WO2019131591A1 - Adhesive, laminate, battery packing material, and battery - Google Patents

Adhesive, laminate, battery packing material, and battery Download PDF

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Publication number
WO2019131591A1
WO2019131591A1 PCT/JP2018/047472 JP2018047472W WO2019131591A1 WO 2019131591 A1 WO2019131591 A1 WO 2019131591A1 JP 2018047472 W JP2018047472 W JP 2018047472W WO 2019131591 A1 WO2019131591 A1 WO 2019131591A1
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WO
WIPO (PCT)
Prior art keywords
anhydride
acid
acid anhydride
adhesive
olefin resin
Prior art date
Application number
PCT/JP2018/047472
Other languages
French (fr)
Japanese (ja)
Inventor
翔 三木
高年 松尾
神山　達哉
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2019542254A priority Critical patent/JP6610985B1/en
Priority to CN201880079869.6A priority patent/CN111479889B/en
Publication of WO2019131591A1 publication Critical patent/WO2019131591A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an adhesive, in particular, a polyolefin-based adhesive suitable for bonding a resin base and a metal base, a laminate obtained using the adhesive, an outer covering material for a secondary battery, and a battery.
  • a secondary battery represented by a lithium ion battery has a configuration in which an electrolytic solution or the like is sealed between a positive electrode, a negative electrode, and between them.
  • a sealing bag for sealing a lead wire for taking out the electricity of the positive electrode and the negative electrode a metal substrate and plastic comprising a heat seal layer made of an olefin resin, a metal foil such as aluminum foil and a metal deposition layer It is known to use the laminated body which bonded together (patent document 1, 2).
  • the olefin resin is nonpolar, adhesion to the metal substrate is difficult.
  • a battery element is sealed by heat-sealing the sealant layers located in the periphery of a battery element, and sealing a battery element.
  • the adhesive for bonding the heat seal layer and the metal substrate needs heat resistance in addition to the adhesiveness between the nonpolar substrate such as an olefin resin and the metal substrate.
  • the present invention has been made in view of such a situation, and it is an object of the present invention to provide an adhesive excellent in adhesion between a nonpolar base such as an olefin resin and a metal base and heat resistance. Do. Furthermore, it is an object of the present invention to provide a laminate obtained using such an adhesive, and a secondary battery package and battery obtained using the laminate.
  • 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 100 parts by mass of the olefin resin (A)
  • the present invention relates to an adhesive that is 0.05 parts by mass or more and 10 parts by
  • the adhesive of the present invention is excellent in the adhesion between a nonpolar substrate such as an olefin resin and a metal substrate, and heat resistance.
  • the laminate of the present invention is excellent in adhesion and heat resistance.
  • the adhesive of the present invention comprises an olefin resin (A), a curing agent (B) containing an epoxy compound, and an acid anhydride (C).
  • A olefin resin
  • B curing agent
  • C acid anhydride
  • olefin resin (A) used in the adhesive of the present invention homopolymers and copolymers of olefin monomers, copolymers of olefin monomers and other monomers, hydrides and halides of these polymers, acids And polymers having a hydrocarbon backbone as a main component, such as modified products into which functional groups such as hydroxyl groups are introduced, and the like, and one or more types can be used in combination. 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.
  • 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 acid anhydride as an olefin resin having an acid group or an acid anhydride group
  • an acid-modified olefin resin (A-2) which is a resin obtained by graft-modifying an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride to a polyolefin.
  • the olefin monomer used for the preparation of the acid-modified olefin resin (A-1) is an olefin having 2 to 8 carbon atoms, such as ethylene, propylene, isobutylene, 1-butene, 4-methyl-1-pentene, Hexene, vinyl cyclohexane and the like can be mentioned.
  • olefins having 3 to 8 carbon atoms are preferable, in particular, propylene and 1-butene are more preferable, and using propylene and 1-butene in combination is particularly preferable for the solvent because the adhesive strength is good. It is preferable from the point which is excellent in tolerance and excellent in adhesive strength.
  • Examples of the ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic acid anhydride used for copolymerization with an olefin-based monomer include, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, and maleic anhydride Acid, 4-methylcyclohex-4-ene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,3, 4,5,8,9,10-Octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-octa-1,3-diketospiro [4.4] non-7-ene, bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride,
  • the reactivity with an olefin monomer, the reactivity with acid anhydride after copolymerization are excellent, and the molecular weight of the compound itself is small, and the functional group concentration in the case of making a copolymer becomes high.
  • maleic anhydride is preferred. These can be used alone or in combination of two or more.
  • a compound having an ethylenically unsaturated group in addition to an olefin monomer, a tyrene unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride, such as styrene, Butadiene, isoprene and the like may be used in combination.
  • the polyolefin used to prepare the acid-modified olefin resin (A-2) includes homopolymers and copolymers of olefins having 2 to 8 carbon atoms, and co-polymers of olefins having 2 to 8 carbon atoms and other monomers. Polymers, etc. may be mentioned.
  • 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 Combination, ⁇ -olefin copolymer such as ethylene / hexene copolymer, ethylene / vinyl acetate copolymer Coalesced, ethylene methyl methacrylate copolymer, ethylene-vinyl acetate-methyl methacrylate copolymer, and the like propylene-1-butene copolymer.
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • LDPE low density polyethylene
  • linear low density polyethylene resin polypropy
  • homopolymers of olefins having 3 to 8 carbon atoms and copolymers of two or more of olefins having 3 to 8 carbon atoms are preferable, from the viewpoint of achieving good adhesion strength, and propylene alone
  • a polymer or a propylene / 1-butene copolymer is more preferable, and a propylene / 1-butene copolymer is particularly preferable in that it is excellent in resistance to a solvent and excellent in adhesive strength.
  • the ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic acid anhydride used for graft modification with a polyolefin is used for copolymerization with an olefin monomer in the preparation of the acid-modified olefin resin (A-1) described above
  • A-1 acid-modified olefin resin
  • maleic anhydride is preferred. These can be used alone or in combination of two or more.
  • the polyolefin in order to cause the polyolefin to react with the ethylenically unsaturated carboxylic acid or the ethylenically unsaturated carboxylic acid anhydride by graft modification, specifically, the polyolefin is melted, and the ethylenically unsaturated carboxylic acid or the ethylenically unsaturated carboxylic acid is melted therein.
  • a method of adding an acid anhydride (grafting monomer) for grafting reaction dissolving a polyolefin in a solvent to form a solution, and adding an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride thereto to cause a grafting reaction Method, mixing polyolefin dissolved in organic solvent and ethylenic unsaturated carboxylic acid or ethylenic unsaturated carboxylic acid anhydride, heating at temperature above softening temperature or melting point of polyolefin, radical polymerization and hydrogen in molten state The method etc. which perform a withdrawal reaction simultaneously are mentioned.
  • the grafting reaction in order to graft-copolymerize the graft monomer efficiently, it is preferable to carry out the grafting reaction in the presence of a radical initiator.
  • the grafting reaction is usually carried out at 60 to 350.degree.
  • the proportion of the radical initiator used is usually in the range of 0.001 to 1 part by weight with respect to 100 parts by weight of the polyolefin before modification.
  • organic peroxides are preferred, such as benzoyl peroxide, dichloro benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne-3, 1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl- 2.5-di (tert-butylperoxy) hexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert- Chill perpivalate and cumyl peroxide, ter
  • the radical initiator may be selected optimally depending on the process of the grafting reaction, and generally, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexine Dialkyl peroxides such as -3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferably used.
  • the adhesion of the metal layer is further improved, and the electrolyte resistance is excellent. It is preferable to use one having an acid value of ⁇ 200 mg KOH / g.
  • the olefin resin (A-3) having a hydroxyl group a copolymer of a polyolefin and a hydroxyl group-containing (meth) acrylic acid ester or a hydroxyl group-containing vinyl ether, or a polyolefin grafted with a hydroxyl group-containing (meth) acrylic acid ester or a hydroxyl group-containing vinyl ether
  • the modified resin is mentioned.
  • the polyolefin those similar to those used for the preparation of the olefin resin (A-2) can be used.
  • the modification method the same method as the method for preparing the acid-modified olefin resin (A-1) or (A-2) can be used.
  • hydroxyl group-containing (meth) acrylates used for modification include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, lactone modified hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate And polypropylene glycol mono (meth) acrylate.
  • hydroxyl group-containing vinyl ether include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether and the like.
  • 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 a hydroxyl value of 1 to 200 mg KOH / g It is preferable to use the one which it has.
  • the polyolefin used for the preparation of the acid-modified olefin resin (A-2) or the olefin resin (A-3) having a hydroxyl group may be used as it is without modification.
  • the weight average molecular weight of the olefin resin (A) is preferably 40,000 or more. In addition, in order to ensure appropriate fluidity, the weight average molecular weight of the olefin resin (A) is preferably 150,000 or less.
  • 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.
  • the melting point of the olefin resin (A) is preferably 50 ° C. or more, more preferably 60 ° C. or more, and more preferably 65 ° C. or more.
  • the melting point of the olefin resin (A) is preferably 120 ° C. or less, more preferably 90 ° C. or less, and still more preferably 85 ° C. or less.
  • the melting point of the olefin resin is measured by DSC (differential scanning calorimetry). Specifically, the temperature is increased from 10 ° C./min to 10 ° C./min, and then cooled to 10 ° C./min to remove the heat history, and then the temperature is reached again at 10 ° C./min. Heat up to the point. The peak temperature at the second temperature rise is taken as the melting point. In addition, the temperature-fall achieving temperature is set to a temperature lower by 50 ° C. or more than the crystallization temperature, and the temperature-rise achieving temperature is set to a temperature higher by about 30 ° C. or more than the melting point temperature. The final temperature for temperature drop and the final temperature for temperature rise are determined by trial measurement.
  • An epoxy compound is used as the curing agent (B). It is not particularly limited as long as it is a compound having an epoxy group in the molecule, and, for example, ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, diglycerin, sorbitol, 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, bisphenol AD type epoxy resin; Aromatic epoxy resins such as phenol novolac resins and novolac type epoxy resins which are glycidyl ales of cresol novolac resins; Polyglycidyl ethers of polyols which are ethylene oxide or propylene oxide adducts of aromatic
  • 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 3,000 or less.
  • a compound other than the epoxy resin may be used in combination.
  • Other curing agents that can be used in combination with the epoxy resin include polyfunctional isocyanate compounds, aziridine group-containing compounds, carbodiimides, oxazolines, amino resins and the like.
  • polyfunctional isocyanate compounds 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 diisocyanates such as hydrogenated diphenylmethane diisocyanate and compounds derived therefrom, ie, isocyanurate, adduct, biuret type, uretdione, allophanate, prepolymer having isocyanate residue (diisocyanate) of the above diisocyanate And low polymers obtained from polyols, or complexes of these.
  • a compound obtained by reacting a part of the isocyanate group of the polyfunctional isocyanate compound as described above with a compound having reactivity with the isocyanate group may be used as a curing agent.
  • Compounds having reactivity with an isocyanate group include compounds containing an amino group such as butylamine, hexylamine, octylamine, 2-ethylhexylamine, dibutylamine, ethylenediamine, benzylamine and aniline: methanol, ethanol, propanol, isopropanol , Hydroxyl-containing compounds such as butanol, hexanol, octanol, 2-ethylhexyl alcohol, dodecyl alcohol, ethylene glycol, propylene glycol, benzyl alcohol, phenol and the like: allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl
  • aziridine group-containing compound for example, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxamide), N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide) Trimethylolpropane-tri- ⁇ -aziridinyl propionate), N, N′-toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, trimethylolpropane-tri- ⁇ (2 -Methylaziridine) propionate, bisisophthaloyl-1-2-methylaziridine, tri-1-aziridinyl phosphine oxide, tris-1-2-methylaziridine phosphine oxide, etc. may be mentioned.
  • carbodiimides 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.
  • Monooxazoline compounds such as 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 2,4-diphenyl-2-oxazoline and the like as oxazoline 2,2 '-(1,3-phenylene) -bis (2-oxazoline), 2,2'-(1,2-ethylene) -bis (2-oxazoline), 2,2 '-(1,4 butylene) And -bis (2-oxazoline), 2,2 '-(1,4-phenylene) -bis (2-oxazoline) and the like.
  • amino resin examples include melamine resin, benzoguanamine resin, urea resin and the like.
  • the compounding amount of the curing agent (B) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass with respect to 100 parts by mass of the olefin resin (A). More preferably it is part or more. 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 5 parts by mass or less with respect to 100 parts by mass of the olefin resin (A). Is more preferred. This makes it possible to develop excellent adhesion and chemical resistance.
  • an acid anhydride (C) a cyclic aliphatic acid anhydride, an aromatic acid anhydride, unsaturated carboxylic acid anhydride etc. are mentioned, It can be used 1 type or in combination of 2 or more types. More specifically, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic acid Anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride , Methylhymic acid anhydride, trialkyl
  • 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 potty tetramethylene ether glycol. Furthermore, copolymerized polyether glycols of two or more of these glycols and / or polyether glycols can also be used.
  • alkylene glycols such as ethylene glycol, propylene glycol and neopentyl glycol
  • polyether glycols such as polyethylene glycol, polypropylene glycol and potty tetramethylene ether glycol.
  • copolymerized polyether glycols of two or more of these glycols and / or polyether glycols can also be used.
  • it is 0.05 mass part or more with respect to 100 mass parts of olefin resin (A), and, as for the compounding quantity of an acid anhydride (C), it is more preferable that it is 0.8 mass part or more. Moreover, it is preferable that it is 10 mass parts or less with respect to 100 mass parts of olefin resin (A), and, as for the compounding quantity of an acid anhydride (C), it is more preferable that it is 8 mass parts or less. Thereby, the adhesion between the adhesive and the metal is improved, and an adhesive having excellent initial adhesive strength and adhesive strength after heat sealing can be obtained.
  • the acid anhydride (C) used by this invention is equipped with a polar group, and is excellent in the affinity to a metal base material.
  • the molecular weight is relatively small, movement is relatively easy. It is thought that the coated adhesive moves to the metal substrate side until it completely cures, and plays a role like a so-called anchor agent, thereby contributing to the improvement of adhesion and heat resistance.
  • the acid anhydride (C) contained in the adhesive is too large, the acid anhydride (C) forms a pseudo low layer between the metal substrate and the adhesive, It is considered that the adhesion is reduced due to this.
