WO2015046378A1 - 接着剤組成物及びそれを用いた熱融着性複合部材 - Google Patents

接着剤組成物及びそれを用いた熱融着性複合部材 Download PDF

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Publication number
WO2015046378A1
WO2015046378A1 PCT/JP2014/075522 JP2014075522W WO2015046378A1 WO 2015046378 A1 WO2015046378 A1 WO 2015046378A1 JP 2014075522 W JP2014075522 W JP 2014075522W WO 2015046378 A1 WO2015046378 A1 WO 2015046378A1
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Prior art keywords
polyolefin resin
weight
resin
adhesive composition
modified polyolefin
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PCT/JP2014/075522
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English (en)
French (fr)
Japanese (ja)
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伊藤　隆浩
友哉 杉木
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東亞合成株式会社
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Publication of WO2015046378A1 publication Critical patent/WO2015046378A1/ja

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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6204—Polymers of olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/02—Open containers
    • B32B2439/06—Bags, sacks, sachets
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives

Definitions

  • the present invention relates to an adhesive composition and a heat-fusible composite member using the adhesive composition. More specifically, it provides excellent adhesion and heat resistance, solvent resistance, etc. at the bonded part after bonding two members, and is useful for bonding a polyolefin resin molded body such as a polyolefin resin film and other members.
  • the present invention relates to an adhesive composition and a heat-fusible composite member obtained by bonding a metal foil such as an aluminum foil and a heat-fusible resin film by using the adhesive composition.
  • Patent Document 1 discloses an adhesive composition for polyolefin sheets containing an acid-modified chlorinated polyolefin resin having a softening point of 70 ° C. to 100 ° C., a specific amount of blocked isocyanate, and an organic solvent.
  • Patent Document 2 discloses an adhesive composition in which a component comprising a carboxylic acid-containing polyolefin resin, a carboxylic acid-containing epoxy resin, a polyisocyanate compound, and, if necessary, an epoxy resin is dissolved and dispersed in an organic solvent. Things are disclosed.
  • These adhesive compositions form a composite as a result of being used to bond a plurality of members. And this composite is applied to uses, such as a sealing container which accommodates foodstuffs, a medicine, etc., a household miscellaneous goods.
  • a sealing container which accommodates foodstuffs, a medicine, etc., a household miscellaneous goods.
  • shape stability can be obtained.
  • shape stability is not necessarily obtained. is not.
  • a molded article made of polyolefin resin such as a polyolefin resin film and a metal product such as metal foil.
  • a polyolefin resin film, an aluminum foil, and a heat-resistant resin film are bonded to form a packaging material, a container, or the like that accommodates an electrochemical cell body for a lithium ion battery including a current collector, an active material layer, an electrolyte layer, and the like.
  • a laminated body is used.
  • the present invention when two members are bonded to form a joined body, sufficient adhesive strength is obtained in a wide temperature range of ⁇ 30 ° C. to 80 ° C., and heat resistance (heat resistant adhesiveness) and solvent resistance at the bonded portion are obtained. It aims at providing the adhesive composition excellent in property. Furthermore, the present invention has an object to provide a heat-fusible composite member in which a metal foil such as an aluminum foil and a heat-fusible resin film such as a polyolefin resin film are joined by this adhesive composition. To do.
  • solvent resistance means that, after two members are bonded with an adhesive composition, when the bonded portion comes into contact with a liquid containing an organic solvent, it does not cause peeling or the like. It means not lost.
  • the present inventors have intensively studied in view of the above problems, and have found that a modified polyolefin resin graft-modified with a modifier containing an ⁇ , ⁇ -unsaturated carboxylic acid or derivative thereof and having a specific dielectric constant in a specific range; It has been found that a composition containing a polyfunctional isocyanate compound can provide excellent adhesiveness, heat resistance (heat resistant adhesiveness) and solvent resistance in an adhesive part after bonding two members. It came to complete. That is, the present invention is as follows. 1.
  • An adhesive composition containing an organic solvent, a modified polyolefin resin that dissolves in the organic solvent, and a polyfunctional isocyanate compound is a resin obtained by graft-modifying an unmodified polyolefin resin with a modifier containing an ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof,
  • An adhesive composition, wherein the modified polyolefin resin measured at a frequency of 1 GHz has a relative dielectric constant of 2.02 to 2.50. 2.
  • the adhesive composition according to 1 or 2 wherein the ⁇ , ⁇ -unsaturated carboxylic acid derivative is at least one selected from the group consisting of itaconic anhydride, maleic anhydride, aconitic anhydride, and citraconic anhydride. object. 4).
  • the adhesive composition according to item. 5 further includes a (meth) acrylic acid ester represented by the following general formula (1), and the modified polyolefin-based resin comprises an ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof and the (meth) acrylic acid. 5.
  • the relative dielectric constant is a value measured according to ASTM D 2520 (cavity resonator perturbation method), and the weight average molecular weight (hereinafter also referred to as “Mw”) is a gel permeation chromatography. (Hereinafter also referred to as “GPC”).
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • the adhesive composition of the present invention is suitable for bonding two members, for example, for bonding a molded body made of a thermoplastic resin such as polyolefin resin and other members (metal member, resin member, etc.). Is preferred. That is, the adhesive composition of the present invention not only adheres between polyolefin resin molded articles such as polyolefin resin films, but also adheres between a polyolefin resin film and a metal foil made of aluminum or the like, a polyolefin resin film, a resin layer, and It can also be used for adhesion to a metal layer in a composite film including a metal layer.
  • the adhesive layer formed after bonding two members using the adhesive composition of the present invention exhibits high adhesive strength at room temperature (25 ° C.), and further has a temperature of about 60 ° C. to 80 ° C. Also has excellent heat resistance (heat adhesion), solvent resistance, and the like.
