KR101941864B1 - Laminate for battery packages, battery package, and battery - Google Patents

Abstract

The present invention provides a laminate for a battery enclosure which has excellent properties and can be produced with high yield and productivity, and which can attain a thin film. A laminate for battery exterior lamination comprising at least a first base layer, a first adhesive layer, a first corrosion inhibiting layer, a stainless steel foil and a second base layer in this order, wherein the first base layer is a layer made of polyolefin, 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 containing a plurality of epoxy groups (B).

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, secondary batteries such as lithium ion batteries and capacitors such as electric double layer capacitors have attracted attention as a storage battery for storing electric energy in conjunction with utilization of natural energy such as sunlight and 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 laminated in this order.

Japanese Laid-Open Patent Publication No. 2012-33393

2. Description of the Related Art [0002] In the field of application of batteries such as secondary batteries, development of compact and large-capacity batteries has been progressing. Similarly, it is required that the laminate for battery external use is made thinner while maintaining excellent properties such as mechanical strength, water resistance and chemical resistance (electrolyte resistance). In general, the mechanical strength, water resistance, chemical resistance (electrolyte resistance) and light shielding property of the battery external laminate are mainly ensured by an inorganic layer such as a metal foil in a battery laminate. As a metal foil, an aluminum foil excellent in workability is widely used (see Patent Document 1).

However, since the aluminum foil is superior in workability to other metal foils, it is possible to produce a laminate with a high yield, while the mechanical strength such as stiffness and the like is lower than that of other metal foils. For this reason, in order to obtain mechanical strength, the thickness of the aluminum foil can not be made to be a certain value or less, and in the current situation where the aluminum foil is used, it is also difficult to make the laminate for battery external use thinner.

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above situation, and an object of the present invention is to provide a battery laminate for thin-film formation and excellent in various characteristics.

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a stainless steel foil is used in place of aluminum foil to adopt a configuration capable of thinning while ensuring mechanical strength such as stab strength. However, when a laminate for external battery use is produced using a stainless steel foil, it has been found that there is a problem of surface defects and electrolyte resistance which are considered to be caused by poor adhesion which can not be seen in conventional aluminum foil. The inventors of the present invention have repeatedly conducted intensive investigations and succeeded in finding out an adhesive capable of favorably bonding a stainless steel foil surface-treated with a corrosion inhibitor to a base layer, thereby completing the present invention.

That is, the present invention adopts the following configuration.

A first aspect of the present invention is a laminate for battery enclosure comprising at least a first base layer, a first adhesive layer, a first corrosion inhibiting layer, a stainless steel foil and a second base layer in this order, Characterized in that the first adhesive layer is a layer made of an adhesive containing 100 parts by mass of the acid-modified polyolefin resin (A) and 1 to 20 parts by mass of a compound containing a plurality of epoxy groups (B) Which is a laminate for battery exterior use.

The compound containing the plurality of epoxy groups is preferably a phenol novolak type epoxy resin.

The epoxy equivalent of the phenol novolak type epoxy resin is preferably 100 to 300.

The phenol novolak type epoxy resin preferably has a bisphenol A structure.

The first corrosion inhibiting layer preferably contains a halogenated metal compound.

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

The first corrosion inhibiting layer preferably contains a resin having a polyvinyl alcohol backbone, a fluorinated metal compound and a phosphoric acid compound.

The thickness of the stainless steel foil is preferably 10 to 30 占 퐉.

The first base layer is preferably homopolypropylene or block polypropylene.

A second aspect of the present invention is a battery outer body having the battery exterior laminate of the first aspect, wherein the battery outer shell has an internal space for housing the battery, and the first base layer side of the battery exterior laminate becomes the internal space side It is a battery external body which is characterized.

A third aspect of the present invention is a battery characterized by comprising the battery casing of the second aspect.

Industrial Applicability 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 yield and productivity. Further, the laminate for battery exterior use of the present invention can be made thin.

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 perspective view showing a process for manufacturing a secondary battery using the laminate for battery exterior according to the present invention.

Hereinafter, the present invention will be described based on preferred embodiments. Hereinafter, the present invention will be described in more detail, but the present invention is not limited unless otherwise specified.

[Battery laminate for battery external use]

(Hereinafter sometimes simply referred to as a " laminate ") of the first embodiment of the present invention comprises at least a first base layer, a first adhesive layer, a first corrosion inhibiting layer, a stainless steel foil, In the order named, a laminate for battery enclosure,

The first base layer is a layer made of polyolefin,

Wherein the first adhesive layer is 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 containing a plurality of epoxy groups (B).

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 laminate 10 according to the present embodiment is a laminate 10 according to the present embodiment in which a first base layer 11, a first adhesive layer 12, a first corrosion inhibiting layer 13, a stainless steel foil 14, 16, a second adhesive layer 17, and a second base layer 15 in this order.

