JP6850539B2 - Battery exterior laminate, battery exterior and battery - Google Patents

Description

The present invention relates to a battery exterior laminate that is good as an exterior body such as a secondary battery or a capacitor, and a battery exterior body and a battery obtained by using the laminate.

Amid growing awareness of the environment, secondary batteries such as lithium-ion batteries and capacitors such as electric double layer capacitors are attracting attention as storage batteries for storing electrical energy as well as utilizing natural energy such as sunlight and wind power. ing.
As the exterior body used for these batteries, a battery exterior laminate in which a metal foil and a resin layer are laminated is used for the purpose of miniaturization and weight reduction. Such a battery exterior laminate is formed by drawing or the like so as to form a tray having recesses to form an exterior container body. Further, in the same manner as the outer body container main body, the battery outer laminate is formed to obtain the outer body lid portion. After storing the battery body in the recess of the exterior container body, the exterior body lid is overlapped so as to cover the stored battery body, and the side edges of the container body and the exterior body lid are adhered to form the exterior. You can get a battery in which the battery body is stored in the body.

For example, in Patent Document 1, a base material layer, an aluminum foil, and an innermost layer made of polypropylene or polyethylene are laminated in this order, and a thin film coating layer is laminated on the innermost layer side surface of the aluminum foil for battery exterior. The laminate is disclosed. More specifically, in Patent Document 1, it is preferable that the thin film coating layer and the innermost layer made of polypropylene or polyethylene layer are adhered to each other via a heat sealant, and an acid-modified polypropylene-based heat sealant. The thin-film coated aluminum foil and the innermost layer are adhered by the laminating process using the above.

Japanese Unexamined Patent Publication No. 2012-333393

As the application fields of batteries such as secondary batteries are expanding and the production of batteries is required to be increased, the outer body of the battery is also required to improve the yield at the time of manufacturing and the production efficiency such as shortening the time. In addition to improving battery characteristics such as miniaturization and large capacity, the battery exterior is also required to have excellent characteristics such as heat resistance and chemical resistance (electrolyte resistance).
However, as in Patent Document 1, when the surface-treated metal foil and the innermost layer resin are laminated and bonded using a heat sealant, it is necessary to apply high temperature and high pressure at the time of laminating, which shortens the manufacturing time. And because it is difficult to reduce the manufacturing cost, there is a limit to the improvement of production efficiency. In addition, laminating at a high temperature may cause wrinkles and deterioration of the innermost layer (polypropylene layer, polyethylene layer, etc.) and metal foil to be bonded, which reduces the yield and of various materials. It led to narrowing the range of choices.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a battery exterior laminate that can be manufactured with high production efficiency and has excellent various characteristics.

As a result of repeated studies to achieve the above object, the present inventors have made an arbitrarily surface-processed metal foil and a base material layer (innermost layer) via an adhesive layer having a specific storage elastic modulus. We have found that by adhering, not only can various characteristics required for the battery exterior laminate be improved, but also production efficiency such as shortening of manufacturing time and improvement of yield can be improved as needed. The present invention has been completed.

That is, the present invention has adopted the following configuration.
The battery exterior laminate according to the first aspect of the present invention is a battery exterior laminate including at least a first base material layer, a first adhesive layer, and a metal foil in this order. a layer base layer comprising a polyolefin, said first adhesive layer, in the dynamic viscoelasticity measurement of the first adhesive layer alone, the storage modulus values are 1.0 × 10 ⁴ at 0.99 ° C. above, characterized in that it is a layer serving as 1.0 × 10 ⁷ or less.
The first adhesive layer is a layer composed of an adhesive containing 100 parts by mass of an acid-modified polyolefin resin (A) and 1 to 20 parts by mass of a compound (B) containing a plurality of epoxy groups. Is preferable.
The compound (B) containing a plurality of epoxy groups is preferably a phenol novolac type epoxy resin.
It is preferable that a first corrosion prevention layer is provided between the first adhesive layer and the metal foil, and the first corrosion prevention layer contains a metal halide compound.
The first corrosion prevention layer preferably further contains a water-soluble resin and a chelating agent or a crosslinkable compound.
The metal halide compound is preferably a chloride of iron, chromium, manganese or zirconium, or a fluoride of iron, chromium, manganese or zirconium.
The metal foil is preferably aluminum, stainless steel, copper, nickel or titanium.
The thickness of the metal foil is preferably 10 to 40 μm.
The battery exterior body of the second aspect of the present invention is a battery exterior body including the battery exterior laminate of the first aspect, has an internal space for accommodating a battery, and is the first of the battery exterior laminates. 1 It is characterized in that the side of the base material layer is the side of the internal space.
The battery of the third aspect of the present invention is characterized by including the battery exterior body of the second aspect.

According to the present invention, it is possible to provide a battery exterior laminate having excellent characteristics and capable of being manufactured with high production efficiency.

It is schematic cross-sectional view which shows 1st Embodiment of the laminated body for battery exterior which concerns on this invention. It is a perspective view which shows an example of the secondary battery produced using the battery exterior laminated body which concerns on this invention. It is a perspective view which shows the process of manufacturing a secondary battery using the battery exterior laminated body which concerns on this invention. It is a figure which shows the storage elastic modulus of the adhesive layer single layer in Experimental Examples 1 to 3 and Comparative Experimental Example 1.

Hereinafter, the present invention will be described based on preferred embodiments.

[Battery exterior laminate]
The battery exterior laminate (hereinafter, may be simply referred to as “laminate”) according to the first aspect of the present invention includes at least a first base material layer, a first adhesive layer, a first corrosion prevention layer, and a first corrosion prevention layer. A battery exterior laminate provided with metal foils in this order, wherein the first base material layer is a layer made of polyolefin, and the first adhesive layer is a dynamic of the first adhesive layer single layer. in viscoelasticity measurement, the value of storage modulus at 0.99 ° C. is 1.0 × 10 ⁴ or more, a layer comprising a 1.0 × 10 ⁷ or less.

FIG. 1 is a cross-sectional view showing a schematic configuration of a battery exterior laminate 10 according to an embodiment of the present invention.
The laminate 10 according to the present embodiment includes a first base material layer 11, a first adhesive layer 12, a first corrosion prevention layer 13, a metal foil 14, a second corrosion prevention layer 15, and a second adhesion. The agent layer 16 and the second base material layer 17 are provided in this order.
That is, in the laminate 10 according to the present embodiment, the first corrosion prevention layer 13 and the second corrosion prevention layer 15 formed on both surfaces of the metal foil 14 and the first adhesive layer 12 on the first corrosion prevention layer 13 It is composed of a seven-layer structure including a first base material layer 11 laminated via a second base material layer 11 and a second base material layer 17 laminated on the second corrosion prevention layer 15 via a second adhesive layer 16.
Hereinafter, each layer will be described in detail.

<First base material layer 11>
The first base material layer 11 is a layer made of polyolefin. Examples of the layer made of polyolefin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, a random copolymer of propylene and ethylene or α-olefin, and a block copolymer of propylene and ethylene or α-olefin. ..
Among them, since the adhesiveness with the first adhesive layer 12 is improved, a block copolymer of homopolypropylene (propylene homopolymer; hereinafter, may be referred to as “homoPP”) and propylene-ethylene block copolymer (hereinafter, referred to as “homoPP”). , "Block PP"), a polypropylene-ethylene random copolymer (hereinafter, may be referred to as "random PP") or the like, polypropylene-based resins are preferable. Of these, homo-PP or block PP is more preferable, and block PP is particularly preferable because it has excellent mechanical strength.
The first base material layer 11 may have a single-layer structure or a multi-layer structure.

The melting point of the layer made of polyolefin used for the first base material layer 11 is not particularly limited as long as it has the heat resistance required for the battery exterior laminate 10.
The thickness of the first base material layer 11 can be, for example, 1 to 200 μm, preferably 5 to 100 μm, and even more preferably 5 to 40 μm.

<First adhesive layer 12>
The first adhesive layer 12 is a layer provided for adhering the first base material layer 11 which is a base material resin layer and the metal foil 14 on which the first corrosion prevention layer 13 is formed on the surface. in the dynamic viscoelasticity measurement of the first adhesive layer 12 monolayers, the value of storage modulus at 0.99 ° C. is 1.0 × 10 ⁴ or more, a layer comprising a 1.0 × 10 ⁷ or less.
The material of the adhesive forming the first adhesive layer 12 is particularly limited as long as it can adhere the above layers well and can satisfy the value of the storage elasticity. Although not, for example, a layer made of an adhesive containing an acid-modified polyolefin resin (A) and a compound (B) containing a plurality of epoxy groups because it can satisfy adhesiveness and storage elasticity. Is preferable.
Hereinafter, the acid-modified polyolefin resin (A) may be referred to as “component (A)”, and the compound (B) containing a plurality of epoxy groups may be referred to as “component (B)”.