  • the adhesive of the present invention can ensure fluidity by expressing an organic solvent (D) in addition to the above-mentioned components, and can exhibit appropriate coatability.
  • organic solvent is not particularly limited as long as it can be removed by volatilization by heating in the drying step during adhesive coating, 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 solvents such as ethyl acetate and butyl acetate; alcohol solvents such as ethanol, methanol, n-propanol, 2-propanol (iso
  • the solubility is excellent, and therefore it is an alicyclic
  • a mixed solvent of a system organic solvent, an ester solvent and an alcohol solvent it is preferable to use a mixed solvent of methylcyclohexane, ethyl acetate and isopropyl alcohol because of its excellent solubility.
  • the amount of the organic solvent used is preferably such that the proportion of the olefin resin (A) is 10 to 30% by mass with respect to the total mass of the olefin resin (A) and the organic solvent (D). Thereby, it can be set as the adhesive agent excellent in coating nature and the wettability to a metal film.
  • additives such as tackifiers, plasticizers, thermoplastic elastomers, reactive elastomers, phosphoric acid compounds, silane coupling agents and adhesion promoters can be used as needed.
  • the content of these additives may be appropriately adjusted within the range that does not impair the function of the adhesive of the present invention.
  • tackifiers examples include rosin-based or rosin ester-based tackifiers, terpene-based or terpene-phenol-based tackifiers, saturated hydrocarbon resins, coumarone-based tackifiers, coumarone-indene-based tackifiers. Agents, styrene resin-based tackifiers, xylene resin-based tackifiers, phenol resin-based tackifiers, petroleum resin-based tackifiers, and the like. These may be used alone or in combination of two or more.
  • plasticizer examples include polyisoprene, polybutene, and process oil.
  • thermoplastic elastomer examples include styrene-butadiene copolymer (SBS), hydrogenated product of styrene-butadiene copolymer (SEBS), SBBS, styrene-isoprene.
  • SEPS styrene-butadiene copolymer
  • SEBS hydrogenated product of styrene-butadiene copolymer
  • SBBS styrene-isoprene.
  • Copolymerized hydrogenated substances SEPS
  • TPS styrene block copolymers
  • TPO olefin-based elastomers
  • reactive elastomers obtained by acid-modifying these elastomers can be mentioned.
  • phosphoric acid compounds include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and hypophosphoric acid, for example, condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, ultraphosphoric acid, etc.
  • silane coupling agent for example, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ - Aminosilanes such as aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, etc .; ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycid Epoxysilanes such as xylpropyltriethoxysilane; vinylsilanes such as vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane,
  • the adhesive of the present invention can be prepared by mixing the above-described components. Under the present circumstances, although each component may be mixed simultaneously and it is good also as an adhesive agent, components other than a hardening agent (B) are previously mixed, the premixer is adjusted, and the hardening agent (B) is mixed at the time of use of an adhesive agent. It is preferable to use a two-component type adhesive because it is excellent in the stability and the workability of the adhesive.
  • the adhesive of the present invention is excellent in the adhesion between a nonpolar substrate such as an olefin resin and a metal substrate, and heat resistance.
  • the laminate of the present invention is disposed between the first substrate, the second substrate, the first substrate and the second substrate, and the first substrate and the second substrate And an adhesive layer to be pasted together.
  • the adhesive layer is a cured coating of the above-mentioned adhesive.
  • other substrates may be included.
  • the adhesive layer for bonding the first substrate to another substrate, and the second substrate to another substrate may or may not be a cured coating of the adhesive of the present invention. Good.
  • first substrate, the second substrate, and other substrates examples include paper, olefin resins, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resins, and fluorine resins.
  • Synthetic resin film obtained from poly (meth) acrylic resin, carbonate resin, polyamide resin, polyimide resin, polyphenylene ether resin, polyphenylene sulfide resin or polyester resin, metal such as copper foil, aluminum foil Foil etc. can be used.
  • the adhesive of the present invention is excellent in the adhesion between a nonpolar substrate such as an olefin resin and a metal substrate, so that one of the first substrate and the second substrate is nonpolar. It is preferable that the other is a metal base, but it 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 substrate and the second substrate, then laminating the other, and curing the adhesive. After applying the adhesive, it is preferable to provide a drying process before laminating the first substrate and the second substrate.
  • a coating method of 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 coating amount of the adhesive is preferably adjusted so that the coating weight after drying is 0.5 to 20.0 g / m 2 .
  • the temperature of the laminating roll at the time of laminating the first substrate and the second substrate is preferably 25 to 120 ° C., and the pressure is preferably 3 to 300 kg / cm 2 . It is preferable to provide an aging process after laminating the first base and the second base.
  • the aging conditions are preferably 25 to 100 ° C. for 12 to 240 hours.
  • the battery packaging material of the present invention comprises, as an example, a first substrate, a second substrate, a third substrate, and a first substrate and a second substrate bonded to each other. And an adhesive layer, and a second adhesive layer for bonding the second base and the third base.
  • 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.
  • the other substrate may be disposed on the side of the third substrate opposite to the side on which the second adhesive layer is provided, with or without the adhesive layer, or the 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.
  • polyethylene, polypropylene, an ethylene-propylene copolymer, etc. can be used. It is preferably a non-oriented film.
  • the thickness of the polyolefin film is not particularly limited, but is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and still more preferably 25 ⁇ m or more. The thickness is preferably 100 ⁇ m or less, more preferably 95 ⁇ m or less, and still more preferably 90 ⁇ m 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 manufacturing a battery to be described later.
  • metal foil aluminum, copper, nickel etc. are mentioned. These metal foils are sandblasted, polished, degreased, etched, surface-treated by immersion in rust inhibitor or spray, trivalent chromium conversion treatment, phosphate conversion treatment, sulfide conversion treatment, anodic oxide film formation, It may be subjected to surface treatment such as fluorine resin coating. Among these, those subjected to trivalent chromium chemical conversion treatment are preferable from the viewpoint of excellent adhesion retention performance (environmental deterioration resistance) and corrosion resistance.
  • the thickness of the metal film is preferably in the range of 10 to 100 ⁇ m from the viewpoint of preventing corrosion.
  • resin films that can be used as the third substrate include resins such as polyester resin, polyamide resin, epoxy resin, acrylic resin, fluorine resin, polyurethane resin, silicone resin, phenol resin, and mixtures and copolymers of these.
  • a film is mentioned.
  • a polyester resin and a polyamide resin are preferably mentioned, and a biaxially stretched polyester resin and a biaxially stretched polyamide resin are more preferably mentioned.
  • the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolymer polyester, polycarbonate and the like.
  • Specific examples of the polyamide resin include nylon 6, nylon 6, 6, copolymer of nylon 6 and nylon 6, 6, nylon 6, 10, polymethaxylylene adipamide (MXD6), etc.
  • 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 form by 2 liquid hardening type resin.
  • the two-component curable resin that forms the coating layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin.
  • 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 ⁇ m.
  • 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 spheres, fibers, plates, indeterminate shapes, and balloons.
  • talc silica, graphite, kaolin, montmorrroid, 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 point Nylon, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel and the like can be mentioned.
  • matting agents may be used alone or in combination of two or more.
  • the surface of the matting agent may be subjected to various surface treatments such as insulation treatment and high dispersion treatment.
  • Heat and pressure air forming method A concave portion is formed by sandwiching the battery packaging material between a lower mold having a hole to which high-temperature, high-pressure air is supplied and an upper mold having a pocket-shaped recess and supplying air while heating and softening. how to.
  • Pre-heater flat plate pneumatic molding method After heating and softening the battery packaging material, the air is supplied by holding it between the lower mold having a hole to which high-pressure air is supplied and the upper mold having a pocket-shaped recess. How to form a recess.
  • Drum-type vacuum forming method A method of forming a recess by vacuuming the recess of a drum having a pocket-shaped recess after partially heating and softening the battery packaging material with a heating drum.
  • -Pin molding method A method in which the bottom sheet is heated and softened and then crimped with a pocket-shaped uneven mold.
  • Pre-heater plug-assisted pressure forming method After heating and softening the battery packaging material, the air is supplied by holding it between the lower mold having a hole to which high-pressure air is supplied and the upper mold having a pocket-shaped recess.
  • the battery packaging material of the present invention can be suitably used as a battery container in which battery elements such as a positive electrode, a negative electrode, and an electrolyte are sealed and housed.
  • the battery of the present invention is a battery packaging material having a positive electrode, a negative electrode, and an electrolyte, in the battery packaging material of the present invention, in which the metal terminal connected to each of the positive electrode and the negative electrode protrudes outward. It is obtained by coating so that flanges (areas where sealant layers are in contact) can be formed on the periphery of the element, and the sealant layers of the flanges are heat sealed and sealed.
  • the battery obtained using the battery packaging material of the present invention may be either a primary battery or a secondary battery, but is preferably a secondary battery.
  • the secondary battery is not particularly limited, and examples thereof include lithium ion batteries, lithium ion polymer batteries, lead storage batteries, nickel hydrogen storage batteries, nickel cadmium storage batteries, nickel iron storage batteries, nickel zinc storage batteries, silver oxide zinc storage batteries, Metal air batteries, polyvalent cation batteries, capacitors, capacitors and the like can be mentioned.
  • lithium ion batteries and lithium ion polymer batteries can be mentioned as preferable applications of the battery packaging material of the present invention.
  • 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 ⁇ m) with a bar coater at a coating amount of 2 g / m 2 (dry) and dried at 80 ° C for 1 minute Thereafter, it was laminated at 100 ° C. with an unstretched polyolefin film (“ET-20” film thickness: 40 ⁇ m manufactured by Okamoto Co., Ltd.).
  • a bar coater at a coating amount of 4 g / m 2 (dry)
  • a 25 ⁇ m-thick stretched polyamide film was laminated.
  • curing (aging) at 80 ° C. for 2 days was performed to obtain a laminate.
  • Example 2 An adhesive was prepared 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 described in Tables 1 and 2, to obtain a laminate.
  • Toyo Tack PMA-L maleic anhydride modified olefin resin, acid value: 35 mg KOH / g, melting point: 70 ° C.
  • Toyo tack PMA-KE manufactured by Toyobo Co., Ltd . maleic anhydride modified olefin resin, acid number: 44 mg KOH / g, melting point: 80 ° C.
  • the acid value of the olefin resin is a coefficient (f) obtained from a calibration curve prepared by using a solution of maleic anhydride in chloroform using FT-IR (FT-IR 4200, manufactured by JASCO Corporation), a maleic anhydride-modified polyolefin solution Calculated using the following formula using the absorbance (I) of the stretching peak (1780 cm -1 ) of the anhydride ring of maleic anhydride and the absorbance (II) of the stretching peak (1720 cm -1 ) of the carbonyl group of maleic acid in .
  • the molecular weight of maleic anhydride is 98.06
  • the molecular weight of potassium hydroxide is 56.11.
  • Bonding strength of the interface between aluminum foil and unstretched polyolefin film of the laminate is 50 mm / min, peeling width 15 mm, peeling form T type using "Autograph AGS-J" manufactured by Shimadzu Corporation. evaluated.
  • the unstretched polyolefin film side of the laminate was valley-folded, and the heat-seal bar was applied to the unstretched polyolefin film sides under the condition of 190 ° C. for 3 seconds. Then, using “Autograph AGS-J” manufactured by Shimadzu Corporation, the interface was evaluated when peeled at 1 cm under the conditions of peeling speed 500 mm / min, peeling width 15 mm, peeling form T type.
  • ⁇ Peeling between unstretched polyolefin film / unstretched polyolefin film is 90% or more (especially excellent in practical use)
  • ⁇ Peeling between unstretched polyolefin film / unstretched polyolefin film is 60% or more and less than 90% (practically excellent)
  • ⁇ Peeling between unstretched polyolefin film / unstretched polyolefin film is 50% or more and less than 60% (practical range)
  • X Peeling between unstretched polyolefin film / unstretched polyolefin film is less than 50%
  • the adhesive of the present invention is more excellent in heat resistance than the adhesive of the comparative example.
  • the adhesive of the present invention is excellent in the adhesion between a nonpolar base such as an olefin resin and a metal base, heat resistance, and the laminate obtained by using the adhesive of the present invention is, for example, a battery packaging material. It can be used suitably.
  • the application of the adhesive of the present invention is not limited to battery packaging materials and laminates therefor, and adhesion between non-polar substrates such as household electric appliance skins, furniture materials, building interior members and metal substrates Are widely available in areas where they are required.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Laminated Bodies (AREA)

Abstract

Provided are an adhesive excellent in adhesion between a non-polar base such as an olefin resin and a metal base and thermal resistance, and a laminate and a battery packing material excellent in thermal resistance obtained by using the adhesive. Provided are an adhesive, comprising: an olefin resin (A); a hardener (B) containing an epoxy compound; and acid anhydride (C), wherein the blending amount of acid anhydride (C) is 0.05-10 parts by mass with respect to 100 parts by mass of the olefin resin (A); a premixture for the adhesive; and a laminate, a battery packing material, and a battery using the adhesive.

Description

接着剤、積層体、電池用包装材及び電池Adhesives, laminates, packaging materials for batteries and batteries
　本発明は、接着剤、詳しくは樹脂基材と金属基材とを接着するのに好適なポリオレフィン系接着剤、当該接着剤を用いて得られる積層体、二次電池用外装材及び電池に関する。 The present invention relates to an adhesive, in particular, a polyolefin-based adhesive suitable for bonding a resin base and a metal base, a laminate obtained using the adhesive, an outer covering material for a secondary battery, and a battery.
　リチウムイオン電池に代表される二次電池は、正極、負極およびその間に、電解液等を封入した構成をとっている。また、正極と負極の電気を外部に取り出すためのリード線を封入するための封入袋として、オレフィン樹脂からなるヒートシール層と、アルミニウム箔等の金属箔や金属蒸着層からなる金属基材とプラスチックを貼り合せた積層体を用いることが知られている（特許文献１、２）。 A secondary battery represented by a lithium ion battery has a configuration in which an electrolytic solution or the like is sealed between a positive electrode, a negative electrode, and between them. In addition, as a sealing bag for sealing a lead wire for taking out the electricity of the positive electrode and the negative electrode, a metal substrate and plastic comprising a heat seal layer made of an olefin resin, a metal foil such as aluminum foil and a metal deposition layer It is known to use the laminated body which bonded together (patent document 1, 2).
