[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2019069896A1 - Adhesive, laminate, battery member, and battery - Google Patents

Adhesive, laminate, battery member, and battery Download PDF

Info

Publication number
WO2019069896A1
WO2019069896A1 PCT/JP2018/036820 JP2018036820W WO2019069896A1 WO 2019069896 A1 WO2019069896 A1 WO 2019069896A1 JP 2018036820 W JP2018036820 W JP 2018036820W WO 2019069896 A1 WO2019069896 A1 WO 2019069896A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
adhesive
acid
group
battery
Prior art date
Application number
PCT/JP2018/036820
Other languages
French (fr)
Japanese (ja)
Inventor
英美 中村
翔 三木
泰 佐藤
良 水口
神山　達哉
和郎 有田
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 JP2019546714A priority Critical patent/JP6642778B2/en
Priority to CN201880060977.9A priority patent/CN111133075B/en
Publication of WO2019069896A1 publication Critical patent/WO2019069896A1/en

Links

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
    • B32B15/092—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 epoxy resins
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • 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
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/198—Sealing members characterised by the material characterised by physical properties, e.g. adhesiveness or hardness
    • 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, a laminate and a member for a battery.
  • a battery represented by a secondary battery such as 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 laminated body in which a metal foil such as aluminum foil or a metal deposition layer and a plastic are laminated is used.
  • a sealing bag is improved in which the sealing reliability is improved by using a maleic acid-modified polyolefin resin for the innermost layer of the laminate and forming the heat seal portion with the same maleic acid-modified polyolefin resin.
  • a maleic acid-modified polyolefin resin is generally used as an adhesive resin because it is excellent in adhesion to metals and heat sealability.
  • it when used as a sealing film for batteries as described above, it exhibits excellent adhesion immediately after lamination at high temperature, but has low electrolytic solution resistance and causes delamination over time, and is used as a sealing film I can not do it.
  • Patent Document 2 discloses a battery including a surface-treated layer formed on the surface of a metal layer and a metal layer, and an adhesive resin layer made of a polyolefin modified with a carboxylic acid group or a derivative thereof formed on the surface-treated layer.
  • the laminated body for electrolyte solution sealing films or the laminated body for battery electrode part protective films is described.
  • Patent Document 3 a polyolefin resin having at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group and a metal salt of carboxylic acid and two or more epoxy groups, and having a molecular weight of 3000
  • An adhesive resin composition which comprises the following epoxidized vegetable oil, and the blending amount of the epoxidized vegetable oil component is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyolefin component.
  • Patent Document 4 contains an acid-modified polyolefin resin and a polyurethane resin, and the polyurethane resin is 0.5 to 100 parts by mass with respect to 100 parts by mass of the polyolefin resin, for a binder for a secondary battery electrode Resin compositions are described.
  • the present invention provides an adhesive comprising an acid group-containing resin and an epoxy compound A containing an aromatic ring and an alkylene chain having 4 to 10 carbon atoms and two or more epoxy groups. It is a thing.
  • the present invention provides a laminate having the adhesive layer in the middle.
  • the present invention provides a battery member having the laminate.
  • the adhesive of the present invention is characterized by containing an acid group-containing resin and an epoxy compound A containing an aromatic ring, an alkylene chain having 4 to 10 carbon atoms and two or more epoxy groups.
  • the acid group-containing resin is a resin having an acid group in the resin.
  • an acid group a carboxyl group, a carboxylic acid anhydride group, a sulfonic acid group, a phosphoric acid group etc. are mentioned.
  • an acid value of 1 to 200 mg KOH / g is preferable because adhesion to a metal is improved. Particularly preferred is 5 to 165 mg KOH / g. If it is 200 mg KOH / g or less, the adhesive strength is high because of excellent flexibility, and if it is 1 mg KOH / g or more, the heat resistance is good.
  • the resin acid value (mg KOH / g) can be determined by the following formula.
  • the acid value can be measured by the following method.
  • Acid value measurement method-2 The acid value (mg KOH / g-resin) refers to the coefficient (f) obtained from the calibration curve prepared with chloroform solution of maleic anhydride using FT-IR (FT-IR 4200 manufactured by Nippon Bunko Co., Ltd.), maleic anhydride Calculated using the following formula using the absorbance (I) of the stretching peak (1780 cm-1) of the anhydride ring of maleic anhydride in the acid-modified polyolefin solution and the absorbance (II) of the stretching peak (1720 cm-1) of the carbonyl group of maleic acid Value.
  • FT-IR 4200 manufactured by Nippon Bunko Co., Ltd.
  • Acid value [(absorbance (I) x (f) x 2 x molecular weight of potassium hydroxide x 1000 (mg) + absorbance (II) x (f) x molecular weight of potassium hydroxide x 1000 (Mg)) / molecular weight of maleic anhydride] Molecular weight of maleic anhydride: 98.06, molecular weight of potassium hydroxide: 56.11
  • resin skeleton as the acid group-containing resin, but acid group-containing polyacrylic acid ester resin, acid group-containing polyurethane resin, and or acid group-containing polyolefin resin are mentioned as preferable resins.
  • (Acid group-containing polyacrylic acid ester resin) As said acid group containing polyacrylic acid ester resin, the copolymer of the polymerizable monomer which has a (meth) acryloyl group and a carboxyl group is mentioned, for example.
  • a polymerizable monomer having a (meth) acryloyl group and a carboxyl group (meth) acrylic acid; ⁇ -carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxy Ethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and modified products thereof such as unsaturated monocarboxylic acids having an ester bond; and maleic acid.
  • Examples of the other polymerizable unsaturated monomer which is optionally polymerized with a monomer having a (meth) acryloyl group and a carboxyl group include the following polymerizable monomers and the like.
  • (meth) acrylics having a fatty alkyl group such as cyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Acid esters;
  • Unsaturated dicarboxylic acid esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate, methyl ethyl itaconate;
  • Diene compounds such as butadiene, isoprene, piperylene, and dimethyl butadiene;
  • Vinyl halides such as vinyl chloride and vinyl bromide and vinylidene halides
  • Vinyl esters such as vinyl acetate and vinyl butyrate
  • Vinyl ethers such as methyl vinyl ether and butyl vinyl ether
  • Vinyl cyanides such as acrylonitrile, methacrylonitrile and vinylidene cyanide
  • N-substituted maleimides such as N-phenyl maleimide and N-cyclohexyl maleimide
  • Fluorine-containing ⁇ -olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; or trifluoromethyl trifluorovinylether, penta (Per) fluoroalkylperfluorovinylethers having 1 to 18 carbon atoms of (per) fluoroalkyl group such as fluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether; 2,2,2-trifluoroethyl (meth) ) Acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, Fluorine-containing compounds such as
  • silyl group-containing (meth) acrylates such as ⁇ -methacryloxypropyltrimethoxysilane
  • N, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylaminopropyl (meth) acrylate Can be mentioned.
  • the other polymerizable unsaturated monomers used when preparing these acid group-containing polyacrylic acid esters may be used alone or in combination of two or more.
  • the acid group-containing polyacrylic acid ester can be obtained by polymerization (copolymerization) using a known conventional method, and the form of copolymerization is not particularly limited. It can be produced by addition polymerization in the presence of a catalyst (polymerization initiator), and may be any of a random copolymer, a block copolymer, a graft copolymer and the like. Further, as the copolymerization method, known polymerization methods such as bulk polymerization method, solution polymerization method, suspension polymerization method and emulsion polymerization method can be used.
  • X 1 represents an aromatic ring or an alicyclic structure, and n 1 and n 2 each independently represent an integer of 0 to 3.
  • R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, or a carbonyl group, and m 1 to m 3 each independently represent an integer of 0 to 3).
  • the compound B is a compound having an isocyanate group represented by the formula (1).
  • X 1 represents an aromatic ring or an alicyclic structure.
  • the aromatic ring structure is preferably an aromatic ring having a carbon number of 6 to 18, and examples thereof include a benzene ring, a naphthalene ring, a phenanthrene ring and an anthracene ring.
  • the aromatic ring may be substituted by at least one fluorine atom, and examples of the aromatic ring substituted by at least one fluorine atom include a perfluorophenyl group and the like.
  • the alicyclic structure is preferably an alicyclic ring having a carbon number of 3 to 20, and may be a single ring or a condensed ring.
  • examples of cycloalkane include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane and the like.
  • examples of monocyclic cycloalkenes include cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, cyclooctene and the like.
  • the fused ring includes bicycloundecane, decahydronaphthalene, norbornene and norbornadiene.
  • examples of polycyclic compounds include cubane, baskettan, and Hausan. Further, it may be a ring structure in which an aromatic ring and an alicyclic ring are combined.
  • X 1 is preferably a benzene ring or a naphthalene ring.
  • n1 and n2 are preferably each independently 0 to 1.
  • More preferable structures of compound B include the following structures.
  • the compound B is a diol compound having a carboxyl group, which is represented by the formula (2).
  • the compound C is preferably a compound in which m3 is 0, and more preferably a case in which R1 is a hydrocarbon group having 1 to 3 carbon atoms.
  • compound C include dimethylol propionic acid and dimethylol butanoic acid.
  • acid group-containing polyolefin resin Specific examples of the skeleton of the acid group-containing polyolefin resin include polyethylene such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene resin, polypropylene, polyisobutylene, poly (1 -Butene), poly 4-methylpentene, polyvinylcyclohexane, polystyrene, poly (p-methylstyrene), poly ( ⁇ -methylstyrene), ethylene / propylene block copolymer, ethylene / propylene random copolymer, ethylene ⁇ butene ⁇ -Olefin copolymer such as ethylene copolymer, ethylene ⁇ 4-methyl-1-pentene copolymer, ethylene ⁇ hexene copolymer, ethylene ⁇ vinyl acetate copolymer, ethylene ⁇ acrylic acid copolymer , Ethylene / methyl methacrylate copolymer, ethylene
  • the acid group-containing monomer may be polymerized to synthesize a resin, or an acid group may be added to the resin later.
  • it is a method of modifying a polyolefin with an unsaturated carboxylic acid or a derivative thereof to synthesize. Graft modification or copolymerization can be used as this modification method.
  • a preferred acid-modified polyolefin resin is a graft-modified polyolefin in which at least one polymerizable ethylenically unsaturated carboxylic acid or derivative thereof is graft-modified or copolymerized to the polyolefin resin before modification.
  • the polyolefin resin before modification include the above-mentioned polyolefin resins. Among them, homopolymers of propylene, copolymers of propylene and an ⁇ -olefin, and the like are preferable. These can be used alone or in combination of two or more.
  • Examples of the ethylenically unsaturated carboxylic acid or derivative thereof which is graft modified or copolymerized to the polyolefin resin before modification are acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4- 4- Methylcyclohex-4-ene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,5 8,9,10-Octahydronaphthalene-2,3-dicarboxylic anhydride, 2-octa-1,3-diketospiro [4.4] non-7-ene, bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophthalic acid anhydride, methyl-bicyclo [2.2.1] hept-5
  • graft the grafting monomer selected from the ethylenically unsaturated carboxylic acids or their derivatives onto the polyolefin resin before modification For example, a method of melting a polyolefin resin and adding a graft monomer thereto for grafting reaction, dissolving a polyolefin resin in a solvent to form a solution, adding a graft monomer thereto for grafting reaction, dissolving it in an organic solvent
  • a 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 resin before modification.
  • acid-modified polyolefin resins for example, maleic anhydride-modified polypropylene, ethylene- (meth) acrylic acid copolymer, ethylene-acrylic acid ester-maleic anhydride terpolymer, or ethylene-methacrylic acid ester- And maleic anhydride terpolymers.
  • Rexpearl EAA "Rexpearl ET", Dow Chemical Co.
  • Primarymacol Mitsui-Dupont Polychemical "Nucrel”
  • Arkema "Bondine” are commercially available.
  • acid-containing resin examples include Tuftec M series manufactured by Asahi Kasei Co., Ltd., and Clayton FG Series manufactured by Clayton Polymer Japan Co., Ltd.
  • the adhesive of the present invention also contains an epoxy compound A containing an aromatic ring and an alkylene chain having 4 to 10 carbon atoms and two or more epoxy groups.
  • the aromatic ring may be a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, a bisphenol structure which may have a substituent, or a substituent.
  • the phenylene group which has an attachment site to o-, m-, p- respectively, 4,4'- biphenylene group, 2,2 ', 6, 6'- tetramethyl-4, 4 '-Biphenyl group, methylene diphenylene group, 2,2-propane-diphenyl group, 1,6-naphthalene group, 2,7-naphthalene group, 1,4-naphthalene group, 1,5-naphthalene group, 2,3 -Naphthalene group, and the following structural formula
  • they are a methylene diphenylene group and a 2, 2- propane diphenyl group from the point which is excellent in the balance of the softness
  • the epoxy compound A is preferably an epoxy compound (A1) represented by the following formula (8).
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are the same or different and each is an aromatic ring which may have a substituent, and X 1 and X 2 are aliphatic hydrocarbon groups. And R 1 , R 2 and R 3 are the same or different and each is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p, q and r are average values of the number of repetitions and p is 0.5 to 5.0, q is 0.5 to 5.0, and r is 0.05 to 0.5.
  • epoxy compound (A1) those having an epoxy equivalent of 150 to 900 g / eq are preferable from the viewpoint that the crosslink density of the cured product obtained is appropriate, and both soft toughness and heat resistance can be provided. Further, those having a viscosity of 2,000 to 20,000 Pa ⁇ s at 25 ° C. of the epoxy compound (A1) are preferable from the viewpoint of good workability and excellent flexibility and adhesion of a cured product, particularly 2
  • the pressure is preferably in the range of 1,000 to 15,000 Pa ⁇ s.
  • At least one of X 1 and X 2 in the formula (1) is a linear alkylene chain having 4 to 10 carbon atoms.
  • X 1 and X 2 in the formula (1) are linear alkylene chains of 4 to 10 carbon atoms.
  • X 1 and X 2 are linear alkylene chains of 4 to 10 carbon atoms.
  • the aromatic ring described above can be used as Ar 1 , Ar 2 , Ar 3 and Ar 4 in the formula (1). That is, a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, a bisphenol structure which may have a substituent, a biphenyl structure which may have a substituent, etc.
  • a benzene ring which may have a substituent
  • a naphthalene ring which may have a substituent
  • a bisphenol structure which may have a substituent
  • a biphenyl structure which may have a substituent
  • phenylene, 4,4'-biphenylene, 2,2 ', 6,6'-tetramethyl-4,4'-biphenyl having binding sites at o-, m- and p- respectively.
  • they are a methylene diphenylene group and a 2, 2- propane diphenyl group from the point which is excellent in the balance of the softness
  • Preferred examples of the epoxy compound (A1) include the following structures (A1-1) to (A1-9).
  • G is a glycidyl group
  • p, q and r are average values of the number of repetitions
  • p is 0.5 to 5.0
  • q is 0.5 to 5.0
  • R is 0.05 to 0.5.
  • Each aromatic ring may have, as a substituent, an alkyl group having 1 to 4 carbon atoms, a halogen atom or the like. Among these, it is most preferable to use those represented by the structural formulas (A1-3) and (A1-4) from the viewpoint of being excellent in the physical property balance of the cured product to be obtained.
  • the method for producing the epoxy compound (A1) is not particularly limited, but diglycidyl ether of aliphatic dihydroxy compound or diglycidyl ester of aliphatic acid compound (c1) and aromatic dihydroxy compound (c2) Using a method in which the hydroxy compound obtained by the reaction of () with the molar ratio (c1) / (c2) in the range of 1 / 1.1 to 1 / 5.0 is further reacted with the epihalohydrins (c3) However, it is preferable from the point which raw material acquisition and reaction are easy.
  • the adhesive of the present invention contains an acid group-containing resin and an epoxy compound A containing an aromatic ring, an alkylene chain having 4 to 10 carbon atoms and two or more epoxy groups.
  • the adhesive of the present invention is excellent in adhesive strength, particularly in initial adhesive strength, and the laminate which is a laminate is flexible, so that it can be suitably used as an adhesive for laminating.
  • the adhesive of the present invention is also suitable as an adhesive for metals because it adheres well to metal layers. Further, since the present adhesive after curing is excellent in electrolytic solution resistance, it is also suitable as a battery adhesive.
  • the adhesive of the present invention may contain an epoxy compound other than the epoxy compound A.
  • an epoxy compound other than the epoxy compound A for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, resorcinol epoxy resin, dihydroxynaphthalene epoxy resin, biphenyl epoxy resin, tetramethylbiphenyl epoxy resin, anthracene, Biphenyl, bisphenol A, bisphenol F, trifunctional or higher epoxy compound having a structure of bisphenol S, solid bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane Type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol no Lac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-convoluted novolak type epoxy resin, naphthol-cresol co-condensed
  • epoxy compound one epoxy compound may be used alone, or a plurality of epoxy compounds may be used in combination.
  • the molar ratio of the epoxy compound A to the other epoxy compound is preferably 100: 0 to 5:95.
  • the adhesive for lamination is particularly preferably 100: 0 to 10:90 from the viewpoint of flexibility.
  • the equivalent ratio (epoxy / acid value) of the acid group contained in the above-mentioned acid group-containing resin and the epoxy group contained in the epoxy compound containing the epoxy compound A is 0.01 to 10 It is preferable to mix
  • the adhesive of the present invention may contain a resin other than the acid group-containing resin and the epoxy compound, as long as the effects of the invention are not impaired.
  • a resin a thermosetting resin or a thermoplastic resin can be used.
  • thermosetting resin is a resin having the property of being substantially insoluble and capable of changing to an infusible property when cured by means of heating or radiation or a catalyst.
  • a thermosetting resin is a resin having the property of being substantially insoluble and capable of changing into infusiblity when it is cured by means such as heating or radiation or a catalyst.
  • thermosetting resins examples thereof include phenol resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, silicone resin, urethane resin, furan resin, ketone resin, xylene resin, heat
  • curable polyimide resins benzoxazine resins, active ester resins, aniline resins, cyanate ester resins, and styrene / maleic anhydride (SMA) resins.
  • SMA styrene / maleic anhydride
  • the thermoplastic resin refers to a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, Polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate Resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyether sulfone Fat, polyarylate resins, thermoplastic polyimide resins, polyamideimi
  • the adhesive of the present invention may use a curing catalyst.
  • a curing catalyst a general epoxy curing agent can be used. Specifically, an amine curing agent, an amide curing agent, an acid anhydride curing agent, a phenol curing agent, an active ester curing agent, Various curing agents such as carboxyl group-containing curing agents and thiol-based curing agents may be used in combination.
  • amide-based curing agent examples include dicyandiamide, and a polyamide resin synthesized from a dimer of linolenic acid and ethylene diamine.
  • acid anhydride type curing agent phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl hexameric anhydride Hydrophthalic anhydride etc. are mentioned.
  • phenolic curing agents include bisphenol A, bisphenol F, bisphenol S, resorcinol, catechol, hydroquinone, fluorene bisphenol, 4,4'-biphenol, 4,4 ', 4 "-trihydroxytriphenylmethane, naphthalenediol, 1 1,2,2-Tetrakis (4-hydroxyphenyl) ethane, calixarene, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc Resin), polyhydric phenol novolak resin synthesized from polyvalent hydroxy compound represented by resorcinol novolak resin and formaldehyde, naphthol aralkyl resin, trimethylo resin Lumethane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-convoluted no
  • a curing accelerator can be used alone or in combination with the above-mentioned curing catalyst.
  • various compounds which accelerate the curing reaction of epoxy compounds can be used, and examples thereof include phosphorus compounds, tertiary amine compounds, imidazole compounds, organic acid metal salts, Lewis acids, amine complexes and the like.
  • the use of imidazole compounds, phosphorus compounds and tertiary amine compounds is preferable, and triphenylphosphine and tertiary compounds are particularly preferable as phosphorus compounds from the viewpoint of excellent curability, heat resistance, electrical properties, moisture resistance and the like.
  • DBU 1,8-diazabicyclo- [5.4.0] -undecene
  • imidazole compounds 2-ethyl-4-methylimidazole is preferred.
  • the curing catalyst and the curing accelerator may or may not be blended, but in the case of blending, it is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the total solid content in the adhesive. Particularly preferred is 0.005 to 5 parts by weight.
  • the adhesive may contain a solvent depending on the application of use.
  • the solvent include organic solvents such as methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acetonitrile, methyl isobutyl ketone, methanol, ethanol, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol Monomethyl ether acetate, methyl cyclohexane and the like can be mentioned.
  • the type and amount of solvent used may be selected appropriately depending on the application.
  • hydrocarbon solvents ketone solvents, ester solvents or alcohol solvents are preferably used.
  • a solvent When a solvent is used, it may be blended after blending the acid group-containing resin and the epoxy compound A, or the acid group-containing resin or the epoxy compound A may be dissolved in the solvent in advance and used as a varnish.
  • the solvent component is preferably 50 to 90 parts by weight in 100 parts by weight of the total amount of the adhesive. More preferably, it is blended so as to be 60 to 85 parts by weight.
  • the adhesive may contain various additives as long as the effects of the present invention are not impaired.
  • additives include catalysts, surfactants, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), rust inhibitors, reactive elastomers, coupling agents, plasticizers, antistatic agents, lubricants.
  • Antiblocking agents, colorants, fillers, nucleating agents, compounds having an oxygen scavenging function, tackifiers, and the like can be exemplified. The content of these additives can be appropriately adjusted and used within the range that does not impair the function of the adhesive of the present invention.
  • the laminate of the present invention is characterized by having the adhesive layer of the present invention in the intermediate layer.
  • the upper and lower layers of the laminate are not particularly limited, and may be selected according to the application.
  • plastics such as polyethylene, polypropylene and polyethylene terephthalate; metals such as iron, aluminum, copper, silver and titanium, metal oxides, wood, paper, composite materials thereof and the like can be mentioned.
  • the adhesive of the present invention is good as an adhesive for metal or metal oxide because the adhesion to a metal or metal oxide layer is very good. Particularly preferably, it is for aluminum.
  • the shape of the upper layer and the lower layer of the laminate is not particularly limited, and may be any shape depending on the purpose, such as a flat plate, a sheet, or one having a curvature on the entire surface or a part of the three-dimensional shape. Further, there is no limitation on the hardness, thickness and the like of the base material.
  • the coating method of the adhesive layer is not particularly limited, and spray method, spin coat method, dip method, roll coat method, blade coat method, doctor roll method, doctor blade method, curtain coat method Slit coating method, screen printing method, ink jet method and the like.
  • the adhesive of the present invention can be suitably used for laminating because the adhesive strength is very high.
  • the dry coating weight is preferably in the range of 0.5 to 20.0 g / m 2 . If it is 0.5 g / m 2 or more, the continuous uniform coating property is good, and if it is 20.0 g / m 2 or less, the solvent removability after coating is good, so the balance between workability and solvent removal property Excellent.
  • the upper layer is overlapped and laminated by dry lamination (dry lamination method) to obtain a laminate.
  • the temperature of the laminating roll is preferably about room temperature to 120 ° C., and the pressure is preferably about 3 to 300 kg / cm 2 .
  • the laminate of the present invention is subjected to aging after preparation.
  • the aging conditions are preferably 25 to 100 ° C. for 12 to 240 hours, during which adhesive strength occurs.
  • the laminate of the present invention which is composed of a metal layer and a plastic layer, can be suitably used as, for example, an electrolytic solution sealing film or an electrode portion protective film of a battery.
  • the plastic layer side is used in contact with a polar organic solvent and / or a salt or the like.
  • a non-aqueous electrolyte containing a polar organic solvent and a salt it is particularly suitable as a secondary battery electrolyte sealing film for a non-aqueous electrolyte battery, solid battery, etc. or a secondary battery electrode part protective film It can be used.
  • the adhesive used in the present invention is excellent in heat sealability, leakage of the non-aqueous electrolyte can be prevented, and the battery can be used for a long time.
  • polar organic solvent examples include aprotic polar solvents such as alkyl carbonates, esters and ketones. Specifically, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ⁇ -butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3- Examples include dioxolane, 4-methyl-1,3-dioxolane, methyl formate, 4-methyl-1,3-dioxomethyl formate, methyl acetate, methyl propionate and the like.
  • the salt include alkali metal salts such as lithium salt, sodium salt and potassium salt.
  • lithium salts such as LiPF 6 , LiBF 4 and Li-imide are generally used.
  • the non-aqueous electrolyte is one in which 0.5 to 3 mmol of the alkali metal salt is dissolved in an aprotic polar organic solvent such as cyclic carbonate, chain carbonate, and a mixture thereof.
  • the laminate of the present invention can be used in contact with the non-aqueous electrolyte which is the polar solvent and / or the salts, particularly a mixture thereof, without causing delamination of the metal layer, adhesive layer and plastic layer over a long period of time It can be used.
  • the battery of the present invention contains the battery member of the present invention.
  • a battery electrolyte solution sealing film, a battery electrode part protection film, etc. are mentioned.
  • the battery of the present invention can be stably used as a battery for a long period of time because the film does not cause delamination, and moreover, the leakage of the non-aqueous electrolyte can be prevented.
  • Varnish 4 which is a solution of an acid group-containing acrylic acid ester resin (E) having a nonvolatile content of 46.8%.
  • Varnish 6 is a solution of an acid group-containing polyurethane resin (G) containing 50% by weight of a carboxyl group-containing urethane resin "DMPA / XDI".
  • the acid value of each of the prepared acid group-containing resins is shown in Table 1 below.
  • the hydroxyl equivalent calculated from GPC of this hydroxy compound (Ph-1) was 262 g / eq, and the average value of n in the structural formula (B-1) calculated from the hydroxyl equivalent was 0.6.
  • Examples 2 to 7 In the same manner as in the method described in Example 1, the components were mixed according to the formulations shown in Table 2 to produce an adhesive and a laminate. In the laminate obtained in each example, the adhesion performance and the electrolytic resistance were evaluated, and the results are shown in Table 2.
  • the adhesive of the present invention is excellent in adhesion, particularly adhesion to a metal or metal oxide layer, and further has electrolytic resistance even at low temperature curing and does not cause delamination over time, so it is an adhesive for laminating. It can be used favorably as an agent or an adhesive for batteries. Further, the obtained laminate can be favorably used as a battery member, and a battery having long-term use stability can be obtained.

