阅读说明：本技术 接着剂、层叠体、电池用包装材、电池用容器及电池 (Adhesive, laminate, battery packaging material, battery container, and battery ) 是由 菅野勉 中村英美 小林裕季 神山达哉 于 2019-05-31 设计创作，主要内容包括：本发明提供一种如烯烃树脂般的非极性的基材与金属基材的接着性、耐热性优异的接着剂、层叠体、电池用包装材、电池用容器及电池。接着剂,包含第一剂与第二剂,所述第一剂包含树脂(A),所述树脂(A)包括含有酸基的树脂(A1),所述第二剂包含环氧化合物(B1),所述环氧化合物(B1)在55℃下的粘度为0.05Pa·s以上、55Pa·s以下,所述接着剂还包含有机磷系化合物(C)、以及咪唑化合物(D),相对于所述树脂(A)100质量份,所述有机磷系化合物(C)的调配量为0.01质量份以上、5质量份以下,相对于所述树脂(A)100质量份,所述咪唑化合物(D)的调配量为0.06质量份以上、0.35质量份以下。(The invention provides an adhesive, a laminate, a battery packaging material, a battery container and a battery, wherein the adhesive has excellent adhesion between a nonpolar base material such as an olefin resin and a metal base material and excellent heat resistance. An adhesive agent comprising a first agent and a second agent, wherein the first agent comprises a resin (A) comprising an acid group-containing resin (A1), the second agent comprises an epoxy compound (B1), the epoxy compound (B1) has a viscosity at 55 ℃ of 0.05 Pa.s or more and 55 Pa.s or less, the adhesive agent further comprises an organic phosphorus compound (C) and an imidazole compound (D), the amount of the organic phosphorus compound (C) is 0.01 to 5 parts by mass per 100 parts by mass of the resin (A), and the amount of the imidazole compound (D) is 0.06 to 0.35 parts by mass per 100 parts by mass of the resin (A).)

1. An adhesive comprising a first agent and a second agent,

the first agent comprises a resin (A) including a resin (A1) containing an acid group,

the second agent contains an epoxy compound (B1), the viscosity of the epoxy compound (B1) at 55 ℃ is 0.05Pa · s or more and 55Pa · s or less,

the adhesive further comprises an organic phosphorus compound (C), and

an imidazole compound (D) which is a compound having a structure represented by the general formula (I),

the amount of the organophosphorus compound (C) is 0.01 to 5 parts by mass based on 100 parts by mass of the resin (A),

the amount of the imidazole compound (D) is 0.06 parts by mass or more and 0.35 parts by mass or less per 100 parts by mass of the resin (a).

2. The adhesive according to claim 1, wherein the acid group-containing resin (A1) comprises a crystalline acid-modified olefin resin.

3. The adhesive according to any one of claims 1 or 5, comprising an anhydride.

4. The adhesive according to claim 1 or 5, wherein the viscosity of the epoxy compound (B1) at 55 ℃ is 0.05 Pa-s or more and 5 Pa-s or less.

5. The adhesive according to claim 1 or 5, wherein an equivalent ratio of the reactive functional group (A) contained in the first agent to the reactive functional group (B) capable of reacting with the functional group (A) contained in the second agent is 0.01 or more and 10 or less, and the equivalent ratio is functional group (A)/functional group (B).

6. A laminate, characterized in that: comprising a first substrate, a second substrate, and an adhesive layer for bonding the first substrate and the second substrate, wherein the adhesive layer is a cured coating film of the adhesive according to any one of claims 1 to 5.

7. A method of manufacturing a laminate, comprising: a step of coating the adhesive according to any one of claims 1 to 5 on a first substrate;

a step of bonding the first substrate and the second substrate via the adhesive; and

aging at 55-100 deg.C for 15 hr.

8. A battery packaging material, comprising: a polyolefin film;

a resin film;

a metal foil disposed between the polyolefin film and the resin film; and

an adhesive layer disposed between the polyolefin film and the metal foil,

the adhesive layer is a hardened coating film of the adhesive according to any one of claims 1 to 5.

9. A battery container obtained by molding the battery packaging material according to claim 8.

10. A battery using the battery container according to claim 9.

Technical Field

The present invention relates to an adhesive, and more particularly to an adhesive suitable for bonding a resin substrate and a metal substrate, a laminate obtained using the adhesive, a packaging material for a secondary battery, a container for a battery, and a battery.

Background

A secondary battery represented by a lithium ion battery has a structure in which a positive electrode, a negative electrode, and an electrolyte solution or the like are sealed between these electrodes. As a sealing bag for sealing a lead wire for conducting electricity between the positive electrode and the negative electrode to the outside, a laminate is known which is obtained by bonding a heat-sealing layer containing an olefin resin, a metal base material containing a metal foil such as an aluminum foil or a metal vapor deposition layer, and a plastic (patent documents 1 and 2).

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent application laid-open No. Hei 09-283101

[ patent document 2] Japanese patent laid-open No. 2007-294381

Disclosure of Invention

[ problems to be solved by the invention ]

When a heat seal layer containing an olefin resin is bonded to a metal substrate via an adhesive, a so-called aging (bonding) step is generally provided in which the curing of the adhesive is accelerated while heating. The curing temperature and curing time in the curing step may be appropriately selected, and for example, it is preferable to perform the curing step at 80 ℃ or less, which is less affected by thermal shrinkage of the olefin resin. On the other hand, the lower the curing temperature and the shorter the curing time, the more difficult the properties of the adhesive tend to be exhibited.

The present invention has been made in view of such circumstances, and an object thereof is to provide an adhesive which is excellent in adhesion between a nonpolar substrate such as an olefin resin and a metal substrate even when it is cured at a low temperature. Further, it is an object of the present invention to provide a laminate obtained using such an adhesive, and a secondary battery packaging material and a battery obtained using the laminate.

