WO2021131812A1 - 接着剤組成物、熱融着性部材、及び、二次電池包材 - Google Patents

接着剤組成物、熱融着性部材、及び、二次電池包材 Download PDF

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Publication number
WO2021131812A1
WO2021131812A1 PCT/JP2020/046367 JP2020046367W WO2021131812A1 WO 2021131812 A1 WO2021131812 A1 WO 2021131812A1 JP 2020046367 W JP2020046367 W JP 2020046367W WO 2021131812 A1 WO2021131812 A1 WO 2021131812A1
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Prior art keywords
adhesive composition
acid
packaging material
battery packaging
adhesive
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PCT/JP2020/046367
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English (en)
French (fr)
Japanese (ja)
Inventor
平岡　秀樹
健太郎 宮村
伊藤　隆浩
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Toagosei Co Ltd
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Toagosei Co Ltd
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Priority to CN202080089224.8A priority Critical patent/CN114867806A/zh
Priority to JP2021567250A priority patent/JPWO2021131812A1/ja
Priority to KR1020227024634A priority patent/KR20220117296A/ko
Publication of WO2021131812A1 publication Critical patent/WO2021131812A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • 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
    • C09J123/30—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 by oxidation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • 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
    • 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

Definitions

  • the present invention relates to an adhesive composition, a heat-sealing member, and a secondary battery packaging material, and can be used in various industrial products in the electric field, the automobile field, and other industrial fields. Belongs to.
  • the hot melt type adhesive composition is used by processing it into a film or sheet, and is used as an adhesive film or sheet in which the adhesive composition is laminated on the surface of a member in the electrical field, the automobile field, and other fields. It is used in various industrial products in the industrial field. Further, as an adhesive composition, there is also known an embodiment in which a solution containing an organic solvent or the like is prepared, directly applied to an adherend, dried, and adhered to the other adherend. Various adhesive compositions for adhering molded bodies or film laminates made of polyolefins having poor adhesiveness to metal members such as iron, aluminum, titanium and other metals used in these fields and their alloys. Has been proposed.
  • Patent Document 1 discloses an adhesive composition in which a component consisting of a carboxylic acid-containing polyolefin, a carboxylic acid-containing epoxy resin, a polyisocyanate compound, and, if necessary, an epoxy resin is dissolved and dispersed in an organic solvent.
  • Patent Document 2 discloses an adhesive composition containing a polyolefin having a carboxyl group or an acid anhydride group, a polyfunctional isocyanate compound, and a solvent, and the glass transition temperature, melting point, and melting energy of the polyolefin are specific values. ing.
  • the acid-modified polyolefin obtained by grafting an organic acid having an unsaturated double bond on a polymer having a low polarity has a highly polar acid-modified site and a polymer main chain having a low polarity. It is used as a base treatment agent for coating polyolefin resins such as polypropylene, and as an adhesive raw material for adhering polyolefins to each other or polar materials such as polyolefins and metals.
  • a general battery packaging material used for a laminated battery has a three-layer structure centered on a metal foil, and an adhesive is used between each layer.
  • the three layers are a base material layer that becomes the outside of the battery after forming a laminated battery, a barrier layer that is formed from a metal foil such as aluminum foil or stainless steel foil and prevents the penetration of moisture and air, and the barrier layer comes into contact with electrodes and an electrolytic solution. It is a sealant layer for the purpose of insulating so as not to prevent it and heat-sealing and bonding the outer peripheral portion, and each layer is also formed by two or more layers.
  • an olefin-based film such as a polypropylene film is used for the sealant layer in contact with the electrolytic solution, and acid-modified polyolefin, acid-modified styrene-based elastomer, or polyhydroxyl containing a cross-linking agent as necessary for adhesion to the aluminum foil.
  • Polyurethane or the like in which polyolefin is crosslinked with an isocyanate-based crosslinking agent is used.
  • an adhesive composed of an acid-modified polyolefin and an isocyanate-based cross-linking agent has been widely used in recent years because it can obtain high adhesive strength.
  • An adhesive composed of an acid-modified polyolefin and a cross-linking agent is mainly used as an adhesive solution dissolved in a solvent, applied to an aluminum foil or a film for a sealant layer, dried, and then dried to bond the aluminum foil and the polyolefin film.
  • Laminated films are manufactured by a method called the laminating method. Further, the laminated film is suitably used for, for example, a laminated secondary battery.
  • Patent Documents 3 or 4 examples include those described in Patent Documents 3 or 4.
  • Patent Document 3 includes a heat-resistant resin stretched film layer as an outer layer, a thermoplastic resin unstretched film layer as an inner layer, and an aluminum foil layer disposed between the layers of both films.
  • the material is characterized in that the thermoplastic resin unstretched film layer and the aluminum foil layer are bonded to each other via an adhesive layer containing a polyolefin resin having a carboxyl group and a polyfunctional isocyanate compound.
  • the packaging material for the battery case is described.
  • Patent Document 4 includes a heat-resistant resin stretched film layer as an outer layer, a thermoplastic resin unstretched film layer as an inner layer, and an aluminum foil layer disposed between the layers of both films.
  • the thermoplastic resin unstretched film layer and the aluminum foil layer are adhered to each other via an adhesive layer containing a polyolefin resin having a carboxyl group and a polyfunctional isocyanate compound, and the polyolefin resin Described is a packaging material for a battery case, wherein the equivalent ratio [NCO] / [OH] of the isocyanate group of the polyfunctional isocyanate compound to the hydroxyl group constituting the carboxyl group is 1.0 to 10.0. There is.
  • Japanese Unexamined Patent Publication No. 4-18480 Japanese Unexamined Patent Publication No. 2015-36385 Japanese Unexamined Patent Publication No. 2010-922703 Japanese Unexamined Patent Publication No. 2014-89985
  • the problem to be solved by the present invention is an adhesive composition for a battery packaging material having excellent adhesive strength in a high temperature (120 ° C.) atmosphere, and a heat-sealing member for a battery packaging material and a secondary battery using the same. To provide packaging material.
  • Means for solving the above problems include the following aspects.
  • Adhesive composition for battery packaging materials ⁇ 4> The adhesive composition for a battery packaging material according to any one of ⁇ 1> to ⁇ 3>, which further contains an organic solvent. ⁇ 5> The battery packaging material according to any one of ⁇ 1> to ⁇ 4>, wherein the acid-modified polyolefin is obtained by grafting an unsaturated carboxylic acid anhydride with a polyolefin to introduce an acid anhydride group.
  • ⁇ 6> The adhesive composition for a battery packaging material according to any one of ⁇ 1> to ⁇ 5>, wherein the acid value of the acid-modified polyolefin is 20 mgKOH / g to 50 mgKOH / g.
  • ⁇ 7> The adhesive composition for a battery packaging material according to any one of ⁇ 1> to ⁇ 6>, wherein the cross-linking agent contains a polyfunctional isocyanate compound.
  • the amount of isocyanate groups in the polyfunctional isocyanate compound with respect to the acid value of the acid-modified polyolefin is 1 molar equivalent to 6 molar equivalents.
  • the polyfunctional isocyanate compound according to ⁇ 10> which comprises an isocyanate compound having an aliphatic ring structure and / or a derivative thereof, and an aliphatic isocyanate compound having no aliphatic ring structure and / or a derivative thereof.
  • Adhesive composition for battery packaging material ⁇ 12> The invention according to any one of ⁇ 1> to ⁇ 11>, wherein the peel strength of the test piece obtained by adhering the aluminum foil and the polyolefin with the adhesive composition at 120 ° C. is 4N / 15 mm or more.
  • Adhesive composition for battery packaging material is 4N / 15 mm or more.
  • An adhesive layer obtained by curing the adhesive composition according to any one of ⁇ 1> to ⁇ 12>, a metal layer bonded to one side of the adhesive layer, and the adhesive.
  • a heat-sealing member for a battery packaging material which comprises a heat-sealing resin layer bonded to the other surface side of the layer.
