JP2020169250A - Adhesive, laminate, battery packaging material, and battery - Google Patents

Abstract

To provide an adhesive excellent in adhesiveness between a nonpolar substrate such as an olefin resin and a metal substrate and heat resistance, and to provide a laminate and a battery packaging material excellent in heat resistance obtained by using the adhesive.SOLUTION: The adhesive contains a first agent and a second agent. The first agent contains a resin (A) containing an acid group-containing resin (A1). The second agent contains an epoxy compound (B1) having a viscosity at 52°C of 0.05 Pa s or more and 25 Pa s or less. The adhesive further contains an organophosphorus compound (C) and an imidazole compound (D). The blending amount of the organophosphorus compound (C) is 0.01 pt.mass or more and 5 pts.mass or less based on 100 pts.mass of the resin (A). The blending amount of the imidazole compound (D) is 0.06 pt.mass or more and 0.35 pt.mass or less based on 100 pts.mass of the resin (A).SELECTED DRAWING: None

Description

The present invention relates to an adhesive, specifically an adhesive suitable for adhering a resin base material and a metal base material, a laminate obtained by using the adhesive, an exterior material for a secondary battery, and a battery.

A secondary battery represented by a lithium ion battery has a configuration in which a positive electrode, a negative electrode, and an electrolytic solution or the like are sealed between them. Further, as an encapsulation bag for encapsulating lead wires for extracting electricity from the positive electrode and the negative electrode to the outside, a heat seal layer made of an olefin resin, a metal base material made of a metal foil such as an aluminum foil, or a metal vapor deposition layer, and plastic. It is known to use a laminated body obtained by laminating the above (Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 09-283101 Japanese Unexamined Patent Publication No. 2007-294381

When the heat seal layer made of an olefin resin and the metal base material are bonded to each other via an adhesive, a so-called aging step is generally provided in which the curing of the adhesive is promoted while heating. The aging temperature and aging time in the aging step may be appropriately selected, but as an example, it is preferably performed at 80 ° C. or lower, which has a small effect of heat shrinkage of the olefin resin. On the other hand, the lower the aging temperature and the shorter the aging time, the more difficult it is for the adhesive to exhibit its characteristics.

The present invention has been made in view of such a situation, and an adhesive having excellent adhesiveness between a non-polar base material such as an olefin resin and a metal base material even when aged at a low temperature. The purpose is to provide. Further, it is an object of the present invention to provide a laminate obtained by using such an adhesive, a secondary battery exterior material and a battery obtained by using the laminate.

The present invention comprises an epoxy compound containing a first agent and a second agent, the first agent containing an acid group-containing resin, and the second agent having a viscosity of 0.05 Pa · s or more and 25 Pa · s or less at 52 ° C. It further contains an organic phosphorus compound and an imidazole compound, and the amount of the organic phosphorus compound compounded is 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin, and the compounding amount of the imidazole compound is the resin. The present invention relates to an adhesive having a mass of 0.06 parts by mass or more and 0.35 parts by mass or less with respect to 100 parts by mass.

The adhesive of the present invention is excellent in adhesiveness and electrolytic solution resistance between a non-polar substrate such as an olefin resin and a metal substrate even when aged at a low temperature. Further, the laminate of the present invention is excellent in adhesiveness and electrolytic solution resistance.

<Adhesive>
The adhesive of the present invention contains a resin containing an acid group-containing resin (A1), a first agent containing an organic phosphorus compound, and an imidazole compound, and has a viscosity at 52 ° C. of 0.05 Pa · s or more and 25 Pa · s or less. Includes a second agent containing the epoxy compound of. Hereinafter, each component of the adhesive of the present invention will be described in detail.

(1st agent)
The first agent contains an acid group-containing resin (A1) as the resin (A). Examples of the acid group contained in the acid group-containing resin (A1) include a carboxyl group, an anhydrous carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. The acid group-containing resin may include only one of these, or may include two or more of them. The resin skeleton of the acid group-containing resin (A1) is not particularly limited, but acrylic resin, urethane resin, olefin resin and the like can be preferably used.

The acid group-containing acrylic resin contains, for example, a monomer having a (meth) acryloyl group and a polymerizable monomer having an acid group as essential components, and polymerizes with other polymerizable unsaturated monomers as necessary. Examples thereof include the copolymer thus obtained. The monomer having a (meth) acryloyl group may also serve as a polymerizable monomer having an acid group. In this case, the acid group-containing acrylic resin is a polymerizable single amount having a (meth) acryloyl group and an acid group. It may be a homopolymer of the body. In the present specification, "(meth) acryloyl group" means one or both of acryloyl group and methacrylic acid group, and "(meth) acrylic acid" means one or both of acrylic acid and methacrylic acid. "Meta) acrylate" refers to one or both of acrylate and methacrylate.

The polymerizable monomer having an acid group includes (meth) acrylic acid; β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethylhexahydro. Compounds with (meth) acryloyl and carboxyl groups, such as phthalic acid and modified lactones thereof;
2- (Meta) acryloyloxyethyl acid phosphate, bis (2- (meth) acryloyloxyethyl) acid phosphate, polyethylene glycol mono (meth) acrylate phosphate, polypropylene glycol mono (meth) acrylate phosphate, poly (Meta) acryloyl such as phosphate ester of alkylene glycol mono (meth) acrylate, methylene (meth) acrylate, trimethylene (meth) acrylate, propylene (meth) acrylate, tetramethylene (meth) acrylate, etc. Compounds with groups and phosphate groups;
2-Sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid or salts thereof, etc. Compound having (meth) acryloyl group and sulfonic acid group;
Examples thereof include crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, and itaconic acid. These may be used alone or in combination of two or more.

Examples of the monomer having a (meth) acryloyl group include, for example.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) Acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate, etc. (Meta) acrylate having an alkyl group having 1 to 22 carbon atoms;

(Meta) acrylates having a cycloalkyl group, such as cyclohexyl (meth) acrylates, isobornyl (meth) acrylates, dicyclopentanyl (meth) acrylates, dicyclopentanyloxyethyl (meth) acrylates;

Benoxyyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. (Meta) acrylate with aromatic ring;

Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, A (meth) acrylate having a hydroxyalkyl group, such as polyalkylene glycol;

2,2,2-Trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, Fluoroalkyl (meth) acrylates such as 2H-heptadecafluorodecyl (meth) acrylate and perfluoroethyloxyethyl (meth) acrylate in which the number of carbon atoms of the carbon of the fluoroalkyl group is 1 to 18;
A silyl group-containing (meth) acrylate such as γ-methacryloxypropyltrimethoxysilane;
N, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate;
And so on.

Other polymerizable unsaturated monomers include dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconic acid, dibutyl itaconic acid, methyl ethyl fumarate, and fumarate. Unsaturated dicarboxylic acid esters such as methylbutyl acid acid and methylethyl itaconic acid;

Styrene derivatives such as styrene, α-methylstyrene, chlorostyrene;
Diene compounds such as butadiene, isoprene, piperylene, dimethyl butadiene;
Vinyl halides such as vinyl chloride and vinyl bromide and vinylidene halide;
Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone;
Vinyl esters such as vinyl acetate and vinyl butyrate;

Vinyl ethers such as methyl vinyl ether and butyl vinyl ether;
Vinyl cyanide such as acrylonitrile, methacrylonitrile, vinylidene cyanide;
Acrylamide and its alkyd-substituted amides;
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

Fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluorostyrene, bromotrifluoroethylene, pentafluoropropylene, hexafluoropropylene; trifluoromethyltrifluorovinyl ether, pentafluoroethyltrifluoro Fluorine-containing ethylenically unsaturated monomers such as vinyl ethers, heptafluoropropyltrifluorovinyl ethers, and other perfluoroalkyl perfluorovinyl ethers having a perfluoroalkyl group having 1 to 18 carbon atoms;
And so on. These other polymerizable unsaturated monomers may be used alone or in combination of two or more.

