CN108473836A - Lamination adhesive composite, laminated body and secondary cell - Google Patents

Lamination adhesive composite, laminated body and secondary cell Download PDF

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Publication number
CN108473836A
CN108473836A CN201780006157.7A CN201780006157A CN108473836A CN 108473836 A CN108473836 A CN 108473836A CN 201780006157 A CN201780006157 A CN 201780006157A CN 108473836 A CN108473836 A CN 108473836A
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CN
China
Prior art keywords
laminated body
adhesive composite
resin
polyolefin resin
lamination
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Granted
Application number
CN201780006157.7A
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Chinese (zh)
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CN108473836B (en
Inventor
中村英美
松尾高年
神山达哉
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Publication of CN108473836A publication Critical patent/CN108473836A/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • 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

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

Abstract

There is provided a kind of laminated body metal layer and plastic layer it is excellent in adhesion, have both low temperature reservation electrolyte resistance, its conservation rate are high, splitting will not also occur as time goes by lamination laminated body adhesive composite, its manufacturing method, used laminated body and secondary cell obtained by the bonding agent of the utilization adhesive composite.A kind of lamination adhesive composite, it contains modified polyolefin resin (A), amorphous polyolefins resin (B) and curing agent (C), wherein, the content of amorphous polyolefins resin (B) relative to the gross mass of modified polyolefin resin (A) and the solid constituent of amorphous polyolefins resin (B) be 0.1 mass % less than 20 mass %.

Description

Lamination adhesive composite, laminated body and secondary cell
Technical field
The present invention relates to lamination adhesive composite, laminated body and secondary cells.
Background technology
Using lithium ion battery as the secondary cell of representative using anode, cathode and structure obtained by being sealed with electrolyte therebetween etc. At.In addition, as enclosed in order to take out the electric power of anode and cathode to the hermetic bag of external lead, using by aluminium foil Etc. metal foils, metal vapor deposition layer be bonded with plastics obtained by laminated body.
The laminated body is required as moisture-proof, heat resistance, solvent resistance, the durability etc. required by secondary cell, so And be especially difficult to obtain the electrolyte-resistant insoluble in electrolyte by low-temperature setting, to the technology solved as needs Project.
For example, proposing a kind of enclosed bag in patent document 1, wherein the innermost layer of laminated body uses maleic acid modified Vistanex, heat-sealing portion is constituted with same maleated polyolefin resin, to make sealing reliability improve.Due to horse Cementability and the heat sealability for coming acid-modified polyolefin resin and metal adhesive are excellent, therefore are used usually as adhesive resin. However, if the diaphragm seal as battery as described above uses, just excellent bonding force is shown after stacking at high temperature, But electrolyte-resistant is low, and splitting occurs as time goes by, can not be used as diaphragm seal.
Patent document 2 describes a kind of battery electrolyte diaphragm seal laminated body or the stacking of battery electrode portion protective film Body, the surface-treated layer formed it includes metal layer, on the surface of metal layer and formed on surface-treated layer by carboxylic acid The adhesive resin layer that the modified polyolefin of base or derivatives thereof is formed.
Patent document 3 describes a kind of adhesive resin composition, and it includes (A) to have selected from anhydride group, carboxyl and carboxylic The polyolefin-based resins of at least one kind of functional group in acid metal salt and (B) have 2 or more epoxy groups and molecular weight be 3000 with Under epoxidized vegetable oil, (B) ingredient is the mass parts of 0.01 mass parts~5 relative to the use level of 100 mass parts of (A) ingredient.
Patent document 4 describes a kind of use in electrode for secondary battery binder resin composition, which is characterized in that it contains Acid-modified polyolefin resin (A) and polyurethane resin (B), relative to (A) 100 mass parts, (B) is the mass of 0.5 mass parts~100 Part.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 9-283101 bulletins
Patent document 2：WO2001/017043 bulletins
Patent document 3：Japanese Unexamined Patent Publication 08-193148 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2010-277959 bulletins
Invention content
Problems to be solved by the invention
In the prior art, as secondary cell laminated body bonding agent, polyene of a large amount of uses containing acidic group has been applied for The patent of hydrocarbon resin.
However, there is only when vistanex only containing acidic group, because high temperature ageing and squeeze out the processes such as lamination due to make it To the excellent adhesion of alkene sheet material, but to the cementability of metal layer deficiency.As a result, as the viscous of laminated body bonding agent It is insufficient to connect intensity.In turn, exist as time goes by and send out in use, electrolyte-resistant is also insufficient in the secondary battery The problem of raw splitting etc..