  • a laminate obtained by bonding a polyolefin resin film, an aluminum foil, and a heat-resistant resin film that is, a product obtained by using the heat-fusible composite member of the present invention, the adhesive composition of the present invention
  • the adhesive composition of the present invention when an encapsulated product containing an electrochemical cell main body for a lithium ion battery is manufactured by adhering a polyolefin resin film and an aluminum foil, the bonded part is excellent at a high temperature when the battery is driven. High resistance to electrolyte (solvent resistance).
  • the heat-fusible composite member of the present invention is excellent in heat resistance (heat-resistant adhesiveness) and solvent resistance, it is suitable for heat seal processing etc., in the form of bags, containers, etc. In the case of a sealed product containing a product, electronic component, electrical product, etc., it is possible to prevent the contents from being altered while maintaining the structure.
  • the adhesive composition of the present invention is an adhesive composition containing an organic solvent, a modified polyolefin resin dissolved in the organic solvent, and a polyfunctional isocyanate compound, wherein the modified polyolefin resin Is a resin obtained by graft-modifying an unmodified polyolefin resin with a modifier containing ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof, and the relative dielectric constant of the modified polyolefin resin measured at a frequency of 1 GHz is 2.02. It is characterized by being up to 2.50.
  • the modified polyolefin resin is a resin having a portion derived from an unmodified polyolefin resin and a graft portion derived from a modifier, and preferably an ⁇ , ⁇ -unsaturated carboxylic acid or a carboxylic acid in the presence of the unmodified polyolefin resin. It is obtained by graft polymerization of a modifier containing the derivative. Production of the modified polyolefin resin by graft polymerization can be performed by a known method, and a radical initiator may be used in the production.
  • the method for producing the modified polyolefin resin for example, a solution method in which the unmodified polyolefin resin is heated and dissolved in a solvent such as toluene and the modifier and the radical initiator are added, a Banbury mixer, a kneader, an extruder, etc. are used. Examples thereof include a melting method in which an unmodified polyolefin resin, a modifier and a radical initiator are melt-kneaded.
  • the method of using the unmodified polyolefin resin, the modifier and the radical initiator is not particularly limited, and these may be added to the reaction system all at once or sequentially.
  • a modification aid for improving the grafting efficiency of ⁇ , ⁇ -unsaturated carboxylic acid, a stabilizer for adjusting resin stability, and the like can be further used.
  • the unmodified polyolefin resin is not particularly limited as long as it has a structural unit derived from olefin, but the number of carbon atoms such as ethylene, propylene, butene, pentene, hexene, heptene, octene, 4-methyl-1-pentene, etc.
  • a homopolymer or copolymer of 2 or more and 20 or less is preferably used.
  • an olefin homopolymer or copolymer having 2 to 6 carbon atoms is particularly preferred.
  • the modified polyolefin resin is A modified resin of ethylene-propylene, propylene-butene or ethylene-propylene-butene copolymer is preferable.
  • flexibility can be provided to the adhesion part after bonding two members as the content rate of a propylene unit is 98 mol% or less.
  • the molecular weight of the unmodified polyolefin resin is not particularly limited.
  • the modifying agent contains ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof.
  • ⁇ , ⁇ -unsaturated carboxylic acid include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, aconitic acid, norbornene dicarboxylic acid and the like.
  • unsaturated polycarboxylic acid derivative include acid anhydrides, acid halides, amides, imides, and esters.
  • itaconic anhydride, maleic anhydride, aconitic anhydride and citraconic anhydride are preferable, and itaconic anhydride and maleic anhydride are particularly preferable in terms of adhesiveness.
  • a modifier it may be one or more selected from ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof, a combination of one or more ⁇ , ⁇ -unsaturated carboxylic acids and one or more derivatives thereof, ⁇ , A combination of two or more ⁇ -unsaturated carboxylic acids or a combination of two or more derivatives of ⁇ , ⁇ -unsaturated carboxylic acids can be used.
  • the modifying agent according to the present invention can contain other compounds (other modifying agents) in addition to the ⁇ , ⁇ -unsaturated carboxylic acid and the like depending on the purpose.
  • compounds (other modifiers) for example, (meth) acrylic acid ester, (meth) acrylic acid, other (meth) acrylic acid derivatives, aromatic vinyl compounds represented by the following general formula (1) And cyclohexyl vinyl ether.
  • These other compounds may be used alone or in combination of two or more.
  • CH 2 CR 1 COOR 2 (1) (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrocarbon group.)
  • R 1 is a hydrogen atom or a methyl group, preferably a methyl group.
  • R 2 is a hydrocarbon group, preferably an alkyl group having 8 to 18 carbon atoms.
  • Examples of the compound represented by the general formula (1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, (meth) Examples include cyclohexyl acrylate and benzyl (meth) acrylate.
  • a modifier further containing a (meth) acrylic acid ester having an alkyl group having 8 to 18 carbon atoms, in particular, octyl (meth) acrylate, It preferably contains lauryl (meth) acrylate, tridecyl (meth) acrylate or stearyl (meth) acrylate.
  • Examples of (meth) acrylic acid derivatives other than (meth) acrylic acid esters include hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and isocyanate-containing (meth) acrylic acid.
  • Examples of the aromatic vinyl compound include styrene, o-methyl styrene, p-methyl styrene, ⁇ -methyl styrene and the like.
  • As the modifier, ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof and another modifier are used in combination to improve the grafting ratio by the modifier, improve the solubility in organic solvents, The property can be further improved.
  • the amount used is ⁇ , ⁇ -unsaturated carboxylic acid and derivatives thereof, and (meth) acrylic acid. It is desirable not to exceed the total amount of esters used.
  • the modified polyolefin resin has a graft portion derived from at least a modifier.
