CN108473836B - Adhesive composition for lamination, laminate, and secondary battery - Google Patents

Adhesive composition for lamination, laminate, and secondary battery Download PDF

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Publication number
CN108473836B
CN108473836B CN201780006157.7A CN201780006157A CN108473836B CN 108473836 B CN108473836 B CN 108473836B CN 201780006157 A CN201780006157 A CN 201780006157A CN 108473836 B CN108473836 B CN 108473836B
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Prior art keywords
polyolefin resin
laminate
adhesive composition
film
mass
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CN201780006157.7A
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CN108473836A (en
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中村英美
松尾高年
神山达哉
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DIC Corp
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DIC Corp
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    • 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)
  • Sealing Battery Cases Or Jackets (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Provided are an adhesive composition for a laminate, which has excellent adhesion between a metal layer and a plastic layer of the laminate, has electrolyte resistance even when cured at low temperatures, has a high retention rate, and does not undergo interlayer peeling with time, a method for producing the same, a laminate using the adhesive composition, and a secondary battery. An adhesive composition for lamination, comprising a modified polyolefin resin (A), an amorphous polyolefin resin (B) and a curing agent (C), wherein the content of the amorphous polyolefin resin (B) is 0.1 mass% or more and less than 20 mass% relative to the total mass of the solid contents of the modified polyolefin resin (A) and the amorphous polyolefin resin (B).

Description

Adhesive composition for lamination, laminate, and secondary battery
Technical Field
The invention relates to an adhesive composition for lamination, a laminate and a secondary battery.
Background
A secondary battery represented by a lithium ion battery is configured by a positive electrode, a negative electrode, and an electrolyte solution or the like sealed therebetween. As a sealing bag for sealing a lead for taking out electric power of the positive electrode and the negative electrode to the outside, a laminate obtained by bonding a metal foil such as an aluminum foil, a metal vapor-deposited layer, and plastic is used.
However, it is difficult to obtain electrolyte-insoluble electrolyte-resistant properties by curing at low temperatures in particular, and this has been a technical problem to be solved.
For example, patent document 1 proposes a sealing bag in which the innermost layer of the laminate is made of a maleic acid-modified polyolefin resin, and the heat seal portion is made of the same maleic acid-modified polyolefin resin, thereby improving the sealing reliability. Maleic acid-modified polyolefin resins are generally used as adhesive resins because they are excellent in adhesion to metals and heat sealability. However, when used as a sealing film for a battery as described above, the sealing film exhibits excellent adhesion immediately after lamination at high temperatures, but has low electrolyte resistance and causes interlayer peeling with time, and thus cannot be used as a sealing film.
Patent document 2 describes a laminate for a battery electrolyte sealing film or a laminate for a battery electrode section protective film, which comprises a metal layer, a surface treatment layer formed on the surface of the metal layer, and an adhesive resin layer formed on the surface treatment layer and made of polyolefin modified with a carboxylic acid group or a derivative thereof.
Patent document 3 describes an adhesive resin composition containing (a) a polyolefin resin having at least 1 functional group selected from an acid anhydride group, a carboxyl group and a carboxylic acid metal salt and (B) an epoxidized vegetable oil having 2 or more epoxy groups and a molecular weight of 3000 or less, wherein the amount of component (B) is 0.01 to 5 parts by mass per 100 parts by mass of component (a).
Patent document 4 describes a resin composition for a binder for a secondary battery electrode, which contains an acid-modified polyolefin resin (a) and a polyurethane resin (B), and is characterized in that the amount of (B) is 0.5 to 100 parts by mass per 100 parts by mass of (a).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 9-283101
Patent document 2: WO2001/017043 publication
Patent document 3: japanese laid-open patent publication No. H08-193148
Patent document 4: japanese patent laid-open publication No. 2010-277959
Disclosure of Invention
Problems to be solved by the invention
In the prior art, as an adhesive for a secondary battery laminate, a patent using a polyolefin resin containing an acid group in a large amount has been filed.
