KR20170100401A - Laminate for battery packages, battery package, and battery - Google Patents

Abstract

The present invention provides a laminated body for a battery case, which can be manufactured with high production efficiency and having various kinds of superior characteristics. The laminated body (10) for a battery case comprises a first base layer (11), a first adhesive layer (12) and a metal foil (14) in at least this sequential order. The first base layer (11) is a layer formed by polyolefin, and the first adhesive layer (12) has a value of storage coefficient of elasticity, which is not less than 1.0 10^4 and not more than 1.0 10^7 at the temperature of 150 C, when measuring dynamic viscoelasticity of a fault of the first adhesive layer (12). The battery case includes the laminated body for a battery case, has an inner space receiving a battery, and allows a first base layer-side of the laminated body for a battery case to be an inner space-side. The battery includes the battery case.

Description

LAMINATE FOR BATTERY PACKAGES, BATTERY PACKAGE, AND BATTERY BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a laminate for battery external application as an external body such as a secondary battery or a capacitor, and a battery external body and a battery obtained by using the laminate.

As awareness of the environment has increased, a secondary battery such as a lithium ion battery or a capacitor such as an electric double layer capacitor has attracted attention as a storage battery for storing electric energy in conjunction with utilization of natural energy such as sunlight or wind power .

As an external body used for these batteries, a laminate for battery exterior lamination in which a metallic foil and a resin layer are laminated is used for the purpose of miniaturization and weight saving. The laminate for external use of the battery is formed by drawing or the like so as to have a tray shape having a concave portion to obtain an external casing body. Further, in the same manner as the above-mentioned outer casing body, the battery casing laminate is molded to obtain an outer casing body. The battery body is housed in the concave portion of the outer casing body, the outer casing body is covered with the cover body so as to cover the battery body housed therein, and the container body and the side shell portion of the casing body are bonded to each other, Is obtained.

For example, Patent Document 1 discloses a laminate for battery exterior lamination in which a base layer, an aluminum foil and an innermost layer composed of a polypropylene or polyethylene layer are stacked in this order and a thin film coating layer is laminated on the innermost layer side of the aluminum foil have. More specifically, in Patent Document 1, it is considered that it is preferable to bond the innermost layer comprising the thin film coating layer and the polypropylene or polyethylene layer via a heat sealant, and it is preferable to laminate the laminate with the acid- Coated aluminum foil and the innermost layer are adhered to each other.

Japanese Laid-Open Patent Publication No. 2012-33393

The application fields of batteries such as secondary batteries have been enlarged to require an increase in the battery production volume. In addition, improvement in the production efficiency such as improvement in the yield at the time of manufacture and shortening of the time has also been demanded in battery outer bodies. In addition, along with improvements in battery properties such as miniaturization and large capacity, excellent properties such as heat resistance and chemical resistance (electrolyte resistance) are required for battery outer shells.

However, in the case of laminating the metal foil subjected to the surface treatment and the innermost layer resin by using a heat sealant as in Patent Document 1, it is necessary to add high temperature and high pressure at the time of laminating, It is difficult to reduce the production efficiency. Further, wrinkling or deterioration may occur in the innermost layer (polypropylene layer, polyethylene layer, or the like) or metal foil to be bonded by performing lamination processing at a high temperature, and this leads to reduction in yield and selection of various materials .

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described situation, and it is an object of the present invention to provide a laminate for battery enclosure which can be manufactured with high production efficiency and is excellent in various characteristics.

As a result of intensive investigations to achieve the above object, the present inventors have found that, by adhering a metal foil, which has been surface-treated arbitrarily, and a base layer (innermost layer) through an adhesive layer having a specific storage modulus, And the production efficiency such as shortening of the production time and improvement of the yield can be improved according to the necessity, thereby completing the present invention.

That is, the present invention adopts the following configuration.

The battery laminate for a battery enclosure according to the first aspect of the present invention comprises at least a first base layer, a first adhesive layer and a metal foil in this order, wherein the first base layer is a polyolefin layer, Wherein the first adhesive layer is a layer having a storage elastic modulus at 150 ° C of not less than 1.0 x 10 ^{4 and not} more than 1.0 x 10 ^{7 in} the dynamic viscoelasticity measurement of the single layer of the first adhesive layer.

It is preferable that the first adhesive layer is a layer composed of an adhesive containing 100 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.

The compound (B) containing a plurality of epoxy groups is preferably a phenol novolak type epoxy resin.

A first corrosion inhibiting layer is provided between the first adhesive layer and the metal foil, and the first corrosion inhibiting layer preferably contains a halogenated metal compound.

It is preferable that the first corrosion inhibiting layer further contains a water-soluble resin and a chelating agent or a crosslinking compound.

The metal halide compound is preferably a fluoride of iron, chromium, manganese, 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 mu m.

The battery casing according to the second aspect of the present invention is a battery casing having the battery casing layered body according to the first aspect, wherein the battery casing has an internal space for accommodating the battery, .

The battery of the third aspect of the present invention is characterized in that it comprises the battery housing of the second aspect.

According to the present invention, it is possible to provide a battery laminate for external use which has excellent characteristics and can be produced with high production efficiency.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a first embodiment of a laminate for covering a battery according to the present invention. Fig.
2 is a perspective view showing an example of a secondary battery manufactured using the laminate for battery exterior according to the present invention.
3 is a perspective view showing a step of manufacturing a secondary battery using the laminate for battery enclosure according to the present invention.
4 is a graph showing storage elastic modulus of a single layer of an adhesive layer in Experimental Examples 1 to 3 and Comparative Experimental Example 1. Fig.

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

[Battery laminate for battery external use]

The laminate for battery enclosure according to the first aspect of the present invention (hereinafter sometimes simply referred to as "laminate") comprises at least a first base layer, a first adhesive layer, a first corrosion inhibiting layer and a metal foil in this order Wherein the first base layer is a layer made of polyolefin and the first adhesive layer has a storage elastic modulus at 150 占 폚 of 1.0 占 10 ⁴ or more and 1.0 x 10 < ⁷ > or less.

1 is a cross-sectional view showing a schematic structure of a laminate 10 for a battery enclosure according to an embodiment of the present invention.

The layered product 10 according to the present embodiment includes the first base layer 11, the first adhesive layer 12, the first corrosion preventing layer 13, the metal foil 14, the second corrosion preventing layer 15 ), A second adhesive layer 16, and a second base layer 17 in this order.

That is, the laminate 10 according to the present embodiment includes the first corrosion preventing layer 13 and the second corrosion preventing layer 15 formed on both surfaces of the metal foil 14, and the first adhesive layer 13 on the first corrosion preventing layer 13, (17) having a first base layer (11) laminated via a first adhesive layer (12) and a second base layer (17) laminated via a second adhesive layer (16) on a second corrosion inhibiting layer (15) Lt; / RTI >

Hereinafter, each layer will be described in detail.

≪ First Base Layer (11) >

The first base 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 an? -Olefin, and a block copolymer of propylene and ethylene or an? have.

Among them, homopolypropylene (propylene homopolymer; hereinafter sometimes referred to as "homo PP") and propylene-ethylene block copolymer (hereinafter referred to as "homopolymer") are more preferable from the viewpoint of improving the adhesiveness with the first adhesive layer 12 , &Quot; block PP "), and a random copolymer of propylene and ethylene (hereinafter sometimes referred to as " random PP "). Above all, homo PP or block PP is more preferable, and block PP is particularly preferable in view of excellent mechanical strength.

