CN107123755A - Battery outer packing layered product, battery external packing body and battery - Google Patents

Abstract

The present invention provide it is a kind of can be prepared with high efficiency and various excellents battery outer packing layered product.The battery outer packing that the present invention is provided is with layered product (10) by least there is the first base material layer (11), first bonding agents layer (12) and metal foil (14) to form successively, it is characterized in that, the first base material layer (11) is the layer that is made up of polyolefin, and first bonding agents layer (12) is that the value of the storage modulus in the Measurement of Dynamic Viscoelasticity of first bonding agents layer (12) individual layer, at 150 DEG C is 1.0 × 10⁴Above and for 1.0 × 10⁷Following layer；The battery external packing body that the present invention is provided has the battery outer packing layered product, it is characterised in that the battery external packing body has the inner space for storing battery, and the first base material layer side of battery outer packing layered product is the inner space side；The battery that the present invention is provided is characterised by, with the battery external packing body.

Description

Laminate for battery outer packaging, battery outer packaging, and battery

technical field

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

Background technique

As people become more aware of the environment, they are attracting attention as storage batteries for storing electrical energy, secondary batteries such as lithium-ion batteries, and capacitors such as electric double-layer capacitors, while utilizing natural energy such as sunlight and wind power.

As an exterior body used for these batteries, for the purpose of downsizing and weight reduction, a battery exterior laminate in which a metal foil and a resin layer are stacked is used. Such a laminated body for battery outer packaging is molded by drawing or the like into a disk shape having a concave portion, and is used as an outer packaging container main body. In addition, the battery outer packaging laminate was molded in the same manner as the outer packaging container main body to obtain an outer packaging lid. After storing the battery main body in the recessed portion of the outer container main body, the outer cover part is stacked so as to cover the stored battery main body, and the side edge parts of the container main body and the outer cover part are bonded, thereby obtaining a battery The main body is housed in the battery of the outer package.

For example, Patent Document 1 discloses a battery outer packaging laminate in which a substrate layer, an aluminum foil, and an innermost layer composed of a polypropylene or polyethylene layer are sequentially laminated, and the innermost layer of the aluminum foil is The face layer is laminated with a thin film coating. More specifically, in Patent Document 1, it is preferable that the film coating layer and the innermost layer composed of polypropylene or polyethylene layer are bonded via a heat-sealing agent, by lamination using an acid-modified polypropylene-based heat-sealing agent. Processing, bonding the film-coated aluminum foil to the innermost layer.

prior art literature

patent documents

Patent Document 1: JP-A-2012-33393

Contents of the invention

The technical problem to be solved in the present invention

With the expansion of the application fields of batteries such as secondary batteries, it is required to increase the output of batteries, and it is also required to improve the production efficiency of the battery outer package during preparation, such as improving the yield and shortening the time. In addition, while improving battery characteristics, such as miniaturization and increase in capacity, excellent characteristics such as heat resistance and chemical resistance (electrolytic solution resistance) are also required for battery outer packaging.

However, when using a heat-sealing agent to laminate and bond the surface-treated metal foil and the innermost resin layer as described in Patent Document 1, it is necessary to add high temperature and high pressure during lamination, and it is difficult to shorten the preparation time or reduce the production cost. Cost, therefore, limited improvement in production efficiency. In addition, by performing lamination processing at high temperature, the innermost layer (polypropylene layer, polyethylene layer, etc.) or metal foil to be bonded may wrinkle or deteriorate, which may lead to a decrease in yield or various materials. The range of choices is narrowed.

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a laminate for battery packaging that can be produced with high productivity and has excellent various properties.

Technical means to solve technical problems

In order to achieve the above object, the inventors of the present application conducted repeated studies, and as a result, found that by bonding the metal foil with any surface treatment to the base material layer (innermost layer) via an adhesive layer having a specific storage modulus, Not only can the various characteristics required for the laminated body for battery packaging be improved, but also the production efficiency can be improved as needed, such as shortening the production time, improving the yield, etc., thereby completing the present invention.

That is, the present invention employs the following configurations.

The battery outer packaging laminate according to the first aspect of the present invention comprises at least a first base material layer, a first adhesive layer, and a metal foil in this order, wherein the first base material layer is made of poly In the layer composed of olefin, the first adhesive layer has a storage modulus value of 1.0×10 ⁴ or more at 150° C. in the dynamic viscoelasticity measurement of the first adhesive layer single layer and is Layers below 1.0×10 ⁷ .

Preferably, the first adhesive layer is a layer composed of an adhesive, and the adhesive contains 100 parts by mass of an acid-modified polyolefin resin (A) and 1 to 20 parts by mass of Compound (B).

The compound (B) containing multiple epoxy groups is preferably novolac epoxy resin.

Preferably, there is a first anticorrosion layer between the first adhesive layer and the metal foil, and the first anticorrosion layer contains a metal halide compound.

The first anticorrosion layer preferably further contains a water-soluble resin, and a chelating agent or a cross-linking compound.

The metal halide compound is preferably iron, chromium, manganese, zirconium chloride, or iron, chromium, manganese, zirconium fluoride.

The metal foil is preferably aluminum, stainless steel, copper, nickel or titanium.

The thickness of the metal foil is preferably 10 to 40 μm.

A battery outer packaging body according to a second aspect of the present invention has the laminated body for battery outer packaging according to the first aspect, wherein the battery outer packaging body has an internal space for accommodating batteries, and the first layer of the laminated body for battery outer packaging is characterized in that: The base layer side is the internal space side.

A battery according to a third aspect of the present invention is characterized in that the battery has the battery exterior body of the second aspect.

Invention effect

According to the present invention, it is possible to provide a laminate for battery packaging that has excellent characteristics and can be produced with high productivity.

Description of drawings

FIG. 1 is a schematic cross-sectional view showing a first embodiment of a battery outer packaging laminate of the present invention;

Fig. 2 is a perspective view showing an example of a secondary battery manufactured using the laminate for battery outer packaging of the present invention;

3 is a perspective view showing a process of producing a secondary battery using the laminate for battery outer packaging of the present invention;

4 is a graph showing the storage modulus of a single adhesive layer in Experimental Examples 1 to 3 and Comparative Experimental Example 1. FIG.

Explanation of reference signs

11: first substrate layer; 12: first adhesive layer; 13: first anticorrosion layer; 14: metal foil; 15: second anticorrosion layer; 16: second adhesive layer; 17: second Second substrate layer

detailed description

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

[Laminates for battery packaging]

The battery outer packaging laminate (hereinafter sometimes simply referred to as "laminate") according to the first aspect of the present invention is formed by having at least a first base material layer, a first adhesive layer, and a metal foil in this order. The first base layer is a layer made of polyolefin, and the first adhesive layer has a storage modulus value of 1.0 at 150° C. in dynamic viscoelasticity measurement of a single layer of the first adhesive layer. A layer of ×10 ⁴ or more and 1.0×10 ⁷ or less.

FIG. 1 is a schematic cross-sectional view showing the structure of a laminated body 10 for battery exterior packaging in one embodiment of the present invention.

The laminated body 10 of this embodiment has a first base material layer 11, a first adhesive layer 12, a first anticorrosion layer 13, a metal foil 14, a second anticorrosion layer 15, a second adhesive layer 16, And the second substrate layer 17.

That is, the laminated body 10 of the present embodiment is composed of seven layers, and has the first anticorrosion layer 13 and the second anticorrosion layer 15 formed on both surfaces of the metal foil 14 , and the second anticorrosion layer 15 via the first adhesive layer 12 . A first substrate layer 11 laminated on an anticorrosion layer 13 , and a second substrate layer 17 laminated on a second anticorrosion layer 15 via a second adhesive layer 16 .

Each layer is described in detail below.

<First Base Material Layer 11>

The first base material layer 11 is a layer made of polyolefin. Examples of layers made of polyolefin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymers of propylene and ethylene or α-olefin, block copolymers of propylene and ethylene or α-olefin Wait.