(Acid-modified polyolefin resin (A))
In the present invention, the acid-modified polyolefin resin (A) (component (A)) is a polyolefin-based resin modified with an unsaturated carboxylic acid or a derivative thereof, and a carboxy group or anhydrous carboxylic acid is contained in the polyolefin-based resin. It has an acid functional group such as a group.
The component (A) is obtained by modifying a polyolefin resin with an unsaturated carboxylic acid or a derivative thereof, copolymerizing an acid functional group-containing monomer with olefins, or the like. Among them, as the component (A), a component obtained by acid-modifying a polyolefin resin is preferable.
Examples of the acid modification method include graft modification in which a polyolefin resin and an acid functional group-containing monomer are melt-kneaded in the presence of a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound.

Examples of the polyolefin-based resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, a copolymer of propylene and ethylene, and a copolymer of propylene and an olefin-based monomer.
Examples of the olefin-based monomer in the case of copolymerization include 1-butene, isobutylene, 1-hexene and the like.
The copolymer may be a block copolymer or a random copolymer.
Among them, as the polyolefin-based resin, a polypropylene-based resin polymerized from propylene such as homopolypropylene (propylene homopolymer), a copolymer of propylene and ethylene, and a copolymer of propylene and butene as a raw material is preferable; in particular. A propylene-1-butene copolymer, that is, a polyolefin resin having a methyl group and an ethyl group in the side chain is preferable. By containing 1-butene, the molecular motion when the resin is heated is promoted, and as a result, the chances of contact between the cross-linking points of the component (A) and the component (B) described later are increased, and as a result, the adherend. Adhesion to the resin is further improved.

The acid functional group-containing monomer is a compound having an ethylenic double bond and a carboxy group or a carboxylic acid anhydride group in the same molecule, and is a compound of various unsaturated monocarboxylic acids, dicarboxylic acids, or dicarboxylic acids. Acid anhydrides can be mentioned.
Examples of the acid functional group-containing monomer having a carboxy group (carboxy group-containing monomer) include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid, and endo. Examples thereof include α, β-unsaturated carboxylic acid monomers such as −bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid (endic acid).
Examples of the acid functional group-containing monomer having a carboxylic acid anhydride group (carboxylic acid anhydride group-containing monomer) include unsaturated dicarboxylic acids such as maleic anhydride, nadicic anhydride, itaconic anhydride, citraconic anhydride, and endic anhydride. Anhydride monomer can be mentioned.
As these acid functional group-containing monomers, one type may be used alone in the component (A), or two or more types may be used in combination.

Among them, as the acid functional group-containing monomer, a monomer containing an acid functional group that reacts well with the epoxy group in the component (B) described later is preferable; an acid anhydride group is used because of its high reactivity with the epoxy group. The acid functional group-containing monomer having an acid functional group is more preferable; the carboxylic acid anhydride group-containing monomer is further preferable; maleic anhydride is particularly preferable.
When some of the acid functional group-containing monomers used for acid modification were unreacted, the unreacted acid functional group-containing monomers were removed in advance in order to prevent the unreacted acid functional group-containing monomers from reducing the adhesive strength. It is preferable to use the one as the component (A).

In the component (A), the component derived from the polyolefin resin or olefins is preferably 50 parts by mass or more with respect to 100 parts by mass of the total amount of the component (A).

The melting point of the component (A) is not particularly limited.
When the first adhesive layer 12 is used as an adhesive layer for dry lamination, the melting point of the component (A) is preferably 50 to 100 ° C, preferably 60 to 98 ° C, and 70 to 98 ° C. More preferably, 75 to 95 ° C. is even more preferable.
By setting the melting point of the component (A) to be equal to or higher than the above lower limit value, the heat resistance of the first adhesive layer 12 can be improved. , The heat resistance and durability after being adhered to the metal foil 14 provided with the first corrosion prevention layer 13 can be improved.
On the other hand, by setting the melting point of the component (A) to the above upper limit value or less, when the component (A) is dissolved in an organic solvent to obtain a solvent-type dry laminating adhesive, the component (A) is dissolved in the organic solvent. Since it is easy to use, a more uniform adhesive can be obtained, and the component (A) and the component (B) react satisfactorily to improve the adhesiveness and durability. Further, by using the component (A) having a melting point equal to or lower than the above upper limit value, the temperature at the time of dry laminating through the first adhesive layer 12 and the aging temperature after laminating can be set to a relatively low temperature. it can. As a result, in the first base material layer 11 bonded by using the first adhesive layer 12, wrinkles due to heat are less likely to occur, and not only the yield at the time of manufacturing is improved, but also the first base material layer 11 Since the heat resistance requirement is relaxed, the range of selection of the material of the first base material layer 11 can be expanded. Further, as a result of being able to perform the laminating process at a relatively low temperature, the laminating process time can be shortened and the amount of energy required for the laminating process can be reduced, so that the production efficiency can be improved and the energy consumption can be reduced. Can be reduced.

On the other hand, if the adhesive used to form the first adhesive layer 12 does not contain an organic solvent and the component (A) and the component (B) described later are melt-kneaded to form an adhesive, ( A) The melting point of the component is preferably 100 ° C to 180 ° C. The first adhesive layer 12 made of such an adhesive can be suitably used as an adhesive layer for thermal laminating.
By using the component (A) having a melting point in the above range, the component (A) and the component (B) described later can be separated from the melting point of the component (A) even when a conventional method or a general apparatus is used. Can be melt-kneaded at a sufficiently high temperature. Further, when the component (A) and the component (B) described later are reacted by using melt kneading, the melting point of the component (B) is preferably lower than that of the component (A), but the melting point in the above range is set. By using the component (A) having the component (A), the degree of freedom in selecting the component (B) can be increased.
Further, as described above, the melting point of the component (A) is preferably higher than the melting point of the component (B) described later, but the melting point of the component (A) is higher than the melting point of the component (B) by 10 ° C. or more. Is more preferable, 20 ° C. or higher is further preferable, and 30 ° C. or higher is particularly preferable. Since the melting point of the component (A) is sufficiently higher than that of the component (B), the component (B) is melted first when melt-kneading is performed, and the component (A) retains the shape of the resin. As a result of permeation and uniform reaction of the component (A) and the component (B), good durability can be obtained.

The molecular weight of the component (A) is not particularly limited, and is not particularly limited as long as it can satisfy the desired melting point as described above, but generally, a resin having a molecular weight of 1000 to 800,000 is used. It is used, preferably 50,000 to 650000, more preferably 80,000 to 550000, and even more preferably 100,000 to 450,000.

Among them, as the component (A), maleic anhydride-modified polypropylene is preferable from the viewpoint of adhesiveness, durability and the like.

(Compound (B) containing a plurality of epoxy groups)
The component (B) is a compound containing a plurality of epoxy groups. The component (B) may be a low molecular weight compound or a high molecular weight compound. From the viewpoint of improving miscibility and compatibility with the component (A), the component (B) is preferably a polymer compound (resin). On the other hand, when the adhesive is a solvent-type adhesive for dry laminating, it is also preferable that the component (B) is a low molecular weight compound from the viewpoint of improving the solubility in an organic solvent.

The structure of the component (B) is not particularly limited as long as it has a plurality of epoxy groups, and examples thereof include a phenoxy resin synthesized from bisphenols and epichlorohydrin; a phenol novolac type epoxy resin; and a bisphenol type epoxy resin. Among them, it is preferable to use a phenol novolac type epoxy resin because the epoxy content per molecule is high and a particularly dense crosslinked structure can be formed together with the component (A).

In the present invention, the phenol novolac type epoxy resin is a compound having a basic structure of a phenol novolac resin obtained by acid condensation of phenol and formaldehyde, and an epoxy group introduced into a part of the structure. The amount of epoxy group introduced per molecule in the phenol novolac type epoxy resin is not particularly limited, but by reacting an epoxy group raw material such as epichlorohydrin with the phenol novolac resin, a large number of phenols present in the phenol novolac resin are present. Since a large number of epoxy groups are introduced into the phenolic hydroxyl group, it is usually a polyfunctional epoxy resin.

Among them, as the phenol novolac type epoxy resin, a bisphenol A novolac type epoxy resin having a phenol novolac structure as a basic skeleton and also having a bisphenol A structure is preferable. The bisphenol A structure in the epoxy resin may be any structure as long as it can be derived from bisphenol A, and the hydroxyl groups at both ends of the bisphenol A may be substituted with a group such as an epoxy group-containing group.
An example of the bisphenol A novolak type epoxy resin is a resin represented by the following general formula (1).

