid cleaning method or an acid activation method, and then a phosphoric acid Cr (chromium) salt, phosphoric acid Ti (titanium) salt, phosphoric acid Zr (zirconium) salt, phosphorus Treatment liquid (aqueous solution) mainly composed of a metal phosphate such as Zn (zinc) salt and a mixture of these metals, or a mixture of a non-metal phosphate and a mixture of these non-metals Treatment liquid (aqueous solution), or a treatment liquid (aqueous solution) composed of a mixture of these with an aqueous synthetic resin such as an acrylic resin, a phenolic resin, or a urethane resin, a
  • CrPO 4 chromium phosphate
  • AlPO 4 aluminum phosphate
  • Al 2 O 3 aluminum oxide
  • Al (OH) x water Zn 2 PO 4 ⁇ 4H 2 O (zinc phosphate hydrate) when treated with an acid-resistant film made of aluminum oxide), AlF x (aluminum fluoride), etc.
  • AlPO 4 aluminum phosphate
  • Al 2 O 3 aluminum oxide
  • Al (OH) x aluminum hydroxide
  • AlF x aluminum fluoride
  • an acid-resistant film for example, at least the surface on the inner layer side of the aluminum foil, first, an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid activity
  • An acid-resistant film can be formed by performing a degreasing process by a known processing method such as a chemical conversion method and then performing a known anodizing process on the degreasing surface.
  • a film of a phosphorus compound (for example, phosphate-based) or a chromium compound (for example, chromic acid-based) can be given.
  • a phosphorus compound for example, phosphate-based
  • a chromium compound for example, chromic acid-based
  • the phosphate system include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, and chromium phosphate.
  • the chromic acid system include chromium chromate.
  • an acid-resistant film by forming an acid-resistant film such as a phosphorus compound (phosphate, etc.), a chromium compound (chromate, etc.), a fluoride, a triazine thiol compound, etc., during emboss molding
  • an acid-resistant film such as a phosphorus compound (phosphate, etc.), a chromium compound (chromate, etc.), a fluoride, a triazine thiol compound, etc.
  • an acid-resistant film such as a phosphorus compound (phosphate, etc.), a chromium compound (chromate, etc.), a fluoride, a triazine thiol compound, etc.
  • an aqueous solution composed of three components of a phenolic resin, a chromium fluoride (3) compound, and phosphoric acid is applied to the aluminum surface, and the dry baking treatment is good.
  • the acid-resistant film includes a layer having cerium oxide, phosphoric acid or phosphate, an anionic polymer, and a crosslinking agent that crosslinks the anionic polymer, and the phosphoric acid or phosphate is 1 to 100 parts by mass may be blended with 100 parts by mass of cerium oxide. It is preferable that the acid-resistant film has a multilayer structure further including a layer having a cationic polymer and a crosslinking agent for crosslinking the cationic polymer.
  • the anionic polymer is poly (meth) acrylic acid or a salt thereof, or a copolymer containing (meth) acrylic acid or a salt thereof as a main component.
  • the said crosslinking agent is at least 1 sort (s) chosen from the group which has a functional group in any one of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent.
  • the phosphoric acid or phosphate is preferably condensed phosphoric acid or condensed phosphate.
  • 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 acid resistant film examples include those containing at least one of phosphate, chromate, fluoride, and triazine thiol.
  • An acid resistant film containing a cerium compound is also preferable.
  • cerium compound cerium oxide is preferable.
  • the acid resistant film examples include a phosphate film, a chromate film, a fluoride film, and a triazine thiol compound film.
  • a phosphate film examples include a phosphate film, a chromate film, a fluoride film, and a triazine thiol compound film.
  • an acid-resistant film one of these may be used, or a plurality of combinations may be used.
  • a treatment liquid composed of a mixture of a metal phosphate and an aqueous synthetic resin, or a mixture of a non-metal phosphate and an aqueous synthetic resin It may be formed with a treatment liquid.
  • the composition of the acid resistant film can be analyzed using, for example, time-of-flight secondary ion mass spectrometry.
  • time-of-flight secondary ion mass spectrometry for example, secondary ions composed of Ce, P and O (for example, at least one kind of Ce2PO 4 + , CePO 4 ⁇ , etc.)
  • secondary ions composed of Ce, P and O for example, at least one kind of Ce2PO 4 + , CePO 4 ⁇ , etc.
  • a peak derived from a secondary ion composed of Cr, P and O for example, at least one kind of CrPO 2 + , CrPO 4 ⁇ , etc.
  • the amount of the acid-resistant film formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited.
  • the chromic acid compound is present per 1 m 2 of the surface of the barrier layer 3.
  • the thickness of the acid-resistant film is not particularly limited, but is preferably about 1 nm to 20 ⁇ m, more preferably about 1 to 100 nm, from the viewpoint of the cohesive strength of the film and the adhesive strength with the barrier layer and the heat-fusible resin layer. More preferably, about 1 to 50 nm is mentioned.
  • the thickness of the acid-resistant film can be measured by observation with a transmission electron microscope, or a combination of observation with a transmission electron microscope and energy dispersive X-ray spectroscopy or electron energy loss spectroscopy.
  • a solution containing a compound used for forming an acid-resistant film is applied to the surface of the barrier layer by a bar coating method, a roll coating method, a gravure coating method, a dipping method, etc., and then the temperature of the barrier layer is 70. It is carried out by heating to a temperature of ⁇ 200 ° C.
  • the barrier 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 process in this manner, it is possible to more efficiently perform the chemical conversion process on the surface of the barrier layer.
  • the adhesive layer 4 is a layer provided between the barrier layer 3 and the heat-fusible resin layer 5 in order to firmly bond them.
  • the probe in the thermomechanical analysis for measuring the displacement of the probe, the probe is installed on the surface of the adhesive layer 4 in the cross section of the battery packaging material, and the probe differential at the start of measurement is measured.
  • the probe is heated from 40 ° C. to 220 ° C. under the conditions of a set value of ⁇ 4 V and a heating rate of 5 ° C./min, the temperature at which the probe position falls below the initial value is 130 ° C. or lower. It is characterized by.
  • the adhesive layer 4 located between the barrier layer 3 and the heat-fusible resin layer 5 has such specific physical properties,
  • the battery element can be kept sealed until the pressure or temperature in the battery rises to a certain level, and the adhesive layer is reached when the pressure or temperature in the battery continues to rise. 4 and a layer adjacent thereto (the barrier layer 3 and the heat-fusible resin layer 5) can be gently opened by promptly causing fine cleavage such as pinholes.
  • the heat sealing resin layer 5 of the first battery packaging material of the present invention is heat-sealed in a state of facing each other, and an aluminum plate as a dummy cell and an electrolyte replacement
  • water is sealed with a battery packaging material and heated to 130 ° C. under vacuum, it is led to gentle opening at a temperature of 130 ° C. or lower.
  • FIGS. 16 to 18 corresponds to the mode of the left side of C
  • the mode of the right side of B corresponds to the mode of the right side of C. Yes.
