JP2019212630A - Laminate for nonaqueous battery exterior package - Google Patents

Abstract

To provide a laminate for a nonaqueous battery exterior package, which can increase mechanical strength of the laminate for the nonaqueous battery exterior package, and which can increase production efficiency of nonaqueous batteries by preventing occurrence of a failure during drawing molding.SOLUTION: A laminate for a nonaqueous battery exterior package comprises a substrate layer, SUS foil and a multilayered sealant layer including a polyolefin-based resin which are laminated in turn. The substrate layer and SUS foil are bonded through a first adhesive layer containing an urethane-based adhesive. The SUS foil and the sealant layer are bonded through a second adhesive layer made of a polyolefin-based resin containing a resin having an epoxy group or oxazoline group. The substrate layer is a laminate film including a monolayer or a multilayer, which is arranged by use of a heat resistance resin film of 200°C or higher in a melting point. At least at a sealant layer side of the SUS foil, a surface coating layer is formed, which is arranged by drying and hardening a water-soluble coating material containing a water-soluble resin, a metal fluoride compound and an organic chelating agent.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a non-aqueous battery exterior laminate used for an exterior material such as a secondary battery such as a lithium ion battery and an electric double layer capacitor.

In recent years, with the growing global environmental problems, the diffusion of electric vehicles and the effective use of natural energy such as wind power generation and solar power generation have become issues. Accordingly, in these technical fields, secondary batteries such as lithium ion batteries and electric double layer capacitors are attracting attention as storage batteries for storing electrical energy.
As an exterior container for storing a lithium ion battery used for an electric vehicle or the like, a container made of a battery exterior laminate in which a metal foil and a resin layer are laminated is used in order to reduce the size and weight ( For example, see Patent Document 1).

In order to produce a secondary battery using an exterior container produced using the battery exterior laminate described above, for example, as follows.
The laminated body for battery exterior is formed by drawing or the like so as to form a tray having a concave portion to obtain a container body. The battery is stored in the recess of the container body. Then, the battery was stored in the outer container by stacking a lid member made of a battery outer laminate on the container body and heat-sealing the flange part of the container body and the side edge of the lid member. Get the next battery.

JP 2000-357494 A

In recent years, in applications such as storage batteries for electric vehicles, exterior containers for large-sized batteries having a larger outer dimension than before, and exterior containers that can increase the internal volume by reducing the thickness of the battery exterior laminates. It has been demanded. However, in an exterior container for a large battery, since it is necessary to form a container body having a deeper recess, technical difficulties are increasing. For example, if the laminated body for battery exterior is deeply drawn, there is a possibility that peeling between the metal foil and the resin layer and damage (breaking etc.) of the laminated body for battery exterior may occur. Moreover, when the thickness of the battery exterior laminate is reduced, there arises a problem that mechanical strength such as puncture strength is lowered.
For this reason, while raising the mechanical strength of the laminated body for battery exteriors, reducing the generation | occurrence | production of the defect at the time of draw forming, and raising the manufacture yield of a non-aqueous battery was requested | required.

  The present invention has been made in view of the above circumstances, and improves the production efficiency of non-aqueous batteries by increasing the mechanical strength of the non-aqueous battery exterior laminate and preventing the occurrence of defects during drawing. It aims at providing the laminated body for non-aqueous battery exteriors which can be made.

In order to solve the above problems, the present invention provides a base material layer, a SUS foil, and a multilayer sealant layer made of a polyolefin resin, which are sequentially laminated, and at least the sealant layer side of the SUS foil has a water-soluble resin. A surface coating layer having a thickness of 0.05 to 1.0 μm is formed by drying and curing a water-soluble paint containing a metal fluoride compound and an organic chelating agent, and the sealant layer is formed of the SUS foil. At least one selected from the group consisting of maleic anhydride-modified polyolefin resin, an alloy material of epoxy group-containing resin and polyolefin resin, and an alloy material of resin having oxazoline group and polyolefin resin The laminated body for non-aqueous battery exterior which has a heat-adhesive polyolefin resin layer containing is provided.
The base material layer is preferably composed of a single-layer or multilayer laminate film using a heat-resistant resin film having a melting point of 200 ° C. or higher.
The base material layer and the SUS foil are preferably bonded via a first adhesive layer made of a urethane-based adhesive.
The SUS foil and the sealant layer are preferably bonded via a second adhesive layer made of a polyolefin resin containing a resin having an epoxy group or an oxazoline group.

According to the present invention, a surface coating layer using a water-soluble paint containing a water-soluble resin, a metal fluoride compound, and an organic chelating agent is formed on at least the sealant layer side of the SUS foil, and the sealant Since the layer has a heat-adhesive polyolefin resin layer, the sealant layer and the SUS foil can be bonded very firmly.
For this reason, when forming a recessed part by drawing, while preventing damage (breaking etc.) of the laminated body for non-aqueous battery exterior, peeling with a sealant layer and SUS foil can be prevented. Therefore, even when deep drawing is performed, it is possible to reduce the occurrence of defects when molding the battery outer casing, improve the production yield of nonaqueous batteries, and improve production efficiency.
Further, by increasing the adhesive strength between the sealant layer and the SUS foil, it is possible to prevent moisture from entering the inside of the battery exterior container from the outside. Therefore, it is possible to suppress the deterioration of the electrolyte over time and to prolong the product life of the secondary battery.

In the present invention, since the mechanical strength (tensile strength and the like) can be increased by using the SUS foil, breakage (breaking and the like) can be reduced when forming the concave portion by drawing. Therefore, it is possible to improve the battery production efficiency by preventing the molding failure of the battery outer casing, and to prevent the battery performance from being lowered or ignited due to the ingress of moisture or the leakage of the electrolyte.
Moreover, since SUS foil with high mechanical strength is used, the durability of the battery exterior container can be enhanced. Therefore, a structure (such as a cover case) for protecting the secondary battery is not required or simplified when the secondary battery is transported or mounted. Therefore, it is possible to reduce the packing cost and downsize the packing device. In addition, since the SUS foil having high mechanical strength is used, the thickness of the battery exterior laminate can be reduced to increase the internal volume, and the volume efficiency of the battery can be improved.
Furthermore, since the SUS foil having the surface coating layer is used, even when the electrolyte is decomposed and acid is generated due to the moisture that has entered the inside of the non-aqueous battery exterior container, deterioration due to corrosion hardly occurs. Therefore, leakage of the electrolytic solution due to corrosion of the metal foil is prevented, and deterioration of battery performance and ignition can be prevented.