The first base layer 11 may have a single-layer structure or a multi-layer structure.

The melting point of the polyolefin layer used in the first base layer 11 is not particularly limited as long as it has the heat resistance required for the battery laminate 10 for a battery.

The thickness of the first base layer 11 may be, for example, 1 to 200 mu m, preferably 5 to 100 mu m, and more preferably 5 to 40 mu m.

≪ First adhesive layer (12) >

The first adhesive layer 12 is a layer formed to adhere the first base layer 11 which is a base resin layer and the metal foil 14 on the surface of which the first corrosion inhibiting layer 13 is formed, (12) In the dynamic viscoelasticity measurement of the single layer, the value of the storage elastic modulus at 150 캜 is 1.0 × 10 ⁴ or more and 1.0 × 10 ⁷ or less.

As the adhesive forming the first adhesive layer 12, the layer can be adhered well, and the material is not particularly limited as long as it is a layer that can satisfy the value of the storage elastic modulus. For example, Is preferably a layer composed of an adhesive containing an acid-modified polyolefin resin (A) and a compound (B) containing a plurality of epoxy groups in that the adhesive property and the storage elastic modulus can be satisfied.

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)) refers to a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, wherein an acidic functional group such as a carboxyl group or a carboxylic anhydride group is contained in the polyolefin- .

The component (A) is obtained by modifying a polyolefin resin with an unsaturated carboxylic acid or a derivative thereof, or copolymerizing an olefin with an acid functional group-containing monomer. Among them, the component (A) is preferably obtained by acid-modifying the polyolefin-based resin.

Examples of the acid modification method include graft modification in which a polyolefin resin and an acidic 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, copolymers of propylene and ethylene, and copolymers of propylene and olefin-based monomers.

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, the polyolefin-based resin is preferably a polypropylene-based resin which is polymerized with propylene as a raw material, such as homopolypropylene (propylene homopolymer), a copolymer of propylene and ethylene, or a copolymer of propylene and butene; Particularly, a propylene-1-butene copolymer, that is, a polyolefin resin having a methyl group and an ethyl group in its side chain is preferable. By containing 1-butene, the molecular motion when the resin is heated is promoted, and the opportunity for the crosslinking points of the component (A) and the crosslinking points of the component (B) to be described later to contact each other is increased. As a result, .

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

Examples of the monomer containing an acidic functional group having a carboxyl group (a monomer containing a carboxyl group) include monomers having a carboxyl group, such as acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid, 2.2.1] -5-heptene-2,3-dicarboxylic acid (endic acid), and the like.

Examples of the acidic functional group-containing monomer (carboxylic anhydride group-containing monomer) having a carboxylic acid anhydride group include unsaturated dicarboxylic acid anhydride monomers such as maleic anhydride, nadic anhydride, itaconic anhydride, citraconic anhydride, .

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

Among them, the acid functional group-containing monomer is preferably a monomer containing an acidic functional group which reacts well with the epoxy group in the component (B) to be described later; More preferably an acidic functional group-containing monomer having an acid anhydride group from the viewpoint of high reactivity with an epoxy group; More preferred are monomers containing carboxylic acid anhydride groups; Maleic anhydride is particularly preferred.

When a part of the acidic functional group-containing monomer used for acid modification is unreacted, in order to prevent the lowering of the adhesive force by the unreacted acidic functional group-containing monomer, the unreacted acidic functional group- Is preferably used.

In the component (A), the component derived from the polyolefin resin or olefin is preferably 50 parts by mass or more based on 100 parts by mass of the total amount of the component (A).

The melting point of the component (A) is not particularly limited.

In the case of using the first adhesive layer 12 as the adhesive layer for dry lamination, the melting point of the component (A) is preferably from 50 to 100 캜, more preferably from 60 to 98 캜, still more preferably from 70 to 98 캜 , And more preferably 75 to 95 캜.

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 more than the above lower limit value. As a result, the first base layer 11, The heat resistance and durability of the metal foil 14 having the corrosion preventive layer 13 after adhesion can be improved.

On the other hand, when the melting point of the component (A) is made to be not more than the upper limit, the component (A) tends to dissolve in the organic solvent when the component (A) is dissolved in the organic solvent to obtain the solvent type dry laminate adhesive , A more uniform adhesive can be obtained, and the component (A) and the component (B) react well to improve the adhesiveness and durability. Further, by using the component (A) having a melting point lower than the upper limit value, the temperature at the time of performing the dry lamination through the first adhesive layer 12 and the aging temperature after the lamination can be made comparatively low. As a result, in the first base layer 11 to be bonded by using the first adhesive layer 12, wrinkles due to heat are less likely to occur, so that the yield at the time of production is improved, and the first base layer 11 ) Can be relaxed, so that the range of selection of the material of the first base layer 11 can be widened. Further, since the laminate can be processed at a relatively low temperature, it is possible to shorten the time for the laminate treatment and reduce the amount of energy required for the laminate treatment, thereby making it possible to improve the production efficiency and reduce the consumed energy.

On the other hand, in a case where the adhesive used for forming the first adhesive layer 12 contains no organic solvent and the adhesive is formed by melt kneading the component (A) and the component (B) described later, The melting point is preferably 100 占 폚 to 180 占 폚. The first adhesive layer 12 made of such an adhesive can be preferably used as the adhesive layer for thermal lamination.

By using the component (A) having the above melting point in the above range, even when the conventional method and general apparatus are used, the component (A) and the component (B) described below are melt-kneaded at a temperature sufficiently higher than the melting point of the component can do. When the component (A) is reacted with the component (B) described later by melt kneading, it is preferable that the melting point of the component (B) is lower than that of the component (A) By using the component (B), the degree of freedom in selecting the component (B) can be increased.

As described above, it is preferable that the melting point of the component (A) is higher than the melting point of the component (B) described later, but the melting point of the component (A) More preferably 20 ° C or higher, and particularly preferably 30 ° C or higher. The melting point of the component (A) is sufficiently higher than that of the component (B), so that the component (B) is first melted when the melt-kneading is carried out to penetrate into the component (A) As a result of the reaction between 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 above-mentioned desired melting point. In general, a resin having a molecular weight of 10,000 to 800,000 is used, preferably 50000 to 650000, More preferably from 55,000 to 100,000, and still more preferably from 100,000 to 45,000.

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

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

(B) is a compound containing a plurality of epoxy groups. The component (B) may be a low molecular compound or a high molecular compound. From the viewpoint of improving the 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 dry laminate adhesive, it is also preferable that the component (B) is a low molecular weight compound from the viewpoint of improving solubility in an organic solvent.

The structure of component (B) is not particularly limited as long as it has a plurality of epoxy groups, and examples thereof include phenoxy resins synthesized by bisphenols and epichlorohydrin; Phenol novolak type epoxy resins; And a bisphenol-type epoxy resin. Among them, it is preferable to use a phenol novolak type epoxy resin in view of the fact that 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 novolak type epoxy resin is a compound having a phenol novolac resin obtained by acid condensation of phenol and formaldehyde as a basic structure and having an epoxy group introduced into a part of its structure. The amount of the epoxy group introduced per molecule in the phenol novolak type epoxy resin is not particularly limited. However, by reacting the epoxy group raw material such as epichlorohydrin with the phenol novolac resin, a large number of phenolic hydroxyl groups present in the phenol novolak resin The epoxy group is usually introduced, so that it is a polyfunctional epoxy resin.