Therefore, problem of the present invention is that, even if providing the metal layer of laminated body and excellent in adhesion, the low temperature of plastic layer Maintenance also has both the lamination laminated body use that electrolyte resistance, its conservation rate are high, splitting will not occur as time goes by Adhesive composite has used laminated body and secondary cell obtained by the bonding agent using the adhesive composite.
The method for solving problem
The inventors of the present invention are studied, and as a result solve the above subject with adhesive composite by a kind of lamination, The lamination adhesive composite contains modified polyolefin resin (A), amorphous polyolefins resin (B) and curing agent (C), In,
The content of amorphous polyolefins resin (B) is relative to modified polyolefin resin (A) and amorphous polyolefins resin (B) Solid constituent gross mass be 0.1 mass % less than 20 mass %.
The effect of invention
In accordance with the invention it is possible to provide laminated body metal layer and plastic layer it is excellent in adhesion, even if low temperature reservation Have both the lamination laminated body bonding agent that electrolyte resistance, its conservation rate are high, splitting will not occur as time goes by Composition has used laminated body and secondary cell obtained by the bonding agent using the adhesive composite.
Specific implementation mode
In order to solve the above problems, the present invention is made of project below.
1. a kind of lamination adhesive composite contains modified polyolefin resin (A), amorphous polyolefins resin (B) With curing agent (C), wherein
The content of amorphous polyolefins resin (B) is relative to modified polyolefin resin (A) and amorphous polyolefins resin (B) Solid constituent gross mass be 0.1 mass % less than 20 mass %；
2. the lamination adhesive composite according to 1., wherein curing agent (C) includes selected from epoxide, more At least one or more in isocyanates, carbodiimide, oxazolines and amino resins；
3. the lamination adhesive composite according to 2., wherein epoxide has 2 or more in 1 molecule Epoxy group and be 3000 or less with 1 or more hydroxyl, weight average molecular weight in 1 molecule；
4. the lamination adhesive composite according to any one of 1.~3., be also added with thermoplastic elastomer (TPE), Tackifier, catalyst, phosphate cpd, reactive elastomer or silane coupling agent；
5. a kind of laminated body, with metal layer and polyolefin resin layer, wherein using described in any one of 1.~4. Lamination uses adhesive composite as the bonding agent of metal layer and polyolefin resin layer；
6. a kind of secondary cell uses the laminated body described in 5. as electrolyte diaphragm seal or electrode portion protective film.
(modified polyolefin resin (A))
In the present invention, as long as can solve the problem of the present invention and there is crystalline vistanex, so that it may with It uses without particular limitation.
In the present invention, various functional groups (such as carboxyl, hydroxyl etc.) have particularly preferably been imported in vistanex and The modified polyolefin resin obtained.In turn, among these modified polyolefin resins, further increased from the adaptation of metal layer, The excellent aspect of electrolyte resistance is set out, more preferably the modified polyolefin resin of the acid value with 1mgKOH/g~200mgKOH/g The improved polyalkene tree of (hereinafter, being denoted as acid-modified polyolefin resin) and/or hydroxyl value with 1mgKOH/g~200mgKOH/g Fat (hereinafter, being denoted as hydroxyl modification vistanex).
In addition, fusing point is preferably 60 DEG C~100 DEG C.
Acid-modified polyolefin resin refers to the vistanex with carboxyl, acid anhydride in molecule, by polyolefin with not Saturated carboxylic acid or derivatives thereof is modified and synthesizes.As its method of modifying, graft modification, copolymerization can be used.
Acid-modified polyolefin resin be by the polymerizable ethylenically unsaturated carboxylic acids of at least one or derivatives thereof graft modification or Graft-modified polyolefin obtained by copolymerization to vistanex before modified.As vistanex before modified, can enumerate Said polyolefins resin, wherein the homopolymer of preferred propylene, the copolymer etc. of propylene and alpha-olefin.They can be used alone 1 Kind, two or more can also be applied in combination.
As the ethylenically unsaturated carboxylic acids that graft modification or copolymerization are carried out to vistanex before modified or its spread out Biology can enumerate such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4- methyl Hexamethylene -4- alkene -1,2- dicarboxylic anhydrides, bicyclic [2.2.2] octyl- 5- alkene -2,3- dicarboxylic anhydrides, 1,2,3,4,5,8,9,10- octahydros Naphthalene -2,3- dicarboxylic anhydrides, 2- octyl-s 1,3- diketone spiral shell [4.4] nonyl- 7- alkene, bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboxylic anhydrides, Maleopimaric acid, tetrabydrophthalic anhydride, methyl-bicyclo [2.2.1] hept- 5- alkene -2,3- dicarboxylic anhydrides, methyl-norborneol - 5- alkene -2,3- dicarboxylic anhydrides, norborneol -5- alkene -2,3- dicarboxylic anhydrides etc..It is preferable to use maleic anhydrides.These substances can be single Solely uses or two or more is applied in combination.