Among them, homopolypropylene (propylene homopolymer; hereinafter sometimes referred to as "homoPP") and propylene-ethylene block copolymer (hereinafter , sometimes referred to as "block PP"), propylene-ethylene random copolymers (hereinafter, sometimes referred to as "random PP") and other polypropylene-based resins. Among them, homopolymer PP or block PP is more preferable, and block PP is particularly preferable because of its excellent mechanical strength.

The first substrate layer 11 may be 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 necessary for the battery exterior laminate 10 .

The thickness of the first base material layer 11 can be set to, for example, 1 to 200 μm, preferably 5 to 100 μm, more preferably 5 to 40 μm.

<First adhesive layer 12>

The first adhesive layer 12 is a layer provided for bonding the first base material layer 11 as a base resin layer and the metal foil 14 on which the first anticorrosion layer 13 is formed. In the dynamic viscoelasticity measurement of the single-layer adhesive layer 12 , the value of the storage modulus at 150° C. is not less than 1.0×10 ⁴ and not more than 1.0×10 ⁷ .

The material of the adhesive forming the first adhesive layer 12 is not particularly limited as long as it can adhere well to the above-mentioned layers, and as long as it is a layer that satisfies the value of the above-mentioned storage modulus, but for example, From the viewpoint of satisfying adhesiveness and storage modulus, a layer composed of an adhesive containing an acid-modified polyolefin resin (A) and a compound (B) containing a plurality of epoxy groups is preferable.

Hereinafter, the acid-modified polyolefin resin (A) may be called "(A) component", and the compound (B) containing several epoxy groups may be called "(B) component".

(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 the polyolefin-based resin has a carboxyl group or a carboxylic acid anhydride group and other acidic functional groups.

(A) The component is obtained by modification|denaturation of the polyolefin resin by unsaturated carboxylic acid or its derivative(s), copolymerization of the monomer containing an acidic functional group, and an olefin, etc. Among these, it is preferable to acid-modify polyolefin resin as (A) component.

As an acid modification method, graft modification of polyolefin resin and acidic functional group-containing monomer is melt-kneaded in the presence of a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound. sex.

Examples of the polyolefin-based resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, a copolymer of propylene and ethylene, a copolymer of propylene and an olefin-based monomer, and the like.

Examples of the olefin-based monomer used for copolymerization include 1-butene, isobutylene, and 1-hexene.

The copolymer may be a block copolymer or a random copolymer.

Among them, the polyolefin-based resin is preferably a polypropylene-based resin polymerized from propylene, such as a homopolypropylene (propylene homopolymer), a copolymer of propylene and ethylene, or a copolymer of propylene and butene, and particularly preferably Propylene-1-butene copolymer is a polyolefin resin with methyl and ethyl groups on the side chain. By containing 1-butene, the molecular movement when the resin is heated is promoted, and the chance of contact between the cross-linking points of the (A) component and the (B) component described later increases, resulting in the adhesion to the adherend be further improved.

The acidic functional group-containing monomer is a compound having an ethylenic double bond, a carboxyl group or a carboxylic acid anhydride group in the same molecule, and various unsaturated monocarboxylic acids, dicarboxylic acids, or anhydrides of dicarboxylic acids can be exemplified. .

Examples of acidic functional group-containing monomers having carboxyl groups (carboxyl group-containing monomers) include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, and citraconic acid. Acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid, endo-bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid (endic acid), etc. Saturated carboxylic acid monomer.

Examples of acidic functional group-containing monomers having carboxylic anhydride groups (carboxylic anhydride group-containing monomers) include unsaturated dicarboxylic anhydrides such as maleic anhydride, nadic anhydride, itaconic anhydride, citraconic anhydride, and Endicos anhydride. anhydride monomer.

These acidic functional group-containing monomers may be used alone or in combination of two or more in the (A) component.

Among them, the acidic functional group-containing monomer is preferably a monomer containing an acidic functional group that reacts well with the epoxy group in the (B) component described later, and is more preferably The acidic functional group-containing monomer having an acid anhydride group is more preferably a carboxylic anhydride group-containing monomer, particularly preferably maleic anhydride.

When a part of the acidic functional group-containing monomer used for acid modification is unreacted, it is preferable to remove the unreacted acidic functional group-containing monomer in advance in order to prevent the unreacted acidic functional group-containing monomer from reducing the adhesive force. The substance of was used as (A) component.

Among (A) components, it is preferable that the component originating in a polyolefin resin or an olefin is 50 mass parts or more with respect to 100 mass parts of total amounts of (A) component.

(A) The melting point of the component 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, more preferably 70 to 98°C, even more preferably It is 75～95℃.

The heat resistance of the first adhesive layer 12 can be improved by setting the melting point of the component (A) to be equal to or higher than the above lower limit, and as a result, the adhesion of the first base material layer 11 via the first adhesive layer 12 can be improved. The heat resistance and durability after the metal foil 14 with the first anti-corrosion layer 13.

On the other hand, when the melting point of (A) component is made below the said upper limit, when (A) component is dissolved in an organic solvent, when obtaining the adhesive agent for solvent-type dry lamination, (A) component becomes easy Dissolved in an organic solvent, thereby obtaining a more uniform adhesive, (A) component and (B) component can react well, and improve adhesion and durability. Moreover, by using (A) component which has a melting point below the said upper limit, the temperature at the time of performing dry lamination via the 1st adhesive layer 12, or the aging temperature after lamination can be made relatively low temperature. As a result, in the first base material layer 11 bonded with the first adhesive layer 12, it is difficult to generate wrinkles due to heat, which not only improves the yield during production, but also eases the resistance of the first base material layer 11. Therefore, the selection range of the material of the first substrate layer 11 can be broadened. In addition, lamination can be performed at a relatively low temperature. As a result, the time for lamination can be shortened, and the energy required for lamination can be reduced, thereby improving production efficiency and reducing energy consumption.

On the other hand, when the adhesive used to form the first adhesive layer 12 does not contain an organic solvent, and the adhesive is formed by melt-kneading the component (A) and the component (B) described later, (A) The melting point of the components is preferably 100°C to 180°C. The first adhesive layer 12 made of this adhesive can be suitably used as an adhesive layer for thermal lamination.

By using component (A) having a melting point in the above range, even when using a normal method and a general device, component (A) and component (B) described later can be performed at a temperature sufficiently higher than the melting point of component (A). Melt kneading. In addition, when the (A) component is reacted with the (B) component described later by melt kneading, it is preferable that the melting point of the (B) component is lower than that of the (A) component, but by using (A) having a melting point in the above range Components can increase the degree of freedom of choice of the (B) component.

In addition, as mentioned above, the melting point of component (A) is preferably higher than the melting point of component (B) described later, but the melting point of component (A) is more preferably higher than the melting point of component (B) by 10°C or more, even more preferably higher than the melting point of component (B). Above 20°C, particularly preferably above 30°C. By making the melting point of the (A) component sufficiently higher than that of the (B) component, when melt kneading is carried out, the (B) component melts first and penetrates into the (A) component in a state where the resin shape is maintained, and the (A) component and (B) The component reacts uniformly, and as a result, good durability can be obtained.

(A) The molecular weight of the component is not particularly limited, as long as it satisfies the above-mentioned desired melting point, it is not particularly limited, and usually a resin with a molecular weight of 10,000 to 800,000 is used, preferably 50,000 to 650,000, more preferably 80,000 to 550,000, and even more preferably 100000～450000.

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

(compound (B) containing a plurality of epoxy groups)

(B) A component is a compound containing several epoxy groups. (B) The component may be a low-molecular compound or a high-molecular compound. It is preferable that (B) component is a polymer compound (resin) from a viewpoint of the miscibility and compatibility with the said (A) component being favorable. On the other hand, when the adhesive is a solvent-type dry lamination adhesive, the component (B) is preferably a low-molecular-weight compound from the viewpoint of good solubility in organic solvents.

