JPWO2019131591A1 - Adhesives, laminates, battery packaging materials and batteries - Google Patents

Abstract

Provide adhesives with excellent adhesiveness and heat resistance between non-polar substrates such as olefin resins and metal substrates, laminates with excellent heat resistance obtained using the adhesives, and battery packaging materials I do. It contains an olefin resin (A), a curing agent (B) containing an epoxy compound, and an acid anhydride (C), and the compounding amount of the acid anhydride (C) is 0.05 to 100 parts by mass of the olefin resin (A). Adhesive not less than 10 parts by mass and not more than 10 parts by mass, a premixture for the adhesive, a laminate using the adhesive, a packaging material for a battery, and a battery.

Description

  The present invention relates to an adhesive, and more particularly to a polyolefin-based adhesive suitable for bonding a resin substrate and a metal substrate, a laminate obtained by using the adhesive, a secondary battery exterior material, and a battery.

  A secondary battery typified by a lithium ion battery has a configuration in which an electrolyte and the like are sealed between a positive electrode, a negative electrode, and the like. In addition, a heat sealing layer made of an olefin resin, a metal base made of a metal foil such as an aluminum foil or a metal vapor-deposited layer, and a plastic encapsulating bag for encapsulating lead wires for taking out electricity of the positive electrode and the negative electrode to the outside. It is known to use a laminate in which is laminated (Patent Documents 1 and 2).

JP 09-283101 A JP 2007-294381 A

  However, since the olefin resin is non-polar, it is difficult to adhere to the metal substrate. When assembling a battery using the above-described laminate, the battery element is sealed by heat-sealing the sealant layers located at the periphery of the battery element to seal the battery element. Therefore, the adhesive for bonding the heat seal layer and the metal substrate needs to have heat resistance in addition to the adhesiveness between the non-polar substrate such as an olefin resin and the metal substrate.

  The present invention has been made in view of such circumstances, and has an object to provide an adhesive having excellent heat resistance and adhesion between a non-polar substrate such as an olefin resin and a metal substrate. I do. Further, it is another object of the present invention to provide a laminate obtained using such an adhesive, a secondary battery exterior material obtained using the laminate, and a battery.

  The present invention includes an olefin resin (A), a curing agent (B) containing an epoxy compound, and an acid anhydride (C), and the compounding amount of the acid anhydride (C) is based on 100 parts by mass of the olefin resin (A). About 0.05 to 10 parts by mass.

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

<Adhesive>
The adhesive of the present invention contains an olefin resin (A), a curing agent (B) containing an epoxy compound, and an acid anhydride (C). Hereinafter, each component of the adhesive of the present invention will be described in detail.

  Examples of the olefin resin (A) used in the adhesive of the present invention include homopolymers and copolymers of olefin monomers, copolymers of olefin monomers and other monomers, hydrides and halides of these polymers, and acids. And a polymer having a hydrocarbon skeleton as a main body, such as a modified product having a functional group such as a hydroxyl group or the like introduced therein, and one type or a combination of two or more types can be used. It is preferable to use a crystalline olefin resin having an acid group or an acid anhydride group and a crystalline olefin resin having a hydroxyl group.

  Examples of the olefin resin having an acid group or an acid anhydride group include an acid-modified olefin resin (A-1) which is a copolymer of an olefin monomer and an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic anhydride. And an acid-modified olefin resin (A-2) which is a resin obtained by graft-modifying a polyolefin with an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic anhydride.

  Examples of the olefin monomer used for preparing the acid-modified olefin resin (A-1) include olefins having 2 to 8 carbon atoms, for example, ethylene, propylene, isobutylene, 1-butene, 4-methyl-1-pentene, Hexene, vinylcyclohexane and the like. Among these, olefins having 3 to 8 carbon atoms are preferable because they have particularly good adhesive strength, and propylene and 1-butene are more preferable. It is preferable because it has excellent resistance and excellent adhesive strength.

  Examples of the ethylenically unsaturated carboxylic acid or the ethylenically unsaturated carboxylic anhydride used for copolymerization with an olefin monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, and maleic anhydride. Acid, 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-octa-1,3-diketospiro [4.4] non-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-dicarbo Acid anhydrides, methyl - norbornene-5-ene-2,3-dicarboxylic acid anhydride, norborn-5-ene-2,3-dicarboxylic anhydride and the like. Among them, particularly, the reactivity with an olefin-based monomer, the reactivity of an acid anhydride after copolymerization is excellent, and the molecular weight of the compound itself is small, and the functional group concentration when the copolymer is formed is high. To maleic anhydride. These can be used alone or in combination of two or more.