  • a secondary battery packaging material containing the heat-sealing member according to ⁇ 13>.
  • an adhesive composition for a battery packaging material having excellent adhesive strength in a high temperature (120 ° C.) atmosphere, and a heat-sealing member for a battery packaging material and a secondary battery packaging material using the same are provided. can do.
  • FIG. 1 It is a schematic perspective view which shows an example of the heat-sealing member for a battery packaging material of this invention. It is a schematic perspective view which shows another example of the heat-sealing member for a battery packaging material of this invention. It is a figure which shows the measurement result of the dynamic viscoelasticity in Example 4 and Comparative Example 10. It is a figure which shows an example of the measurement of the glass transition temperature (Tg) in Example 1.
  • Tg glass transition temperature
  • the adhesive composition for a battery packaging material of the present invention contains an acid-modified polyolefin and a cross-linking agent, and the adhesive composition is cross-linked.
  • the storage elasticity at 120 ° C. by dynamic viscoelasticity measurement of the cured product is 2 MPa or more.
  • a general battery packaging material (also referred to as "battery packaging material”) used for a laminated battery has a three-layer structure centered on a metal foil such as aluminum foil, and an adhesive is provided between each layer. used.
  • the three layers are a support layer that becomes the outside of the battery after the laminated battery is formed, a barrier layer that is formed from a metal foil such as aluminum foil or stainless steel foil and hinders the penetration of moisture, and the barrier layer is prevented from coming into contact with electrodes or an electrolytic solution.
  • This is a sealant layer for the purpose of heat-sealing and bonding the outer peripheral portions, and each layer is also formed by two or more layers.
  • a film made of polyamide or polyester is used as the support layer, and since it does not come into contact with the electrolytic solution, it is relatively easy to adhere to the metal foil with an adhesive.
  • acid-modified polyolefin or acid-modified styrene-based elastomer containing a cross-linking agent, polyurethane cross-linked with polyhydroxy polyester and an isocyanate cross-linking agent, etc. are used as necessary.
  • Olefin-based films such as polypropylene films, which are widely used as sealant layers, have low polarity and excellent chemical resistance, so they have good durability even when in contact with electrolytic solutions, but due to their excellent properties, they have poor adhesion. It is also known as a material, and it is required to improve the characteristics of the adhesive used.
  • the laminated battery When the temperature of a laminated secondary battery rises due to heat generated by charging and discharging or heat from the outside, the heat-sealed part of the battery packaging material and the strength of the adhesive decrease, and the battery may explode, leading to a fire. It was. Conventionally, small secondary batteries for mobile applications are relatively easy to dissipate heat and the temperature is difficult to rise, but the battery capacity and size tend to increase as mobile devices become larger and more sophisticated. There is a concern that the heat resistance of the battery packaging material will be insufficient. In addition, when using a larger secondary battery such as an electric vehicle, the laminated battery has the advantage of having a larger battery capacity per volume than a battery that is covered with a metal can such as a cylinder, and has heat dissipation.
  • an acid-modified polyolefin as an adhesive layer for the purpose of firmly adhering an aluminum foil to a polyolefin layer called a sealant layer.
  • a typical step of producing the laminate of the polyolefin layer and the aluminum foil the non-acid-modified polyolefin and the acid-modified polyolefin are each melted and extruded from the die so that the acid-modified polyolefin layer is on the aluminum foil side.
  • a heat laminating method in which the layers are pressure-bonded while being layered on top of each other, or an adhesive solution in which an acid-modified polyolefin and, if necessary, a cross-linking agent are dissolved in a solvent is applied to an aluminum foil or a film for a sealant layer, dried, and then the aluminum foil and the polyolefin film are attached.
  • a dry laminating method for matching can be mentioned.
  • an adhesive composition for a battery packaging material having excellent adhesive strength in a high temperature atmosphere can be provided by adopting the above configuration.
  • the mechanism of action of the excellent effect by this is not clear, but it is estimated as follows.
  • the heat resistance after curing is such that the storage elastic modulus at 120 ° C. by dynamic viscoelasticity measurement of the cured product containing an acid-modified polyolefin and a cross-linking agent and cross-linking the adhesive composition is 2 MPa or more.
  • An adhesive composition for a battery packaging material having excellent adhesive strength in a high temperature atmosphere can be obtained, as well as being able to suppress a decrease in peel strength in a high temperature atmosphere.
  • the "acid-modified polyolefin” is referred to as “acid-modified polyolefin (A)” or “component (A)".
  • “isocyanate compound of hydrocarbon having an alicyclic structure and / or its derivative (B)” and the like, which will be described later, are also referred to as “component (B)” and the like.
  • adhesive composition for battery packaging material adhesive composition for battery packaging material
  • acrylic acid and / or methacrylic acid is referred to as (meth) acrylic acid.
  • the adhesive composition for a battery packaging material of the present invention has a storage elastic modulus at 120 ° C. of 2 MPa or more as measured by dynamic viscoelasticity measurement of a cured product obtained by cross-linking the adhesive composition, and has an adhesive force in a high temperature atmosphere. From the above viewpoint, it is preferably 2.5 MPa or more, more preferably 3.0 MPa or more, and particularly preferably 3.5 MPa or more. Further, the upper limit is preferably 20 MPa or less, more preferably 10 MPa or less, from the viewpoint of adhesive force in a high temperature atmosphere.
  • the method for measuring the storage elastic modulus at 120 ° C. by the dynamic viscoelasticity measurement of the cured product obtained by cross-linking the adhesive composition shall be carried out by the following method.
  • the adhesive composition containing the cross-linking agent is poured into a polyethylene cup to a thickness of about 0.5 mm after drying, air-dried, and then left in an oven at 40 ° C. for 5 days to carry out the cross-linking reaction. Proceed to use as a test piece for viscoelasticity measurement.
  • Using the obtained test piece for viscoelasticity measurement (DMS6100 type, manufactured by Seiko Instruments Inc.), measure the storage elastic modulus in the temperature range from -20 ° C to 130 ° C under the temperature rise condition of 2 ° C / min. To do. Further, the measurement of the glass transition temperature and the confirmation of the rubber-like flat region, which will be described later, shall be performed by the same method as the method for measuring the storage elastic modulus.
  • the glass transition temperature of the cured product obtained by cross-linking the adhesive composition is preferably less than 120 ° C. from the viewpoint of adhesive strength in a high temperature atmosphere. It is more preferably 110 ° C. or lower, and particularly preferably 100 ° C. or lower.
  • the adhesive composition for a battery packaging material of the present invention has a storage elastic modulus curve in the dynamic viscoelasticity measurement of a cured product obtained by cross-linking the adhesive composition from the viewpoint of adhesive force in a high temperature atmosphere. It is preferable that the rubber-like flat region is shown at 120 ° C., and it is more preferable that the storage elastic modulus curve shows at least the rubber-like flat region in the region of 115 ° C.
  • the elastic modulus curve shows at least a rubber-like flat region in a region of 110 ° C. or higher and 120 ° C. or lower.
  • the temperature range up to the glass transition temperature Tg is called the glass region. In this region, the storage elastic modulus gradually decreases as the temperature rises.
  • the glass transition temperature approaches Tg there is a temperature range in which the storage elastic modulus greatly decreases as the temperature rises. This temperature range is called the glass-rubber transition region. After that, there is a temperature range in which the storage elastic modulus does not change significantly even if the temperature is raised. This temperature range is called the rubber-like flat region.
  • the rubber-like flat region In the rubber-like flat region, the molecular chains of the polymer move, but are not completely melted.
  • the rubber-like flat region is preferably a region in which the amount of change in the storage elastic modulus is 0.1 MPa / ° C. or less in a temperature region higher than the glass transition temperature, for example.
  • the component (A) is an acid-modified polyolefin and may have an acid anhydride group and an acidic group. Further, the component (A) preferably has an acid anhydride group. Further, as the component (A), it is preferable that the acid-modified polyolefin is obtained by grafting an unsaturated carboxylic acid anhydride onto the polyolefin to introduce an acid anhydride group.