In order to make the grafted monomers in ethylenically unsaturated carboxylic acids or derivatives thereof graft on polyolefin tree before modified Various methods may be used in fat.Can enumerate for example by vistanex melting, add grafted monomers and bringing it about thereto and connect The method of branch reaction；Vistanex is dissolved in solvent solution is made, adds grafted monomers thereto and bring it about connecing The method of branch reaction；The vistanex for being dissolved in organic solvent and above-mentioned unsaturated carboxylic acid etc. are mixed, in said polyolefins The softening temperature of resin or temperature more than fusing point are heated, and are carried out at the same time free radical polymerization in the molten state and dehydrogenation is anti- The method etc. answered.In order to make above-mentioned grafted monomers efficiently carry out graft copolymerization in any case, preferably draw in free radical Implement graft reaction in the presence of hair agent.Graft reaction usually carries out under conditions of 60 DEG C~350 DEG C.Radical initiator Use ratio is relative to the range that 100 mass parts of vistanex before modified are usually the mass parts of 0.001 mass parts~1.
As the modified polyolefin resin (A) of the present invention, the copolymerization for example by the alkene of carbon number 2~8 below can be enumerated Product obtained by the copolymer of object, the alkene of carbon number 2~8 and other monomers is modified as described above.
Specifically, it is poly- to enumerate such as high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE), linea low density The polyethylene such as vinyl, polypropylene, polyisobutene, poly- (1- butylene), poly- 4- methylpentenes, polyvinyl eyclohexane, polyphenyl Ethylene, poly- (p-methylstyrene), poly- (α-methylstyrene), Ethylene-Propylene Block Copolymer, ethylene-propylene random copolymerization The alpha olefin copolymers such as object, ethylene-butene-1 copolymer, ethylene -4 methyl 1 pentene copolymer, ethylene-hexene co-polymers； Vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene methyl methacrylate copolymer, ethylene-acetate second Enester-methylmethacrylate copolymer, ionomer resin etc..In turn, can also use by these polyolefin carry out chlorination and The chloridized polyolefin obtained.
As the acid-modified polyolefin resin being used in the present invention, for example maleic anhydride modified polypropylene, second can be enumerated Alkene-(methyl) acrylic copolymer, ethylene-acrylate-maleic anhydride terpolymer or ethylene-methyl acrylate- Maleic anhydride terpolymer.Specifically, " Modic ", the Mitsui Chemicals (strain) as Mitsubishi Chemical's (strain) manufacture manufacture " Admer ", " Unistole ", Japan spin " Toyotac " of (strain) manufacture, " Youmex " of Sanyo's chemical conversion (strain) manufacture, Japan " Primacor ", the Du that " Rexpearl EAA ", " Rexpearl ET ", the DOW Chemical (strain) of polyethylene (strain) manufacture manufacture " Nucrel " of Pont-MITSUI Polychemicals Co., Ltd. manufacture, " Bondine " of ARKEMA companies manufacture and It carries out commercially available.
Hydroxyl modification vistanex is the vistanex with hydroxyl in molecule, is that polyolefin is contained hydroxyl with aftermentioned Base (methyl) acrylate or hydroxyl vinyl ethers carry out graft modification or copolymerization and synthesize.Polyolefin tree before modified The case where fat, method of modifying are with acid-modified polyolefin resin is identical.
As above-mentioned hydroxyl (methyl) acrylate, (methyl) hydroxy-ethyl acrylate can be enumerated；(methyl) acrylic acid hydroxyl Propyl ester, (methyl) glycerol acrylate；Lactone-modified (methyl) hydroxy-ethyl acrylate, (methyl) polyalkylene glycol acrylate ester, (first Base) acrylic acid polypropylene glycol ester etc., as above-mentioned hydroxyl vinyl ethers, 2- hydroxyethyl vinyl ethers, diethyl two can be enumerated Alcohol mono vinyl ether, 4- hydroxybutyl vinyl ethers etc..
(amorphous polyolefins resin (B))
In the present invention, it as long as can solve the problem of the present invention, then can use without particular limitation non-crystalline Vistanex.
