WO2024162419A1 - 硬化性熱伝導性接着剤 - Google Patents

硬化性熱伝導性接着剤 Download PDF

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Publication number
WO2024162419A1
WO2024162419A1 PCT/JP2024/003186 JP2024003186W WO2024162419A1 WO 2024162419 A1 WO2024162419 A1 WO 2024162419A1 JP 2024003186 W JP2024003186 W JP 2024003186W WO 2024162419 A1 WO2024162419 A1 WO 2024162419A1
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Prior art keywords
thermally conductive
conductive adhesive
adhesive
agent
curable
Prior art date
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Ceased
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PCT/JP2024/003186
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English (en)
French (fr)
Japanese (ja)
Inventor
森本　晃平
淳士 古川
達矢 岩本
哲朗 吉岡
祐輔 小林
達哉 飯野
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Priority to EP24750368.3A priority Critical patent/EP4660275A1/en
Priority to JP2024510439A priority patent/JPWO2024162419A1/ja
Priority to KR1020257025329A priority patent/KR20250140530A/ko
Priority to CN202480010074.5A priority patent/CN120897974A/zh
Publication of WO2024162419A1 publication Critical patent/WO2024162419A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/223—Di-epoxy compounds together with monoepoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C08G59/502—Polyalkylene polyamines
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/64—Heating or cooling; Temperature control characterised by the shape of the cells
    • H01M10/647—Prismatic or flat cells, e.g. pouch cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive materials
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • C08K2201/005—Additives being defined by their particle size in general
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
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    • C09J2463/00—Presence of epoxy resin
    • 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 a curable thermally conductive adhesive.
  • Thermally conductive resin compositions that are curable and liquid are widely known. For example, they are filled between a heat generating element and a heat sink, and then cured to form a cured product, which is then used as a thermally conductive member such as a heat dissipating gap filler that transfers heat generated by the heat generating element to the heat sink.
  • a thermally conductive member such as a heat dissipating gap filler that transfers heat generated by the heat generating element to the heat sink.
  • thermally conductive resin compositions are often filled between each component such as a battery cell, a battery module, a battery pack, etc., for the purpose of fixing each component and improving heat dissipation.
  • Several technologies related to such thermally conductive compositions have been reported.
  • Patent Document 1 discloses an invention relating to a thermally conductive composition having low thermal resistance and high reliability, the thermally conductive composition comprising a tri- or higher functional epoxy resin having no aromatic skeleton, a liquid bi- or lower functional epoxy resin, a curing agent, a silane compound having no functional groups other than alkoxy groups, and a thermally conductive filler.
  • Patent Document 2 describes an invention relating to a thermally conductive curable composition as a thermal interface material having high thermal conductivity, which comprises a first part containing a catalyst, a ceramic filler mixture, a low volatility organic liquid, and water, and a second part containing a silyl-modified reactive polymer, a low volatility organic liquid, and a ceramic filler mixture.
  • Patent Document 3 describes an invention relating to a curable composition that contains a polyol including a hydrogenated polybutadiene polyol, a polyisocyanate, a phosphoric acid ester having a specific structure, an inorganic filler, and a plasticizer, as a urethane-based composition that has excellent adhesion to a substrate and does not decrease in adhesion over time, and in which the content of the inorganic filler is 83 to 93% by weight.
  • a polyol including a hydrogenated polybutadiene polyol, a polyisocyanate, a phosphoric acid ester having a specific structure, an inorganic filler, and a plasticizer
  • Thermal conductive members formed by curing conventional thermally conductive compositions are used between adherends such as heat generating bodies and heat dissipating bodies as described above, but in practical use environments, they cannot keep up with the changes in the gap between adherends that occur when exposed to low- to high-temperature thermal cycles, and may peel off from the adherends. This leads to a decrease in strength as a structural member and a decrease in heat dissipation properties, and the thermal conductive member is no longer able to fulfill its intended role of fixing various members and increasing heat dissipation.
  • the present invention aims to provide a curable thermally conductive adhesive that has high adhesive strength to an adherend and is capable of forming a thermally conductive component that is unlikely to peel off from the adherend even after undergoing a thermal cycle from low to high temperatures.
  • the present inventors conducted extensive research and found that the above problems can be solved by a curable thermally conductive adhesive that contains a curable binder and a thermally conductive filler, in which the adhesive strength of a cured product of the adhesive is at least a certain level, and the storage modulus G' and loss tangent tan ⁇ of the cured product, which are obtained by dynamic viscoelasticity measurement under specific conditions, satisfy specific relational expressions, and thus completed the present invention.
  • the inventors also discovered that the above problems can also be solved by a curable thermally conductive adhesive that contains a curable binder and a thermally conductive filler, wherein the adhesive has a cured product having an adhesive strength of at least a certain level and a shear elongation of at least a certain level, and thus completed the present invention.
  • the present invention provides the following [1] to [20].
  • a curable thermally conductive adhesive containing a curable binder and a thermally conductive filler wherein the adhesive strength of a cured product obtained by curing the curable thermally conductive adhesive at 60°C for 24 hours is 0.3 MPa or more, and the storage modulus G' and loss tangent tan ⁇ obtained by dynamic viscoelastic measurement of the cured product at 25°C and a frequency of 0.1 Hz satisfy the following formula (1): 1og10(G') ⁇ 4.29 ⁇ tan ⁇ +6 Formula (1)
  • a curable thermally conductive adhesive containing a curable binder and a thermally conductive filler wherein the adhesive strength of the cured product obtained by curing the curable thermally conductive adhesive at 60°C for 24 hours is 0.3 MPa or more, and the shear elongation of the cured product at a thickness of 2 mm, measured using a cationic electrodeposition coated substrate and a polyethylene terephthalate (PET) substrate, is 0.25 mm
  • the curable thermally conductive adhesive according to any one of [1] to [7] above, wherein the curable binder is a binder containing an epoxy resin and a curing agent, a binder containing an organic polymer having a hydrolyzable silyl group, or a binder containing a polyol and a polyisocyanate.
  • the molecular weight of the curing agent is 300 or more.
  • a battery assembly comprising the thermally conductive member described in [18] above.
  • the present invention provides a curable thermally conductive adhesive that can form a thermally conductive component that has high adhesion to an adherend and is unlikely to peel off from the adherend even after undergoing a thermal cycle from low to high temperatures.
  • FIG. 2 is a schematic diagram showing a container set according to one embodiment.
  • FIG. 2 is a schematic diagram showing a container set according to one embodiment.
  • 1 is a perspective view showing a representative configuration of a battery module according to the present invention;
  • FIG. 2 is a perspective view showing a typical configuration of a battery cell included in a battery module.
  • FIG. 1 is a perspective view showing a battery assembly having a cell-to-pack structure.
  • FIG. 2 is a diagram showing the relationship between the data of each of the examples and comparative examples and formula (1).
  • the curable thermally conductive adhesive of the present invention is a curable thermally conductive adhesive that contains a curable binder and a thermally conductive filler, and the adhesive strength of the cured product obtained by curing the curable thermally conductive adhesive at 60°C for 24 hours is 0.3 MPa or more, and the storage modulus G' and loss tangent tan ⁇ obtained by dynamic viscoelasticity measurement of the cured product at 25°C and a frequency of 0.1 Hz satisfy the following formula (1): 1og10(G') ⁇ 4.29 ⁇ tan ⁇ +6 Formula (1)
  • a curable thermally conductive adhesive is a curable thermally conductive adhesive containing a curable binder and a thermally conductive filler, and the adhesive strength of the cured product obtained by curing the curable thermally conductive adhesive at 60°C for 24 hours is 0.3 MPa or more, and the shear elongation of the cured product at a thickness of 2 mm, measured using a cationic electrodeposition coated substrate and a polyethylene terephthalate (PET) substrate, is 0.25 mm or more.
  • the curable thermally conductive adhesive (hereinafter sometimes simply referred to as "adhesive") of the present invention will be described in detail below.
  • the adhesive of the present invention satisfies the following formula (1) when the storage modulus G' and loss tangent tan ⁇ obtained by measuring dynamic viscoelasticity of the cured product obtained by curing the adhesive at 60°C for 24 hours at 25°C and a frequency of 0.1 Hz are G' and tan ⁇ , respectively.
  • 1og10(G') is the logarithm of the storage modulus G' with the base being 10.
  • the unit of the storage modulus G' is Pascal.
  • Formula (1) indicates that 1og10(G') is smaller than the value of "4.29 ⁇ tan ⁇ + 6.” If the above formula (1) is not satisfied, the thermal conductive member formed by curing the adhesive cannot follow the change in the gap between the adherends that occurs when the adhesive is exposed to a thermal cycle from low temperature to high temperature, and the thermal conductive member is likely to peel off from the adherend.
  • the thermally conductive member formed by curing the adhesive is less likely to peel off from the adherend in a thermal cycle from low temperature to high temperature.
  • the reason for this is presumed to be as follows. If the storage modulus of the thermally conductive member formed by curing the adhesive is too high, sufficient flexibility is lost, and the material cannot follow the change in the gap between the adherends in the low-temperature to high-temperature thermal cycle in the actual usage environment, and peeling is likely to occur at the interface between the adherend and the thermally conductive member. As a result, this leads to a decrease in heat dissipation characteristics and a decrease in strength as a structural member.
  • the storage modulus of the cured product needs to be adjusted to a certain degree low. And, in order to follow the temperature change in the low-temperature to high-temperature thermal cycle, quick stress relaxation is required. Therefore, in addition to the above-mentioned adjustment of the storage modulus, it is necessary for tan ⁇ to be somewhat large. For this reason, it is considered necessary for the storage modulus and tan ⁇ to satisfy a certain relationship expressed by formula (1).