［式（１）中、Ｒ^１〜Ｒ^６はそれぞれ独立に水素原子又はメチル基であり、ｎは０〜１０の整数であり、Ｒ^Ｘはエポキシ基を有する基である。］

In Expression ^(1), R 1 ~R ⁶ are each independently a hydrogen atom or a methyl group, n is an integer of 0, ^{R X} is a group having an epoxy group. ]

In formula (1), R ^{1 to} R ⁶ are independently hydrogen atoms or methyl groups, respectively. When n is an integer of 2 or more, R ³ and R ⁴ may be the same or different, respectively.
The resin represented by the formula (1) preferably satisfies at least one of the following (i) to (iii).
(I) Both R ¹ and R ² are methyl groups, (ii) ^{both R 3} and R ⁴ are methyl groups, and both (iii) R ⁵ and R ⁶ are methyl groups. For example, the above (i) is satisfied. Therefore, in the formula (1), ^{the carbon atom to which R 1} and R ² are bonded and the two hydroxyphenyl groups to which the carbon atom is bonded form a structure derived from bisphenol A.

In formula (1), ^RX is a group having an epoxy group. Examples of the group having an epoxy group include an epoxy group, a combination of an epoxy group and an alkylene group, and the like, and a glycidyl group is preferable.

The epoxy equivalent of the bisphenol A novolak type epoxy resin is preferably 100 to 300, more preferably 200 to 300. The epoxy equivalent (g / eq) is the molecular weight of the epoxy resin per epoxy group, and the smaller this value is, the more epoxy groups are in the resin. By using an epoxy resin having a relatively small epoxy equivalent, the adhesiveness between the epoxy resin and the adherend is good even when the amount of the epoxy resin added is relatively small, and the epoxy resin and the acid modification are made. It is sufficiently crosslinked with the polyolefin resin.

Examples of such phenol novolac type epoxy resins include jER154, jER157S70, and jER-157S65 manufactured by Mitsubishi Chemical Corporation; EPICLON N-730A, EPICLON N-740, EPICLON N-770, and EPICLON N-775 manufactured by DIC Corporation. Commercially available products such as (trade name) can also be used.

By using the epoxy resin as described above, both the acid functional group of the component (A) and the epoxy group of the component (B) are carboxy groups contained in the adherend (particularly, the first corrosion prevention layer 13). By functioning as an adhesive functional group, it is possible to exhibit excellent adhesiveness to the first base material layer 11 and the metal foil 14 having the first corrosion prevention layer 13 on the surface. It is thought that it will be possible.
Further, a part of the acid functional group of the component (A) reacts with a part of the epoxy group of the component (B), and the crosslinked structure of the component (A) and the component (B) is formed in the first adhesive layer. As a result of being formed in 12, it is considered that the strength of the first adhesive layer 12 is reinforced by this crosslinked structure, and good durability as well as excellent adhesiveness can be obtained.

The first adhesive layer 12 preferably contains 1 to 20 parts by mass of the component (B) with respect to 100 parts by mass of the component (A), and preferably contains 1 to 20 parts by mass of the component (A). 5 to 10 parts by mass of the component (B) is more preferable, and 5 to 7 parts by mass of the component (B) is particularly preferable with respect to 100 parts by mass of the component (A).

(Arbitrary ingredient)
The adhesive used in the present invention may or may not further contain an organic solvent.
By containing an organic solvent and making it a liquid adhesive, it can be made into a solvent-type dry laminating adhesive. The first adhesive layer 12 is formed by applying and drying such a liquid adhesive on a lower layer (for example, the surface of the metal foil 14 provided with the first corrosion prevention layer 13). Can be done. By selecting coating instead of extrusion molding, the adhesive layer can be formed with a thinner layer, the adhesive layer can be thinned, and the entire laminate using the adhesive layer can be thinned.
On the other hand, when the organic solvent is not contained, the adhesive layer suitable for thermal lamination or the like can be formed by melt-kneading the component (A) and the component (B) and then extruding or the like.

When an organic solvent is contained, the above-mentioned component (A), component (B), and other optional components (details will be described later) are preferably dissolved as the organic solvent to be used to obtain a uniform solution. The solvent is not particularly limited as long as it can be used, and any known solvent can be used as the solvent for the solution type adhesive. Further, the liquid adhesive can usually be used by being applied on an adherend (for example, the surface of the metal foil 14 provided with the first corrosion prevention layer 13) and then volatilizing the organic solvent by heating or the like. Therefore, from the viewpoint of facilitating volatilization, an organic solvent having a boiling point of 150 ° C. or lower is preferable as the organic solvent.
Specific examples of the organic solvent include toluene, xylene, anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, simene and mesityrene. Aromatic solvents such as; aliphatic solvents such as n-hexane; ketone solvents such as methyl ethyl ketone, acetone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; methyl lactate, ethyl lactate, acetic acid. Ester solvents such as methyl, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; alcohol solvents such as methanol, ethanol and isopropyl alcohol; ethylene glycol, diethylene glycol, propylene glycol , Polyhydric alcohol solvent such as dipropylene glycol and the like.

One type of organic solvent may be used alone, or two or more types may be used in combination as a mixed solvent. In the case of using a mixed solvent, it is also preferable to use a combination of an organic solvent that dissolves the component (A) well and an organic solvent that dissolves the component (B) well. As such a combination, a combination of toluene, which dissolves the component (A) well, and methyl ethyl ketone, which dissolves the component (B) well, is preferable. When a mixed solvent is used, the above components (A), (B) and the like may be dissolved after mixing two or more organic solvents in advance; each of the components (A) and (B). After dissolving the components in each good solvent, a plurality of kinds of organic solvents in which each component is dissolved may be mixed.
When a plurality of types of organic solvents are mixed and used, the ratio of each organic solvent is not particularly limited. For example, when toluene and methyl ethyl ketone are used in combination, the mixing ratio of these is toluene: methyl ethyl ketone = 60 to 60 to. 95: 5 to 40 (mass ratio) is preferable, and toluene: methyl ethyl ketone = 70 to 90: 10 to 30 (mass ratio) is more preferable.

The adhesive used in the present invention may contain other components in addition to the above components (A), (B) and organic solvent. Examples of other components include miscible additives and additional resins, and more specifically, catalysts, cross-linking agents, plasticizers, stabilizers, colorants and the like can be used.

In the solid content of the adhesive used in the present invention, the component (A) is contained in an amount of more than 50 parts by mass and 99.5 parts by mass or less, and the component (B) is contained in an amount of 0.5 parts by mass or more and less than 50 parts by mass. It is preferable to be done. That is, more than half of the solid content of the adhesive is the component (A) in terms of mass ratio, and the adhesive used in the present invention contains the component (A) as the main component. More preferably, it is 0.5 to 30 parts by mass of the component (B) with respect to 70 to 99.5 parts by mass of the component (A); more preferably, it is (more preferably) with respect to 80 to 99 parts by mass of the component (A). B) 1 to 20 parts by mass of the component; 2 to 10 parts by mass of the (B) component is particularly preferable with respect to 90 to 98 parts by mass of the (A) component.

Further, even when the adhesive used in the present invention contains a solid component other than the component (A) and the component (B) as an optional component, the component (A) is always the main component. Therefore, even when an arbitrary component is contained, the component (A) in the total solid content of the adhesive is more than 50 parts by mass. For example, 70 to 99.5 parts by mass of the component (A), 0.5 to 29.5 parts by mass of the component (B), and 0.5 to 29.5 parts by mass of the other components in the total solid content. An adhesive containing and can be mentioned.

When the adhesive used in the present invention contains an organic solvent, the amount of the organic solvent used is particularly limited as long as it can satisfactorily dissolve each component such as the component (A), the component (B), and the optional component. However, in general, the solid content concentration is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, still more preferably 7 to 20% by mass.

^{The adhesive used in the present invention has a storage elastic modulus of 1.0 × 10 4 at} 150 ° C. in the dynamic viscoelasticity measurement of a single layer of the first adhesive layer 12 formed by using the adhesive. 1.0 a × 10 ^7, more preferably ^{5.0 × 10 4 ~9.5 × 10 5} , more preferably ^{3.0 × 10 5 ~8.0 × 10 5} .
Further, in the dynamic viscoelasticity measurement of a single layer of the first adhesive layer 12 which is formed by using the adhesive, the value of storage modulus at 60 ° C. is preferably 1.0 × 10 ⁶ or more , 1.0 × 10 ^{6 to} 1.0 × 10 ⁸ Pa is more preferable, and 5.0 × 10 ^{6 to} 5.0 × 10 ⁷ is even more preferable.
That is, the value of the storage elastic modulus at 150 ° C. is preferably 1/1000 to 1/1, and more preferably 1/1000 to 1/1 with respect to the value of the storage elastic modulus at 60 ° C. , 1/500 to 1/1, and particularly preferably 1/100 to 1/1.
That is, the adhesive used in the present invention not only has a sufficient elastic modulus at 60 ° C., but also the elastic modulus does not decrease too much even at a relatively high temperature of 150 ° C., and can maintain an elastic modulus in an appropriate range. It is preferable that it is a thing. The first adhesive layer 12 formed by using an adhesive having such a storage elastic modulus does not easily change its shape even at a relatively high temperature and maintains a good shape. Therefore, the first adhesive is adhered. Similarly, the shape, adhesiveness, etc. of the battery exterior laminate 10 having the agent layer 12 are kept good even at high temperatures, and it is possible to obtain the battery exterior laminate 10 having good high temperature resistance.