[ means for solving problems ]

The present invention relates to an adhesive agent comprising a first agent and a second agent, wherein the first agent comprises a resin containing an acid group, the second agent comprises an epoxy compound having a viscosity at 52 ℃ of 0.05 Pa.s or more and 25 Pa.s or less, the adhesive agent further comprises an organic phosphorus compound and an imidazole compound, the amount of the organic phosphorus compound is 0.01 to 5 parts by mass per 100 parts by mass of the resin, and the amount of the imidazole compound is 0.06 to 0.35 parts by mass per 100 parts by mass of the resin.

[ Effect of the invention ]

The adhesive of the present invention is excellent in adhesion between a nonpolar substrate such as an olefin resin and a metal substrate and in electrolyte solution resistance even when cured at a low temperature. The laminate of the present invention is excellent in adhesion and electrolyte resistance.

Detailed Description

< Adhesives >

The adhesive of the present invention comprises: a first agent comprising a resin (A) including a resin (A1) containing an acid group; and a second agent containing an epoxy compound having a viscosity of 0.05 pas or more and 25 pas or less at 52 ℃; further comprises an organophosphorus compound and an imidazole compound. The components of the adhesive of the present invention will be described in detail below.

(first agent)

The first agent contains a resin (a1) containing an acid group as the resin (a). Examples of the acid group included in the acid group-containing resin (a1) include: carboxyl group, carboxylic anhydride group, sulfonic group, phosphoric group, etc. The acid group-containing resin may include only one of these, or may include two or more of these. The resin skeleton of the acid group-containing resin (a1) is not particularly limited, and an acrylic resin, a urethane resin, an olefin resin, or the like can be preferably used.

Examples of the acrylic resin containing an acid group include copolymers obtained by polymerizing a monomer having a (meth) acryloyl group and a polymerizable monomer having an acid group as essential components, and if necessary, other polymerizable unsaturated monomers. The monomer having a (meth) acryloyl group may also be a polymerizable monomer having an acid group, and in this case, the acrylic resin containing an acid group may be a homopolymer of the polymerizable monomer having a (meth) acryloyl group and an acid group. In the present specification, the term "(meth) acryloyl group" means one or both of an acryloyl group and a methacryloyl group, the term "(meth) acrylic acid" means one or both of acrylic acid and methacrylic acid, and the term "(meth) acrylate" means one or both of an acrylate and a methacrylate.

Examples of the polymerizable monomer having an acid group include: (meth) acrylic acid; compounds having a (meth) acryloyl group and a carboxyl group such as β -carboxyethyl (meth) acrylate, 2-acryloyloxyethylsuccinic acid (2-acryloyloxyethylsuccinic acid), 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethylhexahydrophthalic acid (2-acryloyloxyethylhexahydrophthalic acid) and lactone-modified products thereof;

compounds having a (meth) acryloyl group and a phosphoric acid group such as 2- (meth) acryloyloxyethyl acid phosphate, bis (2- (meth) acryloyloxyethyl) acid phosphate, phosphoric acid ester of polyethylene glycol mono (meth) acrylate, phosphoric acid ester of polypropylene glycol mono (meth) acrylate, phosphoric acid ester of polyalkylene glycol mono (meth) acrylate, phosphomethylene (meth) acrylate, phosphotrimethylene (meth) acrylate, phosphopropylene (meth) acrylate, and phosphotetramethylene (meth) acrylate;

compounds having a (meth) acryloyl group and a sulfonic acid group such as 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropane sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, or salts thereof;

crotonic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, and the like. These may be used alone or in combination of two or more.

Examples of the monomer having a (meth) acryloyl group include:

(meth) acrylic esters having an alkyl group having 1 to 22 carbon atoms, such as 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, and eicosyl (meth) acrylate;

(meth) acrylates having a cycloalkyl group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, and the like;

(meth) acrylates having an aromatic ring such as benzoyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate;

(meth) acrylates having a hydroxyalkyl group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glyceryl (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and polyalkylene glycol;

fluoroalkyl (meth) acrylates having 1 to 18 carbon atoms in a fluoroalkyl group such as 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 2H-heptadecafluorodecyl (meth) acrylate, and perfluoroethyloxyethyl (meth) acrylate;

a silane group-containing (meth) acrylate such as γ -methacryloxypropyltrimethoxysilane;

n, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, and N, N-diethylaminopropyl (meth) acrylate.

Examples of the other polymerizable unsaturated monomer include: unsaturated dicarboxylic acid esters such as dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate, and methyl ethyl itaconate;

styrene derivatives such as styrene, α -methylstyrene and chlorostyrene;

diene (diene) compounds such as butadiene, isoprene, pentadiene and dimethylbutadiene;

vinyl halides (vinyl halides) or vinylidene halides (vinylidenehalides) such as vinyl chloride and vinyl bromide;

unsaturated ketones such as methyl ketene and butyl ketene;

vinyl esters such as vinyl acetate and vinyl butyrate;

vinyl ethers such as methyl vinyl ether and butyl vinyl ether;

vinyl cyanides such as acrylonitrile, methacrylonitrile, and vinylidene cyanide;

acrylamide or alkyd-substituted amides thereof;

n-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

fluorine-containing α -olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene and hexafluoropropylene; perfluoroalkyl perfluorovinyl ethers having a perfluoroalkyl group of 1 to 18 carbon atoms such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether, and heptafluoropropyl trifluorovinyl ether; and fluorine-containing ethylenically unsaturated monomers.

These other polymerizable unsaturated monomers may be used alone or in combination of two or more.

The acrylic resin containing an acid group can be obtained by polymerization (copolymerization) using a known and conventional method, and the polymerization (copolymerization) form is not particularly limited. Any of random copolymers, block copolymers, graft copolymers, and the like can be used. 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.

The urethane resin having an acid group includes a reaction product of a composition containing a compound represented by the following formula (3) and a compound represented by the following formula (4).