  To prepare the acid-modified olefin resin (A-1), in addition to the olefinic monomer, the thylene unsaturated carboxylic acid or the ethylenically unsaturated carboxylic anhydride, and other compounds having an ethylenically unsaturated group, for example, styrene, Butadiene, isoprene and the like may be used in combination.

  Examples of the polyolefin used for preparing the acid-modified olefin resin (A-2) include homopolymers and copolymers of olefins having 2 to 8 carbon atoms and copolymers of olefins having 2 to 8 carbon atoms with other monomers. For example, high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyethylene such as linear low-density polyethylene resin, polypropylene, polyisobutylene, poly (1-butene), and the like. Poly (4-methyl-1-pentene), polyvinylcyclohexane, ethylene / propylene block copolymer, ethylene / propylene random copolymer, ethylene / 1-butene copolymer, ethylene / 4-methyl-1-pentene copolymer Copolymer, α-olefin copolymer such as ethylene / hexene copolymer, ethylene / vinyl acetate copolymer Body, ethylene methyl methacrylate copolymer, ethylene-vinyl acetate-methyl methacrylate copolymer, and the like propylene-1-butene copolymer. Among these, homopolymers of olefins having 3 to 8 carbon atoms and copolymers of two or more olefins having 3 to 8 carbon atoms are preferable from the viewpoint of particularly good adhesive strength, and propylene homopolymer is preferable. A polymer or a propylene / 1-butene copolymer is more preferred, and a propylene / 1-butene copolymer is particularly preferred because it has excellent resistance to solvents and excellent adhesive strength.

  As the ethylenically unsaturated carboxylic acid or the ethylenically unsaturated carboxylic anhydride used for graft modification with a polyolefin, the ethylenically unsaturated carboxylic acid or the ethylenically unsaturated carboxylic acid anhydride is used for copolymerization with an olefin monomer in the preparation of the acid-modified olefin resin (A-1) described above. The same ones can be used. Maleic anhydride is preferred because the reactivity of the functional group after graft modification is high and the functional group concentration of the graft-modified polyolefin is high. These can be used alone or in combination of two or more.

  In order to react an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride with a polyolefin by graft modification, specifically, the polyolefin is melted, and an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid is added thereto. A method in which an acid anhydride (graft monomer) is added to cause a graft reaction, a polyolefin is dissolved in a solvent to form a solution, and an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride is added thereto to perform a graft reaction. Method, a polyolefin dissolved in an organic solvent, mixed with an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride, heated at a temperature above the softening temperature or melting point of the polyolefin, radical polymerization and hydrogen in a molten state A method in which the extraction reaction is performed at the same time is exemplified.

  In either case, it is preferable to carry out the graft reaction in the presence of a radical initiator in order to efficiently graft-copolymerize the graft monomer. The grafting reaction is usually performed at 60 to 350 ° C. The usage ratio of the radical initiator is usually in the range of 0.001 to 1 part by weight based on 100 parts by weight of the polyolefin before modification.

  As the radical initiator, an organic peroxide is preferable, for example, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne-3, 1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl- 2.5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylper-sec-octoate, tert-butyl Ruperupibareto and cumyl perpivalate and tert- butyl hydroperoxide diethyl acetate. Other azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate can also be used.

  As the radical initiator, an optimum one may be selected depending on the process of the graft reaction, and usually, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne Dialkyl peroxides such as -3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferably used.

  When the acid-modified olefin resin (A-1) or the acid-modified olefin resin (A-2) is used as the olefin resin (A), since the adhesion of the metal layer is further improved and the electrolyte resistance is excellent, 1 It is preferable to use one having an acid value of 200 mgKOH / g.

  As the olefin resin having a hydroxyl group (A-3), a copolymer of a polyolefin and a hydroxyl group-containing (meth) acrylate or a hydroxyl group-containing vinyl ether, or a hydroxyl group-containing (meth) acrylate or a hydroxyl group-containing vinyl ether grafted to the polyolefin. Modified resins are mentioned. As the polyolefin, those similar to those used for adjusting the olefin resin (A-2) can be used. As the modification method, the same method as the method for preparing the acid-modified olefin resins (A-1) and (A-2) can be used.