特開平０９－２８３１０１号公報Japanese Patent Application Laid-Open No. 09-283101 特開２００７－２９４３８１号公報JP 2007-294381 A
　しかしながら、オレフィン樹脂は非極性であるため、金属基材との接着が困難である。また、上述した積層体を用いて電池を組み立てる際には、電池素子の周縁に位置するシーラント層同士を熱融着して電池素子を密封することにより電池素子が封止される。このためヒートシール層と金属基材とを貼り合せる接着剤には、オレフィン樹脂のような非極性の基材と金属基材との接着性に加え、耐熱性が必要である。 However, since the olefin resin is nonpolar, adhesion to the metal substrate is difficult. Moreover, when assembling a battery using the laminated body mentioned above, a battery element is sealed by heat-sealing the sealant layers located in the periphery of a battery element, and sealing a battery element. For this reason, the adhesive for bonding the heat seal layer and the metal substrate needs heat resistance in addition to the adhesiveness between the nonpolar substrate such as an olefin resin and the metal substrate.
　本発明は、このような状況に鑑みなされたものであって、オレフィン樹脂のような非極性の基材と金属基材との接着性、耐熱性に優れた接着剤を提供することを目的とする。さらに、このような接着剤を用いて得られる積層体、当該積層体を用いて得られる二次電池外装材および電池を提供することを目的とする。 The present invention has been made in view of such a situation, and it is an object of the present invention to provide an adhesive excellent in adhesion between a nonpolar base such as an olefin resin and a metal base and heat resistance. Do. Furthermore, it is an object of the present invention to provide a laminate obtained using such an adhesive, and a secondary battery package and battery obtained using the laminate.
　本発明は、オレフィン樹脂（Ａ）、エポキシ化合物を含む硬化剤（Ｂ）、酸無水物（Ｃ）を含み、酸無水物（Ｃ）の配合量が、オレフィン樹脂（Ａ）１００質量部に対して０．０５質量部以上１０質量部以下である接着剤に関する。 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 100 parts by mass of the olefin resin (A) The present invention relates to an adhesive that is 0.05 parts by mass or more and 10 parts by
　本発明の接着剤は、オレフィン樹脂のような非極性の基材と金属基材との接着性、耐熱性に優れる。また、本発明の積層体は接着性、耐熱性に優れる。 The adhesive of the present invention is excellent in the adhesion between a nonpolar substrate such as an olefin resin and a metal substrate, and heat resistance. In addition, the laminate of the present invention is excellent in adhesion and heat resistance.
＜接着剤＞
　本発明の接着剤は、オレフィン樹脂（Ａ）、エポキシ化合物を含む硬化剤（Ｂ）、酸無水物（Ｃ）を含む。以下、本発明の接着剤の各成分について詳細に説明する。 <Adhesive>
The adhesive of the present invention comprises 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.
　本発明の接着剤に用いられるオレフィン樹脂（Ａ）としては、オレフィンモノマーの単独重合体や共重合体、オレフィンモノマーと他のモノマーとの共重合体、これら重合体の水素化物やハロゲン化物、酸や水酸基等の官能基を導入した変性体等、炭化水素骨格を主体とする重合体が挙げられ、１種または２種以上を組み合わせて用いることができる。酸基又は酸無水物基を有する結晶性オレフィン樹脂、水酸基を有する結晶性オレフィン樹脂を用いることが好ましい。 As the olefin resin (A) used in the adhesive of the present invention, homopolymers and copolymers of olefin monomers, copolymers of olefin monomers and other monomers, hydrides and halides of these polymers, acids And polymers having a hydrocarbon backbone as a main component, such as modified products into which functional groups such as hydroxyl groups are introduced, and the like, and one or more types can be used in combination. 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.
　酸基又は酸無水物基を有するオレフィン樹脂としては、オレフィン系モノマーと、エチレン性不飽和カルボン酸またはエチレン性不飽和カルボン酸無水物との共重合体である酸変性オレフィン樹脂（Ａ－１）や、ポリオレフィンにエチレン性不飽和カルボン酸またはエチレン性不飽和カルボン酸無水物をグラフト変性した樹脂である酸変性オレフィン樹脂（Ａ－２）が挙げられる。 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 acid anhydride as an olefin resin having an acid group or an acid anhydride group And an acid-modified olefin resin (A-2) which is a resin obtained by graft-modifying an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride to a polyolefin.
　酸変性オレフィン樹脂（Ａ－１）の調整に用いられるオレフィン系モノマーとしては、炭素原子数が２～８のオレフィン、例えば、エチレン、プロピレン、イソブチレン、１－ブテン、４－メチル－１－ペンテン、ヘキセン、ビニルシクロヘキサンなどが挙げられる。これらのなかでも特に接着強度が良好なものとなることから炭素原子数３～８のオレフィンが好ましく、プロピレン、及び１－ブテンがより好ましく、とりわけプロピレンと１－ブテンとを併用することが溶剤に対する耐性に優れ、接着強度に優れる点から好ましい。 The olefin monomer used for the preparation of the acid-modified olefin resin (A-1) is an olefin having 2 to 8 carbon atoms, such as ethylene, propylene, isobutylene, 1-butene, 4-methyl-1-pentene, Hexene, vinyl cyclohexane and the like can be mentioned. Among these, olefins having 3 to 8 carbon atoms are preferable, in particular, propylene and 1-butene are more preferable, and using propylene and 1-butene in combination is particularly preferable for the solvent because the adhesive strength is good. It is preferable from the point which is excellent in tolerance and excellent in adhesive strength.
　オレフィン系モノマーとの共重合に用いられるエチレン性不飽和カルボン酸またはエチレン性不飽和カルボン酸無水物としては、例えば、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、シトラコン酸、メサコン酸、無水マレイン酸、４－メチルシクロヘキセ－４－エン－１，２－ジカルボン酸無水物、ビシクロ［２．２．２］オクト－５－エン－２，３－ジカルボン酸無水物、１，２，３，４，５，８，９，１０－オクタヒドロナフタレン－２，３－ジカルボン酸無水物、２－オクタ－１，３－ジケトスピロ［４．４］ノン－７－エン、ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボン酸無水物、マレオピマル酸、テトラヒドロフタル酸無水物、メチル－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボン酸無水物、メチル―ノルボルネン－５－エン－２，３－ジカルボン酸無水物、ノルボルン－５－エン－２，３－ジカルボン酸無水物等が挙げられる。これらのなかでも特にオレフィン系モノマーとの反応性、共重合した後の酸無水物の反応性に優れ、かつ、該化合物自体の分子量が小さく共重合体にした場合の官能基濃度が高くなる点から無水マレイン酸が好ましい。これらは単独で、あるいは２種以上併用して使用することができる。 Examples of the ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic acid anhydride used for copolymerization with an olefin-based monomer include, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, and maleic anhydride Acid, 4-methylcyclohex-4-ene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,3, 4,5,8,9,10-Octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-octa-1,3-diketospiro [4.4] non-7-ene, bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, methyl-bicyclo [2.2.1] hept-5-ene-2,3-dical Phosphate anhydride, methyl - norbornene-5-ene-2,3-dicarboxylic acid anhydride, norborn-5-ene-2,3-dicarboxylic anhydride and the like. Among these, particularly, the reactivity with an olefin monomer, the reactivity with acid anhydride after copolymerization are excellent, and the molecular weight of the compound itself is small, and the functional group concentration in the case of making a copolymer becomes high. And maleic anhydride is preferred. These can be used alone or in combination of two or more.
　酸変性オレフィン樹脂（Ａ－１）の調整には、オレフィン系モノマー、チレン性不飽和カルボン酸またはエチレン性不飽和カルボン酸無水物に加え、その他のエチレン性不飽和基を持つ化合物、例えばスチレン、ブタジエン、イソプレン等を併用してもよい。 In the preparation of the acid-modified olefin resin (A-1), a compound having an ethylenically unsaturated group in addition to an olefin monomer, a tyrene unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride, such as styrene, Butadiene, isoprene and the like may be used in combination.
　酸変性オレフィン樹脂（Ａ－２）の調整に用いられるポリオレフィンとしては、炭素原子数２～８のオレフィンの単独重合体や共重合体、炭素原子数２～８のオレフィンと他のモノマーとの共重合体等が挙げられ、具体的には、例えば、高密度ポリエチレン（ＨＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、線状低密度ポリエチレン樹脂などのポリエチレン、ポリプロピレン、ポリイソブチレン、ポリ（１－ブテン）、ポリ（４－メチル－１－ペンテン）、ポリビニルシクロヘキサン、エチレン・プロピレンブロック共重合体、エチレン・プロピレンランダム共重合体、エチレン・１－ブテン共重合体、エチレン・４－メチル－１－ペンテン共重合体、エチレン・へキセン共重合体などのα―オレフィン共重合体、エチレン・酢酸ビニル共重合体、エチレン・メチルメタクリレート共重合体、エチレン・酢酸ビニル・メチルメタクリレート共重合体、プロピレン・１－ブテン共重合体などが挙げられる。これらの中で特に接着強度が良好なものとなる点から炭素原子数３～８のオレフィンの単独重合体、炭素原子数３～８のオレフィンの２種以上の共重合体が好ましく、プロピレンの単独重合体、又はプロピレン・１－ブテン共重合体がより好ましく、とりわけプロピレン・１－ブテン共重合体が溶剤に対する耐性に優れ、接着強度に優れる点から好ましい。 The polyolefin used to prepare the acid-modified olefin resin (A-2) includes homopolymers and copolymers of olefins having 2 to 8 carbon atoms, and co-polymers of olefins having 2 to 8 carbon atoms and other monomers. Polymers, etc. may be mentioned. Specifically, for example, 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 Combination, α-olefin copolymer such as ethylene / hexene copolymer, ethylene / vinyl acetate copolymer Coalesced, ethylene methyl methacrylate copolymer, ethylene-vinyl acetate-methyl methacrylate copolymer, and the like propylene-1-butene copolymer. Among them, homopolymers of olefins having 3 to 8 carbon atoms and copolymers of two or more of olefins having 3 to 8 carbon atoms are preferable, from the viewpoint of achieving good adhesion strength, and propylene alone A polymer or a propylene / 1-butene copolymer is more preferable, and a propylene / 1-butene copolymer is particularly preferable in that it is excellent in resistance to a solvent and excellent in adhesive strength.
　ポリオレフィンとのグラフト変性に用いられるエチレン性不飽和カルボン酸またはエチレン性不飽和カルボン酸無水物としては、上述した、酸変性オレフィン樹脂（Ａ－１）の調整においてオレフィン系モノマーとの共重合に用いられるものと同様のものを用いることができる。グラフト変性後の官能基の反応性が高く、また、グラフト変性したポリオレフィンの官能基濃度が高くなる点から無水マレイン酸が好ましい。これらは単独で、あるいは２種以上併用して使用することができる。 The ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic acid anhydride used for graft modification with a polyolefin is used for copolymerization with an olefin monomer in the preparation of the acid-modified olefin resin (A-1) described above The same as those described above can be used. From the viewpoint of high reactivity of the functional group after graft modification and high functional group concentration of the graft modified polyolefin, maleic anhydride is preferred. These can be used alone or in combination of two or more.
　グラフト変性によりポリオレフィンにエチレン性不飽和カルボン酸またはエチレン性不飽和カルボン酸無水物を反応させるには、具体的には、ポリオレフィンを溶融し、そこにエチレン性不飽和カルボン酸またはエチレン性不飽和カルボン酸無水物（グラフトモノマー）を添加してグラフト反応させる方法、ポリオレフィンを溶媒に溶解して溶液とし、そこにエチレン性不飽和カルボン酸またはエチレン性不飽和カルボン酸無水物を添加してグラフト反応させる方法、有機溶剤に溶解したポリオレフィンと、エチレン性不飽和カルボン酸またはエチレン性不飽和カルボン酸無水物とを混合し、ポリオレフィンの軟化温度または融点以上の温度で加熱し溶融状態にてラジカル重合と水素引き抜き反応を同時に行う方法等が挙げられる。 Specifically, in order to cause the polyolefin to react with the ethylenically unsaturated carboxylic acid or the ethylenically unsaturated carboxylic acid anhydride by graft modification, specifically, the polyolefin is melted, and the ethylenically unsaturated carboxylic acid or the ethylenically unsaturated carboxylic acid is melted therein. A method of adding an acid anhydride (grafting monomer) for grafting reaction, dissolving a polyolefin in a solvent to form a solution, and adding an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride thereto to cause a grafting reaction Method, mixing polyolefin dissolved in organic solvent and ethylenic unsaturated carboxylic acid or ethylenic unsaturated carboxylic acid anhydride, heating at temperature above softening temperature or melting point of polyolefin, radical polymerization and hydrogen in molten state The method etc. which perform a withdrawal reaction simultaneously are mentioned.
　いずれの場合にもグラフトモノマーを効率よくグラフト共重合させるためには、ラジカル開始剤の存在下にグラフト反応を実施することが好ましい。グラフト反応は、通常６０～３５０℃の条件で行われる。ラジカル開始剤の使用割合は変性前のポリオレフィン１００重量部に対して、通常０．００１～１重量部の範囲である。 In any case, in order to graft-copolymerize the graft monomer efficiently, it is preferable to carry out the grafting reaction in the presence of a radical initiator. The grafting reaction is usually carried out at 60 to 350.degree. The proportion of the radical initiator used is usually in the range of 0.001 to 1 part by weight with respect to 100 parts by weight of the polyolefin before modification.
