CN111133075B - Adhesive, laminate, member for battery, and battery - Google Patents
Adhesive, laminate, member for battery, and battery Download PDFInfo
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- CN111133075B CN111133075B CN201880060977.9A CN201880060977A CN111133075B CN 111133075 B CN111133075 B CN 111133075B CN 201880060977 A CN201880060977 A CN 201880060977A CN 111133075 B CN111133075 B CN 111133075B
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- resin
- adhesive
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- acid
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Classifications
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- 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 of a single cell or a single battery
- H01M50/102—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
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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
- B32B15/092—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
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- 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 of a single cell or a single battery
- 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 of a single cell or a single battery
- 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
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- 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
Abstract
The invention provides an adhesive, which is characterized by comprising an acid group-containing resin and an epoxy compound A, wherein the epoxy compound A contains an aromatic ring, an alkylene chain with 4-10 carbon atoms and more than two epoxy groups. In addition, the adhesive in which the acid group-containing resin is an acid group-containing polyacrylate resin, an acid group-containing polyurethane resin, and/or an acid group-containing polyolefin resin is provided. The present invention also provides a laminate using the adhesive, a battery member containing the laminate, and a battery having the battery member.
Description
Technical Field
The invention relates to an adhesive, a laminate, and a battery member.
Background
A battery represented by a secondary battery such as a lithium ion battery has a positive electrode, a negative electrode, and an electrolyte solution and the like sealed therebetween. As a sealing bag for sealing a lead for taking out electricity from the positive electrode and the negative electrode to the outside, a laminate obtained by bonding a metal foil such as an aluminum foil or a metal vapor-deposited layer to plastic is used.
For example, patent document 1 proposes an enclosing bag in which the innermost layer of the laminate is formed of a maleic acid-modified polyolefin resin, and the heat seal portion is formed 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 temperature, 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: the adhesive resin layer 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 containing polyolefin modified by carboxylic acid groups or derivatives thereof.
Patent document 3 describes an adhesive resin composition containing: 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 carboxylate salt; and an epoxidized vegetable oil having two or more epoxy groups and a molecular weight of 3000 or less, wherein the amount of the epoxidized vegetable oil component blended is 0.01 to 5 parts by mass per 100 parts by mass of the polyolefin component.
Patent document 4 describes a resin composition for a binder for secondary battery electrodes, which contains an acid-modified polyolefin resin and a polyurethane resin, and is characterized in that the polyurethane resin is contained in an amount of 0.5 to 100 parts by mass per 100 parts by mass of the polyolefin resin.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. H09-283101
Patent document 2: WO2007/017043 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
The present invention addresses the problem of providing an adhesive that has excellent adhesive strength and also has excellent electrolyte resistance. Also provided are a laminate using the adhesive, a battery member containing the laminate, and a battery having the battery member.
Means for solving the problems
The present inventors have made extensive studies and, as a result, have found that: the above object can be achieved by an adhesive containing an acid group-containing resin and an epoxy resin having a specific structure.
ADVANTAGEOUS EFFECTS OF INVENTION
That is, the present invention provides an adhesive comprising: 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.
Further, a laminate is provided, which is characterized in that the adhesive layer is provided in the intermediate layer.
Further, a battery member is provided with the laminate.
Detailed Description
< resins containing acid groups >
The adhesive of the present invention is characterized by comprising: 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. Examples of the acid group include a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, and a phosphoric acid group. The acid group-containing resin is preferably one having an acid value of 1mgKOH/g to 200mgKOH/g, since adhesion to a metal is improved. Particularly preferably 5mgK OH/g to 165 mgKOH/g. When the content is 200mgKOH/g or less, the flexibility is excellent and the adhesive strength is high, and when the content is 1mgKOH/g or more, the heat resistance is good.
(method of measuring acid value)
The acid number refers to the number of milligrams (mg) of potassium hydroxide required to neutralize the acid content present in sample 1 g. Specifically, the measurement can be carried out by dissolving a weighed sample in a solvent having a volume ratio of toluene/methanol of 70/30, dropping a 1% phenolphthalein alcohol solution in a few drops in advance, dropping a 0.1mol/L potassium hydroxide alcohol solution in the solution, and confirming the color change point, and the measurement can be obtained by the following calculation formula.
Acid value measurement method-1
Acid value (mgKOH/g) ((V.times.FX5.61)/S)
V: amount of 0.1mol/L Potassium hydroxide solution used (mL)
F: titre of 0.1mol/L KOH alcoholic solution
S: sample Collection volume (g)
5.61: potassium hydroxide equivalent (mg) in 0.1mol/L Potassium hydroxide solution 1mL
When the sample is a resin solution, the resin acid value (mgKOH/g) can be determined by the following calculation formula.
Resin acid value (mgKOH/g) ═ acid value of resin solution (mgKOH/g)/NV (%) × 100
NV: non-volatile component (%)
In addition, when the solubility of the sample in an organic solvent is low and the measurement is difficult due to precipitation or the like, the acid value can be measured by the following method.
Acid value measuring method-2
So-called acid value (mgKOH/g-resin)The values refer to a coefficient (f) obtained from a calibration curve prepared from a chloroform solution using maleic anhydride by FT-IR (FT-IR 4200, manufactured by JEOL Ltd.), and a sub-condensation peak of anhydrous ring of maleic anhydride in a maleic anhydride-modified polyolefin solution (1780 cm)-1) Absorbance of (1) and a methylene condensation peak of a carbonyl group of maleic acid (1720 cm)-1) The absorbance (II) of (2) is calculated by the following formula.
Acid value (mgKOH/g-resin) [ (absorbance (I) × (f) × 2 × molecular weight of potassium hydroxide × 1000(mg) + absorbance (II) × (f) × molecular weight of potassium hydroxide × 1000 (mg))/molecular weight of maleic anhydride ]
Molecular weight of maleic anhydride: 98.06, molecular weight of potassium hydroxide: 56.11
The acid group-containing resin is not particularly limited in resin skeleton, and preferable resins include an acid group-containing polyacrylate resin, an acid group-containing polyurethane resin, and/or an acid group-containing polyolefin resin.