  • graft weight the content ratio of the graft portion contained in the modified polyolefin resin
  • the modified polyolefin resin has a graft portion derived from ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof.
  • the graft weight of the graft portion derived from the ⁇ , ⁇ -unsaturated carboxylic acid or derivative thereof is 0.1 to 20% by weight with respect to 100% by weight of the modified polyolefin resin from the viewpoint of adhesiveness. %, More preferably 0.2 to 18% by weight.
  • the modified polyolefin resin is excellent in solubility in an organic solvent, and particularly excellent in adhesion to an adherend made of a metal or the like.
  • sufficient adhesiveness with respect to the to-be-adhered body which consists of resin etc. can be acquired as the graft weight is 20 weight% or less.
  • the graft weight derived from the ⁇ , ⁇ -unsaturated carboxylic acid or derivative thereof in the modified polyolefin resin can be determined by alkali titration, but the ⁇ , ⁇ -unsaturated carboxylic acid derivative does not have an acid group.
  • the graft weight can be determined by Fourier transform infrared spectroscopy.
  • the modified polyolefin resin includes a graft portion derived from the (meth) acrylic acid ester represented by the general formula (1)
  • the graft weight is 0.1% with respect to 100% by weight of the modified polyolefin resin. It is preferably ⁇ 30% by weight, more preferably 0.3 to 25% by weight.
  • the graft weight is 0.1 to 30% by weight, the modified polyolefin resin is excellent in solubility in an organic solvent, excellent in compatibility with other resins or elastomers described later, and applied to an adherend. Adhesiveness can be further improved.
  • the graft weight in the obtained modified polyolefin resin can be determined by Fourier transform infrared spectroscopy.
  • the radical initiator used in the production of the modified polyolefin resin can be appropriately selected from known ones.
  • organic peroxides such as 5-dimethyl-2,5-di (t-butylperoxy) hexane and cumene hydroperoxide.
  • modification aid that can be used for the production of the modified polyolefin resin
  • modification aid examples include divinylbenzene, hexadiene, dicyclopentadiene, and the like.
  • stabilizer examples include hydroquinone, benzoquinone, nitrosophenylhydroxy compound, and the like.
  • the modified polyolefin resin according to the present invention is a resin having a specific dielectric constant in a specific range measured at a frequency of 1 GHz.
  • the relative dielectric constant is a value that varies depending on the characteristics of the dipole of the modified polyolefin skeleton and side chains.
  • the relative dielectric constant of the modified polyolefin resin can be changed depending on the types of ⁇ , ⁇ -unsaturated carboxylic acid and (meth) acrylic acid ester used for modification, and the graft ratio.
  • the relative dielectric constant is 2.02 to 2.50, preferably 2.03 to 2.45.
  • the relative dielectric constant of the modified polyolefin resin is in the above range, the adhesion to a material with poor adhesion such as polyolefin, the adhesion to a highly polar material such as metal, and the stability of the composition are improved. . Furthermore, since the bonded part after bonding the two members into a composite is excellent in solvent resistance, for example, it contacts the highly polar organic solvent contained in the electrolyte solution of the electrochemical cell main body for lithium ion batteries. Even so, it has excellent durability (shape stability) as a composite. Therefore, the composition containing the specific modified polyolefin-based resin is suitable as an adhesive for a polyolefin resin film and an aluminum foil constituting a packaging material or the like for housing an electrochemical cell main body for a lithium ion battery.
  • the weight average molecular weight (Mw) of the modified polyolefin resin is preferably 30,000 to 250,000, more preferably 50,000 to 200,000.
  • Mw weight average molecular weight
  • it is excellent in solubility in an organic solvent and initial adhesion to an adherend, and further in solvent resistance at the bonded portion after bonding.
  • the melting point of the modified polyolefin resin is not particularly limited, but is preferably 50 to 90 ° C., more preferably 60 to 85 ° C. When the melting point is 50 ° C. to 90 ° C., sufficient adhesive strength can be obtained, the stability of the adhesive composition is improved, and particularly sufficient storage at a low temperature (eg, 0 ° C. to 15 ° C.). Stability can be obtained.
  • the melting point is a value measured by a differential scanning calorimeter (hereinafter also referred to as “DSC”).
  • the adhesive composition of the present invention contains an organic solvent that dissolves the modified polyolefin resin, the properties of the composition are usually liquid.
  • This organic solvent is preferably an organic solvent that is easily volatilized and removed by heating the adhesive composition.
  • organic solvents include aromatic organic solvents such as toluene and xylene, aliphatic organic solvents such as n-hexane, alicyclic organic solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane, acetone, and methyl ethyl ketone.
  • Ketone organic solvents such as methanol and ethanol, ester organic solvents such as ethyl acetate and butyl acetate, and propylene glycol ethers such as propylene glycol methyl ether, propylene glycol ethyl ether and propylene glycol-t-butyl ether Based organic solvents and the like.
  • These organic solvents may be used alone or in combination of two or more.
  • an alcohol-based organic solvent can be further used in combination in order to increase the storage stability of the adhesive composition.
  • the weight ratio between the organic solvent and the modified polyolefin resin is not particularly limited. This weight ratio can be set according to the type of the organic solvent and the modified polyolefin resin.
  • the content of the modified polyolefin resin is preferably 5 to 25% by weight, particularly preferably 10 to 20% by weight, when the total of the organic solvent and the modified polyolefin resin is 100% by weight. If it is such a content rate, it will be easy to apply
  • the polyfunctional isocyanate compound has an action of reacting with a carboxyl group of the modified polyolefin resin to cure the adhesive composition.
  • This polyfunctional isocyanate compound is not particularly limited as long as it has two or more isocyanate groups in one molecule, and various aromatic, aliphatic, and alicyclic isocyanate compounds, A modified product of the isocyanate compound can be used.