It is a schematic sectional drawing which shows 1st Embodiment of the laminated body for non-aqueous battery exteriors which concerns on this invention. It is a perspective view which shows an example of the secondary battery produced using the laminated body for non-aqueous battery exteriors of FIG. It is a perspective view which shows the process of manufacturing the secondary battery of a previous figure. It is a schematic sectional drawing which shows 2nd Embodiment of the laminated body for non-aqueous battery exteriors which concerns on this invention. It is a schematic sectional drawing which shows the 1st modification of the laminated body for battery exterior shown in FIG. It is a schematic sectional drawing which shows the 2nd modification of the laminated body for battery exterior shown in FIG. It is a schematic sectional drawing which shows the 3rd modification of the laminated body for battery exterior shown in FIG. It is a schematic sectional drawing which shows the 4th modification of the laminated body for battery exterior shown in FIG.

  FIG. 1 shows a battery exterior laminate 10 that is a first embodiment of a non-aqueous battery exterior laminate (hereinafter sometimes simply referred to as a battery exterior laminate) according to the present invention. 2 shows a non-aqueous battery exterior container 20 for a lithium ion battery manufactured using the battery exterior laminate 10 according to the present invention (hereinafter also simply referred to as a battery exterior container 20). A secondary battery 40 is shown.

In FIG. 2, the perspective view of the secondary battery 40 using the battery exterior container 20 which is an example of the battery exterior container of this invention is shown. The secondary battery 40 is one in which a lithium ion battery 27 is included in a battery exterior container 20.
The battery exterior container 20 is a first embodiment of the battery exterior laminate according to the present invention, in which the container body 30 made of the battery exterior laminate 10 and the lid member 33 made of the battery exterior laminate 10 are stacked. The peripheral edge portion 29 is formed by heat sealing. Reference numeral 28 denotes an electrode lead connected to the positive electrode and the negative electrode of the lithium ion battery 27.

As shown in FIG. 1, the battery exterior laminate 10 according to the present invention has a structure in which a base material layer 11, a SUS foil 12, and a sealant layer 13 are laminated in this order. In this specification, SUS foil refers to a metal foil made of stainless steel.
The base material layer 11 and the SUS foil 12 are bonded to each other by the first adhesive layer 14. A printing layer 15 is formed on the SUS foil 12 side (the lower surface side in FIG. 1) of the base material layer 11. Surface coating layers 17 and 18 are formed on the sealant layer 13 side (lower surface side in FIG. 1) and the base material layer 11 side (upper surface side in FIG. 1) of the SUS foil 12, respectively.
In addition, although this laminated body 10 for battery exteriors has the printing layer 15, the printing layer 15 does not need to be.

Hereinafter, each layer will be described in detail.
The base material layer 11 is not particularly limited as long as it has sufficient mechanical strength. For example, polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); nylon ( A synthetic resin film made of polyamide resin such as Ny); polyolefin resin such as expanded polypropylene (OPP); polyether ether ketone (PEEK), polyphenylene sulfide (PPS), or the like can be used.
The thickness of the base material layer 11 can be 3-25 micrometers, for example.

  The base material layer 11 may have a single layer structure or a multilayer structure. Examples of the base material layer 11 having a multilayer structure include a two-layer film in which a polyethylene terephthalate (PET) resin film is laminated on a biaxially stretched polyamide resin film (ONy). The base material layer may have a multilayer structure in which three or more films are laminated.

  The base material layer 11 is preferably composed of a single-layer or multilayer film using a heat-resistant resin film having a melting point of 200 ° C. or higher. Examples of such a heat resistant resin film include a PET film, a PEN film, a PBT film, a nylon film, a PEEK film, and a PPS film, and a PET film that is advantageous in terms of cost is particularly preferable. By using such a heat-resistant resin film, the heat resistance of the battery exterior laminate 10 can be increased, and the durability of the secondary battery 40 can be improved.

The SUS foil 12 is a stainless steel metal foil, and is made of, for example, austenite, ferrite, martensite, or other stainless steel. Examples of austenite include SUS304, 316, 301, etc., ferrite include SUS430, and martensite includes SUS410.
Since SUS foil 12 has higher mechanical strength such as tensile strength than other metal foils such as aluminum foil, the occurrence of pinholes is reduced when forming recesses by drawing, thereby reducing battery leakage. Can hardly occur. Moreover, since the SUS foil 12 is superior in corrosion resistance compared to other metal foils, it is less likely to deteriorate due to corrosion.

The thickness of the SUS foil 12 can be, for example, 5 μm to 100 μm. The thickness of the SUS foil 12 is preferably 5 μm to 50 μm.
By setting the thickness of the SUS foil 12 to 5 μm or more, sufficient strength (such as puncture strength) can be given to the battery outer laminate 10 and durability of the secondary battery 40 can be enhanced. Moreover, sufficient drawability can be given to the laminated body 10 for battery exteriors by setting the thickness of the SUS foil 12 to 50 μm or less.

The surface coating layers 17 and 18 are layers formed by drying and curing a water-soluble paint containing a water-soluble resin, a metal fluoride compound, and an organic chelating agent.
The thicknesses of the surface coating layers 17 and 18 are each 0.05 μm or more (preferably a thickness exceeding 0.2 μm). By setting the thickness of the surface coating layers 17 and 18 to 0.05 μm or more, sufficient corrosion resistance is given to the battery exterior laminate 10, the adhesive strength between the SUS foil 12 and the sealant layer 13, and SUS The adhesive strength between the foil 12 and the upper layer side can be increased.
The thickness of the surface coating layers 17 and 18 is 1.0 μm or less (preferably 0.5 μm or less). By setting the thickness of the surface coating layers 17 and 18 to 1.0 μm or less, the adhesive strength between the SUS foil 12 and the sealant layer 13 can be increased, and the material cost can be suppressed.
The thickness of the surface coating layers 17 and 18 is preferably in the range of more than 0.2 μm and 0.5 μm or less.