(polyacrylate resin having acid group)
Examples of the acid group-containing polyacrylate resin include copolymers of polymerizable monomers having a (meth) acryloyl group and a carboxyl group. Specifically, examples of the polymerizable monomer having a (meth) acryloyl group and a carboxyl group include: (meth) acrylic acid; unsaturated monocarboxylic acids having an ester bond such as β -carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate and lactone-modified products thereof; maleic acid, and the like.
Examples of the other polymerizable unsaturated monomer to be polymerized with the monomer having a (meth) acryloyl group and a carboxyl group as required include the following polymerizable monomers.
Examples thereof include: (1) (meth) acrylate esters having an alkyl group having 1 to 22 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, and behenyl (meth) acrylate;
(2) (meth) acrylates having an aliphatic alkyl group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate;
(3) (meth) acrylates having an aromatic ring such as benzoyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiglycol (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate;
(4) hydroxyethyl (meth) acrylate; hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate; acrylic esters having a hydroxyalkyl group such as (meth) acrylic esters having a polyalkylene glycol group, such as lactone-modified hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate;
(5) unsaturated dicarboxylic acid esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate, and methyl ethyl itaconate;
(6) styrene derivatives such as styrene, alpha-methylstyrene and chlorostyrene;
(7) diene compounds such as butadiene, isoprene, piperylene and dimethylbutadiene;
(8) vinyl halides such as vinyl chloride and vinyl bromide, and vinylidene halides;
(9) unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone;
(10) vinyl esters such as vinyl acetate and vinyl butyrate;
(11) vinyl ethers such as methyl vinyl ether and butyl vinyl ether;
(12) vinyl cyanides such as acrylonitrile, methacrylonitrile, and vinylidene cyanide;
(13) acrylamide, alkyd-substituted amides thereof;
(14) n-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
(15) fluorine-containing α -olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; or (per) fluoroalkyl-perfluorovinyl ethers having 1 to 18 carbon atoms of (per) fluoroalkyl groups such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether; fluorine-containing ethylenically unsaturated monomers such as (per) fluoroalkyl (meth) acrylates having 1 to 18 carbon atoms in (per) fluoroalkyl groups, such as 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 2H-heptadecafluorodecyl (meth) acrylate, or perfluoroethyloxyethyl (meth) acrylate;
(16) silyl group-containing (meth) acrylates such as γ -methacryloxypropyltrimethoxysilane;
(17) n, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, or N, N-diethylaminopropyl (meth) acrylate.
The other polymerizable unsaturated monomers used in the preparation of these acid group-containing polyacrylates may be used alone or in combination of two or more.
The acid group-containing polyacrylate can be obtained by polymerizing (copolymerizing) the above-mentioned acid group-containing polyacrylate by a known and conventional method, and the copolymerization form thereof is not particularly limited. The copolymer may 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. In addition, the copolymerization method may be a known polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method.
(acid group-containing polyurethane resin)
Examples of the acid group-containing polyurethane resin include resins obtained by reacting a compound B represented by the following formula (1) with a compound C represented by the following formula (2).
[ solution 1]
(in the formula (1), X1Each of n1 and n2 independently represents an integer of 0 to 3. )
[ solution 2]
(in the formula (2), R1Represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms or a carbonyl group, and m1 to m3 each independently represents an integer of 0 to 3. )
< Compound B >
The compound B is a compound having an isocyanate group represented by the above formula (1). In the compound B, X1Represents an aromatic ring or an alicyclic ring structure.
The aromatic ring structure is preferably an aromatic ring having 6 to 18 carbon atoms, and examples thereof include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. The aromatic ring may be substituted with at least one fluorine atom, and examples of the aromatic ring substituted with at least one fluorine atom include perfluorophenyl groups and the like.
The alicyclic structure is preferably an alicyclic ring having 3 to 20 carbon atoms, and may be a single ring or a condensed ring. As the monocyclic ring, cycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane and the like. Examples of monocyclic cycloalkenes include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclooctene. Examples of the condensed ring include bicycloundecane, decahydronaphthalene, norbornene, norbornadiene, and the like.
Examples of the polycyclic compounds include cubane, tropane and atriane.
Further, the ring structure may be a combination of an aromatic ring and an alicyclic ring.
In the compound B, X1Preferably a benzene ring or a naphthalene ring.
Preferably, n1 and n2 are each independently 0 to 1.
Further preferable structures of the compound B include the following structures.
[ solution 3]
[ solution 4]
[ solution 5]
[ solution 6]
[ solution 7]
< Compound C >
The compound B is a diol compound having a carboxyl group represented by the above formula (2).
As the compound C, a compound wherein m3 is 0 is preferable, and R is more preferable1In the case of a C1-3 hydrocarbon group.
Further preferable structures of the compound C include dimethylolpropionic acid and dimethylolbutyric acid.
(polyolefin resin having acid group)
Specific examples of the skeleton of the acid group-containing polyolefin resin include: polyethylene such as High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), and linear low density polyethylene resin, polypropylene, polyisobutylene, poly (1-butene), poly (4-methylpentene), polyvinylcyclohexane, polystyrene, poly (p-methylstyrene), poly (alpha-methylstyrene), ethylene-propylene block copolymers, ethylene-propylene random copolymers, ethylene-butene-1 copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-hexene copolymers and other α -olefin copolymers, 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 also be used.
For introducing an acid group into the resin, a known and conventional method may be used. The resin may be synthesized by polymerizing the acid group-containing monomer, or the acid group may be added to the resin later. The polyolefin is preferably synthesized by modifying a polyolefin with an unsaturated carboxylic acid or a derivative thereof. As the modification method, graft modification or copolymerization may be used.