  • the storage modulus G' and loss tangent tan ⁇ of the thermally conductive adhesive of the present invention satisfy the following requirements. That is, when tan ⁇ is less than 0.5, the storage modulus G' is preferably less than 3 ⁇ 10 7 Pa, when tan ⁇ is 0.5 or more and less than 0.6, the storage modulus G' is preferably less than 2.83 ⁇ 10 8 Pa, and when tan ⁇ is 0.6 or more, the storage modulus G' is preferably less than 1 ⁇ 10 9 Pa.
  • the storage modulus G' and tan ⁇ can be adjusted, for example, by the molecular structure, such as the molecular weight, of the curable binder contained in the adhesive, and the contents of additives, such as a thermally conductive filler and a dispersant.
  • the adhesive of the present invention has a shear elongation of 0.25 mm or more when the adhesive is cured at 60° C. for 24 hours.
  • the shear elongation is the shear elongation of the cured product having a thickness of 2 mm, measured using a cationic electrodeposition coated substrate and a polyethylene terephthalate (PET) substrate. If the shear elongation is less than 0.25 mm, the adhesive will not be able to follow the change in the gap between adherends that occurs when the adhesive is exposed to a thermal cycle of low to high temperatures, and the thermally conductive member formed by curing the adhesive will be prone to peeling off from the adherend.
  • the shear elongation is preferably 0.29 mm or more, preferably 0.30 mm or more, preferably 0.31 mm or more, more preferably 0.5 mm or more, more preferably 0.94 mm or more, even more preferably 1.0 mm or more, even more preferably 2.0 mm or more, and even more preferably 3.0 mm or more.
  • the shear elongation is preferably 10.0 mm or less, more preferably 5.0 mm or less, more preferably 4.0 mm or less, and more preferably 3.71 mm or less.
  • the shear elongation is preferably 0.25 mm or more and 10.0 mm or less, preferably 0.29 mm or more and 5.0 mm or less, preferably 0.30 mm or more and 4.0 mm or less, preferably 0.31 mm or more and 3.71 mm or less, and more preferably 0.94 mm or more and 3.71 mm or less.
  • the shear elongation is measured by a tensile shear test, specifically, the shear elongation is measured on a cured product (test piece) that is prepared by applying the adhesive between two substrates and curing the adhesive for 24 hours at 60° C. That is, the shear elongation is the elongation of the cured product (test piece) measured until the cured product (test piece), which is the adhesive joint, breaks due to a load (shear stress) that tries to displace the substrates in opposite directions, and means the amount of deformation (length: mm) in the longitudinal direction of the cured product (test piece) from the start of measurement until breakage.
  • a load shear stress
  • the shear elongation can be adjusted, for example, by the molecular structure, such as the molecular weight, of the curable binder contained in the adhesive, or the content of additives, such as a thermally conductive filler and a dispersant.
  • the failure mode of the cured product confirmed in the tensile shear test is preferably cohesive failure. By having the failure mode be cohesive failure, the adhesive can adequately fix adherends such as heating elements and heat sinks, and it becomes easier to suppress a decrease in strength as a structural member.
  • the adhesive of the present invention has an adhesive strength of 0.3 MPa or more when the adhesive is cured at 60° C. for 24 hours. If the adhesive strength is less than 0.3 MPa, it becomes difficult to fix various components forming the battery structure, such as a heating element and a heat sink, with an appropriate adhesive strength due to the cured product formed by the adhesive, and peeling of the cured product may occur, resulting in a decrease in heat dissipation.
  • the adhesive strength is preferably 0.4 MPa or more, more preferably 0.43 MPa or more, more preferably 0.6 MPa or more, more preferably 0.68 MPa or more, even more preferably 1 MPa or more, even more preferably 2 MPa or more, and even more preferably 2.41 MPa or more.
  • the adhesive strength is preferably 5 MPa or less, more preferably 4 MPa or less, more preferably 3.49 MPa or less, and more preferably 3.18 MPa or less.
  • the adhesive strength is, for example, preferably 0.3 MPa or more and 5 MPa or less, more preferably 0.4 MPa or more and 4 MPa or less, more preferably 0.43 MPa or more and 3.49 MPa or less, and more preferably 0.6 MPa or more and 3.18 MPa or less.
  • the adhesive strength of the cured product of the adhesive means the tensile shear strength, which is the breaking strength of the cured product measured by a tensile shear test similar to the measurement of the shear elongation described above.
  • ⁇ Gel point> In the adhesive of the present invention, when the gel point at which the storage modulus and the loss modulus become equal is confirmed at 60 minutes or more from the start of the measurement when measured by a rheometer at a constant temperature of 50 ° C., it is preferable.
  • a curable thermally conductive composition whose gel point is confirmed at 60 minutes or more from the start of the measurement has excellent washability when the adhesive is applied to an adherend and then removed from the adherend as necessary.
  • the gel point is an index of the curability of the adhesive, and it is considered that if the time until the gel point is confirmed is long, the curing speed is slow, which increases the washability.
  • the time from the start of measurement until the gel point is confirmed is preferably 100 minutes or more, more preferably 120 minutes or more, more preferably 130 minutes or more, and more preferably 140 minutes or more, from the viewpoint of improving cleanability, and is preferably 300 minutes or less, more preferably 200 minutes or less, and more preferably 150 minutes or less, from the viewpoint of ensuring a certain level of adhesion to an adherend.
  • the gel point of the adhesive can be adjusted by the composition of the curable binder contained in the adhesive (for example, the equivalent ratio of the resin and the curing agent) and the type of catalyst.
  • the gel point is the point at which the storage modulus and loss modulus become equal when measured with a rheometer at a constant temperature of 50°C.
  • the method for measuring the time until the gel point appears is as described in the Examples.
  • the adhesive of the present invention contains a curable binder.
  • the curable binder forms a matrix resin when cured.
  • the thermally conductive member obtained by curing the adhesive has a structure in which a thermally conductive filler is dispersed in the matrix resin.
  • the hardenable binder may be heat-curable, photo-curable, or moisture-curable, but is preferably heat-curable or moisture-curable.
  • the binder may be either a one-component curing type or a two-component curing type, but is preferably a two-component curing type.
  • the two-component curing type is used by mixing the first agent and the second agent, and curing is preferably initiated by mixing the first agent and the second agent.
  • the first agent may contain a base agent
  • the second agent may contain a curing agent.
  • the curable binder is not particularly limited as long as it can be cured to form a matrix resin, but is preferably any one of silicone-based, epoxy-based, urethane-based, acrylic-based, and organic polymers having a hydrolyzable silyl group, and among these, epoxy-based, urethane-based, silicone-based, and organic polymers having a hydrolyzable silyl group are more preferred, epoxy-based, and organic polymers having a hydrolyzable silyl group are even more preferred, and organic polymers having a hydrolyzable silyl group are even more preferred.
  • the binder is preferably a binder containing an epoxy resin and a curing agent, a binder containing an organic polymer having a hydrolyzable silyl group, or a binder containing a polyol and a polyisocyanate.
  • Epoxy binder is preferably composed of an epoxy resin as a main agent and a curing agent. Therefore, in the case of a two-part curing type, the first agent preferably contains the epoxy resin and the second agent preferably contains the curing agent. The following describes in detail the case where an epoxy-based binder is used.
  • the epoxy resin may be a compound having one or more epoxy groups.
  • the epoxy resin may be a polyfunctional epoxy resin having two or more epoxy groups, or a monofunctional epoxy resin having one epoxy group.
  • the adhesive can easily adjust the adhesive strength of the cured product to an appropriate range.
  • the adhesive preferably contains at least a multifunctional epoxy resin, which allows the adhesive to appropriately form crosslinks and easily increase adhesive strength. It is more preferable that the adhesive further contains a monofunctional epoxy resin in addition to the polyfunctional epoxy resin. By further containing the monofunctional epoxy resin, the adhesive can prevent the crosslink density after curing from becoming too high, and can easily increase the elongation.
  • the mass ratio of the monofunctional epoxy resin to the polyfunctional epoxy resin is preferably 10/90 or more and 90/10 or less, more preferably 10/90 or more and 70/30 or less, even more preferably 15/85 or more and 50/50 or less, and still more preferably 15/85 or more and 40/60 or less.
  • Polyfunctional epoxy resins include bifunctional and trifunctional ones, and preferably bifunctional epoxy resins are used.
  • Specific examples of polyfunctional epoxy resins include phenol novolac type epoxy resins, resorcinol type epoxy resins, epoxy resins having a bisphenol skeleton, epoxy resins having a naphthalene skeleton, epoxy resins having a fluorene skeleton, epoxy resins having a biphenyl skeleton, epoxy resins having a bi(glycidyloxyphenyl)methane skeleton, epoxy resins having a xanthene skeleton, epoxy resins having an anthracene skeleton, epoxy resins having a pyrene skeleton, and other epoxy resins having an aromatic skeleton.
  • Epoxy resins also include aliphatic epoxy resins.
  • Examples of the epoxy resin having a bisphenol skeleton include epoxy resins having a bisphenol skeleton of bisphenol A type, bisphenol F type, or bisphenol S type.
  • the resorcinol type epoxy resin may, for example, be resorcinol diglycidyl ether.
  • Examples of the epoxy resin having a naphthalene skeleton include 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidylnaphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene, and 1,2,5,6-tetraglycidylnaphthalene.
  • Examples of the epoxy resin having a fluorene skeleton include 9,9-bis(4-glycidyloxyphenyl)fluorene, 9,9-bis(4-glycidyloxy-3-methylphenyl)fluorene, 9,9-bis(4-glycidyloxy-3-chlorophenyl)fluorene, 9,9-bis(4-glycidyloxy-3-bromophenyl)fluorene, 9,9-bis(4-glycidyloxy-3-fluorophenyl)fluorene, 9,9-bis(4-glycidyloxy-3-methoxyphenyl)fluorene, 9,9-bis(4-glycidyloxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-glycidyloxy-3,5-dichlorophenyl)fluorene, and 9,9-bis(4-glycidyloxy-3,5-dibromophen
  • Examples of epoxy resins having a biphenyl skeleton include 4,4'-diglycidylbiphenyl and 4,4'-diglycidyl-3,3',5,5'-tetramethylbiphenyl.