As the water-soluble resin, it is preferable to use one or more of a polyvinyl alcohol resin and a polyvinyl ether resin.
The polyvinyl alcohol resin is at least one water-soluble resin selected from polyvinyl alcohol resins and modified polyvinyl alcohol resins.
The polyvinyl alcohol resin can be produced, for example, by saponifying a polymer of a vinyl ester monomer or a copolymer thereof.
As a polymer of a vinyl ester monomer or a copolymer thereof, a homopolymer of a vinyl ester monomer such as a fatty acid vinyl ester such as vinyl formate, vinyl acetate, vinyl butyrate, an aromatic vinyl ester such as vinyl benzoate, or the like Examples thereof include copolymers and copolymers of other monomers copolymerizable therewith.
Examples of other copolymerizable monomers include olefins such as ethylene and propylene, ether group-containing monomers such as alkyl vinyl ether, carbonyl groups such as diacetone acrylamide, diacetone (meth) acrylate, allyl acetoacetate, and acetoacetate. Examples include (ketone group) -containing monomers, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride, vinyl halides such as vinyl chloride and vinylidene chloride, and unsaturated sulfonic acids.
The saponification degree of the polyvinyl alcohol-based resin is usually preferably 90 to 100 mol%, more preferably 95 mol% or more.

Examples of polyvinyl alcohol resins that can be used in the present invention include alkyl ether-modified polyvinyl alcohol resins, carbonyl-modified polyvinyl alcohol resins, acetoacetyl-modified polyvinyl alcohol resins, acetamide-modified polyvinyl alcohol resins, acrylonitrile-modified polyvinyl alcohol resins, and carboxyl-modified polyvinyl alcohol resins. , Silicone-modified polyvinyl alcohol resin, ethylene-modified polyvinyl alcohol resin and the like. Among these, alkyl ether modified polyvinyl alcohol resin, carbonyl modified polyvinyl alcohol resin, carboxyl modified polyvinyl alcohol resin, and acetoacetyl modified polyvinyl alcohol resin are preferable.
Examples of commercially available polyvinyl alcohol resins that are generally available include J-Poval DF-20 (trade name) manufactured by Nippon Vineyard Popal Co., Ltd., and Crossmer H Series manufactured by Nippon Carbide Industries Co., Ltd. ( Product name). A polyvinyl alcohol-type resin may use 1 type, or 2 or more types of mixtures.

  Polyvinyl ether resins include ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, norbornyl vinyl ether, allyl vinyl ether, norbornenyl vinyl ether, 2-hydroxy Examples include homopolymers or copolymers of aliphatic vinyl ethers such as ethyl vinyl ether and diethylene glycol monovinyl ether, and copolymers of other monomers copolymerizable therewith. Examples of the other monomer copolymerizable with the vinyl ether monomer include those similar to the other monomers copolymerizable with the vinyl ester monomer described above.

In particular, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxypropyl vinyl ether, and other polyvinyl ether resins containing a hydroxyl group-containing aliphatic vinyl ether as a monomer, such as monovinyl ethers of various glycols and polyhydric alcohols, are water-soluble. And a crosslinking reaction with respect to a hydroxyl group is possible, so that it can be suitably used in the present invention.
These polyvinyl ether resins undergo saponification treatment unlike vinyl alcohol resins produced via vinyl ester polymers because vinyl ether monomers can be used in the resin production (polymerization) process. It can be manufactured without. Further, a copolymer containing a vinyl ester monomer and a vinyl ether monomer, or a vinyl alcohol-vinyl ether copolymer obtained by saponification thereof can also be used. Mixtures of polyvinyl alcohol resins other than polyvinyl ether resins and polyvinyl ether resins can also be used.

  As the water-soluble resin, either one of polyvinyl alcohol resin and polyvinyl ether resin may be used, or both may be used in combination.

Since the metal fluoride compound needs to be mixed with the aforementioned water-soluble resin, it is preferable to have water solubility.
Specific examples of the metal fluoride compound include chromium fluoride, iron fluoride, zirconium fluoride, titanium fluoride, hafnium fluoride, titanium hydrofluoric acid, and salts thereof.
The metal fluoride compound has an effect of improving the electrolytic solution resistance. That is, the surface of the SUS foil 12 can be passivated and the corrosion resistance against the electrolytic solution can be enhanced. The metal fluoride compound also has an action of crosslinking the water-soluble resin.

The organic chelating agent contained in the water-soluble paint is an organic substance that can chemically bond with a cation to form a metal ion complex.
The organic chelating agent binds a metal compound (such as chromium oxide) derived from a metal fluoride compound and the water-soluble resin to increase the compressive strength of the surface coating layers 17 and 18. Even if the thickness of the surface coating layer is, for example, more than 0.2 μm and 1.0 μm or less, the surface coating layers 17 and 18 are not embrittled and cracking or peeling does not occur. For this reason, the adhesive strength between the SUS foil 12 and the sealant layer 13 and the adhesive strength between the SUS foil 12 and the upper layer side can be increased.
The organic chelating agent has a function of making the water-soluble resin water resistant by chemically reacting with the water-soluble resin or the metal fluoride metal compound.

As organic chelating agents, for example, aminocarboxylic acid chelating agents, phosphonic acid chelating agents, oxycarboxylic acid chelating agents, and (poly) phosphoric acid chelating agents can be used.
Examples of aminocarboxylic acid chelating agents include nitrilotriacetic acid (NTA), hydroxyethyliminodiacetic acid (HIDA), ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), Triethylenetetramine hexaacetic acid (TTHA), transcyclohexanediaminetetraacetic acid (CyDTA), 1,2-propanediaminetetraacetic acid (1,2-PDTA), 1,3-propanediaminetetraacetic acid (1,3-PDTA), 1,4-butanediaminetetraacetic acid (1,4-BDTA), 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA-OH), glycol etherdiaminetetraacetic acid (GEDTA), ethylenediamine orthohydroxyphenylacetic acid (EDHPA) ), S-ethylenediamine disuccinic acid (SS-EDDS), ethylenediamine disuccinic acid (EDDS), β-alanine diacetic acid (ADA), methylglycine diacetic acid (MGDA), L-aspartic acid-N, N-diacetic acid (ASDA) ), L-glutamic acid-N, N-diacetic acid (GLDA), N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid (HBEDDA).
Examples of the phosphonic acid chelating agent include N, N, N-trimethylenephosphonic acid (NTMP), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), ethylenediamine-N, N, N ′, N ′. -Tetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC).
Examples of oxycarboxylic acid chelating agents include glycolic acid, citric acid, malic acid, gluconic acid, glucoheptonic acid, and the like.
Examples of the (poly) phosphate chelating agent include metaphosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid, and salts thereof.
Examples of commercially available organic chelating agents that are generally available include Kirest PD-4H (trade name) (PDTA) and Kirest PH-540 (trade name) (EDTMP) manufactured by Kirest Corporation.