Among them, the phenol novolak type epoxy resin is preferably a bisphenol A novolak type epoxy resin having a phenol novolac structure as a basic skeleton and having a bisphenol A structure in combination. Here, the bisphenol A structure in the epoxy resin may be a structure that can be derived from bisphenol A, and both terminal hydroxyl groups of bisphenol A may be substituted with groups such as epoxy group-containing groups.

An example of the bisphenol A novolak type epoxy resin is a resin represented by the following formula (1).

[In the 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 the 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, R ³ and R ⁴ may be the same or different.

It is preferable that at least one of the following (i) to (iii) is satisfied in the resin represented by the formula (1).

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

For example, by satisfying the above (i), it is possible to constitute a structure in which a carbon atom to which R ¹ and R ² bond in the formula (1) and two hydroxyphenyl groups to which the carbon atom is bonded are derived from bisphenol A do.

In the formula (1), R ^X 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 among these, 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. The smaller the value, the more epoxy groups in the resin. By using an epoxy resin having a relatively small epoxy equivalent, even when the amount of the epoxy resin added is relatively small, the adhesion between the epoxy resin and the adherend becomes good, and the epoxy resin and the acid-modified polyolefin resin are sufficiently crosslinked.

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

By using the epoxy resin as described above, both the acidic functional group of the component (A) and the epoxy group of the component (B) are excellent in adhesion to an adherend (particularly, a functional group such as a carboxyl group of the first corrosion inhibiting layer 13) It is believed that the metal foil 14 having the first base layer 11 and the first corrosion inhibiting layer 13 on its surface can exert excellent adhesion by functioning as a functional group.

Further, a part of the acidic functional group of the component (A) reacts with a part of the epoxy group of the component (B) to form a crosslinked structure of the component (A) and the component (B) in the first adhesive layer 12 , It is considered that the strength of the first adhesive layer 12 is reinforced by the cross-linking structure, and excellent durability is obtained with excellent adhesion.

It is preferable that 1 to 20 parts by mass of the component (B) is contained in the first adhesive layer 12 with respect to 100 parts by mass of the component (A), more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the component ) Is more preferable, and 5 to 7 parts by mass of the component (B) is particularly preferable relative to 100 parts by mass of the component (A).

(Optional component)

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

By using an organic solvent and forming a liquid adhesive, a solvent type dry laminate adhesive can be obtained. The first adhesive layer 12 can be formed by applying and drying such a liquid adhesive on a layer serving as a lower layer (for example, a surface on which the first corrosion preventing layer 13 of the metal foil 14 is formed) and drying. By selecting the application instead of the extrusion molding, the adhesive layer can be formed in a thinner layer, making it possible to make the adhesive layer thinner and thin the entire laminate body using the adhesive layer.

On the other hand, when an organic solvent is not contained, a preferable adhesive layer can be formed on a thermal laminate or the like by melting and kneading the component (A) and the component (B), and then performing extrusion molding.

In the case of containing an organic solvent, the organic solvent to be used is not particularly limited as long as it can dissolve the component (A), the component (B) and other optional components (to be described later in detail) And any solvent known in the art can be used as the solvent of the solution type adhesive. The liquid adhesive is usually applied on an adherend (for example, the surface on which the first corrosion preventive layer 13 of the metal foil 14 is formed), and then the organic solvent is volatilized by heating or the like. Therefore, from the viewpoint of facilitating the volatilization, the organic solvent is preferably an organic solvent having a boiling point of 150 DEG C or less.

Specific organic solvents include, for example, toluene, xylene, anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene , Aromatic solvents such as isopropylbenzene, cymene, and mesitylene; aliphatic solvents such as n-hexane; Ketone solvents such as methyl ethyl ketone, acetone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; Ester solvents such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate; Alcohol solvents such as methanol, ethanol and isopropyl alcohol; And polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol.

The organic solvents may be used singly or in combination of two or more. In the case of using a mixed solvent, it is also preferable to use an organic solvent which dissolves the component (A) well and an organic solvent which dissolves the component (B) well. As such a combination, a combination of toluene which satisfactorily dissolves the component (A) and methyl ethyl ketone which dissolves the component (B) well is preferable. When a mixed solvent is used, two or more kinds of organic solvents may be mixed in advance, and then the above components (A) and (B) may be dissolved; It is also possible to mix plural kinds of organic solvents in which each component of component (A) and component (B) is dissolved in each good solvent, and then each component is dissolved.

When a plurality of kinds 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 thereof is preferably toluene: methyl ethyl ketone = 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 further contain other components in addition to the component (A), the component (B) and the organic solvent. Other components include miscible additives and additional resins. More specifically, catalysts, crosslinking agents, plasticizers, stabilizers, coloring agents and the like can be used.

Among the solid components of the adhesive used in the present invention, the component (A) is contained in an amount of more than 50 parts by mass and not more than 99.5 parts by mass, and the component (B) is contained in an amount of not less than 0.5 parts by mass and less than 50 parts by mass. That is, in the solid component of the adhesive, the component (A) is more than half of the solid component in the mass ratio, and the adhesive used in the present invention contains the component (A) as a main component. More preferably 0.5 to 30 parts by mass of the component (B) relative to 70 to 99.5 parts by mass of the component (A); More preferably, it is 1 to 20 parts by mass of the component (B) relative to 80 to 99 parts by mass of the component (A); Particularly preferred is 2 to 10 parts by mass of the component (B) relative to 90 to 98 parts by mass of the component (A).

In addition, even when the adhesive used in the present invention contains a solid component other than the component (A) and the component (B) as optional components, the component (A) is necessarily 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, an adhesive containing 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 other components, among all the solid components.

When the adhesive used in the present invention contains an organic solvent, the amount of the organic solvent to be used is not particularly limited as long as it is an amount capable of dissolving the components (A), (B) and optional components well, In general, the solid concentration is preferably from 3 to 30 mass%, more preferably from 5 to 25 mass%, and even more preferably from 7 to 20 mass%.

The adhesive used in the present invention has a storage elastic modulus at 150 ° C of 1.0 × 10 ^{4 to} 1.0 × 10 ^{7 in} a dynamic viscoelasticity measurement of a single layer of the first adhesive layer 12 formed using the adhesive , And more preferably from 5.0 x 10 ^{4 to} 8.5 x 10 ^{5, and} still more preferably from 3.0 x 10 ^{5 to} 8.0 x 10 ⁵ .

In the dynamic viscoelasticity measurement of the single layer of the first adhesive layer 12 formed using the adhesive, the value of the storage elastic modulus at 60 캜 is preferably 1.0 x 10 ⁶ or more, more preferably 1.0 x 10 ^{6 to} 1.0 × 10 ⁸ Pa, and more ^{preferably, 5.0 × 10 6 ~5.0 × 10} 7 are more preferred.

That is, the value of the storage modulus at 150 占 폚 is preferably 1/10000 to 1/1, more preferably 1/1000 to 1/1, more preferably 1/1000 to 1/1 as compared with the value of the storage modulus at 60 占 폚. / 500 to 1/1, and particularly preferably 1/100 to 1/1.