That is, the layered product 10 according to the present embodiment includes the first corrosion preventing layer 13 and the second corrosion preventing layer 16 formed on both surfaces of the stainless steel foil 14, and the first adhesive And a second base layer 15 laminated on the second corrosion preventing layer 16 with a second adhesive layer 17 interposed therebetween, the first base layer 11 being laminated via the layer 12, .

Hereinafter, each layer will be described in detail.

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 "). Of these, block PP is particularly preferable because homo PP or block PP is more preferable and mechanical strength is excellent.

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 30 占 퐉.

The first adhesive layer 12 is a layer made 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 containing a plurality of epoxy groups (B).

As described above, the battery exterior laminate is required to have various properties such as mechanical strength, water resistance, and chemical resistance (electrolyte resistance). A large number of these characteristics are occupied by the metal foil in the laminate for battery external use, and the metallic foil of the battery exterior body plays a very important role in view of the durability of the battery. It has been a common practice to use a metal foil subjected to anti-corrosive treatment so that the metal foil is not deteriorated by rust or the like during use of the battery.

As to aluminum foil which has been conventionally used, the constitution of a corrosion inhibiting treatment agent (corrosion inhibiting layer) having a good corrosion prevention effect is widely known.

On the other hand, in the present invention, a stainless steel foil is employed for the purpose of achieving both thinning and mechanical strength (stiction strength, etc.). Although it is known that stainless steel is difficult to rust in metal, it is preferable that the stainless steel foil of the battery laminate for use in an extreme situation, such as being able to contact an electrolytic solution, is rust-inhibited as in the conventional case. The anti-corrosive agent capable of imparting a satisfactory anti-corrosive effect to the stainless steel foil and the anti-corrosive agent for the conventional aluminum foil may have different compositions.

However, as a result of forming the first corrosion inhibiting layer made of such a rust-inhibiting agent for stainless steel foil on the surface of the stainless steel foil, the conventional anticorrosion layer surface and the surface of the first base layer can not be satisfactorily adhered to each other, Which can cause surface defects.

The inventors of the present invention conducted further investigations and found that 100 parts by mass of the acid-modified polyolefin resin (A) and 100 parts by mass of the acid-modified polyolefin resin (A), which are adhesives capable of satisfactorily adhering the rust preventive layer (first corrosion- An adhesive containing 1 to 20 parts by mass of (B) a compound containing a plurality of epoxy groups.

By using the first base layer, the first adhesive layer made of such an adhesive, the first corrosion inhibiting layer, and the stainless steel foil, it is possible to (1) improve the mechanical strength (stiffness and the like) (2) improvement of the anticorrosive effect of the stainless steel foil by the first corrosion inhibiting layer and accordingly durability, (3) improvement of the mechanical strength (peel strength etc.) by the first adhesive layer, and poor adhesion at the time of producing the laminate Reduction in occurrence of surface defects and improvement in yield can be achieved.

·glue

In the present invention, the adhesive forming the first adhesive layer 12 contains 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.

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) is a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof and has an acidic functional group such as a carboxyl group or a carboxylic anhydride group in the polyolefin resin.

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 resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, a random copolymer of propylene and ethylene or an? -Olefin, a block copolymer of propylene and ethylene or an? . Among them, homopolypropylene (propylene homopolymer; hereinafter sometimes referred to as "homo PP"), a block copolymer of propylene-ethylene (hereinafter also referred to as "block PP"), a random copolymer of propylene and ethylene (Hereinafter sometimes referred to as " random PP "), and random PP is particularly preferable.

Examples of the olefins in the case of copolymerization include olefin-based monomers such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, and -olefin.

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 (monomer containing a carboxyl group) include monomers 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 acid anhydride group-containing monomer) having a carboxylic 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 acidic functional group-containing monomer is preferably an acidic functional group-containing monomer having an acid anhydride group in view of high reactivity with the component (B) described later, more preferably a carboxylic acid anhydride group-containing monomer, desirable.

In the case where a part of the acidic functional group-containing monomer used for acid modification is unreacted, the unreacted acidic functional group-containing monomer is removed in advance to prevent the lowering of the adhesive force by the unreacted acidic functional group- As shown in Fig.

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.

For example, in the case where the adhesive used in the present invention contains no organic solvent and the adhesive is formed by melt kneading the component (A) and the component (B) described later, the melting point of the component (A) 180 < / RTI > The adhesive layer 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 below by using 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.

On the other hand, 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 50 to 100 ° C. It is possible to form a layer made of an adhesive containing a polyolefin having a relatively low melting point at a melting point of 50 to 100 DEG C so that the adhesive strength of the first adhesive layer is improved at a relatively low temperature at which distortion does not occur, The stainless steel foil having the first corrosion inhibiting layer and the first base layer can be bonded to each other through the adhesive layer.