The amount of the water-soluble resin contained in the water-soluble paint is preferably 0.1 to 1% by mass.
By setting the addition amount of the water-soluble resin to 0.1% by mass or more, the adhesive strength between the SUS foil 12 and the sealant layer 13 can be increased. Moreover, the adhesive strength of the SUS foil 12 and the sealant layer 13 can be increased by setting the addition amount of the water-soluble resin to 1% by mass or less.

The amount of the metal fluoride compound contained in the water-soluble paint is suitably 0.1 to 2.5% by mass (preferably 0.8 to 2.5% by mass).
By making the addition amount of the metal fluoride compound 0.1% by mass or more, the corrosion resistance of the SUS foil 12 with respect to the electrolytic solution can be enhanced. Moreover, by setting the addition amount of the metal fluoride compound to 2.5% by mass or less, it is possible to avoid precipitation in the water-soluble paint and suppress unevenness of the coating film.

The amount of the organic chelating agent contained in the water-soluble paint is suitably 0.1 to 1% by mass (preferably 0.3 to 1% by mass).
By setting the addition amount of the metal fluoride compound to 0.1% by mass or more, the compressive strength of the surface coating layers 17 and 18 can be increased, and cracking and peeling of the surface coating layers 17 and 18 can be suppressed. Moreover, sufficient intensity | strength can be given to the surface coating layers 17 and 18 by the addition amount of an organic chelating agent being 1 mass% or less.

  The surface coating layers 17 and 18 can be formed by applying the water-soluble paint to the SUS foil 12 and performing heat drying, baking adhesion, and crosslinking in an oven or the like.

  In the battery exterior laminate 10 shown in FIG. 1, the surface coating layers 17 and 18 are formed on both surfaces of the SUS foil 12, but the surface coating layer is formed at least on the sealant layer 13 side of the SUS foil 12. It only has to be done. In other words, a configuration in which the surface coating layer 18 is omitted from the battery exterior laminate 10 of FIG. 1 (battery exterior laminate 60 shown in FIG. 5) is also possible.

In FIG. 1, the first adhesive layer 14 is not particularly limited as long as the base material layer 11 and the SUS foil 12 can be bonded to each other. For example, the first adhesive layer 14 can be formed using a urethane-based adhesive, an epoxy-based adhesive, or the like.
The first adhesive layer 14 can be formed by, for example, dry lamination.
The thickness of the 1st adhesive bond layer 14 can be 1-10 micrometers, for example. By setting the thickness within this range, the base material layer 11 and the SUS foil 12 can be bonded with a sufficiently high adhesive force, and delamination can be prevented.

In the battery exterior laminate 10 according to the present invention, the coating layer 16 can be formed on the outer surface side (upper surface side in FIG. 1) of the base material layer 11.
The coating layer 16 (first coating layer) is a urethane resin, acrylic resin, polyvinylidene chloride, vinylidene chloride-vinyl chloride copolymer resin, maleic anhydride-modified polypropylene resin, polyester resin, epoxy resin, phenol resin, phenoxy resin, Selected from resin group consisting of fluororesin, cellulose ester resin, cellulose ether resin, polyamide resin, polyphenylene ether resin (PPE), polyphenylene sulfide resin (PPS), polyaryl ether resin (PAE), polyether ether ketone resin (PEEK) Formed of at least one kind of resin.
In the coating layer 16, one type of resins constituting the resin group may be used alone, or two or more types may be used in combination.
The coating layer 16 is preferably made of a material having excellent heat resistance.
1 has the coating layer 16 formed on the outer surface side of the base material layer 11, the battery exterior laminate of the present invention has a configuration without a coating layer (for example, The battery exterior laminate 70) shown in FIG.

The coating layer 16 is desirably the outermost layer of the battery exterior laminate 10.
By forming the coating layer 16, it is possible to enhance the insulation of the battery outer laminate 10 and to prevent the surface of the battery outer laminate 10 from being damaged. Further, even when the battery exterior laminate 10 touches the electrolyte, it is possible to prevent changes in appearance (discoloration, etc.).

The coating layer 16 is preferably a thin film cured layer formed by applying and drying a solvent-type paint prepared by dissolving the resin in an organic solvent.
Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, normal hexane, cyclohexane, methylcyclohexane, normal heptane, tridecane, and tetradecane; ethyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, normal acetate Ester solvents such as propyl and isopropyl acetate; ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, DIBK (diisobutyl ketone), cyclohexanone, and DAA (diacetone alcohol); methanol, ethanol, butanol, propanol, isopropyl Alcohol solvents such as alcohol and normal propyl alcohol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, ethylene glycol Examples include alcohol ether solvents such as rudimethyl ether. One of these organic solvents may be used alone, or two or more thereof may be used in combination.
You may add additives, such as a desiccant and a stabilizer, to a solvent-type coating material.

  The solvent-type paint for forming the coating layer 16 can be applied by a known printing method such as an offset printing method, a gravure printing method, or a screen printing method.

The coating layer 16 can be colored by adding an achromatic or chromatic colorant to the solvent-based paint.
The color of the coating layer 16 can be arbitrarily selected. The coating layer 16 may be uniformly colored over the entire region (or a partial region), or a plurality of regions may be colored in mutually different colors (or the same color as each other).
The coating layer 16 can also be colored so as to display characters, figures, images, patterns and the like. These characters and the like may represent, for example, product names and manufacturers.
By coloring the coating layer 16, the designability of the battery exterior laminate 10 can be enhanced.

