CN110607141A - Adhesive, laminate, battery packaging material, battery container, and battery - Google Patents

Adhesive, laminate, battery packaging material, battery container, and battery Download PDF

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Publication number
CN110607141A
CN110607141A CN201910468858.3A CN201910468858A CN110607141A CN 110607141 A CN110607141 A CN 110607141A CN 201910468858 A CN201910468858 A CN 201910468858A CN 110607141 A CN110607141 A CN 110607141A
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CN
China
Prior art keywords
group
resin
acid
adhesive
battery
Prior art date
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Granted
Application number
CN201910468858.3A
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Chinese (zh)
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CN110607141B (en
Inventor
中村英美
神山达哉
佐藤泰
水口良
中村信哉
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • C09J123/02—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 not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869—Acids or derivatives thereof
    • 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
    • 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
    • C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C09J125/08—Copolymers of styrene
    • C09J125/14—Copolymers of styrene with unsaturated esters
    • 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
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/1245—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the external coating on the casing
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Wrappers (AREA)

Abstract

The invention provides an adhesive which is excellent in adhesion between a nonpolar base material such as an olefin resin and a metal base material even when cured at a low temperature, a laminate obtained using the adhesive, a secondary battery packaging material obtained using the laminate, a battery container, and a battery. An adhesive agent, a laminate using the same, a battery packaging material, and a battery, wherein the adhesive agent comprises an acid group-containing resin (A) and a curing agent (B), wherein the curing agent (B) comprises an epoxy compound (B1) as an essential component, and the epoxy compound (B1) has a structure in which an aromatic hydrocarbon group (a1) having a bonding site with another group in an aromatic nucleus and a hydrocarbon group (a2) containing an ether bond or a linear alkylene group (a3) having 2 to 15 carbon atoms are bonded via an acetal bond (a4), and has a structure in which a glycidyloxy group is bonded to the aromatic hydrocarbon group (a 1).

Description

Adhesive, laminate, battery packaging material, battery container, and battery
Technical Field
The present invention relates to an adhesive, and more particularly to an adhesive suitable for bonding a resin substrate and a metal substrate, a laminate obtained using the adhesive, a packaging material for a secondary battery, a container for a battery, and a battery.
Background
A secondary battery represented by a lithium ion battery has a structure in which a positive electrode, a negative electrode, and an electrolyte solution or the like are sealed between these electrodes. As a sealing bag for sealing a lead wire for conducting electricity between the positive electrode and the negative electrode to the outside, a laminate is known which is obtained by bonding a heat-sealing layer containing an olefin resin, a metal base material containing a metal foil such as an aluminum foil or a metal vapor deposition layer, and a plastic material with an adhesive (patent document 1 and patent document 2).
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. 2016-132716
[ patent document 2] International publication No. 2014/123183 Manual
Disclosure of Invention
[ problems to be solved by the invention ]
When a heat seal layer containing an olefin resin is bonded to a metal substrate via an adhesive, a so-called aging (bonding) step is generally provided in which the curing of the adhesive is accelerated while heating. The curing temperature and curing time in the curing step may be appropriately selected, and for example, it is preferable to perform the curing step at 80 ℃ or less, which is less susceptible to thermal shrinkage of the olefin (olefin) resin. On the other hand, the lower the curing temperature and the shorter the curing time, the more difficult the properties of the adhesive tend to be exhibited.
The present invention has been made in view of such circumstances, and an object thereof is to provide an adhesive which is excellent in adhesion between a nonpolar substrate such as an olefin resin and a metal substrate even when it is cured at a low temperature. Further, it is an object of the present invention to provide a laminate obtained using such an adhesive, and a secondary battery packaging material and a battery obtained using the laminate.
[ means for solving problems ]
The present invention relates to an adhesive comprising an acid group-containing resin (A) and a curing agent (B), wherein the curing agent (B) comprises an epoxy compound (B1) as an essential component, and the epoxy compound (B1) has a structure in which an aromatic hydrocarbon group (a1) having a bonding site with another group in an aromatic nucleus and a hydrocarbon group (a2) containing an ether bond or a linear alkylene group (a3) having 2 to 15 carbon atoms are bonded to each other via an acetal bond (a4), and has a structure in which a glycidyloxy group is bonded to the aromatic hydrocarbon group (a 1).
[ Effect of the invention ]
The adhesive of the present invention is excellent in adhesion between a nonpolar substrate such as an olefin resin and a metal substrate even when cured at a low temperature. The laminate of the present invention is excellent in adhesion and electrolyte resistance.
Detailed Description
< Adhesives >
The adhesive of the present invention comprises an acid group-containing resin (a) and a curing agent (B), wherein the curing agent (B) comprises an epoxy compound (B1) as an essential component, and the epoxy compound (B1) has a structure in which an aromatic hydrocarbon group (a1) having a bonding site with another group in an aromatic nucleus and a hydrocarbon group (a2) containing an ether bond or a linear alkylene group (a3) having 2 to 15 carbon atoms are bonded via an acetal bond (a4), and has a structure in which a glycidyloxy group is bonded to the aromatic hydrocarbon group (a 1). The components of the adhesive of the present invention will be described in detail below.
The acid group included in the acid group-containing resin (a) used in the adhesive of the present invention includes: carboxyl group, carboxylic anhydride group, sulfonic group, phosphoric group, etc. The acid group-containing resin (a) may include only one of these, or may include two or more of these.
In order to improve the adhesion to a metal, the acid value of the resin containing an acid group is preferably 1mgKOH/g or more, more preferably 5mgKOH/g or more, and preferably 200mgKOH/g or less, more preferably 165mgKOH/g or less. When the ratio is 200mgKOH/g or less, the flexibility is excellent, and when the ratio is 1mgKOH/g or more, the heat resistance is good.
In the present invention, the acid value means the acid value of the solid content and the number of milligrams (mg) of potassium hydroxide required for neutralizing the acid content in 1g of the sample. The weighed sample was dissolved in a solvent of 70/30 (volume ratio) toluene/methanol, and several drops of a 1% phenolphthalein alcohol solution were added in advance, and 0.1mol/L potassium hydroxide alcohol solution was added dropwise thereto to confirm the color change point, and the color change point was calculated using the following calculation formula.
Acid value (mgKOH/g) ═ V x F x 5.61)/S
V: 0.1mol/L Potassium hydroxide solution dropping amount (mL)
F: titre of 0.1mol/L alcoholic potassium hydroxide solution
S: sample Collection volume (g)
5.61: potassium hydroxide equivalent (mg) in 0.1mol/L Potassium hydroxide solution 1mL
When the sample used for the measurement is a resin solution, the solid acid value is calculated by using the following calculation formula.
Acid value (mgKOH/g) ═ acid value of resin solution (mgKOH/g)/NV (%) × 100
NV: nonvolatile fraction of sample (%)
The resin skeleton of the acid group-containing resin (a) is not particularly limited, and an acrylic resin, a urethane resin, an olefin resin, or the like can be preferably used.
Examples of the acrylic resin containing an acid group include copolymers obtained by polymerizing a monomer having a (meth) acryloyl group and a polymerizable monomer having an acid group as essential components, and if necessary, other polymerizable unsaturated monomers. The monomer having a (meth) acryloyl group may also be a polymerizable monomer having an acid group, and in this case, the acrylic resin containing an acid group may be a homopolymer of the polymerizable monomer having a (meth) acryloyl group and an acid group. In the present specification, the term "(meth) acryloyl group" means one or both of an acryloyl group and a methacryloyl group, the term "(meth) acrylic acid" means one or both of acrylic acid and methacrylic acid, and the term "(meth) acrylate" means one or both of an acrylate and a methacrylate.