Among them, as the component (A), a maleic anhydride-modified polypropylene is preferable from the viewpoint of adhesiveness and a suitable melting point.

(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. (B) is preferably a polymer compound (resin) from the viewpoint of improving the miscibility with the component (A). On the other hand, it is also preferable that the component (B) is a low molecular weight compound from the viewpoint of improving solubility in a 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 from 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 phenolic 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 novolak structure as a basic skeleton and having a bisphenol A structure in combination. Here, the bisphenol A structure in the phenol novolak-type epoxy resin may be a structure derived from bisphenol A, and both terminal hydroxyl groups of bisphenol A may be substituted with groups such as epoxy group-containing groups.

As an example of the bisphenol A novolak type epoxy resin, a resin represented by the following formula (1) can be mentioned.

[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 the resin represented by the formula (1) satisfies at least any one of the following (i) to (iii).

(i) both R ¹ and R ² are methyl groups, (ii) both R ³ and R ⁴ are methyl groups, and (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 them, a glycidyl group is preferable.

The epoxy equivalent of the bisphenol A novolak type epoxy resin is preferably 100 to 300, more preferably 200 to 300. The epoxy equivalent (g / eq) is the molecular weight of the epoxy resin per epoxy group, and the smaller the value, the more epoxy groups in the resin. By using a phenol novolak type epoxy resin having a relatively small epoxy equivalent, even when the amount of the phenol novolak type epoxy resin added is relatively small, the adhesion between the phenol novolak type epoxy resin and the adherend becomes good, The phenol novolak type epoxy resin and the component (A) sufficiently crosslink.

Examples of such bisphenol A 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 of the acidic functional group of the component (A) and the epoxy group of the component (B) function as an adhesive functional group to an adherend (in particular, a functional group such as a hydroxyl group contained in the adherend) It is considered that it is possible to exert excellent adhesion to the layer 11 and the first corrosion inhibiting layer 13.

A part of the acid 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), and the strength of the resin is reinforced by the crosslinked structure And it is considered that excellent durability is obtained together with excellent adhesion.

In the adhesive used in the present invention, the component (B) is contained in an amount of 1 to 20 parts by mass based on 100 parts by mass of the component (A). More preferably, the amount of the component (B) is 5 to 10 parts by mass, and most preferably the amount of the component (B) is 5 to 7 parts by mass based on 100 parts by mass of the component (A) to be.

The adhesive used in the present invention may suitably contain miscible additives, an additional resin, a plasticizer, a stabilizer, a colorant, and the like depending on the purpose.

Further, the adhesive of the present invention may or may not further contain an organic solvent.

When an organic solvent is contained and made into a liquid adhesive, for example, a preferable adhesive for dry laminates can be used. The adhesive layer can be formed by applying and drying such a liquid adhesive on a layer to be a lower layer.

On the other hand, when an organic solvent is not contained, an adhesive layer preferable for thermal lamination can be formed by melting and kneading an acid-modified polyolefin resin and an epoxy resin, followed by extrusion molding or the like.

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 above-mentioned resin preferably, and for example, toluene and the like can be used. The amount of the organic solvent to be used is not particularly limited, but the solid content is preferably 3 to 30 mass%, more preferably 5 to 25 mass%, and further preferably 10 to 20 mass%.

The thickness of the first adhesive layer 12 may be, for example, 0.5 to 10 占 퐉. By setting the thickness to be within this range, the first base layer 11 and the stainless steel foil 14 can be bonded with a high adhesive force, and delamination between layers can be prevented.

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

The first corrosion inhibiting 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 stainless steel foil 14. By forming the first corrosion preventive layer 13, it is possible to impart a rust prevention effect to the stainless steel foil.

Among them, it is preferable that the first corrosion inhibiting layer 13 further contains a water-soluble resin, and it is preferable that the first corrosion inhibiting layer 13 is formed by applying a water-soluble resin, a halogenated metal compound and a water-soluble paint containing a chelating agent, desirable.

· Water-soluble paints

(Water-soluble resin)

As the water-soluble resin, it is preferable to use at least one of a polyvinyl alcohol-based resin and a polyvinyl ether-based resin.

The polyvinyl alcohol-based resin is at least one water-soluble resin selected from a polyvinyl alcohol resin and a modified polyvinyl alcohol resin.

The polyvinyl alcohol-based resin can be produced, for example, by saponifying a polymer of a vinyl ester-based 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, vinyl fatty acid esters such as vinyl butyrate, and aromatic vinyl esters such as vinyl benzoate, And copolymers of other 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, vinyl halides such as vinyl chloride and vinylidene chloride, and unsaturated sulfonic acids.

The degree of saponification of the polyvinyl alcohol-based resin is preferably 90 to 100 mol%, more preferably 95 mol% or more.