An adhesive having a storage elastic modulus as described above can be easily obtained by using the above-mentioned components (A) and (B) in combination. This is because the acid functional group of the component (A) and the epoxy group of the component (B) are crosslinked to maintain the elastic modulus even at a relatively high temperature.

The value of the storage elastic modulus in the dynamic viscoelasticity measurement can be measured as follows, for example.
First, an adhesive was applied onto an arbitrary non-adhesive base material such as fluororesin, heated at 110 ° C. for 300 seconds to dry (completely volatilize the organic solvent), and aged at 80 ° C. for 3 days (aged at 80 ° C. for 3 days). After the cross-linking is completed), the base material is peeled off to form an adhesive layer having a thickness of 0.3 mm (corresponding to a single layer of the first adhesive layer 12). The storage elastic modulus can be measured by measuring the formed adhesive layer with a known dynamic viscoelasticity measuring device. As the dynamic viscoelasticity measuring device, a dynamic viscoelasticity measuring device “RSA-3” (trade name) manufactured by TA Instrument can be used. The vibration frequency when measuring the storage elastic modulus is, for example, 1 Hz.

The thickness of the first adhesive layer 12 can be, for example, 0.1 to 50 μm, preferably 0.5 to 10 μm, and more preferably 0.7 to 5 μm. By setting the thickness within this range, the first base material layer 11 and the metal foil 14 provided with the first corrosion prevention layer 13 can be adhered with a high adhesive force, and delamination can be prevented. ..

<First corrosion prevention layer 13>
In this embodiment, the first corrosion prevention layer 13 is a layer for preventing corrosion of the metal foil 14 due to rust or the like.
The first corrosion prevention layer 13 preferably contains a metal halide compound, and the surface of the metal foil 14 may be directly plated with a metal halide compound as described later. By providing such a first corrosion prevention layer 13, it is possible to satisfactorily impart a rust prevention effect to the metal foil.
Further, the first corrosion prevention layer 13 preferably further contains a water-soluble resin and a chelating agent or a crosslinkable compound in addition to the metal halide compound. Therefore, the first corrosion prevention layer 13 preferably contains a metal halide compound, a water-soluble resin, and a chelating agent or a crosslinkable compound; the first corrosion prevention layer 13 is water-soluble with the halogen compound. It is preferably formed by applying an aqueous solution containing the resin and a chelating agent or a crosslinkable compound on the lower layer, and then drying and curing the mixture. Hereinafter, the material forming the first corrosion prevention layer 13 may be referred to as a “corrosion prevention treatment agent”.

(Metal halide compound)
The metal halide compound has an action of improving chemical resistance such as electrolytic solution resistance. That is, the surface of the metal foil 14 can be passivated and the corrosion resistance to the electrolytic solution can be improved. When the first corrosion prevention layer 13 contains a water-soluble resin described later, the metal halide also has an action of cross-linking the water-soluble resin.
The metal halide compound is preferably water-soluble in view of its miscibility with a water-soluble resin described later and the case where it is dispersed and applied to a water-soluble medium.
Examples of the metal halide compound include chromium halide, iron halide, zirconium halide, titanium halide, hafnium halide, hydrohydrogenate titanium halide, and salts thereof. Examples of the halogen atom include chlorine, bromine and fluorine, and chlorine or fluorine is preferable. Further, fluorine is particularly preferable. Since the metal halide compound contains fluorine, it becomes possible to generate hydrofluoric acid (HF) from the corrosion prevention treatment agent depending on the conditions.
Further, the metal halide compound may have an atom other than a halogen atom or a metal.
Among them, as the metal halide compound, chlorides or fluorides of iron, chromium, manganese or zirconium are preferable.

(Water-soluble resin)
As the water-soluble resin, it is preferable to use at least one selected from the group consisting of polyvinyl alcohol resins or derivatives thereof and polyvinyl ether resins.

The polyvinyl alcohol resin or a derivative thereof is preferably a polyvinyl alcohol resin or a modified polyvinyl alcohol resin.
The polyvinyl alcohol resin can be produced, for example, by saponifying a polymer of a vinyl ester-based monomer or a copolymer thereof.
Examples of the polymer of the vinyl ester-based monomer or its copolymer include a homopolymer of a fatty acid vinyl ester such as vinyl formate, vinyl acetate and vinyl butyrate, and a homopolymer of a vinyl ester-based monomer such as an aromatic vinyl ester such as vinyl benzoate. Examples thereof include a copolymer and a copolymer of another monomer copolymerizable therewith.
Other copolymerizable monomers include, for example, 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 acetoacetic acid ester. Examples thereof 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.
These monomers can be polymerized by a conventional method.

Examples of the modified polyvinyl alcohol resin include alkyl ether-modified polyvinyl alcohol resin, carbonyl-modified polyvinyl alcohol resin, acetoacetyl-modified polyvinyl alcohol resin, acetoamide-modified polyvinyl alcohol resin, acrylic nitrile-modified polyvinyl alcohol resin, carboxyl-modified polyvinyl alcohol resin, and silicone-modified polyvinyl alcohol. Examples thereof include resins and ethylene-modified polyvinyl alcohol resins.
Among these, acid-modified polyvinyl alcohol resins such as carboxyl-modified polyvinyl alcohol resin and acetoacetyl-modified polyvinyl alcohol resin are preferable.

The degree of saponification of the polyvinyl alcohol resin or the modified polyvinyl alcohol resin is preferably 90 mol% or more, more preferably 90 to 99.9 mol%, still more preferably 95 to 99 mol%.
The (modified) polyvinyl alcohol resin is saponified by having both a hydrophobic group derived from the side chain of the polynyl ester (for example, an acetyl group in the case of vinyl acetate) and a hydrophilic hydroxyl group obtained by saponification. It can react better with the surface of the metal foil as compared with a resin having a degree of 100 mol%, that is, a resin having only a hydrophilic hydroxyl group.

Commercially available products of polyvinyl alcohol resin or its derivatives include, for example, J-Poval DF-20 and AP-17 (both trade names) manufactured by Japan Vam & Poval Co., Ltd., and Nippon Carbide Industries (Nippon Carbide Industries). Examples include the Crosmer H series (trade name) manufactured by Co., Ltd. As the polyvinyl alcohol resin or a derivative thereof, one kind or a mixture of two or more kinds may be used.

Examples of the polyvinyl ether-based resin 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, and 2-hydroxy. Examples thereof 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-based monomer include those similar to the other monomers copolymerizable with the vinyl ester-based monomer described above.
In particular, polyvinyl ether-based resins containing an aliphatic vinyl ether having a hydroxyl group as a monomer, such as 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxypropyl vinyl ether, and monovinyl ethers of various glycols and polyhydric alcohols, are water-soluble. And can be crosslinked with a hydroxyl group, so that it can be suitably used in the present invention.
Since the vinyl ether monomer can be used in the resin production (polymerization) step, these polyvinyl ether-based resins undergo a saponification treatment unlike the polyvinyl alcohol-based resins produced via the vinyl ester-based polymer. It can be manufactured without any. Further, a copolymer containing a vinyl ester-based monomer and a vinyl ether-based monomer, or a vinyl alcohol-vinyl ether copolymer obtained by saponifying the copolymer can also be used. A mixture of a polyvinyl alcohol-based resin other than the polyvinyl ether-based resin and a polyvinyl ether-based resin can also be used.

As the water-soluble resin, only one of the polyvinyl alcohol resin or a derivative thereof and the polyvinyl ether-based resin may be used, or both may be used in combination.

(Chelating agent)
A chelating agent is a material that can coordinate-bond to a metal ion to form a metal ion complex.
The chelating agent binds a metal compound derived from a metal halide compound (chromium oxide or the like) and the water-soluble resin to increase the compressive strength of the first corrosion prevention layer 13, so that the first corrosion prevention layer 13 has a chelating agent. Even when the thickness exceeds, for example, 0.2 μm and is 1.0 μm or less, the first corrosion prevention layer 13 does not become brittle and crack or peel off. Therefore, the adhesive strength and adhesiveness between the metal foil 14 and the first adhesive layer 12 and the adhesive strength and adhesiveness between the metal foil 14 and the layer on the upper layer side thereof can be enhanced.
In addition, the chelating agent has an action of making the water-soluble resin water-resistant by chemically reacting with the water-soluble resin or the metal halide.

