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WO2022138807A1 - Curable resin composition and adhesive agent - Google Patents

Curable resin composition and adhesive agent Download PDF

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Publication number
WO2022138807A1
WO2022138807A1 PCT/JP2021/047831 JP2021047831W WO2022138807A1 WO 2022138807 A1 WO2022138807 A1 WO 2022138807A1 JP 2021047831 W JP2021047831 W JP 2021047831W WO 2022138807 A1 WO2022138807 A1 WO 2022138807A1
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WO
WIPO (PCT)
Prior art keywords
weight
component
resin composition
curable resin
core
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/047831
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French (fr)
Japanese (ja)
Inventor
敏彦 岡本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kaneka Corp
Original Assignee
Kaneka Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kaneka Corp filed Critical Kaneka Corp
Priority to CN202180086056.1A priority Critical patent/CN116635229A/en
Priority to JP2022571614A priority patent/JPWO2022138807A1/ja
Publication of WO2022138807A1 publication Critical patent/WO2022138807A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • 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
    • 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/02—Copolymers with acrylonitrile
    • C09J109/04—Latex
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • 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
    • H01M10/65—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • 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 two-component curable resin composition containing an epoxy resin and an adhesive containing the same.
  • compositions are known as adhesives (for example, Patent Document 1). Further, the cured product obtained by curing the epoxy resin composition has strength, heat resistance, water resistance, chemical resistance and electrical insulation. Excellent for such things. Therefore, the epoxy resin composition is used in a wide range of applications such as industrial use and civil engineering and construction use. Currently, various epoxy resin compositions have been developed (for example, Patent Documents 2 to 4 and the like).
  • One embodiment of the present invention has been made in view of the above problems, and an object thereof is a novel curable resin composition which is superior to the conventional one as a two-component type or multi-component type epoxy resin composition. To provide things.
  • the present inventors have completed the present invention as a result of diligent studies to solve the above-mentioned problems.
  • the curable resin composition according to the embodiment of the present invention is a two-component curable resin composition, which comprises a first component containing an epoxy resin (A) and an epoxy curing agent (D).
  • the curable resin composition further contains a polymer particle (B) having a core-shell structure including a core layer and a shell layer, and aluminum hydroxide (C).
  • the total weight of the aluminum hydroxide (C) in the total weight of 100% by weight of the curable resin composition is 55% by weight or more and 85% by weight or less, and the average particle size of the aluminum hydroxide (C) is 11 ⁇ m or more. It is 200 ⁇ m or less.
  • the curable resin composition according to another embodiment of the present invention is a two-component curable resin composition, in which the first component containing the epoxy resin (A) and the epoxy curing agent (D) are used. ), And the curable resin composition further contains polymer particles (B) having a core-shell structure including a core layer and a shell layer, and aluminum hydroxide (C).
  • the total weight of the aluminum hydroxide (C) in 100% by weight of the total weight of the curable resin composition is 55% by weight or more and 85% by weight or less, and the average particle size of the polymer particles (B) is 0.
  • the ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer / weight of the shell layer) in the polymer particles (B) is 65/35 to It is 92/8, and the shell layer of the polymer particles (B) is obtained by polymerizing the monomer component containing 55 wt% or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of the monomer component.
  • the monomer component contains 10 to 100 wt% of an alkyl (meth) acrylate having 1 carbon atom and 0 to 80 wt% of an alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the monomer component.
  • Curable resin composition It is a polymer, and the monomer component contains 10 to 100 wt% of an alkyl (meth) acrylate having 1 carbon atom and 0 to 80 wt% of an alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the monomer component.
  • the curable resin composition according to another embodiment of the present invention is a two-component type or multi-component type curable resin composition, which is a first component containing an epoxy resin (A) and an epoxy.
  • the curable resin composition contains a second component containing a curing agent (D), and the curable resin composition further comprises a polymer particle (B) having a core-shell structure including a core layer and a shell layer, and the polymer particles (B) having a core-shell structure are contained in one molecule ( i) It contains one aromatic ring and (ii) a compound (G) having at least two phenolic hydroxyl groups, and is located in the ortho position with respect to the phenolic hydroxyl group in the compound (G).
  • the number of tertiary alkyl groups is 0 or 1 in one molecule
  • the epoxy curing agent (D) is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, or an amine-terminated butadiene nitrile.
  • the first embodiment relates to a two-component curable resin composition containing an epoxy resin and an adhesive containing the same.
  • Patent Document 1 discloses a battery module in which a battery cell is fixed to a module case with a heat conductive adhesive.
  • the curable resin composition used for the device is flame-retardant in order to enhance safety against fire and other accidents that may occur due to heat accumulation during charging / discharging. It is required to show sex, and it is desired to show V-0 grade in UL 94 V Test (Vertical Burning Test).
  • the EV battery has a structure in which a large number of battery cells are arranged in parallel, and shear stress is applied due to an external impact such as a vehicle collision, so that each battery cell is fixed to the battery case by adhesion.
  • the agent is required to have high adhesive strength and impact resistance.
  • Epoxy resins on the other hand, have excellent dimensional stability, mechanical strength, electrical insulation properties, heat resistance, water resistance, chemical resistance, etc., and therefore adhesives, sealants, etc. It is widely used in electric devices as a curable resin composition.
  • Patent Document 2 discloses a technique for improving the toughness and impact resistance of a obtained cured product by dispersing polymer fine particles in a curable resin composition containing a curable resin such as an epoxy resin as a main component. ing.
  • lithium-ion batteries have the property of being sensitive to heat, and it is difficult to use a heat-curable one-component epoxy-based curable resin composition.
  • a two-component epoxy-based curable resin composition that can be cured at room temperature or at a low temperature close to room temperature is disclosed in Patent Document 3 and the like.
  • a heat conductive filler such as aluminum hydroxide or alumina
  • the mechanical strength, toughness, and impact resistance of the cured product obtained by curing the curable resin composition may decrease.
  • a cured product of an epoxy resin widely used in electric devices has a problem that it has a low fracture toughness and exhibits a very brittle property.
  • Patent Document 1 did not have sufficient impact resistance and had room for improvement. Further, Patent Documents 2 to 3 do not describe a technique for improving impact resistance in an epoxy-based curable resin composition in which an epoxy resin and a large amount of aluminum hydroxide are combined.
  • the invention according to the first embodiment is a cured product in which an epoxy resin and aluminum hydroxide are blended and which exhibits excellent thermal conductivity, flame retardancy, adhesive strength, and impact peeling adhesiveness. It is an object of the present invention to provide a two-component curable resin composition that can be cured at room temperature or at a low temperature close to room temperature.
  • the present inventors have conducted a two-component type containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
  • a two-component type containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
  • the invention according to the first embodiment is a curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
  • the first component and / or the second component further contains the polymer particles (B) having a core-shell structure and the aluminum hydroxide (C), and the aluminum hydroxide (C) with respect to the total weight of the curable resin composition.
  • the average particle size of the aluminum hydroxide (C) is 11 ⁇ m or more and 200 ⁇ m or less
  • the curable resin composition is a two-component type or a multi-component type. It relates to a curable resin composition which is a mold.
  • the cured product obtained by the epoxy resin and a high amount of aluminum hydroxide can exhibit excellent thermal conductivity, flame retardancy, and adhesive strength.
  • the toughness improving effect of the polymer particles having a core-shell structure is effectively exhibited by using aluminum hydroxide having a specific average particle size.
  • the cured product obtained from the curable resin composition according to the first embodiment can exhibit excellent impact resistance. That is, according to the first embodiment, it is possible to provide a cured product exhibiting excellent thermal conductivity, flame retardancy, adhesive strength, and impact-resistant peeling adhesiveness, and it can be cured even at room temperature or a low temperature close to room temperature.
  • a two-component curable resin composition can be provided.
  • the first embodiment is curable containing at least an epoxy resin (A), polymer particles (B) having a core-shell structure, aluminum hydroxide (C), and an epoxy curing agent (D). It is a resin composition.
  • the curable resin composition according to the first embodiment contains a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D) as essential components, and further, if necessary. It is a two-component type or multi-component type curable resin composition in which other components such as a color toner and a curability adjusting agent are mixed and used immediately before use. Further, the curable resin composition according to the first embodiment further contains polymer particles (B) having a core-shell structure and aluminum hydroxide (C).
  • the polymer particles (B) and aluminum hydroxide (C) having a core-shell structure are preferably contained in the first component and / or the second component, respectively.
  • the curable resin composition according to the first embodiment may contain another component, if necessary, in addition to the first component and the second component.
  • epoxy resin (A) "polymer particles (B)”, “aluminum hydroxide (C)” and “epoxy curing agent (D)” are “component (A)” and “component”, respectively. It may be expressed as “(B) component”, “(C) component” and “(D) component”.
  • adheresive strength and “impact peeling adhesiveness” are collectively referred to as “adhesiveness”.
  • the adhesive strength is evaluated by the shear adhesive strength (MPa). That is, the adhesive strength is intended to be the value of the shear adhesive strength (MPa). The larger the value of the shear adhesive strength (MPa) after curing, the more excellent the curable resin composition is in the adhesive strength.
  • the impact resistance peeling adhesiveness can be evaluated by the dynamic split resistance measured at 23 ° C. according to ISO 11343. That is, the impact resistance peeling adhesiveness is intended to be the value of the dynamic split resistance force (kN / m). The larger the value of the dynamic split resistance after curing, the better the impact-resistant peeling adhesiveness of the curable resin composition.
  • the curable resin composition of the first embodiment contains an epoxy resin (A) as a curable resin as a first component.
  • the epoxy resin various epoxy resins can be used.
  • examples of the polyalkylene glycol diglycidyl ether include polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether. More specific examples of the glycol diglycidyl ether include neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether and the like. Will be.
  • aliphatic polybasic acid diglycidyl ester examples include dimer acid diglycidyl ester, adipate diglycidyl ester, sebacic acid diglycidyl ester, and maleic acid diglycidyl ester.
  • Specific examples of the glycidyl ether of the dihydric or higher polyhydric alcohol include trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil modified polyglycidyl ether, propoxylated glycerin triglycidyl ether, and sorbitol. Examples include polyglycidyl ether.
  • Examples of the epoxy compound obtained by adding a polybasic acid or the like to an epoxy resin include a dimer of tall oil fatty acid (dimeric acid) and bisphenol A as described in International Publication No. 2010-098950. Examples thereof include an addition reaction product with a type epoxy resin.
  • the polyalkylene glycol diglycidyl ether, the glycol diglycidyl ether, the diglycidyl ester of the aliphatic polybasic acid, and the glycidyl ether of the divalent or higher polyhydric aliphatic alcohol are epoxy resins having a relatively low viscosity.
  • epoxy resin (A) preferably contains a polyepoxy as a reactive diluent.
  • the monoepoxide functions as a reactive diluent as described later, but is not contained in the epoxy resin (A).
  • the content of the epoxy resin that functions as the reactive diluent is preferably 0.5 to 30% by weight, more preferably 2 to 20% by weight, still more preferably 5 to 15% by weight in the component (A).
  • the chelate-modified epoxy resin is a reaction product of an epoxy resin and a compound (chelate ligand) containing a chelate functional group, and when the curable resin composition to which the epoxy resin is added is used as an adhesive for vehicles, Adhesion to the surface of a metal substrate contaminated with an oily substance can be improved.
  • the chelate functional group is a functional group of a compound having a plurality of coordination positions capable of coordinating to a metal ion in the molecule, and is, for example, a phosphorus-containing acid group (for example, -PO (OH) 2 ) or a carboxylic acid group (-).
  • the amount of the chelate-modified epoxy resin used in the component (A) is preferably 0.1 to 10% by weight, more preferably 0.5 to 3% by weight.
  • the rubber-modified epoxy resin is a reaction product obtained by reacting rubber with an epoxy group-containing compound and having 1.1 or more, preferably two or more epoxy groups on average per molecule.
  • rubber examples include acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), hydrogenated nitrile rubber (HNBR), ethylene propylene rubber (EPDM), acrylic rubber (ACM), butyl rubber (IIR), butadiene rubber, and polypropylene oxide.
  • NBR acrylonitrile butadiene rubber
  • SBR styrene butadiene rubber
  • HNBR hydrogenated nitrile rubber
  • EPDM ethylene propylene rubber
  • ACM acrylic rubber
  • IIR butadiene rubber
  • polypropylene oxide examples thereof include rubber-based polymers such as polyoxyalkylenes such as polyethylene oxide and polytetramethylene oxide.
  • the rubber-based polymer preferably has a reactive group such as an amino group, a
  • a rubber-modified epoxy resin is a product obtained by reacting these rubber-based polymers with an epoxy resin in an appropriate compounding ratio by a known method.
  • acrylonitrile-butadiene rubber-modified epoxy resin and polyoxyalkylene-modified epoxy resin are preferable from the viewpoint of adhesive strength and impact-resistant peeling adhesiveness of the obtained curable resin composition, and acrylonitrile-butadiene rubber-modified epoxy resin is preferable. More preferred.
  • the acrylonitrile-butadiene rubber-modified epoxy resin can be obtained, for example, by reacting a carboxyl group-terminated NBR (CTBN) with a bisphenol A type epoxy resin.
  • CBN carboxyl group-terminated NBR
  • the content of the acrylonitrile monomer component in the acrylonitrile-butadiene rubber is 5 to 40 weights from the viewpoint of the adhesive strength and the impact-resistant peeling adhesiveness of the obtained curable resin composition. % Is preferred, 10 to 35% by weight is more preferable, and 15 to 30% by weight is even more preferable. From the viewpoint of workability of the obtained curable resin composition, 20 to 30% by weight is particularly preferable.
  • “workability of the curable resin composition” is intended to be workability in work (coating, etc.) using the curable resin composition.
  • an addition reaction product of an amino group-terminated polyoxyalkylene and an epoxy resin (hereinafter, also referred to as an “adduct”) is also included in the rubber-modified epoxy resin.
  • the adduct can be easily produced by a known method, for example, as described in US Pat. No. 5,084532, US Pat. No. 6,015865, and the like.
  • the epoxy resin used in producing the adduct include specific examples of the component (A) described above, but bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable, and bisphenol A type epoxy resin is preferable. Is more preferable.
  • amino group-terminated polyoxyalkylenes used in the production of adducts include, for example, Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, manufactured by Huntsman. Examples include Jeffamine T-5000.
  • the average number of epoxide-reactive end groups per molecule in the rubber is preferably 1.5 to 2.5, more preferably 1.8 to 2.2.
  • the "epoxide-reactive end group” is intended to be an end group having reactivity with an epoxy group.
  • the number average molecular weight of rubber is preferably 1000 to 10000, more preferably 2000 to 8000, and particularly preferably 3000 to 6000 in terms of polystyrene-equivalent molecular weight measured by GPC.
  • the method for producing the rubber-modified epoxy resin can be produced by reacting rubber with an epoxy group-containing compound in a large amount of epoxy group-containing compound. Specifically, it is preferably produced by reacting 2 equivalents or more of an epoxy group-containing compound with 1 equivalent of an epoxy-reactive terminal group in rubber. It is more preferable that the obtained product reacts with an epoxy group-containing compound in an amount sufficient to form a mixture of the adduct of the rubber and the epoxy group-containing compound and the free epoxy group-containing compound.
  • a rubber-modified epoxy resin is produced by heating to a temperature of 100 to 250 ° C.
  • the epoxy group-containing compound used in producing the rubber-modified epoxy resin is not particularly limited, but bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable, and bisphenol A type epoxy resin is more preferable.
  • the epoxy resin can be modified by pre-reacting with the bisphenol component.
  • the bisphenol component used for the modification is preferably 3 to 35 parts by weight, more preferably 5 to 25 parts by weight, based on 100 parts by weight of the rubber component in the rubber-modified epoxy resin.
  • a cured product obtained by curing a curable resin composition containing a modified rubber-modified epoxy resin has excellent adhesive durability after high-temperature exposure and also has excellent impact resistance at low temperatures.
  • the glass transition temperature (Tg) of the rubber-modified epoxy resin is not particularly limited, but is preferably ⁇ 25 ° C. or lower, more preferably ⁇ 35 ° C. or lower, further preferably ⁇ 40 ° C. or lower, and particularly preferably ⁇ 50 ° C. or lower.
  • the number average molecular weight of the rubber-modified epoxy resin is preferably 1500 to 40,000, more preferably 3000 to 30000, and particularly preferably 4000 to 20000 in terms of polystyrene-equivalent molecular weight measured by GPC.
  • the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 1 to 4, more preferably 1.2 to 3, and particularly preferably 1.5 to 2.5.
  • the rubber-modified epoxy resin can be used alone or in combination of two or more.
  • the amount of the rubber-modified epoxy resin used in the component (A) is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, further preferably 5 to 30% by weight, and particularly preferably 10 to 20% by weight.
  • the urethane-modified epoxy resin is obtained by reacting a compound containing a group having a reactivity with an isocyanate group and an epoxy group with a urethane prepolymer containing an isocyanate group, and the epoxy group is averaged per molecule. It is a reaction product having 1.1 or more, preferably 2 or more.
  • a urethane-modified epoxy resin can be obtained by reacting a hydroxy group-containing epoxy compound with a urethane prepolymer.
  • the number average molecular weight of the urethane-modified epoxy resin is preferably 1500 to 40,000, more preferably 3000 to 30000, and particularly preferably 4000 to 20000 in terms of polystyrene-equivalent molecular weight measured by GPC.
  • the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 1 to 4, more preferably 1.2 to 3, and particularly preferably 1.5 to 2.5.
  • Urethane-modified epoxy resin can be used alone or in combination of two or more.
  • the amount of the urethane-modified epoxy resin used in the component (A) is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, further preferably 5 to 30% by weight, and particularly preferably 10 to 20% by weight.
  • those having at least two epoxy groups in one molecule have high curability, high flexibility after curing, and improve impact peeling resistance by blending core-shell polymer particles (B). It is preferable because it has an excellent effect.
  • a compound having two epoxy groups in one molecule is preferable.
  • the bisphenol A type epoxy resin and the bisphenol F type epoxy resin have a high elastic modulus of the obtained cured product, are excellent in heat resistance and adhesiveness, and are relatively inexpensive. Therefore, the epoxy resin (A) is preferably a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin. Further, the epoxy resin (A) is particularly preferably a bisphenol A type epoxy resin because a curable resin composition capable of providing a cured product having excellent heat resistance can be obtained at a low price.
  • an epoxy resin having an epoxy equivalent of less than 220 is preferable because of its high elastic modulus and heat resistance of the obtained cured product, and an epoxy equivalent of 90 or more and less than 210 is more preferable, and 150 or more and less than 200 is preferable. More preferred.
  • the bisphenol A type epoxy resin and the bisphenol F type epoxy resin having an epoxy equivalent of less than 220 are preferable because they are liquid at room temperature and the obtained curable resin composition is easy to handle.
  • the bisphenol A type epoxy resin and the bisphenol F type epoxy resin having an epoxy equivalent of 220 or more and less than 5000 in 100% by weight of the component (A) are preferably 40% by weight or less, more preferably 20% by weight or less. When it is contained in the range of, the obtained cured product is preferable because it has excellent impact resistance.
  • the curable resin composition of the first embodiment contains polymer particles having a core-shell structure as the component (B) in the first component and / or the second component.
  • the polymer particles (B) have a core-shell structure means that the polymer particles (B) have a core layer and a shell layer.
  • the curable resin composition contains the component (B)
  • the obtained cured product for example, an adhesive layer
  • the curable resin composition contains the component (B)
  • the adhesive strength of the obtained cured product tends to be excellent.
  • the component (B) may be contained only in the first component, may be contained only in the second component, or may be contained in both the first component and the second component.
  • the component (B) may be swollen or the like due to the small molecule compound contained in the component (D) in the second component. Therefore, from the viewpoint of storage stability of the composition, the component (B) is preferably contained in at least the first component, and more preferably contained only in the first component.
  • the "polymer particles (B) having a core-shell structure" are also referred to as "core-shell polymer particles (B)".
  • the core-shell polymer particles (B) may or may not have an epoxy group in the shell layer.
  • the shell layer of the core-shell polymer particles (B) may or may not have an epoxy group. Since the obtained cured product has excellent impact resistance and peeling adhesiveness, the core-shell polymer particles (B) preferably have an epoxy group in the shell layer.
  • the content of the epoxy group contained in the shell layer with respect to the total weight of the shell layer of the core-shell polymer particles (B) is the impact-resistant peeling of the obtained cured product.
  • the viewpoint of adhesiveness it is preferably more than 0 mmol / g and 2.0 mmol / g or less, more preferably 0.1 mmol / g or more and 2.0 mmol / g or less, and 0.3 mmol / g or more 1 It is more preferably 5.5 mmol / g or less.
  • aggregation of the core-shell polymer particles (B) is suppressed, and the core-shell polymer particles (B) can be dispersed in the cured product in the form of primary particles, and as a result, the impact-resistant peeling adhesiveness of the cured product is improved. It is speculated that it can be done.
  • the component (B) is preferably contained only in the first component. Further, from the viewpoint of storage stability of the curable resin composition, the core-shell polymer particles (B) preferably have no epoxy group in the shell layer. When the core-shell polymer particles (B) are added to the second component containing the epoxy curing agent (D) described later, which has reactivity with the epoxy group, the component (B) does not have an epoxy group in the shell layer. The one is preferable.
  • the curable resin composition contains (i) core-shell polymer particles (B) having an epoxy group in the shell layer in the first component, and (ii) having an epoxy group in the shell layer in the second component. It may contain core-shell polymer particles (B) that do not.
  • the particle size of the core-shell polymer particles (B) is not particularly limited.
  • the volume average particle diameter (Mv) of the core-shell polymer particles (B) in the first embodiment is preferably 0.01 ⁇ m to 2.00 ⁇ m (10 nm to 2000 nm), preferably 0.03 ⁇ m to 0.60 ⁇ m. (30 nm to 600 nm) is more preferable, 0.05 ⁇ m to 0.40 ⁇ m (50 nm to 400 nm) is more preferable, 0.10 ⁇ m to 0.30 ⁇ m (100 nm to 300 nm) is more preferable, and 0.15 ⁇ m to 0.30 ⁇ m.
  • the volume average particle diameter (Mv) of the core-shell polymer particles (B) is (a) 0.01 ⁇ m or more, the viscosity of the curable resin composition is low, so that workability is good, and (b) 2. When it is 00 ⁇ m or less, the polymerization time of the component (B) is shortened and the industrial productivity is increased.
  • the volume average particle diameter (Mv) of the polymer particles can be measured with respect to the latex of the polymer particles using Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.).
  • the sex resin composition is preferable because it has a low viscosity and is easy to handle.
  • the core-shell polymer particles (B) there are two or more maximum values in the number distribution of the particle size of the core-shell polymer particles (B), and from the viewpoint of labor and cost during manufacturing. , It is more preferable that there are 2 to 3 maximum values, and it is further preferable that there are 2 maximum values. In particular, it is preferable to contain 10 to 90% by weight of core-shell polymer particles having a volume average particle diameter of 10 nm or more and less than 150 nm, and 90 to 10% by weight of core-shell polymer particles having a volume average particle diameter of 150 nm or more and 2000 nm or less.
  • the core-shell polymer particles (B) are dispersed in the state of primary particles in the curable resin composition.
  • the core-shell polymer particles are dispersed in the state of primary particles means that the core-shell polymer particles are dispersed substantially independently (without contact).
  • a part of the curable resin composition is dissolved in a solvent such as methyl ethyl ketone, and the particle size is measured by a particle size measuring device or the like by laser light scattering. It can be confirmed by this.
  • the value of the volume average particle diameter (Mv) / number average particle diameter (Mn) measured by the particle diameter measurement is not particularly limited, but is preferably 3.0 or less, more preferably 2.5 or less, and 2.0. The following is more preferable, and 1.5 or less is particularly preferable. If the volume average particle diameter (Mv) / number average particle diameter (Mn) is 3.0 or less, it is considered that the core-shell polymer particles (B) are well dispersed, and the impact resistance of the obtained cured product is increased. Physical properties such as adhesiveness are improved.
  • the volume average particle diameter (Mv) / number average particle diameter (Mn) can be determined by measuring using Microtrac UPA (manufactured by Nikkiso Co., Ltd.) and dividing Mv by Mn.
  • stable dispersion of the core-shell polymer particles means that the core-shell polymer particles do not aggregate, separate, or precipitate in the continuous layer, and are constantly under normal conditions for a long period of time. It means a state of being dispersed over.
  • the distribution of the core-shell polymer particles in the continuous layer does not change substantially, and even if these compositions are heated within a non-hazardous range to reduce the viscosity and stir, they are “stable”. It is preferable to be able to maintain "dispersion”.
  • core-shell polymer particles (B) may be used alone, or two or more types may be used in combination.
  • the structure of the core-shell polymer particles (B) is not particularly limited, but it is preferable to have two or more layers. It is also possible to have a structure of three or more layers composed of an intermediate layer covering the core layer and a shell layer further covering the intermediate layer.
  • the core layer is preferably an elastic core layer having rubber properties in order to increase the toughness of the cured product of the curable resin composition.
  • the elastic core layer preferably has a gel content of 60% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more. It is particularly preferable that it is 95% by weight or more.
  • the gel content referred to in the present specification is when 0.5 g of crumb obtained by coagulation and drying is immersed in 100 g of toluene, allowed to stand at 23 ° C. for 24 hours, and then the insoluble and soluble components are separated. , Means the ratio of insoluble matter to the total amount of insoluble matter and soluble matter.
  • the core layer preferably contains at least one selected from the group consisting of diene-based rubber, (meth) acrylate-based rubber, and organosiloxane-based rubber.
  • the effect of improving the impact-resistant peeling adhesiveness of the obtained cured product is high, and the affinity with the epoxy resin (A) is low, so that the viscosity increases over time due to the swelling of the core layer due to the component (A).
  • the core layer preferably contains a diene-based rubber because it is unlikely to occur.
  • Examples of the conjugated diene-based monomer constituting the diene-based rubber include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, 2-methyl-1,3-butadiene and the like. These conjugated diene-based monomers may be used alone or in combination of two or more.
  • the content of the conjugated diene-based monomer is preferably in the range of 50 to 100% by weight, more preferably in the range of 70 to 100% by weight, and in the range of 90 to 100% by weight. It is more preferable to have.
  • the content of the conjugated diene-based monomer is 50% by weight or more, the impact-resistant peeling adhesiveness of the obtained cured product can be improved.
  • vinyl-based monomer copolymerizable with the conjugated diene-based monomer examples include vinyl allenes such as styrene, ⁇ -methylstyrene, monochlorostyrene and dichlorostyrene; vinylcarboxylic acids such as acrylic acid and methacrylic acid; Vinyl cyanes such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride, vinyl bromide and chloroprene; vinyl acetate; alkenes such as ethylene, propylene, butylene and isobutylene; diallyl phthalate, triallyl cyanurate, tri Examples thereof include polyfunctional monomers such as allyl isocyanurate and divinylbenzene. These vinyl-based monomers may be used alone or in combination of two or more. Styrene is particularly preferable.
  • the content of the vinyl-based monomer copolymerizable with the conjugated diene-based monomer is preferably in the range of 0 to 50% by weight, more preferably in the range of 0 to 30% by weight. It is preferably in the range of 0 to 10% by weight, more preferably in the range of 0 to 10% by weight.
  • the content of the vinyl-based monomer copolymerizable with the conjugated diene-based monomer is 50% by weight or less, the impact-resistant peeling adhesiveness of the obtained cured product can be improved.
  • Diene-based rubbers are made of diene rubber because they have a high effect of improving impact resistance and peeling adhesiveness, and because they have a low affinity with the epoxy resin (A), they are unlikely to increase in viscosity over time due to swelling of the core layer.
  • Butadiene rubber using 1,3-butadiene and / or butadiene-styrene rubber which is a copolymer of 1,3-butadiene and styrene is preferable, and butadiene rubber is more preferable. Further, butadiene-styrene rubber is preferable in that the transparency of the cured product obtained by adjusting the refractive index can be enhanced.
  • the (meth) acrylate-based rubber contains 50 to 100% by weight of at least one monomer selected from the group consisting of (meth) acrylate-based monomers, and other vinyl-based rubbers capable of copolymerizing with the (meth) acrylate-based monomer. It is preferably a rubber elastic body obtained by polymerizing a monomer mixture containing 0 to 50% by weight of a monomer.
  • Examples of the (meth) acrylate-based monomer include (i) methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and dodecyl (meth).
  • Alkyl (meth) acrylates such as acrylates, stearyl (meth) acrylates and behenyl (meth) acrylates;
  • Aromatic ring-containing (meth) acrylates such as phenoxyethyl (meth) acrylates and benzyl (meth) acrylates;
  • Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate;
  • glycidyl (meth) such as (iv) glycidyl (meth) acrylate and glycidylalkyl (meth) acrylate.
  • Examples of other vinyl-based monomers copolymerizable with the (meth) acrylate-based monomer include vinyl allenes such as (i) styrene, ⁇ -methylstyrene, monochlorostyrene, and dichlorostyrene; (ii) acrylic acid and methacrylic acid.
  • Vinyl carboxylic acids such as (iii) acrylonitrile, vinyl cyanides such as methacrylonitrile;
  • vinyl halides such as vinyl chloride, vinyl bromide, chloroprene;
  • vinyl acetate ethylene, styrene.
  • Alkenes such as butylene, isobutylene;
  • Polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene and the like can be mentioned. These vinyl-based monomers may be used alone or in combination of two or more. Styrene is particularly preferable because the refractive index can be easily increased.
  • organosiloxane rubber The organosiloxane-based rubber is composed of, for example, (i) an alkyl or aryl 2-substituted silyloxy unit such as (i) dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, dimethylsilyloxy-diphenylsilyloxy.
  • Polysiloxane-based polymers (ii) Polysiloxane-based polymers composed of alkyl or aryl 1-substituted silyloxy units, such as organohydrogensilyloxy in which a part of the alkyl in the side chain is substituted with a hydrogen atom, and the like can be mentioned. .. These polysiloxane-based polymers may be used alone or in combination of two or more. Of these, dimethylsilyloxy, methylphenylsilyloxy, and dimethylsilyloxy-diphenylsilyloxy are preferable because they can impart heat resistance to the cured product, and dimethylsilyloxy is most preferable because they can be easily obtained.
  • the polysiloxane-based polymer moiety is 80% by weight or more (more preferably) with the entire organosiloxane-based rubber as 100% by weight so as not to impair the heat resistance of the cured product. 90% by weight or more) is preferably contained.
  • the glass transition temperature of the core layer (hereinafter, may be simply referred to as “Tg”) is preferably 0 ° C. or lower, more preferably ⁇ 20 ° C. or lower, and more preferably ⁇ 20 ° C. or lower in order to increase the toughness of the obtained cured product. It is more preferably 40 ° C. or lower, and particularly preferably ⁇ 60 ° C. or lower.
  • the volume average particle size of the core layer is not particularly limited, but is preferably 0.03 ⁇ m to 2 ⁇ m, more preferably 0.05 ⁇ m to 1 ⁇ m, more preferably 0.12 ⁇ m to 0.50 ⁇ m, and 0.12 ⁇ m to 0.28 ⁇ m. Is more preferable, and 0.14 to 0.25 ⁇ m is even more preferable.
  • the volume average particle size of the core layer can be measured by using Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.) for the latex of the core layer.
  • the ratio of the core layer is not particularly limited.
  • the proportion of the core layer is preferably 40% by weight to 97% by weight, more preferably 60% by weight to 95% by weight, still more preferably 70% by weight to 93% by weight, assuming that the entire core-shell polymer particles (B) are 100% by weight. , 80% by weight to 90% by weight are particularly preferable.
  • the ratio of the core layer is 40% by weight or more, the impact-resistant peeling adhesiveness of the obtained cured product can be improved.
  • the ratio of the core layer is 97% by weight or less, the core-shell polymer particles are less likely to aggregate, the curable resin composition has a lower viscosity, and the workability can be improved.
  • the ratio of the weight of the core layer to the weight of the shell layer is not particularly limited.
  • the ratio (weight of the core layer / weight of the shell layer) is 65/35 to 92 / because the workability of the curable resin composition becomes better and the impact resistance of the cured product becomes better. It is preferably 8, more preferably 68/32 to 91/9, and even more preferably 70/30 to 90/10.
  • the core layer often has a single-layer structure, but it may have a multi-layer structure composed of a layer having rubber elasticity. Further, when the core layer has a multi-layer structure, the polymer composition of each layer may be different within the scope of the above disclosure.
  • an intermediate layer may be formed between the core layer and the shell layer.
  • the following rubber surface crosslinked layer may be formed as the intermediate layer. From the viewpoint of the effect of improving the toughness of the obtained cured product and the effect of improving the impact resistance peeling adhesiveness, it is preferable not to contain an intermediate layer, and it is particularly preferable not to contain the following rubber surface crosslinked layer.
  • the ratio of the intermediate layer to 100 parts by weight of the core layer is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, still more preferably 0.5 to 10 parts by weight. 1 to 5 parts by weight is particularly preferable.
  • the rubber surface crosslinked layer is polymerized with a rubber surface crosslinked layer component composed of 30 to 100% by weight of a polyfunctional monomer having two or more radically polymerizable double bonds in one molecule and 0 to 70% by weight of another vinyl monomer. It is composed of an intermediate layer polymer, which has an effect of lowering the viscosity of the curable resin composition and an effect of improving the dispersibility of the core-shell polymer particles (B) in the component (A). It also has the effect of increasing the crosslink density of the core layer and increasing the graft efficiency of the shell layer.
  • polyfunctional monomer do not include conjugated diene-based monomers such as butadiene, and allylalkyl (meth) acrylates such as allyl (meth) acrylate and allylalkyl (meth) acrylate; allyloxyalkyl (meth).
  • the outermost shell layer of the core-shell polymer particles is a polymer obtained by polymerizing a monomer for forming a shell layer.
  • the polymer (shell polymer) constituting the shell layer improves the compatibility between the core-shell polymer particles (B) and the component (A), and the core-shell polymer particles (B) in the curable resin composition or the cured product thereof. Plays a role in enabling dispersion in the form of primary particles.
  • Such a shell polymer is preferably grafted on the core layer and / or the intermediate layer.
  • the monomer component used for forming the shell layer is a core polymer forming a core layer (in the case where an intermediate layer is formed, the core polymer also includes an intermediate layer polymer forming an intermediate layer. , The same), it is preferable that the shell polymer and the core polymer are substantially chemically bonded (when the intermediate layer is formed, the shell polymer and the intermediate layer polymer are chemically bonded). It is also preferable).
  • the shell polymer is formed by graft-polymerizing the shell layer forming monomer in the presence of the core polymer, and by doing so, the shell polymer is graft-polymerized to the core polymer, and is one of the core polymers. It covers a part or the whole.
  • This polymerization operation can be carried out by adding a monomer for forming a shell polymer layer to the latex of the core polymer prepared in the state of an aqueous polymer latex and polymerizing the latex.
  • the core-shell polymer particles (B) at least a part of the shell polymer forming the shell layer may be graft-polymerized (graft-bonded) to the core polymer, and the core layer and the shell layer have a complete layer structure. It does not have to be formed. In other words, the shell polymer does not have to cover the entire core layer. In the core-shell polymer particles (B), a part of the shell polymer may penetrate into the core layer. In the core-shell polymer particles (B), it is preferable that a part of the shell polymer covers the core layer, in other words, a part of the shell polymer is present on the outermost surface of the core-shell polymer particles (B) (the outermost layer). (Form) is preferable.
  • the composition of the monomer for forming the shell layer is not particularly limited.
  • the shell layer forming monomer include aromatic vinyl monomers, vinyl cyan monomers, and (meth) acrylate monomers from the viewpoint of compatibility and dispersibility of the core-shell polymer particles (B) in the curable resin composition.
  • a (meth) acrylate monomer is more preferred.
  • the shell layer forming monomer preferably contains a metal metaclerite. These shell layer forming monomers may be used alone or in combination as appropriate.
  • the type and content ratio of the structural units contained in the shell layer are not particularly limited.
  • the shell layer is selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers and (meth) acrylate monomers. It is preferable to include a structural unit derived from a monomer of a species or more, and more preferably to contain a structural unit derived from a (meth) acrylate monomer.
  • the shell layer preferably contains a structural unit derived from a metal metaclerite.
  • the total amount of the aromatic vinyl monomer, the vinyl cyan monomer, and the (meth) acrylate monomer is preferably 10.0% by weight to 99.5% by weight in 100% by weight of the monomer for forming the shell layer, and 50. 0% by weight to 99.0% by weight is more preferable, 65.0% by weight to 98.0% by weight is more preferable, 67.0% by weight to 80.0% by weight is particularly preferable, and 67.0 to 85.0% by weight is particularly preferable. % By weight is most preferred.
  • the shell layer is a structural unit derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers and (meth) acrylate monomers in 100% by weight of the shell layer (shell polymer). , 10.0% by weight to 99.5% by weight, more preferably 50.0% by weight to 99.0% by weight, and 65.0% by weight to 98.0% by weight. Is more preferable, 67.0% by weight to 80.0% by weight is particularly preferable, and 67.0 to 85.0% by weight is most preferable.
  • aromatic vinyl monomer examples include vinylbenzenes such as styrene, ⁇ -methylstyrene, p-methylstyrene, and divinylbenzene.
  • vinyl cyanomer examples include acrylonitrile, methacrylonitrile, and the like.
  • the (meth) acrylate monomer examples include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; and (meth) acrylic acid hydroxyalkyl esters. Be done.
  • (meth) acrylic acid hydroxyalkyl ester examples include hydroxy linear alkyl (meth) such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
  • Acrylate particularly hydroxy straight chain C1-6 alkyl (meth) acrylate); caprolactone-modified hydroxy (meth) acrylate; hydroxy-branched alkyl such as ⁇ - (hydroxymethyl) methyl acrylate, ⁇ - (hydroxymethyl) ethyl acrylate ( Hydroxyl group-containing (meth) acrylates such as mono (meth) acrylates of polyester diols (particularly saturated polyester diols) obtained from meta) acrylates, divalent carboxylic acids (phthalic acids, etc.) and dihydric alcohols (propylene glycol, etc.). And so on.
  • the shell layer of the first embodiment has a copolymer weight obtained by polymerizing a shell layer forming monomer containing 55% by weight or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of the shell layer forming monomer. It is preferably coalesced.
  • the shell layer of the first embodiment preferably contains 55% by weight or more of a structural unit derived from an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of the shell layer.
  • the shell layer of the first embodiment is a copolymer obtained by polymerizing a monomer component containing 65% by weight or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of a monomer for forming a shell layer. It is more preferable, it is more preferably a copolymer obtained by polymerizing a monomer component containing 75% by weight or more, and further preferably it is a copolymer obtained by polymerizing a monomer component containing 78% by weight or more. It is particularly preferable that the copolymer is obtained by polymerizing a monomer component containing 83% by weight or more.
  • the shell layer forming monomer contains an alkyl (meth) acrylate having 1 to 4 carbon atoms in the above-mentioned range, it has an advantage that the workability of the curable resin composition is improved.
  • alkyl (meth) acrylates having 1 to 4 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate and other (meth) acrylic acid alkyl esters.
  • the shell layer forming monomer of the first embodiment contains 10% by weight to 100% by weight of an alkyl (meth) acrylate having 1 carbon atom and an alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the monomer for forming a shell layer. Is preferably contained in an amount of 0% by weight to 80% by weight.
  • the shell layer of the first embodiment contains 10% by weight to 100% by weight of the structural unit derived from the alkyl (meth) acrylate having 1 carbon atom and the constitution derived from the alkyl (meth) acrylate having 4 carbon atoms.
  • the unit is preferably contained in an amount of 0% by weight to 80% by weight.
  • the shell layer forming monomer of the first embodiment more preferably contains 11% by weight to 95% by weight of an alkyl (meth) acrylate having 1 carbon atom in 100% by weight of the shell layer forming monomer, and 12% by weight to 12% by weight. It is more preferably contained in an amount of 92% by weight, further preferably contained in an amount of 13% by weight to 55% by weight, and particularly preferably contained in an amount of 14% by weight to 50% by weight.
  • the shell layer forming monomer of the first embodiment preferably contains 1% by weight to 89% by weight of an alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the shell layer forming monomer.
  • the shell layer forming monomer constituting the shell layer of the core-shell polymer particles (B) contains an alkyl (meth) acrylate having 1 carbon atom and / or an alkyl (meth) acrylate having 4 carbon atoms in the above range, the core-shell polymer Since the interaction between the particles (B) and the component (C) can be appropriately controlled, the curable resin composition has an advantage that the viscosity is suppressed to a low level and the workability is improved.
  • alkyl (meth) acrylate having 1 carbon atom methyl methacrylate and methyl acrylate can be used.
  • alkyl (meth) acrylate having 4 carbon atoms n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, and t-butyl methacrylate can be used.
  • the shell layer forming monomer of the first embodiment contains both an alkyl (meth) acrylate having 1 carbon atom and an alkyl (meth) acrylate having 4 carbon atoms. It is preferable to have, and it is more preferable to contain 13% by weight to 55% by weight of the alkyl (meth) acrylate having 1 carbon atom and 20% by weight to 74% by weight of the alkyl (meth) acrylate having 4 carbon atoms.
  • the shell layer of the first embodiment preferably has both a structural unit derived from an alkyl (meth) acrylate having 1 carbon atom and a structural unit derived from an alkyl (meth) acrylate having 4 carbon atoms. It may contain 13% by weight to 55% by weight of a structural unit derived from an alkyl (meth) acrylate having 1 carbon atom and 20% by weight to 74% by weight of a structural unit derived from an alkyl (meth) acrylate having 4 carbon atoms. preferable.
  • the shell layer forming monomer of the first embodiment the total of the alkyl (meth) acrylate having 1 carbon atom and the alkyl (meth) acrylate having 4 carbon atoms is 100% by weight in 100% by weight of the monomer for forming the shell layer. You don't have to be.
  • the shell layer forming monomer of the first embodiment is (a) an alkyl (meth) acrylate having 1 carbon atom and (b) an alkyl (meth) having 4 carbon atoms in 100% by weight of the shell layer forming monomer.
  • the total of the monomers other than the acrylate and (c) the alkyl (meth) acrylate having 1 carbon atom and the alkyl (meth) acrylate having 4 carbon atoms may be 100% by weight. That is, the monomer for forming the shell layer of the first embodiment may contain a monomer other than the alkyl (meth) acrylate having 1 carbon atom and the alkyl (meth) acrylate having 4 carbon atoms.
  • the shell layer forming monomer contains an aromatic vinyl monomer and / or a vinyl cyan monomer, that is, when the shell layer contains a structural unit derived from an aromatic vinyl monomer and / or a structural unit derived from a vinyl cyan monomer.
  • the compatibility and dispersibility of the core-shell polymer particles (B) in the curable resin composition are improved.
  • the workability of the curable resin composition can be improved. Therefore, in the first embodiment, 100% by weight of the monomer for forming the shell layer is obtained.
  • the content of the aromatic vinyl monomer in the mixture may be 30% by weight or less, 20% by weight or less, 10% by weight or less, or 8% by weight or less.
  • the content of the structural unit derived from the aromatic vinyl monomer in 100% by weight of the shell layer may be 30% by weight or less, or may be 20% by weight or less. It may be 10% by weight or less, 8% by weight or less, or 6% by weight or less. Further, from the viewpoint of improving the workability of the curable resin composition, in the first embodiment, the content of the vinyl cyan monomer in 100% by weight of the monomer for forming the shell layer may be 10% by weight, and 8 It may be 5% by weight or less, 4% by weight or less, 3% by weight or less, or 2% by weight or less.
  • the content of the structural unit derived from the vinyl cyanomer in 100% by weight of the shell layer is preferably 10% by weight or less, may be 8% by weight or less, and may be 5% by weight or less. It may be 4% by weight or less, 3% by weight or less, or 2% by weight or less.
  • the shell layer forming monomer may further have a (meth) acrylate monomer having 5 or more carbon atoms.
  • the shell layer may further have a structural unit derived from the (meth) acrylate monomer having 5 or more carbon atoms.
  • Specific examples of the (meth) acrylate monomer having 5 or more carbon atoms include 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate.
  • Epoxy as a monomer for forming a shell layer from the viewpoint of chemically bonding with the component (A) in order to maintain a good dispersed state without agglomeration of the core-shell polymer particles (B) in the cured product or the curable resin composition Contains one or more selected from the group consisting of a group, an oxetane group, a hydroxyl group, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, a benzoxazine group, and a cyanate ester group. It is preferable to contain a reactive group-containing monomer, and in particular, a monomer having an epoxy group is preferable.
  • the shell layer is preferably a polymer obtained by graft-polymerizing a monomer for forming a shell layer containing a monomer component having an epoxy group onto a core layer (core polymer). According to this configuration, the obtained cured product has an advantage that it has excellent impact resistance and peeling adhesiveness.
  • the monomer having an epoxy group is preferably contained in an amount of 0% by weight to 90% by weight in 100% by weight of the monomer for forming a shell layer from the viewpoint of impact resistance peeling adhesiveness and storage stability, and is preferably from 1% by weight to 90% by weight. 50% by weight is more preferable, 2% by weight to 35% by weight is further preferable, and 3% by weight to 20% by weight is particularly preferable.
  • the shell layer preferably has a structural unit derived from a monomer having an epoxy group. Further, the shell layer preferably contains 0% by weight to 90% by weight of a structural unit derived from a monomer having an epoxy group in 100% by weight of the shell layer, and more preferably 1% by weight to 50% by weight. It is more preferably contained in an amount of% to 35% by weight, and particularly preferably contained in an amount of 3% by weight to 20% by weight.
  • the monomer having an epoxy group is preferably used for forming the shell layer, and more preferably used only for forming the shell layer.
  • a polyfunctional monomer having two or more radically polymerizable double bonds is used as the monomer for forming the shell layer, the swelling of the core-shell polymer particles is prevented in the curable resin composition, and the curable resin composition is also used. It is preferable because the viscosity of the product is low and the handleability tends to be good.
  • a polyfunctional monomer having two or more radically polymerizable double bonds is used as the monomer for forming the shell layer. It is preferable not to use it.
  • the polyfunctional monomer may be contained in, for example, 0% by weight to 20% by weight, preferably 1% by weight to 20% by weight, more preferably in 100% by weight of the monomer for forming the shell layer. Is 5% by weight to 15% by weight.
  • the monomer having a hydroxyl group as the reactive group-containing monomer include hydroxy linear alkyl (for example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. Meta) acrylate (particularly hydroxy linear C1-6 alkyl (meth) acrylate); caprolactone-modified hydroxy (meth) acrylate; hydroxy branching of ⁇ - (hydroxymethyl) methyl acrylate, ⁇ - (hydroxymethyl) ethyl acrylate and the like.
  • hydroxy linear alkyl for example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.
  • Meta acrylate (particularly hydroxy linear C1-6 alkyl (meth) acrylate); caprolactone-modified hydroxy (meth) acrylate; hydroxy branching of ⁇ - (hydroxy
  • Hydroxy group-containing (meth) such as mono (meth) acrylate of polyester diol (particularly saturated polyester diol) obtained from alkyl (meth) acrylate, divalent carboxylic acid (phthalic acid etc.) and dihydric alcohol (propylene glycol etc.) Examples include acrylates.
  • the monomer having an epoxy group examples include glycidyl group-containing vinyl monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and allyl glycidyl ether.
  • polyfunctional monomer having two or more radically polymerizable double bonds As a specific example of the polyfunctional monomer having two or more radically polymerizable double bonds, the same monomer as the above-mentioned polyfunctional monomer is exemplified, but allyl methacrylate and triallyl isocyanurate are preferable.
  • the shell layer of the first embodiment is preferably, for example, a polymer of the following shell layer forming monomers: (a) 0 to 50% by weight (preferably 1 to 50% by weight) of an aromatic vinyl monomer (particularly styrene). , More preferably 2 to 48% by weight), (b) vinyl cyan monomer (particularly acrylonitrile) 0 to 50% by weight (preferably 0 to 30% by weight, more preferably 10 to 25% by weight), (c) (meth). ) Acrylomonomer (particularly methylmethacrylate) 0-100% by weight (preferably 5-100% by weight, more preferably 70-95% by weight), and (d) Monomer having an epoxy group (particularly glycidylmethacrylate) 1-50% by weight. % (Preferably 2 to 35% by weight, more preferably 3 to 20% by weight) for shell layer forming monomer (total 100% by weight).
  • % Preferably 2 to 35% by weight, more preferably 3 to 20% by weight
  • the shell layer of the first embodiment is preferably, for example, a polymer of the following shell layer forming monomer: (a) 10 to 100 weight by weight of an alkyl (meth) acrylate monomer having 1 carbon atom (particularly methyl methacrylate). % (Preferably 11 to 95% by weight, particularly preferably 14 to 50% by weight), (b) 0 to 80% by weight (preferably 1 to 78% by weight) of an alkyl (meth) acrylate monomer (particularly butyl acrylate) having 4 carbon atoms.
  • % Particularly preferably 35 to 72% by weight
  • aromatic vinyl monomer particularly styrene
  • vinyl cyan monomer (d)
  • acrylonitrile is 10% by weight or less (preferably 5% by weight or less, more preferably 0% by weight)
  • a monomer having an epoxy group is 0 to 45% by weight (preferably 0 to 25% by weight).
  • a monomer for forming a shell layer (100% by weight in total).
  • the shell layer may be formed by containing other monomer components in addition to the above-mentioned monomer components.
  • the glass transition temperature of the shell layer (hereinafter, may be simply referred to as “Tg”) is preferably ⁇ 45 ° C. or higher and 110 ° C. or lower from the viewpoint of improving the workability of the curable resin composition. It is more preferably 40 ° C. or higher and 100 ° C. or lower, further preferably ⁇ 35 ° C. or higher and 50 ° C. or lower, and particularly preferably ⁇ 30 ° C. or higher and 10 ° C. or lower.
  • the graft ratio of the shell layer is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.
  • the curable resin composition may have a lower viscosity.
  • the calculation method of the graft ratio is as described below. First, the aqueous latex containing the core-shell polymer particles is coagulated and dehydrated, and finally dried to obtain a powder of the core-shell polymer particles. Next, 2 g of the powder of the core-shell polymer particles is immersed in 100 g of methyl ethyl ketone (MEK) at 23 ° C. for 24 hours, and then the MEK-soluble component is separated from the MEK-soluble component, and the methanol-insoluble component is further separated from the MEK-soluble component. Then, the graft ratio is calculated by obtaining the ratio of the MEK insoluble matter to the total amount of the MEK insoluble matter and the methanol insoluble matter.
  • MEK methyl ethyl ketone
  • ⁇ Manufacturing method of core-shell polymer particles ⁇ Manufacturing method of core layer
  • the formation of the core layer constituting the core-shell polymer particles (B) can be produced by, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization, etc., for example, International Publication No. 2005/0284546 and International Publication No. 2006/070664.
  • the method described in 1 can be used.
  • the intermediate layer can be formed by polymerizing a monomer for forming an intermediate layer by a known radical polymerization.
  • a monomer for forming an intermediate layer by a known radical polymerization.
  • the shell layer can be formed by polymerizing a monomer for forming a shell layer by a known radical polymerization.
  • a core layer or a polymer particle precursor composed by coating the core layer with an intermediate layer is obtained as an emulsion
  • the polymerization of the shell layer forming monomer is preferably carried out by an emulsion polymerization method, for example, internationally. It can be manufactured according to the method described in Publication No. 2005/08546.
  • Examples of the emulsifier (dispersant) that can be used in emulsifying polymerization include alkyl or aryl sulfonic acid represented by dioctyl sulfosuccinic acid and dodecylbenzene sulfonic acid, alkyl or aryl ether sulfonic acid, and alkyl or aryl represented by dodecyl sulfate.
  • Dispersants such as polyvinyl alcohol, alkyl-substituted cellulose, polyvinylpyrrolidone, and polyacrylic acid derivatives can be mentioned. These emulsifiers (dispersants) may be used alone or in combination of two or more.
  • emulsifier dispersant
  • a small amount of emulsifier (dispersant) as long as it does not interfere with the dispersion stability of the aqueous latex of the polymer particles.
  • the emulsifier (dispersant) can be easily removed by washing with water, and adverse effects on the finally obtained cured product can be easily prevented.
  • a known initiator that is, 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, ammonium persulfate and the like can be used as the thermally decomposable initiator. ..
  • organic peroxides such as t-butylperoxyisopropyl carbonate, paramentanhydroperoxide, cumenehydroperoxide, dicumyl peroxide, t-butylhydroperoxide, di-t-butyl peroxide, and t-hexyl peroxide.
  • Oxides; peroxides such as inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, and optionally sodium formaldehyde sulfoxylate, reducing agents such as glucose, and optionally iron sulfate (II).
  • a chelating agent such as disodium ethylenediamine tetraacetate, and if necessary, a phosphorus-containing compound such as sodium pyrophosphate can be used in combination with a redox-type initiator.
  • a redox-type initiator system When a redox-type initiator system is used, polymerization can be carried out even at a low temperature at which the peroxide does not substantially undergo thermal decomposition, and the polymerization temperature can be set in a wide range, which is preferable. Of these, it is preferable to use organic peroxides such as cumene hydroperoxide, dicumyl peroxide, and t-butyl hydroperoxide as the redox-type initiator.
  • the amount of the initiator used, and when the redox-type initiator is used, the amount of the reducing agent, transition metal salt, chelating agent, etc. used can be used within a known range. Further, when polymerizing a monomer having two or more radically polymerizable double bonds, a known chain transfer agent can be used in a known range. Additional surfactants can be used, but this is also in the known range.