The acid group-containing acrylic resin is obtained by polymerizing (copolymerizing) using a known and commonly used method, and the polymerization (copolymerization) form thereof is not particularly limited. It may be any of a random copolymer, a block copolymer, a graft copolymer and the like. It can be produced by addition polymerization in the presence of a catalyst (polymerization initiator). Known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used.

Examples of the acid group-containing urethane resin include reaction products of a composition containing a compound represented by the following formula (3) and a compound represented by the following formula (4).

（式（３）中、Ｘ_１はアルキル基を介してまたは直接に２以上のイソシアネート基が結合し、さらに置換基を有していてもよい芳香環または脂環構造を表し、ｎ１およびｎ２はそれぞれ独立して０以上３以下の整数を表す。）

(In formula (3), X ₁ represents an aromatic ring or alicyclic structure to which two or more isocyanate groups are bonded via an alkyl group or directly, and may further have a substituent, and n1 and n2 represent an aromatic ring or an alicyclic structure. Each independently represents an integer of 0 or more and 3 or less.)

（式（４）中、Ｒ_７は水素原子または炭素原子数１以上３以下の炭化水素基またはカルボニル基を表し、ｍ１〜ｍ３はそれぞれ独立して０以上３以下の整数を表す。）

(In the formula (4), R ₇ represents a hydrogen atom or a hydrocarbon group or a carbonyl group having 1 or more and 3 or less carbon atoms, and m1 to m3 independently represent an integer of 0 or more and 3 or less.)

The aromatic ring structure of the compound represented by the above formula (3) is preferably an aromatic ring having 6 or more and 18 or less carbon atoms, and examples thereof include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. .. Further, the aromatic ring of the compound represented by the above formula (3) may be substituted with at least one fluorine atom, and examples thereof include a perfluorophenyl group.

The alicyclic structure of the compound represented by the above formula (3) is preferably one having 3 or more and 20 or less carbon atoms, and may be a monocyclic ring, a polycyclic ring, or a condensed ring. It may have a ring structure in which an alicyclic ring and an aromatic ring are combined.
Examples of the monocyclic structure include cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane; cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, etc. Cycloalkene; etc. Examples of the polycyclic structure include cubane, basketane, and housane. Examples of the fused ring structure include bicycloundecane, decahydronaphthalene, norbornene and norbornadiene.

Preferred specific examples of the compound represented by the above formula (3) include m-xylene diisocyanate, p-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate and the like. Can be mentioned.

As the compound represented by the above formula (4), m3 is preferably 0. Further, as the compound represented by the above formula (4), it is preferable that R ₇ is a hydrocarbon group having 1 or more carbon atoms and 3 or less carbon atoms.
Preferred specific examples of the compound represented by the above formula (4) include dimethylolpropionic acid and trimethylolbutanoic acid.

Examples of the acid group-containing olefin resin include homopolymers or copolymers of acid group-containing monomers, copolymers of acid group-containing monomers and olefin-based monomers, and modified acid group-containing monomers of polyolefins.

As the acid group-containing monomer used for preparing the homopolymer or copolymer of the acid group-containing monomer, ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic acid anhydride is preferable. Specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohexe-4-ene-1,2-dicarboxylic acid anhydride, bicyclo [2. 2.2] Oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2- Octa-1,3-diketospiro [4.4] non-7-ene, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, maleopimalic acid, tetrahydrophthalic acid anhydride, Methyl-bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylic acid anhydride, Methyl-norbornene-5-ene-2,3-dicarboxylic acid anhydride, Norborn-5-ene-2, Examples thereof include 3-dicarboxylic acid anhydride.

The acid group-containing monomer used for preparing the copolymer of the acid group-containing monomer and the olefin-based monomer is the same as the above-mentioned homopolymer of the acid group-containing monomer or the acid group-containing monomer used for preparing the copolymer. Can be used. It may be used alone or in combination of two or more. It is preferable to use maleic anhydride.

Examples of the olefin-based monomer used for preparing the copolymer of the acid group-containing monomer and the olefin-based monomer include olefins having 2 to 8 carbon atoms, such as ethylene, propylene, isobutylene, 1-butene, and 4-methyl-. Examples thereof include 1-pentene, hexene and vinylcyclohexane. Among these, olefins having 3 to 8 carbon atoms are preferable, propylene and 1-butene are more preferable, and propylene and 1-butene are particularly used in combination with respect to the solvent because the adhesive strength is particularly good. It is preferable because it has excellent resistance and adhesive strength.

In order to prepare the copolymer of the acid group-containing monomer and the olefin-based monomer, in addition to the acid group-containing monomer and the olefin-based monomer described above, other compounds having an ethylenically unsaturated group such as styrene, butadiene, isoprene and the like are used. It may be used together.

As the acid group-containing monomer used for preparing the modified acid group-containing monomer of polyolefin, the same as the above-mentioned homopolymer of the acid group-containing monomer or the same acid group-containing monomer used for preparing the copolymer should be used. Can be done. It may be used alone or in combination of two or more. It is preferable to use maleic anhydride.

Examples of the polyolefin used for preparing the acid group-containing monomer modified product of polyolefin include homopolymers and copolymers of olefins having 2 to 8 carbon atoms, and copolymers of olefins having 2 to 8 carbon atoms and other monomers. Examples thereof include high-density polyethylene (HDPE), low-density polyethylene (LDPE), and polyethylene such as linear low-density polyethylene resin, polypropylene, polyisobutylene, poly (1-butene), and poly (4-methyl-). 1-pentene), polyvinylcyclohexane, ethylene / propylene block copolymer, ethylene / propylene random copolymer, ethylene / 1-butene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / hexene Copolymers, α-olefin copolymers such as propylene / 1-butene copolymers, ethylene / vinyl acetate copolymers, ethylene / methyl methacrylate copolymers, ethylene / vinyl acetate / methyl methacrylate copolymers, ionomer resins And so on. Among these, a homopolymer of an olefin having 3 to 8 carbon atoms and two or more copolymers of an olefin having 3 to 8 carbon atoms are preferable from the viewpoint of particularly good adhesive strength, and propylene alone. A polymer or a propylene / 1-butene copolymer is more preferable, and a propylene / 1-butene copolymer is particularly preferable because it has excellent resistance to a solvent and excellent adhesive strength.

Examples of the method for modifying polyolefin with an acid group-containing monomer include graft modification and copolymerization. To react an acid group-containing monomer with a polyolefin by graft modification, specifically, a method of melting the polyolefin and adding an acid group-containing monomer (graft monomer) to the polyolefin for a graft reaction, or dissolving the polyolefin in a solvent. A method of making a solution by adding a graft monomer to the graft reaction, mixing the polyolefin dissolved in an organic solvent and the graft monomer, heating at a temperature higher than the softening temperature of the polyolefin or the melting point, and radical polymerization in a molten state. And a method of simultaneously performing the hydrogen abstraction reaction and the like.

In either case, in order to efficiently carry out the graft copolymerization of the graft monomer, it is preferable to carry out the graft reaction in the presence of a radical initiator. The graft reaction is usually carried out under the condition of 60 to 350 ° C. The ratio of the radical initiator used is usually in the range of 0.001 to 1 part by weight with respect to 100 parts by weight of the polyolefin before modification.

The weight average molecular weight of the acid group-containing olefin resin is preferably 40,000 or more in order to improve the adhesiveness. Further, in order to ensure appropriate fluidity, the weight average molecular weight of the acid group-containing olefin resin is preferably 200,000 or less.