  • diisocyanate compounds such as toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, and modified products obtained by adduct modification of these compounds with isocyanurate-modified, burette-modified, trimethylolpropane, and the like, isocyanates
  • isocyanates Are blocked isocyanates which are stabilized by masking with a blocking agent.
  • These polyfunctional isocyanate compounds may be used alone or in combination of two or more. In the present invention, a compound having 3 or more isocyanate groups in one molecule is preferable. In the adhesive composition of the present invention, this polyfunctional isocyanate compound is usually dissolved in an organic solvent.
  • polyfunctional isocyanate compound Commercially available products can be used as the polyfunctional isocyanate compound.
  • Commercially available products modified with isocyanurate “Coronate HX” (trade name) manufactured by Nippon Polyurethane Industry Co., Ltd., “Duranate TPA-100” manufactured by Asahi Kasei Chemicals Corporation ( Product name), “Takenate D-170N” (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd., and the like.
  • Examples of commercially available burette-modified products include “Takenate D-165NN” (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.
  • the weight ratio of the modified polyolefin resin and the polyfunctional isocyanate compound in the adhesive composition is not particularly limited, it constitutes an isocyanate group (NCO) possessed by the polyfunctional isocyanate compound and a carboxyl group possessed by the modified polyolefin resin.
  • the equivalent ratio (NCO / OH) with the hydroxy group (OH) is preferably 0.01 to 12.0, more preferably 0.05 to 12.0, still more preferably 0.1 to 10.0, Preferably, both are contained so as to be 0.1 to 9.0.
  • the equivalent ratio is 0.01 to 12.0, an adhesive composition having excellent initial adhesion to an adherend can be obtained, and sufficient cross-linking can be achieved after bonding two members. It is possible to form an adhesive layer (adhesive portion) made of a cured product having a density and excellent in flexibility and the like.
  • the adhesive composition of the present invention includes, in addition to a modified polyolefin resin and a polyfunctional isocyanate compound, a reaction accelerator, a tackifier resin, a non-acid-modified thermoplastic elastomer, a non-acid-modified thermoplastic resin, a plastic An agent or the like can also be contained.
  • the reaction accelerator has an effect of promoting the reaction between the modified polyolefin resin and the polyfunctional isocyanate compound.
  • the reaction accelerator include organotin compounds and tertiary amines.
  • the organotin compound include dioctyltin fatty acids having 3 to 10 carbon atoms in the alkyl group such as dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, and dioctyltin dimaleate. These compounds may be used alone or in combination of two or more.
  • Tertiary amines include tetraalkylethylenediamines such as tetramethylethylenediamine; N, N′-dialkylbenzylamines such as dimethylbenzylamine; triethylenediamine, pentamethyldiethylenetriamine, N-ethylmorphine, N-methylmorphylline. 1-methyl-4-dimethylamine ethyl piperazine and the like. These compounds may be used alone or in combination of two or more.
  • an organotin compound and a tertiary amine can be used in combination.
  • the adhesive composition of the present invention contains a reaction accelerator, the content ratio of the reaction accelerator is 0.01 to 1 when the total of the resin components including the modified polyolefin resin is 100 parts by weight. It is preferable that it is a weight part.
  • tackifier examples include polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, and hydrogenated petroleum resins. These tackifiers may be used alone or in combination of two or more.
  • examples of the polyterpene resin include ⁇ -pinene polymers, ⁇ -pinene polymers, and copolymers of these with phenol or bisphenol A.
  • the rosin resin include natural rosin, polymerized rosin, and ester derivatives thereof.
  • Aliphatic petroleum resins, also referred to as C 5 resins are generally resin synthesized from C 5 fraction of oil.
  • An alicyclic petroleum resin is also referred to as a C 9 resin, and is generally a resin synthesized from a C 9 fraction of petroleum.
  • the copolymerized petroleum resin is also referred to as a C 5 / C 9 copolymer resin.
  • the hydrogenated hydrocarbon resin is generally produced by hydrogenation of the various petroleum resins described above.
  • thermoplastic elastomer examples include styrene-ethylenebutylene-styrene block copolymers, styrene-ethylenepropylene-styrene block copolymers, and the like.
  • the thermoplastic resin not modified with acid is preferably ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin, wax or the like.
  • the plasticizer is preferably a liquid rubber such as polyisoprene or polybutene, or process oil.
  • the content of the tackifier, the thermoplastic elastomer, etc. is preferably 70% by weight or less, more preferably 60 to 10% by weight, when the adhesive composition of the present invention containing them is 100% by weight. %, More preferably 50 to 20% by weight. Thereby, it can be set as the adhesive composition which has sufficient adhesiveness, heat-resistant adhesiveness, etc.
  • the method for producing the adhesive composition of the present invention is usually selected according to the type of the contained component.
  • the modified polyolefin resin is dissolved in an organic solvent, and then the resulting solution is mixed with other components other than the polyfunctional isocyanate compound, and then the resulting mixture and the polyfunctional isocyanate compound are mixed. It is a method of mixing.
  • the temperature at the time of mixing is usually 40 ° C. or lower, preferably 10 ° C. to 30 ° C.
  • the coating film is dried and the organic solvent is volatilized to produce a dried coating film, that is, a cured product.
  • the drying temperature of the coating film is not particularly limited, and is preferably 30 ° C. to 100 ° C. from the viewpoint of workability.
  • the dry coating film contains a reaction product of a modified polyolefin resin and a polyfunctional isocyanate, that is, a compound obtained by reacting a carboxyl group in the modified polyolefin resin and an isocyanate group in the polyfunctional isocyanate.
  • the reaction product acts as an adhesive that bonds the two members together.
  • a method such as pressure bonding at a temperature of 80 ° C. or higher can be applied.