Examples of the hydroxyl group-containing (meth) acrylate used for the modification include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate. And polypropylene glycol mono (meth) acrylate.
Examples of the hydroxyl group-containing vinyl ether include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether.

  When the olefin resin (A-3) having a hydroxyl group is used as the olefin resin (A), the adhesion of the metal layer is further improved and the electrolyte resistance is excellent, so that the hydroxyl value of 1 to 200 mgKOH / g is used. It is preferable to use those having.

  As the olefin resin (A), the polyolefin used for adjusting the above-mentioned acid-modified olefin resin (A-2) or olefin resin having a hydroxyl group (A-3) may be used without modification.

  In order to improve the adhesiveness, the weight average molecular weight of the olefin resin (A) is preferably 40,000 or more. Further, the weight average molecular weight of the olefin resin (A) is preferably 150,000 or less in order to secure appropriate fluidity.

  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.

Measurement device: Tosoh Corporation HLC-8320GPC
Column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent Tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodisperse polystyrene sample: 0.2% by mass of resin in solid tetrahydrofuran solution filtered through a microfilter (100 μl)

  The melting point of the olefin resin (A) 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 olefin resin (A) is preferably 120 ° C. or lower, more preferably 90 ° C. or lower, and even more preferably 85 ° C. or lower.

  The melting point of the olefin resin is measured by DSC (differential scanning calorimetry). Specifically, the temperature is raised from the temperature dropping temperature to the temperature rising temperature at 10 ° C./min, cooled to the temperature dropping temperature at 10 ° C./min to remove the heat history, and then again raised at the temperature of 10 ° C./min. Raise the temperature to the point. The peak temperature at the second temperature rise is defined as the melting point. In addition, the temperature to be lowered is set to a temperature lower than the crystallization temperature by 50 ° C. or more, and the temperature to be raised is set to a temperature higher by about 30 ° C. than the melting point temperature. The temperature drop and the temperature rise are determined by trial measurement.

An epoxy compound is used as the curing agent (B). There is no particular limitation as long as the compound has an epoxy group in the molecule.Examples include ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, diglycerin, sorbitol, and spiro. Polyglycidyl ether type epoxy resin of aliphatic polyol such as glycol or hydrogenated bisphenol A;
Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and bisphenol AD type epoxy resin;
Aromatic epoxy resins such as phenol novolak resins and novolak type epoxy resins which are glycidyl ales of cresol novolak resins;
Polyglycidyl ether of a polyol which is an ethylene oxide or propylene oxide adduct of an aromatic polyhydroxy compound such as bisphenol A, bisphenol F, bisphenol S, bisphenol AD;
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 Cycloaliphatic polyepoxy resins 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;
Bisepoxy resin of a hydrocarbon diene such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α-pinene or vinylcyclohexene;
Epoxy resin of a diene polymer such as polybutadiene or polyisoprene;
Glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexane, diglycidylaniline, tetraglycidylmethaxylylenediamine;
Epoxy resins containing a heterocyclic ring such as triazine and hydantoin are exemplified.
These epoxy resins may be used alone or in combination of two or more.

  The epoxy compound 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.

  As the curing agent (B), a compound other than the epoxy resin may be used in combination. Examples of other curing agents that can be used in combination with the epoxy resin include a polyfunctional isocyanate compound, an aziridine group-containing compound, carbodiimide, 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-naphthalene diisocyanate, hexamethylene diisocyanate, and bis (4-isocyanatecyclohexyl). ) Diisocyanates such as methane or hydrogenated diphenylmethane diisocyanate and compounds derived therefrom, that is, isocyanurates, adducts, biurets, uretdiones, allophanates, and prepolymers having an isocyanate residue of the diisocyanate And a low polymer obtained from a polyol), or a composite thereof.

  A compound obtained by reacting a part of the isocyanate group of the polyfunctional isocyanate compound with a compound having reactivity with the isocyanate group may be used as a curing agent. Examples of compounds having reactivity with isocyanate groups include compounds having an amino group 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 a hydroxyl group: allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, neopentyl Glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, cyclohexane dimethanol di Compounds having an epoxy group such as glycidyl ether: acetic acid, butanoic acid, hexanoic acid, octanoic acid, succinic acid, adipic acid, sebacic acid, compounds containing a carboxylic acid such as phthalic acid.