  • the adhesive layer 4 and the heat-fusible resin layer 5 are in a bag shape (inner bag) and the battery element is sealed. Is considered to be maintained.
  • the region (inner bag) of the adhesive layer 4 and the heat-fusible resin layer 5 peeled from the barrier layer 3 is subjected to fine cleavage (such as H in FIG. 16). It is considered that the unsealed state is obtained under mild conditions.
  • the second mechanism when the battery is heated up to a certain temperature (for example, about 80 to 120 ° C.) from the state shown in FIG. 17A, as shown in FIG. At this time, the agglomerated detachment occurs in at least a part, and at this time, the agglomerated and exfoliated portion of the adhesive layer 4 and the heat-fusible resin layer 5 in contact with the agglomerated detachable bag are in a bag shape (inner bag) and the battery element is sealed. It is thought to maintain. Subsequently, as shown in FIG.
  • a certain temperature for example, about 80 to 120 ° C.
  • the region where the adhesive layer 4 is agglomerated and peeled and the heat-fusible resin layer 5 (inner bag) in contact with the region are finely cleaved such as pinholes (H in FIG. 17). It is considered that the unsealed state will occur under mild conditions.
  • the adhesive layer 4 is formed of a plurality of layers, when peeling occurs inside the adhesive layer 4, peeling occurs at least at a part of the interface between the plurality of layers, and a pin is formed in the peeled area. A minute break such as a hole may occur, and the opened state may be obtained under mild conditions.
  • the battery packaging material of the present invention is used for a battery whose opening temperature is set to about 120 ° C. or less. It is preferable.
  • the opening temperature is more preferably about 80 to 95 ° C.
  • the battery element can be kept sealed until the pressure and temperature in the battery rise to a certain level, and the pressure and temperature in the battery continue to rise continuously.
  • the temperature at which the position of the probe is lower than the initial value is preferably about 60 to 130 ° C., more preferably 60 About 90 ° C can be mentioned.
  • the temperature at which the probe position is lowered from the initial value is about 60 to 90 ° C., it is possible to lead to gentle opening at an opening temperature of about 80 ° C. to 95 ° C.
  • the first battery packaging material of the present invention is measured by placing the probe on the surface of the adhesive layer 4 in the cross section of the battery packaging material in the thermomechanical analysis for measuring the displacement of the probe.
  • the setting value of the deflection of the probe at the start is -4 V, the temperature at which the probe position becomes the highest point when the probe is heated from 40 ° C. to 220 ° C. under the condition of a heating rate of 5 ° C./min.
  • it is preferably about 100 ° C. or less, preferably about 50 to 100 ° C., more preferably 50 to 70 ° C., and still more preferably about 50 to 65 ° C.
  • the probe in the thermomechanical analysis for measuring the displacement amount of the probe, the probe is placed on the surface of the adhesive layer 4 in the cross section of the battery packaging material, and the measurement at the start of measurement is performed.
  • the probe is heated from 40 ° C. to 220 ° C. under the conditions that the probe deflection is set at ⁇ 4 V and the temperature rising rate is 5 ° C./min, the temperature at which the probe position becomes the highest point is 100 ° C. It is characterized by the following.
  • the adhesive layer 4 located between the barrier layer 3 and the heat-fusible resin layer 5 has such specific physical properties,
  • the battery element can be kept sealed until the pressure or temperature in the battery rises to a certain level, and the adhesive layer is reached when the pressure or temperature in the battery continues to rise. 4 and a layer adjacent thereto (the barrier layer 3 and the heat-fusible resin layer 5) can be gently opened by promptly causing fine cleavage such as pinholes.
  • the heat-fusible resin layers 5 of the second battery packaging material of the present invention are heat-sealed in a state of facing each other, and an aluminum plate as a dummy cell and an alternative to the electrolytic solution
  • water is sealed with a battery packaging material and heated to 130 ° C. under vacuum, it is led to gentle opening at a temperature of 130 ° C. or lower.
  • the above-mentioned three mechanisms are conceivable as in the case of the first battery packaging material.
  • the second battery packaging material of the present invention is measured by placing the probe on the surface of the adhesive layer 4 in the cross section of the battery packaging material in the thermomechanical analysis for measuring the displacement of the probe.
  • the setting value of the deflection of the probe at the start is -4 V, the temperature at which the probe position becomes the highest point when the probe is heated from 40 ° C. to 220 ° C. under the condition of a heating rate of 5 ° C./min.
  • it is preferably 50 to 100 ° C., more preferably 50 to 70 ° C.
  • the second battery packaging material of the present invention starts measurement by installing a probe on the surface of the adhesive layer 4 in the cross section of the battery packaging material in thermomechanical analysis for measuring the displacement of the probe.
  • the temperature at which the probe position falls below the initial value is It is preferably 130 ° C. or less, more preferably about 60 to 130 ° C., and further preferably about 60 to 90 ° C.
  • thermomechanical analysis for measuring the displacement amount of the probe for example, as shown in the conceptual diagram of FIG. (Measurement start A in FIG. 5).
  • the cross section at this time is a portion where the cross section of the adhesive layer 4 obtained by cutting in the thickness direction so as to pass through the central portion of the battery packaging material is exposed.
  • FIG. 4 shows the probe installation position 4a. Cutting can be performed using a commercially available rotary microtome or the like.
  • the amount of displacement is measured for battery packaging materials used in batteries encapsulating electrolytes, etc., the portions where the heat-fusible resin layers of the battery packaging materials are heat-sealed together. In the same manner as described above, measurement is performed by cutting in the thickness direction.
  • thermomechanical analysis device An atomic force microscope to which a cantilever with a heating mechanism can be attached can be used as a thermomechanical analysis device.
  • a thermomechanical analysis device For example, an afm plus system manufactured by ANASIS INSTRUMENTS is used, and a cantilever ThermoLever AN2-200 (spring) is used as a probe.
  • a constant of 0.5-3 N / m) can be used.
  • the tip radius of the probe 11 is 30 nm or less, the set value of the deflection of the probe 11 is ⁇ 4 V, and the temperature rising rate is 5 ° C./min.
  • the surface of the adhesive layer 4 expands by the heat from the probe as shown in FIG.
  • the probe 11 is pushed up, and the position of the probe 11 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, the probe 11 is pierced into the adhesive layer 4 as shown in FIG. 5C, and the position of the probe 11 is lowered.
  • thermomechanical analysis for measuring the displacement of the probe 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. Start measurement. The displacement of the probe is measured by preparing a cross section along the thickness direction of the battery packaging material, measuring the cross section at five locations (see FIG.
  • the thickness direction and the vertical direction of the cross section may be any direction (for example, TD), and the temperature at which the position of the probe is lower than the initial value in any direction may be 130 ° C. or lower. . Also, calibration is performed five times and an average value is adopted.
  • the thermal behavior of only the adhesive layer can be measured in a state close to the state of use in a battery. That is, when the material for the adhesive layer is applied to a film substrate or the like, and the softening temperature or the like is measured from the surface by TMA or the like, the thickness required for the measurement is 10 times or more thicker than the actual thickness of the adhesive layer.