[ solution 1]

(in the formula (3), X₁An aromatic ring or alicyclic ring structure in which two or more isocyanate groups are bonded through an alkyl group or directly and which may further have a substituent, and n1 and n2 each independently represent an integer of 0 to 3 inclusive)

[ solution 2]

(in the formula (4), R₇Represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms or a carbonyl group, and m1 to m3 each independently represents an integer of 0 to 3 inclusive)

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

The alicyclic structure of the compound represented by the formula (3) is preferably an alicyclic ring having 3 to 20 carbon atoms, and may be any of a monocyclic ring, a polycyclic ring, and a fused ring. The ring structure may be a combination of an alicyclic ring and an aromatic ring.

Examples of the monocyclic structure include cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane; and cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclooctene. Examples of the polycyclic structure include cubane, basketane, and houseane. Examples of the condensed ring structure include bicycloundecane, decahydronaphthalene, norbornene, norbornadiene, and the like.

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

As the compound represented by the formula (4), m3 is preferably 0. In addition, as the compound represented by the formula (4), R is preferable₇Is a hydrocarbon group having 1 to 3 carbon atoms.

Preferable specific examples of the compound represented by the formula (4) include dimethylolpropionic acid and dimethylolbutyric acid.

As the acid group-containing olefin resin, there may be mentioned: homopolymers or copolymers of acid group-containing monomers, copolymers of acid group-containing monomers and olefin monomers, acid group-containing monomer modifications of polyolefins, and the like.

The acid group-containing monomer used for producing a homopolymer or copolymer of an acid group-containing monomer is preferably an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride. Specifically, there may be mentioned: acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohex-4-ene-1, 2-dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2, 3-dicarboxylic anhydride, 1,2,3,4,5,8,9, 10-octahydronaphthalene-2, 3-dicarboxylic anhydride, 2-oct-1, 3-diketospiro [4.4] keto-7-ene, bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, methyl-bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylic anhydride, methyl-norborn-5-ene-2, 3-dicarboxylic anhydride, norborn-5-ene-2, 3-dicarboxylic anhydride, and the like.

As the acid group-containing monomer used for preparing the copolymer of the acid group-containing monomer and the olefin-based monomer, the same monomer as the acid group-containing monomer used for preparing the homopolymer or copolymer of the acid group-containing monomer can be used. Can be used alone or in combination of two or more. Maleic anhydride is preferably used.

The olefin monomer used for preparing the copolymer of the acid group-containing monomer and the olefin monomer includes olefins having 2 to 8 carbon atoms, and examples thereof include: ethylene, propylene, isobutylene, 1-butene, 4-methyl-1-pentene, hexene, vinylcyclohexane, and the like. Of these, particularly, in terms of good adhesion strength, the olefin having 3 to 8 carbon atoms is preferable, and propylene and 1-butene are more preferable, and in terms of excellent resistance to solvents and excellent adhesion strength, the combined use of propylene and 1-butene is particularly preferable.

In the production of the copolymer of the acid group-containing monomer and the olefin-based monomer, not only the acid group-containing monomer and the olefin-based monomer, but also other compounds having an ethylenically unsaturated group, such as styrene, butadiene, isoprene, and the like, may be used in combination.

As the acid group-containing monomer used for preparing the acid group-containing monomer modification of the polyolefin, the same monomer as the acid group-containing monomer used for preparing the homopolymer or copolymer of the acid group-containing monomer can be used. Can be used alone or in combination of two or more. Maleic anhydride is preferably used.

Examples of the polyolefin used as the modified product of the acid group-containing monomer for producing the polyolefin include: homopolymers or copolymers of olefins having 2 to 8 carbon atoms, copolymers of olefins having 2 to 8 carbon atoms with other monomers, and the like, and examples thereof include: high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyethylene such as linear low-density polyethylene resin, polypropylene, polyisobutylene, poly (1-butene), 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 copolymer, propylene-1-butene copolymer, and other α -olefin copolymers, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate-methyl methacrylate copolymer, ionomer resin, and the like. Of these, in particular, in terms of the adhesion strength being good, a homopolymer of an olefin having 3 to 8 carbon atoms or a copolymer of two or more kinds of olefins having 3 to 8 carbon atoms is preferable, and a homopolymer of propylene or a propylene/1-butene copolymer is more preferable, and in terms of the resistance to a solvent being excellent and the adhesion strength being excellent, a propylene/1-butene copolymer is particularly preferable.

Examples of the method for modifying a polyolefin with a monomer having an acid group include graft modification and copolymerization. When the monomer having an acid group is reacted with the polyolefin by graft modification, specific examples thereof include: a method in which a polyolefin is melted and a monomer having an acid group (graft monomer) is added thereto to carry out a graft reaction; a method in which a polyolefin is dissolved in a solvent to prepare a solution, and a graft monomer is added thereto to carry out a graft reaction; a method of mixing a polyolefin dissolved in an organic solvent with a graft monomer, and heating the mixture at a temperature not lower than the softening temperature or the melting point of the polyolefin to simultaneously perform radical polymerization and dehydrogenation in a molten state.

In either case, the graft copolymerization is preferably carried out in the presence of a radical initiator in order to efficiently graft-polymerize the graft monomer. The grafting reaction is generally carried out at from 60 ℃ to 350 ℃. The amount of the radical initiator used is usually in the range of 0.001 to 1 part by weight based on 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 for satisfactory adhesion. In order to ensure appropriate fluidity, the weight average molecular weight of the olefin resin containing an acid group 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.