Landscapes

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

Abstract

The present invention provides an adhesive that is characterized by containing an acid-group-containing resin and an epoxy compound A that contains an aromatic ring, a C4–10 alkylene chain, and at least two epoxy groups. Also provided is an adhesive in which the acid-group-containing resin is an acid-group-containing polyacrylic acid ester resin, an acid-group-containing polyurethane resin, and/or an acid-group-containing polyolefin resin. The present invention also provides a laminate that uses the adhesive, a battery member that contains the laminate, and a battery that includes the battery member.

Description

接着剤、積層体、電池用部材及び電池Adhesive, laminate, member for battery and battery
　本発明は、接着剤、積層体および電池用部材に関する。 The present invention relates to an adhesive, a laminate and a member for a battery.
　リチウムイオン電池等の二次電池に代表される電池は、正極、負極及びその間に、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、アルミニウム箔等の金属箔や金属蒸着層とプラスチックを貼り合わせた積層体が使用される。 A battery represented by a secondary battery such as 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 laminated body in which a metal foil such as aluminum foil or a metal deposition layer and a plastic are laminated is used.
　例えば、特許文献１には、積層体の最内層にマレイン酸変性ポリオレフィン樹脂を使用し、ヒートシール部を同様のマレイン酸変性ポリオレフィン樹脂で構成することにより、密封信頼性を向上させた封入袋が提案されている。マレイン酸変性ポリオレフィン樹脂は金属との接着性及びヒートシール性に優れるため、一般的には接着性樹脂として使用されている。しかし、上記のような電池の封止フィルムとして使用すると、高温での積層直後には優れた接着力を示すが、耐電解液性が低く、経時で層間剥離を生じ、封止フィルムとして使用することができない。 For example, in Patent Document 1, a sealing bag is improved in which the sealing reliability is improved by using a maleic acid-modified polyolefin resin for the innermost layer of the laminate and forming the heat seal portion with the same maleic acid-modified polyolefin resin. Proposed. A maleic acid-modified polyolefin resin is generally used as an adhesive resin because it is excellent in adhesion to metals and heat sealability. However, when used as a sealing film for batteries as described above, it exhibits excellent adhesion immediately after lamination at high temperature, but has low electrolytic solution resistance and causes delamination over time, and is used as a sealing film I can not do it.
　特許文献２には、金属層と金属層の表面に形成された表面処理層と表面処理層上に形成されたカルボン酸基、又はその誘導体が変性されたポリオレフィンからなる接着性樹脂層を含む電池電解液封止フィルム用積層体又は電池電極部保護フィルム用積層体について記載されている。 Patent Document 2 discloses a battery including a surface-treated layer formed on the surface of a metal layer and a metal layer, and an adhesive resin layer made of a polyolefin modified with a carboxylic acid group or a derivative thereof formed on the surface-treated layer. The laminated body for electrolyte solution sealing films or the laminated body for battery electrode part protective films is described.
　特許文献３には、酸無水物基、カルボキシル基及びカルボン酸金属塩からなる群から選ばれた少なくとも１種の官能基を有するポリオレフィン系樹脂及びエポキシ基を２個以上有し、かつ分子量が３０００以下であるエポキシ化植物油からなり、ポリオレフィン成分１００質量部に対するエポキシ化植物油成分の配合量が０．０１～５質量部である接着性樹脂組成物について記載されている。 In Patent Document 3, a polyolefin resin having at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group and a metal salt of carboxylic acid and two or more epoxy groups, and having a molecular weight of 3000 An adhesive resin composition is described which comprises the following epoxidized vegetable oil, and the blending amount of the epoxidized vegetable oil component is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyolefin component.
　特許文献４には、酸変性ポリオレフィン樹脂及びポリウレタン樹脂を含有し、ポリオレフィン樹脂１００質量部に対して、ポリウレタン樹脂が０．５～１００質量部であることを特徴とする二次電池電極用バインダー用樹脂組成物について記載されている。 Patent Document 4 contains an acid-modified polyolefin resin and a polyurethane resin, and the polyurethane resin is 0.5 to 100 parts by mass with respect to 100 parts by mass of the polyolefin resin, for a binder for a secondary battery electrode Resin compositions are described.
特開平０９－２８３１０１号公報Japanese Patent Application Laid-Open No. 09-283101 ＷＯ２００７／０１７０４３号公報WO 2007/017043 特開平０８－１９３１４８号公報Japanese Patent Application Publication No. 08-193148 特開２０１０－２７７９５９号公報JP, 2010-277959, A
　本発明の課題は、接着強度に優れ、なおかつ耐電解液性にも優れた接着剤を提供することにある。また、該接着剤を用いた積層体、該積層体を含有する電池用部材、及び該電池用部材を有する電池を提供することにある。 An object of the present invention is to provide an adhesive which is excellent in adhesive strength and also excellent in electrolytic solution resistance. Another object of the present invention is to provide a laminate using the adhesive, a battery member containing the laminate, and a battery having the battery member.
　本発明者らは、鋭意検討の結果、酸基含有樹脂と特定の構造を有するエポキシ樹脂とを含有する接着剤が、上記課題を解決できることを見出した。 MEANS TO SOLVE THE PROBLEM The present inventors discovered that the adhesive agent containing an acidic radical containing resin and the epoxy resin which has a specific structure can solve the said subject as a result of earnest examination.
　すなわち本発明は、酸基含有樹脂と、芳香環および炭素数4－１０のアルキレン鎖及び2つ以上のエポキシ基を含有するエポキシ化合物Aとを含有することを特徴とする、接着剤を提供するものである。 That is, the present invention provides an adhesive comprising an acid group-containing resin and an epoxy compound A containing an aromatic ring and an alkylene chain having 4 to 10 carbon atoms and two or more epoxy groups. It is a thing.
　さらに、該接着剤層を中間に有することを特徴とする積層体を提供するものである。 Further, the present invention provides a laminate having the adhesive layer in the middle.
　さらに、該積層体を有する電池用部材を提供するものである。 Furthermore, the present invention provides a battery member having the laminate.
＜酸基含有樹脂＞
　本発明の接着剤は、酸基含有樹脂と、芳香環および炭素数4－１０のアルキレン鎖及び2つ以上のエポキシ基を含有するエポキシ化合物Aとを含有することを特徴とする。 <Acid group-containing resin>
The adhesive of the present invention is characterized by containing an acid group-containing resin and an epoxy compound A containing an aromatic ring, an alkylene chain having 4 to 10 carbon atoms and two or more epoxy groups.
　酸基含有樹脂とは、樹脂中に酸基を有する樹脂である。酸基としては、カルボキシル基、無水カルボン酸基、スルホン酸基、リン酸基等が挙げられる。酸基含有樹脂としては、酸価が１～２００ｍｇＫＯＨ／ｇであると、金属との密着性が向上する為好ましい。特に好ましくは５～１６５ｍｇＫＯＨ／ｇである。２００ｍｇＫＯＨ／ｇ以下であれば柔軟性に優れるため接着強度が高くなり、１ｍｇＫＯＨ／ｇ以上であれば耐熱性が良好である。 The acid group-containing resin is a resin having an acid group in the resin. As an acid group, a carboxyl group, a carboxylic acid anhydride group, a sulfonic acid group, a phosphoric acid group etc. are mentioned. As the acid group-containing resin, an acid value of 1 to 200 mg KOH / g is preferable because adhesion to a metal is improved. Particularly preferred is 5 to 165 mg KOH / g. If it is 200 mg KOH / g or less, the adhesive strength is high because of excellent flexibility, and if it is 1 mg KOH / g or more, the heat resistance is good.
（酸価測定方法）
　酸価とは、試料１ｇ中に存在する酸分を、中和するのに必要な水酸化カリウムのｍｇ数である。具体的には、秤量した試料を体積比でトルエン／メタノール＝７０／３０の溶媒に溶かし、１％フェノールフタレインアルコール溶液を数滴滴下しておき、そこに０．１ｍｏｌ／Ｌの水酸化カリウムアルコール溶液を滴下して、変色点を確認する方法により測定することができ、下記の計算式で求めることができる。 (Acid number measurement method)
The acid value is the number of mg of potassium hydroxide necessary to neutralize the acid component present in 1 g of the sample. Specifically, the weighed sample is dissolved in a solvent of toluene / methanol = 70/30 in volume ratio, and several drops of 1% phenolphthalein alcohol solution are dropped, and 0.1 mol / L potassium hydroxide is added thereto. It can measure by the method of dripping an alcohol solution and confirming a color change point, and can obtain | require by the following formula.
酸価測定方法－１
酸価（ｍｇＫＯＨ／ｇ）＝（Ｖ×Ｆ×５．６１）／Ｓ
Ｖ：０．１ｍｏｌ／Ｌ水酸化カリウムアルコール溶液の使用量（ｍＬ）
Ｆ：０．１ｍｏｌ／Ｌ水酸化カリウムアルコール溶液の力価
Ｓ：試料の採取量（ｇ）
５．６１：０．１ｍｏｌ／Ｌ水酸化カリウムアルコール溶液１ｍＬ中の水酸化カリウム相当量（ｍｇ） Acid value measurement method-1
Acid value (mg KOH / g) = (V x F x 5.61) / S
V: Use amount of 0.1 mol / L potassium hydroxide alcohol solution (mL)
F: titer S of 0.1 mol / L potassium hydroxide alcohol solution: amount of sample collected (g)
5.61: Equivalent amount (mg) of potassium hydroxide in 1 mL of 0.1 mol / L potassium hydroxide alcohol solution
試料が樹脂溶液の場合は、下記の計算式で樹脂酸価（ｍｇＫＯＨ／ｇ）を求めることができる。 When the sample is a resin solution, the resin acid value (mg KOH / g) can be determined by the following formula.
樹脂酸価（ｍｇＫＯＨ／ｇ）＝樹脂溶液の酸価（ｍｇＫＯＨ／ｇ）/ＮＶ（％）×１００
ＮＶ：不揮発分（％） Resin acid value (mg KOH / g) = acid value of resin solution (mg KOH / g) / NV (%) × 100
NV: Non-volatile content (%)
　また、有機溶媒への試料の溶解性が低く、析出などをして、測定困難な場合は、以下の方法でも酸価を測定することができる。 In addition, when the solubility of the sample in the organic solvent is low and it is difficult to measure due to precipitation or the like, the acid value can be measured by the following method.
酸価測定方法－２
酸価（ｍｇＫＯＨ／ｇ－ｒｅｓｉｎ）とは、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。
酸価（ｍｇＫＯＨ／ｇ－ｒｅｇｉｎ）＝［（吸光度（Ｉ）×（ｆ）×２×水酸化カリウムの分子量×１０００（ｍｇ）＋吸光度（ＩＩ）×（ｆ）×水酸化カリウムの分子量×１０００（ｍｇ））／無水マレイン酸の分子量］
無水マレイン酸の分子量：９８．０６、水酸化カリウムの分子量：５６．１１ Acid value measurement method-2
The acid value (mg KOH / g-resin) refers to the coefficient (f) obtained from the calibration curve prepared with chloroform solution of maleic anhydride using FT-IR (FT-IR 4200 manufactured by Nippon Bunko Co., Ltd.), maleic anhydride Calculated using the following formula using the absorbance (I) of the stretching peak (1780 cm-1) of the anhydride ring of maleic anhydride in the acid-modified polyolefin solution and the absorbance (II) of the stretching peak (1720 cm-1) of the carbonyl group of maleic acid Value.
Acid value (mg KOH / g-regin) = [(absorbance (I) x (f) x 2 x molecular weight of potassium hydroxide x 1000 (mg) + absorbance (II) x (f) x molecular weight of potassium hydroxide x 1000 (Mg)) / molecular weight of maleic anhydride]
Molecular weight of maleic anhydride: 98.06, molecular weight of potassium hydroxide: 56.11
　酸基含有樹脂としては、樹脂骨格にとくに限定は無いが、酸基含有ポリアクリル酸エステル樹脂、酸基含有ポリウレタン樹脂及びまたは酸基含有ポリオレフィン樹脂などが好ましい樹脂として挙げられる。 There is no particular limitation on the resin skeleton as the acid group-containing resin, but acid group-containing polyacrylic acid ester resin, acid group-containing polyurethane resin, and or acid group-containing polyolefin resin are mentioned as preferable resins.
（酸基含有ポリアクリル酸エステル樹脂）
前記酸基含有ポリアクリル酸エステル樹脂としては、例えば、（メタ）アクリロイル基及びカルボキシル基を有する重合性単量体の共重合体が挙げられる。具体的には、（メタ）アクリロイル基及びカルボキシル基を有する重合性単量体としては、（メタ）アクリル酸；β―カルボキシエチル（メタ）アクリレート、２－アクリロイルオキシエチルコハク酸、２－アクリロイルオキシエチルフタル酸、２－アクリロイルオキシエチルヘキサヒドロフタル酸及びこれらのラクトン変性物等エステル結合を有する不飽和モノカルボン酸；マレイン酸等が挙げられる。 (Acid group-containing polyacrylic acid ester resin)
As said acid group containing polyacrylic acid ester resin, the copolymer of the polymerizable monomer which has a (meth) acryloyl group and a carboxyl group is mentioned, for example. Specifically, as a polymerizable monomer having a (meth) acryloyl group and a carboxyl group, (meth) acrylic acid; β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxy Ethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and modified products thereof such as unsaturated monocarboxylic acids having an ester bond; and maleic acid.
　（メタ）アクリロイル基及びカルボキシル基を有する単量体と必要に応じて重合させる他の重合性不飽和単量体としては、例えば、以下の重合性単量体と等が挙げられる。 Examples of the other polymerizable unsaturated monomer which is optionally polymerized with a monomer having a (meth) acryloyl group and a carboxyl group include the following polymerizable monomers and the like.
　（１）（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸－ｎ－ブチル、（メタ）アクリル酸－ｔ－ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸ドコシル等の炭素数１～２２のアルキル基を持つ（メタ）アクリル酸エステル類； (1) methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate , Hepsil (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, (Meth) acrylic acid esters having an alkyl group having 1 to 22 carbon atoms such as stearyl (meth) acrylate, octadecyl (meth) acrylate, and docosyl (meth) acrylate;
　（２）（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸イソボロニル、（メタ）アクリル酸ジシクロペンタニル、（メタ）アクリル酸ジシクロペンテニルオキシエチル等の脂式のアルキル基を有する（メタ）アクリル酸エステル類； (2) (meth) acrylics having a fatty alkyl group such as cyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Acid esters;
　（３）（メタ）アクリル酸ベンゾイルオキシエチル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸フェニルエチル、（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸フェノキシジエチレングリコール、（メタ）アクリル酸２－ヒドロキシ－３－フェノキシプロピル等の芳香環を有する（メタ）アクリル酸エステル類； (3) Benzoyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2- (meth) acrylate (Meth) acrylic esters having an aromatic ring such as hydroxy-3-phenoxypropyl;
（４）（メタ）アクリル酸ヒドロキエチル；（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸グリセロール；ラクトン変性（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ポリエチレングリコール、（メタ）アクリル酸ポリプロピレングリコールなどのポリアルキレングリコール基を有する（メタ）アクリル酸エステル等のヒドロキシアルキル基を有するアクリル酸エステル類； (4) Hydroxyethyl (meth) acrylate; Hydroxypropyl (meth) acrylate, Hydroxybutyl (meth) acrylate, Glycerol (meth) acrylate; Lactone modified hydroxyethyl (meth) acrylate, Polyethylene (meth) acrylate Acrylic acid esters having a hydroxyalkyl group such as (meth) acrylic acid ester having a polyalkylene glycol group such as glycol, polypropylene glycol (meth) acrylic acid;
（５）フマル酸ジメチル、フマル酸ジエチル、フマル酸ジブチル、イタコン酸ジメチル、イタコン酸ジブチル、フマル酸メチルエチル、フマル酸メチルブチル、イタコン酸メチルエチルなどの不飽和ジカルボン酸エステル類； (5) Unsaturated dicarboxylic acid esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate, methyl ethyl itaconate;
（６）スチレン、α－メチルスチレン、クロロスチレンなどのスチレン誘導体類； (6) Styrene, α-methylstyrene, styrene derivatives such as chlorostyrene;
（７）ブタジエン、イソプレン、ピペリレン、ジメチルブタジエンなどのジエン系化合物類； (7) Diene compounds such as butadiene, isoprene, piperylene, and dimethyl butadiene;
（８）塩化ビニル、臭化ビニルなどのハロゲン化ビニルやハロゲン化ビニリデン類； (8) Vinyl halides such as vinyl chloride and vinyl bromide and vinylidene halides;
（９）メチルビニルケトン、ブチルビニルケトンなどの不飽和ケトン類； (9) Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone;
（１０）酢酸ビニル、酪酸ビニルなどのビニルエステル類； (10) Vinyl esters such as vinyl acetate and vinyl butyrate;
（１１）メチルビニルエーテル、ブチルビニルエーテルなどのビニルエーテル類； (11) Vinyl ethers such as methyl vinyl ether and butyl vinyl ether;
（１２）アクリロニトリル、メタクリロニトリル、シアン化ビニリデンなどのシアン化ビニル類； (12) Vinyl cyanides such as acrylonitrile, methacrylonitrile and vinylidene cyanide;
（１３）アクリルアミドやそのアルキド置換アミド類； (13) acrylamide and its alkyd substituted amides;
（１４）Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミドなどのＮ－置換マレイミド類； (14) N-substituted maleimides such as N-phenyl maleimide and N-cyclohexyl maleimide;