However, when only a polyolefin resin containing only an acid group is present, the adhesion to an olefin sheet is excellent due to high-temperature aging, extrusion lamination, and other steps, but the adhesion to a metal layer is insufficient. As a result, the adhesive strength as an adhesive for laminates is insufficient. Further, when used in a secondary battery, the electrolyte resistance is insufficient, and there is a problem that interlayer peeling or the like occurs with the passage of time.
Accordingly, an object of the present invention is to provide an adhesive composition for a laminate, which has excellent adhesion between a metal layer and a plastic layer of a laminate, has electrolyte resistance even when cured at low temperature, has a high retention rate, and does not cause interlayer peeling with time, a laminate obtained using the adhesive composition, and a secondary battery.
Means for solving the problems
The present inventors have conducted studies and as a result, have solved the above-mentioned problems by providing an adhesive composition for lamination comprising a modified polyolefin resin (A), an amorphous polyolefin resin (B) and a curing agent (C),
the content of the amorphous polyolefin resin (B) is 0.1 mass% or more and less than 20 mass% with respect to the total mass of the solid contents of the modified polyolefin resin (a) and the amorphous polyolefin resin (B).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide an adhesive composition for a laminate, which has excellent adhesion between a metal layer and a plastic layer of a laminate, has electrolyte resistance even when cured at low temperatures, has a high retention rate, and does not cause interlayer peeling with time, a laminate obtained using the adhesive composition, and a secondary battery.
Detailed Description
In order to solve the above problem, the present invention is constituted by the following items.
1. An adhesive composition for lamination comprising a modified polyolefin resin (A), an amorphous polyolefin resin (B) and a curing agent (C),
the content of the amorphous polyolefin resin (B) is 0.1 mass% or more and less than 20 mass% with respect to the total mass of the solid contents of the modified polyolefin resin (a) and the amorphous polyolefin resin (B);
2. the adhesive composition for lamination according to 1, wherein the curing agent (C) contains at least 1 or more selected from the group consisting of an epoxy compound, a polyisocyanate, a carbodiimide, an oxazoline and an amino resin;
3. the adhesive composition for lamination according to claim 2, wherein the epoxy compound has 2 or more epoxy groups in 1 molecule and 1 or more hydroxyl groups in 1 molecule, and has a weight average molecular weight of 3000 or less;
4. the adhesive composition for lamination according to any one of claims 1 to 3, further added with a thermoplastic elastomer, a tackifier, a catalyst, a phosphoric acid compound, a reactive elastomer, or a silane coupling agent;
5. a laminate comprising a metal layer and a polyolefin resin layer, wherein the adhesive composition for lamination according to any one of 1 to 4 is used as an adhesive for the metal layer and the polyolefin resin layer;
6. a secondary battery using the laminate as described in 5 as an electrolyte sealing film or an electrode portion protective film.
(modified polyolefin resin (A))
In the present invention, any polyolefin resin having crystallinity, which can solve the problems of the present invention, can be used without particular limitation.
In the present invention, a modified polyolefin resin obtained by introducing various functional groups (for example, carboxyl group, hydroxyl group, etc.) into a polyolefin resin is particularly preferable. Further, among these modified polyolefin resins, from the viewpoint of further improving the adhesion of the metal layer and excellent electrolyte resistance, a modified polyolefin resin having an acid value of 1mgKOH/g to 200mgKOH/g (hereinafter referred to as an acid-modified polyolefin resin) and/or a modified polyolefin resin having a hydroxyl value of 1mgKOH/g to 200mgKOH/g (hereinafter referred to as a hydroxyl-modified polyolefin resin) is more preferable.
The melting point is preferably 60 to 100 ℃.
The acid-modified polyolefin resin is a polyolefin resin having a carboxyl group or a carboxylic anhydride group in the molecule, and is synthesized by modifying a polyolefin with an unsaturated carboxylic acid or a derivative thereof. As a method for modifying the polymer, graft modification and copolymerization may be used.
The acid-modified polyolefin resin is a graft-modified polyolefin obtained by graft-modifying or copolymerizing at least 1 polymerizable ethylenically unsaturated carboxylic acid or a derivative thereof to a polyolefin resin before modification. The polyolefin resin before modification includes the above-mentioned polyolefin resins, and among them, homopolymers of propylene, copolymers of propylene and α -olefins, and the like are preferable. These can be used alone in 1 kind, also can be combined with more than 2 kinds.