A measuring device: HLC-8320GPC manufactured by Tosoh corporation

Pipe column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Co Ltd

A detector: RI (differential refractometer)

Data processing: multi-station (Multi station) GPC-8020 model II manufactured by Tosoh corporation

The measurement conditions were as follows: the temperature of the column is 40 DEG C

Solvent tetrahydrofuran

Flow rate 0.35 ml/min

The standard is as follows: monodisperse polystyrene

Sample preparation: a tetrahydrofuran solution (0.2 mass% in terms of solid content of the resin) was filtered through a microfilter (100. mu.l)

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

The melting point of the olefin resin containing an acid group is measured by Differential Scanning Calorimetry (DSC). Specifically, the temperature is raised from the temperature reduction end temperature to the temperature rise end temperature at 10 ℃/min, then the temperature is cooled to the temperature reduction end temperature at 10 ℃/min, and after the thermal hysteresis is removed, the temperature is raised again to the temperature rise achievement point at 10 ℃/min. The peak temperature at the second temperature rise was defined as the melting point. The temperature at which the temperature decrease is completed is set to a temperature 50 ℃ or higher lower than the crystallization temperature, and the temperature at which the temperature increase is completed is set to a temperature 30 ℃ or higher than the melting point temperature. The temperature decrease completion temperature and the temperature increase completion temperature are determined by performing a test measurement.

Specific examples of such an acid group-containing olefin resin include: maleic anhydride-modified polypropylene, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylate-maleic anhydride terpolymers, and the like. As commercially available products of olefin resins containing an acid group, there can be mentioned: "MODIC" series manufactured by mitsubishi chemical (stock), "Aldrich (ADMER)" series manufactured by mitsubishi chemical (stock), "UNISTOLE" series manufactured by vinyon (stock), "TOYO-TAC" series manufactured by toyankee chemical (stock), "UMEX (UMEX)" series manufactured by mitsui chemical (stock), "REXPEARL (REXPEARL) EAA" series manufactured by japan polyethylene (stock), "REXPEARL (REXPEARL) ET" series, "pimaco" (Primacor) series manufactured by dow chemical (stock), "Niukel (NUCREL)" series manufactured by mitsui chemical (stock), and "BONDINE (bond)" series manufactured by ARKEMA (arkinsona).

As the acid group-containing resin (a1), resins other than those described above can be used, and examples thereof include taftatai (Tuftec) M series manufactured by asahi chemical corporation, Kraton polmer Japan, Kraton FG series manufactured by Kraton polmer Japan.

The first agent may contain not only the resin (a1) containing an acid group but also a resin (a2) having no reactive functional group as the resin (a). 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 reduced, and the resistance to the electrolyte is improved.

Examples of the resin (A2) include homopolymers or 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: polyethylene such as High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), linear low density polyethylene resin, polypropylene, polyisobutylene, poly (1-butene), 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 copolymer, and other α -olefin copolymers, ethylene-methyl methacrylate copolymer, propylene-1-butene copolymer, and the like. Of these, in particular, from the viewpoint of improving the adhesive strength, a homopolymer of an olefin having 3 to 8 carbon atoms or a copolymer of two or more kinds of olefins having 3 to 8 carbon atoms is preferable, a homopolymer or a copolymer of propylene is more preferable, and a homopolymer of propylene is more preferable.

The weight average molecular weight of the resin (A2) is preferably 2000 to 200,000 in terms of high solubility in a solvent and improved coatability. The weight average molecular weight of the resin (A2) is more preferably 20,000 to 180,000, and still more preferably 40,000 to 160,000.

The melting point of the resin (A2) is preferably 50 to 100 ℃. The melting point of 50 ℃ or higher can improve the electrolyte resistance more reliably, and the melting point of 100 ℃ or lower can maintain good coatability. The melting point of the resin (A2) is more preferably 60 to 95 ℃, and still more preferably 70 to 90 ℃.

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

In addition, the acid value of the first agent is used: the coefficient (f) obtained from a calibration curve prepared using a Fourier transform Infrared Spectrometer (FT-IR) (FT-IR 4200, manufactured by Nippon spectral Co., Ltd.) and a chloroform solution of maleic anhydride, and the expansion and contraction peak (1780 cm) of the anhydride ring of maleic anhydride in the maleic anhydride-modified polyolefin solution^-1) Absorbance of (I) and a stretching peak of a carbonyl group of maleic acid (1720 cm)^-1) The absorbance (II) of (1), and a value calculated by the following formula. In the following formula, the molecular weight of maleic anhydride was 98.06 and the molecular weight of potassium hydroxide was 56.11.

[ number 1]

(second agent)

The second agent contains an epoxy compound (B1) as a so-called curing agent (B) having reactivity with the acid group-containing resin (A1), and the viscosity of the epoxy compound (B1) at 52 ℃ is 0.05Pa · s or more and 25Pa · s or less. The viscosity of the epoxy compound (B1) was measured using a rotational viscometer on a cone plate (cone plate): the measurement was carried out at 1 ℃ XR 25. 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, there can be mentioned: polyglycidyl ether type epoxy resins of aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, hexylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, diglycerol, sorbitol, spiroglycol, and hydrogenated bisphenol a;

bisphenol epoxy resins such as bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol AD epoxy resin;

aromatic epoxy resins such as novolak type epoxy resins which are glycidyl ethers of phenol novolak resins or cresol novolak resins;

polyglycidyl ethers of polyhydric alcohols which are ethylene oxide or propylene oxide adducts of aromatic polyhydroxy compounds such as bisphenol a, bisphenol F, bisphenol S, and bisphenol AD;

polyglycidyl ether type epoxy resins of polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; cyclic aliphatic polyepoxy resins such as bis (3, 4-epoxycyclohexylmethyl) hexanoate and 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexylcarboxylate;

polyglycidyl ester type epoxy resins of polycarboxylic acids such as propane tricarboxylic acid, butane tetracarboxylic acid, adipic acid, phthalic acid, terephthalic acid, and trimellitic acid;

diepoxy resins of hydrocarbon dienes such as butadiene, hexadiene, octadiene, dodecanediene, cyclooctadiene, α -pinene and vinylcyclohexene;

epoxy resins of diene polymers such as polybutadiene and polyisoprene;

glycidyl amine type epoxy resins such as tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, tetraglycidyl bisaminomethylcyclohexane, diglycidyl aniline, and tetraglycidyl m-xylylenediamine;

epoxy resins containing heterocyclic rings such as triazine and hydantoin.