　ラジカル開始剤としては、有機ペルオキシドが好ましく、例えばベンゾイルペルオキシド、ジクロルベンゾイルペルオキシド、ジクミルペルオキシド、ジ－ｔｅｒｔ－ブチルペルオキシド、２，５－ジメチル－２，５－ジ（ペルオキシドベンゾエート）ヘキシン―３、１，４－ビス（ｔｅｒｔ－ブチルペルオキシイソプロピル）ベンゼン、ラウロイルペルオキシド、ｔｅｒｔ－ブチルペルアセテート、２，５－ジメチル－２，５－ジ（ｔｅｒｔ－ブチルペルオキシ）ヘキシン－３、２，５－ジメチル―２．５－ジ（ｔｅｒｔ－ブチルペルオキシ）ヘキサン、ｔｅｒｔ－ブチルペルベンゾエート、ｔｅｒｔ－ブチルペルフェニルアセテート、ｔｅｒｔ－ブチルペルイソブチレート、ｔｅｒｔ－ブチルペル―ｓｅｃ－オクトエート、ｔｅｒｔ－ブチルペルピバレート、クミルペルピバレートおよびｔｅｒｔ－ブチルペルジエチルアセテートなどがあげられる。その他アゾ化合物、例えばアゾビスイソブチロニトリル、ジメチルアゾイソブチレートなどを用いることもできる。 As the radical initiator, organic peroxides are preferred, such as benzoyl peroxide, dichloro benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne-3, 1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl- 2.5-di (tert-butylperoxy) hexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert- Chill perpivalate and cumyl perpivalate and tert- butyl hydroperoxide diethyl acetate. Other azo compounds such as azobisisobutyronitrile, dimethylazoisobutyrate and the like can also be used.
　ラジカル開始剤は、グラフト反応のプロセスにより最適なものを選定すればよいが、通常ジクミルペルオキシド、ジ－ｔｅｒｔ－ブチルペルオキシド、２，５－ジメチル－２，５－ジ（ｔｅｒｔ－ブチルペルオキシ）ヘキシン－３、２，５－ジメチル－２，５－ジ（ｔｅｒｔ－ブチルペルオキシ）ヘキサン、１，４－ビス（ｔｅｒｔ－ブチルペルオキシイソプロピル）ベンゼン等のジアルキルペルオキシドが好ましく用いられる。 The radical initiator may be selected optimally depending on the process of the grafting reaction, and generally, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexine Dialkyl peroxides such as -3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferably used.
　オレフィン樹脂（Ａ）として酸変性オレフィン樹脂（Ａ－１）や酸変性オレフィン樹脂（Ａ－２）を用いる場合には、金属層の密着性がより向上し、耐電解質性に優れることから、１～２００ｍｇＫＯＨ／ｇの酸価を有するものを用いることが好ましい。 When the acid-modified olefin resin (A-1) or the acid-modified olefin resin (A-2) is used as the olefin resin (A), the adhesion of the metal layer is further improved, and the electrolyte resistance is excellent. It is preferable to use one having an acid value of ̃200 mg KOH / g.
　水酸基を有するオレフィン樹脂（Ａ－３）としては、ポリオレフィンと水酸基含有（メタ）アクリル酸エステルや水酸基含有ビニルエーテルとの共重合体や、ポリオレフィンに水酸基含有（メタ）アクリル酸エステルや水酸基含有ビニルエーテルをグラフト変性した樹脂が挙げられる。ポリオレフィンは、オレフィン樹脂（Ａ－２）の調整に用いるものと同様のものを用いることができる。変性方法としては、酸変性オレフィン樹脂（Ａ－１）、（Ａ－２）の調整方法と同様の方法を用いることができる。 As the olefin resin (A-3) having a hydroxyl group, a copolymer of a polyolefin and a hydroxyl group-containing (meth) acrylic acid ester or a hydroxyl group-containing vinyl ether, or a polyolefin grafted with a hydroxyl group-containing (meth) acrylic acid ester or a hydroxyl group-containing vinyl ether The modified resin is mentioned. As the polyolefin, those similar to those used for the preparation of the olefin resin (A-2) can be used. As the modification method, the same method as the method for preparing the acid-modified olefin resin (A-1) or (A-2) can be used.
　変性に用いる水酸基含有（メタ）アクリル酸エステルとしては、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、グリセロール（メタ）アクリレート、ラクトン変性ヒドロキシエチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等が挙げられる。
　水酸基含有ビニルエーテルとしては、２－ヒドロキシエチルビニルエーテル、ジエチレングリコールモノビニルエーテル、４－ヒドロキシブチルビニルエーテル等が挙げられる。 Examples of hydroxyl group-containing (meth) acrylates used for modification include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, lactone modified hydroxyethyl (meth) acrylate, 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, 4-hydroxybutyl vinyl ether and the like.
　オレフィン樹脂（Ａ）として、水酸基を有するオレフィン樹脂（Ａ－３）を用いる場合には、金属層の密着性がより向上し、耐電解質性に優れることから、１～２００ｍｇＫＯＨ／ｇの水酸基価を有するものを用いることが好ましい。 When an 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 a hydroxyl value of 1 to 200 mg KOH / g It is preferable to use the one which it has.
　オレフィン樹脂（Ａ）として、上述した酸変性オレフィン樹脂（Ａ－２）や水酸基を有するオレフィン樹脂（Ａ－３）の調整に用いるポリオレフィンを、変性せずにそのまま用いてもよい。 As the olefin resin (A), the polyolefin used for the preparation of the acid-modified olefin resin (A-2) or the olefin resin (A-3) having a hydroxyl group may be used as it is without modification.
　接着性を良好なものとするためオレフィン樹脂（Ａ）の重量平均分子量は４０，０００以上であることが好ましい。また、適度な流動性を確保するためオレフィン樹脂（Ａ）の重量平均分子量は１５０，０００以下であることが好ましい。 In order to improve adhesion, the weight average molecular weight of the olefin resin (A) is preferably 40,000 or more. In addition, in order to ensure appropriate fluidity, the weight average molecular weight of the olefin resin (A) is preferably 150,000 or less.
　尚、本願発明において、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）は、下記条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定される値である。 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.
　測定装置　；東ソー株式会社製　ＨＬＣ－８３２０ＧＰＣ
　カラム　　；東ソー株式会社製　ＴＳＫｇｅｌ　４０００ＨＸＬ、ＴＳＫｇｅｌ　３０００ＨＸＬ、ＴＳＫｇｅｌ　２０００ＨＸＬ、ＴＳＫｇｅｌ　１０００ＨＸＬ
　検出器　　；ＲＩ（示差屈折計）
　データ処理；東ソー株式会社製　マルチステーションＧＰＣ－８０２０ｍｏｄｅｌＩＩ
　測定条件　；カラム温度　４０℃
　　　　　　　溶媒　　　　テトラヒドロフラン
　　　　　　　流速　　　　０．３５ｍｌ／分
　標準　　　；単分散ポリスチレン
　試料　　　；樹脂固形分換算で０．２質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ） Measuring device; Tosoh Co., Ltd. HLC-8320 GPC
Column; Tosoh Corp. TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL
Detector; RI (differential refractometer)
Data processing; Tosoh Corp. multi station GPC-8020 model II
Measurement condition: Column temperature 40 ° C
Solvent: Tetrahydrofuran Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene sample: 0.2% by mass of tetrahydrofuran solution in terms of resin solid content filtered with a microfilter (100 μl)
　オレフィン樹脂（Ａ）の融点は５０℃以上であることが好ましく、６０℃以上であることがより好ましく、６５℃以上であることがより好ましい。オレフィン樹脂（Ａ）の融点は１２０℃以下であることが好ましく、９０℃以下であることがより好ましく、８５℃以下であることがより好ましい。 The melting point of the olefin resin (A) is preferably 50 ° C. or more, more preferably 60 ° C. or more, and more preferably 65 ° C. or more. The melting point of the olefin resin (A) is preferably 120 ° C. or less, more preferably 90 ° C. or less, and still more preferably 85 ° C. or less.
　オレフィン樹脂の融点はＤＳＣ（示差走査熱量分析）により測定する。具体的には降温到達温度から昇温到達温度まで１０℃／ｍｉｎで昇温後、１０℃／ｍｉｎで降温到達温度まで冷却して熱履歴を除去した後、再度１０℃／ｍｉｎで昇温到達点まで昇温する。２度目に昇温した際のピーク温度を融点とする。また、降温到達温度は結晶化温度よりも５０℃以上低い温度に、昇温到達温度は融点温度よりも３０℃位以上高い温度に設定する。降温到達温度、昇温到達温度は試測定して決定する。 The melting point of the olefin resin is measured by DSC (differential scanning calorimetry). Specifically, the temperature is increased from 10 ° C./min to 10 ° C./min, and then cooled to 10 ° C./min to remove the heat history, and then the temperature is reached again at 10 ° C./min. Heat up to the point. The peak temperature at the second temperature rise is taken as the melting point. In addition, the temperature-fall achieving temperature is set to a temperature lower by 50 ° C. or more than the crystallization temperature, and the temperature-rise achieving temperature is set to a temperature higher by about 30 ° C. or more than the melting point temperature. The final temperature for temperature drop and the final temperature for temperature rise are determined by trial measurement.
　硬化剤（Ｂ）としては、エポキシ化合物を用いる。分子内にエポキシ基を有する化合物であれば特に限定されず、例えば、エチレングリコール、プロピレングリコール、ヘキサンジオール、ネオペンチルグリコール、トリメチロールエタン、トリメチロールプロパン、ペンタエリトリトール、グリセリン、ジグリセリン、ソルビトール、スピログリコールもしくは水添ビスフェノールＡ等の脂肪族ポリオールのポリグリシジルエーテル型エポキシ樹脂；
　ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂等のビスフェノール型エポキシ樹脂；
　フェノールノボラック樹脂やクレゾールノボラック樹脂のグリシジルエールであるノボラック型エポキシ樹脂等の芳香族エポキシ樹脂；
　ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ビスフェノールＡＤなどの芳香族系ポリヒドロキシ化合物のエチレンオキシドもしくはプロピレンオキシド付加体であるポリオールのポリグリシジルエーテル；
　ポリエチレングリコール、ポリプロピレングリコールもしくはポリテトラメチレングリコール等のポリエーテルポリオールのポリグリシジルエーテル型エポキシ樹脂；ビス（３，４－エポキシシクロヘキシルメチル）アジペート、３，４－エポキシシクロヘキシルメチル－３’，４’－エポキシシクロヘキシルカルボキシレート等の環状脂肪族型ポリエポキシ樹脂；
　プロパントリカルボン酸、ブタンテトラカルボン酸、アジピン酸、フタル酸、テレフタル酸もしくはトリメリット酸等のポリカルボン酸のポリグリシジルエステル型エポキシ樹脂；
　ブタジエン、ヘキサジエン、オクタジエン、ドデカジエン、シクロオクタジエン、α－ピネンもしくはビニルシクロヘキセン等の炭化水素系ジエンのビスエポキシ樹脂；
　ポリブタジエンもしくはポリイソプレン等のジエンポリマーのエポキシ樹脂；
　テトラグリシジルジアミノジフェニルメタン、トリグリシジルパラアミノフェノール、テトラグリシジルビスアミノメチルシクロヘキサン、ジグリシジルアニリン、テトラグリシジルメタキシリレンジアミン等のグリシジルアミン型エポキシ樹脂；
　トリアジン、ヒダントイン等の複素環を含有するエポキシ樹脂が挙げられる。
　これらのエポキシ樹脂は単独で用いてもよいし、２種以上組み合わせて用いてもよい。 An epoxy compound is used as the curing agent (B). It is not particularly limited as long as it is a compound having an epoxy group in the molecule, and, for example, ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, diglycerin, sorbitol, 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, bisphenol AD type epoxy resin;
Aromatic epoxy resins such as phenol novolac resins and novolac type epoxy resins which are glycidyl ales of cresol novolac resins;
Polyglycidyl ethers of polyols which are ethylene oxide or propylene oxide adducts of aromatic polyhydroxy compounds 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 cyclohexyl carboxylate;
Polyglycidyl ester type epoxy resin of polycarboxylic acid such as propanetricarboxylic acid, butanetetracarboxylic acid, adipic acid, phthalic acid, terephthalic acid or trimellitic acid;
Bisepoxy resins of hydrocarbon dienes such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α-pinene or vinylcyclohexene;
Epoxy resins of diene polymers such as polybutadiene or polyisoprene;
Glycidyl amine type epoxy resins such as tetraglycidyl diaminodiphenylmethane, triglycidyl paraaminophenol, tetraglycidyl bisaminomethyl cyclohexane, diglycidyl aniline, tetraglycidyl metaxylylene diamine, etc .;
There may be mentioned epoxy resins containing heterocycles such as triazine and hydantoin.
These epoxy resins may be used alone or in combination of two or more.
　また、本発明に用いられるエポキシ化合物は、１分子中に２つ以上のエポキシ基と１つ以上の水酸基を備え、重量平均分子量が３０００以下であるエポキシ化合物であることが好ましい。 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 3,000 or less.
　硬化剤（Ｂ）として、エポキシ樹脂以外の化合物を併用してもよい。エポキシ樹脂と併用可能な他の硬化剤としては、多官能イソシアネート化合物、アジリジン基含有化合物、カルボジイミド、オキサゾリン、アミノ樹脂などが挙げられる。 As the curing agent (B), a compound other than the epoxy resin may be used in combination. Other curing agents that can be used in combination with the epoxy resin include polyfunctional isocyanate compounds, aziridine group-containing compounds, carbodiimides, oxazolines, amino resins and the like.
　多官能イソシアネート化合物としては、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、イソホロンジイソシアネート、１，５－ナフタレンジイソシアネート、ヘキサメチレンジイソシアネート、ビス（４－イソシアネートシクロヘキシル）メタン、若しくは水添化ジフェニルメタンジイソシアネート等のジイソシアネートおよびこれらから誘導された化合物、即ち、前記ジイソシアネートのイソシアヌレート体、アダクト体、ビウレット型、ウレトジオン体、アロファネート体、イソシアネート残基を有するプレポリマー（ジイソシアネートとポリオールから得られる低重合体）、若しくはこれらの複合体等が挙げられる。 As polyfunctional isocyanate compounds, 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 diisocyanates such as hydrogenated diphenylmethane diisocyanate and compounds derived therefrom, ie, isocyanurate, adduct, biuret type, uretdione, allophanate, prepolymer having isocyanate residue (diisocyanate) of the above diisocyanate And low polymers obtained from polyols, or complexes of these.