That is, it is preferable that the adhesive used in the present invention not only has a sufficient elastic modulus at 60 ° C but also can maintain an elastic modulus within a proper range without excessively lowering the elastic modulus even at a relatively high temperature of 150 ° C. Since the first adhesive layer 12 formed using such an adhesive having a storage elastic modulus is difficult to change its shape even at a relatively high temperature and is kept in a good shape, the laminate for a battery enclosure 12 having the first adhesive layer 12 The shape and the adhesiveness of the battery 10 can be satisfactorily maintained even at a high temperature, and it is possible to obtain the laminate 10 for battery enclosure having good high temperature resistance.

Such an adhesive having a storage elastic modulus can be easily obtained by using the aforementioned component (A) and component (B) in combination. This is because the crosslinking between the acidic functional group of the component (A) and the epoxy group of the component (B) maintains the elastic modulus even at a relatively high temperature.

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

First, an adhesive is applied on an arbitrary substrate to which a fluororesin or the like is not adhered, followed by heating at 110 DEG C for 300 seconds to dry (completely volatilize the organic solvent) and aging treatment at 80 DEG C for 3 days , The base material is 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 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 Co., Ltd. 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 may be, for example, 0.1 to 50 탆, preferably 0.5 to 10 탆, and more preferably 0.7 to 5 탆. By setting the thickness to be within this range, the metal foil 14 on which the first base layer 11 and the first corrosion preventive layer 13 are formed can be adhered with a high adhesive force, thereby preventing delamination.

<First Corrosion Preventing Layer (13)>

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

The first corrosion preventing layer 13 preferably contains a halogenated metal compound and the halogenated metal compound to be described later may be directly plated on the surface of the metal foil 14. By forming the first corrosion preventing layer 13, It is possible to impart a rust-preventive effect in a satisfactory manner.

In addition to the halogenated metal compound, the first corrosion inhibiting layer 13 preferably further contains a water-soluble resin and a chelating agent or a crosslinking compound. Therefore, it is preferable that the first corrosion inhibiting layer 13 contains a metal halide compound, a water-soluble resin, a chelating agent or a crosslinking compound; The first corrosion inhibiting layer 13 is preferably formed by applying an aqueous solution containing a halogen compound, a water-soluble resin, a chelating agent or a crosslinking compound onto a layer to be a lower layer, followed by drying and curing. Hereinafter, the material forming the first corrosion inhibiting layer 13 may be referred to as a &quot; corrosion inhibiting treatment agent &quot;.

(Metal halide compound)

The metal halide compound has an effect of improving the chemical resistance such as electrolyte resistance. That is, the surface of the metal foil 14 can be made passivated, and the corrosion resistance against the electrolytic solution can be enhanced. In the case where the first corrosion inhibiting layer 13 contains a water-soluble resin to be described later, the metal halide compound also has a function of crosslinking the water-soluble resin.

It is preferable that the metal halide compound has water-solubility in consideration of miscibility with a water-soluble resin to be described later, or a case where it is dispersed in an aqueous medium and applied.

The halogenated metal compound includes, for example, chromium halide, iron halide, zirconium halide, titanium halide, hafnium halide, titanium hydrohalide, and salts thereof. Examples of the halogen atom include chlorine, bromine and fluorine, and chlorine or fluorine is preferable. Particularly preferably, it is fluorine. Since the halogenated metal compound contains fluorine, it is possible to generate hydrofluoric acid (HF) from the corrosion inhibitor according to the conditions.

The halogenated metal compound may have a halogen atom or an atom other than a metal.

Among them, the halogenated metal compound is preferably a chloride or fluoride of iron, chromium, manganese or zirconium.

(Water-soluble resin)

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

The polyvinyl alcohol resin or 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 the polymer or copolymer of the vinyl ester monomer include homopolymers or copolymers of vinyl ester monomers such as vinyl formate, vinyl acetate and vinyl butyrate, aromatic vinyl esters such as vinyl benzoate, and the like And copolymers of monomers.

Examples of the other copolymerizable monomer include olefins such as ethylene and propylene, ether group-containing monomers such as alkyl vinyl ether, diacetone acrylamide, diacetone (meth) acrylate, allyl acetoacetate and acetoacetic ester Monomers containing a carbonyl group (ketone group), unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride, halogenated vinyls 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 an alkylether-modified polyvinyl alcohol resin, a carbonyl-modified polyvinyl alcohol resin, an acetoacetyl-modified polyvinyl alcohol resin, an acetamide-modified polyvinyl alcohol resin, an acrylonitrile-modified polyvinyl alcohol resin, Polyvinyl alcohol resins, silicone-modified polyvinyl alcohol 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 modified polyvinyl alcohol resin is preferably 90 mol% or more, more preferably 90 to 99.9 mol%, further preferably 95 to 99 mol%.

(Denatured) polyvinyl alcohol resin has both a hydrophobic group derived from the side chain of the polyvinyl ester (for example, an acetyl group if it is vinyl acetate) and a hydrophilic hydroxyl group obtained by saponification so that the saponification degree is 100 mol% Can react with the surface of the metal foil better than a resin having only a hydrophilic hydroxyl group.

Commercially available polyvinyl alcohol resins or derivatives thereof are commercially available, for example, J-POVARU DF-20, AP-17 (all trade names), Nippon Kabaido Kogyo Co., Crossmersh series (trade name) manufactured by K.K. The polyvinyl alcohol resin or its derivative may be used alone or in a mixture of two or more.

Examples of the polyvinyl ether type 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 and norbornyl vinyl ether , Homopolymers or copolymers of aliphatic vinyl ethers such as allyl vinyl ether, norbornenyl vinyl ether, 2-hydroxyethyl vinyl ether and diethylene glycol monovinyl ether, and copolymers of other monomers copolymerizable therewith . The other monomers copolymerizable with the vinyl ether-based monomer may be the same as the other monomers copolymerizable with the above-mentioned vinyl ester-based monomer.

In particular, polyvinyls containing monomers such as 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxypropyl vinyl ether, and other various glycol or monovinyl ethers of polyhydric alcohols, The ether-based resin has water-solubility and can be used favorably in the present invention because it can perform a crosslinking reaction with hydroxyl groups.

Unlike a polyvinyl alcohol-based resin produced via a vinyl ester-based polymer, these polyvinyl ether-based resins can be produced without saponification because they can be used in the production (polymerization) of a resin of a vinyl ether monomer Do. Further, a copolymer containing a vinyl ester monomer and a vinyl ether monomer, or a vinyl alcohol-vinyl ether copolymer obtained by saponifying the same may 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 be used.

As the water-soluble resin, either a polyvinyl alcohol resin or its derivative and a polyvinyl ether-based resin may be used alone or both of them may be used in combination.

(Chelating agent)

The chelating agent is a material capable of coordinating to a metal ion to form a metal ion complex.

The chelating agent binds the water-soluble resin to a metal compound (such as chromium oxide) derived from a halogenated metal compound to increase the compressive strength of the first corrosion inhibiting layer 13, so that the thickness of the first corrosion inhibiting layer 13 is, for example, The first corrosion inhibiting layer 13 is brittle and does not crack or peel off even if it is more than 0.2 탆 and 1.0 탆 or less. Therefore, the adhesion strength and adhesion between the metal foil 14 and the first adhesive layer 12 and the adhesion strength and adhesion between the metal foil 14 and the layer on the upper layer can be enhanced.

In addition, the chelating agent has a function of hydrating the water-soluble resin by chemically reacting with the water-soluble resin or the metal halide compound.