In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device; HLC-8320GPC manufactured by Tosoh Corporation
Column; TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

The acid group-containing olefin resin is preferably crystalline. The melting point of the acid group-containing olefin resin is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 65 ° C. or higher. The melting point of the acid group-containing olefin resin is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and even more preferably 90 ° C. or lower.

The melting point of the acid group-containing olefin resin is measured by DSC (Differential Scanning Calorimetry). Specifically, after raising the temperature from the temperature at which the temperature falls to the temperature at which the temperature rises at 10 ° C./min, the temperature is cooled to the temperature at which the temperature falls at 10 ° C./min to remove the heat history, and then the temperature rises again at 10 ° C. The temperature rises to the point. The melting point is the peak temperature when the temperature is raised for the second time. Further, the temperature at which the temperature falls is set to a temperature 50 ° C. or higher lower than the crystallization temperature, and the temperature at which the temperature rises is reached is set to a temperature about 30 ° C. or higher higher than the melting point temperature. The temperature at which the temperature falls and the temperature at which the temperature rises rise are determined by trial measurement.

Specific examples of such an acid group-containing olefin resin include maleic anhydride-modified polypropylene, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate-maleic anhydride ternary copolymer and the like. .. Commercially available acid group-containing olefin resins include "Modic" series manufactured by Mitsubishi Chemicals, Inc., "Admer" series, "Unistor" series, and "Toyotack" series manufactured by Toyobo Co., Ltd. "Umex" series manufactured by Sanyo Kasei Co., Ltd., "Lexpearl EAA" series manufactured by Nippon Polyethylene Co., Ltd., "Lexpearl ET" series, "Primacol" series manufactured by Dow Chemicals Co., Ltd., Mitsui Dupont Polychemical Examples include the "Nucrel" series and the "Bondain" series made by Alchema.

As the acid group-containing resin (A1), those other than those described above can be used, and examples thereof include Tough Tech M series manufactured by Asahi Kasei Corporation and Kraton FG series manufactured by Kraton Polymer Japan Co., Ltd.

The first agent may contain, as the resin (A), a resin (A2) having no reactive functional group in addition to the acid group-containing resin (A1). The resin (A2) is preferably a crystalline olefin resin. When the resin (A2) is a crystalline olefin resin, the polarity of the cured coating film of the adhesive is lowered, and the resistance to the electrolytic solution is improved.

The resin (A2) includes homopolymers and copolymers of olefins having 2 to 8 carbon atoms, such as ethylene, propylene, isobutylene, 1-butene, 4-methyl-1-pentene, hexene, and vinylcyclohexane. , Copolymers of olefins having 2 to 8 carbon atoms and other monomers, and specific examples thereof include high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene resin. Polyethylene, polypropylene, polyisobutylene, poly (1-butene), poly (4-methyl-1-pentene), polyvinylcyclohexane, ethylene / propylene block copolymer, ethylene / propylene random copolymer, ethylene / 1- Butene copolymer, α-olefin copolymer such as ethylene / 4-methyl-1-pentene copolymer, ethylene / hexene copolymer, ethylene / methyl methacrylate copolymer, propylene / 1-butene copolymer And so on. Among these, a homopolymer of an olefin having 3 to 8 carbon atoms and two or more copolymers of an olefin having 3 to 8 carbon atoms are preferable from the viewpoint of particularly good adhesive strength, and propylene alone. Polymers or copolymers are more preferred, and propylene homopolymers are more preferred.

The resin (A2) is highly soluble in a solvent and has improved coatability. Therefore, the weight average molecular weight is preferably 2000 to 200,000. The weight average molecular weight of the resin (A2) is more preferably 20,000 to 180,000, and even more preferably 40,000 to 160,000.

The melting point of the resin (A2) is preferably 50 ° C to 100 ° C. When the melting point is 50 ° C. or higher, the electrolytic resistance can be improved more reliably, and when the melting point is 100 ° C. or lower, the coatability can be kept good. The melting point of the resin (A2) is more preferably 60 to 95 ° C, more preferably 70 to 90 ° C.

The acid value of the first agent is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, preferably 200 mgKOH / g or less, and more preferably 165 mgKOH / g or less. If it is 200 mgKOH / g or less, the flexibility is excellent, and if it is 1 mgKOH / g or more, the heat resistance is good.

The acid value of the first agent is a coefficient (f) obtained from a calibration curve prepared by using FT-IR (FT-IR4200, manufactured by JASCO Corporation) and a chloroform solution of maleic anhydride, and a maleic anhydride-modified polyolefin. The value calculated by the following formula using the absorbance (I) of the expansion and contraction peak (1780 cm ^-1 ) of the anhydrous ring of maleic anhydride and the absorbance (II) of the expansion and contraction peak (1720 cm ^-1 ) of the carbonyl group of maleic anhydride in the solution. is there. In the following formula, maleic anhydride has a molecular weight of 98.06 and potassium hydroxide has a molecular weight of 56.11.

(Second agent)
The second agent contains an epoxy compound (B1) having a viscosity at 52 ° C. of 0.05 Pa · s or more and 25 Pa · s or less as a so-called curing agent (B) having reactivity with the acid group-containing resin (A1). The viscosity of the epoxy compound (B1) is measured on a cone plate: 1 ° x R25 using a rotary viscometer. The epoxy compound (B1) is not particularly limited as long as it satisfies the above viscosity range and has an epoxy group in the molecule, and conventionally known compounds can be used. As an example, polyglycidyl ether of an aliphatic polyol such as ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, diglycerin, sorbitol, spiroglycol or hydrogenated bisphenol A. Mold epoxy resin;
Bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin;
Aromatic epoxy resins such as phenol novolac resin and novolac type epoxy resin which is glycidyl ale of cresol novolak resin;
Ethylene oxide of aromatic polyhydroxy compounds such as bisphenol A, bisphenol F, bisphenol S, bisphenol AD, or polyglycidyl ether of polyol which is an adduct of propylene oxide;
Polyglycidyl ether type epoxy resin of polyether polyol such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3', 4'-epoxy Cyclic aliphatic polyepoxy resin such as cyclohexylcarboxylate;
Polyglycidyl ester type epoxy resin of polycarboxylic acid such as propanetricarboxylic acid, butanetetracarboxylic acid, adipic acid, phthalic acid, terephthalic acid or trimellitic acid;
Hydrocarbon diene bisepoxy resins such as butadiene, hexadiene, octadiene, dodecadien, cyclooctadiene, α-pinene or vinylcyclohexene;
Diene polymer epoxy resin such as polybutadiene or polyisoprene;
Glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexane, diglycidylaniline, and tetraglycidylmethoxylylenediamine;
Epoxy resins containing a heterocycle such as triazine and hydantoin can be mentioned.
These epoxy resins may be used alone or in combination of two or more.

The epoxy compound (B1) preferably has a viscosity at 52 ° C. of 0.05 Pa · s or more and 5 Pa · s or less, and more preferably 0.05 Pa · s or more and 2 Pa · s or less. Further, the epoxy compound (B1) used in the present invention is preferably an epoxy compound having two or more epoxy groups and one or more hydroxyl groups in one molecule and having a weight average molecular weight of 3000 or less.

The second agent may contain a compound (B3) reactive with an epoxy compound (B2) or an acid group-containing resin (A1) described later, but even in that case, the curing agent (B) contained in the second agent. The ratio of the epoxy compound (B1) to the total is preferably 40% or more. As a result, an adhesive having good adhesiveness and electrolytic solution resistance can be obtained even when aging is performed at a low temperature. The ratio of the epoxy compound (B1) to the curing agent (B) is more preferably 50% or more, and more preferably 80% or more. The total amount of the curing agent (B) may be the epoxy compound (B1).