  Examples of the aziridine group-containing compound include N, N′-hexamethylene-1,6-bis (1-aziridinecarboxamide) and N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide). , Trimethylolpropane-tri-β-aziridinylpropionate), N, N'-toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, trimethylolpropane-tri-β (2 -Methylaziridine) propionate, bisisophthaloyl-1-methylaziridine, tri-1-aziridinylphosphine oxide, tris-1-methylaziridinephosphine oxide and the like.

  Examples of the carbodiimide include N, N'-di-o-toluylcarbodiimide, N, N'-diphenylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N, N'-bis (2,6- 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-toluylcarbodiimide 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 ′-(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 resin include a melamine resin, a benzoguanamine resin, and a urea resin.

  The compounding amount of the curing agent (B) is preferably at least 0.01 part by mass, more preferably at least 0.1 part by mass, and preferably at least 0.5 part by mass, per 100 parts by mass of the olefin resin (A). It is more preferred that the amount be at least one part. Further, the compounding amount of the curing agent (B) is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and more preferably 5 parts by mass or less based on 100 parts by mass of the olefin resin (A). Is more preferable. Thereby, excellent adhesiveness and chemical resistance can be exhibited.

  Examples of the acid anhydride (C) include a cyclic aliphatic acid anhydride, an aromatic acid anhydride, an unsaturated carboxylic acid anhydride and the like, and one or a combination of two or more kinds can be used. More specifically, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazeleic anhydride, polysebacic acid Anhydride, poly (ethyl octadecane diacid) anhydride, poly (phenylhexadecane diacid) anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride , Methylhymic acid anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, ethylene glycol bistrimellitate dianhydride, hetanoic anhydride, nadic anhydride, Without methyl nadic acid , 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4- Examples thereof include tetrahydro-1-naphthalene succinic dianhydride and 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride.

  Further, as the acid anhydride (C), a compound obtained by modifying the above compound with glycol may be used. 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. Further, copolymerized polyether glycols of two or more of these glycols and / or polyether glycols can also be used.

  The compounding amount of the acid anhydride (C) is preferably at least 0.05 part by mass, more preferably at least 0.8 part by mass, per 100 parts by mass of the olefin resin (A). Further, the compounding amount of the acid anhydride (C) is preferably 10 parts by mass or less, more preferably 8 parts by mass or less based on 100 parts by mass of the olefin resin (A). Thereby, the adhesiveness between the adhesive and the metal is improved, and the adhesive having excellent initial adhesive strength and adhesive strength after heat sealing can be obtained.

  The reason why the adhesive of the present invention is excellent in adhesiveness and heat resistance is not clear, but is presumed as follows. The acid anhydride (C) used in the present invention has a polar group and is excellent in affinity for a metal substrate. In addition, since the molecular weight is relatively small, it is relatively easy to move. It is considered that the applied adhesive moves toward the metal base material by the time it is completely cured, and plays a role as a so-called anchor agent, thereby contributing to the improvement of adhesiveness and heat resistance. On the other hand, when the amount of the acid anhydride (C) contained in the adhesive is too large, the acid anhydride (C) forms a pseudo-low-strength layer between the metal substrate and the adhesive, It is considered that the adhesiveness is reduced due to this.

  The adhesive of the present invention can secure the fluidity by adding an organic solvent (D) in addition to the above-mentioned components, and can exhibit appropriate coating properties. Such an organic solvent is not particularly limited as long as it can be volatilized and removed by overheating in a drying step at the time of applying an adhesive. For example, aromatic organic solvents such as toluene and xylene; n-hexane, Aliphatic organic solvents such as n-heptane; alicyclic organic solvents such as cyclohexane and methylcyclohexane; halogen organic solvents such as trichloroethylene, dichloroethylene, chlorobenzene and chloroform; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Ester-based solvents such as ethyl acetate and butyl acetate; alcohol-based solvents such as ethanol, methanol, n-propanol, 2-propanol (isopropyl alcohol), butanol, and hexanol; diisopropyl ether, butyl cellosolve, and tetrahydride Ether solvents such as furan, dioxane, butyl carbitol; glycol ether solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol mono Glycol ester solvents such as ethyl ether acetate may be used, and these may be used alone or in combination of two or more.

  Even when a chlorine-free olefin resin, an olefin resin having an acid group or an acid anhydride group or an olefin resin having a hydroxyl group is used as the olefin resin (A), the alicyclic group It is preferable to use a mixed solvent of an organic solvent, an ester solvent, and an alcohol solvent. In particular, when an olefin resin having an acid group or an acid anhydride group is used, a mixed solvent of methylcyclohexane, ethyl acetate, and isopropyl alcohol is preferably used because of excellent solubility.