  • an acid anhydride group-containing monomer or a polyolefin modified with an acidic group-containing monomer and an acid anhydride group-containing monomer is preferable because it has high normal temperature peeling strength and high temperature peeling strength.
  • the monomer forming the monomer unit constituting the polyolefin of the component (A) include ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene and 1-octene.
  • Examples include ⁇ -olefins.
  • ⁇ -olefin represents an ⁇ -olefin having 4 or more carbon atoms unless otherwise specified.
  • the monomer at least one monomer selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, and 1-hexene is preferable.
  • a poorly adhesive non-polar polyolefin resin such as crystalline polyethylene or polypropylene
  • it is composed of ethylene, propylene and 1-butene in that high temperature peel strength and electrolytic solution resistance can be improved.
  • At least one monomer selected from the group is more preferred.
  • Preferred polyolefins used as raw materials for the component (A) are polyethylene, polypropylene, a random copolymer of propylene and ethylene, a block copolymer of propylene and ethylene, a random copolymer of ethylene and ⁇ -olefin, and ethylene and ⁇ -.
  • Examples thereof include block copolymers of olefins, random copolymers of propylene and ⁇ -olefins, block copolymers of propylene and ⁇ -olefins, and the like.
  • the ⁇ -olefin include 1-butene, isobutylene, 1-hexene and 1-octene.
  • a propylene-ethylene copolymer or propylene-in that high-temperature peeling strength and electrolytic solution resistance can be improved.
  • Polypropylene-based polymers such as 1-butene copolymer and propylene-ethylene-1-butene copolymer are more preferable, and propylene-1-butene copolymer is particularly preferable.
  • the propylene unit in the polyolefin is 50% by weight or more.
  • the content of the monomer unit composed of 1-butene in the polyolefin (A) constitutes the polyolefin (A) from the viewpoint of peel strength and high temperature peel strength. It is preferably 5 mol% to 40 mol%, more preferably 10 mol% to 30 mol%, based on all the monomer units.
  • the acidic group examples include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group and the like, and among these, a carboxylic acid group is preferable in that modification is easy.
  • the acid anhydride group examples include a carboxylic acid anhydride group, a sulfonic acid anhydride group, a phosphoric acid anhydride group, and the like. Among these, a raw material is easily available and modification is easy. Therefore, a carboxylic acid anhydride group is preferable.
  • a known method can be adopted.
  • a known radical polymerization initiator such as an organic peroxide or an aliphatic azo compound in melt-kneading or an organic solvent
  • an acid anhydride group-containing monomer, or an acid anhydride group-containing monomer and an acid anhydride group-containing Examples thereof include graft modification in which a monomer is added to a polyolefin.
  • a method of copolymerizing an acid anhydride group-containing monomer, an acidic group-containing monomer, an acid anhydride group-containing monomer, and olefins and the like can be mentioned.
  • the component (A) may be further graft-modified with a (meth) acrylic acid alkyl ester, and the (meth) acrylic acid alkyl ester can improve the stability when the adhesive composition is made into a solution. Therefore, an esterified product of an alkyl alcohol having 8 to 18 carbon atoms and (meth) acrylic acid (hereinafter referred to as "(meth) acrylic acid long chain alkyl ester”) is preferable.
  • Benzoyl peroxide dicumyl peroxide, lauroyl peroxide, di It is preferable to use an organic peroxide such as -t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and cumenehydroperoxide, which is a reaction aid and resin stability. Stabilizers for the adjustment of can be used.
  • reaction aid examples include styrene, o-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, divinylbenzene, hexadiene, dicyclopentadiene and the like.
  • stabilizers include hydroquinone, benzoquinone, nitrosophenylhydroxy compounds and the like.
  • Acidic group-containing monomer The acidic group-containing monomer used as a raw material for the component (A) is a compound having an ethylenically double bond, a carboxylic acid group, etc. in the same molecule, and various unsaturated monocarboxylic acid compounds and Examples thereof include unsaturated dicarboxylic acid compounds and unsaturated tricarboxylic acid compounds.
  • unsaturated monocarboxylic acid compounds include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid and the like.
  • unsaturated dicarboxylic acid compound examples include maleic acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, nadic acid, endic acid and the like.
  • Examples of unsaturated tricarboxylic acid compounds include aconitic acid.
  • an unsaturated dicarboxylic acid compound and an unsaturated tricarboxylic acid compound are preferable, and itaconic acid, maleic acid and aconitic acid are particularly preferable, because they are easily modified and have excellent adhesiveness.
  • acidic group-containing monomers only one type may be used, or two or more types may be used in combination.
  • the unreacted acidic group-containing monomer used for the modification is subjected to a known method such as heat distillation, reprecipitation purification, etc. in order to suppress an adverse effect on the adhesive strength. It is preferable to use the one obtained by removing the above as the component (A).
  • the amount of the graft is preferably 0.10% by weight to 30% by weight. 0.10% by weight or more is preferable, and 0.50% by weight or more is more preferable, in that the solubility of the adhesive composition in a solvent and the adhesiveness to a material such as a metal adherend can be maintained. Further, 30% by weight or less is preferable, 20% by weight or less is more preferable, and 10% by weight or less is particularly preferable, in that sufficient adhesiveness can be obtained.
  • the amount of graft of the acidic group-containing monomer can be measured by a known method. For example, it can be determined by alkaline titration, Fourier transform infrared spectroscopy or nuclear magnetic resonance spectroscopy (NMR).
  • Acid anhydride group-containing monomer used as a raw material for the component (A) is a compound having an ethylenic double bond, a carboxylic acid anhydride group, or the like in the same molecule, and is unsaturated. Examples thereof include an acid anhydride of a monocarboxylic acid compound, an acid anhydride of the unsaturated dicarboxylic acid compound, and an acid anhydride of the unsaturated tricarboxylic acid compound.
  • acid anhydride of the unsaturated monocarboxylic acid compound examples include acrylic acid anhydride, methacrylic acid anhydride, crotonic acid anhydride and isocrotonic acid anhydride.
  • acid anhydride of the unsaturated dicarboxylic acid compound examples include maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, tetrahydrophthalic acid anhydride, nadic acid anhydride, endic acid anhydride and the like. ..
  • acid anhydride of the unsaturated tricarboxylic acid compound examples include aconitic acid anhydride and the like.
  • the acid anhydride group-containing monomer examples include an acid anhydride of an unsaturated dicarboxylic acid compound and an acid anhydride of an unsaturated tricarboxylic acid compound in that they are easily modified and have excellent adhesiveness.
  • an acid anhydride group-containing monomer an acid anhydride of an unsaturated dicarboxylic acid compound is preferable, and an itaconic acid anhydride and / or a maleic anhydride is particularly preferable.
  • the amount of free carboxylic acid in the acid-modified polyolefin can be reduced, which is preferable because the pot life of the solution containing the component (A) and the cross-linking agent becomes long.
  • These acid anhydride group-containing monomers may be used alone or in combination of two or more.
  • unreacted acid anhydride is used by a known method such as heat distillation or reprecipitation purification in order to suppress an adverse effect on the adhesive force. It is preferable to use the one from which the material-containing monomer has been removed as the component (A).
  • the graft amount is preferably 0.10% by weight to 30% by weight. 0.10% by weight or more is preferable, and 0.50% by weight or more is more preferable, in that the solubility of the adhesive composition in a solvent and the adhesiveness to a material such as a metal adherend can be maintained. Further, 30% by weight or less is preferable, 20% by weight or less is more preferable, and 10% by weight or less is particularly preferable, in that sufficient adhesiveness can be obtained.
  • the amount of graft of the acid anhydride group-containing monomer can be measured by a known method. For example, it can be obtained by alkaline titration method or Fourier transform infrared spectroscopy.