As the chelating agent, for example, an aminocarboxylic acid-based chelating agent, a phosphonic acid-based chelating agent, an oxycarboxylic acid-based chelating agent, and a (poly) phosphoric acid-based chelating agent can be used.

Examples of the aminocarboxylic acid-based chelating agent include nitrilotriacetic acid (NTA), hydroxyethyliminodiacetic acid (HIDA), ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminetetraacetic acid (DTPA), and the like. Triethylenediaminetetraacetic acid (TTHA), transcyclohexanediaminetetraacetic acid (CyDTA), 1,2-propanediaminetetraacetic acid (1,2-PDTA), 1,3-propanediaminetetraacetic acid (1,3-PDTA), 1,4-Butandiaminetetraacetic acid (1,4-BDTA), 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA-OH), glycol etherdiaminetetraacetic acid (GEDTA), ethylenediaminetetrathohydroxyphenylacetic acid (EDHPA) ), SS-Ethylenediaminediaminediamine disuccinic acid (SS-EDDS), ethylenediaminediaminediamine disuccinic acid (EDDS), β-alanine diacetic acid (ADA), methylglycine diacetic acid (MGDA), L-aspartic acid-N, N-diacetate (ASDA), L-glutamic acid-N, N-diacetic acid (GLDA), N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid (HBEDDA) can be mentioned.

The phosphonic acid-based chelating agent is not particularly limited as long as it is a compound having a −P (= O) (OH) ₂ structure derived from phosphonic acid (HP (= O) (OH) _{2), and is, for example, N.} , N, N-trimethylenphosphonic acid (NTMP), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid (EDTMP), diethylenetriaminepenta Methylenephosphonic acid (DTPMP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), nitrilotris (methylenephosphonic acid) (NTMP), and the like.

Examples of the oxycarboxylic acid-based chelating agent include glycolic acid, citric acid, malic acid, gluconic acid, and glucoheptonic acid.

Examples of the (poly) phosphoric acid-based chelating agent include phosphoric acid, metaphosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid, and salts thereof.

Commercially available chelating agents include, for example, aminocarboxylic acid-based chelating agents such as Kirest PD-4H (PDTA); Kirest PH-540 (EDTMP), Kirest PH-210 (HEDP), Kirest PH-320. (NTMP), phosphonic acid-based chelating agents such as Kirest PH-430 (PBTC) (all of which are chelating agents manufactured by Kirest Co., Ltd., and the notation is a trade name) can be mentioned.

Among them, as the chelating agent, a phosphoric acid-based chelating agent (phosphoric acid compound) such as a phosphonic acid-based chelating agent and a (poly) phosphoric acid-based chelating agent is preferable, and a phosphonic acid-based chelating agent is more preferable.

(Crosslinkable compound)
The crosslinkable compound refers to a compound that can react with the water-soluble resin to form a crosslinked structure. By using such a crosslinkable compound, the above-mentioned water-soluble resin and the crosslinkable compound form a dense crosslinked structure in the first corrosion prevention layer 13, and the passivation and corrosion resistance of the surface of the metal foil 14 are formed. Can be further improved.
The crosslinkable compound is not particularly limited as long as it can react with a hydrophilic group (for example, a carboxy group, a carboxylic acid group, etc.) in the water-soluble resin to form a crosslinked structure. Examples thereof include a compound having an epoxy group and a compound having an oxazoline group.

As the compound having an epoxy group, the same compound as the “compound (B) containing a plurality of epoxy groups” described in the description of the adhesive of the first adhesive layer 12 can be used.

The compound having an oxazoline group is a compound having the (monovalent group having a bond at the 2-position of the oxazoline ring (C 3 _{H 5 NO))} the structure oxazoline group.
Specific examples of the compound having an oxazoline group include an oxazoline group-containing styrene resin. For example, when the water-soluble resin has a carboxy group, the following cross-linking reaction occurs and an amide ester bond is formed. Will be done. As a result, the strength of the water-soluble resin and the first corrosion prevention layer 13 is reinforced by this crosslinked structure, and good corrosion prevention ability can be obtained.

Among them, as the compound having an oxazoline group, a resin obtained by copolymerizing a styrene-based monomer and an oxazoline group-containing monomer is preferable.
As the styrene-based monomer, styrene and its derivatives can be used. Specifically, alkyl styrenes such as styrene, α-methyl styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, and octyl styrene; chloro. Examples thereof include halogenated styrene such as styrene, fluorostyrene, bromostyrene, dibromostyrene and iodostyrene. Of these, styrene is preferable.

The skeleton of the oxazoline group-containing monomer is not particularly limited as long as it is a monomer containing an oxazoline group and capable of copolymerizing with a styrene-based monomer, but a monomer having an oxazoline group and a vinyl group is preferable. Can be used.
Examples of the oxazoline group-containing vinyl monomer include 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 4,4-Dimethyl-2-isopropenyl-2-oxazoline, 4-acryloyl-oxymethyl-2,4-dimethyl-2-oxazoline, 4-methacryloyloxymethyl-2,4-dimethyl-2-oxazoline, 4 − Methacryloyloxymethyl-2-phenyl-4-methyl-2-oxazoline, 2- (4-vinylphenyl) -4,4-dimethyl-2-oxazoline, 4-ethyl-4-hydroxymethyl-2-isopropenyl- Examples thereof include 2-oxazoline and 4-ethyl-4-carboethoxymethyl-2-isopropenyl-2-oxazoline. Of these, 2-isopropenyl-2-oxazoline is preferable.

As the styrene-based monomer and the oxazoline group-containing monomer, one type may be used alone, or two or more types may be used in combination.
Further, the compound having an oxazoline group may contain one or more of other monomers in addition to the styrene-based monomer and the oxazoline group-containing monomer. The other monomers are not particularly limited as long as they can be copolymerized with these monomers, and examples thereof include (meth) acrylate monomers, (meth) acrylic ester monomers, and (meth) acrylamide monomers.
In the compound having an oxazoline group, the composition ratio of each monomer is not particularly limited, but 5 to 50% by mass, more preferably 10 to 30% by mass, based on all the monomers constituting the compound having an oxazoline group. A resin obtained by copolymerizing the oxazoline group-containing monomer of the above is preferable. By using the oxazoline group-containing monomer within the above range, the water-soluble resin and the compound having an oxazoline group can be sufficiently crosslinked to obtain good corrosion resistance.

The number average molecular weight of the compound having an oxazoline group is preferably 30,000 to 250,000, more preferably 50,000 to 200,000, further preferably 60,000 to 100,000, and most preferably 60,000 to 80,000. By using a compound having an oxazoline group having a number average molecular weight within the above range, the compatibility between the acid-modified polyolefin resin and the compound having an oxazoline group is improved, and the water-soluble resin and the compound having an oxazoline group are sufficiently crosslinked. It becomes possible to make it.

As such a compound having an oxazoline group, a commercially available product such as Epocross RPS-1005 (trade name) manufactured by Nippon Shokubai Co., Ltd. can be used.

In the corrosion prevention treatment agent, only one of the chelating agent and the crosslinkable compound may be used, or both may be used in combination. Among them, it is preferable to use either a chelating agent or a crosslinkable compound in combination with the above-mentioned metal halide compound and water-soluble resin.
The water-soluble resin is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, still more preferably 10 to 15% by mass, based on the total solid content of the corrosion prevention treatment agent. Further, the metal halide compound is preferably 20 to 60% by mass, more preferably 30 to 55% by mass, and further preferably 40 to 50% by mass in the total solid content of the corrosion prevention treatment agent. The chelating agent and / or the crosslinkable compound is preferably 20 to 60% by mass, more preferably 30 to 50% by mass, still more preferably 35 to 45% by mass, based on the total solid content of the corrosion prevention treatment agent.

The corrosion prevention treatment agent can be produced by dissolving a water-soluble resin, a metal halide compound, a chelating agent and / or a crosslinkable compound in a solvent containing water. Water is preferable as the solvent.
The solid content concentration in the corrosion prevention treatment agent can be appropriately determined in consideration of the coatability of the first corrosion prevention layer 13 and the like, but is generally 0.1 to 10% by mass.

The thickness of the first corrosion prevention layer 13 is preferably 0.05 μm or more, more preferably more than 0.1 μm. By setting the thickness of the first corrosion prevention layer 13 to 0.05 μm or more, sufficient corrosion resistance is given to the battery exterior laminate 10, and the adhesive strength between the metal foil 14 and the first adhesive layer 12 is increased. Further, the adhesive strength between the metal foil 14 and the first base material layer 11 can be increased.
The thickness of the first corrosion prevention layer 13 is preferably 1.0 μm or less, more preferably 0.5 μm or less. By setting the thickness of the first corrosion prevention layer 13 to 1.0 μm or less, the adhesive strength between the metal foil 14 and the first adhesive layer 12 can be increased, and the material cost can be suppressed.