  • Examples of epoxy resins having a bi(glycidyloxyphenyl)methane skeleton include 1,1'-bi(2,7-glycidyloxynaphthyl)methane, 1,8'-bi(2,7-glycidyloxynaphthyl)methane, 1,1'-bi(3,7-glycidyloxynaphthyl)methane, 1,8'-bi(3,7-glycidyloxynaphthyl)methane, 1,1'-bi(3,5-glycidyloxynaphthyl)methane, 1,8'-bi(3,5-glycidyloxynaphthyl)methan
  • Examples of epoxy resins having a xanthene skeleton include 1,3,4,5,6,8-hexamethyl-2,7-bis-glycidylmethoxy-9-phenyl-9H-xanthene, etc.
  • Examples of epoxy resins having an anthracene skeleton include those having one or more anthracene skeletons and two or more epoxy groups or glycidyl groups in one molecule.
  • the epoxy resin having a pyrene skeleton includes those having one or more pyrene skeletons and two or more epoxy groups or glycidyl groups in one molecule.
  • Aliphatic epoxy resins include polyalkylene glycol diglycidyl ethers such as butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl ether.
  • the aliphatic epoxy resin may be an epoxy resin having an alicyclic skeleton, and examples thereof include epoxy resins having a dicyclopentadiene skeleton and epoxy resins having an adamantane skeleton.
  • An example of an epoxy resin having a dicyclopentadiene skeleton is dicyclopentadiene dioxide.
  • An example of an epoxy resin having an adamantane skeleton is 1,3-bis(4-glycidyloxyphenyl)adamantane and 2,2-bis(4-glycidyloxyphenyl)adamantane. Furthermore, hydrogenated or modified products of the above-listed epoxy resins can also be used as the epoxy resin.
  • polyfunctional epoxy resins from the viewpoint of improving adhesive strength and mechanical strength, preferred are epoxy resins having an aromatic ring, more preferred are epoxy resins having a phenyl group, and even more preferred are bisphenol-type epoxy resins, which are epoxy resins having a bisphenol skeleton.
  • the polyfunctional epoxy resins may be used alone or in combination of two or more kinds.
  • monofunctional epoxy resins include phenyl glycidyl ethers such as alkylphenyl glycidyl ethers, such as phenyl glycidyl ether, 4-t-butylphenyl glycidyl ether, cresyl glycidyl ether, and nonylphenyl glycidyl ether, and monofunctional epoxy resins having an aromatic ring, such as 1-glycidylnaphthalene and 2-glycidylnaphthalene.
  • phenyl glycidyl ethers such as alkylphenyl glycidyl ethers, such as phenyl glycidyl ether, 4-t-butylphenyl glycidyl ether, cresyl glycidyl ether, and nonylphenyl glycidyl ether
  • monofunctional epoxy resins having an aromatic ring such as 1-glycidylnaphthal
  • aliphatic monofunctional epoxy resins are also preferred, and specifically, glycidyl ethers of aliphatic alcohols and the like can be mentioned.
  • the aliphatic alcohol may be one having a branched structure or one having a straight chain, but from the viewpoint of improving elongation, it is preferable that it is a straight chain.
  • the aliphatic alcohol may have, for example, about 4 to 24 carbon atoms, but from the viewpoint of improving elongation, it is preferable that it has 10 to 20 carbon atoms.
  • the aliphatic alcohol is preferably a saturated aliphatic alcohol from the viewpoint of improving elongation.
  • Specific examples of the glycidyl ethers of aliphatic alcohols include butyl glycidyl ether, decyl glycidyl ether, lauryl glycidyl ether, myristyl glycidyl ether, cetyl glycidyl ether, and stearyl glycidyl ether.
  • the monofunctional epoxy resin may be other than the above, and examples thereof include monofunctional epoxy resins having a glycidyl group but not having an ether group, such as 1,2-epoxybutane and propylene oxide.
  • the monofunctional epoxy resin from the viewpoint of improving elongation, it is preferable to use an aliphatic monofunctional epoxy resin, and among them, it is preferable to use a glycidyl ether of an aliphatic alcohol.
  • the monofunctional epoxy resin may be used alone or in combination of two or more kinds.
  • the epoxy resin preferably contains an epoxy resin having an aromatic ring, particularly a phenyl group.
  • the epoxy resin having an aromatic ring such as a phenyl group may be a monofunctional epoxy resin or a polyfunctional epoxy resin.
  • the aromatic ring, particularly the phenyl group forms a stacking structure after curing, making it easier for the epoxy resin to form a pseudo-crosslinked structure in the cured product. This makes it easier to increase the mechanical strength and the adhesive strength.
  • the epoxy resin preferably contains a polyfunctional epoxy resin, and the polyfunctional epoxy resin preferably has an aromatic ring, particularly a phenyl group.
  • the molecular weight of the epoxy resin is preferably 200 or more, more preferably 250 or more, and even more preferably 280 or more.
  • the molecular weight of the epoxy resin is preferably 200 or more, more preferably 250 or more, and even more preferably 280 or more.
  • the molecular weight of the epoxy resin to be used is, for example, 2000 or less, and preferably 1000 or less.
  • the epoxy resin is preferably liquid at room temperature (25° C.).
  • the molecular weight of the epoxy resin described above or the molecular weight of the curing agent described below can be measured, for example, by a mass spectrometer (GC-MS or LC-MS).
  • the epoxy equivalent of the epoxy resin is preferably 1000 g/eq or less, more preferably 500 g/eq or less, even more preferably 375 g/eq or less, and is preferably 100 g/eq or more, more preferably 125 g/eq or more, even more preferably 140 g/eq or less.
  • the curing agent is not particularly limited as long as it reacts with the epoxy resin, and examples thereof include amine curing agents, phenolic curing agents, acid anhydride curing agents, and thiol curing agents. Among these, it is preferable to use an amine curing agent from the viewpoint of curing properties with the epoxy resin.
  • the amine curing agent is a component that has an amino group and reacts with the epoxy resin to cure the adhesive.
  • the amine curing agent may be a polyamine such as a diamine or a triamine, or may be a monoamine, but is preferably a polyamine such as a diamine or a triamine.
  • the amine curing agent may be an aliphatic amine or an aromatic ring-containing amine.
  • the amine curing agent may be any amine having two or more active hydrogens in the amino group, but it is preferable to use amines having three or more active hydrogens in the amino group in one molecule.
  • the amine curing agent has three or more active hydrogens in the amino group, which makes it easier to crosslink and improve the adhesive strength of the adhesive.
  • the number of active hydrogens in the amino group is preferably four or more, more preferably five or more.
  • the upper limit of the number of active hydrogens in the amino group is not particularly limited, but is, for example, 12, preferably 10, more preferably 8.
  • aliphatic amines include, but are not limited to, polyoxyethylene diamine, poly(oxyethylene/oxypropylene) diamine, polyoxypropylene diamine, poly(oxybutylene/oxypropylene) diamine, polyethylene glycol bis(propylamine), trimethylolpropane poly(oxypropylene) triamine, glyceryl poly(oxypropylene) triamine and other polyoxyalkylene polyamines, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, branched or straight-chain alkanediamines such as 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 1,20-eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-octanediamine, 2-methyl
  • the aromatic ring-containing amine may be, but is not limited to, an aromatic amine in which an amino group is directly bonded to an aromatic ring, such as m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, mesitylene-2,6-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltolylene-2,6-diamine, biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, or 2,6-naphthylenediamine, or an amine in which an amino group is not directly bonded to an aromatic ring, such as m-xylylenediamine, p-xylylenediamine, or a reaction product of m-xylylenediamine and s
  • the amine curing agent may be a polyamidoamine, an esteramine, or the like.
  • the amine curing agent is preferably an aliphatic amine from the viewpoint of increasing the curing speed, more preferably a polyoxyalkylene polyamine or a branched or linear alkane diamine, and even more preferably a polyoxyalkylene polyamine from the viewpoint of improving the elongation.
  • the amine curing agent may be used alone or in combination of two or more kinds.
  • the amine curing agent is preferably liquid at room temperature (25° C.).
  • the active hydrogen equivalent of the amine curing agent is not particularly limited, but is, for example, 15 g/eq or more, preferably 25 g/eq or more, more preferably 40 g/eq or more, and is, for example, 1000 g/eq or less, preferably 600 g/eq or less, more preferably 300 g/eq or less.
  • the equivalent ratio (NH/Ep ratio) of active hydrogen of the amino group of the amine curing agent to the epoxy group of the epoxy resin is preferably greater than 1 and not greater than 2.7.
  • the equivalent ratio (NH/Ep ratio) is within this range, the crosslink density can be prevented from becoming higher than necessary, the elongation of the cured product can be easily improved, the storage modulus and tan ⁇ can be easily adjusted to the desired range, and the above formula (1) can be easily satisfied.
  • the equivalent ratio (NH/Ep ratio) is more preferably 1.05 or more, even more preferably 1.1 or more, and even more preferably 1.2 or more.
  • the equivalent ratio (NH/Ep) is preferably 2.7 or less, more preferably 2.6 or less, and even more preferably 2.5 or less. Therefore, the equivalent ratio (NH/Ep) is more preferably 1.05 to 2.7, even more preferably 1.1 to 2.7, even more preferably 1.1 to 2.6, and even more preferably 1.2 to 2.5.
  • the equivalent ratio (NH/Ep) is preferably greater than 1, more preferably 1.20 or greater, and even more preferably 1.50 or greater.
  • the equivalent ratio (NH/Ep) is preferably 2.70 or less, more preferably 2.60 or less, and even more preferably 2.50 or less. Therefore, in condition 1, the equivalent ratio (NH/Ep) is preferably greater than 1 and less than 2.70, more preferably 1.20 to 2.60, and even more preferably 1.50 to 2.50.