  • the ring opening rate of the anhydrous ring of the acid anhydride group in the polyolefin (A) is 30% or less from the viewpoint of liquid stability and adhesive strength in a high temperature atmosphere. Is preferable, 20% or less is more preferable, and 10% or less is particularly preferable.
  • the lower limit of the ring-opening rate is 0%.
  • the ring opening rate of the anhydrous ring of the acid anhydride group in the polyolefin (A) is preferably more than 0% and more than 1% from the viewpoint of adhesive strength. Is more preferable.
  • the ring-opening rate of the anhydrous ring of the acid anhydride group in the polyolefin (A) shall be measured by the following method.
  • the quantification of carboxy groups and their anhydrides can be measured by methods such as infrared absorption (IR) spectroscopy, NMR (nuclear magnetic resonance), and titration.
  • IR infrared absorption
  • NMR nuclear magnetic resonance
  • titration since the amount of grafted acid is smaller than that of the polymer main chain, the error is large, and it is difficult to compare the acid anhydride ring with the ring-opened one.
  • the polymer is precipitated during the titration and the error is large. Therefore, analysis by infrared absorption spectrum is preferable.
  • the height of the absorption peak derived from the acid anhydride group is standardized based on the absorption peak that is not affected by the acid anhydride group or water, and the standardized acid anhydride group.
  • the ring opening rate can be estimated by comparing the heights of the rings.
  • the modified polymer is vacuum dried at 130 ° C. to 150 ° C. for 2 hours or more so that the infrared absorption peak of the carboxy group cannot be observed, and the infrared absorption spectrum in that state is defined as a spectrum having a ring closure rate of 100%.
  • the height of the absorption peak derived from the acid anhydride group and the carboxy group can be determined by determining the height of the absorption peak of the acid anhydride group or water.
  • the ring opening rate can be estimated by standardizing the unaffected absorption peak as a reference and comparing the peak heights of the standardized acid anhydride group and the carboxy group.
  • a method for obtaining the component (A) in which the anhydrous ring of the acid anhydride group is opened a method of opening the ring during the production of the component (A) or adding water to the anhydrous ring of the acid anhydride group after the production of the component (A).
  • a method of opening the ring by disassembly or the like a method of modifying the ring with an acid anhydride group-containing monomer having an anhydrous ring opened, or adding water, alcohol, an amine compound or the like together with the acid anhydride group-containing monomer.
  • a method of opening the ring of the acid anhydride group by hydrolysis or the like a method of dissolving the component (A) in a solvent and then adding a predetermined amount of water, an alcohol or an amine compound and heating the group, or a method of heating the component (A).
  • a method of dissolving after long-term exposure to humidified conditions There is a method of dissolving after long-term exposure to humidified conditions.
  • a method for quantitatively opening the ring of the acid anhydride group a method of adding a predetermined amount of water, alcohol, an amine compound or the like and heating is preferable.
  • (meth) Acrylic Acid Long Chain Alkyl Ester Specific examples of the (meth) acrylic acid long chain alkyl ester used as a raw material for the component (A) include octyl (meth) acrylic acid, lauryl (meth) acrylic acid, and (meth) acrylic. Examples thereof include tridecyl acid acid and stearyl (meth) acrylate, and octyl (meth) acrylate and (meth) acrylic in that the adhesiveness when a poorly adhesive non-polar polyolefin resin is used as an adherend can be significantly improved. Lauryl acid acid and tridecyl (meth) acrylate are preferred.
  • the graft amount of the (meth) acrylic acid long chain alkyl ester in the component (A) is preferably 0.10% by weight to 20% by weight. 0.10% by weight or more is preferable in that the solubility of the component (A) in a solvent, compatibility with other resins, and adhesiveness can be well maintained. Further, 20% by weight or less is preferable, 10% by weight or less is more preferable, and 5.0% by weight or less is particularly preferable, from the viewpoint of being able to maintain good adhesiveness.
  • the graft amount of the (meth) acrylic acid long chain alkyl ester can be measured by a known method. For example, it can be obtained by Fourier transform infrared spectroscopy or 1 H-NMR method.
  • a monomer other than the acidic group-containing monomer, the acid anhydride group-containing monomer and the (meth) acrylic acid long-chain alkyl ester (hereinafter, “other monomers") is used as long as the characteristics of the present invention are not impaired. ".) Can be used together.
  • monomers include (meth) acrylic acid long-chain alkyl esters such as hydroxyethyl (meth) acrylic acid, benzyl (meth) acrylic acid, glycidyl (meth) acrylic acid, and (meth) acrylic acid containing isocyanate.
  • examples thereof include unsaturated monomers copolymerizable with olefins such as (meth) acrylic acid ester, styrene, cyclohexyl vinyl ether, and dicyclopentadiene.
  • the adhesiveness and solubility in a solvent, and the amount of grafts of an acidic group-containing monomer, an acid anhydride group-containing monomer, and a (meth) acrylic acid long-chain alkyl ester can be further improved. ..
  • the amount of the other monomer used preferably does not exceed the total amount of grafts of the acidic group-containing monomer, the acid anhydride group-containing monomer, and the (meth) acrylic acid long-chain alkyl ester.
  • the component (A) may be a polyolefin having an acidic group and / or an acid anhydride group and an ethylenically unsaturated group, depending on the intended purpose, as long as the characteristics of the present invention are not impaired.
  • Examples of the method for introducing an ethylenically unsaturated group into the component (A) include a hydroxyl group-containing ethylenically unsaturated monomer such as hydroxyethyl (meth) acrylate with respect to an acidic group and / or an acid anhydride group.
  • a method of adding an epoxy group-containing ethylenically unsaturated monomer such as glycidyl (meth) acrylate can be mentioned.
  • the weight average molecular weight of the component (A) is preferably 15,000 to 200,000. From the viewpoint of improving the normal temperature peel strength and the electrolytic solution resistance, 15,000 or more is preferable, 30,000 or more is more preferable, and 40,000 or more is particularly preferable. Further, 200,000 or less is preferable, and 150,000 or less is more preferable, in that the solubility in the organic solvent in the adhesive composition can be improved.
  • the weight average molecular weight is a polystyrene-equivalent value of the molecular weight measured by gel permeation chromatography.
  • the melting point of the component (A) is preferably 50 ° C to 110 ° C. From the viewpoint that sufficient peel strength can be obtained, 50 ° C. or higher is preferable, and 60 ° C. or higher is more preferable. Further, 110 ° C. or lower is preferable, and 100 ° C. or lower is more preferable, in terms of solubility in a solvent and suppression of deterioration of fluidity of the composition due to polymer crystallization during storage at a low temperature.
  • the melt flow rate of the component (A) is preferably 50 g / 10 min to 1,000 g / 10 min (190 ° C. / 2.17 kg), preferably 100 g / 10 min, from the viewpoint of coatability and high-temperature peel strength. More preferably, it is ⁇ 800 g / 10 min (190 ° C. / 2.17 kg).
  • the melt flow rate in the present invention shall be measured in an automatic measurement mode using a melt indexer G-02 manufactured by Toyo Seiki Seisakusho Co., Ltd. at a furnace temperature of 190 ° C. and a load of 2.17 kg.
  • the acid value of the component (A) in the present invention is the acid value of the acid anhydride ring opened to form all carboxy groups, and has the adhesive strength in a high temperature atmosphere and the liquid stability of the adhesive composition. From the viewpoint, it is preferably 10 mgKOH / g to 80 mgKOH / g, and more preferably 20 mgKOH / g to 50 mgKOH / g.
  • the acid value in the present invention can be measured by neutralization titration or infrared absorption spectrum as described later.
  • the component (A) may be used alone or in combination of two or more.
  • the content of the component (A) is preferably 50% by weight to 99% by weight with respect to 100% by weight of the solid content of the adhesive composition in that it is excellent in high temperature peel strength and electrolytic solution resistance. , 60% by weight to 95% by weight, more preferably 70% by weight to 90% by weight.