（１５）フッ化ビニル、フッ化ビニリデン、トリフルオロエチレン、クロロトリフルオロエチレン、ブロモトリフルオロエチレン、ペンタフルオロプロピレン若しくはヘキサフルオロプロピレンの如きフッ素含有α－オレフィン類；またはトリフルオロメチルトリフルオロビニルエーテル、ペンタフルオロエチルトリフルオロビニルエーテル若しくはヘプタフルオロプロピルトリフルオロビニルエーテルの如き（パー）フルオロアルキル基の炭素数が１から１８なる（パー）フルオロアルキル・パーフルオロビニルエーテル類；２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル（メタ）アクリレート、１Ｈ，１Ｈ，２Ｈ，２Ｈ－ヘプタデカフルオロデシル（メタ）アクリレート若しくはパーフルオロエチルオキシエチル（メタ）アクリレートの如き（パー）フルオロアルキル基の炭素数が１から１８なる（パー）フルオロアルキル（メタ）アクリレート類等のフッ素含有エチレン性不飽和単量体類； (15) Fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; or trifluoromethyl trifluorovinylether, penta (Per) fluoroalkylperfluorovinylethers having 1 to 18 carbon atoms of (per) fluoroalkyl group such as fluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether; 2,2,2-trifluoroethyl (meth) ) Acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, Fluorine-containing compounds such as (per) fluoroalkyl (meth) acrylates having 1 to 18 carbon atoms of a (per) fluoroalkyl group such as H-heptadecafluorodecyl (meth) acrylate or perfluoroethyloxyethyl (meth) acrylate Ethylenically unsaturated monomers;
（１６）γ－メタクリロキシプロピルトリメトキシシラン等のシリル基含有（メタ）アクリレート類； (16) silyl group-containing (meth) acrylates such as γ-methacryloxypropyltrimethoxysilane;
（１７）Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート若しくはＮ，Ｎ－ジエチルアミノプロピル（メタ）アクリレート等のＮ，Ｎ－ジアルキルアミノアルキル（メタ）アクリレート等が挙げられる。 (17) N, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylaminopropyl (meth) acrylate Can be mentioned.
これらの酸基含有ポリアクリル酸エステルを調製する際に用いる他の重合性不飽和単量体は、単独で用いても良いし、２種以上を併用しても良い。 The other polymerizable unsaturated monomers used when preparing these acid group-containing polyacrylic acid esters may be used alone or in combination of two or more.
前記酸基含有ポリアクリル酸エステルは、公知慣用の方法を用いて重合（共重合）させれば得られ、その共重合形態は特に制限されない。触媒（重合開始剤）の存在下に、付加重合により製造することができ、ランダム共重合体、ブロック共重合体、グラフト共重合体等のいずれでもよい。また共重合方法も塊状重合法、溶液重合法、懸濁重合法、乳化重合法等の公知の重合方法が使用できる。 The acid group-containing polyacrylic acid ester can be obtained by polymerization (copolymerization) using a known conventional method, and the form of copolymerization is not particularly limited. It can be produced by addition polymerization in the presence of a catalyst (polymerization initiator), and may be any of a random copolymer, a block copolymer, a graft copolymer and the like. Further, as the copolymerization method, known polymerization methods such as bulk polymerization method, solution polymerization method, suspension polymerization method and emulsion polymerization method can be used.
（酸基含有ポリウレタン樹脂）
　前記酸含有ポリウレタン樹脂としては、下記式（１）で表される化合物Ｂと、下記式（２）で表される化合物Ｃとを反応して得られた樹脂が挙げられる。 (Acid group-containing polyurethane resin)
As said acid containing polyurethane resin, the resin obtained by reacting the compound B represented by following formula (1), and the compound C represented by following formula (2) is mentioned.
Figure JPOXMLDOC01-appb-C000002
 ・・・（１）
Figure JPOXMLDOC01-appb-C000002
 ... (1)
（式（１）において、Ｘ１は芳香環または脂環構造を表し、ｎ１およびｎ２はそれぞれ独立して０～３の整数を表す。） (In Formula (1), X 1 represents an aromatic ring or an alicyclic structure, and n 1 and n 2 each independently represent an integer of 0 to 3.)
Figure JPOXMLDOC01-appb-C000003
 ・・・（２）
Figure JPOXMLDOC01-appb-C000003
 ... (2)
（式（２）において、Ｒ１は水素原子または炭素数１～３の炭化水素基またはカルボニル基を表し、ｍ１～ｍ３はそれぞれ独立して０～３の整数を表す。） (In formula (2), R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, or a carbonyl group, and m 1 to m 3 each independently represent an integer of 0 to 3).
＜化合物Ｂ＞
　化合物Ｂは、前記式（１）で表されるイソシアネート基を有する化合物である。化合物Ｂにおいて、Ｘ１は芳香環または脂環構造を表す。 <Compound B>
The compound B is a compound having an isocyanate group represented by the formula (1). In compound B, X 1 represents an aromatic ring or an alicyclic structure.
　芳香環構造としては、炭素数６～１８の芳香環であることが好ましく、ベンゼン環、ナフタレン環、フェナントレン環、アントラセン環などが挙げられる。前記芳香環としては、少なくとも１つのフッ素原子により置換されていてもよく、少なくとも１つのフッ素原子で置換された芳香環としては、パーフルオロフェニル基などが挙げられる。
　また、脂環構造としては炭素数３～２０の脂環が好ましく、単環であっても縮合環であってもかまわない。単環としては、シクロアルカンにはシクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン、シクロノナン、シクロデカン、シクロウンデカン、シクロドデカンなどがある。また、単環のシクロアルケンにはシクロプロペン、シクロブテン、シクロプロペン、シクロヘキセン、シクロヘプテン、シクロオクテンなどが挙げられる。縮合環としては、ビシクロウンデカンやデカヒドロナフタレン、ノルボルネンやノルボルナジエンなどがある。
　また多環式化合物にはキュバン、バスケタン、ハウサン等が挙げられる。
　また、芳香環と脂環を組み合わせた環構造であっても構わない。 The aromatic ring structure is preferably an aromatic ring having a carbon number of 6 to 18, and examples thereof include a benzene ring, a naphthalene ring, a phenanthrene ring and an anthracene ring. The aromatic ring may be substituted by at least one fluorine atom, and examples of the aromatic ring substituted by at least one fluorine atom include a perfluorophenyl group and the like.
The alicyclic structure is preferably an alicyclic ring having a carbon number of 3 to 20, and may be a single ring or a condensed ring. As the single ring, examples of cycloalkane include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane and the like. In addition, examples of monocyclic cycloalkenes include cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, cyclooctene and the like. The fused ring includes bicycloundecane, decahydronaphthalene, norbornene and norbornadiene.
In addition, examples of polycyclic compounds include cubane, baskettan, and Hausan.
Further, it may be a ring structure in which an aromatic ring and an alicyclic ring are combined.
　化合物Ｂにおいて、Ｘ１は好ましくはベンゼン環またはナフタレン環である。
　また、ｎ１およびｎ２はそれぞれ独立して０～１であることが好ましい。 In compound B, X 1 is preferably a benzene ring or a naphthalene ring.
In addition, n1 and n2 are preferably each independently 0 to 1.
　化合物Ｂのさらに好ましい構造としては、以下の構造が挙げられる。 More preferable structures of compound B include the following structures.
Figure JPOXMLDOC01-appb-C000004
 ・・・（３）
Figure JPOXMLDOC01-appb-C000004
 ... (3)
Figure JPOXMLDOC01-appb-C000005
 ・・・（４）
Figure JPOXMLDOC01-appb-C000005
 ... (4)
Figure JPOXMLDOC01-appb-C000006
 ・・・（５）
Figure JPOXMLDOC01-appb-C000006
 ... (5)
Figure JPOXMLDOC01-appb-C000007
 ・・・（６）
Figure JPOXMLDOC01-appb-C000007
 ... (6)
Figure JPOXMLDOC01-appb-C000008
 ・・・（７）
Figure JPOXMLDOC01-appb-C000008
 ... (7)
＜化合物Ｃ＞
　化合物Ｂは、前記式（２）で表される、カルボキシル基を有するジオール化合物である。 <Compound C>
The compound B is a diol compound having a carboxyl group, which is represented by the formula (2).
化合物Ｃにおいて、好ましくは、ｍ３が０である化合物であり、更に好ましくはＲ１が炭素数１～３の炭化水素基である場合である。 The compound C is preferably a compound in which m3 is 0, and more preferably a case in which R1 is a hydrocarbon group having 1 to 3 carbon atoms.
化合物Ｃのさらに好ましい構造としては、ジメチロールプロピオン酸、及びジメチロールブタン酸が挙げられる。 Further preferred structures of compound C include dimethylol propionic acid and dimethylol butanoic acid.
（酸基含有ポリオレフィン樹脂）
前記酸基含有ポリオレフィン樹脂の骨格としては、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－メチルペンテン、ポリビニルシクロヘキサン、ポリスチレン、ポリ（ｐ－メチルスチレン）、ポリ（α－メチルスチレン）、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・ブテン－１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・アクリル酸共重合体、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、アイオノマー樹脂などを挙げることができる。更に、これらポリオレフィンを塩素化した塩素化ポリオレフィンも使用することができる。 (Acid group-containing polyolefin resin)
Specific examples of the skeleton of the acid group-containing polyolefin resin include polyethylene such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene resin, polypropylene, polyisobutylene, poly (1 -Butene), poly 4-methylpentene, polyvinylcyclohexane, polystyrene, poly (p-methylstyrene), poly (α-methylstyrene), ethylene / propylene block copolymer, ethylene / propylene random copolymer, ethylene · butene Α-Olefin copolymer such as ethylene copolymer, ethylene · 4-methyl-1-pentene copolymer, ethylene · hexene copolymer, ethylene · vinyl acetate copolymer, ethylene · acrylic acid copolymer , Ethylene / methyl methacrylate copolymer, ethylene / vinegar Examples include acid vinyl methyl methacrylate copolymer, ionomer resin and the like. Furthermore, chlorinated polyolefins obtained by chlorinating these polyolefins can also be used.
　樹脂に酸基を導入するには、公知慣用の方法を用いればよい。酸基含有モノマーを重合して樹脂を合成しても良いし、樹脂に後から酸基を付加してもよい。好ましくは、ポリオレフィンを不飽和カルボン酸またはその誘導体で変性し、合成する方法である。この変性方法としては、グラフト変性や共重合化を用いることができる。 In order to introduce an acid group into the resin, known and conventional methods may be used. The acid group-containing monomer may be polymerized to synthesize a resin, or an acid group may be added to the resin later. Preferably, it is a method of modifying a polyolefin with an unsaturated carboxylic acid or a derivative thereof to synthesize. Graft modification or copolymerization can be used as this modification method.
　好ましい酸変性ポリオレフィン樹脂は、少なくとも１つの重合可能なエチレン性不飽和カルボン酸またはその誘導体を、変性前のポリオレフィン樹脂にグラフト変性あるいは共重合化したグラフト変性ポリオレフィンである。変性前のポリオレフィン樹脂としては上述のポリオレフィン樹脂が挙げられるが、その中でもプロピレンの単独重合体、プロピレンとα－オレフィンとの共重合体、等が好ましい。これらは１種単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 A preferred acid-modified polyolefin resin is a graft-modified polyolefin in which at least one polymerizable ethylenically unsaturated carboxylic acid or derivative thereof is graft-modified or copolymerized to the polyolefin resin before modification. Examples of the polyolefin resin before modification include the above-mentioned polyolefin resins. Among them, homopolymers of propylene, copolymers of propylene and an α-olefin, and the like are preferable. These can be used alone or in combination of two or more.
　変性前のポリオレフィン樹脂にグラフト変性あるいは共重合化するエチレン性不飽和カルボン酸またはその誘導体としては、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などをあげることができる。好ましくは無水マレイン酸が使用される。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 derivative thereof which is graft modified or copolymerized to the polyolefin resin before modification are acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4- 4- Methylcyclohex-4-ene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,5 8,9,10-Octahydronaphthalene-2,3-dicarboxylic anhydride, 2-octa-1,3-diketospiro [4.4] non-7-ene, bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophthalic acid anhydride, methyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid Anhydride, methyl - norbornene-5-ene-2,3-dicarboxylic anhydride, and the like norborn-5-ene-2,3-dicarboxylic anhydride. Preferably, maleic anhydride is used. These can be used alone or in combination of two or more.
　エチレン性不飽和カルボン酸またはその誘導体から選ばれるグラフトモノマーを変性前のポリオレフィン樹脂にグラフトさせるには、種々の方法を採用することができる。例えば、ポリオレフィン樹脂を溶融し、そこにグラフトモノマーを添加してグラフト反応させる方法、ポリオレフィン樹脂を溶媒に溶解して溶液とし、そこにグラフトモノマー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樹脂と、前記不飽和カルボン酸等とを混合し、前記ポリオレフィン樹脂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。いずれの場合にも前記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樹脂１００重量部に対して、通常０．００１～１重量部の範囲である。 Various methods can be employed to graft the grafting monomer selected from the ethylenically unsaturated carboxylic acids or their derivatives onto the polyolefin resin before modification. For example, a method of melting a polyolefin resin and adding a graft monomer thereto for grafting reaction, dissolving a polyolefin resin in a solvent to form a solution, adding a graft monomer thereto for grafting reaction, dissolving it in an organic solvent The method of mixing a polyolefin resin, the said unsaturated carboxylic acid, etc., heating at the temperature more than the softening temperature or melting point of the said polyolefin resin, and simultaneously performing radical polymerization and hydrogen abstraction reaction in a molten state etc. is mentioned. In any case, in order to graft copolymerize the graft monomer efficiently, it is preferable to carry out a 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 resin before modification.
これらの酸変性ポリオレフィン樹脂としては、例えば、無水マレイン酸変性ポリプロピレン、エチレン-（メタ）アクリル酸共重合体、エチレン－アクリル酸エステル－無水マレイン酸三元共重合体、またはエチレン－メタクリル酸エステル－無水マレイン酸三元共重合体が挙げられる。具体的には、三菱化学（株）製「モディック」、三井化学（株）製「アドマー」、「ユニストール」、東洋紡（株）製「トーヨータック」、三洋化成（株）製「ユーメックス」、日本ポリエチレン（株）製「レクスパールＥＡＡ」「レクスパールＥＴ」、ダウ・ケミカル（株）製「プリマコール」、三井・デュポンポリケミカル製「ニュクレル」、アルケマ製「ボンダイン」として市販されている。  As these acid-modified polyolefin resins, for example, maleic anhydride-modified polypropylene, ethylene- (meth) acrylic acid copolymer, ethylene-acrylic acid ester-maleic anhydride terpolymer, or ethylene-methacrylic acid ester- And maleic anhydride terpolymers. Specifically, "Modic" manufactured by Mitsubishi Chemical Co., Ltd., "Admar" manufactured by Mitsui Chemicals Co., Ltd., "Unistor", "Toyotac" manufactured by Toyobo Co., Ltd., "Yumex" manufactured by Sanyo Kasei Co., Ltd., Nippon Polyethylene Co., Ltd. "Rexpearl EAA" "Rexpearl ET", Dow Chemical Co. "Primacol", Mitsui-Dupont Polychemical "Nucrel", and Arkema "Bondine" are commercially available.
（その他酸基含有樹脂）
その他酸基含有樹脂としては、酸含有エラストマーとして、例えば旭化成株式会社製のタフテックＭシリーズや、クレイトンポリマージャパン株式会社製のクレイトンＦＧシーリーズ等が挙げられる。 (Other acid group-containing resin)
In addition, as the acid group-containing resin, examples of acid-containing elastomers include Tuftec M series manufactured by Asahi Kasei Co., Ltd., and Clayton FG Series manufactured by Clayton Polymer Japan Co., Ltd.
＜芳香環および炭素数4－１０のアルキレン鎖及び2つ以上のエポキシ基を含有するエポキシ化合物A＞
　本発明の接着剤は、芳香環および炭素数4－１０のアルキレン鎖及び2つ以上のエポキシ基を含有するエポキシ化合物Aも含有する。 <Epoxy Compound A Containing an Aromatic Ring, an Alkylene Chain of 4 to 10 Carbon Atoms, and Two or More Epoxy Groups>
The adhesive of the present invention also contains an epoxy compound A containing an aromatic ring and an alkylene chain having 4 to 10 carbon atoms and two or more epoxy groups.
　芳香環としては、置換基を有していてもよいベンゼン環、置換基を有していてもよいナフタレン環、置換基を有していてもよいビスフェノール構造、置換基を有していてもよいビフェニル構造等が挙げられ、例えば、ｏ－、ｍ－、ｐ－にそれぞれ結合部位を有するフェニレン基、４，４’－ビフェニレン基、２，２’，６，６’－テトラメチル－４，４’－ビフェニル基、メチレンジフェニレン基、２，２－プロパン－ジフェニル基、１，６－ナフタレン基、２，７－ナフタレン基、１，４－ナフタレン基、１，５－ナフタレン基、２，３－ナフタレン基、及び下記構造式 The aromatic ring may be a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, a bisphenol structure which may have a substituent, or a substituent. The biphenyl structure etc. are mentioned, For example, the phenylene group which has an attachment site to o-, m-, p- respectively, 4,4'- biphenylene group, 2,2 ', 6, 6'- tetramethyl-4, 4 '-Biphenyl group, methylene diphenylene group, 2,2-propane-diphenyl group, 1,6-naphthalene group, 2,7-naphthalene group, 1,4-naphthalene group, 1,5-naphthalene group, 2,3 -Naphthalene group, and the following structural formula
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
で表される基等を挙げる事ができ、得られる硬化物の柔軟性と強靭性のバランスに優れる点からメチレンジフェニレン基、２，２－プロパン－ジフェニル基であることが好ましい。  It is preferable that they are a methylene diphenylene group and a 2, 2- propane diphenyl group from the point which is excellent in the balance of the softness | flexibility and toughness of the hardened | cured material obtained.
　エポキシ化合物Aとしては、具体的には以下の式（８）で表されるエポキシ化合物（A1）が好ましい。 Specifically, the epoxy compound A is preferably an epoxy compound (A1) represented by the following formula (8).