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

Examples of the aminocarboxylic acid chelating agent include nitrilo triacic acid (NTA), hydroxyethyl imino acid acetic acid (HIDA), ethylenediamine disuccinic acid (EDTA), hydroxyethylethylenediamine triacetic acid (HEDTA), diethylene (DTPA), triethylenetetramine acetic acid (TTHA), transcyclohexanediaminesacetic acid (CyDTA), 1,2-propanediamine succinate (1,2-PDTA), 1,3- (1,3-PDTA), 1,4-butanediamine succinate (1,4-BDTA), 1,3-diamino-2-hydroxypropanesulfonic acid (DPTA-OH), glycol ether diaminesacetic acid GEDTA), ethylenediamine orthohydroxyphenyl acetic acid (EDHPA), SS-ethylenediamine disuccinic acid (SS-EDDS), ethylenediamine disuccinic acid (EDDS), beta -alanine acetic acid (ADA), methylglycine diacetic acid N, N'-diacetic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'- (HBEDDA). &Lt; / RTI &gt;

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 a phosphonic acid (HP (═O) (OH) ₂ ) N, N ', N'-tetramethylenephosphonic acid (EDTMP), ethylenediamine-N, N'-tetramethylenephosphonic acid Diethylenetriaminepenta methylenephosphonic acid (DTPMP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), and nitrilotris (methylenephosphonic acid) (NTMP).

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

(Poly) phosphoric acid type chelating agents include phosphoric acid, metaphosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid and salts thereof.

Commercially available products of commercially available chelating agents include, for example, aminocarboxylic acid chelating agents such as keyrest PD-4H (PDTA); Phosphonic acid chelating agents such as keyrests PH-540 (EDTMP), keyrest PH-210 (HEDP), keyrest PH-320 (NTMP) and keyrest PH- ), And the notation is a trade name).

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

(Crosslinkable compound)

The crosslinkable compound refers to a compound capable of reacting with the water-soluble resin to form a crosslinked structure. By using such a crosslinking compound, the water-soluble resin and the crosslinking compound described above form a dense crosslinked structure in the first corrosion inhibiting layer 13, and the passivity and corrosion resistance of the surface of the metal foil 14 can be further improved .

The crosslinkable compound is not particularly limited as long as it is capable of reacting with a hydrophilic group (for example, a carboxyl group, a carboxylic acid group or the like) in a water-soluble resin to form a crosslinked structure, and examples thereof include compounds having an epoxy group, Group may be mentioned.

As the compound having an epoxy group, the same compound as the &quot; compound (B) containing a plurality of epoxy groups &quot; 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 an oxazoline group (a monovalent group having a bonding number at the 2-position of the oxazoline ring (C ₃ H ₅ NO)) in its structure.

Specific examples of the oxazoline group-containing compound include oxazoline group-containing styrene resins. For example, in the case where the water-soluble resin has a carboxyl group, the following crosslinking reaction occurs to form an amide ester bond do. As a result, the strength of the water-soluble resin and the first corrosion-preventive layer 13 is reinforced by the cross-linking structure, and a good anti-corrosion ability is obtained.

Among them, as the compound having an oxazoline group, a resin obtained by copolymerization of a styrene-based monomer and an oxazoline group-containing monomer is preferable.

As the styrene-based monomer, styrene and its derivatives can be used. Specific examples thereof include alkylstyrenes such as styrene,? -Methylstyrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; And halogenated styrenes such as chlorostyrene, fluorostyrene, bromostyrene, dibromostyrene, and iodostyrene. Among them, styrene is preferable.

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

Examples of the oxazoline group-containing vinyl monomers include 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, Oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, 4-acryloyloxymethyl-2,4-dimethyl-2-oxazoline, 4- methacryloyloxy Methyl-2-oxazoline, 2- (4-vinylphenyl) -4,4-dimethyl-2-oxazoline, 4-methacryloyloxymethyl- 4-hydroxymethyl-2-isopropenyl-2-oxazoline, 4-ethyl-4-carboethoxymethyl-2-isopropenyl- . Among them, 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.

The oxazoline group-containing compound may contain at least one monomer other than the styrene-based monomer and the oxazoline group-containing monomer. The other monomers are not particularly limited as long as they are copolymerizable with these monomers. 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 it is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on the entire monomer constituting the oxazoline group- A resin obtained by copolymerizing a zolinic group-containing monomer is preferable. By using the oxazoline group-containing monomer within the above range, the water-soluble resin and the compound having an oxazoline group are sufficiently crosslinked to obtain good corrosion resistance.

The number average molecular weight of the compound having an oxazoline group is preferably from 3 to 250,000, more preferably from 50,000 to 200,000, even more preferably from 60,000 to 100,000, and most preferably from 60,000 to 80,000. By using a compound having an oxazoline group within the above range of the number average molecular weight, the compatibility of the acid-modified polyolefin resin with the compound having an oxazoline group is improved and it becomes possible to sufficiently crosslink the compound having a water-soluble resin and an oxazoline group.

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

In the corrosion-inhibiting treatment agent, either the chelating agent or the crosslinking compound may be used alone or both of them may be used in combination. Among them, it is preferable that either the chelating agent or the crosslinkable compound can be used in combination with the above-described metal halide compound and the water-soluble resin.

The water-soluble resin is preferably contained in an amount of 3 to 30 mass%, more preferably 5 to 20 mass%, and still more preferably 10 to 15 mass%, of the total solids content of the corrosion inhibitor. The halogenated metal compound is preferably 20 to 60% by mass, more preferably 30 to 55% by mass, and still more preferably 40 to 50% by mass in the total solid content of the corrosion inhibitor. The chelating agent and / or the crosslinkable compound is preferably contained in an amount of from 20 to 60 mass%, more preferably from 30 to 50 mass%, and still more preferably from 35 to 45 mass%, of the total solids content of the corrosion inhibitor.

The corrosion inhibitor can be prepared by dissolving a water-soluble resin, a metal halide compound, a chelating agent and / or a crosslinking compound in a solvent containing water. The solvent is preferably water.

The solid content concentration in the corrosion preventive treatment agent can be suitably determined in consideration of the coatability and the like of the first corrosion preventive layer 13, but may be generally from 0.1 to 10 mass%.

The thickness of the first corrosion preventing layer 13 is preferably 0.05 탆 or more, more preferably 0.1 탆 or more. The thickness of the first corrosion preventing layer 13 is set to 0.05 m or more so that sufficient corrosion resistance is imparted to the laminate 10 for battery exterior lamination and the adhesion strength between the metal foil 14 and the first adhesive layer 12, 14 and the first base layer 11 can be increased.

The thickness of the first corrosion inhibiting layer 13 is preferably 1.0 탆 or less, more preferably 0.5 탆 or less. By setting the thickness of the first corrosion preventing layer 13 to 1.0 m or less, the bonding strength between the metal foil 14 and the first adhesive layer 12 can be increased and the material cost can be suppressed.

<Metal foil (14)>

The metal foil 14 plays an important role in reducing the leakage of contents (for example, liquid leakage of the battery) enclosed by the laminate in the battery laminate 10. In addition, by using a metal having a high mechanical strength, it is possible to reduce the occurrence of pinholes when the battery housing recess is formed by drawing molding using the laminate 10 for battery exterior laminate 10, and as a result, (For example, liquid leakage of the battery) can be reduced.