Examples of the ethylenically unsaturated carboxylic acid or derivative thereof to be graft-modified or copolymerized with the polyolefin resin before modification include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohex-4-ene-1, 2-dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2, 3-dicarboxylic anhydride, 1,2,3,4,5,8,9, 10-octahydronaphthalene-2, 3-dicarboxylic anhydride, 2-oct-1, 3-diketospiro [4.4] non-7-ene, bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, methyl-bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylic anhydride, methyl-norborn-5-ene-2, 3-dicarboxylic anhydride, and the like. Maleic anhydride is preferably used. These may be used alone or in combination of 2 or more.
In order to graft a graft monomer selected from ethylenically unsaturated carboxylic acids or derivatives thereof to the polyolefin resin before modification, various methods can be employed. Examples thereof include a method in which a polyolefin resin is melted, and a graft monomer is added thereto to cause a graft reaction; a method in which a polyolefin resin is dissolved in a solvent to prepare a solution, and a graft monomer is added thereto to cause a graft reaction; a method in which a polyolefin resin dissolved in an organic solvent is mixed with the unsaturated carboxylic acid or the like, heated at a temperature not lower than the softening temperature or the melting point of the polyolefin resin, and subjected to radical polymerization and dehydrogenation simultaneously in a molten state. In any case, in order to graft-copolymerize the graft monomer efficiently, it is preferable to carry out the graft reaction in the presence of a radical initiator. The grafting reaction is generally carried out at a temperature of from 60 ℃ to 350 ℃. The amount of the radical initiator used is usually in the range of 0.001 to 1 part by mass per 100 parts by mass of the polyolefin resin before modification.
Examples of the modified polyolefin resin (a) of the present invention include copolymers of olefins having 2 to 8 carbon atoms, and copolymers of olefins having 2 to 8 carbon atoms and other monomers, which are modified as described above.
Specific examples thereof include α -olefin copolymers such as High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), polyethylene such as linear low density polyethylene resin, polypropylene, polyisobutylene, poly (1-butene), poly 4-methylpentene, polyvinylcyclohexane, polystyrene, poly (p-methylstyrene), poly (α -methylstyrene), ethylene-propylene block copolymers, ethylene-propylene random copolymers, ethylene-1-butene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-hexene copolymers and the like; ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-vinyl acetate-methyl methacrylate copolymers, ionomer resins, and the like. Further, chlorinated polyolefins obtained by chlorinating these polyolefins may be used.
Examples of the acid-modified polyolefin resin used in the present invention include maleic anhydride-modified polypropylene, ethylene- (meth) acrylic acid copolymer, ethylene-acrylic ester-maleic anhydride terpolymer, or ethylene-methacrylic ester-maleic anhydride terpolymer. Specifically, "Modic" manufactured by mitsubishi chemical corporation, "Admer" and "Unistole" manufactured by mitsubishi chemical corporation, "Toyotac" manufactured by donnakai chemical corporation, "Youmex" manufactured by sanyo chemical corporation, "Rexpearl EAA" and "Rexpearl ET" manufactured by japan polyethylene corporation, "Primacor" manufactured by dow chemical corporation, "dur Pont-MITSUI polychemics co., ltd.
The hydroxyl-modified polyolefin resin is a polyolefin resin having a hydroxyl group in the molecule, and is synthesized by graft-modifying or copolymerizing a polyolefin with a hydroxyl group-containing (meth) acrylate or a hydroxyl group-containing vinyl ether, which will be described later. The polyolefin resin before modification and the modification method are the same as in the case of the acid-modified polyolefin resin.
Examples of the hydroxyl group-containing (meth) acrylate include hydroxyethyl (meth) acrylate; hydroxypropyl (meth) acrylate, glycerol (meth) acrylate; lactone-modified hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and the like, and examples of the hydroxyl-containing vinyl ether include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether.
(amorphous polyolefin resin (B))
In the present invention, an amorphous polyolefin resin may be used without particular limitation as long as the object of the present invention can be achieved.