<Metal leaf 14>
The metal leaf 14 plays an important role in the battery exterior laminate 10 in order to reduce leakage of the contents sealed by the laminate (for example, battery liquid leakage). Further, by using a metal having high mechanical strength, it is possible to reduce the occurrence of pinholes when the battery exterior laminate 10 is used and the recess for storing the battery is formed by drawing molding, and as a result, the laminate is formed. It is possible to reduce the leakage of the contents sealed by the body (for example, the leakage of the battery).
The metal foil 14 is not particularly limited as long as it is a thinly spread metal or alloy, and is a metal foil such as aluminum, copper, lead, zinc, iron, nickel, titanium, chromium; stainless steel or the like. Alloy foil can be mentioned. The stainless steel foil is not particularly limited as long as it is made of stainless steel such as austenitic stainless steel, ferritic stainless steel, and martensitic stainless steel. Examples of the austenitic system include SUS304, 316, 301 and the like, examples of the ferrite system include SUS430 and the like, and examples of the martensitic system include SUS410 and the like.
Among them, aluminum foil or stainless steel foil is preferable from the viewpoint of workability, availability, price, strength (piercing strength, tensile strength, etc.), corrosion resistance, etc., and stainless steel is particularly preferable from the viewpoint of piercing strength. Foil is preferred.

The thickness of the metal foil 14 is preferably 100 μm or less, preferably 5 to 40 μm, more preferably 10 to 30 μm, and particularly preferably 10 to 20 μm. By setting it to the above lower limit value or more, sufficient mechanical strength can be given to the battery exterior laminate 10 and the durability of the battery can be enhanced when it is used for a battery such as a secondary battery. Further, by setting the thickness of the metal foil 14 to the above upper limit value or less, the battery exterior laminate 10 can be made sufficiently thin, and sufficient drawing workability can be provided.

<Second corrosion prevention layer 15>
The second corrosion prevention layer 15 has the same structure as the first corrosion prevention layer 13. Although the second corrosion prevention layer 15 is provided in this embodiment, the second corrosion prevention layer 15 has an arbitrary configuration in the present invention.

<Second adhesive layer 16>
The second adhesive layer 16 may have the same structure as the first adhesive layer 12, or may be a layer made of an adhesive such as a general urethane-based adhesive or an epoxy-based adhesive. The thickness of the second adhesive layer 16 can be, for example, 0.5 to 10 μm. By setting the thickness within this range, the second base material layer 17 and the metal foil 14 can be adhered with a high adhesive force, and delamination can be prevented. Although the second adhesive layer 16 is provided in this embodiment, the second adhesive layer 16 has an arbitrary configuration in the present invention.

<Second base material layer 17>
The second base material layer 17 is not particularly limited as long as it has sufficient mechanical strength, and is, for example, a polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); A polyamide resin such as nylon (Ny); a polyolefin resin such as stretched polypropylene (OPP); a synthetic resin film made of polyetheretherketone (PEEK), polyphenylene sulfide (PPS), or the like can be used. Of these, PET film is preferable.
The thickness of the second base material layer 17 can be, for example, 1 to 50 μm, preferably 1 to 30 μm, and even more preferably 3 to 11 μm.

The second base material layer 17 may have a single-layer structure or a multi-layer structure. As an example of the second base material layer 17 having a multilayer structure, a bilayer film in which a polyethylene terephthalate (PET) resin film is laminated on a biaxially stretched polyamide resin film (ONy) can be mentioned. The second base material layer 17 may have a multilayer structure in which three or more films are laminated.
Further, in the embodiment shown in FIG. 1, the second base material layer 17 is the outermost layer. Therefore, the second base material layer may have a desired color and design by containing a colorant such as a pigment in addition to the resin.

The second base material layer 17 is preferably made of a single-layer or multi-layer 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 PET film, PEN film, PBT film, nylon film, PEEK film, PPS film and the like, and PET film which 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 enhanced, and the durability of the battery in which the battery exterior laminate 10 is used can be improved. Although the second base material layer 17 is provided in this embodiment, the second base material layer 17 has an arbitrary configuration in the present invention.

In the battery exterior laminate 10 shown in FIG. 1, the first corrosion prevention layer 13 and the second corrosion prevention layer 15 are formed on both sides of the metal foil 14, but the battery exterior using the battery exterior laminate 10 is used. It is the first base material layer 11 side that is on the inner surface side of the body and can come into contact with the electrolytic solution or the like. Therefore, the corrosion prevention layer may be formed at least on the side of the first base material layer 11 of the metal foil 14. That is, from the battery exterior laminate 10 of FIG. 1, the second corrosion prevention layer 15, the second adhesive layer 16 and the second base material layer 17 (particularly the second corrosion prevention layer 15, the second adhesive layer 16) are formed. It is also possible to omit the configuration.

In the battery exterior laminate 10 shown in FIG. 1, the second base material layer 17 is the outermost layer, but the second base material layer 17 is further on the outer surface side, or the second corrosion prevention layer 15 to the second base layer. It is also possible to form the coating layer on the outermost layer without providing the material layer 17.
The coating layer (first coating layer) is 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, fluororesin. , Cellulosic ester resin, cellulose ether resin, polyamide resin, polyvinylidene ether resin (PPE), polyvinylidene sulfide resin (PPS), polyarylether resin (PAE), polyetheretherketone resin (PEEK). It is made of at least one type of resin. The coating layer is preferably made of a material having excellent heat resistance. These resins may be used alone or in combination of two or more.
The coating layer is preferably a thin film cured layer formed by applying and drying a solvent-based paint prepared by dissolving the resin in a general organic solvent.
By forming the coating layer, the insulating property of the battery exterior laminate 10 can be enhanced, and the surface of the battery exterior laminate 10 can be prevented from being scratched. Further, even when the battery exterior laminate 10 comes into contact with the electrolytic solution, it is possible to prevent a change in appearance (discoloration, etc.).
Further, the coating layer can be colored by adding a colorant or a pigment to the solvent-based paint that forms the coating layer. In addition, the coating layer can be colored or printed so as to display characters, figures, images, patterns, etc. to enhance the design.
The thickness of the coating layer can be, for example, 0.1 to 20 μm, preferably 2 to 10 μm.

In the battery exterior laminate 10 shown in FIG. 1, the second base material layer 17 and the second adhesive layer 16 are in direct contact with each other, but in order to enhance the design on the inner surface side of the second base material layer 17. It is also possible to provide a printing layer of.
The print layer can have the same structure as the coating layer described above.

The thickness of the battery exterior laminate 10 is preferably 10 to 200 μm, more preferably 20 to 100 μm, and even more preferably 30 to 80 μm.

Examples of the battery in which the battery exterior laminate 10 is used include those using an organic electrolyte as an electrolytic solution, such as a secondary battery such as a lithium ion battery which is a secondary battery, and a capacitor such as an electric double layer capacitor. .. The organic electrolyte is generally one in which carbonic acid esters such as propylene carbonate (PC), diethyl carbonate (DEC), and ethylene carbonate are used as a medium, but the organic electrolyte is not particularly limited thereto.

In the battery exterior laminate of the present invention, for example, a step of forming a first corrosion prevention layer 13 on one side of a metal foil 14, and forming a first adhesive layer 12 on the formed first corrosion prevention layer 13. It can be produced by a method having a step and a step of arranging the first base material layer 11 and the formed first adhesive layer 12 so as to be in contact with each other and laminating the laminate.
Hereinafter, a detailed description will be given.

First, the first corrosion prevention layer 13 is formed on one side of the metal foil 14.
Specifically, the anticorrosion treatment agent as described above is applied to the surface of the metal foil 14, and then heat-dried. At this time, only the first corrosion prevention layer 13 may be formed by applying the corrosion prevention treatment agent to only one side of the metal foil 14, or by applying the corrosion prevention treatment agent to both sides of the metal foil 14. The second corrosion prevention layer 15 may be formed at the same time. When the second corrosion prevention layer 15 is provided, the second corrosion prevention layer 15 is preferably formed at a stage before the formation of the first adhesive layer 12 and the like, and at the same time as the first corrosion prevention layer 13. It is more preferably formed.
Further, when the first corrosion prevention layer 13 and the second corrosion prevention layer 15 are formed at the same time, the metal foil 14 is immersed in the corrosion prevention treatment agent to adhere the corrosion prevention treatment agent to both sides of the metal foil 14, and then the metal foil 14 is adhered. It is also preferable to heat-dry.

Next, the first adhesive layer 12 is formed on the first corrosion prevention layer 13.
Specifically, a layer made of the adhesive as described above is formed on the surface of the metal foil 14 provided with the first corrosion prevention layer 13, and if necessary, it is heated and dried.