As such olefin resin, preferably amorphism, specifically, APEL (cyclic olefin copolymer/tri- can be enumerated Well chemical company system), TOPAS (cyclic olefin copolymer/Polyplastics corporations), Zeonor (cyclic olefine copolymer/ Zeon Corporation systems), ARTON (cyclic olefin copolymer/JSR corporations), Asahimelt (the poly- ɑ-alkene of amorphism/ Rising sun chemical synthesis corporation), the vistanexes such as RT (the poly- ɑ-alkene of amorphism/KF Chemicals corporations).
The bonding agent of the present invention can use radical initiator, as preferred initiator, can enumerate imidazoles system certainly By base initiator, but it is not limited to them.
For example, it is pungent to enumerate triphenylphosphine, 1,8- diazabicyclos (5.4.0) endecatylene -7 (DBU)-phenates, DBU- Hydrochlorate etc..
(curing agent (C))
The curing agent (C) being used in the present invention can enumerate selected from epoxide, polyisocyanates, carbodiimide, Curing agent in oxazoline and melmac.As the content of preferred curing agent, it can enumerate and meet curing agent (C) phase For the quality % (curing agent (C) of the gross mass of the solid constituent of modified polyolefin resin (A) and modified polyolefin resin (B) Quality/(quality of quality+modified polyolefin resin (B) of modified polyolefin resin (A))) be 0.5~5 (quality %) this The condition of range.In the case of less than 0.5 mass %, obtain electrolyte resistance deterioration as a result, more than 5 mass % when, initially Intensity and electrolyte resistance deterioration, can not solve the problem of the present invention.
As the curing agent of the present invention, particularly preferred epoxide.
For example, can enumerate ethylene glycol, propylene glycol, hexylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, The diglycidyl ether-type asphalt mixtures modified by epoxy resin of the polyalcohols such as pentaerythrite, glycerine, diglycerol, D-sorbite, spiral shell glycol or hydrogenated bisphenol A Fat.
In turn, the diglycidyl ether-type epoxy resins such as bisphenol-A, Bisphenol F, bisphenol S, bisphenol-A D can be enumerated；As phenol The aromatic epoxy resins such as the phenol aldehyde type epoxy resin of glycidol ether of phenolic resin, cresol novolac resin；Aromatic system is more The diglycidyl ether-type epoxy resin of the polyalcohols such as the ethylene oxide or propylene oxide adduct of hydroxy compounds.
In turn, the poly epihydric alcohol of the polyether polyol such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol can be enumerated Ether type epoxy；Bis- (3,4- epoxycyclohexyl-methyls) esters of adipic acid, 3,4- epoxycyclohexyl-methyls -3 ', 4 '-epoxy hexamethylenes The annular aliphatics type poly epoxy resin such as yl carboxylic acid ester.
In turn, tricarballylic acid, butane tetracarboxylic acid, adipic acid, phthalic acid, terephthalic acid (TPA) or inclined benzene three can be enumerated The poly glycidyl ester type epoxy resin of the polybasic carboxylic acids such as acid；Butadiene, hexadiene, octadiene, 12 carbon diene, ring pungent two The bifunctional epoxy resin of the hydrocarbon systems diene such as alkene, australene or vinylcyclohexene.
In turn, the epoxy resin of the diene polymers such as polybutadiene or polyisoprene can be enumerated；Or four glycidol The double aminomethyl cyclohexanes of base diaminodiphenyl-methane, four glycidyl group, diglycidylaniline or four glycidols The epoxy containing various heterocycles of the glycidyl amine type epoxy resins such as base m-xylene diamine or triazine or hydantoins etc Resin etc..
Among these substances, if using aromatic epoxy resins such as bisphenol A type epoxy resins, adaptation and corrosion resistance Well, therefore preferably.
As concrete example, as bisphenol A type epoxy resin, can enumerate DIC (strain) manufactures " EPICLON 850,860, 1050,1055,2055 ", " jER828,834,1001,1002,1004,1007 " etc. of Mitsubishi Chemical's (strain) manufacture.
Alternatively, it is also possible to be in 1 molecule in 2 or more epoxy groups and 1 molecule with 1 or more hydroxyl, Weight average molecular weight is epoxy resin of 3000 epoxides below as required ingredient.
As polyisocyanates, well known diisocyanate can be preferably used and derive obtained a variety ofization by them Close object.