A pigment or dye can be used as the colorant.
Examples of pigments include quinacridone, anthraquinone, perylene, perinone, diketopyrrolopyrrole, isoindolinone, condensed azo, benzimidazolone, monoazo, insoluble azo, naphthol, and flavan. Organic pigments such as throne, anthrapyrimidine, quinophthalone, pyranthrone, pyrazolone, thioindigo, anthanthrone, dioxazine, phthalocyanine, and indanthrone; metal complexes such as nickel dioxin yellow and copper azomethine yellow; Examples thereof include metal oxides such as titanium oxide, iron oxide and zinc oxide; metal salts such as barium sulfate and calcium carbonate; inorganic pigments such as carbon black, aluminum and mica.
Examples of the dye include azo series, quinoline series, stilbene series, thiazole series, indigoid series, anthraquinone series, and oxazine series.
The coating layer 16 may be colored by using a solvent-type paint containing ink. The ink is prepared by adding the colorant to an ink binder resin such as urethane or acrylic.

The thickness of the coating layer 16 can be 0.1 μm or more, for example. More preferably, the coating layer 16 has a thickness of 2 μm or more.
By making the thickness of the coating layer 16 2 μm or more, it is possible to enhance the insulation and to enhance the effect of preventing the surface of the battery exterior laminate 10 from being damaged. Moreover, even when the battery outer laminate 10 touches the electrolyte, it is possible to reliably prevent changes in appearance (discoloration, etc.).
The thickness of the coating layer 16 can be set to 20 μm or less, for example. By setting the thickness of the coating layer 16 in the range of 2 to 20 μm, the overall thickness of the battery exterior laminate 10 can be suppressed.

The static friction coefficient (based on JIS K7125) of the surface of the coating layer 16 is preferably 0.3 or less.
By setting the static friction coefficient within this range, it is possible to reduce damage and deformation of the battery exterior laminate 10 at the time of drawing and facilitate drawing.

The printing layer 15 (second coating layer) can have the same configuration as the coating layer 16.
The print layer 15 is formed of a material exemplified as a material usable for the coating layer 16 (at least one resin selected from the resin group). The constituent material of the printing layer 15 may be the same as the constituent material of the coating layer 16, or may be a material different from the constituent material of the coating layer 16.
Like the coating layer 16, the printed layer 15 is preferably a thin film cured layer formed by applying and drying a solvent-type paint prepared by dissolving the resin in an organic solvent.
Similar to the coating layer 16, the print layer 15 and the first adhesive layer 14 can be colored by adding the colorant to the solvent-based paint. The colors of the printing layer 15 and the first adhesive layer 14 can be arbitrarily selected. The printing layer 15 and the first adhesive layer 14 may be uniformly colored over the entire region (or a partial region), or a plurality of regions may be colored in different colors (or the same color as each other). May be.
The printing layer 15 and the first adhesive layer 14 can also be colored so as to display characters, figures, images, patterns, and the like. These characters and the like may represent, for example, product names and manufacturers. By coloring the printing layer 15 and the first adhesive layer 14, the design of the battery exterior laminate 10 can be improved.
The thickness of the printing layer 15 is 0.1 μm to 10 μm, for example.
The printing layer 15 is formed by a known printing method such as an offset printing method, a gravure printing method, or a screen printing method.

  In addition, although the laminated body 10 for battery exteriors of the example of FIG. 1 has the printed layer 15, the structure without the printed layer 15 (battery laminated body 80 shown in FIG. 7) is also possible. Moreover, the structure (laminated body 90 for battery exterior shown in FIG. 8) which the surface coating layer 18, the coating layer 16, and the printing layer 15 were excluded from the laminated body 10 for battery exteriors of FIG. 1 is also possible.

The sealant layer 13 is made of a polyolefin resin and is the innermost layer in the secondary battery 40 (see FIG. 2).
The reason why the sealant layer 13 is the innermost side is that the polyolefin-based resin is excellent in resistance to an electrolyte solution of a lithium ion battery and has good heat sealability. Here, the heat sealing property is the stability of the seal at a high temperature.
The polyolefin resin constituting the sealant layer 13 preferably contains mainly either a polypropylene resin or a polyethylene resin.

The sealant layer 13 has a multi-layer structure, and has an maleic anhydride-modified polyolefin resin (first polyolefin resin), an alloy material of epoxy group-containing resin and polyolefin resin (second polyolefin resin) on the interface side with the SUS foil 12. And a layer made of a heat-adhesive polyolefin resin containing at least one selected from the group consisting of an alloy material (third polyolefin resin) of a resin having an oxazoline group and a polyolefin resin (third polyolefin resin).
As said thermoadhesive polyolefin resin, 1 type may be used independently among the above-mentioned 1st-3rd polyolefin resin, and 2 or more types may be mixed and used for it.

As shown in FIG. 1, the sealant layer 13 can have a two-layer structure including a first layer 13 a made of the heat-adhesive polyolefin resin and a second layer 13 b made of polypropylene resin. The first layer 13 a is a layer on the interface side with the SUS foil 12.
As long as the sealant layer 13 has a multilayer structure having a layer made of the above heat-adhesive polyolefin resin on the interface side with the SUS foil 12, the number of layers is not limited to the illustrated example. For example, a structure having three or more layers may be used.

Since the first to third polyolefin resins described above are firmly bonded to the water-soluble resin contained in the surface coating layer 17, the bonding strength between the sealant layer 13 and the surface coating layer 17 can be increased.
When using 2 or more types among the above-mentioned 1st-3rd polyolefin resin, it is preferable to knead | mix these polyolefin resins and to alloy.

The maleic anhydride-modified polyolefin resin is obtained by modifying a part of the polyolefin resin molecule with maleic anhydride.
Examples of commercially available maleic anhydride-modified polyolefin resins that are generally available include Mitsui Chemicals, Inc., trade name Admer (as acid-modified polyethylene, for example, SF600, SF700, NE060, acid-modified polypropylene, for example, QF551), Mitsubishi Product name Modic (manufactured by Kagaku Co., Ltd.) (as acid-modified polyethylene, for example, M545, as acid-modified polypropylene, for example, P555), and the like.