  The amount of the organic solvent used is preferably such that the ratio of the olefin resin (A) to the total mass of the olefin resin (A) and the organic solvent (D) is 10 to 30% by mass. Thereby, an adhesive having excellent coating properties and wettability to a metal film can be obtained.

  As the adhesive of the present invention, various additives such as a tackifier, a plasticizer, a thermoplastic elastomer, a reactive elastomer, a phosphoric acid compound, a silane coupling agent, and an adhesion promoter can be used as needed. 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 tackifiers that can be used here include, for example, rosin-based or rosin-ester-based tackifiers, terpene-based or terpene-phenol-based tackifiers, saturated hydrocarbon resins, cumarone-based tackifiers, and cumarone-indene-based tackifiers. Agents, styrene resin-based tackifiers, xylene resin-based tackifiers, phenolic resin-based tackifiers, petroleum resin-based tackifiers, 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), hydrogenated styrene-butadiene copolymer (SEBS), SBBS, and styrene-isoprene. Hydrogenated copolymers (SEPS), styrene block copolymers (TPS), olefin-based elastomers (TPO), and the like, and reactive elastomers include those obtained by acid-modifying these elastomers.

  As the phosphoric acid compound, for example, hypophosphorous acid, phosphorous acid, orthophosphoric acid, phosphoric acid such as hypophosphoric acid, for example, metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, condensed phosphoric acid such as ultraphosphoric acid, for example, Monomethyl orthophosphate, Monoethyl orthophosphate, Monopropyl orthophosphate, Monobutyl orthophosphate, Mono-2-ethylhexyl orthophosphate, Monophenyl orthophosphate, Monomethyl phosphite, Monoethyl phosphite, Monoethyl phosphite, Monopropyl phosphite, Monobutyl phosphite , Mono-2-ethylhexyl phosphite, monophenyl phosphite, di-2-ethylhexyl orthophosphate, dimethyl orthophosphite, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, phosphorous acid Di-2-ethylhexyl, diphenyl phosphite, etc. Mono-, di-esterified products, mono-, di-esterified products from condensed phosphoric acid and alcohols, for example, those obtained by adding an epoxy compound such as ethylene oxide or propylene oxide to the above-mentioned phosphoric acids, for example, aliphatic or aromatic diglycidyl Epoxy phosphates obtained by adding the above-mentioned phosphoric acids to ether are exemplified.

  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 and N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Epoxy silanes such as xypropyltriethoxysilane; vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane; hexamethyldisilazane, γ-merca DOO trimethoxysilane and the like.

  Examples of the adhesion promoter include 2-methylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2. Compounds such as -ethyl-4-methylimidazole, triethylamine, triethylenediamine, N'-methyl-N- (2-dimethylaminoethyl) piperazine, 1,8-diazabicyclo [5.4.0] undecene (DBU) Tertiary amines such as 1,5-diazabicyclo [4.3.0] -nonene, 6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene, and tertiary amines such as phenol and octyl. Acid, quaternized tetraphenylborate salt, etc. to make amine salt, triallylsulfo Cationic catalysts such as sodium hexafluoroantimonate, diallyliodonium hexafluoroantimonate, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-butylphenyl) phosphine, diphenylphosphine, phenyl Organic phosphine compounds such as phosphine are exemplified. These may be used alone or in combination of two or more.

  The adhesive of the present invention can be prepared by mixing the above components. At this time, each component may be mixed at the same time to form an adhesive. However, components other than the curing agent (B) are mixed in advance to adjust the premixture, and the curing agent (B) is mixed when the adhesive is used. It is preferable to use a two-part adhesive which is excellent in stability and workability of the adhesive.

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

<Laminate>
The laminate of the present invention is disposed between a first base material, a second base material, a first base material and a second base material, and includes a first base material and a second base material. And an adhesive layer for bonding together. The adhesive layer is a cured coating film of the above-mentioned adhesive. The base material may further include another base material in addition to the first base material and the second base material. The first base material and the other base material, the adhesive layer for bonding the second base material and 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, an olefin resin, an acrylonitrile-butadiene-styrene copolymer (ABS resin), a polyvinyl chloride resin, a fluorine resin, Synthetic resin films obtained from poly (meth) acrylic resins, carbonate resins, polyamide resins, polyimide resins, polyphenylene ether resins, polyphenylene sulfide resins and polyester resins, metals such as copper foil and aluminum foil A foil or the like can be used.