  • the thermal behavior differs because the degree of curing and the bonding state when actually used as a battery packaging material are different. In this case, the influence of the thermal behavior of the film substrate or the like may overlap, and it cannot be said that the thermomechanical properties of only the adhesive layer are measured.
  • the adhesive layer 4 is formed of a resin capable of bonding the barrier layer 3 and the heat-fusible resin layer 5.
  • the resin used for forming the adhesive layer 4 the adhesive mechanism, the kind of the adhesive component, and the like can be the same as the adhesive exemplified in the adhesive layer 2.
  • polyolefin resins such as polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, carboxylic acid-modified cyclic polyolefin exemplified in the above-described heat-fusible resin layer 5 can also be used. .
  • the resin constituting the adhesive layer 4 may or may not include a polyolefin skeleton, and preferably includes a polyolefin skeleton.
  • the fact that the resin constituting the adhesive layer 4 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited.
  • infrared spectroscopy when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm -1 and near the wave number 1780 cm -1.
  • the acid modification degree is low, the peak may be small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.
  • the adhesive layer 4 preferably contains an acid-modified polyolefin.
  • the acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of polyolefin with an acid component such as carboxylic acid.
  • the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof.
  • Polyolefins to be modified 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 (eg, random copolymers of propylene and ethylene); ethylene-butene-propylene terpolymers and the like.
  • polyethylene and polypropylene are preferable.
  • maleic anhydride-modified polyolefin among the acid-modified polyolefins, maleic anhydride-modified polyolefin, and further maleic anhydride-modified polypropylene are particularly preferable.
  • the adhesive layer 4 is a cured resin composition containing an acid-modified polyolefin and a curing agent. More preferably, it is a product.
  • Preferred examples of the acid-modified polyolefin include those described above.
  • the adhesive layer 4 is a cured product of a resin composition containing an acid-modified polyolefin and at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and a compound having an epoxy group.
  • the resin composition is preferably a cured product of a resin composition containing an acid-modified polyolefin and at least one selected from the group consisting of a compound having an isocyanate group and a compound having an epoxy group.
  • the contact bonding layer 4 contains at least 1 sort (s) selected from the group which consists of a urethane resin, ester resin, and an epoxy resin, and it is more preferable that the adhesive layer 4 contains a urethane resin and an epoxy resin.
  • the ester resin for example, an amide ester resin is preferable.
  • Amide ester resins are generally formed by the reaction of carboxyl groups and oxazoline groups.
  • the adhesive layer 4 is more preferably a cured product of a resin composition containing at least one of these resins and the acid-modified polyolefin.
  • the presence of the unreacted material is, for example, infrared spectroscopy, It can be confirmed by a method selected from Raman spectroscopy, time-of-flight secondary ion mass spectrometry (TOF-SIMS) and the like.
  • the curing agent having a heterocyclic ring include a curing agent having an oxazoline group and a curing agent having an epoxy group.
  • the curing agent having a C ⁇ N bond include a curing agent having an oxazoline group and a curing agent having an isocyanate group.
  • the curing agent having a C—O—C bond examples include a curing agent having an oxazoline group, a curing agent having an epoxy group, and a urethane resin.
  • the adhesive layer 4 is a cured product of a resin composition containing these curing agents, for example, gas chromatography mass spectrometry (GCMS), infrared spectroscopy (IR), time-of-flight secondary ion mass spectrometry (TOF) -SIMS) and X-ray photoelectron spectroscopy (XPS).
  • GCMS gas chromatography mass spectrometry
  • IR infrared spectroscopy
  • TOF time-of-flight secondary ion mass spectrometry
  • XPS X-ray photoelectron spectroscopy
  • the compound having an isocyanate group is not particularly limited, but a polyfunctional isocyanate compound is preferably used from the viewpoint of effectively improving the adhesion between the acid-resistant film and the adhesive layer 4.
  • the polyfunctional isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups.
  • Specific examples of the polyfunctional isocyanate-based curing agent include pentane diisocyanate (PDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and polymerization and nurate of these. And a mixture thereof and a copolymer with another polymer.
  • the content of the compound having an isocyanate group in the adhesive layer 4 is preferably in the range of 0.1 to 50% by mass, preferably 0.5 to 40% by mass in the resin composition constituting the adhesive layer 4. More preferably, it is in the range.
  • the compound having an oxazoline group is not particularly limited as long as it is a compound having an oxazoline skeleton.
  • Specific examples of the compound having an oxazoline group include those having a polystyrene main chain and those having an acrylic main chain.
  • the Epocross series by Nippon Shokubai Co., Ltd. etc. are mentioned, for example.
  • the ratio of the compound having an oxazoline group in the adhesive layer 4 is preferably in the range of 0.1 to 50% by mass, and in the range of 0.5 to 40% by mass in the resin composition constituting the adhesive layer 4. More preferably. Thereby, the adhesiveness of the barrier layer 3 (or acid-resistant film
  • 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 is preferably about 50 to 2000, more preferably about 100 to 1000, and still more preferably about 200 to 800.
  • 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 trimethylolpropane glycidyl ether derivative, bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and the like.
  • 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 0.1 to 50% by mass and preferably in the range of 0.5 to 40% by mass in the resin composition constituting the adhesive layer 4. Is more preferable. Thereby, the adhesiveness of the barrier layer 3 (or acid-resistant film
  • the adhesive layer 4 is a cured resin composition containing at least one selected from the group consisting of a compound having an isocyanate group, a compound having an oxazoline group, and an epoxy resin, and the acid-modified polyolefin.
  • the acid-modified polyolefin functions as a main agent, and the compound having an isocyanate group, the compound having an oxazoline group, and the epoxy resin each function as a curing agent.
  • the thickness of the adhesive layer 4 is preferably about 30 ⁇ m or less, more preferably about 20 ⁇ m or less, more preferably about 5 ⁇ m or less, and the lower limit is about 0.1 ⁇ m or more, about 0.5 ⁇ m or more,
  • the thickness ranges are preferably about 0.1 to 30 ⁇ m, about 0.1 to 20 ⁇ m, about 0.1 to 5 ⁇ m, about 0.5 to 30 ⁇ m, about 0.5 to 20 ⁇ m, 0.5 to For example, about 5 ⁇ m.
  • the carbodiimide curing agent is not particularly limited as long as it is a compound having at least one carbodiimide group (—N ⁇ C ⁇ N—).
  • a polycarbodiimide compound having at least two carbodiimide groups is preferable.
  • the curing agent may be composed of two or more kinds of compounds.
  • the content of the curing agent in the resin composition forming the adhesive layer 4 is preferably in the range of about 0.1 to 50% by mass, more preferably in the range of about 0.1 to 30% by mass, More preferably, it is in the range of about 0.1 to 10% by mass.
  • the adhesive layer 4 can also be suitably formed using, for example, an adhesive.