  • Conditions such as polymerization temperature, pressure, and deoxidation at the time of polymerization can be applied within a known range.
  • the polymerization of the monomer for forming the intermediate layer may be carried out in one stage or in two or more stages.
  • a method of adding a monomer for forming an intermediate layer to an emulsion of a rubber elastic body constituting an elastic core layer at a time a method of continuously adding a monomer, or a method of adding an elastic core layer to a reactor in which a monomer for forming an intermediate layer is preliminarily charged. It is possible to adopt a method of performing polymerization after adding an emulsion of a constituent rubber elastic body.
  • the content of the core-shell polymer particles in the curable resin composition is determined from the balance between the ease of handling of the obtained curable resin composition and the effect of improving the toughness of the obtained cured product.
  • the amount is preferably 1 part to 100 parts by weight, more preferably 5 parts by weight to 90 parts by weight, still more preferably 10 parts by weight to 80 parts by weight, and 20 parts by weight with respect to 100 parts by weight of the epoxy resin (A). From 70 parts by weight is even more preferable, and 30 parts by weight to 60 parts by weight is particularly preferable.
  • the curable resin composition of the first embodiment contains aluminum hydroxide having an average particle size of 11 ⁇ m or more and 200 ⁇ m or less as the component (C) in the first component and / or the second component.
  • the curable resin composition of the first embodiment contains the component (C)
  • the obtained cured product is said to be excellent in thermal conductivity and flame retardancy (for example, flame retardancy evaluated by a vertical combustion test (UL94)).
  • UL94 vertical combustion test
  • the total weight of aluminum hydroxide (C) with respect to the total weight of the curable resin composition is 55% by weight or more and 85% by weight or less.
  • the component (C) may be contained only in the first component, may be contained only in the second component, or may be contained in both the first component and the second component. From the viewpoint of blending the component (C) in a large amount in the curable resin composition, the component (C) is preferably contained in at least the first component, and may be contained in both the first component and the second component. More preferred.
  • Aluminum hydroxide is a white powder crystal represented by a chemical formula of Al (OH) 3 or Al 2 O 3.3H 2 O, and is generally produced by the Bayer process using bauxite as a raw material. As for aluminum hydroxide, there are products having various average particle sizes depending on the classification.
  • the aluminum hydroxide used in the first embodiment has an average particle size of 11 ⁇ m or more and 200 ⁇ m or less.
  • the component (C) may be a coupling-treated component in order to improve the adhesiveness with the component (A). This makes it possible to improve physical properties such as impact resistance, strength, and water resistance of the obtained cured product.
  • These coupling treatment agents are not particularly limited, and examples thereof include silane-based coupling agents, chromium-based coupling agents, titanium-based coupling agents, aluminum-based coupling agents, zirconium-based coupling agents, and the like. Among these, a silane coupling agent is preferable, and an epoxy silane coupling agent is more preferable. Further, the coupling treatment agent may be used alone or in combination of two or more.
  • the average particle size of the component (C) is determined from the viewpoint of achieving both impact resistance and adhesive strength of the obtained cured product, and the component (C) in the curable resin composition before curing. From the viewpoint of suppressing sedimentation over time, it is essential that the size is 11 ⁇ m or more and 200 ⁇ m or less, preferably 12 ⁇ m or more and 150 ⁇ m or less, 13 ⁇ m or more and 100 ⁇ m or less, more preferably 15 ⁇ m or more and 50 ⁇ m or less, and 17 ⁇ m or more and 30 ⁇ m or less. Especially preferable.
  • the average particle size of the component (C) can be obtained from the measurement using the laser scattering method particle size measuring device, and is the particle size (Dp50) corresponding to the integrated particle size distribution rate of 50% by volume. ..
  • the average particle size of the entire component can be calculated.
  • the total weight of aluminum hydroxide (C) with respect to the total weight of the curable resin composition improves the obtained cured product properties (heat conductivity, flame retardancy, adhesive strength, and impact resistance).
  • the composition is 55% by weight or more and 85% by weight or less, preferably 57% by weight or more and 80% by weight or less, and 60% by weight or more and 76% by weight.
  • weight% or less is more preferable, 62% by weight or more and 73% by weight or less is further preferable, and 65% by weight or more and 70% by weight or less is particularly preferable.
  • the content (blending amount) of the aluminum hydroxide (C) with respect to 100 parts by weight of the epoxy resin (A) improves the obtained cured product characteristics (thermal conductivity, flame retardancy, adhesive strength, and impact resistance). From the viewpoint of improving the workability of the composition before curing, it is preferably 250 parts by weight or more and 750 parts by weight or less, more preferably 300 parts by weight or more and 700 parts by weight or less, and 350 parts by weight. It is more preferably 650 parts by weight or less, and particularly preferably 400 parts by weight or more and 600 parts by weight or less.
  • the component (C) one type may be used alone, or two or more types may be used in combination.
  • the polymer particles (B) and aluminum hydroxide (C) having a core-shell structure are preferably contained in the first component and / or the second component, respectively.
  • the polymer particles (B) and the aluminum hydroxide (C) may or may not be contained in the same component, but when the component (B) and the component (C) are contained, the first component is used. It is preferable that the component (B) and the component (C) are contained as one component, and the component (C) is contained as the second component.
  • the component (C) is blended in a large amount of 55% by weight or more and 85% by weight or less in the curable resin composition.
  • the average particle size of the component (C) is set to 11 ⁇ m or more and 200 ⁇ m or less, the effect of improving the impact resistance of the component (B) described above can be maintained high.
  • the reason is presumed to be appropriate from the theory of the plastic deformation region related to the rubber particle addition system as follows (see Hajime Kishi et al., "Journal of the Japan Adhesive Society, Vol. 40, No. 5, 177-183"). ).
  • KIC and ⁇ of the two-component epoxy adhesive toughened with the core-shell polymer particles are 1.5 MPa ⁇ m 1/2 and 50 MPa, respectively
  • rp is 48 ⁇ m
  • the plastic deformation region rp is approximately a number.
  • the size is about 10 to 100 ⁇ m.
  • the curable resin composition of the first embodiment is highly filled with aluminum hydroxide (C) in the range of 55% by weight or more and 85% by weight or less, and aluminum hydroxide having a small particle size of about several ⁇ m.
  • C aluminum hydroxide
  • the distance between the aluminum hydroxide particles is about several ⁇ m, a sufficient plastic deformation region cannot be secured, and a certain degree of plastic deformation region can be finally secured by the aluminum hydroxide particles larger than 10 ⁇ m, and the core-shell polymer. It is presumed that the toughness improving effect of the particles (B) was exhibited.
  • the curable resin composition of the first embodiment can contain a thermally conductive filler other than aluminum hydroxide.
  • a thermally conductive filler other than aluminum hydroxide For example, silica, alumina, aluminum nitride, boron nitride, silicon nitride, ZnO, SiC, BeO and the like can be mentioned.
  • the content of the thermally conductive filler other than aluminum hydroxide in the curable resin composition is preferably 1 to 300 parts by weight, more preferably 2 to 200 parts by weight, based on 100 parts by weight of the epoxy resin (A). ⁇ 100 parts by weight is particularly preferable.
  • the curable resin composition of the first embodiment can contain a flame retardant other than aluminum hydroxide.
  • a flame retardant other than aluminum hydroxide for example, magnesium hydroxide, ammonium polyphosphate, tricresyl phosphate, triethyl phosphate, triphenyl phosphate, tris (chloropropyl) phosphate, dimethyl methylphosphonate, brominated polyether polyol, ammonium carbonate, and melamine cyanurate, etc. Can be mentioned.
  • the content of the flame retardant other than aluminum hydroxide in the curable resin composition is preferably 1 to 100 parts by weight, more preferably 2 to 70 parts by weight, and 5 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin (A).
  • the weight part is particularly preferable.
  • the curable resin composition of the first embodiment contains an epoxy curing agent as the component (D) in the second component.
  • the component (D) is a compound (including an oligomer or a polymer) containing an active hydrogen group capable of reacting with the epoxy resin (A) to form a crosslink even at a low temperature of about room temperature.
  • the epoxy curing agent (D) has reactivity with an epoxy group near room temperature (for example, 5 ° C to 50 ° C or less).
  • the epoxy curing agent (D) has reactivity with an epoxy group at a low temperature as compared with an epoxy curing agent for heat curing.
  • the epoxy curing agent (D) is used in combination with the polymer particles (B) and the compound (G) described later, it does not require heat treatment at a high temperature of more than 50 ° C., and has excellent fast curing property and good adhesion. It has the effect of achieving both strength and strength.
  • the epoxy curing agent (D) of the first embodiment is not particularly limited, and various epoxy curing agents can be used.
  • the epoxy curing agent (D) of the first embodiment include (a) and (a-1) aromatic amines, aliphatic amines, alicyclic amines, amidoamines, amine-terminated polyethers and amine-terminated butadiene nitrile rubbers.
  • (a-2) their modified products, amine-based curing agents, and (b) mercaptan-based curing agents, and the like can be mentioned.
  • an amine-based curing agent is more preferable from the viewpoint of the adhesive strength of the obtained cured product.
  • the epoxy curing agent (D) of the first embodiment has (a) an aliphatic amine, an alicyclic amine, an amidoamine, and an amine terminal from the viewpoint of curability (fast curing) at room temperature.
  • an aliphatic amine, an alicyclic amine, an amidoamine, and an amine terminal from the viewpoint of curability (fast curing) at room temperature.
  • aliphatic amines aliphatic amines, alicyclic amines, amidamines, amine-terminated polyethers, amine-terminated butadiene nitrile rubbers, modified aliphatic amines, and modified alicyclic amines.
  • the epoxy curing agent (D) of the first embodiment is (a-1) an amine-terminated polyether and an amine-terminated butadiene nitrile rubber from the viewpoint of (a) impact resistance of the obtained cured product. It is preferable to contain one or more selected from the group consisting of (a-2) amine-terminated polyether and amine-terminated butadiene nitrile rubber, and more preferably one or more selected from the group consisting of (b). ) Further, from the viewpoint of curability, it is more preferable to contain an amine-terminated butadiene nitrile rubber, and further preferably an amine-terminated butadiene nitrile rubber.
  • the epoxy curing agent (D) of the first embodiment is (a-1) alicyclic amine, amidoamine, amine-terminated polyether from the viewpoint of (a) adhesive strength of the obtained cured product.
  • Amine-terminated butadiene nitrile rubber, modified alicyclic amine, modified amidamine, modified amine-terminated polyether and modified amine-terminated butadiene nitrile rubber may contain one or more selected from the group.
  • (a-2) alicyclic amines, amidamines, amine-terminated polyethers, amine-terminated butadiene nitrile rubbers, modified alicyclic amines, modified amidamines, modified amine-terminated polyethers and amine-terminated butadiene nitriles. It is more preferably one or more selected from the group consisting of modified rubbers, and (b-1) from the viewpoint of curability, (b-1) from the group consisting of alicyclic amines and amine-terminated butadiene nitrile rubbers.
  • the epoxy curing agent (D) of the first embodiment has an alicyclic amine, an amine-terminated butadiene nitrile rubber, a modified alicyclic amine and an amine-terminated butadiene nitrile from the viewpoint of adhesive strength and curability of the obtained cured product.
  • modified rubber products from alicyclic amines, amine-terminated butadiene nitrile rubbers, modified alicyclic amines, and modified amine-terminated butadiene nitrile rubbers. It is more preferable that the number is at least one selected from the group.
  • aromatic amine examples include meta-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone and the like.
  • aliphatic amine examples include chain aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diproprendamine, diethylaminopropylamine and hexamethylenediamine, and fatty aromatic amines such as methaxylenediamine. Can be mentioned.
  • alicyclic amine examples include N-aminoethylpyverazine, bis (4-amino-3-methylcyclohexyl) methane, mensendiamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, and spiroacetaldiamine. 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, norbornandiamine, tricyclodecanediamine, 1,3-bisaminomethylcyclohexane, etc. Can be mentioned.
  • the amidoamine is a compound produced by condensing a dimer of tall oil fatty acid (dimer acid) with a polyamine such as triethylenetetramine or tetraethylenepentamine, and commercially available amidoamines include Versamide 140 and Versamide. 115 and the like can be mentioned.
  • the amine-terminated polyether contains a main chain of polyether and has an amine-terminated amine group having preferably 1 to 4 (more preferably 1.5 to 3) amino groups and / or imino groups on average per molecule.
  • Examples of commercially available amine-terminated polyethers include Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, and Jeffamine T-5000 manufactured by Huntsman.
  • the amine-terminated butadiene nitrile rubber has an average of 1 to 4 (more preferably 1.5 to 3) amino groups and / or imino groups per molecule, and has an acrylonitrile monomer content in the main chain.
  • Examples of commercially available amine-terminated rubber include Hyper 1300X16 ATBN manufactured by CVC.
  • Modifications of the amine-based curing agent include polyamine epoxy resin adducts, which are reaction products of various polyamines such as the above-mentioned aliphatic amines and alicyclic amines with less than the same amount of epoxy resin, polyamines, methyl ethyl ketones, and isobutylmethyls. Examples thereof include ketimines which are products of dehydration reaction with ketones such as ketones.
  • the mercaptan-based curing agent includes pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris (2-).
  • pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris (2-).
  • the ratio of the number of moles of the epoxy group of the epoxy resin (A) to the number of moles of the active hydrogen group of the epoxy curing agent (D) (the number of moles of the epoxy group / the number of moles of the active hydrogen group) is. From the viewpoint of the quick-curing property of the curable resin composition and the adhesive strength and impact resistance of the obtained cured product, it is preferably 0.5 or more and 1.6 or less, and 1.1 or more and 1.6 or less. Is more preferable, 1.1 or more and 1.5 or less is further preferable, and 1.2 or more and 1.4 or less is particularly preferable.
  • the content (blending amount) of the epoxy curing agent (D) with respect to 100 parts by weight of the epoxy resin (A) is from the viewpoint of achieving both the adhesive strength and impact resistance of the obtained cured product, and the first component and the second component. From the viewpoint of ease of mixing with the components, it is preferably 15 parts by weight or more and 300 parts by weight or less, more preferably 20 parts by weight or more and 200 parts by weight or less, and 30 parts by weight or more and 150 parts by weight or less. It is more preferably 40 parts by weight or less, and particularly preferably 40 parts by weight or more and 100 parts by weight or less.
  • the component (D) one type may be used alone, or two or more types may be used in combination.
  • the curable resin composition of the first embodiment may or may not contain an aromatic amine.
  • the curable resin composition of the first embodiment preferably contains substantially no aromatic amine because the obtained cured product has excellent stretchable physical properties when heated.
  • substantially free of aromatic amines is intended that the content of aromatic amines in 100 parts by weight of the curable resin composition is 1000 ppm or less.
  • the aromatic amine include meta-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone and the like.
  • Epoxy curing agent that exhibits activity at high temperatures other than component (D)> An epoxy curing agent exhibiting activity at a high temperature other than an epoxy curing agent containing an active hydrogen group that can react with an epoxy resin at a low temperature (such as the above-mentioned amine-based curing agent and mercaptan-based curing agent) can be used for curing the first embodiment. It can be contained within a range that does not impair the curing rate of the sex resin composition.
  • the epoxy curing agent that exhibits activity at high temperatures include acid anhydride-based curing agents; boron trifluoride-amine complex; dicyandiamide; and organic acid hydrazide.
  • the acid anhydride-based curing agent requires a higher temperature than the amine-based curing agent, but has a long pot life, and the cured product has a good balance of physical properties such as electrical properties, chemical properties, and mechanical properties. .. More specifically, the acid anhydride-based curing agent includes polysevacinic acid polyanhydride, polyazelineic acid polyanhydride, succinic anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl-substituted succinic anhydride, and dodecenyl succinic acid.
  • Acid Anhydride Maleic Anhydrous, Tricarbaryl Anhydride, Nadic Anhydrous, Methylnadic Acid Anhydride, Linolic Acid Additive with Maleic Anhydrous, Alkylated Terminal alkylene Tetrahydrophthalic Anhydrous, Methyltetrahydrophthalic Anhydrous, Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, dichloromaleic anhydride, Chloronadic acid anhydride, chlorendic acid anhydride, maleic anhydride-grafted polybutadiene and the like can be mentioned.
  • boron trifluoride-amine complex examples include boron trifluoride-monoethylamine, boron trifluoride-piperidine, boron trifluoride-triethylamine, and boron trifluoride-aniline. can.
  • organic acid hydrazide examples include adipic acid dihydrazide, stearic acid dihydrazide, isophthalic acid dihydrazide, and semicarbazide.
  • the content (blending amount) of the epoxy curing agent exhibiting activity at high temperatures other than the component (D) in the curable resin composition is 0.1 part by weight or more and 30 parts by weight with respect to 100 parts by weight of the epoxy resin (A). It is preferably 0.5 parts by weight or more, more preferably 20 parts by weight or less, further preferably 1 part by weight or more and 15 parts by weight or less, and 2 parts by weight or more and 10 parts by weight or less. It is particularly preferable to have.
  • the curable resin composition of the first embodiment can contain an epoxy curing accelerator (E) in the first component and / or the second component.
  • the component (E) is a compound that is difficult to react with the epoxy resin (A) to form a crosslink, but the curing reaction between the epoxy resin (A) and the epoxy curing agent (D) can be accelerated.
  • the component (E) can be used in combination with an epoxy curing agent having high curability at room temperature, such as aliphatic amines, alicyclic amines, amidoamines, amine-terminated polyethers, amine-terminated butadiene nitrile rubbers, and modified products thereof. , Those showing a remarkable acceleration effect are preferable.
  • the component (E) may be contained only in the first component, may be contained only in the second component, or may be contained in both the first component and the second component. From the viewpoint of the storage stability of the curable resin composition, the component (E) is preferably contained only in the second component.
  • component (E) examples include C1-C12 alkylene imidazole, N-aryl imidazole, 2-methyl imidazole, 2-ethyl-2-methyl imidazole, N-butyl imidazole, 1-cyanoethyl-2-undecyl imidazolium.
  • Imidazoles such as trimellitate, an addition product of epoxy resin and imidazole; tertiary amines such as N, N-dimethylpiperazine, diazabicycloundecene, diazabicyclononen, triethylenediamine, benzyldimethylamine, triethylamine; 2- (Dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol incorporated into a poly (p-vinylphenol) matrix, p -Pphenols such as t-butylphenol, phenol, 4-methoxyphenol, resorcinol, catechol, 4-t-butylcatechol; and the like.
  • tertiary amines such as N, N-dimethylpiperazine, diazabicycloundecene, diazabicyclononen, triethylenediamine, benzyldimethyl
  • phenols are preferable from the viewpoint of the effect of improving curability, and divalent phenols such as resorcinol, catechol, and 4-t-butylcatechol are more preferable.
  • the component (E) may be used alone or in combination of two or more.
  • the blending amount of the epoxy curing accelerator (E) with respect to 100 parts by weight of the epoxy resin (A) is preferably 0.1 part by weight or more and 30 parts by weight or less from the viewpoint of improving curability and storage stability. It is more preferably 2 parts by weight or more and 20 parts by weight or less, further preferably 2 parts by weight or more and 15 parts by weight or less, and particularly preferably 3 parts by weight or more and 10 parts by weight or less.
  • the curable resin composition of the first embodiment can contain a silane coupling agent (F) in the first component and / or the second component.
  • the component (F) serves as an adhesive aid that holds both the surface of the adherend such as glass and metal and the curable resin composition.
  • silane coupling agent (F) examples include isocyanate group-containing silanes such as ⁇ -isocyanapropyltrimethoxysilane, ⁇ -isoxapropyltriethoxysilane, and ⁇ -isocyanapropylmethyldimethoxysilane; ⁇ -aminopropyltrimethoxy.
  • silane coupling agent (F) which is an epoxy group-containing silane may be referred to as "epoxy silane coupling agent (F1)".
  • the component (F) may be contained only in the first component, may be contained only in the second component, or may be contained in both the first component and the second component.
  • the group (a) and (F) are composed of isocyanate group-containing silanes, epoxy group-containing silanes (epoxysilane coupling agent (F1)) and isocyanurate silanes.
  • the component (F) is contained only in the first component, and the components (b) and (F) contain amino group-containing silanes, ketimine-type silanes and mercapto groups.
  • the component (F) is contained only in the second component.
  • the blending amount of the silane coupling agent (F) with respect to 100 parts by weight of the epoxy resin (A) is preferably 0.1 part by weight or more and 20 parts by weight or less from the viewpoint of improving adhesiveness and storage stability. It is more preferably 2 parts by weight or more and 15 parts by weight or less, further preferably 2 parts by weight or more and 10 parts by weight or less, and particularly preferably 3 parts by weight or more and 7 parts by weight or less.
  • the curable resin composition Since the obtained curable resin composition has excellent storage stability and the cured product obtained by curing the curable resin composition has excellent adhesive strength, the curable resin composition contains (F) as the first component. ), It is more preferable to contain an epoxy silane coupling agent (F1).
  • the curable resin composition can be used as a reinforcing agent such as blocked urethane for the purpose of further improving performance such as toughness, impact resistance, adhesive strength (shear adhesiveness (shear adhesive strength)), and peeling adhesiveness.
  • An epoxy-unmodified rubber-based polymer may be contained, if necessary.
  • the fortifier may be used alone or in combination of two or more.
  • Blocked urethane is an elastomer type, and is a variety of blocks containing a urethane group and / or a urea group, and all or part of the terminal isocyanate group of the compound having an isocyanate group at the terminal has an active hydrogen group. It is a compound capped with an agent. In particular, a compound in which all of the terminal isocyanate groups are capped with a blocking agent is preferable. For such a compound, for example, an organic polymer having an active hydrogen-containing group at the terminal is reacted with an excess polyisocyanate compound to have a urethane group and / or a urea group in the main chain and an isocyanate group at the terminal. It is obtained by capping all or a part of the isocyanate groups with a blocking agent having an active hydrogen group after making the polymer (urethane prepolymer) having the polymer (urethane prepolymer) or at the same time.
  • blocked urethane examples include the compounds described in International Publication No. 2016/163491.
  • the number average molecular weight of the blocked urethane is preferably 2000 to 40,000, more preferably 3000 to 30000, and particularly preferably 4000 to 20000 in terms of polystyrene-equivalent molecular weight measured by GPC.
  • the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 1 to 4, more preferably 1.2 to 3, and particularly preferably 1.5 to 2.5.
  • Blocked urethane can be used alone or in combination of two or more.
  • the amount of blocked urethane is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, and particularly preferably 5 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin (A).
  • the amount of blocked urethane is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, and particularly preferably 5 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin (A).
  • it is 1 part by weight or more, the effect of improving toughness, impact resistance, adhesiveness and the like is good, and when it is 50 parts by weight or less, the elastic modulus of the obtained cured product is high.
  • the rubber-based polymer may be contained (blended) in the curable resin composition without being modified so as not to react with the epoxy resin.
  • the rubber polymer examples include acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), hydrogenated nitrile rubber (HNBR), ethylene propylene rubber (EPDM), acrylic rubber (ACM), butyl rubber (IIR), and butadiene rubber.
  • NBR acrylonitrile butadiene rubber
  • SBR styrene butadiene rubber
  • HNBR hydrogenated nitrile rubber
  • EPDM ethylene propylene rubber
  • ACM butyl rubber
  • butadiene rubber Polyoxyalkylenes such as polypropylene oxide, polyethylene oxide and polytetramethylene oxide, and rubber-based polymers can be mentioned.
  • the rubber-based polymer preferably has a reactive group such as an amino group, a hydroxy group, or a carboxyl group at the end.
  • NBR and polyoxyalkylene are preferable from the viewpoint of adhesiveness and impact resistance peeling adhesiveness of the obtained curable resin composition, NBR
  • the glass transition temperature (Tg) of the rubber-based polymer is not particularly limited, but is preferably ⁇ 25 ° C. or lower, more preferably ⁇ 35 ° C. or lower, further preferably ⁇ 40 ° C. or lower, and particularly preferably ⁇ 50 ° C. or lower. ..
  • the number average molecular weight of the rubber-based polymer is preferably 1500 to 40,000, more preferably 3000 to 30000, and particularly preferably 4000 to 20000 in terms of polystyrene-equivalent molecular weight measured by GPC.
  • the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 1 to 4, more preferably 1.2 to 3, and particularly preferably 1.5 to 2.5.
  • the rubber polymer can be used alone or in combination of two or more.
  • the amount of the rubber-based polymer is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, and particularly preferably 5 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin (A).
  • the effect of improving toughness, impact resistance, adhesiveness and the like is good, and when it is 50 parts by weight or less, the elastic modulus of the obtained cured product is high.
  • the curable resin composition can contain an inorganic filler other than aluminum hydroxide (C).
  • an inorganic filler other than the component (C) for example, silicic acid and / or silicate can be used, and specific examples thereof include dry silica, wet silica, aluminum silicate, magnesium silicate, and silicic acid. Calcium, wollastonite, talc, etc. can be mentioned.
  • the dry silica is also called fumed silica, and is produced by chemically treating the surface-untreated hydrophilic fumed silica and the silanol group portion of the hydrophilic fumed silica with silane or siloxane.
  • hydrophobic fumed silica is preferable from the viewpoint of dispersibility in the component (A) and the component (D).
  • Humed silica can be imparted with thixotropic properties by being added to the first component and the second component, and exhibits a sagging prevention effect.
  • inorganic fillers other than the component (C) include reinforcing fillers such as dolomite and carbon black; heavy calcium carbonate, collagen carbonate, wollastonite, magnesium carbonate, titanium oxide, second oxide. Examples thereof include iron, fine aluminum powder, zinc oxide, and active zinc flower.
  • the inorganic filler other than the component (C) is surface-treated with a surface treatment agent.
  • a surface treatment agent By the surface treatment, the dispersibility of the inorganic filler other than the component (C) in the curable resin composition is improved, and as a result, various physical properties of the obtained cured product are improved.
  • the inorganic filler other than the component (C) one type may be used alone, or two or more types may be used in combination.
  • the content (usage amount) of the inorganic filler other than the component (C) is preferably 1 to 100 parts by weight, more preferably 2 to 70 parts by weight, and 5 to 40 parts by weight with respect to 100 parts by weight of the component (A). Parts are more preferable, and 7 to 20 parts by weight are particularly preferable.
  • the curable resin composition can contain a monoepoxide, if necessary.
  • the monoepoxide can function as a reactive diluent.
  • Specific examples of the monoepoxide include an aliphatic glycidyl ether such as butyl glycidyl ether, an aromatic glycidyl ether such as phenyl glycidyl ether and cresyl glycidyl ether, and an aromatic glycidyl ether such as 2-ethylhexyl glycidyl ether having 8 to 10 carbon atoms.
  • An ether consisting of an alkyl group and a glycidyl group for example, an ether composed of a phenyl group having 6 to 12 carbon atoms and a glycidyl group which can be replaced with an alkyl group having 2 to 8 carbon atoms such as p-tert butylphenyl glycidyl ether, for example, dodecyl.
  • Ether consisting of an alkyl group having 12 to 14 carbon atoms such as glycidyl ether and a glycidyl group; for example, an aliphatic glycidyl ester such as glycidyl (meth) acrylate and glycidyl maleate; versatic acid glycidyl ester, neodecanoic acid glycidyl ester, glycidyl laurate.
  • examples thereof include glycidyl esters of aliphatic carboxylic acids having 8 to 12 carbon atoms such as esters; and pt-butyl benzoic acid glycidyl esters.
  • the content (usage) of monoepoxide in the curable resin composition is preferably 0.1 to 20 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the component (A). 10 parts by weight is more preferable, and 1 to 5 parts by weight is particularly preferable. When it is 0.1 part by weight or more, the effect of reducing the viscosity is good, and when it is 20 parts by weight or less, the physical properties such as adhesiveness are good.
  • the curable resin composition may contain other compounding components (additives), if necessary.
  • Other compounding components include radical curable resins, thermoplastic initiators, photocurable resins, photopolymerization initiators, azotype chemical foaming agents, expanders such as heat-expandable microballoons, and fibers such as aramid-based pulp. Pulps, colorants such as pigments and dyes, extender pigments, UV absorbers, antioxidants, stabilizers (antigels), plastics, leveling agents, defoaming agents, antistatic agents, lubricants, thickeners. , Low shrinkage agent, organic filler, thermoplastic resin, desiccant, dispersant, solvent and the like.
  • the “content” of each component in the curable resin composition may be read as the “blending amount” of each component.
  • the method for producing the curable resin composition is not particularly limited.
  • a composition containing an epoxy resin (A) as a curable resin as the first component of the curable resin composition and core-shell polymer particles as the component (B) (hereinafter, also referred to as “polymer particle-containing composition”).
  • the polymer particle-containing composition is preferably a composition in which the core-shell polymer particles (B) are dispersed in the state of primary particles.
  • compositions in which the core-shell polymer particles (B) are dispersed in the state of primary particles
  • various methods can be used, for example, the composition was obtained in the state of an aqueous latex.
  • a method of removing unnecessary components such as water after contacting the core-shell polymer particles (B) with the component (A), the core-shell polymer particles (B) extracted after once extracting the core-shell polymer particles (B) into an organic solvent.
  • the component (A) are mixed and then the organic solvent is removed.
  • Specific methods for producing the polymer particle-containing composition include, in order, an aqueous latex containing the core-shell polymer particles (B) (specifically, a reaction mixture after producing the core-shell polymer particles (B) by emulsification polymerization).
  • the obtained aggregates of the core-shell polymer particles (B) are mixed with the organic solvent again, and the organic solvent of the core-shell polymer particles (B) is obtained.
  • It is preferably prepared by including a second step of obtaining a dispersion liquid and a third step of further mixing the organic solvent dispersion liquid with the component (A) and then distilling off the organic solvent from the obtained mixture. ..
  • the component (A) is liquid at 23 ° C. because the third step is facilitated.
  • “Liquid at 23 ° C” means that the softening point is 23 ° C or lower, and shows fluidity at 23 ° C.
  • the component (C) In contrast to the composition (polymer particle-containing composition) in which the core-shell polymer particles (B) are dispersed in the component (A) obtained through the above steps in the state of primary particles, the component (C) and, if necessary, are required.
  • the additional component (A) and other components such as component (E) and / or component (F)
  • a stirrer such as a planetary mixer
  • the core-shell polymer particles (B) are primary.
  • the first component of the curable resin composition dispersed in the state of particles can be obtained.
  • the component (D), the component (C), and other components are mixed with a stirrer such as a planetary mixer.
  • the second component of the curable resin composition can be obtained by mixing the mixture.
  • the first component and the second component containing or not containing the core-shell polymer particles (B) are mixed and curable.
  • An embodiment of producing a resin composition has been described.
  • the first component and the second component containing the core-shell polymer particles (B) are mixed to produce a curable resin composition. May be good.
  • the first component containing the epoxy resin (A) and the second component containing the epoxy curing agent (D) are prepared separately. It is preferable that the first component and the second component are mixed immediately before use (which can be said to be immediately before the bonding operation of the adherend or immediately before the curing of the curable resin composition).
  • a disperser having a high mechanical shearing force such as a three-paint roll, a roll mill, and a kneader, is used to obtain powdery core-shell polymer particles (B) obtained by solidifying by a method such as salting out and then drying. It can be used to redisperse in component (A) or in component (D). At this time, by applying a mechanical shearing force at a high temperature, the component (B) can be efficiently redispersed.
  • the temperature at which the component (B) is redispersed in the component (A) or the component (D) is preferably 50 to 200 ° C, more preferably 70 to 170 ° C, further preferably 80 to 150 ° C, and 90 to 90 to. 120 ° C. is particularly preferable.
  • a cured product can be obtained by uniformly mixing the first component and the second component of the curable resin composition using a static mixer or the like, and curing the obtained mixture at a curing temperature described later. Since it is considered that the core-shell polymer particles (B) are uniformly dispersed in the first component obtained by the above-mentioned method, the core-shell polymer is considered to be uniformly dispersed in the cured product obtained by using such a first component. It is considered that the particles (B) are uniformly dispersed.
  • a cured product obtained by curing the curable resin composition is also an embodiment of the present invention (for example, the first to third embodiments).
  • the cured product according to one embodiment of the present invention has an advantage of being excellent in adhesive strength.
  • the cured product according to one embodiment of the present invention also has an advantage of being excellent in impact resistance peeling adhesiveness.
  • the curable resin composition can be applied to the substrate by any method. According to a preferred embodiment, it can be applied at a low temperature of about room temperature, and it can also be heated and applied if necessary.
  • the first component and the second component of the curable resin composition can be applied while being uniformly mixed by a static mixer connected to the tip of the device after being discharged from the fixed quantity discharge device. It is also possible to fill each cartridge of the double cartridge type caulking gun to which the static mixer is connected to the tip with the first component and the second component of the curable resin composition, and manually extrude and apply the curable resin composition. It can also be extruded onto the substrate in the form of beads, monofilaments or swirls using a coating robot.
  • the viscosity of the curable resin composition at the coating temperature is not particularly limited, and is preferably about 150 to 600 Pa ⁇ s in the extruded bead method and preferably about 100 Pa ⁇ s in the swirl coating method. In the high volume coating method using a speed flow device, about 20 to 400 Pa ⁇ s is preferable.
  • the curable resin composition is preferably used as a material for an adhesive because the obtained cured product has excellent adhesive strength and impact resistance.
  • An adhesive containing a curable resin composition is also an embodiment of the present invention (for example, first to third embodiments).
  • the adhesive according to one embodiment of the present invention (for example, the first to third embodiments) is said to have excellent quick-curing properties, and the obtained cured product (adhesive layer) has excellent adhesive strength and impact resistance. Has advantages.
  • a base material such as wood, plastic, or glass
  • the base material include various plastic substrates such as steel materials such as cold rolled steel and hot-dip zinc-plated steel, aluminum materials such as aluminum and coated aluminum, general-purpose plastics, engineering plastics, and composite materials such as CFRP and GFRP. Be done.
  • the adhesive according to one embodiment of the present invention is preferably an adhesive for a secondary battery.
  • the method described in International Publication No. 2016/137303 will be given as a method for manufacturing a battery module using an adhesive containing a curable resin composition, and a site and method for applying the adhesive to the module. Can be done.
  • the curable resin composition has excellent adhesiveness. Therefore, it is preferable to use the curable resin composition as an adhesive for adhering (bonding) two substrates.
  • the laminate thus obtained includes two substrates and an adhesive layer in which an adhesive containing a curable resin composition is cured between the two substrates.
  • the adhesive layer is also an embodiment of the present invention (for example, first to third embodiments).
  • the laminate according to one embodiment of the present invention (for example, the first embodiment to the third embodiment) can be obtained by, for example, the following method: (1) An adhesive containing a curable resin composition, one of them or Apply to both substrates; (2) contact the substrates so that the adhesive is placed between the two substrates to be joined; (3) cure the adhesive in that state 2 Join the sheets of substrate.
  • the laminate according to one embodiment of the present invention (for example, the first embodiment to the third embodiment) thus obtained is preferable because it exhibits high adhesive strength.
  • curable resin composition and the adhesive containing the curable resin composition are excellent in toughness, they are suitable for joining dissimilar substrates having different linear expansion coefficients.
  • the curable resin composition and the adhesive containing the curable resin composition can also be used for joining components for aerospace, particularly exterior metal components.
  • the curing temperature of the curable resin composition is not particularly limited, but is preferably 5 ° C to 60 ° C, more preferably 10 ° C to 50 ° C, and further preferably 15 ° C to 40 ° C from the viewpoint of easy curing near room temperature. It is preferable, and 20 ° C to 30 ° C is particularly preferable.
  • the curable resin composition is a structural adhesive for vehicles and aircraft, an adhesive for secondary batteries such as EV battery cells, an adhesive such as a structural adhesive for wind power generation, a paint, and a glass fiber for obtaining a composite material. And / or materials for laminating with carbon fibers, materials for printed wiring boards, solder resists, interlayer insulating films, build-up materials, adhesives for FPCs, electrical insulating materials such as encapsulants for electronic parts such as semiconductors and LEDs, Diebond materials, underfills, mounting materials for semiconductors (eg ACF, ACP, NCF, NCP, etc.), encapsulants for display equipment (eg liquid crystal panels and OLED displays) and lighting equipment (eg OLED lighting), concrete repair It is preferably used for applications such as composite materials.
  • the curable resin composition is particularly useful as an adhesive for a secondary battery.
  • the curable resin composition When used as a composite material, it can be used in a wide range of molding methods without any particular limitation. Specifically, the hand lay-up method, spray-up method, pull-fusion method, filament winding method, matched die method, prepreg method, centrifugal molding method, liquid molding method, hot press method, casting method, injection molding method, continuous method. It can be molded by a known molding method such as a lamination method, a resin transfer molding (RTM) method, a vacuum bag molding method, or a cold press method.
  • the curable resin composition is suitable as a composite material with glass fiber or carbon fiber, and as a raw material for BMC (bulk molding compound) or SMC (sheet molding compound).
  • the application site is not particularly limited, but specifically, artificial marble applications such as kitchen counters, wash bowls, bathtubs, and wall materials, resin concrete, tanks, pressure vessels, industrial pipes, factory pipes, joints, and pipes. , Corrugated sheet, helmet, pole, blade for wind power generation, piping of pump oil sampling system of oil field such as soccer rod pump, electrical parts, automobile parts, railroad vehicle parts, ship parts, aircraft parts, industrial machinery parts, construction materials, It is suitable as a structural member for furniture, musical instruments, etc., and as a sheet material for decorative boards, decorative sheets, etc.
  • the second embodiment relates to a two-component curable resin composition containing an epoxy resin and an adhesive containing the same.
  • thermosetting one-component curable resin composition can reduce the viscosity of the composition by raising the temperature at the time of application, but the two-component curable resin composition that can be cured at a low temperature is applied. It is desirable to lower the temperature at the time, and a two-component curable resin composition having a low viscosity and good workability is desired.
  • a heat conductive filler such as aluminum hydroxide or alumina
  • the viscosity of the curable resin composition may increase and the workability may decrease.
  • a cured product of an epoxy resin widely used in electric devices has a problem that it has a low fracture toughness and exhibits a very brittle property.
  • Patent Document 1 did not have sufficient impact resistance and had room for improvement. Further, Patent Documents 2 to 3 do not describe a technique for improving workability in an epoxy-based curable resin composition in which an epoxy resin and a large amount of aluminum hydroxide are combined.
  • the invention according to the second embodiment has low viscosity and good workability while blending an epoxy resin and aluminum hydroxide, and has excellent thermal conductivity, flame retardancy, and adhesive strength. It is an object of the present invention to provide a curable resin composition of a two-component type which gives a cured product as shown and can be cured at room temperature or a low temperature close to room temperature.
  • the present inventors have made a two-component type containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
  • a two-component type containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
  • the invention according to the second embodiment is a two-component curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
  • the curable resin composition further contains the polymer particles (B) having a core-shell structure and the aluminum hydroxide (C), and the aluminum hydroxide (C) with respect to the total weight of the curable resin composition.
  • the total weight of the polymer particles (B) having the core-shell structure is 55% by weight or more and 85% by weight or less, and the average particle size of the polymer particles (B) having the core-shell structure is 0.15 ⁇ m or more and 0.30 ⁇ m or less.
  • the weight ratio of the core layer / shell layer of (B) is 65/35 to 92/8, and the polymer particles (B) having the core-shell structure have an alkyl (meth) acrylate having a shell layer having 1 to 4 carbon atoms. It is a copolymer of a monomer component containing 55 wt% or more of, and as a monomer component constituting the shell layer, an alkyl (meth) acrylate having 1 carbon atom is used in an amount of 10 to 100 wt% and an alkyl (meth) acrylate having 4 carbon atoms is used.
  • the present invention relates to a curable resin composition containing 0 to 80 wt%.
  • the cured product obtained by the epoxy resin and a high amount of aluminum hydroxide exhibits excellent thermal conductivity, flame retardancy, and adhesive strength.
  • the viscosity of the curable resin composition can be lowered. That is, according to the second embodiment, a cured product exhibiting excellent thermal conductivity, flame retardancy, and adhesive strength can be provided, the viscosity is low, the workability is good, and even at room temperature or a low temperature close to room temperature. It is possible to provide a curable resin composition of a two-component type that can be cured.
  • the second embodiment is curable containing at least an epoxy resin (A), polymer particles (B) having a core-shell structure, aluminum hydroxide (C), and an epoxy curing agent (D). It is a resin composition.
  • the curable resin composition according to the second embodiment contains a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D) as essential components, and further, if necessary. It is a two-component curable resin composition in which other components such as a color toner and a curability adjusting agent are mixed and used immediately before use. Further, the curable resin composition according to the second embodiment further contains polymer particles (B) having a core-shell structure and aluminum hydroxide (C).
  • the polymer particles (B) and aluminum hydroxide (C) having a core-shell structure are preferably contained in the first component and / or the second component, respectively.
  • the curable resin composition according to the second embodiment may contain another component, if necessary, in addition to the first component and the second component.
  • the cured product obtained by the epoxy resin and a high amount of aluminum hydroxide can exhibit excellent thermal conductivity, flame retardancy, and adhesive strength. Further, in the curable resin composition according to the second embodiment, the viscosity of the curable resin composition can be lowered by using polymer particles having a core-shell structure having a specific average particle diameter and a specific composition. ..
  • the curable resin composition of the second embodiment contains polymer particles having a core-shell structure as the component (B) in the first component and / or the second component.
  • the average particle size of the core-shell polymer particles (B) is 0.15 ⁇ m or more and 0.30 ⁇ m or less from the viewpoint of industrial productivity and workability of the curable resin composition. It is preferably 0.16 ⁇ m or more and 0.28 ⁇ m or less, more preferably 0.17 ⁇ m or more and 0.27 ⁇ m or less, and further preferably 0.18 ⁇ m or more and 0.25 ⁇ m or less.
  • the average particle size of the core-shell polymer particles (B) is (a) 0.15 ⁇ m or more, the viscosity of the curable resin composition becomes lower, so that the workability becomes better.
  • the thickness is 0.30 ⁇ m or less, the polymerization time of the component (B) becomes shorter and the industrial productivity becomes higher.
  • the ratio of the weight of the core layer to the weight of the shell layer makes the workability of the curable resin composition better. Moreover, since the impact resistance of the cured product becomes better, it is essential that the content is 65/35 to 92/8, preferably 68/32 to 91/9, and 70/30 to 90 /. It is more preferably 10.
  • the shell layer has 1 to 1 carbon atoms in 100% by weight of the monomer component (monomer for forming the shell layer). It is essential that the copolymer is obtained by polymerizing a monomer component (monomer for forming a shell layer) containing 55% by weight or more of the alkyl (meth) acrylate of 4, and the monomer component containing 65% by weight or more is polymerized. It is preferably a copolymer obtained by polymerizing a monomer component containing 75% by weight or more, and more preferably a copolymer obtained by polymerizing a monomer component containing 78% by weight or more. Is more preferable, and a copolymer formed by polymerizing a monomer component containing 83% by weight or more is particularly preferable.
  • the shell layer of the second embodiment contains 55% by weight or more of a structural unit derived from an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of the shell layer. It is preferably contained in an amount of 7% by weight or more, more preferably 75% by weight or more, further preferably 78% by weight or more, and particularly preferably 83% by weight or more.
  • the monomer component (monomer for forming the shell layer) constituting the shell layer of the core-shell polymer particles (B) contains 10% by weight of an alkyl (meth) acrylate having 1 carbon atom in 100% by weight of the monomer component. It is essential to contain ⁇ 100% by weight, preferably 11% by weight to 95% by weight, more preferably 12% by weight to 92% by weight, and preferably 13% by weight to 55% by weight. It is more preferably contained in an amount of 14% by weight to 50% by weight, and particularly preferably contained in an amount of 14% by weight to 50% by weight.
  • the monomer component (monomer for forming the shell layer) constituting the shell layer of the core-shell polymer particles (B) contains no alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the monomer component. It is essential to contain 1% by weight to 80% by weight, preferably 1% by weight to 89% by weight, more preferably 1% by weight to 88% by weight, and 1% to 87% by weight. It is preferably 1% by weight to 86% by weight, more preferably 1% by weight to 78% by weight, more preferably 2% by weight to 76% by weight, and 5% by weight to 76% by weight.
  • the shell layer forming monomer constituting the shell layer of the core-shell polymer particles (B) contains an alkyl (meth) acrylate having 1 carbon atom and / or an alkyl (meth) acrylate having 4 carbon atoms in the above range, the core-shell polymer Since the interaction between the particles (B) and the component (C) can be appropriately controlled, the curable resin composition has an advantage that the viscosity is suppressed to a low level and the workability is improved.
  • the content of aluminum hydroxide (C) in the curable resin composition is 55% by weight or more and 85% by weight or less in 100% by weight of the total weight of the curable resin composition, as described later. It is very high and therefore the component (B) has a high probability of coming into contact with the component (C). Therefore, in the second embodiment, the shell polymer of the component (B) has a monomer composition such that the interaction with the surface of the highly polar component (C) is small, so that the viscosity of the curable resin composition is small. It is important to keep it low and improve workability.
  • the shell layer of the core-shell polymer particles (B) has a specific configuration as described above.
  • the shell layer of the core-shell polymer particles (B) to be mixed with the epoxy resin generally has a composition that enhances compatibility with the epoxy resin, but the above-mentioned component (B) is specified in the second embodiment.
  • the average particle size and the specific composition of the above are considered to be a unique design optimized in combination with the compounding composition of the second embodiment containing a large amount of aluminum hydroxide (C).
  • the specific average particle size and the specific composition of the component (B) described above in the second embodiment are unique configurations found by the present inventor during the diligent study on the second embodiment.
  • the shell layer forming monomer of the second embodiment contains both an alkyl (meth) acrylate having 1 carbon atom and an alkyl (meth) acrylate having 4 carbon atoms. It is preferable to have, and it is more preferable to contain 13% by weight to 55% by weight of the alkyl (meth) acrylate having 1 carbon atom and 20% by weight to 74% by weight of the alkyl (meth) acrylate having 4 carbon atoms.
  • the shell layer of the second embodiment preferably has both a structural unit derived from an alkyl (meth) acrylate having 1 carbon atom and a structural unit derived from an alkyl (meth) acrylate having 4 carbon atoms. It may contain 13% by weight to 55% by weight of a structural unit derived from an alkyl (meth) acrylate having 1 carbon atom and 20% by weight to 74% by weight of a structural unit derived from an alkyl (meth) acrylate having 4 carbon atoms. preferable.
  • the monomer component of the second embodiment does not need to have a total of 100% by weight of the alkyl (meth) acrylate having 1 carbon atom and the alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the monomer component.
  • the monomer component of the second embodiment is (a) an alkyl (meth) acrylate having 1 carbon atom, (b) an alkyl (meth) acrylate having 4 carbon atoms, and (c) in 100% by weight of the monomer component.
  • the total of the monomers other than the alkyl (meth) acrylate having 1 carbon atom and the alkyl (meth) acrylate having 4 carbon atoms may be 100% by weight. That is, the monomer component of the second embodiment may contain a monomer other than the alkyl (meth) acrylate having 1 carbon atom and the alkyl (meth) acrylate having 4 carbon atoms.
  • the shell layer-forming monomer is, for example, an aromatic vinyl monomer and / or vinyl. It may further have a cyan monomer.
  • the fragrance in 100% by weight of the monomer for forming the shell layer
  • the content of the group vinyl monomer is preferably 30% by weight or less, more preferably 20% by weight or less, more preferably 10% by weight or less, more preferably 8% by weight or less, still more preferably 6% by weight or less, and 5% by weight or less.
  • the content of the vinyl cyan monomer in 100% by weight of the monomer for forming the shell layer is preferably 10% by weight or less, preferably 8% by weight. % Or less is more preferable, 5% by weight or less is more preferable, 4% by weight or less is more preferable, 3% by weight or less is more preferable, 2% by weight or less is further preferable, 1% by weight or less is further preferable, and 0% by weight is used. It is particularly preferable that the following (that is, it does not contain a vinyl cyan monomer).
  • the shell layer is a copolymer formed by polymerizing a shell layer forming monomer (100% by weight in total) in which (% by weight, more preferably 3 to 20% by weight) is combined.
  • the curable resin composition of the second embodiment contains aluminum hydroxide as the component (C) in the first component and / or the second component.
  • the curable resin composition of the second embodiment contains the component (C)
  • the obtained cured product is said to be excellent in thermal conductivity and flame retardancy (for example, flame retardancy evaluated by a vertical combustion test (UL94)).
  • UL94 vertical combustion test
  • the total weight of aluminum hydroxide (C) with respect to the total weight of the curable resin composition is 55% by weight or more and 85% by weight or less.
  • the average particle size of the component (C) is not particularly limited.
  • the average particle size of the component (C) is determined from the viewpoint of achieving both impact resistance and adhesive strength of the obtained cured product, and the component (E) in the curable resin composition before curing. From the viewpoint of suppressing sedimentation over time, it is preferably 11 ⁇ m or more and 200 ⁇ m or less, more preferably 12 ⁇ m or more and 150 ⁇ m or less, further preferably 13 ⁇ m or more and 100 ⁇ m or less, further preferably 15 ⁇ m or more and 50 ⁇ m or less, and 17 ⁇ m or more and 30 ⁇ m or less. Especially preferable.
  • the total weight of the aluminum hydroxide (C) with respect to the total weight of the curable resin composition improves the obtained cured product properties (heat conductivity, flame retardancy, adhesive strength, and impact resistance).
  • the composition is 55% by weight or more and 85% by weight or less, preferably 57% by weight or more and 80% by weight or less, and 60% by weight or more and 76% by weight.
  • weight% or less is more preferable, 62% by weight or more and 73% by weight or less is further preferable, and 65% by weight or more and 70% by weight or less is particularly preferable.
  • the curable resin composition of the second embodiment may contain a heat conductive filler other than aluminum hydroxide (other than component (C)) and / or a flame retardant other than aluminum hydroxide (other than component (C)).
  • a heat conductive filler other than aluminum hydroxide other than component (C)
  • a flame retardant other than aluminum hydroxide other than component (C)
  • the curable resin composition of the second embodiment contains an epoxy curing agent as the component (D) in the second component.
  • Each embodiment of the "epoxy curing agent (D)" in the second embodiment (type, content, preferred embodiments thereof, etc.) is described in the section ⁇ Epoxy curing agent (D)> in the first embodiment. Since it is the same as the above, the description is incorporated and the description is omitted here.
  • the curable resin composition of the second embodiment can contain an epoxy curing accelerator (E) in the first component and / or the second component.
  • an epoxy curing accelerator (E) in the first component and / or the second component.
  • Each aspect (type, content, preferred embodiment thereof, etc.) of the "epoxy curing accelerator (E)" in the second embodiment will be described in the section ⁇ Epoxy curing accelerator (E)> in the first embodiment. Since it is the same as the one described above, the description is used and the description is omitted here.
  • the curable resin composition of the second embodiment can contain a silane coupling agent (F) in the first component and / or the second component.
  • a silane coupling agent (F) in the first component and / or the second component.
  • Each aspect (type, content, preferred embodiment thereof, etc.) of the "silane coupling agent (F)" in the second embodiment will be described in the section ⁇ Silane coupling agent (F)> in the first embodiment. Since it is the same as the one described above, the description is used and the description is omitted here.
  • a third embodiment relates to a curable resin composition, a cured product, an adhesive and a laminate.
  • the two-component epoxy resin composition using an aliphatic amine-based curing agent cures at a low temperature. Therefore, the two-component epoxy resin composition does not require heating equipment or the like for curing.
  • the cured product obtained by curing a two-component epoxy resin composition is excellent in strength, heat resistance, water resistance, chemical resistance, electrical insulation, etc., and is therefore used in a wide range of applications such as industrial and civil engineering and construction. Has been done.
  • various two-component epoxy resin compositions have been developed (for example, Patent Document 4).
  • the quick-curing property of the two-component adhesive is important.
  • a two-component adhesive used for fixing a battery of an electric vehicle (EV) is also required to have quick curing property.
  • the third embodiment has been made in view of the above problems, and an object thereof is to provide a novel two-component or multi-component curable resin composition having excellent quick-curing properties.
  • epoxy resin (A) In addition to the specific epoxy curing agent, it has one aromatic ring in one molecule and at least two phenolic hydroxyl groups, and is a tertiary located at the ortho position with respect to the phenolic hydroxyl groups.
  • the number of alkyl groups is 0 or 1 in one molecule, a two-component type or multi-component type curable resin composition having excellent rapid curability can be obtained.
