TW201937780A - Adhesive, laminate, battery packing material, and battery - Google Patents

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

Adhesive, laminated body, battery packaging material and battery

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

A secondary battery typified by a lithium ion battery has a configuration in which a positive electrode, a negative electrode, and an electrolytic solution are sealed between them. In addition, as a sealing bag for encapsulating a lead for taking out electricity of the positive electrode and the negative electrode to the outside, a metal base material and plastic using a heat-sealing layer containing an olefin resin, a metal foil such as an aluminum foil, or a metal vapor-deposited layer are known A laminated body (Patent Documents 1 and 2).

Prior art literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 09-283101

Patent Document 2 Japanese Patent Laid-Open No. 2007-294381

However, since olefin resin is non-polar, it is difficult to adhere to a metal substrate. When assembling a battery using the above-mentioned laminated body, The sealing elements located on the periphery of the battery element are thermally welded to each other to seal the battery element, thereby packaging the battery element. Therefore, the adhesive for bonding the heat-sealing layer and the metal substrate requires heat resistance in addition to the non-polar substrate such as an olefin resin and the adhesion of the metal substrate.

The present invention has been made in view of such circumstances, and an object thereof is to provide a non-polar base material such as an olefin resin and a metal base material which are excellent in adhesiveness and heat resistance. Furthermore, an object is to provide a laminated body obtained using such an adhesive, a secondary battery exterior material, and a battery obtained using the laminated body.

The present invention relates to an adhesive agent comprising: an olefin resin (A), a hardener (B) containing an epoxy compound, an acid anhydride (C), and a blending amount of the acid anhydride (C) relative to the olefin resin (A) 100 The mass part is 0.05 mass part or more and 10 mass parts or less.

The adhesive system of the present invention is excellent in adhesion and heat resistance of non-polar substrates and metal substrates such as olefin resins. Moreover, the laminated system of this invention is excellent in adhesiveness and heat resistance.

A form for implementing the invention <Adhesive>

The adhesive of the present invention includes an olefin resin (A), a hardener (B) containing an epoxy compound, and an acid anhydride (C). Hereinafter, each component of the adhesive agent of this invention is demonstrated in detail.

Examples of the olefin resin (A) used in the adhesive of the present invention include homopolymers and copolymers of olefin monomers, copolymers of olefin monomers and other monomers, hydrides and halides of these polymers. A polymer mainly composed of a hydrocarbon skeleton such as a modified body obtained by introducing a functional group such as oxygen or a hydroxyl group can be used alone or in combination of two or more kinds. It is preferable to use a crystalline olefin resin having an acid group or an acid anhydride group and a crystalline olefin resin having a hydroxyl group.

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

Examples of the olefin-based monomer used in the preparation of the acid-modified olefin resin (A-1) include olefins having 2 to 8 carbon atoms, for example, ethylene, propylene, isobutylene, 1-butene, and 4 -Methyl-1-pentene, hexene, vinylcyclohexane and the like. Among them, olefins having 3 to 8 carbon atoms are preferred, and propylene and 1-butene are particularly preferred from the standpoint of improved adhesion strength, and particularly from the viewpoint of excellent solvent resistance and excellent adhesion strength. From the viewpoint, it is preferable to use propylene and 1-butene in combination.

Examples of the ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic acid anhydride used in copolymerization with an olefin-based monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and citraconic acid. Zhongkang Acid, maleic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3 , 4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-octane-1,3-dionespiro [4.4] non-7-ene, bicyclo [2.2.1] heptane -5-ene-2,3-dicarboxylic anhydride, maleic acid, tetrahydrobenzenedicarboxylic anhydride, methyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, methyl -Norborn-5-ene-2,3-dicarboxylic anhydride, norborn-5-ene-2,3-dicarboxylic anhydride, etc. Among them, in particular, the reactivity with an olefin-based monomer and the reactivity of an acid anhydride after copolymerization are excellent, and when the compound itself has a small molecular weight, the functional group concentration in the case of a copolymer becomes high, Maleic anhydride is preferred. These can be used individually or in combination of 2 or more types.

In the preparation of the acid-modified olefin resin (A-1), in addition to an olefin-based monomer, an ethylenically unsaturated carboxylic acid, or an ethylenically unsaturated carboxylic acid anhydride, a compound having another ethylenically unsaturated group can be used in combination, for example, Styrene, butadiene, isoprene, etc.