  • an adhesive for example, a non-crystalline polyolefin resin (A) having a carboxyl group, a polyfunctional isocyanate compound (B), and a tertiary amine having no functional group that reacts with the polyfunctional isocyanate compound (B) ( C), the polyfunctional isocyanate compound (B) is contained in an amount of 0.3 to 10 mol of the isocyanate group with respect to 1 mol of the total carboxyl groups, and 1 mol of the total carboxyl groups. And the one formed from the adhesive composition containing the tertiary amine (C) in the range of 1 to 10 mol.
  • a styrene-type thermoplastic elastomer (A), a tackifier (B), and a polyisocyanate (C) are contained, a styrene-type thermoplastic elastomer (A), a tackifier ( B) and 20 to 90% by mass of the styrenic thermoplastic elastomer (A) and 10 to 80% by mass of the tackifier (B) in a total of 100% by mass with the styrene thermoplastic elastomer (A).
  • the temperature at which the probe position falls below the initial value and the temperature at which the probe position reaches the highest point are not only the type of resin contained in the adhesive, but also the molecular weight of the resin. And the number of crosslinking points, the ratio between the main agent and the curing agent, the dilution ratio, the drying temperature, the aging temperature, the aging time, and the like.
  • the thickness of the adhesive layer 4 is not particularly limited as long as it functions as an adhesive layer.
  • the adhesive exemplified in the adhesive layer 2 is used, it is preferably about 2 to 10 ⁇ m, more preferably 2 to For example, about 5 ⁇ m.
  • the resin exemplified in the heat-fusible resin layer 5 is used, it is preferably about 2 to 50 ⁇ m, more preferably about 10 to 40 ⁇ m.
  • a cured product of an acid-modified polyolefin and a curing agent it is preferably about 30 ⁇ m or less, more preferably about 0.1 to 20 ⁇ m, and still more preferably about 0.5 to 5 ⁇ m.
  • the thickness after drying and curing is about 1 to 30 g / m 2 .
  • the adhesive layer 4 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 4 can be formed by applying the resin composition and curing it by heating or the like.
  • the heat-fusible resin layer 5 corresponds to the innermost layer, and is a layer that heat-fuses 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 is not particularly limited as long as it can be heat-sealed, and examples thereof include polyolefins, cyclic polyolefins, carboxylic acid-modified polyolefins, and carboxylic acid-modified cyclic polyolefins. It is done. That is, the resin constituting the heat-fusible resin layer 5 may or may not include a polyolefin skeleton, and preferably includes a polyolefin skeleton.
  • the resin constituting the heat-fusible resin layer 5 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited.
  • infrared spectroscopy when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm -1 and near the wave number 1780 cm -1.
  • the acid modification degree is low, the peak may be small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.
  • polystyrene resin examples include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymer (for example, block copolymer of propylene and ethylene), polypropylene And polypropylenes such as random copolymers of propylene and ethylene (eg, terpolymers of ethylene-butene-propylene).
  • polyethylene and polypropylene are preferable.
  • the cyclic polyolefin is a copolymer of an olefin and a cyclic monomer
  • examples of the olefin that is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, and isoprene. Is mentioned.
  • 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, and norbornadiene.
  • cyclic alkene is preferable, and norbornene is more preferable.
  • the carboxylic acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of the polyolefin with carboxylic acid.
  • Examples of the carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.
  • the carboxylic acid-modified cyclic polyolefin is obtained by copolymerizing a part of the monomer constituting the cyclic polyolefin in place of the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, or by ⁇ , ⁇ with respect to the cyclic polyolefin.
  • the cyclic polyolefin to be modified with carboxylic acid 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.
  • carboxylic acid-modified polyolefin is preferable; carboxylic acid-modified polypropylene is more preferable.
  • 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.
  • a lubricant may be present if necessary.
  • the lubricant is not particularly limited, and a known lubricant can be used, and examples thereof include those exemplified in the base material layer 1 described above.
  • One type of lubricant may be used alone, or two or more types may be used in combination.
  • the amount of lubricant present on the surface of the heat-fusible resin layer 5 is not particularly limited. From the viewpoint of improving the moldability of the electronic packaging material, it is preferably 10 to 50 mg at a temperature of 24 ° C. and a humidity of 60%. / M 2 , more preferably about 15 to 40 mg / m 2 .
  • the heat-fusible resin layer 5 may contain a lubricant. Further, the lubricant present on the surface of the heat-fusible resin layer 5 may be one obtained by leaching the lubricant contained in the resin constituting the heat-fusible resin layer 5, or the heat-fusible resin layer. 5 may be obtained by applying a lubricant to the surface.
  • the seal strength (N / 15 mm) in the 120 ° C. environment of the portion where the heat-fusible resin layers 5 are heat-sealed is the seal strength (N / 15 mm) in the 25 ° C. environment. Is preferably 1/8 or less, more preferably in the range of 1/18 to 1/8.
  • the upper limit of the seal strength in the 120 ° C. environment of the portion where the heat-fusible resin layers 5 are heat-sealed is preferably about 20 N / 15 mm or less, more preferably about 18N / 15mm or less, more preferably about 15N / 15mm or less, and the lower limit is preferably about 2N / 15mm or more, more preferably about 3N / 15mm or more, preferably about 5N / 15mm or more.
  • the preferable range of the sealing strength is about 2 to 20 N / 15 mm, about 2 to 18 N / 15 mm, about 2 to 15 N / 15 mm, about 3 to 20 N / 15 mm, about 3 to 18 N / 15 mm, about 3 to 15 N / Examples include about 15 mm, about 5 to 20 N / 15 mm, about 5 to 18 N / 15 mm, and about 5 to 15 N / 15 mm.
  • the upper limit of the seal strength in the 100 ° C. environment of the portion where the heat-fusible resin layers 5 are heat-sealed is preferably about 30 N / 15 mm or less, more preferably about 25 N / 15 mm or less, more preferably about 22.9 N / 15 mm or less, and the lower limit is preferably about 3 N / 15 mm or more, more preferably about 5 N / 15 mm or more, preferably about 8 N / 15 mm or more.
  • the preferable range of the seal strength is about 3 to 30 N / 15 mm, about 3 to 25 N / 15 mm, about 3 to 22.9 N / 15 mm, about 5 to 30 N / 15 mm, about 5 to 25 N / 15 mm, about 5 to Examples include about 22.9 N / 15 mm, about 8 to 30 N / 15 mm, about 8 to 25 N / 15 mm, and about 8 to 22.9 N / 15 mm.
  • the sealing strength of the battery packaging material at each measurement temperature is measured in accordance with JIS K7127: 1999.
  • a battery packaging material in which a TD (Transverse Direction) width is cut into a 15 mm strip is prepared. Specifically, as shown in FIG. 14, first, the battery packaging material is cut into 60 mm (TD) ⁇ 200 mm (MD (Machine Direction)) (FIG. 14 a). Next, the battery packaging material is folded in two at the position of the fold P (middle of the MD) so that the heat-fusible resin layers face each other (FIG. 14b).
  • the heat-sealable resin layers are heat-sealed under the conditions of a seal width of 7 mm, a temperature of 190 ° C., a surface pressure of 1.0 MPa, and 3 seconds (FIG. 14c).
  • the shaded portion S is a portion that is heat sealed.