These epoxy resins may be used alone or in combination of two or more.

The viscosity of the epoxy compound (B1) at 52 ℃ is more preferably 0.05Pa · s or more and 5Pa · s or less, and is more preferably 0.05Pa · s or more and 2Pa · s or less. 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 a weight average molecular weight of 3000 or less.

The second agent may contain an epoxy compound (B2) described later or a compound (B3) reactive with the acid group-containing resin (a1), but in this case, it is also preferable that the proportion of the epoxy compound (B1) in the curing agent (B) contained in the second agent is four or more. This makes it possible to produce an adhesive having good adhesion and electrolyte resistance even when the curing is performed at low temperature. The proportion of the epoxy compound (B1) in the curing agent (B) is more preferably five or more, and still more preferably eight or more. The total amount of hardener (B) can also be epoxy compound (B1).

The second agent may also contain an epoxy compound (B2) other than the epoxy compound (B1). The structure of the epoxy compound (B2) is the same as that of the epoxy compound (B1). When not only the epoxy compound (B1) but also the epoxy compound (B2) is used, the amount of the epoxy compound (B2) to be blended is preferably six or less, more preferably five or less, and still more preferably two or less of the curing agent (B).

The second agent may be used in combination with a compound (B3) other than the epoxy compound (B1) which is reactive with the acid group-containing resin (a 1). Examples of the other compound (B3) which can be used in combination with the epoxy compound (B1) include: polyfunctional isocyanate compounds, aziridine group-containing compounds, carbodiimides, oxazolines, amino resins, and the like.

As the polyfunctional isocyanate compound, there can be mentioned: diisocyanates such as 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate, bis (4-isocyanatocyclohexyl) methane, or hydrogenated diphenylmethane diisocyanate, and compounds derived therefrom, i.e., isocyanurates, adducts, biuret types, uretdione (uretdione) bodies, allophanate (allophanate) bodies, prepolymers having an isocyanate residue (oligomers obtained from diisocyanates and polyols), or complexes thereof.

A compound obtained by reacting a part of the isocyanate groups of the polyfunctional isocyanate compound described above and a compound having reactivity with the isocyanate groups may also be used as the hardener. As compounds reactive with isocyanate groups, mention may be made of: amino group-containing compounds such as butylamine, hexylamine, octylamine, 2-ethylhexylamine, dibutylamine, ethylenediamine, benzylamine, and aniline; hydroxyl group-containing compounds such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, octanol, 2-ethylhexyl alcohol, lauryl alcohol, ethylene glycol, propylene glycol, benzyl alcohol, and phenol; compounds having an epoxy group such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol glycidyl ether, and cyclohexanedimethanol diglycidyl ether; and carboxylic acid-containing compounds such as acetic acid, butyric acid, caproic acid, caprylic acid, succinic acid, adipic acid, sebacic acid, and phthalic acid.

Examples of the aziridinyl group-containing compound include: n, N '-hexamethylene-1, 6-bis (1-aziridinecarboxamide), N' -diphenylmethane-4, 4 '-bis (1-aziridinecarboxamide), trimethylolpropane-tris- β -aziridinylpropionate), N' -toluene-2, 4-bis (1-aziridinecarboxamide), triethylenemelamine, trimethylolpropane-tris- β (2-methylaziridine) propionate, bis-isophthaloyl-1-2-methylaziridine, tris-1-aziridinyloxyphosphine oxide, tris-1-2-methylaziridine phosphine oxide, and the like.

Examples of carbodiimides include: n, N '-di-o-benzoylcarbodiimide, N' -diphenylcarbodiimide, N '-di-2, 6-dimethylphenylcarbodiimide, N' -bis (2, 6-diisopropylphenyl) carbodiimide, N '-dioctyldecylcarbodiimide, N-toluoyl-N' -cyclohexylcarbodiimide, n, N '-di-2, 2-tert-butylphenyl carbodiimide, N-toluoyl-N' -phenylcarbodiimide, N '-di-p-aminophenyl carbodiimide, N' -di-p-hydroxyphenyl carbodiimide, N '-di-cyclohexylcarbodiimide, N' -di-p-toluoyl-carbodiimide, and the like.

As oxazoline (oxazoline), there may be mentioned: 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2, 5-dimethyl-2-oxazoline, 2, 4-diphenyl-2-oxazoline and other monooxazoline compounds, 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.

Examples of the amino (amino) resin include: melamine resins, benzoguanamine resins, urea resins, and the like.

When the second agent contains the compound (B3) reactive with the acid group-containing resin (a1), the amount of the compound (B3) to be blended is preferably six or less, more preferably five or less, and still more preferably two or less of the curing agent (B).

The amount of the curing agent (B) to be blended is preferably adjusted within a range in which the equivalent ratio of the reactive functional group (a) contained in the first agent to the reactive functional group (B) contained in the second agent, which is capable of reacting with the functional group (a) of the first agent (functional group (a)/functional group (B)), is 0.01 to 10, and more preferably 0.1 to 5.0. This makes it possible to produce an adhesive excellent in adhesion and electrolyte resistance.

(organic phosphorus Compound)

The adhesive of the present invention further comprises an organophosphorus compound (C). The organophosphorus compound (C) includes organophosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-butylphenyl) phosphine, diphenylphosphine, and phenylphosphine, and may be used alone or in combination of two or more.

The amount of the organophosphorus compound (C) is 0.01 to 5 parts by mass based on 100 parts by mass of the first resin. This makes it possible to produce an adhesive agent having good adhesive strength and electrolyte resistance even when aged at low temperatures. The amount of the organophosphorus compound (C) to be blended is more preferably 0.01 part by mass or more and 0.5 part by mass or less, and still more preferably 0.01 part by mass or more and 0.1 part by mass or less, based on 100 parts by mass of the resin in the first part, because the effect begins to saturate when the amount reaches a certain level.