The preferred acid-modified polyolefin resin is a graft-modified polyolefin obtained by graft-modifying or copolymerizing at least one polymerizable ethylenically unsaturated carboxylic acid or a derivative thereof with a polyolefin resin before modification. The polyolefin resin before modification includes the above-mentioned polyolefin resins, and among them, a homopolymer of propylene, a copolymer of propylene and an α -olefin, and the like are preferable. These may be used alone or in combination of two or more.
Examples of the ethylenically unsaturated carboxylic acid or derivative thereof graft-modified or copolymerized to 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] keto-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, methyl-cyclohex-4-ene-1, 2-dicarboxylic anhydride, 3-dicarboxylic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyl-bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylic anhydride, norborn-5-ene-2, 3-dicarboxylic anhydride, and the like. Maleic anhydride is preferably used. These may be used alone or in combination of two 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 of melting a polyolefin resin and adding a graft monomer thereto to perform 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 perform a graft reaction; a method of mixing a polyolefin resin dissolved in an organic solvent with the unsaturated carboxylic acid or the like, and heating the mixture at a temperature not lower than the softening temperature or the melting point of the polyolefin resin to simultaneously perform radical polymerization and dehydrogenation in a molten state. In either case, the graft copolymerization is preferably carried out in the presence of a radical initiator in order to efficiently graft-copolymerize the graft monomer. 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 weight based on 100 parts by weight of the polyolefin resin before modification.
Examples of the acid-modified polyolefin resin include: maleic anhydride modified polypropylene, ethylene- (meth) acrylic acid copolymer, ethylene-acrylate-maleic anhydride terpolymer, or ethylene-methacrylate-maleic anhydride terpolymer. Specifically, "Madisch (MODIC)" manufactured by mitsubishi chemical corporation, "ADMER (ADMER)" manufactured by mitsubishi chemical corporation, "UNISTOLE", "TOYO (TAC)" manufactured by donyan spinning corporation, "UMEX (UMEX) manufactured by mitsui chemical corporation," REXPEARL (REXPEARL) EAA "," REXPEARL (REXPEARL) ET "manufactured by japan polyethylene corporation," Primmacmak (PRIMACOR) "manufactured by dow chemical corporation," nikkell (crenul) "manufactured by dupont chemical corporation, and" BONDINE (BONDINE) "manufactured by ARKEMA (ARKEMA) are commercially available.
(other resins containing acid groups)
Examples of the acid-containing elastomer include taftatai (Tuftec) M series manufactured by asahi chemicals co, Kraton polymers (Japan) and Kraton FG series manufactured by Japan polymers corporation.
< 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 also contains an epoxy compound A containing an aromatic ring, an alkylene chain having 4 to 10 carbon atoms, and two or more epoxy groups.
Examples of the aromatic ring include: benzene ring optionally having a substituent, naphthalene ring optionally having a substituent, bisphenol structure optionally having a substituent, biphenyl structure optionally having a substituent and the like, for example, there can be mentioned: phenylene group, 4 '-biphenylene group, 2', 6, 6 '-tetramethyl-4, 4' -biphenylene group, methylenediphenylene group, 2-propane-diphenyl group, 1, 6-naphthyl group, 2, 7-naphthyl group, 1, 4-naphthyl group, 1, 5-naphthyl group, 2, 3-naphthyl group, a group represented by the following structural formula, and the like each having a bonding site at the o-, m-, and p-positions,
[ solution 8]
From the viewpoint of excellent balance between flexibility and toughness of the obtained cured product, methylene diphenylene and 2, 2-propane-diphenyl are preferable.
Specifically, the epoxy compound a is preferably an epoxy compound (a1) represented by the following formula (8).
[ solution 9]
(wherein Ar is1、Ar2、Ar3、Ar4Is optionally the same or different aromatic ring optionally having a substituent, X1、X2Is an aliphatic hydrocarbon radical, R1、R2、R3Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p, q and r are the same or different, and the average value of the number of repetition of p is 0.5 to 5.0, q is 0.5 to 5.0, and r is 0.05 to 0.5)
The epoxy compound (A1) is preferably one having an epoxy equivalent of 150 to 900g/eq in view of achieving an appropriate crosslink density of the cured product and achieving both of flexibility, toughness and heat resistance. From the viewpoint of good workability and excellent flexibility and adhesion of the cured product, the epoxy compound (a1) preferably has a viscosity of 2000 to 20000Pa · s, particularly preferably 2000 to 15000Pa · s, at 25 ℃.
X in the above formula (1)1、X2At least one of the alkylene groups is a straight alkylene chain having 4 to 10 carbon atoms. This is because if the carbon number is too short, flexibility is lost and adhesion is reduced, and if it is too long, reactivity is reduced and adhesion is reduced. Preferably X1、X2Both of them are the case of a straight-chain alkylene chain having 4 to 10 carbon atoms. In addition, in the case where importance is attached to the heat resistance, hardness, and moisture resistance of the obtained cured product, X in the above formula (1)1、X2Those containing alicyclic structures may also be used.
Ar in the above formula (1)1、Ar2、Ar3、Ar4The aromatic ring may be used. Namely, there can be mentioned: benzene ring optionally having a substituent, naphthalene ring optionally having a substituent, bisphenol structure optionally having a substituent, biphenyl structure optionally having a substituent and the like, for example, there can be mentioned: phenylene group, 4 '-biphenylene group, 2', 6, 6 '-tetramethyl-4, 4' -biphenylene group, methylenediphenylene group, 2-propane-diphenyl group, 1, 6-naphthyl group, 2, 7-naphthyl group, 1, 4-naphthyl group, 1, 5-naphthyl group, 2, 3-naphthyl group, a group represented by the following structural formula, and the like each having a bonding site at the o-, m-, and p-positions,
[ solution 10]
From the viewpoint of excellent balance between flexibility and toughness of the obtained cured product, methylene diphenylene and 2, 2-propane-diphenyl are preferable.