Examples of the polyolefin used in the preparation of the acid-modified olefin resin (A-2) include homopolymers and copolymers of olefins having 2 to 8 carbon atoms, olefins having 2 to 8 carbon atoms, and others Specific examples of monomer copolymers include polyethylenes such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene resins, polypropylene, polyisobutylene, and the like. Poly (1-butene), poly (4-methyl-1-pentene), polyvinylcyclohexane, ethylene. Propylene block copolymer, ethylene. Random copolymers of propylene and ethylene. 1-butene copolymer, ethylene. 4-methyl-1-pentene copolymer, ethylene. Alpha-olefin copolymers such as hexene copolymers, ethylene. Vinyl acetate copolymer, ethylene. Methyl methacrylate copolymer, ethylene. Vinyl acetate. Methyl methacrylate copolymer, propylene. 1-butene copolymerization Things. Among them, a homopolymer of an olefin having 3 to 8 carbon atoms, and a copolymer of two or more olefins having 3 to 8 carbon atoms are particularly preferable from the viewpoint of improving the bonding strength. Homopolymer of propylene, or propylene. The 1-butene copolymer is particularly preferably propylene in terms of excellent solvent resistance and excellent adhesion strength. 1-butene copolymer.

As the ethylenically unsaturated carboxylic acid or the ethylenically unsaturated carboxylic acid anhydride used in the graft modification with polyolefin, it is possible to use the same with the olefin in the preparation of the acid-modified olefin resin (A-1) as described above. Copolymerized monomers are the same. From the viewpoint that the reactivity of the functional group after the graft modification is high and the functional group concentration of the graft-modified polyolefin becomes higher, maleic anhydride is preferred. These can be used individually or in combination of 2 or more types.

Specific examples of the reaction of the ethylenically unsaturated carboxylic acid or the ethylenically unsaturated carboxylic acid anhydride with the polyolefin by graft modification include melting the polyolefin and adding the ethylenically unsaturated carboxylic acid thereto. Or an ethylenically unsaturated carboxylic anhydride (graft monomer) to perform a graft reaction; a polyolefin is dissolved in a solvent to make a solution, and an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic anhydride is added to A method for performing a graft reaction; mixing a polyolefin dissolved in an organic solvent with an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride, and heating at a temperature above the softening temperature of the polyolefin or a melting point to melt A method of simultaneously performing radical polymerization and dehydrogenation reaction in a state.

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

As the radical initiator, an organic peroxide is preferable, and examples thereof include benzophenazine peroxide, dichlorobenzophenazine peroxide, dicumyl peroxide, and di-tert-butyl peroxide. Compounds, 2,5-dimethyl-2,5-bis (benzoate peroxide) hexyne-3, 1,4-bis (tertiary butyl isopropyl) benzene, lauryl peroxide Tert-butyl peroxyacetate, 2,5-dimethyl-2,5-di (tertiary butyl peroxide) hexyne-3, 2,5-dimethyl-2,5-di (per Oxidized tert-butyl) hexane, tert-butyl peroxybenzoate, tert-butyl peroxyphenylacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxyoctanoate, peroxidation Tertiary butyl pivalate, cumene peroxypivalate and tertiary butyl peroxydiethyl acetate. In addition, azo compounds such as azobisisobutyronitrile, dimethylazoisobutyrate, and the like can also be used.

Free radical initiators, as long as the most suitable one is selected according to the process of grafting reaction, usually preferred: dicumyl peroxide, di-tertiary butyl peroxide, 2,5-dimethyl -2,5-Di (tertiary butyl peroxide) hexyne-3, 2,5-dimethyl-2,5-di (tertiary butyl peroxide) hexane, 1,4-bis (per Dialkyl peroxides such as tertiary butyl isopropyl) benzene are oxidized.

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

Examples of the olefin resin (A-3) having a hydroxyl group include a copolymer of a polyolefin, a hydroxyl group-containing (meth) acrylate, and a hydroxyl group-containing vinyl ether. Polymer; a resin obtained by graft-modifying a hydroxyl-containing (meth) acrylate and a hydroxyl-containing vinyl ether onto a polyolefin. As the polyolefin, the same materials as 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 resins (A-1) and (A-2) can be used.

Examples of the hydroxy-containing (meth) acrylate for modification include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, and lactone-modified ( Hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like.

Examples of the hydroxyl-containing vinyl ether include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether.

When an olefin resin (A-3) having a hydroxyl group is used as the olefin resin (A), from the viewpoint of further improving the adhesion of the metal layer and excellent electrolyte resistance, it is preferable to use an olefin resin having 1 to 200 mgKOH / g. Hydroxyl valence.

The polyolefin used in the preparation of the acid-modified olefin resin (A-2) and the olefin resin (A-3) having a hydroxyl group may be used as the olefin resin (A) without being modified.

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 moderate fluidity, the weight average molecular weight of the olefin resin (A) is preferably 150,000 or less.

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

Measuring device: HLC-8320GPC manufactured by Tosoh Co., Ltd.

Column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL, manufactured by Tosoh Co., Ltd.

Detector: RI (differential refractometer)

Data processing: Multistation GPC-8020model II manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40 ℃

Solvent tetrahydrofuran

Flow rate 0.35ml / min

Standard: Monodisperse Polystyrene

Sample: A microfilter was used to filter a tetrahydrofuran solution having a resin solid content of 0.2% by mass (100 μl)

The melting point of the olefin resin (A) is preferably 50 ° C or higher, more preferably 60 ° C or higher, and even more preferably 65 ° C or higher. The melting point of the olefin resin (A) is preferably 120 ° C or lower, more preferably 90 ° C or lower, and even more preferably 85 ° C or lower.