The second agent may contain an epoxy compound (B2) other than the epoxy compound (B1). Examples of the structure of the epoxy compound (B2) include those similar to those of the epoxy compound (B1). When the epoxy compound (B2) is used in addition to the epoxy compound (B1), the blending amount of the epoxy compound (B2) is preferably 60% or less, preferably 50% or less of the curing agent (B). It is more preferably 20% or less.

As the second agent, a compound (B3) having reactivity with the acid group-containing resin (A1) other than the epoxy compound (B1) may be used in combination. Examples of the other compound (B3) that can be used in combination with the epoxy compound (B1) include a polyfunctional isocyanate compound, an aziridine group-containing compound, a carbodiimide, an oxazoline, and an amino resin.

Examples of the polyfunctional isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalenedi isocyanate, hexamethylene diisocyanate, and bis (4-isocyanate cyclohexyl). ) Diisocyanates such as methane or hydrogenated diphenylmethane diisocyanates and compounds derived from them, that is, prepolymers (diisocyanates) having isocyanurates, adducts, biuret types, uretdiones, allophanates, and isocyanate residues of the diisocyanates. And a low polymer obtained from polyol), or a complex thereof and the like.

A compound obtained by reacting a part of the isocyanate groups of the above-mentioned polyfunctional isocyanate compound with a compound having reactivity with the isocyanate group may be used as a curing agent. Compounds that have reactivity with isocyanate groups include amino group-containing compounds such as butylamine, hexylamine, octylamine, 2-ethylhexylamine, dibutylamine, ethylenediamine, benzylamine, and aniline: methanol, ethanol, propanol, and isopropanol. , Butanol, Hexanol, Octanol, 2-ethylhexyl alcohol, dodecyl alcohol, ethylene glycol, propylene glycol, benzyl alcohol, phenol and other compounds containing hydroxyl groups: allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, neopentyl Compounds having an epoxy group such as glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, cyclohexanedimethanol diglycidyl ether: acetic acid, butanoic acid, hexanoic acid, octanoic acid, succinic acid, adipic acid, sebacic acid, phthal Examples thereof include compounds containing carboxylic acids such as acids.

Examples of the aziridine group-containing compound include N, N'-hexamethylene-1,6-bis (1-aziridinecarboxyamide) and N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide). , Trimethylolpropan-tri-β-aziridinyl propionate), N, N'-toluene-2,4-bis (1-aziridinecarboxyamide), triethylenemelamine, trimethylalopropan-tri-β (2) -Methylaziridine) propionate, bisisophthaloyl-2-methylaziridine, tri-1-aziridinylphosphine oxide, tris-1--2-methylaziridinephosphine oxide and the like can be mentioned.

Examples of carbodiimides include N, N'-di-o-toluyl carbodiimide, N, N'-diphenylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, and N, N'-bis (2,6-bis). Diisopropylphenyl) carbodiimide, N, N'-dioctyldecylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N, N'-di-2,2-tert. -Butylphenylcarbodiimide, N-triyl-N'-phenylcarbodiimide, N, N'-di-p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-di-cyclohexylcarbodiimide , N, N'-di-p-toluyl carbodiimide and the like.

Examples of the oxazoline include monooxazoline compounds such as 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline and 2,4-diphenyl-2-oxazoline, 2. , 2'-(1,3-phenylene) -bis (2-oxazoline), 2,2'-(1,2-ethylene) -bis (2-oxazoline), 2,2'-(1,4 butylene) -Bis (2-oxazoline), 2,2'-(1,4-phenylene) -bis (2-oxazoline) and the like can be mentioned.

Examples of the amino resin include melamine resin, benzoguanamine resin, urea resin and the like.

When the second agent contains a compound (B3) reactive with the acid group-containing resin (A1), the blending amount thereof is preferably 60% or less of the curing agent (B), and preferably 50% or less. It is preferably 20% or less, and more preferably 20% or less.

The blending amount of the curing agent (B) is the reactive functional group (A) contained in the first agent and the reactive functional group contained in the second agent and capable of reacting with the functional group (A) of the first agent. The equivalent ratio with the group (B) (functional group (A) / functional group (B)) is preferably adjusted in the range of 0.01 or more and 10 or less, more preferably 0.1 or more and 5.0 or less. Is. As a result, an adhesive having excellent adhesiveness and electrolytic solution resistance can be obtained.

(Organophosphorus compounds)
The adhesive of the present invention further contains an organic phosphorus compound (C). Examples of the organophosphorus compound (C) include organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-butylphenyl) phosphine, diphenylphosphine, and phenylphosphine. Can be mentioned alone or in combination of two or more.

The blending amount of the organic phosphorus compound (C) is 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin of the first agent. As a result, it is possible to obtain an adhesive having good adhesive strength and electrolytic solution resistance even when aging is performed at a low temperature. Since the effect of the organophosphorus compound (C) begins to saturate when it reaches a certain amount, it should be 0.01 part by mass or more and 0.5 part by mass or less with respect to 100 parts by mass of the resin of the first agent. It is more preferable that the amount is 0.01 parts by mass or more and 0.1 parts by mass or less.

The organic phosphorus compound (C) may be premixed with the first agent or the second agent, or may be added when the first agent and the second agent are mixed.

(Imidazole compound)
The adhesive of the present invention further comprises an imidazole compound (D). Examples of the imidazole compound (D) include 2-methylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-cyanoethyl. Examples thereof include -2-ethyl-4-methylimidazole, and these can be used alone or in combination of two or more.

The blending amount of the imidazole compound (D) is 0.06 parts by mass or more and 0.35 parts by mass or less with respect to 100 parts by mass of the resin of the first agent. As a result, it is possible to obtain an adhesive having good adhesive strength and electrolytic solution resistance even when aging is performed at a low temperature. The blending amount of the imidazole compound (D) is more preferably 0.06 parts by mass or more and 0.30 parts by mass or less, and 0.06 parts by mass or more and 0.25 parts by mass with respect to 100 parts by mass of the resin of the first agent. More preferably, it is less than or equal to a part.

The imidazole compound (D) may be pre-blended in the first agent, or may be added when the first agent and the second agent are mixed.

The reason why the adhesive of the present invention is excellent in adhesive strength and electrolytic solution resistance even when aged at a particularly low temperature is not clear, but it is presumed as follows. Within the above viscosity range, the epoxy compound (B1) can be uniformly dispersed in the resin (A) in a solution state in the coating film during aging after the organic solvent (E) has been dried. The appropriate amount of the organophosphorus compound (C) and the imidazole compound (D) present here promotes the reaction between the acid group-containing resin (A1) and the curing agent (B) extremely preferably, and makes the electrolytic solution resistant. It is considered to be an excellent cured coating film.
On the other hand, if the viscosity is too low, the epoxy compound (B1) cannot be dispersed in the resin (A) and is unevenly distributed, and the acid group-containing resin (A1) cannot be appropriately crosslinked, which affects the adhesive strength and the electrolyte resistance. However, if the viscosity of the epoxy compound (B2) is too high, the adhesive will not spread sufficiently on the substrate in the low temperature range, and the reaction will be sufficient even in the presence of the organic phosphorus compound (C) and the imidazole compound (D). It is presumed that it will not be promoted. If the amount of the imidazole compound (D) is too large, the excess imidazole compound (D) may adversely affect the cured coating film, shorten the pot life, and reduce the storage stability of the adhesive.