(B) The structure of the component is not particularly limited as long as it has a plurality of epoxy groups, for example, phenoxy resin synthesized from bisphenols and epichlorohydrin; novolak epoxy resin; bisphenol Type epoxy resin, etc. Among them, since the epoxy group content per molecule is high, a particularly dense cross-linked structure can be formed together with the component (A), so novolak epoxy resin is preferably used.

In the present invention, the novolak epoxy resin is a compound having a novolak resin obtained by acid-condensing phenol and formaldehyde as a basic structure, and epoxy groups are introduced into a part of the structure. The amount of epoxy groups introduced per molecule in the novolac epoxy resin is not particularly limited, but by reacting epoxy-based raw materials such as epichlorohydrin with the novolac resin, the phenol present in a large amount in the novolac resin A large number of epoxy groups are introduced into the hydroxyl group, so it is usually a multifunctional epoxy resin.

Among them, as the novolac epoxy resin, a bisphenol A novolak epoxy resin having a novolac structure as a basic skeleton and a bisphenol A structure is preferable. Moreover, the bisphenol A structure in an epoxy resin should just be a structure derivable from bisphenol A, and the hydroxyl group at both ends of bisphenol A may be substituted with groups, such as an epoxy group-containing group.

As an example of a bisphenol A novolac epoxy resin, the resin represented by following General formula (1) is mentioned.

[chemical formula 1]

[In formula (1), R ¹ to R ⁶ are each independently a hydrogen atom or a methyl group, n is an integer of 0 to 10, and R ^X is a group having an epoxy group. ]

In formula (1), R ¹ to R ⁶ are each independently a hydrogen atom or a methyl group. When n is an integer of 2 or more, each of R ³ and R ⁴ may be the same or different.

Among the resins represented by the formula (1), it is preferable that at least any one of the following (i) to (iii) is satisfied.

(i) R ¹ and R ² are both methyl; (ii) R ³ and R ⁴ are both methyl; (iii) R ⁵ and R ⁶ are both methyl.

For example, by satisfying the above (i), in formula ( ¹ ), the carbon atoms bonded to R1 and R2 and the ^two hydroxyphenyl groups bonded to the carbon atoms constitute a structure derived from bisphenol A.

In formula (1), R ^X is a group having an epoxy group. As a group which has an epoxy group, an epoxy group, the combination of an epoxy group and an alkylene group, etc. are mentioned, Among them, a glycidyl group is preferable.

The epoxy equivalent of the bisphenol A novolac epoxy resin is preferably 100-300, more preferably 200-300. Epoxy equivalent (g/eq) is the molecular weight of epoxy resin per epoxy group, the smaller the value, the more epoxy groups in the resin. By using an epoxy resin with a small epoxy equivalent, even when the amount of epoxy resin added is set to a small amount, the adhesiveness between the epoxy resin and the adherend is good, and the epoxy resin and the above-mentioned Acid-modified polyolefin resins are fully cross-linked.

As such novolac epoxy resins, jER154, jER157S70, jER-157S65 manufactured by Mitsubishi Chemical Corporation; EPICLON N-730A, EPICLON N-740, EPICLON N-770, EPICLON N-775 ( The above are all products sold in the market such as product names).

By using the above-mentioned epoxy resin, both the acidic functional group of the above-mentioned (A) component and the epoxy group of the (B) component exert an adhesive property on the adherend (especially the functional group such as the carboxyl group that the first anticorrosion layer 13 has). The function of the functional group can thereby exhibit excellent adhesion to the first base material layer 11 and the metal foil 14 having the first anticorrosion layer 13 on the surface.

In addition, a part of the acidic functional group of the (A) component reacts with a part of the epoxy group of the (B) component to form a cross-linked structure of the (A) component and (B) component in the first adhesive layer 12, As a result, the strength of the first adhesive layer 12 is enhanced by this crosslinked structure, and good durability can be obtained while obtaining excellent adhesiveness.

The first adhesive layer 12 preferably contains 1 to 20 parts by mass of component (B) relative to 100 parts by mass of component (A); more preferably contains 5 to 20 parts by mass of component (B) relative to 100 parts by mass of component (A). 10 mass parts; It is especially preferable to contain 5-7 mass parts of (B) component with respect to 100 mass parts of (A) components.

(optional ingredient)

The adhesive used in the present invention may or may not contain an organic solvent.

By containing an organic solvent and forming a liquid adhesive, it can be used as a solvent-type dry lamination adhesive. The first adhesive layer 12 can be formed by applying and drying such a liquid adhesive on a lower layer (for example, the surface of the metal foil 14 on which the first anticorrosion layer 13 is provided). By selective coating instead of extrusion molding, the adhesive layer can be formed in a thinner layer, and thinning of the adhesive layer and thinning of the entire laminate using the adhesive layer become possible.

On the other hand, when an organic solvent is not contained, an adhesive layer suitable for thermal lamination or the like can be formed by melt-kneading (A) component and (B) component, followed by extrusion molding or the like.

In the case of containing an organic solvent, as the organic solvent used, as long as the above-mentioned (A) component, (B) component and other optional components used as needed (details will be described later) can be appropriately dissolved to form a uniform The solution is not particularly limited, and any solvent can be used from solvents known as solvents for solution-type adhesives. In addition, the liquid adhesive can be used by volatilizing the organic solvent by heating or the like after being applied to an adherend (for example, the surface of the metal foil 14 on which the first anticorrosion layer 13 is provided) usually. Therefore, the organic solvent is preferably an organic solvent having a boiling point of 150° C. or lower from the viewpoint of easy volatilization.

Specific examples of organic solvents include toluene, xylene, anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, Aromatic solvents such as diethylbenzene, pentylbenzene, cumene, cymene, and mesitylene; aliphatic solvents such as n-hexane; methyl ethyl ketone, acetone, cyclohexanone, Ketone solvents such as methyl n-pentanone, methyl isopentyl ketone, and 2-heptanone; methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate , methyl methoxy propionate, ethyl ethoxy propionate and other ester solvents; methanol, ethanol, isopropanol and other alcohol solvents; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and other polyols solvent etc.

One kind of organic solvent may be used alone, or two or more kinds may be used in combination as a mixed solvent. In the case of a mixed solvent, it is preferable to use an organic solvent that dissolves (A) component well and an organic solvent that dissolves (B) component well in combination. Such a combination is preferably a combination of toluene that dissolves (A) component well and methyl ethyl ketone that dissolves (B) component well. In the case of using a mixed solvent, two or more organic solvents can be mixed in advance, and on this basis, the above-mentioned (A) component, (B) component, etc. can be dissolved; it is also possible to mix (A) component, ( After each component of the B) component is dissolved in each good solvent, a plurality of organic solvents in which each component is dissolved are mixed.

When a plurality 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 is preferably toluene:methyl ethyl ketone=60～95:5～40( mass ratio), more preferably toluene:methyl ethyl ketone=70～90:10～30 (mass ratio).

The adhesive used in the present invention may contain other components in addition to the above-mentioned (A) component, (B) component, and organic solvent. As other components, there may be mentioned additives having mixing properties or additional resins, and more specifically, catalysts, crosslinking agents, plasticizers, stabilizers, colorants, and the like may be used.

In the solid content of the adhesive used in the present invention, it is preferable to contain (A) component exceeding 50 mass parts to 99.5 mass parts or less, and contain (B) component 0.5 mass part or more to less than 50 mass parts. That is, in the solid content of an adhesive, (A) component exceeds half quantity in mass ratio, and the adhesive used for this invention contains (A) component as a main component. More preferably, the (B) component is 0.5-30 mass parts with respect to (A) component 70-99.5 mass parts, It is still more preferable that (B) component is 1-20 mass parts with respect to (A) component 80-99 mass parts , It is particularly preferable that (B) component is 2-10 mass parts with respect to (A) component 90-98 mass parts.