The melting point of the olefin resin is measured by DSC (Differential Scanning Calorimetry). Specifically, the temperature was raised from the temperature reduction temperature to the temperature increase temperature at 10 ° C / min, and then cooled to 10 ° C / min to the temperature decrease temperature to remove the thermal history, and then the temperature was again increased to 10 ° C / min to the temperature increase reach point. The peak temperature at the time of the second temperature rise was set as the melting point. In addition, the temperature reduction reaching temperature is set to a temperature that is 50 ° C. or more lower than the crystallization temperature, and the temperature increase reaching temperature is set to a temperature that is approximately 30 ° C. or more higher than the melting point temperature. The temperature reaches the lowering temperature and the temperature reaches the temperature.

As the hardener (B), an epoxy compound is used. The compound is not particularly limited as long as it is a compound having an epoxy group in the molecule, and examples thereof include ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, Polyglycidyl ether epoxy resin of aliphatic polyhydric alcohols such as neopentyl tetraol, glycerol, diglycerol, sorbitol, spirodiol, or hydrogenated bisphenol A; bisphenol A epoxy resin, bisphenol F-ring Oxygen resins, bisphenol S-type epoxy resins, bisphenol AD-type epoxy resins and other bisphenol-type epoxy resins; phenol novolac resins, cresol novolac resins, glycidyl ethers, novolac-type epoxy resins, and other aromatic Group epoxy resins; polyglycidyl ethers of polyhydric alcohols of ethylene oxide or propylene oxide adducts of aromatic polyhydroxy compounds such as bisphenol A, bisphenol F, bisphenol S, and bisphenol AD; Polyglycidyl ether epoxy resin of polyether polyols such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; bis (3,4-epoxycyclohexylmethyl) adipate, 3, Cycloaliphatic polyepoxy resins such as 4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylformate; propanetricarboxylic acid, butane Polyglycidyl ester epoxy resins of polycarboxylic acids such as alkanetetracarboxylic acid, adipic acid, phthalic acid, terephthalic acid, or trimellitic acid; butadiene, hexadiene, octadiene, dodecanediene Epoxy resins of diene such as olefin, cyclooctadiene, α-pinene or vinyl cyclohexene; epoxy resins of diene polymers such as polybutadiene or polyisoprene; tetrashrink Glycidyl diamino diphenylmethane, triglycidyl p-aminophenol, tetraglycidyl bisaminomethylcyclohexane, diglycidyl aniline, tetraglycidyl metaxylylene diamine, and other glycidol Amine type epoxy resin; three And epoxy resins containing heterocycles, such as hydantoin.

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

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 per molecule and having a weight average molecular weight of 3,000 or less.

As the hardener (B), a compound other than an epoxy resin may be used in combination. Examples of other curing agents that can be used in combination with epoxy resins include polyfunctional isocyanate compounds, nitrogen-containing propidyl compounds, carbodiimides, Oxazoline, amine-based resin, etc.

Examples of the polyfunctional isocyanate compound include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and 1,5-naphthalene Diisocyanates such as diisocyanate, hexamethylene diisocyanate, bis (4-isocyanate cyclohexyl) methane, or hydrogenated diphenylmethane diisocyanate, and compounds derived therefrom, that is, the isotricyanates of the aforementioned diisocyanates Compounds, adducts, biuret type, uretdione, urethane, prepolymers with isocyanate residues (oligomers derived from diisocyanates and polyols), or their composites Wait.

As the hardener, a compound obtained by reacting an isocyanate group which is a part of the polyfunctional isocyanate compound as described above and a compound having reactivity with the isocyanate group can be used. Examples of compounds having reactivity with isocyanate groups include amine-containing compounds such as butylamine, hexylamine, octylamine, 2-ethylhexylamine, dibutylamine, ethylenediamine, benzylamine, and aniline. ; Methanol, ethanol, propanol, isopropanol, butane Alcohol, hexanol, octanol, 2-ethylhexanol, dodecyl alcohol, ethylene glycol, propylene glycol, benzyl alcohol, phenol and other compounds containing hydroxyl groups; allyl glycidyl ether, 2-ethylhexyl Glycidyl ether, phenyl glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, cyclohexanedimethanol diglycidyl ether and other compounds having epoxy groups; acetic acid, Compounds containing carboxylic acids, such as butyric acid, caproic acid, caprylic acid, succinic acid, adipic acid, sebacic acid, and phthalic acid, and the like.