  • the content of tri- or higher functional epoxy resins being less than 10 mass % means that, of all the epoxy resins contained in the adhesive, less than 10 mass % of the epoxy resins are tri- or higher functional (i.e., have three or more epoxy groups in the molecule), and also includes the case where the content is 0 mass %, i.e., no tri- or higher functional epoxy groups are contained.
  • the content of the amine curing agent having two primary amino groups in one molecule and one or more reactive amino groups being 30% by mass or more means that, of all the amine curing agents contained in the adhesive, 30% by mass or more of the amine curing agents have two primary amino groups in one molecule and one or more reactive amino groups.
  • the reactive amino group is an amino group having an active hydrogen group, and may be either a primary amino group or a secondary amino group.
  • the equivalent ratio (NH/Ep) is preferably greater than 1, more preferably 1.05 or greater, and even more preferably 1.10 or greater.
  • the equivalent ratio (NH/Ep) is preferably 2.00 or less, more preferably 1.80 or less, and even more preferably 1.60 or less. Therefore, in the case of condition 2, the equivalent ratio (NH/Ep) is, for example, preferably greater than 1 and less than 2.00, more preferably 1.05 to 1.80, and even more preferably 1.10 to 1.60.
  • the equivalent ratio (NH/Ep) is preferably greater than 1, more preferably 1.05 or greater, and even more preferably 1.10 or greater.
  • the equivalent ratio (NH/Ep) is preferably 2.70 or less, more preferably 2.60 or less, and even more preferably 2.50 or less. Therefore, in condition 3, the equivalent ratio (NH/Ep) is preferably greater than 1 and less than 2.70, more preferably 1.05 to 2.60, and even more preferably 1.10 to 2.50.
  • the equivalent ratio (NH/Ep) is preferably greater than 1, more preferably 1.05 or greater, and even more preferably 1.10 or greater.
  • the equivalent ratio (NH/Ep) is preferably 2.00 or less, more preferably 1.80 or less, and even more preferably 1.60 or less. Therefore, in condition 4, the equivalent ratio (NH/Ep) is preferably greater than 1 and less than 2.00, more preferably 1.05 to 1.80, and even more preferably 1.10 to 1.60.
  • the equivalent ratio (NH/Ep) is synonymous with the ratio of the number of active hydrogens in amino groups to the number of epoxy groups contained in the adhesive, and can be determined by calculating the equivalent weights of epoxy groups and active hydrogens in amino groups as follows.
  • the epoxy group equivalent can be obtained by dividing the content (g) of the epoxy resin contained in the adhesive by the epoxy equivalent (g/eq). However, when two or more epoxy resins are contained, the epoxy group equivalent can be obtained by summing the values obtained by dividing the content (g) of each epoxy resin by the epoxy equivalent (g/eq).
  • the equivalent of active hydrogen of the amino group can be obtained by dividing the content (g) of the amine in the adhesive by the active hydrogen equivalent (g/eq) of the amine. However, when two or more amines are contained, the equivalent can be obtained by summing the values obtained by dividing the content (g) of each amine by its active hydrogen equivalent (g/eq).
  • the epoxy equivalent (g/eq) can be obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups per molecule.
  • the active hydrogen equivalent (g/eq) can be obtained by dividing the molecular weight of the amine by the number of active hydrogens per molecule.
  • the molecular weight, the number of epoxy groups, and the number of active hydrogens can be measured by a mass spectrometer (GC-MS or LC-MS).
  • GC-MS mass spectrometer
  • the number of epoxy groups and the number of active hydrogens per molecule can be identified by NMR (1H NMR, etc.).
  • the sample is a mixture, it is preferable to measure NMR after isolating each component by GPC (gel permeation chromatography) or HPLC (high performance liquid chromatography).
  • GPC gel permeation chromatography
  • HPLC high performance liquid chromatography
  • the number of active hydrogens in the amine is 1 for NHR2 (secondary amino group) and 2 for NH2R (primary amino group) (wherein in NHR2 and NH2R , R is a functional group other than active hydrogen, i.e., a part of the amine other than the NH or NH2 ).
  • the molecular weight of the curing agent is not particularly limited, but is preferably at least 300, and more preferably at least 400.
  • the molecular weight of the curing agent is, for example, 3,000 or less, and preferably 1,500 or less.
  • the curing agent is preferably liquid at room temperature (25° C.).
  • the silicone-based binder may be either a condensation curing type silicone resin or an addition reaction curing type silicone resin.
  • the addition reaction curing type silicone resin is preferably made of a silicone resin constituting a base material and a curing agent for curing the base material.
  • the addition reaction curing type silicone resin it is preferable to use an organopolysiloxane having an alkenyl group as the base material and an organohydrogenpolysiloxane as the curing agent.
  • the adhesive of the present invention preferably contains an organic polymer having a hydrolyzable silyl group as a binder.
  • an organic polymer having a hydrolyzable silyl group By containing an organic polymer having a hydrolyzable silyl group, the adhesive can easily adjust the adhesive strength of the cured product to an appropriate range.
  • the hydrolyzable silyl group in the organic polymer is hydrolyzed by moisture such as humidity to form a silanol group, and then the silanol groups undergo condensation polymerization with each other or with the hydrolyzable silyl group to form a siloxane bond. This causes the organic polymer to form a crosslinked structure and harden to obtain a rubber-like elastic body.
  • the silanol group refers to a hydroxyl group (Si-OH) directly bonded to a silicon atom.
  • the hydrolyzable silyl group is a group in which 1 to 3 hydrolyzable groups are bonded to a silicon atom.
  • the hydrolyzable group of the hydrolyzable silyl group is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group.
  • alkoxysilyl group is preferred because hydrolysis reaction is mild.
  • trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group
  • dialkoxysilyl groups such as dimethoxymethylsilyl group, and diethoxymethylsilyl group
  • monoalkoxysilyl groups such as methoxydimethylsilyl group, and ethoxydimethylsilyl group.
  • dialkoxysilyl group is more preferred, and dimethoxymethylsilyl group is particularly preferred.
  • the main chain of the organic polymer having a hydrolyzable silyl group may be linear or branched, but is preferably linear. That is, the organic polymer having a hydrolyzable silyl group of the present invention preferably has a hydrolyzable silyl group at the end of a linear main chain.
  • the above formula (1) is more likely to be satisfied in dynamic viscoelasticity measurement, and the cured product is more likely to elongate, improving conformability.
  • the terminal silylation rate of the organic polymer having a hydrolyzable silyl group is preferably 70% or more, more preferably 80% or more, and even more preferably 85% or more. When the terminal silylation rate is a certain level or more, it becomes easier to appropriately adjust the curing property and elongation property of the adhesive.
  • the terminal silylation rate means the ratio of the silylated terminals to all the terminals of the organic polymer having a hydrolyzable silyl group. There is no particular upper limit to the terminal silylation rate, but it is, for example, 100% or less, and in practical use, it can be 99% or less.
  • the terminal silylation rate of an organic polymer having a hydrolyzable silyl group can be determined by 1 H-NMR.
  • the average number of hydrolyzable silyl groups in one molecule of the organic polymer having a hydrolyzable silyl group is preferably 1 to 3.
  • the adhesive has good curing properties and extensibility, and is more likely to satisfy formula (1) in dynamic viscoelasticity measurement.
  • the average number of hydrolyzable silyl groups in one molecule of an organic polymer having a hydrolyzable silyl group can be calculated based on the concentration of hydrolyzable silyl groups in the organic polymer determined by 1H -NMR and the number average molecular weight of the polymer determined by GPC.
  • the method of introducing hydrolyzable silyl groups into an organic polymer is not particularly limited, and examples of such methods include (1) a method of hydrosilylation in which an organic polymer modified with an unsaturated group in the molecule is reacted with a hydrosilane having a hydrolyzable silyl group, (2) a method of reacting an organic polymer modified with an unsaturated group in the molecule with a compound having a mercapto group and a hydrolyzable silyl group, and (3) a method of reacting an organic polymer having a functional group in the molecule with a compound having a functional group that is reactive to the functional group and a hydrolyzable silyl group.
  • Specific examples of such methods include the reaction of an isocyanate group with a hydroxyl group, the reaction of an isocyanate group with an amino group, and the reaction of an isocyanate group with a mercapto group.
  • the organic polymer containing a hydrolyzable silyl group is not particularly limited, and examples thereof include polyalkylene oxides such as polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymers, and polypropylene oxide-polybutylene oxide copolymers; saturated hydrocarbon polymers; polychloroprene, polyisoprene, copolymers of isoprene or butadiene with acrylonitrile and/or styrene; polybutadiene, copolymers of isoprene or butadiene with acrylonitrile and styrene; (meth)acrylate polymers obtained by radical polymerization of monomers such as ethyl (meth)acrylate and butyl (meth)acrylate; Examples of such polymers include vinyl polymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, and sty
  • polyalkylene oxides are preferred as organic polymers from the viewpoint of achieving desired ranges of adhesive strength and elongation after curing.
  • polyalkylene oxides having hydrolyzable silyl groups are preferred as organic polymers having hydrolyzable silyl groups.
  • polypropylene oxide is particularly preferred.
  • the number average molecular weight (Mn) of the organic polymer containing a hydrolyzable silyl group is preferably 6,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more.
  • the number average molecular weight (Mn) of the organic polymer containing a hydrolyzable silyl group is, for example, not more than 70000, and preferably not more than 50000.
  • the number average molecular weight (Mn) is the average value of the number average molecular weights of the organic polymers used.
  • the number average molecular weight of an organic polymer containing a hydrolyzable silyl group means a value measured by gel permeation chromatography (GPC) in terms of polystyrene.
  • GPC gel permeation chromatography
  • a Shodex KF604 manufactured by Tosoh can be used as the GPC column using the ACQUITY APC system manufactured by Waters, and the measurement can be performed at a column temperature of 40°C and a flow rate of 0.3 ml/min using tetrahydrofuran as the solvent.