  • the adhesive composition of the present invention contains a cross-linking agent.
  • the cross-linking agent may be any cross-linking agent capable of reacting at least with an acid group or an acid anhydride group in the component (A) to cross-link, and a known cross-linking agent can be used.
  • Examples of the cross-linking agent include a polyfunctional isocyanate compound, a polyfunctional epoxy compound, a polyfunctional carbodiimide compound, a polyfunctional oxazoline compound, and a polyfunctional aziridine compound. These monofunctional compounds can also be used in combination for the purpose of adjusting the viscosity of the solution and adjusting the elastic modulus and elongation of the cured product.
  • the cross-linking agent preferably contains a polyfunctional isocyanate compound from the viewpoint of curability and adhesive strength in a high temperature atmosphere.
  • a polyfunctional isocyanate compound an isocyanate compound having an aliphatic ring structure and / or a derivative thereof (B) and an aliphatic isocyanate compound having no aliphatic ring structure and / or a derivative thereof (C) are preferably used.
  • the cross-linking agent is an isocyanate compound having an aliphatic ring structure and / or a derivative thereof (B) and an aliphatic isocyanate compound having no aliphatic ring structure from the viewpoint of curability and adhesive strength in a high temperature atmosphere.
  • polyfunctional isocyanate compound other than the component (B) and the component (C) include diphenylmethane diisocyanate, xylylene diisocyanate, and their biuret, isocyanurate, and adduct compounds.
  • the component (B) Since the component (B) has good compatibility with the component (A), it has a high effect of increasing the crosslink density of the cured product, improving the high temperature peel strength and reducing the swelling of the adhesive composition due to the electrolytic solution or the like. Yes, the component (C) has the effect of improving the adhesion to the adherend.
  • Component (B) is an isocyanate compound having an alicyclic structure (hereinafter referred to as “component (b)”) and / or a derivative thereof.
  • component (b) examples include hydrogenated xylylene diisocyanate (structural isomers 1,2-bis (isocyanatemethyl) cyclohexane, 1,3-bis (isocyanatemethyl) cyclohexane and 1,4-bis (isocyanate).
  • Methyl) cyclohexane as well as these steric isomers, 4,4'-methylenebis (cyclohexylisocyanate) and its structural isomers (2,2'-methylenebis (cyclohexylisocyanate) and 2,4'-methylenebis ( Cyclohexyl isocyanate)), and these three isomers, norbornan dimethyl isocyanate, isophorone diisocyanate (including isomers) and the like can be mentioned.
  • a diisocyanate compound having at least one alicyclic structure is preferable because it has a high effect of improving high-temperature peel strength.
  • isophorone diisocyanate, hydrogenated xylylene diisocyanate, and 4, 4'-methylenebis (cyclohexyl isocyanate) and its isomers are particularly preferred.
  • a compound containing an isocyanurate bond, a burette bond, a urethane bond and / or an allophanate bond is preferable, and a compound containing an isocyanurate bond is particularly preferable.
  • the derivative of the component (b) may have a urea bond and / or a uretdione bond.
  • ком ⁇ онент (b) a commercially available product can be used.
  • isocyanate compounds having an alicyclic structure HMDI (manufactured by Manka Kagaku Japan Co., Ltd.), Death Module W (manufactured by Sumika Covestro Urethane Co., Ltd.), Fortimo (manufactured by Mitsui Chemicals Co., Ltd.), Takenate 600 (manufactured by Mitsui Chemicals, Inc.) Examples thereof include Mitsui Chemicals Co., Ltd.), Cosmonate NBDI (Mitsui Chemicals Co., Ltd.), and IPDI (Beyond Industries Limited).
  • Component (C) is an aliphatic isocyanate compound having no alicyclic structure (hereinafter referred to as “component (c)”) and / or a derivative thereof.
  • component (c) a component having a linear alkyl group having 4 to 18 carbon atoms is preferable because it has a high effect of improving the peel strength of the adhesive composition at room temperature.
  • Specific examples of the component (c) include hexamethylene diisocyanate, pentamethylene diisocyanate, tetramethylene diisocyanate, and the like, and the component (c) has a high effect of improving adhesion to an adherend. Methylene diisocyanate is preferred.
  • a compound containing an isocyanurate bond, a bullet bond, a urethane bond and / or an allophanate bond is preferable, and the effect of improving the adhesion to the adherend is high, and the normal temperature peel strength and the electrolytic solution resistance are high.
  • a compound containing an isocyanurate bond is particularly preferable because it can improve the properties.
  • the derivative of the component (c) may have a urea bond and / or a uretdione bond.
  • a commercially available product can be used as the derivative of the component (c).
  • Commercially available products of compounds having an isocyanurate bond include Duranate TPA-100 (manufactured by Asahi Kasei Co., Ltd.), Duranate MFA-75B (manufactured by Asahi Kasei Co., Ltd.), Duranate TUL-100 (manufactured by Asahi Kasei Co., Ltd.), and Duranate TSA.
  • Module N3200 (manufactured by Sumika Covestro Urethane Co., Ltd.) and the like can be mentioned.
  • Commercially available compounds with urethane bonds include Duranate P301-75E (manufactured by Asahi Kasei Co., Ltd.) and Sumijour HT (manufactured by Sumika Cobestro Urethane Co., Ltd.), which are adducts of hexamethylene diisocyanate and trimethylolpropane. And so on.
  • Examples of commercially available compounds having an allophanate bond include Death Module XP2580 (manufactured by Sumika Covestro Urethane Co., Ltd.).
  • the weight ratio of the component (A) to the isocyanate compound in the adhesive composition of the present invention is not particularly limited, but the amount of the isocyanate group in the polyfunctional isocyanate compound with respect to the acid value of the acid-modified polyolefin is the initial adhesive force. From the viewpoint of adhesive strength in a high temperature atmosphere, 0.01 molar equivalent to 12.0 molar equivalent is preferable with respect to 1 molar equivalent of the carboxy group obtained from the acid value of the component (A), and 0.5 molar equivalent. To 10 molar equivalents are more preferred, and 1 molar equivalents to 6 molar equivalents are particularly preferred.
  • the ratio of the contents of the component (B) and the component (C) in the adhesive composition of the present invention is such that the component (B) is 100% by weight when the total amount of the component (B) and the component (C) is 100% by weight. It is preferably 10% by weight to 100% by weight, and the component (C) is 0% by weight to 90% by weight.
  • the component (B) is more preferably 20% by weight to 90% by weight, and particularly preferably 30% by weight to 90% by weight, because it has a high effect of increasing the crosslink density of the cured product and can improve the high temperature peel strength.
  • the component (C) is more preferably 10% by weight to 80% by weight, particularly preferably 10% by weight to 70% by weight, in that the adhesion to the adherend can be improved.
  • the adhesive composition of the present invention only one type of cross-linking agent may be used, or two or more types may be used in combination.
  • the content of the cross-linking agent is 1 weight based on 100 parts by weight of the total amount of the component (A) and the cross-linking agent from the viewpoint of the adhesive force in a normal temperature (25 ° C.) atmosphere and the adhesive force in a high temperature atmosphere.
  • the amount is preferably from 10 parts by weight to 60 parts by weight, more preferably from 10 parts by weight to 60 parts by weight, and particularly preferably from 15 parts by weight to 50 parts by weight.
  • the value of is preferably 0.1 to 10, more preferably 0.5 to 6, and 1 to 6 from the viewpoint of the adhesive force in a normal temperature atmosphere and the adhesive force in a high temperature atmosphere. It is particularly preferable to have.
  • the adhesive composition of the present invention preferably contains an organic solvent.
  • the organic solvent is added, for example, for the purpose of dissolving the component (A).
  • organic solvent examples 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, methylethylketone and the like.
  • Ketone-based organic solvent alcohol-based organic solvent such as methanol and ethanol, ester-based organic solvent such as ethyl acetate and butyl acetate
  • propylene glycol ether such as propylene glycol methyl ether, propylene glycol ethyl ether and propylene glycol-t-butyl ether.