Moreover, when the adhesive agent used for this invention contains solid components other than (A) component and (B) component as an arbitrary component, (A) component must be a main component. Therefore, even when optional components are contained, the (A) component exceeds 50 parts by mass in the total solid content of the adhesive. For example, the adhesive which contains (A) component 70-99.5 mass parts, (B) component 0.5-29.5 mass parts, and other components 0.5-29.5 mass parts in total solid content is mentioned.

When the adhesive used in the present invention contains an organic solvent, the amount of the organic solvent used is not particularly limited as long as each component such as (A) component, (B) component, and optional component can be well dissolved, but usually the solid content The concentration is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 7 to 20% by mass.

The adhesive used in the present invention has a storage modulus value of 1.0×10 ⁴ at 150° C. in the dynamic viscoelasticity measurement of the first adhesive layer 12 formed using the adhesive. ~1.0×10 ⁷ , more preferably 5.0×10 ⁴ to 9.5×10 ⁵ , even more preferably 3.0×10 ⁵ to 8.0×10 ⁵ .

In addition, in the dynamic viscoelasticity measurement of the first adhesive layer 12 monolayer formed using this adhesive, the value of the storage elastic modulus at 60° C. is preferably 1.0×10 ⁶ or more, more preferably 1.0 ×10 ⁶ to 1.0×10 ⁸ , more preferably 5.0×10 ⁶ to 5.0×10 ⁷ .

That is, the value of the storage modulus at 150°C is preferably 1/10000 to 1/1, more preferably 1/1000 to 1/1, and even more preferably 1/500 to 1/1, particularly preferably 1/100 to 1/1.

That is, the adhesive used in the present invention preferably not only has a sufficient elastic modulus at 60°C, but also maintains an elastic modulus in an appropriate range without excessively lowering the elastic modulus even at a relatively high temperature of 150°C. The first adhesive layer 12 formed using an adhesive having such a storage elastic modulus is difficult to change in shape even at a relatively high temperature, and the shape is well maintained. Therefore, the first adhesive layer 12 has the The shape, adhesiveness, and the like of the laminated body 10 for battery outer packaging can also be maintained well at high temperatures, and the laminated body 10 for battery outer packaging having excellent high temperature resistance can be obtained.

The adhesive agent which has the said storage elastic modulus can be obtained easily by combining the said (A) component and (B) component. This is because the elastic modulus can be maintained even at relatively high temperature by crosslinking the acidic functional group of (A) component and the epoxy group of (B) component.

The value of the storage modulus in dynamic viscoelasticity measurement can be measured, for example as follows.

First, apply an adhesive on any substrate that is not bonded with fluororesin, heat at 110°C for 300 seconds, dry it (to completely volatilize the organic solvent), and perform aging treatment at 80°C for 3 days (complete After cross-linking), the substrate was peeled off to form an adhesive layer (corresponding to a single layer of the first adhesive layer 12 ) having a thickness of 0.3 mm. The storage modulus can be measured by measuring the formed adhesive layer using a known dynamic viscoelasticity measuring device. As a dynamic viscoelasticity measuring device, a dynamic viscoelasticity measuring device "RSA-3" (trade name) of TA Instrument Co., Ltd. or the like can be used. The vibration frequency when measuring the storage modulus is, for example, 1 Hz.

The thickness of the first adhesive layer 12 is, 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 anticorrosion layer 13 can be bonded with high adhesive force, and delamination can be prevented.

<First anti-corrosion layer 13>

In this embodiment, the first anticorrosion layer 13 is a layer for preventing corrosion due to rust of the metal foil 14 or the like.

The first anticorrosion layer 13 preferably contains a metal halide compound, and a metal halide compound described later may be directly plated on the surface of the metal foil 14 . By providing such a first anti-corrosion layer 13, a good anti-rust effect can be imparted to the metal foil.

In addition, the first anticorrosion layer 13 preferably contains a water-soluble resin, a chelating agent, or a crosslinking compound in addition to the metal halide compound. Therefore, as the first anticorrosion layer 13, it is preferable to contain a metal halide compound, a water-soluble resin, and a chelating agent or a cross-linking compound. Alternatively, an aqueous solution of a crosslinkable compound is applied on the lower layer, dried and cured. Hereinafter, the material forming the first anticorrosion layer 13 may be referred to as an "anticorrosion treatment agent".

(metal halide compound)

The metal halide compound has the effect of improving chemical resistance such as electrolyte resistance. That is, the surface of the metal foil 14 can be passivated, and the corrosion resistance against the electrolytic solution can be improved. When the first anticorrosion layer 13 contains a water-soluble resin described later, the metal halide compound also has the function of crosslinking the water-soluble resin.

The metal halide compound is preferably water-soluble in view of miscibility with a water-soluble resin described later or when it is dispersed in a water-soluble medium and applied.

As a metal halide compound, a chromium halide, an iron halide, a zirconium halide, a titanium halide, a hafnium halide, a titanium hydrohalide, salts of these, etc. are mentioned, for example. The halogen atom may, for example, be chlorine, bromine or fluorine, preferably chlorine or fluorine. Furthermore, fluorine is particularly preferred. By making the metal halide compound contain fluorine, hydrofluoric acid (HF) can be generated from the anticorrosion treatment agent depending on conditions.

In addition, the metal halide compound may have atoms other than halogen atoms and metals.

Among them, the chloride or fluoride of iron, chromium, manganese, or zirconium is preferable as the metal halide compound.

(water soluble resin)

As the water-soluble resin, it is preferable to use at least one selected from the group consisting of polyvinyl alcohol resin or its derivative, and polyvinyl ether resin.

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 monomer or a copolymer thereof.

Examples of polymers of vinyl ester monomers or copolymers thereof include fatty acid vinyl esters such as vinyl formate, vinyl acetate, and vinyl butyrate, or vinyl esters such as aromatic vinyl esters such as vinyl benzoate. Homopolymers or copolymers of ester monomers, and copolymers of other monomers that can be copolymerized with them.

Examples of other copolymerizable monomers include olefins such as ethylene and propylene, ether group-containing monomers such as alkyl vinyl ethers, diacetone acrylamide, diacetone (meth)acrylate, allyl acetoacetate, etc. Carbonyl (ketone)-containing monomers such as esters and acetoacetates, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride, vinyl halides such as vinyl chloride or vinylidene chloride, and unsaturated sulfonic acids class etc.

These monomers can be polymerized by a usual method.

Examples of modified polyvinyl alcohol resins include alkyl ether-modified polyvinyl alcohol resins, carbonyl-modified polyvinyl alcohol resins, acetoacetyl-modified polyvinyl alcohol resins, acetamide-modified polyvinyl alcohol resins, acrylic Nitrile-modified polyvinyl alcohol resin, carboxyl-modified polyvinyl alcohol resin, silicone-modified polyvinyl alcohol resin, ethylene-modified polyvinyl alcohol resin, etc.

Among them, acid-modified polyvinyl alcohol resins such as carboxy-modified polyvinyl alcohol resins and acetoacetyl-modified polyvinyl alcohol resins 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 %, even more preferably 95 to 99 mol %.

The (modified) polyvinyl alcohol resin has both a hydrophobic group derived from a vinyl ester side chain (for example, in the case of vinyl acetate, the hydrophobic group is an acetyl group) and a hydrophilic polyvinyl alcohol obtained by saponification. Hydroxyl groups react favorably with the surface of the metal foil as compared with a resin having a degree of saponification of 100 mol %, that is, only hydrophilic hydroxyl groups.

Commercially available polyvinyl alcohol resins or derivatives thereof include, for example, J-POVALDF-20 and AP-17 (both trade names) manufactured by JAPAN VAM & POVAL CO., LTD. CROSSMER H series (trade name) manufactured by NIPPON CARBIDE INDUSTRIES Co., Inc., etc. One kind or a mixture of two or more kinds of polyvinyl alcohol resin or its derivatives can also be used.

Examples of 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-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, etc. Homopolymers or copolymers of aliphatic vinyl ethers, and copolymers of other monomers that can be copolymerized with them, etc. Examples of other monomers copolymerizable with vinyl ether monomers include the same monomers as other monomers copolymerizable with vinyl ester monomers described above.