(Organic solvent)
The adhesive of the present invention can secure fluidity and exhibit appropriate coatability by further blending an organic solvent (E) in addition to the above components. The organic solvent (E) is not particularly limited as long as it can be volatilized and removed by overheating in the drying step at the time of coating the adhesive. For example, an aromatic organic solvent such as toluene or xylene; n An aliphatic organic solvent such as −hexane and n-heptane; an alicyclic organic solvent such as cyclohexane and methylcyclohexane; a halogen organic solvent such as trichloroethylene, dichloroethylene, chlorobenzene and chloroform; and methylethylketone, methylisobutylketone and cyclohexanone. Ketone solvent; ester solvent such as ethyl acetate, butyl acetate; alcohol solvent such as ethanol, methanol, n-propanol, 2-propanol (isopropyl alcohol), butanol, hexanol; diisopropyl ether, butyl cellosolve, tetrahydrofuran, dioxane, butyl Ether-based solvents such as carbitol; glycol ether-based solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ethylene glycol monomethyl ether acetate, proprene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc. Examples thereof include glycol ester-based solvents, and these may be used alone or in combination of two or more.

Since the acid group-containing resin (A1) is excellent in solubility, it is preferable to use a mixed solvent of an alicyclic organic solvent and an ester solvent. In particular, when an olefin resin having an acid group or an acid anhydride group is used as the acid group-containing resin (A1), it is preferable to use a mixed solvent of methylcyclohexane and ethyl acetate because of its excellent solubility. Further, in order to improve the solubility of the acid group-containing resin (A1), a mixed solvent of an alicyclic organic solvent, an ester solvent and an alcohol solvent may be used. At this time, the alcohol solvent is preferably isopropyl alcohol, 2-butanol or the like.

Further, in order to improve the solubility of the epoxy compound (B1), an aromatic organic solvent or a ketone solvent may be used in combination with the mixed solvent of the alicyclic organic solvent and the ester solvent. At this time, toluene is preferably mentioned as the aromatic organic solvent, and methyl ethyl ketone is preferably mentioned as the ketone solvent.

The amount of the organic solvent (E) used is preferably such that the ratio of the resin (A) to the total mass of the resin (A) and the organic solvent (E) is 5 to 30% by mass. This makes it possible to obtain an adhesive having excellent coatability and wettability to a metal film.

As the adhesive of the present invention, various additives such as acid anhydride, adhesion accelerator, tackifier, plasticizer, thermoplastic elastomer, reactive elastomer, phosphoric acid compound, silane coupling agent and the like are used as needed. Can be done. The content of these additives may be appropriately adjusted within a range that does not impair the function of the adhesive of the present invention.

Examples of the acid anhydride include cyclic aliphatic acid anhydride, aromatic acid anhydride, unsaturated carboxylic acid anhydride and the like, and one type or a combination of two or more types can be used. More specifically, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, dodecenyl succinic anhydride, polyazipic acid anhydride, polyazereic acid anhydride, polysevacinic acid. Anhydrous, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride , Methyl hymic acid anhydride, trialkyltetrahydrophthalic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bistrimericate dianhydride, het acid anhydride, nadic acid anhydride, Methylnadic acid anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2, Examples thereof include 3,4-tetrahydro-1-naphthalene succinic anhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride and the like.

Moreover, you may use the above-mentioned compound modified with glycol as an acid anhydride. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol and potitetramethylene ether glycol. Furthermore, copolymerized polyether glycols of two or more kinds of these glycols and / or polyether glycols can also be used.

The blending amount of the acid anhydride is preferably 0.01 part by mass or more, and more preferably 0.8 part by mass or more with respect to 100 parts by mass of the resin (A). The blending amount of the acid anhydride is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and 1.5 parts by mass or less with respect to 100 parts by mass of the resin (A). Is more preferable. As a result, the adhesiveness between the adhesive and the metal is improved, and it is possible to obtain an adhesive having excellent initial adhesive strength and adhesive strength after heat sealing.

The reason why the adhesive is excellent in adhesiveness and heat resistance by using the acid anhydride is not clear, but it is presumed as follows. The acid anhydride has a polar group and has an excellent affinity for a metal substrate. Moreover, since the molecular weight is relatively small, it is relatively easy to move. It is considered that the applied adhesive moves to the metal base material side before it is completely cured and plays a role like a so-called anchoring agent, thereby contributing to the improvement of adhesiveness and heat resistance.

Adhesion promoters include triethylamine, triethylenediamine, N'-methyl-N- (2-dimethylaminoethyl) piperazine, 1,8-diazabicyclo [5.4.0] undecene (DBU), 1,5-diazabicyclo [ 4.3.0] -Nonene, 6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene, tertiary amines such as compounds represented by the following structural formulas (5) to (15) and Examples thereof include compounds obtained by converting these tertiary amines into amine salts with phenol, octyl acid, quaternized tetraphenylborate salt and the like, and cationic catalysts such as triarylsulfonium hexafluoroantimonate and diallyliodonium hexafluoroantimonate. These may be used alone or in combination of two or more. In the following structural formulas (5) to (15), the hydrogen atom bonded to the carbon atom is omitted.

Examples of the tackifier include a rosin-based or rosin ester-based tackifier, a terpene-based or terpene-phenol-based tackifier, a saturated hydrocarbon resin, a kumaron-based tackifier, a kumaron-inden-based tackifier, and a styrene resin-based tackifier. Examples thereof include a tackifier, a xylene resin-based tackifier, a phenol resin-based tackifier, and a petroleum resin-based tackifier. Each of these may be used alone, or two or more types may be used in combination.

Examples of the plasticizer include polyisoprene, polybutene, procel oil and the like, and examples of the thermoplastic elastomer include a styrene-butadiene copolymer (SBS), a hydrogenated product of a styrene-butadiene copolymer (SEBS), SBBS, and a styrene-isoprene. Examples of the copolymerized hydrogen additive (SEPS), styrene block copolymer (TPS), olefin elastomer (TPO) and the like are examples of the reactive elastomer obtained by acid-modifying these elastomers.

Examples of the phosphoric acid compound include phosphoric acids such as hypophosphoric acid, phosphoric acid, orthophosphoric acid and hypophosphoric acid, and condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid and ultraphosphoric acid, for example. Monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monophenyl orthophosphate, monomethyl phosphite, monoethyl phosphite, monopropyl phosphite, monobutyl phosphite , Mono-2-ethylhexyl phosphite, monophenyl phosphite, di-2-ethylhexyl orthophosphate, dimethyl diphenyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, phosphite Monos such as di-2-ethylhexyl and diphenyl phosphite, diesterates, monos from condensed phosphoric acid and alcohols, diesterates, for example, the above phosphoric acids are added with epoxy compounds such as ethylene oxide and propylene oxide. Examples thereof include epoxy phosphoric acid esters obtained by adding the above-mentioned phosphoric acids to an aliphatic or aromatic diglycidyl ether.

Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) -γ-. Aminosilanes such as aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Epoxysilanes such as xypropyltriethoxysilane; vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane; hexamethyldisilazane, γ-mercaptopropyl Examples thereof include trimethoxysilane.

The adhesive of the present invention can be prepared by mixing each of the above-mentioned components. At this time, each component may be mixed at the same time to form an adhesive. For example, components other than the curing agent (B) may be mixed in advance to adjust the premixure, and the curing agent (B) may be used when the adhesive is used. A two-component type to be mixed, a first agent containing a resin (A) as a main component, a second agent containing a curing agent (B) as a main component, and other components (for example, an organic phosphorus compound (C) and an imidazole compound). It is preferable to use a third agent containing (D)) as a three-component (or more) adhesive mixed immediately before the use of the adhesive because the adhesive is excellent in stability and workability. In the present specification, two-component adhesives and three-component (or more) adhesives are collectively referred to as multi-component adhesives.