The olefin resin is preferably amorphous, and specific examples thereof include polyolefin resins such as APEL (cyclic olefin copolymer/mitsui chemical), TOPAS (cyclic olefin copolymer/polyplastic), Zeonor (cyclic olefin copolymer/Zeon Corporation), ARTON (cyclic olefin copolymer/JSR), Asahimelt (amorphous poly a-olefin/asahi chemical), and RT (amorphous poly a-olefin/KF Chemicals).
The adhesive of the present invention may use a radical initiator, and a preferable initiator includes, but is not limited to, an imidazole-based radical initiator.
Examples thereof include triphenylphosphine, 1, 8-diazabicyclo (5.4.0) undecene-7 (DBU) -phenoxide, and DBU-octanoate.
(curing agent (C))
Examples of the curing agent (C) used in the present invention include curing agents selected from epoxy compounds, polyisocyanates, carbodiimides, oxazolines, and melamine resins. The preferable content of the curing agent is a content satisfying a condition that the mass% of the curing agent (C) with respect to the total mass of the solid components of the modified polyolefin resin (a) and the modified polyolefin resin (B) (mass of the curing agent (C/(mass of the modified polyolefin resin (a) + mass of the modified polyolefin resin (B)) is 0.5 to 5 (mass%). When the amount is less than 0.5% by mass, the result of deterioration in electrolyte resistance is obtained, and when the amount is more than 5% by mass, the initial strength and electrolyte resistance deteriorate, and the problem of the present invention cannot be solved.
As the curing agent of the present invention, an epoxy compound is particularly preferable.
Examples thereof include diglycidyl ether type epoxy resins of polyhydric alcohols such as ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, diglycerol, sorbitol, spiroglycol, and hydrogenated bisphenol A.
Further, diglycidyl ether type epoxy resins such as bisphenol a, bisphenol F, bisphenol S, bisphenol AD, and the like; aromatic epoxy resins such as novolac epoxy resins which are glycidyl ethers of phenol novolac resins and cresol novolac resins; diglycidyl ether type epoxy resins of polyhydric alcohols such as ethylene oxide or propylene oxide adducts of aromatic polyhydroxy compounds.
Further, there may be mentioned polyglycidyl ether type epoxy resins of polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; and cyclic aliphatic polyepoxy resins such as bis (3, 4-epoxycyclohexylmethyl) adipate and 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexylcarboxylate.
Further, there may be mentioned polyglycidyl ester type epoxy resins of polycarboxylic acids such as propane tricarboxylic acid, butane tetracarboxylic acid, adipic acid, phthalic acid, terephthalic acid and trimellitic acid; a diepoxy resin of a hydrocarbon diene such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α -pinene or vinylcyclohexene.
Further, examples thereof include epoxy resins of diene polymers such as polybutadiene and polyisoprene; or glycidyl amine type epoxy resins such as tetraglycidyl diaminodiphenylmethane, tetraglycidyl bisaminomethylcyclohexane, diglycidyl aniline, and tetraglycidyl m-xylylenediamine, and epoxy resins containing various heterocycles such as triazine and hydantoin, and the like.
Among these, aromatic epoxy resins such as bisphenol a epoxy resins are preferably used because they have good adhesion and corrosion resistance.
Specific examples of the bisphenol a epoxy resin include "EPICLON 850, 860, 1050, 1055, 2055" manufactured by DIC corporation and "jER 828, 834, 1001, 1002, 1004, 1007" manufactured by mitsubishi chemical corporation.
The epoxy resin may contain, as an essential component, an epoxy compound having 2 or more epoxy groups in 1 molecule and 1 or more hydroxyl groups in 1 molecule, and having a weight average molecular weight of 3000 or less.
As the polyisocyanate, known diisocyanates and various compounds derived therefrom can be preferably used.
Examples thereof include diisocyanates such as 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate, bis (4-isocyanatocyclohexyl) methane or hydrogenated diphenylmethane diisocyanate, and compounds derived therefrom, i.e., isocyanurate bodies, adduct bodies, biuret types, urea-diisocyanate bodies, allophanate bodies of the above diisocyanates, prepolymers having an isocyanate residue (oligomers obtained from a diisocyanate and a polyol), or composites thereof, in addition, a compound obtained by reacting a part of the isocyanate groups of the isocyanate compound with a compound reactive to isocyanate groups may be used as the curing agent.