For example, 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, phenylenedimethylidyne diisocyanate can be enumerated Ester, methyl diphenylene diisocyanate, isophorone diisocyanate, 1,5- naphthalene diisocyanates, hexa-methylene diisocyanate Ester, bis- (4- isocyanate cyclohexyls) diisocyanate such as methane or hydrogenated diphenyl methane diisocyanate and by they derive Isocyanuric acid ester body, adduction body, biuret form, two ketoboidies of urea, the allophanic acid of obtained compound, i.e. above-mentioned diisocyanate Ester body, prepolymer (oligomer obtained by diisocyanate and polyalcohol) with isocyanate residue or they answer Object etc. is closed, alternatively, it is also possible to use a part of isocyanate group of above-mentioned isocyanate compound to have with to isocyanate group Compound is as curing agent obtained by having reactive compound to react.
There is reactive compound as to isocyanate group, butylamine, hexylamine, octylame, 2 ethyl hexylamine, two can be enumerated The compounds containing amino such as butylamine, ethylenediamine, benzylamine, aniline；It is methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, hexanol, pungent The compounds containing hydroxyl such as alcohol, 2-Ethylhexyl Alcohol, dodecanol, ethylene glycol, propylene glycol, benzyl alcohol, phenol；Allyl contracts Water glycerin ether, 2- hexyl glycidyl ethers, phenyl glycidyl ether, neopentylglycol diglycidyl ether, 1,6-HD Glycidol ether, cyclohexanedimethanodiglycidyl diglycidyl ether etc. have the compounds of epoxy group；It is acetic acid, butyric acid, caproic acid, pungent The compound etc. containing carboxylic acid such as acid, succinic acid, adipic acid, decanedioic acid, phthalic acid.
As carbodiimide, N ,-two toluoyl base carbodiimides of N ', N, N '-diphenyl carbodiimide, N can be enumerated, - two -2,6- 3,5-dimethylphenyls carbodiimides of N ', N, bis- (2,6- diisopropyl phenyls) carbodiimides of N ' -, N, the N '-dioctyl last of the ten Heavenly stems Base carbodiimide, N- toluyls-N '-carbodicyclo hexylimide, N,-two -2,2- tert-butyl-phenyls carbodiimides of N ', N- toluene Acyl group-N '-phenyl carbodiimide, N ,-two p-aminophenyl carbodiimides of N ', N ,-two p-hydroxybenzene carbodiimides of N ', N, N '-dicyclohexylcarbodiimides, N ,-two toluoyl base carbodiimides of N ' etc..
Zuo Wei oxazolines can enumerate 2- oxazolines, 2- methyl -2- oxazolines, 2- phenyl -2- oxazolines, 2,5- dimethyl - 2- oxazolines, the mono- oxazoline compounds of 2,4- diphenyl -2- oxazoline Deng；2,2 '-(1,3- phenylenes) bis- (2- oxazolines), 2, 2 '-(1,2- ethylidene) bis- (2- oxazolines), 2,2 '-(1,4- butylidenes) bis- (2- oxazolines), 2,2 '-(1,4- phenylenes) are double (2- oxazolines) etc..
As amino resins, melmac, benzoguanamine resin, urea resin etc. can be enumerated.
(other additives)
In the present invention, as other additives, known usual thermoplastic elastomer (TPE), tackifier, catalysis can be used Agent, phosphate cpd, reactive elastomer or silane coupling agent.The content of these additives can not damage bonding of the present invention It suitably adjusts and uses in the range of the function of agent.
(laminated body)
The laminated body of the present invention be using the present invention lamination adhesive composite by the metal layers such as aluminium foil and polyethylene, One or more plastic layers in polyester such as the polyolefin sheets such as polypropylene, polyethylene terephthalate etc. be bonded and .
Also, the lamination adhesive composite of the present invention for example can form adhesive linkage in the following manner：Make it It is suitable in ester series solvent, ketone series solvent, aromatic hydrocarbon, aliphatic hydrocarbon, clicyclic hydrocarbon etc. with arbitrary ratio dissolution/dispersion Solvent or dispersant are coated on metal foil and drying using coating method well known to rolling method, gravure coating process, stick coating method etc..
The dry coating weight of the lamination adhesive composite of the present invention is preferably 0.5g/m2~20.0g/m2Range It is interior.Less than 0.5g/m2When, there are difficulty for the uniformity aspect of coating film thickness, on the other hand, are more than 20.0g/m2When, after coating Solvent removal also reduces, and operability significantly reduces, and leads to the problem of residual solvent.