  The adhesive of the present invention has excellent adhesiveness between a non-polar substrate such as an olefin resin and a metal substrate, so that one of the first substrate and the second substrate is a non-polar substrate And the other is preferably a metal substrate, but is not limited thereto.

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 after applying the adhesive and before laminating the first base material and the second base material.
As a method of applying the adhesive, a gravure coater method, a microgravure coater method, a reverse coater method, a bar coater method, a roll coater method, a die coater method, or 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 tends to decrease, and if it exceeds 20.0 g / m ² , the solvent releasability after coating also decreases, and workability and problems of residual solvent tend to occur. Become.

When laminating the first base material and the second base material, the temperature of the laminating roll is preferably 25 to 120 ° C., and the pressure is preferably ³ to 300 kg / cm ² .
After bonding the first base material and the second base material, an aging step is preferably provided. Aging conditions are preferably 25 to 100 ° C. and 12 to 240 hours.

<Battery packaging materials>
As an example, the battery packaging material of the present invention includes a first base material, a second base material, a third base material, and a first base material for bonding the first base material and the second base material. An adhesive layer, and a second adhesive layer for bonding the second base material and the third base material are included. The first substrate is a polyolefin film, and the second substrate is a metal foil. The third substrate is a resin film of nylon, polyester, or the like. 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 side of the third substrate opposite to the side on which the second adhesive layer is provided, another substrate may be disposed with or without an adhesive layer, or a coating layer may be provided. Good. It is not necessary to provide another base material or a 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. Preferably, it is 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 further preferably 25 μm or more. Further, it is preferably 100 μm or less, more preferably 95 μm or less, and even more 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 a battery described below is manufactured.

  Examples of the metal foil include aluminum, copper, and nickel. These metal foils are sandblasted, polished, degreased, etched, surface-treated by dipping or spraying a rust inhibitor, trivalent chromium conversion, phosphate conversion, sulfide conversion, anodic oxide film formation, Surface treatment such as fluororesin coating may be applied. Among them, those subjected to a trivalent chromium chemical conversion treatment are preferable from the viewpoint of excellent adhesion retention performance (environmental degradation resistance) and corrosion resistance. The thickness of the metal film is preferably in the range of 10 to 100 μm from the viewpoint of preventing corrosion.

  Examples of the resin film that can be used as the third substrate include polyester resin, polyamide resin, epoxy resin, acrylic resin, fluorine resin, polyurethane resin, silicon resin, phenol resin, and resins such as mixtures and copolymers thereof. Film. Among these, a polyester resin and a polyamide resin are preferred, and a biaxially stretched polyester resin and a biaxially stretched polyamide resin are more preferred. 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 polymethaxylylene adipamide (MXD6). Can be

  The coating layer can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, or the like. It is preferable to use 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. Further, a matting agent may be blended 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. Also, the shape of the matting agent is not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an irregular shape, and a balloon shape. Specific examples of the matting agent include talc, silica, graphite, kaolin, montmorilloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, and 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 point Nylon, cross-linked acryl, cross-linked styrene, cross-linked polyethylene, benzoguanamine, gold, aluminum, copper, nickel and the like. One of these matting agents may be used alone, or two or more thereof may be used in combination. Among these matting agents, preferred are silica, barium sulfate, and titanium oxide from the viewpoint of dispersion stability, cost, and the like. The surface of the matting agent may be subjected to various surface treatments such as an insulation treatment and a high dispersibility treatment.

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

Heating and pressure forming method: A battery packaging material is sandwiched between a lower mold having holes to which high-temperature, high-pressure air is supplied and an upper mold having pocket-shaped recesses, and air is supplied while heating and softening to form recesses. how to.
・ Pre-heater flat-plate air-pressure molding method: After heating and softening the battery packaging material, sandwich it between a lower mold having a hole to which high-pressure air is supplied and an upper mold having a pocket-shaped recess, and supply air. A method for forming a recess.
Drum type vacuum forming method: A method in which after a battery packaging material is partially heated and softened with a heating drum, the concave portion of a drum having a pocket-shaped concave portion is evacuated to form a concave portion.
-Pin molding method: A method in which a bottom material sheet is heat-softened and then pressure-bonded with a pocket-shaped uneven mold.
・ Preheater plug assist pressure-air molding method: After heating and softening the battery packaging material, sandwich it between a lower mold with a hole to which high-pressure air is supplied and an upper mold with a pocket-shaped recess, and supply air. A method of forming a concave portion, in which a convex plug is raised and lowered during molding to assist molding.