Examples of the compound having reactivity with an isocyanate group include amino group-containing compounds such as butylamine, hexylamine, octylamine, 2-ethylhexylamine, dibutylamine, ethylenediamine, benzylamine, and aniline; hydroxyl group-containing compounds such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, octanol, 2-ethylhexanol, dodecanol, ethylene glycol, propylene glycol, benzyl alcohol, and phenol; compounds having an epoxy group such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol glycidyl ether, and cyclohexanedimethanol diglycidyl ether; and carboxylic acid-containing compounds such as acetic acid, butyric acid, caproic acid, caprylic acid, succinic acid, adipic acid, sebacic acid, and phthalic acid.
Examples of the carbodiimide include N, N '-di-o-toluoyl carbodiimide, N' -diphenyl carbodiimide, N '-di-2, 6-dimethylphenyl carbodiimide, N' -bis (2, 6-diisopropylphenyl) carbodiimide, N '-dioctyldecyl carbodiimide, N-toluoyl-N' -cyclohexyl carbodiimide, n, N '-di-2, 2-tert-butylphenyl carbodiimide, N-toluoyl-N' -phenylcarbodiimide, N '-di-p-aminophenylcarbodiimide, N' -di-p-hydroxyphenylcarbodiimide, N '-dicyclohexylcarbodiimide, N' -di-p-toluoyl-carbodiimide, and the like.
Examples of the oxazoline include monooxazoline compounds such as 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2, 5-dimethyl-2-oxazoline, and 2, 4-diphenyl-2-oxazoline; 2,2 '- (1, 3-phenylene) bis (2-oxazoline), 2' - (1, 2-ethylene) bis (2-oxazoline), 2 '- (1, 4-butylene) bis (2-oxazoline), 2' - (1, 4-phenylene) bis (2-oxazoline), and the like.
Examples of the amino resin include melamine resin, benzoguanamine resin, and urea resin.
(other additives)
In the present invention, as other additives, known and conventional thermoplastic elastomers, tackifiers, catalysts, phosphoric acid compounds, reactive elastomers, or silane coupling agents can be used. The content of these additives may be appropriately adjusted and used within a range not to impair the function of the adhesive of the present invention.
(laminated body)
The laminate of the present invention is obtained by bonding a metal layer such as an aluminum foil to 1 or more plastic layers of a polyolefin sheet such as polyethylene or polypropylene, or a polyester such as polyethylene terephthalate, using the adhesive composition for lamination of the present invention.
The adhesive composition for lamination of the present invention can form an adhesive layer, for example, by: the metal foil is dissolved/dispersed in an appropriate solvent or dispersant such as an ester-based solvent, a ketone-based solvent, an aromatic hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon or the like at an arbitrary ratio, and is applied to the metal foil by a known coating method such as a roll coating method, a gravure coating method, a bar coating method or the like and dried.
The dry coating weight of the adhesive composition for lamination of the present invention is preferably 0.5g/m2～20.0g/m2Within the range of (1). Less than 0.5g/m2In this case, the coating film thickness is difficult to be uniform, and on the other hand, the coating film thickness is more than 20.0g/m2In the case, the solvent removability after coating is also lowered, the workability is remarkably lowered, and a problem of residual solvent is caused.
The laminate of the present invention can be obtained by applying the adhesive composition for lamination of the present invention to one side of the metal foil, and then laminating the metal foil with the plastic layer by dry lamination (dry lamination method). Preferably, the temperature of the laminating roller is about room temperature to 120 ℃, and the pressure is 3kg/cm2～300kg/cm2Left and right.
The laminate of the present invention is preferably aged after production. The preferred temperature of the aging conditions is 25 ℃ to 80 ℃ and the time is 12 hours to 240 hours, during which the adhesive strength is developed.