Examples of the polyvinyl alcohol-based resin include an alkyl ether-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, Modified polyvinyl alcohol resins, silicone-modified polyvinyl alcohol resins, and ethylene-modified polyvinyl alcohol resins. Among these, an alkyl ether-modified polyvinyl alcohol resin, a carbonyl-modified polyvinyl alcohol resin, a carboxyl-modified polyvinyl alcohol resin and an acetoacetyl-modified polyvinyl alcohol resin are preferable.

Commercially available polyvinyl alcohol resins generally available include, for example, J-POVARU DF-20 (trade name), manufactured by Nippon Sake Bee Povalu Co., Ltd., crossmers manufactured by Nippon Kayaku Co., H series (trade name). The polyvinyl alcohol-based resin may be used alone or as a mixture of two or more thereof.

Examples of the polyvinyl ether-based resin include ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, , 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 . Examples of other monomers copolymerizable with the vinyl ether-based monomer include the same 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 one of a polyvinyl alcohol-based resin and a polyvinyl ether-based resin may be used, or both of them may be used in combination.

(Metal halide compound)

The halogenated metal compound preferably has water solubility in that it needs to be mixed with the above-mentioned water-soluble resin.

The halogenated metal compound includes, for example, chromium halide, iron halide, zirconium halide, titanium halide, hafnium halide, titanium hydrohalide acid and salts thereof. Examples of the halogen atom include chlorine, bromine and fluorine, preferably chlorine or fluorine. Particularly preferably, it is fluorine.

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

The metal halide compound has an effect of improving the chemical resistance such as electrolyte resistance. That is, the surface of the stainless steel foil 14 is made passivated, and the corrosion resistance against the electrolytic solution can be enhanced. The halogenated metal compound also has a function of crosslinking the water-soluble resin.

(Chelating agent)

Water-soluble paints contain chelating agents. 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, The first corrosion inhibiting layer 13 is not brittle and cracks and peeling do not occur even when the thickness is more than 0.2 탆 and not more than 1.0 탆. Therefore, the adhesive strength between the stainless steel foil 14 and the first adhesive layer 12 and the bonding strength between the stainless steel foil 14 and the layer on the upper layer can be increased.

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), hydroxyethyl ethylenediamine triacetic acid (HEDTA) (DTPA), triethylenetetramine acetic acid (TTHA), transcyclohexanediaminesacetic acid (CyDTA), 1,2-propanediamine succinate (1,2-PDTA), 1,3-propanediamine (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 ), L-aspartic acid-N, N-diacid (ASDA), L-glutamic acid-N, N-diacetic acid (GLDA), N, N'- - Isochol acid (HBEDDA).

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-trimethylenesphosphonic acid (NTMP), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), ethylenediamine-N, N, N ' , 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) phosphate-based 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-based chelating agent and a (poly) phosphoric acid based cheating agent is preferable, and a phosphonic acid-based chelating agent is more preferable.

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 solid content of the water-soluble paint. The content of the halogenated metal compound in the total solids of the water-soluble paint is preferably from 20 to 60 mass%, more preferably from 30 to 55 mass%, and even more preferably from 40 to 50 mass%. Of the total solids content of the water-soluble paint, the amount of the chelating agent is preferably from 20 to 60 mass%, more preferably from 30 to 50 mass%, still more preferably from 35 to 45 mass%.

The water-soluble paint can be produced by dissolving a water-soluble resin, a metal halide compound, and a chelating agent in a solvent containing water. The solvent is preferably water.

The solid content concentration in the water-soluble paint can be suitably determined in consideration of the coatability and the like of the first corrosion inhibiting layer 13, but may be generally from 0.1 to 10% by 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 preventive layer 13 is 0.05 占 퐉 or more so that sufficient corrosion resistance is imparted to the battery laminate 10 and the adhesive strength between the stainless steel foil 14 and the first adhesive layer 12, And the bonding strength between the stainless steel foil 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 preventive layer 13 to 1.0 m or less, the adhesive strength between the stainless steel foil 14 and the first adhesive layer 12 can be increased and the material cost can be suppressed.

The stainless steel foil 14 is a metal foil made of stainless steel, for example, made of stainless steel such as austenitic, ferritic, martensitic or the like. Examples of the austenite system include SUS304, 316, and 301, ferritic stainless steel such as SUS430, and martensitic stainless steel such as SUS410.

Compared to other metal foils such as aluminum foil, the stainless steel foil 14 has high mechanical strength such as stabbing strength and tensile strength. Therefore, even when the stainless steel foil 14 is used at a thickness of 40 占 퐉 or less, . As a result, the entire stainless steel foil 14 and the laminated body 10 can be thinned.

In addition, since the mechanical strength is high, it is possible to reduce the occurrence of pinholes when the concave portion is formed by drawing-forming, and consequently to reduce leakage of the sealed contents (for example, liquid leakage of the battery) It becomes possible. Further, since the stainless steel foil 14 is excellent in corrosion resistance as compared with other metal foils, deterioration due to corrosion can be well prevented.