  • the epoxy curing agent (D) and the epoxy curing agent (D) are aliphatic amines, alicyclic amines, amidamines, amine-terminated polyethers, and amine-terminated. At least one selected from the group consisting of butadiene nitrile rubber, modified aliphatic amines, modified alicyclic amines, modified amidamines, modified amine-terminated polyethers and modified amine-terminated butadiene nitrile rubbers. That is all.
  • curable resin composition according to the third embodiment may be referred to as a "third curable resin composition”.
  • the third curable resin composition has the above-mentioned structure, it has an advantage that it can exhibit excellent quick-curing property.
  • "fast curing property” is intended to be a property that can be cured in a short time (for example, about several minutes to several hours) at around room temperature (for example, 5 ° C to 50 ° C). That is, the third curable resin composition does not require heat treatment at a high temperature of more than 50 ° C., and is used at a temperature of 5 ° C. to 50 ° C. or lower for a short time (for example, about several minutes to several hours). It has the advantage that it can be cured with.
  • the third curable resin composition contains the epoxy resin (A) as the first component, and in other words, it can be said to be a two-component epoxy resin composition or a multi-component epoxy resin composition. Therefore, the third curable resin composition also has an advantage of being excellent in adhesive strength.
  • a two-component urethane-based composition containing a urethane resin as a main component is also known.
  • the two-component urethane-based composition has a fast-curing property that can be cured in a short time as compared with the two-component epoxy resin composition.
  • the two-component urethane-based composition has a problem that the strength and heat resistance of the obtained cured product tend to be insufficient as compared with the two-component epoxy resin composition.
  • the two-component adhesive used to fix the battery of an electric vehicle (EV) is often required to have both quick curing and strength.
  • the third curable resin composition has excellent adhesive strength and quick curability. Therefore, the third curable resin composition can be particularly preferably used as a two-component adhesive for fixing a battery of an electric vehicle (EV).
  • EV electric vehicle
  • the third curable resin composition contains polymer particles (B) having a core-shell structure including a core layer and a shell layer, so that the third curable resin composition is impact-resistant and peel-bonded. It also has the advantage of being excellent in sex.
  • the curable resin composition of the third embodiment contains polymer particles having a core-shell structure as the component (B) in the first component and / or the second component.
  • the polymer particles (B) having a core-shell structure in the third embodiment for example, the composition of the core layer, the composition of the shell layer and their preferred embodiments, etc.
  • the ⁇ polymer having a core-shell structure in the first embodiment etc. Since it is the same as that described in the section of particle (B)>, the description thereof is incorporated, and the description thereof is omitted here.
  • the curable resin composition of the third embodiment has (i) one aromatic ring in one molecule as (G) component in the first component and / or the second component, and (ii) at least. It contains a compound (G) having two phenolic hydroxyl groups.
  • the number of tertiary alkyl groups located at the ortho position with respect to the phenolic hydroxyl group is 0 or 1 in one molecule.
  • the compound (G) has an effect of improving the curing rate of the curable resin composition while maintaining good adhesive strength when used in combination with the polymer particles (B) and the epoxy curing agent (D) described later. Further, the curable resin composition of the third embodiment needs to be heat-treated at a high temperature of more than 50 ° C. by containing the compound (G) together with the polymer particles (B) and the epoxy curing agent (D) described later. It exhibits excellent fast-curing properties and can be cured in a short time as compared with a curable resin composition containing no compound (G).
  • the component (G) may be contained only in the first component, may be contained only in the second component, or may be contained in both the first component and the second component. From the viewpoint of the storage stability of the curable resin composition, the component (G) is preferably contained only in the second component.
  • the aromatic ring means a cyclic hydrocarbon and a heterocyclic compound satisfying Hückel's rule.
  • Specific examples of the aromatic ring include benzene, naphthalene, azulene, anthracene, pyrrole, pyridine, furan, thiophene and the like.
  • benzene is particularly preferable from the viewpoints of the effect of improving the quick-curing property and the availability.
  • the phenolic hydroxyl group means a hydroxyl group bonded to a carbon atom of an aromatic ring.
  • the positions of the two phenolic hydroxyl groups are not particularly limited and may be located on any carbon atom of the aromatic ring.
  • the two phenolic hydroxyl groups may be in any positional relationship of the ortho-position, the meta-position, or the para-position with respect to each other, but exhibit an excellent effect of improving fast-curing property. Therefore, it is more preferable to have an ortho-position or a meta-position positional relationship, and it is further preferable to have a meta-position positional relationship.
  • Compound (G) may have at least one additional substituent on the aromatic ring in addition to the two phenolic hydroxyl groups, as long as the effect according to the embodiment of the present invention is not impaired.
  • the further substituent is not particularly limited, but is, for example, an alkyl group having 8 or less carbon atoms (methyl group, ethyl group, propyl group, 1-methylethyl group (isopropyl group), butyl group, 1,1-dimethylethyl group). (Tart-butyl group) and the like), halogens (chlorine, bromine, iodine) and the like.
  • the compound (G) has a tertiary alkyl group (for example, tert-butyl group) as a further substituent
  • the number of tertiary alkyl groups located at the ortho position with respect to the phenolic hydroxyl group is 1. There are 0 or 1 in the molecule.
  • the number of tertiary alkyl groups located at the ortho position with respect to the phenolic hydroxyl group is two or more in one molecule of compound (G)
  • the effect of improving quick curability cannot be obtained and the time required for curing is not obtained. It is not preferable because it increases. The reason for this is not clear, but it can be presumed that the steric hindrance caused by the tertiary alkyl group hinders the effect of improving the fast curability.
  • the compound (G) has no substituent other than the two phenolic hydroxyl groups on the aromatic ring.
  • the configuration has an advantage that the effect of improving the quick curing property is enhanced.
  • resorcinol, catechol, hydroquinone and methylhydroquinone are more preferable, resorcinol and catechol are more preferable, and resorcinol is particularly preferable, because they exhibit an excellent effect of improving fast curing property.
  • the compound (G) may be used alone or in combination of two or more.
  • the curable resin composition of the third embodiment preferably contains 1 to 25 parts by weight of the compound (G) with respect to 100 parts by weight of the epoxy resin (A), and contains 2 to 20 parts by weight. It is more preferable to contain 3 to 15 parts by weight, and particularly preferably 4 to 10 parts by weight.
  • the content of the compound (G) is 1 part by weight or more with respect to 100 parts by weight of the epoxy resin (A)
  • the effect of improving the quick curability of the compound (G) is satisfactorily exhibited (b).
  • the amount is 25 parts by weight or less, the curable resin composition has an advantage that the storage stability is good and it is easy to handle.
  • the curable resin composition of the third embodiment As a curing aid for accelerating the curing rate with the epoxy curing agent (D) described later, compounds having a phenolic hydroxyl group such as bisphenol A and 2,4,6-tris (dimethylaminomethyl) phenol are known. .. Compounds having two aromatic rings and two phenolic hydroxyl groups in one molecule, such as bisphenol A, are difficult to handle because their use is regulated by environmental regulations and the like. Therefore, in the curable resin composition of the third embodiment, the smaller the content of the compound (bisphenol A) having two aromatic rings and two phenolic hydroxyl groups in one molecule is preferable, for example, an epoxy resin (epoxy resin). A) It is preferably 3 parts by weight or less with respect to 100 parts by weight. However, the curable resin composition of the third embodiment is a compound having two aromatic rings and two phenolic hydroxyl groups in one molecule, as long as the effect according to the embodiment of the present invention is not impaired. For example, it may contain bisphenol
  • the content of the compound (bisphenol A) having two aromatic rings and two phenolic hydroxyl groups in one molecule is 100 parts by weight of the epoxy resin (A). It may be 2 parts by weight or less, 1 part by weight or less, 0.5 parts by weight or less, or less than 0.1 parts by weight.
  • the present inventor uses one molecule of 2,4,6-tris (dimethylaminomethyl) phenol or the like as a curing agent instead of the epoxy curing agent (D) described later. It was independently found that the effect of improving the quick-curing property was not sufficient when a compound having a phenolic hydroxyl group was used. However, as long as the effect according to the embodiment of the present invention is not impaired, the curable resin composition of the third embodiment is a compound having one phenolic hydroxyl group in one molecule (for example, 2, 4, 6). -Tris (dimethylaminomethyl) phenol) may be contained.
  • the curable resin composition of the third embodiment may or may not further contain aluminum hydroxide (C).
  • the curable resin composition of the third embodiment preferably contains aluminum hydroxide (C) in the first component and / or the second component.
  • the curable resin composition of the third embodiment contains the component (C)
  • the obtained cured product is said to be excellent in thermal conductivity and flame retardancy (for example, flame retardancy evaluated by a vertical combustion test (UL94)).
  • UL94 vertical combustion test
  • the average particle size of the component (C) is not particularly limited.
  • the average particle size of the component (C) is determined from the viewpoint of achieving both impact resistance and adhesive strength of the obtained cured product, and the component (C) in the curable resin composition before curing. From the viewpoint of suppressing sedimentation over time, it is preferably 11 ⁇ m or more and 200 ⁇ m or less, more preferably 12 ⁇ m or more and 150 ⁇ m or less, further preferably 13 ⁇ m or more and 100 ⁇ m or less, further preferably 15 ⁇ m or more and 50 ⁇ m or less, and 17 ⁇ m or more and 30 ⁇ m or less. Especially preferable.
  • the total weight of aluminum hydroxide (C) with respect to the total weight of the curable resin composition is not particularly limited.
  • the total weight of the aluminum hydroxide (C) with respect to the total weight of the curable resin composition improves the obtained cured product properties (heat conductivity, flame retardancy, adhesive strength, and impact resistance). From the viewpoint of improving the workability of the composition before curing, it is preferably 55% by weight or more and 85% by weight or less, more preferably 57% by weight or more and 80% by weight or less, and 60% by weight or more and 76% by weight. % Or less is more preferable, 62% by weight or more and 73% by weight or less is further preferable, and 65% by weight or more and 70% by weight or less is particularly preferable.
  • the curable resin composition of the third embodiment may contain a heat conductive filler other than aluminum hydroxide (other than component (C)) and / or a flame retardant other than aluminum hydroxide (other than component (C)).
  • a heat conductive filler other than aluminum hydroxide other than component (C)
  • a flame retardant other than aluminum hydroxide other than component (C)
  • the curable resin composition of the third embodiment contains an epoxy curing agent as the component (D) in the second component.
  • an epoxy curing agent (D) an amine-based curing agent is preferably used.
  • the amine-based curing agent is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified aliphatic amine, a modified alicyclic amine, or an amidoamine.
  • the epoxy curing agent (D) is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified product of an aliphatic amine, or a modified product of an alicyclic amine.
  • the curable resin composition is curable (fast) at room temperature. It has the advantage of being excellent in curability).
  • the epoxy curing agent (D) may be used alone or in combination of two or more.
  • the epoxy curing agent (D) of the third embodiment is (a-1) an amine-terminated polyether and an amine-terminated butadiene nitrile rubber from the viewpoint of (a) impact resistance of the obtained cured product. It is preferable to contain one or more selected from the group consisting of (a-2) amine-terminated polyether and amine-terminated butadiene nitrile rubber, and more preferably one or more selected from the group consisting of (b). ) Further, from the viewpoint of curability, it is more preferable to contain an amine-terminated butadiene nitrile rubber, and further preferably an amine-terminated butadiene nitrile rubber.
  • the epoxy curing agent (D) of the third embodiment is (a-1) alicyclic amine, amidoamine, amine-terminated polyether from the viewpoint of (a) adhesive strength of the obtained cured product.
  • Amine-terminated butadiene nitrile rubber, modified alicyclic amine, modified amidamine, modified amine-terminated polyether and modified amine-terminated butadiene nitrile rubber may contain one or more selected from the group.
  • (a-2) alicyclic amines, amidamines, amine-terminated polyethers, amine-terminated butadiene nitrile rubbers, modified alicyclic amines, modified amidamines, modified amine-terminated polyethers and amine-terminated butadiene nitriles. It is more preferably one or more selected from the group consisting of modified rubbers, and (b-1) from the viewpoint of curability, (b-1) from the group consisting of alicyclic amines and amine-terminated butadiene nitrile rubbers.
  • the epoxy curing agent (D) of the third embodiment has an alicyclic amine, an amine-terminated butadiene nitrile rubber, a modified alicyclic amine, and an amine-terminated butadiene nitrile from the viewpoint of adhesive strength and curability of the obtained cured product.
  • modified rubbers from alicyclic amines, amine-terminated butadiene nitrile rubbers, modified alicyclic amines and modified amine-terminated butadiene nitrile rubbers. It is more preferable that the number is at least one selected from the group.
  • the description of the first embodiment is appropriately incorporated for aspects other than the above-mentioned matters.
  • An epoxy curing agent exhibiting activity at a high temperature other than an epoxy curing agent containing an active hydrogen group that can react with an epoxy resin at a low temperature can be used to cure the third embodiment. It can be contained within a range that does not impair the curing rate of the sex resin composition.
  • the components other than the ⁇ (D) component in the first embodiment are used. Since it is the same as that described in the section of "Epoxy curing agent exhibiting activity at high temperature", the description thereof is incorporated, and the description thereof is omitted here.
  • the first component and / or the second component may be referred to as an epoxy curing accelerator (H) other than the compound (G) (hereinafter, referred to as “(H) component”). Yes.) May be contained.
  • the component (H) is a compound that is difficult to form a crosslink by reacting with the epoxy resin (A), but the curing reaction between the epoxy resin (A) and the epoxy curing agent (D) can be accelerated.
  • the component (H) is preferably a component (D) that exhibits a remarkable curing acceleration effect when used in combination with the component (D), that is, an epoxy curing agent having high curability at room temperature.
  • the component (H) may be contained only in the first component, may be contained only in the second component, or may be contained in both the first component and the second component. From the viewpoint of the storage stability of the curable resin composition, the component (H) is preferably contained only in the second component.
  • component (H) examples include alkylene imidazole having 1 to 12 (C1-C12) carbon atoms, N-aryl imidazole, 2-methyl imidazole, 2-ethyl-2-methyl imidazole, and N-butyl imidazole.
  • Imidazoles such as 1-cyanoethyl-2-undecylimidazolium trimellitate, an addition product of epoxy resin and imidazole; N, N-dimethylpiperazine, diazabicycloundecene, diazabicyclononen, triethylenediamine, benzyl.
  • Tertiary amines such as dimethylamine and triethylamine; 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4 incorporated into poly (p-vinylphenol) matrix
  • examples thereof include phenols such as 6-tris (dimethylaminomethyl) phenol, pt-butylphenol, phenol, and 4-methoxyphenol; and the like.
  • imidazoles and phenols are preferable from the viewpoint of the effect of improving curability, and phenols such as 2,4,6-tris (dimethylaminomethyl) phenol are more preferable.
  • the component (H) one type may be used alone, or two or more types may be used in combination.
  • the content of the epoxy curing accelerator (H) with respect to 100 parts by weight of the epoxy resin (A) in the curable resin composition of the third embodiment is from the viewpoint of achieving both the effect of improving curability and the storage stability.
  • 0.1 part by weight or more and 30 parts by weight or less are preferable, 1 part by weight or more and 20 parts by weight or less are more preferable, 2 parts by weight or more and 15 parts by weight or less are further preferable, and 3 parts by weight or more and 10 parts by weight or less are particularly preferable.
  • One embodiment of the present invention may have the following configuration.
  • a two-component curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
  • the curable resin composition further contains polymer particles (B) having a core-shell structure and aluminum hydroxide (C), and the total weight of the aluminum hydroxide (C) with respect to the total weight of the curable resin composition.
  • the curable resin composition is 55% by weight or more and 85% by weight or less, and the average particle size of the aluminum hydroxide (C) is 11 ⁇ m or more and 200 ⁇ m or less.
  • the ratio of the number of moles of the epoxy group of the epoxy resin (A) to the number of moles of the active hydrogen group of the epoxy curing agent (D) is 0.5 or more and 1.5 or less [A1].
  • [A5] One or more amine curing agents selected from the group consisting of an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, and an amine-terminated butadiene nitrile rubber, or a curing agent thereof.
  • the polymer particles (B) having a core-shell structure have one or more core layers selected from the group consisting of a diene-based rubber, a (meth) acrylate-based rubber, and an organosiloxane-based rubber [A1].
  • the curable resin composition according to any one of [A10].
  • the polymer particles (B) having the core-shell structure are graft-polymerized on the core layer with one or more monomer components selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth) acrylate monomers.
  • the curable resin composition according to any one of [A1] to [A12], which has a shell layer made of.
  • the polymer particles (B) having the core-shell structure have an epoxy group in the shell layer, and the content of the epoxy group in the shell layer is 0.1 to 2.0 mmol with respect to the total amount of the shell layer.
  • the curable resin composition according to any one of [A1] to [A15], which is / g or less.
  • a laminate comprising two base materials and an adhesive layer obtained by joining the two base materials and having the adhesive according to [A19] or [A20] cured.
  • One embodiment of the present invention may have the following configuration.
  • a two-component curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
  • the product further contains polymer particles (B) having a core-shell structure and aluminum hydroxide (C), and the total weight of the aluminum hydroxide (C) is 55% by weight based on the total weight of the curable resin composition.
  • the average particle size of the polymer particles (B) having the core-shell structure of 85% by weight or less is 0.15 ⁇ m or more and 0.30 ⁇ m or less, and the core layer / shell layer of the polymer particles (B) having the core-shell structure.
  • the weight ratio is 65/35 to 92/8, and the polymer particles (B) having the core-shell structure include a monomer component in which the shell layer contains 55 wt% or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms.
  • a curable resin which is a polymer and contains 10 to 100 wt% of an alkyl (meth) acrylate having 1 carbon atom and 0 to 80 wt% of an alkyl (meth) acrylate having 4 carbon atoms as a monomer component constituting the shell layer. Composition.
  • the ratio of the number of moles of the epoxy group of the epoxy resin (A) to the number of moles of the active hydrogen group of the epoxy curing agent (D) is 0.5 or more and 1.5 or less [B1].
  • [B5] One or more amine curing agents selected from the group consisting of an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, and an amine-terminated butadiene nitrile rubber, or a curing agent thereof.
  • the polymer particles (B) having a core-shell structure have one or more core layers selected from the group consisting of a diene-based rubber, a (meth) acrylate-based rubber, and an organosiloxane-based rubber [B1].
  • the curable resin composition according to any one of [B10].
  • the polymer particles (B) having the core-shell structure are graft-polymerized with one or more monomer components selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth) acrylate monomers on the core layer.
  • the curable resin composition according to any one of [B1] to [B12], which has a shell layer made of.
  • the polymer particles (B) having the core-shell structure have an epoxy group in the shell layer, and the content of the epoxy group in the shell layer is 0.1 to 2.0 mmol with respect to the total amount of the shell layer.
  • the curable resin composition according to any one of [B1] to [B15], which is / g or less.
  • [B21] A laminate comprising two base materials and an adhesive layer obtained by joining the two base materials and having the adhesive according to [B19] or [B20] cured.
  • One embodiment of the present invention may have the following configuration.
  • a two-component or multi-component curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
  • the curable resin composition further comprises a polymer particle (B) having a core-shell structure including a core layer and a shell layer, (i) one aromatic ring in one molecule, and (ii) at least two phenols.
  • the number of tertiary alkyl groups contained in the compound (G) having a sex hydroxyl group and located at the ortho position with respect to the phenolic hydroxyl group in the compound (G) is 0 or 1 in one molecule.
  • the epoxy curing agent (D) is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified product of an aliphatic amine, or a modified product of an alicyclic amine.
  • a curable resin composition which is at least one selected from the group consisting of a modified product of amidamine, a modified product of an amine-terminated polyether, and a modified product of an amine-terminated butadiene nitrile rubber.
  • [C2] The ratio of the number of moles of the epoxy group of the epoxy resin (A) to the number of moles of the active hydrogen group of the epoxy curing agent (D) (number of moles of the epoxy group / number of moles of the active hydrogen group). ) Is 0.5 or more and 1.6 or less, the curable resin composition according to [C1].
  • the epoxy curing agent (D) is at least one selected from the group consisting of alicyclic amines, amine-terminated butadiene nitrile rubbers, modified alicyclic amines, and modified amine-terminated butadiene nitrile rubbers.
  • the curable resin composition according to any one of [C1] to [C3].
  • the content of the epoxy curing agent (D) in 100 parts by weight of the epoxy resin (A) in the curable resin composition is 15 parts by weight or more and 300 parts by weight or less, [C1] to [C6]. ]
  • the curable resin composition according to any one of.
  • the content of the aluminum hydroxide (C) in 100 parts by weight of the epoxy resin (A) in the curable resin composition is 250 parts by weight or more and 750 parts by weight or less, according to [C6]. Curable resin composition.
  • the shell layer has an epoxy group and has an epoxy group.
  • the invention according to any one of [C1] to [C12], wherein the content of the epoxy group contained in the shell layer with respect to the total weight of the shell layer is more than 0 mmol / g and 2.0 mmol / g or less. Curable resin composition.
  • [C19] A laminate comprising two base materials and an adhesive layer obtained by curing the adhesive according to [C17] or [C18] between the two base materials.
  • One embodiment of the present invention may have the following configuration.
  • a two-component curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D), and the curable resin.
  • the composition further contains polymer particles (B) having a core-shell structure including a core layer and a shell layer, and aluminum hydroxide (C), and the water in 100% by weight of the total weight of the curable resin composition.
  • a curable resin composition having a total weight of aluminum oxide (C) of 55% by weight or more and 85% by weight or less, and an average particle size of aluminum hydroxide (C) of 11 ⁇ m or more and 200 ⁇ m or less.
  • the average particle size of the polymer particles (B) is 0.15 ⁇ m or more and 0.30 ⁇ m or less, and the ratio of the weight of the core layer to the weight of the shell layer in the polymer particles (B) (the core).
  • the weight of the layer / the weight of the shell layer) is 65/35 to 92/8, and the shell layer of the polymer particles (B) is an alkyl (meth) having 100% by weight of the monomer component and 1 to 4 carbon atoms in the monomer component.
  • the epoxy curing agent (D) contains an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified aliphatic amine, a modified alicyclic amine, and an amidoamine.
  • the curable resin composition further contains (i) one aromatic ring and (ii) a compound (G) having at least two phenolic hydroxyl groups in one molecule, and the compound.
  • G the number of tertiary alkyl groups located at the ortho position with respect to the phenolic hydroxyl group is 0 or 1 in one molecule
  • the epoxy curing agent (D) is an aliphatic amine.
  • [X5] The ratio of the number of moles of the epoxy group of the epoxy resin (A) to the number of moles of the active hydrogen group of the epoxy curing agent (D) (the number of moles of the epoxy group of the epoxy resin (A) / the said The curable resin composition according to any one of [X1] to [X4], wherein the epoxy curing agent (D) has a molar number of active hydrogen groups of 0.5 or more and 1.5 or less.
  • the polymer particles (B) have a diene-based rubber in the core layer, and the diene-based rubber is a butadiene rubber and / or a butadiene-styrene rubber.
  • the curable resin composition according to any one.
  • the polymer particles (B) have an epoxy group in the shell layer, and the content of the epoxy group in the shell layer is 0.1 to 2.0 mmol / g or less with respect to the total amount of the shell layer.
  • the curable resin composition according to any one of [X1] to [X7].
  • [X13] A laminated body containing two base materials and an adhesive layer obtained by curing the adhesive according to [X12], wherein the adhesive layer is a bonding of the two base materials.
  • a two-component curable resin composition contains a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
  • the curable resin composition further contains polymer particles (B) having a core-shell structure including a core layer and a shell layer and aluminum hydroxide (C), and the total weight of the curable resin composition is 100 weight.
  • the total weight of the aluminum hydroxide (C) in% is 55% by weight or more and 85% by weight or less, the average particle size of the polymer particles (B) is 0.15 ⁇ m or more and 0.30 ⁇ m or less, and the polymer.
  • the ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer / weight of the shell layer) in the particles (B) is 65/35 to 92/8, and the polymer particles (B)
  • the shell layer is a copolymer obtained by polymerizing the monomer component containing 55 wt% or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of the monomer component, and the monomer component is the monomer.
  • a curable resin composition containing 10 to 100 wt% of an alkyl (meth) acrylate having 1 carbon atom and 0 to 80 wt% of an alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the component.
  • a two-component or multi-component curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
  • the curable resin composition further comprises a polymer particle (B) having a core-shell structure including a core layer and a shell layer, (i) one aromatic ring in one molecule, and (ii) at least two.
  • the number of tertiary alkyl groups contained in the compound (G) having a phenolic hydroxyl group and located at the ortho position with respect to the phenolic hydroxyl group in the compound (G) is 0 or 0 in one molecule.
  • the epoxy curing agent (D) is one, and the epoxy curing agent (D) is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified product of an aliphatic amine, or a modified product of an alicyclic amine.
  • a curable resin composition which is at least one selected from the group consisting of a modified product of an amidamine, a modified product of an amine-terminated polyether and a modified product of an amine-terminated butadiene nitrile rubber.
  • Example A The first embodiment will be described in more detail below with reference to Example A, but the present invention is not limited to these Examples A.
  • the average particle size of each of the polybutadiene rubber particles in the polybutadiene rubber latex described in the production example and the core-shell polymer particles (B) in the core-shell polymer latex was measured by the following method.
  • the volume average particle diameter (Mv) of the particles dispersed in the aqueous latex was measured using Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.).
  • a sample diluted with deionized water was used as a measurement sample. For the measurement, input the refractive index of water and the refractive index of each core-shell polymer particle (B), and adjust the sample concentration so that the measurement time is 600 seconds and the Signal Level is in the range of 0.6 to 0.8. I went there.
  • Formation of core layer Production example A1 Preparation of polybutadiene rubber latex (R-2) 200 parts by weight of water, 0.03 parts by weight of tripotassium phosphate, 0.002 parts of disodium ethylenediamine tetraacetate (EDTA) in a pressure-resistant polymerizer. Add 0.001 part by weight of ferrous sulfate heptahydrate (FE) and 1.55 part by weight of sodium dodecylbenzene sulfonate (SDBS), and sufficiently replace with nitrogen while stirring. After removing oxygen, 100 parts by weight of butadiene (Bd) was added to the system and the temperature was raised to 45 ° C.
  • FE ferrous sulfate heptahydrate
  • SDBS sodium dodecylbenzene sulfonate
  • EDTA ethylene glycol
  • FE ethylene glycol
  • SFS styrene
  • AN acrylonitrile
  • GMA glycidyl methacrylate
  • CHP cumenhydroperoxide
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (AL-1) was 0.21 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0.5 mmol / g.
  • Production Example A2-2 Preparation of Core-Shell Polymer Latex (AL-2) The same as Production Example A2-1 except that the shell monomer was changed to 5 parts by weight of MMA, 6 parts by weight of ST, and 2 parts by weight of AN, and an aqueous solution containing core-shell polymer particles. Latex (AL-2) was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (AL-2) was 0.21 ⁇ m. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0.0 mmol / g.
  • Production Example A2-3 Preparation of Core-Shell Polymer Latex (AL-3) The same as Production Example A2-1 except that the shell monomer was changed to 3 parts by weight of MMA, 6 parts by weight of ST, 2 parts by weight of AN, and 2 parts by weight of GMA, and the core-shell polymer was used.
  • An aqueous latex (AL-3) containing particles was obtained.
  • the conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (AL-3) was 0.21 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.
  • Production Example A2-4 Preparation of Core-Shell Polymer Latex (AL-4) The same as Production Example A2-1 except that the shell monomer was changed to 1 part by weight of MMA, 6 parts by weight of ST, 2 parts by weight of AN, and 4 parts by weight of GMA, and the core-shell polymer was used.
  • An aqueous latex (AL-4) containing particles was obtained.
  • the conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (AL-4) was 0.21 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 2.2 mmol / g.
  • Production Example A2-5 Preparation of Core-Shell Polymer Latex (AL-5) The same as in Production Example A2-1 except that the shell monomer was changed to 13 parts by weight of MMA to obtain an aqueous latex (AL-5) containing core-shell polymer particles. rice field.
  • the conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (AL-5) was 0.21 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0.0 mmol / g.
  • a slurry liquid consisting of a floating aggregate and an aqueous phase partially containing an organic solvent was obtained.
  • 360 g of the aqueous phase was discharged from the discharge port at the bottom of the tank, leaving an agglomerate containing a part of the aqueous phase.
  • 90 g of MEK was added to the obtained aggregate and mixed uniformly to obtain a dispersion in which the core-shell polymer particles were uniformly dispersed.
  • 60 g of an epoxy resin (A-1; manufactured by Mitsubishi Chemical Corporation, JER828: liquid bisphenol A type epoxy resin) as a component (A) was mixed with this dispersion.
  • MEK was removed from this mixture with a rotary evaporator. In this way, a dispersion (AM-1) in which core-shell polymer particles were dispersed in an epoxy resin was obtained.
  • Production Example A3-2 Preparation of Dispersion (AM-2) In Production Example A3-1, (AL-2) obtained in Production Example A2-2 was used instead of (AL-1) as the core-shell polymer latex.
  • a dispersion (AM-2) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example A3-1 except for the above.
  • Production Example A3-3 Preparation of Dispersion (AM-3) In Production Example A3-1, (AL-3) obtained in Production Example A2-3 was used instead of (AL-1) as the core-shell polymer latex.
  • a dispersion (AM-3) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example A3-1 except for the above.
  • Production Example A3-4 Preparation of Dispersion (AM-4) In Production Example A3-1, (AL-4) obtained in Production Example A2-4 was used instead of (AL-1) as the core-shell polymer latex.
  • a dispersion (AM-4) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example A3-1 except for the above.
  • Production Example A3-5 Preparation of Dispersion (AM-5) In Production Example A3-1, (AL-5) obtained in Production Example A2-5 was used instead of (AL-1) as the core-shell polymer latex. , Epoxy in the same manner as in Production Example A3-1 except that 60 g of epoxy resin (A-2; manufactured by Hexion, EPON863: liquid bisphenol F type epoxy resin) was used instead of 60 g of epoxy resin (A-1). A dispersion (AM-5) in which core-shell polymer particles were dispersed in a resin was obtained.
  • a dispersion (AM-5) in which core-shell polymer particles were dispersed in a resin was obtained.
  • Examples A1 to 17, Comparative Examples A1 to 8 Each component was weighed according to the formulations shown in Tables 1 to 3 and mixed well to obtain the first component and the second component of the two-component curable resin composition.
  • Each composition obtained by thoroughly mixing the first component and the second component in Table 2 is obtained by combining two cold-rolled steel plates (SPCC-SD) or aluminum plates (SPCC-SD) having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm. It was applied to A-5052P), bonded so that the adhesive layer had a width of 25 mm ⁇ a length of 12.5 mm ⁇ a thickness of 0.13 mm, and cured under the conditions of 23 ° C. ⁇ 7 days to obtain a laminated body.
  • SPCC-SD cold-rolled steel plates
  • SPCC-SD aluminum plates
  • the shear adhesion strength was measured with MPa as the unit under the measurement conditions where the measurement temperature was 23 ° C and the test speed was 1.3 mm / min. The results are shown in Table 2.
  • each composition obtained by defoaming was poured between two glass plates sandwiching a spacer having a thickness of 3 mm, and cured under the conditions of 23 ° C. ⁇ 7 days. , A cured plate having a thickness of 3 mm was obtained. This hardened plate was cut to obtain two disk-shaped samples having a diameter of 20 mm.
  • the thermal conductivity of the cured product was measured by a method of sandwiching a 4 ⁇ size sensor between two samples using a hot disk method thermal conductivity measuring device TPA-501 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.).
  • each composition obtained by defoaming was poured between two glass plates sandwiching a spacer having a thickness of 3 mm, and cured under the conditions of 23 ° C. ⁇ 7 days. , A cured plate having a thickness of 3 mm was obtained. This hardened plate was cut into strips having a thickness of 127 mm ⁇ 12.7 mm ⁇ 3 mm, and evaluated according to the UL-94 20 mm vertical combustion test (V test). The test results are shown in the order of "V-0", “V-1", and "V-2" from the one with the best flame retardancy, and those that do not pass the UL-94 V test are classified as "non-standard". ..
  • compositions of Examples A1 and 3 to 8 and Comparative Examples A1 to 5 all have the same composition except for the component (C) added, only the type of the component (C) is different.
  • the compositions of Examples A1 to 3 to 8 have a large average particle size of aluminum hydroxide used, whereas the compositions of Comparative Examples A1 to 5 have a small average particle size of aluminum hydroxide, and the examples have a large average particle size. Compared with A1, 3-8, the impact resistance peeling adhesiveness is low.
  • composition of Example A2 is a compounding composition in which the epoxy curing accelerator (E) is added to the composition of Example A1, and the impact resistance peeling adhesiveness is also excellent.
  • compositions of Examples A9 to 11 and Comparative Example A6 all have the same composition except for the component (C) added, only the type of the component (C) is different.
  • the compositions of Examples A9 to 11 have a large average particle size of aluminum hydroxide used, whereas the composition of Comparative Example A6 has a small average particle size of aluminum hydroxide, which is the same as that of Examples A9 to 11. In comparison, the impact resistance peeling adhesiveness is low.
  • compositions of Examples A9 and 12 to 14 all have the same composition except for the component (B) added, except for the component (B).
  • the components (B) used in the compositions of Examples A9 and 12 to 14 differ in the epoxy group content of the shell layer. Comparison between the case where the shell layer does not contain an epoxy group (Example A12), the case where the epoxy group content of the shell layer is 0.5 mmol / g (Example A9), and the case where the shell layer contains 1.1 mmol / g (Example A13). It showed good impact resistance and peeling adhesiveness.
  • compositions of Examples A15 to 17 and Comparative Example A7 all have the same composition except for the amount of the added component (C) but the amount of the component (C).
  • Comparative Example A7 in which the total weight of the component (C) was small with respect to the total weight of the curable resin composition, the thermal conductivity was relatively low, and the UL-94 flame retardancy test failed (non-standard).
  • Comparative Example A8 containing no component (C) the thermal conductivity was low, and the UL-94 flame retardancy test failed (non-standard).
  • Example B The second embodiment will be described in more detail with reference to Example B below, but the present invention is not limited to these Examples B.
  • Example B Formation of core layer
  • the core layer is R-2 obtained by the method described in the above-mentioned "Production Example A1; Preparation of Polybutadiene Rubber Latex (R-2)" in [Example A]. It was used. Therefore, the description in the section "Production Example A1; Preparation of Polybutadiene Rubber Latex (R-2)" in [Example A] is referred to, and the description thereof is omitted here.
  • shell monomers (9 parts by weight of methyl methacrylate (MMA), 1 part by weight of glycidyl methacrylate (GMA)), and cumenhydroper.
  • a mixture of 0.14 parts by weight of oxide (CHP) was added continuously over 120 minutes.
  • 0.04 part by weight of CHP was added, and stirring was continued for another 2 hours to complete the polymerization to obtain an aqueous latex (BL-1) containing core-shell polymer particles.
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-1) was 0.21 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0.7 mmol / g.
  • Production Example B2-2 Preparation of Core-Shell Polymer Latex (BL-2)
  • the polybutadiene rubber prepared in Production Example A1 was placed in a glass reactor equipped with a thermometer, agitator, reflux condenser, nitrogen inlet, and a monomer addition device.
  • 262 parts by weight of latex (R-2) (including 87 parts by weight of polybutadiene rubber particles) and 57 parts by weight of deionized water were charged and stirred at 60 ° C. while performing nitrogen substitution.
  • a mixture of shell monomer 11 parts by weight of MMA, 2 parts by weight of GMA
  • 0.06 part by weight of CHP was continuously added over 120 minutes. Was added.
  • 0.04 part by weight of CHP was added, and stirring was continued for another 2 hours to complete the polymerization to obtain an aqueous latex (BL-2) containing core-shell polymer particles.
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-2) was 0.21 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.
  • Production Example B2-3 Preparation of Core-Shell Polymer Latex (BL-3) The same as Production Example B2-2 except that the shell monomer was changed to 2 parts by weight of MMA, 9 parts by weight of butyl acrylate (BA), and 2 parts by weight of GMA, and the core shell was used.
  • An aqueous latex (BL-3) containing polymer particles was obtained.
  • the conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-3) was 0.21 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.
  • Production Example B2-4 Preparation of Core-Shell Polymer Latex (BL-4) Polybutadiene rubber prepared in Production Example A1 in a glass reactor equipped with a thermometer, agitator, reflux condenser, nitrogen inlet, and monomer addition device. 223 parts by weight of latex (R-2) (including 74 parts by weight of polybutadiene rubber particles) and 83 parts by weight of deionized water were charged and stirred at 60 ° C. while performing nitrogen substitution.
  • R-2 latex
  • R-2 including 74 parts by weight of polybutadiene rubber particles
  • aqueous latex (BL-4) containing core-shell polymer particles 120 parts by weight of the shell monomer (4 parts by weight of MMA, 18 parts by weight of BA, 4 parts by weight of GMA) and 0.12 parts by weight of CHP are mixed. It was added continuously over a minute. After completion of the addition, 0.04 part by weight of CHP was added, and the mixture was further stirred for 2 hours to complete the polymerization to obtain an aqueous latex (BL-4) containing core-shell polymer particles.
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-4) was 0.22 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.
  • Production Example B2-5 Preparation of Core-Shell Polymer Latex (BL-5) The same as Production Example B2-2 except that the shell monomer was changed to BA11 parts by weight and GMA2 parts by weight, and the aqueous latex (BL-) containing core-shell polymer particles was used. 5) was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-5) was 0.21 ⁇ m. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.
  • Production Example B2-6 Preparation of Core-Shell Polymer Latex (BL-6) The same as Production Example B2-2 except that the shell monomer was changed to 1 part by weight of MMA, 6 parts by weight of ST, 2 parts by weight of AN, and 4 parts by weight of GMA, and the core-shell polymer was used.
  • An aqueous latex (BL-6) containing particles was obtained.
  • the conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-6) was 0.21 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 2.2 mmol / g.
  • Production Example B2-7 Preparation of Core-Shell Polymer Latex (BL-7) The same as Production Example B2-1 except that the shell monomer was changed to 8 parts by weight of MMA and 2 parts by weight of GMA, and an aqueous latex containing core-shell polymer particles (BL- 7) was obtained.
  • the conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-7) was 0.21 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.4 mmol / g.
  • Production Example B2-8 Preparation of Core-Shell Polymer Latex (BL-8) The same as Production Example B2-1 except that the shell monomer was changed to 6 parts by weight of MMA and 4 parts by weight of GMA, and an aqueous latex containing core-shell polymer particles (BL- 8) was obtained.
  • the conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-8) was 0.21 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 2.8 mmol / g.
  • Production Example B2-9; Preparation of Core-Shell Polymer Latex (BL-9) The same as Production Example B2-2 except that the shell monomer was changed to 6 parts by weight of MMA and 7 parts by weight of BA, and the aqueous latex containing core-shell polymer particles (BL- 9) was obtained.
  • the conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-9) was 0.21 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0 mmol / g.
  • Production Example B2-10 Preparation of Core-Shell Polymer Latex (BL-10) The same as Production Example B2-2 except that the shell monomer was changed to 5 parts by weight of MMA, 6 parts by weight of BA, and 2 parts by weight of GMA, and an aqueous solution containing core-shell polymer particles. Latex (BL-10) was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-10) was 0.21 ⁇ m. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.
  • the conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-11) was 0.21 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0 mmol / g.
  • Production Example B2-13 Preparation of Core Shell Polymer Latex (BL-13) Polybutadiene rubber prepared in Production Example A1 in a glass reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet, and monomer addition device.
  • 241 parts by weight of latex (R-1) including 80 parts by weight of polybutadiene rubber particles
  • 71 parts by weight of deionized water were charged and stirred at 60 ° C. while performing nitrogen substitution.
  • aqueous latex (BL-13) containing core-shell polymer particles 0.04 part by weight of CHP was added, and the mixture was further stirred for 2 hours to complete the polymerization to obtain an aqueous latex (BL-13) containing core-shell polymer particles.
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-13) was 0.09 ⁇ m.
  • the content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0 mmol / g.
  • Production Example B2-14 Preparation of Core-Shell Polymer Latex (BL-14)
  • the polybutadiene rubber prepared in Production Example A1 was placed in a glass reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet, and monomer addition device.
  • 145 parts by weight of latex (R-2) (including 48 parts by weight of polybutadiene rubber particles) and 135 parts by weight of deionized water were charged and stirred at 60 ° C. while performing nitrogen substitution.
  • aqueous latex (BL-14) containing core-shell polymer particles After adding 0.004 parts by weight of EDTA, 0.001 parts by weight of FE, and 0.3 parts by weight of SFS, shell monomers (8 parts by weight of MMA, 16 parts by weight of BA, 20 parts by weight of BMA, 8 parts by weight of GMA), and 0.24 parts by weight of CHP. The mixture was added continuously over 240 minutes. After completion of the addition, 0.04 part by weight of CHP was added, and the mixture was further stirred for 2 hours to complete the polymerization to obtain an aqueous latex (BL-14) containing core-shell polymer particles. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-14) was 0.24 ⁇ m. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.
  • a slurry liquid consisting of a floating aggregate and an aqueous phase partially containing an organic solvent was obtained.
  • 360 g of the aqueous phase was discharged from the discharge port at the bottom of the tank, leaving an agglomerate containing a part of the aqueous phase.
  • 90 g of MEK was added to the obtained aggregate and mixed uniformly to obtain a dispersion in which the core-shell polymer particles were uniformly dispersed.
  • 60 g of an epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER828: liquid bisphenol A type epoxy resin) as a component (A) was mixed with this dispersion.
  • MEK was removed from this mixture with a rotary evaporator. In this way, a dispersion (BM-1) in which core-shell polymer particles were dispersed in an epoxy resin was obtained.
  • Examples B1 to 17, Comparative Examples B1 to 6 Each component was weighed according to the formulations shown in Tables 4 to 7 and mixed well to obtain the first component and the second component of the two-component curable resin composition.
  • Each composition obtained by mixing the first component and the second component of Tables 4 to 6 well is obtained by combining two SPCC steel plates or aluminum plates (A-5052P) having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm.
  • the adhesive layer was bonded so as to have a width of 25 mm, a length of 12.5 mm, and a thickness of 0.13 mm, and was cured under the conditions of 23 ° C. ⁇ 7 days to obtain a laminated body.
  • Shear adhesion strength was measured with MPa as the unit under measurement conditions with a measurement temperature of 23 ° C and a test speed of 1.3 mm / min.
  • each composition obtained by defoaming was poured between two glass plates sandwiching a spacer having a thickness of 3 mm, and cured under the conditions of 23 ° C. ⁇ 7 days. , A cured plate having a thickness of 3 mm was obtained. This hardened plate was cut to obtain two disk-shaped samples having a diameter of 20 mm.
  • the thermal conductivity of the cured product was measured by a method of sandwiching a 4 ⁇ size sensor between two samples using a hot disk method thermal conductivity measuring device TPA-501 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.).
  • each composition obtained by defoaming was poured between two glass plates sandwiching a spacer having a thickness of 3 mm, and cured under the conditions of 23 ° C. ⁇ 7 days. , A cured plate having a thickness of 3 mm was obtained. This hardened plate was cut into strips having a thickness of 127 mm ⁇ 12.7 mm ⁇ 3 mm, and evaluated according to the UL-94 20 mm vertical combustion test (V test). The test results are shown in the order of "V-0", “V-1", and "V-2" from the one with the best flame retardancy, and those that do not pass the UL-94 V test are classified as "non-standard". ..
  • compositions of Examples B1 to 4 and Comparative Examples B1 to 2 have the same composition except for the added component (B) but the component (B).
  • the component (B) used in the compositions of Examples B1 to B4 contains an alkyl (meth) acrylate having 1 to 4 carbon atoms as a main component (55% by weight or more) as a monomer component constituting the shell layer, and The content of the alkyl (meth) acrylate having 4 carbon atoms is 80% by weight or less.
  • Comparative Example B1 of the shell layer having an alkyl (meth) acrylate having 4 carbon atoms having a content of 85% by weight did not measure the shear adhesive strength because the viscosity was very high and the workability was poor.
  • Comparative Example B2 of the shell layer having a small amount of alkyl (meth) acrylate having 1 to 4 carbon atoms as a main component of 8% by weight and containing other monomer components as a main component was first compared with Examples B1 to 4.
  • the viscosity of the components was high, and the shear adhesion of the obtained cured product was also low.
  • Examples B1 and 2 have the same first component, but the second component of Example B2 is obtained by reducing the addition amount of each combination of the second component of Example B1 by 0.75 times.
  • the ratio of the number of moles of epoxy groups in the component (A) / the number of moles of active hydrogen groups in the component (D) is high, the composition has an excess of epoxy, and the shear adhesiveness is low. showed that.
  • compositions of Examples B5 and 7 to 10 all have the same composition except for the added component (B) but different from the component (B).
  • the composition of Example B8 having a large content of epoxy groups in the shell layer of the component (B) showed a value of low impact resistance peeling adhesiveness.
  • the composition of Example B9, which does not contain an epoxy group in the shell layer of the component (B) also showed a value of relatively low impact resistance peeling adhesiveness. From this result, the ratio of the number of moles of the epoxy group in the component (A) / the number of moles of the active hydrogen group in the component (D) is effective for the shear adhesion strength, and the epoxy in the shell layer of the component (B). It is considered that the amount of the group is effective for the impact resistance peeling adhesiveness.
  • compositions of Examples B11 to 14 and Comparative Examples B3 to 5 have the same composition except for the added component (B) but the component (B).
  • the component (B) used in the compositions of Examples B11 to 14 has an average particle size of 0.15 to 0.30 ⁇ m, a core layer / shell layer weight ratio of 65/35 to 92/8, and a shell layer.
  • the monomer component constituting the above is mainly composed of an alkyl (meth) acrylate having 1 to 4 carbon atoms (55% by weight or more).
  • the viscosity of the first component is high and the workability is poor.
  • the composition of Comparative Example B5 showed a low impact-resistant peeling adhesiveness, it is considered that the weight ratio of the core layer / shell layer of the component (B) is effective for the impact-resistant peeling adhesiveness.
  • Example B12 and Comparative Example B4 which do not contain an epoxy group in the shell layer of the component (B), also showed a value of relatively low impact resistance peeling adhesiveness. From this result, it is considered that the amount of the epoxy group in the shell layer of the component (B) is effective for the impact resistance peeling adhesiveness.
  • Example B15 to 17 containing the component (A), the component (B), and the component (C) in the first component, and the components (C) and (D) in the second component. It can be seen that the component-type curable resin composition has high thermal conductivity, excellent flame retardancy, low viscosity, and excellent workability.
  • compositions of Examples B15 to 17 and Comparative Example B6 all have the same composition except for the amount of the added component (C) but the amount of the component (C).
  • the thermal conductivity was relatively low, and the UL-94 flame retardancy test failed (non-standard).
  • Example C The second embodiment will be described in more detail below with reference to Example C, but the present invention is not limited to these Examples C.
  • Example C Formation of core layer
  • the core layer is R-2 obtained by the method described in the above-mentioned "Production Example A1; Preparation of Polybutadiene Rubber Latex (R-2)" in [Example A]. It was used. Therefore, the description in the section "Production Example A1; Preparation of Polybutadiene Rubber Latex (R-2)" in [Example A] is referred to, and the description thereof is omitted here.
  • EDTA methyl methacrylate
  • ST styrene
  • AN acrylonitrile
  • CHP cumenhydroperoxide
  • a slurry liquid consisting of a floating aggregate and an aqueous phase partially containing an organic solvent was obtained.
  • 360 g of the aqueous phase was discharged from the discharge port at the bottom of the tank, leaving an agglomerate containing a part of the aqueous phase.
  • 90 g of MEK was added to the obtained aggregate and mixed uniformly to obtain a dispersion in which the core-shell polymer particles (B) were uniformly dispersed.
  • This dispersion was mixed with 60 g of an epoxy resin (A-1; manufactured by Mitsubishi Chemical Corporation, JER828: liquid bisphenol A type epoxy resin, epoxy equivalent: 184 to 194 g / eq) as a component (A).
  • MEK was removed from this mixture with a rotary evaporator. In this way, a dispersion (M-1) in which the core-shell polymer particles (B) were dispersed in the epoxy resin was obtained.
  • Production Example C3-2 Preparation of Dispersion (M-2)
  • epoxy resin (A-2 manufactured by Hexion, EPON863: bisphenol F type epoxy) Resin, epoxy equivalent: 165 to 174 g / eq) 60 g
  • a dispersion (M-2) in which core-shell polymer particles (B) were dispersed in an epoxy resin. ..
  • Examples C1 to 23 Comparative Examples C1 to 7
  • Each component was weighed according to the formulations shown in Tables 8 to 12 and mixed well to obtain the first component and the second component of the two-component curable resin composition.
  • the two-component curable resin composition obtained in Examples C1 to 23 is the curable resin composition (two-component curable resin composition) according to the third embodiment.
  • ⁇ Curing time> The change in viscosity of each two-component curable resin composition obtained by mixing the first component and the second component in Table 8 or 9 at 50 ° C. with time was measured using a "Bohlin CVO leometer" manufactured by Malvern. , PP25 was used, and the measurement was performed at a plate gap of 0.2 mm and a shear rate of 5s -1 . Viscosity measurement is performed every 10 seconds, the viscosity immediately after mixing the first component and the second component is taken as the initial viscosity, and the time until the viscosity reaches 10 times the initial viscosity is measured, and this is called the curing time. did. The shorter the curing time, the better the curing property.
  • Each of the two-component curable resin compositions obtained by mixing the first component and the second component of Tables 8 to 12 well was formed into two aluminum plates having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm.
  • A-5052P) or cold-rolled steel sheet is coated, and the applied two-component curable resin composition (adhesive layer) is bonded so as to have a width of 25 mm, a length of 12.5 mm, and a thickness of 0.25 mm.
  • a laminate was obtained by curing under the conditions of ° C. ⁇ 7 days.
  • Shear adhesion strength was measured with MPa as the unit under measurement conditions with a measurement temperature of 23 ° C and a test speed of 1.3 mm / min. The results are shown in Tables 8 to 12.
  • the dynamic split resistance (impact peeling adhesiveness) was evaluated for each two-component curable resin composition in Table 10 by the following method.
  • the two-component curable resin composition of Examples C1, 2, 7 to 12 using the component (G) having no substituent other than the phenolic hydroxyl group on the aromatic ring is the shearing of the obtained cured product. It can be seen that the adhesive strength is high and the adhesiveness is also excellent.
  • the two-component curable resin composition of Examples C9 to 10 containing an epoxysilane coupling agent as the component (F) has a particularly high shear adhesive strength of the obtained cured product and is excellent in adhesiveness. I understand.
  • Comparative Example C1 containing no component (G) Comparative Example C2 containing two phenolic hydroxyl groups and a compound having two tertiary alkyl groups at the ortho position thereof, and one. It can be seen that the two-component curable resin compositions of Comparative Examples C3 to C6 containing the compound having a phenolic hydroxyl group have a long curing time and are inferior in curability.
  • the two-component curable resin composition of Examples C15 to 17 in which the ratio of the number of moles is in the range of 1.1 to 1.6 is the same as that of Example C14 in which the ratio of the number of moles is 1.0.
  • the obtained cured product shows a high value in shear adhesive strength, and the ratio of the number of moles is 1.1 to 1.6. It can be seen that the adhesiveness of the object is particularly excellent.
  • the two-component curable resin composition of Examples C18 to 19 containing an epoxysilane coupling agent as the component (F) has a particularly high shear adhesive strength of the obtained cured product and is excellent in adhesiveness. I understand.
  • the two-component curable resin compositions of C20 to 23 have good shear adhesion strength of the obtained cured product.
  • the components other than the component (G) have almost no effect on the curing time. Therefore, the two-component curable resin compositions of Examples C13 to 23 are highly likely to show a curing time similar to that of Examples C1 or 2, and at least the two-component curable resin compositions of Comparative Examples C1 to C7. It is shorter than the curing time of.
  • a novel curable resin composition which is superior to the conventional one as a two-component type or multi-component type epoxy resin composition.
  • a cured product exhibiting excellent thermal conductivity, flame retardancy, adhesive strength, and impact-resistant peeling adhesiveness, and it can be cured at room temperature or a low temperature close to room temperature.
  • a two-component curable resin composition can be provided.
  • a cured product exhibiting excellent thermal conductivity, flame retardancy, and adhesive strength, having a low viscosity and good workability, and even at room temperature or a low temperature close to room temperature.
  • the curable resin composition according to one embodiment of the present invention is an adhesive for structural adhesives for vehicles and aircraft, adhesives for secondary batteries such as EV battery cells, and structural adhesives for wind power generation. , Paints, materials for laminating with glass fibers and / or carbon fibers to obtain composite materials, materials for printed wiring boards, solder resists, interlayer insulating films, build-up materials, adhesives for FPCs, semiconductors, LEDs, etc.
  • Electrical insulation materials such as encapsulants for parts, die bond materials, underfills, mounting materials for semiconductors (eg ACF, ACP, NCF, NCP, etc.), display equipment (eg liquid crystal panels and OLED displays, etc.) and lighting equipment (eg OLED). It can be preferably used as a sealing material for lighting, etc.), a composite material for repairing concrete, and the like, and in particular, it can be preferably used as an adhesive for a secondary battery.
  • semiconductors eg ACF, ACP, NCF, NCP, etc.
  • display equipment eg liquid crystal panels and OLED displays, etc.
  • lighting equipment eg OLED