  • the polymer containing hydrolyzable silyl groups can be a commercially available product.
  • examples of polyalkylene oxide polymers having a polypropylene oxide main chain skeleton and dimethoxysilyl groups at the ends of the main chain skeleton include Asahi Glass Co., Ltd.'s product names "Exestar A2410” and “Exestar S4530” and Kaneka Corporation's product names "S203", "SAT350", and "SAX010".
  • At least one of the first and second agents may contain an organic polymer having a hydrolyzable silyl group, but it is preferable that both the first and second agents contain an organic polymer having a hydrolyzable silyl group.
  • the urethane-based binder may be, for example, one that is made of a polyol compound as a main agent and a polyisocyanate compound as a curing agent. Therefore, in the case of a two-component curing type, it is preferable that the first agent contains a polyol compound and the second agent contains a polyisocyanate compound.
  • the urethane-based binder will be described in detail below.
  • the polyol compound used in the present invention is not particularly limited, but examples thereof include polyester polyols, polyether polyols, polycarbonate polyols, and polymer polyols.
  • the polyester polyol may be a polyester polyol having an aromatic ring or an aliphatic polyester polyol.
  • examples of the polyester polyol include polyester polyols obtained by reacting a polyvalent carboxylic acid with a polyol, and caprolactone polyols such as poly- ⁇ -caprolactone polyol obtained by ring-opening polymerization of ⁇ -caprolactone.
  • divalent carboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, and dodecamethylene dicarboxylic acid.
  • polyols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and cyclohexanediol.
  • polyether polyols examples include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, polymethyltetramethylene glycol, and random copolymers or block copolymers of these alkylene glycols or derivatives thereof.
  • the polyether polyol may be a polyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to an initiator having two or more active hydrogen atoms.
  • an alkylene oxide e.g., ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.
  • the initiator include aliphatic polyhydric alcohols, more specifically, glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, and cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, tetrafunctional alcohols such as pentaerythritol, and highly functional alcohols such as sucrose and sorbitol.
  • glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, and cyclohe
  • alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine
  • alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine
  • aliphatic amines such as alkanolamines such as monoethanolamine and diethanolamine
  • aromatic amines such as aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, and Mannich condensation products.
  • it may be a bisphenol-type polyalkylene polyol obtained by addition reaction of an alkylene oxide to the active hydrogen moiety of a bisphenol-type molecular skeleton.
  • polycarbonate polyols examples include poly(3-methyl-1,5-pentylene carbonate) diol, polypentamethylene carbonate diol, and polytetramethylene carbonate diol.
  • polymer polyols examples include polymers obtained by graft polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, or methacrylate with an aromatic polyol, an alicyclic polyol, an aliphatic polyol, or a polyester polyol, and a hydrogenated product of polybutadiene polyol.
  • aromatic polyols used in the production of polymer polyols include bisphenol A, bisphenol F, phenol novolac, and cresol novolac.
  • Examples of alicyclic polyols used in the production of polymer polyols include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.
  • Examples of aliphatic polyols used in the production of polymer polyols include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.
  • polyether polyols are preferred, and polyalkylene glycols are even more preferred.
  • polyether polyols it becomes easier to satisfy formula (1) in dynamic viscoelasticity measurements of the cured adhesive, and the extensibility is also good.
  • the average molecular weight of the polyol compound is not particularly limited, but is preferably 300 or more, more preferably 500 or more, and even more preferably 700 or more. By increasing the average molecular weight of the polyol compound, it becomes easier to satisfy formula (1) in the dynamic viscoelasticity measurement of the cured product of the adhesive, and the shear elongation value can be increased.
  • the average molecular weight of the polyol compound is not particularly limited, but is, for example, 20,000 or less, preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,500 or less.
  • the hydroxyl value may be measured in accordance with JIS K 1557-1.
  • polyisocyanate compound examples include aromatic polyisocyanate compounds and aliphatic polyisocyanate compounds.
  • aromatic polyisocyanate compounds include diphenylmethane diisocyanate, tolylene diisocyanate, and naphthalene-1,5-diisocyanate.
  • Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanatemethyl)cyclohexane, and dicyclohexylmethane diisocyanate.
  • the polyisocyanate compound may be the above-mentioned modified product, a liquid modified product of diphenylmethane diisocyanate, polymeric MDI, or the like, or may be a biuret, isocyanurate, or adduct of the above-mentioned polyisocyanate compound.
  • the acrylic binder may be any component that forms an acrylic polymer by curing, and examples thereof include various acrylic compounds such as alkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, (meth)acrylic acid, (meth)acrylamides, and urethane (meth)acrylate.
  • the acrylic binder may also contain a vinyl monomer that is copolymerizable with the acrylic compound.
  • the acrylic binder may be at least partially a polymer of an acrylic compound, or a copolymer of an acrylic compound and a vinyl monomer.
  • the adhesive of the present invention contains a thermally conductive filler.
  • the thermally conductive filler By containing the thermally conductive filler, the thermal conductivity of the adhesive is improved.
  • the thermally conductive filler may be contained in either the first agent or the second agent, but it is preferable to contain the thermally conductive filler in both the first agent and the second agent.
  • thermally conductive filler examples include metals, metal oxides, metal nitrides, metal hydroxides, carbon materials, oxides, nitrides, carbides, etc.
  • the shape of the thermally conductive filler includes spherical and amorphous powders.
  • examples of metals include aluminum, copper, nickel, etc.
  • examples of metal oxides include aluminum oxide, magnesium oxide, zinc oxide, etc., such as alumina
  • examples of metal nitrides include aluminum nitride.
  • metal hydroxides examples include aluminum hydroxide.
  • carbon materials include spherical graphite, etc.
  • oxides, nitrides, and carbides other than metals include quartz, boron nitride, and silicon carbide.
  • metal oxides, metal nitrides, metal hydroxides, carbon materials, oxides, nitrides, and carbides other than metals are preferred, and metal oxides and metal hydroxides are more preferred.
  • aluminum oxide is preferred from the viewpoint of improving the heat dissipation properties of the thermally conductive member, and aluminum hydroxide is preferred when it is desired to improve flame retardancy or to reduce the specific gravity of the inorganic filler to reduce the weight of the adhesive.
  • the ratio (volume ratio) of the filling rate of aluminum hydroxide to the filling rate of aluminum oxide is preferably 0.1 to 30, more preferably 0.2 to 15, and even more preferably 0.3 to 10.
  • the thermally conductive filler may be used alone or in combination of two or more of the above.
  • the average particle size of the thermally conductive filler is preferably 0.1 ⁇ m or more and 200 ⁇ m or less, more preferably 0.5 ⁇ m or more and 150 ⁇ m or less, and even more preferably 1 ⁇ m or more and 110 ⁇ m or less. It is preferable to use a small-particle-size thermally conductive filler having an average particle size of 0.1 ⁇ m or more and 5 ⁇ m or less in combination with a large-particle-size thermally conductive filler having an average particle size of more than 5 ⁇ m and 200 ⁇ m or less in combination as the thermally conductive filler. By using thermally conductive fillers with different average particle sizes, the filling rate can be increased.
  • the average particle size of the thermally conductive filler can be measured by observation using an electron microscope, etc. More specifically, for example, the particle sizes of 50 arbitrary thermally conductive fillers can be measured using an electron microscope or an optical microscope, and the average value (arithmetic mean value) can be used as the average particle size.
  • the content (filling rate) of the thermally conductive filler in the adhesive is preferably 50% by volume or more relative to the total volume of the adhesive. If the content is equal to or more than the lower limit, a certain level of thermal conductivity can be imparted to the adhesive. From the viewpoint of improving thermal conductivity, the content is more preferably 55% by volume or more. In addition, the content of the thermally conductive filler in the adhesive is preferably 85% by volume or less with respect to the volume of the entire adhesive. By making the content of the thermally conductive filler equal to or less than the above upper limit, the thermally conductive filler can be properly dispersed in the adhesive, and the viscosity of the adhesive can be prevented from becoming higher than necessary.
  • the content of the thermally conductive filler in the adhesive is more preferably 80% by volume or less, more preferably 70% by volume or less, and even more preferably 60% by volume or less.
  • the amount of the thermally conductive filler in the adhesive is not particularly limited, but is preferably 300 parts by mass or more and 3,000 parts by mass or less, more preferably 400 parts by mass or more and 2,000 parts by mass or less, even more preferably 450 parts by mass or more and 1,500 parts by mass or less, and even more preferably 500 parts by mass or more and 1,300 parts by mass or less, per 100 parts by mass of the binder and plasticizer combined.
  • the adhesive of the present invention may contain a plasticizer.
  • a plasticizer By containing a plasticizer, the adhesive tends to have a low storage modulus and a high shear elongation. In addition, the viscosity tends to be low, improving workability.
  • the adhesive of the present invention preferably contains a plasticizer when an organic polymer having a hydrolyzable silyl group is used as the binder or when a urethane-based binder is used. In the case of a two-component curing type, the plasticizer may be contained in either the first part or the second part, but it is preferable that the plasticizer be contained in both the first part and the second part.
  • the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, organic phosphorus-based plasticizers such as organic phosphate plasticizers and organic phosphite plasticizers, and epoxy-based plasticizers such as sulfonamides and epoxidized soybean oil.
  • the plasticizer is preferably an organic ester plasticizer.
  • the monobasic organic acid esters include glycol esters obtained by reacting glycol with a monobasic organic acid. Examples of the glycols include triethylene glycol, tetraethylene glycol, and tripropylene glycol.
  • Examples of the monobasic organic acids include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl acid, n-octylic acid, 2-ethylhexyl acid, n-nonylic acid, decylic acid, and benzoic acid.
  • polybasic organic acid ester examples include ester compounds of a polybasic organic acid and an alcohol having a linear or branched structure having 3 to 10 carbon atoms.