The thickness of the stainless steel 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. Further, by making the thickness of the stainless steel foil 14 equal to or smaller than the upper limit value, the laminate body 10 for battery exterior can be made sufficiently thin and sufficient drawability can be imparted.

The second corrosion preventing layer 16 has the same structure as the first corrosion preventing layer 13.

The second adhesive layer 17 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, an epoxy adhesive, or the like. The thickness of the second adhesive layer 17 may be, for example, 0.5 to 10 mu m. By setting the thickness to be within this range, the second base layer 15 and the stainless steel foil 14 can be bonded with a high adhesive force, and interlayer delamination can be prevented.

The second base layer 15 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 15 may be, for example, 1 to 50 탆, preferably 1 to 30 탆, more preferably 3 to 11 탆.

The second base layer 15 may have a single-layer structure or a multi-layer structure. Examples of the second base layer 15 having a multilayer structure include a two-layer film in which a polyethylene terephthalate (PET) resin film is laminated on a biaxially stretched polyamide resin film (ONy). Here, the second base layer 15 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 15 is the outermost layer. Therefore, the second base layer may contain a coloring agent such as a pigment in addition to the resin, so that the second base layer may have a desired color or design.

The second base layer 15 is preferably made of a single-layer or multilayer film using a heat-resistant resin film having a melting point of 200 ° C or higher. Examples of such a heat-resistant resin film include a PET film, a PEN film, a PBT film, a nylon film, a PEEK film, a PPS film, and the like. 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.

The first corrosion preventing layer 13 and the second corrosion preventing layer 16 are formed on both sides of the stainless steel foil 14 in the battery laminate 10 shown in Fig. 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 outer body. Therefore, the corrosion inhibiting layer may be formed at least on the side of the first base layer 11 of the stainless steel foil 14. That is, the second corrosion preventive layer 16 may be omitted from the battery laminate 10 of Fig.

In the battery laminate 10 shown in Fig. 1, the second base layer 15 is the outermost layer, but a coating layer may be further formed on the outer surface side of the second base layer 15.

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 탆, preferably 2 to 10 탆.

The second base layer 15 and the second adhesive layer 17 are in direct contact with each other in the battery laminate 10 shown in Fig. 1, but the inner surface side of the second base layer 15 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 500 mu m, more preferably 20 to 200 mu m, and further preferably 30 to 100 mu m.

Examples of the battery in which the laminate body 10 for external use of a battery is used include a secondary battery such as a lithium ion battery as a secondary battery or a capacitor such as an electric double layer capacitor or the like using an organic electrolyte. 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 exterior laminate of the present invention can be produced by, for example, a process of forming a first corrosion inhibiting layer on one side of a stainless steel foil, a step of forming a first adhesive layer on the formed first corrosion inhibiting layer, And a step of disposing the first adhesive layer in contact with the first adhesive layer and laminating the laminate.

This will be described in detail below.

First, the first corrosion preventive layer 13 is formed on one side of the stainless steel foil 14.

Specifically, the water-soluble paint as described above is coated on the surface of the stainless steel foil 14, followed by heating and drying. Only the first corrosion preventive layer 13 may be formed by applying a water-soluble paint to only one side of the stainless steel foil 14 or the water-soluble paint may be applied to both surfaces of the stainless steel foil 14, May be simultaneously formed. When the second corrosion preventing layer 16 is formed, the second corrosion preventing layer 16 is preferably formed at a stage before the first adhesive layer 12 is formed, and the first corrosion preventing layer 13, It is more preferable to be formed at the same time.

When the first corrosion preventing layer 13 and the second corrosion preventing layer 16 are simultaneously formed, the stainless steel foil 14 is immersed in a water-soluble paint to adhere the water-soluble paint to both surfaces of the stainless steel foil 14, It is also preferable to 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 stainless steel 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, the volatile component capable of reacting with the epoxy group such as water is removed beforehand from the apparatus, and when volatile components are generated during the reaction, Do. 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 resin composition 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 is 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, the film is placed on the first adhesive layer, and then dry lamination is performed. The temperature of the dry laminate is not particularly limited as long as the temperature at which the first base layer 11 and the first corrosion preventive layer 13 and the stainless steel foil 14 are favorably bonded via the first adhesive layer, Can be determined in consideration of the material and the melting point of the adhesive constituting the adhesive layer 12. The temperature at the time of dry lamination 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 stainless steel foil 14 are bonded via the first adhesive layer 12, It becomes possible to adopt the same dry laminate. Further, by employing a dry laminate in place of a thermal laminate requiring heating at a temperature higher than 200 DEG C during lamination, the temperature at the time of lamination can be significantly lowered.