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Abstract

The present invention addresses the problem of providing a curable resin composition that is superior as a two-component or multi-component epoxy resin composition as compared to the prior art. Provided is a curable resin composition including an epoxy resin, an epoxy curing agent, and polymer particles, wherein either (i) a specific amount of aluminum hydroxide of a specific particle size is further included, (ii) aluminum hydroxide is further included and the polymer particles are of a specific configuration, or (iii) a compound having a specific configuration is further included and the epoxy curing agent is of a specific configuration.

Description

硬化性樹脂組成物及び接着剤Curable resin composition and adhesive

　本発明は、エポキシ樹脂を含む二成分型の硬化性樹脂組成物、及び、それを含む接着剤に関する。 The present invention relates to a two-component curable resin composition containing an epoxy resin and an adhesive containing the same.

　接着剤として様々な組成物が知られている（例えば、特許文献１）また、エポキシ樹脂組成物を硬化して得られる硬化物は、強度、耐熱性、耐水性、耐薬品性および電気絶縁性などに優れる。そのため、エポキシ樹脂組成物は、工業用及び土木建築用等の幅広い用途で用いられている。現在、エポキシ樹脂組成物として、様々なものが開発されている（例えば、特許文献２～４など）。 Various compositions are known as adhesives (for example, Patent Document 1). Further, the cured product obtained by curing the epoxy resin composition has strength, heat resistance, water resistance, chemical resistance and electrical insulation. Excellent for such things. Therefore, the epoxy resin composition is used in a wide range of applications such as industrial use and civil engineering and construction use. Currently, various epoxy resin compositions have been developed (for example, Patent Documents 2 to 4 and the like).

ＷＯ２０１６－１３７３０３号公報WO2016-137303 Gazette ＷＯ２００９－０３４９６６号公報WO2009-034966 Gazette ＷＯ２００９－０２５９９１号公報WO2009-02591A Gazette 特開２０１７－１４９８８７号公報Japanese Unexamined Patent Publication No. 2017-1498887

　しかしながら、上述のような従来技術は、二成分型または多成分型のエポキシ樹脂組成物として十分なものでなく、さらなる改善の余地があった。 However, the above-mentioned prior art is not sufficient as a two-component or multi-component epoxy resin composition, and there is room for further improvement.

　本発明の一実施形態は、前記問題点に鑑みなされたものであり、その目的は、二成分型または多成分型のエポキシ樹脂組成物として従来と比して優れた、新規の硬化性樹脂組成物を提供することである。 One embodiment of the present invention has been made in view of the above problems, and an object thereof is a novel curable resin composition which is superior to the conventional one as a two-component type or multi-component type epoxy resin composition. To provide things.

　本発明者らは、前記課題を解決するため鋭意検討した結果、本発明を完成させるに至った。 The present inventors have completed the present invention as a result of diligent studies to solve the above-mentioned problems.

　すなわち、本発明の一実施形態に係る硬化性樹脂組成物は、二成分型の硬化性樹脂組成物であって、エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含み、前記硬化性樹脂組成物は、更に、コア層とシェル層とを含むコアシェル構造を有するポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）とを含有し、前記硬化性樹脂組成物の総重量１００重量％における前記水酸化アルミニウム（Ｃ）の総重量が、５５重量％以上８５重量％以下であり、前記水酸化アルミニウム（Ｃ）の平均粒子径が、１１μｍ以上２００μｍ以下である。 That is, the curable resin composition according to the embodiment of the present invention is a two-component curable resin composition, which comprises a first component containing an epoxy resin (A) and an epoxy curing agent (D). The curable resin composition further contains a polymer particle (B) having a core-shell structure including a core layer and a shell layer, and aluminum hydroxide (C). The total weight of the aluminum hydroxide (C) in the total weight of 100% by weight of the curable resin composition is 55% by weight or more and 85% by weight or less, and the average particle size of the aluminum hydroxide (C) is 11 μm or more. It is 200 μm or less.

　また、本発明の別の一実施形態に係る硬化性樹脂組成物は、二成分型の硬化性樹脂組成物であって、エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含み、前記硬化性樹脂組成物は、更に、コア層とシェル層とを含むコアシェル構造を有するポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）とを含有し、前記硬化性樹脂組成物の総重量１００重量％における前記水酸化アルミニウム（Ｃ）の総重量が、５５重量％以上８５重量％以下であり、前記ポリマー粒子（Ｂ）の平均粒子径が、０．１５μｍ以上０．３０μｍ以下であり、前記ポリマー粒子（Ｂ）における、前記シェル層の重量に対する前記コア層の重量の比（前記コア層の重量／前記シェル層の重量）が、６５／３５～９２／８であり、前記ポリマー粒子（Ｂ）の前記シェル層が、モノマー成分１００重量％中炭素数１～４のアルキル（メタ）アクリレートを５５ｗｔ％以上含有する当該モノマー成分を重合してなる共重合体であり、前記モノマー成分は、当該モノマー成分１００重量％中、炭素数１のアルキル（メタ）アクリレートを１０～１００ｗｔ％および炭素数４のアルキル（メタ）アクリレートを０～８０ｗｔ％含有する、硬化性樹脂組成物。 Further, the curable resin composition according to another embodiment of the present invention is a two-component curable resin composition, in which the first component containing the epoxy resin (A) and the epoxy curing agent (D) are used. ), And the curable resin composition further contains polymer particles (B) having a core-shell structure including a core layer and a shell layer, and aluminum hydroxide (C). The total weight of the aluminum hydroxide (C) in 100% by weight of the total weight of the curable resin composition is 55% by weight or more and 85% by weight or less, and the average particle size of the polymer particles (B) is 0. .15 μm or more and 0.30 μm or less, and the ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer / weight of the shell layer) in the polymer particles (B) is 65/35 to It is 92/8, and the shell layer of the polymer particles (B) is obtained by polymerizing the monomer component containing 55 wt% or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of the monomer component. It is a polymer, and the monomer component contains 10 to 100 wt% of an alkyl (meth) acrylate having 1 carbon atom and 0 to 80 wt% of an alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the monomer component. Curable resin composition.

　また、本発明の別の一実施形態に係る硬化性樹脂組成物は、二成分型または多成分型の硬化性樹脂組成物であって、エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含み、前記硬化性樹脂組成物は、更に、コア層とシェル層とを含むコアシェル構造を有するポリマー粒子（Ｂ）と、１分子中に（ｉ）１個の芳香環、および（ｉｉ）少なくとも２個のフェノール性水酸基を有する化合物（Ｇ）と、を含有し、前記化合物（Ｇ）において、前記フェノール性水酸基に対してオルト位に位置する第三級アルキル基の個数は、１分子中に０個又は１個であり、前記エポキシ硬化剤（Ｄ）が、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上である、硬化性樹脂組成物。 Further, the curable resin composition according to another embodiment of the present invention is a two-component type or multi-component type curable resin composition, which is a first component containing an epoxy resin (A) and an epoxy. The curable resin composition contains a second component containing a curing agent (D), and the curable resin composition further comprises a polymer particle (B) having a core-shell structure including a core layer and a shell layer, and the polymer particles (B) having a core-shell structure are contained in one molecule ( i) It contains one aromatic ring and (ii) a compound (G) having at least two phenolic hydroxyl groups, and is located in the ortho position with respect to the phenolic hydroxyl group in the compound (G). The number of tertiary alkyl groups is 0 or 1 in one molecule, and the epoxy curing agent (D) is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, or an amine-terminated butadiene nitrile. At least one selected from the group consisting of rubber, modified aliphatic amines, modified alicyclic amines, modified amidamines, modified amine-terminated polyethers and modified amine-terminated butadiene nitrile rubbers. There is a curable resin composition.