Since the thickness of the bottom material after molding is uniform, a preheater plug-assist air pressure molding method, which is a heating vacuum molding method, is preferred.
The battery packaging material of the present invention thus obtained can be suitably used as a battery container for sealingly housing battery elements such as a positive electrode, a negative electrode, and an electrolyte.

<Battery>
The battery of the present invention includes a battery element having a positive electrode, a negative electrode, and an electrolyte, and a battery element having the metal terminals connected to each of the positive electrode and the negative electrode protruding outward with the battery packaging material of the present invention. It is obtained by covering the periphery of the element so that a flange portion (a region where the sealant layers are in contact with each other) can be formed, and sealing the sealant layers of the flange portion by heat sealing.

  The battery obtained by using the battery packaging material of the present invention may be any of a primary battery and a secondary battery, but is preferably a secondary battery. The secondary battery is not particularly limited, 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, Examples include a metal-air battery, a polyvalent cation battery, a capacitor, and a capacitor. Among these secondary batteries, suitable applications of the battery packaging material of the present invention include lithium ion batteries and lithium ion polymer batteries.

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

(Example 1)
100 parts of TOYOTAC PMA-L as olefin resin (A), 0.05 part of triphenylphosphine, 1.0 part of FTR-8120, and 0.1 part of EPICLON B-570-H as acid anhydride (C) Was dissolved in a mixed solvent (cyclomethylhexane / ethyl acetate / isopropyl alcohol = 71/8/1) to make the nonvolatile content 20%. Next, 2.0 parts of Denacol EX-321 was added as a curing agent (B) containing an epoxy compound, and the mixture was stirred well to prepare the adhesive of Example 1.

The prepared adhesive was applied to a glossy surface of an aluminum foil (aluminum foil “1N30H” manufactured by Toyo Aluminum Co., Ltd .: film thickness 30 μm) at a coating amount of 2 g / m ² (dry) with a bar coater and dried at 80 ° C. for 1 minute. Then, it was bonded at 100 ° C. to an unstretched polyolefin film (“OK-20” film thickness: 40 μm, manufactured by Okamoto Corporation). Next, on the mat surface of the aluminum foil, "Dick Dry LX-906" (manufactured by DIC Corporation) was used as a main agent, and "KW-75" (manufactured by DIC Corporation) was used as a curing agent. / 10 was applied by a bar coater at an application amount of 4 g / m ² (dry), and a stretched polyamide film having a thickness of 25 μm was laminated. Thereafter, curing (aging) was performed at 80 ° C. for 2 days to obtain a laminate.

(Examples 2 to 10)
The adhesive was adjusted in the same manner as in Example 1 except that the composition of the adhesive used for laminating the aluminum foil and the unstretched polyolefin film was changed to the composition shown in Tables 1 and 2, to obtain a laminate.

(Comparative Examples 1 to 5)
The adhesive was adjusted in the same manner as in Example 1 except that the composition of the adhesive used for laminating the aluminum foil and the unstretched polyolefin film was changed to the composition shown in Table 3, and a laminate was obtained.

The details of the compounds used in Examples and Comparative Examples are as follows.
Toyotack PMA-L: maleic anhydride-modified olefin resin, acid value: 35 mgKOH / g, melting point: 70 ° C., Toyobo Tec PMA-KE: maleic anhydride-modified olefin resin, Toyobo Co., acid value: 44 mgKOH / g, melting point: 80 ° C, Toyobo FTR8120: Styrene resin, Mitsui Chemicals EPICRON B-570-H: Methyltetrahydrophthalic anhydride, DIC YH-306: Trialkyltetrahydrophthalic anhydride, Mitsubishi Chemical Deconal EX- 321: Trimethylolpropane polyglycidyl ether type epoxy resin, Nagase ChemteX EPICLON 860: Bisphenol A type epoxy resin, DIC EPICLON N-665: Cresol novolak type epoxy resin, DIC

In addition, the acid value of the olefin resin is calculated by using a FT-IR (FT-IR4200, manufactured by JASCO Corporation), a coefficient (f) obtained from a calibration curve prepared with a chloroform solution of maleic anhydride, and a maleic anhydride-modified polyolefin solution. And the absorbance (I) at the stretching peak (1780 cm ^-1 ) of the maleic anhydride ring and the absorbance (II) at the stretching peak (1720 cm ^-1 ) of the carbonyl group of maleic acid. . In the following formula, the molecular weight of maleic anhydride was 98.06, and the molecular weight of potassium hydroxide was 56.11.