　上述したような多官能イソシアネート化合物の一部のイソシアネート基を、イソシアネート基と反応性を有する化合物と反応させて得られる化合物を硬化剤として使用してもよい。イソシアネート基と反応性を有する化合物としては、ブチルアミン、ヘキシルアミン、オクチルアミン、２－エチルヘキシルアミン、ジブチルアミン、エチレンジアミン、ベンジルアミン、アニリン等のアミノ基を含有する化合物類：メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ヘキサノール、オクタノール、２－エチルヘキシルアルコール、ドデシルアルコール、エチレングリコール、プロピレングリコール、ベンジルアルコール、フェノール等の水酸基を含有する化合物類：アリルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールグリシジルエーテル、シクロヘキサンジメタノールジグリシジルエーテル等のエポキシ基を有する化合物類：酢酸、ブタン酸、ヘキサン酸、オクタン酸、コハク酸、アジピン酸、セバシン酸、フタル酸等のカルボン酸を含有する化合物等が挙げられる。 A compound obtained by reacting a part of the isocyanate group of the polyfunctional isocyanate compound as described above with a compound having reactivity with the isocyanate group may be used as a curing agent. Compounds having reactivity with an isocyanate group include compounds containing an amino group such as butylamine, hexylamine, octylamine, 2-ethylhexylamine, dibutylamine, ethylenediamine, benzylamine and aniline: methanol, ethanol, propanol, isopropanol , Hydroxyl-containing compounds such as butanol, hexanol, octanol, 2-ethylhexyl alcohol, dodecyl alcohol, ethylene glycol, propylene glycol, benzyl alcohol, phenol and the like: 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.
　アジリジン基含有化合物としては、例えば、Ｎ，Ｎ´－ヘキサメチレン－１，６－ビス（１－アジリジンカルボキシアミド）、Ｎ，Ｎ´－ジフェニルメタン－４，４´－ビス（１－アジリジンカルボキシアミド）、トリメチロールプロパン－トリ－β－アジリジニルプロピオネート）、Ｎ，Ｎ´－トルエン－２，４－ビス（１－アジリジンカルボキシアミド）、トリエチレンメラミン、トリメチロールプロパン－トリ－β（２－メチルアジリジン）プロピオネート、ビスイソフタロイル－１－２－メチルアジリジン、トリ－１－アジリジニルフォスフィンオキサイド、トリス－１－２－メチルアジリジンフォスフィンオキサイド等が挙げられる。 As the aziridine group-containing compound, for example, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxamide), N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide) Trimethylolpropane-tri-β-aziridinyl propionate), N, N′-toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, trimethylolpropane-tri-β (2 -Methylaziridine) propionate, bisisophthaloyl-1-2-methylaziridine, tri-1-aziridinyl phosphine oxide, tris-1-2-methylaziridine phosphine oxide, etc. may be mentioned.
　カルボジイミドとしては、Ｎ，Ｎ’－ジ－ｏ－トルイルカルボジイミド、Ｎ，Ｎ’－ジフェニルカルボジイミド、Ｎ，Ｎ’－ジ－２，６－ジメチルフェニルカルボジイミド、Ｎ，Ｎ’―ビス（２，６－ジイソプロピルフェニル）カルボジイミド、Ｎ，Ｎ’－ジオクチルデシルカルボジイミド、Ｎ－トリイル－Ｎ’－シクロヘキシルカルボジイミド、Ｎ，Ｎ’－ジ－２，２－ｔｅｒｔ．－ブチルフェニルカルボジイミド、Ｎ－トリイル－Ｎ’－フェニルカルボジイミド、Ｎ，Ｎ’－ジ－ｐ－アミノフェニルカルボジイミド、Ｎ，Ｎ’－ジ－ｐ－ヒドロキシフェニルカルボジイミド、Ｎ，Ｎ’－ジ－シクロヘキシルカルボジイミド、Ｎ，Ｎ’－ジ－ｐ－トルイルカルボジイミド等が挙げられる。 Examples of carbodiimides 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 And N, N'-di-p-toluylcarbodiimide and the like.
　オキサゾリンとしては、２－オキサゾリン、２－メチル－２－オキサゾリン、２－フェニル－２－オキサゾリン、２，５－ジメチル－２－オキサゾリン、２，４－ジフェニル－２－オキサゾリンなどのモノオキサゾリン化合物、２，２’－（１，３－フェニレン）－ビス（２－オキサゾリン）、２，２’－（１，２－エチレン）－ビス（２－オキサゾリン）、２，２’－（１，４ブチレン）－ビス（２－オキサゾリン）、２，２’－（１，４－フェニレン）－ビス（２－オキサゾリン）などが挙げられる。 Monooxazoline compounds such as 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 2,4-diphenyl-2-oxazoline and the like as oxazoline 2,2 '-(1,3-phenylene) -bis (2-oxazoline), 2,2'-(1,2-ethylene) -bis (2-oxazoline), 2,2 '-(1,4 butylene) And -bis (2-oxazoline), 2,2 '-(1,4-phenylene) -bis (2-oxazoline) and the like.
　アミノ樹脂としては、メラミン樹脂、ベンゾグアナミン樹脂、尿素樹脂等が挙げられる。 Examples of the amino resin include melamine resin, benzoguanamine resin, urea resin and the like.
　硬化剤（Ｂ）の配合量は、オレフィン樹脂（Ａ）１００質量部に対して０．０１質量部以上であることが好ましく、０．１質量部以上であることがより好ましく、０．５質量部以上であることがさらに好ましい。また、硬化剤（Ｂ）の配合量は、オレフィン樹脂（Ａ）１００質量部に対して１０質量部以下であることが好ましく、８質量部以下であることがより好ましく、５質量部以下であることがさらに好ましい。これにより、優れた接着性と耐薬品性とを発現することができる。 The compounding amount of the curing agent (B) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass with respect to 100 parts by mass of the olefin resin (A). More preferably it is part or more. 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 5 parts by mass or less with respect to 100 parts by mass of the olefin resin (A). Is more preferred. This makes it possible to develop excellent adhesion and chemical resistance.
　酸無水物（Ｃ）としては、環状脂肪族酸無水物、芳香族酸無水物、不飽和カルボン酸無水物等が挙げられ、１種または２種以上を組み合わせて用いることができる。より具体的には、例えば、フタル酸無水物、トリメリット酸無水物、ピロメリット酸無水物、ベンゾフェノンテトラカルボン酸無水物、ドデセニルコハク酸無水物、ポリアジピン酸無水物、ポリアゼライン酸無水物、ポリセバシン酸無水物、ポリ（エチルオクタデカン二酸）無水物、ポリ（フェニルヘキサデカン二酸）無水物、テトラヒドロフタル酸無水物、メチルテトラヒドロフタル酸無水物、メチルヘキサヒドロフタル酸無水物、ヘキサヒドロフタル酸無水物、メチルハイミック酸無水物、トリアルキルテトラヒドロフタル酸無水物、メチルシクロヘキセンジカルボン酸無水物、メチルシクロヘキセンテトラカルボン酸無水物、エチレングリコールビストリメリテート二無水物、ヘット酸無水物、ナジック酸無水物、メチルナジック酸無水物、５－（２，５－ジオキソテトラヒドロ－３－フラニル）－３－メチル－３－シクロヘキサン－１，２－ジカルボン酸無水物、３，４－ジカルボキシ－１，２，３，４－テトラヒドロ－１－ナフタレンコハク酸二無水物、１－メチル－ジカルボキシ－１，２，３，４－テトラヒドロ－１－ナフタレンコハク酸二無水物等が挙げられる。 As an acid anhydride (C), a cyclic aliphatic acid anhydride, an aromatic acid anhydride, unsaturated carboxylic acid anhydride etc. are mentioned, It can be used 1 type or in combination of 2 or more types. More specifically, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic acid Anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride , Methylhymic acid anhydride, trialkyltetrahydrophthalic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bis trimellitate dianhydride, hetic acid anhydride, nadic acid anhydride, No methyl nadic acid , 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2,3,4- Examples thereof include tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride and the like.
　また、酸無水物（Ｃ）として上述した化合物をグリコールで変性したものを用いてもよい。変性に用いることができるグリコールとしては、エチレングリコール、プロピレングリコール、ネオペンチルグリコール等のアルキレングリコール類；ポリエチレングリコール、ポリプロピレングリコール、ポチテトラメチレンエーテルグリコール等のポリエーテルグリコール類等が挙げられる。更には、これらのうちの２種類以上のグリコール及び／又はポリエーテルグリコールの共重合ポリエーテルグリコールを用いることもできる。 Moreover, you may use what modified | denatured the compound mentioned above as an acid anhydride (C) by glycol. 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 potty tetramethylene ether glycol. Furthermore, copolymerized polyether glycols of two or more of these glycols and / or polyether glycols can also be used.
　酸無水物（Ｃ）の配合量は、オレフィン樹脂（Ａ）１００質量部に対して０．０５質量部以上であることが好ましく、０．８質量部以上であることがより好ましい。また、酸無水物（Ｃ）の配合量は、オレフィン樹脂（Ａ）１００質量部に対して１０質量部以下であることが好ましく、８質量部以下であることがより好ましい。これにより、接着剤と金属との密着性が向上し、初期接着強度とヒートシール後の接着強度に優れた接着剤とすることができる。 It is preferable that it is 0.05 mass part or more with respect to 100 mass parts of olefin resin (A), and, as for the compounding quantity of an acid anhydride (C), it is more preferable that it is 0.8 mass part or more. Moreover, it is preferable that it is 10 mass parts or less with respect to 100 mass parts of olefin resin (A), and, as for the compounding quantity of an acid anhydride (C), it is more preferable that it is 8 mass parts or less. Thereby, the adhesion between the adhesive and the metal is improved, and an adhesive having excellent initial adhesive strength and adhesive strength after heat sealing can be obtained.
　本発明の接着剤が接着性、耐熱性に優れる理由は定かではないが、次のように推測される。本発明で用いる酸無水物（Ｃ）は極性基を備え、金属基材への親和性に優れる。また、比較的分子量が小さいために、相対的に移動が容易である。塗工した接着剤が完全に硬化するまでに間に金属基材側に移動し、いわゆるアンカー剤のような役割を果たすことで接着性、耐熱性の向上に寄与していると考えられる。一方、接着剤に含まれる酸無水物（Ｃ）の量が多すぎると、酸無水物（Ｃ）が金属基材と接着剤との間に擬似的に強度の低い層を形成してしまい、これに起因して接着性が低下すると考えられる。 Although the reason why the adhesive of the present invention is excellent in adhesiveness and heat resistance is not clear, it is presumed as follows. The acid anhydride (C) used by this invention is equipped with a polar group, and is excellent in the affinity to a metal base material. In addition, since the molecular weight is relatively small, movement is relatively easy. It is thought that the coated adhesive moves to the metal substrate side until it completely cures, and plays a role like a so-called anchor agent, thereby contributing to the improvement of adhesion 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 layer between the metal substrate and the adhesive, It is considered that the adhesion is reduced due to this.
　本発明の接着剤は、上記各成分に加え、さらに有機溶剤（Ｄ）を配合することにより流動性を確保し、適正な塗工性を発現させることができる。このような有機溶剤としては、接着剤塗工時の乾燥工程における過熱により揮発させて除去できるものであれば特に限定されず、例えば、トルエン、キシレン等の芳香族系有機溶剤；ｎ－ヘキサン、ｎ－ヘプタン等の脂肪族系有機溶剤；シクロヘキサン、メチルシクロヘキサン等の脂環族系有機溶剤；トリクロロエチレン、ジクロロエチレン、クロロベンゼン、クロロホルム等のハロゲン系有機溶剤；メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン系溶剤；酢酸エチル、酢酸ブチル等のエステル系溶剤；エタノール、メタノール、ｎ－プロパノール、２－プロパノール（イソプロピルアルコール）、ブタノール、ヘキサノール等のアルコール系溶剤；ジイソプロピルエーテル、ブチルセロソルブ、テトラヒドロフラン、ジオキサン、ブチルカルビトール等のエーテル系溶剤；ジエチレングリコールモノメチルエーテル、トリエチレングルコールモノメチルエーテル、プロピレングリコールモノメチルエーテル等のグリコールエーテル系溶剤；エチレングリコールモノメチルエーテルアセテート、プロプレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート等のグリコールエステル系溶剤等が挙げられ、これらは単独で使用しても良いし、２種以上を併用しても良い。 The adhesive of the present invention can ensure fluidity by expressing an organic solvent (D) in addition to the above-mentioned components, and can exhibit appropriate coatability. Such an organic solvent is not particularly limited as long as it can be removed by volatilization by heating in the drying step during adhesive coating, 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 solvents such as ethyl acetate and butyl acetate; alcohol solvents such as ethanol, methanol, n-propanol, 2-propanol (isopropyl alcohol), butanol, and hexanol; diisopropyl ether, butyl cellosolve, tetrahydrofuran 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 Examples thereof include glycol ester solvents such as ethyl ether acetate, and these may be used alone or in combination of two or more.
　オレフィン樹脂（Ａ）として、非塩素系のオレフィン樹脂、酸基又は酸無水物基を有するオレフィン樹脂や水酸基を有するオレフィン樹脂を用いた場合であってもその溶解性に優れることから、脂環族系有機溶剤と、エステル系溶剤と、アルコール系溶剤の混合溶媒を用いることが好ましい。特に、酸基又は酸無水物基を有するオレフィン樹脂を用いた場合にはその溶解性に優れることからメチルシクロヘキサンと酢酸エチルとイソプロピルアルコールとの混合溶媒を用いることが好ましい。 Even when a non-chlorinated 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 solubility is excellent, and therefore it is an alicyclic It is preferable to use a mixed solvent of a system 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, it is preferable to use a mixed solvent of methylcyclohexane, ethyl acetate and isopropyl alcohol because of its excellent solubility.
　有機溶剤の使用量としては、オレフィン樹脂（Ａ）と有機溶剤（Ｄ）との合計質量に対する、オレフィン樹脂（Ａ）の割合が１０～３０質量％となる割合であることが好ましい。これにより、塗工性、金属フィルムへの濡れ性に優れた接着剤とすることができる。 The amount of the organic solvent used is preferably such that the proportion of the olefin resin (A) is 10 to 30% by mass with respect to the total mass of the olefin resin (A) and the organic solvent (D). Thereby, it can be set as the adhesive agent excellent in coating nature and the wettability to a metal film.
　本発明の接着剤は、必要に応じて粘着付与剤、可塑剤、熱可塑性エラストマー、反応性エラストマー、リン酸化合物、シランカップリング剤、接着促進剤等の各種添加剤を用いることができる。これらの添加剤の含有量は、本発明の接着剤の機能を損なわない範囲内で適宜調整すればよい。 In the adhesive of the present invention, various additives such as tackifiers, plasticizers, thermoplastic elastomers, reactive elastomers, phosphoric acid compounds, silane coupling agents and adhesion promoters can be used as needed. The content of these additives may be appropriately adjusted within the range that does not impair the function of the adhesive of the present invention.