The adhesive of the present invention is excellent in adhesiveness and heat resistance between a non-polar substrate such as an olefin resin and a metal substrate.

<Laminated body>
The laminate of the present invention is arranged between the first base material, the second base material, the first base material and the second base material, and the first base material and the second base material are arranged. Includes an adhesive layer to bond with. The adhesive layer is a cured coating film of the above-mentioned adhesive. In addition to the first base material and the second base material, other base materials may be contained. The adhesive layer for bonding the first base material to the other base material and the second base material to the other base material may or may not be a cured coating film of the adhesive of the present invention. Good.

Examples of the first base material, the second base material, and other base materials include paper, olefin resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, and fluororesin. Metals such as poly (meth) acrylic resin, carbonate resin, polyamide resin, polyimide resin, polyphenylene ether resin, synthetic resin film obtained from polyphenylene sulfide resin or polyester resin, copper foil, aluminum foil Foil or the like can be used.

Since the adhesive of the present invention has excellent adhesiveness between a non-polar base material such as an olefin resin and a metal base material, one of the first base material and the second base material is a non-polar base material. The other is preferably, but is not limited to, a metal base material.

The laminate of the present invention is obtained by applying the adhesive of the present invention to one of the first base material and the second base material, then laminating the other, and curing the adhesive. It is preferable to provide a drying step between the application of the adhesive and the laminating of the first base material and the second base material.
As the adhesive coating method, a gravure coater method, a microgravure coater method, a reverse coater method, a bar coater method, a roll coater method, a die coater method and the like can be used. The amount of the adhesive applied is preferably adjusted so that the applied weight after drying is 0.5 to 20.0 g / m ² . If it is less than 0.5 g / m ² , the continuous uniform coating property is likely to be lowered, and if it is more than 20.0 g / m ² , the solvent releasability after coating is also lowered, and the workability is easily lowered and the problem of residual solvent is likely to occur. Become.

The temperature of the laminating roll when laminating the first base material and the second base material is preferably 25 to 120 ° C., and the pressure is preferably ³ to 300 kg / cm ² .
It is preferable to provide an aging step after laminating the first base material and the second base material. The aging conditions are preferably 25 to 100 ° C. and 12 to 240 hours.

In particular, the adhesive of the present invention exerts an excellent effect even when the aging temperature is 60 ° C. or lower, further 55 ° C. or lower, which is considerably lower than the reaction temperature of a normal acid and epoxy, and has good initial adhesive strength. Shows electrolytic solution resistance. When aging is performed at 60 ° C. or lower, the aging time is preferably 24 hours or more. The upper limit of the aging time is not particularly limited, but a sufficient effect is exhibited in about 168 hours. From the viewpoint of the balance between the aging temperature and the aging time, it is preferable to carry out the aging step at 40 to 60 ° C. for 24 to 168 hours.

<Battery packaging material>
As an example, the packaging material for a battery of the present invention has a first base material, a second base material, a third base material, a first base material, and a second base material bonded together. It includes an adhesive layer and a second adhesive layer for bonding the second base material and the third base material. The first base material is a polyolefin film, and the second base material is a metal foil. The third base material is a resin film such as nylon or polyester. The first adhesive layer is a cured coating film of the adhesive of the present invention. The second adhesive layer may or may not be a cured coating of the adhesive of the present invention. Another substrate may be placed on the opposite side of the third substrate from which the second adhesive layer is provided, with or without an adhesive layer, or a coating layer may be provided. Good. It is not necessary to provide another base material or coating layer.

The polyolefin film may be appropriately selected from conventionally known olefin resins. For example, although not particularly limited, polyethylene, polypropylene, ethylene propylene copolymer and the like can be used. It is preferably a non-stretched film. The film thickness of the polyolefin film is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 25 μm or more. Further, it is preferably 100 μm or less, more preferably 95 μm or less, and further preferably 90 μm or less.
The first base material functions as a sealant layer when the battery packaging materials of the present invention are heat-sealed and bonded to each other when the battery described later is manufactured.

Examples of the metal foil include aluminum, copper, nickel and the like. These metal foils are sandblasted, polished, degreased, etched, surface-treated by rust preventive immersion or spraying, trivalent chromium chemical conversion treatment, phosphate chemical conversion treatment, sulfide chemical conversion treatment, anodic oxide film formation, etc. It may be surface-treated such as a fluororesin coating. Among these, those subjected to trivalent chromium chemical conversion treatment are preferable because they are excellent in adhesion retention performance (environmental deterioration resistance) and corrosion resistance. Further, the thickness of this metal film is preferably in the range of 10 to 100 μm from the viewpoint of corrosion prevention.

Examples of the resin film that can be used as the third base material include polyester resin, polyamide resin, epoxy resin, acrylic resin, fluororesin, polyurethane resin, silicon resin, phenol resin, and resins such as mixtures and copolymers thereof. Film is mentioned. Among these, polyester resin and polyamide resin are preferable, and biaxially stretched polyester resin and biaxially stretched polyamide resin are more preferable. Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolymerized polyester, and polycarbonate. Specific examples of the polyamide resin include nylon 6, nylon 6, 6, a copolymer of nylon 6 and nylon 6, 6, nylon 6, 10, and polymethoxylylen adipamide (MXD6). Be done.

The coating layer can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, or the like. It is preferably formed of a two-component curable resin. Examples of the two-component curable resin forming the coating layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Moreover, you may mix the matting agent in the coating layer.

Examples of the matting agent include fine particles having a particle size of about 0.5 nm to 5 μm. The material of the matting agent is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances. The shape of the matting agent is also not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an amorphous shape, and a balloon shape. Specific examples of the matting agent include talc, silica, graphite, kaolin, montmoriloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, and aluminum oxide. , Neodium oxide, Antimon oxide, Titanium oxide, Serium oxide, Calcium sulfate, Barium sulfate, Calcium carbonate, Calcium silicate, Lithium carbonate, Calcium benzoate, Calcium silicate, Magnesium stearate, Carbon black, Carbon nanotubes, High melting point Examples thereof include nylon, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper and nickel. These matting agents may be used alone or in combination of two or more. Among these matting agents, preferably silica, barium sulfate, and titanium oxide are mentioned from the viewpoint of dispersion stability and cost. Further, the matting agent may be subjected to various surface treatments such as an insulating treatment and a highly dispersible treatment on the surface.

Such a laminate is molded so that the polyolefin film, which is the first base material, is inside the third base material when it is used as a battery, and becomes the secondary battery exterior material of the present invention. The molding method is not particularly limited, and examples thereof include the following methods.

-Heat-compressed air molding method: The packaging material for batteries is sandwiched between a lower mold with holes for supplying high-temperature and high-pressure air and an upper mold with pocket-shaped recesses, and air is supplied while being heated and softened to form recesses. how to.
-Preheater flat plate type compressed air molding method: After heating and softening the packaging material for batteries, air is supplied by sandwiching it between a lower mold with holes for supplying high-pressure air and an upper mold with pocket-shaped recesses. A method of forming a recess.
-Drum type vacuum forming method: A method in which a battery packaging material is partially heated and softened with a heating drum, and then the concave portion of a drum having a pocket-shaped concave portion is evacuated to form the concave portion.
-Pin molding method: A method in which the bottom material sheet is heat-softened and then crimped with a pocket-shaped uneven mold.
-Preheater plug assist compressed air molding method: After heating and softening the packaging material for batteries, air is supplied by sandwiching it between a lower mold with holes for supplying high-pressure air and an upper mold with pocket-shaped recesses. A method of forming a concave portion, which assists molding by raising and lowering a convex plug at the time of molding.