The metal foil 14 is not particularly limited as long as it is a thin metal foil or an alloy, and includes metal foil such as aluminum, copper, lead, zinc, iron, nickel, titanium and chromium; And an alloy foil such as stainless steel. The stainless steel foil is not particularly limited as long as it is made of a stainless steel such as an austenitic, ferritic or martensitic stainless steel. Examples of the austenite system include SUS304, 316, and 301, the ferrite system includes SUS430, and the martensite system includes SUS410 and the like.

Among them, an aluminum foil or a stainless steel foil is preferable from the viewpoints of processability, availability, price, strength (stuck strength, tensile strength, etc.), corrosion resistance and the like. Stainless steel foil is preferable from the viewpoint of stuck strength.

The thickness of the metal foil 14 is preferably 100 占 퐉 or less, more preferably 5 to 40 占 퐉, more preferably 10 to 30 占 퐉, and particularly preferably 10 to 20 占 퐉. By setting the upper limit value to be equal to or more than the lower limit value, sufficient mechanical strength is given to the laminate 10 for battery exterior use and durability of the battery can be increased when used in a battery such as a secondary battery. In addition, by making the thickness of the metal foil 14 equal to or smaller than the upper limit value, the battery laminate 10 can be made sufficiently thin and sufficient drawability can be imparted.

<Second Corrosion Preventing Layer (15)>

The second corrosion preventing layer (15) has the same structure as the first corrosion preventing layer (13). In the present embodiment, the second corrosion preventing layer 15 is formed, but the second corrosion preventing layer 15 has an arbitrary structure in the present invention.

&Lt; Second adhesive layer (16) &gt;

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 adhesive, epoxy adhesive, or the like. The thickness of the second adhesive layer 16 may be, for example, 0.5 to 10 mu m. By setting the thickness to be within this range, the second base layer 17 and the metal foil 14 can be bonded with a high adhesive force, and interlayer separation can be prevented. In this embodiment, the second adhesive layer 16 is formed, but the second adhesive layer 16 has an arbitrary structure in the present invention.

&Lt; Second base layer (17) &gt;

The second base layer 17 is not particularly limited as long as it has sufficient mechanical strength. For example, a polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT) ; Polyamide resins such as nylon (Ny); Polyolefin resins such as stretched polypropylene (OPP); Polyether ether ketone (PEEK), polyphenylene sulfide (PPS), and the like can be used. Of these, a PET film is preferable.

The thickness of the second base layer 17 may be, for example, 1 to 50 탆, preferably 1 to 30 탆, more preferably 3 to 11 탆.

The second base layer 17 may have a single-layer structure or a multi-layer structure. An example of the second base layer 17 having a multilayer structure is a two-layer film in which a polyethylene terephthalate (PET) resin film is laminated on a biaxially stretched polyamide resin film (ONy). Here, the second base layer 17 may be a multilayer structure in which three or more films are laminated.

Further, in the embodiment shown in Fig. 1, the second base layer 17 is the outermost layer. For this reason, the second base layer may contain a coloring agent such as pigment in addition to the resin, so that the second base layer may have a desired color or design.

The second base 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 a PET film, a PEN film, a PBT film, a nylon film, a PEEK film, and a PPS film, but a 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 laminate 10 can be improved, and the durability of the battery laminate 10 can be improved. Although the second base layer 17 is formed in this embodiment, the second base layer 17 has an arbitrary structure in the present invention.

The first corrosion preventing layer 13 and the second corrosion preventing layer 15 are formed on both sides of the metal foil 14 in the laminate 10 for battery enclosure shown in Fig. 1. However, the battery enclosure 10 using the laminate 10 for battery enclosure It is the first base layer 11 side that can be in contact with the electrolyte or the like on the inner surface side of the sieve. Therefore, the corrosion inhibiting layer may be formed at least on the first base layer 11 side of the metal foil 14. That is, the second corrosion preventing layer 15, the second adhesive layer 16 and the second base layer 17 (particularly, the second corrosion preventing layer 15, the second adhesive layer 16, Layer 16) may be omitted.

The second substrate layer 17 is the outermost layer in the battery laminate 10 shown in Fig. 1, but the second substrate layer 17 may be provided on the outer surface side of the second base layer 17, It is also possible to form the coating layer on the outermost layer without forming the coating layer 17.

The coating layer (the first coating layer) may be formed of a resin such as urethane resin, acrylic resin, polyvinylidene chloride, vinylidene chloride-vinyl chloride copolymer resin, maleic anhydride-modified polypropylene resin, polyester resin, epoxy resin, phenol resin, (PEEK), which is made of a resin, a cellulose ester resin, a cellulose ether resin, a polyamide resin, a polyphenylene ether resin (PPE), a polyphenylene sulfide resin (PPS), a polyaryl ether resin (PAE), and a polyether ether ketone resin And at least one resin selected from resin groups. The coating layer is preferably made of a material having excellent heat resistance. These resins may be used singly or in combination of two or more kinds.

The coating layer is preferably a thin film-hardened layer formed by dissolving the resin in a general organic solvent and applying and drying the prepared solvent-type paint.

By forming the coating layer, it is possible to increase the insulating property of the battery exterior laminate 10 and prevent the surface of the battery exterior laminate 10 from being scratched. Further, even when the battery exterior laminate 10 is in contact with the electrolytic solution, it is possible to prevent a change in appearance (discoloration or the like).

The coating layer can be colored by adding a coloring agent or a pigment to a solvent-type paint forming the coating layer. In addition, the coating layer may be colored or printed so as to display characters, figures, images, shapes, and the like to enhance designability.

The thickness of the coating layer may be, for example, 0.1 to 20 占 퐉, preferably 2 to 10 占 퐉.

The second base layer 17 and the second adhesive layer 16 are in direct contact with each other in the battery laminate 10 shown in Fig. 1, but the inner surface of the second base layer 17 has a printed layer May be formed.

The print layer can have the same configuration as the above-described coating layer.

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

Examples of the battery in which the battery laminate 10 is used include a secondary battery such as a lithium ion battery, which is a secondary battery, or an electrolyte such as a capacitor such as an electric double layer capacitor. As the organic electrolyte, a carbonate is generally used as a medium such as propylene carbonate (PC), diethyl carbonate (DEC), ethylene carbonate and the like, but not particularly limited thereto.

The battery laminate for use in the present invention can be produced by, for example, a process of forming a first corrosion inhibiting layer 13 on one surface of a metal foil 14, a step of forming a first adhesive layer 12 on the formed first corrosion inhibiting layer 13 And a step of disposing the first base layer 11 and the first adhesive layer 12 formed so as to be in contact with each other and laminating the laminate.

This will be described in detail below.

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

Specifically, the above-mentioned corrosion-inhibiting treatment agent is applied to the surface of the metal foil 14 and then heated and dried. At this time, only the first corrosion preventing layer 13 may be formed by applying the corrosion preventing treatment agent to only one side of the metal foil 14, or the second corrosion preventing layer 15 May be simultaneously formed. The second corrosion preventive layer 15 is preferably formed at a stage prior to the formation of the first adhesive layer 12 and the like in the case where the second corrosion preventive layer 15 is formed. It is more preferable to be formed at the same time.

In the case where the first corrosion preventing layer 13 and the second corrosion preventing layer 15 are simultaneously formed, the metal foil 14 is immersed in the corrosion inhibiting treatment agent, the anti-corrosion treatment agent is attached to both surfaces of the metal foil 14, It is also preferable to heat and dry.