The organophosphorus compound (C) may be previously prepared in 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-2-ethyl-4-methylimidazole, and two or more kinds thereof may be used alone or in combination.

The amount of the imidazole compound (D) is 0.06 parts by mass or more and 0.35 parts by mass or less based on 100 parts by mass of the resin of the first part. This makes it possible to produce an adhesive agent having good adhesive strength and electrolyte resistance even when aged at low temperatures. The amount of the imidazole compound (D) to be blended is more preferably 0.06 part by mass or more and 0.30 part by mass or less, and still more preferably 0.06 part by mass or more and 0.25 part by mass or less, with respect to 100 parts by mass of the resin of the first part.

The imidazole compound (D) may be prepared in advance in the first dose, or may be added when the first dose is mixed with the second dose.

The reason why the adhesive of the present invention is excellent in adhesive strength and electrolyte resistance particularly when cured at low temperature is not determined, but it is presumed as follows. When the viscosity is in the above range, the epoxy compound (B1) can be homogeneously dispersed in the resin (a) in a solution state in the coating film in the curing process after drying the organic solvent (E). It is considered that the presence of the organic phosphorus compound (C) and the imidazole compound (D) in appropriate amounts therein extremely suitably promotes the reaction between the acid group-containing resin (a1) and the curing agent (B), and thereby forms a cured coating film having excellent electrolyte resistance.

On the other hand, it is presumed that: if the viscosity is too low, the epoxy compound (B1) is not dispersed but unevenly present in the resin (a), and the acid group-containing resin (a1) cannot be appropriately crosslinked to affect the adhesion strength or the electrolyte resistance, and if the viscosity of the epoxy compound (B2) is too high, the adhesive does not sufficiently wet and spread on the substrate in a low temperature region, and the reaction is not sufficiently accelerated even in the presence of the organophosphorus compound (C) and the imidazole compound (D). If the imidazole compound (D) is too much, the remaining imidazole compound (D) may adversely affect the cured coating film, shorten the life, and reduce the storage stability of the adhesive.

(organic solvent)

The adhesive of the present invention can exhibit proper coatability while securing fluidity by blending not only the above-mentioned components but also the organic solvent (E). Such an organic solvent (E) is not particularly limited as long as it can be volatilized and removed by heating in the drying step at the time of adhesive application, and examples thereof include: aromatic organic solvents such as toluene and xylene; aliphatic organic solvents such as n-hexane and n-heptane; alicyclic organic solvents such as cyclohexane and methylcyclohexane; halogen-based organic solvents such as trichloroethylene, dichloroethylene, chlorobenzene, and chloroform; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; alcohol solvents such as ethanol, methanol, n-propanol, 2-propanol (isopropanol), butanol, and hexanol; ether solvents such as diisopropyl ether, butyl cellosolve, tetrahydrofuran, dioxane, and butyl carbitol; glycol ether solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and propylene glycol monomethyl ether; and glycol ester solvents such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate, which may be used alone or in combination of two or more.

The acid group-containing resin (a1) is preferably a mixed solvent of an alicyclic organic solvent and an ester solvent in terms of excellent solubility. 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 in terms of excellent solubility. In order to further 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. In this case, the alcohol solvent is preferably isopropanol, 2-butanol or the like.

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. In this case, toluene is preferably used as the aromatic organic solvent, and methyl ethyl ketone is preferably used as the ketone solvent.

The amount of the organic solvent (E) used is preferably such that the proportion of the resin (a) is 5 to 30 mass% based on the total mass of the resin (a) and the organic solvent (E). This makes it possible to produce an adhesive excellent in coatability and wettability with respect to a metal film.

The adhesive of the present invention may contain various additives such as acid anhydride, adhesion promoter, adhesion imparting agent, plasticizer, thermoplastic elastomer, reactive elastomer, phosphoric acid compound, and silane coupling agent, as required. The content of these additives may be appropriately adjusted within a range not to impair the function of the adhesive of the present invention.

Examples of the acid anhydride include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, and unsaturated carboxylic acid anhydrides, and one or two or more kinds of acid anhydrides may be used in combination. More specifically, for example, there may be mentioned: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecylsuccinic anhydride, polyhexamic anhydride, polyazelaic anhydride, polysebacic anhydride, poly (ethyloctadecanedioic) anhydride, poly (phenylhexadecanedioic) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethyltetrahydrophthalic anhydride (MHAC), trialkyltetrahydrophthalic anhydride, methylcyclohexanedicarboxylic anhydride, methylcyclohexanetetracarboxylic anhydride, ethylene glycol ditrimellitic dianhydride, biotic anhydride (HET anhydride), nadic anhydride (nadic anhydride), methylnadic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1, 2-dicarboxylic anhydride, 3, 4-dicarboxy-1, 2,3, 4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1, 2,3, 4-tetrahydro-1-naphthalene succinic dianhydride, and the like.

As the acid anhydride, an acid anhydride obtained by modifying the above compound with a diol can be used. Examples of diols which can be used for the modification include: alkanediols such as ethylene glycol, propylene glycol and neopentyl glycol; polyether glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol. Further, a copolymerized polyether diol of two or more kinds of these diols and/or polyether diols may also be used.

The amount of the acid anhydride blended is preferably 0.01 parts by mass or more, more preferably 0.8 parts by mass or more, per 100 parts by mass of the resin (a). The amount of the acid anhydride blended is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and still more preferably 1.5 parts by mass or less, per 100 parts by mass of the resin (a). This improves the adhesion between the adhesive and the metal, and enables the production of an adhesive having excellent initial adhesion strength and excellent adhesion strength after heat sealing.