As the resin having an epoxy group, those obtained by modifying a part of the polyolefin resin molecule into an epoxy group and those obtained by melt-mixing an epoxy compound or a resin having an epoxy group with a polyolefin resin can be used. .
As a commercially available product suitable as an epoxy compound that can be used in the present invention, for example, “Epicoat 1001” manufactured by Mitsubishi Chemical Corporation is available.
In addition, as a resin having an epoxy group, there is “MODIPA-A4100” manufactured by NOF Corporation.

As the resin having an oxazoline group, those obtained by modifying a part of the polyolefin resin molecule into an oxazoline group and those obtained by melt-mixing an oxazoline compound with a polyolefin resin can be used.
Examples of the oxazoline compound that can be used in the present invention include 2-isopropenyl-2-oxazoline. Examples of commercially available products suitable as the oxazoline compound include “Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd.

The thickness of the sealant layer 13 is preferably 20 μm to 50 μm. By setting the thickness of the sealant layer 13 within this range, it is possible to increase the pressure strength of the heat seal portion and to suppress the intrusion of moisture into the battery exterior container 20.
In addition, by setting the thickness of the sealant layer 13 in this range, the overall thickness of the battery outer laminate 10 can be suppressed, and the secondary battery 40 can be thinned.

Since the sealant layer 13 has the above-described heat-adhesive polyolefin resin layer, it can be bonded to the SUS foil 12 by heat lamination.
The adhesive strength between the sealant layer 13 and the SUS foil 12 is measured by a measuring method B (180 degree peeling) defined in JIS C6471, and is preferably 5 N / 15 mm or more.

  The overall thickness of the battery exterior laminate 10 can be, for example, 100 μm or less. Thereby, the secondary battery 40 can be thinned.

The battery exterior laminate 10 preferably has a tensile elongation at break of 40% or more in both the MD direction and the TD direction.
When the tensile elongation at break is within this range, the corner portion is sufficiently stretched when the concave portion is formed by drawing, so that it does not break.
The tensile elongation at break is determined when measured at a tensile speed of 50 mm / min according to JIS K7127.

  Examples of the non-aqueous battery in which the battery exterior laminate is used include those using an organic electrolyte as the electrolyte, such as a lithium ion battery or an electric double layer capacitor which is a secondary battery. As the organic electrolyte, those using carbonate esters such as propylene carbonate (PC), diethyl carbonate (DEC), and ethylene carbonate as a medium are common, but not particularly limited thereto.

Next, a method for manufacturing the secondary battery 40 shown in FIG. 2 will be described.
First, as shown in FIG. 3A, the battery exterior laminate 10 is formed by drawing or the like so as to have a tray shape having the recesses 31 to obtain the container body 30. The depth of the recessed part 31 can be 2 mm or more, for example.
A lithium ion battery (lithium ion battery 27 in FIG. 2) is accommodated in the recess 31 of the container body 30.
Next, as shown in FIG. 3 (b), the lid member 33 made of the battery exterior laminate 10 is stacked on the container body 30, and the flange portion 32 of the container body 30 and the peripheral portion 34 of the lid member 33 are heat sealed. By doing so, the secondary battery 40 shown in FIG. 2 is obtained.

In the battery exterior laminate 10 according to the present invention, a surface coating layer using a water-soluble paint containing a water-soluble resin, a metal fluoride compound, and an organic chelating agent on at least the sealant layer 13 side of the SUS foil 12. 17 is formed, and the sealant layer 13 includes the heat-adhesive polyolefin resin layer. Therefore, the sealant layer 13 and the SUS foil 12 can be bonded very firmly.
For this reason, when forming a recessed part by drawing, the damage (breaking etc.) of the laminated body 10 for battery exteriors can be reduced, and peeling with the sealant layer 13 and the SUS foil 12 can be prevented. Therefore, even when deep drawing is performed, it is possible to reduce the occurrence of defects when forming the battery exterior container 20, improve the manufacturing yield of the secondary battery 40, and improve the production efficiency. Further, in the battery exterior laminate 10, by increasing the adhesive strength between the sealant layer 13 and the SUS foil 12, it is possible to prevent moisture from entering the battery exterior container 20 from the outside. Therefore, it is possible to suppress the deterioration of the electrolytic solution with time and to prolong the product life of the secondary battery 40.

In the battery exterior laminate 10 according to the present invention, the mechanical strength (tensile strength, etc.) can be increased by using the SUS foil 12, and therefore, when forming a recess by drawing, damage (breaking, etc.) is reduced. it can. Therefore, it is possible to prevent the molding failure of the battery exterior container 20 and improve the production efficiency of the secondary battery 40, and to prevent the battery performance from being deteriorated or ignited due to moisture intrusion or electrolyte leakage.
Moreover, since the SUS foil 12 having high mechanical strength is used, the durability of the battery outer packaging container 20 can be enhanced. Therefore, a structure (such as a cover case) for protecting the secondary battery 40 during transportation or mounting of the secondary battery 40 becomes unnecessary or can be simplified. Therefore, it is possible to reduce the packing cost and downsize the packing device. In addition, since the SUS foil having high mechanical strength is used, the thickness of the battery exterior laminate can be reduced to increase the internal volume, and the volume efficiency of the battery can be improved.
Furthermore, since the SUS foil 12 having the surface coating layer 17 is used, even when the electrolyte is decomposed and acid is generated due to the moisture that has entered the inside of the battery exterior container 20, deterioration due to corrosion hardly occurs. Therefore, leakage of the electrolytic solution due to corrosion of the metal foil is prevented, and deterioration of battery performance and ignition can be prevented.

FIG. 4 shows a battery exterior laminate 50 that is a second embodiment of the battery exterior laminate of the present invention.
The laminated body 50 for battery exterior according to the present invention is provided with a second adhesive layer 19 made of a polyolefin resin containing a resin having an epoxy group or an oxazoline group between the SUS foil 12 and the sealant layer 13. ing. The battery outer laminate 50 is different from the battery outer laminate 10 shown in FIG. 1 in that the SUS foil 12 and the sealant layer 13 are bonded by the second adhesive layer 19.
In the battery exterior laminate 50, the adhesive strength between the SUS foil 12 and the sealant layer 13 can be increased by the second adhesive layer 19.

(Measuring method)
Measurement method of adhesive strength between SUS foil and sealant layer: Measured by peeling measurement method A (90 ° direction peeling) defined in JIS C6471 “Testing method for copper-clad laminate for flexible printed wiring board”.