Generally, when high heat is added to a stainless steel foil which is difficult to expand due to its low thermal conductivity, warpage (curling) in the width direction of the stainless steel foil is apt to occur. When such a stainless steel 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 is not in contact with the roll, Folding or wrinkling may occur at the time of thermocompression bonding. When the stainless steel foil is heated to a high temperature at which distortion does not occur, the productivity may be lowered due to a reduction in the processing speed or an increase in the required amount of heat.

When the dry laminate is employed in the production of the cell exterior laminate of this embodiment, it is possible to suppress the occurrence of folding and wrinkles, and to produce a preferable laminate for battery exterior lamination.

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 for forming the second corrosion preventing layer 16, the second adhesive layer 17 and the second base layer 15 is not particularly limited. For example, a second adhesive layer ( 17 are formed so as 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 preventing layer 13, the stainless steel foil 14 and the second corrosion preventing layer 16 And the second adhesive layer 17 and the second corrosion preventing layer 16 are brought into contact with each other so as to be in contact with each other, so that the laminate for battery enclosure 10 composed of 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 preventive layer 16 may not be formed but may have a six-layer structure.

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 15 that does not contact the second adhesive layer 17 , 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, this is obtained by molding the battery enclosure laminate of the first aspect into a desired shape so that the first base layer is in contact with the inner space, and sealing the end portion as necessary.

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 an organic electrolyte, for example, a capacitor such as an electric double layer capacitor.

As an example, a perspective view of the secondary battery 40 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.

Next, as shown in Fig. 3 (b), the lid portion 33 formed of the laminate body 10 for a battery exterior body is overlaid on the container body 30, and the flange portion 32 of the container body 30, The secondary battery 40 shown in Fig. 2 is obtained by heat-sealing the peripheral portion 34 of the secondary battery 33 as 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.

The battery of the present invention can also be manufactured as follows.

First, as shown in Fig. 4 (a), a portion of one end in the longitudinal direction of the rectangular battery outer layer 50 is pressed from the first base layer side of the battery outer layer 50 by drawing or the like, To obtain a formed body 55 having the concave portion 51. The depth of the concave portion 51 can be, for example, 2 mm or more.

Next, a lithium ion battery (lithium ion battery 27 in FIG. 2) is housed in the concave portion 51 of the molded body 55, although the illustration is omitted.

Next, in a part of the other end side where the concave portion 51 of the formed body 55 is not formed, the folded body is bent toward the first base layer side so as to form a folding line L extending in the width direction of the formed body 55 . Here, in the molded body 55, the region on the concave portion 51 side with respect to the folding line L is referred to as a " first region 551 ", a region on the opposite side to the concave portion 51 with respect to the folding line L, Quot; second area 552 ".

The first base layer of the periphery 52 of the concave portion 51 in the first region 551 and the first base layer in the second region 552 overlapping the periphery 52 54). As a result, the second region 552 overlaps the concave portion 51 of the first region 551.

Next, as shown in Fig. 4 (b), the first base layer around the concave portion 51 and the first base layer of the second region 552 are heat-sealed to form a battery case made of one member The secondary battery 60 is obtained. That is, in the battery shown in Fig. 4 (b), the upper surface of the concave portion 51 is covered with the second region 552, so that the inner space accommodating the battery by the concave portion 51 and the second region 552 .

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, Comparative Examples 1 to 5]

(Examples 1 to 5)

First, a stainless steel foil having a thickness of 20 占 퐉 was prepared. A water-soluble paint (coating amount: 12 g / m 2) was applied to both surfaces of the stainless steel foil and heated and dried in an oven at 200 ° C to form a first corrosion preventing layer and a second corrosion preventing layer having thicknesses shown in Table 1, respectively.

The water-soluble paint contains 0.2% by mass of a polyvinyl alcohol skeleton-containing amorphous polymer having hydroxyl groups, 0.8% by mass of FeCl ₂ .4H ₂ O, nitrilotris (methylenephosphonic acid) (trade name: Keyrest PH-320, (Manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in water.

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. 100 parts by mass of a maleic anhydride-modified polypropylene (melting point 15 ° C) and 7 parts by mass of a novolak type epoxy resin (trade name: jER157S70, viscosity = 80, epoxy equivalent = 210) By mass for 10 minutes at room temperature.

The first adhesive layer in the laminate including the stainless steel foil and the first base layer made of the polypropylene resin film having a thickness of 6 占 퐉 were laminated by dry lamination at 120 占 폚.

Further, a urethane adhesive (subject: TM-K55 (trade name, manufactured by TOYOTO MOTON CO., LTD.) And a curing agent: CAT-10L (trade name) were laminated on a second base layer made of a stretched polyethylene terephthalate (Trade name, manufactured by Toyo Moton Co., Ltd.)) was formed 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.

The surface defects of the obtained battery exterior laminate were visually observed and evaluated under the following evaluation conditions. The results are shown in Table 1 as " surface defects ".