By the way that after the lamination adhesive composite of the side of the above-mentioned metal foil coating present invention, superimposed plastic layer simultaneously leads to Dry lamination (dry type layered manner) is crossed to be bonded, to which the laminated body of the present invention can be obtained.It is preferred that the temperature of laminating roll is Room temperature~120 DEG C or so, pressure 3kg/cm2~300kg/cm2Left and right.
In addition, the laminated body of the present invention preferably carries out aging after manufacturing.The preferable temperature of aging condition is 25 DEG C~80 DEG C, the time be 12 hours~240 hours, generate adhesive strength during this period.
(secondary cell)
The laminated body of the present invention can be as one-shot battery or the electrolyte diaphragm seal or electrode portion protective film of secondary cell It uses, in this case, so that plastic layer side and polar organic solvent and/or salt etc. is contacted and use.Especially by making It is used in the state of being contacted with the nonaqueous electrolyte containing polar organic solvent and salt, can especially be used as nonaqueous electrolyte The secondary cell electrolyte diaphragm seal or electrode for secondary battery portion protective film of battery, solid state battery etc. suitably uses.The feelings Under condition, by being folded and being sealed in a manner of keeping plastic layer relative to each other, so as to be used with hermetic bag as battery. Since the heat sealability for the bonding agent being used in the present invention is excellent, the leakage of nonaqueous electrolyte can be prevented, it can conduct Battery and be used for a long time.
As above-mentioned polar organic solvent, polar solvent of aprotic, such as alkyl carbonate, ester, ketone etc. can be enumerated. Specifically, ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, methyl ethyl carbonate, carbonic acid two can be enumerated Ethyl ester, gamma-butyrolacton, 1,2- dimethoxy-ethanes, tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- dioxolanes, 4- methyl- 1,3- dioxolanes, methyl formate, formic acid 4- methyl-1,3-dioxies methyl esters, methyl acetate, methyl propionate etc..
As salt, the alkali metal salts such as lithium salts, sodium salt, sylvite can be enumerated.When for battery use, usually using LiPF6、 LiBF4, the lithium salts such as Li- acid imides.
Nonaqueous electrolyte is that above-mentioned alkali metal salt is dissolved in cyclic carbonate, chain carbonic acid with 0.5mmoL~3mmoL Obtained by the aprotic polars organic solvents such as ester, their mixture.
Even if the laminated body of the present invention is with above-mentioned polar solvent and/or salt, particularly as their mixture It is used in the state of nonaqueous electrolyte contact, the splitting of metal layer, adhesive linkage, plastic layer will not occur, it can be long-term Ground uses.
The battery of the present invention is protected with the battery electrolyte diaphragm seal or battery electrode portion formed by above-mentioned laminated body The battery of film.The battery of the present invention can prevent the leakage of nonaqueous electrolyte since splitting will not occur for above-mentioned film, Therefore it can steadily in the long term be used as battery.
As shown above, the metal layer of laminated body of the invention and the bonding force of plastic layer are excellent, also, for polarity The endurance of organic solvent or salt is excellent, and splitting will not occur with the contacts such as nonaqueous electrolyte.It therefore, will in this way Laminated body be used as the battery of battery electrolyte diaphragm seal or battery electrode portion protective film and close as secondary cell electrolyte The secondary cell of sealer or electrode for secondary battery portion protective film can use steadily in the long term.
Embodiment
Hereinafter, specifically describing the present invention by embodiment.It states " part " and indicates mass parts.
(embodiment 1)
100 parts of Hardren NS-2002,0.4 part of TOPAS5013S-04,0.01 part of Curezol1B2MZ, 0.01 part three Toluene is added in such a way that nonvolatile component reaches 20% simultaneously in Phenylphosphine, 0.2 part of FTR-8120,0.2 part of Epiclon N-695 It is sufficiently stirred, with bar coater, (dry type) is coated with 5g/m on aluminium foil2, after keeping it 1 minute dry at 80 DEG C, with 100 DEG C and CPP films (polyolefin film " ZK-93KM ", 70 μm (beautiful film processing (strain) systems in east)) are bonded, and coating material (laminated body 1) is made.Make the layer Stack 1 after aging 5 days, measures initial bond strenght at 70 DEG C.
(embodiment 2)~(embodiment 7)
Other than the composition proportion described in table 1, bonding agent is made similarly to Example 1.In turn, utilization and laminated body 1 same production method, makes the laminated body in each embodiment.
For the laminated body obtained in each case, evaluation adhesive property, electrolyte resistance (conservation rate), table 1 shows its knot Fruit.It should be noted that the condition respectively tested is as follows.