Especially 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxypropyl vinyl ether, monovinyl ether of other various diols or polyols, etc., in monomers A polyvinyl ether resin containing an aliphatic vinyl ether having a hydroxyl group is suitable for the present invention because it is water-soluble and capable of a crosslinking reaction with the hydroxyl group.

These polyvinyl ether resins can be produced without saponification unlike polyvinyl alcohol resins produced via vinyl ester polymers, since vinyl ether monomers can be used in the resin production (polymerization) process. In addition, a copolymer containing a vinyl ester monomer and a vinyl ether monomer, or a vinyl alcohol-vinyl ether copolymer obtained by saponifying them can also be used. A mixture of a polyvinyl alcohol-based resin and a polyvinyl ether-based resin other than the polyvinyl ether-based resin may also be used.

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

(chelating agent)

A chelating agent is a material capable of coordinating with metal ions to form a metal ion complex.

The chelating agent combines the metal compound (chromium oxide, etc.) from the metal halide compound with the water-soluble resin to increase the compressive strength of the first anticorrosion layer 13, so even if the thickness of the first anticorrosion layer 13 exceeds 0.2 μm and is When the thickness is 1.0 μm or less, the first anticorrosion layer 13 will not become embrittled and crack or peel off. Therefore, the adhesive strength and adhesiveness between the metal foil 14 and the 1st adhesive layer 12, and the adhesive strength and adhesiveness between the metal foil 14 and the upper layer side layer can be improved.

In addition, the chelating agent has the effect of making the water-soluble resin water-resistant by chemically reacting with the water-soluble resin or the metal halide compound.

As the chelating agent, for example, aminocarboxylic acid-based chelating agents, phosphonic acid-based chelating agents, oxycarbonic acid (oxycarbonic acid)-based, (poly)phosphoric acid-based chelating agents can be used.

Examples of aminocarboxylic acid chelating agents include nitrilotriacetic acid (NTA), hydroxyethyliminodiacetic acid (HIDA), ethylenediaminetetraacetic acid (EDTA), and hydroxyethylethylenediaminetriacetic acid. (HEDTA), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTHA), trans-cyclohexanediaminetetraacetic 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 ether diamine tetraacetic acid (GEDTA), ethylenediamine o-hydroxyphenylacetic acid (EDHPA), SS-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).

The phosphonic acid 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 ), for example, N,N,N-trimethylenephosphonic acid (NTMP), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), ethylenediamine-N,N,N',N'-tetramethylene Phosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), nitrilotris(methylene phosphonic acid) (NTMP).

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

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

As commercially available chelating agents, for example, aminocarboxylic acid chelating agents such as Chelest PD-4H (PDTA); Chelest PH-540 (EDTMP), Chelest PH-210 (HEDP) , ChelestPH-320 (NTMP), Chelest PH-430 (PBTC) and other phosphonic acid chelating agents (the above are all chelating agents manufactured by Chelest Co., Ltd., marked as trade names).

Among them, as the chelating agent, phosphoric acid-based chelating agents (phosphoric acid compounds) such as phosphonic acid-based chelating agents and (poly)phosphoric acid-based chelating agents are preferred, and phosphonic acid-based chelating agents are more preferred.

(crosslinking compound)

The cross-linking compound refers to a compound capable of reacting with the water-soluble resin to form a cross-linking structure. By using such a cross-linking compound, in the first anti-corrosion layer 13, the water-soluble resin and the cross-linking compound can form a dense cross-linking structure, further improving the passivation and corrosion resistance of the surface of the metal foil 14. .

The cross-linkable compound is not particularly limited as long as it can react with a hydrophilic group (for example, carboxyl group, carboxylic acid group, etc.) in the water-soluble resin to form a cross-linked structure. A compound with an oxazoline group or a compound with an oxazoline group.

As the compound having an epoxy group, the same compound as the "multiple epoxy group-containing compound (B)" described in the description of the adhesive of the first adhesive layer 12 can be used.

The "compound having an oxazoline group" refers to a compound having an oxazoline group (a monovalent group having an atomic bond at the 2-position of the oxazoline ring (C ₃ H ₅ NO )) within the structure.

As a compound having an oxazoline group, specifically, styrenic resins containing an oxazoline group can be exemplified. For example, when the water-soluble resin has a carboxyl group, the following crosslinking reaction can occur to form an amide ester bond . As a result, the strength of the water-soluble resin and the first anticorrosion layer 13 is enhanced by the crosslinked structure, and good anticorrosion performance is obtained.

[chemical formula 2]

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 styrenic monomer, styrene and its derivatives can be used. Specifically, styrene, α-methylstyrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, Alkylstyrenes such as ethylene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene; chlorostyrene, fluorostyrene, bromostyrene, dibromostyrene, iodobenzene Ethylene and other halogenated styrenes, etc. Among them, styrene is preferred.

The skeleton of the oxazoline group-containing monomer is not particularly limited as long as it is a monomer containing an oxazoline group and copolymerizable with a styrene-based monomer, but a monomer having an oxazoline group and a vinyl group can be suitably used .

Examples of oxazoline group-containing vinyl monomers include 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-dimethyl -2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, 4-acryloyl-hydroxy Methyl-2,4-dimethyl-2-oxazoline, 4-methacryloyl hydroxymethyl-2,4-dimethyl-2-oxazoline, 4-methacryloyl hydroxymethyl -2-phenyl-4-methyl-2-oxazoline, 2-(4-vinylphenyl)-4,4-dimethyl-2-oxazoline, 4-ethyl-4-hydroxy Methyl-2-isopropenyl-2-oxazoline, 4-ethyl-4-ethoxycarbonylmethyl-2-isopropenyl-2-oxazoline and the like. Among them, 2-isopropenyl-2-oxazoline is preferable.

As the styrene-based monomer and the oxazoline group-containing monomer, one kind may be used alone, or two or more kinds may be used in combination.

In addition, the compound having an oxazoline group may contain one or more other monomers in addition to the vinyl monomer and the oxazoline group-containing monomer. The other monomers are not particularly limited as long as they can be copolymerized with these monomers, for example, (meth)acrylate (acrylate) monomer, (meth)acrylate (acrylic ester) monomer, (meth) ) acrylamide monomer, etc.

In the compound having an oxazoline group, the composition ratio of each monomer is not particularly limited, but it is preferably 5 to 50% by mass, more preferably 10% by mass, relative to all monomers constituting the compound having an oxazoline group. A resin obtained by copolymerizing ~30% by mass of an oxazoline group-containing monomer. 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 cross-linked 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, still more preferably 60,000 to 100,000, and most preferably 60,000 to 80,000. Be the compound that has oxazoline group in the above-mentioned range by using number-average molecular weight, can improve the compatibility of acid-modified polyolefin resin and the compound that has oxazoline group, can make water-soluble resin and have oxazoline group compounds are fully crosslinked.

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

In the anticorrosion treatment agent, only one of the chelating agent and the crosslinking compound may be used, or both may be used in combination. Among them, it is preferable to use any one of a chelating agent and 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, and still more preferably 10 to 15% by mass in the total solid content of the anticorrosion treatment agent. In addition, the metal halide compound is preferably 20 to 60% by mass, more preferably 30 to 55% by mass, and even more preferably 40 to 50% by mass in the total solid content of the anticorrosion treatment agent. The chelating agent and/or the crosslinking compound is preferably 20 to 60% by mass, more preferably 30 to 50% by mass, and still more preferably 35 to 45% by mass in the total solid content of the anticorrosion treatment agent.

The anticorrosion treatment agent can be prepared by dissolving a water-soluble resin, a metal halide compound, and a chelating agent and/or a crosslinking compound in a solvent containing water. As a solvent, water is preferable.

The solid content concentration in the anticorrosion treatment agent can be appropriately determined in consideration of the applicability of the first anticorrosion layer 13 and the like, but it can usually be set to 0.1 to 10% by mass.