Examples of the polymerizable monomer having an acid group include: (meth) acrylic acid; compounds having a (meth) acryloyl group and a carboxyl group such as β -carboxyethyl (meth) acrylate, 2-acryloyloxyethylsuccinic acid (2-acryloyloxyethylsuccinic acid), 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethylhexahydrophthalic acid (2-acryloyloxyethylhexahydrophthalic acid) and lactone-modified products thereof;
compounds having a (meth) acryloyl group and a phosphoric acid group such as 2- (meth) acryloyloxyethyl acid phosphate, bis (2- (meth) acryloyloxyethyl) acid phosphate, phosphoric acid ester of polyethylene glycol mono (meth) acrylate, phosphoric acid ester of polypropylene glycol mono (meth) acrylate, phosphoric acid ester of polyalkylene glycol mono (meth) acrylate, phosphomethylene (meth) acrylate, phosphotrimethylene (meth) acrylate, phosphopropylene (meth) acrylate, and phosphotetramethylene (meth) acrylate;
compounds having a (meth) acryloyl group and a sulfonic acid group such as 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropane sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, or salts thereof;
crotonic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, and the like. These may be used alone or in combination of two or more.
Examples of the monomer having a (meth) acryloyl group include:
(meth) acrylic 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, pentyl (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, octadecyl (meth) acrylate, and eicosyl (meth) acrylate;
(meth) acrylates having a cycloalkyl group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, and the like;
(meth) acrylates having an aromatic ring such as benzoyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate;
(meth) acrylates having a hydroxyalkyl group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glyceryl (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and polyalkylene glycol;
fluoroalkyl (meth) acrylates having 1 to 18 carbon atoms in a fluoroalkyl group 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, and perfluoroethyloxyethyl (meth) acrylate;
a silane group-containing (meth) acrylate such as γ -methacryloxypropyltrimethoxysilane;
n, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, and N, N-diethylaminopropyl (meth) acrylate.
Examples of the other polymerizable unsaturated monomer include: unsaturated dicarboxylic acid esters such as dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate, and methyl ethyl itaconate;
styrene derivatives such as styrene, α -methylstyrene and chlorostyrene;
diene (diene) compounds such as butadiene, isoprene, pentadiene and dimethylbutadiene;
vinyl halides (vinyl halides) or vinylidene halides (vinylidenehalides) such as vinyl chloride and vinyl bromide;
unsaturated ketones such as methyl ketene and butyl ketene;
vinyl esters such as vinyl acetate and vinyl butyrate;
vinyl ethers such as methyl vinyl ether and butyl vinyl ether;
vinyl cyanides such as acrylonitrile, methacrylonitrile, and vinylidene cyanide;
acrylamide or alkyd-substituted amides thereof;
n-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
fluorine-containing α -olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene and hexafluoropropylene; perfluoroalkyl perfluorovinyl ethers having a perfluoroalkyl group of 1 to 18 carbon atoms such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether, and heptafluoropropyl trifluorovinyl ether; and fluorine-containing ethylenically unsaturated monomers.
These other polymerizable unsaturated monomers may be used alone or in combination of two or more.
The acrylic resin containing an acid group can be obtained by polymerization (copolymerization) using a known and conventional method, and the polymerization (copolymerization) form is not particularly limited. Any of random copolymers, block copolymers, graft copolymers, and the like can be used. Can be produced by addition polymerization in the presence of a catalyst (polymerization initiator). Known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used.
The urethane resin having an acid group includes a reaction product of a composition containing a compound represented by the following formula (3) and a compound represented by the following formula (4).
[ solution 1]
(in the formula (3), X1Represents an aromatic ring or an alicyclic ring structure, and n1 and n2 each independently represent an integer of 0 to 3 inclusive)
[ solution 2]
(in the formula (4), R7Represents 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 inclusive)
The aromatic ring structure of the compound represented by the formula (3) 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 of the compound represented by the formula (3) may be substituted with at least one fluorine atom, and examples thereof include perfluorophenyl groups.
The alicyclic structure of the compound represented by the formula (3) is preferably an alicyclic ring having 3 to 20 carbon atoms, and may be any of a monocyclic ring, a polycyclic ring, and a fused ring. The ring structure may be a combination of an alicyclic ring and an aromatic ring.
Examples of the monocyclic structure include cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane; and cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclooctene. Examples of the polycyclic structure include cubane, basketane, and houseane. Examples of the condensed ring structure include bicycloundecane, decahydronaphthalene, norbornene, norbornadiene, and the like.
Preferred specific examples of the compound represented by the formula (3) include: m-xylene diisocyanate, p-xylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 1, 5-naphthalene diisocyanate, and the like.
As the compound represented by the formula (4), m3 is preferably 0. In addition, as the compound represented by the formula (4), R is preferable7Is a hydrocarbon group having 1 to 3 carbon atoms.
Preferable specific examples of the compound represented by the formula (4) include dimethylolpropionic acid and dimethylolbutyric acid.
As the acid group-containing olefin resin, there may be mentioned: homopolymers or copolymers of acid group-containing monomers, copolymers of acid group-containing monomers and olefin monomers, acid group-containing monomer modifications of polyolefins, and the like.
The acid group-containing monomer used for producing a homopolymer or copolymer of an acid group-containing monomer is preferably an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride. Specifically, there may be mentioned: 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, norborn-5-ene-2, 3-dicarboxylic anhydride, and the like.
As the acid group-containing monomer used for preparing the copolymer of the acid group-containing monomer and the olefin-based monomer, the same monomer as the acid group-containing monomer used for preparing the homopolymer or copolymer of the acid group-containing monomer can be used. Can be used alone or in combination of two or more. Maleic anhydride is preferably used.
The olefin monomer used for preparing the copolymer of the acid group-containing monomer and the olefin monomer includes olefins having 2 to 8 carbon atoms, and examples thereof include: ethylene, propylene, isobutylene, 1-butene, 4-methyl-1-pentene, hexene, vinylcyclohexane, and the like. Of these, particularly, in terms of good adhesion strength, the olefin having 3 to 8 carbon atoms is preferable, and propylene and 1-butene are more preferable, and in terms of excellent resistance to solvents and excellent adhesion strength, the combined use of propylene and 1-butene is particularly preferable.
In the production of the copolymer of the acid group-containing monomer and the olefin-based monomer, not only the acid group-containing monomer and the olefin-based monomer, but also other compounds having an ethylenically unsaturated group, such as styrene, butadiene, isoprene, and the like, may be used in combination.
As the acid group-containing monomer used for preparing the acid group-containing monomer modification of the polyolefin, the same monomer as the acid group-containing monomer used for preparing the homopolymer or copolymer of the acid group-containing monomer can be used. Can be used alone or in combination of two or more. Maleic anhydride is preferably used.
Examples of the polyolefin used as the modified product of the acid group-containing monomer for producing the polyolefin include: homopolymers or copolymers of olefins having 2 to 8 carbon atoms, copolymers of olefins having 2 to 8 carbon atoms with other monomers, and the like, and examples thereof include: high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyethylene such as linear low-density polyethylene resin, polypropylene, polyisobutylene, poly (1-butene), poly (4-methyl-1-pentene), polyvinylcyclohexane, ethylene-propylene block copolymer, ethylene-propylene random copolymer, ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-hexene copolymer, propylene-1-butene copolymer, and other α -olefin copolymers, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate-methyl methacrylate copolymer, ionomer resin, and the like. Of these, in particular, in terms of the adhesion strength being good, a homopolymer of an olefin having 3 to 8 carbon atoms or a copolymer of two or more kinds of olefins having 3 to 8 carbon atoms is preferable, and a homopolymer of propylene or a propylene/1-butene copolymer is more preferable, and in terms of the resistance to a solvent being excellent and the adhesion strength being excellent, a propylene/1-butene copolymer is particularly preferable.
Examples of the method for modifying a polyolefin with a monomer having an acid group include graft modification and copolymerization. When the monomer having an acid group is reacted with the polyolefin by graft modification, specific examples thereof include: a method in which a polyolefin is melted and a monomer having an acid group (graft monomer) is added thereto to carry out a graft reaction; a method in which a polyolefin is dissolved in a solvent to prepare a solution, and a graft monomer is added thereto to carry out a graft reaction; a method of mixing a polyolefin dissolved in an organic solvent with a graft monomer, and heating the mixture at a temperature not lower than the softening temperature or the melting point of the polyolefin 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-polymerize the graft monomer. The grafting reaction is generally carried out at 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 before modification.