  • the test piece is obtained by cutting into MD (cut at the position of the two-dot chain line in FIG. 14d) so that the width of TD is 15 mm (FIG. 14e).
  • the test piece 13 is allowed to stand at each measurement temperature for 2 minutes, and in each measurement temperature environment, the heat-fusible resin layer of the heat-sealing part is peeled off at a speed of 300 mm / min with a tensile tester (FIG. 15). .
  • the maximum strength at the time of peeling is defined as seal strength (N / 15 mm).
  • seal strength N / 15 mm.
  • the test piece 13 sometimes breaks. When the test piece 13 is broken, the breaking strength is taken as the seal strength.
  • the distance between chucks is 50 mm.
  • the test piece When measuring the seal strength, the test piece may break at a position different from the seal part without peeling off the seal part. This occurs when the peel strength of the seal portion is greater than the breaking strength of the test piece. When the test piece is broken at a position different from the seal portion, the seal strength is evaluated to be equal to or higher than the break strength.
  • the rolling direction of an aluminum foil or the like constituting the barrier layer is MD
  • the direction perpendicular to the same plane as MD is TD.
  • the rolling direction of the aluminum foil or the like can be confirmed by a rolling mark of the aluminum foil or the like.
  • the thickness of the heat-fusible resin layer 5 is not particularly limited as long as it functions as a heat-fusible resin layer.
  • the thickness is about 100 ⁇ m or less, preferably about 85 ⁇ m or less, more preferably about 15 to 85 ⁇ m. Is mentioned.
  • the thickness of the adhesive layer 4 is 10 ⁇ m or more
  • the thickness of the heat-fusible resin layer 5 is preferably about 85 ⁇ m or less, more preferably about 15 to 45 ⁇ m.
  • the thickness of the heat-fusible resin layer 5 is preferably about 20 ⁇ m or more, more preferably about 35 to 85 ⁇ m.
  • the base material layer 1 (barrier layer of the base material layer 1) is optionally formed. If necessary, a surface coating layer 6 may be provided on the side opposite to (3).
  • the surface coating layer 6 is a layer located in the outermost layer when the battery is assembled.
  • the surface coating layer 6 can be formed of, for example, polyvinylidene chloride, a polyester resin, a urethane resin, an acrylic resin, an epoxy resin, or the like. Of these, the surface coating layer 6 is preferably formed of a two-component curable resin. Examples of the two-component curable resin for forming the surface coating layer 6 include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Moreover, you may mix
  • the additive to be added may function as, for example, a matting agent, and the surface coating layer may function as a mat layer.
  • Examples of the additive include fine particles having a particle diameter of 0.5 nm to 5 ⁇ m.
  • the material of the additive is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances.
  • the shape of the additive is not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an indeterminate shape, and a balloon shape.
  • Specific additives include talc, silica, graphite, kaolin, montmorilloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, Neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, alumina, carbon black, carbon nanotubes, high Melting
  • money, aluminum, copper, nickel etc. are mentioned.
  • additives may be used individually by 1 type, and may be used in combination of 2 or more type.
  • silica, barium sulfate, and titanium oxide are preferably used from the viewpoints of dispersion stability and cost.
  • the surface of the additive may be subjected to various surface treatments such as insulation treatment and high dispersibility treatment.
  • the method for forming the surface coating layer 6 is not particularly limited, and examples thereof include a method in which a two-component curable resin for forming the surface coating layer 6 is applied to one surface of the base material layer 1.
  • the additive may be added to the two-component curable resin, mixed, and then applied.
  • the thickness of the surface coating layer 6 is not particularly limited as long as the above function as the surface coating layer 6 is exhibited.
  • the thickness is about 0.5 to 10 ⁇ m, preferably about 1 to 5 ⁇ m.
  • the production method of the battery packaging material of the present invention is not particularly limited as long as a laminate in which layers of a predetermined composition are laminated is obtained. That is, in the first method for producing a packaging material for a battery according to the present invention, at least a base material layer, a barrier layer, an adhesive layer, and a heat-fusible resin layer are laminated in this order. In the thermomechanical analysis for measuring the displacement of the probe as an adhesive layer, the probe is set on the adhesive layer surface of the cross section of the laminate, and the deflection setting value of the probe at the start of measurement is When the probe is heated from 40 ° C. to 220 ° C.
  • the laminate is formed by laminating at least the base material layer, the barrier layer, the adhesive layer, and the heat-fusible resin layer in this order.
  • the probe is set on the adhesive layer surface of the cross section of the laminate, and the deflection setting value of the probe at the start of measurement is There is a method of using a probe whose temperature reaches a maximum of 100 ° C. or less when the probe is heated from 40 ° C. to 220 ° C. under the condition of ⁇ 4 V and a temperature increase rate of 5 ° C./min. .
  • a laminate in which the base material layer 1, the adhesive layer 2, and the barrier layer 3 are laminated in this order (hereinafter also referred to as “laminate A”) is formed.
  • the laminate A is formed by applying an adhesive used for forming the adhesive layer 2 on the base layer 1 or the barrier layer 3 whose surface is subjected to a chemical conversion treatment, if necessary, a gravure coating method, After applying and drying by a coating method such as a roll coating method, the barrier layer 3 or the base material layer 1 can be laminated and the adhesive layer 2 can be cured by a dry laminating method.
  • the adhesive layer 4 and the heat-fusible resin layer 5 are laminated on the barrier layer 3 of the laminate A in this order.
  • a method of laminating the adhesive layer 4 and the heat-fusible resin layer 5 on the barrier layer 3 of the laminate A by coextrusion (coextrusion laminating method) (2) a separate adhesive layer 4 And a layered product of the heat-fusible resin layer 5 and a method of laminating the layered product on the barrier layer 3 of the layered product A by a thermal laminating method.
  • Adhering to the barrier layer 3 of the layered product A An adhesive for forming the layer 4 is formed by extrusion or solution coating, and is laminated at a high temperature by drying or baking, and a heat-fusible resin layer 5 previously formed into a sheet on the adhesive layer 4 is formed.
  • Laminate A and heat-fusible resin layer 5 are pasted through layer 4 The method (sandwich lamination method), and the like to match.
  • the surface coating layer 6 When the surface coating layer 6 is provided, the surface coating layer 6 is laminated on the surface of the base material layer 1 opposite to the barrier layer 3.
  • the surface coating layer 6 can be formed by, for example, applying the above-described resin for forming the surface coating layer 6 to the surface of the base material layer 1.
  • the order of the step of laminating the barrier layer 3 on the surface of the base material layer 1 and the step of laminating the surface coating layer 6 on the surface of the base material layer 1 are not particularly limited.
  • the barrier layer 3 may be formed on the surface of the base material layer 1 opposite to the surface coating layer 6.
  • Hot roll contact type hot air is further formed. You may use for heat processing of a formula, a near-infrared type, or a far-infrared type. An example of such heat treatment conditions is 150 to 250 ° C. for 1 to 5 minutes.