Figure JPOXMLDOC01-appb-C000010
 ・・・（８）
Figure JPOXMLDOC01-appb-C000010
 ... (8)
（式中、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４は同一でも異なっていても良い、置換基を有していてもよい芳香環であり、Ｘ１、Ｘ２は脂肪族炭化水素基であり、Ｒ１、Ｒ２、Ｒ３は同一でも異なっていても良い水素原子又は炭素数１～４のアルキル基であり、ｐ、ｑ、ｒは繰り返し数の平均値でｐは０．５～５．０であり、ｑは０．５～５．０であり、ｒは０．０５～０．５である。） (Wherein, Ar 1 , Ar 2 , Ar 3 and Ar 4 are the same or different and each is an aromatic ring which may have a substituent, and X 1 and X 2 are aliphatic hydrocarbon groups. And R 1 , R 2 and R 3 are the same or different and each is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p, q and r are average values of the number of repetitions and p is 0.5 to 5.0, q is 0.5 to 5.0, and r is 0.05 to 0.5.)
　エポキシ化合物（Ａ１）について、エポキシ当量が１５０～９００ｇ／ｅｑであるものは、得られる硬化物の架橋密度が適当であり、柔軟強靭性と耐熱性とを兼備できる点から好ましいものである。又、前記エポキシ化合物（Ａ１）の２５℃における粘度が２，０００～２０，０００Ｐａ・ｓであるものが、作業性が良好で、硬化物の柔軟性と密着性に優れる点から好ましく、特に２，０００～１５，０００Ｐａ・ｓであることが好ましい。 With regard to the epoxy compound (A1), those having an epoxy equivalent of 150 to 900 g / eq are preferable from the viewpoint that the crosslink density of the cured product obtained is appropriate, and both soft toughness and heat resistance can be provided. Further, those having a viscosity of 2,000 to 20,000 Pa · s at 25 ° C. of the epoxy compound (A1) are preferable from the viewpoint of good workability and excellent flexibility and adhesion of a cured product, particularly 2 The pressure is preferably in the range of 1,000 to 15,000 Pa · s.
　前記式（１）中のＸ１、Ｘ２のうち少なくとも１つが炭素数４～１０の直鎖状のアルキレン鎖である。炭素数が短すぎると柔軟性が損なわれて接着力が低くなり、長すぎると反応性が低下し接着力が低くなるからである。好ましくは、Ｘ１、Ｘ２の両方が炭素数４～１０の直鎖状のアルキレン鎖である場合である。又、得られる硬化物の耐熱性や硬度、耐湿性を重要視する場合には、前記式（１）中のＸ１、Ｘ２として、脂環構造を含有するものを用いることもできる。   At least one of X 1 and X 2 in the formula (1) is a linear alkylene chain having 4 to 10 carbon atoms. When the carbon number is too short, the flexibility is impaired to lower the adhesive strength. When the carbon number is too long, the reactivity is lowered to lower the adhesive strength. Preferably, both X 1 and X 2 are linear alkylene chains of 4 to 10 carbon atoms. When importance is placed on the heat resistance, hardness, and moisture resistance of the obtained cured product, those having an alicyclic structure can also be used as X 1 and X 2 in the formula (1).
　前記式（１）中のＡｒ１、Ａｒ２、Ａｒ３、Ａｒ４としては、前述の芳香環を用いることが出来る。すなわち、置換基を有していてもよいベンゼン環、置換基を有していてもよいナフタレン環、置換基を有していてもよいビスフェノール構造、置換基を有していてもよいビフェニル構造等が挙げられ、例えば、ｏ－、ｍ－、ｐ－にそれぞれ結合部位を有するフェニレン基、４，４’－ビフェニレン基、２，２’，６，６’－テトラメチル－４，４’－ビフェニル基、メチレンジフェニレン基、２，２－プロパン－ジフェニル基、１，６－ナフタレン基、２，７－ナフタレン基、１，４－ナフタレン基、１，５－ナフタレン基、２，３－ナフタレン基、及び下記構造式 The aromatic ring described above can be used as Ar 1 , Ar 2 , Ar 3 and Ar 4 in the formula (1). That is, a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, a bisphenol structure which may have a substituent, a biphenyl structure which may have a substituent, etc. For example, phenylene, 4,4'-biphenylene, 2,2 ', 6,6'-tetramethyl-4,4'-biphenyl having binding sites at o-, m- and p- respectively. Group, methylene diphenylene group, 2,2-propane-diphenyl group, 1,6-naphthalene group, 2,7-naphthalene group, 1,4-naphthalene group, 1,5-naphthalene group, 2,3-naphthalene group , And the following structural formula
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
で表される基等を挙げる事ができ、得られる硬化物の柔軟性と強靭性のバランスに優れる点からメチレンジフェニレン基、２，２－プロパン－ジフェニル基であることが好ましい。  It is preferable that they are a methylene diphenylene group and a 2, 2- propane diphenyl group from the point which is excellent in the balance of the softness | flexibility and toughness of the hardened | cured material obtained.
　エポキシ化合物（Ａ１）として、好ましい構造としては以下の（Ａ１－１）から（Ａ１－９）の構造が挙げられる。 Preferred examples of the epoxy compound (A1) include the following structures (A1-1) to (A1-9).
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　上記各構造式において、Ｇはグリシジル基であり、ｐ、ｑ、ｒは繰り返し数の平均値であってｐは０．５～５．０であり、ｑは０．５～５．０であり、ｒは０．０５～０．５である。又、各芳香環には炭素数１～４のアルキル基、ハロゲン原子等を置換基として有していても良い。これらの中でも、得られる硬化物の物性バランスに優れる点から、前記構造式（Ａ１－3）、（Ａ１－４）で表されるものを用いることが最も好ましい。 In each of the above structural formulas, G is a glycidyl group, p, q and r are average values of the number of repetitions, p is 0.5 to 5.0, and q is 0.5 to 5.0. , R is 0.05 to 0.5. Each aromatic ring may have, as a substituent, an alkyl group having 1 to 4 carbon atoms, a halogen atom or the like. Among these, it is most preferable to use those represented by the structural formulas (A1-3) and (A1-4) from the viewpoint of being excellent in the physical property balance of the cured product to be obtained.
　エポキシ化合物（Ａ１）の製造方法としては、特に限定されるものではないが、脂肪族系ジヒドロキシ化合物のジグリシジルエーテル又は脂肪族系酸化合物のジグリシジルエステル（ｃ１）と芳香族系ジヒドロキシ化合物（ｃ２）とを、モル比（ｃ１）／（ｃ２）が１／１．１～１／５．０の範囲で反応させて得られるヒドロキシ化合物を更にエピハロヒドリン類（ｃ３）と反応ささる方法を用いることが、原料入手や反応が容易である点から好ましい。 The method for producing the epoxy compound (A1) is not particularly limited, but diglycidyl ether of aliphatic dihydroxy compound or diglycidyl ester of aliphatic acid compound (c1) and aromatic dihydroxy compound (c2) Using a method in which the hydroxy compound obtained by the reaction of () with the molar ratio (c1) / (c2) in the range of 1 / 1.1 to 1 / 5.0 is further reacted with the epihalohydrins (c3) However, it is preferable from the point which raw material acquisition and reaction are easy.
＜接着剤＞
　本発明の接着剤は、酸基含有樹脂と、芳香環および炭素数4－１０のアルキレン鎖及び2つ以上のエポキシ基を含有するエポキシ化合物Aとを含有する。
　本発明の接着剤は接着強度、特に初期接着力に優れ、積層体であるラミネート物が柔軟なことから、ラミネート用の接着剤として好適に使用可能である。また、本発明の接着剤は、金属層に良好に接着することから、金属用接着剤としても好適である。また、硬化後の本接着剤は耐電解液性にも優れることから、電池用接着剤としても好適である。　 <Adhesive>
The adhesive of the present invention contains an acid group-containing resin and an epoxy compound A containing an aromatic ring, an alkylene chain having 4 to 10 carbon atoms and two or more epoxy groups.
The adhesive of the present invention is excellent in adhesive strength, particularly in initial adhesive strength, and the laminate which is a laminate is flexible, so that it can be suitably used as an adhesive for laminating. The adhesive of the present invention is also suitable as an adhesive for metals because it adheres well to metal layers. Further, since the present adhesive after curing is excellent in electrolytic solution resistance, it is also suitable as a battery adhesive.
＜その他エポキシ化合物＞
　本発明の接着剤には、エポキシ化合物Ａ以外のエポキシ化合物を含んでよい。例えばビスフェノール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、レゾルシン型エポキシ樹脂、ジヒドロキシナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂、アントラセン、ビフェニル、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳの構造を有する３官能以上のエポキシ化合物、固形ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン－フェノール付加反応型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフトール－フェノール共縮ノボラック型エポキシ樹脂、ナフトール－クレゾール共縮ノボラック型エポキシ樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂型エポキシ樹脂、ビフェニル変性ノボラック型エポキシ樹脂等が挙げられる。 <Other epoxy compounds>
The adhesive of the present invention may contain an epoxy compound other than the epoxy compound A. For example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, resorcinol epoxy resin, dihydroxynaphthalene epoxy resin, biphenyl epoxy resin, tetramethylbiphenyl epoxy resin, anthracene, Biphenyl, bisphenol A, bisphenol F, trifunctional or higher epoxy compound having a structure of bisphenol S, solid bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane Type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol no Lac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-convoluted novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolac type epoxy resin Etc.
　エポキシ化合物としては、１種のエポキシ化合物を単独で用いてよく、複数のエポキシ化合物を組み合わせて用いてもよい。 As the epoxy compound, one epoxy compound may be used alone, or a plurality of epoxy compounds may be used in combination.
　本発明において、エポキシ化合物Ａとその他のエポキシ化合物との比率は、モル比で１００：０～５：９５が好ましい。ラミネート用接着剤としては、柔軟性の面から１００：０～１０：９０が特に好ましい。 In the present invention, the molar ratio of the epoxy compound A to the other epoxy compound is preferably 100: 0 to 5:95. The adhesive for lamination is particularly preferably 100: 0 to 10:90 from the viewpoint of flexibility.
＜配合比＞
　接着剤を調整するには、上記した酸基含有樹脂が含有する酸基と、エポキシ化合物Ａを含むエポキシ化合物が含有するエポキシ基との当量比（エポキシ／酸価）が、０．０１～１０となるように配合することが好ましい。より好ましくは、０．１～５となるように配合する。
　当量比が０．０１以上であれば耐熱性に優れ、１０以下であれば接着力に優れるからである。 <Composition ratio>
In order to adjust the adhesive, the equivalent ratio (epoxy / acid value) of the acid group contained in the above-mentioned acid group-containing resin and the epoxy group contained in the epoxy compound containing the epoxy compound A is 0.01 to 10 It is preferable to mix | blend so that it may become. More preferably, it is blended so as to be 0.1-5.
When the equivalent ratio is 0.01 or more, the heat resistance is excellent, and when it is 10 or less, the adhesion is excellent.
＜その他樹脂＞
　また、本発明の接着剤は、発明の効果を損ねない範囲で、酸基含有樹脂とエポキシ化合物以外の樹脂を含有しても構わない。樹脂としては、熱硬化性樹脂や熱可塑性樹脂を用いることができる。 <Other resin>
Further, the adhesive of the present invention may contain a resin other than the acid group-containing resin and the epoxy compound, as long as the effects of the invention are not impaired. As the resin, a thermosetting resin or a thermoplastic resin can be used.
　熱硬化性樹脂とは、加熱または放射線や触媒などの手段によって硬化される際に実質的に不溶かつ不融性に変化し得る特性を持った樹脂である。その具体例としては、熱硬化性樹脂とは、加熱または放射線や触媒などの手段によって硬化される際に実質的に不溶かつ不融性に変化し得る特性を持った樹脂である。その具体例としては、フェノール樹脂、ユリア樹脂、メラミン樹脂、ベンゾグアナミン樹脂、アルキド樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、ジアリルテレフタレート樹脂、シリコーン樹脂、ウレタン樹脂、フラン樹脂、ケトン樹脂、キシレン樹脂、熱硬化性ポリイミド樹脂、ベンゾオキサジン樹脂、活性エステル樹脂、アニリン樹脂、シアネートエステル樹脂、スチレン・無水マレイン酸（ＳＭＡ）樹脂、などが挙げられる。これらの熱硬化性樹脂は１種または２種以上を併用して用いることができる。 A thermosetting resin is a resin having the property of being substantially insoluble and capable of changing to an infusible property when cured by means of heating or radiation or a catalyst. As a specific example thereof, a thermosetting resin is a resin having the property of being substantially insoluble and capable of changing into infusiblity when it is cured by means such as heating or radiation or a catalyst. Specific examples thereof include phenol resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, silicone resin, urethane resin, furan resin, ketone resin, xylene resin, heat Examples thereof include curable polyimide resins, benzoxazine resins, active ester resins, aniline resins, cyanate ester resins, and styrene / maleic anhydride (SMA) resins. These thermosetting resins can be used alone or in combination of two or more.
　熱可塑性樹脂とは、加熱により溶融成形可能な樹脂を言う。その具体例としてはポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ゴム変性ポリスチレン樹脂、アクリロニトリル－ブタジエン－スチレン（ＡＢＳ）樹脂、アクリロニトリル－スチレン（ＡＳ）樹脂、ポリメチルメタクリレート樹脂、アクリル樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリエチレンテレフタレート樹脂、エチレンビニルアルコール樹脂、酢酸セルロース樹脂、アイオノマー樹脂、ポリアクリロニトリル樹脂、ポリアミド樹脂、ポリアセタール樹脂、ポリブチレンテレフタレート樹脂、ポリ乳酸樹脂、ポリフェニレンエーテル樹脂、変性ポリフェニレンエーテル樹脂、ポリカーボネート樹脂、ポリサルホン樹脂、ポリフェニレンスルフィド樹脂、ポリエーテルイミド樹脂、ポリエーテルサルフォン樹脂、ポリアリレート樹脂、熱可塑性ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルエーテルケトン樹脂、ポリケトン樹脂、液晶ポリエステル樹脂、フッ素樹脂、シンジオタクチックポリスチレン樹脂、環状ポリオレフィン樹脂などが挙げられる。これらの熱可塑性樹脂は１種または２種以上を併用して用いることができる。 The thermoplastic resin refers to a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, Polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate Resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyether sulfone Fat, polyarylate resins, thermoplastic polyimide resins, polyamideimide resins, polyether ether ketone resin, polyketone resin, liquid crystal polyester resins, fluorine resins, syndiotactic polystyrene resin, cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.
＜硬化触媒＞
　本発明の接着剤は、硬化触媒を使用してもよい。
硬化触媒としては、一般的なエポキシ硬化剤を利用することができ、具体的にはアミン系硬化剤、アミド系硬化剤、酸無水物系硬化剤、フェノール系硬化剤、活性エステル系硬化剤、カルボキシル基含有硬化剤、チオール系硬化剤などの各種の硬化剤を併用してもかまわない。 <Curing catalyst>
The adhesive of the present invention may use a curing catalyst.
As a curing catalyst, a general epoxy curing agent can be used. Specifically, an amine curing agent, an amide curing agent, an acid anhydride curing agent, a phenol curing agent, an active ester curing agent, Various curing agents such as carboxyl group-containing curing agents and thiol-based curing agents may be used in combination.
　具体的には、アミン系硬化剤としてはジアミノジフェニルメタン、ジアミノジフェニルエタン、ジアミノジフェニルエーテル、ジアミノジフェニルスルホン、オルトフェニレンジアミン、メタフェニレンジアミン、パラフェニレンジアミン、メタキシレンジアミン、パラキシレンジアミン、ジエチルトルエンジアミン、ジエチレントリアミン、トリエチレンテトラミン、イソホロンジアミン、イミダゾ－ル、ＢＦ３－アミン錯体、グアニジン誘導体、グアナミン誘導体等が挙げられる。 Specifically, as an amine curing agent, diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenyl sulfone, orthophenylene diamine, metaphenylene diamine, paraphenylene diamine, metaxylene diamine, paraxylene diamine, paraxylene diamine, diethyl toluene diamine, diethylene triamine And triethylenetetramine, isophorone diamine, imidazole, BF3-amine complex, guanidine derivative, guanamine derivative and the like.
　アミド系硬化剤としては、ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂等が挙げられる。
　酸無水物系硬化剤としては、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられる。
　フェノール系硬化剤としては、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、レゾルシン、カテコール、ハイドロキノン、フルオレンビスフェノール、４，４’－ビフェノール、４，４’，４”－トリヒドロキシトリフェニルメタン、ナフタレンジオール、１，１，２，２－テトラキス（４－ヒドロキシフェニル）エタン、カリックスアレーン、フェノールノボラック樹脂、クレゾールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂（ザイロック樹脂）、レゾルシンノボラック樹脂に代表される多価ヒドロキシ化合物とホルムアルデヒドから合成される多価フェノールノボラック樹脂、ナフトールアラルキル樹脂、トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ナフトールノボラック樹脂、ナフトール－フェノール共縮ノボラック樹脂、ナフトール－クレゾール共縮ノボラック樹脂、ビフェニル変性フェノール樹脂（ビスメチレン基でフェノール核が連結された多価フェノール化合物）、ビフェニル変性ナフトール樹脂（ビスメチレン基でフェノール核が連結された多価ナフトール化合物）、アミノトリアジン変性フェノール樹脂（メラミン、ベンゾグアナミンなどでフェノール核が連結された多価フェノール化合物）やアルコキシ基含有芳香環変性ノボラック樹脂（ホルムアルデヒドでフェノール核及びアルコキシ基含有芳香環が連結された多価フェノール化合物）等の多価フェノール化合物が挙げられる。
　これらの硬化触媒は、単独でも２種類以上の併用でも構わない。 Examples of the amide-based curing agent include dicyandiamide, and a polyamide resin synthesized from a dimer of linolenic acid and ethylene diamine.
As an acid anhydride type curing agent, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl hexameric anhydride Hydrophthalic anhydride etc. are mentioned.