Examples of the nitrogen-containing propidyl compound include N, N'-hexamethylene-1,6-bis (1-aziridinecarboxyamidoamine) and N, N'-diphenylmethane- 4,4'-bis (1-aziridinecarboxyamidoamine), trimethylolpropane-tri-β-aziridinylpropionate), N, N'-toluene-2,4-bis (1 -Aziridinylcarboxamidine), triethylene melamine, trimethylolpropane-tri-β (2-methylaziridine) propionate, bisisophthalamidinyl-1-2-methyl nitrogen Propidium, tri-1-aziridinylphosphine oxide, ginsyl-2-methylaziridinephosphine oxide, etc.

Examples of the carbodiimide include N, N'-di-o-tolylfluorenylcarbodiimide, N, N'-diphenylcarbodiimide, N, N'-di-2,6-di Methylphenylcarbodiimide, N, N'-bis (2,6-diisopropylphenyl) carbodiimide, N, N'-dioctyldecylcarbodiimide, N-toluene Fluorenyl-N'-cyclohexylcarbodiimide, N, N'-di-2,2-tert-butylphenylcarbodiimide, N-toluenyl-N'-phenylcarbodiimide , N, N'-di-p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-dicyclohexylcarbodiimide, N, N'- Di-p-toluenylcarbodiimide and the like.

As Examples of oxazolines include 2- Oxazoline, 2-methyl-2- Oxazoline, 2-phenyl-2- Oxazoline, 2,5-dimethyl-2- Oxazoline, 2,4-diphenyl-2- Oxazoline Oxazoline compounds; 2,2 '-(1,3-phenylene) -bis (2- Oxazoline), 2,2 '-(1,2-ethylene) -bis (2- Oxazoline), 2,2 '-(1,4-butylene) -bis (2- Oxazoline), 2,2 '-(1,4-phenylene) -bis (2- Oxazoline) and the like.

Examples of the amine-based resin include a melamine resin, a benzoguanamine resin, and a urea resin.

The blending amount of the hardener (B) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the olefin resin (A). The blending amount of the hardener (B) is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and still more preferably 5 parts by mass or less based on 100 parts by mass of the olefin resin (A). Thereby, excellent adhesiveness and chemical resistance can be exhibited.

Examples of the acid anhydride (C) include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, and unsaturated carboxylic acid anhydrides, and they can be used alone or in combination of two or more. More specifically, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, Polysebacic anhydride, poly (ethyloctadecanoic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydro Phthalic anhydride, methyl humic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, ethylene glycol bistrimellitic dianhydride, chlorobridged anhydride, Nadic acid anhydride, methyl nadic acid anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 1-methyl-dicarboxyl-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid Dianhydride, etc.

In addition, a substance obtained by modifying the above-mentioned compound with a diol can be used as the acid anhydride (C). Examples of diols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; and polyethylene glycols, polypropylene glycol, and polytetramethylene ether glycol. Ether glycols, etc. Furthermore, a copolymerized polyether diol of two or more of these diols and / or polyether diols can also be used.

The blending amount of the acid anhydride (C) is preferably 0.05 parts by mass or more, more preferably 0.8 parts by mass or more, based on 100 parts by mass of the olefin resin (A). The blending amount of the acid anhydride (C) is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, based on 100 parts by mass of the olefin resin (A). Thereby, it is possible to prepare an adhesive with improved adhesion between the adhesive and the metal, and excellent initial bonding strength and excellent bonding strength after heat sealing.

The reason why the adhesive system of the present invention is excellent in adhesiveness and heat resistance is not clear, but it is estimated as follows. The acid anhydride (C) used in the present invention has a polar group and has excellent affinity for a metal substrate. In addition, it is relatively easy to move due to its small molecular weight. It is considered that the applied adhesive moves to the side of the metal base material until it is completely hardened, and functions as a so-called anchor, thereby contributing to improvement in adhesion and heat resistance. On the other hand, if the amount of the acid anhydride (C) contained in the adhesive is too large, the acid anhydride (C) virtually forms a low-strength layer between the metal substrate and the adhesive, which is considered to cause a decrease in adhesion.

The adhesive of the present invention, in addition to the above-mentioned components, can be blended with an organic solvent (D) to ensure fluidity and exhibit suitable coating properties. The organic solvent is not particularly limited as long as it can be volatilized and removed by heating in the drying step when the adhesive is applied, and examples thereof include aromatics such as toluene and xylene. Organic solvents; aliphatic organic solvents such as n-hexane and n-heptane; cycloaliphatic 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, cyclohexanone; ester solvents such as ethyl acetate, butyl acetate; ethanol, methanol, n-propanol, 2-propanol (isopropanol ), Alcohol solvents such as butanol, hexanol; diisopropyl ether, butyl cyrus, tetrahydrofuran, di Ether solvents such as alkane and butylcarbitol; glycol ether solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ethylene glycol monomethyl ether B Glycol ester solvents such as acid esters, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and the like may be used alone or in combination of two or more.