  • 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 in a package for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte. That is, a battery element including at least a positive electrode, a negative electrode, and an electrolyte can be accommodated in a package formed of the battery packaging material of the present invention to obtain a battery.
  • a battery element including at least a positive electrode, a negative electrode, and an electrolyte is used in the battery packaging material of the present invention, with the metal terminal 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
  • a battery using the packaging material is provided.
  • 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.
  • Example 1 As a base material layer, a polyethylene terephthalate film and a nylon film were laminated by coextrusion, and a biaxially stretched laminated film was prepared.
  • a barrier layer composed of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 40 ⁇ m) provided with an acid-resistant film by subjecting both surfaces to chemical conversion treatment on the surface of the biaxially stretched nylon film is dry-laminated.
  • a two-component polyurethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of the aluminum foil, and an adhesive layer (thickness 3 ⁇ m) was formed on the barrier layer.
  • the aluminum foil used as the barrier layer is provided with an acid resistant film containing cerium oxide and phosphate.
  • the acid-resistant film was analyzed as follows. First, it peeled off between the barrier layer and the cured resin layer. At this time, physical peeling was performed without using water, an organic solvent, an aqueous solution of acid or alkali, or the like. Since the cured resin layer remained on the surface of the barrier layer after peeling between the barrier layer and the cured resin layer, the remaining cured resin layer was removed by etching with Ar-GCIB. The surface of the barrier layer thus obtained was analyzed for an acid-resistant film using time-of-flight secondary ion mass spectrometry.
  • Measuring device Time-of-flight secondary ion mass spectrometer TOF.
  • SIMS5 Measurement conditions Primary ion: Double charged ion of Bismuth cluster (Bi3 ++) Primary ion acceleration voltage: 30 kV Mass range (m / z): 0-1500 Measurement range: 100 ⁇ m ⁇ 100 ⁇ m Number of scans: 16 scan / cycle Number of pixels (one side): 256 pixels Etching ions: Ar gas cluster ion beam (Ar-GCIB) Etching ion acceleration voltage: 5.0 kV
  • an amorphous polyolefin resin having a carboxyl group and an adhesive composed of a polyfunctional isocyanate compound are applied and dried at 100 ° C., and the resulting laminate has a barrier layer side.
  • An unstretched polypropylene film was passed between two rolls set at 60 ° C. and bonded, thereby laminating an adhesive layer / heat-sealable resin layer on the metal foil.
  • the obtained laminate was cured (aged) at 40 ° C. for 1 day and at 40 ° C.
  • a biaxially stretched polyethylene terephthalate film (5 ⁇ m) / adhesive (1 ⁇ m) / biaxially stretched nylon film ( 20 ⁇ m) / adhesive layer (3 ⁇ m) / barrier layer (40 ⁇ m) / adhesive layer (2 ⁇ m) / unstretched polypropylene film (80 ⁇ m) were laminated in this order to obtain a battery packaging material.
  • Table 1 shows the layer structure of the battery packaging material.
  • erucic acid amide was present as a lubricant on the innermost layer side (the side opposite to the barrier layer) of the unstretched polypropylene film.
  • Example 2 Biaxially stretched polyethylene terephthalate film (5 ⁇ m) / adhesive in the same manner as in Example 1 except that an unstretched lapolypropylene film (thickness 40 ⁇ m) was used instead of the unstretched polypropylene film (thickness 80 ⁇ m).
  • a battery packaging material in which (1 ⁇ m) / 2-axis stretched nylon film (20 ⁇ m) / adhesive layer (3 ⁇ m) / barrier layer (40 ⁇ m) / adhesive layer (2 ⁇ m) / unstretched polypropylene film (40 ⁇ m) is laminated in this order. Obtained.
  • erucic acid amide was present as a lubricant on the innermost layer side (the side opposite to the barrier layer) of the unstretched polypropylene film.
  • Table 1 shows the layer structure of the battery packaging material.
  • the aluminum foil used as the barrier layer is provided with an acid resistant film containing cerium oxide and phosphate.
  • the analysis result of the acid resistant film was the same as that of Example 1.
  • Example 3 and Comparative Example 1 As the base material layer, a laminated film in which a biaxially stretched polyethylene terephthalate film (thickness 12 ⁇ m) and a biaxially stretched nylon film (thickness 15 ⁇ m) were laminated by a dry lamination method was prepared.
  • the biaxially stretched polyethylene terephthalate film and the biaxially stretched nylon film are bonded with a polyurethane adhesive using a polyol and an isocyanate curing agent (thickness after curing is 3 ⁇ m).
  • a barrier layer composed of an aluminum foil JIS H4160: 1994 A8021H-O, thickness 40 ⁇ m
  • an acid-resistant film by subjecting both surfaces to chemical conversion treatment on the surface of the biaxially stretched nylon film
  • a barrier layer composed of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 40 ⁇ m) provided with an acid-resistant film by subjecting both surfaces to chemical conversion treatment on the surface of the biaxially stretched nylon film is dry-laminated.
  • a two-component polyurethane adhesive a polyol compound and an aromatic isocyanate compound
  • the biaxially stretched polyethylene terephthalate film / adhesive / A biaxially stretched nylon film / adhesive layer / barrier layer laminate was prepared.
  • the aluminum foil used as a barrier layer is provided with an acid resistant film containing chromium oxide and phosphate.
  • the analysis of the acid-resistant film on the barrier layer was performed using time-of-flight secondary ion mass spectrometry as in Example 1. As a result, secondary ions composed of Cr, P and O such as CrPO 2 + and CrPO 4 ⁇ were detected from the acid-resistant film.
  • Example 3 using an elastomeric adhesive composition containing a polyolefin polyol and a polyfunctional isocyanate curing agent (thickness after curing is 3 ⁇ m), the barrier layer side of the obtained laminate, By adhering a stretched polypropylene film (thickness: 80 ⁇ m), an adhesive layer / heat-sealable resin layer was laminated on the barrier layer. Next, the obtained laminated body was aged in a temperature environment of 80 ° C. for 24 hours, and finally heated at 190 ° C. for 2 minutes.
  • Comparative Example 1 a resin composition containing an acid-modified polyolefin and an epoxy resin was applied to the barrier layer side of the obtained laminate so as to have a thickness of 3 ⁇ m after curing, and the temperature was 60 ° C. at 60 ° C. It was dried for 2 seconds to form an adhesive layer. Next, an unstretched polypropylene film (CPP) was laminated on the adhesive layer by a dry lamination method to form a heat-fusible resin layer. The obtained laminates were aged for 24 hours in a 70 ° C. environment.
  • CPP unstretched polypropylene film
  • Example 3 biaxially stretched polyethylene terephthalate film (12 ⁇ m) / adhesive (3 ⁇ m) / biaxially stretched nylon film (15 ⁇ m) / adhesive layer (3 ⁇ m) / barrier layer (40 ⁇ m) ) / Adhesive layer (3 ⁇ m) / unstretched polypropylene film (80 ⁇ m) was obtained in this order.
  • erucic acid amide was present as a lubricant on the innermost layer side (the side opposite to the barrier layer) of the unstretched polypropylene film.