When the adhesive is a thermal laminating adhesive that does not contain an organic solvent, the components (A) and (B) are melt-kneaded to react both components, and then applied onto the first corrosion prevention layer 13. The first adhesive layer 12 is formed by drying.
For melt-kneading, known devices such as a uniaxial extruder, a multi-screw extruder, a Banbury mixer, a plast mill, and a heating roll kneader can be used. In order to suppress the decomposition of epoxy groups during melt-kneading, volatile components that can react with epoxy groups such as moisture should be removed to the outside of the device in advance, and if volatile components are generated during the reaction, degassing. It is desirable to discharge it to the outside of the device at any time. When the acid-modified polyolefin resin has an acid anhydride group as an acid functional group, it is preferable because the reactivity with the epoxy group is high and the reaction can be carried out under more mild conditions. The heating temperature at the time of melt-kneading is preferably selected from the range of 240 to 300 ° C. in that both components are sufficiently melted and do not thermally decompose. The kneading temperature can be measured by a method such as bringing a thermocouple into contact with the adhesive in a molten state immediately after being extruded from the melt-kneading apparatus.

When the adhesive is a dry laminating adhesive containing an organic solvent, the component (A) and the component (B) are dissolved in the organic solvent, and then this solution is applied onto the first corrosion prevention layer 13. The first adhesive layer 12 is formed by drying. Further, the formation of the first adhesive layer 12 may be performed as a series of steps using a known dry laminator or the like together with the laminating step with the first base material layer 11 described later.

After that, the first base material layer 11 and the formed first adhesive layer 12 are arranged so as to be in contact with each other, and the laminated body is laminated. The laminate may be a dry laminate or a thermal laminate, but a dry laminate at 70 to 150 ° C. is preferable. The pressure during dry lamination is preferably 0.1 to 0.5 MPa.
Specifically, a film constituting the first base material layer 11 is prepared in advance, the film is arranged on the first adhesive layer, and then laminating is performed. The temperature of the laminate is not particularly limited as long as it is a temperature at which the first base material layer 11, the first corrosion prevention layer 13 and the metal foil 14 are satisfactorily adhered to each other via the first adhesive layer. It can be determined in consideration of the material and melting point of the adhesive constituting the first adhesive layer 12. In the case of dry laminating, the temperature is generally 70 to 150 ° C, preferably 80 to 120 ° C.

Since the battery exterior laminate of this embodiment has a structure in which the first base material layer 11, the first corrosion prevention layer 13, and the metal foil 14 are bonded via the first adhesive layer 12, the above-mentioned is described at the time of bonding. It is also possible to adopt such a dry laminate. By adopting dry laminating as needed, it is possible to significantly reduce the temperature at the time of laminating.
Generally, when high heat is applied to a metal foil having low thermal conductivity and difficult to expand, distortion (curl) is likely to occur in the width direction of the metal foil. When heat laminating is performed using such a metal foil, heat is not sufficiently propagated in the plane, and there are some parts that are not in contact with the thermocompression bonding rollers in the width direction, or they are not in contact with the rolls. The strain itself may cause creases or wrinkles during thermocompression bonding. Further, when the metal foil is heated to a high temperature at which distortion does not occur, the production efficiency may decrease due to a decrease in processing speed or an increase in the required amount of heat. In addition, by lowering the temperature at the time of laminating, it is possible to prevent whitening due to heat of the first base material layer 11, prevent deterioration of the first base material layer 11, and select the first base material layer 11. It becomes possible to widen the width.
When the dry laminate is used in the production of the battery exterior laminate of this embodiment, it is possible to suppress the occurrence of breakage, wrinkles, whitening of the resin, etc., and to produce a suitable battery exterior laminate with high production efficiency. it can.

The step of forming the first adhesive layer 12 and the step of arranging the first base material layer 11 and performing (dry) laminating are performed by using a (dry) laminating apparatus known as a series of steps. May be good.

The method for forming the second corrosion prevention layer 15, the second adhesive layer 16, and the second base material layer 17 is not particularly limited, but for example, the second adhesive layer 16 is placed on the second base material layer 17 in advance. Is formed into a laminated body composed of two layers. Then, the two-layer laminate and the laminate having the first base material layer 11, the first adhesive layer 12, the first corrosion prevention layer 13, the metal foil 14, and the second corrosion prevention layer 15 are secondly bonded to each other. By dry laminating the agent layer 16 and the second corrosion prevention layer 15 so as to be in contact with each other, the battery exterior laminate 10 composed of seven layers can be manufactured.

Although one embodiment of the present invention has been described above based on the battery exterior laminate 10 shown in FIG. 1, the technical scope of the present invention is not limited to the above-described embodiment and deviates from the gist of the present invention. It is possible to make various changes to the extent that it does not.
For example, the second corrosion prevention layer 15 may not be provided and may have a six-layer structure. Further, the second corrosion prevention layer 15, the second adhesive layer 16 and the second base material layer 17 may not be provided, and a four-layer structure may be formed, and the first corrosion prevention layer 13, the second corrosion prevention layer 15, and the second adhesion may be formed. The agent layer 16 and the second base material layer 17 may not be provided, and a three-layer structure may be formed.
Further, another layer is provided on the side of the first base material layer 11 that does not come into contact with the first adhesive layer 12 or the side of the second base material layer 17 that does not come into contact with the second adhesive layer 16, and the seven layers or It may be composed of eight or more layers.

[Battery exterior]
The battery exterior body of the second aspect of the present invention is a battery exterior body including the battery exterior laminate of the first aspect, has an internal space for accommodating the battery, and is the first of the battery exterior laminates. The battery exterior is such that the side of the base material layer is the side of the internal space. Specifically, it is obtained by molding the battery exterior laminate of the first aspect into a desired shape so that the first base material layer faces the internal space, and sealing the ends as necessary. It is a thing.
The shape, size, etc. of the battery exterior are not particularly limited, and can be appropriately determined according to the type of battery used.
The battery exterior may be composed of one member, or may be formed by combining two or more members (for example, a container body and a lid) as described later with reference to FIG. Good.

[battery]
The battery of the third aspect of the present invention includes the battery exterior of the second aspect.
Examples of the battery include a secondary battery such as a lithium ion battery, which is a secondary battery, and a capacitor such as an electric double layer capacitor, which uses an organic electrolyte as an electrolytic solution. Since the battery exterior laminate of the present invention has high electrolytic solution resistance, it is possible to obtain a battery that can operate suitably even when an electrolytic solution containing _{LiPF 6 or the like is used.}
As an example, a perspective view of the secondary battery 40 is shown in FIG. The secondary battery 40 is a battery outer container 20 containing a lithium ion battery 27.
In the battery exterior container 20, the container body 30 made of the battery exterior laminate 10 of the first aspect of the present invention and the lid portion 33 made of the battery exterior laminate 10 are overlapped, and the peripheral edge portion 29 is heat-sealed. It is formed by. Reference numeral 28 is an electrode lead connected to the positive electrode and the negative electrode of the lithium ion battery 27.

The battery shown in FIG. 2 can be manufactured as follows.
First, as shown in FIG. 3A, the battery exterior laminate 10 is molded by drawing or the like so as to form a tray having recesses 31 to obtain a container body 30. The depth of the recess 31 can be, for example, 2 mm or more.
A lithium ion battery (lithium ion battery 27 in FIG. 2) is housed in the recess 31 of the container body 30.
Next, as shown in FIG. 3B, the lid 33 made of the battery exterior laminate 10 is placed on the container body 30, and the flange 32 of the container body 30 and the peripheral edge 34 of the lid 33 are heat-sealed. By doing so, the secondary battery 40 shown in FIG. 2 can be obtained. That is, in the battery shown in FIG. 3, the upper surface of the container body 30 is covered with the lid portion 33, so that the recess 31 and the lid portion 33 form an internal space for accommodating the battery.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these examples.

[Examples 1 to 15, Comparative Examples 1 to 5]
<Examples 1 to 15, Comparative Examples 1 to 5>
First, the metal leaf shown in Table 1 was prepared. ^{The anticorrosion treatment agent (coating amount 12 g / m 2} ) shown in Table 1 is applied to both sides of the metal foil, dried by heating in an oven at 200 ° C., and the first corrosion preventive layer having a thickness of 0.2 μm and the first. 2 Corrosion prevention layers were formed on both sides.

Then, the first adhesive was applied onto the formed first corrosion prevention layer to form a first adhesive layer having a thickness of 3 μm. The first adhesive is prepared by mixing a solution in which the component (A) shown in Table 1 is dissolved in toluene as an organic solvent and a solution in which the component (B) shown in Table 1 is dissolved in methyl ethyl ketone as an organic solvent. I got it. The mass part of each component in Table 1 is the final blending amount after mixing. In addition, the amount of solvent in the solution of the adhesive was adjusted so that the final solid content was 9% by mass. The final mixing ratio (mass ratio) of methyl ethyl ketone and toluene was 1: 1.