(measuring device)
・ Adhesive strength measuring device: Manufacturer name: Shimadzu Corporation, Model: AUTOGRAPH AGS-100A tensile tester

Example 1
A base material layer made of a stretched polyethylene terephthalate (PET) resin film having a thickness of 12 μm was prepared.
This base material layer and a SUS foil having a thickness of 30 μm were laminated by dry lamination via an adhesive layer (thickness 3 μm) made of a urethane-based adhesive.
A water-soluble paint was applied to both surfaces of the SUS foil (coating amount 0.2 g / m ² ), dried by heating in an oven at 200 ° C., and baked and crosslinked to form a surface coating layer.
The water-soluble paint is 0.1% by mass of polyvinyl alcohol resin (PVA resin) (manufactured by Nippon Carbide Industry Co., Ltd., trade name: Crosmer H) (water-soluble resin), CrF ₃ / 3H ₂ O (fluorine). It is an aqueous solution containing 0.8% by mass of a metal compound) and 0.3% by mass of PDTA (manufactured by Kirest Co., Ltd., trade name: Kirest PD-4H) (organic chelating agent).

A sealant layer having a thickness of 30 μm was formed on the surface of the surface coating layer.
The sealant layer has a first layer (thermoadhesive polyolefin resin layer) (thickness 15 μm) made of an alloy material of a resin having an epoxy group and a polyolefin resin, and a second layer (thickness 15 μm) made of a polypropylene resin. A layer structure was adopted. The first layer is a layer on the interface side with the SUS foil (see the sealant layer 13 in FIG. 1).
As the “resin having an epoxy group”, 1.5 mass of a hydroxyl group-containing epoxy compound (manufactured by Mitsubishi Chemical, product name / Epicoat 1001) is added to maleic anhydride-modified polypropylene resin (manufactured by Mitsui Chemicals, Inc., product name / Admer resin). Polypropylene resin with epoxy groups introduced by% blend compound was used.
This “resin having an epoxy group” and polypropylene resin (product name / Admer resin, manufactured by Mitsui Chemicals, Inc.) were mixed at a ratio of 1: 1 (mass ratio) to obtain an alloy material.
This alloy material and a polypropylene resin (product name / Admer resin, manufactured by Mitsui Chemicals, Inc.) are coextruded to have a two-layer structure having a first layer made of the alloy material and a second layer made of the polypropylene resin. Thus, the battery outer laminate of Example 1 was obtained.

A test piece was collected from the battery outer laminate, and this test piece was immersed in an electrolytic solution (ethylene carbonate (EC) / diethyl carbonate (DEC) 1: 1 vol% solution added with 1 mol / liter of LiPF ₆ ), The temperature was maintained at 80 ° C. for 24 hours.
Next, the test piece after the electrolytic solution immersion treatment was immersed in pure water for 30 minutes.
About the test piece before electrolyte solution immersion, after electrolyte solution immersion, and after water immersion treatment, the adhesive strength between the SUS foil and the sealant layer was measured. The measurement results are shown in Table 1.

(Example 2)
Other than using an addition amount of polyvinyl alcohol resin (water-soluble resin) of 0.2 mass% and using EDTMP-8H (trade name: Kirest PH-540, manufactured by Kirest Co., Ltd.) as an organic chelating agent. Obtained the laminated body for battery exteriors like Example 1. FIG.
The adhesive strength of this laminate for battery exterior was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

Example 3
A battery exterior laminate was obtained in the same manner as in Example 1 except that EDTMP · 8H (trade name: Kirest PH-540, manufactured by Kirest Co., Ltd.) was used as the organic chelating agent.
The adhesive strength of this laminate for battery exterior was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Example 4)
As a water-soluble resin, a polyvinyl alcohol-based resin (manufactured by Nippon Vinegar Poval Co., Ltd., trade name: DF-20) is used, and the addition amount is set to 0.2% by mass. Thus, a laminate for battery exterior was obtained.
The adhesive strength of this laminate for battery exterior was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Example 5)
As a water-soluble resin, a polyvinyl alcohol-based resin (manufactured by Nippon Vinegar Poval Co., Ltd., trade name: DF-20) is used, and its addition amount is 0.5% by mass, and the addition amount of a metal fluoride compound Is 1.5 mass%, and EDTMP-8H (trade name: Kirest PH-540, manufactured by Kirest Co., Ltd.) is used as the organic chelating agent, and the addition amount is 0.5 mass%. Obtained the laminated body for battery exteriors like Example 1. FIG.
The adhesive strength of this laminate for battery exterior was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Example 6)
As a water-soluble resin, a polyvinyl alcohol resin (manufactured by Nippon Vinegar Poval Co., Ltd., trade name: DF-20) is used, and the addition amount is 1.0% by mass, and the addition amount of the metal fluoride compound And 2.5% by mass, and EDTMP · 8H (trade name: Kirest PH-540, manufactured by Kirest Co., Ltd.) is used as the organic chelating agent, and the addition amount is 1.0% by mass. Obtained the laminated body for battery exteriors like Example 1. FIG.
The adhesive strength of this laminate for battery exterior was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Example 7)
A battery exterior laminate was obtained in the same manner as in Example 1 except that the amount of water-soluble paint applied was 0.05 g / m ² .
The adhesive strength of this laminate for battery exterior was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Example 8)
Other than using an addition amount of polyvinyl alcohol resin (water-soluble resin) of 0.2 mass% and using EDTMP-8H (trade name: Kirest PH-540, manufactured by Kirest Co., Ltd.) as an organic chelating agent. Obtained the laminated body for battery exteriors like Example 1. FIG.
The adhesive strength of this laminate for battery exterior was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

Example 9
A battery exterior laminate in the same manner as in Example 1 except that the sealant layer has a single layer structure (thickness 30 μm) made of maleic anhydride-modified polypropylene resin (product name: Admer resin, manufactured by Mitsui Chemicals, Inc.). Got.
The adhesive strength of this laminate for battery exterior was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Example 10)
A laminated body for battery exterior was obtained in the same manner as in Example 1 except that the sealant layer had a single layer structure (thickness 30 μm) made of an alloy material of a resin having an oxazoline group and a polyolefin resin.
“Epocross RPS1005” manufactured by Nippon Shokubai Co., Ltd. was used as the resin having an oxazoline group. As the polyolefin resin, maleic anhydride-modified polypropylene resin (product name / Admer resin, manufactured by Mitsui Chemicals, Inc.) was used.
The alloy material was obtained by mixing resin which has an oxazoline group, and maleic anhydride modified polyolefin resin by 2:98 (mass ratio).
The adhesive strength of this laminate for battery exterior was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Comparative Example 1)
The adhesive strength of the battery exterior laminate obtained in the same manner as in Example 1 was measured in the same manner as in Example 1 except that no water-soluble resin was added. The measurement results are shown in Table 1.