The weight average molecular weight of the acid group-containing olefin resin is preferably 40,000 or more for satisfactory adhesion. In order to ensure appropriate fluidity, the weight average molecular weight of the olefin resin containing an acid group is preferably 150,000 or less.
In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by Gel Permeation Chromatography (GPC) under the following conditions.
A measuring device: HLC-8320GPC manufactured by Tosoh corporation
Pipe column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Co Ltd
A detector: RI (differential refractometer)
Data processing: multi-station (Multi station) GPC-8020 model II manufactured by Tosoh corporation
The measurement conditions were as follows: the temperature of the column is 40 DEG C
Solvent tetrahydrofuran
Flow rate 0.35 ml/min
The standard is as follows: monodisperse polystyrene
Sample preparation: a tetrahydrofuran solution (0.2 mass% in terms of solid content of the resin) was filtered through a microfilter (100. mu.l)
The olefin resin containing an acid group is preferably crystalline. The melting point of the acid group-containing olefin resin is preferably 50 ℃ or higher, more preferably 60 ℃ or higher, and still more preferably 65 ℃ or higher. The melting point of the olefin resin containing an acid group is preferably 120 ℃ or lower, more preferably 100 ℃ or lower, and still more preferably 90 ℃ or lower.
The melting point of the olefin resin containing an acid group is measured by Differential Scanning Calorimetry (DSC). Specifically, the temperature was raised from the temperature decrease end temperature to the temperature increase end temperature at 10 ℃/min, then cooled to the temperature decrease end temperature at 10 ℃/min, and after thermal hysteresis (thermal history) was removed, the temperature was again raised to the temperature increase achievement point at 10 ℃/min. The peak temperature at the second temperature rise was defined as the melting point. The temperature at which the temperature decrease is completed is set to a temperature 50 ℃ or higher lower than the crystallization temperature, and the temperature at which the temperature increase is completed is set to a temperature 30 ℃ or higher than the melting point temperature. The temperature decrease completion temperature and the temperature increase completion temperature are determined by performing a test measurement.
Specific examples of such an acid group-containing olefin resin include: maleic anhydride-modified polypropylene, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylate-maleic anhydride terpolymers, and the like. As commercially available products of olefin resins containing an acid group, there can be mentioned: "MODIC" series manufactured by mitsubishi chemical (stock), "Aldrich (ADMER)" series manufactured by mitsubishi chemical (stock), "UNISTOLE" series manufactured by vinyon (stock), "TOYO-TAC" series manufactured by toyankee chemical (stock), "UMEX (UMEX)" series manufactured by mitsui chemical (stock), "REXPEARL (REXPEARL) EAA" series manufactured by japan polyethylene (stock), "REXPEARL (REXPEARL) ET" series, "pimaco" (Primacor) series manufactured by dow chemical (stock), "Niukel (NUCREL)" series manufactured by mitsui chemical (stock), and "BONDINE (bond)" series manufactured by ARKEMA (arkinsona).
As the acid group-containing resin, resins other than those described above may be used, and examples thereof include taftatai (Tuftec) M series manufactured by asahi chemical corporation, Kraton FG series manufactured by Japan Kraton polumer Japan, inc.
The curing agent (B) contains an epoxy compound (B1), wherein the epoxy compound (B1) has a structure in which an aromatic hydrocarbon group (a1) having a bonding site with another group on an aromatic nucleus and a hydrocarbon group (a2) containing an ether bond or a linear alkylene group (a3) having 2 to 15 carbon atoms are bonded via an acetal bond (a4), and has a structure in which a glycidyloxy group is bonded to the aromatic hydrocarbon group (a 1).
The aromatic hydrocarbon group (a1) having a bond site to the aromatic nucleus in the epoxy compound (B1) is a hydrocarbon group having a bond site to another structural unit in the aromatic nucleus in the aromatic hydrocarbon compound. Specific examples of the aromatic hydrocarbon group (a1) include:
(i) comprising hydrocarbon radicals having only one benzene ring structure
(ii) A hydrocarbon group having a structure in which benzene rings are bonded to each other via a single bond
(iii) A hydrocarbon group having a structure in which benzene rings are bonded to each other via aliphatic carbon atoms
(iv) A hydrocarbon group having a structure in which benzene rings are bonded via an aliphatic cyclic hydrocarbon group
(v) A hydrocarbon group having a structure in which a plurality of benzene rings are condensed and polycyclic
(vi) A hydrocarbon group having a structure in which benzene rings are bonded through an aralkyl group.
(i) As the aromatic hydrocarbon group(s) there may be mentioned phenylene groups having a bonding site at each of the ortho-position (o-), meta-position (m-), and para-position (p-).
(ii) Examples of the aromatic hydrocarbon group of (2) include 4,4 '-biphenylene group and 2,2', 6 '-tetramethyl-4, 4' -biphenyl group.
(iii) Examples of the aromatic hydrocarbon group of (ii) include methylene diphenylene, 2' -propane-diphenyl, and groups represented by the following structural formulae (iii-1) to (iii-3).
[ solution 3]
(iv) As the aromatic hydrocarbon group(s) there may be mentioned groups represented by the following structural formulae (iv-1) to (iv-3). In the structural formula (iv-1) and the structural formula (iv-3), the bonding site of the aliphatic cyclic hydrocarbon group is an arbitrary secondary carbon atom of ethylene or propylene forming a ring.
[ solution 4]
(v) Examples of the aromatic hydrocarbon group of (a) include naphthyl groups such as 1, 6-naphthyl group and 2, 7-naphthyl group, 1, 4-naphthyl group, 1, 5-naphthyl group, 2, 3-naphthyl group, and groups represented by the following structures (v-1) and (v-2).
[ solution 5]
(vi) As the aromatic hydrocarbon group(s) in (1), there may be mentioned groups represented by the following structures (vi-1) and (vi-2).
[ solution 6]
Among these structures, the aromatic hydrocarbon group of (iii) is preferable, and methylene diphenylene group (methylene diphenylene group) and 2,2-propane-diphenyl group (2, 2-propane-diphenylene group) are particularly preferable.
Examples of the ether bond-containing hydrocarbon group (a2) include: poly (ethyleneoxy) ethyl groups such as ethyleneoxyethyl, di (ethyleneoxy) ethyl, and tri (ethyleneoxy) ethyl groups formed by addition polymerization of ethylene oxide;
poly (propyleneoxy) propyl groups such as propyleneoxypropyl, di (propyleneoxy) propyl, and tri (propyleneoxy) propyl groups formed by addition polymerization of propylene oxide;
a group in which an ethyleneoxy group and a propyleneoxy group coexist, which is obtained by addition copolymerization of ethylene oxide and propylene oxide (an ethylene oxide-propylene oxide copolymer); and alkyleneoxyalkylene groups.
The hydrocarbon group (a2) containing an ether bond shows a tendency that the greater the number of alkylene units, the higher the flexibility of the epoxy resin, but the lower the crosslinking density. Therefore, in view of the balance of these properties, the number of alkylene groups in the ether bond-containing hydrocarbon group (a2) is preferably 2 to 4.
The linear alkylene group (a3) having 2 to 15 carbon atoms substantially contains a linear carbon atom chain. The branched structure may be adopted locally to the extent that it does not affect flexibility, but in terms of flexibility, a linear alkylene group having no branching is preferable.
An acetal bond (a4) between an aromatic hydrocarbon group (a1) having a bonding site with another group in an aromatic nucleus and a hydrocarbon group (a2) containing an ether bond or a linear alkylene group (a3) having 2 to 15 carbon atoms is represented by the following formula (5).
[ solution 7]
In the formula (5), R8Selected from hydrogenAtom, methyl, ethyl, propyl, or tert-butyl. Among these structures, R is most preferable in terms of ease of production of the bifunctional epoxy resin itself8Methyl acetal bond (methyl acetal bond).