  • system organic solvents examples include system organic solvents.
  • the adhesive composition of the present invention only one type of organic solvent may be used, or two or more types may be used in combination.
  • the organic solvent is preferably an organic solvent that can be easily volatilized and removed by heating or the like of the adhesive composition, and in particular, an aromatic or alicyclic organic solvent and an ester-based or ketone-based organic solvent. It is preferable to use the mixed solvent of.
  • the weight ratio between the organic solvent and the component (A) is not particularly limited, and this weight ratio can be set depending on the type of the organic solvent and the component (A) and the like. Further, the weight ratio can be set for the purpose of adjusting the viscosity and the solid content concentration in consideration of the suitability for the coating device.
  • the content of the component (A) is preferably 5% by weight to 25% by weight, particularly preferably 10% by weight to 20% by weight, when the total of the organic solvent and the component (A) is 100% by weight. With such a content, the adhesive composition can be easily applied to the adherend and the workability is excellent.
  • the adhesive composition of the present invention contains an organic solvent, a component (A), and a cross-linking agent containing the components (B) and (C), but various components may be added depending on the purpose. Can be blended.
  • other components include curing catalysts, styrene-based thermoplastic elastomers, tackifiers, antioxidants, hindered amine-based light stabilizers, ultraviolet absorbers, antistatic agents, flame retardants, colorants, and dispersants. Adhesion-imparting agents, defoaming agents, leveling agents, plasticizers, lubricants, fillers and the like can be mentioned. As the other components, only one of the illustrated compounds may be used, or two or more of them may be used in combination.
  • Curing catalyst The curing catalyst can be blended for the purpose of promoting the cross-linking reaction between the component (A) and the isocyanate compound and obtaining excellent adhesive performance.
  • the adhesive composition of the present invention preferably further contains a curing catalyst from the viewpoint of easiness of curing and adhesive performance, and the curing catalyst includes a tertiary amine, a metal carboxylate, a complex salt and an organic substance. Metal compounds and the like are preferable.
  • tertiary amine examples include tetraalkylethylenediamine such as tetramethylethylenediamine; N, N'-dialkylbenzylamine such as dimethylbenzylamine; triethylenediamine, pentamethyldiethylenetriamine, N-ethylmorphylin, and N-methylmol.
  • Phylline, 1-methyl-4-dimethylamine ethylpiperazin and 1,8-diazabicyclo [5.4.0] undecene-7 and the like can be mentioned.
  • metal carboxylates and complex salts metal carboxylates and complex salts
  • metal octanates such as metal acetate, metal hexanate, metal 2-ethylhexanoate, metal neodecanoate, metal laurate, metal stearate, etc.
  • metal carboxylates such as metal oleate and metal complex salts such as metal acetylacetonate.
  • the organometallic compound is not particularly limited as long as it is a metal compound having a bond between a metal atom and a carbon atom, and examples thereof include organometallic oxides.
  • the metal is preferably one or more metals selected from the group consisting of the metals of Group 7, Group 12, and Group 14 of the periodic table. These may be used alone or in combination of two or more.
  • any of tin, zinc and manganese carboxylates and acetylacetonate And organometallic compounds are more preferred.
  • Zinc distearate Zinc distearate, zinc (II) acetylacetonate, bis (2-ethylhexanoic acid) manganese and the like.
  • dibutyltin dilaurate, dioctyltin dilaurate, and / or dioctyltin oxide are more preferable from the viewpoint of the balance between adhesiveness, electrolyte resistance and heat resistance of the adhesive layer.
  • a tertiary amine and a metal carboxylate, a complex salt or an organometallic compound can be used in combination.
  • the content ratio of the curing catalyst is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the total amount of the components (A) to (C).
  • Adhesive Composition contains a component (A) and a cross-linking agent, preferably a cross-linking containing an organic solvent, a component (A), and a component (B) and a component (C). It contains an agent, more preferably a curing catalyst.
  • the viscosity of the adhesive composition of the present invention at 25 ° C. is preferably 10 to 5,000 mPa ⁇ s. 10 mPa ⁇ s or more is preferable from the viewpoint of excellent coatability. Further, in terms of excellent leveling property, 5,000 mPa ⁇ s or less is preferable, and 1,000 mPa ⁇ s or less is more preferable.
  • the adhesive composition of the present invention is suitable for adhering a polyolefin resin molded body to another member (metal member, resin member, etc.), and is not limited to polyolefin resin molded bodies such as polyolefin resin films, but also polyolefin. It can also be used for adhesion between a resin film and a metal foil made of aluminum or the like, adhesion between a polyolefin resin film and a metal layer in a composite film having a resin layer and a metal layer, and the like.
  • the adhesive layer has high normal temperature peel strength and high temperature peel strength, is excellent in adhesiveness, and has high electrolytic solution resistance, so that it can be preferably used as a packaging material for lithium ion batteries.
  • the peel strength of the test piece obtained by adhering the aluminum foil and the polyolefin with the adhesive composition at 120 ° C. is 4N / 15 mm or more from the viewpoint of the adhesive strength in a high temperature atmosphere. It is preferably 4.5 N / 15 mm or more, and particularly preferably 4.5 N / 15 mm or more and 10 N / 15 mm or less.
  • the method for measuring the peel strength of the test piece obtained by adhering the aluminum foil and polypropylene with the adhesive composition at 120 ° C. shall be as follows. Using an applicator bar, the adhesive composition was applied to the chromate-treated surface of a chromate-treated aluminum foil having a thickness of 40 ⁇ m, a width of 10 cm, and a length of 20 cm so that the adhesive thickness after drying was about 2 ⁇ m. Apply and dry in an oven at 80 ° C. for 1 minute.
  • the corona discharge-treated surface of the unstretched polypropylene film with corona discharge treatment on one side is overlapped with the adhesive-coated surface of the aluminum foil, crimped with a thermal laminator having a roll temperature of 80 ° C, and then left in an oven at 40 ° C for 5 days.
  • the cross-linking reaction is advanced, and the film is cut into a width of 15 mm to obtain a test piece for a peeling test.
  • the peeling strength between the aluminum foil and the polypropylene film is measured by a T peeling test at a crosshead speed of 100 mm / min.
  • the measurement temperature may be appropriately selected, and is, for example, 120 ° C.
  • the adhesive composition of the present invention can be produced by a known method.
  • it is a method of mixing a solution obtained by dissolving the component (A) in an organic solvent and other components other than the isocyanate compound, and then mixing the obtained mixture and the isocyanate compound.
  • the temperature at the time of mixing is preferably 40 ° C. or lower, more preferably 10 ° C. to 30 ° C.
  • the isocyanate compound and the curing catalyst may be mixed and prepared by mixing with the component (A), the organic solvent, and other components.
  • the heat-sealing member for battery packaging material of the present invention is bonded to an adhesive layer obtained by curing the adhesive composition of the present invention on one surface side of the adhesive layer. It includes a metal layer and a heat-sealing resin layer bonded to the other surface side of the adhesive layer.
  • Schematic representations of the heat-sealing members of the present invention are shown in FIGS. 1 and 2. That is, the thermosetting member 1 of FIG. 1 sequentially includes a thermosetting resin layer 11, an adhesive layer 12, and a metal layer 13. Further, the thermosetting member 1 of FIG. 2 is sequentially provided with a thermosetting resin layer 11, an adhesive layer 12, a metal layer 13, and another layer 14.
  • the shape of the heat-sealing member of the present invention may be appropriately set according to the intended use and the like, and is not particularly limited, and examples thereof include a film shape and a sheet shape.
  • the thermosetting resin layer is a layer containing a resin that is melted by heat and can fuse a material forming a layer on one side and a material forming a layer on the other side.
  • the thermosetting 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 resin, polyamide resin, polyester resin and the like. Among these, polyolefin resins are preferable because they can be heat-sealed with sufficient strength.