Examples of phenolic curing agents include bisphenol A, bisphenol F, bisphenol S, resorcinol, catechol, hydroquinone, fluorene bisphenol, 4,4'-biphenol, 4,4 ', 4 "-trihydroxytriphenylmethane, naphthalenediol, 1 1,2,2-Tetrakis (4-hydroxyphenyl) ethane, calixarene, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc Resin), polyhydric phenol novolak resin synthesized from polyvalent hydroxy compound represented by resorcinol novolak resin and formaldehyde, naphthol aralkyl resin, trimethylo resin Lumethane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-convoluted novolak resin, naphthol-cresol co-convoluted novolak resin, biphenyl-modified phenol resin (polyphenol compound in which a phenol nucleus is linked with bis methylene group), biphenyl Modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified phenol resin (polyphenol compound in which phenol nucleus is linked by melamine, benzoguanamine etc.), alkoxy group-containing aromatic ring modified novolac resin Polyhydric phenol compounds such as (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde) can be mentioned.
These curing catalysts may be used alone or in combination of two or more.
　さらに、硬化促進剤を単独で、あるいは前記の硬化触媒と併用することもできる。硬化促進剤としてエポキシ化合物の硬化反応を促す種々の化合物が使用でき、例えば、リン系化合物、第３級アミン化合物、イミダゾール化合物、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。この中でも、イミダゾール化合物、リン系化合物、第３級アミン化合物の使用が好ましく、特に硬化性、耐熱性、電気特性、耐湿信頼性等に優れる点から、リン系化合物ではトリフェニルホスフィン、第３級アミンでは１，８－ジアザビシクロ－［５．４．０］－ウンデセン（ＤＢＵ）、イミダゾール化合物では2-エチル-4-メチルイミダゾールが好ましい。 Furthermore, a curing accelerator can be used alone or in combination with the above-mentioned curing catalyst. As a curing accelerator, various compounds which accelerate the curing reaction of epoxy compounds can be used, and examples thereof include phosphorus compounds, tertiary amine compounds, imidazole compounds, organic acid metal salts, Lewis acids, amine complexes and the like. Among these, the use of imidazole compounds, phosphorus compounds and tertiary amine compounds is preferable, and triphenylphosphine and tertiary compounds are particularly preferable as phosphorus compounds from the viewpoint of excellent curability, heat resistance, electrical properties, moisture resistance and the like. For amines, 1,8-diazabicyclo- [5.4.0] -undecene (DBU) is preferred, and for imidazole compounds, 2-ethyl-4-methylimidazole is preferred.
　硬化触媒及び硬化促進剤は配合してもしなくても構わないが、配合する場合、接着剤中の全固形分合計１００重量部に対し、０．００１～１０重量部であることが好ましい。特に好ましくは０．００５～５重量部である。 The curing catalyst and the curing accelerator may or may not be blended, but in the case of blending, it is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the total solid content in the adhesive. Particularly preferred is 0.005 to 5 parts by weight.
＜溶剤＞
　接着剤は、使用用途に応じて溶剤を含有してもよい。溶剤としては有機溶剤が挙げられ、例えばメチルエチルケトン、アセトン、酢酸エチル、酢酸ブチル、トルエン、ジメチルホルムアミド、アセトニトリル、メチルイソブチルケトン、メタノール、エタノール、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、エチルジグリコールアセテート、プロピレングリコールモノメチルエーテルアセテート、メチルシクロヘキサン等が挙げられる。溶剤の種類及び使用量は使用用途によって適宜選択すればよい。 <Solvent>
The adhesive may contain a solvent depending on the application of use. Examples of the solvent include organic solvents such as methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acetonitrile, methyl isobutyl ketone, methanol, ethanol, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol Monomethyl ether acetate, methyl cyclohexane and the like can be mentioned. The type and amount of solvent used may be selected appropriately depending on the application.
　特にドライラミネート用接着剤とする場合は、炭化水素系溶剤、ケトン系溶剤、エステル系溶剤又はアルコール系溶媒が好ましく用いられる。 In particular, in the case of using as an adhesive for dry lamination, hydrocarbon solvents, ketone solvents, ester solvents or alcohol solvents are preferably used.
　溶剤を用いる場合、酸基含有樹脂及びエポキシ化合物Ａを配合した後に配合しても構わないし、酸基含有樹脂またはエポキシ化合物Ａをあらかじめ溶剤に溶解させワニスとして用いても構わない。 When a solvent is used, it may be blended after blending the acid group-containing resin and the epoxy compound A, or the acid group-containing resin or the epoxy compound A may be dissolved in the solvent in advance and used as a varnish.
　溶剤を用いる場合、接着剤全量１００重量部のうち、溶剤成分が５０～９０重量部であることが好ましい。より好ましくは、６０～８５重量部となるように配合される。 When a solvent is used, the solvent component is preferably 50 to 90 parts by weight in 100 parts by weight of the total amount of the adhesive. More preferably, it is blended so as to be 60 to 85 parts by weight.
　接着剤は、本発明の効果を損なわない範囲で、各種の添加剤を含有してもよい。添加剤としては、例えば、触媒、界面活性剤、安定剤（酸化防止剤、熱安定剤、紫外線吸収剤等）、防錆剤、反応性エラストマー、カップリング剤、可塑剤、帯電防止剤、滑剤、ブロッキング防止剤、着色剤、フィラー、結晶核剤、酸素捕捉機能を有する化合物、粘着付与剤等が例示できる。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して用いることができる。 The adhesive may contain various additives as long as the effects of the present invention are not impaired. Examples of additives include catalysts, surfactants, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), rust inhibitors, reactive elastomers, coupling agents, plasticizers, antistatic agents, lubricants. Antiblocking agents, colorants, fillers, nucleating agents, compounds having an oxygen scavenging function, tackifiers, and the like can be exemplified. The content of these additives can be appropriately adjusted and used within the range that does not impair the function of the adhesive of the present invention.
＜積層体＞
　本発明の積層体は、本発明の接着剤層を中間層に有することを特徴とする。
　積層体の上層および下層については特に限定は無く、用途に応じて選択すればよい。たとえば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート等のプラスチック；鉄、アルミニウム、銅、銀、チタン等の金属や金属酸化物、木材、紙、それらの複合材等が挙げられる。 <Laminate>
The laminate of the present invention is characterized by having the adhesive layer of the present invention in the intermediate layer.
The upper and lower layers of the laminate are not particularly limited, and may be selected according to the application. For example, plastics such as polyethylene, polypropylene and polyethylene terephthalate; metals such as iron, aluminum, copper, silver and titanium, metal oxides, wood, paper, composite materials thereof and the like can be mentioned.
　この中でも、本発明の接着剤は、金属または金属酸化物層に対する接着性が非常に良好であることから、金属または金属酸化物用接着剤として良好である。特に好ましくはアルミニウム用である。 Among these, the adhesive of the present invention is good as an adhesive for metal or metal oxide because the adhesion to a metal or metal oxide layer is very good. Particularly preferably, it is for aluminum.
　積層体の上層および下層の形状は特に限定は無く、平板、シート状、あるいは３次元形状全面にまたは一部に曲率を有するもの等目的に応じた任意の形状であってよい。また、基材の硬度、厚み等にも制限はない。 The shape of the upper layer and the lower layer of the laminate is not particularly limited, and may be any shape depending on the purpose, such as a flat plate, a sheet, or one having a curvature on the entire surface or a part of the three-dimensional shape. Further, there is no limitation on the hardness, thickness and the like of the base material.
　本発明の積層体において、接着剤層の塗工方法としては特に限定は無く、スプレー法、スピンコート法、ディップ法、ロールコート法、ブレードコート法、ドクターロール法、ドクターブレード法、カーテンコート法、スリットコート法、スクリーン印刷法、インクジェット法等が挙げられる。 In the laminate of the present invention, the coating method of the adhesive layer is not particularly limited, and spray method, spin coat method, dip method, roll coat method, blade coat method, doctor roll method, doctor blade method, curtain coat method Slit coating method, screen printing method, ink jet method and the like.
＜ラミネート＞
　本発明の接着剤は、接着強度が非常に高いことから、ラミネート用として好適に使用可能である。ラミネート用接着剤とする場合、乾燥塗布重量は０．５～２０．０ｇ／ｍ２の範囲内が好ましい。０．５ｇ／ｍ２以上であれば連続均一塗布性が良好であり、２０．０ｇ／ｍ２以下であれば塗布後における溶剤離脱性が良好であることから、作業性と脱溶剤性のバランスに優れている。 <Lamination>
The adhesive of the present invention can be suitably used for laminating because the adhesive strength is very high. When used as a laminating adhesive, the dry coating weight is preferably in the range of 0.5 to 20.0 g / m 2 . If it is 0.5 g / m 2 or more, the continuous uniform coating property is good, and if it is 20.0 g / m 2 or less, the solvent removability after coating is good, so the balance between workability and solvent removal property Excellent.
　ラミネート方法としては、下層に本発明の接着剤を塗工後、上層を重ねてドライラミネーション（乾式積層法）により貼り合わせることで、ラミネート積層体が得られる。ラミネートロールの温度は室温～１２０℃程度、圧力は、３～３００ｋｇ／ｃｍ２程度が好ましい。
　また、本発明のラミネート積層体は、作製後エージングを行うことが好ましい。エージング条件は、好ましい温度は２５～１００℃、時間は１２～２４０時間であり、この間に接着強度が生じる。 As a laminating method, after the adhesive of the present invention is applied to the lower layer, the upper layer is overlapped and laminated by dry lamination (dry lamination method) to obtain a laminate. The temperature of the laminating roll is preferably about room temperature to 120 ° C., and the pressure is preferably about 3 to 300 kg / cm 2 .
In addition, it is preferable that the laminate of the present invention is subjected to aging after preparation. The aging conditions are preferably 25 to 100 ° C. for 12 to 240 hours, during which adhesive strength occurs.
＜電池用部材＞
　金属層とプラスチック層とで構成された本発明の積層体は、電池の電解液封止フィルムまたは電極部保護フィルム等として好適に使用可能である。この場合、プラスチック層側に極性有機溶媒及び／または塩類等と接触させて使用する。特に極性有機溶媒及び塩を含む非水電解質と接触させる状態で使用することにより、特に非水電解質電池、固体電池等の二次電池電解液封止フィルムまたは二次電池電極部保護フィルムとして好適に使用することができる。この場合、プラスチック層が対向するように折り重ねてヒートシールすることにより、電池用封止袋として使用することができる。本発明で用いている接着剤はヒートシール性に優れるため、非水電解質の漏洩を防止し、電池として長期使用が可能になる。 <Member for battery>
The laminate of the present invention, which is composed of a metal layer and a plastic layer, can be suitably used as, for example, an electrolytic solution sealing film or an electrode portion protective film of a battery. In this case, the plastic layer side is used in contact with a polar organic solvent and / or a salt or the like. In particular, when used in contact with a non-aqueous electrolyte containing a polar organic solvent and a salt, it is particularly suitable as a secondary battery electrolyte sealing film for a non-aqueous electrolyte battery, solid battery, etc. or a secondary battery electrode part protective film It can be used. In this case, it can be used as a battery sealing bag by folding it so that the plastic layers face each other and heat sealing. Since the adhesive used in the present invention is excellent in heat sealability, leakage of the non-aqueous electrolyte can be prevented, and the battery can be used for a long time.
　前記極性有機溶媒としては、非プロトン性の極性溶媒、例えばアルキルカーボネート、エステル、ケトンなどがあげられる。具体的には、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、γ－ブチロラクトン、１，２－ジメトキシエタン、テトラハイドロフラン、２－メチルテトラハイドロフラン、１，３－ジオキソラン、４－メチル－１，３－ジオキソラン、メチルフォーメート、４－メチル－１，３－ジオキソメチルフォーメート、メチルアセテート、メチルプロピオネートなどが挙げられる。
塩としては、リチウム塩、ナトリウム塩、カリウム塩等のアルカリ金属塩があげられる。電池用としてはＬｉＰＦ６、ＬｉＢＦ４、Ｌｉ－イミド等のリチウム塩が一般的に使用される。 Examples of the polar organic solvent include aprotic polar solvents such as alkyl carbonates, esters and ketones. Specifically, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3- Examples include dioxolane, 4-methyl-1,3-dioxolane, methyl formate, 4-methyl-1,3-dioxomethyl formate, methyl acetate, methyl propionate and the like.
Examples of the salt include alkali metal salts such as lithium salt, sodium salt and potassium salt. For the battery, lithium salts such as LiPF 6 , LiBF 4 and Li-imide are generally used.
　非水電解質は環状炭酸エステル、鎖状炭酸エステル、それらの混合物等の非プロトン性極性有機溶媒に前記アルカリ金属塩が０．５～３ｍｍｏｌ溶解したものである。
本発明の積層体は前記極性溶媒及び／または塩類、特にそれらの混合物である非水電解質と接触する状態で使用しても金属層、接着層、プラスチック層の層間剥離を生じることなく、長期にわたって使用することができる。 The non-aqueous electrolyte is one in which 0.5 to 3 mmol of the alkali metal salt is dissolved in an aprotic polar organic solvent such as cyclic carbonate, chain carbonate, and a mixture thereof.
The laminate of the present invention can be used in contact with the non-aqueous electrolyte which is the polar solvent and / or the salts, particularly a mixture thereof, without causing delamination of the metal layer, adhesive layer and plastic layer over a long period of time It can be used.
＜電池＞
　本発明の電池は、本発明の電池用部材を含有するものである。本発明の積層体を有する電池用部材としては、電池電解液封止フィルムや電池電極部保護フィルムなどが挙げられる。本発明の電池は、上記フィルムが層間剥離を生じず、しかも非水電解質の漏洩を防止することができるので、電池として長期間安定して使用することができる。 <Battery>
The battery of the present invention contains the battery member of the present invention. As a member for batteries which has a laminated body of this invention, a battery electrolyte solution sealing film, a battery electrode part protection film, etc. are mentioned. The battery of the present invention can be stably used as a battery for a long period of time because the film does not cause delamination, and moreover, the leakage of the non-aqueous electrolyte can be prevented.
　本発明を以下実施例を持って説明するが、本発明は実施例に限定されるものではない。なお、特に記述のない場合、単位は重量換算である。 EXAMPLES The present invention will be described by way of examples, but the present invention is not limited to the examples. In addition, when there is no description in particular, a unit is weight conversion.
（調整例１）　ワニス１の調整
　プロピレン／１－ブテン共重合体３００ｇとトルエン１Ｌを窒素雰囲気下で１４５℃に昇温し、プロピレン／１－ブテン共重合体をトルエンに溶解させた。さらに撹拌しながら無水マレイン酸３８ｇ、ジ－ｔｅｒｔ－ブチルパーオキシド１６ｇを４時間かけて系に供給し、続けて１４５℃で２時間撹拌した。冷却後、多量のアセトンを投入して、無水マレイン酸変性プロピレン／１－ブテン共重合体（１）を沈殿させ、ろ過し、アセトンで洗浄した後、真空乾燥して白色の固体を得た。得られた固体を２０部、メチルシクロヘキサン７２部、酢酸エチル７部、イソプロピルアルコール（ＩＰＡ）１部をよく撹拌し、不揮発分が２０．０％の溶液であるワニス１を得た。 Preparation Example 1 Preparation of Varnish 1 300 g of a propylene / 1-butene copolymer and 1 L of toluene were heated to 145 ° C. in a nitrogen atmosphere, and the propylene / 1-butene copolymer was dissolved in toluene. With further stirring, 38 g of maleic anhydride and 16 g of di-tert-butyl peroxide were fed into the system over 4 hours, followed by stirring at 145 ° C. for 2 hours. After cooling, a large amount of acetone was added to precipitate a maleic anhydride-modified propylene / 1-butene copolymer (1), which was filtered, washed with acetone, and vacuum-dried to obtain a white solid. Twenty parts of the obtained solid, 72 parts of methylcyclohexane, 7 parts of ethyl acetate and 1 part of isopropyl alcohol (IPA) were well stirred to obtain Varnish 1 which is a solution having a non-volatile content of 20.0%.
（調整例２）　ワニス２の調整
　ＧＭＰ７５５０Ｅ（酸変性オレフィン樹脂、ロッテケミカル社製）１６部、アウローレン３５０Ｓ（酸変性オレフィン樹脂、日本製紙製）４部、メチルシクロヘキサン７２部、酢酸エチル５部、イソプロピルアルコール（ＩＰＡ）３部をよく撹拌し、不揮発分が２０．５％の溶液であるワニス２を調整した。 Preparation Example 2 Preparation of Varnish 16 16 parts of GMP 7550 E (acid-modified olefin resin, made by Lotte Chemical Co., Ltd.), 4 parts of lauren 350 S (acid-modified olefin resin, made by Nippon Paper Industries), 72 parts of methylcyclohexane, 5 parts of ethyl acetate, 3 parts of isopropyl alcohol (IPA) was well stirred, and varnish 2 which is a solution having a non-volatile content of 20.5% was prepared.
（調整例３）　ワニス３の調整
Poly(ethylene-co-acrylie acid)を２０部、トルエンを７２部、イソプロピルアルコール（ＩＰＡ）を８部入れて良く攪拌し、不揮発分が１９．９％であるワニス３を作成した。 Preparation Example 3 Preparation of Varnish 3
20 parts of Poly (ethylene-co-acrylic acid), 72 parts of toluene and 8 parts of isopropyl alcohol (IPA) were added and stirred well to prepare Varnish 3 having a non-volatile content of 19.9%.
（調整例４）　ワニス４の調整