  • the adhesive composition of the present invention is a composite comprising a polyolefin resin film, a polyolefin resin film, an adhesive between a polyolefin resin film and a metal foil made of aluminum, a polyolefin resin film, a resin layer, and a metal layer. It is suitable for adhesion with a metal layer in a film.
  • the adhesive composition may be applied to the surface of only one member or to the surfaces of both members.
  • the adhesive composition of the present invention is excellent in solvent resistance in an adhesive layer (adhesive part) after bonding two members.
  • the adhesive composition of the present invention provides solvent resistance in a wide temperature range of, for example, ⁇ 30 ° C. to 80 ° C. Therefore, in the use etc. which are mentioned later, the durability in the adhesive bond layer (adhesion part) between two members, ie, the shape stability as a composite, can be obtained.
  • the heat-fusible composite member of the present invention includes an adhesive layer formed by curing the adhesive composition of the present invention, a metal layer bonded to one side of the adhesive layer, and an adhesive. And a heat-fusible resin layer bonded to the other surface side of the layer.
  • a schematic view of the heat-fusible composite member of the present invention is shown in FIGS. That is, the heat-fusible composite member 1 of FIG. 1 includes a heat-fusible resin layer 11, an adhesive layer 12, and a metal layer 13 in order.
  • the heat-fusible composite member 1 of FIG. 2 includes a heat-fusible resin layer 11, an adhesive layer 12, a metal layer 13, and another layer 14 in order.
  • the heat-fusible composite member of the present invention can have a sheet shape, a shape having a recess or a groove, and the like.
  • the “heat-fusible resin layer” is a layer containing a resin that is melted and fused by heat.
  • the heat-fusible resin layer is preferably a layer containing a resin that melts at a temperature of 50 ° C. to 200 ° C.
  • the resin having such properties include polyolefin resins, polyamide resins, and polyester resins.
  • polyolefin resin is preferable because it can be heat-sealed with sufficient strength.
  • polypropylene is preferable as the polyolefin resin.
  • dimensional change shrinkage
  • unstretched polypropylene is more preferable.
  • the above heat-fusible resin layer is made of a lubricant, a filler, a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a colorant, a dispersant, an adhesion-imparting agent, etc., if necessary. It may be a layer containing an additive.
  • the thickness of the heat-fusible resin layer is not particularly limited depending on the resin material and the like, but is usually 10 to 200 ⁇ m.
  • the thickness is preferably 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m, and still more preferably 60 to 100 ⁇ m.
  • a heat-fusible composite member such as a container or a packaging material that does not easily break and gives a highly durable sealed product or encapsulated product.
  • the “adhesive layer” is a layer formed by curing the adhesive composition described above, that is, from a cured product containing a reaction product of a modified polyolefin resin and a polyfunctional isocyanate compound. It is a layer.
  • the thickness of the adhesive layer is not particularly limited, but is preferably 1 to 20 ⁇ m, particularly preferably 2 to 10 ⁇ m. If the thickness of the adhesive layer is 1 to 20 ⁇ m, the heat-fusible composite member can be easily processed, for example, when it is in the form of a sheet.
  • the “metal layer” is a layer containing a metal (including an alloy).
  • the metal or alloy is not particularly limited, but aluminum is usually used because of excellent workability.
  • the thickness of the metal layer is not particularly limited depending on the material and the like. When the metal layer is made of, for example, aluminum, it is preferably 20 to 100 ⁇ m, particularly preferably 20 to 80 ⁇ m, and further preferably 30 to 60 ⁇ m.
  • the heat-fusible composite member of the present invention includes a metal layer
  • another layer 14 can be provided on the surface of the metal layer 13 as shown in FIG.
  • the material constituting the other layer preferably contains a resin from the viewpoint of protecting the metal layer. That is, the other layer is preferably a resin layer.
  • This resin is not particularly limited, and may be a polyamide resin, a polyester resin, or the like.
  • the transparency of the resin layer is not particularly limited, but when the resin layer is transparent or translucent using a heat-fusible composite member, an article is contained or packaged, and a sealed product, an encapsulated product, etc. An excellent appearance can be obtained.
  • the thickness of the other layer is not particularly limited, and is preferably 30 to 60 ⁇ m, particularly preferably 30 to 50 ⁇ m.
  • the manufacturing method of the heat-fusible composite member shown in FIG. 1 is as follows. (1) The adhesive composition is applied to the surface of a metal foil or metal film for forming the metal layer 13, and then the organic solvent in the composition is removed to form the adhesive layer 12. A method in which a heat-fusible resin layer 11-forming resin film (heat-fusible resin film) is brought into contact with the surface on which the adhesive layer 12 is formed, and is bonded while heating. (2) The adhesive composition is applied to the surface of the resin film for forming the heat-fusible resin layer 11 (heat-fusible resin film), and then the organic solvent in the composition is removed to remove the adhesive layer 12. Then, a metal foil or the like for forming the metal layer 13 is brought into contact with the surface on which the adhesive layer 12 has been formed, and is subjected to pressure bonding while heating.
  • the manufacturing method of the heat-fusible composite member shown in FIG. 2 is as follows. (3) The adhesive composition is applied to the surface of the metal layer 13 in the composite film having the resin layer constituting the other layer 14 and the metal layer 13 formed on one surface side of the resin layer by vapor deposition or the like. Thereafter, the organic solvent in the composition is removed to form the adhesive layer 12, and then the surface on which the adhesive layer 12 is formed and the resin film for forming the heat-fusible resin layer 11 (heat-sealing) A pressure-sensitive adhesive film is heated and brought into contact.
  • the adhesive composition is applied to the surface of the resin film for forming the heat-fusible resin layer 11 (heat-fusible resin film), and then the organic solvent in the composition is removed to remove the adhesive layer 12.
  • a composite film having a resin layer constituting another layer 14 and a metal layer 13 formed on one surface side of the resin layer by vapor deposition or the like A method in which the surface on which the metal layer 13 is formed is brought into contact with the metal layer 13 and heated and heated.