  • polybasic organic acid examples include adipic acid, sebacic acid, azelaic acid, and 1,2-cyclohexanedicarboxylic acid.
  • organic ester plasticizer examples include triethylene glycol di-2-ethylpropanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, 1,3-propylene glycol di-2-ethylbutyrate, 1,4-butylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, Examples of suitable plasticizers include di-2-ethylhexanoate, dipropylene glycol di-2-
  • the organic phosphorus plasticizer examples include tributoxyethyl phosphate, isodecylphenyl phosphate, and triisopropyl phosphate.
  • the plasticizer is preferably a diester plasticizer represented by the following formula (1) or (2).
  • R1 and R2 each represent an organic group having 2 to 10 carbon atoms
  • R3 represents an ethylene group, an isopropylene group or an n-propylene group
  • p represents an integer of 3 to 10.
  • R1 and R2 each preferably represent an organic group having 5 to 10 carbon atoms, and more preferably represent an organic group having 6 to 10 carbon atoms.
  • R4 and R5 each represent a hydrocarbon group having 3 to 10 carbon atoms
  • R6 represents a hydrocarbon group having 2 to 10 carbon atoms.
  • R4 and R5 each preferably have 4 to 9 carbon atoms, and more preferably have 6 to 9 carbon atoms.
  • the hydrocarbon groups of R4 and R5 are preferably alkyl groups.
  • the alkyl group may be linear or may have a branched structure.
  • R6 preferably has 4 to 9 carbon atoms, and more preferably has 5 to 8 carbon atoms.
  • the hydrocarbon group of R6 is preferably an aliphatic hydrocarbon group, and more preferably an unsaturated aliphatic hydrocarbon group.
  • R6 may be linear or may have a branched or cyclic structure, and preferably has a cyclic structure.
  • the plasticizer preferably contains triethylene glycol di-2-ethylhexanoate (3GO), diisononyl 1,2-cyclohexanedicarboxylate (DINCH), triethylene glycol di-2-ethylbutyrate (3GH) or triethylene glycol di-2-ethylpropanoate.
  • 3GO triethylene glycol di-2-ethylhexanoate
  • DICH diisononyl 1,2-cyclohexanedicarboxylate
  • GGH triethylene glycol di-2-ethylbutyrate
  • the plasticizer more preferably contains triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH) or diisononyl 1,2-cyclohexanedicarboxylate (DINCH), and even more preferably contains triethylene glycol di-2-ethylhexanoate or diisononyl 1,2-cyclohexanedicarboxylate (DINCH).
  • 3GO triethylene glycol di-2-ethylhexanoate
  • GGH triethylene glycol di-2-ethylbutyrate
  • DINCH diisononyl 1,2-cyclohexanedicarboxylate
  • the content of the plasticizer in the adhesive is preferably 30 parts by mass or more and 300 parts by mass or less, more preferably 50 parts by mass or more and 200 parts by mass or less, and even more preferably 80 parts by mass or more and 180 parts by mass or less, relative to 100 parts by mass of the binder. If the amount of the plasticizer is equal to or more than these lower limits, it becomes easier to adjust the storage modulus low, and the value of the shear elongation tends to increase. In addition, the viscosity of the composition decreases, and the workability improves.
  • the amount of the plasticizer is equal to or less than these upper limits, the amount of the binder can be made equal to or more than a certain amount, so that the reaction points with the thermally conductive filler can be secured equal to or more than a certain amount, and the adhesive strength tends to increase.
  • the content of the plasticizer in each of the first and second parts is preferably within the above range.
  • the binder, or the binder and plasticizer may be the main components, and the total amount of the binder and plasticizer per 100 parts by mass of the components of the adhesive other than the thermally conductive filler is, for example, 60 parts by mass or more and 100 parts by mass or less, preferably 70 parts by mass or more and 100 parts by mass or less, and more preferably 80 parts by mass or more and 100 parts by mass or less.
  • the total amount of the binder and the plasticizer in each of the first and second parts is preferably within the above range.
  • the adhesive of the present invention may contain a dispersant.
  • a dispersant By containing a dispersant, it becomes easier to disperse the thermally conductive filler in the binder, and it becomes easier to increase the filling rate of the thermally conductive filler.
  • the dispersant include polymer-based dispersants.
  • the polymer-based dispersants include polymer compounds having functional groups. Examples of the polymer compounds include acrylic, vinyl, polyester, polyurethane, polyether, epoxy, polystyrene, amino, and silicone compounds.
  • the functional groups include carboxyl groups, phosphoric acid groups, sulfonic acid groups, carboxylate groups, phosphoric acid ester groups, sulfonic acid ester groups, hydroxyl groups, amino groups, quaternary ammonium bases, and amide groups.
  • the dispersant may be other than the polymer dispersant, and for example, an alkoxysilane compound or the like may be used.
  • the dispersant may be contained in either the first or second agent, whichever contains the thermally conductive filler. Therefore, the dispersant may be contained in either the first or second agent, but is preferably contained in both the first and second agents.
  • the content of the dispersant in the adhesive is preferably 0.1 parts by mass to 25 parts by mass, more preferably 0.5 parts by mass to 20 parts by mass, and even more preferably 1 part by mass to 10 parts by mass, relative to 100 parts by mass of the binder.
  • the adhesive may contain a curing catalyst that promotes the reaction of the binder.
  • a curing catalyst that promotes the reaction of the binder.
  • the adhesive preferably contains a silanol condensation catalyst.
  • the silanol condensation catalyst By containing the silanol condensation catalyst, the adhesive is more likely to undergo condensation polymerization of the hydrolyzable silyl group, and the curing property is improved.
  • the silanol condensation catalyst may be contained in either the first or second agent, but it is preferable to contain it in the first agent and not in the second agent.
  • Silanol condensation catalysts include organotin compounds such as dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis(dibutyltin laurate) oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(monoester maleate), tin octoate, dibutyltin octoate, dioctyltin oxide, dioctyltin diversatate, dioctyltin distearate, dibutyltin bis(triethoxysilicate), bis(dibutyltin bistriethoxysilicate) oxide, dibutyltin oxybisethoxysilicate, and 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, and organotitanium compounds such as tetra
  • the content of the silanol condensation catalyst in the adhesive is preferably 1 part by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 6 parts by mass or less, per 100 parts by mass of the organic polymer containing a hydrolyzable silyl group. If the content of the silanol condensation catalyst is equal to or more than these lower limits, the curing speed can be increased, and if the content of the silanol condensation catalyst is equal to or less than these upper limits, a decrease in the storage stability of the composition can be suppressed.
  • the adhesive When an organic polymer having a hydrolyzable silyl group is used as a binder, the adhesive preferably contains water. By containing water, the adhesive can proceed with the reaction between organic polymers having a hydrolyzable silyl group, and can be cured quickly to the inside of the adhesive.
  • water may be contained in either the first agent or the second agent, but it is preferable to contain water in the second agent and not in the first agent. This makes it possible to prevent water from coming into contact with the silanol catalyst before the first agent and the second agent are mixed in the case of a two-component curing type.
  • the water content in the adhesive is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, and even more preferably 1 part by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the organic polymer having a hydrolyzable silyl group.
  • the adhesive may contain a dehydrating agent.
  • the dehydrating agent is preferably used in the case of a two-component curing type. By using the dehydrating agent, it is possible to prevent the curing from progressing due to water accidentally mixed in before the first and second parts are mixed.
  • the dehydrating agent may be contained in either the first or second agent, but it is preferable to contain it in the first agent and not in the second agent. This allows the first agent to contain the dehydrating agent and the second agent to contain water. In this case, it is more preferable that the first agent further contains a silanol catalyst.
  • dehydrating agents include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane, and ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate.
  • These dehydrating agents may be used alone or in combination of two or more. Of these, vinyltrimethoxysilane is preferred.
  • the content of the dehydrating agent in the adhesive is preferably 0.5 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less, per 100 parts by mass of the organic polymer having a hydrolyzable silyl group contained in the adhesive. If the content of the dehydrating agent is equal to or more than these lower limits, hardening during storage is more easily suppressed, and if the content of the dehydrating agent is equal to or less than these upper limits, a decrease in hardening caused by the dehydrating agent is less likely to occur.
  • the adhesive may contain an adhesion promoter, and preferably contains an adhesion promoter when the adhesive contains an organic polymer having a hydrolyzable silyl group.
  • an adhesion promoter By containing an adhesion promoter, the adhesive can further improve the adhesiveness of the cured product of the adhesive.
  • the adhesion promoter may be contained in either the first agent or the second agent, but it is preferable to contain the adhesion promoter in the first agent and not in the second agent. This makes the storage stability of the second agent good even if the second agent contains water.
  • an aminosilane coupling agent is preferable.
  • the aminosilane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N,N'-bis-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(triethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(methyldimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(trimethoxysilyl)propyl]hexamethylenediamine, and N,N'-bis-[3-(tri
  • N-(2-aminoethyl)-3-aminopropyltrimethoxysilane is preferable.
  • the content of the adhesion promoter in the adhesive is preferably 0.5 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the binder.
  • the adhesive strength of the cured product formed is likely to be improved, and when the content of the adhesion promoter is equal to or less than these upper limits, the cured product formed can be prevented from becoming brittle, and therefore a decrease in adhesive strength can be suppressed.
  • the adhesive of the present invention may contain additives other than those mentioned above, and such additives include reaction rate control agents that suppress the reaction between the base agent and the curing agent, thixotropy imparting agents, flame retardants, antioxidants, ultraviolet absorbers, pigments, anti-settling agents, colorants such as dyes, compatibilizers, etc.
  • compatibilizers include lower alcohols such as butyl carbitol, ethanol, and isopropanol.
  • the adhesive of the present invention may be in the form of a one-component type or a two-component type comprising a first part and a second part, but from the viewpoint of storage stability, the two-component type is preferred.