Since the wall thickness of the bottom material after molding is uniform, the preheater plug assist compressed air molding method, which is a heating vacuum forming method, is preferable.
The battery packaging material of the present invention thus obtained can be suitably used as a battery container for sealing and accommodating battery elements such as a positive electrode, a negative electrode, and an electrolyte.

<Battery>
The battery of the present invention is a battery in which a battery element including a positive electrode, a negative electrode, and an electrolyte is projected outward from the metal terminals connected to each of the positive electrode and the negative electrode in the battery packaging material of the present invention. It is obtained by covering the peripheral edge of the element so that a flange portion (a region where the sealant layers come into contact with each other) can be formed, and heat-sealing the sealant layers of the flange portion with each other.

The battery obtained by using the battery packaging material of the present invention may be either a primary battery or a secondary battery, but is preferably a secondary battery. The secondary battery is not particularly limited, and for example, a lithium ion battery, a lithium ion polymer battery, a lead storage battery, a nickel / hydrogen storage battery, a nickel / cadmium storage battery, a nickel / iron storage battery, a nickel / zinc storage battery, a silver oxide / zinc storage battery, etc. Examples thereof include metal air batteries, multivalent cation batteries, capacitors, and capacitors. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries can be mentioned as suitable application targets of the battery packaging material of the present invention.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The composition and other values are based on mass unless otherwise specified.

<Synthesis of epoxy compounds>
(Synthesis of Epoxy Compound 1)
A flask equipped with a thermometer and a stirrer was charged with 228 g (1.00 mol) of bisphenol A and 172 g (0.85 mol) of triethylene glycol divinyl ether (manufactured by ISP: trade name Rapi-Cure DVE-3) at 120 ° C. After 1 hour to raise the temperature, the mixture was further reacted at 120 ° C. for 6 hours to obtain 400 g of transparent semi-solid modified polyhydric phenols.
The obtained modified polyhydric phenols (ph-1a) have peaks of M + = 658 and M + = 1088 corresponding to the theoretical structure of n = 1 and n = 2 in the NMR spectrum (13C) and the mass spectrum. Therefore, it was confirmed that the structure was represented by the following structural formula Ep1'. The hydroxyl equivalent of the modified polyhydric phenols is 364 g / eq. The viscosity is 40 mPa · s (150 ° C., ICI viscometer), and the average value of m in the following structural formula Ep1'calculated from the hydroxyl group equivalent is 3.21 for the component m ≧ 1 and the component m ≧ 0. It was 1.16.

400 g (hydroxyl equivalent 364 g / eq.) Of modified polyhydric phenols, 925 g (10 mol) of epichlorohydrin, and 185 g of n-butanol obtained in a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer were charged and dissolved. .. Then, the temperature was raised to 65 ° C. while purging with nitrogen gas, the pressure was reduced to an azeotropic pressure, and 122 g (1.5 mol) of a 49% sodium hydroxide aqueous solution was added dropwise over 5 hours. Stirring was continued for 0.5 hours after the completion of the dropping. During this period, the distillate distilled off by azeotrope was separated by a Dean-Stark trap to remove the aqueous layer, and the organic layer was reacted while being returned to the reaction system. Then, unreacted epichlorohydrin was distilled under reduced pressure and distilled off. To the obtained crude epoxy resin, 1000 g of methyl isobutyl ketone and 100 g of n-butanol were added and dissolved, and 20 g of a 10% aqueous sodium hydroxide solution was further added to this solution and reacted at 80 ° C. for 2 hours, after which the pH of the washing solution was medium. Washing with 300 g of water was repeated 3 times until it became sex. Then, the inside of the system was dehydrated by azeotropic filtration, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 457 g of a transparent liquid epoxy compound. The epoxy compound is represented by the following structural formula Ep1 because peaks of M + = 770 and M + = 1200 corresponding to the theoretical structure of n = 1 and n = 2 were obtained in the NMR spectrum (13C) and the mass spectrum. It was confirmed that the epoxy compound 1 of the structure was contained.

The obtained epoxy compound 1 is a mixture of a compound having n = 0 in the above structural formula Ep1 and a compound having n = 1 or more, and when confirmed by GPC, 20% by mass of the compound having n = 0 in the mixture was obtained. It was contained in proportion. The epoxy equivalent of this epoxy compound 1 is 462 g / eq. The viscosity is 12000 mPa · s (25 ° C., Canon Fenceke method), and the average value of n in the structural formula Ea-1 calculated from the epoxy equivalent is 2.97 for the component of n ≧ 1, and n ≧ 0. The component of was 1.35.

(Synthesis of Epoxy Compound 2)
Diglycidyl ether of 1,6-hexanediol (manufactured by DIC Co., Ltd .: trade name EPICLON 726D, epoxy equivalent 124 g / eq) 744 g (6 equivalents) and bisphenol A (hydroxyl equivalent 114 g /) in a flask equipped with a thermometer and a stirrer. 1368 g (12 equivalents) of eq) was charged, and the temperature was raised to 140 ° C. for 30 minutes, and then 5 g of a 4% sodium hydroxide aqueous solution was charged. Then, it took 30 minutes to raise the temperature to 150 ° C., and further reacted at 150 ° C. for 3 hours. Then, a neutralized amount of sodium phosphate was added to obtain 2090 g of a hydroxy compound. Since the peaks of M ⁺ = 687 corresponding to the theoretical structure of o in the NMR spectrum (13C) and the mass spectrum and M ⁺ = 1145 corresponding to the theoretical structure of o of 2 were obtained, the following structural formula (EP2) was obtained. It was confirmed that it contained a hydroxy compound having a structure represented by'). The hydroxyl group equivalent calculated from GPC of this hydroxy compound was 262 g / eq, and the average value of o in the following structural formula (EP2') calculated from the hydroxyl group equivalent was 0.6.

261 g (hydroxyl equivalent 261 g / eq.) Of the hydroxy compound obtained above, 1110 g (12 mol) of epichlorohydrin, and 222 g of n-butanol were charged and dissolved in a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer. Then, while performing nitrogen gas purging, the temperature was raised to 65 ° C., the pressure was reduced to an azeotropic pressure, and 122 g (1.5 mol) of a 49% sodium hydroxide aqueous solution was added dropwise over 5 hours. Then, stirring was continued for 0.5 hours under this condition. During this period, the distillate distilled off by azeotrope was separated by a Dean-Stark trap, the aqueous layer was removed, and the organic layer was returned to the reaction system for reaction. Then, unreacted epichlorohydrin was distilled under reduced pressure and distilled off. To the obtained crude epoxy resin, 1000 g of methyl isobutyl ketone and 100 g of n-butanol were added and dissolved. Further, 20 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water was repeated 3 times with 300 g of water until the pH of the washing liquid became neutral. Then, the inside of the system was dehydrated by azeotrope, and after undergoing microfiltration, the solvent was distilled off under reduced pressure to obtain 380 g of liquid epoxy compound 2. This epoxy compound 2 has a theoretical structure of M + = 798, p = 2, q = 2, r = 0, which corresponds to the theoretical structure of p = 1, q = 1, r = 0 from the NMR spectrum (13C) and the mass spectrum. Since the peak of M + = 1257 corresponding to the above was obtained, it was confirmed that the epoxy compound 2 having the structure represented by the following structural formula (Ep2) was contained. The obtained epoxy compound 2 contains a compound having p = 0, q = 0, r = 0 in the following structural formula (Ep2), and when confirmed by GPC, p = 0, q = 0, r in the mixture. The compound containing = 0 was contained in a proportion of 29% by weight. The epoxy equivalent of this epoxy compound 2 is 350 g / eq. The viscosity was 2000 Pa · s (25 ° C., E-type viscosity method), and the average value of r in the following structural formula (Ep2) calculated from the epoxy equivalent was 0.1.