(measurement of initial bond strenght)
In the Tensilon experiments of A＆D corporations, sample is cut into 15mm wide, measures 180 ° of peel strength (N/ 15mm)。
(conservation rate of electrolyte resistance)
Make laminated body in electrolyte " ethylene carbonate:Methyl ethyl carbonate:Dimethyl carbonate=1:1:1 (wt%)+LiPF6： 1moL+ vinylene carbonates：It is impregnated 7 days with 85 DEG C in 1wt% ", the conservation rate by impregnating front and back adhesive strength is implemented as follows Evaluation.
○：60% or more, △：60%~50%, ×：50% or less
：It can not measure
[table 1]
Material name Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7
topAS 5013S-04 0.4 1.0 2.0 4.0
topAS 8007F-04 2.0
RT2304 0.5
RT2715 1.0
Hardren NS-2002 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Curezol 1B2MZ 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Triphenylphosphine 0.01 0.01 0.01 0.01 0.01 0.01 0.01
FTR-8120 0.2 0.2 0.2 0.2 0.2
Denacol EX-321 0.2
Epiclon N-695 0.2 0.2 0.2 0.2 0.2 0.2
Amorphism alkene containing ratio 2% 5% 9% 9% 17% 2% 5%
Initial bond strenght (N/ 15mm) 14.9 15.6 15.0 13.0 12.4 16.7 15.7
Electrolyte resistance ○ ○ ○ ○ ○ ○ ○
Hardren NS-2002 (corporation is spun by Japan) modified polyolefin resin nonvolatile component is that 20% fusing point is 69.7℃
TOPAS 5013S-04 (Polyplastics corporations) amorphous polyolefins resin nonvolatile component is 100% Tg is 134 DEG C
TOPAS 8007F-04 (Polyplastics corporations) amorphous polyolefins resin nonvolatile component is 100% Tg is 78 DEG C
RT2304 (REXtac, LLC corporation) amorphous polyolefins resin nonvolatile component is that 100%Tg is -29 DEG C
RT2715 (REXtac, LLC corporation) amorphous polyolefins resin nonvolatile component is that 100%Tg is -23 DEG C
Curezol 1B2MZ (Shikoku Chem's system) imidazoles nonvolatile component is 100%
FTR-8120 (Mitsui Chemicals, Inc.'s system) tackifier nonvolatile component is 100%
Denacol EX-321 (Nagase ChemteX Corporation systems) aliphatic epoxy resin
Epoxide equivalent is that 140 nonvolatile components are 100%
Epiclon N-695 (Dainippon Ink Chemicals's system) phenol aldehyde type epoxy resin
Epoxide equivalent is that 215 nonvolatile components are 100%
(comparative example 1)~(comparative example 5)
It is same as embodiment to make laminated body other than being coordinated as shown in table 2 as comparative example, use this Laminated body, evaluation initial bond strenght, electrolyte resistance (conservation rate).
Show the result in table 2.
[table 2]
Material name Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
5013S-04 0.0 0.0 5.0 20.0
RT2304 5.5
Hardren NS-2002 100.0 100.0 100.0 100.0
Curezol 1B2MZ 0.01 0.01 0.01 0.01
Triphenylphosphine 0.01 0.01 0.01 0.01 0.01
FTR-8120 0.2 0.2 0.2 0.2 0.2
Denacol EX-321 0.4
Epiclon N-695 0.2 0.2 0.2 0.2
Amorphism alkene containing ratio 0% 0% 20% 100% 22%
Initial bond strenght (N/15mm) 15.3 15.0 14.0 0.0 13.8
Electrolyte resistance × × × - ×
According to the above results：The adhesive composite of the present invention passes through the alkene piece low with polarity in metal layers such as aluminium foils It is used between material, excellent cementability is shown carrying out aging at low temperature.
In addition, in the case that the laminated body is used as secondary cell laminated body, for propene carbonate, ethylene carbonate Etc solvent, lithium hexafluoro phosphate etc electrolyte there is excellent patience interlayer does not also therefore occur as time goes by Stripping.
As can be known from the above results：The lamination for meeting the constitutive requirements of the present invention is the gold of laminated body with adhesive composite Belong to layer and plastic layer it is excellent in adhesion, have both low temperature reservation the high lamination of electrolyte resistance, its conservation rate with Nian Jie Agent composition.
Industrial availability
Electrolyte resistance is had both using lamination laminated body obtained by bonding agent of the present invention, as time goes by will not Splitting occurs, therefore can suitably be used as the laminated body of secondary cell.