By using such an epoxy compound (B1), an adhesive excellent in adhesion between a nonpolar substrate such as an olefin resin and a metal substrate even when cured at a low temperature can be provided. The reason is not specified, but is estimated as follows. That is, since the epoxy compound (B1) has a structure derived from a hydrocarbon group (a2) containing an ether bond or a linear alkylene group (a3) having 2 to 15 carbon atoms, it is considered that the epoxy compound has excellent mobility at low temperature, is easily subjected to a crosslinking reaction with an acid group of the acid group-containing resin (a), and exhibits excellent adhesion even when cured at low temperature.
Specific chemical structures of such epoxy compounds (B1) include those in which the aromatic hydrocarbon group (a1) having a bonding site with another group in the aromatic nucleus, the hydrocarbon group (a2) containing an ether bond, the alkylene group (a3) having 2 to 15 carbon atoms, and the acetal bond (a4) are arbitrarily combined. Examples of these include the structures of the following structural formulae.
[ solution 8]
[ solution 9]
[ solution 10]
In each structural formula Ea-1-Ea-17, n is a natural number and the average value is 1.2-5. The compounds represented by the above-mentioned structural formulae may also be exemplified by resins each having a substituent such as a methyl group or a halogen atom in the aromatic nucleus. In the structural formula Ea-16, the bonding position of the aliphatic cyclic hydrocarbon group is an arbitrary secondary carbon atom of ethylene or propylene forming a ring.
Among these epoxy compounds (B1), compounds represented by the following general formula 1 are preferable in particular in terms of excellent balance between flexibility and toughness of the cured coating film, excellent adhesive strength and moldability when formed into an adhesive, and excellent water resistance. Specific examples of the epoxy compound (B1) represented by the following general formula 1 include compounds represented by the structural formulae Ea-1 to Ea-14.
[ solution 11]
(in the general formula 1, R1And R2Each represents a hydrogen atom or a methyl group, R3～R6Each represents a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom; x represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, or an alkylene group having 2 to 15 carbon atoms; in addition, n is a natural number and is 1.2 to 5 on average)
The epoxy compound (B1) is obtained by reacting a bifunctional phenol compound (a1'), a diol (a2') of a hydrocarbon compound containing an ether bond or a diol (a3') of a substantially linear hydrocarbon having 2 to 15 carbon atoms with a carbonyl compound to acetalize the resulting product, and then glycidylating the obtained bifunctional phenol.
Alternatively, the epoxy compound (B1) is obtained by reacting a bifunctional phenol compound (a1'), a divinyl ether of a hydrocarbon compound containing an ether bond (a2 ″), or a divinyl ether of a substantially linear hydrocarbon having 2 to 15 carbon atoms (a3 ″), and then reacting the obtained bifunctional phenol resin with epichlorohydrin.
The curing agent (B) may contain not only the epoxy compound (B1) but also an epoxy compound (B2) represented by the following general formula 2.
[ solution 12]
(in the general formula 2, R1And R2Each represents a hydrogen atom or a methyl group, R3～R6Each independently represents a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom)
It is also preferable to use not only the epoxy compound (B1) but also a combination of the epoxy compound (B2). This reduces the viscosity of the curing agent (adhesive), and provides good workability when applied to various applications. In addition, the adhesion strength becomes good. Specific examples of the epoxy compound (B2) include compounds in which n is 0 in the structural formula Ea-1 or the structural formula Ea-2.
In the case of using the epoxy compound (B1) and the epoxy compound (B2) together, the ratio of the epoxy compound (B2) to the total amount of the epoxy compound (B1) and the epoxy compound (B2) is preferably 10% by mass or more and 40% by mass or less.
The mixture of the epoxy compound (B1) and the epoxy compound (B2) preferably has an epoxy equivalent of 250 g/equivalent or more and 1000 g/equivalent or less and a viscosity of 2000 mPas or more and 150000 mPas or less at 25 ℃.
The curing agent (B) may contain not only the epoxy compound (B1) but also an epoxy compound (B3) other than the epoxy compound (B1) and the epoxy compound (B2). Alternatively, the epoxy compound (B3) other than the epoxy compound (B1) and the epoxy compound (B2) may be contained in addition to the epoxy compound (B1) and the epoxy compound (B2). Examples of the epoxy compound (B3) include:
polyglycidyl ether type epoxy resins of aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, hexylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, diglycerol, sorbitol, spiroglycol, and hydrogenated bisphenol a;
bisphenol epoxy resins such as bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol AD epoxy resin;
aromatic epoxy resins such as novolak type epoxy resins which are glycidyl ethers of phenol novolak resins or cresol novolak resins;
polyglycidyl ethers of polyhydric alcohols which are ethylene oxide or propylene oxide adducts of aromatic polyhydroxy compounds such as bisphenol a, bisphenol F, bisphenol S, and bisphenol AD;
polyglycidyl ether type epoxy resins of polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; cyclic aliphatic polyepoxy resins such as bis (3, 4-epoxycyclohexylmethyl) hexanoate and 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexylcarboxylate;
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;
diepoxy resins of hydrocarbon dienes such as butadiene, hexadiene, octadiene, dodecanediene, cyclooctadiene, α -pinene and vinylcyclohexene;
epoxy resins of diene polymers such as polybutadiene and polyisoprene;
glycidyl amine type epoxy resins such as tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, tetraglycidyl bisaminomethylcyclohexane, diglycidyl aniline, and tetraglycidyl m-xylylenediamine;
epoxy resins containing heterocyclic rings such as triazine and hydantoin.
These epoxy resins may be used alone or in combination of two or more.
The epoxy compound (B3) preferably contains two or more epoxy groups and one or more hydroxyl groups in one molecule, and has a weight average molecular weight of 3000 or less.
In the case of using the epoxy compound (B1) and the epoxy compound (B3) together, the ratio of the epoxy compound (B3) to the total amount of the epoxy compound (B1) and the epoxy compound (B3) is preferably 10 mol% or less in terms of epoxy groups. When flexibility of the cured product is required, it is preferably 5 mol% or less.
When the epoxy compound (B1), the epoxy compound (B2), and the epoxy compound (B3) are used in combination, the ratio of the epoxy compound (B3) to the total amount of the epoxy compound (B1), the epoxy compound (B2), and the epoxy compound (B3) is preferably 10 mol% or less in terms of epoxy groups. When flexibility of the cured product is required, it is preferably 5 mol% or less.
The epoxy compounds (B1) to (B3) are preferably used in such a range that the equivalent ratio (epoxy group/carboxyl group) of the carboxyl group contained in the acid group-containing resin (a) to the epoxy group contained in the epoxy compounds (B1) to (B3) is 0.01 to 10. This enables to form an adhesive having excellent heat resistance and adhesion. The equivalent ratio (epoxy group/carboxyl group) of the carboxyl group contained in the acid group-containing resin (a) to the epoxy group contained in the epoxy compounds (B1) to (B3) is more preferably 0.1 or more, and still more preferably 5 or less.
As the curing agent (B), a compound other than the epoxy resin may be used in combination within a range not impairing the effects of the present invention. Examples of other curing agents that can be used in combination with the epoxy resin include polyfunctional isocyanate compounds, aziridine group-containing compounds, carbodiimides, oxazolines, amino resins, and the like.
As the polyfunctional isocyanate compound, there can be mentioned: 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., isocyanurates, adducts, biuret types, uretdione (uretdione) bodies, allophanate (allophanate) bodies, prepolymers having an isocyanate residue (oligomers obtained from diisocyanates and polyols), or complexes thereof.
A compound obtained by reacting a part of the isocyanate groups of the polyfunctional isocyanate compound described above and a compound having reactivity with the isocyanate groups may also be used as the hardener. As compounds reactive with isocyanate groups, mention may be made of: 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-ethylhexyl alcohol, lauryl alcohol, 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 aziridinyl group-containing compound include: n, N '-hexamethylene-1, 6-bis (1-aziridinecarboxamide), N' -diphenylmethane-4, 4 '-bis (1-aziridinecarboxamide), trimethylolpropane-tris- β -aziridinylpropionate), N' -toluene-2, 4-bis (1-aziridinecarboxamide), triethylenemelamine, trimethylolpropane-tris- β (2-methylaziridine) propionate, bis-isophthaloyl-1-2-methylaziridine, tris-1-aziridinyloxyphosphine oxide, tris-1-2-methylaziridine phosphine oxide, and the like.