As the epoxy compound (A1), the following structures (A1-1) to (A1-9) are cited as preferable structures.
[ solution 11]
[ solution 12]
[ solution 13]
In each structural formula, G is glycidyl, p, q and r are the average value of the number of repetition and p is 0.5 to 5.0, q is 0.5 to 5.0 and r is 0.05 to 0.5. Each aromatic ring may have an alkyl group having 1 to 4 carbon atoms, a halogen atom, or the like as a substituent. Among them, those represented by the above-mentioned structural formulae (A1-3) and (A1-4) are most preferable from the viewpoint of excellent balance of physical properties of the resulting cured product.
The method for producing the epoxy compound (a1) is not particularly limited, and from the viewpoint of availability of raw materials or easiness of reaction, the following method is preferably used: a method in which a diglycidyl ether of an aliphatic dihydroxy compound or a diglycidyl ester of an aliphatic acid compound (c1) is reacted with an aromatic dihydroxy compound (c2) at a molar ratio (c1)/(c2) in the range of 1/1.1 to 1/5.0, and the thus-obtained hydroxy compound is further reacted with an epichlorohydrin (c 3).
< adhesive agent >
The adhesive of the present invention comprises: 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 initial adhesive strength, and is flexible as a laminate of a laminate, and therefore can be suitably used as an adhesive for lamination. The adhesive of the present invention is also suitable as an adhesive for metals because it can satisfactorily adhere to a metal layer. The cured adhesive is also excellent in electrolyte resistance, and therefore is suitable as an adhesive for a battery.
< other epoxy Compound >
The adhesive of the present invention may contain an epoxy compound other than the epoxy compound a. Examples thereof include: bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AD-type epoxy resin, resorcinol-type epoxy resin, dihydroxynaphthalene-type epoxy resin, biphenyl-type epoxy resin, tetramethylbiphenyl-type epoxy resin, trifunctional or higher epoxy compound having a structure of anthracene, biphenyl, bisphenol A, bisphenol F, or bisphenol S, solid bisphenol A-type epoxy resin, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, triphenylmethane-type epoxy resin, tetraphenylethane-type epoxy resin, dicyclopentadiene-phenol addition reaction-type epoxy resin, phenol aralkyl-type epoxy resin, naphthol novolac-type epoxy resin, naphthol aralkyl-type epoxy resin, naphthol-phenol cocondensate-type epoxy resin, naphthol-cresol cocondensate-type epoxy resin, naphthol AD-type epoxy resin, resorcinol-type epoxy resin, dihydroxynaphthalene-type epoxy resin, biphenyl-type epoxy resin, and/bisphenol A-type epoxy resin, Aromatic hydrocarbon formaldehyde resin-modified phenol resin-type epoxy resins, biphenyl-modified novolac-type epoxy resins, and the like.
As the epoxy compound, one epoxy compound may be used alone, or a plurality of epoxy compounds may be used in combination.
In the invention, the molar ratio of the epoxy compound A to other epoxy compounds is preferably 100: 0-5: 95. The laminating adhesive is preferably 100: 0 to 10: 90 in terms of flexibility.
< mixing ratio >
In order to produce the adhesive, it is preferable to mix the acid group contained in the acid group-containing resin and the epoxy group contained in the epoxy compound containing the epoxy compound A so that the equivalent ratio (epoxy/acid value) is 0.01 to 10. More preferably 0.1 to 5.
This is because the equivalent ratio is 0.01 or more, the heat resistance is excellent, and the adhesive strength is excellent when the equivalent ratio is 10 or less.
< other resins >
The adhesive of the present invention may contain a resin other than the acid-group-containing resin and the epoxy compound within a range not to impair the effects of the present invention. As the resin, a thermosetting resin or a thermoplastic resin can be used.
The thermosetting resin is a resin having a property of being substantially insoluble and changeable to infusibility when cured by means of heating, radiation, a catalyst, or the like. Specifically, the thermosetting resin is a resin having a property of being substantially insoluble and changeable to infusibility when cured by means of heating, radiation, a catalyst, or the like. Specific examples thereof include: phenol resins, urea resins, melamine resins, benzoguanamine resins, alkyd resins, unsaturated polyester resins, vinyl ester resins, diallyl terephthalate resins, silicone resins, urethane resins, furan resins, ketone resins, xylene resins, thermosetting polyimide resins, benzoxazine resins, active ester resins, aniline resins, cyanate ester resins, styrene-maleic anhydride (SMA) resins, and the like. One kind or two or more kinds of these thermosetting resins may be used in combination.
The thermoplastic resin is 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, polyethersulfone resin, polyacrylate resin, thermoplastic polyimide resin, polyamideimide resin, polyetheretherketone resin, polyketone resin, polyamide resin, polyethylene terephthalate resin, and polyethylene terephthalate resin, polyethylene terephthalate resin, polyethylene resin, and polyethylene resin, liquid crystal polyester resins, fluorine resins, syndiotactic polystyrene resins, cyclic polyolefin resins, and the like. These thermoplastic resins may be used singly or in combination of two or more.
< curing catalyst >
The adhesives of the present invention may also use a curing catalyst.
As the curing catalyst, a general epoxy curing agent can be used, and specifically, various curing agents such as an amine curing agent, an amide curing agent, an acid anhydride curing agent, a phenol curing agent, an active ester curing agent, a carboxyl group-containing curing agent, and a thiol curing agent can be used in combination.
Specifically, examples of the amine-based curing agent include diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenyl ether, diaminodiphenyl sulfone, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, diethyltoluenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, imidazole, BF 3-amine complex, guanidine derivatives, and guanamine derivatives.
Examples of the amide curing agent include dicyandiamide and polyamide resins synthesized from a dimer of linolenic acid and ethylenediamine.