Claims (6)

1. a kind of lamination adhesive composite containing modified polyolefin resin (A), amorphous polyolefins resin (B) and is consolidated Agent (C), wherein
The content of amorphous polyolefins resin (B) is relative to crystallinity modified polyolefin resin (A) and amorphous polyolefins resin (B) gross mass of solid constituent is 0.1 mass % less than 20 mass %.
2. lamination adhesive composite according to claim 1, wherein curing agent (C) include selected from epoxide, At least one or more in polyisocyanates, carbodiimide, oxazolines and amino resins.
3. lamination adhesive composite according to claim 2, wherein epoxide in 1 molecule have 2 with On epoxy group and be 3000 or less with 1 or more hydroxyl, weight average molecular weight in 1 molecule.
4. lamination adhesive composite described in any one of claim 1 to 3 is also added with thermoplastic elastic Body, tackifier, catalyst, phosphate cpd, reactive elastomer or silane coupling agent.
5. a kind of laminated body, with metal layer and polyolefin resin layer, wherein described in any one of Claims 1 to 44 Lamination use adhesive composite as the bonding agent of metal layer and polyolefin resin layer.
6. a kind of secondary cell uses the laminated body described in claim 5 as electrolyte diaphragm seal or electrode portion protective film.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113784839A (en) * 2019-04-26 2021-12-10 日东电工株式会社 Adhesive and adhesive tape
CN114156576A (en) * 2021-11-26 2022-03-08 江苏睿捷新材料科技有限公司 Outer packaging material for electrolyte-resistant lithium ion battery device and battery

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102647985B1 (en) * 2018-03-07 2024-03-15 도아고세이가부시키가이샤 Adhesive composition and laminate with adhesive layer using the same
JP7093533B2 (en) * 2018-06-04 2022-06-30 協立化学産業株式会社 A secondary battery comprising a heat-meltable adhesive composition, a method for manufacturing an electrode laminate, and an electrode laminate.
JP7310298B2 (en) * 2018-06-15 2023-07-19 Dic株式会社 Adhesives, laminates, packaging materials for batteries and batteries
TW202000835A (en) * 2018-06-15 2020-01-01 日商Ｄｉｃ股份有限公司 Adhesive, laminate, battery packaging material, battery container and battery suitable for adhesion between a metal substrate and a nonpolar substrate such as an olefin resin
JP7275774B2 (en) * 2019-04-02 2023-05-18 Dic株式会社 Adhesives, laminates, packaging materials for batteries and batteries
JP7188055B2 (en) * 2018-12-20 2022-12-13 Dic株式会社 Adhesives, laminates, battery members and batteries
CN116670227A (en) * 2021-02-08 2023-08-29 巴塞尔聚烯烃意大利有限公司 Polyolefin composition for functional films
WO2022179788A1 (en) * 2021-02-26 2022-09-01 Basell Polyolefine Gmbh Printing platform for extrusion additive manufacturing

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014238978A (en) * 2013-06-07 2014-12-18 大日本印刷株式会社 Packaging material for battery
CN105315934A (en) * 2014-08-01 2016-02-10 东洋油墨Sc控股株式会社 Adhesive composite, laminate body, electricity storage device packaging material, electricity storage device container, andelectricity storage device,
WO2016031342A1 (en) * 2014-08-27 2016-03-03 東洋紡株式会社 Low dielectric adhesive composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014238978A (en) * 2013-06-07 2014-12-18 大日本印刷株式会社 Packaging material for battery
CN105315934A (en) * 2014-08-01 2016-02-10 东洋油墨Sc控股株式会社 Adhesive composite, laminate body, electricity storage device packaging material, electricity storage device container, andelectricity storage device,
JP2016035035A (en) * 2014-08-01 2016-03-17 東洋インキＳｃホールディングス株式会社 Adhesive composition, laminate, packaging material for electricity storage device, container for electricity storage device, and electricity storage device
WO2016031342A1 (en) * 2014-08-27 2016-03-03 東洋紡株式会社 Low dielectric adhesive composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113784839A (en) * 2019-04-26 2021-12-10 日东电工株式会社 Adhesive and adhesive tape
CN114156576A (en) * 2021-11-26 2022-03-08 江苏睿捷新材料科技有限公司 Outer packaging material for electrolyte-resistant lithium ion battery device and battery
WO2023093072A1 (en) * 2021-11-26 2023-06-01 江苏睿捷新材料科技有限公司 Outer packaging material of electrolyte-resistant lithium ion battery device, and battery

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