Examples of carbodiimides include: n, N '-di-o-benzoylcarbodiimide, N' -diphenylcarbodiimide, N '-di-2, 6-dimethylphenylcarbodiimide, N' -bis (2, 6-diisopropylphenyl) carbodiimide, N '-dioctyldecylcarbodiimide, N-toluoyl-N' -cyclohexylcarbodiimide, n, N '-di-2, 2-tert-butylphenyl carbodiimide, N-toluoyl-N' -phenylcarbodiimide, N '-di-p-aminophenyl carbodiimide, N' -di-p-hydroxyphenyl carbodiimide, N '-di-cyclohexylcarbodiimide, N' -di-p-toluoyl-carbodiimide, and the like.
As oxazoline (oxazoline), there may be mentioned: 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2, 5-dimethyl-2-oxazoline, 2, 4-diphenyl-2-oxazoline and other monooxazoline compounds, 2,2'- (1, 3-phenylene) -bis (2-oxazoline), 2,2' - (1, 2-ethylene) -bis (2-oxazoline), 2,2'- (1, 4-butylene) -bis (2-oxazoline), 2,2' - (1, 4-phenylene) -bis (2-oxazoline) and the like.
Examples of the amino (amino) resin include: melamine resins, benzoguanamine resins, urea resins, and the like.
The adhesive of the present invention may contain not only the acid group-containing resin (a) and the curing agent (B), but also various additives such as an adhesion-imparting agent, a plasticizer, a thermoplastic elastomer, a reactive elastomer, a phosphoric acid compound, a silane coupling agent, an acid anhydride, and an adhesion promoter, if necessary. The content of these additives may be appropriately adjusted within a range not to impair the function of the adhesive of the present invention.
Examples of the adhesion imparting agent that can be used here include: rosin-based or rosin ester-based tackiness imparting agents, terpene-based or terpene-phenol-based tackiness imparting agents, saturated hydrocarbon resins, coumarin-based tackiness imparting agents, coumarin-indene-based tackiness imparting agents, styrene resin-based tackiness imparting agents, xylene resin-based tackiness imparting agents, phenol resin-based tackiness imparting agents, petroleum resin-based tackiness imparting agents, and the like. These may be used alone or in combination of two or more.
Examples of the plasticizer include polyisoprene, polybutene, and process oil, examples of the thermoplastic elastomer include styrene-butadiene copolymer (SBS), styrene-butadiene copolymer hydrogenated product (SEBS), styrene-butadiene-butylene-styrene copolymer (SBBS), styrene-isoprene copolymer hydrogenated product (SEPS), styrene block copolymer (TPS), and olefin elastomer (TPO), and examples of the reactive elastomer include elastomers obtained by acid-modifying these elastomers.
Examples of the phosphoric acid compound include: phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid and hypophosphorous acid, for example, condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid and perphosphoric acid, for example, monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monophenyl orthophosphate, monomethyl phosphite, monoethyl phosphite, monopropyl phosphite, monobutyl phosphite, mono-2-ethylhexyl phosphite, monophenyl phosphite, di-2-ethylhexyl orthophosphate, dimethyl diphenylphosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, di-2-ethylhexyl phosphite and diphenyl phosphite, monoesters and diesters derived from condensed phosphoric acids and alcohols, for example, addition of ethylene oxide to the phosphoric acids, ethylene oxide to the phosphoric acids, Examples of the epoxy compound include epoxy phosphates obtained by adding the above-mentioned phosphoric acid compound to aliphatic or aromatic diglycidyl ether.
Examples of the silane coupling agent include: aminosilanes such as γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethyldimethoxysilane, and N-phenyl- γ -aminopropyltrimethoxysilane; epoxysilanes such as beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-glycidoxypropyltriethoxysilane; vinyl silanes such as vinyltris (β -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and γ -methacryloxypropyltrimethoxysilane; hexamethyldisilazane, gamma-mercaptopropyltrimethoxysilane, and the like.
Examples of the acid anhydride include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, and unsaturated carboxylic acid anhydrides, and one or two or more kinds of acid anhydrides may be used in combination. More specifically, for example, there may be mentioned: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecylsuccinic anhydride, polyhexamic anhydride, polyazelaic anhydride, polysebacic anhydride, poly (ethyloctadecanedioic) anhydride, poly (phenylhexadecanedioic) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethyltetrahydrophthalic anhydride (MHAC), trialkyltetrahydrophthalic anhydride, methylcyclohexanedicarboxylic anhydride, methylcyclohexanetetracarboxylic anhydride, ethylene glycol ditrimellitic dianhydride, biotic anhydride (HET anhydride), nadic anhydride (nadic anhydride), methylnadic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1, 2-dicarboxylic anhydride, 3, 4-dicarboxy-1, 2,3, 4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1, 2,3, 4-tetrahydro-1-naphthalene succinic dianhydride, and the like.
As the acid anhydride, an acid anhydride obtained by modifying the above compound with a diol can be used. Examples of diols which can be used for the modification include: alkanediols such as ethylene glycol, propylene glycol and neopentyl glycol; polyether glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol. Further, two or more of these diols and/or a copolyether diol of a polyether diol may be used.
The amount of the acid anhydride blended is preferably 0.05 parts by mass or more, more preferably 0.8 parts by mass or more, per 100 parts by mass of the acid group-containing resin (a). The amount of the acid anhydride blended is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, per 100 parts by mass of the acid group-containing resin (a). This improves the adhesion between the adhesive and the metal, and enables the production of an adhesive having excellent initial adhesion strength and excellent adhesion strength after heat sealing.
Examples of the adhesion promoter include: imidazole compounds such as 2-methylimidazole, 1, 2-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole, tertiary amines such as triethylamine, triethylenediamine, N' -methyl-N- (2-dimethylaminoethyl) piperidine, 1, 8-diazabicyclo [5.4.0] undecene (DBU), 1, 5-diazabicyclo [4.3.0] -nonene and 6-dibutylamino-1, 8-diazabicyclo [5.4.0] undecene, and amine salts of these tertiary amines with phenol, octylic acid, quaternary tetraphenylborate and the like, cationic catalysts such as triallylsulfonium hexafluoroantimonate and diallyliodohexafluoroantimonate, and organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-butylphenyl) phosphine, diphenylphosphine, and phenylphosphine. These may be used alone or in combination of two or more.
The adhesive of the present invention can exhibit proper coatability while securing fluidity by blending not only the above-mentioned components but also an organic solvent. Such an organic solvent is not particularly limited as long as it can be volatilized and removed by heating in the drying step at the time of application of the adhesive, and examples thereof include: aromatic organic solvents such as toluene and xylene; aliphatic organic solvents such as n-hexane and n-heptane; alicyclic organic solvents such as cyclohexane and methylcyclohexane; halogen-based organic solvents such as trichloroethylene, dichloroethylene, chlorobenzene, and chloroform; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; alcohol solvents such as ethanol, methanol, n-propanol, 2-propanol (isopropanol), butanol, and hexanol; ether solvents such as diisopropyl ether, butyl cellosolve, tetrahydrofuran, dioxane, and butyl carbitol; glycol ether solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and propylene glycol monomethyl ether; and glycol ester solvents such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate, which may be used alone or in combination of two or more.
In the case of using an organic solvent, the organic solvent may be prepared by mixing the acid group-containing resin (a) and the curing agent (B), or the adhesive may be prepared by dissolving at least one of the acid group-containing resin (a) and the curing agent (B) in an organic solvent in advance.
The amount of the organic solvent to be blended is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, of the organic solvent component, per 100 parts by mass of the total amount of the adhesive. Further, it is preferably 90 parts by mass or less, and more preferably 85 parts by mass or less.
The adhesive of the present invention can be prepared by mixing the components. In this case, the respective components may be mixed at the same time to prepare an adhesive, but in terms of excellent stability and workability of the adhesive, it is preferable to prepare a two-pack type adhesive in which a pre-mixture (premix) is prepared by mixing components other than the curing agent (B) in advance and the curing agent (B) is mixed when the adhesive is used.