  • the adhesive composition is often applied to the surface of a metal layer in a composite film including a metal layer forming material such as a metal foil, or a metal layer and another layer (resin layer), but is not particularly limited.
  • a metal foil it is preferable to use an aluminum foil having a thickness of 20 to 100 ⁇ m.
  • the heat-fusible composite member in which breakage is suppressed can be easily formed.
  • a metal layer contains aluminum and another layer (resin layer) contains a polyamide resin, a polyester resin, etc. Further, when the heat-fusible composite member shown in FIG.
  • the other layer 14 forming film may be a polyamide resin or a polyester resin. It is preferable to use a film including the like.
  • a heat-fusible resin film a polyolefin resin film, a polyamide resin film, a polyester resin film, or the like can be used as a heat-fusible resin film. These resin films can be films obtained by film forming methods such as an extrusion method, a cast molding method, a T-die method, and an inflation method.
  • the thickness of the heat-fusible resin film is usually 10 to 200 ⁇ m.
  • a polyolefin resin film is preferable because heat fusion for completing a heat-fusible composite member and heat fusion at the time of producing an encapsulated product containing an article can be easily performed.
  • An unstretched polypropylene film is particularly preferred. When this unstretched polypropylene film is used, the preferred thickness is 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m, and still more preferably 60 to 100 ⁇ m.
  • the method for applying the adhesive composition is not particularly limited, and conventionally known methods can be applied.
  • the composition can be applied using, for example, a bar coater, a gravure coater or the like.
  • the thickness of the coating film and its drying temperature are not particularly limited.
  • the drying temperature of the coating film is preferably 30 ° C. to 100 ° C.
  • the resin component is subjected to pressure bonding or the like while being heated to a temperature in consideration of the melting point and melt viscosity of the resin component based on the modified polyolefin resin.
  • the heating conditions and pressure bonding conditions for completing the heat-fusible composite member are not particularly limited, and are set according to the material of the metal foil, the material of the heat-fusible resin film, the melting temperature, the composition of the adhesive layer, etc. It is preferable to do.
  • the heat-fusible resin layer contains unstretched polypropylene, it is difficult to break and has excellent durability including heat resistance and solvent resistance up to about 80 ° C.
  • the sealing container may be, for example, a molded product obtained by processing a sheet-like heat-fusible composite member, an adhesive composition, a metal foil for forming a metal layer, etc., and heat-sealing. It may be a molded product obtained by using a functional resin film and a molding die. A part of the heat-fusible resin layer in a sealing container, bag body, packaging material, etc. is suitable for heat-sealing with other parts. It is possible to prevent alteration of the contents while maintaining the above.
  • Measurement method and evaluation method 1-1 Weight average molecular weight (Mw) GPC measurement was performed under the following conditions to determine Mw of the polyolefin resin before and after modification. For Mw, the retention time measured by GPC was converted based on the retention time of standard polystyrene.
  • Apparatus HLC-8220GPC (manufactured by Tosoh Corporation) Column: TSKgel GMHXL 2 (Tosoh Corporation) Column temperature: 40 ° C Eluent: Tetrahydrofuran 1.00 ml / min Detector: RI
  • a method for determining the resin acid value (AV) by alkali titration is shown below.
  • the resin acid value (AV) is calculated by the following formula using the titration amounts of (3) and (4).
  • Resin acid value (mgKOH / g) [(AB) ⁇ 56.1 ⁇ f ⁇ 1/100] / W
  • B Blank test titration (ml)
  • W Sampling amount (g) f: Factor of 1 / 100N potassium hydroxide solution
  • f ⁇ 1/100 Normality of 1 / 100N potassium hydroxide
  • Graft weight% of graft part derived from (meth) acrylic acid ester in modified polyolefin resin The graft weight of the graft part derived from (meth) acrylic acid ester such as lauryl methacrylate and octyl acrylate was measured by Fourier transform infrared spectroscopy.
  • Relative dielectric constant of modified polyolefin resin (1) Production of resin sheet The modified polyolefin resin is set in a heat press machine manufactured by Shin-Fuji Metal Industry Co., Ltd. set at a temperature equal to or higher than its melting point, and the sheet is placed under a pressure of 5 MPa for 1 minute. After being molded into a shape, it was cooled at 20 ° C. under a pressure of 5 MPa for 1 minute to produce a resin sheet having a thickness of about 0.1 to 1 mm. Next, the resin sheet was cut to obtain a test piece having a predetermined size. (2) Measurement of relative permittivity Measurement was performed by a cavity resonator perturbation method according to ASTM D 2520.
  • Specimen size length 80mm x width 1.5mm
  • Frequency 1GHz
  • Test environment 23 ° C., 50%
  • RH Test equipment PNA-L network analyzer N5230A (manufactured by Agilent Technologies), for cavity resonator 1 GHz; CP431 (manufactured by Kanto Electronics Application Development Co., Ltd.)
  • Viscosity of Adhesive Composition According to JIS K 6833-1, BM type rotational viscometer manufactured by Tokimec Co., Ltd., spindle No. 2 was used, and the viscosity was measured under the conditions of a temperature of 25 ° C. ⁇ 0.5 ° C. and a rotational speed of 60 rpm.
  • T peeling adhesive strength was measured to evaluate adhesiveness.
  • the adhesive composition was applied to an aluminum foil (100 mm ⁇ 200 mm ⁇ 40 ⁇ m) whose surface was subjected to chemical conversion treatment with a bar coater. Thereafter, drying was performed at 80 ° C. for 60 seconds and further at 180 ° C. for 20 seconds, and the organic solvent contained in the adhesive composition was removed to form an adhesive layer having a thickness of 4 ⁇ m.