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応装置に、トルエン１２０　ｇを仕込んだ後、窒素気流下に約１時間かけて系内温度が約１００℃になるまで昇温し、１時間保温した。次いで、あらかじめスチレン１１７ｇ、アクリル酸１２．６ｇ、ラウリルメタクリレート５０．４ｇ、ｔ－ブチルパーオキシエチルヘキサノエイト（日産化学株式会社製パーブチルＯ）３．６ｇからなる混合液を仕込んだ滴下ロートより、窒素気流下に混合液を約４時間要して系内に滴下し、６時間同温度に保温した。冷却して、トルエン９０ｇを加えることで、不揮発分が４６．８％である酸基含有アクリル酸エステル樹脂（Ｅ）の溶液であるワニス４を得た。 Preparation Example 4 Preparation of Varnish 4 After 120 g of toluene was charged into a reactor equipped with a stirring device, a cooling pipe, a dropping funnel and a nitrogen introducing pipe, the temperature in the system was about 1 hour under a nitrogen stream. The temperature was raised to 100 ° C. and kept warm for 1 hour. Then, from the dropping funnel, a mixed solution consisting of 117 g of styrene, 12.6 g of acrylic acid, 50.4 g of lauryl methacrylate, and 3.6 g of t-butylperoxyethyl hexanoate (Perbutyl O manufactured by Nissan Chemical Industries, Ltd.) is charged in advance. The mixture was dropped for about 4 hours in a nitrogen stream, dropped into the system, and kept at the same temperature for 6 hours. After cooling, 90 g of toluene was added to obtain Varnish 4 which is a solution of an acid group-containing acrylic acid ester resin (E) having a nonvolatile content of 46.8%.
（調整例５）　ワニス５の調整
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応装置に、トルエン５０ｍＬを仕込んだ後、３０分間アルゴンガスをバブリングして系内を置換した。アルゴン導入口を液面から上げ、フローに変更後、浴温１３５℃のオイルバスに浸漬し、攪拌を開始した。系内が一定温度に到達した後、メタクリル酸シクロヘキシル３８．２０ｇ、メタクリル酸イソボルニル８．６５ｇ、アクリル酸３．２０ｇ、２，２‘－アゾビスイソブチロニトリル１１８ｍｇの５ｍLトルエン溶液、の4種を混合した溶液を1時間かけて滴下した。アルゴンフロー下、浴温を保ったまま4時間加熱攪拌後、２，２‘－アゾビスイソブチロニトリル１１９ｍｇの５ｍLトルエン溶液を滴下し、再び浴温を保ったまま4時間加熱攪拌した。室温に冷却後、得られた僅かに白色に濁った均一な溶液を、約１．２リットルのメタノールに投入し、再沈させた。引き続き、沈殿をメタノールにて3回洗浄し、ついで４０℃にて一晩減圧乾燥したところ、白色の固体が４８ｇ得られた。得られた白色個体をトルエンに溶解し、酸基含有アクリル酸エステル樹脂（Ｆ）の溶液であるワニス５を得た。酸価が、１１．３ｍｇＫＯＨ／ｇ、不揮発分が３０．０％であった。 Preparation Example 5 Preparation of Varnish 5 Into a reaction apparatus equipped with a stirrer, a cooling pipe, a dropping funnel, and a nitrogen introducing pipe, 50 mL of toluene was charged, and then argon gas was bubbled for 30 minutes to replace the inside of the system. The argon inlet was raised from the liquid level, and after changing to flow, it was immersed in an oil bath with a bath temperature of 135 ° C. to start stirring. After reaching a certain temperature in the system, 4 kinds of 38.20 g of cyclohexyl methacrylate, 8.65 g of isobornyl methacrylate, 3.20 g of acrylic acid, 5 mg of toluene solution of 118 mg of 2,2'-azobisisobutyro nitrile, 4 kinds of Was added dropwise over 1 hour. After heating and stirring for 4 hours while maintaining the bath temperature under argon flow, a 5 mL toluene solution of 119 mg of 2,2′-azobisisobutyronitrile was added dropwise, and the heating and stirring were continued for 4 hours while the bath temperature was maintained again. After cooling to room temperature, the slightly white cloudy homogeneous solution obtained was poured into about 1.2 liters of methanol and reprecipitated. Subsequently, the precipitate was washed three times with methanol and then dried under reduced pressure overnight at 40 ° C. to obtain 48 g of a white solid. The obtained white solid was dissolved in toluene to obtain Varnish 5 which is a solution of an acid group-containing acrylic acid ester resin (F). The acid value was 11.3 mg KOH / g, and the nonvolatile content was 30.0%.
（調整例６）　ワニス６の調整
　撹拌装置、温度計、冷却管、滴下装置を備えたガラスフラスコに、ＤＭＰＡ（２，２－ジメチロールプロパン酸）９０重量部、溶媒としてメチルエチルケトン５４重量部、テトラヒドロフラン８１重量部を仕込み、窒素気流下にて攪拌した。次いで、ＸＤＩ（キシリレンジイソシアネート、商品名：タケネート５００、三井化学製）５６重量部を仕込み、６０℃に昇温した。１時間撹拌した後、４０℃以下まで温度を下げてから、更にＸＤＩ５６重量部を仕込み、再度６０℃に昇温した。赤外分光法でイソシアネート基の消失が確認されるまで反応を継続した。次いで、希釈溶媒としてメタノール１４８重量部を加え、カルボキシル基を含有するウレタン樹脂「ＤＭＰＡ／ＸＤＩ」を５０重量％含有する酸基含有ポリウレタン樹脂（Ｇ）の溶液であるワニス６を得た。 Preparation Example 6 Preparation of Varnish 90 In a glass flask equipped with a stirrer, thermometer, condenser and dropping device, 90 parts by weight of DMPA (2,2-dimethylolpropanoic acid), 54 parts by weight of methyl ethyl ketone as a solvent, tetrahydrofuran 81 parts by weight was charged and stirred under nitrogen stream. Subsequently, 56 parts by weight of XDI (xylylene diisocyanate, trade name: Takenate 500, manufactured by Mitsui Chemicals) was charged, and the temperature was raised to 60 ° C. After stirring for 1 hour, the temperature was lowered to 40 ° C. or less, 56 parts by weight of XDI was further charged, and the temperature was raised again to 60 ° C. The reaction was continued until disappearance of the isocyanate group was confirmed by infrared spectroscopy. Subsequently, 148 parts by weight of methanol was added as a dilution solvent to obtain Varnish 6, which is a solution of an acid group-containing polyurethane resin (G) containing 50% by weight of a carboxyl group-containing urethane resin "DMPA / XDI".
（調整例７）　ワニス７の調整
　ポリオレフィン樹脂ハイワックスＮＬ１００（三井化学社製）を２０部、トルエンを８０部を入れて良く攪拌し、不揮発分が２０．１％の溶液であるワニス７を作成した。 Preparation Example 7 Preparation of Varnish 20 20 parts of Polyolefin Resin Hi-Wax NL100 (manufactured by Mitsui Chemicals, Inc.) and 80 parts of toluene are added and stirred well to prepare Varnish 7 which is a solution having a nonvolatile content of 20.1%. did.
　用意した酸基含有樹脂について、各樹脂の酸価を以下表１に示す。なお、酸価の測定方法としては、酸基含有ポリオレフィン樹脂は前述した酸価測定方法－２、酸基含有ポリアクリル酸エステル樹脂及び酸基含有ポリウレタン樹脂については酸価測定方法－１を利用した。 The acid value of each of the prepared acid group-containing resins is shown in Table 1 below. In addition, as a method of measuring the acid value, the acid group-containing polyolefin resin used the acid value measurement method-2 described above, and the acid group-containing polyacrylic acid ester resin and the acid group-containing polyurethane resin used the acid value measurement method-1 .
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
合成例１　ジヒドロキシ化合物（Ｐｈ－１）の合成
　温度計、撹拌機を取り付けたフラスコに１，６－ヘキサンジオールのジグリシジルエーテル（ＤＩＣ株式会社製：商品名ＥＰＩＣＬＯＮ ７２６Ｄ、エポキシ当量１２４ｇ／ｅｑ）７４４ｇ（６当量）とビスフェノールＡ（水酸基当量１１４ｇ／ｅｑ）１３６８ｇ（１２当量）を仕込み、１４０℃まで３０分間要して昇温した後、４％水酸化ナトリウム水溶液５ｇを仕込んだ。その後、３０分間要して１５０℃まで昇温し、さらに１５０℃で３時間反応させた。その後、中和量のリン酸ソーダを添加し、ヒドロキシ化合物（Ｐｈ－１）２０９０ｇを得た。このヒドロキシ化合物（Ｐｈ－１）は、ＮＭＲスペクトル（１３Ｃ）から、また、マススペクトルで前記一般式（１）のｎが１の理論構造に相当するＭ＋＝６８７、及びｎが２の理論構造に相当するＭ＋＝１１４５のピークが得られたことから下記構造式（Ｂ－１）で表される構造のヒドロキシ化合物を含有することが確認された。このヒドロキシ化合物（Ｐｈ－１）のＧＰＣより算出した水酸基当量は２６２ｇ／ｅｑ、水酸基当量から算出した構造式（Ｂ－１）中のｎの平均値は０．６であった。 Synthesis Example 1 Synthesis of dihydroxy compound (Ph-1) Diglycidyl ether of 1,6-hexanediol in a flask equipped with a thermometer and a stirrer (manufactured by DIC Corporation: trade name EPICLON 726D, epoxy equivalent 124 g / eq) 744 g (6 equivalents) and 1368 g (12 equivalents) of bisphenol A (hydroxyl equivalent of 114 g / eq) were charged, and heated to 140 ° C. for 30 minutes, and then 5 g of a 4% aqueous solution of sodium hydroxide was charged. Thereafter, the temperature was raised to 150 ° C. in 30 minutes, and the reaction was further carried out at 150 ° C. for 3 hours. Thereafter, a neutralization amount of sodium phosphate was added to obtain 2090 g of a hydroxy compound (Ph-1). From the NMR spectrum ( 13 C), this hydroxy compound (Ph-1) also has M + = 687 corresponding to the theoretical structure in which n is 1 in the general formula (1) in the mass spectrum, and the theory that n is 2 From the fact that a peak of M + = 1145 corresponding to the structure was obtained, it was confirmed that the compound contained a hydroxy compound having a structure represented by the following structural formula (B-1). The hydroxyl equivalent calculated from GPC of this hydroxy compound (Ph-1) was 262 g / eq, and the average value of n in the structural formula (B-1) calculated from the hydroxyl equivalent was 0.6.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　合成例２　エポキシ化合物（Ｅｐ－１）の合成
　温度計、滴下ロート、冷却管、撹拌機を取り付けたフラスコに実施例１で得られたヒドロキシ化合物（Ｐｈ－１）２６１ｇ（水酸基当量２６１ｇ／ｅｑ．）、エピクロルヒドリン１１１０ｇ（１２モル）、ｎ－ブタノール２２２ｇを仕込み溶解させた。その後、窒素ガスパージを施しながら、６５℃に昇温した後に、共沸する圧力までに減圧して、４９％水酸化ナトリウム水溶液１２２ｇ（１．５モル）を５時間かけて滴下した。次いでこの条件下で０．５時間撹拌を続けた。この間、共沸で留出してきた留出分をディーンスタークトラップで分離して、水層を除去し、有機層を反応系内に戻しながら反応した。その後、未反応のエピクロルヒドリンを減圧蒸留して留去させた。それで得られた粗エポキシ樹脂にメチルイソブチルケトン１０００ｇとｎ－ブタノール１００ｇを加え溶解した。更にこの溶液に１０％水酸化ナトリウム水溶液２０ｇを添加して８０℃で２時間反応させた後に洗浄液のＰＨが中性となるまで水３００ｇで水洗を３回繰り返した。次いで共沸によって系内を脱水し精密濾過を経た後に溶媒を減圧下で留去して液状のエポキシ樹脂（Ｅｐ－１）３８０ｇを得た。このエポキシ樹脂（Ｅｐ－１）は、ＮＭＲスペクトル（１３Ｃ）から、またマススペクトルで前記構造式（Ａ１－３）中のｐ＝１、ｑ＝１、ｒ＝０の理論構造に相当するＭ＋＝７９８、ｐ＝２、ｑ＝２、ｒ＝０の理論構造に相当するＭ＋＝１２５７のピークが得られたことから前記構造式（Ａ１－３）で表される構造のエポキシ樹脂を含有することが確認された。得られたエポキシ樹脂（Ｅｐ－１）は、前記構造式（Ａ１－３）においてｐ＝０、ｑ＝０、ｒ＝０の化合物を含んでおり、ＧＰＣで確認したところ該混合物中ｐ＝０、ｑ＝０、ｒ＝０の化合物を２９重量％の割合で含有するものであった。また、このエポキシ樹脂（Ｅｐ－１）のエポキシ当量は３５０ｇ／ｅｑ．、粘度は２０００Ｐａ・ｓ（２５℃，Ｅ型粘度法）、エポキシ当量から算出される前記構造式（Ａ１－３）中のｒの平均値は０．１であった。 Synthesis Example 2 Synthesis of Epoxy Compound (Ep-1) 261 g (hydroxyl equivalent: 261 g / eq.) Of the hydroxy compound (Ph-1) obtained in Example 1 in a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer. ), 1110 g (12 moles) of epichlorohydrin, and 222 g of n-butanol were added and dissolved. Thereafter, the temperature was raised to 65 ° C. while performing nitrogen gas purge, and the pressure was reduced to an azeotropic pressure, and 122 g (1.5 mol) of a 49% aqueous solution of sodium hydroxide was added dropwise over 5 hours. Stirring was then continued for 0.5 hours under these conditions. During this time, the azeotropically distilled distillate was separated by a Dean-Stark trap, the aqueous layer was removed, and the organic layer was reacted while being returned to the reaction system. Thereafter, the unreacted epichlorohydrin was distilled off under reduced pressure. To the crude epoxy resin thus obtained, 1000 g of methyl isobutyl ketone and 100 g of n-butanol were added and dissolved. Further, 20 g of a 10% aqueous solution of sodium hydroxide was added to this solution and allowed to react at 80 ° C. for 2 hours. Washing with 300 g of water was repeated three times until the pH of the washing solution became neutral. Then, the system was azeotropically dehydrated by azeotropic distillation, and after precision filtration, the solvent was distilled off under reduced pressure to obtain 380 g of liquid epoxy resin (Ep-1). This epoxy resin (Ep-1) has M + corresponding to the theoretical structure of p = 1, q = 1, r = 0 in the structural formula (A1-3) in NMR spectrum ( 13 C) and mass spectrum. Since the peak of M + = 1257 corresponding to the theoretical structure of = 798, p = 2, q = 2, r = 0 is obtained, the epoxy resin of the structure represented by the structural formula (A1-3) is contained. That was confirmed. The obtained epoxy resin (Ep-1) contains a compound of p = 0, q = 0, r = 0 in the above structural formula (A1-3), and it is confirmed by GPC that p = 0 in the mixture , Q = 0, r = 0 in a proportion of 29% by weight. Moreover, the epoxy equivalent of this epoxy resin (Ep-1) is 350 g / eq. The viscosity was 2000 Pa · s (25 ° C., E-type viscosity method), and the average value of r in the structural formula (A1-3) calculated from the epoxy equivalent was 0.1.
（実施例１）接着剤１の作成
ワニス１を１００部、エポキシ化合物（Ｅｐ－１）を０．７部、Triphenylphosphineを０．０１部、酢酸エチルを３部、イソプロピルアルコールを１部入れてよく攪拌し、不揮発分２０％の接着剤１を作成した。 (Example 1) Preparation of adhesive 1 100 parts of varnish 1, 0.7 parts of epoxy compound (Ep-1), 0.01 parts of triphenylphosphine, 3 parts of ethyl acetate and 1 part of isopropyl alcohol The mixture was stirred to prepare an adhesive 1 having a nonvolatile content of 20%.
＜積層体の作成＞
アルミフォイル（「１Ｎ３０Ｈ」３０μｍ　東洋アルミニウム社製）に実施例１で作成した接着剤１をバーコーターで５ｇ／ｍ２（ｄｒｙ）塗布し、８０℃－１分乾燥させた後、ＣＰＰフィルム（ポリオレフィンフィルム「ＥＴ－２０」４０μｍ　オカモト社製）と１００℃で貼り合せて積層体１を作製した。
その後、７０℃－５日エージングさせた後に初期接着強度を測定した。 <Creating a laminate>
After applying 5 g / m 2 (dry) of the adhesive 1 prepared in Example 1 to an aluminum foil (“1N 30 H” 30 μm, manufactured by Toyo Aluminum Co., Ltd.) with a bar coater and drying at 80 ° C. for 1 minute, CPP film (polyolefin The laminate 1 was produced by laminating the film “ET-20” 40 μm (manufactured by Okamoto Co., Ltd.) at 100 ° C.
Thereafter, the initial adhesive strength was measured after aging at 70 ° C. for 5 days.
＜初期接着強度の測定＞
（株）エー・アンド・ディー製テンシロン試験において、積層体を１５ｍｍ幅にカットし、１８０°剥離強度を測定した。 <Measurement of initial adhesion strength>
The laminate was cut into a width of 15 mm and the 180 ° peel strength was measured in the A & D Tensilon test.
＜耐電解液性＞
　電解液として、エチレンカーボネート：エチルメチルカーボネート：ジメチルカーボネート＝１：１：１（ｗｔ％）混合液にＬｉＰＦ6：１ｍｏｌ％とビニレンカーボネート：１ｗｔ％を添加した溶液を用意した。
　積層体１を電解液３５gに８５℃－７日間浸漬させ、浸漬前後の接着強度の保持率から以下のとおりに評価を実施した。
　接着強度保持率（％）＝浸漬後の接着強度（Ｎ／１５ｍｍ）／浸漬前の接着強度（Ｎ／１５ｍｍ）
　◎：８０％以上、○：８０～６０％、×：６０％以下 <Electrolyte resistance>
As electrolyte solution, the solution which added LiPF 6: 1mol% and vinylene carbonate 1wt% to ethylene carbonate: ethyl methyl carbonate: dimethyl carbonate = 1: 1: 1 (wt%) mixed solution was prepared.
The laminate 1 was immersed in 35 g of an electrolytic solution at 85 ° C. for 7 days, and evaluation was carried out as follows from the retention of adhesive strength before and after immersion.
Adhesive strength retention (%) = Adhesive strength after immersion (N / 15 mm) / Adhesive strength before immersion (N / 15 mm)
◎: 80% or more, ○: 80 to 60%, ×: 60% or less
実施例２～７
　実施例１に記載の方法と同様にして、表２に示す配合に従って各成分を混合し、接着剤および積層体を作製した。
　各例で得られた積層体において、接着性能ならびに耐電解質性を評価しその結果を表２示す。 Examples 2 to 7
In the same manner as in the method described in Example 1, the components were mixed according to the formulations shown in Table 2 to produce an adhesive and a laminate.
In the laminate obtained in each example, the adhesion performance and the electrolytic resistance were evaluated, and the results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
キュアゾール2E4MZ（四国化成工業社製イミダゾール系硬化剤）　不揮発分１００％
エピクロンＨＰ－４７００（ＤＩＣ社製ナフタレン型エポキシ）　不揮発分１００％ Cuazole 2E4MZ (imidazole-based curing agent manufactured by Shikoku Kasei Kogyo Co., Ltd.) Nonvolatile content 100%
Epiclon HP-4700 (Naphthalene-type epoxy manufactured by DIC) 100% nonvolatile content
　本発明の接着剤は、接着性、特に金属または金属酸化物層との接着性に優れ、更に、低温養生でも耐電解質性を兼ね備え、経時で層間剥離を生じることがないことから、ラミネート用接着剤や電池用接着剤として良好に使用可能である。また、得られる積層体は電池用部材として良好に使用可能であり、長期間の使用安定性を有する電池が得られる。 The adhesive of the present invention is excellent in adhesion, particularly adhesion to a metal or metal oxide layer, and further has electrolytic resistance even at low temperature curing and does not cause delamination over time, so it is an adhesive for laminating. It can be used favorably as an agent or an adhesive for batteries. Further, the obtained laminate can be favorably used as a battery member, and a battery having long-term use stability can be obtained.