The thickness of the first anticorrosion layer 13 is preferably 0.05 μm or more, more preferably more than 0.1 μm. By setting the thickness of the first anticorrosion layer 13 to 0.05 μm or more, sufficient corrosion resistance can be imparted to the laminated body 10 for battery exterior packaging, and adhesion between the metal foil 14 and the first adhesive layer 12 can be improved. strength, and the bonding strength between the metal foil 14 and the first base material layer 11.

In addition, the thickness of the first anticorrosion layer 13 is preferably 1.0 μm or less, more preferably 0.5 μm or less. By setting the thickness of the first anticorrosion layer 13 to 1.0 μm or less, it is possible to suppress material costs while increasing the bonding strength between the metal foil 14 and the first adhesive layer 12 .

＜Metal foil 14＞

The metal foil 14 plays an important role in reducing leakage of the contents sealed in the laminated body 10 for battery exterior packaging (for example, liquid leakage of the battery). In addition, by using a metal with high mechanical strength, pinholes can be reduced when the battery housing recess is formed by drawing molding using the laminated body 10 for battery outer packaging. Leakage of contents (e.g. liquid leakage from batteries).

The metal foil 14 is not particularly limited as long as it is a thinly stretched metal or alloy, and examples thereof include metal foils such as aluminum, copper, lead, zinc, iron, nickel, titanium, and chromium; stainless steel, etc. alloy foil. The stainless steel foil is not particularly limited as long as it is made of stainless steel such as austenitic, ferrite, and martensitic stainless steel. As the austenite type, there are SUS304, SUS316, SUS301, etc.; as the ferrite type, SUS430 etc. are mentioned; As the martensite type, SUS410 etc. are mentioned, for example.

Among them, aluminum foil or stainless steel foil is preferable from the standpoints of processability, ease of acquisition, price, strength (puncture strength, tensile strength, etc.), corrosion resistance, etc., especially from the standpoint of puncture strength. For stainless steel foil.

The thickness of the metal foil 14 is preferably 100 μm or less, preferably 5 to 40 μm, more preferably 10 to 30 μm, particularly preferably 10 to 20 μm. By setting it as more than the said lower limit, sufficient mechanical strength can be given to the laminated body 10 for battery exteriors, and when used for batteries, such as a secondary battery, the durability of a battery can be improved. Moreover, by making the thickness of the metal foil 14 below the said upper limit, the laminated body 10 for battery exteriors can be made thin enough, and sufficient drawability can be provided.

<Second anti-corrosion layer 15>

The second anticorrosion layer 15 has the same structure as the first anticorrosion layer 13 . In this embodiment, the second anticorrosion layer 15 is provided, but the second anticorrosion layer 15 has any structure 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 polyurethane adhesive or an epoxy adhesive. The thickness of the second adhesive layer 16 can be set to, for example, 0.5 to 10 μm. By setting the thickness into this range, the second base material layer 17 and the metal foil 14 can be bonded with high adhesive force, and delamination can be prevented. In this form, although the 2nd adhesive bond layer 16 is provided, the 2nd adhesive bond layer 16 has an arbitrary structure in this invention.

<Second base material layer 17>

The second base material layer 17 is not particularly limited as long as it has sufficient mechanical strength, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene terephthalate Polyester resins such as butylene glycol (PBT); polyamide resins such as nylon (Ny); polyolefin resins such as stretched polypropylene (OPP); composed of polyether ether ketone (PEEK), polyphenylene sulfide (PPS), etc. synthetic resin film. Among them, a PET film is preferable.

The thickness of the second base material layer 17 is, for example, 1 to 50 μm, preferably 1 to 30 μm, and more preferably 3 to 11 μm.

The second substrate layer 17 may be a single-layer structure or a multi-layer structure. As an example of the second base material layer 17 having a multilayer structure, a double-layer film in which a polyethylene terephthalate (PET) resin film is laminated on a biaxially stretched polyamide resin film (ONy) can be cited. . In addition, the second base material layer 17 may have a multilayer structure in which three or more films are laminated.

In addition, in the embodiment shown in FIG. 1 , the second base material layer 17 is the outermost layer. Therefore, by containing a coloring material such as a pigment other than the resin, the second base material layer can also have a desired color or design.

The second base material layer 17 is preferably constituted by a single-layer or multi-layer film using a heat-resistant resin film having a melting point of 200° C. or higher. Such heat-resistant resin films include, for example, PET films, PEN films, PBT films, nylon films, PEEK films, PPS films, and the like, but PET films are particularly preferred in terms of cost. By using such a heat-resistant resin film, the heat resistance of the laminated body 10 for battery exteriors can be improved, and the durability of the battery using the laminated body 10 for battery exteriors can be improved. In this form, although the 2nd base material layer 17 is provided, the 2nd base material layer 17 has an arbitrary structure in this invention.

In the laminated body 10 for battery outer packaging shown in FIG. In the battery outer package, the inner side that can be in contact with the electrolytic solution and the like is the side of the first base material layer 11 . Therefore, the anticorrosion layer may be formed at least on the first base material layer 11 side of the metal foil 14 . That is, it is also possible to omit the second anticorrosion layer 15, the second adhesive layer 16, and the second base material layer 17 (especially the second anticorrosion layer 15, The structure of the second adhesive layer 16).

In the laminated body 10 for battery outer packaging shown in FIG. layer, or the outermost layer is formed of a coating without providing the second anticorrosion layer 15 to the second base material layer 17 .

The coating (first coating) is selected from polyurethane 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, cellulose ester resin, cellulose ether resin, polyamide resin, polyphenylene ether resin (PPE), polyphenylene sulfide resin (PPS), polyarylether resin (PAE) , polyether ether ketone resin (PEEK) at least one resin in the group of resins formed. The coating layer is preferably made of a material excellent in 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 above-mentioned resin in a general organic solvent.

By forming a coating layer, the insulation of the laminated body 10 for battery exteriors can be improved, and damage to the surface of the laminated body 10 for battery exteriors can be prevented. Moreover, even when the laminated body 10 for battery exteriors contacts an electrolytic solution, the change (discoloration etc.) of an external appearance can be prevented.

In addition, the coating can be colored by adding a colorant or pigment to the solvent-based paint used to form the coating. In addition, in order to express characters, graphics, images, patterns, etc., coloring or printing may be applied to the coating layer to improve design.

The thickness of the coating can be set to, for example, 0.1 to 20 μm, preferably 2 to 10 μm.

In the laminated body 10 for battery outer packaging shown in FIG. 1, the second base material layer 17 is in direct contact with the second adhesive layer 16, but a A printed layer that improves design.

The printing layer can be provided in 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 using the battery exterior laminate 10 include secondary batteries such as lithium ion batteries, capacitors such as electric double layer capacitors, and batteries using an organic electrolyte for the electrolytic solution. As an organic electrolyte, generally, a carbonate such as propylene carbonate (PC), diethyl carbonate (DEC), or ethylene carbonate is used as a medium, but it is not particularly limited thereto.

The laminated body for battery outer packaging of the present invention can be produced, for example, by a method having the following steps: a step of forming the first anticorrosion layer 13 on one side of the metal foil 14; a process of an adhesive layer 12; and a process of laminating the laminate by placing the first base material layer 11 in contact with the formed first adhesive layer 12.

The details will be described below.

First, the first anticorrosion layer 13 is formed on one surface of the metal foil 14 .

Specifically, the above-mentioned anticorrosion treatment agent is applied to the surface of the metal foil 14, followed by heating and drying. At this time, only the first anti-corrosion layer 13 can be formed by coating the anti-corrosion treatment agent on only one side of the metal foil 14, and the second anti-corrosion layer 13 can also be formed by coating the anti-corrosion treatment agent on both sides of the metal foil 14 at the same time. Corrosion layer 15. In addition, when the second anticorrosion layer 15 is provided, the second anticorrosion layer 15 is preferably formed before the formation of the first adhesive layer 12 and the like, and is more preferably formed simultaneously with the first anticorrosion layer 13 .