Examples of the acid anhydride curing agent include: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like.
Examples of the phenol-based curing agent include: bisphenol A, bisphenol F, bisphenol S, resorcinol, catechol, hydroquinone, fluorene bisphenol, 4 '-bisphenol, 4', 4 "-trihydroxy triphenylmethane, naphthalenediol, 1, 2, 2-tetrakis (4-hydroxyphenyl) ethane, calixarene, a phenol novolac resin, a cresol novolac resin, an aromatic hydrocarbon formaldehyde resin-modified phenol resin, a dicyclopentadiene phenol addition type resin, a phenol aralkyl resin (neophenol resin), a polyphenol novolac resin synthesized from a polyhydric hydroxyl compound and formaldehyde as typified by a resorcinol novolac resin, a naphthol aralkyl resin, a trimethylolmethane resin, a tetrahydroxyphenyl ethane resin, a naphthol novolac resin, a naphthol-phenol co-condensation novolac resin, a naphthol-cresol co-condensation novolac resin, a naphthol-phenol co-condensation novolac resin, a phenol aldehyde, a phenol aldehyde, a phenol, a phenol aldehyde, a phenol aldehyde, a phenol, a, A biphenyl-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked by a dimethylene group), a biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are linked by a dimethylene group), an aminotriazine-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked by melamine, benzoguanamine, or the like), an alkoxy group-containing aromatic ring-modified novolak resin (a polyhydric phenol compound in which phenol nuclei and an alkoxy group-containing aromatic ring are linked by formaldehyde), and other polyhydric phenol compounds.
These curing catalysts may be used alone or in combination of two or more.
Further, the curing accelerator may be used alone or in combination with the curing catalyst. As the curing accelerator, various compounds which accelerate the curing reaction of the epoxy compound can be used, and examples thereof include phosphorus compounds, tertiary amine compounds, imidazole compounds, organic acid metal salts, lewis acids, and amine complex salts. Among them, an imidazole compound, a phosphorus compound, and a tertiary amine compound are preferably used, and particularly, from the viewpoint of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, and the like, the phosphorus compound is preferably triphenylphosphine, the tertiary amine is preferably 1, 8-diazabicyclo- [5.4.0] -undecene (DBU), and the imidazole compound is preferably 2-ethyl-4-methylimidazole.
The curing catalyst and the curing accelerator may or may not be blended, and when blended, the amount is preferably 0.001 to 10 parts by weight based on 100 parts by weight of the total solid content in the adhesive. Particularly preferably 0.005 to 5 parts by weight.
< solvent >
The adhesive may contain a solvent according to the use application. Examples of the solvent include organic solvents, such as: methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acrylonitrile, methyl isobutyl ketone, methanol, ethanol, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, methylcyclohexanone, and the like. The kind and amount of the solvent may be appropriately selected depending on the intended use.
In particular, when the adhesive is used as a dry laminating adhesive, a hydrocarbon solvent, a ketone solvent, an ester solvent or an alcohol solvent is preferably used.
When a solvent is used, the acid group-containing resin and the epoxy compound a may be mixed, or the acid group-containing resin or the epoxy compound a may be dissolved in the solvent in advance and used in the form of a varnish.
When a solvent is used, the solvent component is preferably 50 to 90 parts by weight based on 100 parts by weight of the total amount of the adhesive. Preferably, the amount is 60 to 85 parts by weight.
The adhesive may contain various additives within a range not to impair the effects of the present invention. Examples of the additives include catalysts, surfactants, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, and the like), rust inhibitors, reactive elastomers, coupling agents, plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, fillers, crystal nucleus agents, compounds having an oxygen trapping function, and adhesion imparting agents. The content of these additives may be appropriately adjusted within a range not impairing the function of the adhesive of the present invention.
< layered product >
The laminate of the present invention is characterized in that the adhesive layer of the present invention is provided on the intermediate layer.
The upper layer and the lower layer of the laminate are not particularly limited, and may be selected according to the application. Examples thereof include plastics such as polyethylene, polypropylene and polyethylene terephthalate; metals such as iron, aluminum, copper, silver, and titanium, or metal oxides, wood, paper, and composites thereof.
Among them, the adhesive of the present invention is excellent as an adhesive for metal or metal oxide because of its excellent adhesion to a metal or metal oxide layer. Particularly preferred for aluminum.
The shape of the upper layer and the lower layer of the laminate is not particularly limited, and may be any shape according to the purpose, such as a flat plate, a sheet, or a three-dimensional shape having a curvature in the whole or a part thereof. Further, the hardness, thickness, etc. of the base material are not limited.
In the laminate of the present invention, the method for applying the adhesive layer is not particularly limited, and examples thereof include: spraying, spin coating, dipping, roll coating, knife roll coating, doctor blade coating, knife blade coating, slit coating, screen printing, ink jet, and the like.
< lamination >
The adhesive of the present invention has very high adhesive strength, and therefore can be suitably used for lamination. In the case of using as a laminating adhesive, the dry coating weight is preferably 0.5g/m2～20.0g/m2Within the range of (1). If it is 0.5g/m2As described above, the continuous uniform coatability is good, and 20.0g/m2Hereinafter, since the solvent release property after coating is good, the balance between workability and solvent release property is excellent.
As a laminating method, a laminated laminate can be obtained by applying the adhesive of the present invention to a lower layer, then laminating the upper layer by dry lamination (dry lamination method), and then laminating. The temperature of the laminating roller is preferably about room temperature to 120 ℃, and the pressure is preferably 3kg/cm2～300kg/cm2Left and right.
The laminated laminate of the present invention is preferably aged after production. The preferred temperature of the aging conditions is from 25 ℃ to 100 ℃ for from 12 hours to 240 hours, during which the bond strength is developed.