Claims (10)

  1. 　酸基含有樹脂と、芳香環および炭素数4－１０のアルキレン鎖及び2つ以上のエポキシ基を含有するエポキシ化合物Aとを含有することを特徴とする、接着剤。 An adhesive comprising: an acid group-containing resin; and an epoxy compound A containing an aromatic ring and an alkylene chain having 4 to 10 carbon atoms and two or more epoxy groups.
  2. 　酸基含有樹脂が酸基含有ポリアクリル酸エステル樹脂、酸基含有ポリウレタン樹脂、及びまたは酸基含有ポリオレフィン樹脂である、請求項１に記載の接着剤。 The adhesive according to claim 1, wherein the acid group-containing resin is an acid group-containing polyacrylic acid ester resin, an acid group-containing polyurethane resin, and / or an acid group-containing polyolefin resin.
  3. 　エポキシ化合物Aが、下記式（１）で表される化合物である、請求項１または２のいずれかに記載の接着剤。
    Figure JPOXMLDOC01-appb-I000001
    ・・・（１）
    （式中、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４は同一でも異なっていても良い、置換基を有していてもよい芳香環であり、Ｘ１、Ｘ２は脂肪族炭化水素基であり、Ｒ１、Ｒ２、Ｒ３は同一でも異なっていても良い水素原子又は炭素数１～４のアルキル基であり、ｐ、ｑ、ｒは繰り返し数の平均値でｐは０．５～５．０であり、ｑは０．５～５．０であり、ｒは０．０５～０．５である。）     The adhesive according to any one of claims 1 and 2, wherein the epoxy compound A is a compound represented by the following formula (1).
    Figure JPOXMLDOC01-appb-I000001
    ... (1)
    (Wherein, Ar 1 , Ar 2 , Ar 3 and Ar 4 are the same or different and each is an aromatic ring which may have a substituent, and X 1 and X 2 are aliphatic hydrocarbon groups. And R 1 , R 2 and R 3 are the same or different and each is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p, q and r are average values of the number of repetitions and p is 0.5 to 5.0, q is 0.5 to 5.0, and r is 0.05 to 0.5.)
  4. 　請求項１～３のいずれか１項に記載のラミネート用接着剤。 The adhesive for lamination according to any one of claims 1 to 3.
  5. 　請求項１～３のいずれか１項に記載の電池用接着剤。 The adhesive for a battery according to any one of claims 1 to 3.
  6. 　請求項１～３のいずれか１項に記載の金属または金属酸化物用接着剤。 An adhesive for metal or metal oxide according to any one of claims 1 to 3.
  7. 　請求項１～６のいずれかに記載の接着剤層を中間層に有することを特徴とする積層体。 A laminate comprising the adhesive layer according to any one of claims 1 to 6 in an intermediate layer.
  8. 　金属層と、プラスチック層とを有する、請求項７に記載の積層体。 The laminate according to claim 7, comprising a metal layer and a plastic layer.
  9. 　請求項７または８に記載の積層体を有する電池用部材。 A member for a battery comprising the laminate according to claim 7 or 8.
  10. 　請求項９に記載の電池用部材を有する電池。 A battery comprising the battery member according to claim 9.
PCT/JP2018/036820 2017-10-04 2018-10-02 Adhesive, laminate, battery member, and battery WO2019069896A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2019546714A JP6642778B2 (en) 2017-10-04 2018-10-02 Adhesive, laminate, battery member, and battery
CN201880060977.9A CN111133075B (en) 2017-10-04 2018-10-02 Adhesive, laminate, member for battery, and battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017194310 2017-10-04
JP2017-194310 2017-10-04