The adhesive of the present invention is excellent in adhesion between a nonpolar substrate such as an olefin resin and a metal substrate even when cured at a low temperature. The adhesive of the present invention is suitable for a method for producing a laminate by a dry lamination method because it is excellent in adhesion between a nonpolar substrate such as an olefin resin and a metal substrate even when cured at low temperature, but can be used as a primer (primer) in the production of a laminate by an extrusion lamination method, for example.
< laminate >
The laminated body comprises a first base material, a second base material and an adhesive layer which is arranged between the first base material and the second base material and is used for bonding the first base material and the second base material. The adhesive layer is a cured coating of the adhesive. The substrate may include not only the first substrate and the second substrate, but also other substrates. The adhesive layer for bonding the first substrate and the other substrate and the second substrate and the other substrate may or may not be a cured coating film of the adhesive of the present invention.
As the first substrate, the second substrate, and other substrates, for example, paper; a synthetic resin film obtained from an olefin-based resin, an acrylonitrile-butadiene-styrene copolymer (ABS resin), a polyvinyl chloride-based resin, a fluorine-based resin, a poly (meth) acrylic resin, a carbonate-based resin, a polyamide-based resin, a polyimide-based resin, a polyphenylene ether-based resin, a polyphenylene sulfide-based resin, or a polyester-based resin; metal foils such as copper foil and aluminum foil.
The adhesive of the present invention is preferably one of the first substrate and the second substrate which is a nonpolar substrate and the other of the first substrate and the second substrate which is a metal substrate, because the adhesive is excellent in adhesion between a nonpolar substrate such as an olefin resin and a metal substrate, but is not limited thereto.
The laminate of the present invention can be obtained, for example, by a so-called dry lamination (dry lamination) method in which the adhesive of the present invention is applied to one of a first substrate and a second substrate, the other is laminated, and the adhesive is cured. It is preferable to provide a drying step between the coating of the adhesive and the lamination of the first base material and the second base material.
As the method of applying the adhesive, a gravure coater method, a micro-gravure coater method, a reverse coater method, a bar coater method can be usedA roll coater system, a die coater system, and the like. The amount of the adhesive applied is preferably 0.5g/m in terms of the coating weight after drying2～20.0g/m2Is adjusted. If it is less than 0.5g/m2When the amount exceeds 20.0g/m, the continuous uniform coatability tends to be lowered2The solvent release property after coating is also lowered, and problems such as lowering of workability and remaining of solvent tend to occur.
The temperature of the laminating roller when laminating the first base material and the second base material is preferably 25 ℃ to 120 ℃ and the pressure is preferably 3kg/cm2～300kg/cm2。
Preferably, the curing step is provided after the first substrate and the second substrate are bonded to each other. The aging conditions are preferably 25 to 100 ℃ for 12 to 240 hours.
As a curing agent for an acid group-containing resin, for example, in the case of using an epoxy compound, the properties of the adhesive tend to be exerted more easily by curing at low temperature than in the case of using an isocyanate compound, but in the case of using the adhesive of the present invention, a laminate excellent in initial adhesive strength and electrolyte resistance can be obtained even if the curing temperature is 50 ℃. When the aging temperature is 50 ℃ or more, the adhesive strength and the electrolyte resistance are also excellent. In addition, in order to ensure the adhesion strength and the electrolyte resistance of the present invention, the aging temperature is more preferably 40 ℃ or higher.
Alternatively, the laminate of the present invention may be obtained by coating one of the first substrate and the second substrate with the adhesive of the present invention as an intermediate coating agent, and then laminating the other by an extrusion lamination method. For example, when the first substrate is a polyolefin film and the second substrate is a metal foil, the adhesive of the present invention is applied to the second substrate as an intermediate coating agent, and then the first substrate is laminated by an extrusion lamination method. It is preferable to provide a drying step between the coating of the adhesive and the lamination of the first base material by the extrusion lamination method. The coating method of the adhesive is not particularly limited, and a gravure roll method is exemplified. On the non-lamination surface of the adhesive, when another substrate is laminated by extrusion lamination, a laminate is obtained by nipping with a rubber roller and a cooling roller.
< packaging Material for Battery >
As an example, the battery packaging material of the present invention includes a first base material, a second base material, a third base material, a first adhesive layer that bonds the first base material to the second base material, and a second adhesive layer that bonds the second base material to the third base material. The first substrate is a polyolefin film and the second substrate is a metal foil. The third base material is a resin film such as nylon or polyester. The first adhesive layer is a cured coating of the adhesive of the present invention. The second adhesive layer may or may not be a cured coating of the adhesive of the present invention. On the opposite side of the third substrate to the second adhesive layer, another substrate may be disposed with or without an adhesive layer therebetween, or a coating layer may be provided. Other substrates or coatings may not be provided.
The polyolefin film may be appropriately selected from conventionally known olefin resins. For example, polyethylene, polypropylene, ethylene-propylene copolymer, etc. can be used, but are not particularly limited. Preferably a non-stretched film. The thickness of the polyolefin film is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 25 μm or more. Further, it is preferably 100 μm or less, more preferably 95 μm or less, and further preferably 90 μm or less.
When a battery described later is manufactured, the first base material functions as a sealant (sealant) layer when the battery packaging materials of the present invention are heat-sealed and bonded to each other.
Examples of the metal foil include aluminum, copper, and nickel. These metal foils may be subjected to surface treatments such as blasting, polishing, degreasing, aging, surface treatment by dipping or spraying with a rust preventive, trivalent chromium chemical synthesis treatment, phosphate chemical synthesis treatment, sulfide chemical synthesis treatment, anodic oxide film formation, and fluororesin coating. Of these, those obtained by applying a trivalent chromium chemical synthesis treatment are preferable in terms of excellent adhesion retention performance (resistance to environmental deterioration) and corrosion resistance. In addition, the thickness of the metal film is preferably in the range of 10 μm to 100 μm from the viewpoint of corrosion prevention.
Examples of the resin film that can be used as the third substrate include resin films of polyester resin, polyamide resin, epoxy resin, acrylic resin, fluororesin, polyurethane resin, silicone resin, phenol resin, and a mixture or copolymer thereof. Of these, polyester resins and polyamide resins are preferable, and biaxially stretched polyester resins and biaxially stretched polyamide resins are more preferable. Specific examples of the polyester resin include: polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolyester, polycarbonate, and the like. Further, as the polyamide resin, specifically, there can be mentioned: nylon 6, copolymers of nylon 6 and nylon 6, nylon 6,10, poly m-xylene adipamide (MXD6), and the like.
The coating layer can be formed using, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, or the like. Preferably, the resin is formed of a two-part curable resin. Examples of the two-component curable resin for forming the coating layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Further, a matting agent may be blended in the coating layer.
Examples of the matting agent include fine particles having a particle diameter of about 0.5nm to 5 μm. The material of the matting agent is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances. The shape of the matting agent is also not particularly limited, and examples thereof include spherical, fibrous, plate-like, amorphous, and balloon-like shapes. Specific examples of the matting agent include: talc, silica, graphite, kaolin, montmorillonite (montmorillonite), synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, carbon black, carbon nanotubes, high-melting nylon, crosslinked acrylic acid, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel, and the like. These matting agents may be used singly or in combination of two or more. Among these matting agents, silicon oxide, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability, cost, and the like. The matting agent may be subjected to various surface treatments such as an insulating treatment and a high-dispersibility treatment in advance.
When a battery is produced, the laminate is molded so that the polyolefin film as the first base material is located inside the third base material, thereby forming the secondary battery packaging material of the present invention. The molding method is not particularly limited, and the following methods are exemplified.
A heated-air-pressure molding method: a method of forming the recess by sandwiching the battery packaging material between a lower mold having a hole to which high-temperature and high-pressure air is supplied and an upper mold having a pocket-shaped recess, and supplying air while heating and softening the upper mold.
A preheater flat plate type air compression molding method: a method of heating and softening the battery packaging material, sandwiching a lower mold having a hole to which high-pressure air is supplied and an upper mold having a pocket-shaped recess, and supplying air to form the recess.