  • polypropylene is preferable. In particular, unstretched polypropylene is more preferable because there is little dimensional change (shrinkage) when a heat-sealing member is used and integrated with another member.
  • the above-mentioned heat-sealing resin layer may be used as 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 the additive of.
  • the thickness of the thermosetting resin layer is not particularly limited depending on the material of the resin and the like, but for example, in the case of a layer containing unstretched polypropylene, it is preferably 10 ⁇ m to 200 ⁇ m, more preferably 20 ⁇ m to 100 ⁇ m. Is. When the thickness of the layer containing unstretched polypropylene is 10 to 200 ⁇ m, it is not easily damaged and a heat-sealed composite product such as a highly durable sealed container can be obtained.
  • the above-mentioned adhesive layer is a layer formed by curing the adhesive composition of the present invention.
  • the thickness of the adhesive layer is not particularly limited, but is preferably 1 ⁇ m to 20 ⁇ m, and particularly preferably 2 ⁇ m to 10 ⁇ m. When the thickness of the adhesive layer is 1 ⁇ m to 20 ⁇ m, it is easy to perform processing such as bending when the heat-sealing member is in the form of a sheet, for example.
  • the above metal layer is a layer containing a metal or an alloy.
  • the metal or alloy include aluminum, iron, titanium, magnesium, copper, nickel, chromium and other metals, and alloys thereof. Among these, aluminum is preferable because it has 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 ⁇ m to 100 ⁇ m, more preferably 20 ⁇ m to 80 ⁇ m, and further preferably 30 ⁇ m to 60 ⁇ m.
  • the heat-sealing 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, an excellent appearance can be obtained when a sealed container or the like is used as a heat-sealing composite product.
  • the other layer may have a multi-layer structure, and may include, for example, an adhesive layer for adhering the resin layer and the metal layer.
  • the adhesive layer in the other layers may be the same as or different from the adhesive layer provided between the thermosetting resin layer and the metal layer.
  • the thickness of the other layer is not particularly limited, and is preferably 5 ⁇ m to 60 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m.
  • the heat-sealing member using the adhesive composition of the present invention has high normal temperature peel strength and high temperature peel strength, is excellent in adhesiveness, and is also excellent in resistance to solvents such as electrolytes, so that the structure is maintained. , It is possible to prevent deterioration of the contents.
  • the manufacturing method of the heat-sealing member shown in FIG. 1 is as follows. (1) The adhesive composition is applied to the surface of a metal foil for forming the metal layer 13, a metal film, or the like, and then the organic solvent in the composition is removed to form the adhesive layer 12, and then the adhesive layer 12 is formed. A method in which a resin film for forming a thermosetting resin layer 11 (hereinafter referred to as "thermosetting resin film”) is brought into contact with a surface on which the adhesive layer 12 is formed and pressure-bonded while heating. (2) The adhesive composition is applied to the surface of the thermosetting resin film, and then the organic solvent in the composition is removed to form the adhesive layer 12, and then the adhesive layer 12 is formed. A method in which a metal foil or the like for forming a metal layer 13 is brought into contact with a surface and crimped while heating.
  • the method for manufacturing the heat-sealing member shown in FIG. 2 is as follows. (3)
  • the adhesive composition is a composite having a resin layer constituting another layer 14 and a metal layer 13 formed on one surface side of the resin layer by bonding or vaporizing a metal foil with an adhesive. It is applied to the surface of the metal layer 13 in the film, and then 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 heat-sealing resin film are formed. A method of crimping while heating.
  • the adhesive composition is applied to the surface of the thermosetting resin film, and then the organic solvent in the composition is removed to form the adhesive layer 12, and then the adhesive layer 12 is formed.
  • the surface of the composite film having the resin layer constituting the other layer 14 and the metal layer 13 formed by vapor deposition or the like on one surface side of the resin layer is brought into contact with the surface of the composite film.
  • a method of crimping while heating A method of extrusion molding a film for forming another layer 14 on the surface of the metal layer 13 in the laminate obtained by the method (1) or (2) above.
  • the adhesive composition is often applied to the surface of a metal layer forming material such as a metal foil or a composite film having 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 ⁇ m to 100 ⁇ m.
  • the metal layer contains aluminum and the other layer (resin layer) contains a polyamide resin, a polyester resin, or the like.
  • a polyamide resin, a polyester resin, or the like can be used. It is preferable to use a film containing.
  • thermosetting resin film a polyolefin resin film, a polyamide resin film, a polyester resin film, or the like can be used. These resin films can be films obtained by film forming methods such as extrusion method, cast molding method, T-die method and inflation method.
  • the thickness of the thermosetting resin film is preferably 10 ⁇ m to 200 ⁇ m.
  • the polyolefin resin film is preferable and is not easily damaged in that heat fusion for completing the heat-sealing member and heat fusion for manufacturing the heat-sealing composite product can be easily performed.
  • a non-stretched polypropylene film is particularly preferable because a heat-sealed composite product such as a sealing container having excellent durability can be obtained.
  • the thickness is preferably 10 ⁇ m to 200 ⁇ m, more preferably 20 ⁇ m to 100 ⁇ m.
  • the adhesive composition can be applied by a conventionally known method, and 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 not particularly limited, and is preferably 30 ° C. to 130 ° C. from the viewpoint of workability.
  • the two members can be bonded without heating, but in the case of producing the heat-sealing member of the present invention.
  • a method of crimping or the like while heating to a temperature in consideration of the melting point, melt viscosity, etc. of the resin component based on the component (A) can be applied.
  • the heating conditions and crimping conditions are, for example, a temperature of 80 ° C., a pressure of 0.3 MPa, and a crimping time of 2 seconds.
  • the conditions for promoting the cross-linking reaction between the component (A) and the isocyanate compound to complete the thermosetting member are not particularly limited, and the material of the metal foil and the material of the metal foil It is preferable to set it according to the material of the thermosetting resin film, the melting temperature, the composition of the adhesive layer, and the like. As the aging condition, heating may be performed at 40 ° C.
  • a polyolefin having an acidic group and / or an acid anhydride group and an ethylenically unsaturated group is used as the component (A), and the aging time is
  • active energy ray curing such as ultraviolet rays and electron beams and heating may be used in combination.
  • the heat-sealing member for battery packaging materials of the present invention can be suitably used as battery packaging materials (battery packaging materials), for example, secondary battery packaging materials such as lithium ion batteries and lithium ion polymer batteries. Can be mentioned. Further, the heat-sealing member of the present invention can be used in various industrial products in the electric field, the automobile field and other industrial fields.
  • Examples of applications in the electrical field other than battery packaging materials include decoration by attaching a decorative sheet, adhesion of metal members and resin, and sealing of electronic components in mobile devices, TV housings, white goods housings, and the like. And so on.
  • Examples of applications in the automobile field include adhesion of exterior materials made of metal / resin in interior / exterior members such as pillars, moldings, door trims, spoilers and roofs, genuine leather, fabrics, instrument panel foam sheets and decorative sheets. There is adhesion of materials.
  • Examples of applications in other industrial fields include adhesion between industrial packaging materials and multilayer films such as barrier films.
  • the heat-sealing member for battery packaging material of the present invention is used as a secondary battery packaging material because it has high normal temperature peeling strength and high temperature peeling strength, excellent adhesiveness, and high electrolytic solution resistance. Is preferable, and a lithium ion battery packaging material is more preferable.
  • MFR Melt flow rate
  • IR1 Dehydration and ring closure method of dibasic acid moiety
  • a polymer graft-modified with maleic anhydride is vacuum dried at 150 ° C. for 2 hours, the dibasic acid moiety formed by ring opening due to moisture absorption or the like cannot be discriminated on the IR spectrum.
  • Dehydration ring closure has progressed to a certain extent. This was cooled to room temperature in a dry state, and the acid anhydride ring was 100% closed.