The first adhesive layer in the laminate containing the metal foil and the first base material layer made of a polypropylene resin (block PP) film having a thickness of 20 μm were laminated by dry lamination at 100 ° C.

Further, a second adhesive layer (thickness 3 μm) made of a urethane adhesive was formed by coating on a second base material layer made of a stretched polyethylene terephthalate (PET) resin film having a thickness of 6 μm and having a black color.
The second adhesive layer and the second corrosion prevention layer in the above-mentioned laminate were opposed to each other and laminated by dry lamination at 80 ° C. to obtain a battery exterior laminate.

<Comparative example 4>
A battery exterior laminate was obtained in the same manner as in Example 1 above, except that the component (B) in the first adhesive was not used. The adhesive of Comparative Example 4 was obtained by mixing a toluene solution in which the component (A) was dissolved and a methyl ethyl ketone in which the component (B) was not dissolved.

In Table 1, each abbreviation has the following meaning. The value in [] is the blending amount (part by mass).
(A) -1: Maleic anhydride-modified polypropylene (melting point 85 ° C)
(A) -2: Maleic anhydride-modified 1-butene-propylene copolymer (melting point 80 ° C.)
(B) -1: "jER154" (trade name; manufactured by Mitsubishi Chemical Corporation; phenol novolac type epoxy resin; viscosity = 80; epoxy equivalent = 180)
(B) -2: Component having 50/50 (mass ratio) of "jER154" and "D-17" (trade name; manufactured by Mitsui Chemicals, Inc .; isocyanate compound) (B) -3: "jER157S70" ( Product name; manufactured by Mitsubishi Chemical Co., Ltd .; phenol novolac type epoxy resin having a bisphenol A structure; viscosity = 80; epoxy equivalent = 210)
(B) -4: Phenoxy resin having no epoxy group and having the terminal epoxy group ring-opened (B) -5: "D-17"
(C) -1: Mixed solvent of toluene / methyl ethyl ketone = 80/20 (mass ratio) AL: Aluminum foil SUS: Stainless steel foil CO: Copper foil NI: Nickel foil R-1: Containing a hydroxyl group with a saponification degree of 95 mol% 0.2% by mass of polyvinyl alcohol skeleton-containing non-crystalline polymer (manufactured by Japan Vam & Poval Co., Ltd., trade name: AP-17; (PVA-1)) and 0.8% by mass of iron chloride. , Oxazoline resin (trade name: WS-500, manufactured by Japan Catalyst Co., Ltd.), aqueous solution made by dissolving 0.7% by mass in water R-2: R-1 above except that iron chloride was changed to chromium fluoride. Aqueous solution similar to R-3: An aqueous solution similar to R-1 except that iron chloride was changed to iron oxide.

(Measurement of storage elastic modulus)
The dynamic viscoelasticity of the first adhesive layer single layer was measured according to JIS K7244 "Plastic-Test method for dynamic mechanical properties".
Specifically, first, the first adhesive of each example shown above is applied onto a fluororesin substrate, heated at 110 ° C. for 300 seconds to completely volatilize the organic solvent, and then 80 ° C. for 3 days. It was aged and completely crosslinked. Then, the base material was peeled off to obtain a single-layer adhesive layer having a thickness of 0.3 mm, a width of 4 mm, and a length of 30 mm. The obtained single-layer adhesive layer was set in a dynamic viscoelasticity measuring device with a chuck distance of 20 mm, and a storage elastic modulus (E) at 150 ° C. when a frequency of 1 Hz and a strain of 0.01% were applied under atmospheric pressure. The value of') was calculated. As the dynamic viscoelasticity measuring device, the dynamic viscoelasticity measuring device "RSA-3" (trade name) manufactured by TA Instrument was used.
The results are also shown in Table 1.

(Heat resistance test)
The battery exterior laminate manufactured in each of the above examples was heat-sealed at 0.3 MPa, 190 ° C., and 3 seconds, T-shaped peeled off in an environment of 85 ° C., and the results of evaluation based on the following criteria were evaluated as " It is shown in Table 1 as "heat resistance".
⊚: 25N / 15mm or more ○: 25N / 15mm or less, 15N / 15mm or more ×: 15N / 15mm or less

(Electrolytic resistance test)
An electrolytic solution containing 1000 ppm of water at 85 ° C. (a solution of ethylene carbonate: diethyl carbonate: dimethyl carbonate = 1: 1: 1 vol% to which 1 mol / liter of _{LiPF 6 was added) was prepared and prepared for the battery exterior of each example.} The test piece of the laminate was immersed in the electrolytic solution for 3 days.
After 3 days, a 90 ° peeling test was performed. The results of evaluation based on the following criteria are shown in Table 1 as "electrolyte resistance".
A: 5N / 15mm or more B: 5N / 15mm or less, 3N / 15mm or more C: 3N / 15mm or less, 1N / 15mm or more D: 1N / 15mm or less

From the results shown in Table 1, Examples 1 to 15 using the battery exterior laminate of the present invention have excellent adhesiveness even under harsh conditions as compared with Comparative Examples 1 to 5. It could be confirmed.

[Experimental Examples 1 to 3 and Comparative Experimental Example 1]
The first adhesive of each example shown in Table 2 was obtained in the same manner as in Examples 1 to 13 and the like. Each abbreviation in Table 2 is the same as described above.
Then, in the same manner as in the storage elastic modulus measurement, the storage elastic modulus was measured while raising the temperature from 20 ° C. to 160 ° C. at a heating rate of 3 ° C./min using a dynamic viscoelasticity measuring device. The results are shown in FIG.

From the results shown in FIG. 4, the adhesive containing the component (A) and the component (B) does not decrease the storage elastic modulus (E'; unit Pa) even at a high temperature, while the adhesive does not contain the component (B). It was confirmed that the agent could not maintain its shape as a result of the storage elastic modulus significantly decreasing at high temperature.

11 1st base material layer, 12 1st adhesive layer, 13 1st corrosion prevention layer, 14 metal foil, 15 2nd corrosion prevention layer, 16 2nd adhesive layer, 17 2nd base material layer

Claims (8)

A battery exterior laminate comprising at least a first base material layer, a first adhesive layer, a first corrosion prevention layer, and a metal foil in this order.
The first base material layer is a layer made of polyolefin.
It said first adhesive layer, in the dynamic viscoelasticity measurement of the first adhesive layer alone, the value of storage modulus at 0.99 ° C. is 1.0 × 10 ⁴ or more, and 1.0 × 10 ⁷ or less Layer and
The first adhesive layer is a phenol novolac type as a compound (B) containing 80 to 99 parts by mass of an acid-modified polyolefin resin (A) and a plurality of epoxy groups out of 100 parts by mass of the solid content of the adhesive. It consists of an adhesive containing 1 to 20 parts by mass of epoxy resin.
A laminate for battery exterior, wherein the first corrosion prevention layer contains a metal halide compound. A battery exterior laminate comprising at least a first base material layer, a first adhesive layer, a first corrosion prevention layer, and a metal foil in this order.
The first base material layer is a layer made of polyolefin.
It said first adhesive layer, in the dynamic viscoelasticity measurement of the first adhesive layer alone, the value of storage modulus at 0.99 ° C. is 1.0 × 10 ⁴ or more, and 1.0 × 10 ⁷ or less Layer and
The first adhesive layer is 80 to 99 parts by mass of the acid-modified polyolefin resin (A) and 1 to 20 parts by mass of the compound (B) containing a plurality of epoxy groups, out of 100 parts by mass of the solid content of the adhesive. It is a layer composed of an adhesive containing a portion and a portion.
The compound (B) containing a plurality of epoxy groups is composed of only a phenol novolac type epoxy resin.
A laminate for battery exterior, wherein the first corrosion prevention layer contains a metal halide compound. The battery exterior laminate according to claim 1 or 2 , wherein the first corrosion prevention layer further contains a water-soluble resin and a chelating agent or a crosslinkable compound. The laminate for battery exterior according to any one of claims 1 to 3 , wherein the metal halide compound is a chloride of iron, chromium, manganese, or zirconium, or a fluoride of iron, chromium, manganese, or zirconium. body. The laminate for battery exterior according to any one of claims 1 to 4 , wherein the metal foil is aluminum, stainless steel, copper, nickel or titanium. The laminate for battery exterior according to any one of claims 1 to 5 , wherein the thickness of the metal foil is 10 to 40 μm. A battery exterior body comprising the battery exterior laminate according to any one of claims 1 to 6.
A battery exterior body having an internal space for accommodating a battery, wherein the side of the first base material layer of the battery exterior laminate is the side of the internal space. A battery comprising the battery exterior according to claim 7.

Images