From the viewpoint of excellent solubility even when a non-chlorine-based olefin resin, an olefin resin having an acid group or an acid anhydride group, and an olefin resin having a hydroxyl group are used as the olefin resin (A), it is preferable to use a fat. A mixed solvent of a cyclic group 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, the solubility is excellent, and a mixed solvent of methylcyclohexane, ethyl acetate, and isopropanol is preferably used.

As the amount of the organic solvent used, the ratio of the olefin resin (A) to the total mass of the olefin resin (A) and the organic solvent (D) is preferably 10 to 30% by mass. This makes it possible to prepare an adhesive that is excellent in coating properties and wettability to a metal thin film.

As the adhesive of the present invention, a tackifier, a plasticizer, a thermoplastic elastomer, a reactive elastomer, and phosphorylation can be used as necessary. Additives, silane coupling agents, and adhesion promoters. The content of these additives may be appropriately adjusted within a range that does not impair the function of the adhesive of the present invention.

Examples of usable tackifiers include rosin-based or turpentyl ester-based tackifiers, terpene-based or terpene-phenol-based tackifiers, saturated hydrocarbon resins, and coumarone-based tackifiers. , Coumarone indene-based tackifier, styrene resin-based tackifier, xylene resin-based tackifier, phenol resin-based tackifier, petroleum resin-based tackifier, etc. These can be used individually or in combination of 2 or more types.

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

Examples of phosphoric acid compounds include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and diphosphoric acid; for example, condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and superphosphoric acid; for example, orthophosphate Methyl ester, 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, diphenyl orthophosphate, dimethyl phosphite Esters, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, di-2-ethylhexyl phosphite, diphenyl phosphite and other mono- and diesters, derived from condensed phosphoric acid and alcohols Monoesters and diesters, substances obtained by adding an epoxy compound such as ethylene oxide and propylene oxide to the aforementioned phosphoric acid, and adding the aforementioned phosphoric acid to, for example, an aliphatic or aromatic di shrink Glyceryl ether and the like obtained from epoxy phosphates.

Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) -γ-aminopropyltrimethoxysilane Amine silanes such as N-β (aminoethyl) -γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, etc .; vinyl ginseng (β -Methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and other vinylsilanes; hexamethyldisilazane Alkane, γ-mercaptopropyltrimethoxysilane, and the like.

Examples of the adhesion promoter include 2-methylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl Imidazole compounds such as 2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, triethylamine, triethylenediamine, N'-methyl-N- (2-di Methylaminoethyl) piper , 1,8-diazabicyclo [5.4.0] undecene (DBU), 1,5-diazabicyclo [4.3.0] -nonene, 6-dibutylamino-1,8- Tertiary amines such as diazabicyclo [5.4.0] undecene and compounds which make these tertiary amines into amine salts using phenol, caprylic acid, quaternary tetraphenylborate, etc. Cationic catalysts such as fluoroantimonate, diallyl hexafluoroantimonate, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, ginseng (4-methylphenyl) phosphine, ginseng ( Organic phosphine compounds such as 4-butylphenyl) phosphine, diphenylphosphine, and phenylphosphine. They can be used alone or in combination of two or more.

The adhesive of the present invention can be prepared by mixing the respective components described above. In this case, the components can be mixed at the same time to form an adhesive. However, from the standpoint of excellent stability and workability of the adhesive, it is preferable to prepare the following two-component type adhesive: the hardener (B) is mixed in advance. The pre-mixture is prepared, and the hardener (B) is mixed when an adhesive is used.

The adhesive system of the present invention is excellent in adhesion and heat resistance of non-polar substrates and metal substrates such as olefin resins.

<Layered body>

The laminated body of this invention includes a 1st base material, a 2nd base material, and the adhesion layer arrange | positioned between a 1st base material and a 2nd base material, and bonding a 1st base material and a 2nd base material. The next layer is a cured coating film of the above-mentioned adhesive. In addition to the first substrate and the second substrate, other substrates may be further included. The adhesive layer which adheres a 1st base material and another base material, and a 2nd base material and another base material may or may not be a hardened coating film of the adhesive agent of this invention.

As the first substrate, the second substrate, and other substrates, for example, paper, olefin resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine Synthetic resin, poly (meth) acrylic resin, carbonate resin, polyamide resin, polyimide resin, polyphenylene ether resin, polyphenylene sulfur resin, polyester resin Resin film, metal foil such as copper foil, aluminum foil, etc.

The adhesive of the present invention is excellent in adhesion between a non-polar base material such as an olefin resin and a metal base material. Therefore, one of the first base material and the second base material is preferably a non-polar base material. One is a metal substrate, but is not limited thereto.

The laminated system of the present invention is obtained by applying the adhesive of the present invention to one of a first substrate and a second substrate, and then laminating the other and curing the adhesive. It is preferable to provide a drying step between the first substrate and the second substrate after the adhesive is applied.