　本発明の一実施形態によれば、二成分型または多成分型のエポキシ樹脂組成物として従来と比して優れた、硬化性樹脂組成物を提供することができるという効果を奏する。 According to one embodiment of the present invention, it is possible to provide a curable resin composition which is superior to the conventional one as a two-component type or multi-component type epoxy resin composition.

　本発明の一実施形態について以下に説明するが、本発明はこれに限定されるものではない。本発明は、以下に説明する各構成に限定されるものではなく、請求の範囲に示した範囲で種々の変更が可能である。また、異なる実施形態または実施例にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態または実施例についても、本発明の技術的範囲に含まれる。さらに、各実施形態にそれぞれ開示された技術的手段を組み合わせることにより、新しい技術的特徴を形成することができる。なお、本明細書中に記載された学術文献および特許文献の全てが、本明細書中において参考文献として援用される。また、本明細書において特記しない限り、数値範囲を表す「Ａ～Ｂ」は、「Ａ以上（Ａを含みかつＡより大きい）Ｂ以下（Ｂを含みかつＢより小さい）」を意図する。 An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope of the claims. The technical scope of the present invention also includes embodiments or examples obtained by appropriately combining the technical means disclosed in different embodiments or examples. Further, by combining the technical means disclosed in each embodiment, new technical features can be formed. In addition, all the academic documents and patent documents described in the present specification are incorporated as references in the present specification. Further, unless otherwise specified in the present specification, "A to B" representing a numerical range is intended to be "A or more (including A and larger than A) and B or less (including B and smaller than B)".

　〔Ｉ．第１実施形態〕
　第１実施形態は、エポキシ樹脂を含む二成分型の硬化性樹脂組成物、及び、それを含む接着剤に関する。 [I. First Embodiment]
The first embodiment relates to a two-component curable resin composition containing an epoxy resin and an adhesive containing the same.

　二次電池や半導体などの電気デバイスは、近年の高機能化にともないデバイスからの発熱量が増大し、デバイスからの放熱が重要となっている。特にワイヤレスモバイル機器や電気自動車（ＥＶ）のバッテリーモジュールなどに使用されるリチウムイオン電池等の二次電池は、充放電時に電池内部で発生する熱が蓄積し電池の内部温度が上昇する為、熱を効率良く放散することは電池の信頼性や寿命に繋がる重要な課題である。特許文献１には、バッテリーセルをモジュールケースに熱伝導性の接着剤で固定されたバッテリーモジュールが開示されている。 For electric devices such as secondary batteries and semiconductors, the amount of heat generated from the device has increased with the recent increase in functionality, and heat dissipation from the device has become important. In particular, secondary batteries such as lithium-ion batteries used in wireless mobile devices and battery modules of electric vehicles (EVs) accumulate heat generated inside the batteries during charging and discharging, and the internal temperature of the batteries rises. Efficiently dissipating the battery is an important issue that leads to the reliability and life of the battery. Patent Document 1 discloses a battery module in which a battery cell is fixed to a module case with a heat conductive adhesive.

　また、特許文献１に記載の様に、充放電時の熱の蓄積に伴って発生し得る火災およびその他の事故に対する安全性を高める為に、前記デバイスに使用する硬化性樹脂組成物は難燃性を示すことが求められ、ＵＬ　９４　Ｖ　Ｔｅｓｔ（Ｖｅｒｔｉｃａｌ　Ｂｕｒｎｉｎｇ　Ｔｅｓｔ）でＶ－０等級を示すことが望まれている。 Further, as described in Patent Document 1, the curable resin composition used for the device is flame-retardant in order to enhance safety against fire and other accidents that may occur due to heat accumulation during charging / discharging. It is required to show sex, and it is desired to show V-0 grade in UL 94 V Test (Vertical Burning Test).

　また、特許文献１に記載の様に、ＥＶバッテリーは、多数の電池セルを並列させる構造であり、車両の衝突などの外部衝撃によりせん断応力が加わる為、各電池セルをバッテリーケースに固定する接着剤には高い接着力と耐衝撃性が求められる。 Further, as described in Patent Document 1, the EV battery has a structure in which a large number of battery cells are arranged in parallel, and shear stress is applied due to an external impact such as a vehicle collision, so that each battery cell is fixed to the battery case by adhesion. The agent is required to have high adhesive strength and impact resistance.

　一方、エポキシ樹脂は、その硬化物が寸法安定性、機械的強度、電気的絶縁特性、耐熱性、耐水性、耐薬品性等の多くの点で優れているため、接着剤や封止剤等の硬化性樹脂組成物として電気デバイスに幅広く使用されている。 Epoxy resins, on the other hand, have excellent dimensional stability, mechanical strength, electrical insulation properties, heat resistance, water resistance, chemical resistance, etc., and therefore adhesives, sealants, etc. It is widely used in electric devices as a curable resin composition.

　特許文献２には、エポキシ樹脂などの硬化性樹脂を主成分とする硬化性樹脂組成物に、ポリマー微粒子を分散させることにより、得られる硬化物の靱性や耐衝撃性を改善する技術が開示されている。 Patent Document 2 discloses a technique for improving the toughness and impact resistance of a obtained cured product by dispersing polymer fine particles in a curable resin composition containing a curable resin such as an epoxy resin as a main component. ing.

　また、リチウムイオン電池は熱に弱い特性があり、加熱硬化型の一成分型エポキシ系硬化性樹脂組成物の使用は困難である。室温または室温に近い低温での硬化が可能な二成分型エポキシ系硬化性樹脂組成物は特許文献３などに開示されている。 In addition, lithium-ion batteries have the property of being sensitive to heat, and it is difficult to use a heat-curable one-component epoxy-based curable resin composition. A two-component epoxy-based curable resin composition that can be cured at room temperature or at a low temperature close to room temperature is disclosed in Patent Document 3 and the like.

　電気デバイスからの放熱性を高めるために、デバイスに使用する硬化性樹脂組成物に水酸化アルミやアルミナなどの熱伝導性フィラーを添加して熱伝導性を高める検討がされている。しかしながら、熱伝導性フィラーの添加に伴って、硬化性樹脂組成物を硬化して得られる硬化物の機械的強度、靭性、および、耐衝撃性が低下する場合がある。更に、電気デバイスに幅広く使用されているエポキシ樹脂の硬化物は破壊靭性が小さく、非常に脆性的な性質を示すという問題がある。 In order to improve the heat dissipation from the electric device, it is being studied to add a heat conductive filler such as aluminum hydroxide or alumina to the curable resin composition used for the device to improve the heat conductivity. However, with the addition of the thermally conductive filler, the mechanical strength, toughness, and impact resistance of the cured product obtained by curing the curable resin composition may decrease. Further, a cured product of an epoxy resin widely used in electric devices has a problem that it has a low fracture toughness and exhibits a very brittle property.

　特許文献１に記載の樹脂組成物は、耐衝撃性が十分ではなく改善の余地があった。また、特許文献２～３には、エポキシ樹脂と多量の水酸化アルミニウムを組合わせたエポキシ系硬化性樹脂組成物における、耐衝撃接着性の改善技術について記載されていない。 The resin composition described in Patent Document 1 did not have sufficient impact resistance and had room for improvement. Further, Patent Documents 2 to 3 do not describe a technique for improving impact resistance in an epoxy-based curable resin composition in which an epoxy resin and a large amount of aluminum hydroxide are combined.

　第１実施形態に係る発明は、上記現状に鑑み、エポキシ樹脂と水酸化アルミニウムを配合し、かつ、優れた熱伝導性、難燃性、接着強度、及び耐衝撃剥離接着性を示す硬化物を与え、室温または室温に近い低温でも硬化し得る二成分型の硬化性樹脂組成物を提供することを目的とする。 In view of the above situation, the invention according to the first embodiment is a cured product in which an epoxy resin and aluminum hydroxide are blended and which exhibits excellent thermal conductivity, flame retardancy, adhesive strength, and impact peeling adhesiveness. It is an object of the present invention to provide a two-component curable resin composition that can be cured at room temperature or at a low temperature close to room temperature.

　本発明者らは上記課題を解決するために鋭意研究を重ねた結果、エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分、を含む二成分型の硬化性樹脂組成物に、コアシェル構造を有するポリマー粒子（Ｂ）と、特定の平均粒子径を有する水酸化アルミニウム（Ｃ）を特定の重量比で配合することで、優れた熱伝導性、難燃性、接着強度、及び耐衝撃剥離接着性を示す硬化物が得られることを見出した。 As a result of diligent research to solve the above problems, the present inventors have conducted a two-component type containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D). By blending the polymer particles (B) having a core-shell structure and the aluminum hydroxide (C) having a specific average particle size in a specific weight ratio in the curable resin composition of the above, excellent thermal conductivity and difficulty are achieved. It has been found that a cured product exhibiting flammability, adhesive strength, and impact-resistant peeling adhesiveness can be obtained.

　すなわち、第１実施形態に係る発明は、エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含む硬化性樹脂組成物であって、前記第一成分および／または前記第二成分に、更に、コアシェル構造を有するポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）を含有し、前記硬化性樹脂組成物の総重量に対する前記水酸化アルミニウム（Ｃ）の総重量が、５５重量％以上８５重量％以下であり、前記水酸化アルミニウム（Ｃ）の平均粒子径が、１１μｍ以上２００μｍ以下であり、前記硬化性樹脂組成物が二成分型または多成分型である、硬化性樹脂組成物に関する。 That is, the invention according to the first embodiment is a curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D). The first component and / or the second component further contains the polymer particles (B) having a core-shell structure and the aluminum hydroxide (C), and the aluminum hydroxide (C) with respect to the total weight of the curable resin composition. ) Is 55% by weight or more and 85% by weight or less, the average particle size of the aluminum hydroxide (C) is 11 μm or more and 200 μm or less, and the curable resin composition is a two-component type or a multi-component type. It relates to a curable resin composition which is a mold.

　第１実施形態に係る硬化性樹脂組成物によれば、エポキシ樹脂と高添加量の水酸化アルミニウムにより得られる硬化物は優れた熱伝導性、難燃性、及び接着強度を発現できる。更に、第１実施形態に係る硬化性樹脂組成物では、特定の平均粒子径の水酸化アルミニウムを用いることでコアシェル構造を有するポリマー粒子による靭性改善効果が効果的に発現される。その結果、第１実施形態に係る硬化性樹脂組成物から得られる硬化物は優れた耐衝撃性を示すことができる。すなわち、第１実施形態によると、優れた熱伝導性、難燃性、接着強度、及び耐衝撃剥離接着性を示す硬化物を与えることができ、かつ、室温または室温に近い低温でも硬化し得る二成分型の硬化性樹脂組成物を提供することができる。 According to the curable resin composition according to the first embodiment, the cured product obtained by the epoxy resin and a high amount of aluminum hydroxide can exhibit excellent thermal conductivity, flame retardancy, and adhesive strength. Further, in the curable resin composition according to the first embodiment, the toughness improving effect of the polymer particles having a core-shell structure is effectively exhibited by using aluminum hydroxide having a specific average particle size. As a result, the cured product obtained from the curable resin composition according to the first embodiment can exhibit excellent impact resistance. That is, according to the first embodiment, it is possible to provide a cured product exhibiting excellent thermal conductivity, flame retardancy, adhesive strength, and impact-resistant peeling adhesiveness, and it can be cured even at room temperature or a low temperature close to room temperature. A two-component curable resin composition can be provided.

　別の表現をすれば、第１実施形態は、少なくとも、エポキシ樹脂（Ａ）、コアシェル構造を有するポリマー粒子（Ｂ）、水酸化アルミニウム（Ｃ）、およびエポキシ硬化剤（Ｄ）を含有する硬化性樹脂組成物である。第１実施形態に係る硬化性樹脂組成物は、エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分とを必須成分として含み、更には、必要に応じてカラートナーや硬化性調整剤など、その他の成分を、使用直前に混合して用いる二成分型または多成分型硬化性樹脂組成物である。また第１実施形態に係る硬化性樹脂組成物は、更に、コアシェル構造を有するポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）を含有する。コアシェル構造を有するポリマー粒子（Ｂ）および水酸化アルミニウム（Ｃ）は、各々、第一成分および／または第二成分に含有されることが好ましい。第１実施形態に係る硬化性樹脂組成物は、第一成分および第二成分以外に、必要に応じて別の成分を含んでいても良い。 In other words, the first embodiment is curable containing at least an epoxy resin (A), polymer particles (B) having a core-shell structure, aluminum hydroxide (C), and an epoxy curing agent (D). It is a resin composition. The curable resin composition according to the first embodiment contains a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D) as essential components, and further, if necessary. It is a two-component type or multi-component type curable resin composition in which other components such as a color toner and a curability adjusting agent are mixed and used immediately before use. Further, the curable resin composition according to the first embodiment further contains polymer particles (B) having a core-shell structure and aluminum hydroxide (C). The polymer particles (B) and aluminum hydroxide (C) having a core-shell structure are preferably contained in the first component and / or the second component, respectively. The curable resin composition according to the first embodiment may contain another component, if necessary, in addition to the first component and the second component.

　本明細書において、「エポキシ樹脂（Ａ）」、「ポリマー粒子（Ｂ）」、「水酸化アルミニウム（Ｃ）」および「エポキシ硬化剤（Ｄ）」は、それぞれ、「（Ａ）成分」、「（Ｂ）成分」、「（Ｃ）成分」および「（Ｄ）成分」と表される場合がある。 In the present specification, "epoxy resin (A)", "polymer particles (B)", "aluminum hydroxide (C)" and "epoxy curing agent (D)" are "component (A)" and "component", respectively. It may be expressed as "(B) component", "(C) component" and "(D) component".

　本明細書において、「接着強度」及び「耐衝撃剥離接着性」をまとめて「接着性」とも称する。 In the present specification, "adhesive strength" and "impact peeling adhesiveness" are collectively referred to as "adhesiveness".

　また、本明細書において、接着強度は、せん断接着強さ（ＭＰａ）によって評価する。すなわち、接着強度とはせん断接着強さ（ＭＰａ）の値を意図する。硬化後のせん断接着強さ（ＭＰａ）の値が大きいほど、硬化性樹脂組成物は、接着強度に優れることを意味する。 Further, in the present specification, the adhesive strength is evaluated by the shear adhesive strength (MPa). That is, the adhesive strength is intended to be the value of the shear adhesive strength (MPa). The larger the value of the shear adhesive strength (MPa) after curing, the more excellent the curable resin composition is in the adhesive strength.

　また、本明細書において、耐衝撃剥離接着性は、ＩＳＯ　１１３４３に従って、２３℃で測定される動的割裂抵抗力によって評価され得る。すなわち、耐衝撃剥離接着性とは動的割裂抵抗力（ｋＮ／ｍ）の値を意図する。硬化後の動的割裂抵抗力の値が大きいほど、硬化性樹脂組成物は、耐衝撃剥離接着性に優れることを意味する。 Further, in the present specification, the impact resistance peeling adhesiveness can be evaluated by the dynamic split resistance measured at 23 ° C. according to ISO 11343. That is, the impact resistance peeling adhesiveness is intended to be the value of the dynamic split resistance force (kN / m). The larger the value of the dynamic split resistance after curing, the better the impact-resistant peeling adhesiveness of the curable resin composition.

　＜エポキシ樹脂（Ａ）＞
　第１実施形態の硬化性樹脂組成物は、硬化性樹脂として、エポキシ樹脂（Ａ）を第一成分に含有する。エポキシ樹脂としては、各種のエポキシ樹脂を使用することができる。例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ノボラック型エポキシ樹脂、ビスフェノールＡプロピレンオキシド付加物のグリシジルエーテル型エポキシ樹脂、水添ビスフェノールＡ（又はＦ）型エポキシ樹脂、フッ素化エポキシ樹脂、テトラブロモビスフェノールＡのグリシジルエーテルなどの難燃型エポキシ樹脂、ｐ－オキシ安息香酸グリシジルエーテルエステル型エポキシ樹脂、ｍ－アミノフェノール型エポキシ樹脂、ジアミノジフェニルメタン系エポキシ樹脂、各種脂環式エポキシ樹脂、Ｎ，Ｎ－ジグリシジルアニリン、Ｎ，Ｎ－ジグリシジル－ｏ－トルイジン、トリグリシジルイソシアヌレート、ジビニルベンゼンジオキシド、レゾルシノールジグリシジルエーテル、ポリアルキレングリコールジグリシジルエーテル、グリコールジグリシジルエーテル、脂肪族多塩基酸のジグリシジルエステル、グリセリンのような二価以上の多価脂肪族アルコールのグリシジルエーテル、キレート変性エポキシ樹脂、ゴム変性エポキシ樹脂、ウレタン変性エポキシ樹脂、ヒダントイン型エポキシ樹脂、石油樹脂などのような不飽和重合体のエポキシ化物、含アミノグリシジルエーテル樹脂や、上記のエポキシ樹脂にビスフェノールＡ（又はＦ）類または多塩基酸類等を付加反応させて得られるエポキシ化合物などが例示されるが、これらに限定されるものではなく、一般に使用されているエポキシ樹脂が使用され得る。これらエポキシ樹脂は単独で用いても良く、２種以上を併用しても良い。 <Epoxy resin (A)>
The curable resin composition of the first embodiment contains an epoxy resin (A) as a curable resin as a first component. As the epoxy resin, various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, novolak type epoxy resin, bisphenol A propylene oxide adduct Flame-retardant epoxy resin such as glycidyl ether type epoxy resin, hydrogenated bisphenol A (or F) type epoxy resin, fluorinated epoxy resin, glycidyl ether of tetrabromobisphenol A, p-oxybenzoate glycidyl ether ester type epoxy resin, m-Aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, divinylbenzenedioxide, resorcinol Diglycidyl ether, polyalkylene glycol diglycidyl ether, glycol diglycidyl ether, diglycidyl ester of aliphatic polybasic acid, glycidyl ether of divalent or higher polyvalent aliphatic alcohol such as glycerin, chelate-modified epoxy resin, rubber-modified Epoxy resins, urethane-modified epoxy resins, hidden-in type epoxy resins, unsaturated polymer epoxies such as petroleum resins, aminoglycidyl ether resins containing aminoglycidyl, and bisphenol A (or F) or polybasic acids in the above epoxy resins. Examples thereof include epoxy compounds obtained by subjecting them to an addition reaction, but the present invention is not limited to these, and commonly used epoxy resins can be used. These epoxy resins may be used alone or in combination of two or more.

　これらのうち、前記ポリアルキレングリコールジグリシジルエーテルとしては、より具体的には、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテルなどが挙げられる。前記グリコールジグリシジルエーテルとしては、より具体的には、ネオペンチルグリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、シクロヘキサンジメタノールジグリシジルエーテルなどが挙げられる。前記脂肪族多塩基酸のジグリシジルエステルとしては、より具体的には、ダイマー酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、マレイン酸ジグリシジルエステルなどが挙げられる。前記二価以上の多価脂肪族アルコールのグリシジルエーテルとしては、より具体的には、トリメチロールプロパントリグリシジルエーテル、トリメチロールエタントリグリシジルエーテル、ひまし油変性ポリグリシジルエーテル、プロポキシ化グリセリントリグリシジルエーテル、ソルビトールポリグリシジルエーテルなどが挙げられる。エポキシ樹脂に多塩基酸類等を付加反応させて得られるエポキシ化合物としては、例えば、国際公開第２０１０－０９８９５０号に記載されているような、トール油脂肪酸の二量体（ダイマー酸）とビスフェノールＡ型エポキシ樹脂との付加反応物が挙げられる。 Among these, examples of the polyalkylene glycol diglycidyl ether include polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether. More specific examples of the glycol diglycidyl ether include neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether and the like. Will be. More specific examples of the aliphatic polybasic acid diglycidyl ester include dimer acid diglycidyl ester, adipate diglycidyl ester, sebacic acid diglycidyl ester, and maleic acid diglycidyl ester. Specific examples of the glycidyl ether of the dihydric or higher polyhydric alcohol include trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil modified polyglycidyl ether, propoxylated glycerin triglycidyl ether, and sorbitol. Examples include polyglycidyl ether. Examples of the epoxy compound obtained by adding a polybasic acid or the like to an epoxy resin include a dimer of tall oil fatty acid (dimeric acid) and bisphenol A as described in International Publication No. 2010-098950. Examples thereof include an addition reaction product with a type epoxy resin.

　前記ポリアルキレングリコールジグリシジルエーテル、前記グリコールジグリシジルエーテル、前記脂肪族多塩基酸のジグリシジルエステル、前記二価以上の多価脂肪族アルコールのグリシジルエーテルは、比較的低い粘度を有するエポキシ樹脂であり、ビスフェノールＡ型エポキシ樹脂やビスフェノールＦ型エポキシ樹脂等の他のエポキシ樹脂と併用すると、反応性希釈剤として機能し、組成物の粘度と硬化物の物性とのバランスを改良することができる。すなわち、前記エポキシ樹脂（Ａ）は、反応性希釈剤としてポリエポキシドを含むことが好ましい。他方、モノエポキシドは、後述する通り、反応性希釈剤として機能するが、エポキシ樹脂（Ａ）には含まれない。これら反応性希釈剤として機能するエポキシ樹脂の含有量は、（Ａ）成分中の０．５～３０重量％が好ましく、２～２０重量％がより好ましく、５～１５重量％が更に好ましい。 The polyalkylene glycol diglycidyl ether, the glycol diglycidyl ether, the diglycidyl ester of the aliphatic polybasic acid, and the glycidyl ether of the divalent or higher polyhydric aliphatic alcohol are epoxy resins having a relatively low viscosity. When used in combination with other epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, it functions as a reactive diluent and can improve the balance between the viscosity of the composition and the physical properties of the cured product. That is, the epoxy resin (A) preferably contains a polyepoxy as a reactive diluent. On the other hand, the monoepoxide functions as a reactive diluent as described later, but is not contained in the epoxy resin (A). The content of the epoxy resin that functions as the reactive diluent is preferably 0.5 to 30% by weight, more preferably 2 to 20% by weight, still more preferably 5 to 15% by weight in the component (A).

　前記キレート変性エポキシ樹脂は、エポキシ樹脂とキレート官能基を含有する化合物（キレート配位子）との反応生成物であり、これを添加した硬化性樹脂組成物を車両用接着剤として用いた場合、油状物質で汚染された金属基材表面への接着性を改善できる。キレート官能基は、金属イオンへ配位可能な配位座を分子内に複数有する化合物の官能基であり、例えば、リン含有酸基（例えば、－ＰＯ（ＯＨ）２）、カルボン酸基（－ＣＯ２Ｈ）、硫黄含有酸基（例えば、－ＳＯ３Ｈ）、アミノ基及び水酸基（特に、芳香環において互いに隣接した水酸基）などが挙げられる。キレート配位子としては、エチレンジアミン、ビピリジン、エチレンジアミン四酢酸、フェナントロリン、ポルフィリン、クラウンエーテル、などが挙げられる。市販されているキレート変性エポキシ樹脂としては、ＡＤＥＫＡ製アデカレジンＥＰ－４９－１０Ｎなどが挙げられる。（Ａ）成分中のキレート変性エポキシ樹脂の使用量は、好ましくは０．１～１０重量％、より好ましくは０．５～３重量％である。 The chelate-modified epoxy resin is a reaction product of an epoxy resin and a compound (chelate ligand) containing a chelate functional group, and when the curable resin composition to which the epoxy resin is added is used as an adhesive for vehicles, Adhesion to the surface of a metal substrate contaminated with an oily substance can be improved. The chelate functional group is a functional group of a compound having a plurality of coordination positions capable of coordinating to a metal ion in the molecule, and is, for example, a phosphorus-containing acid group (for example, -PO (OH) 2 ) or a carboxylic acid group (-). CO 2 H), sulfur-containing acid groups (eg, —SO 3 H), amino groups and hydroxyl groups (particularly, hydroxyl groups adjacent to each other in the aromatic ring) and the like. Examples of the chelating ligand include ethylenediamine, bipyridine, ethylenediaminetetraacetic acid, phenanthroline, porphyrin, crown ether, and the like. Examples of commercially available chelate-modified epoxy resins include ADEKA's ADEKA REGIN EP-49-10N. The amount of the chelate-modified epoxy resin used in the component (A) is preferably 0.1 to 10% by weight, more preferably 0.5 to 3% by weight.

　前記ゴム変性エポキシ樹脂は、ゴムとエポキシ基含有化合物とを反応させて得た、１分子当り平均して、エポキシ基を１．１個以上、好ましくは２個以上有する反応生成物である。ゴムとしては、アクリロニトリルブタジエンゴム（ＮＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、水素添加ニトリルゴム（ＨＮＢＲ）、エチレンプロピレンゴム（ＥＰＤＭ）、アクリルゴム（ＡＣＭ）、ブチルゴム（ＩＩＲ）、ブタジエンゴム、ポリプロピレンオキシドやポリエチレンオキシドやポリテトラメチレンオキシド等のポリオキシアルキレン、などのゴム系重合体を挙げることができる。該ゴム系重合体は、アミノ基、ヒドロキシ基、またはカルボキシル基等の反応性基を末端に有するものが好ましい。これらのゴム系重合体とエポキシ樹脂とを公知の方法により適宜の配合比にて反応させた生成物がゴム変性エポキシ樹脂である。これらの中でも、アクリロニトリル－ブタジエンゴム変性エポキシ樹脂や、ポリオキシアルキレン変性エポキシ樹脂が、得られる硬化性樹脂組成物の接着強度および耐衝撃剥離接着性の観点から好ましく、アクリロニトリル－ブタジエンゴム変性エポキシ樹脂がより好ましい。なお、アクリロニトリル－ブタジエンゴム変性エポキシ樹脂は、例えば、カルボキシル基末端ＮＢＲ（ＣＴＢＮ）とビスフェノールＡ型エポキシ樹脂との反応により得られる。 The rubber-modified epoxy resin is a reaction product obtained by reacting rubber with an epoxy group-containing compound and having 1.1 or more, preferably two or more epoxy groups on average per molecule. Examples of rubber include acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), hydrogenated nitrile rubber (HNBR), ethylene propylene rubber (EPDM), acrylic rubber (ACM), butyl rubber (IIR), butadiene rubber, and polypropylene oxide. Examples thereof include rubber-based polymers such as polyoxyalkylenes such as polyethylene oxide and polytetramethylene oxide. The rubber-based polymer preferably has a reactive group such as an amino group, a hydroxy group, or a carboxyl group at the end. A rubber-modified epoxy resin is a product obtained by reacting these rubber-based polymers with an epoxy resin in an appropriate compounding ratio by a known method. Among these, acrylonitrile-butadiene rubber-modified epoxy resin and polyoxyalkylene-modified epoxy resin are preferable from the viewpoint of adhesive strength and impact-resistant peeling adhesiveness of the obtained curable resin composition, and acrylonitrile-butadiene rubber-modified epoxy resin is preferable. More preferred. The acrylonitrile-butadiene rubber-modified epoxy resin can be obtained, for example, by reacting a carboxyl group-terminated NBR (CTBN) with a bisphenol A type epoxy resin.

　前記アクリロニトリル－ブタジエンゴム変性エポキシ樹脂において、アクリロニトリル－ブタジエンゴム中のアクリロニトリル単量体成分の含有量は、得られる硬化性樹脂組成物の接着強度および耐衝撃剥離接着性の観点から、５～４０重量％が好ましく、１０～３５重量％がより好ましく、１５～３０重量％が更に好ましい。得られる硬化性樹脂組成物の作業性の観点から、２０～３０重量％が特に好ましい。 In the acrylonitrile-butadiene rubber modified epoxy resin, the content of the acrylonitrile monomer component in the acrylonitrile-butadiene rubber is 5 to 40 weights from the viewpoint of the adhesive strength and the impact-resistant peeling adhesiveness of the obtained curable resin composition. % Is preferred, 10 to 35% by weight is more preferable, and 15 to 30% by weight is even more preferable. From the viewpoint of workability of the obtained curable resin composition, 20 to 30% by weight is particularly preferable.

　本明細書において、「硬化性樹脂組成物の作業性」とは、硬化性樹脂組成物を用いる作業（塗布等）における作業性を意図する。 In the present specification, "workability of the curable resin composition" is intended to be workability in work (coating, etc.) using the curable resin composition.

　また、例えば、アミノ基末端ポリオキシアルキレンとエポキシ樹脂との付加反応生成物（以下、「付加物」とも呼ぶ。）もまた、ゴム変性エポキシ樹脂に含まれる。前記付加物の製造は、例えば、米国特許第５０８４５３２号や米国特許第６０１５８６５号等に記載されているように、公知の方法で簡易に製造することができる。付加物を製造する際に使用される前記エポキシ樹脂は、例えば、前述した（Ａ）成分の具体例が挙げられるが、ビスフェノールＡ型エポキシ樹脂やビスフェノールＦ型エポキシ樹脂が好ましく、ビスフェノールＡ型エポキシ樹脂がより好ましい。付加物を製造する際に使用される、市販されている前記アミノ基末端ポリオキシアルキレンは、例えば、Ｈｕｎｔｓｍａｎ社製のＪｅｆｆａｍｉｎｅ　Ｄ－２３０、Ｊｅｆｆａｍｉｎｅ　Ｄ－４００、Ｊｅｆｆａｍｉｎｅ　Ｄ－２０００、Ｊｅｆｆａｍｉｎｅ　Ｄ－４０００、Ｊｅｆｆａｍｉｎｅ　Ｔ－５０００などが挙げられる。 Further, for example, an addition reaction product of an amino group-terminated polyoxyalkylene and an epoxy resin (hereinafter, also referred to as an “adduct”) is also included in the rubber-modified epoxy resin. The adduct can be easily produced by a known method, for example, as described in US Pat. No. 5,084532, US Pat. No. 6,015865, and the like. Examples of the epoxy resin used in producing the adduct include specific examples of the component (A) described above, but bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable, and bisphenol A type epoxy resin is preferable. Is more preferable. Commercially available amino group-terminated polyoxyalkylenes used in the production of adducts include, for example, Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, manufactured by Huntsman. Examples include Jeffamine T-5000.

　前記ゴム中の１分子当たりの平均のエポキシド反応性末端基の数は、１．５～２．５個が好ましく、１．８～２．２個がより好ましい。なお、「エポキシド反応性末端基」とは、エポキシ基との反応性を有する末端基を意図する。 The average number of epoxide-reactive end groups per molecule in the rubber is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. The "epoxide-reactive end group" is intended to be an end group having reactivity with an epoxy group.

　ゴムの数平均分子量は、ＧＰＣで測定したポリスチレン換算分子量にて、１０００～１００００が好ましく、２０００～８０００がより好ましく、３０００～６０００が特に好ましい。 The number average molecular weight of rubber is preferably 1000 to 10000, more preferably 2000 to 8000, and particularly preferably 3000 to 6000 in terms of polystyrene-equivalent molecular weight measured by GPC.

　ゴム変性エポキシ樹脂の製法について特に制限は無く、例えば、多量のエポキシ基含有化合物中でゴムとエポキシ基含有化合物とを反応させて製造することができる。具体的には、ゴム中の１当量のエポキシ反応性末端基当たり、２当量以上のエポキシ基含有化合物を反応させて製造することが好ましい。得られる生成物が、ゴムとエポキシ基含有化合物との付加体と、遊離のエポキシ基含有化合物との混合物となるのに十分な量のエポキシ基含有化合物を反応させることがより好ましい。例えば、フェニルジメチル尿素やトリフェニルホスフィンなどの触媒の存在下で、１００～２５０℃の温度に加熱することにより、ゴム変性エポキシ樹脂は製造される。ゴム変性エポキシ樹脂を製造する際に使用されるエポキシ基含有化合物は特に制限は無いが、ビスフェノールＡ型エポキシ樹脂やビスフェノールＦ型エポキシ樹脂が好ましく、ビスフェノールＡ型エポキシ樹脂がより好ましい。なお、ゴム変性エポキシ樹脂の製造時に過剰量のエポキシ基含有化合物が使用された場合には、反応後に残存する未反応のエポキシ基含有化合物は、本明細書でいうゴム変性エポキシ樹脂には含まれないものとする。 There are no particular restrictions on the method for producing the rubber-modified epoxy resin, and for example, it can be produced by reacting rubber with an epoxy group-containing compound in a large amount of epoxy group-containing compound. Specifically, it is preferably produced by reacting 2 equivalents or more of an epoxy group-containing compound with 1 equivalent of an epoxy-reactive terminal group in rubber. It is more preferable that the obtained product reacts with an epoxy group-containing compound in an amount sufficient to form a mixture of the adduct of the rubber and the epoxy group-containing compound and the free epoxy group-containing compound. For example, a rubber-modified epoxy resin is produced by heating to a temperature of 100 to 250 ° C. in the presence of a catalyst such as phenyldimethylurea or triphenylphosphine. The epoxy group-containing compound used in producing the rubber-modified epoxy resin is not particularly limited, but bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable, and bisphenol A type epoxy resin is more preferable. When an excessive amount of the epoxy group-containing compound is used in the production of the rubber-modified epoxy resin, the unreacted epoxy group-containing compound remaining after the reaction is contained in the rubber-modified epoxy resin referred to in the present specification. Make it not exist.

　ゴム変性エポキシ樹脂では、ビスフェノール成分と予備反応させることでエポキシ樹脂を改質することができる。改質に使用するビスフェノール成分は、ゴム変性エポキシ樹脂中のゴム成分１００重量部に対し、３～３５重量部が好ましく、５～２５重量部がより好ましい。改質されたゴム変性エポキシ樹脂を含有する硬化性樹脂組成物を硬化してなる硬化物は、高温曝露後の接着耐久性に優れ、また、低温時の耐衝撃性にも優れる。 In the rubber-modified epoxy resin, the epoxy resin can be modified by pre-reacting with the bisphenol component. The bisphenol component used for the modification is preferably 3 to 35 parts by weight, more preferably 5 to 25 parts by weight, based on 100 parts by weight of the rubber component in the rubber-modified epoxy resin. A cured product obtained by curing a curable resin composition containing a modified rubber-modified epoxy resin has excellent adhesive durability after high-temperature exposure and also has excellent impact resistance at low temperatures.

　ゴム変性エポキシ樹脂のガラス転移温度（Ｔｇ）は、特に制限は無いが、－２５℃以下が好ましく、－３５℃以下がより好ましく、－４０℃以下が更に好ましく、－５０℃以下が特に好ましい。 The glass transition temperature (Tg) of the rubber-modified epoxy resin is not particularly limited, but is preferably −25 ° C. or lower, more preferably −35 ° C. or lower, further preferably −40 ° C. or lower, and particularly preferably −50 ° C. or lower.

　ゴム変性エポキシ樹脂の数平均分子量は、ＧＰＣで測定したポリスチレン換算分子量にて、１５００～４００００が好ましく、３０００～３００００がより好ましく、４０００～２００００が特に好ましい。分子量分布（重量平均分子量と数平均分子量との比）は、１～４が好ましく、１．２～３がより好ましく、１．５～２．５が特に好ましい。 The number average molecular weight of the rubber-modified epoxy resin is preferably 1500 to 40,000, more preferably 3000 to 30000, and particularly preferably 4000 to 20000 in terms of polystyrene-equivalent molecular weight measured by GPC. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 1 to 4, more preferably 1.2 to 3, and particularly preferably 1.5 to 2.5.

　ゴム変性エポキシ樹脂は、単独でまたは２種以上を組み合わせて使用することができる。 The rubber-modified epoxy resin can be used alone or in combination of two or more.

　（Ａ）成分中のゴム変性エポキシ樹脂の使用量は、１～５０重量％が好ましく、２～４０重量％がより好ましく、５～３０重量％が更に好ましく、１０～２０重量％が特に好ましい。 The amount of the rubber-modified epoxy resin used in the component (A) is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, further preferably 5 to 30% by weight, and particularly preferably 10 to 20% by weight.

　前記ウレタン変性エポキシ樹脂は、イソシアネート基との反応性を有する基とエポキシ基とを含有する化合物と、イソシアネート基を含有するウレタンプレポリマーを反応させて得た、１分子当り平均して、エポキシ基を１．１個以上、好ましくは２個以上有する反応生成物である。例えば、ヒドロキシ基含有エポキシ化合物とウレタンプレポリマーを反応させることにより、ウレタン変性エポキシ樹脂が得られる。 The urethane-modified epoxy resin is obtained by reacting a compound containing a group having a reactivity with an isocyanate group and an epoxy group with a urethane prepolymer containing an isocyanate group, and the epoxy group is averaged per molecule. It is a reaction product having 1.1 or more, preferably 2 or more. For example, a urethane-modified epoxy resin can be obtained by reacting a hydroxy group-containing epoxy compound with a urethane prepolymer.

　ウレタン変性エポキシ樹脂の数平均分子量は、ＧＰＣで測定したポリスチレン換算分子量にて、１５００～４００００が好ましく、３０００～３００００がより好ましく、４０００～２００００が特に好ましい。分子量分布（重量平均分子量と数平均分子量との比）は、１～４が好ましく、１．２～３がより好ましく、１．５～２．５が特に好ましい。 The number average molecular weight of the urethane-modified epoxy resin is preferably 1500 to 40,000, more preferably 3000 to 30000, and particularly preferably 4000 to 20000 in terms of polystyrene-equivalent molecular weight measured by GPC. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 1 to 4, more preferably 1.2 to 3, and particularly preferably 1.5 to 2.5.

　ウレタン変性エポキシ樹脂は、単独でまたは２種以上を組み合わせて使用することができる。 Urethane-modified epoxy resin can be used alone or in combination of two or more.

　（Ａ）成分中のウレタン変性エポキシ樹脂の使用量は、１～５０重量％が好ましく、２～４０重量％がより好ましく、５～３０重量％が更に好ましく、１０～２０重量％が特に好ましい。 The amount of the urethane-modified epoxy resin used in the component (A) is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, further preferably 5 to 30% by weight, and particularly preferably 10 to 20% by weight.

　これらのエポキシ樹脂の中でもエポキシ基を一分子中に少なくとも２個有するものが、硬化性が高く、硬化後の可撓性に富み、コアシェルポリマー粒子（Ｂ）の配合による耐衝撃剥離性を向上させる効果に優れるなどの点から好ましい。特に、エポキシ基を一分子中に２個有する化合物が好ましい。 Among these epoxy resins, those having at least two epoxy groups in one molecule have high curability, high flexibility after curing, and improve impact peeling resistance by blending core-shell polymer particles (B). It is preferable because it has an excellent effect. In particular, a compound having two epoxy groups in one molecule is preferable.

　（Ａ）成分として、前記のエポキシ樹脂の中でも、ビスフェノールＡ型エポキシ樹脂およびビスフェノールＦ型エポキシ樹脂は、得られる硬化物の弾性率が高く、耐熱性および接着性に優れ、比較的安価である。そのため、エポキシ樹脂（Ａ）は、ビスフェノールＡ型エポキシ樹脂および／またはビスフェノールＦ型エポキシ樹脂であることが好ましい。また、耐熱性に優れる硬化物を提供し得る硬化性樹脂組成物を低価格で得ることができることから、エポキシ樹脂（Ａ）は、ビスフェノールＡ型エポキシ樹脂であることが特に好ましい。 Among the above-mentioned epoxy resins as the component (A), the bisphenol A type epoxy resin and the bisphenol F type epoxy resin have a high elastic modulus of the obtained cured product, are excellent in heat resistance and adhesiveness, and are relatively inexpensive. Therefore, the epoxy resin (A) is preferably a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin. Further, the epoxy resin (A) is particularly preferably a bisphenol A type epoxy resin because a curable resin composition capable of providing a cured product having excellent heat resistance can be obtained at a low price.

　また、各種のエポキシ樹脂の中でも、エポキシ当量が２２０未満のエポキシ樹脂は、得られる硬化物の弾性率および耐熱性が高いため好ましく、エポキシ当量は９０以上２１０未満がより好ましく、１５０以上２００未満が更に好ましい。 Among various epoxy resins, an epoxy resin having an epoxy equivalent of less than 220 is preferable because of its high elastic modulus and heat resistance of the obtained cured product, and an epoxy equivalent of 90 or more and less than 210 is more preferable, and 150 or more and less than 200 is preferable. More preferred.

　特に、エポキシ当量が２２０未満のビスフェノールＡ型エポキシ樹脂およびビスフェノールＦ型エポキシ樹脂は、常温で液体であり、得られる硬化性樹脂組成物の取扱い性が良いため好ましい。 In particular, the bisphenol A type epoxy resin and the bisphenol F type epoxy resin having an epoxy equivalent of less than 220 are preferable because they are liquid at room temperature and the obtained curable resin composition is easy to handle.

　（Ａ）成分が、（Ａ）成分１００重量％中、エポキシ当量が２２０以上５０００未満のビスフェノールＡ型エポキシ樹脂およびビスフェノールＦ型エポキシ樹脂を、好ましくは４０重量％以下、より好ましくは２０重量％以下の範囲で含む場合、得られる硬化物が耐衝撃性に優れるため好ましい。 The bisphenol A type epoxy resin and the bisphenol F type epoxy resin having an epoxy equivalent of 220 or more and less than 5000 in 100% by weight of the component (A) are preferably 40% by weight or less, more preferably 20% by weight or less. When it is contained in the range of, the obtained cured product is preferable because it has excellent impact resistance.

　＜コアシェル構造を有するポリマー粒子（Ｂ）＞
　第１実施形態の硬化性樹脂組成物は、第一成分および／または前記第二成分中に、（Ｂ）成分として、コアシェル構造を有するポリマー粒子を含有する。ここで、「ポリマー粒子（Ｂ）がコアシェル構造を有する」とは、ポリマー粒子（Ｂ）が、コア層とシェル層とを有することを意図する。 <Polymer particles (B) having a core-shell structure>
The curable resin composition of the first embodiment contains polymer particles having a core-shell structure as the component (B) in the first component and / or the second component. Here, "the polymer particles (B) have a core-shell structure" means that the polymer particles (B) have a core layer and a shell layer.