< Member for Battery >
The laminate of the present invention composed of a metal layer and a plastic layer can be suitably used as an electrolyte sealing film, an electrode portion protective film, or the like of a battery. In this case, a polar organic solvent and/or a salt or the like is used in contact with the plastic layer side. In particular, the film is preferably used in a state of being in contact with a nonaqueous electrolyte containing a polar organic solvent and a salt, and thus can be particularly preferably used as a secondary battery electrolyte sealing film or a secondary battery electrode protective film in a nonaqueous electrolyte battery, a solid battery, or the like. In this case, the plastic sheet is folded so as to face each other and heat-sealed, whereby the plastic sheet can be used as a sealing bag for a battery. The adhesive used in the present invention has excellent heat sealability, and thus prevents leakage of the nonaqueous electrolyte, and can be used as a battery for a long period of time.
Examples of the polar organic solvent include aprotic polar solvents such as alkyl carbonates, esters, and ketones. Specifically, there may be mentioned: 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-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 battery applications, LiPF is generally used6、LiBF4Lithium salts such as Li-imide.
The nonaqueous electrolyte is obtained by dissolving 0.5 to 3mmol of the above alkali metal salt in an aprotic polar organic solvent such as a cyclic carbonate, a chain carbonate, or a mixture thereof.
The laminate of the present invention can be used for a long period of time without causing interlayer peeling of the metal layer, the adhesive layer, and the plastic layer even when the laminate is used in a state of being in contact with the polar solvent and/or the salt, particularly the nonaqueous electrolyte which is a mixture thereof.
< Battery >
The battery of the present invention includes the battery member of the present invention. Examples of the battery member having the laminate of the present invention include a battery electrolyte sealing film and a battery electrode protective film. In the battery of the present invention, the film does not cause interlayer peeling, and leakage of the nonaqueous electrolyte can be prevented, so that the battery can be stably used for a long period of time.
Examples
The present invention will be described below with reference to examples, but the present invention is not limited to the examples. When not particularly described, the unit is a weight conversion.
Preparation example 1 preparation of varnish 1
300g of a propylene/1-butene copolymer and 1L of toluene were heated to 145 ℃ under a nitrogen atmosphere to dissolve the propylene/1-butene copolymer in toluene. Further, 38g of maleic anhydride and 16g of di-t-butyl peroxide were supplied to the system over 4 hours while stirring, and the system was further stirred at 145 ℃ for 2 hours. After cooling, a large amount of acetone was charged to precipitate and filter the maleic anhydride-modified propylene/1-butene copolymer (1), and the resulting product was washed with acetone and then dried under vacuum to obtain a white solid. 20 parts of the obtained solid, 72 parts of methylcyclohexane, 7 parts of ethyl acetate, and 1 part of isopropyl alcohol (IPA) were sufficiently stirred to obtain varnish 1 which was a solution containing 20.0% of nonvolatile components.
Preparation example 2 preparation of varnish 2
GMP7550E (acid-modified olefin resin, available from lesday chemical corporation) 16 parts, AUROREN 350S (acid-modified olefin resin, available from japan paper company) 4 parts, methylcyclohexane 72 parts, ethyl acetate 5 parts, and isopropyl alcohol (IPA)3 parts were sufficiently stirred to prepare varnish 2 which was a solution containing 20.5% nonvolatile components.
Preparation example 3 preparation of varnish 3
20 parts of an ethylene-acrylic acid copolymer, 72 parts of toluene, and 8 parts of isopropyl alcohol (IPA) were added thereto and sufficiently stirred to prepare a varnish 3 containing 19.9% nonvolatile components.
Preparation example 4 preparation of varnish 4
After 120g of toluene was added to a reaction apparatus equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube, the temperature was raised to about 100 ℃ in a nitrogen stream for about 1 hour, and the temperature was maintained for 1 hour. Then, from a dropping funnel to which a mixed solution containing 117g of styrene, 12.6g of acrylic acid, 50.4g of lauryl methacrylate and 3.6g of t-butyl peroxyethylhexanoate (Perbutyl O manufactured by nippon chemical corporation) was added in advance, the mixed solution was dropped into the system under a nitrogen flow for about 4 hours, and the system was maintained at the same temperature for 6 hours. Cooling was conducted and 90g of toluene was added, thereby obtaining a solution containing the acid group-containing acrylate resin (E) having a nonvolatile content of 46.8%, namely varnish 4.
Preparation example 5 preparation of varnish 5
After 50mL of toluene was added to a reaction apparatus equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, the inside of the system was replaced by bubbling argon gas for 30 minutes. After the argon introduction port was lifted from the liquid surface and changed to a fluid state, the vessel was immersed in an oil bath having a bath temperature of 135 ℃ to start stirring. After the system reached a certain temperature, four kinds of mixed solutions of 38.20g of cyclohexyl methacrylate, 8.65g of isobornyl methacrylate, 3.20g of acrylic acid, and 118mg of 2, 2' -azobisisobutyronitrile in 5mL of toluene were added dropwise over 1 hour. After stirring while maintaining the bath temperature for 4 hours under argon gas flow, 119mg of 2, 2' -azobisisobutyronitrile in 5mL of toluene was added dropwise, and stirring while maintaining the bath temperature for 4 hours was carried out again. After cooling to room temperature, the obtained slightly white turbid homogeneous solution was put into about 1.2L of methanol and reprecipitated. Then, the precipitate was washed 3 times with methanol, followed by drying under reduced pressure at 40 ℃ overnight, and as a result, 48g of a white solid was obtained. The obtained white solid was dissolved in toluene to obtain varnish 5 which is a solution of the acid group-containing acrylate resin (F). The acid value was 11.3mgKOH/g, and the nonvolatile content was 30.0%.