In addition, when forming the first anticorrosion layer 13 and the second anticorrosion layer 15 at the same time, it is also preferable to immerse the metal foil 14 in the anticorrosion treatment agent, make the anticorrosion treatment agent adhere to both surfaces of the metal foil 14, and then heat dry.

Next, the first adhesive layer 12 is formed on the first anticorrosion layer 13 .

Specifically, a layer made of the above-mentioned adhesive is formed on the surface of the metal foil 14 on which the first anticorrosion layer 13 is provided, and it is heated and dried as necessary.

When the adhesive is an adhesive for thermal lamination that does not contain an organic solvent, the (A) component and (B) component are melt-kneaded to allow the two components to react, and the first anticorrosion layer 13 By applying and drying, the first adhesive layer 12 is formed.

For the melt-kneading, known devices such as a single-screw extruder, a multi-screw extruder, a Bunbury mixer, a plastic mixer (Plastmill), and a heated roll kneader can be used. In order to suppress the decomposition of epoxy groups during melt kneading, it is best to remove moisture and other volatile components that can react with epoxy groups outside the device in advance, and when volatile components are generated during the reaction, they should be discharged outside the device at any time by degassing, etc. . When the acid-modified polyolefin resin has an acid anhydride group as an acidic functional group, it is preferable because it has high reactivity with epoxy groups and can react under milder conditions. The heating temperature during melt-kneading is preferably selected from the range of 240 to 300° C. from the viewpoint of sufficiently melting the two components without thermal decomposition. In addition, 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 a melt-kneading apparatus.

In addition, when the adhesive is an adhesive for dry lamination containing an organic solvent, after dissolving the components (A) and (B) in the organic solvent, the solution is applied on the first anticorrosion layer 13 and dried to form the first adhesive layer 12 . In addition, the formation of the first adhesive layer 12 can be performed in a series of steps using a known dry laminator or the like in parallel with the lamination step with the first base material layer 11 which will be described later.

Then, the first base material layer 11 is placed so as to be in contact with the formed first adhesive layer 12, and this laminated body is laminated. Lamination may be dry lamination or thermal lamination, but dry lamination at 70 to 150°C is preferred. The pressure at the time of dry lamination is preferably 0.1 to 0.5 MPa.

Specifically, a film constituting the first base material layer 11 is prepared in advance, and the film is placed on the first adhesive layer, followed by lamination. The lamination temperature is not particularly limited as long as it is a temperature at which the first base material layer 11, the first anticorrosion layer 13 and the metal foil 14 can be well bonded via the first adhesive layer. The material and melting point of the adhesive of layer 12 are determined. The temperature during dry lamination is usually 70 to 150°C, preferably 80 to 120°C.

The laminated body for battery outer packaging of this embodiment has a structure in which the first base material layer 11, the first anticorrosion layer 13 and the metal foil 14 are bonded via the first adhesive layer 12. dry lamination. By employing dry lamination as needed, the temperature during lamination can be greatly reduced.

Generally, when a high heat is applied to a metal foil that has low thermal conductivity and is difficult to expand, warpage (curl) tends to occur in the width direction of the metal foil. When using such a metal foil for heat lamination, the heat cannot be sufficiently propagated in the plane, and sometimes there is a part in the width direction that does not come into contact with the heat press roll, or does not come into contact with the roll, sometimes due to warping itself breaks or creases. In addition, when the metal foil is heated to such a high temperature that warpage does not occur, the production efficiency is low due to a reduction in the processing speed and an increase in the amount of heat required. In addition, by lowering the temperature at the time of lamination, whitening due to heat of the first base material layer 11 can also be prevented, and deterioration of the first base material layer 11 can be prevented, and the selection range of the first base material layer 11 can be broadened. .

In addition, when dry lamination is used in the production of the laminate for battery exterior of this embodiment, the occurrence of breakage, wrinkles, whitening of the resin, etc. can be suppressed, and a suitable laminate for battery exterior can be produced with high production efficiency.

In addition, the step of forming the first adhesive layer 12 and the step of providing the first base material layer 11 for (dry) lamination can be performed in a series of steps using a known (dry) lamination device.

The formation methods of the second anticorrosion layer 15, the second adhesive layer 16, and the second base material layer 17 are not particularly limited, but for example, the second adhesive layer 16 can be formed on the second base material layer 17 in advance, A laminate composed of two layers was formed. In addition, the two-layer laminate, the first base material layer 11, the first adhesive layer 12, the first anticorrosive The laminated body of the corrosion layer 13, the metal foil 14, and the 2nd anticorrosion layer 15 was dry laminated|stacked, and the laminated body 10 for battery outer packages which consists of seven layers was produced.

As mentioned above, one embodiment of the present invention has been described based on the laminated body 10 for battery outer packaging shown in FIG. Various changes can be added.

For example, the second anti-corrosion layer 15 may not be provided, and a six-layer structure may be used. In addition, the second anticorrosion layer 15, the second adhesive layer 16, and the second base material layer 17 may not be provided, and a four-layer structure may not be provided, and the first anticorrosion layer 13 and the second anticorrosion layer may not be provided. 15. The second adhesive layer 16 and the second base material layer 17 are configured in three layers.

In addition, it may be provided on the side of the first base material layer 11 that is not in contact with the first adhesive layer 12 or the side of the second base layer 17 that is not in contact with the second adhesive layer 16 . For other layers, it is set as a structure with seven layers or more than eight layers.

[Battery outer package]

A battery outer package according to a second aspect of the present invention is a battery outer package having the battery outer package laminate according to the first aspect, which has an internal space for accommodating batteries, and the first base material layer side of the battery outer package laminate for the interior space side. Specifically, the battery exterior laminate of the first aspect is molded into a desired shape so that the first base material layer faces the internal space, and the end portion is sealed as necessary.

The shape, size, etc. of the battery outer package are not particularly limited, and may be appropriately determined according to the type of battery to be used.

The battery outer package may be composed of one member, or may be formed by combining two or more members (for example, a container main body and a cover portion) as described later using FIG. 2 .

[Battery]

A battery according to a third aspect of the present invention has the battery exterior body according to the second aspect.

The battery may, for example, be a secondary battery such as a lithium ion battery, or a capacitor such as an electric double layer capacitor, in which an organic electrolyte is used as an electrolytic solution. Since the battery outer packaging laminate of the present invention has high electrolytic solution resistance, even when an electrolytic solution containing LiPF ₆ or the like is used, a battery that can operate suitably can be obtained.

As an example, a perspective view of a secondary battery 40 is shown in FIG. 2 . The secondary battery 40 includes a lithium ion battery 27 contained in the container 20 for battery exterior packaging.

The battery outer packaging container 20 is formed by overlapping the container main body 30 composed of the battery outer packaging laminate 10 according to the first aspect of the present invention and the cover portion 33 composed of the battery outer packaging laminate 10, and facing the peripheral edge portion 29. Formed by heat sealing. Reference numeral 28 denotes electrode leads connected to the positive and negative electrodes of the lithium ion battery 27 .

The battery shown in Fig. 2 can be prepared in the following manner.

First, as shown in (a) of FIG. 3 , the laminated body 10 for battery outer packaging is molded into a disk shape having a concave portion 31 by drawing molding or the like to obtain a container main body 30 . The depth of the recessed part 31 can be set to 2 mm or more, for example.

A lithium-ion battery (lithium-ion battery 27 in FIG. 2 ) is housed in the recess 31 of the container body 30 .

Then, as shown in (b) in FIG. Heat sealing was performed to obtain a secondary battery 40 as shown in FIG. 2 . That is, in the battery as shown in FIG. 3 , by covering the upper surface of the container body 30 with the lid portion 33 , the recess 31 and the lid portion 33 form an internal space for accommodating the battery.

Example

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these examples.