　硬化性樹脂組成物が（Ｂ）成分を含む場合、（Ｂ）成分による靱性改良効果によって、得られる硬化物（例えば接着層）は耐衝撃剥離接着性に優れる。また、硬化性樹脂組成物が（Ｂ）成分を含む場合、得られる硬化物の接着強度が優れる傾向がある。（Ｂ）成分は第一成分のみに含有してもよく、第二成分のみに含有してもよく、第一成分と第二成分の双方に含有してもよい。（Ｂ）成分は、第二成分中の（Ｄ）成分などに含まれる低分子化合物により膨潤などが生じる可能性がある。そのため、組成物の貯蔵安定性の観点から、（Ｂ）成分は、少なくとも第一成分に含有することが好ましく、第一成分のみに含有することがより好ましい。以下では、「コアシェル構造を有するポリマー粒子（Ｂ）」を、「コアシェルポリマー粒子（Ｂ）」ともいう。 When the curable resin composition contains the component (B), the obtained cured product (for example, an adhesive layer) is excellent in impact resistance and peeling adhesiveness due to the toughness improving effect of the component (B). Further, when the curable resin composition contains the component (B), the adhesive strength of the obtained cured product tends to be excellent. The component (B) may be contained only in the first component, may be contained only in the second component, or may be contained in both the first component and the second component. The component (B) may be swollen or the like due to the small molecule compound contained in the component (D) in the second component. Therefore, from the viewpoint of storage stability of the composition, the component (B) is preferably contained in at least the first component, and more preferably contained only in the first component. Hereinafter, the "polymer particles (B) having a core-shell structure" are also referred to as "core-shell polymer particles (B)".

　コアシェルポリマー粒子（Ｂ）は、シェル層にエポキシ基を有するものであってもよく、有しないものであってもよい。換言すれば、コアシェルポリマー粒子（Ｂ）のシェル層は、エポキシ基を有していてもよく、エポキシ基を有していなくてもよい。得られる硬化物が耐衝撃剥離接着性に優れることから、コアシェルポリマー粒子（Ｂ）は、シェル層にエポキシ基を有するものが好ましい。コアシェルポリマー粒子（Ｂ）のシェル層がエポキシ基を有する場合、コアシェルポリマー粒子（Ｂ）のシェル層の総重量に対する、前記シェル層が有するエポキシ基の含有量は、得られる硬化物の耐衝撃剥離接着性の観点から、０ｍｍｏｌ／ｇを超えて２．０ｍｍｏｌ／ｇ以下であることが好ましく、０．１ｍｍｏｌ／ｇ以上２．０ｍｍｏｌ／ｇ以下であることがより好ましく、０．３ｍｍｏｌ／ｇ以上１．５ｍｍｏｌ／ｇ以下であることがより好ましい。これにより、コアシェルポリマー粒子（Ｂ）の凝集が抑制され、コアシェルポリマー粒子（Ｂ）が硬化物中に一次粒子の状態で分散することができ、その結果、硬化物の耐衝撃剥離接着性が改善され得ると推測される。シェル層にエポキシ基を有する場合には、（Ｂ）成分は、第一成分のみに含有することが好ましい。また、硬化性樹脂組成物の貯蔵安定性の観点から、コアシェルポリマー粒子（Ｂ）は、シェル層にエポキシ基を有しないものが好ましい。エポキシ基との反応性を有する後述のエポキシ硬化剤（Ｄ）を含有する第二成分に、コアシェルポリマー粒子（Ｂ）を添加する場合には、（Ｂ）成分はシェル層にエポキシ基を有しないものが好ましい。 The core-shell polymer particles (B) may or may not have an epoxy group in the shell layer. In other words, the shell layer of the core-shell polymer particles (B) may or may not have an epoxy group. Since the obtained cured product has excellent impact resistance and peeling adhesiveness, the core-shell polymer particles (B) preferably have an epoxy group in the shell layer. When the shell layer of the core-shell polymer particles (B) has an epoxy group, the content of the epoxy group contained in the shell layer with respect to the total weight of the shell layer of the core-shell polymer particles (B) is the impact-resistant peeling of the obtained cured product. From the viewpoint of adhesiveness, it is preferably more than 0 mmol / g and 2.0 mmol / g or less, more preferably 0.1 mmol / g or more and 2.0 mmol / g or less, and 0.3 mmol / g or more 1 It is more preferably 5.5 mmol / g or less. As a result, aggregation of the core-shell polymer particles (B) is suppressed, and the core-shell polymer particles (B) can be dispersed in the cured product in the form of primary particles, and as a result, the impact-resistant peeling adhesiveness of the cured product is improved. It is speculated that it can be done. When the shell layer has an epoxy group, the component (B) is preferably contained only in the first component. Further, from the viewpoint of storage stability of the curable resin composition, the core-shell polymer particles (B) preferably have no epoxy group in the shell layer. When the core-shell polymer particles (B) are added to the second component containing the epoxy curing agent (D) described later, which has reactivity with the epoxy group, the component (B) does not have an epoxy group in the shell layer. The one is preferable.

　硬化性樹脂組成物は、（ｉ）第一成分中に、シェル層にエポキシ基を有するコアシェルポリマー粒子（Ｂ）を含有し、かつ（ｉｉ）第二成分中に、シェル層にエポキシ基を有しないコアシェルポリマー粒子（Ｂ）を含有していてもよい。 The curable resin composition contains (i) core-shell polymer particles (B) having an epoxy group in the shell layer in the first component, and (ii) having an epoxy group in the shell layer in the second component. It may contain core-shell polymer particles (B) that do not.

　第１実施形態において、コアシェルポリマー粒子（Ｂ）の粒子径は特に限定されない。工業的生産性を考慮すると、第１実施形態におけるコアシェルポリマー粒子（Ｂ）の体積平均粒子径（Ｍｖ）は０．０１μｍ～２．００μｍ（１０ｎｍ～２０００ｎｍ）が好ましく、０．０３μｍ～０．６０μｍ（３０ｎｍ～６００ｎｍ）がより好ましく、０．０５μｍ～０．４０μｍ（５０ｎｍ～４００ｎｍ）がより好ましく、０．１０μｍ～０．３０μｍ（１００ｎｍ～３００ｎｍ）がより好ましく、０．１５μｍ～０．３０μｍであることがより好ましく、０．１６μｍ～０．２８μｍであることがより好ましく、０．１７μｍ～０．２７μｍであることがより好ましく、０．１８μｍ～０．２５μｍであることが更に好ましい。コアシェルポリマー粒子（Ｂ）の体積平均粒子径（Ｍｖ）が、（ａ）０．０１μｍ以上である場合、硬化性樹脂組成物の粘度が低くなるため、作業性が良好となり、（ｂ）２．００μｍ以下である場合、（Ｂ）成分の重合時間が短くなり、工業的生産性が高くなる。なお、本明細書において、ポリマー粒子の体積平均粒子径（Ｍｖ）は、ポリマー粒子のラテックスについて、マイクロトラックＵＰＡ１５０（日機装株式会社製）を用いて測定することができる。 In the first embodiment, the particle size of the core-shell polymer particles (B) is not particularly limited. Considering industrial productivity, the volume average particle diameter (Mv) of the core-shell polymer particles (B) in the first embodiment is preferably 0.01 μm to 2.00 μm (10 nm to 2000 nm), preferably 0.03 μm to 0.60 μm. (30 nm to 600 nm) is more preferable, 0.05 μm to 0.40 μm (50 nm to 400 nm) is more preferable, 0.10 μm to 0.30 μm (100 nm to 300 nm) is more preferable, and 0.15 μm to 0.30 μm. It is more preferably 0.16 μm to 0.28 μm, more preferably 0.17 μm to 0.27 μm, and even more preferably 0.18 μm to 0.25 μm. When the volume average particle diameter (Mv) of the core-shell polymer particles (B) is (a) 0.01 μm or more, the viscosity of the curable resin composition is low, so that workability is good, and (b) 2. When it is 00 μm or less, the polymerization time of the component (B) is shortened and the industrial productivity is increased. In the present specification, the volume average particle diameter (Mv) of the polymer particles can be measured with respect to the latex of the polymer particles using Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.).

　コアシェルポリマー粒子（Ｂ）は、硬化性樹脂組成物中において、その粒子径の個数分布において、前記体積平均粒子径の０．５倍以上、１倍以下の半値幅を有することが、得られる硬化性樹脂組成物が低粘度で取扱い易いため好ましい。 The curing obtained that the core-shell polymer particles (B) have a half-price width of 0.5 times or more and 1 times or less of the volume average particle diameter in the number distribution of the particle diameters in the curable resin composition. The sex resin composition is preferable because it has a low viscosity and is easy to handle.

　上述の特定の粒子径分布を容易に実現する観点から、コアシェルポリマー粒子（Ｂ）の粒子径の個数分布において、極大値が２個以上存在することが好ましく、製造時の手間やコストの観点から、極大値が２～３個存在することがより好ましく、極大値が２個存在することが更に好ましい。特に、体積平均粒子径が１０ｎｍ以上１５０ｎｍ未満のコアシェルポリマー粒子１０～９０重量％と、体積平均粒子径が１５０ｎｍ以上２０００ｎｍ以下のコアシェルポリマー粒子９０～１０重量％を含むことが好ましい。 From the viewpoint of easily realizing the above-mentioned specific particle size distribution, it is preferable that there are two or more maximum values in the number distribution of the particle size of the core-shell polymer particles (B), and from the viewpoint of labor and cost during manufacturing. , It is more preferable that there are 2 to 3 maximum values, and it is further preferable that there are 2 maximum values. In particular, it is preferable to contain 10 to 90% by weight of core-shell polymer particles having a volume average particle diameter of 10 nm or more and less than 150 nm, and 90 to 10% by weight of core-shell polymer particles having a volume average particle diameter of 150 nm or more and 2000 nm or less.

　コアシェルポリマー粒子（Ｂ）は硬化性樹脂組成物中で１次粒子の状態で分散していることが好ましい。本明細書における「コアシェルポリマー粒子が１次粒子の状態で分散している」（以下、一次分散とも呼ぶ。）とは、コアシェルポリマー粒子同士が実質的に独立して（接触なく）分散していることを意味し、その分散状態は、例えば、硬化性樹脂組成物の一部をメチルエチルケトンのような溶剤に溶解し、これをレーザー光散乱による粒子径測定装置等により、その粒子径を測定することにより確認できる。 It is preferable that the core-shell polymer particles (B) are dispersed in the state of primary particles in the curable resin composition. In the present specification, "the core-shell polymer particles are dispersed in the state of primary particles" (hereinafter, also referred to as primary dispersion) means that the core-shell polymer particles are dispersed substantially independently (without contact). In the dispersed state, for example, a part of the curable resin composition is dissolved in a solvent such as methyl ethyl ketone, and the particle size is measured by a particle size measuring device or the like by laser light scattering. It can be confirmed by this.

　前記粒子径測定による体積平均粒子径（Ｍｖ）／個数平均粒子径（Ｍｎ）の値は、特に制限されないが、３．０以下であることが好ましく、２．５以下がより好ましく、２．０以下が更に好ましく、１．５以下が特に好ましい。体積平均粒子径（Ｍｖ）／個数平均粒子径（Ｍｎ）が３．０以下であれば、コアシェルポリマー粒子（Ｂ）が良好に分散していると考えられ、得られる硬化物の耐衝撃性や接着性などの物性が良好になる。 The value of the volume average particle diameter (Mv) / number average particle diameter (Mn) measured by the particle diameter measurement is not particularly limited, but is preferably 3.0 or less, more preferably 2.5 or less, and 2.0. The following is more preferable, and 1.5 or less is particularly preferable. If the volume average particle diameter (Mv) / number average particle diameter (Mn) is 3.0 or less, it is considered that the core-shell polymer particles (B) are well dispersed, and the impact resistance of the obtained cured product is increased. Physical properties such as adhesiveness are improved.

　なお、体積平均粒子径（Ｍｖ）／個数平均粒子径（Ｍｎ）は、マイクロトラックＵＰＡ（日機装株式会社製）を用いて測定し、ＭｖをＭｎで除することによって求めることができる。 The volume average particle diameter (Mv) / number average particle diameter (Mn) can be determined by measuring using Microtrac UPA (manufactured by Nikkiso Co., Ltd.) and dividing Mv by Mn.

　また、コアシェルポリマー粒子の「安定な分散」とは、コアシェルポリマー粒子が、連続層中で凝集したり、分離したり、沈殿したりすることなく、定常的に通常の条件下にて、長期間に渡って、分散している状態を意味する。また、コアシェルポリマー粒子の連続層中での分布も実質的に変化せず、また、これらの組成物を危険がない範囲で加熱することで粘度を下げて攪拌したりしても、「安定な分散」を保持できることが好ましい。 Further, "stable dispersion" of the core-shell polymer particles means that the core-shell polymer particles do not aggregate, separate, or precipitate in the continuous layer, and are constantly under normal conditions for a long period of time. It means a state of being dispersed over. In addition, the distribution of the core-shell polymer particles in the continuous layer does not change substantially, and even if these compositions are heated within a non-hazardous range to reduce the viscosity and stir, they are "stable". It is preferable to be able to maintain "dispersion".

　コアシェルポリマー粒子（Ｂ）は１種を単独で用いても良く、２種以上を併用しても良い。 One type of core-shell polymer particles (B) may be used alone, or two or more types may be used in combination.

　コアシェルポリマー粒子（Ｂ）の構造は特に限定されないが、２層以上を有することが好ましい。また、コア層を被覆する中間層と、この中間層をさらに被覆するシェル層とから構成される３層以上の構造を有することも可能である。 The structure of the core-shell polymer particles (B) is not particularly limited, but it is preferable to have two or more layers. It is also possible to have a structure of three or more layers composed of an intermediate layer covering the core layer and a shell layer further covering the intermediate layer.

　以下、コアシェルポリマー粒子（Ｂ）の各層について具体的に説明する。 Hereinafter, each layer of the core-shell polymer particles (B) will be specifically described.

　≪コア層≫
　コア層は、硬化性樹脂組成物の硬化物の靱性を高めるために、ゴムとしての性質を有する弾性コア層であることが好ましい。ゴムとしての性質を有するためには、弾性コア層は、ゲル含量が６０重量％以上であることが好ましく、８０重量％以上であることがより好ましく、９０重量％以上であることがさらに好ましく、９５重量％以上であることが特に好ましい。なお、本明細書でいうゲル含量とは、凝固、乾燥により得られたクラム０．５ｇをトルエン１００ｇに浸漬し、２３℃で２４時間静置した後に不溶分と可溶分を分別したときの、不溶分と可溶分の合計量に対する不溶分の比率を意味する。 ≪Core layer≫
The core layer is preferably an elastic core layer having rubber properties in order to increase the toughness of the cured product of the curable resin composition. In order to have the properties of rubber, the elastic core layer preferably has a gel content of 60% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more. It is particularly preferable that it is 95% by weight or more. The gel content referred to in the present specification is when 0.5 g of crumb obtained by coagulation and drying is immersed in 100 g of toluene, allowed to stand at 23 ° C. for 24 hours, and then the insoluble and soluble components are separated. , Means the ratio of insoluble matter to the total amount of insoluble matter and soluble matter.

　コア層は、ジエン系ゴム、（メタ）アクリレート系ゴム、及びオルガノシロキサン系ゴムからなる群より選択される１種以上を含むことが好ましい。得られる硬化物の耐衝撃剥離接着性の改善効果が高い点、及び、エポキシ樹脂（Ａ）との親和性が低いために（Ａ）成分によるコア層の膨潤に起因する経時での粘度上昇が起こりにくい点から、コア層は、ジエン系ゴムを含むことが好ましい。 The core layer preferably contains at least one selected from the group consisting of diene-based rubber, (meth) acrylate-based rubber, and organosiloxane-based rubber. The effect of improving the impact-resistant peeling adhesiveness of the obtained cured product is high, and the affinity with the epoxy resin (A) is low, so that the viscosity increases over time due to the swelling of the core layer due to the component (A). The core layer preferably contains a diene-based rubber because it is unlikely to occur.

　（ジエン系ゴム）
　前記ジエン系ゴムを構成する共役ジエン系単量体としては、例えば、１，３－ブタジエン、イソプレン、２－クロロ－１，３－ブタジエン、２－メチル－１，３－ブタジエンなどが挙げられる。これらの共役ジエン系単量体は、単独で用いても、２種以上を組み合わせて用いてもよい。 (Diene rubber)
Examples of the conjugated diene-based monomer constituting the diene-based rubber include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, 2-methyl-1,3-butadiene and the like. These conjugated diene-based monomers may be used alone or in combination of two or more.

　前記共役ジエン系単量体の含有量は、コア層の５０～１００重量％の範囲であることが好ましく、７０～１００重量％の範囲であることがより好ましく、９０～１００重量％の範囲であることが更に好ましい。共役ジエン系単量体の含有量が５０重量％以上であると、得られる硬化物の耐衝撃剥離接着性がより良好になり得る。 The content of the conjugated diene-based monomer is preferably in the range of 50 to 100% by weight, more preferably in the range of 70 to 100% by weight, and in the range of 90 to 100% by weight. It is more preferable to have. When the content of the conjugated diene-based monomer is 50% by weight or more, the impact-resistant peeling adhesiveness of the obtained cured product can be improved.

　共役ジエン系単量体と共重合可能なビニル系単量体としては、例えば、スチレン、α－メチルスチレン、モノクロロスチレン、ジクロロスチレンなどのビニルアレーン類；アクリル酸、メタクリル酸などのビニルカルボン酸類；アクリロニトリル、メタクリロニトリルなどのビニルシアン類；塩化ビニル、臭化ビニル、クロロプレンなどのハロゲン化ビニル類；酢酸ビニル；エチレン、プロピレン、ブチレン、イソブチレンなどのアルケン類;ジアリルフタレート、トリアリルシアヌレート、トリアリルイソシアヌレート、ジビニルベンゼンなどの多官能性モノマーなどが挙げられる。これらのビニル系単量体は、単独で用いても、２種以上を組み合わせて用いてもよい。特に好ましくはスチレンである。 Examples of the vinyl-based monomer copolymerizable with the conjugated diene-based monomer include vinyl allenes such as styrene, α-methylstyrene, monochlorostyrene and dichlorostyrene; vinylcarboxylic acids such as acrylic acid and methacrylic acid; Vinyl cyanes such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride, vinyl bromide and chloroprene; vinyl acetate; alkenes such as ethylene, propylene, butylene and isobutylene; diallyl phthalate, triallyl cyanurate, tri Examples thereof include polyfunctional monomers such as allyl isocyanurate and divinylbenzene. These vinyl-based monomers may be used alone or in combination of two or more. Styrene is particularly preferable.

　前記共役ジエン系単量体と共重合可能なビニル系単量体の含有量は、コア層の０～５０重量％の範囲であることが好ましく、０～３０重量％の範囲であることがより好ましく、０～１０重量％の範囲であることが更に好ましい。共役ジエン系単量体と共重合可能なビニル系単量体の含有量が５０重量％以下であると、得られる硬化物の耐衝撃剥離接着性がより良好になり得る。 The content of the vinyl-based monomer copolymerizable with the conjugated diene-based monomer is preferably in the range of 0 to 50% by weight, more preferably in the range of 0 to 30% by weight. It is preferably in the range of 0 to 10% by weight, more preferably in the range of 0 to 10% by weight. When the content of the vinyl-based monomer copolymerizable with the conjugated diene-based monomer is 50% by weight or less, the impact-resistant peeling adhesiveness of the obtained cured product can be improved.

　耐衝撃剥離接着性の改良効果が高い点、および、エポキシ樹脂（Ａ）との親和性が低いためにコア層の膨潤に起因する経時での粘度上昇が起こり難い点から、ジエン系ゴムは、１，３－ブタジエンを用いるブタジエンゴム、および／または、１，３－ブタジエンとスチレンの共重合体であるブタジエン－スチレンゴムであることが好ましく、ブタジエンゴムがより好ましい。また、ブタジエン－スチレンゴムは、屈折率の調整により得られる硬化物の透明性を高めることができる点で好ましい。 Diene-based rubbers are made of diene rubber because they have a high effect of improving impact resistance and peeling adhesiveness, and because they have a low affinity with the epoxy resin (A), they are unlikely to increase in viscosity over time due to swelling of the core layer. Butadiene rubber using 1,3-butadiene and / or butadiene-styrene rubber which is a copolymer of 1,3-butadiene and styrene is preferable, and butadiene rubber is more preferable. Further, butadiene-styrene rubber is preferable in that the transparency of the cured product obtained by adjusting the refractive index can be enhanced.

　（（メタ）アクリレート系ゴム）
　前記（メタ）アクリレート系ゴムは、（メタ）アクリレート系モノマーからなる群より選ばれる少なくとも１種のモノマーを５０～１００重量％、及び、（メタ）アクリレート系モノマーと共重合可能な他のビニル系モノマーを０～５０重量％含有するモノマー混合物を重合して得られるゴム弾性体であることが好ましい。 ((Meta) acrylate rubber)
The (meth) acrylate-based rubber contains 50 to 100% by weight of at least one monomer selected from the group consisting of (meth) acrylate-based monomers, and other vinyl-based rubbers capable of copolymerizing with the (meth) acrylate-based monomer. It is preferably a rubber elastic body obtained by polymerizing a monomer mixture containing 0 to 50% by weight of a monomer.

　前記（メタ）アクリレート系モノマーとしては、例えば、（ｉ）メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレートなどのアルキル（メタ）アクリレート類；（ｉｉ）フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレートなどの芳香環含有（メタ）アクリレート類；（ｉｉｉ）２－ヒドロキシエチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートなどのヒドロキシアルキル（メタ）アクリレート類；（ｉｖ）グリシジル（メタ）アクリレート、グリシジルアルキル（メタ）アクリレートなどのグリシジル（メタ）アクリレート類；（ｖ）アルコキシアルキル（メタ）アクリレート類；（ｖｉ）アリル（メタ）アクリレート、およびアリルアルキル（メタ）アクリレートなどのアリルアルキル（メタ）アクリレート類；（ｖｉｉ）モノエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレートなどの多官能性（メタ）アクリレート類などが挙げられる。これらの（メタ）アクリレート系モノマーは、１種類を単独で用いても、２種以上を組み合わせて用いてもよい。（メタ）アクリレート系モノマーとしては、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、及び２－エチルヘキシル（メタ）アクリレートが好ましい。 Examples of the (meth) acrylate-based monomer include (i) methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and dodecyl (meth). ) Alkyl (meth) acrylates such as acrylates, stearyl (meth) acrylates and behenyl (meth) acrylates; (ii) Aromatic ring-containing (meth) acrylates such as phenoxyethyl (meth) acrylates and benzyl (meth) acrylates; iii) Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; glycidyl (meth) such as (iv) glycidyl (meth) acrylate and glycidylalkyl (meth) acrylate. Acrylates; (v) alkoxyalkyl (meth) acrylates; (vi) allyl (meth) acrylates, and allylalkyl (meth) acrylates such as allylalkyl (meth) acrylates; (vi) monoethylene glycol di (meth) Examples thereof include polyfunctional (meth) acrylates such as acrylates, triethylene glycol di (meth) acrylates, and tetraethylene glycol di (meth) acrylates. These (meth) acrylate-based monomers may be used alone or in combination of two or more. As the (meth) acrylate-based monomer, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferable.

　（メタ）アクリレート系モノマーと共重合可能な他のビニル系モノマーとしては、例えば、（ｉ）スチレン、α－メチルスチレン、モノクロロスチレン、ジクロロスチレンなどのビニルアレーン類；（ｉｉ）アクリル酸、メタクリル酸などのビニルカルボン酸類；（ｉｉｉ）アクリロニトリル、メタクリロニトリルなどのビニルシアン類；（ｉｖ）塩化ビニル、臭化ビニル、クロロプレンなどのハロゲン化ビニル類；（ｖ）酢酸ビニル；（ｖｉ）エチレン、プロピレン、ブチレン、イソブチレンなどのアルケン類;（ｖｉｉ）ジアリルフタレート、トリアリルシアヌレート、トリアリルイソシアヌレート、ジビニルベンゼンなどの多官能性モノマーなどが挙げられる。これらのビニル系モノマーは、１種類を単独で用いても、２種以上を組み合わせて用いてもよい。屈折率を容易に大きくすることができる点から、特に好ましくはスチレンである。 Examples of other vinyl-based monomers copolymerizable with the (meth) acrylate-based monomer include vinyl allenes such as (i) styrene, α-methylstyrene, monochlorostyrene, and dichlorostyrene; (ii) acrylic acid and methacrylic acid. Vinyl carboxylic acids such as (iii) acrylonitrile, vinyl cyanides such as methacrylonitrile; (iv) vinyl halides such as vinyl chloride, vinyl bromide, chloroprene; (v) vinyl acetate; (vi) ethylene, styrene. , Alkenes such as butylene, isobutylene; (vii) Polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene and the like can be mentioned. These vinyl-based monomers may be used alone or in combination of two or more. Styrene is particularly preferable because the refractive index can be easily increased.

　（オルガノシロキサン系ゴム）
　前記オルガノシロキサン系ゴムとしては、例えば、（ｉ）ジメチルシリルオキシ、ジエチルシリルオキシ、メチルフェニルシリルオキシ、ジフェニルシリルオキシ、ジメチルシリルオキシ－ジフェニルシリルオキシなどの、アルキル又はアリール２置換シリルオキシ単位から構成されるポリシロキサン系ポリマー；（ｉｉ）側鎖のアルキルの一部が水素原子に置換されたオルガノハイドロジェンシリルオキシなどの、アルキル又はアリール１置換シリルオキシ単位から構成されるポリシロキサン系ポリマーなどが挙げられる。これらのポリシロキサン系ポリマーは、１種類を単独で用いても、２種以上を組み合わせて用いてもよい。中でも、ジメチルシリルオキシ、メチルフェニルシリルオキシ、及びジメチルシリルオキシ－ジフェニルシリルオキシが硬化物に耐熱性を付与することができることから好ましく、ジメチルシリルオキシが容易に入手できることから最も好ましい。コア層がオルガノシロキサン系ゴムから形成される態様において、ポリシロキサン系ポリマー部位は、硬化物の耐熱性を損なわないために、オルガノシロキサン系ゴム全体を１００重量％として８０重量％以上（より好ましくは９０重量％以上）含有していることが好ましい。 (Organosiloxane rubber)
The organosiloxane-based rubber is composed of, for example, (i) an alkyl or aryl 2-substituted silyloxy unit such as (i) dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, dimethylsilyloxy-diphenylsilyloxy. Polysiloxane-based polymers; (ii) Polysiloxane-based polymers composed of alkyl or aryl 1-substituted silyloxy units, such as organohydrogensilyloxy in which a part of the alkyl in the side chain is substituted with a hydrogen atom, and the like can be mentioned. .. These polysiloxane-based polymers may be used alone or in combination of two or more. Of these, dimethylsilyloxy, methylphenylsilyloxy, and dimethylsilyloxy-diphenylsilyloxy are preferable because they can impart heat resistance to the cured product, and dimethylsilyloxy is most preferable because they can be easily obtained. In the embodiment in which the core layer is formed of the organosiloxane-based rubber, the polysiloxane-based polymer moiety is 80% by weight or more (more preferably) with the entire organosiloxane-based rubber as 100% by weight so as not to impair the heat resistance of the cured product. 90% by weight or more) is preferably contained.

　コア層のガラス転移温度（以下、単に「Ｔｇ」と称する場合がある）は、得られる硬化物の靱性を高めるために、０℃以下であることが好ましく、－２０℃以下がより好ましく、－４０℃以下が更に好ましく、－６０℃以下であることが特に好ましい。 The glass transition temperature of the core layer (hereinafter, may be simply referred to as “Tg”) is preferably 0 ° C. or lower, more preferably −20 ° C. or lower, and more preferably −20 ° C. or lower in order to increase the toughness of the obtained cured product. It is more preferably 40 ° C. or lower, and particularly preferably −60 ° C. or lower.

　また、コア層の体積平均粒子径は特に限定されないが、０．０３μｍ～２μｍが好ましく、０．０５μｍ～１μｍがより好ましく、０．１２μｍ～０．５０μｍがより好ましく、０．１２μｍ～０．２８μｍがより好ましく、０．１４～０．２５μｍがさらに好ましい。コア層の体積平均粒子径がこの範囲内であると、コア層を安定的に製造することができ、また、硬化物の耐熱性および耐衝撃性が良好なものとなり得る。なお、本明細書において、コア層の体積平均粒子径は、コア層のラテックスについて、マイクロトラックＵＰＡ１５０（日機装株式会社製）を用いて測定することができる。 The volume average particle size of the core layer is not particularly limited, but is preferably 0.03 μm to 2 μm, more preferably 0.05 μm to 1 μm, more preferably 0.12 μm to 0.50 μm, and 0.12 μm to 0.28 μm. Is more preferable, and 0.14 to 0.25 μm is even more preferable. When the volume average particle size of the core layer is within this range, the core layer can be stably produced, and the heat resistance and impact resistance of the cured product can be good. In the present specification, the volume average particle size of the core layer can be measured by using Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.) for the latex of the core layer.

　第１実施形態のコアシェルポリマー粒子（Ｂ）において、コア層の割合は特に限定されない。当該コア層の割合は、コアシェルポリマー粒子（Ｂ）全体を１００重量％として４０重量％～９７重量％が好ましく、６０重量％～９５重量％がより好ましく、７０重量％～９３重量％が更に好ましく、８０重量％～９０重量％が特に好ましい。コア層の割合が４０重量％以上であると、得られる硬化物の耐衝撃剥離接着性がより良好になり得る。コア層の割合が９７重量％以下であると、コアシェルポリマー粒子が凝集し難く、硬化性樹脂組成物がより低粘度となり、作業性がより良好になり得る。 In the core-shell polymer particles (B) of the first embodiment, the ratio of the core layer is not particularly limited. The proportion of the core layer is preferably 40% by weight to 97% by weight, more preferably 60% by weight to 95% by weight, still more preferably 70% by weight to 93% by weight, assuming that the entire core-shell polymer particles (B) are 100% by weight. , 80% by weight to 90% by weight are particularly preferable. When the ratio of the core layer is 40% by weight or more, the impact-resistant peeling adhesiveness of the obtained cured product can be improved. When the ratio of the core layer is 97% by weight or less, the core-shell polymer particles are less likely to aggregate, the curable resin composition has a lower viscosity, and the workability can be improved.

　第１実施形態のコアシェルポリマー粒子（Ｂ）において、シェル層の重量に対するコア層の重量の比（コア層の重量／シェル層の重量）は、特に限定されない。当該比（コア層の重量／シェル層の重量）は、硬化性樹脂組成物の作業性がより良好となり、かつ硬化物の耐衝撃接着性がより良好となることから、６５／３５～９２／８であることが好ましく、６８／３２～９１／９であることがより好ましく、７０／３０～９０／１０であることがより好ましい。 In the core-shell polymer particles (B) of the first embodiment, the ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer / weight of the shell layer) is not particularly limited. The ratio (weight of the core layer / weight of the shell layer) is 65/35 to 92 / because the workability of the curable resin composition becomes better and the impact resistance of the cured product becomes better. It is preferably 8, more preferably 68/32 to 91/9, and even more preferably 70/30 to 90/10.

　コア層は単層構造であることが多いが、ゴム弾性を有する層からなる多層構造であってもよい。また、コア層が多層構造の場合は、各層のポリマー組成は、前記開示の範囲内で各々相違していてもよい。 The core layer often has a single-layer structure, but it may have a multi-layer structure composed of a layer having rubber elasticity. Further, when the core layer has a multi-layer structure, the polymer composition of each layer may be different within the scope of the above disclosure.

　≪中間層≫
　コア層とシェル層の間に、必要により、中間層を形成させてもよい。特に、中間層として、以下のゴム表面架橋層を形成させてもよい。得られる硬化物の靱性を改良させる効果および耐衝撃剥離接着性を改良させる効果の点からは、中間層を含有しないことが好ましく、特に、以下のゴム表面架橋層を含有しないことが好ましい。 ≪Middle class≫
If necessary, an intermediate layer may be formed between the core layer and the shell layer. In particular, the following rubber surface crosslinked layer may be formed as the intermediate layer. From the viewpoint of the effect of improving the toughness of the obtained cured product and the effect of improving the impact resistance peeling adhesiveness, it is preferable not to contain an intermediate layer, and it is particularly preferable not to contain the following rubber surface crosslinked layer.

　中間層が存在する場合、コア層１００重量部に対する中間層の割合は、０．１～３０重量部が好ましく、０．２～２０重量部がより好ましく、０．５～１０重量部がさらに好ましく、１～５重量部が特に好ましい。 When the intermediate layer is present, the ratio of the intermediate layer to 100 parts by weight of the core layer is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, still more preferably 0.5 to 10 parts by weight. 1 to 5 parts by weight is particularly preferable.

　前記ゴム表面架橋層は、一分子内にラジカル重合性二重結合を２以上有する多官能性モノマー３０～１００重量％、及びその他のビニルモノマー０～７０重量％からなるゴム表面架橋層成分を重合してなる中間層ポリマーからなり、硬化性樹脂組成物の粘度を低下させる効果、コアシェルポリマー粒子（Ｂ）の（Ａ）成分への分散性を向上させる効果を有する。また、コア層の架橋密度を上げたりシェル層のグラフト効率を高める効果も有する。 The rubber surface crosslinked layer is polymerized with a rubber surface crosslinked layer component composed of 30 to 100% by weight of a polyfunctional monomer having two or more radically polymerizable double bonds in one molecule and 0 to 70% by weight of another vinyl monomer. It is composed of an intermediate layer polymer, which has an effect of lowering the viscosity of the curable resin composition and an effect of improving the dispersibility of the core-shell polymer particles (B) in the component (A). It also has the effect of increasing the crosslink density of the core layer and increasing the graft efficiency of the shell layer.

　前記多官能性モノマーの具体例としては、ブタジエンなどの共役ジエン系モノマーは含まれず、アリル（メタ）アクリレート、アリルアルキル（メタ）アクリレート等のアリルアルキル（メタ）アクリレート類；アリルオキシアルキル（メタ）アクリレート類；（ポリ）エチレングリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート等の（メタ）アクリル基を２個以上有する多官能（メタ）アクリレート類；ジアリルフタレート、トリアリルシアヌレート、トリアリルイソシアヌレート、ジビニルベンゼン等が例示されるが、好ましくはアリルメタクリレート、トリアリルイソシアヌレートである。本明細書において（メタ）アクリレートとは、アクリレートおよび／またはメタクリレートを意味する。 Specific examples of the polyfunctional monomer do not include conjugated diene-based monomers such as butadiene, and allylalkyl (meth) acrylates such as allyl (meth) acrylate and allylalkyl (meth) acrylate; allyloxyalkyl (meth). Acrylate; (poly) ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate and the like ( Meta) Polyfunctional (meth) acrylates having two or more acrylic groups; diallylphthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene and the like are exemplified, but allyl methacrylate and triallyl isocyanurate are preferable. .. As used herein, the term (meth) acrylate means acrylate and / or methacrylate.

　≪シェル層≫
　コアシェルポリマー粒子の最も外側に存在するシェル層は、シェル層形成用モノマーを重合して得られた重合体である。シェル層を構成する重合体（シェルポリマー）は、コアシェルポリマー粒子（Ｂ）と（Ａ）成分との相溶性を向上させ、硬化性樹脂組成物、又はその硬化物中においてコアシェルポリマー粒子（Ｂ）が一次粒子の状態で分散することを可能にする役割を担う。 ≪Shell layer≫
The outermost shell layer of the core-shell polymer particles is a polymer obtained by polymerizing a monomer for forming a shell layer. The polymer (shell polymer) constituting the shell layer improves the compatibility between the core-shell polymer particles (B) and the component (A), and the core-shell polymer particles (B) in the curable resin composition or the cured product thereof. Plays a role in enabling dispersion in the form of primary particles.

　このようなシェルポリマーは、好ましくは前記コア層及び／又は中間層にグラフトしている。なお、以下、「コア層にグラフトしている」という場合、このコア層に中間層が形成されている時には、中間層にグラフトしている態様も含むものとする。より正確には、シェル層の形成に用いるモノマー成分が、コア層を形成するコアポリマー（中間層を形成した場合には、コアポリマーには、中間層を形成する中間層ポリマーも含まれる。以下、同じ）にグラフト重合して、実質的にシェルポリマーとコアポリマーとが化学結合していることが好ましい（中間層を形成した場合には、シェルポリマーと中間層ポリマーとが化学結合していることも好ましい）。即ち、好ましくは、シェルポリマーは、コアポリマーの存在下に前記シェル層形成用モノマーをグラフト重合させることで形成され、このようにすることで、コアポリマーにグラフト重合されており、コアポリマーの一部又は全体を覆っている。この重合操作は、水性のポリマーラテックス状態で調製されたコアポリマーのラテックスに対して、シェルポリマー層形成用モノマーを加えて重合させることで実施できる。 Such a shell polymer is preferably grafted on the core layer and / or the intermediate layer. In the following, when the term "grafted to the core layer" is used, when the intermediate layer is formed in the core layer, the aspect of grafting to the intermediate layer is also included. More precisely, the monomer component used for forming the shell layer is a core polymer forming a core layer (in the case where an intermediate layer is formed, the core polymer also includes an intermediate layer polymer forming an intermediate layer. , The same), it is preferable that the shell polymer and the core polymer are substantially chemically bonded (when the intermediate layer is formed, the shell polymer and the intermediate layer polymer are chemically bonded). It is also preferable). That is, preferably, the shell polymer is formed by graft-polymerizing the shell layer forming monomer in the presence of the core polymer, and by doing so, the shell polymer is graft-polymerized to the core polymer, and is one of the core polymers. It covers a part or the whole. This polymerization operation can be carried out by adding a monomer for forming a shell polymer layer to the latex of the core polymer prepared in the state of an aqueous polymer latex and polymerizing the latex.

　なお、コアシェルポリマー粒子（Ｂ）では、シェル層を形成するシェルポリマーの少なくとも一部が、コアポリマーにグラフト重合（グラフト結合）していればよく、コア層とシェル層とが完全な層構造を形成していなくてもよい。言い換えれば、シェルポリマーは、コア層の全てを覆っていなくてもよい。コアシェルポリマー粒子（Ｂ）では、シェルポリマーの一部が、コア層に入り込んでいてもよい。コアシェルポリマー粒子（Ｂ）では、シェルポリマーの一部がコア層を覆っていることが好ましく、換言すれば、シェルポリマーの一部がコアシェルポリマー粒子（Ｂ）の最表面に存在する（最外層を形成する）ことが好ましい。 In the core-shell polymer particles (B), at least a part of the shell polymer forming the shell layer may be graft-polymerized (graft-bonded) to the core polymer, and the core layer and the shell layer have a complete layer structure. It does not have to be formed. In other words, the shell polymer does not have to cover the entire core layer. In the core-shell polymer particles (B), a part of the shell polymer may penetrate into the core layer. In the core-shell polymer particles (B), it is preferable that a part of the shell polymer covers the core layer, in other words, a part of the shell polymer is present on the outermost surface of the core-shell polymer particles (B) (the outermost layer). (Form) is preferable.

　シェル層形成用モノマーの組成、すなわちシェル層形成用モノマーに含まれるモノマーの種類および含有比率は特に限定されない。シェル層形成用モノマーとしては、コアシェルポリマー粒子（Ｂ）の硬化性樹脂組成物中での相溶性及び分散性の点から、例えば、芳香族ビニルモノマー、ビニルシアンモノマー、又は（メタ）アクリレートモノマーが好ましく、（メタ）アクリレートモノマーがより好ましい。特に、シェル層形成用モノマーは、メタルメタクレリートを含むことが好ましい。これらシェル層形成用モノマーは、１種を単独で用いてもよく、適宜組み合わせて用いてもよい。 The composition of the monomer for forming the shell layer, that is, the type and content ratio of the monomer contained in the monomer for forming the shell layer is not particularly limited. Examples of the shell layer forming monomer include aromatic vinyl monomers, vinyl cyan monomers, and (meth) acrylate monomers from the viewpoint of compatibility and dispersibility of the core-shell polymer particles (B) in the curable resin composition. Preferably, a (meth) acrylate monomer is more preferred. In particular, the shell layer forming monomer preferably contains a metal metaclerite. These shell layer forming monomers may be used alone or in combination as appropriate.

　換言すれば、シェル層に含まれる構成単位の種類および含有比率は特に限定されない。コアシェルポリマー粒子（Ｂ）の硬化性樹脂組成物中での相溶性及び分散性の点から、シェル層は、芳香族ビニルモノマー、ビニルシアンモノマーおよび（メタ）アクリレートモノマーからなる群から選択される１種以上のモノマーに由来する構成単位を含むことが好ましく、（メタ）アクリレートモノマーに由来する構成単位を含むことがより好ましい。特に、シェル層は、メタルメタクレリートに由来する構成単位を含むことが好ましい。 In other words, the type and content ratio of the structural units contained in the shell layer are not particularly limited. From the viewpoint of compatibility and dispersibility of the core-shell polymer particles (B) in the curable resin composition, the shell layer is selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers and (meth) acrylate monomers. It is preferable to include a structural unit derived from a monomer of a species or more, and more preferably to contain a structural unit derived from a (meth) acrylate monomer. In particular, the shell layer preferably contains a structural unit derived from a metal metaclerite.

　芳香族ビニルモノマー、ビニルシアンモノマー、及び（メタ）アクリレートモノマーの合計量は、シェル層形成用モノマー１００重量％中に、１０．０重量％～９９．５重量％であることが好ましく、５０．０重量％～９９．０重量％がより好ましく、６５．０重量％～９８．０重量％が更に好ましく、６７．０重量％～８０．０重量％が特に好ましく、６７．０～８５．０重量％が最も好ましい。 The total amount of the aromatic vinyl monomer, the vinyl cyan monomer, and the (meth) acrylate monomer is preferably 10.0% by weight to 99.5% by weight in 100% by weight of the monomer for forming the shell layer, and 50. 0% by weight to 99.0% by weight is more preferable, 65.0% by weight to 98.0% by weight is more preferable, 67.0% by weight to 80.0% by weight is particularly preferable, and 67.0 to 85.0% by weight is particularly preferable. % By weight is most preferred.