A: No defect in the surface was observed per 1 m < 2 >.

B: 1 to 5 defects in the surface were observed per 1 m 2.

C: 6 to 10 defects in the surface were observed per 1 m < 2 >

D: More than 11 defects in the surface were observed per 1 m < 2 >.

3 g of an electrolytic solution (a solution of ethylene carbonate: diethyl carbonate: dimethyl carbonate = 1: 1: 1 vol% in which 1 mol / liter of LiPF ₆ was added) 30 mm x 50 mm, heat seal width 7 mm). The three bags were sealed in a thermostatic chamber at 85 DEG C for 2,000 hours.

After the lapse of 2000 hours, the three-chamber sealed bag was opened, and the presence or absence of peeling of the inner layer from the metal foil was visually observed, and the evaluation was carried out according to the following evaluation criteria. The results are shown in Table 1 as " electrolyte resistance. &Quot;

A: No peeling was observed

B: A slight exfoliation was observed, but within acceptable limits

C: Peeling was observed

D: Peeled across the entire surface

The test piece after immersing the electrolyte solution was immersed in pure water for 10 hours, taken out from the pure water, and visually observed by visual observation. The results of evaluation by the following evaluation criteria are shown in Table 1 as " after immersion in water ".

A: No peeling was observed

B: A slight exfoliation was observed, but within acceptable limits

C: Peeling was observed

D: Peeled across the entire surface

The battery external laminate was cut into a size of 200 mm x 100 mm to obtain a test piece. This test piece was set in a device for cold forming of a size of 100 mm x 50 mm, and embossing was carried out under the condition of a drawing depth of 6 mm. Observation was made with naked eyes or an optical microscope with regard to breakage and occurrence of pinholes in the molded elongate portion. The same test was carried out ten times, and the results were evaluated in accordance with the following evaluation criteria are shown in Table 1 as " moldability ".

A: No breakage occurred in the molded extension portion, and pinholes were not generated.

B: A slight rupture occurred within the allowable range in the stretch forming part, or a sample in which pinholes occurred was 1 to 3 samples out of 10 samples.

C: A small fracture occurred in the molding extrusion or a sample in which pinholes occurred was 1 to 5 samples out of 10 samples.

D: A large breakage occurred in the molding extrusion, or a sample in which pinholes occurred was 6 or more out of 10 samples.

(Examples 6 to 10)

A laminate for battery exterior lamination was manufactured in the same manner as in Example 3 except that the adhesive shown in Table 1 was used as the first adhesive for forming the first adhesive layer, and the same evaluations as in Example 1 were carried out. The results are shown in Table 1.

(Example 11)

A laminate for battery exterior lamination was produced in the same manner as in Example 3 except that the first adhesive layer and the first base layer were changed to dry laminate at 120 ° C at 200 ° C and evaluated in the same manner as in Example 1 . The results are shown in Table 1.

(Example 12)

A laminate for battery exterior lamination was produced in the same manner as in Example 3 except that the first base layer was changed from the block PP film to the random PP film, and the same evaluations as in Example 1 were carried out. The results are shown in Table 1.

(Examples 13 to 14)

A laminate for battery exterior lamination was produced in the same manner as in Example 3 except that a stainless steel foil having a thickness of 20 占 퐉 was changed to a stainless steel foil having a thickness shown in Table 1 and evaluated in the same manner as in Example 1. [ The results are shown in Table 1.

(Example 15)

A laminate for battery exterior lamination was produced in the same manner as in Example 1 except that the first and second corrosion inhibiting layers were formed by chromium fluoride plating to obtain first and second corrosion preventing layers each having a thickness of 250 탆, The same evaluation was made. The results are shown in Table 1.

(Comparative Example 1)

As the metal foil, an aluminum foil having a thickness of 20 mu m was used in place of the stainless steel foil, and an adhesive having only a maleic anhydride-modified polypropylene (melting point 80 DEG C) as the first adhesive agent and not having a phenol novolac- A battery laminate for battery exterior was manufactured in the same manner as in Example 11 except that the same evaluation as in Example 1 was made. The results are shown in Table 1.

(Comparative Example 2)

As the metal foil, an aluminum foil having a thickness of 20 탆 was used in place of the stainless steel foil, and 0.8% by mass of CrF ₃ 쨌 3H ₂ O was used instead of FeCl ₂揃 4H ₂ O of 0.8% by mass of the first and second corrosion- A battery laminate for battery exterior was manufactured in the same manner as in Example 3 except that it was used and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)

A laminate for battery exterior lamination was produced in the same manner as in Example 3 except that an adhesive having only a maleic anhydride-modified polypropylene (melting point 80 ° C) and no phenol novolak type epoxy resin was used as the first adhesive, . The results are shown in Table 1.