  • the adhesive may be cured by mixing and leaving at room temperature (25°C), but it may also be cured by heating after mixing.
  • the adhesive may be cured by heating, by light, or by moisture. If the adhesive is cured by heating, it is preferable to heat the adhesive to about 50 to 300°C, for example.
  • the mass ratio of the first agent to the second agent may be, for example, from 0.25 to 4, but is preferably 1 or a value close to 1, specifically preferably from 0.8 to 1.2, more preferably from 0.9 to 1.1, and even more preferably from 0.95 to 1.05.
  • the adhesive can be easily prepared.
  • both the first and second components are liquid at room temperature (25° C.) from the viewpoint of ease of handling.
  • the first agent when the binder is an epoxy or urethane type, the first agent may contain an epoxy resin or a polyol compound, and the second agent may contain a curing agent such as an amine curing agent or a polyisocyanate compound.
  • the first agent preferably contains an epoxy resin or a polyol compound, but does not contain a curing agent such as an amine curing agent or a polyisocyanate compound.
  • the first agent may contain a curing agent such as an amine curing agent or a polyisocyanate compound, as long as it does not react with the contained epoxy resin or polyol compound.
  • the second agent preferably contains a curing agent such as an amine curing agent or a polyisocyanate compound, but does not contain an epoxy resin or a polyol compound.
  • the second agent may contain an epoxy resin or a polyol compound, as long as it does not react with the contained curing agent such as an amine curing agent or a polyisocyanate compound.
  • the binder is an organic polymer having a hydrolyzable silyl group
  • the organic polymer having a hydrolyzable silyl group is preferably contained in both the first agent and the second agent as described above.
  • the thermally conductive filler is contained in both the first and second agents, but it is more preferable that the filling rates of the thermally conductive filler in the first and second agents are approximately the same.
  • the ratio of the filling rate of the thermally conductive filler in the second agent to the filling rate of the thermally conductive filler in the first agent is preferably 0.67 to 1.5, more preferably 0.83 to 1.2, and even more preferably 0.91 to 1.1.
  • plasticizers In two-part types, plasticizers, dispersants, curing catalysts, water, dehydrating agents, adhesion promoters, and other additives may be included in either or both of the first and second parts as necessary, as detailed above.
  • the first and second agents are filled in separate containers; specifically, the first agent is filled in the first container and the second agent is filled in the second container.
  • the first and second containers may be separate or integrated. By integrating the first and second containers, it becomes easier to supply them as a container set to the demand destination.
  • the first container filled with the first agent and the second container filled with the second agent may be collectively referred to as a container set.
  • Containers include, but are not limited to, syringes, cartridges, pails, drums, etc.
  • a two-liquid parallel type syringe As shown in FIG. 1, a two-liquid parallel type syringe 30 is an integrated unit in which a first syringe 31 constituting a first container and a second syringe 32 constituting a second container are arranged in parallel.
  • the first agent 35 and the second agent 36 filled in the syringes 31 and 32 are preferably discharged from the syringes as a dispenser and mixed.
  • the container set consists of a first cartridge constituting the first container and a second cartridge constituting the second container, and these cartridges may be integrated.
  • the cartridges are usually set in syringes (e.g., a first syringe and a second syringe), and the first agent delivered from the first cartridge and the second agent delivered from the second cartridge are preferably mixed by being discharged from the respective outlets of the first syringe and the second syringe using each syringe as a dispenser.
  • the first and second agents may be mixed in a mixer such as a static mixer.
  • a mixer such as a static mixer.
  • the static mixer 38 is connected to the outlet 31A of the first syringe 31 and the outlet 32A of the second syringe 32, and the first agent 35 and the second agent 36 discharged from the outlets 31A and 32A can be mixed inside the mixer 38.
  • the mixture (curable thermally conductive adhesive) obtained by mixing in the mixer 38 may be discharged from the outlet 39 of the mixer 38.
  • Each of the syringes 31, 32 may have a structure in which the openings of the barrels 33A, 34A, into which the first agent 35 and the second agent 36 are respectively filled, are closed by lids 33B, 34B.
  • the first agent 35 and the second agent 36 may be ejected from each of the ejection ports 31A, 32A by being pushed out by pistons (not shown) inserted from the openings after the lids 33B, 34B are removed.
  • the container set may include a first pail 41 that constitutes the first container and is filled with a first agent 45, and a second pail 42 that constitutes the second container and is filled with a second agent 46, as shown in FIG. 2.
  • Each pail 41, 42 includes, for example, a container body 43A, 44A that is filled with the first agent 45 and the second agent 46 and has an opening, and a lid 43B, 44B that closes the opening of each container body 43A, 44A.
  • the first agent and the second agent may be obtained by mixing the components constituting the first agent and the second agent, respectively.
  • the adhesive is a one-liquid type
  • the components constituting the adhesive may be obtained by mixing them.
  • the method of mixing the components is not particularly limited, but for example, the components constituting the binder (e.g., the base agent, the curing agent, etc.), the thermally conductive filler, and further additives such as a plasticizer and a dispersant that are mixed as necessary may be added, and then the mixture may be prepared by stirring or kneading.
  • the thermally conductive filler may be surface-treated with a dispersant before being mixed with the components constituting the binder.
  • the thermally conductive filler is surface-modified in advance by being surface-treated with a dispersant in advance.
  • the thermally conductive filler that has been surface-modified in advance may then be mixed with the components constituting the binder to prepare the adhesive, or the first or second agent of the adhesive.
  • the method of pre-treating the surface with a dispersant is not particularly limited, and may be a known method, for example, a wet treatment method, a dry treatment method, etc. may be used.
  • a thermally conductive filler is added and mixed in a treatment liquid in which a dispersant is dispersed or dissolved in a solvent, and then the dispersant is bonded or attached to the surface of the thermally conductive filler by drying, heat treatment, washing, etc.
  • the dry treatment method is a method of surface treatment without using a dispersion medium, and specifically, a dispersant is mixed with a thermally conductive filler, stirred with a mixer, etc., and then heat treated to bond or attach the dispersant to the surface of the thermally conductive filler.
  • the adhesive of the present invention may be used as a thermally conductive member.
  • the adhesive of the present invention becomes a thermally conductive member when cured.
  • the thermally conductive member of the present invention is a cured product of the adhesive, and includes a polymer matrix and a thermally conductive filler.
  • the polymer matrix is made of a cured product obtained by curing a binder, and the thermally conductive filler is dispersed in the polymer matrix and held by the polymer matrix.
  • the thermally conductive member may be used by being disposed between two members such as a heat generating body and a heat dissipating body.
  • Examples of the heat generating body include electronic components that generate heat, such as a battery.
  • Examples of the heat dissipating body include cooling members such as a housing, a heat sink, and a cooling plate.
  • the adhesive and thermally conductive member of the present invention can be used in various applications, for example, in various electronic device applications such as battery assemblies such as lithium ion battery (LiB) assemblies, power electronic devices, electronic packaging, LEDs, solar cells, and electric grids.
  • battery assemblies such as lithium ion battery (LiB) assemblies
  • the adhesive and thermally conductive member are preferably used in battery assemblies, and more preferably used in LiB assemblies. Therefore, in a preferred embodiment of the present invention, a battery assembly including the thermally conductive member described above is provided.
  • the battery assemblies such as LiB assemblies can be preferably used in automobiles such as electric vehicles.
  • the adhesive and thermally conductive member of the present invention are preferably used as a gap material in the battery assembly.
  • the adhesive and thermally conductive member of the present invention are preferably used in a battery module, and more preferably used as a gap material in the battery module.
  • the thermally conductive member of the present invention is applied to a battery module is described.
  • the battery module includes a gap material made of a thermally conductive material, a plurality of battery cells, and a module housing that stores the plurality of battery cells, and the gap material is disposed inside the module housing.
  • the gap material made of a thermally conductive material is filled between the battery cells and between the battery cells and the module housing, and the filled gap material is in close contact with the battery cells and the module housing.
  • the gap material between the battery cells has the function of maintaining the battery cells spaced apart from each other.
  • the gap material between the battery cells and the module housing is in close contact with both the battery cells and the module housing, and has the function of transferring heat generated in the battery cells to the module housing.
  • FIG. 3 shows a specific configuration of the battery module.
  • FIG. 4 shows a specific configuration of each battery cell.
  • a plurality of battery cells 11 are arranged inside the battery module 10.
  • Each battery cell 11 is laminated and enclosed in a flexible exterior film, and the overall shape is a flat body with a thickness smaller than the height and width.
  • the positive electrode 11a and the negative electrode 11b of such a battery cell 11 may be exposed to the outside, and the central part 11c of the flat surface may be formed thicker than the crimped end part 11d.
  • the surface of each battery cell 11 is covered with a resin material. By covering the surface of each battery cell 10 with a resin material, it becomes easier to ensure insulation.
  • the resin material is not particularly limited, but examples include polyester resin such as PET (polyethylene terephthalate), polyimide resin, olefin resin such as polypropylene resin, polycarbonate resin, etc., and among these, PET is more preferable.
  • the battery cells 11 are arranged so that their flat surfaces face each other.
  • the gap material 13 is not filled so as to entirely cover the multiple battery cells 11 stored inside the module housing 12.
  • the gap material 13 is filled so as to fill the gaps that exist in a portion (bottom portion) of the interior of the module housing 12.
  • the gap material 13 is filled between the battery cells 11 and between the battery cells 11 and the module housing 12, and is in close contact with the surfaces of the battery cells 11 in these portions and the inner surface of the module housing 12.
  • the gap material 13 filled between the battery cells 11 is adhered to the surfaces of both battery cells 11, and the gap material 13 itself has appropriate elasticity and flexibility, so that even if an external force is applied that displaces the gap between the battery cells 11, it can mitigate distortion and deformation caused by the external force. Therefore, the gap material 13 has the function of maintaining the separation state between the battery cells 11.