Preparation example 6 preparation of varnish 6
In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 90 parts by weight of DMPA (2, 2-dimethylolpropionic acid), 54 parts by weight of methylethylketone as a solvent, and 81 parts by weight of tetrahydrofuran were added, and stirring was performed under a nitrogen stream. Then, 56 parts by weight of XDI (xylylene diisocyanate, trade name: Takenate 500, manufactured by Mitsui chemical Co., Ltd.) was added thereto, and the temperature was raised to 60 ℃. After stirring for 1 hour, the temperature was lowered to 40 ℃ or lower, and then 56 parts by weight of XDI was further added, and the temperature was raised again to 60 ℃. The reaction was continued until disappearance of the isocyanate group was confirmed by infrared spectroscopy. Subsequently, 148 parts by weight of methanol as a diluting solvent was added to obtain varnish 6, which is a 50 wt% solution of acid-group-containing urethane resin (G) containing a carboxyl-group-containing urethane resin "DMPA/XDI".
Preparation example 7 preparation of varnish 7
20 parts of a polyolefin resin Hi-wax NL 100 (manufactured by Mitsui chemical Co., Ltd.) and 80 parts of toluene were added thereto and sufficiently stirred to prepare a varnish 7 which was a solution containing 20.1% of nonvolatile components.
With respect to the prepared acid group-containing resins, the acid values of the respective resins are shown in table 1 below. The acid value of the acid group-containing polyolefin resin was measured by the above-described acid value measurement method-2, and the acid group-containing polyacrylate resin and the acid group-containing polyurethane resin were measured by the acid value measurement method-1.
[ Table 1]
Synthesis example 1 Synthesis of dihydroxy Compound (Ph-1)
A flask equipped with a thermometer and a stirrer was charged with 744g (6 equivalents) of diglycidyl ether of 1, 6-hexanediol (product name: EPICLON 726D, epoxy equivalent 124g/eq) and 1368g (12 equivalents) of bisphenol A (hydroxyl equivalent 114g/eq) and heated to 140 ℃ over 30 minutes, and then 5g of a 4% aqueous solution of sodium hydroxide was added. Thereafter, the temperature was raised to 150 ℃ over 30 minutes, and the reaction was continued at 150 ℃ for 3 hours. Thereafter, a neutralizing amount of sodium phosphate was added to obtain 2090g of a hydroxy compound (Ph-1). According to NMR spectrum (13C) And obtaining M corresponding to the theoretical structure of formula (1) wherein n is 1 by mass spectrometry+687 and M corresponding to the theoretical structure where n is 2+The peak of 1145 confirmed that the hydroxy compound (Ph-1) contained a hydroxy compound having a structure represented by the following structural formula (B-1). The hydroxyl group equivalent of the hydroxyl compound (Ph-1) calculated by GPC was 262g/eq, and the average value of n in the structural formula (B-1) calculated from the hydroxyl group equivalent was 0.6.
[ solution 14]
Synthesis example 2 Synthesis of epoxy Compound (Ep-1)
261g (hydroxyl equivalent: 261g/eq.) of the hydroxyl compound (Ph-1) obtained in example 1, 1110g (12 moles) of epichlorohydrin, and 222g of n-butanol were added to and dissolved in a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer. Thereafter, while purging with nitrogen, the temperature was raised to 65 ℃ and then reduced to an azeotropic pressure, and 122g (1.5 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was then continued under these conditions for 0.5 hour. Meanwhile, the distillate component distilled off as an azeotrope was separated by a dean-stark separator, the aqueous layer was removed, and the organic layer was returned to the reaction system for reaction. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 1000g of methyl isobutyl ketone and 100g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 20g of a 10% aqueous sodium hydroxide solution was added to the solution and reacted at 80 ℃ for 2 hours, and then washing with 300g of water was repeated 3 times until the pH of the washing solution became neutral. Then, the inside of the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 380g of a liquid epoxy resin (Ep-1). According to NMR spectrum (13C) And obtaining M corresponding to a theoretical structure of p 1, q 1, r 0 in the above structural formula (a1-3) by mass spectrometry+798 and M corresponding to the theoretical structure of p-2, q-2, r-0+The peak 1257 confirmed that the epoxy resin (Ep-1) contained an epoxy resin having a structure represented by the structural formula (a 1-3). The obtained epoxy resin (Ep-1) contained the compound of the formula (a1-3) in which p was 0, q was 0, and r was 0, and as a result of confirmation by GPC, the compound of p was 0, q was 0, and r was 0 was contained in the mixture at a ratio of 29 wt%. The epoxy resin (Ep-1) had an epoxy equivalent of 350 g/eq. and a viscosity of 2000 pas (25 ℃ C., type E viscosity method), and the average value of r in the structural formula (A1-3) calculated from the epoxy equivalent was 0.1.
Example 1 preparation of adhesive 1
100 parts of varnish 1, 0.7 part of epoxy compound (Ep-1), 0.01 part of triphenylphosphine, 3 parts of ethyl acetate, and 1 part of isopropyl alcohol were added thereto and sufficiently stirred to prepare adhesive 1 having a nonvolatile content of 20%.
< preparation of laminate >
Adhesive 1 prepared in example 1 was applied at 5g/m using a bar coater2The film was applied (dry) to an aluminum foil ("1N 30H" 30 μm, manufactured by toyoyo aluminum corporation) and dried at 80 ℃ for 1 minute, and then laminated to a CPP film (polyolefin film "ET-20" 40 μm, manufactured by oka corporation) at 100 ℃ to prepare a laminate 1.
Thereafter, the resultant was aged at 70 ℃ for 5 days, and then the initial adhesive strength was measured.
< measurement of initial adhesion Strength >
In the Tencilon test manufactured by A & D, the laminate was cut to a width of 15mm, and the 180 ℃ peel strength was measured.
< electrolyte resistance >
As an electrolyte, a mixed solution of ethylene carbonate, ethylmethyl carbonate and dimethyl carbonate (wt%) to which LiPF was added was prepared6: 1 mol% and vinylene carbonate: 1 wt% solution.