As a method of applying the adhesive, a gravure coater method, a micro gravure coater method, a reverse coater method, a bar coater method, a roll coater method, a die coater method, and the like can be used. The application amount of the adhesive is preferably adjusted so that the application weight after drying becomes 0.5 to 20.0 g / m ² . If it is less than 0.5 g / m ² , continuous and uniform coatability tends to decrease, and if it exceeds 20.0 g / m ² , the solvent release property after coating also decreases, and problems such as a decrease in workability and residual solvents tend to occur.

The temperature of the lamination roll when 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 .

After the first substrate and the second substrate are bonded, it is preferable to provide an aging step. The aging conditions are preferably 25 to 100 ° C and 12 to 240 hours.

<Battery packaging material>

The battery packaging material of the present invention includes, as an example, a first substrate, a second substrate, a third substrate, a first adhesive layer that bonds the first substrate and the second substrate, and a second substrate The second adhesive layer in which the substrate and the third substrate are bonded together. The first base material is a polyolefin film, and the second base material is a metal foil. The third base material is a resin film such as nylon or polyester. The first adhesive layer is a cured coating film of the adhesive of the present invention. The second adhesive layer may or may not be the cured coating film of the adhesive of the present invention. The third substrate may be further permeable or non-permeable on the side opposite to the second adhesive layer. Other substrates may be arranged on the ground, and a coating layer may be provided. It is not necessary to provide another base material and a coating layer.

The polyolefin film may be appropriately selected from conventionally known olefin resins. For example, it is not particularly limited, and polyethylene, polypropylene, and ethylene-propylene copolymer can be used. An unstretched film is preferred. The film thickness of the polyolefin film is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 25 μm or more. The thickness is preferably 100 μm or less, more preferably 95 μm or less, and even more preferably 90 μm or less.

The first base material functions as a sealing layer when the battery packaging material of the present invention is heat-sealed to be bonded to each other when a battery described later is manufactured.

Examples of the metal foil include aluminum, copper, and nickel. These metal foils may be subjected to sandblasting treatment, grinding treatment, degreasing treatment, etching treatment, surface treatment by dipping or spraying a rust inhibitor, trivalent chromium conversion treatment, phosphate conversion treatment, sulfide conversion treatment, formation of an anodized film, It is obtained by coating a surface treatment such as a fluororesin. Among them, a metal foil to which a trivalent chromium conversion treatment is applied is preferable from the viewpoint of excellent adhesion retention performance (environmental degradation resistance) and corrosion resistance. In addition, from the viewpoint of preventing corrosion, the thickness of the metal thin film is preferably in a range of 10 to 100 μm.

Examples of the resin film that can be used as the third substrate include polyester resin, polyamide resin, epoxy resin, acrylic resin, fluororesin, polyurethane resin, silicone resin, phenol resin, and Resin films such as mixtures and copolymers thereof. Among them, the better ones Out: Polyester resin and polyamide resin, more preferably, biaxially stretched polyester resin and biaxially stretched polyamide resin. Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolymerized polyester, Polycarbonate, etc. Specific examples of the polyamide resin include nylon 6, nylon 6,6, a copolymer of nylon 6 and nylon 6,6, nylon 6,10, polyhexamethylene xylylenediamine ( MXD6) and so on.

The coating layer can be formed by, for example, polyvinylidene chloride, a polyester resin, a urethane resin, an acrylic resin, an epoxy resin, or the like. It is preferably formed of a two-liquid curable resin. Examples of the two-liquid curable resin forming the coating layer include a two-liquid curable urethane resin, a two-liquid curable polyester resin, and a two-liquid curable epoxy resin. In addition, a matting agent may be blended in the coating layer.

Examples of the matting agent include fine particles having a particle diameter of about 0.5 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 not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an irregular shape, and a balloon shape. Specific examples of the matting agent include talc, silica, graphite, kaolin, montmorillonite, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, and 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 Ene, benzoguanamine, gold, aluminum, copper, nickel, etc. These matting agents may be used individually by 1 type, and may be used in combination of 2 or more type. Among these matting agents, from the viewpoints of dispersion stability, cost, and the like, preferred examples include silicon oxide, barium sulfate, and titanium oxide. In addition, the matting agent can be subjected to various surface treatments such as insulation treatment and high-dispersion treatment on the surface.

When the polyolefin film of the first base material is formed to be inward of the third base material when the battery is produced, such a laminate is molded to form a secondary battery exterior material of the present invention. There are no particular restrictions on the molding method, and the following methods are exemplified.

． Heating air compression molding method: A method of sandwiching a packaging material for a battery between a lower mold having holes for supplying high-temperature and high-pressure air and an upper mold having pocket-shaped recesses, and supplying air while heating and softening to form the recesses.

． Preheater flat-type air compression molding method: A method of heating and softening a battery packaging material, sandwiching a lower mold having holes for supplying high-pressure air, and an upper mold having pocket-shaped recesses, and supplying air to form the recesses.

． Drum-type vacuum forming method: After heating and softening the battery packaging material locally with a heating drum, the concave portion of the drum having a pocket-shaped concave portion is evacuated to form the concave portion.