　ここで使用し得る粘着付与剤としては、例えば、ロジン系又はロジンエステル系粘着付与剤、テルペン系又はテルペンフェノール系粘着付与剤、飽和炭化水素樹脂、クマロン系粘着付与剤、クマロンインデン系粘着付与剤、スチレン樹脂系粘着付与剤、キシレン樹脂系粘着付与剤、フェノール樹脂系粘着付与剤、石油樹脂系粘着付与剤などが挙げられる。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。 Examples of tackifiers that can be used herein include rosin-based or rosin ester-based tackifiers, terpene-based or terpene-phenol-based tackifiers, saturated hydrocarbon resins, coumarone-based tackifiers, coumarone-indene-based tackifiers. Agents, styrene resin-based tackifiers, xylene resin-based tackifiers, phenol resin-based tackifiers, petroleum resin-based tackifiers, and the like. These may be used alone or in combination of two or more.
　可塑剤としては、ポリイソプレン、ポリブテン、プロセルオイル等が挙げられ、熱可塑性エラストマーとしてはスチレン・ブタジエン共重合物（ＳＢＳ）、スチレン・ブタジエン共重合の水素添加物（ＳＥＢＳ）、ＳＢＢＳ、スチレン・イソプレン共重合の水素添加物（ＳＥＰＳ）、スチレンブロック共重合体（ＴＰＳ）、オレフィン系エラストマー（ＴＰＯ）等が、反応性エラストマーはこれらのエラストマーを酸変性したものが挙げられる。 Examples of the plasticizer include polyisoprene, polybutene, and process oil. Examples of the thermoplastic elastomer include styrene-butadiene copolymer (SBS), hydrogenated product of styrene-butadiene copolymer (SEBS), SBBS, styrene-isoprene. Copolymerized hydrogenated substances (SEPS), styrene block copolymers (TPS), olefin-based elastomers (TPO), etc., and reactive elastomers obtained by acid-modifying these elastomers can be mentioned.
　リン酸化合物としては、例えば次亜リン酸、亜リン酸、オルトリン酸、次リン酸等のリン酸類、例えばメタリン酸、ピロリン酸、トリポリリン酸、ポリリン酸、ウルトラリン酸等の縮合リン酸類、例えばオルトリン酸モノメチル、オルトリン酸モノエチル、オルトリン酸モノプロピル、オルトリン酸モノブチル、オルトリン酸モノ－２－エチルヘキシル、オルトリン酸モノフェニル、亜リン酸モノメチル、亜リン酸モノエチル、亜リン酸モノプロピル、亜リン酸モノブチル、亜リン酸モノ－２－エチルヘキシル、亜リン酸モノフェニル、オルトリン酸ジ－２－エチルヘキシル、オルトリン酸ジフェニル亜リン酸ジメチル、亜リン酸ジエチル、亜リン酸ジプロピル、亜リン酸ジブチル、亜リン酸ジ－２－エチルヘキシル、亜リン酸ジフェニル等のモノ、ジエステル化物、縮合リン酸とアルコール類とからのモノ、ジエステル化物、例えば前記のリン酸類に、例えばエチレンオキシド、プロピレンオキシド等のエポキシ化合物を付加させたもの、例えば脂肪族又は芳香族のジグリシジルエーテルに前記のリン酸類を付加させて得られるエポキシリン酸エステル類等が挙げられる。 Examples of phosphoric acid compounds include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and hypophosphoric acid, for example, condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, ultraphosphoric acid, etc. Monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monophenyl orthophosphate, monomethyl phosphite, monoethyl phosphite, monopropyl phosphite, monobutyl phosphite , Mono-2-ethylhexyl phosphite, monophenyl phosphite, di-2-ethylhexyl orthophosphate, dimethyl diphenyl phosphite orthophosphate, diethyl phosphite, dipropyl phosphite, dipropyl phosphite, phosphite Di-2-ethylhexyl, diphenyl phosphite Mono-, di-esterified compounds, mono-, di-esterified compounds from condensed phosphoric acid and alcohols, such as those obtained by adding an epoxy compound such as ethylene oxide or propylene oxide to the above-mentioned phosphoric acids, such as aliphatic or aromatic di Epoxy phosphoric acid esters obtained by adding the above-mentioned phosphoric acid to glycidyl ether may, for example, be mentioned.
　シランカップリング剤としては例えば、γ－アミノプロピルトリエトキシシラン、γ－アミノプロピルトリメトキシシラン、Ｎ－β（アミノエチル）－γ－アミノプロピルトリメトキシシラン、Ｎ－β（アミノエチル）－γ－アミノプロピルトリメチルジメトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等のアミノシラン；β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン等のエポキシシラン；ビニルトリス（β－メトキシエトキシ）シラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン等のビニルシラン；ヘキサメチルジシラザン、γ－メルカプトプロピルトリメトキシシラン等を挙げることが出来る。 As a silane coupling agent, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ- Aminosilanes such as aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc .; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Epoxysilanes such as xylpropyltriethoxysilane; vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc .; hexamethyldisilazane, γ-mel Hept trimethoxysilane and the like.
　接着促進剤としては、２－メチルイミダゾール、１，２－ジメチルイミダゾール、２－フェニル－４－メチルイミダゾール、２－エチル－4－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－シアノエチル－２－エチル－４－メチルイミダゾール等のイミダゾール系化合物、トリエチルアミン、トリエチレンジアミン、Ｎ’－メチル－Ｎ－（２－ジメチルアミノエチル）ピペラジン、１，８－ジアザビシクロ［５．４．０］ウンデセン（ＤＢＵ）、１，５－ジアザビシクロ［４．３．０］－ノネン、６－ジブチルアミノ－１，８－ジアザビシクロ［５．４．０］ウンデセン等の３級アミン類及びこれら３級アミン類をフェノール、オクチル酸、４級化テトラフェニルボレート塩等でアミン塩にした化合物、トリアリルスルホニウムヘキサフルオロアンチモネート、ジアリルヨードニウムヘキサフルオロアンチモネート等のカチオン触媒、トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、トリス（４－メチルフェニル）ホスフィン、トリス（４－ブチルフェニル）ホスフィン、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン化合物などが挙げられる。これらは単独で使用しても良いし、２種以上を併用しても良い。 As an adhesion promoter, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2 Imidazole 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 the like, phenols and octyls of these tertiary amines Compounds that have been converted to amine salts with acids, quaternized tetraphenylborate salts, etc., triallylsul Cationic catalysts such as phonium hexafluoroantimonate, diallyliodonium hexafluoroantimonate, tributylphosphine, methyl diphenyl phosphine, triphenyl phosphine, tris (4-methylphenyl) phosphine, tris (4-butylphenyl) phosphine, diphenyl phosphine, Organic phosphine compounds such as phenyl phosphine and the like can be mentioned. These may be used alone or in combination of two or more.
　上述した各成分を混合することにより本発明の接着剤を調整することができる。この際、各成分は同時に混合して接着剤としてもよいが、硬化剤（Ｂ）以外の成分を予め混合してプレミクスチャーを調整しておき、接着剤の使用時に硬化剤（Ｂ）を混合する２液型の接着剤とすることが接着剤の安定性、作業性に優れることから好ましい。 The adhesive of the present invention can be prepared by mixing the above-described components. Under the present circumstances, although each component may be mixed simultaneously and it is good also as an adhesive agent, components other than a hardening agent (B) are previously mixed, the premixer is adjusted, and the hardening agent (B) is mixed at the time of use of an adhesive agent. It is preferable to use a two-component type adhesive because it is excellent in the stability and the workability of the adhesive.
　本発明の接着剤は、オレフィン樹脂のような非極性の基材と金属基材との接着性、耐熱性に優れる。 The adhesive of the present invention is excellent in the adhesion between a nonpolar substrate such as an olefin resin and a metal substrate, and heat resistance.
＜積層体＞
　本発明の積層体は、第１の基材と、第２の基材と、第１の基材と第２の基材との間に配置され、第１の基材と第２の基材とを貼り合せる接着層とを含む。接着層は、上述した接着剤の硬化塗膜である。第１の基材、第２の基材に加えてさらに他の基材を含んでいてもよい。第１の基材と他の基材、第２の基材と他の基材とを貼り合せる接着層は、本発明の接着剤の硬化塗膜であってもよいし、そうでなくてもよい。 <Laminate>
The laminate of the present invention is disposed between the first substrate, the second substrate, the first substrate and the second substrate, and the first substrate and the second substrate And an adhesive layer to be pasted together. The adhesive layer is a cured coating of the above-mentioned adhesive. In addition to the first substrate and the second substrate, other substrates may be included. The adhesive layer for bonding the first substrate to another substrate, and the second substrate to another substrate may or may not be a cured coating of the adhesive of the present invention. Good.
　第１の基材、第２の基材、他の基材としては、例えば、紙、オレフィン系樹脂、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ樹脂）、ポリ塩化ビニル系樹脂、フッ素系樹脂、ポリ（メタ）アクリル系樹脂、カーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリフェニレンエーテル系樹脂、ポリフェニレンスルフィド系樹脂やポリエステル系樹脂から得られた合成樹脂フィルム、銅箔、アルミニウム箔の様な金属箔等を用いることが出来る。 Examples of the first substrate, the second substrate, and other substrates include paper, olefin resins, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resins, and fluorine resins. Synthetic resin film obtained from poly (meth) acrylic resin, carbonate resin, polyamide resin, polyimide resin, polyphenylene ether resin, polyphenylene sulfide resin or polyester resin, metal such as copper foil, aluminum foil Foil etc. can be used.
　本発明の接着剤は、オレフィン樹脂のような非極性の基材と、金属基材との接着性に優れるため、第１の基材と第２の基材のうち一方が非極性の基材であり、他方が金属基材であることが好ましいが、これに限定されない。 The adhesive of the present invention is excellent in the adhesion between a nonpolar substrate such as an olefin resin and a metal substrate, so that one of the first substrate and the second substrate is nonpolar. It is preferable that the other is a metal base, but it is not limited thereto.
　本発明の積層体は、第１の基材と第２の基材の一方に本発明の接着剤を塗布し、次いで他方を積層し、接着剤を硬化させて得られる。接着剤を塗布した後、第１の基材と第２の基材とを積層するまでの間に乾燥工程を設けることが好ましい。
　接着剤の塗工方式としては、グラビアコーター方式、マイクログラビアコーター方式、リバースコーター方式、バーコーター方式、ロールコーター方式、ダイコーター方式等を用いることが出来る。接着剤の塗布量は、乾燥後の塗布重量が０．５～２０．０ｇ／ｍ２となるよう調整することが好ましい。０．５ｇ／ｍ２を下回ると連続均一塗布性が低下し易くなり、２０．０ｇ／ｍ２を上回ると塗布後における溶剤離脱性も低下し、作業性の低下や残留溶剤の問題が生じ易くなる。 The laminate of the present invention is obtained by applying the adhesive of the present invention to one of the first substrate and the second substrate, then laminating the other, and curing the adhesive. After applying the adhesive, it is preferable to provide a drying process before laminating the first substrate and the second substrate.
As a coating method of 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 coating amount of the adhesive is preferably adjusted so that the coating 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 removability after coating also decreases, and the problem of workability deterioration and residual solvent tends to occur. Become.
　第１の基材と第２の基材とを積層する際のラミネートロールの温度は２５～１２０℃、圧力は３～３００ｋｇ／ｃｍ２であることが好ましい。
　第１の基材と第２の基材とを貼り合せた後、エージング工程を設けることが好ましい。エージング条件は、２５～１００℃、１２～２４０時間であることが好ましい。 The temperature of the laminating roll at the time of laminating the first substrate and the second substrate is preferably 25 to 120 ° C., and the pressure is preferably 3 to 300 kg / cm 2 .
It is preferable to provide an aging process after laminating the first base and the second base. The aging conditions are preferably 25 to 100 ° C. for 12 to 240 hours.
＜電池用包装材＞
　本発明の電池用包装材は、一例として、第１の基材と、第２の基材と、第３の基材と、第１の基材と第２の基材を貼り合せる第１の接着層と、第２の基材と第３の基材とを貼り合せる第２の接着層とを含む。第１の基材はポリオレフィンフィルムであり、第２の基材は金属箔である。第３の基材はナイロン、ポリエステル等の樹脂フィルムである。第１の接着層は本発明の接着剤の硬化塗膜である。第２の接着層は本発明の接着剤の硬化塗膜であってもよいし、そうでなくてもよい。第３の基材の第２の接着層が設けられるのとは反対側に、さらに接着層を介して、または介さずに他の基材を配置してもよいし、コーティング層を設けてもよい。他の基材やコーティング層を設けなくてもよい。 <Packaging material for battery>
The battery packaging material of the present invention comprises, as an example, a first substrate, a second substrate, a third substrate, and a first substrate and a second substrate bonded to each other. And an adhesive layer, and a second adhesive layer for bonding the second base and the third base. 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. The other substrate may be disposed on the side of the third substrate opposite to the side on which the second adhesive layer is provided, with or without the adhesive layer, or the coating layer may be provided. Good. It is not necessary to provide another base material or a coating layer.
　ポリオレフィンフィルムとしては、従来から公知のオレフィン樹脂の中から適宜選択すればよい。例えば、特に限定されないが、ポリエチレン、ポリプロピレン、エチレンプロピレン共重合体などを用いることができる。無延伸フィルムであることが好ましい。ポリオレフィンフィルムの膜厚は、特に限定されないが、１０μｍ以上であることが好ましく、２０μｍ以上であることがより好ましく、２５μｍ以上であることがさらに好ましい。また、１００μｍ以下であることが好ましく、９５μｍ以下であることがより好ましく、９０μｍ以下であることがさらに好ましい。
　第１の基材は、後述する電池を製造する際に、本発明の電池用包装材同士をヒートシールして貼り合せる際のシーラント層として機能する。 The polyolefin film may be appropriately selected from conventionally known olefin resins. For example, although not particularly limited, polyethylene, polypropylene, an ethylene-propylene copolymer, etc. can be used. It is preferably a non-oriented 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. The thickness is preferably 100 μm or less, more preferably 95 μm or less, and still 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 manufacturing a battery to be described later.