  • Table 1 shows the layer structure of the battery packaging material.
  • Example 4 A biaxially stretched nylon film (thickness 25 ⁇ m) was prepared as a base material layer. Next, a barrier layer composed of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 40 ⁇ m) provided with an acid-resistant film by subjecting both surfaces to chemical conversion treatment on the surface of the biaxially stretched nylon film is dry-laminated. Laminated by the method. Specifically, a two-component polyurethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of the aluminum foil, and an adhesive layer (thickness 3 ⁇ m) was formed on the barrier layer.
  • a barrier layer composed of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 40 ⁇ m) provided with an acid-resistant film by subjecting both surfaces to chemical conversion treatment on the surface of the biaxially stretched nylon film is dry-laminated. Laminated by the method. Specifically, a two-component polyurethane adhesive (a polyol compound and an
  • the laminate of biaxially stretched nylon film / adhesive layer / barrier layer is carried out by aging treatment at 40 ° C. for 24 hours.
  • the aluminum foil used as a barrier layer is provided with an acid resistant film containing chromium oxide and phosphate.
  • the analysis of the acid-resistant film on the barrier layer was performed using time-of-flight secondary ion mass spectrometry as in Example 1. As a result, secondary ions composed of Cr, P and O such as CrPO 2 + and CrPO 4 ⁇ were detected from the acid-resistant film.
  • Example 4 using an elastomeric adhesive composition containing a polyolefin polyol and a polyfunctional isocyanate curing agent (thickness after curing is 3 ⁇ m), the barrier layer side of the obtained laminate, By adhering a stretched polypropylene film (thickness 40 ⁇ m), an adhesive layer / heat-sealable resin layer was laminated on the barrier layer. Next, the obtained laminate was aged at 80 ° C. for 24 hours, and finally heated at 190 ° C.
  • Comparative Example 2 A biaxially stretched nylon film (thickness 15 ⁇ m) was prepared as a base material layer. Next, a barrier layer composed of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 35 ⁇ m) provided with an acid-resistant film by subjecting both surfaces to chemical conversion treatment on the surface of the biaxially stretched nylon film is dry-laminated. Laminated by the method. Specifically, a two-component polyurethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of the aluminum foil, and an adhesive layer (thickness 3 ⁇ m) was formed on the barrier layer.
  • a barrier layer composed of an aluminum foil (JIS H4160: 1994 A8021H-O, thickness 35 ⁇ m) provided with an acid-resistant film by subjecting both surfaces to chemical conversion treatment on the surface of the biaxially stretched nylon film is dry-laminated. Laminated by the method. Specifically, a two-component polyurethane adhesive (a polyol compound
  • the laminate of biaxially stretched nylon film / adhesive layer / barrier layer is carried out by aging treatment at 40 ° C. for 24 hours.
  • the aluminum foil used as a barrier layer is provided with an acid resistant film containing chromium oxide and phosphate.
  • the analysis of the acid-resistant film on the barrier layer was performed using time-of-flight secondary ion mass spectrometry as in Example 1. As a result, secondary ions composed of Cr, P and O such as CrPO 2 + and CrPO 4 ⁇ were detected from the acid-resistant film.
  • a resin composition containing an acid-modified polyolefin and an epoxy resin is applied to the barrier layer side of the obtained laminate so as to have a cured thickness of 3 ⁇ m, and dried at 80 ° C. for 60 seconds for adhesion. A layer was formed.
  • an unstretched polypropylene film (CPP, 30 ⁇ m) was laminated on the adhesive layer by a dry lamination method to form a heat-fusible resin layer.
  • the obtained laminates were each aged for 24 hours in an environment of 70 ° C., whereby biaxially stretched nylon film (15 ⁇ m) / adhesive layer (3 ⁇ m) / barrier layer (35 ⁇ m) / adhesive layer (3 ⁇ m) / unstretched polypropylene A battery packaging material in which films (30 ⁇ m) were laminated in this order was obtained.
  • erucic acid amide was present as a lubricant on the innermost layer side (the side opposite to the barrier layer) of the unstretched polypropylene film.
  • Table 1 shows the layer structure of the battery packaging material.
  • Example 5 A biaxially stretched polyethylene terephthalate film (thickness 9 ⁇ m) was prepared as a base material layer.
  • a two-component polyurethane adhesive (the resin is a polyol compound and an aromatic isocyanate compound, and carbon black is blended so as to be 10% by mass) is applied to one surface of the base material layer, An adhesive layer (thickness 3 ⁇ m) was formed on the base material layer.
  • the biaxially stretched polyethylene terephthalate film is subjected to an aging treatment at 40 ° C. for 24 hours.
  • a laminate of / adhesive layer / barrier layer was produced.
  • the stainless steel foil used as a barrier layer is provided with an acid resistant film containing chromium oxide and phosphate.
  • the analysis of the acid-resistant film on the barrier layer was performed using time-of-flight secondary ion mass spectrometry as in Example 1. As a result, secondary ions composed of Cr, P and O such as CrPO 2 + and CrPO 4 ⁇ were detected from the acid-resistant film.
  • an amorphous polyolefin resin having a carboxyl group and an adhesive composed of a polyfunctional isocyanate compound are applied and dried at 100 ° C., and the resulting laminate has a barrier layer side.
  • a non-stretched polypropylene film (CPP, thickness 23 ⁇ m) was passed between two rolls set at 60 ° C. to adhere, thereby laminating an adhesive layer / heat-sealable resin layer on the barrier layer.
  • an ink in which a resin (80% by mass) made of polyester polyol and an isocyanate curing agent and silica particles (20% by mass) is mixed is printed by gravure coating, and the surface having a thickness of 3 ⁇ m.
  • a coating layer (matte layer) was formed.
  • the obtained laminate was cured (aged) at 40 ° C. for 1 day and at 40 ° C.
  • a mat layer (3 ⁇ m) / biaxially stretched polyethylene terephthalate film (9 ⁇ m) / adhesive layer ( 3 ⁇ m) / barrier layer (20 ⁇ m) / adhesive layer (3 ⁇ m) / unstretched polypropylene film (23 ⁇ m) was laminated in this order to obtain a battery packaging material.
  • erucic acid amide was present as a lubricant on the innermost layer side (the side opposite to the barrier layer) of the unstretched polypropylene film.
  • Table 1 shows the layer structure of the battery packaging material.
  • Comparative Example 3 In Comparative Example 3, a battery packaging material was produced by changing the aging condition of the adhesive layer from Example 3. Specifically, in Comparative Example 3, instead of the aging condition of the laminate in Example 3 “aging at 80 ° C. for 24 hours and finally heating at 190 ° C. for 2 minutes”, “60 ° C. A biaxially stretched polyethylene terephthalate film (as in Example 3 except that it was aged in a temperature environment for 12 hours, aged in a temperature environment of 80 ° C. for 72 hours, and finally heated at 190 ° C. for 2 minutes).
  • the numerical value in parentheses in the layer structure means thickness ( ⁇ m).