The reason why the adhesive has excellent adhesiveness and heat resistance by using the acid anhydride is not clearly understood, but it is assumed as follows. The acid anhydride includes a polar group and is excellent in affinity for a metal substrate. In addition, the molecular weight is relatively small and therefore relatively easy to move. Before the applied adhesive is completely cured, the acid anhydride migrates to the metal substrate side and acts as a so-called anchor (anchor), which is considered to contribute to improvement of adhesion and heat resistance.

Examples of the adhesion promoter include: tertiary amines such as triethylamine, triethylenediamine, N' -methyl-N- (2-dimethylaminoethyl) piperidine, 1, 8-diazabicyclo [5.4.0] undecene (DBU), 1, 5-diazabicyclo [4.3.0] -nonene, 6-dibutylamino-1, 8-diazabicyclo [5.4.0] undecene, and compounds represented by the following structural formulae (5) to (15), compounds obtained by converting these tertiary amines into amine salts using phenol, octylic acid, quaternary tetraphenylborate, and the like, and cationic catalysts such as triallylsulfonium hexafluoroantimonate and diallyliodohexafluoroantimonate. These may be used alone or in combination of two or more. In the following structural formulae (5) to (15), a hydrogen atom bonded to a carbon atom is omitted.

[ solution 3]

Examples of the adhesion-imparting agent include: rosin-based or rosin ester-based tackiness imparting agents, terpene-based or terpene-phenol-based tackiness imparting agents, saturated hydrocarbon resins, coumarin-based tackiness imparting agents, coumarin-indene-based tackiness imparting agents, styrene resin-based tackiness imparting agents, xylene resin-based tackiness imparting agents, phenol resin-based tackiness imparting agents, petroleum resin-based tackiness imparting agents, and the like. These may be used alone or in combination of two or more.

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

Examples of the phosphoric acid compound include: phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid and hypophosphorous acid, for example, condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid and perphosphoric 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 diphenylphosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, di-2-ethylhexyl phosphite and diphenyl phosphite, monoesters and diesters derived from condensed phosphoric acids and alcohols, for example, addition of ethylene oxide to the phosphoric acids, ethylene oxide to the phosphoric acids, Examples of the epoxy compound include epoxy phosphates obtained by adding the above-mentioned phosphoric acid compound to aliphatic or aromatic diglycidyl ether.

Examples of the silane coupling agent include: aminosilanes such as γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethyldimethoxysilane, and N-phenyl- γ -aminopropyltrimethoxysilane; epoxysilanes such as beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-glycidoxypropyltriethoxysilane; vinyl silanes such as vinyltris (β -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and γ -methacryloxypropyltrimethoxysilane; hexamethyldisilazane, gamma-mercaptopropyltrimethoxysilane, and the like.

The adhesive of the present invention can be prepared by mixing the components. In this case, the respective components may be mixed at the same time to prepare an adhesive, but in terms of excellent stability and workability of the adhesive, it is preferable to prepare, for example, a two-pack type adhesive in which a pre-mixture (premix) is prepared by mixing components other than the curing agent (B) in advance and the curing agent (B) is mixed at the time of using the adhesive, and a three-pack type adhesive in which a first agent mainly composed of the resin (a), a second agent mainly composed of the curing agent (B), and a third agent containing other components (for example, the organophosphorus compound (C) and the imidazole compound (D)) are mixed just before using the adhesive. In the present specification, a two-pack type adhesive and a three-pack type (or more) adhesive are collectively referred to as a multi-pack type adhesive.

The adhesive of the present invention is excellent in adhesion to a nonpolar substrate such as an olefin resin and a metal substrate, and heat resistance.

< laminate >

The laminated body comprises a first base material, a second base material and an adhesive layer which is arranged between the first base material and the second base material and is used for bonding the first base material and the second base material. The adhesive layer is a cured coating of the adhesive. The substrate may include not only the first substrate and the second substrate, but also other substrates. The adhesive layer for bonding the first substrate and the other substrate and the second substrate and the other substrate may or may not be a cured coating film of the adhesive of the present invention.

As the first substrate, the second substrate, and other substrates, for example, paper; a synthetic resin film obtained from an olefin-based resin, an acrylonitrile-butadiene-styrene copolymer (ABS resin), a polyvinyl chloride-based resin, a fluorine-based resin, a poly (meth) acrylic resin, a carbonate-based resin, a polyamide-based resin, a polyimide-based resin, a polyphenylene ether-based resin, a polyphenylene sulfide-based resin, or a polyester-based resin; metal foils such as copper foil and aluminum foil.

The adhesive of the present invention is preferably one of the first substrate and the second substrate which is a nonpolar substrate and the other of the first substrate and the second substrate which is a metal substrate, because the adhesive is excellent in adhesion between a nonpolar substrate such as an olefin resin and a metal substrate, but is not limited thereto.

The laminate of the present invention can be obtained by coating one of the first substrate and the second substrate with the adhesive of the present invention, then laminating the other, and hardening the adhesive. It is preferable to provide a drying step between the coating of the adhesive and the lamination of the first base material and the second base material.

As the method of applying the adhesive, a gravure coater method, a microgravure coater method, a reverse coater method, a bar coater method, and the like can be usedA coater system, a roll coater system, a die coater system, and the like. The amount of the adhesive applied is preferably 0.5g/m in terms of the coating weight after drying²～20.0g/m²Is adjusted. If it is less than 0.5g/m²When the amount exceeds 20.0g/m, the continuous uniform coatability tends to be lowered²The solvent release property after coating is also lowered, and problems such as lowering of workability and remaining of solvent tend to occur.

The temperature of the laminating roller when laminating the first base material and the second base material is preferably 25 ℃ to 120 ℃ and the pressure is preferably 3kg/cm²～300kg/cm²。

Preferably, the curing step is provided after the first substrate and the second substrate are bonded to each other. The aging conditions are preferably 25 to 100 ℃ for 12 to 240 hours.