(Secondary Battery)
The laminate of the present invention can be used as an electrolyte sealing film or an electrode portion protective film for a primary battery or a secondary battery, and 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, the film can be suitably used as a secondary battery electrolyte sealing film or a secondary battery electrode protective film of a nonaqueous electrolyte battery, a solid battery, or the like by being used in a state of being in contact with a nonaqueous electrolyte containing a polar organic solvent and a salt. In this case, the plastic layers are folded so as to face each other and heat-sealed, whereby the battery can be used as a sealing bag. Since the adhesive used in the present invention has excellent heat sealability, leakage of the nonaqueous electrolyte can be prevented, and the battery can be used for a long period of time.
Examples of the polar organic solvent include aprotic polar solvents such as alkyl carbonates, esters, and ketones. Specific examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, γ -butyrolactone, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, methyl formate, 4-methyl-1, 3-dioxolane, 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 battery applications, LiPF is generally used6、LiBF4Lithium salts such as Li-imide.
The nonaqueous electrolyte is obtained by dissolving the alkali metal salt in an aprotic polar organic solvent such as a cyclic carbonate, a chain carbonate, or a mixture thereof at 0.5 to 3 mmoL.
The laminate of the present invention can be used for a long period of time without causing delamination of the metal layer, the adhesive layer, and the plastic layer even when used in a state in which the laminate is in contact with the polar solvent and/or the salt, particularly the nonaqueous electrolyte which is a mixture thereof.
The battery of the present invention is a battery having a battery electrolyte sealing film or a battery electrode protective film formed of the above laminate. 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 interlayer peeling and leakage of the nonaqueous electrolyte can be prevented.
As described above, the laminate of the present invention has excellent adhesion between the metal layer and the plastic layer, excellent durability against polar organic solvents or salts, and no interlayer peeling even when in contact with a nonaqueous electrolyte or the like. Therefore, a battery using such a laminate as a battery electrolyte sealing film or a battery electrode portion protective film, and a secondary battery using such a laminate as a secondary battery electrolyte sealing film or a secondary battery electrode portion protective film can be stably used for a long period of time.
Examples
The present invention will be described in detail with reference to examples. The expression "parts" means parts by mass.
(example 1)
To 100 parts of Hardren NS-2002, 0.4 part of TOPAS5013S-04, 0.01 part of Curezol1B2MZ, 0.01 part of triphenylphosphine, 0.2 part of FTR-8120, 0.2 part of Epiclon N-695 was added toluene so that the nonvolatile content became 20%, followed by thoroughly stirring, and (dry) coating 5g/m on an aluminum foil with a bar coater2After drying at 80 ℃ for 1 minute, the film was laminated to a CPP film (polyolefin film "ZK-93 KM", 70 μm, manufactured by Toray film Co., Ltd.) at 100 ℃ to prepare a coated article (laminate 1). The laminate 1 was aged at 70 ℃ for 5 days, and then the initial adhesive strength was measured.
(example 2) to (example 7)
Adhesives were prepared in the same manner as in example 1, except for the component ratios shown in table 1. Further, the laminate in each example was produced by the same production method as that of the laminate 1.
The laminates obtained in the respective examples were evaluated for adhesive performance and electrolyte resistance (retention rate), and the results are shown in table 1. The conditions of each test are as follows.
(measurement of initial adhesion Strength)
In the Tensilon test manufactured by A & D, a test piece was cut into a width of 15mm, and the 180 DEG peel strength (N/15mm) was measured.
(maintenance ratio of electrolyte resistance)
The laminate was placed in an electrolyte solution of 1:1:1 (wt%) of ethylene carbonate, ethylmethyl carbonate and dimethyl carbonate + LiPF6: 1moL + vinylene carbonate: 1 wt% "was immersed at 85 ℃ for 7 days, and the adhesion strength retention before and after immersion was evaluated as follows.