(Comparative Example 2)
Battery exterior obtained in the same manner as in Example 1 except that no metal fluoride compound is added and that EDTMP · 8H (trade name: Kirest PH-540, manufactured by Kirest Co., Ltd.) is used as the organic chelating agent. For the laminate, the adhesive strength was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Comparative Example 3)
About the laminated body for battery exterior obtained in the same manner as in Example 1 except that the addition amount of the polyvinyl alcohol-based resin (water-soluble resin) is 0.2% by mass and the organic chelating agent is not added. The adhesive strength was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Comparative Example 4)
The adhesive strength of the laminate for battery exterior obtained in the same manner as in Example 1 was measured in the same manner as in Example 1 except that the addition amount of the metal fluoride compound was 3% by mass. The measurement results are shown in Table 1.

(Comparative Example 5)
Other than using an addition amount of polyvinyl alcohol resin (water-soluble resin) of 0.2 mass% and using EDTMP-8H (trade name: Kirest PH-540, manufactured by Kirest Co., Ltd.) as an organic chelating agent. Was measured in the same manner as in Example 1 for the battery exterior laminate obtained in the same manner as in Example 1. The measurement results are shown in Table 1.

According to the measurement results shown in Table 1, in the laminated body for battery exterior of Examples 1 to 10 in which the surface coating layer containing the water-soluble paint, the metal fluoride compound, and the organic chelating agent was formed, any of the three components It was confirmed that the adhesive strength between the SUS foil and the sealant layer was higher than that of the laminates for battery exteriors of Comparative Examples 1 to 3 in which the surface coating layer lacking such was formed.
In addition, the battery exterior laminate of Comparative Example 4 has a high concentration of the metal fluoride compound of 3% by mass. Therefore, when an organic chelate is added, the solubility is lowered and the coating is precipitated, so the coating film has a lot of unevenness. It became brittle.
Moreover, since the coating amount of the battery exterior laminate of Comparative Example 5 is as thick as 1.2 g / m ² (the calculated thickness of the coating film is 1.2 μm), the adhesive strength between the SUS foil and the sealant layer is low. became.
Further, when the density of the water-soluble paint containing the water-soluble resin, the metal fluoride compound, and the organic chelating agent is 1 g / cm ³ , the water-soluble paint having a coating amount of 0.2 g / m ² is dried and cured. The thickness of the surface coating layer is 0.2 μm. Therefore, the thickness of the surface coating layer in the laminate for battery exterior is 0.2 μm in Examples 1 to 6 and Comparative Examples 1 to 5, respectively, 0.05 μm in Example 7, and 1. It is 0 μm, and in Comparative Example 7, it is 1.2 μm.

Although the measurement results are not described in Table 1, the addition amount of the polyvinyl alcohol resin (water-soluble resin) is 0.05% by mass, and EDTMP · 8H (Chirest Co., Ltd.) is used as the organic chelating agent. The adhesive strength was measured in the same manner as in Example 1 for the laminate for battery exterior obtained in the same manner as in Example 1 except that manufactured product name: Kyrest PH-540) was used. As a result, the initial value, the value after immersion in the electrolyte, and the value after immersion in the electrolyte were 10 (N / 15 mm), 4 (N / 15 mm), and 2 (N / 15 mm), respectively.
Although the measurement results are not shown in Table 1, the addition amount of the polyvinyl alcohol resin (water-soluble resin) is set to 1.5% by mass, and EDTMP · 8H (Chirest Co., Ltd.) is used as the organic chelating agent. The adhesive strength was measured in the same manner as in Example 1 for the laminate for battery exterior obtained in the same manner as in Example 1 except that manufactured product name: Kyrest PH-540) was used. As a result, the initial value, the value after immersion in the electrolyte, and the value after immersion in the electrolyte were 8 (N / 15 mm), 4 (N / 15 mm), and 2 (N / 15 mm), respectively.

DESCRIPTION OF SYMBOLS 10,50 ... Non-aqueous battery exterior laminate, 11 ... Base material layer, 12 ... SUS foil, 13 ... Sealant layer, 14 ... First adhesive layer, 15 ... Print layer, 16 ... Coating layer, 17, 18 ... surface coating layer, 19 ... second adhesive layer, 20 ... non-aqueous battery exterior container, 27 ... lithium ion battery, 40 ... secondary battery.

Claims (1)

A base material layer, a SUS foil, and a multilayer sealant layer made of polyolefin resin are laminated in order,
The base material layer and the SUS foil are bonded via a first adhesive layer made of a urethane adhesive,
The SUS foil and the sealant layer are bonded via a second adhesive layer made of a polyolefin resin containing a resin having an epoxy group or an oxazoline group,
The base material layer is a single-layer or multilayer laminate film using a heat-resistant resin film having a melting point of 200 ° C. or higher,
A surface coating layer obtained by drying and curing a water-soluble paint containing a water-soluble resin, a metal fluoride compound, and an organic chelating agent is formed on at least the sealant layer side of the SUS foil.
The metal fluoride compound has a function of crosslinking the water-soluble resin;
The organic chelating agent is an organic substance that can chemically bond with a cation to form a metal ion complex, and acts to make the water-soluble resin water resistant by chemically reacting with the water-soluble resin or metal fluoride compound. Having
The sealant layer is made of maleic anhydride-modified polyolefin resin, an alloy material of a resin having an epoxy group and a polyolefin resin, and an alloy material of a resin having an oxazoline group and a polyolefin resin on the interface side with the SUS foil. A non-aqueous battery exterior laminate comprising a heat-adhesive polyolefin resin layer containing one or more selected from a resin group.

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