　金属箔としては、アルミニウム、銅、ニッケル等が挙げられる。これらの金属箔は、サンドブラスト処理、研磨処理、脱脂処理、エッチング処理、防錆剤浸漬又はスプレーによる表面処理、３価クロム化成処理、リン酸塩化成処理、硫化物化成処理、陽極酸化被膜形成、フッ素樹脂コーティング等の表面処理を施したものであってもよい。これらのなかでも３価クロム化成処理を施したものが密着性保持性能（耐環境劣化性）、防食性に優れる点から好ましい。また、この金属フィルムの厚みは腐食防止の観点から１０～１００μｍの範囲であることが好ましい。 As metal foil, aluminum, copper, nickel etc. are mentioned. These metal foils are sandblasted, polished, degreased, etched, surface-treated by immersion in rust inhibitor or spray, trivalent chromium conversion treatment, phosphate conversion treatment, sulfide conversion treatment, anodic oxide film formation, It may be subjected to surface treatment such as fluorine resin coating. Among these, those subjected to trivalent chromium chemical conversion treatment are preferable from the viewpoint of excellent adhesion retention performance (environmental deterioration 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.
　第３の基材として用いることができる樹脂フィルムとしては、ポリエステル樹脂、ポリアミド樹脂、エポキシ樹脂、アクリル樹脂、フッ素樹脂、ポリウレタン樹脂、珪素樹脂、フェノール樹脂、及びこれらの混合物や共重合物等の樹脂フィルムが挙げられる。これらの中でも、好ましくはポリエステル樹脂、ポリアミド樹脂が挙げられ、より好ましくは２軸延伸ポリエステル樹脂、２軸延伸ポリアミド樹脂が挙げられる。ポリエステル樹脂としては、具体的には、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、共重合ポリエステル、ポリカーボネート等が挙げられる。また、ポリアミド樹脂としては、具体的には、ナイロン６、ナイロン６，６、ナイロン６とナイロン６，６との共重合体、ナイロン６，１０、ポリメタキシリレンアジパミド（ＭＸＤ６）等が挙げられる。 Examples of resin films that can be used as the third substrate include resins such as polyester resin, polyamide resin, epoxy resin, acrylic resin, fluorine resin, polyurethane resin, silicone resin, phenol resin, and mixtures and copolymers of these. A film is mentioned. Among these, a polyester resin and a polyamide resin are preferably mentioned, and a biaxially stretched polyester resin and a biaxially stretched polyamide resin are more preferably mentioned. Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolymer polyester, polycarbonate and the like. Specific examples of the polyamide resin include nylon 6, nylon 6, 6, copolymer of nylon 6 and nylon 6, 6, nylon 6, 10, polymethaxylylene adipamide (MXD6), etc. Be
　コーティング層は、例えばポリ塩化ビニリデン、ポリエステル樹脂、ウレタン樹脂、アクリル樹脂、エポキシ樹脂などにより形成することができる。２液硬化型樹脂により形成することが好ましい。コーティング層を形成する２液硬化型樹脂としては、例えば、２液硬化型ウレタン樹脂、２液硬化型ポリエステル樹脂、２液硬化型エポキシ樹脂などが挙げられる。また、コーティング層には、マット化剤を配合してもよい。 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 form by 2 liquid hardening type resin. Examples of the two-component curable resin that forms 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.
　マット化剤としては、例えば、粒径が０．５ｎｍ～５μｍ程度の微粒子が挙げられる。マット化剤の材質については、特に制限されないが、例えば、金属、金属酸化物、無機物、有機物等が挙げられる。また、マット化剤の形状についても、特に制限されないが、例えば、球状、繊維状、板状、不定形、バルーン状等が挙げられる。マット化剤として、具体的には、タルク，シリカ，グラファイト、カオリン、モンモリロイド、モンモリロナイト、合成マイカ、ハイドロタルサイト、シリカゲル、ゼオライト、水酸化アルミニウム、水酸化マグネシウム、酸化亜鉛，酸化マグネシウム，酸化アルミニウム，酸化ネオジウム，酸化アンチモン、酸化チタン、酸化セリウム、硫酸カルシウム，硫酸バリウム、炭酸カルシウム，ケイ酸カルシウム、炭酸リチウム、安息香酸カルシウム，シュウ酸カルシウム，ステアリン酸マグネシウム、カーボンブラック、カーボンナノチューブ類、高融点ナイロン、架橋アクリル、架橋スチレン、架橋ポリエチレン、ベンゾグアナミン、金、アルミニウム、銅、ニッケル等が挙げられる。これらのマット化剤は、１種単独で使用してもよく、また２種以上を組み合わせて使用してもよい。これらのマット化剤の中でも、分散安定性やコスト等の観点から、好ましくはりシリカ、硫酸バリウム、酸化チタンが挙げられる。また、マット化剤には、表面に絶縁処理、高分散性処理等の各種表面処理を施しておいてもよい。 Examples of the matting agent include fine particles having a particle size of about 0.5 nm to 5 μm. The material of the matting agent is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances. The shape of the matting agent is also not particularly limited, and examples thereof include spheres, fibers, plates, indeterminate shapes, and balloons. As a matting agent, specifically, talc, silica, graphite, kaolin, montmorrroid, 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 point Nylon, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel and the like can be mentioned. These matting agents may be used alone or in combination of two or more. Among these matting agents, preferred are silica, barium sulfate and titanium oxide from the viewpoint of dispersion stability and cost. In addition, the surface of the matting agent may be subjected to various surface treatments such as insulation treatment and high dispersion treatment.
　このような積層体を、電池とした際に第１の基材であるポリオレフィンフィルムが第３の基材よりも内側になるようにして成型し、本発明の二次電池外装材となる。成型方法としては、特に制限はなく、一例として以下のような方法が挙げられる。 When such a laminate is made into a battery, it is molded so that the polyolefin film which is the first base is on the inner side than the third base, and it becomes the secondary battery exterior material of the present invention. There is no restriction | limiting in particular as a shaping | molding method, The following methods are mentioned as an example.
・加熱圧空成型法：電池用包装材を高温、高圧のエアーが供給される孔を有する下型と、ポケット形状の凹部を有する上型に挟み、加熱軟化させながらエアーを供給して凹部を形成する方法。 
・プレヒーター平板式圧空成型法：電池用包装材を加熱軟化させた後、高圧のエアーが供給される孔を有する下型と、ポケット形状の凹部を有する上型に挟み、エアーを供給して凹部を形成する方法。
・ドラム式真空成型法：電池用包装材を加熱ドラムで部分的に加熱軟化後、ポケット形状の凹部を有するドラムの該凹部を真空引きして凹部を成型する方法。 
・ピン成型法：底材シートを加熱軟化後ポケット形状の凹凸金型で圧着する方法。 
・プレヒータープラグアシスト圧空成型法：電池用包装材を加熱軟化させた後、高圧のエアーが供給される孔を有する下型と、ポケット形状の凹部を有する上型に挟み、エアーを供給して凹部を形成する方法であって、成型の際に、凸形状のプラグを上昇及び降下をさせて成型を補助する方法。  · Heat and pressure air forming method: A concave portion is formed by sandwiching the battery packaging material between a lower mold having a hole to which high-temperature, high-pressure air is supplied and an upper mold having a pocket-shaped recess and supplying air while heating and softening. how to.
· Pre-heater flat plate pneumatic molding method: After heating and softening the battery packaging material, the air is supplied by holding it between the lower mold having a hole to which high-pressure air is supplied and the upper mold having a pocket-shaped recess. How to form a recess.
Drum-type vacuum forming method: A method of forming a recess by vacuuming the recess of a drum having a pocket-shaped recess after partially heating and softening the battery packaging material with a heating drum.
-Pin molding method: A method in which the bottom sheet is heated and softened and then crimped with a pocket-shaped uneven mold.
· Pre-heater plug-assisted pressure forming method: After heating and softening the battery packaging material, the air is supplied by holding it between the lower mold having a hole to which high-pressure air is supplied and the upper mold having a pocket-shaped recess. A method of forming a recess, wherein during molding, the convex plug is raised and lowered to assist molding.
　成型後の底材の肉厚が均一であることから、加熱真空成型法であるプレヒータープラグアシスト圧空成型法が好ましい。
　このようにして得られた本発明の電池用包装材は、正極、負極、電解質等の電池素子を密封して収容する電池用容器として好適に使用することができる。 Since the thickness of the bottom material after molding is uniform, a preheater plug assist pressure forming method, which is a heating vacuum forming method, is preferable.
The battery packaging material of the present invention thus obtained can be suitably used as a battery container in which battery elements such as a positive electrode, a negative electrode, and an electrolyte are sealed and housed.
＜電池＞
　本発明の電池は、正極、負極、及び電解質を備えた電池素子を、本発明の電池用包装材で、前記正極及び負極の各々に接続された金属端子が外側に突出させた状態で、電池素子の周縁にフランジ部（シーラント層同士が接触する領域）が形成できるようにして被覆し、前記フランジ部のシーラント層同士をヒートシールして密封させることによって得られる。 <Battery>
The battery of the present invention is a battery packaging material having a positive electrode, a negative electrode, and an electrolyte, in the battery packaging material of the present invention, in which the metal terminal connected to each of the positive electrode and the negative electrode protrudes outward. It is obtained by coating so that flanges (areas where sealant layers are in contact) can be formed on the periphery of the element, and the sealant layers of the flanges are heat sealed and sealed.
　本発明の電池用包装材を用いて得られる電池としては、一次電池、二次電池のいずれであってもよいが、好ましくは二次電池である。二次電池としては特に制限されず、例えば、リチウムイオン電池、リチウムイオンポリマー電池、鉛蓄電池、ニッケル・水素蓄電池、ニッケル・カドミウム蓄電池、ニッケル・鉄蓄電池、ニッケル・亜鉛蓄電池、酸化銀・亜鉛蓄電池、金属空気電池、多価カチオン電池、コンデンサー、キャパシター等が挙げられる。これらの二次電池の中でも、本発明の電池用包装材の好適な適用対象として、リチウムイオン電池及びリチウムイオンポリマー電池が挙げられる。 The battery obtained using the battery packaging material of the present invention may be either a primary battery or a secondary battery, but is preferably a secondary battery. The secondary battery is not particularly limited, and examples thereof include lithium ion batteries, lithium ion polymer batteries, lead storage batteries, nickel hydrogen storage batteries, nickel cadmium storage batteries, nickel iron storage batteries, nickel zinc storage batteries, silver oxide zinc storage batteries, Metal air batteries, polyvalent cation batteries, capacitors, capacitors and the like can be mentioned. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries can be mentioned as preferable applications of the battery packaging material of the present invention.
　以下、実施例と比較例により本発明を説明するが、本発明はこれに限定されるものではない。配合組成その他の数値は特記しない限り質量基準である。 Hereinafter, the present invention will be described by way of Examples and Comparative Examples, but the present invention is not limited thereto. Composition and other values are on a mass basis unless otherwise stated.
（実施例１）
　オレフィン樹脂（Ａ）としてトーヨタックＰＭＡ－Ｌを１００部、トリフェニルホスフィンを０．０５部、ＦＴＲ－８１２０を１．０部、酸無水物（Ｃ）としてＥＰＩＣＬＯＮ　Ｂ－５７０－Ｈを０．１部、を混合溶媒（シクロメチルヘキサン／酢酸エチル／イソプロピルアルコール＝７１／８／１）に溶解させ、不揮発分２０％にした。次いでエポキシ化合物を含む硬化剤（Ｂ）としてデナコールＥＸ-３２１を２．０部加え、よく攪拌して実施例１の接着剤を調製した。 Example 1
As an olefin resin (A) 100 parts of Toyotac PMA-L, 0.05 parts of triphenylphosphine, 1.0 parts of FTR-8120, and 0.1 parts of EPICLON B-570-H as acid anhydride (C) Were dissolved in a mixed solvent (cyclomethylhexane / ethyl acetate / isopropyl alcohol = 71/8/1) to a nonvolatile content of 20%. Next, 2.0 parts of Denacol EX-321 as a curing agent (B) containing an epoxy compound was added and stirred well to prepare an adhesive of Example 1.
　調製した接着剤をアルミニウム箔（東洋アルミニウム社製アルミニウム箔「１Ｎ３０Ｈ」：膜厚３０μｍ）の光沢面にバーコーターで塗布量２ｇ／ｍ２（ｄｒｙ）で塗布し、８０℃－１分間乾燥させた後、未延伸ポリオレフィンフィルム（オカモト株式会社製「ＥＴ－２０」膜厚：４０μｍ）と１００℃で貼り合せた。次にアルミニウム箔のマット面に「ディックドライ　ＬＸ－９０６」（ＤＩＣ株式会社製）を主剤とし、「ＫＷ－７５」（ＤＩＣ株式会社製）を硬化剤として、重量比が主剤／硬化剤＝１００／１０となるように配合した接着剤をバーコーターで塗布量４ｇ／ｍ２（ｄｒｙ）で塗布した後、厚さ２５μｍの延伸ポリアミドフィルムを積層した。その後８０℃２日間の養生（エージング）を行い、ラミネート物を得た。 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) with a bar coater at a coating amount of 2 g / m 2 (dry) and dried at 80 ° C for 1 minute Thereafter, it was laminated at 100 ° C. with an unstretched polyolefin film (“ET-20” film thickness: 40 μm manufactured by Okamoto Co., Ltd.). Next, on the matte side of the aluminum foil, “Dick Dry LX-906” (made by DIC Corporation) is the main agent and “KW-75” (made by DIC Corporation) is the hardening agent, and the weight ratio is main agent / hardening agent = 100 After coating the adhesive compounded so as to be / 10 with a bar coater at a coating amount of 4 g / m 2 (dry), a 25 μm-thick stretched polyamide film was laminated. Thereafter, curing (aging) at 80 ° C. for 2 days was performed to obtain a laminate.
（実施例２～１０）
アルミニウム箔と未延伸ポリオレフィンフィルムの貼り合せに用いる接着剤の配合を表１、２に記載の配合に変更した以外は実施例１と同様にして接着剤を調整し、ラミネート物を得た。 (Examples 2 to 10)
An adhesive was prepared 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 described in Tables 1 and 2, to obtain a laminate.