  • IR3 Preparation of sample for infrared absorption spectrum measurement A small amount of the acid-modified polyolefin obtained in IR1 is taken out, sandwiched between two fluororesin sheets having a thickness of 1 mm, and pressed by a hot press at 100 ° C. to form a film. did. This film-like sample was placed in a moisture-proof bag, sealed, and left at room temperature for 1 day or longer to proceed with crystallization. According to the study of the present inventor, if the infrared absorption spectrum is measured without proceeding with this crystallization, the acid value tends to be slightly overestimated, and the acid value measurement result becomes stable after being left for 1 day or more. Therefore, it was left at room temperature for a while.
  • IR4 Measurement of infrared absorption spectrum The above film sample was measured by a transmission method using an FT-IR measuring device (Nicolette iS50 manufactured by Thermo Fisher Scientific Co., Ltd.).
  • AC1 35 g of non-acid-modified polymer pellets and dodecylsuccinic anhydride (additive-free, 1 g, 2 g, 4 g) were weighed and heated to 170 ° C. Labplast Mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) And stirred by heating to prepare four kinds of samples having different dodecylsuccinic anhydride contents.
  • AC2 A small amount of this was cut out, and a film was prepared by a hot press heated to 100 ° C. in the same manner as in the method described in IR3.
  • maleic anhydride was graft-reacted with the polyolefin to obtain an acid-modified polyolefin.
  • the conditions of the extruder were a maximum temperature of 150 ° C., a screw rotation speed of 200 rpm, and an extrusion speed of 1 kg / h.
  • the acid value of the obtained acid-modified polyolefin was 41.1 mgKOH / g (with a carboxy group content of 0.73 mmol / g), and the melt flow rate measured at 190 ° C. and a load of 2.17 kg was 91 g / 10 minutes.
  • Example 1 15 g of the acid-modified polyolefin obtained in Synthesis Example 1 and 85 g of a mixed solvent of methylcyclohexane and methyl ethyl ketone (mixing ratio 80:20) were placed in a glass bottle, sealed tightly, and dissolved in a water bath at 70 ° C. until uniform, and then a solution. was cooled to room temperature. To this, 0.0015 g of dibutyltin laurate was added, and the mixture was stirred and mixed to prepare a polymer solution.
  • a mixed solvent of methylcyclohexane and methyl ethyl ketone mixing ratio 80:20
  • a cross-linking agent (Duranate TPA-100 manufactured by Asahi Kasei Co., Ltd.) containing an isocyanurate of hexamethylene diisocyanate as a main component was added to the polymer solution to form a carboxy group when all the acid anhydride rings in the acid-modified polyolefin were opened.
  • the isocyanate group was added so as to be 1.5 times the amount, and the mixture was stirred and mixed. At this time, the ratio of the cross-linking agent added to the total amount of the acid-modified polyolefin and the cross-linking agent was 16.6% by weight.
  • this solution was applied to the chromate-treated surface of a chromate-treated aluminum foil having a thickness of 40 ⁇ m, a width of 10 cm, and a length of 20 cm so that the adhesive thickness after drying was about 2 ⁇ m. Then, it was dried in an oven at 80 ° C. for 1 minute.
  • the corona discharge-treated surface of the unstretched polypropylene film with corona discharge treatment on one side is overlapped with the adhesive-coated surface of the aluminum foil, crimped with a thermal laminator having a roll temperature of 80 ° C, and then left in an oven at 40 ° C for 5 days.
  • the cross-linking reaction was advanced, and the film was cut into a width of 15 mm to prepare a test piece for a peeling test.
  • an adhesive solution containing a cross-linking agent is poured into a polyethylene cup to a thickness of about 0.5 mm after drying, air-dried, and then left in an oven at 40 ° C. for 5 days.
  • the cross-linking reaction was carried out to prepare a test piece for viscoelasticity measurement.
  • Example 2 With the compositions summarized in Table 2, a test piece for peeling test and a test piece for measuring viscoelasticity were prepared in the same manner as in Example 1.
  • ⁇ Dynamic viscoelasticity measurement method The dynamic viscoelasticity of the adhesive composition was measured by the following method.
  • the adhesive composition is poured into a polyethylene mold and air-dried, and then cured at 40 ° C. for 5 days to prepare a sheet having a thickness of about 0.5 mm, which is cut into strips having a width of about 5 mm and bonded. It was used to measure the dynamic viscoelasticity of the cured product.
  • DMS6100 manufactured by Hitachi High-Tech Science Corporation, measurements were taken at a heating rate of 20 ° C./min and a frequency of 1 Hz at least between ⁇ 20 ° C. and 130 ° C.
  • Example 4 the measurement results of the storage elastic modulus in Example 4 and Comparative Example 10 are shown in FIG.
  • E'on the vertical axis represents the storage elastic modulus (Pa), and Temp. Represents a temperature (° C.), respectively, such as "1.E + 08" represents "1 ⁇ 10 8" or the like.
  • 1 ⁇ 10 6 Pa 1 MPa.
  • FIG. 4 shows a schematic diagram of an example of measuring the glass transition temperature (Tg) in Example 1.
  • E'on the vertical axis represents the storage elastic modulus (Pa)
  • Temp. Represents the temperature (° C.), and "1.
  • E + 06" and the like represent "1 x 10 6 " and the like, respectively.
  • Tables 2 and 3 mean parts by weight, and the abbreviations in Tables 2 and 3 mean the following.
  • TPA100 Crosslinking agent containing an isocyanurate of hexamethylene diisocyanate as the main component (Duranate TPA-100 manufactured by Asahi Kasei Corporation)
  • TUL100 A low-viscosity cross-linking agent containing an isocyanurate of hexamethylene diisocyanate as a main component (Duranate TUL-100 manufactured by Asahi Kasei Corporation).
  • D127N Cross-linking agent containing the isocyanurate of hydrogenated xylylene diisocyanate as the main component (Takenate D127N manufactured by Mitsui Chemicals, Inc.)
  • a peeling test at 25 ° C. and a peeling test at 120 ° C. were performed. At 25 ° C., all the samples showed good peel strength, but at 120 ° C., the peel strength was 4N / 15mm or more in all of the examples, whereas it was less than 4N / 15mm in the comparative example. .. Further, in the dynamic viscoelasticity measurement results of the sample obtained by curing these adhesive compositions, it was a rubber-like flat region which was a region above the glass transition temperature of the cured product at 120 ° C. in both Examples and Comparative Examples.
  • the storage elastic modulus at 120 ° C. was 2 MPa or more in the example and less than 2 MPa in the comparative example. A positive correlation was observed between the storage elastic modulus and the peel strength at 120 ° C., and when the storage elastic modulus was 2 MPa or more, the peel strength was 4 N / 15 mm or more.
  • the acid anhydride ring of an acid-modified olefin is an amino group and an acid anhydride ring formed by reacting with an isocyanate group after opening the ring with water in the air to form a carboxy group, or by reacting an isocyanate group with water. React to form an amide bond (including a biuret bond, an isocyanate bond, an allophanate bond, etc.) and crosslink.
  • the metal-adhesive interface is highly adhered at a high temperature in the combination of the acid-modified polyolefin having a high acid value and the appropriate amount of the cross-linking agent.
  • the elastic modulus of the cured adhesive By increasing the elastic modulus of the cured adhesive while ensuring the properties, it is easy to obtain high peel strength even at high temperatures where the cured adhesive exceeds the glass transition temperature.
  • the cross-linking agent As the cross-linking agent, the peel strength at high temperature tends to be high even when the amount of the cross-linking agent added is the same as that of the combination of the isocyanate having an aliphatic ring structure and the aliphatic isocyanate.
  • the present invention relates to an adhesive composition for a battery packaging material, a heat-sealing member for a battery packaging material using the same, and a secondary battery packaging material, and can be used for various battery packaging materials. It belongs to these technical fields.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
PCT/JP2020/046367 2019-12-23 2020-12-11 接着剤組成物、熱融着性部材、及び、二次電池包材 Ceased WO2021131812A1 (ja)

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