　換言すれば、シェル層は、シェル層（シェルポリマー）１００重量％中、芳香族ビニルモノマー、ビニルシアンモノマーおよび（メタ）アクリレートモノマーからなる群から選択される１種以上のモノマーに由来する構成単位を合計で、１０．０重量％～９９．５重量％含むことが好ましく、５０．０重量％～９９．０重量％含むことがより好ましく、６５．０重量％～９８．０重量％含むことが更に好ましく、６７．０重量％～８０．０重量％含むことが特に好ましく、６７．０～８５．０重量％含むことが最も好ましい。 In other words, the shell layer is a structural unit derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers and (meth) acrylate monomers in 100% by weight of the shell layer (shell polymer). , 10.0% by weight to 99.5% by weight, more preferably 50.0% by weight to 99.0% by weight, and 65.0% by weight to 98.0% by weight. Is more preferable, 67.0% by weight to 80.0% by weight is particularly preferable, and 67.0 to 85.0% by weight is most preferable.

　前記芳香族ビニルモノマーの具体例としては、スチレン、α－メチルスチレン、ｐ－メチルスチレン、ジビニルベンゼン等のビニルベンゼン類が挙げられる。 Specific examples of the aromatic vinyl monomer include vinylbenzenes such as styrene, α-methylstyrene, p-methylstyrene, and divinylbenzene.

　前記ビニルシアンモノマーの具体例としては、アクリロニトリル、又はメタクリロニトリル等が挙げられる。 Specific examples of the vinyl cyanomer include acrylonitrile, methacrylonitrile, and the like.

　前記（メタ）アクリレートモノマーの具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレートなどの（メタ）アクリル酸アルキルエステル；（メタ）アクリル酸ヒドロキシアルキルエステル等が挙げられる。 Specific examples of the (meth) acrylate monomer include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; and (meth) acrylic acid hydroxyalkyl esters. Be done.

　前記（メタ）アクリル酸ヒドロキシアルキルエステルの具体例としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシ直鎖アルキル（メタ）アクリレート（特に、ヒドロキシ直鎖Ｃ１－６アルキル（メタ）アクリレート）；カプロラクトン変性ヒドロキシ（メタ）アクリレート；α－（ヒドロキシメチル）アクリル酸メチル、α－（ヒドロキシメチル）アクリル酸エチル等のヒドロキシ分岐アルキル（メタ）アクリレート、二価カルボン酸（フタル酸等）と二価アルコール（プロピレングリコール等）とから得られるポリエステルジオール（特に飽和ポリエステルジオール）のモノ（メタ）アクリレート等のヒドロキシル基含有（メタ）アクリレート類等が挙げられる。 Specific examples of the (meth) acrylic acid hydroxyalkyl ester include hydroxy linear alkyl (meth) such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Acrylate (particularly hydroxy straight chain C1-6 alkyl (meth) acrylate); caprolactone-modified hydroxy (meth) acrylate; hydroxy-branched alkyl such as α- (hydroxymethyl) methyl acrylate, α- (hydroxymethyl) ethyl acrylate ( Hydroxyl group-containing (meth) acrylates such as mono (meth) acrylates of polyester diols (particularly saturated polyester diols) obtained from meta) acrylates, divalent carboxylic acids (phthalic acids, etc.) and dihydric alcohols (propylene glycol, etc.). And so on.

　第１実施形態のシェル層は、シェル層形成用モノマー１００重量％中に、炭素数１～４のアルキル（メタ）アクリレートを５５重量％以上含有するシェル層形成用モノマーを重合してなる共重合体であることが好ましい。換言すれば、第１実施形態のシェル層は、シェル層１００重量％中、炭素数１～４のアルキル（メタ）アクリレートに由来する構成単位を５５重量％以上含有することが好ましい。第１実施形態のシェル層は、シェル層形成用モノマー１００重量％中に、炭素数１～４のアルキル（メタ）アクリレートを６５重量％以上含有するモノマー成分を重合してなる共重合体であることが好ましく、７５重量％以上含有するモノマー成分を重合してなる共重合体であることがより好ましく、７８重量％以上含有するモノマー成分を重合してなる共重合体であることが更に好ましく、８３重量％以上含有するモノマー成分を重合してなる共重合体であることが特に好ましい。シェル層形成用モノマーが炭素数１～４のアルキル（メタ）アクリレートを上述した範囲で含む場合、硬化性樹脂組成物の作業性が良好になるという利点を有する。 The shell layer of the first embodiment has a copolymer weight obtained by polymerizing a shell layer forming monomer containing 55% by weight or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of the shell layer forming monomer. It is preferably coalesced. In other words, the shell layer of the first embodiment preferably contains 55% by weight or more of a structural unit derived from an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of the shell layer. The shell layer of the first embodiment is a copolymer obtained by polymerizing a monomer component containing 65% by weight or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of a monomer for forming a shell layer. It is more preferable, it is more preferably a copolymer obtained by polymerizing a monomer component containing 75% by weight or more, and further preferably it is a copolymer obtained by polymerizing a monomer component containing 78% by weight or more. It is particularly preferable that the copolymer is obtained by polymerizing a monomer component containing 83% by weight or more. When the shell layer forming monomer contains an alkyl (meth) acrylate having 1 to 4 carbon atoms in the above-mentioned range, it has an advantage that the workability of the curable resin composition is improved.

　炭素数１～４のアルキル（メタ）アクリレートの具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレートなどの（メタ）アクリル酸アルキルエステルが挙げられる。 Specific examples of alkyl (meth) acrylates having 1 to 4 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate and other (meth) acrylic acid alkyl esters.

　第１実施形態のシェル層形成用モノマーは、シェル層形成用モノマー１００重量％中、炭素数１のアルキル（メタ）アクリレートを１０重量％～１００重量％、および炭素数４のアルキル（メタ）アクリレートを０重量％～８０重量％含有することが好ましい。換言すれば、第１実施形態のシェル層は、炭素数１のアルキル（メタ）アクリレートに由来する構成単位を１０重量％～１００重量％、および炭素数４のアルキル（メタ）アクリレートに由来する構成単位を０重量％～８０重量％含有することが好ましい。 The shell layer forming monomer of the first embodiment contains 10% by weight to 100% by weight of an alkyl (meth) acrylate having 1 carbon atom and an alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the monomer for forming a shell layer. Is preferably contained in an amount of 0% by weight to 80% by weight. In other words, the shell layer of the first embodiment contains 10% by weight to 100% by weight of the structural unit derived from the alkyl (meth) acrylate having 1 carbon atom and the constitution derived from the alkyl (meth) acrylate having 4 carbon atoms. The unit is preferably contained in an amount of 0% by weight to 80% by weight.

　第１実施形態のシェル層形成用モノマーは、シェル層形成用モノマー１００重量％中、炭素数１のアルキル（メタ）アクリレートを１１重量％～９５重量％含有することがより好ましく、１２重量％～９２重量％含有することがより好ましく、１３重量％～５５重量％含有することが更に好ましく、１４重量％～５０重量％含有することが特に好ましい。第１実施形態のシェル層形成用モノマーは、シェル層形成用モノマー１００重量％中、炭素数４のアルキル（メタ）アクリレートを１重量％～８９重量％含有することが好ましく、１重量％～８８重量％含有することがより好ましく、１重量％～８７重量％含有することが好ましく、１重量％～８６重量％含有することが好ましく、１重量％～７８重量％含有することがより好ましく、２重量％～７６重量％含有することがより好ましく、５重量％～７６重量％含有することがより好ましく、８重量％～７６重量％含有することがより好ましく、２０重量％～７４重量％含有することがより好ましく、３５重量％～７２重量％含有することがより好ましく、３５重量％～６０重量％含有することがさらに好ましく、３５重量％～５０重量％含有することが特に好ましい。コアシェルポリマー粒子（Ｂ）のシェル層を構成するシェル層形成用モノマーが、炭素数１のアルキル（メタ）アクリレートおよび／または炭素数４のアルキル（メタ）アクリレートを上述した範囲で含む場合、コアシェルポリマー粒子（Ｂ）と（Ｃ）成分との相互作用を適切にコントロールできるため、硬化性樹脂組成物の粘度が低く抑えられ、作業性が良好となるという利点を有する。 The shell layer forming monomer of the first embodiment more preferably contains 11% by weight to 95% by weight of an alkyl (meth) acrylate having 1 carbon atom in 100% by weight of the shell layer forming monomer, and 12% by weight to 12% by weight. It is more preferably contained in an amount of 92% by weight, further preferably contained in an amount of 13% by weight to 55% by weight, and particularly preferably contained in an amount of 14% by weight to 50% by weight. The shell layer forming monomer of the first embodiment preferably contains 1% by weight to 89% by weight of an alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the shell layer forming monomer. It is more preferably contained in an amount of 1% by weight to 87% by weight, preferably 1% by weight to 86% by weight, more preferably 1% by weight to 78% by weight, and 2% by weight. It is more preferably contained in an amount of 7% by weight to 76% by weight, more preferably 5% by weight to 76% by weight, more preferably 8% by weight to 76% by weight, and 20% by weight to 74% by weight. It is more preferably 35% by weight to 72% by weight, further preferably 35% by weight to 60% by weight, and particularly preferably 35% by weight to 50% by weight. When the shell layer forming monomer constituting the shell layer of the core-shell polymer particles (B) contains an alkyl (meth) acrylate having 1 carbon atom and / or an alkyl (meth) acrylate having 4 carbon atoms in the above range, the core-shell polymer Since the interaction between the particles (B) and the component (C) can be appropriately controlled, the curable resin composition has an advantage that the viscosity is suppressed to a low level and the workability is improved.

　炭素数１のアルキル（メタ）アクリレートとしては、メチルメタクリレート、及びメチルアクリレートを用いることができる。炭素数４のアルキル（メタ）アクリレートとしては、ｎ－ブチルアクリレート、ｎ－ブチルメタクリレート、イソブチルアクリレート、イソブチルメタクリレート、ｔ－ブチルアクリレート、及びｔ－ブチルメタクリレートを用いることができる。 As the alkyl (meth) acrylate having 1 carbon atom, methyl methacrylate and methyl acrylate can be used. As the alkyl (meth) acrylate having 4 carbon atoms, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, and t-butyl methacrylate can be used.

　硬化性樹脂組成物の作業性をより良好にする観点から、第１実施形態のシェル層形成用モノマーは、炭素数１のアルキル（メタ）アクリレート及び炭素数４のアルキル（メタ）アクリレートの両方を有することが好ましく、炭素数１のアルキル（メタ）アクリレートを１３重量％～５５重量％、および炭素数４のアルキル（メタ）アクリレートを２０重量％～７４重量％含有することがより好ましい。換言すれば、第１実施形態のシェル層は、炭素数１のアルキル（メタ）アクリレートに由来する構成単位及び炭素数４のアルキル（メタ）アクリレートに由来する構成単位の両方を有することが好ましく、炭素数１のアルキル（メタ）アクリレートに由来する構成単位を１３重量％～５５重量％、および炭素数４のアルキル（メタ）アクリレートに由来する構成単位を２０重量％～７４重量％含有することが好ましい。 From the viewpoint of improving the workability of the curable resin composition, the shell layer forming monomer of the first embodiment contains both an alkyl (meth) acrylate having 1 carbon atom and an alkyl (meth) acrylate having 4 carbon atoms. It is preferable to have, and it is more preferable to contain 13% by weight to 55% by weight of the alkyl (meth) acrylate having 1 carbon atom and 20% by weight to 74% by weight of the alkyl (meth) acrylate having 4 carbon atoms. In other words, the shell layer of the first embodiment preferably has both a structural unit derived from an alkyl (meth) acrylate having 1 carbon atom and a structural unit derived from an alkyl (meth) acrylate having 4 carbon atoms. It may contain 13% by weight to 55% by weight of a structural unit derived from an alkyl (meth) acrylate having 1 carbon atom and 20% by weight to 74% by weight of a structural unit derived from an alkyl (meth) acrylate having 4 carbon atoms. preferable.

　なお、第１実施形態のシェル層形成用モノマーは、シェル層形成用モノマー１００重量％中、炭素数１のアルキル（メタ）アクリレートおよび炭素数４のアルキル（メタ）アクリレートの合計が１００重量％となる必要はない。換言すれば、第１実施形態のシェル層形成用モノマーは、シェル層形成用モノマー１００重量％中、（ａ）炭素数１のアルキル（メタ）アクリレート、（ｂ）炭素数４のアルキル（メタ）アクリレート、並びに（ｃ）炭素数１のアルキル（メタ）アクリレートおよび炭素数４のアルキル（メタ）アクリレート以外のモノマーの合計が１００重量％となればよい。すなわち、第１実施形態のシェル層形成用モノマーは、炭素数１のアルキル（メタ）アクリレートおよび炭素数４のアルキル（メタ）アクリレート以外のモノマーを含んでいてもよい。 In the shell layer forming monomer of the first embodiment, the total of the alkyl (meth) acrylate having 1 carbon atom and the alkyl (meth) acrylate having 4 carbon atoms is 100% by weight in 100% by weight of the monomer for forming the shell layer. You don't have to be. In other words, the shell layer forming monomer of the first embodiment is (a) an alkyl (meth) acrylate having 1 carbon atom and (b) an alkyl (meth) having 4 carbon atoms in 100% by weight of the shell layer forming monomer. The total of the monomers other than the acrylate and (c) the alkyl (meth) acrylate having 1 carbon atom and the alkyl (meth) acrylate having 4 carbon atoms may be 100% by weight. That is, the monomer for forming the shell layer of the first embodiment may contain a monomer other than the alkyl (meth) acrylate having 1 carbon atom and the alkyl (meth) acrylate having 4 carbon atoms.

　シェル層形成モノマーが芳香族ビニルモノマーおよび／またはビニルシアンモノマーを含有する場合、すなわち、シェル層が芳香族ビニルモノマーに由来する構成単位および／またはビニルシアンモノマーに由来する構成単位を含有する場合、コアシェルポリマー粒子（Ｂ）の硬化性樹脂組成物中での相溶性及び分散性が良好となる。一方で、（Ｂ）成分と（Ｃ）成分との相互作用を小さくすることにより、硬化性樹脂組成物の作業性を良好にできることから、第１実施形態において、シェル層形成用モノマー１００重量％中の芳香族ビニルモノマーの含有量は３０重量％以下であってもよく、２０重量％以下であってもよく、１０重量％以下であってもよく、８重量％以下であってもよく、６重量％以下であってもよい。換言すれば、第１実施形態において、シェル層１００重量％中の芳香族ビニルモノマーに由来する構成単位の含有量は３０重量％以下であってもよく、２０重量％以下であってもよく、１０重量％以下であってもよく、８重量％以下であってもよく、６重量％以下であってもよい。また、硬化性樹脂組成物の作業性を良好にする観点から、第１実施形態において、シェル層形成用モノマー１００重量％中のビニルシアンモノマーの含有量は１０重量％であってもよく、８重量％以下であってもよく、５重量％以下であってもよく、４重量％以下であってもよく、３重量％以下であってもよく、２重量％以下であってもよい。換言すれば、第１実施形態において、シェル層１００重量％中のビニルシアンモノマーに由来する構成単位の含有量は１０重量％以下が好ましく、８重量％以下であってもよく、５重量％以下であってもよく、４重量％以下であってもよく、３重量％以下であってもよく、２重量％以下であってもよい。 When the shell layer forming monomer contains an aromatic vinyl monomer and / or a vinyl cyan monomer, that is, when the shell layer contains a structural unit derived from an aromatic vinyl monomer and / or a structural unit derived from a vinyl cyan monomer. The compatibility and dispersibility of the core-shell polymer particles (B) in the curable resin composition are improved. On the other hand, by reducing the interaction between the component (B) and the component (C), the workability of the curable resin composition can be improved. Therefore, in the first embodiment, 100% by weight of the monomer for forming the shell layer is obtained. The content of the aromatic vinyl monomer in the mixture may be 30% by weight or less, 20% by weight or less, 10% by weight or less, or 8% by weight or less. It may be 6% by weight or less. In other words, in the first embodiment, the content of the structural unit derived from the aromatic vinyl monomer in 100% by weight of the shell layer may be 30% by weight or less, or may be 20% by weight or less. It may be 10% by weight or less, 8% by weight or less, or 6% by weight or less. Further, from the viewpoint of improving the workability of the curable resin composition, in the first embodiment, the content of the vinyl cyan monomer in 100% by weight of the monomer for forming the shell layer may be 10% by weight, and 8 It may be 5% by weight or less, 4% by weight or less, 3% by weight or less, or 2% by weight or less. In other words, in the first embodiment, the content of the structural unit derived from the vinyl cyanomer in 100% by weight of the shell layer is preferably 10% by weight or less, may be 8% by weight or less, and may be 5% by weight or less. It may be 4% by weight or less, 3% by weight or less, or 2% by weight or less.

　シェル層形成モノマーとして、炭素数５以上の（メタ）アクリレートモノマーをさらに有していてもよい。換言すれば、シェル層は、炭素数５以上の（メタ）アクリレートモノマーに由来する構成単位をさらに有していてもよい。炭素数５以上の（メタ）アクリレートモノマーの具体例としては、２－エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート等が挙げられる。 As the shell layer forming monomer, it may further have a (meth) acrylate monomer having 5 or more carbon atoms. In other words, the shell layer may further have a structural unit derived from the (meth) acrylate monomer having 5 or more carbon atoms. Specific examples of the (meth) acrylate monomer having 5 or more carbon atoms include 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate.

　硬化物や硬化性樹脂組成物中でコアシェルポリマー粒子（Ｂ）が凝集せずに良好な分散状態を維持するために、（Ａ）成分と化学結合させる観点から、シェル層形成用モノマーとして、エポキシ基、オキセタン基、水酸基、アミノ基、イミド基、カルボン酸基、カルボン酸無水物基、環状エステル、環状アミド、ベンズオキサジン基、及びシアン酸エステル基からなる群から選ばれる１種以上を含有する反応性基含有モノマーを含有することが好ましく、特に、エポキシ基を有するモノマーが好ましい。 Epoxy as a monomer for forming a shell layer from the viewpoint of chemically bonding with the component (A) in order to maintain a good dispersed state without agglomeration of the core-shell polymer particles (B) in the cured product or the curable resin composition. Contains one or more selected from the group consisting of a group, an oxetane group, a hydroxyl group, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, a benzoxazine group, and a cyanate ester group. It is preferable to contain a reactive group-containing monomer, and in particular, a monomer having an epoxy group is preferable.

　シェル層は、エポキシ基を有するモノマー成分を含むシェル層形成用モノマーを、コア層（コアポリマー）にグラフト重合してなる重合体であることが好ましい。当該構成によると、得られる硬化物が耐衝撃剥離接着性に優れるという利点を有する。 The shell layer is preferably a polymer obtained by graft-polymerizing a monomer for forming a shell layer containing a monomer component having an epoxy group onto a core layer (core polymer). According to this configuration, the obtained cured product has an advantage that it has excellent impact resistance and peeling adhesiveness.

　エポキシ基を有するモノマーは、耐衝撃剥離接着性や貯蔵安定性の観点から、シェル層形成用モノマー１００重量％中に、０重量％～９０重量％含まれていることが好ましく、１重量％～５０重量％がより好ましく、２重量％～３５重量％が更に好ましく、３重量％～２０重量％が特に好ましい。 The monomer having an epoxy group is preferably contained in an amount of 0% by weight to 90% by weight in 100% by weight of the monomer for forming a shell layer from the viewpoint of impact resistance peeling adhesiveness and storage stability, and is preferably from 1% by weight to 90% by weight. 50% by weight is more preferable, 2% by weight to 35% by weight is further preferable, and 3% by weight to 20% by weight is particularly preferable.

　換言すれば、シェル層は、エポキシ基を有するモノマーに由来する構成単位を有することが好ましい。また、シェル層は、シェル層１００重量％中、エポキシ基を有するモノマーに由来する構成単位を０重量％～９０重量％含むことが好ましく、１重量％～５０重量％含むことがより好ましく、２重量％～３５重量％含むことが更に好ましく、３重量％～２０重量％含むことが特に好ましい。 In other words, the shell layer preferably has a structural unit derived from a monomer having an epoxy group. Further, the shell layer preferably contains 0% by weight to 90% by weight of a structural unit derived from a monomer having an epoxy group in 100% by weight of the shell layer, and more preferably 1% by weight to 50% by weight. It is more preferably contained in an amount of% to 35% by weight, and particularly preferably contained in an amount of 3% by weight to 20% by weight.

　エポキシ基を有するモノマーは、シェル層の形成に使用することが好ましく、シェル層の形成のみに使用することがより好ましい。 The monomer having an epoxy group is preferably used for forming the shell layer, and more preferably used only for forming the shell layer.

　また、シェル層形成用モノマーとして、ラジカル重合性二重結合を２個以上有する多官能性モノマーを使用すると、硬化性樹脂組成物中においてコアシェルポリマー粒子の膨潤を防止し、また、硬化性樹脂組成物の粘度が低く取扱い性がよくなる傾向があるため好ましい。一方、得られる硬化物の靱性を改良させる効果および耐衝撃剥離接着性を改良させる効果の点からは、シェル層形成用モノマーとして、ラジカル重合性二重結合を２個以上有する多官能性モノマーを使用しないことが好ましい。 Further, when a polyfunctional monomer having two or more radically polymerizable double bonds is used as the monomer for forming the shell layer, the swelling of the core-shell polymer particles is prevented in the curable resin composition, and the curable resin composition is also used. It is preferable because the viscosity of the product is low and the handleability tends to be good. On the other hand, from the viewpoint of the effect of improving the toughness of the obtained cured product and the effect of improving the impact resistance peeling adhesiveness, a polyfunctional monomer having two or more radically polymerizable double bonds is used as the monomer for forming the shell layer. It is preferable not to use it.

　多官能性モノマーは、シェル層形成用モノマー１００重量％中に、例えば、０重量％～２０重量％含まれていてもよく、１重量％～２０重量％含まれていることが好ましく、より好ましくは、５重量％～１５重量％である。 The polyfunctional monomer may be contained in, for example, 0% by weight to 20% by weight, preferably 1% by weight to 20% by weight, more preferably in 100% by weight of the monomer for forming the shell layer. Is 5% by weight to 15% by weight.

　前記反応性基含有モノマーとして水酸基を有するモノマーの具体例としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシ直鎖アルキル（メタ）アクリレート（特に、ヒドロキシ直鎖Ｃ１－６アルキル（メタ）アクリレート）；カプロラクトン変性ヒドロキシ（メタ）アクリレート；α－（ヒドロキシメチル）アクリル酸メチル、α－（ヒドロキシメチル）アクリル酸エチル等のヒドロキシ分岐アルキル（メタ）アクリレート、二価カルボン酸（フタル酸等）と二価アルコール（プロピレングリコール等）とから得られるポリエステルジオール（特に飽和ポリエステルジオール）のモノ（メタ）アクリレート等のヒドロキシル基含有（メタ）アクリレート類等が挙げられる。 Specific examples of the monomer having a hydroxyl group as the reactive group-containing monomer include hydroxy linear alkyl (for example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. Meta) acrylate (particularly hydroxy linear C1-6 alkyl (meth) acrylate); caprolactone-modified hydroxy (meth) acrylate; hydroxy branching of α- (hydroxymethyl) methyl acrylate, α- (hydroxymethyl) ethyl acrylate and the like. Hydroxy group-containing (meth) such as mono (meth) acrylate of polyester diol (particularly saturated polyester diol) obtained from alkyl (meth) acrylate, divalent carboxylic acid (phthalic acid etc.) and dihydric alcohol (propylene glycol etc.) Examples include acrylates.

　前記エポキシ基を有するモノマーの具体例としては、グリシジル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル、アリルグリシジルエーテル等のグリシジル基含有ビニルモノマーが挙げられる。 Specific examples of the monomer having an epoxy group include glycidyl group-containing vinyl monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and allyl glycidyl ether.

　前記ラジカル重合性二重結合を２個以上有する多官能性モノマーの具体例としては、上述の多官能性モノマーと同じモノマーが例示されるが、好ましくはアリルメタクリレート、トリアリルイソシアヌレートである。 As a specific example of the polyfunctional monomer having two or more radically polymerizable double bonds, the same monomer as the above-mentioned polyfunctional monomer is exemplified, but allyl methacrylate and triallyl isocyanurate are preferable.

　第１実施形態のシェル層は、例えば、以下のシェル層形成用モノマーのポリマーであることが好ましい：（ａ）芳香族ビニルモノマー（特にスチレン）０～５０重量％（好ましくは１～５０重量％、より好ましくは２～４８重量％）、（ｂ）ビニルシアンモノマー（特にアクリロニトリル）０～５０重量％（好ましくは０～３０重量％、より好ましくは１０～２５重量％）、（ｃ）（メタ）アクリレートモノマー（特にメチルメタクリレート）０～１００重量％（好ましくは５～１００重量％、より好ましくは７０～９５重量％）、および（ｄ）エポキシ基を有するモノマー（特にグリシジルメタクリレート）１～５０重量％（好ましくは２～３５重量％、より好ましくは３～２０重量％）を組み合わせたシェル層形成用モノマー（合計１００重量％）。これにより、所望の靱性改良効果と機械特性をバランス良く実現することができる。 The shell layer of the first embodiment is preferably, for example, a polymer of the following shell layer forming monomers: (a) 0 to 50% by weight (preferably 1 to 50% by weight) of an aromatic vinyl monomer (particularly styrene). , More preferably 2 to 48% by weight), (b) vinyl cyan monomer (particularly acrylonitrile) 0 to 50% by weight (preferably 0 to 30% by weight, more preferably 10 to 25% by weight), (c) (meth). ) Acrylomonomer (particularly methylmethacrylate) 0-100% by weight (preferably 5-100% by weight, more preferably 70-95% by weight), and (d) Monomer having an epoxy group (particularly glycidylmethacrylate) 1-50% by weight. % (Preferably 2 to 35% by weight, more preferably 3 to 20% by weight) for shell layer forming monomer (total 100% by weight). As a result, the desired toughness improving effect and mechanical properties can be realized in a well-balanced manner.

　また、第１実施形態のシェル層は、例えば、以下のシェル層形成用モノマーのポリマーであることが好ましい：（ａ）炭素数１のアルキル（メタ）アクリレートモノマー（特にメチルメタクリレート）１０～１００重量％（好ましくは１１～９５重量％、特に好ましくは１４～５０重量％）、（ｂ）炭素数４のアルキル（メタ）アクリレートモノマー（特にブチルアクリレート）０～８０重量％（好ましくは１～７８重量％、特に好ましくは３５～７２重量％）、（ｃ）芳香族ビニルモノマー（特にスチレン）３０重量％以下（好ましくは１０重量％以下、より好ましくは０重量％）、（ｄ）ビニルシアンモノマー（特にアクリロニトリル）１０重量％以下（好ましくは５重量％以下、より好ましくは０重量％）、および（ｅ）エポキシ基を有するモノマー（特にグリシジルメタクリレート）０～４５重量％（好ましくは０～２５重量％、より好ましくは３～２０重量％）を組み合わせたシェル層形成用モノマー（合計１００重量％）。これにより、所望の靱性を改良させる効果と作業性をバランス良く実現することができる。 Further, the shell layer of the first embodiment is preferably, for example, a polymer of the following shell layer forming monomer: (a) 10 to 100 weight by weight of an alkyl (meth) acrylate monomer having 1 carbon atom (particularly methyl methacrylate). % (Preferably 11 to 95% by weight, particularly preferably 14 to 50% by weight), (b) 0 to 80% by weight (preferably 1 to 78% by weight) of an alkyl (meth) acrylate monomer (particularly butyl acrylate) having 4 carbon atoms. %, Particularly preferably 35 to 72% by weight), (c) aromatic vinyl monomer (particularly styrene) 30% by weight or less (preferably 10% by weight or less, more preferably 0% by weight), (d) vinyl cyan monomer (d) In particular, acrylonitrile) is 10% by weight or less (preferably 5% by weight or less, more preferably 0% by weight), and (e) a monomer having an epoxy group (particularly glycidyl methacrylate) is 0 to 45% by weight (preferably 0 to 25% by weight). , More preferably 3 to 20% by weight), a monomer for forming a shell layer (100% by weight in total). Thereby, the effect of improving the desired toughness and the workability can be realized in a well-balanced manner.

　これらのモノマー成分は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。シェル層は、上記モノマー成分の他に、他のモノマー成分を含んで形成されてもよい。 These monomer components may be used alone or in combination of two or more. The shell layer may be formed by containing other monomer components in addition to the above-mentioned monomer components.

　シェル層のガラス転移温度（以下、単に「Ｔｇ」と称する場合がある）は、硬化性樹脂組成物の作業性を良好にする観点から、－４５℃以上１１０℃以下であることが好ましく、－４０℃以上１００℃以下がより好ましく、－３５℃以上５０℃以下が更に好ましく、－３０℃以上１０℃以下であることが特に好ましい。 The glass transition temperature of the shell layer (hereinafter, may be simply referred to as “Tg”) is preferably −45 ° C. or higher and 110 ° C. or lower from the viewpoint of improving the workability of the curable resin composition. It is more preferably 40 ° C. or higher and 100 ° C. or lower, further preferably −35 ° C. or higher and 50 ° C. or lower, and particularly preferably −30 ° C. or higher and 10 ° C. or lower.

　シェル層のグラフト率は、７０％以上であることが好ましく、８０％以上であることがより好ましく、９０％以上であることがさらに好ましい。グラフト率が７０％以上であると、硬化性樹脂組成物がより低粘度となり得る。 The graft ratio of the shell layer is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. When the graft ratio is 70% or more, the curable resin composition may have a lower viscosity.

　前記グラフト率の算出方法は次に記載の通りである。先ず、コアシェルポリマー粒子を含有する水性ラテックスを凝固・脱水し、最後に乾燥してコアシェルポリマー粒子のパウダーを得る。次いで、コアシェルポリマー粒子のパウダー２ｇをメチルエチルケトン（ＭＥＫ）１００ｇに２３℃で２４時間浸漬した後にＭＥＫ可溶分をＭＥＫ不溶分と分離し、さらにＭＥＫ可溶分からメタノール不溶分を分離する。そして、ＭＥＫ不溶分とメタノール不溶分との合計量に対するＭＥＫ不溶分の比率を求めることによってグラフト率を算出する。 The calculation method of the graft ratio is as described below. First, the aqueous latex containing the core-shell polymer particles is coagulated and dehydrated, and finally dried to obtain a powder of the core-shell polymer particles. Next, 2 g of the powder of the core-shell polymer particles is immersed in 100 g of methyl ethyl ketone (MEK) at 23 ° C. for 24 hours, and then the MEK-soluble component is separated from the MEK-soluble component, and the methanol-insoluble component is further separated from the MEK-soluble component. Then, the graft ratio is calculated by obtaining the ratio of the MEK insoluble matter to the total amount of the MEK insoluble matter and the methanol insoluble matter.

　≪コアシェルポリマー粒子の製造方法≫
　（コア層の製造方法）
　コアシェルポリマー粒子（Ｂ）を構成するコア層の形成は、例えば、乳化重合、懸濁重合、マイクロサスペンジョン重合などによって製造することができ、例えば国際公開第２００５／０２８５４６号や国際公開２００６／０７０６６４号に記載の方法を用いることができる。 ≪Manufacturing method of core-shell polymer particles≫
(Manufacturing method of core layer)
The formation of the core layer constituting the core-shell polymer particles (B) can be produced by, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization, etc., for example, International Publication No. 2005/0284546 and International Publication No. 2006/070664. The method described in 1 can be used.

　（シェル層および中間層の形成方法）
　中間層は、中間層形成用モノマーを公知のラジカル重合により重合することによって形成することができる。コア層を構成するゴム弾性体をエマルジョンとして得た場合には、中間層形成用モノマーの重合は乳化重合法により行うことが好ましい。 (Method of forming shell layer and intermediate layer)
The intermediate layer can be formed by polymerizing a monomer for forming an intermediate layer by a known radical polymerization. When the rubber elastic body constituting the core layer is obtained as an emulsion, it is preferable to polymerize the monomer for forming the intermediate layer by an emulsion polymerization method.

　シェル層は、シェル層形成用モノマーを、公知のラジカル重合により重合することによって形成することができる。コア層、または、コア層を中間層で被覆して構成されるポリマー粒子前駆体をエマルジョンとして得た場合には、シェル層形成用モノマーの重合は乳化重合法により行うことが好ましく、例えば、国際公開第２００５／０２８５４６号に記載の方法に従って製造することができる。 The shell layer can be formed by polymerizing a monomer for forming a shell layer by a known radical polymerization. When a core layer or a polymer particle precursor composed by coating the core layer with an intermediate layer is obtained as an emulsion, the polymerization of the shell layer forming monomer is preferably carried out by an emulsion polymerization method, for example, internationally. It can be manufactured according to the method described in Publication No. 2005/08546.

　乳化重合において用いることができる乳化剤（分散剤）としては、ジオクチルスルホコハク酸やドデシルベンゼンスルホン酸などに代表されるアルキルまたはアリールスルホン酸、アルキルまたはアリールエーテルスルホン酸、ドデシル硫酸に代表されるアルキルまたはアリール硫酸、アルキルまたはアリールエーテル硫酸、アルキルまたはアリール置換燐酸、アルキルまたはアリールエーテル置換燐酸、ドデシルザルコシン酸に代表されるＮ－アルキルまたはアリールザルコシン酸、オレイン酸やステアリン酸などに代表されるアルキルまたはアリールカルボン酸、アルキルまたはアリールエーテルカルボン酸などの各種の酸類、これら酸類のアルカリ金属塩またはアンモニウム塩などのアニオン性乳化剤（分散剤）；アルキルまたはアリール置換ポリエチレングリコールなどの非イオン性乳化剤（分散剤）；ポリビニルアルコール、アルキル置換セルロース、ポリビニルピロリドン、ポリアクリル酸誘導体などの分散剤が挙げられる。これらの乳化剤（分散剤）は、単独で用いても、２種以上を組み合わせて用いてもよい。 Examples of the emulsifier (dispersant) that can be used in emulsifying polymerization include alkyl or aryl sulfonic acid represented by dioctyl sulfosuccinic acid and dodecylbenzene sulfonic acid, alkyl or aryl ether sulfonic acid, and alkyl or aryl represented by dodecyl sulfate. Sulfuric acid, alkyl or aryl ether sulfuric acid, alkyl or aryl substituted phosphoric acid, alkyl or aryl ether substituted phosphoric acid, N-alkyl or aryl zarcosic acid typified by dodecyl sarcosic acid, alkyl represented by oleic acid or stearic acid or Various acids such as arylcarboxylic acids, alkyl or aryl ether carboxylic acids, anionic emulsifiers (dispersants) such as alkali metal or ammonium salts of these acids; nonionic emulsifiers (dispersants) such as alkyl or aryl substituted polyethylene glycols. ); Dispersants such as polyvinyl alcohol, alkyl-substituted cellulose, polyvinylpyrrolidone, and polyacrylic acid derivatives can be mentioned. These emulsifiers (dispersants) may be used alone or in combination of two or more.

　ポリマー粒子の水性ラテックスの分散安定性に支障を来さない限り、乳化剤（分散剤）の使用量は少なくすることが好ましい。また、乳化剤（分散剤）は、その水溶性が高いほど好ましい。水溶性が高いと、乳化剤（分散剤）の水洗除去が容易になり、最終的に得られる硬化物への悪影響を容易に防止できる。 It is preferable to use a small amount of emulsifier (dispersant) as long as it does not interfere with the dispersion stability of the aqueous latex of the polymer particles. The higher the water solubility of the emulsifier (dispersant), the more preferable it is. When the water solubility is high, the emulsifier (dispersant) can be easily removed by washing with water, and adverse effects on the finally obtained cured product can be easily prevented.

　乳化重合法を採用する場合には、公知の開始剤、すなわち２，２’－アゾビスイソブチロニトリル、過酸化水素、過硫酸カリウム、過硫酸アンモニウムなどを熱分解型開始剤として用いることができる。 When the emulsion polymerization method is adopted, a known initiator, that is, 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, ammonium persulfate and the like can be used as the thermally decomposable initiator. ..

　また、ｔ－ブチルパーオキシイソプロピルカーボネート、パラメンタンハイドロパーオキサイド、クメンハイドロパーオキサイド、ジクミルパーオキサイド、ｔ－ブチルハイドロパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ｔ－ヘキシルパーオキサイドなどの有機過酸化物；過酸化水素、過硫酸カリウム、過硫酸アンモニウムなどの無機過酸化物といった過酸化物と、必要に応じてナトリウムホルムアルデヒドスルホキシレート、グルコースなどの還元剤、および必要に応じて硫酸鉄（ＩＩ）などの遷移金属塩、さらに必要に応じてエチレンジアミン四酢酸二ナトリウムなどのキレート剤、さらに必要に応じてピロリン酸ナトリウムなどのリン含有化合物などを併用したレドックス型開始剤を使用することもできる。 In addition, organic peroxides such as t-butylperoxyisopropyl carbonate, paramentanhydroperoxide, cumenehydroperoxide, dicumyl peroxide, t-butylhydroperoxide, di-t-butyl peroxide, and t-hexyl peroxide. Oxides; peroxides such as inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, and optionally sodium formaldehyde sulfoxylate, reducing agents such as glucose, and optionally iron sulfate (II). ) And the like, and if necessary, a chelating agent such as disodium ethylenediamine tetraacetate, and if necessary, a phosphorus-containing compound such as sodium pyrophosphate can be used in combination with a redox-type initiator.

　レドックス型開始剤系を用いた場合には、前記過酸化物が実質的に熱分解しない低い温度でも重合を行うことができ、重合温度を広い範囲で設定できるようになり好ましい。中でもクメンハイドロパーオキサイド、ジクミルパーオキサイド、ｔ－ブチルハイドロパーオキサイドなどの有機過酸化物をレドックス型開始剤として用いることが好ましい。前記開始剤の使用量、レドックス型開始剤を用いる場合には前記還元剤・遷移金属塩・キレート剤などの使用量は公知の範囲で用いることができる。またラジカル重合性二重結合を２以上有するモノマーを重合するに際しては公知の連鎖移動剤を公知の範囲で用いることができる。追加的に界面活性剤を用いることができるが、これも公知の範囲である。 When a redox-type initiator system is used, polymerization can be carried out even at a low temperature at which the peroxide does not substantially undergo thermal decomposition, and the polymerization temperature can be set in a wide range, which is preferable. Of these, it is preferable to use organic peroxides such as cumene hydroperoxide, dicumyl peroxide, and t-butyl hydroperoxide as the redox-type initiator. The amount of the initiator used, and when the redox-type initiator is used, the amount of the reducing agent, transition metal salt, chelating agent, etc. used can be used within a known range. Further, when polymerizing a monomer having two or more radically polymerizable double bonds, a known chain transfer agent can be used in a known range. Additional surfactants can be used, but this is also in the known range.

　重合に際しての重合温度、圧力、脱酸素などの条件は、公知の範囲のものが適用できる。また、中間層形成用モノマーの重合は１段で行なっても２段以上で行なっても良い。例えば、弾性コア層を構成するゴム弾性体のエマルジョンに中間層形成用モノマーを一度に添加する方法、連続追加する方法の他、あらかじめ中間層形成用モノマーが仕込まれた反応器に弾性コア層を構成するゴム弾性体のエマルジョンを加えてから重合を実施する方法などを採用することができる。 Conditions such as polymerization temperature, pressure, and deoxidation at the time of polymerization can be applied within a known range. Further, the polymerization of the monomer for forming the intermediate layer may be carried out in one stage or in two or more stages. For example, a method of adding a monomer for forming an intermediate layer to an emulsion of a rubber elastic body constituting an elastic core layer at a time, a method of continuously adding a monomer, or a method of adding an elastic core layer to a reactor in which a monomer for forming an intermediate layer is preliminarily charged. It is possible to adopt a method of performing polymerization after adding an emulsion of a constituent rubber elastic body.

　（Ｂ）成分としてコアシェルポリマー粒子を用いる場合、得られる硬化性樹脂組成物の取扱いやすさと、得られる硬化物の靭性改良効果のバランスから、硬化性樹脂組成物におけるコアシェルポリマー粒子の含有量は、エポキシ樹脂（Ａ）１００重量部に対して、１重量部～１００重量部であることが好ましく、５重量部～９０重量部がより好ましく、１０重量部～８０重量部がさらに好ましく、２０重量部～７０重量部がより更に好ましく、３０重量部～６０重量部が特に好ましい。 When the core-shell polymer particles are used as the component (B), the content of the core-shell polymer particles in the curable resin composition is determined from the balance between the ease of handling of the obtained curable resin composition and the effect of improving the toughness of the obtained cured product. The amount is preferably 1 part to 100 parts by weight, more preferably 5 parts by weight to 90 parts by weight, still more preferably 10 parts by weight to 80 parts by weight, and 20 parts by weight with respect to 100 parts by weight of the epoxy resin (A). From 70 parts by weight is even more preferable, and 30 parts by weight to 60 parts by weight is particularly preferable.