(Comparative Example 4)

A laminate for battery exterior lamination was manufactured in the same manner as in Example 1 except that the first corrosion preventing layer and the second corrosion preventing layer were not formed, and the same evaluations as in Example 1 were carried out. The results are shown in Table 1.

(Comparative Example 5)

A laminate for battery exterior lamination was manufactured in the same manner as in Example 3 except that the adhesive shown in Table 1 was used as the first adhesive for forming the first adhesive layer, and the same evaluations as in Example 1 were carried out. The results are shown in Table 1.

In Table 1, the respective weak symbols have the following meanings.

(bPP): block polypropylene

(rPP): random polypropylene

(Ad-NV1): 100 parts by mass of maleic anhydride-modified polypropylene (melting point 80 占 폚) and 5 parts by mass of solid content 15% by mass of novolac epoxy resin (trade name: jER154, epoxy equivalent = 178) Of toluene solution adhesive

(Ad-NV2): 100 parts by mass of a maleic anhydride-modified polypropylene (melting point 80 占 폚), and 2 parts by mass of a novolak epoxy resin jER154 in toluene solution with a solid content of 15%

(Ad-NV3): 100 parts by mass of maleic anhydride-modified polypropylene (melting point 80 占 폚), and 7 parts by mass of novolak epoxy resin jER154 in toluene solution with a solid content of 15%

(Ad-NV4): 100 parts by mass of maleic anhydride-modified polypropylene (melting point 80 占 폚) and 10 parts by mass of a novolak epoxy resin jER154 in toluene solution with a solid content of 15%

(Ad-NV5): 100 parts by mass of maleic anhydride-modified polypropylene (melting point 80 占 폚) and 15% by mass of novolak epoxy resin jER154 in toluene solution with a solid content of 15%

(Ad-NV6): 100 parts by mass of a maleic anhydride-modified polypropylene (melting point: 140 ° C) and 5 parts by mass of an novolac epoxy resin jER154

(Ad-BPNV): 100 parts by mass of maleic anhydride-modified polypropylene (melting point 80 占 폚) and 100 parts by mass of a phenol novolak type epoxy resin having a bisphenol A structure (trade name: jER157S70, viscosity = 80; 210) having a solid content of 15% and having 5 parts by mass of a toluene solution adhesive

(Ad-PN): 100 parts by mass of a maleic anhydride-modified polypropylene (melting point 80 ° C) and 5 parts by mass of a phenoxy resin (trade name: Epikote 1001, epoxy equivalent: 450) % Toluene solution adhesive

(Ad-PP): Adhesive having 100 parts by mass of maleic anhydride-modified polypropylene (melting point: 140 ° C)

(SUS): Stainless steel obsession

(AL): Aluminum foil

As is apparent from the results shown in Table 1, the battery laminate for Examples 1 to 15 suppressed the generation of surface defects, reduced peeling even when contacted with an electrolytic solution or water, and had good moldability. (Formability, moldability, mechanical strength, chemical resistance and water resistance) as compared with the battery laminate of Comparative Examples 1 to 5.

[Examples 16 to 24]

In Example 3, the use of 0.8% by mass of the metal halide shown in Table 2 instead of 0.8% by mass of FeCl ₂ .4H ₂ O in the first corrosion preventing layer and the second corrosion preventing layer . The evaluation method and evaluation criteria are the same as in Example 1 and the like. The results are shown in Table 2.

From the results shown in Table 2, it was confirmed that the effects of the present invention were obtained even when various compounds were used as metal halide compounds.

Claims (11)

A laminate for battery exterior lamination comprising at least a first base layer, a first adhesive layer, a first corrosion inhibiting layer, a stainless steel foil and a second base layer in this order,
The first base layer is a layer made of polyolefin,
Wherein the first adhesive layer is composed of an adhesive containing 100 parts by mass of the acid-modified polyolefin resin (A) and 2 to 7 parts by mass of the compound (B) containing a plurality of epoxy groups,
Wherein the compound containing the plurality of epoxy groups is a phenol novolak type epoxy resin having an epoxy equivalent of 100 to 300. delete delete The method according to claim 1,
Wherein the phenol novolak type epoxy resin has a bisphenol A structure. The method according to claim 1,
Wherein the first corrosion inhibiting layer contains a halogenated metal compound. 6. The method of claim 5,
Wherein the metal halide compound is a chloride or fluoride of iron, chromium, manganese or zirconium. 6. The method of claim 5,
Wherein the first corrosion inhibiting layer contains a resin having a polyvinyl alcohol skeleton, a metal fluoride compound, and a phosphoric acid compound. The method according to claim 1,
Wherein the stainless steel foil has a thickness of 10 to 30 占 퐉. The method according to claim 1,
Wherein the first base layer is homopolypropylene or block polypropylene. A battery external body comprising the laminate for battery external application of claim 1,
And the first base layer side of the laminate for battery external application is the internal space side. A battery comprising the battery casing according to claim 10.

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