Drum vacuum forming method: the method comprises heating and softening the packaging material for battery locally with a heating drum, and vacuum-sucking the packaging material for battery into the recessed part of the drum having the recessed part in the shape of a bag to mold the recessed part.
Needle (pin) molding method: and a method of heating and softening the substrate sheet and then pressing the substrate sheet with a bag-shaped concave-convex mold.
A pre-heater plug auxiliary pressure-air forming method: the method comprises heating and softening the packaging material for battery, sandwiching a lower mold having a hole and an upper mold having a pocket-shaped recess, to which high-pressure air is supplied, and supplying air to form the recess, wherein a convex plug is raised and lowered during molding to assist molding.
The pre-heater plug-assist press-air molding method, which is a heating vacuum molding method, is preferable because the wall thickness of the molded base material is uniform.
The battery packaging material of the present invention obtained as described above can be suitably used as a battery container for sealing and storing battery elements such as a positive electrode, a negative electrode, and an electrolyte.
< Battery >
The battery of the present invention is obtained by using the battery packaging material of the present invention, covering a battery element including a positive electrode, a negative electrode, and an electrolyte so that flange portions (regions where sealant layers contact each other) can be formed at the peripheral edge of the battery element in a state where metal terminals connected to the positive electrode and the negative electrode, respectively, protrude to the outside, and heat-sealing the sealant layers of the flange portions to each other to seal the battery element.
The battery obtained using the battery packaging material of the present invention may be either a primary battery or a secondary battery, and is preferably a secondary battery. The secondary battery is not particularly limited, and examples thereof include a lithium ion battery, a lithium ion polymer battery, a lead storage battery, a nickel-hydrogen storage battery, a nickel-cadmium storage battery, a nickel-iron storage battery, a nickel-zinc storage battery, a silver-zinc oxide storage battery, a metal air battery, a polyvalent cation battery, a capacitor (condenser), and a capacitor (capacitor). Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries are suitable as the battery packaging material of the present invention.
[ examples ]
The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, the composition and other numerical values are used as quality standards.
< preparation of resin varnish containing acid group >
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
16 parts of GMP7550E (acid-modified olefin resin, manufactured by Lotte Chemical Co.), 4 parts of Orland (AUROREN)350S (acid-modified olefin resin, manufactured by Japan paper-making), 72 parts of methylcyclohexane, 5 parts of ethyl acetate, and 3 parts of isopropyl alcohol (IPA) were sufficiently stirred to prepare varnish 2 which was a solution having a nonvolatile content of 20.5%.
Preparation example 3 preparation of varnish 3
20 parts by weight of Poly (ethylene-co-acrylic acid) acrylic acid (Poly (ethylene-co-acrylic acid) acrylic acid) (polyethylene/acrylic acid copolymer, manufactured by Aldrich) 20 parts, 72 parts of toluene, and 8 parts of isopropyl alcohol (IPA) were sufficiently stirred to obtain varnish 3 having a nonvolatile content of 19.9%.
Preparation example 4 preparation of varnish 4
120g of toluene was charged into a reaction apparatus comprising a stirrer, a thermometer, a cooling tube, a dropping funnel and a nitrogen inlet tube, and the temperature in the system was raised to 100 ℃ under a nitrogen flow for about 1 hour, followed by heat preservation 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 Perbutyl (tbutyl) O (tert-butyl peroxyethylhexanoate, manufactured by nipponk chemical corporation) was added in advance, the mixed solution was dropped under a nitrogen flow for about 4 hours, and stirred at 100 ℃ for 6 hours. After cooling, 90g of toluene was added to obtain varnish 4 which was an acrylic resin solution containing an acid group and having a nonvolatile content of 46.8%.
Preparation example 5 preparation of varnish 5
50mL of toluene was charged into a reaction apparatus including a stirring apparatus, a cooling tube, a dropping funnel and a nitrogen introduction tube, and the inside of the system was replaced by bubbling argon (bubbling) 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 temperature in the system reached a certain temperature, a mixture 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 was added dropwise over 1 hour. After stirring for 4 hours while maintaining the bath temperature under argon gas flow, a 5mL toluene solution of 118mg of 2,2' -azobisisobutyronitrile was added dropwise, and stirring was again performed for 4 hours while maintaining the bath temperature. After cooling to room temperature, the obtained slightly white turbid homogeneous solution was poured into about 1.2L of methanol and precipitated. The precipitate was washed 3 times with methanol and then dried overnight at 40 ℃ under reduced pressure to obtain 48g of a white solid. The obtained white solid was dissolved in toluene to obtain varnish 5 which was an acrylic resin solution containing an acid group and having a nonvolatile content of 30.0%.
Preparation example 6 preparation of varnish 6
90 parts of 2, 2-dimethylolpropionic acid (DMPA), 54 parts of methyl ethyl ketone and 81 parts of tetrahydrofuran were added to a reaction apparatus comprising a stirring apparatus, a thermometer, a cooling tube, a dropping funnel and a nitrogen introduction tube, and stirred under a nitrogen stream. Subsequently, 56 parts of Takenate 500 (xylene diisocyanate, 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 ℃, 56 parts of tacrine (Takenate) were further added, and the temperature was again raised to 60 ℃. The reaction was continued until disappearance of the isocyanate group was confirmed by infrared spectroscopy. Subsequently, 148 parts of methanol as a dilution solvent was added to obtain varnish 6, which is a 50% solution of the carboxyl group-containing urethane resin.
Preparation example 7 preparation of varnish 7
20 parts of Hi-wax (Hi-wax) NL100 (olefin resin, manufactured by Mitsui chemical Co., Ltd.) and 80 parts of toluene were sufficiently stirred to obtain varnish 7 which was a solution containing 20.1% of nonvolatile matter.
The solid acid values of varnish 1 to varnish 7 were measured and summarized in Table 1. The acid value of the olefin resin having an acid group is measured by a Fourier transform Infrared Spectroscopy (Fourier transform Infrared Spectroscopy) method. The acid value of the acrylic resin containing an acid group and the urethane resin containing an acid group is measured by the method calculated from the amount of the alcoholic potassium hydroxide solution added dropwise.
[ Table 1]
< Synthesis of epoxy Compound >
(Synthesis example 1)
(Synthesis of modified Polyphenol (ph-1 a))
228g of bisphenol A (1.00 mol) and 172g (0.85 mol) of triethylene glycol divinyl ether (product of ISP company: Rapi-Cure DVE-3) were added to a flask equipped with a thermometer and a stirrer, and the mixture was heated to 120 ℃ over 1 hour, and then reacted at 120 ℃ for 6 hours to obtain 400g of a transparent semisolid modified polyphenol (ph-1 a).
From Nuclear Magnetic Resonance (NMR) spectrum (13C) and peaks of M + ═ 658 and M + ═ 1088, which obtained theoretical structures corresponding to n ═ 1 and n ═ 2 in the mass spectrum, it was confirmed that the obtained modified polyphenol (ph-1a) had a structure represented by the following structural formula Pa-1. The modified polyphenol (ph-1a) had a hydroxyl group equivalent of 364g/eq and a viscosity of 40mPa · s (150 ℃ C., ICI viscometer), and the average value of n in the following structural formula Pa-1, calculated from the hydroxyl group equivalent, was 3.21 in the component n ≧ 1 and 1.16 in the component n ≧ 0.
[ solution 13]
(Synthesis of epoxy resin (ep-1 a))
400g (364 g/eq. hydroxyl equivalent) of the obtained modified polyphenol (ph-1a), 925g (10 moles) of epichlorohydrin, and 185g 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 continued for 0.5 hour after the end of the dropwise addition. Meanwhile, a Dean-Stark trap (Dean-Stark trap) was used to separate a distillate distilled off at the time of azeotropy, remove an aqueous layer, and return an organic layer to the reaction system to carry out a reaction. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. To the crude epoxy resin obtained was added 1000g of methyl isobutyl ketone and 100g of n-butanol and dissolved, and 20g of a 10% aqueous sodium hydroxide solution was added to the solution and reacted at 80 ℃ for 2 hours, and then the solution was washed with 300g of water repeatedly 3 times until the pH of the washing solution was neutral. Then, the inside of the system was dehydrated by azeotropic distillation, followed by microfiltration and then solvent removal by distillation under reduced pressure to obtain 457g of a transparent liquid epoxy resin (ep-1 a). From the NMR spectrum (13C) and the mass spectrum, peaks corresponding to theoretical structures of n ═ 1 and n ═ 2, M + ═ 770 and M + ═ 1200 were obtained, and it was confirmed that the epoxy resin (ep-1a) contained an epoxy resin having a structure represented by the structural formula Ea-1.