(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 was measured under the conditions of a peeling speed of 50 mm / min, a peeling width of 15 mm, and a peeling type T-type. evaluated.

(Heat-resistant)
Even when trying to measure the adhesive strength of the laminate after heat sealing, the polyolefin film may be broken and peeled not between the polyolefin film and the aluminum foil but between the heat-sealed polyolefin films. Evaluation of heat resistance by comparison of adhesive strength before and after heat sealing is not always accurate. Therefore, the heat resistance was evaluated as follows.

The unstretched polyolefin film side of the laminate was folded in a valley, and the unstretched polyolefin film sides were applied with a heat seal bar at 190 ° C. for 3 seconds. Next, using "Autograph AGS-J" manufactured by Shimadzu Corporation, the interface at the time of peeling 1 cm under the conditions of a peeling speed of 500 mm / min, a peeling width of 15 mm, and a peeling form T type was evaluated.
：: 90% or more of peeling between unstretched polyolefin film / unstretched polyolefin film (particularly excellent in practical use)
：: Peeling between unstretched polyolefin film / unstretched polyolefin film is 60% or more and less than 90% (excellent in practical use)
Δ: Peeling between unstretched polyolefin film / unstretched polyolefin film is 50% or more and less than 60% (practical range)
×: Peeling between unstretched polyolefin film / unstretched polyolefin film is less than 50%

  As is clear from Tables 1 to 3, the adhesive of the present invention has better heat resistance than the adhesive of the comparative example.

  The adhesive of the present invention is excellent in adhesiveness between a non-polar substrate such as an olefin resin and a metal substrate, excellent in heat resistance, and a laminate obtained by using the adhesive of the present invention is used, for example, in a battery packaging material. It can be suitably used. Further, the use of the adhesive of the present invention is not limited to battery packaging materials and laminates therefor. Is widely available in fields where

Claims (10)

  It contains an olefin resin (A), a curing agent (B) containing an epoxy compound, and an acid anhydride (C), and the compounding amount of the acid anhydride (C) is 0.1 to 100 parts by mass of the olefin resin (A). An adhesive of not less than 05 parts by mass and not more than 10 parts by mass.   The acid anhydride (C) contains at least one selected from the group consisting of an acid anhydride and a glycol-modified acid anhydride, and the acid anhydride is phthalic anhydride, trimellitic anhydride, pyromellitic Acid anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazeleic anhydride, polysebacic anhydride, poly (ethyl octadecane diacid) anhydride, poly (phenyl hexadecane diacid) anhydride Anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride Product, methylcyclohexenetetracarboxylic anhydride, ethi Glycol bistrimellitate dianhydride, heptic 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-naphthalenesuccinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro The adhesive according to claim 1, wherein the adhesive is at least one selected from the group consisting of -1-naphthalene succinic dianhydride.   3. The adhesive according to claim 1, wherein the olefin resin (A) has an acid group or a hydroxyl group.   The adhesive according to any one of claims 1 to 3, wherein the amount of the curing agent (B) is 0.01 to 10 parts by mass based on 100 parts by mass of the olefin resin (A).   5. The composition according to claim 1, further comprising at least one adhesion promoter selected from the group consisting of an imidazole compound, a tertiary amine, a salt of a tertiary amine, a cationic catalyst, and an organic phosphine compound. An adhesive according to claim 1.   An adhesive premixture containing an olefin resin (A), a curing agent (B) containing an epoxy compound, and an acid anhydride (C), comprising the olefin resin (A) and the acid anhydride (C). A premixture in which the content of the acid anhydride (C) is 0.05 to 10 parts by mass based on 100 parts by mass of the olefin resin (A).   6. A method according to claim 1, further comprising a first base, a second base, and an adhesive layer for bonding the first base and the second base. 13. A laminate, which is a cured coating film of the adhesive described in the above item. A polyolefin film,
A resin film,
A metal foil disposed between the polyolefin film and the resin film,
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.