（比較例１～５）
アルミニウム箔と未延伸ポリオレフィンフィルムの貼り合せに用いる接着剤の配合を表３に記載の配合に変更した以外は実施例１と同様にして接着剤を調整し、ラミネート物を得た。 (Comparative Examples 1 to 5)
An adhesive was prepared 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 described in Table 3, to obtain a laminate.
　なお、実施例、比較例で用いた化合物の詳細は以下の通りである。
トーヨータックＰＭＡ－Ｌ：無水マレイン酸変性オレフィン樹脂、酸価：３５ｍｇＫＯＨ／ｇ、融点：７０℃、東洋紡社製
トーヨータックＰＭＡ－ＫＥ：無水マレイン酸変性オレフィン樹脂、酸価：４４ｍｇＫＯＨ／ｇ、融点：８０℃、東洋紡社製
ＦＴＲ８１２０：スチレン樹脂、三井化学社製
ＥＰＩＣＲＯＮ　Ｂ－５７０－Ｈ：メチルテトラヒドロフタル酸無水物、ＤＩＣ社製
ＹＨ－３０６：トリアルキルテトラヒドロ無水フタル酸、三菱化学社製
デコナール　ＥＸ－３２１：トリメチロールプロパンポリグリシジルエーテル型エポキシ樹脂、ナガセケムテックス社製
ＥＰＩＣＬＯＮ　８６０：ビスフェノールＡ型エポキシ樹脂、ＤＩＣ社製
ＥＰＩＣＬＯＮ　Ｎ－６６５：クレゾールノボラック型エポキシ樹脂、ＤＩＣ社製 The details of the compounds used in Examples and Comparative Examples are as follows.
Toyo Tack PMA-L: maleic anhydride modified olefin resin, acid value: 35 mg KOH / g, melting point: 70 ° C. Toyo tack PMA-KE manufactured by Toyobo Co., Ltd .: maleic anhydride modified olefin resin, acid number: 44 mg KOH / g, melting point: 80 ° C., FTR 8120 manufactured by Toyobo Co., Ltd .: styrene resin, EPICRON B-570-H manufactured by Mitsui Chemicals, Inc., methyltetrahydrophthalic anhydride, YH-306 manufactured by DIC, trialkyltetrahydrophthalic anhydride, Deconal manufactured by Mitsubishi Chemical Co., Ltd. 321: trimethylolpropane polyglycidyl ether type epoxy resin, Nagase Chemtex Co., Ltd. EPICLON 860: bisphenol A epoxy resin, DIC EPICLON N-665: cresol novolac epoxy resin, DIC Co.
　なおオレフィン樹脂の酸価は、ＦＴ－ＩＲ（日本分光社製、ＦＴ－ＩＲ４２００）を使用し、無水マレイン酸のクロロホルム溶液によって作成した検量線から得られる係数（ｆ）、無水マレイン酸変性ポリオレフィン溶液における無水マレイン酸の無水環の伸縮ピーク（１７８０ｃｍ-1）の吸光度（Ｉ）とマレイン酸のカルボニル基の伸縮ピーク（１７２０ｃｍ-1）の吸光度（ＩＩ）を用いて下記式により算出した値である。下記式において無水マレイン酸の分子量を９８．０６、水酸化カリウムの分子量は５６．１１とした。 The acid value of the olefin resin is a coefficient (f) obtained from a calibration curve prepared by using a solution of maleic anhydride in chloroform using FT-IR (FT-IR 4200, manufactured by JASCO Corporation), a maleic anhydride-modified polyolefin solution Calculated using the following formula using the absorbance (I) of the stretching peak (1780 cm -1 ) of the anhydride ring of maleic anhydride and the absorbance (II) of the stretching peak (1720 cm -1 ) of the carbonyl group of maleic acid in . In the following formula, the molecular weight of maleic anhydride is 98.06, and the molecular weight of potassium hydroxide is 56.11.
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
（初期接着強度の測定）
　株式会社島津製作所の「オートグラフＡＧＳ－Ｊ」を使用し、前記ラミネート物のアルミニウム箔と未延伸ポリオレフィンフィルムの界面の接着強度を剥離速度５０ｍｍ／ｍｉｎ、剥離幅１５ｍｍ、剥離形態Ｔ型の条件で評価した。 (Measurement of initial adhesion strength)
Bonding strength of the interface between aluminum foil and unstretched polyolefin film of the laminate is 50 mm / min, peeling width 15 mm, peeling form T type using "Autograph AGS-J" manufactured by Shimadzu Corporation. evaluated.
（耐熱性）
　ヒートシール後のラミネート物の接着強度を測定しようとしても、ポリオレフィンフィルムが破損し、ポリオレフィンフィルムとアルミニウム箔との間ではなく、ヒートシールされたポリオレフィンフィルム同士の間で剥離していく場合がある。ヒートシール前後での接着強度の比較による耐熱性の評価は必ずしも正確ではない。このため、耐熱性については以下のようにして評価した。 (Heat-resistant)
Even if it is going to measure the adhesive strength of the laminate after heat sealing, a polyolefin film may be broken and it may peel between heat-sealed polyolefin films instead of between a polyolefin film and an aluminum foil. The evaluation of heat resistance by comparison of adhesive strength before and after heat sealing is not necessarily accurate. For this reason, the heat resistance was evaluated as follows.
　前記ラミネート物の未延伸ポリオレフィンフィルム側を谷折りし、未延伸ポリオレフィンフィルム側同士を１９０℃３秒の条件でヒートシールバーを当てた。次いで株式会社島津製作所の「オートグラフＡＧＳ－Ｊ」を使用し、剥離速度５００ｍｍ／ｍｉｎ、剥離幅１５ｍｍ、剥離形態Ｔ型の条件で１ｃｍ剥離させたときの界面を評価した。
◎：未延伸ポリオレフィンフィルム／未延伸ポリオレフィンフィルム間の剥離が９０％以上（実用上特に優れる）
○：未延伸ポリオレフィンフィルム／未延伸ポリオレフィンフィルム間の剥離が６０％以上９０％未満（実用上優れる）
△：未延伸ポリオレフィンフィルム／未延伸ポリオレフィンフィルム間の剥離が５０％以上６０％未満（実用域）
×：未延伸ポリオレフィンフィルム／未延伸ポリオレフィンフィルム間の剥離が５０％未満 The unstretched polyolefin film side of the laminate was valley-folded, and the heat-seal bar was applied to the unstretched polyolefin film sides under the condition of 190 ° C. for 3 seconds. Then, using “Autograph AGS-J” manufactured by Shimadzu Corporation, the interface was evaluated when peeled at 1 cm under the conditions of peeling speed 500 mm / min, peeling width 15 mm, peeling form T type.
◎: Peeling between unstretched polyolefin film / unstretched polyolefin film is 90% or more (especially excellent in practical use)
○: Peeling between unstretched polyolefin film / unstretched polyolefin film is 60% or more and less than 90% (practically excellent)
Δ: Peeling between unstretched polyolefin film / unstretched polyolefin film is 50% or more and less than 60% (practical range)
X: Peeling between unstretched polyolefin film / unstretched polyolefin film is less than 50%
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１～表３から明らかなように、本発明の接着剤は比較例の接着剤よりも耐熱性に優れる。 As apparent from Tables 1 to 3, the adhesive of the present invention is more excellent in heat resistance than the adhesive of the comparative example.
　本発明の接着剤はオレフィン樹脂のような非極性の基材と金属基材との接着性、耐熱性に優れ、本発明の接着剤を用いて得られる積層体は、例えば電池用包装材に好適に用いることができる。また本発明の接着剤の用途としては電池用包装材やそのための積層体に限定されず、家電外板、家具用素材、建築内装用部材など非極性の基材と金属基材との接着性が必要とされる分野に広く利用可能である。 The adhesive of the present invention is excellent in the adhesion between a nonpolar base such as an olefin resin and a metal base, heat resistance, and the laminate obtained by using the adhesive of the present invention is, for example, a battery packaging material. It can be used suitably. The application of the adhesive of the present invention is not limited to battery packaging materials and laminates therefor, and adhesion between non-polar substrates such as household electric appliance skins, furniture materials, building interior members and metal substrates Are widely available in areas where they are required.

Claims (10)

  1. 　オレフィン樹脂（Ａ）、エポキシ化合物を含む硬化剤（Ｂ）、酸無水物（Ｃ）を含み、前記酸無水物（Ｃ）の配合量が前記オレフィン樹脂（Ａ）１００質量部に対して０．０５質量部以上１０質量部以下である接着剤。 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. 0 to 100 parts by mass of the olefin resin (A). An adhesive that is 05 parts by mass or more and 10 parts by mass or less.
  2. 　前記酸無水物（Ｃ）が、酸無水物及び酸無水物のグリコール変性物からなる群から選ばれる少なくとも１種を含み、前記酸無水物がフタル酸無水物、トリメリット酸無水物、ピロメリット酸無水物、ベンゾフェノンテトラカルボン酸無水物、ドデセニルコハク酸無水物、ポリアジピン酸無水物、ポリアゼライン酸無水物、ポリセバシン酸無水物、ポリ（エチルオクタデカン二酸）無水物、ポリ（フェニルヘキサデカン二酸）無水物、テトラヒドロフタル酸無水物、メチルテトラヒドロフタル酸無水物、メチルヘキサヒドロフタル酸無水物、ヘキサヒドロフタル酸無水物、メチルハイミック酸無水物、トリアルキルテトラヒドロフタル酸無水物、メチルシクロヘキセンジカルボン酸無水物、メチルシクロヘキセンテトラカルボン酸無水物、エチレングリコールビストリメリテート二無水物、ヘット酸無水物、ナジック酸無水物、メチルナジック酸無水物、５－（２，５－ジオキソテトラヒドロ－３－フラニル）－３－メチル－３－シクロヘキサン－１，２－ジカルボン酸無水物、３，４－ジカルボキシ－１，２，３，４－テトラヒドロ－１－ナフタレンコハク酸二無水物、１－メチル－ジカルボキシ－１，２，３，４－テトラヒドロ－１－ナフタレンコハク酸二無水物からなる群から選ばれる少なくとも１種である請求項１に記載の接着剤。 The acid anhydride (C) contains at least one member selected from the group consisting of acid anhydride and glycol-modified acid anhydride, and the acid anhydride is phthalic anhydride, trimellitic anhydride, pyromellitic acid. Acid anhydride, benzophenone tetracarboxylic acid anhydride, dodecenyl succinic acid anhydride, polyadipic acid anhydride, polyazelaic acid anhydride, polysebacic acid anhydride, poly (ethyl octadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride , Tetrahydrophthalic anhydride, Methyltetrahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Hexahydrophthalic anhydride, Methylhymic anhydride, Trialkyltetrahydrophthalic anhydride, Methylcyclohexene dicarboxylic acid anhydride , Methylcyclohexene tetracarboxylic acid anhydride, Glycol bis trimellitate dianhydride, hetic anhydride, nadic anhydride, methyl nadic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1 , 2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydrofuran The adhesive according to claim 1, which is at least one member selected from the group consisting of -1-naphthalene succinic acid dianhydride.
  3. 　前記オレフィン樹脂（Ａ）が、酸基または水酸基を有することを特徴とする請求項１または２に記載の接着剤。 The adhesive according to claim 1, wherein the olefin resin (A) has an acid group or a hydroxyl group.
  4. 　前記硬化剤（Ｂ）の配合量が前記オレフィン樹脂（Ａ）１００質量部に対して０．０１質量部以上１０質量部以下である請求項１乃至３のいずれか一項に記載の接着剤。 The adhesive agent as described in any one of the Claims 1 thru | or 3 whose compounding quantity of the said hardening | curing agent (B) is 0.01 mass part or more and 10 mass parts or less with respect to 100 mass parts of said olefin resin (A).
  5. 　イミダゾール系化合物、３級アミン類、３級アミン類の塩、カチオン触媒、有機ホスフィン化合物からなる群から選ばれる少なくとも１種の接着促進剤を含むことを特徴とする請求項１乃至４のいずれか一項に記載の接着剤。 5. At least one adhesion promoter selected from the group consisting of imidazole compounds, tertiary amines, salts of tertiary amines, cationic catalysts, organic phosphine compounds, and the like. The adhesive according to one item.
  6. 　オレフィン樹脂（Ａ）、エポキシ化合物を含む硬化剤（Ｂ）、酸無水物（Ｃ）を含む接着剤用プレミクスチャーであって、前記オレフィン樹脂（Ａ）と前記酸無水物（Ｃ）とを含み、前記酸無水物（Ｃ）の含有量が前記オレフィン樹脂（Ａ）１００質量部に対して０．０５質量部以上１０質量部以下であるプレミクスチャー。 It is a premixer for adhesives containing an olefin resin (A), a curing agent (B) containing an epoxy compound, and an acid anhydride (C), which contains the olefin resin (A) and the acid anhydride (C). The premixer whose content of the said acid anhydride (C) is 0.05 mass part or more and 10 mass parts or less with respect to 100 mass parts of said olefin resin (A).
  7. 　第１の基材と、第２の基材と、前記第１の基材と前記第２の基材とを貼り合せる接着層とを含み、前記接着層が請求項１乃至５のいずれか一項に記載の接着剤の硬化塗膜であることを特徴とする積層体。 The adhesive layer which bonds together the 1st substrate, the 2nd substrate, and the 1st substrate and the 2nd substrate, and the above-mentioned adhesion layer is any one of Claims 1-5. It is a cured coating film of the adhesive as described in a term, The laminated body characterized by the above-mentioned.
  8. 　ポリオレフィンフィルムと、
    　樹脂フィルムと、
    　前記ポリオレフィンフィルムと前記樹脂フィルムとの間に配置された金属箔と、
    　前記ポリオレフィンフィルムと前記金属箔との間に配置された接着層と、を含み、
    　前記接着層が請求項１乃至５のいずれか一項に記載の接着剤の硬化塗膜であることを特徴とする電池用包装材。     Polyolefin film,
    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.
  9. 　請求項８に記載の電池用包装材を成型してなる電池用容器。 A battery container formed by molding the battery packaging material according to claim 8.
  10. 　請求項９に記載の電池用容器を使用してなる電池。   A battery comprising the battery container according to claim 9.
PCT/JP2018/047472 2017-12-26 2018-12-25 Adhesive, laminate, battery packing material, and battery WO2019131591A1 (en)

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