  • PET polyethylene terephthalate
  • Ny nylon
  • AD is an adhesive layer formed by coextrusion
  • DL is an adhesive layer formed by a dry lamination method
  • ALM is an aluminum foil
  • CPP is formed from unstretched polypropylene. It means a heat-fusible resin layer.
  • thermomechanical analysis device A probe is installed on the surface of the adhesive layer in the cross section of each battery packaging material (the probe tip radius is 30 nm or less, the probe deflection is set to -4V), and the probe is heated from 40 ° C. to a predetermined temperature (FIG. 6). (The temperature at the right end of the plot shown in the graph of FIG. 11) was heated (temperature increase rate: 5 ° C./min), and the displacement of the probe was measured. Details of the measurement conditions are as follows.
  • thermomechanical analysis apparatus An afm plus system manufactured by ANASIS INSTRUMENTS was used as a thermomechanical analysis apparatus, and a cantilever ThermoLever AN2-200 (spring constant 0.5-3 N / m) was used as a 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 to 10 V, speed 0.2 V /
  • the set value for the second and the deflection is -4V. 6 (Example 1), FIG. 7 (Example 2), FIG. 8 (Example 3), and FIG. 9 (FIG.
  • FIGS. 6 to 9 are graphs showing the relationship between the heating temperature and the displacement of the probe position (Defection (V)), respectively.
  • Example 4 Example 4
  • FIG. 10 Comparative Example 1
  • FIG. 11 Comparative Example 2.
  • FIGS. 6 to 9 in the battery packaging materials obtained in Examples 1 to 4, when the probe was heated from 40 ° C. to 220 ° C. in the thermomechanical analysis for measuring the displacement of the probe, 130 It can be seen that the position of the probe is lower than the initial value at a temperature of °C or less. Further, in Examples 1 to 4, it can be seen that the temperature at which the position of the probe reaches the highest point is 100 ° C. or less.
  • each battery packaging material was cut into 80 mm (MD) ⁇ 160 mm (TD) (FIG. 12 a).
  • TD 160 mm
  • a molding die female die having a diameter of 31.6 mm (MD) ⁇ 54.5 mm (TD) from the center of the TD to one side from the center of the TD and a corresponding molding die.
  • a mold male was cold-molded to a depth of 3.0 mm with a presser pressure of 0.1 MPa, and a recess M was formed at the center (FIG. 12a).
  • the clearance between the male mold and the female mold was 0.3 mm.
  • the molded packaging material for the battery was folded in half at the position of the fold P (intermediate of TD) so that the concave portion M was inside (FIG. 12b).
  • the part where the heat-fusible resin layers overlap each other was heat-sealed along the MD (190 ° C., 3 seconds, surface pressure 1.0 MPa, 7 mm width) (FIG. 12 c).
  • the hatched portion S is a portion that is heat sealed.
  • an aluminum plate AL (30 mm ⁇ 52 mm, thickness 3 mm) and 0.5 g of water were sealed as dummy cells from the opening E which was not heat-sealed (FIG.
  • test battery 12d was sandwiched between two stainless steel plates 20 and fixed with a fixing spacer 21. At this time, the interval W between the two stainless steel plates was set to 7.0 mm.
  • the test battery 12 is placed in an oven that can be depressurized, the pressure in the oven is set to 0 atm, and the temperature is increased to 120 ° C. at a rate of 3 ° C./min.
  • the temperature at the time of opening was confirmed.
  • Table 2 In the JIS regulations, the oven temperature is used as a reference, but in this example, the sample temperature was used as a reference in order to evaluate the sealing performance in more detail.
  • the reason why the evacuation was performed was that it was assumed that gas was generated inside the actual battery and the internal pressure increased.
  • the reason why the stainless steel plate and the fixing spacer 21 are used is that the battery is normally fixed by a case or the like, and is to prevent the battery from expanding and swelling too much.
  • the sealing strength of the battery packaging material at each measurement temperature of 25 ° C. environment, 80 ° C. environment, 100 ° C. environment, and 120 ° C. environment was measured as follows.
  • a battery packaging material cut into a strip shape with a TD width of 15 mm was prepared. Specifically, as shown in FIG. 14, first, each battery packaging material was cut into 60 mm (TD) ⁇ 200 mm (MD) (FIG. 14 a). Next, the battery packaging material was folded in two at the position of the fold line P (in the middle of the MD) so that the heat-fusible resin layers were opposed to each other (FIG. 14b).
  • the heat-fusible resin layers were heat-sealed under the conditions of a seal width of 7 mm, a temperature of 190 ° C., a surface pressure of 1.0 MPa, and 3 seconds (FIG. 14c).
  • the shaded portion S is a portion that is heat sealed.
  • test piece 13 is allowed to stand at each measurement temperature (25 ° C., 80 ° C., 100 ° C., 120 ° C.) for 2 minutes, and is pulled in the environment of each measurement temperature (25 ° C., 80 ° C., 100 ° C., 120 ° C.).
  • a testing machine manufactured by Shimadzu Corporation, AG-Xplus (trade name)
  • the heat-fusible resin layer of the heat-sealing part was peeled off by 15 mm at a speed of 300 mm / min (FIG. 15).
  • the maximum strength at the time of peeling was defined as seal strength (N / 15 mm).
  • the distance between chucks is 50 mm.
  • Table 2 The results are shown in Table 2.
  • the breaking strength was listed as the seal strength in Table 2 (the numerical value marked with * in Table 2 is the breaking strength).
  • the seal strength is an average value measured three times.
  • the battery using the battery packaging material of Example 1-5 was not opened at a temperature of about 80 ° C., and was opened at a temperature of 120 ° C. or lower, which is a higher temperature. The opening was gentle. On the other hand, in the battery using the battery packaging material of Comparative Example 13, the battery was not opened even when the temperature exceeded 120 ° C.

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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)
  • Laminated Bodies (AREA)
  • Gas Exhaust Devices For Batteries (AREA)

Abstract

L'invention fournit un matériau d'enveloppe pour batterie dont la sécurité est garantie, y compris dans le cas où une élévation de la pression et de la température à l'intérieur d'une batterie se poursuit de manière constante. Plus précisément, l'invention concerne un matériau d'enveloppe pour batterie qui est configuré à partir d'un stratifié équipé dans l'ordre au moins d'une couche de matériau de base, d'une couche barrière, d'une couche d'adhésion et d'une couche de résine à adhésion thermique. Selon une analyse thermomécanique mesurant la quantité de déplacement d'une sonde, ladite sonde est disposée à la surface de ladite couche d'adhésion d'un plan transversal dudit stratifié. La valeur d'établissement de la déviation de ladite sonde au début de la mesure, équivaut à -4V. La température telle que la position de ladite sonde est inférieure à une valeur initiale, est inférieure ou égale à 130°C lorsque ladite sonde est chauffée de 40°C à 220°C dans des conditions de vitesse d'élévation de la température de 5°C/ minute.
PCT/JP2017/036385 2016-10-05 2017-10-05 Matériau d'enveloppe pour batterie ainsi que procédé de fabrication de celui-ci, et batterie Ceased WO2018066671A1 (fr)

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