The laminate 1 was immersed in 35g of an electrolyte solution at 85 ℃ for 7 days, and evaluated from the retention of adhesive strength before and after immersion as described below.
Adhesion strength retention (%) bonding strength after immersion (N/15 mm)/bonding strength before immersion (N/15mm)
Very good: 80% or more, O: 80% -60%, x: less than 60%
Examples 2 to 7
Adhesives and laminates were prepared by mixing the respective components in accordance with the compounding shown in table 2 in the same manner as the method described in example 1.
The laminates obtained in the respective examples were evaluated for adhesive performance and electrolyte resistance, and the results are shown in table 2.
[ Table 2]
[ Table 3]
Curezol 2E4MZ (imidazole-based curing agent manufactured by four chemical industries, Ltd.) had a nonvolatile content of 100%
EPICLON HP-4700 (naphthalene type epoxy available from DIC) nonvolatile content 100%
Industrial applicability
The adhesive of the present invention is excellent in adhesion, particularly adhesion to a metal or metal oxide layer, and further has electrolyte resistance even under low-temperature curing, and does not cause interlayer peeling with time, and therefore, can be suitably used as a laminating adhesive or a battery adhesive. In addition, the obtained laminate can be suitably used as a battery member, and a battery having long-term use stability can be obtained.
Claims (14)
1. An adhesive characterized by comprising an acid group-containing resin and an epoxy compound, wherein the epoxy compound comprises an epoxy compound A containing an aromatic ring, an alkylene chain having 4 to 10 carbon atoms and two or more epoxy groups,
the epoxy compound A is a compound represented by the following formula (8),
in the formula (8), Ar1、Ar2、Ar3、Ar4Are optionally the same or differentOptionally substituted aromatic ring, X1、X2Is an aliphatic hydrocarbon radical, R1、R2、R3Is hydrogen atom or alkyl group with 1 to 4 carbon atoms, p, q and r are equal or different, p is 0.5 to 5.0, q is 0.5 to 5.0, r is 0.05 to 0.5.
2. The adhesive according to claim 1, wherein the acid group-containing resin is at least one selected from the group consisting of an acid group-containing polyacrylate resin, an acid group-containing polyurethane resin, and an acid group-containing polyolefin resin.
3. The adhesive according to claim 2, wherein the acid-group-containing polyurethane resin is a reaction product of a compound represented by the following formula (1) and a compound represented by the following formula (2),
in the formula (1), X1Represents an aromatic ring or an alicyclic ring structure, n1 and n2 each independently represent an integer of 0 to 3,
in the formula (2), R1Represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms or a carbonyl group, and m1 to m3 each independently represents an integer of 0 to 3.
4. The adhesive according to any one of claims 1 to 3, wherein the epoxy equivalent of the epoxy compound A is 150 to 900 g/eq.
5. The adhesive according to any one of claims 1 to 3, wherein the viscosity of the epoxy compound A at 25 ℃ is 2000 Pa-s to 20000 Pa-s.
6. The adhesive according to any one of claims 1 to 3, wherein the equivalent ratio of the acid group contained in the acid group-containing resin to the epoxy group contained in the epoxy compound is 0.01 to 10.
7. The adhesive according to any one of claims 1 to 3, wherein the epoxy compound further contains an epoxy compound other than the epoxy compound A, and the amount of the epoxy compound other than the epoxy compound A in the total amount of the epoxy compound A and the epoxy compound other than the epoxy compound A is 95 mol% or less.
8. The adhesive according to any one of claims 1 to 3, which is a laminating adhesive.
9. The adhesive according to any one of claims 1 to 3, which is an adhesive for a battery.
10. The adhesive according to any one of claims 1 to 3, which is an adhesive for metal or metal oxide.
11. A laminate comprising an adhesive layer according to any one of claims 1 to 10 in an intermediate layer.
12. The laminate according to claim 11, which comprises a metal layer and a plastic layer.
13. A battery member having the laminate according to claim 11 or 12.
14. A battery having the member for a battery according to claim 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017194310 | 2017-10-04 | ||
| JP2017-194310 | 2017-10-04 | ||
| PCT/JP2018/036820 WO2019069896A1 (en) | 2017-10-04 | 2018-10-02 | Adhesive, laminate, battery member, and battery |
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| CN111133075A CN111133075A (en) | 2020-05-08 |
| CN111133075B true CN111133075B (en) | 2021-11-23 |
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| CN201880060977.9A Active CN111133075B (en) | 2017-10-04 | 2018-10-02 | Adhesive, laminate, member for battery, and battery |
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| Country | Link |
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| JP (1) | JP6642778B2 (en) |
| CN (1) | CN111133075B (en) |
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|---|---|---|---|---|
| KR20220049543A (en) * | 2019-09-26 | 2022-04-21 | 도요보 가부시키가이샤 | Assembly and laminate for fuel cell |
| JP7254670B2 (en) * | 2019-09-26 | 2023-04-10 | 東洋紡株式会社 | laminate |
| CN114341301B (en) * | 2019-10-08 | 2023-09-29 | 东洋纺Mc株式会社 | Polyolefin adhesive composition |
| CN114787311B (en) * | 2019-12-25 | 2023-05-09 | Dic株式会社 | Adhesive, laminate, packaging material for battery, and battery |
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- 2018-10-02 JP JP2019546714A patent/JP6642778B2/en active Active
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| CN106459703A (en) * | 2014-06-11 | 2017-02-22 | 东洋纺株式会社 | Polyolefin-based adhesive composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6642778B2 (en) | 2020-02-12 |
| JPWO2019069896A1 (en) | 2020-04-23 |
| WO2019069896A1 (en) | 2019-04-11 |
| TWI775959B (en) | 2022-09-01 |
| TW201932568A (en) | 2019-08-16 |
| CN111133075A (en) | 2020-05-08 |
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