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

Specifically, a layer of the above-described adhesive is formed on the surface of the metal foil 14 on which the first corrosion preventive layer 13 is formed, and if necessary, the layer is heated and dried.

When the adhesive is an adhesive for a thermal laminate containing no organic solvent, the components (A) and (B) are melted and kneaded to react the first component and the second component, and then the first component is coated on the first corrosion- An adhesive layer 12 is formed.

For the melt kneading, known devices such as a single screw extruder, a multi-screw extruder, a Banbury mixer, a plastmill, and a heating roll kneader can be used. In order to suppress the decomposition of the epoxy group at the time of melt kneading, volatile components which can react with epoxy such as water are preferably removed from the apparatus in advance, and when volatile components are generated during the reaction, they are preferably discharged to the outside of the apparatus from time to time by degassing . When the acid-modified polyolefin resin has an acid anhydride group as an acid functional group, it is preferable that the acid-modified polyolefin resin has high reactivity with an epoxy group and enables a reaction under milder conditions. The heating temperature at the time of melt kneading is preferably selected within the range of 240 to 300 DEG C in that both components are sufficiently melted and not thermally decomposed. Here, the kneading temperature can be measured by a method such as bringing the thermocouple into contact with the adhesive in a molten state immediately after being extruded from the melt kneading apparatus.

When the adhesive is an adhesive for dry lamination comprising an organic solvent, the components (A) and (B) are dissolved in an organic solvent, the solution is applied on the first corrosion inhibiting layer (13) 1 adhesive layer 12 is formed. The first adhesive layer 12 may be formed as a series of processes by using a known dry laminator or the like in addition to a lamination process with a first base layer 11 described later.

Thereafter, the first base layer 11 and the first adhesive layer 12 formed are brought into contact with each other, and the laminate is laminated. The laminate may be a dry laminate or a thermal laminate, but preferably a dry laminate at 70 to 150 캜. The pressure at the time of dry laminating is preferably 0.1 to 0.5 MPa.

Specifically, a film constituting the first base layer 11 is prepared in advance, and the film is placed on the first adhesive layer, followed by lamination. The temperature of the laminate is not particularly limited as long as it is a temperature at which the first base layer 11 and the first corrosion preventing layer 13 and the metal foil 14 are favorably adhered via the first adhesive layer, ) In consideration of the material and melting point of the adhesive constituting the adhesive layer. In the case of the dry laminate, the temperature is generally 70 to 150 캜, preferably 80 to 120 캜.

Since the battery exterior laminate of this embodiment has a structure in which the first base layer 11, the first corrosion inhibiting layer 13 and the metal foil 14 are bonded to each other with the first adhesive layer 12 interposed therebetween, It is also possible to adopt a dry laminate as shown in Fig. By adopting a dry laminate as required, the temperature at the time of laminating can be remarkably lowered.

Generally, when high heat is applied to a metal foil which is difficult to expand due to its low thermal conductivity, twisting (curling) tends to occur in the width direction of the metal foil. When such a metal foil is used for thermal lamination, heat is not sufficiently propagated in the surface, and a portion which is not in contact with the thermocompression rollers in the width direction is generated, or the thermocompression rollers are not in contact with the roll, Folding or wrinkling may occur at the time of pressing. In addition, when heating is performed to a high temperature at which the metal foil does not cause warping, the production efficiency may be lowered due to a decrease in the processing speed or an increase in the required heat quantity. By lowering the temperature at the time of laminating, it is possible to prevent whitening due to heat of the first base layer 11 and prevent deterioration of the first base layer 11, It becomes possible to widen the width.

When the dry laminate is employed in the production of the battery laminate for use in this embodiment, the occurrence of folding, wrinkling, whitening of the resin, and the like can be suppressed, and a preferable laminate for battery lamination can be produced with high production efficiency.

Here, the step of forming the first adhesive layer 12 and the step of (dry) laminating the first base layer 11 may be performed using a known (dry) lamination apparatus as a series of steps .

The method of forming the second corrosion preventing layer 15, the second adhesive layer 16 and the second base layer 17 is not particularly limited. For example, a second adhesive layer ( 16) are formed to form a laminate composed of two layers. The laminate having the two-layer laminate and the first base layer 11, the first adhesive layer 12, the first corrosion inhibiting layer 13, the metal foil 14 and the second corrosion preventing layer 15 , And the second adhesive layer (16) and the second corrosion preventing layer (15) are in contact with each other, so that the laminate for battery enclosure (10) comprising seven layers can be manufactured.

As described above, one embodiment of the present invention has been described based on the battery laminate 10 shown in Fig. 1. However, the technical scope of the present invention is not limited to the above-described embodiment, It is possible to make various changes.

For example, the second corrosion preventing layer 15 may not be formed but may have a six-layer structure.

The first corrosion preventing layer 13, the second corrosion preventing layer 15, the second adhesive layer 16, and the second substrate layer 17 may be formed to have a four-layer structure. ), The second adhesive layer 16, and the second base layer 17 may be omitted.

Another layer is formed on the side of the first base layer 11 that does not contact the first adhesive layer 12 or on the side of the second base layer 17 that is not in contact with the second adhesive layer 16 , Seven layers, or eight layers or more.

[Battery external body]

The battery exterior body of the second aspect of the present invention is a battery exterior body having the battery exterior laminate of the first aspect, wherein the battery exterior body has an internal space for housing the battery, wherein the first base layer side of the battery exterior laminate Is a battery external body. Specifically, it is obtained by molding the battery enclosing laminate of the first aspect into a desired shape so that the first base layer faces the inner space, sealing the end portion as necessary, and the like.

The shape, size and the like of the battery exterior body are not particularly limited, and can be appropriately determined depending on the type of the battery to be used.

The battery external body may be composed of one member or may be formed by combining two or more members (for example, a container body and a lid portion) as described later using Fig.

[battery]

The battery of the third aspect of the present invention comprises the battery housing 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, in which an organic electrolyte is used as an electrolytic solution. Since the battery laminate for use in a battery of the present invention has a high electrolyte resistance, it is possible to obtain a battery which can operate favorably even when an electrolyte solution containing LiPF ₆ or the like is used.

A perspective view of the secondary battery 40 as an example is shown in Fig. The secondary battery (40) contains the lithium ion battery (27) in the battery external container (20).

The battery external container 20 is obtained by overlapping the container body 30 made of the laminate body 10 for battery exterior of the first aspect of the present invention and the lid portion 33 made of the laminate body 10 for battery exterior, As shown in Fig. Reference numeral 28 denotes 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. 3 (a), the battery laminate 10 is molded into a tray shape having a concave portion 31 by drawing or the like to obtain a container body 30. [ The depth of the concave portion 31 can be, for example, 2 mm or more.

A lithium ion battery (lithium ion battery 27 in Fig. 2) is accommodated in the concave portion 31 of the container main body 30.

3 (b), the lid portion 33 formed of the laminate body 10 for a battery exterior body is superimposed on the container body 30, and the flange portion 32 and the lid portion 33 by heat sealing the periphery 34 of the secondary battery 40 shown in Fig. 3, the upper surface of the container body 30 is covered with the lid portion 33, so that an internal space for accommodating the battery is formed by the concave portion 31 and the lid portion 33.