The obtained epoxy resin (ep-1a) was a mixture of the compound of the structural formula Ea-1 in which n was 0 and a compound in which n was 1 or more, and as a result of confirmation by GPC, the compound in which n was 0 was contained at a ratio of 20 mass%. The epoxy equivalent of the epoxy resin (ep-1a) was 462g/eq, the viscosity was 12000mPa · s (25 ℃, Cannon-Fenske method), and the average value of n in the structural formula Ea-1 calculated from the epoxy equivalent was 2.97 in the component of n ≧ 1 and 1.35 in the component of n ≧ 0.
(Synthesis example 2)
(Synthesis of modified Polyphenol (ph-2 a))
Modified polyphenol (ph-2a) was obtained in the same manner as in the synthesis of modified polyphenol (ph-1a) of synthesis example 1, except that the amount of triethylene glycol divinyl ether (DVE-3) was changed to 101 g. The modified polyphenol (ph-2a) had a hydroxyl group equivalent of 262g/eq and a viscosity of 60mPa · s (150 ℃, ICI viscometer), and the average value of n in the following structural formula Pa-1, calculated from the hydroxyl group equivalent, was 2.21 in the component n ≧ 1 and 0.69 in the component n ≧ 0.
(Synthesis of epoxy resin (ep-2 a))
Epoxy resin (ep-2a)395g was obtained in the same manner as in the synthesis of epoxy resin (ep-1a) of Synthesis example 1, except that the modified polyphenol as a raw material was changed from (ph-1a) to 329g of (ph-2 a). The obtained epoxy resin (ep-2a) was a mixture of the compound of the structural formula Ea-1 in which n was 0 and a compound in which n was 1 or more, and as a result of confirmation by GPC, the compound in which n was 0 was contained at a ratio of 30 mass%. The epoxy resin (ep-2a) had an epoxy equivalent of 350g/eq and a viscosity of 90000 mPas (25 ℃, an E-type viscometer, and the average value of n in the structural formula Ea-1 calculated from the epoxy equivalent was 2.18 in the case of the component n ≧ 1 and 0.84 in the case of the component n ≧ 0.
< preparation of adhesive >
(example 1)
100 parts of varnish 1, 0.5 part of epoxy compound (ep-1a), 0.03 part of Curezol (Curezol)2E4MZ (imidazole-based curing agent, manufactured by Sikko chemical industries, Ltd., nonvolatile content 100%), 0.01 part of triphenylphosphine, 3 parts of ethyl acetate, and 2 parts of isopropyl alcohol were sufficiently stirred to prepare an adhesive of example 1 having a nonvolatile content of 20%.
Adhesive 1 of example 1 was applied at 4g/m using a bar coater2(Dry) the film was coated on an aluminum foil (1N30, manufactured by Toyo aluminum Co., Ltd., film thickness 30 μm), dried at 80 ℃ for 1 minute, and then bonded to a non-oriented polypropylene film (ET-20, manufactured by Okamoto Co., Ltd., film thickness 40 μm) at 100 ℃. Thereafter, the mixture was aged at 50 ℃ for 5 days to obtain a laminate of example 1.
(example 2-example 10)
An adhesive was prepared in the same manner as in example 1 except that the adhesive formulation was as shown in tables 2 and 3, to obtain a laminate.
Comparative examples 1 to 5
An adhesive was prepared in the same manner as in example 1 except that the formulation of the adhesive was as shown in table 4, to obtain a laminate.
The epoxy compound (HP-4700) used in the comparative example was a naphthalene type epoxy compound manufactured by Diegon (DIC) Co.
< evaluation >
The evaluation was performed as follows, and the results are shown in tables 2 to 4.
(measurement of initial adhesion Strength)
The adhesion strength of the cured laminate was evaluated under the conditions of a peel width of 15mm and a peel form of T-type using a Tencilon (Tensilon) manufactured by A & D (Strand).
(electrolyte resistance)
As an electrolyte, a solution prepared from ethylene carbonate: ethyl methyl carbonate: dimethyl carbonate ═ 1: 1: 1 (wt%) mixed solution with LiPF6The amount of ethylene carbonate added was 1 mol% and 1 wt% respectively.
The cured laminate was immersed in 35g of an electrolyte solution at 85 ℃ for 7 days, and evaluated in terms of the retention of adhesive strength before and after immersion as described below.
O: over 60 percent
And (delta): more than 40 percent and less than 60 percent
X: less than 40 percent
[ Table 2]
[ Table 3]
[ Table 4]
As is clear from tables 2 to 4, when aging is performed at a low temperature, the adhesive of the present invention is superior in initial adhesive strength and electrolyte resistance to the adhesive of the comparative example.
[ Industrial Applicability ]
The adhesive of the present invention is excellent in adhesion between a nonpolar substrate such as an olefin resin and a metal substrate even when cured at a low temperature, and a laminate obtained using the adhesive of the present invention can be suitably used for a battery packaging material, for example. The adhesive of the present invention is not limited to a battery packaging material or a laminate used for the battery packaging material, and can be widely used in the field of adhesion between a metal substrate and a substrate requiring non-polarity, such as an outer plate of a home appliance, a material for furniture, and an interior member for a building.

Claims (9)

1. An adhesive agent comprising a resin (A) having an acid group and a curing agent (B) comprising an epoxy compound, wherein the curing agent (B) comprises an epoxy compound (B1), and the epoxy compound (B1) has a structure in which an aromatic hydrocarbon group (a1) having a bonding site with another group in an aromatic nucleus and a hydrocarbon group (a2) having an ether bond or a linear alkylene group (a3) having 2 to 15 carbon atoms are bonded via an acetal bond (a4), and has a structure in which a glycidyloxy group is bonded to the aromatic hydrocarbon group (a 1).
2. The adhesive according to claim 1, wherein the epoxy compound (B1) is represented by the following general formula 1,
[ solution 14]
In the general formula 1, R1And R2Each represents a hydrogen atom or a methyl group, R3～R6Each represents a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom; x represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, or an alkylene group having 2 to 15 carbon atoms; in addition, n is a natural number and is 1.2 to 5 on average.
3. The adhesive according to claim 1 or 2, wherein the acid group-containing resin (a) is at least one selected from the group consisting of an acid group-containing acrylic resin, an acid group-containing urethane resin, and an acid group-containing olefin resin.
4. The adhesive according to claim 1 or 2, wherein the epoxy compound (B1) is used in a range in which an equivalent ratio (epoxy group/carboxyl group) of a carboxyl group contained in the acid group-containing resin (a) to an epoxy group contained in the hardener (B) is 0.01 or more and 10 or less.
5. The adhesive according to claim 1 or 2, wherein the hardener (B) comprises an epoxy compound (B2) represented by the following general formula 2,
[ solution 15]
In the general formula 2, R1And R2Each represents a hydrogen atom or a methyl group, R3～R6Each independently represents a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom.
6. A laminate, characterized in that: comprising a first substrate, a second substrate, and an adhesive layer for bonding the first substrate and the second substrate, wherein the adhesive layer is a cured coating film of the adhesive according to any one of claims 1 to 5.
7. A battery packaging material, comprising: a polyolefin film;
a resin film;
a metal foil disposed between the polyolefin film and the resin film; and
an adhesive layer disposed between the polyolefin film and the metal foil,
the adhesive layer is a hardened coating film of the adhesive according to any one of claims 1 to 5.
8. A battery container obtained by molding the battery packaging material according to claim 7.
9. A battery using the battery container according to claim 8.
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