  • an unstretched polypropylene film having a thickness of 80 ⁇ m (hereinafter abbreviated as “CPP film”) is bonded to the surface of the adhesive layer as a heat-fusible resin film, and an aluminum foil is used by using a thermal gradient tester. The surface was pressed and pressed. The bonding conditions at this time were a temperature of 180 ° C., a pressure of 0.3 MPa, and a pressure bonding time of 2 seconds. Thereafter, this integrated product was housed in a hot-air circulating oven adjusted to 40 ° C. for 3 days to obtain a heat-fusible composite member having a thickness of 124 ⁇ m.
  • T-peel adhesion strength A heat-fusible composite member was cut into a 15 mm width, and an aluminum foil and a CPP film were used using an application test device “Autograph AGS-J” (model name) manufactured by Shimadzu Corporation. T peel adhesion strength (N / 15 mm) was measured. The measurement conditions are a temperature of 25 ° C. and 80 ° C., and a tensile speed of 100 mm / min.
  • Electrolytic Solution Resistance Test Ethylene carbonate, diethyl carbonate and dimethyl carbonate were mixed at 1: 1: 1 (weight ratio), and lithium hexafluorophosphate was added thereto so that the concentration was 1 mol / L. Was prepared. The test piece for measuring the peel adhesive strength was immersed in an electrolytic solution at 80 ° C. for 8 days, and then the T peel adhesive strength was measured at 25 ° C. and 100 mm / min.
  • aconitic anhydride 1.5 parts by weight of aconitic anhydride, 3 parts by weight of octyl acrylate, and 0.5 parts by weight of benzoyl peroxide were added dropwise over 3 hours, and the reaction was further continued for 1 hour.
  • the reaction solution was cooled to room temperature, poured into a large excess of acetone and purified, and the weight average molecular weight was 150,000, Tm was 90 ° C., the graft weight of aconitic anhydride was 1.2% by weight, A modified polyolefin resin 1 having a graft weight of octyl acrylate of 2.8% by weight and a relative dielectric constant of 2.12 was obtained.
  • the carboxyl group content was 23.1 mmol / 100 g.
  • the first barrel, the second barrel, the third barrel, the fourth barrel, the fifth barrel, the sixth barrel, and the seventh barrel are continuous. Modification in each barrel using a twin screw extruder having a screw with an outer diameter ⁇ of 58 mm and a ratio of the screw length (L) to screw diameter (D) (L / D) of 42 A polyolefin resin was produced.
  • the resulting modified polyolefin resin 2 has a weight average molecular weight of 110,000, Tm of 80 ° C., graft weight of the graft portion derived from maleic anhydride is 1.1% by weight, and graft portion of the graft portion derived from lauryl methacrylate. The weight was 3.6% by weight and the relative dielectric constant was 2.14. The carboxyl group content was 22.4 mmol / 100 g.
  • the resulting modified polyolefin-based resin 3 has a weight average molecular weight of 60,000, Tm of 60 ° C., graft weight of the graft part derived from itaconic anhydride is 7.5% by weight, and graft part of the graft part derived from tridecyl acrylate.
  • the weight was 4.6% by weight and the relative dielectric constant was 2.23.
  • the carboxyl group content was 134 mmol / 100 g.
  • the resulting modified polyolefin resin 4 has a weight average molecular weight of 180,000, Tm of 90 ° C., graft weight of the graft portion derived from citraconic anhydride is 9.4% by weight, and graft portion of the graft portion derived from stearyl methacrylate The weight was 13.8% by weight and the relative dielectric constant was 2.34.
  • the carboxyl group content was 168 mmol / 100 g.
  • the resulting modified polyolefin resin 5 has a weight average molecular weight of 80,000, Tm of 70 ° C., graft weight of the graft part derived from maleic anhydride is 16% by weight, and graft weight of the graft part derived from lauryl methacrylate is
  • the relative dielectric constant was 24% by weight and the relative dielectric constant was 2.44.
  • the carboxyl group content was 326 mmol / 100 g.
  • Synthesis Example 6 The same procedure as in Synthesis Example 2 except that 0.5 parts by weight of itaconic anhydride was used instead of 1.5 parts by weight of maleic anhydride, and 0.7 parts by weight of octyl methacrylate was used instead of 4 parts by weight of lauryl methacrylate.
  • the modified polyolefin resin 6 was obtained.
  • the resulting modified polyolefin resin 6 has a weight average molecular weight of 100,000, Tm of 80 ° C., graft weight of the graft part derived from itaconic anhydride is 0.3% by weight, and graft part of the graft part derived from octyl methacrylate.
  • the weight was 0.5% by weight and the relative dielectric constant was 2.03.
  • the carboxyl group content was 5.4 mmol / 100 g.
  • the resulting modified polyolefin resin 7 has a weight average molecular weight of 200,000, a Tm of 90 ° C., a graft weight of the graft portion derived from citraconic anhydride of 8.4% by weight, and a relative dielectric constant of 2.28. there were.
  • the carboxyl group content was 150 mmol / 100 g.
  • Synthesis example 8 The same procedure as in Synthesis Example 2 was performed except that 24 parts by weight of itaconic anhydride was used instead of 1.5 parts by weight of maleic anhydride, and 4 parts by weight of tridecyl acrylate was used instead of 4 parts by weight of lauryl methacrylate. A polyolefin resin 8 was obtained. The resulting modified polyolefin resin 8 has a weight average molecular weight of 120,000, Tm of 85 ° C., graft weight of the graft part derived from itaconic anhydride is 22.6% by weight, and graft weight of the graft part derived from tridecyl acrylate. Was 3.1 wt%, and the relative dielectric constant was 2.54. The carboxyl group content was 403 mmol / 100 g.