Publications (1)

Publication Number Publication Date
WO2019069896A1 true WO2019069896A1 (en) 2019-04-11

Family

ID=65994913

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/036820 WO2019069896A1 (en) 2017-10-04 2018-10-02 Adhesive, laminate, battery member, and battery

Country Status (4)

Country Link
JP (1) JP6642778B2 (en)
CN (1) CN111133075B (en)
TW (1) TWI775959B (en)
WO (1) WO2019069896A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021070606A1 (en) * 2019-10-08 2021-04-15 東洋紡株式会社 Polyolefin-based adhesive composition
WO2021131722A1 (en) * 2019-12-25 2021-07-01 Dic株式会社 Adhesive, stack, packaging material, battery-use packaging material, and battery
US20220085389A1 (en) * 2020-09-14 2022-03-17 Institute of Nuclear Energy Research, Atomic Energy Council, Executive Yuan, R.O.C. Method of Electrode Fabrication for Super-Thin Flow-Battery
CN114450827A (en) * 2019-09-26 2022-05-06 东洋纺株式会社 Fuel cell assembly and laminate
CN114450152A (en) * 2019-09-26 2022-05-06 东洋纺株式会社 Laminated body
WO2023145670A1 (en) * 2022-01-25 2023-08-03 パナソニックＩｐマネジメント株式会社 Battery packaging material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095046A (en) * 1990-02-06 1992-03-10 Exxon Chemical Patents Inc. Hot melt adhesive of ethylene/unsaturated acid copolymer and epoxy crosslinker
JP2005320477A (en) * 2004-05-11 2005-11-17 Japan Epoxy Resin Kk Highly flexible resin and curable resin composition
WO2014050686A1 (en) * 2012-09-25 2014-04-03 Dic株式会社 Laminate adhesive, and laminate and rechargeable battery using same
WO2015190411A1 (en) * 2014-06-11 2015-12-17 東洋紡株式会社 Polyolefin-based adhesive composition
JP2016183223A (en) * 2015-03-25 2016-10-20 東洋インキＳｃホールディングス株式会社 Adhesive composition, laminate, packaging material for power storage device, container for power storage device, and power storage device

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4815877B2 (en) * 2005-05-31 2011-11-16 Ｄｉｃ株式会社 Epoxy resin composition, cured product thereof, novel hydroxy compound, novel epoxy resin and production method thereof
JP5773201B2 (en) * 2011-08-15 2015-09-02 Dic株式会社 Thermal adhesive sheet
US11038230B2 (en) * 2016-01-21 2021-06-15 Mitsui Chemicals, Inc. Composition, laminate, packaging material, battery case packaging material, and battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095046A (en) * 1990-02-06 1992-03-10 Exxon Chemical Patents Inc. Hot melt adhesive of ethylene/unsaturated acid copolymer and epoxy crosslinker
JP2005320477A (en) * 2004-05-11 2005-11-17 Japan Epoxy Resin Kk Highly flexible resin and curable resin composition
WO2014050686A1 (en) * 2012-09-25 2014-04-03 Dic株式会社 Laminate adhesive, and laminate and rechargeable battery using same
WO2015190411A1 (en) * 2014-06-11 2015-12-17 東洋紡株式会社 Polyolefin-based adhesive composition
JP2016183223A (en) * 2015-03-25 2016-10-20 東洋インキＳｃホールディングス株式会社 Adhesive composition, laminate, packaging material for power storage device, container for power storage device, and power storage device

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114450827A (en) * 2019-09-26 2022-05-06 东洋纺株式会社 Fuel cell assembly and laminate
CN114450827B (en) * 2019-09-26 2023-12-01 东洋纺株式会社 Joint body for fuel cell and laminate
CN114450152B (en) * 2019-09-26 2023-06-02 东洋纺株式会社 Laminate body
CN114450152A (en) * 2019-09-26 2022-05-06 东洋纺株式会社 Laminated body
CN114341301A (en) * 2019-10-08 2022-04-12 东洋纺株式会社 Polyolefin adhesive composition
WO2021070606A1 (en) * 2019-10-08 2021-04-15 東洋紡株式会社 Polyolefin-based adhesive composition
JPWO2021070606A1 (en) * 2019-10-08 2021-11-11 東洋紡株式会社 Polyolefin-based adhesive composition
CN114341301B (en) * 2019-10-08 2023-09-29 东洋纺Mc株式会社 Polyolefin adhesive composition
JP7006845B2 (en) 2019-12-25 2022-01-24 Dic株式会社 Adhesives, laminates, packaging materials, battery packaging materials, batteries
JPWO2021131722A1 (en) * 2019-12-25 2021-12-23 Dic株式会社 Adhesives, laminates, packaging materials, battery packaging materials, batteries
WO2021131722A1 (en) * 2019-12-25 2021-07-01 Dic株式会社 Adhesive, stack, packaging material, battery-use packaging material, and battery
US20220085389A1 (en) * 2020-09-14 2022-03-17 Institute of Nuclear Energy Research, Atomic Energy Council, Executive Yuan, R.O.C. Method of Electrode Fabrication for Super-Thin Flow-Battery
WO2023145670A1 (en) * 2022-01-25 2023-08-03 パナソニックＩｐマネジメント株式会社 Battery packaging material

Also Published As

Publication number Publication date
TWI775959B (en) 2022-09-01
CN111133075B (en) 2021-11-23
JP6642778B2 (en) 2020-02-12
JPWO2019069896A1 (en) 2020-04-23
CN111133075A (en) 2020-05-08
TW201932568A (en) 2019-08-16

Similar Documents

Publication Publication Date Title
JP6642778B2 (en) Adhesive, laminate, battery member, and battery
TWI722223B (en) Polyolefin adhesive composition
JP5664836B2 (en) Laminate adhesive, laminate using the same, and secondary battery
US10131823B2 (en) Polyolefin-based adhesive composition
JP5875029B1 (en) Laminate adhesive, laminate using the same, and secondary battery
US8198381B2 (en) Phenol aralkyl epoxy resin with secondary hydroxyl groups
JP7188055B2 (en) Adhesives, laminates, battery members and batteries
JP7310298B2 (en) Adhesives, laminates, packaging materials for batteries and batteries
CN109563385B (en) Polyolefin adhesive composition
WO2016075975A1 (en) Adhesive for laminate, layered body, and secondary cell
JP6083493B1 (en) Laminate adhesive, laminate using the same, and secondary battery
CN114746458A (en) Aqueous resin composition, coating film, and method for forming coating film
JP2019182976A (en) Adhesive, laminate, battery component and battery
JP7275774B2 (en) Adhesives, laminates, packaging materials for batteries and batteries
CN110607149B (en) Adhesive, laminate, battery packaging material, battery container, and battery
JP2012184294A (en) Gas barrier epoxy resin composition
KR20190035748A (en) Polyolefin-based adhesive composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18863996

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019546714

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18863996

Country of ref document: EP

Kind code of ref document: A1