  • the gap material 13 filled in the gap between the battery cell 11 and the inner surface of the module housing 12 is also tightly bonded to the surface of the battery cell 11 and the inner surface of the module housing 12. As a result, heat generated inside the battery cell 11 is transferred via the gap material 13 bonded to the surface of the battery cell 11 to the inner surface of the module housing 12 which is in close contact with the other surface of the gap material 13.
  • the gap material 13 may be formed in the battery module 10 by applying a liquid adhesive with a general dispenser and then curing the liquid adhesive.
  • a liquid adhesive with a general dispenser and then curing the liquid adhesive.
  • the two-component adhesive is easy to store, and if mixed immediately before use, it is difficult to harden when applied with a dispenser, and can be quickly hardened after application.
  • Application with a dispenser is also preferable in that the liquid adhesive can be filled relatively deep inside the housing 12 of the battery module 10.
  • the gap material 13 that covers the battery cells 11 preferably covers 20 to 40% of each battery cell 11 on one side of the battery cell 11. By covering 20% or more, the battery cells 11 can be stably held. In addition, by sufficiently covering the battery cells that generate a large amount of heat, heat dissipation efficiency is improved. On the other hand, by covering 40% or less, heat generated from the battery cells 11 can be efficiently dissipated, and weight increase and deterioration of workability can be prevented. In order to improve heat dissipation efficiency, it is preferable to cover the side of the battery cells 11 where the electrodes 11a and 11b are located with the gap material 13, and it is more preferable to cover the entire electrodes 11a and 11b with the gap material 13. As described above, the battery module 10 can dissipate heat generated from the battery cells 11 to the module housing 12 via the gap material 13.
  • the gap material 13 is also preferably used in a battery pack that has multiple battery modules 10 inside.
  • a battery pack generally comprises multiple battery modules 10 and a battery pack housing that houses the multiple battery modules 10.
  • the gap material 13 can be provided between the battery modules 10 and the battery pack housing. This allows the heat dissipated to the module housing 12 as described above to be further dissipated to the battery pack housing, enabling effective heat dissipation.
  • examples of the battery assembly are described as a battery module or a battery pack including a battery module, but the battery assembly may also be applied to a battery assembly that does not have a battery module, and it is also preferable to apply the battery assembly to a battery assembly having a cell-to-pack structure, for example.
  • a schematic diagram of a battery assembly having a cell-to-pack structure is shown in Fig. 5.
  • a battery assembly 20 having a cell-to-pack structure includes a plurality of battery cells 21 and a battery pack housing, and the plurality of battery cells 21 are bonded to a base member 25 constituting the battery pack housing via a gap material 23 made of a thermally conductive member (cured product of an adhesive).
  • the base member 25 may constitute a cooling plate or the like.
  • the base member 25 constituted by a cooling plate or the like may have an uneven surface, and the battery cells 21 may be bonded to the uneven surface of the base member 25 via the gap material 23.
  • the gap material 23 in the battery assembly 20 may be formed in the same manner as the gap material 13 in the battery module, for example, by using a general dispenser.
  • the adhesive of the present invention has a sufficiently high adhesive strength after curing, and therefore can provide good adhesion between the battery cell 21 and the base member 25. Furthermore, the adhesive of the present invention is not easily peeled off even after repeated temperature changes, and can be used stably.
  • the adhesive of the present invention can provide good reworkability and adhesion not only in the case of a cell-to-pack structure, but also in other battery assemblies such as the battery module shown in FIG. 3 and components other than battery assemblies.
  • components other than the battery cells such as base members such as a cooling plate, a battery module, a module housing, and a housing for a battery pack, may be covered with or made of a resin material. Even in such cases, the components can be appropriately bonded together by using the adhesive of the present invention as a gap material disposed between the components.
  • the evaluation was performed by the following method. ⁇ Dynamic viscoelasticity measurement>
  • the adhesive was applied to the surface of the silicone-based release-treated PET film using an applicator so that the thickness after curing was 1 mm.
  • the adhesive applied to the silicone-based release-treated PET film was then cured under an environment of 60° C. for 24 hours, and then the silicone-based release-treated PET film was peeled off to obtain a sheet-like cured product.
  • the obtained sheet-like cured product with a thickness of 1 mm was cut into a strip of 10 mm x 30 mm and subjected to dynamic viscoelasticity measurement.
  • the dynamic viscoelasticity measurement was performed using a dynamic viscoelasticity measuring device ("DVA-200" manufactured by IT Measurement & Control Co., Ltd.) under the following measurement conditions: tensile condition, strain of 1%, temperature range of 20°C to 80°C, and heating rate of 5°C/min, at a frequency of 0.1 Hz.
  • the storage modulus and loss modulus at 25°C were measured, and tan ⁇ was also calculated.
  • the case where formula (1) was satisfied was rated as "A”
  • the case where formula (1) was not satisfied was rated as "B".
  • the adhesive strength of the adhesives in each of the Examples and Comparative Examples was measured by the following method in accordance with DIN EN 1465.
  • a glass fiber-reinforced PET film (“Rynite FR530 PET”, manufactured by Nippon Test Panel Co., Ltd.) measuring 25 mm in width, 100 mm in length and 2 mm in thickness, and a cationic electrodeposition coated substrate (KLT plate, "material: SPCC-SD, specifications: cationic electrodeposition coating (black)", manufactured by Nippon Test Panel Co., Ltd.) measuring 25 mm in width, 100 mm in length and 2 mm in thickness were prepared.
  • an adhesive was applied to the longitudinal end of one of the PET films over the entire width of the film, with a length of 12.5 mm, so that the thickness after curing was 2 mm.
  • the longitudinal end of the KLT plate was placed on the applied adhesive, and left in that state in an environment of 60°C for 24 hours to cure the adhesive and obtain a measurement sample.
  • one marker was placed on the PET film of the measurement sample, and another marker was placed on the KLT plate at a position 1 cm away from the marker in the longitudinal direction.
  • the obtained measurement sample was subjected to a tensile shear test in which the measurement sample was pulled in the longitudinal direction at a tensile speed of 10 mm/sec under an environment of 25° C.
  • the shear elongation was calculated by observing the positions of the two markers with a camera when the measurement sample broke. This measurement method does not reflect the influence of the jig used to fix the measurement sample, and therefore the shear elongation can be measured more accurately.
  • the tensile shear test was carried out using "68TM-30" manufactured by Instron Corp.
  • the camera used was "AVE 2" manufactured by Instron Corp.
  • the thermal conductivity of the adhesive of each of the Examples and Comparative Examples was determined by a method for measuring thermal resistance using a measuring device in accordance with ASTM D5470-06. Specifically, the adhesive was placed in a larger amount than the thickness at the time of measurement so as to cover the measurement die on the heating element side, and then sandwiched between heat sinks and compressed under a load of 30 psi until the adhesive thickness reached 1.0 mm, 1.5 mm, and 2.0 mm, and the thermal resistance of each thickness was measured. The thickness was adjusted with a spacer.
  • Epoxy resin 1 Multifunctional epoxy resin Bisphenol F type epoxy resin, product name "jER806", manufactured by Mitsubishi Chemical Corporation, molecular weight 330, epoxy equivalent 165 g/eq, number of functional groups 2
  • Epoxy resin 2 Monofunctional epoxy resin, aliphatic glycidyl ether (aliphatic alcohol is C12-14), trade name “Epogose ML”, manufactured by Yokkaichi Synthetic Co., Ltd., epoxy equivalent 282 g/eq, number of functional groups 1
  • Organic polymer 1 having a hydrolyzable silyl group Kaneka Corporation's “MS Polymer SAT350", number average molecular weight 6,800, linear type, terminal silylation rate 91%, organic polymer having dimethoxymethylsilyl groups at both ends of polypropylene oxide.
  • Organic polymer 3 having a hydrolyzable silyl group AGC Corporation's "S4530", number average molecular weight 25,000, linear type, terminal silylation rate 86%, organic polymer having dimethoxymethylsilyl groups at both ends of polypropylene oxide.
  • Aluminum hydroxide 1 average particle size: 1 ⁇ m
  • Aluminum hydroxide 2 average particle size: 10 ⁇ m
  • Aluminum hydroxide 3 average particle size: 105 ⁇ m
  • Alumina 1 Average particle size: 12.5 ⁇ m
  • Alumina 2 average particle size: 42.8 ⁇ m
  • Alumina 3 average particle size: 80.7 ⁇ m
  • Dispersant 1 BYK-Chemie "DISPERBYK-102”
  • Dispersant 2 BYK-Chemie "DISPERBYK-106"
  • Agents A and B were prepared according to the formulations in Tables 1 and 2. Agents A and B were then mixed in a mass ratio of 1:1 to prepare an adhesive, and various evaluations were performed.
  • the adhesives of Examples 1 to 7 had an adhesive strength of 0.3 MPa or more in the cured state, and as shown in FIG. 6 , satisfied formula (1) in the dynamic viscoelasticity measurement. Furthermore, they had a shear elongation of 0.25 mm or more, and showed good results in the thermal cycle test. On the other hand, although the adhesives of Comparative Examples 1 to 3 had an adhesive strength of 0.3 MPa or more in the cured product, they did not satisfy formula (1) in the dynamic viscoelasticity measurement, and furthermore, the shear elongation was less than 0.25 mm, and the results of the thermal cycle test were inferior to those of the Examples.
  • Battery assembly 10 Battery module 11, 21 Battery cell 12 Battery module housing (module housing) 13, 23 Gap material 20 Battery assembly 25 Base member 30 Syringe 31 First syringe 31A Discharge port of first syringe 32 Second syringe 32A Discharge port of second syringe 33A, 34A Barrel 33B, 34B Barrel lid 35, 45 First agent 36, 46 Second agent 38 Mixer 39 Discharge port of mixer 41 First pail 42 Second pail 43A, 44A Container body having an opening 43B, 44B Lid for closing the opening of the container body

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