O: more than 60%, and Δ: 60% -50% and x: less than 50%
-: cannot measure
[ Table 1]
Name of raw materials Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 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
Content of non-crystalline olefin 2％ 5％ 9％ 9％ 17％ 2％ 5％
Initial adhesion Strength (N/15mm) 14.9 15.6 15.0 13.0 12.4 16.7 15.7
Resistance to electrolyte solution ○ ○ ○ ○ ○ ○ ○
Hardren NS-2002 (manufactured by Toyo Boseki Co.) modified polyolefin resin having a 20% melting point of 69.7 ℃ C. as a nonvolatile component
TOPAS5013S-04 (manufactured by Polyplastic Inc.) amorphous polyolefin resin having 100% Tg of 134 ℃ non-volatile fraction
TOPAS 8007F-04 (manufactured by Polyplastic Inc.) amorphous polyolefin resin with 100% Tg of 78 ℃ non-volatile component
RT2304(REXtac, manufactured by LLC) amorphous polyolefin resin having 100% Tg of-29 ℃ as non-volatile component
RT2715(REXtac, manufactured by LLC) amorphous polyolefin resin has a 100% Tg of-23 ℃ non-volatile fraction
Curezol1B2MZ (product of Sizhou Kagaku Co., Ltd.) having an imidazole nonvolatile content of 100%
FTR-8120 (manufactured by Mitsui chemical Co., Ltd.) tackifier non-volatile component 100%
Denacol EX-321 (manufactured by Nagase ChemteX Corporation) aliphatic epoxy resin
The epoxy equivalent is 140% of the nonvolatile components and is 100%
Epiclon N-695 (available from DIC Co., Ltd.) phenol novolac epoxy resin
The epoxy equivalent is 100 percent of the nonvolatile components of 215 percent
Comparative examples 1 to 5
As comparative examples, laminates were produced in the same manner as in examples except that the components were blended as shown in table 2, and the initial adhesive strength and electrolyte resistance (retention ratio) were evaluated using the laminates.
The results are shown in Table 2.
[ Table 2]
Name of raw materials 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
Content of non-crystalline olefin 0％ 0％ 20％ 100％ 22％
Initial adhesion Strength (N/15mm) 15.3 15.0 14.0 0.0 13.8
Resistance to electrolyte solution × × × - ×
According to the above results: the adhesive composition of the present invention exhibits excellent adhesion even when aged at low temperatures by being used between a metal layer such as an aluminum foil and an olefin sheet having low polarity.
When the laminate is used as a laminate for a secondary battery, the laminate does not undergo interlayer peeling with the passage of time because the laminate has excellent resistance to solvents such as propylene carbonate and ethylene carbonate, and electrolytes such as lithium hexafluorophosphate.
From the above results, it is clear that: the laminating adhesive composition satisfying the requirements of the present invention is a laminating adhesive composition having excellent adhesion between the metal layer and the plastic layer of the laminate, and also having electrolyte resistance and high retention rate even when cured at low temperature.
Industrial applicability
The laminate obtained using the laminating adhesive of the present invention has electrolyte resistance and is free from delamination with time, and therefore can be suitably used as a laminate for a secondary battery.

Claims (6)

1. A film which is an electrolyte sealing film or an electrode portion protective film for a battery and which comprises a laminate obtained by laminating a metal layer and a polyolefin resin layer using an adhesive composition for lamination comprising a crystalline modified polyolefin resin (A), an amorphous polyolefin resin (B) and a curing agent (C),
the content of the amorphous polyolefin resin (B) is 0.1 mass% or more and 9 mass% or less with respect to the total mass of the solid components of the crystalline modified polyolefin resin (a) and the amorphous polyolefin resin (B).
2. The film according to claim 1, wherein the curing agent (C) comprises at least 1 selected from epoxy compounds, polyisocyanates, carbodiimides, oxazolines, and amino resins.
3. The film according to claim 2, wherein the epoxy compound has 2 or more epoxy groups in 1 molecule and 1 or more hydroxyl groups in 1 molecule, and has a weight average molecular weight of 3000 or less.
4. The film according to claim 1, wherein at least 1 selected from the group consisting of a thermoplastic elastomer, a tackifier, a catalyst, a phosphoric acid compound, a reactive elastomer, and a silane coupling agent is further added to the adhesive composition for lamination.
5. The film according to any one of claims 1 to 4, wherein the metal layer is an aluminum foil and the polyolefin resin layer is a polypropylene film.
6. A secondary battery using the film according to any one of claims 1 to 5 as an electrolyte sealing film or an electrode portion protective film.
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US20240052148A1 (en) * 2021-02-08 2024-02-15 Basell Poliolefine Italia S.R.L. Polyolefin composition for functional films
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