  • Synthesis Example 9 A modified polyolefin resin 9 was obtained in the same manner as in Synthesis Example 2 except that the amount of maleic anhydride used was 5 parts by weight and that 40 parts by weight of methyl methacrylate was used instead of 4 parts by weight of lauryl methacrylate. .
  • the resulting modified polyolefin resin 9 has a weight average molecular weight of 130,000, Tm of 85 ° C., graft weight of the graft part derived from maleic anhydride is 4.7% by weight, and graft part of the graft part derived from methyl methacrylate. The weight was 36% by weight and the relative dielectric constant was 2.53.
  • the carboxyl group content was 95.9 mmol / 100 g.
  • Synthesis Example 10 The same procedure as in Synthesis Example 2 except that 0.02 part by weight of itaconic anhydride was used instead of 1.5 parts by weight of maleic anhydride, and 0.02 part by weight of octyl methacrylate was used instead of 4 parts by weight of lauryl methacrylate.
  • the modified polyolefin resin 10 was obtained.
  • the resulting modified polyolefin resin 10 has a weight average molecular weight of 100,000, Tm of 80 ° C., graft weight of the graft part derived from itaconic anhydride is 0.01% by weight, and graft part graft derived from octyl methacrylate.
  • the weight was 0.03% by weight and the relative dielectric constant was 2.01.
  • the carboxyl group content was 0.2 mmol / 100 g.
  • Example 1 Production and Evaluation of Adhesive Composition 15 g of the modified polyolefin resin 1 synthesized in Synthesis Example 1, 68 g of methylcyclohexane and 17 g of methyl ethyl ketone were charged into a 300 ml flask equipped with a condenser and a stirrer, and stirred at 60 ° C. for 10 minutes to obtain a solution. After cooling this solution to room temperature, 1.5 mg of dibutyltin dilaurate (hereinafter referred to as “DBTL”) was added as a reaction accelerator and further mixed, and the viscosity at 25 ° C. was 170 mPa ⁇ s. A liquid resin composition having a concentration of 15% by weight was obtained.
  • DBTL dibutyltin dilaurate
  • Example 2-8 The adhesive composition was the same as in Example 1 except that the modified polyolefin resin obtained in Synthesis Examples 2 to 7 was used as the modified polyolefin resin, and the amount of the polyfunctional isocyanate compound was changed to the amount shown in Table 1. I got a thing. And said various evaluation was performed. The evaluation results are shown in Table 1.
  • Comparative Examples 1 to 3 The adhesive composition was the same as in Example 1 except that the modified polyolefin resin obtained in Synthesis Examples 8 to 10 was used as the modified polyolefin resin and the amount of the polyfunctional isocyanate compound was changed to the amount shown in Table 1. I got a thing. And said various evaluation was performed. The evaluation results are shown in Table 1.
  • the adhesive compositions of Examples 1 to 8 have a T peel adhesion strength as high as 15 N or more at 25 ° C., and the T peel adhesion strength at 80 ° C. is also 10 N or more. Moreover, sufficient adhesive strength was obtained even after the test for resistance to electrolytic solution at 80 ° C.
  • Comparative Example 1 and Comparative Example 2 using a modified polyolefin resin having a high relative dielectric constant outside the range of the present invention the stability of the solution is not sufficient, and the T peel adhesion strength at 25 ° C. is 10 N. The T peel adhesion strength at 80 ° C. was also low, and the adhesive strength after the electrolytic solution resistance test was further reduced.
  • Comparative Example 3 using a modified polyolefin resin having a low relative dielectric constant outside the scope of the present invention was inferior to Comparative Example 1 and Comparative Example 2.
  • the adhesive composition of the present invention is suitable for bonding between a polyolefin resin molded body and other members (metal member, resin member, etc.), and not only bonding between polyolefin resin molded bodies such as polyolefin resin films. It can also be used for adhesion between a polyolefin resin film and a metal layer in a composite film comprising a resin layer and a metal layer. Furthermore, the adhesive composition of the present invention is also suitable for forming bags, containers and the like for sealing foods, chemicals, chemical products, electronic parts, electrical products and the like by heat sealing.
  • the heat-fusible composite member of the present invention includes an adhesive layer (adhesive portion) formed by the adhesive composition of the present invention, heat resistance (heat-resistant adhesiveness) and electrolytic solution resistance (solvent resistance) Excellent. Therefore, the heat-fusible resin layer is formed of, for example, a polyolefin resin film, and the polyolefin resin film and the aluminum foil are bonded by the adhesive composition of the present invention, and further derived from the aluminum foil.
  • the heat-fusible composite member in which a film containing a polyamide resin, a polyester resin, or the like is bonded to the metal layer to be used can be suitably used as a packaging material or a container for an electrochemical cell main body for a lithium ion battery.
  • the heat-fusible composite member of the present invention when used for a packaging material or a container of an electrochemical cell main body for a lithium ion battery, the battery is stored or used after being sealed by heat sealing or the like. At the same time, the shape of the heat-fusible composite member as an integrated product can be maintained. That is, the sealed product containing the battery changes in temperature not only in the storage or use place, in a specific season, but also in charge or discharge during driving. For example, at a temperature of about 60 ° C. to 80 ° C. Also, it is possible to obtain durable adhesion between the two members.

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JPWO2020090818A1 (ja) * 2018-10-29 2021-10-07 東亞合成株式会社 接着剤組成物及びそれを用いた熱融着性部材
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WO2020090818A1 (ja) * 2018-10-29 2020-05-07 東亞合成株式会社 接着剤組成物及びそれを用いた熱融着性部材
US12071499B2 (en) 2019-08-29 2024-08-27 Nippon Paper Industries Co., Ltd. Modified polyolefin resin and dispersion composition thereof
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JP2021161132A (ja) * 2020-03-30 2021-10-11 三井化学株式会社 組成物、積層体、包材、電池用包材および電池
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