Example

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 and Comparative Examples 1 to 13]

&Lt; Examples 1 to 15 and Comparative Examples 1 to 3 and 5 &gt;

First, a metal foil shown in Table 1 was prepared. The surface of the metal foil was coated with a corrosion inhibitor (coating amount: 12 g / m 2) shown in Table 1, and dried by heating in an oven at 200 ° C to form a first corrosion inhibiting layer and a second corrosion preventing layer each having a thickness of 0.2 탆.

Thereafter, the first adhesive was applied onto the formed first corrosion preventing layer to form a first adhesive layer having a thickness of 3 m. The first adhesive is obtained by mixing a solution in which component (A) shown in Table 1 is dissolved in toluene as an organic solvent and a solution in which component (B) shown in Table 1 is dissolved in methyl ethyl ketone as an organic solvent. The mass parts of the respective components in Table 1 are the final mixing amounts after mixing. The amount of the solvent in the solution was adjusted so that the final solids content was 9 mass%. The final mixing ratio (ratio by mass) of methyl ethyl ketone to toluene was 1: 1.

The first adhesive layer in the laminate including the metal foil and the first base layer made of the polypropylene resin (block PP) film having a thickness of 20 占 퐉 were laminated by dry lamination at 100 占 폚.

Further, a second adhesive layer (thickness 3 占 퐉) made of a urethane-based adhesive was formed on the second base layer made of a stretched polyethylene terephthalate (PET) resin film having a black thickness of 6 占 퐉 by coating.

The second adhesive layer and the second corrosion preventive layer in the laminate thus obtained were opposed to each other and laminated by dry lamination at 80 DEG C to obtain a battery laminate.

&Lt; Comparative Example 4 &

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

In Table 1, the respective abbreviations have the following meanings respectively. The values in [] are the compounding amount (parts 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)

(Epoxy equivalent: 80, epoxy equivalence: 180) (B) -1: "jER154" (trade name; manufactured by Mitsubishi Chemical Corporation; phenol novolak type epoxy resin;

(Mass ratio) of "jER154" and "D-17" (trade name, manufactured by Mitsui Chemicals, Inc., isocyanate compound)

(Phenol novolak type epoxy resin having a bisphenol A structure, viscosity = 80, epoxy equivalent = 210) manufactured by Mitsubishi Chemical Corporation) (B) -3: "jER157S70"

(B) -4: a phenoxy resin having no epoxy group and having an opening at the terminal epoxy group

(B) -5: "D-17"

(C) -1: mixed solvent of toluene / methyl ethyl ketone = 80/20 (by mass)

AL: Aluminum foil

SUS: Stainless steel obsession

CO: Copper foil

NI: Nickel foil

R-1: 0.2 mass% of a polyvinyl alcohol skeleton-containing amorphous polymer having a degree of saponification of 95 mol% and having a hydroxyl group (trade name: AP-17; (PVA-1) An aqueous solution obtained by dissolving 0.8 mass% of iron chloride and 0.7 mass% of an oxazoline resin (trade name: WS-500, manufactured by Nippon Shokubai Co., Ltd.) in water

R-2: The same aqueous solution as R-1 except that the iron chloride was changed to chromium fluoride

R-3: An aqueous solution same as R-1 except that iron chloride was changed to iron oxide

(Measurement of storage elastic modulus)

The dynamic viscoelasticity measurement of the single layer of the first adhesive layer was carried out in accordance with JIS K7244 &quot; Plastics - Test Method of Dynamic Mechanical Properties &quot;.

Specifically, first, the first adhesive of each of the examples shown above was applied to the fluororesin substrate, and the organic solvent was completely volatilized by heating at 110 DEG C for 300 seconds, followed by aging treatment at 80 DEG C for 3 days to complete crosslinking. Thereafter, 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 in a dynamic viscoelasticity measuring apparatus with a chuck of 20 mm, and the value of the storage elastic modulus (E ') at 150 ° C when a frequency of 1 Hz and a distortion of 0.01% was applied at atmospheric pressure was obtained. As a dynamic viscoelasticity measuring device, a dynamic viscoelasticity measuring device "RSA-3" (trade name) of TA Instrument was used.

The results are shown in Table 1.

(Heat resistance test)

The battery laminate prepared in each of the above examples was subjected to heat sealing at 0.3 MPa and 190 deg. C for 3 sec and subjected to T-peeling under the environment of 85 deg. C, and the results were evaluated according to the following criteria as "heat resistance"

?: 25 N / 15 mm or more

?: Less than 25 N / 15 mm, 15 N / 15 mm or more

X: less than 15 N / 15 mm

(Electrolyte test)

(Ethylene carbonate: diethyl carbonate: dimethyl carbonate = 1: 1: 1 vol% solution) in which 1000 ppm of water was contained at 85 캜 (1 mol / liter of LiPF ₆ added) was prepared and the battery exterior laminate The test piece was immersed in the electrolytic solution for 3 days.

After three days, a 90 deg. Peel test was carried out. The results of evaluation based on the following criteria are shown in Table 1 as &quot; electrolytic solution resistance &quot;.

A: 5N / 15㎜ or more

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

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

D: Less than 1N / 15 mm

From the results shown in Table 1, it was confirmed that Examples 1 to 15 using the laminate for battery enclosure of the present invention had excellent adhesiveness even under severe conditions as compared with Comparative Examples 1 to 5.

[Experimental Examples 1 to 3, 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. The abbreviations in Table 2 are the same as above.

Thereafter, the storage elastic modulus was measured using a dynamic viscoelasticity measuring apparatus while raising the temperature from 20 ° C to 160 ° C at a rate of 3 ° C / min. The results are shown in Fig.

4 shows that the adhesive containing the component (A) and the component (B) does not lower the storage elastic modulus (E ') (unit Pa) even at a high temperature while the adhesive containing no component , It was confirmed that the shape could not be maintained.

11: first base layer, 12: first adhesive layer, 13: first corrosion preventing layer, 14: metal foil, 15: second corrosion preventing layer, 16: second adhesive layer, 17:

Claims (10)

A laminate for battery exterior lamination comprising at least a first base layer, a first adhesive layer and a metal foil in this order,
The first base layer is a layer made of polyolefin,
Wherein the first adhesive layer is a layer having a storage elastic modulus at 150 占 폚 of 1.0 占⁰⁴ or more and 1.0 占⁰⁷ or less in the dynamic viscoelasticity measurement of the first adhesive layer single layer. sieve. The method according to claim 1,
Wherein the first adhesive layer is a layer formed of an adhesive containing 100 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. 3. The method of claim 2,
Wherein the compound (B) containing a plurality of epoxy groups is a phenol novolak type epoxy resin. 4. The method according to any one of claims 1 to 3,
Further comprising a first corrosion inhibiting layer between the first adhesive layer and the metal foil,
Wherein the first corrosion inhibiting layer contains a metal halide compound. 5. The method of claim 4,
Wherein the first corrosion inhibiting layer further contains a water-soluble resin and a chelating agent or a crosslinking compound. 5. The method of claim 4,
Wherein the halogenated metal compound is a chloride of iron, chromium, manganese, zirconium, or a fluoride of iron, chromium, manganese or zirconium. 4. The method according to any one of claims 1 to 3,
Wherein the metal foil is aluminum, stainless steel, copper, nickel or titanium. 4. The method according to any one of claims 1 to 3,
Wherein the metal foil has a thickness of 10 to 40 占 퐉. A battery external body having the laminate for battery exterior use according to any one of claims 1 to 3,
And the first base layer side of the laminate for battery external application is the internal space side. A battery comprising the battery housing of claim 9.

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