<Adhesive adjustment>
(Example 1)
Toyotac PMA-KE: 100 parts, triphenylphosphine: 0.04 parts, curesol 2E4MZ: 0.06 parts, jER cure YH306: 1 part are dissolved in a mixed solvent (cyclomethylhexane / ethyl acetate = 71/8). , The non-volatile content was set to 20%. Next, 5.0 parts of EPICLON TSR-960 was added and stirred well to prepare the adhesive of Example 1.

(Examples 2 to 5)
The adhesives of Examples 2 to 5 were adjusted in the same manner as in Example 1 except that the formulations shown in Table 2 were changed.
(Comparative Examples 1 to 4)
The adhesives of Comparative Examples 1 to 4 were prepared in the same manner as in Example 1 except that the formulations shown in Table 3 were changed.

The details of the compounds used in Examples and Comparative Examples are as follows.
Toyo Tuck PMA-KE: Maleic anhydride-modified olefin resin, acid value: 44 mgKOH / g, melting point: 80 ° C., Toyobo Curesol 2E4MZ: 2-ethyl-4-methyl-imidazole, Shikoku Kasei Kogyo Co., Ltd. jER Cure YH- 306: Trialkyltetrahydromaleic anhydride, EPICLON TSR-960 manufactured by Mitsubishi Chemical Corporation, solvent-free rubber-modified epoxy resin, DENALEX FCA-061L manufactured by DIC Corporation, polybutadiene type epoxy resin, manufactured by Nagase ChemteX Corporation

Table 1 shows the viscosities of the epoxy compounds used in Examples and Comparative Examples at 52 ° C. The viscosity of the epoxy compound was measured at 52 ° C. using BROOKFIELD R / S Plus RHEOMETER as a measuring device and C50-1 as a jig.

The acid value of the olefin resin is a coefficient (f) obtained from a calibration curve prepared with a chloroform solution of maleic anhydride using FT-IR (FT-IR4200, manufactured by Nippon Kogaku Co., Ltd.), in a maleic anhydride-modified polyolefin solution. It is a value calculated by the following formula using the absorbance (I) of the expansion and contraction peak (1780 cm ^-1 ) of the anhydrous ring of maleic anhydride and the absorbance (II) of the expansion and contraction peak (1720 cm ^-1 ) of the carbonyl group of maleic anhydride. In the following formula, the molecular weight of maleic anhydride was 98.06, and the molecular weight of potassium hydroxide was 56.11.

<Laminated body>
(Example 1)
The adhesive of Example 1 was applied to the glossy surface of a chromate-treated aluminum foil (film thickness: 40 μm) with a bar coater at a coating amount of 4 g / m ² (dry), dried at 80 ° C. for 1 minute, and then unstretched polyolefin. It was bonded to a film (film thickness: 40 μm) at 100 ° C. Next, on the matte surface of the aluminum foil, "Dick Dry LX-906" (manufactured by DIC Corporation) is used as the main agent, and "KW-75" (manufactured by DIC Corporation) is used as the curing agent, and the weight ratio is the main agent / curing agent = 100. The adhesive blended so as to be 1/10 was applied with a bar coater at a coating amount of 4 g / m ² (dry), and then a stretched polyamide film having a thickness of 25 μm was laminated. Then, it was cured (aged) at 50 ° C. for 3 days to obtain a laminate of Example 1.

(Examples 2 to 5)
The adhesive was adjusted in the same manner as in Example 1 except that the adhesive used for bonding the aluminum foil and the unstretched polyolefin film was changed to obtain a laminate.

(Comparative Examples 1 to 4)
The adhesive was adjusted in the same manner as in Example 1 except that the adhesive used for bonding the aluminum foil and the unstretched polyolefin film was changed to obtain a laminate.

<Evaluation>
(Measurement of initial adhesive strength)
Using "Autograph AGS-J" manufactured by Shimadzu Corporation, the adhesive strength at the interface between the aluminum foil of the laminate and the unstretched polyolefin film is evaluated under the conditions of peeling speed 50 mm / min, peeling width 15 mm, and peeling form T type. did. 8.0N / 15mm or more was regarded as acceptable.

(Electrolytic resistance)
As the electrolytic solution, a solution obtained by adding each of a mixed solution of ethylene carbonate: ethyl methyl carbonate: dimethyl carbonate = 1: 1: 1 (wt%) so that LiPF6 is 1 mol / l, vinylene carbonate is 1 wt%, and water is 1000 ppm. I prepared it. The aged laminate was immersed in 35 g of an electrolytic solution at 85 ° C. for 7 days. Before the electrolytic solution was dried, the adhesive strength at the interface between the aluminum foil of the laminate and the unstretched polyolefin film was measured under the conditions of a peeling speed of 50 mm / min, a peeling width of 15 mm, and a peeling form of T type. It was evaluated as follows from the retention rate of the adhesive strength before and after immersion.
〇: 60% or more Δ: 40% or more and less than 60% ×: less than 40%

As is clear from Tables 2 and 3, the adhesive of the present invention is superior in initial adhesive strength and electrolytic solution resistance to the adhesives of Comparative Examples.

The adhesive of the present invention is excellent in adhesiveness and heat resistance between a non-polar base material such as an olefin resin and a metal base material, and the laminate obtained by using the adhesive of the present invention can be used as a packaging material for batteries, for example. It can be preferably used. Further, the use of the adhesive of the present invention is not limited to the packaging material for batteries and the laminate for that purpose, and the adhesiveness between non-polar base materials such as home appliance outer panels, furniture materials, and building interior members and metal base materials. Is widely available in fields where

Claims (10)

Including the first agent and the second agent,
The first agent contains a resin (A) containing an acid group-containing resin (A1).
The second agent contains an epoxy compound (B1) having a viscosity at 52 ° C. of 0.05 Pa · s or more and 25 Pa · s or less.
Furthermore, with the organic phosphorus compound (C),
Includes imidazole compound (D),
The blending amount of the organic phosphorus compound (C) is 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin (A).
An adhesive in which the blending amount of the imidazole compound (D) is 0.06 parts by mass or more and 0.35 parts by mass or less with respect to 100 parts by mass of the resin (A). The adhesive according to claim 1, wherein the acid-modified resin (A1) contains a crystalline acid-modified olefin resin. The adhesive according to any one of claims 1 or 2, which comprises an acid anhydride. The adhesive according to any one of claims 1 to 3, wherein the epoxy compound (B1) has a viscosity of 0.05 Pa · s or more and 2 Pa · s or less at 52 ° C. Equivalent ratio (functional group) of the reactive functional group (A) contained in the first agent to the reactive functional group (B) contained in the second agent and reactive with the functional group (A). The adhesive according to any one of claims 1 to 4, wherein the (A) / functional group (B)) is 0.01 or more and 10 or less. A first base material, a second base material, and an adhesive layer for adhering the first base material and the second base material are included, and the adhesive layer is any one of claims 1 to 5. A laminate characterized by being a cured coating film of the adhesive according to item 1. The step of applying the adhesive according to any one of claims 1 to 5 to the first base material, and
A step of bonding the first base material and the second base material via the adhesive, and
A method for producing a laminate, which comprises a step of aging at 25 ° C. or higher and 100 ° C. or lower for 12 hours or longer. Polyolefin film and
With resin film
A metal foil arranged between the polyolefin film and the resin film,
Includes an adhesive layer disposed between the polyolefin film and the metal foil.
A packaging material for a battery, wherein the adhesive layer is a cured coating film of the adhesive according to any one of claims 1 to 5. A battery container obtained by molding the battery packaging material according to claim 8. A battery using the battery container according to claim 9.