． Pin molding method: A method of heating and softening a substrate sheet and then crimping it with a pocket-shaped concave-convex mold.

． Preheater plug-assisted air compression molding method: After heating and softening the battery packaging material, it is sandwiched between a lower mold having a hole for supplying high-pressure air, A method for forming a recessed portion by supplying air to an upper mold having a pocket-shaped recessed portion, and a method of raising and lowering a convex plug to assist molding during molding.

From the viewpoint of uniform wall thickness of the formed substrate, the preheater plug-assisted air-pressure forming method of the heating vacuum forming method is preferred.

The battery packaging material of the present invention obtained by operating in this manner can be suitably used as a container for a battery that contains and seals battery elements such as a positive electrode, a negative electrode, and an electrolyte.

<Battery>

The battery of the present invention is obtained by forming a flange portion (a region where the sealing layers are in contact with each other) on a peripheral edge of the battery element in a state where the metal terminals respectively connected to the positive electrode and the negative electrode are projected to the outside. The battery element provided with the positive electrode, the negative electrode, and the electrolyte is covered with the battery packaging material of the present invention, and the sealing layers of the flange portions are heat-sealed to seal each other.

The battery obtained by using the battery packaging material of the present invention may be any of a primary battery and a secondary battery, and is preferably a secondary battery. The secondary battery is not particularly limited, and examples thereof include a lithium ion battery, a lithium ion polymer battery, a lead storage battery, and nickel. Hydrogen battery, nickel. Cadmium batteries, nickel. Iron batteries, nickel. Zinc battery, silver oxide. Zinc batteries, metal-air batteries, polyvalent cation batteries, condensers, capacitors, etc. Among these secondary batteries, suitable applications of the battery packaging material of the present invention include lithium-ion batteries and lithium-ion polymer batteries.

[Example]

Hereinafter, the present invention will be described by examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, the blend composition and other values are based on mass.

(Example 1)

100 parts of TOYO-TAC PMA-L as olefin resin (A), 0.05 parts of triphenylphosphine, 1.0 part of FTR-8120, and 0.1 part of EPICLON B-570-H as anhydride (C) were dissolved in a mixed solvent (ring Methylhexane / ethyl acetate / isopropanol = 71/8/1), making it 20% of non-volatile content. Next, 2.0 parts of Denacol EX-321 was added as a hardening | curing agent (B) containing an epoxy compound, and it stirred sufficiently, and prepared the adhesive agent of Example 1.

The prepared adhesive was coated on a glossy surface of an aluminum foil (aluminum foil "1N30H" manufactured by Toyo Aluminium: film thickness 30 μm) with a bar coater at a coating amount of 2 g / m ² (dry) at 80 ° C. for 1 minute. After drying, it was bonded to an unstretched polyolefin film ("ET-20" made by Okamoto Co., Ltd., film thickness: 40 µm) at 100 ° C. Next, the following adhesive was applied to the matte side of the aluminum foil with a bar coater at a coating amount of 4 g / m ² (dry), and then a stretched polyamide film having a thickness of 25 μm was laminated. "DICDRY LX-906" (manufactured by DIC Co., Ltd.) is used as the main agent, and "KW-75" (manufactured by DIC Co., Ltd.) is used as the hardener, and the weight ratio becomes the main agent / hardener = 100/10 Combined. Then, it aged at 80 degreeC for 2 days (ageing), and obtained the laminated body.

(Examples 2 to 10)

A laminate was obtained in the same manner as in Example 1 except that the composition of the adhesive used for bonding the aluminum foil and the unstretched polyolefin film was changed to the composition described in Tables 1 and 2.

(Comparative Examples 1 to 5)

A laminate was obtained in the same manner as in Example 1 except that the composition of the adhesive used for bonding the aluminum foil and the unstretched polyolefin film was changed to the composition described in Table 3.

The details of the compounds used in the examples and comparative examples are as follows.

TOYO-TAC PMA-L: maleic anhydride modified olefin resin, acid value: 35mgKOH / g, melting point: 70 ° C, manufactured by Toyobo Corporation

TOYO-TAC PMA-KE: Maleic anhydride modified olefin resin, acid value: 44mgKOH / g, melting point: 80 ° C, manufactured by Toyobo Co., Ltd.

FTR8120: styrene resin, made by Mitsui Chemicals

EPICLON B-570-H: Methyltetrahydrophthalic anhydride, manufactured by DIC Corporation

YH-306: Trialkyltetrahydrophthalic anhydride, manufactured by Mitsubishi Chemical Corporation

Denacol EX-321: Trimethylolpropane polyglycidyl ether epoxy resin, manufactured by Nagase Chemtex

EPICLON 860: Bisphenol A epoxy resin, manufactured by DIC Corporation

EPICLON N-665: Cresol novolac epoxy resin, manufactured by DIC Corporation

The acid value of the olefin resin is FT-IR (manufactured by JASCO Corporation, FT-IR4200), and the coefficient (f) obtained from a calibration curve made from a chloroform solution of maleic anhydride, The absorbance (I) of the stretching peak (1780 cm ^-1 ) of the anhydride ring of maleic anhydride in the polyolefin solution and the absorbance (II) of the stretching peak (1720 cm ^-1 ) of the carbonyl group of maleic acid are as follows. The value calculated by the formula. In the following formula, the molecular weight of maleic anhydride is 98.06, and the molecular weight of potassium hydroxide is 56.11.