[Examples 1-15, Comparative Examples 1-13]

<Examples 1-15, Comparative Examples 1-3, 5>

First, the metal foils shown in Table 1 were prepared. The anti-corrosion treatment agent shown in Table 1 was applied on both sides of the metal foil (coating amount: 12 g/m ² ), heated and dried in an oven at 200° C., and the first anti-corrosion treatment agent with a thickness of 0.2 μm was formed on both sides. layer and the second anti-corrosion layer.

After that, a first adhesive was applied on the formed first anticorrosion layer to form a first adhesive layer with a thickness of 3 μm. The first adhesive is prepared by mixing a solution obtained by dissolving component (A) shown in Table 1 in toluene as an organic solvent, and a solution obtained by dissolving component (B) shown in Table 1 in methyl ethyl ketone as an organic solvent. obtained as a solution. The mass parts of each component in Table 1 is the final compounding quantity after mixing. In addition, the amount of solvent in the solution of the binder was adjusted so that the final solid content was 9% by mass. The final mixing ratio (mass ratio) of methyl ethyl ketone and toluene is 1:1.

The first adhesive layer of the laminate including 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.

In addition, on the second substrate layer made of a stretched polyethylene terephthalate (PET) resin film having a thickness of 6 μm, a second substrate layer made of a polyurethane adhesive is applied. The adhesive layer is molded (thickness 3 μm).

The second adhesive layer was opposed to the second anticorrosion layer in the laminate obtained above, and laminated by dry lamination at 80° C. to obtain a laminate for battery exterior packaging.

＜Comparative example 4＞

A laminate for battery exterior packaging was obtained in the same manner as in Example 1 above except that the component (B) in the first adhesive was not used. Moreover, the adhesive agent of the comparative example 4 was obtained by mixing the toluene solution which melt|dissolved (A) component, and the methyl ethyl ketone which did not melt|dissolve (B) component.

[Table 1]

In Table 1, each abbreviation has the following meanings respectively. The numerical value in [ ] is a compounding quantity (mass part).

(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; novolak epoxy resin; viscosity=80; epoxy equivalent=180)

(B)-2: A component containing "jER154" and "D-17" (trade name; manufactured by Mitsui Chemicals; isocyanate compound) at a ratio of 50/50 (mass ratio)

(B)-3: "jER157S70" (trade name; manufactured by Mitsubishi Chemical Corporation; novolac epoxy resin having a bisphenol A structure; viscosity=80; epoxy equivalent=210)

(B)-4: Phenoxy resin which does not have an epoxy group and ring-opens the epoxy group at the terminal

(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: 0.2% by mass of a polyvinyl alcohol skeleton-containing non-crystalline polymer having a saponification degree of 95% by mole (manufactured by JAPAN VAM & POVAL CO., LTD., trade name: AP-17; (PVA-1) ), 0.8% by mass of ferric chloride, and 0.7% by mass of an oxazoline resin (trade name: WS-500, manufactured by Nippon Shokubai Co., Ltd.) were dissolved in water.

R-2: The same aqueous solution as R-1 above, except that ferric chloride is changed to chromium fluoride

R-3: The same aqueous solution as R-1 above, except that ferric chloride is replaced with ferric oxide

(Storage modulus measurement)

The dynamic viscoelasticity measurement of the single layer of the first adhesive layer was performed in accordance with JIS K7244 "Plastic-Dynamic Mechanical Properties Test Method".

Specifically, first, the first adhesive of each example shown above is coated on a fluororesin base material, heated at 110°C for 300 seconds, and after the organic solvent is completely evaporated, it is carried out at 80°C for 3 days. Ripening treatment to make it fully cross-linked. Then, the substrate 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 placed on a dynamic viscoelasticity measuring device with a chuck distance of 20 mm, and the storage elastic modulus (E') at 150°C was obtained under atmospheric pressure at an applied frequency of 1 Hz and a strain of 0.01%. value. As a dynamic viscoelasticity measuring device, a dynamic viscoelasticity measuring device "RSA-3" (trade name) of TA Instruments was used.

The results are shown in Table 1 together.

(heat resistance test)

The laminates for battery outer packaging prepared in the above examples were heat-sealed at 0.3 MPa·190°C·3 seconds, T-peeled in an environment of 85°C, and evaluated according to the following criteria. The results were rated as "heat resistance "Represented in Table 1.

◎: 25N/15mm or more

○: less than 25N/15mm and more than 15N/15mm

×: less than 15N/15mm

(Electrolyte resistance test)

An electrolyte solution at 85° C. containing 1000 ppm of water (a solution of ethylene carbonate: diethyl carbonate: dimethyl carbonate = 1:1:1 volume % added with 1 mol/L of LiPF ₆ ) was prepared, and the prepared The test pieces of the battery outer packaging laminates of the respective examples were immersed in the electrolytic solution for 3 days.

After 3 days, a 90° peel test was performed. Evaluation was performed according to the following criteria, and the evaluation results are shown in Table 1 as "electrolyte solution resistance".

A: 5N/15mm or more

B: less than 5N/15mm, and more than 3N/15mm

C: less than 3N/15mm, and more than 1N/15mm

D: Less than 1N/15mm

From the results shown in Table 1, it can be confirmed that Examples 1 to 15 using the laminate for battery outer packaging of the present invention have excellent adhesiveness even under severe conditions, compared with Comparative Examples 1 to 5. .

[Experimental Examples 1 to 3, Comparative Experimental Example 1]

In the same manner as in Examples 1 to 13, etc., the first adhesives of the respective examples shown in Table 2 were obtained. Each abbreviation in Table 2 is the same as above.

Then, the storage 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 in the same manner as the storage modulus measurement. The result is shown in FIG. 4 .

[Table 2]

From the results shown in Fig. 4, it can be confirmed that the adhesive containing (A) component and (B) component does not decrease in storage modulus (E'; unit Pa) even at high temperature. On the other hand, in In an adhesive that does not contain the component (B), the storage elastic modulus significantly decreases at high temperature, and as a result, the shape cannot be maintained.

Claims (10)

1. A laminated body for battery outer packaging, which is formed by having at least a first base material layer, a first adhesive layer and a metal foil in this order, characterized in that, The first substrate layer is a layer made of polyolefin, The first adhesive layer has a storage modulus value at 150° C. of 1.0×10 ⁴ to 1.0×10 ⁷ in dynamic viscoelasticity measurement of a single layer of the first adhesive layer. layer. 2. The battery outer packaging laminate according to claim 1, wherein the first adhesive layer is a layer composed of an adhesive, and the adhesive contains 100 parts by mass of acid-modified polyolefin A resin (A) and 1 to 20 parts by mass of a compound (B) containing a plurality of epoxy groups. 3 . The laminate for battery exterior packaging according to claim 2 , wherein the compound (B) containing a plurality of epoxy groups is a novolac epoxy resin. 4 . 4. The laminate for battery outer packaging according to any one of claims 1 to 3, further comprising a first anticorrosion layer between the first adhesive layer and the metal foil, The first anticorrosion layer contains a metal halide compound. 5 . The battery outer packaging laminate according to claim 4 , wherein the first anticorrosion layer further contains a water-soluble resin, and a chelating agent or a crosslinkable compound. 6 . The battery outer packaging laminate according to claim 4 or 5 , wherein the metal halide compound is a chloride of iron, chromium, manganese, or zirconium, or a fluoride of iron, chromium, manganese, or zirconium. 7. The laminate for battery exterior packaging according to any one of claims 1 to 6, wherein the metal foil is aluminum, stainless steel, copper, nickel or titanium. 8 . The battery outer packaging laminate according to claim 1 , wherein the metal foil has a thickness of 10 to 40 μm. 9. A battery outer packaging body comprising the battery outer packaging laminate according to any one of claims 1 to 8, wherein: This battery exterior body has an internal space for accommodating a battery, and the side of the first base material layer of the laminate for battery exterior packaging is the side of this interior space. 10. A battery, characterized in that the battery has the battery outer packaging body according to claim 9.