The adhesive of the present invention exhibits excellent effects particularly when the curing temperature is 60 ℃ or lower, and further 55 ℃ or lower, which is much lower than the reaction temperature of an ordinary acid and an epoxy group, and exhibits good initial adhesive strength and electrolyte resistance. When the aging is carried out at 60 ℃ or lower, the aging time is preferably 24 hours or more. The upper limit of the aging time is not particularly limited, and a sufficient effect is exhibited when the time is about 168 hours. From the viewpoint of the balance between the aging temperature and the aging time, it is preferable to perform the aging step at 40 to 60 ℃ for 24 to 168 hours.

< packaging Material for Battery >

As an example, the battery packaging material of the present invention includes a first base material, a second base material, a third base material, a first adhesive layer that bonds the first base material to the second base material, and a second adhesive layer that bonds the second base material to the third base material. The first substrate is a polyolefin film and the second substrate 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 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. On the opposite side of the third substrate to the second adhesive layer, another substrate may be disposed with or without an adhesive layer therebetween, or a coating layer may be provided. Other substrates or coatings may not be provided.

The polyolefin film may be appropriately selected from conventionally known olefin resins. For example, polyethylene, polypropylene, ethylene-propylene copolymer, etc. can be used, but are not particularly limited. Preferably a non-stretched film. The thickness of the polyolefin film is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, and still more 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.

When a battery described later is manufactured, the first base material functions as a sealant (sealant) layer when the battery packaging materials of the present invention are heat-sealed and bonded to each other.

Examples of the metal foil include aluminum, copper, and nickel. These metal foils may be subjected to surface treatments such as blasting, polishing, degreasing, aging, surface treatment by dipping or spraying with a rust preventive, trivalent chromium chemical synthesis treatment, phosphate chemical synthesis treatment, sulfide chemical synthesis treatment, anodic oxide film formation, and fluororesin coating. Of these, those obtained by applying a trivalent chromium chemical synthesis treatment are preferable in terms of excellent adhesion retention performance (resistance to environmental deterioration) and corrosion resistance. In addition, the thickness of the metal film is preferably in the range of 10 μm to 100 μm from the viewpoint of corrosion prevention.

Examples of the resin film that can be used as the third substrate include resin films of polyester resin, polyamide resin, epoxy resin, acrylic resin, fluororesin, polyurethane resin, silicone resin, phenol resin, and a mixture or copolymer thereof. Of these, polyester resins and polyamide resins are preferable, and biaxially stretched polyester resins and biaxially stretched polyamide resins are more preferable. Specific examples of the polyester resin include: polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolyester, polycarbonate, and the like. Further, as the polyamide resin, specifically, there can be mentioned: nylon 6, copolymers of nylon 6 and nylon 6, nylon 6,10, poly m-xylene adipamide (MXD6), and the like.

The coating layer can be formed using, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, or the like. Preferably, the resin is formed of a two-part curable resin. Examples of the two-component curable resin for forming the coating layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Further, a matting agent may be blended in the coating layer.

Examples of the matting agent include fine particles having a particle diameter of about 0.5nm 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 spherical, fibrous, plate-like, amorphous, and balloon-like shapes. Specific examples of the matting agent include: talc, silica, graphite, kaolin, montmorillonite (montmorillonite), synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, carbon black, carbon nanotubes, high-melting nylon, crosslinked acrylic acid, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel, and the like. These matting agents may be used singly or in combination of two or more. Among these matting agents, silicon oxide, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability, cost, and the like. The matting agent may be subjected to various surface treatments such as an insulating treatment and a high-dispersibility treatment in advance.

When a battery is produced, the laminate is molded so that the polyolefin film as the first base material is located inside the third base material, thereby forming the secondary battery packaging material of the present invention. The molding method is not particularly limited, and the following methods are exemplified.

A heated-air-pressure molding method: a method of forming the recess by sandwiching the battery packaging material between a lower mold having a hole to which high-temperature and high-pressure air is supplied and an upper mold having a pocket-shaped recess, and supplying air while heating and softening the upper mold.

A preheater flat plate type air compression molding method: a method of heating and softening the battery packaging material, sandwiching a lower mold having a hole to which high-pressure air is supplied and an upper mold having a pocket-shaped recess, and supplying air to form the recess.

Drum vacuum forming method: the method comprises heating and softening the packaging material for battery locally with a heating drum, and vacuum-sucking the packaging material for battery into the recessed part of the drum having the recessed part in the shape of a bag to mold the recessed part.

Needle (pin) molding method: and a method of heating and softening the substrate sheet and then pressing the substrate sheet with a bag-shaped concave-convex mold.

A pre-heater plug auxiliary pressure-air forming method: the method comprises heating and softening the packaging material for battery, sandwiching a lower mold having a hole and an upper mold having a pocket-shaped recess, to which high-pressure air is supplied, and supplying air to form the recess, wherein a convex plug is raised and lowered during molding to assist molding.

The pre-heater plug-assist press-air molding method, which is a heating vacuum molding method, is preferable because the wall thickness of the molded base material is uniform.

The battery packaging material of the present invention obtained as described above can be suitably used as a battery container for sealing and storing battery elements such as a positive electrode, a negative electrode, and an electrolyte.

< Battery >

The battery of the present invention is obtained by using the battery packaging material of the present invention, covering a battery element including a positive electrode, a negative electrode, and an electrolyte so that flange portions (regions where sealant layers contact each other) can be formed at the peripheral edge of the battery element in a state where metal terminals connected to the positive electrode and the negative electrode, respectively, protrude to the outside, and heat-sealing the sealant layers of the flange portions to each other to seal the battery element.

The battery obtained using the battery packaging material of the present invention may be either a primary battery or a secondary battery, and is preferably a secondary battery. The secondary battery is not particularly limited, and examples thereof include 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-zinc oxide storage battery, a metal air battery, a polyvalent cation battery, a capacitor (condenser), and a capacitor (capacitor). Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries are suitable as the battery packaging material of the present invention.