(Measurement of initial bonding strength)

The "AutoGraph AGS-J" of Shimadzu Corporation was used to evaluate the bonding strength at the interface between the aluminum foil of the laminate and the unstretched polyolefin film under the conditions of a peeling speed of 50 mm / min, a peeling width of 15 mm, and a peeling shape T-shape. .

(Heat resistance)

Even if the adhesive strength of the heat-sealed laminate is to be measured, the polyolefin film may be broken, and the heat-sealed polyolefin film may not be peeled between the polyolefin film and the aluminum foil. The heat resistance evaluation based on the comparison of the bonding strengths before and after heat sealing is not necessarily correct. Therefore, the heat resistance was evaluated as follows.

The unstretched polyolefin film side of the aforementioned laminate was concavely folded, and the unstretched polyolefin film side was abutted against a heat-sealing rod at 190 ° C. for 3 seconds. Then use Shimadzu Corporation's "AutoGraph AGS-J" evaluated the interface when peeling 1 cm under conditions of a peeling speed of 500 mm / min, a peeling width of 15 mm, and a peeling shape T-shape.

◎: 90% or more of peeling between unstretched polyolefin film / unstretched polyolefin film (especially excellent in practical use)

○: The peeling between the unstretched polyolefin film / unstretched polyolefin film is 60% or more and less than 90% (excellent practically)

△: The peeling between the unstretched polyolefin film / unstretched polyolefin film is 50% or more and less than 60% (practical area)

×: peeling between unstretched polyolefin film / unstretched polyolefin film is less than 50%

As shown in Tables 1 to 3, the adhesive system of the present invention is superior in heat resistance to that of the comparative example.

Industrial availability

The adhesive of the present invention is excellent in adhesion and heat resistance of a non-polar base material such as an olefin resin and a metal base material, and the laminated body obtained by using the adhesive of the present invention can be suitably used, for example, as a packaging material for a battery. In addition, the application of the adhesive of the present invention is not limited to a battery packaging material and a laminated body used therefor, and can be widely used for external panels of home appliances, Fields that require adhesion of non-polar substrates and metal substrates, such as furniture materials and building interior components.

Claims (10)

An adhesive comprising: an olefin resin (A), a hardening agent (B) containing an epoxy compound, and an acid anhydride (C), and a blending amount of the acid anhydride (C) is 100 masses relative to the olefin resin (A). Parts are 0.05 mass parts or more and 10 mass parts or less. The adhesive according to claim 1, wherein the acid anhydride (C) contains at least one selected from the group consisting of an acid anhydride and a glycol-modified product of the acid anhydride, and the acid anhydride is selected from the group consisting of phthalic anhydride, trimellitic anhydride, and cumene Tetracarboxylic acid anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly (ethyloctadecanoic acid) anhydride, poly (phenyl Hexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhumic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene Dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol bistrimellitic dianhydride, chlorobridged anhydride, nadic anhydride, methylnadic anhydride, 5- (2,5-dimeric Oxytetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydro-1-naphthalene At least one selected from the group of succinic dianhydride and 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride. The adhesive according to claim 1 or 2, wherein the olefin resin (A) has an acid group or a hydroxyl group. The adhesive according to any one of claims 1 to 3, wherein the blending amount of the hardener (B) is 0.01 to 10 parts by mass relative to 100 parts by mass of the olefin resin (A). The adhesive according to any one of claims 1 to 4, which comprises a compound comprising an imidazole-based compound, a tertiary amine, a tertiary amine, a cationic catalyst, An adhesion promoter of at least one selected from the group of organic phosphine compounds. A premix comprising: an olefin resin (A), a hardener (B) containing an epoxy compound, and a premix for an adhesive for an acid anhydride (C), comprising the olefin resin (A) and the acid anhydride (C) The content of the acid anhydride (C) is 0.05 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the olefin resin (A). A laminated body comprising: a first base material, a second base material, and an adhesive layer bonded to the first base material and the second base material, wherein the adhesive layer is any one of claims 1 to 5 A hardened coating of an adhesive. A packaging material for a battery, comprising: a polyolefin film, a resin film, a metal foil disposed between the polyolefin film and the resin film, and an adhesive layer disposed between the polyolefin film and the metal foil The adhesive layer is a cured coating film of the adhesive according to any one of claims 1 to 5. A battery container is formed by molding the battery packaging material according to claim 8. A battery comprising a battery container according to claim 9.