　＜水酸化アルミニウム（Ｃ）＞
　第１実施形態の硬化性樹脂組成物は、第一成分および／または前記第二成分中に、（Ｃ）成分として、平均粒子径が１１μｍ以上２００μｍ以下である水酸化アルミニウムを含有する。第１実施形態の硬化性樹脂組成物が（Ｃ）成分を含む場合、得られる硬化物は熱伝導性および難燃性（例えば垂直燃焼試験（ＵＬ９４）で評価される難燃性）に優れるという利点を有する。 <Aluminum hydroxide (C)>
The curable resin composition of the first embodiment contains aluminum hydroxide having an average particle size of 11 μm or more and 200 μm or less as the component (C) in the first component and / or the second component. When the curable resin composition of the first embodiment contains the component (C), the obtained cured product is said to be excellent in thermal conductivity and flame retardancy (for example, flame retardancy evaluated by a vertical combustion test (UL94)). Has advantages.

　第１実施形態において、硬化性樹脂組成物の総重量に対する水酸化アルミニウム（Ｃ）の総重量は、５５重量％以上８５重量％以下であることが必須である。 In the first embodiment, it is essential that the total weight of aluminum hydroxide (C) with respect to the total weight of the curable resin composition is 55% by weight or more and 85% by weight or less.

　（Ｃ）成分は第一成分のみに含有してもよく、第二成分のみに含有してもよく、第一成分と第二成分の双方に含有してもよい。（Ｃ）成分を硬化性樹脂組成物中に多量に配合する観点から、（Ｃ）成分は、少なくとも第一成分に含有することが好ましく、第一成分と第二成分の双方に含有することがより好ましい。 The component (C) may be contained only in the first component, may be contained only in the second component, or may be contained in both the first component and the second component. From the viewpoint of blending the component (C) in a large amount in the curable resin composition, the component (C) is preferably contained in at least the first component, and may be contained in both the first component and the second component. More preferred.

　水酸化アルミニウムは、Ａｌ（ＯＨ）３又はＡｌ２Ｏ３・３Ｈ２Ｏなる化学式で表わされる白色粉末結晶であり、一般にボーキサイトを原料としてバイヤー法にて製造される。水酸化アルミニウムは、分級により、様々な平均粒子径を有する製品が存在する。 Aluminum hydroxide is a white powder crystal represented by a chemical formula of Al (OH) 3 or Al 2 O 3.3H 2 O, and is generally produced by the Bayer process using bauxite as a raw material. As for aluminum hydroxide, there are products having various average particle sizes depending on the classification.

　第１実施形態において用いる水酸化アルミニウムは、平均粒子径が１１μｍ以上２００μｍ以下であることが肝要である。 It is important that the aluminum hydroxide used in the first embodiment has an average particle size of 11 μm or more and 200 μm or less.

　（Ｃ）成分は、（Ａ）成分との接着性を向上させるためにカップリング処理したものでもよい。これにより、得られる硬化物の耐衝撃性、強度、耐水性等の物性を向上させることができる。これら、カップリング処理剤としては、特に限定されるものではないが、シラン系カップリング剤、クロム系カップリング剤、チタン系カップリング剤、アルミニウム系カップリング剤、ジルコニウム系カップリング剤等が挙げられ、これらの中でも、シラン系カップリング剤が好ましく、エポキシシランカップリング剤がより好ましい。また、カップリング処理剤は単独で用いても、２種以上を組み合わせて用いてもよい。 The component (C) may be a coupling-treated component in order to improve the adhesiveness with the component (A). This makes it possible to improve physical properties such as impact resistance, strength, and water resistance of the obtained cured product. These coupling treatment agents are not particularly limited, and examples thereof include silane-based coupling agents, chromium-based coupling agents, titanium-based coupling agents, aluminum-based coupling agents, zirconium-based coupling agents, and the like. Among these, a silane coupling agent is preferable, and an epoxy silane coupling agent is more preferable. Further, the coupling treatment agent may be used alone or in combination of two or more.

　第１実施形態において、（Ｃ）成分の平均粒子径は、得られる硬化物の耐衝撃性と接着強度との両立の観点と、硬化前の硬化性樹脂組成物中での（Ｃ）成分の経時での沈降を抑制する観点から、１１μｍ以上２００μｍ以下であることが必須であり、１２μｍ以上１５０μｍ以下が好ましく、１３μｍ以上１００μｍ以下がより好ましく、１５μｍ以上５０μｍ以下が更に好ましく、１７μｍ以上３０μｍ以下が特に好ましい。 In the first embodiment, the average particle size of the component (C) is determined from the viewpoint of achieving both impact resistance and adhesive strength of the obtained cured product, and the component (C) in the curable resin composition before curing. From the viewpoint of suppressing sedimentation over time, it is essential that the size is 11 μm or more and 200 μm or less, preferably 12 μm or more and 150 μm or less, 13 μm or more and 100 μm or less, more preferably 15 μm or more and 50 μm or less, and 17 μm or more and 30 μm or less. Especially preferable.

　なお、本明細書において、（Ｃ）成分の平均粒子径は、レーザー散乱法粒度測定器を用いた測定から求めることができ、積算粒度分布率５０体積％に対応する粒子径（Ｄｐ５０）である。 In the present specification, the average particle size of the component (C) can be obtained from the measurement using the laser scattering method particle size measuring device, and is the particle size (Dp50) corresponding to the integrated particle size distribution rate of 50% by volume. ..

　異なる平均粒子径を有する複数種の（Ｃ）成分を用いる場合には、（Ｃ）成分の総量に対する各（Ｃ）成分の重量％にそれぞれの平均粒子径を乗じて得られた値の加重平均により（Ｃ）成分全体の平均粒子径を計算することができる。 When multiple types of (C) components having different average particle sizes are used, the weighted average of the values obtained by multiplying the weight% of each (C) component with respect to the total amount of the (C) components by the respective average particle size. (C) The average particle size of the entire component can be calculated.

　第１実施形態において、硬化性樹脂組成物の総重量に対する水酸化アルミニウム（Ｃ）の総重量は、得られる硬化物特性（熱伝導性、難燃性、接着強度、及び耐衝撃性）を向上させる観点と、硬化前の組成物の作業性を向上させる観点から、５５重量％以上８５重量％以下であることが必須であり、５７重量％以上８０重量％以下が好ましく、６０重量％以上７６重量％以下がより好ましく、６２重量％以上７３重量％以下が更に好ましく、６５重量％以上７０重量％以下が特に好ましい。 In the first embodiment, the total weight of aluminum hydroxide (C) with respect to the total weight of the curable resin composition improves the obtained cured product properties (heat conductivity, flame retardancy, adhesive strength, and impact resistance). From the viewpoint of improving the workability of the composition before curing, it is essential that the composition is 55% by weight or more and 85% by weight or less, preferably 57% by weight or more and 80% by weight or less, and 60% by weight or more and 76% by weight. By weight% or less is more preferable, 62% by weight or more and 73% by weight or less is further preferable, and 65% by weight or more and 70% by weight or less is particularly preferable.

　前記エポキシ樹脂（Ａ）１００重量部に対する前記水酸化アルミニウム（Ｃ）の含有量（配合量）は、得られる硬化物特性（熱伝導性、難燃性、接着強度、及び耐衝撃性）を向上させる観点と、硬化前の組成物の作業性を向上させる観点から、２５０重量部以上７５０重量部以下であることが好ましく、３００重量部以上７００重量部以下であることがより好ましく、３５０重量部以上６５０重量部以下であることが更に好ましく、４００重量部以上６００重量部以下であることが特に好ましい。（Ｃ）成分は１種を単独で使用してもよいし、２種以上を併用してもよい。 The content (blending amount) of the aluminum hydroxide (C) with respect to 100 parts by weight of the epoxy resin (A) improves the obtained cured product characteristics (thermal conductivity, flame retardancy, adhesive strength, and impact resistance). From the viewpoint of improving the workability of the composition before curing, it is preferably 250 parts by weight or more and 750 parts by weight or less, more preferably 300 parts by weight or more and 700 parts by weight or less, and 350 parts by weight. It is more preferably 650 parts by weight or less, and particularly preferably 400 parts by weight or more and 600 parts by weight or less. As the component (C), one type may be used alone, or two or more types may be used in combination.

　上述のように、コアシェル構造を有するポリマー粒子（Ｂ）および水酸化アルミニウム（Ｃ）は、各々、第一成分および／または第二成分中に、含有されることが好ましい。この際、ポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）は同一成分内に含まれていてもよいし含まれていなくてもよいが、（Ｂ）成分と（Ｃ）成分を含む場合、第一成分として（Ｂ）成分および（Ｃ）成分を含み、第二成分として（Ｃ）成分を含むことが好ましい。 As described above, the polymer particles (B) and aluminum hydroxide (C) having a core-shell structure are preferably contained in the first component and / or the second component, respectively. At this time, the polymer particles (B) and the aluminum hydroxide (C) may or may not be contained in the same component, but when the component (B) and the component (C) are contained, the first component is used. It is preferable that the component (B) and the component (C) are contained as one component, and the component (C) is contained as the second component.

　なお、第１実施形態において、（Ｃ）成分は硬化性樹脂組成物中に５５重量％以上８５重量％以下と多量に配合している。しかしながら、第１実施形態では、（Ｃ）成分の平均粒子径を１１μｍ以上２００μｍ以下とすることによって、前述の（Ｂ）成分による耐衝撃性を改良させる効果を高く維持することができるが、その理由は以下の様にゴム粒子添加系に関する塑性変形領域の理論から妥当であると推定している（岸肇ら、「日本接着学会誌，Ｖｏｌ．４０，Ｎｏ．５，１７７－１８３」を参照）。 In the first embodiment, the component (C) is blended in a large amount of 55% by weight or more and 85% by weight or less in the curable resin composition. However, in the first embodiment, by setting the average particle size of the component (C) to 11 μm or more and 200 μm or less, the effect of improving the impact resistance of the component (B) described above can be maintained high. The reason is presumed to be appropriate from the theory of the plastic deformation region related to the rubber particle addition system as follows (see Hajime Kishi et al., "Journal of the Japan Adhesive Society, Vol. 40, No. 5, 177-183"). ).

　平面ひずみ場の塑性変形領域ｒｐはＩｒｗｉｎの式より、樹脂靭性値ＫＩＣと引張降伏応力σを用いて、ｒｐ＝１／６π×（ＫＩＣ／σ）２と表される。ここで、コアシェルポリマー粒子で強靭化した２液エポキシ接着剤のＫＩＣとσを、それぞれ１．５ＭＰａ・ｍ１／２と５０ＭＰａと仮定するとｒｐは４８μmとなり、塑性変形領域ｒｐは概ね数十～１００μｍ位の大きさとなる。 The plastic deformation region r p of the plane strain field is expressed as r p = 1 / 6π × (K IC / σ) 2 by using the resin toughness value K IC and the tensile yield stress σ from the Irwin equation. Here, assuming that the KIC and σ of the two-component epoxy adhesive toughened with the core-shell polymer particles are 1.5 MPa · m 1/2 and 50 MPa, respectively, rp is 48 μm, and the plastic deformation region rp is approximately a number. The size is about 10 to 100 μm.

　一方、第１実施形態の硬化性樹脂組成物中には水酸化アルミニウム（Ｃ）が５５重量％以上８５重量％以下の範囲で高充填されており、数μｍ程度の小粒子径の水酸化アルミニウムを用いた場合には水酸化アルミニウム粒子間の距離は数μｍ程となり、十分な塑性変形領域を確保できず、１０μｍよりも大きい水酸化アルミニウム粒子によって漸くある程度の塑性変形領域を確保でき、コアシェルポリマー粒子（Ｂ）による靭性改善効果が発現したものと推定される。 On the other hand, the curable resin composition of the first embodiment is highly filled with aluminum hydroxide (C) in the range of 55% by weight or more and 85% by weight or less, and aluminum hydroxide having a small particle size of about several μm. When is used, the distance between the aluminum hydroxide particles is about several μm, a sufficient plastic deformation region cannot be secured, and a certain degree of plastic deformation region can be finally secured by the aluminum hydroxide particles larger than 10 μm, and the core-shell polymer. It is presumed that the toughness improving effect of the particles (B) was exhibited.

　＜水酸化アルミニウム以外の熱伝導性フィラー＞
　第１実施形態の硬化性樹脂組成物は、水酸化アルミニウム以外の熱伝導性フィラーを含有することができる。例えば、シリカ、アルミナ、窒化アルミニウム、窒化ホウ素、窒化ケイ素、ＺｎＯ、ＳｉＣ、および、ＢｅＯなどが挙げられる。 <Thermal conductive filler other than aluminum hydroxide>
The curable resin composition of the first embodiment can contain a thermally conductive filler other than aluminum hydroxide. For example, silica, alumina, aluminum nitride, boron nitride, silicon nitride, ZnO, SiC, BeO and the like can be mentioned.

　硬化性樹脂組成物における水酸化アルミニウム以外の熱伝導性フィラーの含有量は、エポキシ樹脂（Ａ）１００重量部に対して、１～３００重量部が好ましく、２～２００重量部がより好ましく、５～１００重量部が特に好ましい。 The content of the thermally conductive filler other than aluminum hydroxide in the curable resin composition is preferably 1 to 300 parts by weight, more preferably 2 to 200 parts by weight, based on 100 parts by weight of the epoxy resin (A). ~ 100 parts by weight is particularly preferable.

　＜水酸化アルミニウム以外の難燃剤＞
　第１実施形態の硬化性樹脂組成物は、水酸化アルミニウム以外の難燃剤を含有することができる。例えば、水酸化マグネシウム、ポリリン酸アンモニウム、トリクレジルホスフェート、トリエチルホスフェート、トリフェニルホスフェート、トリス（クロロプロピル）ホスフェート、メチルホスホン酸ジメチル、臭素化ポリエーテルポリオール、炭酸アンモニウム、および、メラミンシアヌレート、などが挙げられる。 <Flame retardants other than aluminum hydroxide>
The curable resin composition of the first embodiment can contain a flame retardant other than aluminum hydroxide. For example, magnesium hydroxide, ammonium polyphosphate, tricresyl phosphate, triethyl phosphate, triphenyl phosphate, tris (chloropropyl) phosphate, dimethyl methylphosphonate, brominated polyether polyol, ammonium carbonate, and melamine cyanurate, etc. Can be mentioned.

　硬化性樹脂組成物における水酸化アルミニウム以外の難燃剤の含有量は、エポキシ樹脂（Ａ）１００重量部に対して、１～１００重量部が好ましく、２～７０重量部がより好ましく、５～５０重量部が特に好ましい。 The content of the flame retardant other than aluminum hydroxide in the curable resin composition is preferably 1 to 100 parts by weight, more preferably 2 to 70 parts by weight, and 5 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin (A). The weight part is particularly preferable.

　＜エポキシ硬化剤（Ｄ）＞
　第１実施形態の硬化性樹脂組成物は、第二成分中に（Ｄ）成分として、エポキシ硬化剤を含有する。 <Epoxy curing agent (D)>
The curable resin composition of the first embodiment contains an epoxy curing agent as the component (D) in the second component.

　（Ｄ）成分は室温程度の低温でもエポキシ樹脂（Ａ）と反応して架橋を形成することが可能な活性水素基を含有する化合物（オリゴマーまたはポリマーも含む）である。 The component (D) is a compound (including an oligomer or a polymer) containing an active hydrogen group capable of reacting with the epoxy resin (A) to form a crosslink even at a low temperature of about room temperature.

　エポキシ硬化剤（Ｄ）は、室温付近（例えば、５℃から５０℃以下）にて、エポキシ基との反応性を有する。エポキシ硬化剤（Ｄ）は、加熱硬化用のエポキシ硬化剤と比較して、低温でエポキシ基との反応性を有する。エポキシ硬化剤（Ｄ）は、ポリマー粒子（Ｂ）および後述の化合物（Ｇ）と併用することにより、５０℃超の高温下での熱処理を必要とせずに、優れた速硬化性と良好な接着強度とを両立させる効果を有する。 The epoxy curing agent (D) has reactivity with an epoxy group near room temperature (for example, 5 ° C to 50 ° C or less). The epoxy curing agent (D) has reactivity with an epoxy group at a low temperature as compared with an epoxy curing agent for heat curing. When the epoxy curing agent (D) is used in combination with the polymer particles (B) and the compound (G) described later, it does not require heat treatment at a high temperature of more than 50 ° C., and has excellent fast curing property and good adhesion. It has the effect of achieving both strength and strength.

　第１実施形態のエポキシ硬化剤（Ｄ）としては、特に限定されず、各種のエポキシ硬化剤を使用することができる。第１実施形態のエポキシ硬化剤（Ｄ）としては、例えば、（ａ）（ａ－１）芳香族アミン、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテルおよびアミン末端ブタジエンニトリルゴム、並びに（ａ－２）それらの変性物、であるアミン系硬化剤、並びに（ｂ）メルカプタン系硬化剤、などが挙げられる。第１実施形態のエポキシ硬化剤（Ｄ）としては、これらの中でも、得られる硬化物の接着強度の観点からアミン系硬化剤がより好ましい。 The epoxy curing agent (D) of the first embodiment is not particularly limited, and various epoxy curing agents can be used. Examples of the epoxy curing agent (D) of the first embodiment include (a) and (a-1) aromatic amines, aliphatic amines, alicyclic amines, amidoamines, amine-terminated polyethers and amine-terminated butadiene nitrile rubbers. In addition, (a-2) their modified products, amine-based curing agents, and (b) mercaptan-based curing agents, and the like can be mentioned. Among these, as the epoxy curing agent (D) of the first embodiment, an amine-based curing agent is more preferable from the viewpoint of the adhesive strength of the obtained cured product.

　第１実施形態のエポキシ硬化剤（Ｄ）は、アミン系硬化剤の中でも、室温での硬化性（速硬化性）の観点から、（ａ）脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される１種以上を含むことが好ましく、（ｂ）脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される１種以上であることがより好ましい。第１実施形態のエポキシ硬化剤（Ｄ）は、アミン系硬化剤の中でも、（ａ）得られる硬化物の耐衝撃性の観点から、（ａ－１）アミン末端ポリエーテルおよびアミン末端ブタジエンニトリルゴムからなる群から選択される１種以上を含むことが好ましく、（ａ－２）アミン末端ポリエーテルおよびアミン末端ブタジエンニトリルゴムからなる群から選択される１種以上であることがより好ましく、（ｂ）更に硬化性の観点からアミン末端ブタジエンニトリルゴムを含むことがより好ましく、アミン末端ブタジエンニトリルゴムであることがさらに好ましい。第１実施形態のエポキシ硬化剤（Ｄ）は、アミン系硬化剤の中でも、（ａ）得られる硬化物の接着強度の観点から、（ａ－１）脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される１種以上を含むことが好ましく、（ａ－２）脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される１種以上であることがより好ましく、（ｂ）更に硬化性の観点から、（ｂ－１）脂環族アミンおよびアミン末端ブタジエンニトリルゴムからなる群より選択される１種以上を含むことがより好ましく、（ｂ－２）脂環族アミンおよびアミン末端ブタジエンニトリルゴムからなる群より選択される１種以上であることがより好ましい。第１実施形態のエポキシ硬化剤（Ｄ）は、得られる硬化物の接着強度および硬化性の観点から、脂環族アミン、アミン末端ブタジエンニトリルゴム、脂環族アミンの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上を含むことがより好ましく、脂環族アミン、アミン末端ブタジエンニトリルゴム、脂環族アミンの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上であることがさらに好ましい。 Among the amine-based curing agents, the epoxy curing agent (D) of the first embodiment has (a) an aliphatic amine, an alicyclic amine, an amidoamine, and an amine terminal from the viewpoint of curability (fast curing) at room temperature. Select from the group consisting of polyethers, amine-terminated butadiene nitrile rubbers, modified aliphatic amines, modified alicyclic amines, modified amidamines, modified amine-terminated polyethers, and modified amine-terminated butadiene nitrile rubbers. It is preferable to contain one or more of them, and (b) aliphatic amines, alicyclic amines, amidamines, amine-terminated polyethers, amine-terminated butadiene nitrile rubbers, modified aliphatic amines, and modified alicyclic amines. , One or more selected from the group consisting of a modified product of amine, a modified product of amine-terminated polyether, and a modified product of amine-terminated butadiene nitrile rubber. Among the amine-based curing agents, the epoxy curing agent (D) of the first embodiment is (a-1) an amine-terminated polyether and an amine-terminated butadiene nitrile rubber from the viewpoint of (a) impact resistance of the obtained cured product. It is preferable to contain one or more selected from the group consisting of (a-2) amine-terminated polyether and amine-terminated butadiene nitrile rubber, and more preferably one or more selected from the group consisting of (b). ) Further, from the viewpoint of curability, it is more preferable to contain an amine-terminated butadiene nitrile rubber, and further preferably an amine-terminated butadiene nitrile rubber. Among the amine-based curing agents, the epoxy curing agent (D) of the first embodiment is (a-1) alicyclic amine, amidoamine, amine-terminated polyether from the viewpoint of (a) adhesive strength of the obtained cured product. , Amine-terminated butadiene nitrile rubber, modified alicyclic amine, modified amidamine, modified amine-terminated polyether and modified amine-terminated butadiene nitrile rubber may contain one or more selected from the group. Preferably, (a-2) alicyclic amines, amidamines, amine-terminated polyethers, amine-terminated butadiene nitrile rubbers, modified alicyclic amines, modified amidamines, modified amine-terminated polyethers and amine-terminated butadiene nitriles. It is more preferably one or more selected from the group consisting of modified rubbers, and (b-1) from the viewpoint of curability, (b-1) from the group consisting of alicyclic amines and amine-terminated butadiene nitrile rubbers. It is more preferable to contain one or more selected species, and more preferably one or more selected from the group consisting of (b-2) alicyclic amines and amine-terminated butadiene nitrile rubbers. The epoxy curing agent (D) of the first embodiment has an alicyclic amine, an amine-terminated butadiene nitrile rubber, a modified alicyclic amine and an amine-terminated butadiene nitrile from the viewpoint of adhesive strength and curability of the obtained cured product. It is more preferable to contain at least one selected from the group consisting of modified rubber products, from alicyclic amines, amine-terminated butadiene nitrile rubbers, modified alicyclic amines, and modified amine-terminated butadiene nitrile rubbers. It is more preferable that the number is at least one selected from the group.

　前記芳香族アミンとしては、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホンなどが挙げられる。 Examples of the aromatic amine include meta-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone and the like.

　前記脂肪族アミンとしては、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジプロプレンジアミン、ジエチルアミノプロピルアミン、ヘキサメチレンジアミンなどの鎖状脂肪族ポリアミン類や、メタキシレンジアミンなどの脂肪芳香族アミン類などが挙げられる。 Examples of the aliphatic amine include chain aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diproprendamine, diethylaminopropylamine and hexamethylenediamine, and fatty aromatic amines such as methaxylenediamine. Can be mentioned.

　前記脂環族アミンとしては、Ｎ－アミノエチルピベラジン、ビス（４－アミノ－３－メチルシクロヘキシル）メタン、メンセンジアミン、イソホロンジアミン、４，４’－ジアミノジシクロヘキシルメタン、スピロアセタールジアミンの一種である３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン、ノルボルナンジアミン、トリシクロデカンジアミン、１，３－ビスアミノメチルシクロヘキサンなどが挙げられる。 Examples of the alicyclic amine include N-aminoethylpyverazine, bis (4-amino-3-methylcyclohexyl) methane, mensendiamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, and spiroacetaldiamine. 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, norbornandiamine, tricyclodecanediamine, 1,3-bisaminomethylcyclohexane, etc. Can be mentioned.

　前記アミドアミンは、トール油脂肪酸の二量体（ダイマー酸）とトリエチレンテトラミンやテトラエチレンペンタミンなどのポリアミンとの縮合により生成する化合物であり、市販されているアミドアミンとしては、Ｖｅｒｓａｍｉｄ　１４０や、Ｖｅｒｓａｍｉｄ　１１５などが挙げられる。 The amidoamine is a compound produced by condensing a dimer of tall oil fatty acid (dimer acid) with a polyamine such as triethylenetetramine or tetraethylenepentamine, and commercially available amidoamines include Versamide 140 and Versamide. 115 and the like can be mentioned.

　前記アミン末端ポリエーテルは、ポリエーテル主鎖を含み、１分子あたり平均して、好ましくは１～４個（より好ましくは１．５～３個）のアミノ基および／またはイミノ基を有するアミン末端ポリエーテルであり、市販されているアミン末端ポリエーテルとしては、Ｈｕｎｔｓｍａｎ社製のＪｅｆｆａｍｉｎｅ　Ｄ－２３０、Ｊｅｆｆａｍｉｎｅ　Ｄ－４００、Ｊｅｆｆａｍｉｎｅ　Ｄ－２０００、Ｊｅｆｆａｍｉｎｅ　Ｄ－４０００、Ｊｅｆｆａｍｉｎｅ　Ｔ－５０００などが挙げられる。 The amine-terminated polyether contains a main chain of polyether and has an amine-terminated amine group having preferably 1 to 4 (more preferably 1.5 to 3) amino groups and / or imino groups on average per molecule. Examples of commercially available amine-terminated polyethers include Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, and Jeffamine T-5000 manufactured by Huntsman.

　前記アミン末端ブタジエンニトリルゴムは、１分子あたり平均して、好ましくは１～４個（より好ましくは１．５～３個）のアミノ基および／またはイミノ基を有し、主鎖のアクリロニトリルモノマー含量が、５～４０質量％（より好ましくは１０～３５質量％、更に好ましくは１５～３０質量％）であるポリブタジエン／アクリロニトリルコポリマーである。市販されているアミン末端ゴムとしては、ＣＶＣ社製のＨｙｐｒｏ　１３００Ｘ１６　ＡＴＢＮなどが挙げられる。 The amine-terminated butadiene nitrile rubber has an average of 1 to 4 (more preferably 1.5 to 3) amino groups and / or imino groups per molecule, and has an acrylonitrile monomer content in the main chain. Is a polybutadiene / acrylonitrile copolymer of 5 to 40% by mass (more preferably 10 to 35% by mass, still more preferably 15 to 30% by mass). Examples of commercially available amine-terminated rubber include Hyper 1300X16 ATBN manufactured by CVC.

　アミン系硬化剤の変性物としては、上述の脂肪族アミンや脂環族アミンなどの各種のポリアミンと等量未満のエポキシ樹脂との反応物であるポリアミンエポキシ樹脂アダクト類やポリアミンとメチルエチルケトンやイソブチルメチルケトン等のケトン類との脱水反応生成物であるケチミン類などが挙げられる。 Modifications of the amine-based curing agent include polyamine epoxy resin adducts, which are reaction products of various polyamines such as the above-mentioned aliphatic amines and alicyclic amines with less than the same amount of epoxy resin, polyamines, methyl ethyl ketones, and isobutylmethyls. Examples thereof include ketimines which are products of dehydration reaction with ketones such as ketones.

　前記メルカプタン系硬化剤としては、より具体的には、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、１，３，５－トリス（２－（３－スルファニルブタノイルオキシ）エチル）－１，３，５－トリアジナンー２，４，６－トリオン、トリメチロールプロパントリス（３－メルカプトブチレート）、チオール末端ポリエーテル、チオール末端ポリスルフィドなどを挙げることができる。 More specifically, the mercaptan-based curing agent includes pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,3,5-tris (2-). (3-Sulfanylbutanoyloxy) ethyl) -1,3,5-triazinan-2,4,6-trione, trimethylolpropanetris (3-mercaptobutyrate), thiol-terminated polyethers, thiol-terminated polysulfides, etc. Can be done.

　前記エポキシ樹脂（Ａ）が有するエポキシ基のモル数と前記エポキシ硬化剤（Ｄ）が有する活性水素基のモル数との比（前記エポキシ基のモル数／前記活性水素基のモル数）は、硬化性樹脂組成物の速硬化性並びに得られる硬化物の接着強度および耐衝撃性の観点から、０．５以上１．６以下であることが好ましく、１．１以上１．６以下であることがより好ましく、１．１以上１．５以下であることがさらに好ましく、１．２以上１．４以下であることが特に好ましい。 The ratio of the number of moles of the epoxy group of the epoxy resin (A) to the number of moles of the active hydrogen group of the epoxy curing agent (D) (the number of moles of the epoxy group / the number of moles of the active hydrogen group) is. From the viewpoint of the quick-curing property of the curable resin composition and the adhesive strength and impact resistance of the obtained cured product, it is preferably 0.5 or more and 1.6 or less, and 1.1 or more and 1.6 or less. Is more preferable, 1.1 or more and 1.5 or less is further preferable, and 1.2 or more and 1.4 or less is particularly preferable.

　前記エポキシ樹脂（Ａ）１００重量部に対する前記エポキシ硬化剤（Ｄ）の含有量（配合量）は、得られる硬化物の接着強度と耐衝撃性との両立の観点、および第一成分と第二成分とを混合する際の混合性し易さの観点から、１５重量部以上３００重量部以下であることが好ましく、２０重量部以上２００重量部以下であることがより好ましく、３０重量部以上１５０重量部以下であることが更に好ましく、４０重量部以上１００重量部以下であることが特に好ましい。（Ｄ）成分は１種を単独で使用してもよいし、２種以上を併用してもよい。 The content (blending amount) of the epoxy curing agent (D) with respect to 100 parts by weight of the epoxy resin (A) is from the viewpoint of achieving both the adhesive strength and impact resistance of the obtained cured product, and the first component and the second component. From the viewpoint of ease of mixing with the components, it is preferably 15 parts by weight or more and 300 parts by weight or less, more preferably 20 parts by weight or more and 200 parts by weight or less, and 30 parts by weight or more and 150 parts by weight or less. It is more preferably 40 parts by weight or less, and particularly preferably 40 parts by weight or more and 100 parts by weight or less. As the component (D), one type may be used alone, or two or more types may be used in combination.

　第１実施形態の硬化性樹脂組成物は、芳香族アミンを含んでいてもよく、含んでいなくてもよい。得られる硬化物の加熱時の伸び物性が優れることから、第１実施形態の硬化性樹脂組成物は、芳香族アミンを実質的に含まないことが好ましい。本明細書において、「芳香族アミンを実質的に含まない」とは、硬化性樹脂組成物１００重量部中の芳香族アミンの含有量が１０００ｐｐｍ以下であることを意図する。芳香族アミンとしては、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホンなどが挙げられる。 The curable resin composition of the first embodiment may or may not contain an aromatic amine. The curable resin composition of the first embodiment preferably contains substantially no aromatic amine because the obtained cured product has excellent stretchable physical properties when heated. As used herein, "substantially free of aromatic amines" is intended that the content of aromatic amines in 100 parts by weight of the curable resin composition is 1000 ppm or less. Examples of the aromatic amine include meta-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone and the like.

　＜（Ｄ）成分以外の高温で活性を示すエポキシ硬化剤＞
　低温でエポキシ樹脂と反応し得る活性水素基を含有するエポキシ硬化剤（上記のアミン系硬化剤やメルカプタン系硬化剤など）以外の、高温で活性を示すエポキシ硬化剤を、第１実施形態の硬化性樹脂組成物の硬化速度を損なわない範囲で含有することが可能である。高温で活性を示すエポキシ硬化剤としては、酸無水物系硬化剤；三フッ化ホウ素-アミン錯体；ジシアンジアミド；有機酸ヒドラジドなどが挙げられる。 <Epoxy curing agent that exhibits activity at high temperatures other than component (D)>
An epoxy curing agent exhibiting activity at a high temperature other than an epoxy curing agent containing an active hydrogen group that can react with an epoxy resin at a low temperature (such as the above-mentioned amine-based curing agent and mercaptan-based curing agent) can be used for curing the first embodiment. It can be contained within a range that does not impair the curing rate of the sex resin composition. Examples of the epoxy curing agent that exhibits activity at high temperatures include acid anhydride-based curing agents; boron trifluoride-amine complex; dicyandiamide; and organic acid hydrazide.

　前記酸無水物系硬化剤はアミン系硬化剤と比較して高温を必要とするが、ポットライフが長く、硬化物は電気的特性、化学的特性、機械的特性などの物性バランスが良好である。酸無水物系硬化剤としては、より具体的には、ポリセバシン酸ポリ無水物、ポリアゼライン酸ポリ無水物、無水コハク酸、シトラコン酸無水物、イタコン酸無水物、アルケニル置換コハク酸無水物、ドデセニルコハク酸無水物、無水マレイン酸、トリカルバリル酸無水物、ナド酸無水物、メチルナド酸無水物、無水マレイン酸によるリノール酸付加物、アルキル化末端アルキレンテトラヒドロフタル酸無水物、メチルテトラヒドロフタル酸無水物、テトラヒドロフタル酸無水物、ヘキサヒドロフタル酸無水物、ピロメリット酸二無水物、トリメリット酸無水物、無水フタル酸、テトラクロロフタル酸無水物、テトラブロモフタル酸無水物、ジクロロマレイン酸無水物、クロロナド酸無水物、およびクロレンド酸無水物、ならびに無水マレイン酸－グラフト化ポリブタジエンなどを挙げることができる。 The acid anhydride-based curing agent requires a higher temperature than the amine-based curing agent, but has a long pot life, and the cured product has a good balance of physical properties such as electrical properties, chemical properties, and mechanical properties. .. More specifically, the acid anhydride-based curing agent includes polysevacinic acid polyanhydride, polyazelineic acid polyanhydride, succinic anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl-substituted succinic anhydride, and dodecenyl succinic acid. Acid Anhydride, Maleic Anhydrous, Tricarbaryl Anhydride, Nadic Anhydrous, Methylnadic Acid Anhydride, Linolic Acid Additive with Maleic Anhydrous, Alkylated Terminal alkylene Tetrahydrophthalic Anhydrous, Methyltetrahydrophthalic Anhydrous, Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, dichloromaleic anhydride, Chloronadic acid anhydride, chlorendic acid anhydride, maleic anhydride-grafted polybutadiene and the like can be mentioned.

　前記三フッ化ホウ素-アミン錯体としては、より具体的には、三フッ化ホウ素-モノエチルアミン、三フッ化ホウ素-ピペリジン、三フッ化ホウ素-トリエチルアミン、三フッ化ホウ素-アニリンなどを挙げることができる。 Specific examples of the boron trifluoride-amine complex include boron trifluoride-monoethylamine, boron trifluoride-piperidine, boron trifluoride-triethylamine, and boron trifluoride-aniline. can.

　前記有機酸ヒドラジドとしては、より具体的には、アジピン酸ジヒドラジド、ステアリン酸ジヒドラジド、イソフタル酸ジヒドラジド、セミカルバジドなどを挙げることができる。 Specific examples of the organic acid hydrazide include adipic acid dihydrazide, stearic acid dihydrazide, isophthalic acid dihydrazide, and semicarbazide.

　硬化性樹脂組成物における、（Ｄ）成分以外の高温で活性を示すエポキシ硬化剤の含有量（配合量）は、前記エポキシ樹脂（Ａ）１００重量部に対して、０．１重量部以上３０重量部以下であることが好ましく、０．５重量部以上２０重量部以下であることがより好ましく、１重量部以上１５重量部以下であることが更に好ましく、２重量部以上１０重量部以下であることが特に好ましい。 The content (blending amount) of the epoxy curing agent exhibiting activity at high temperatures other than the component (D) in the curable resin composition is 0.1 part by weight or more and 30 parts by weight with respect to 100 parts by weight of the epoxy resin (A). It is preferably 0.5 parts by weight or more, more preferably 20 parts by weight or less, further preferably 1 part by weight or more and 15 parts by weight or less, and 2 parts by weight or more and 10 parts by weight or less. It is particularly preferable to have.

　＜エポキシ硬化促進剤（Ｅ）＞
　第１実施形態の硬化性樹脂組成物は、第一成分および／または前記第二成分中に、エポキシ硬化促進剤（Ｅ）を含有することができる。（Ｅ）成分は、エポキシ樹脂（Ａ）と反応して架橋を形成することが困難な化合物であるが、エポキシ樹脂（Ａ）とエポキシ硬化剤（Ｄ）による硬化反応を加速することができる。特に（Ｅ）成分は、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、やそれらの変性物など、室温での硬化性が高いエポキシ硬化剤との併用により、顕著な加速効果を示すものが好ましい。 <Epoxy curing accelerator (E)>
The curable resin composition of the first embodiment can contain an epoxy curing accelerator (E) in the first component and / or the second component. The component (E) is a compound that is difficult to react with the epoxy resin (A) to form a crosslink, but the curing reaction between the epoxy resin (A) and the epoxy curing agent (D) can be accelerated. In particular, the component (E) can be used in combination with an epoxy curing agent having high curability at room temperature, such as aliphatic amines, alicyclic amines, amidoamines, amine-terminated polyethers, amine-terminated butadiene nitrile rubbers, and modified products thereof. , Those showing a remarkable acceleration effect are preferable.

　（Ｅ）成分は第一成分のみに含有してもよく、第二成分のみに含有してもよく、第一成分と第二成分の双方に含有してもよい。硬化性樹脂組成物の貯安性の観点から、（Ｅ）成分は、第二成分のみに含有することが好ましい。 The component (E) may be contained only in the first component, may be contained only in the second component, or may be contained in both the first component and the second component. From the viewpoint of the storage stability of the curable resin composition, the component (E) is preferably contained only in the second component.

　（Ｅ）成分としては、例えば、Ｃ１－Ｃ１２アルキレンイミダゾール、Ｎ－アリールイミダゾール、２－メチルイミダゾール、２－エチル－２－メチルイミダゾール、Ｎ－ブチルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾリウム・トリメリテート、エポキシ樹脂とイミダゾールとの付加生成物、などのイミダゾール類；Ｎ，Ｎ－ジメチルピペラジン、ジアザビシクロウンデセン、ジアザビシクロノネン、トリエチレンジアミン、ベンジルジメチルアミン、トリエチルアミンなどの３級アミン類；２－（ジメチルアミノメチル）フェノール、２，４，６－トリス（ジメチルアミノメチル）フェノール、ポリ（ｐ－ビニルフェノール）マトリックスに組み込まれた２，４，６－トリス（ジメチルアミノメチル）フェノール、ｐ－ｔ－ブチルフェノール、フェノール、４－メトキシフェノール、レゾルシノール、カテコール、４－ｔ－ブチルカテコールなどのフェノール類；等が挙げられる。これらの中でも、硬化性改善効果の観点からフェノール類が好ましく、レゾルシノール、カテコール、４－ｔ－ブチルカテコールなどの２価フェノール類がより好ましい。（Ｅ）成分は、単独で用いてもよく、２種以上を併用してもよい。 Examples of the component (E) include C1-C12 alkylene imidazole, N-aryl imidazole, 2-methyl imidazole, 2-ethyl-2-methyl imidazole, N-butyl imidazole, 1-cyanoethyl-2-undecyl imidazolium. Imidazoles such as trimellitate, an addition product of epoxy resin and imidazole; tertiary amines such as N, N-dimethylpiperazine, diazabicycloundecene, diazabicyclononen, triethylenediamine, benzyldimethylamine, triethylamine; 2- (Dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol incorporated into a poly (p-vinylphenol) matrix, p -Pphenols such as t-butylphenol, phenol, 4-methoxyphenol, resorcinol, catechol, 4-t-butylcatechol; and the like. Among these, phenols are preferable from the viewpoint of the effect of improving curability, and divalent phenols such as resorcinol, catechol, and 4-t-butylcatechol are more preferable. The component (E) may be used alone or in combination of two or more.

　前記エポキシ樹脂（Ａ）１００重量部に対する前記エポキシ硬化促進剤（Ｅ）の配合量は、硬化性の向上効果と保存安定性の観点から、０．１重量部以上３０重量部以下が好ましく、１重量部以上２０重量部以下がより好ましく、２重量部以上１５重量部以下が更に好ましく、３重量部以上１０重量部以下が特に好ましい。 The blending amount of the epoxy curing accelerator (E) with respect to 100 parts by weight of the epoxy resin (A) is preferably 0.1 part by weight or more and 30 parts by weight or less from the viewpoint of improving curability and storage stability. It is more preferably 2 parts by weight or more and 20 parts by weight or less, further preferably 2 parts by weight or more and 15 parts by weight or less, and particularly preferably 3 parts by weight or more and 10 parts by weight or less.

　＜シランカップリング剤（Ｆ）＞
　第１実施形態の硬化性樹脂組成物は、第一成分および／または前記第二成分中に、シランカップリング剤（Ｆ）を含有することができる。 <Silane coupling agent (F)>
The curable resin composition of the first embodiment can contain a silane coupling agent (F) in the first component and / or the second component.

　硬化性樹脂組成物が（Ｆ）成分を含有する場合、当該（Ｆ）成分は、ガラスおよび金属等の被着体表面と硬化性樹脂組成物との両者をとりもつ接着助剤の役割を果たす。 When the curable resin composition contains the component (F), the component (F) serves as an adhesive aid that holds both the surface of the adherend such as glass and metal and the curable resin composition.

　シランカップリング剤（Ｆ）の具体例としては、γ－イソシアネートプロピルトリメトキシシラン、γ－イソシアネートプロピルトリエトキシシラン、γ－イソシアネートプロピルメチルジメトキシシラン等のイソシアネート基含有シラン類；γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－アミノプロピルメチルジメトキシシラン、γ－（２－アミノエチル）アミノプロピルトリメトキシシラン、γ－（２－アミノエチル）アミノプロピルメチルジメトキシシラン、γ－（２－アミノエチル）アミノプロピルトリエトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等のアミノ基含有シラン類；Ｎ－（１，３－ジメチルブチリデン）－３－（トリエトキシシリル）－１－プロパンアミン等のケチミン型シラン類；γ－メルカプトプロピルトリメトキシシラン、γ－メルカプトプロピルトリエトキシシラン、γ－メルカプトプロピルメチルジメトキシシラン等のメルカプト基含有シラン類；γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、γ－グリシドキシプロピルメチルジメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリエトキシシラン等のエポキシ基含有シラン類；トリス（３－トリメトキシシリルプロピル）イソシアヌレート等のイソシアヌレートシラン類、等を挙げることができる。これらの中でも、エポキシ基含有シラン類が得られる硬化物の接着強度の観点から好ましい。 Specific examples of the silane coupling agent (F) include isocyanate group-containing silanes such as γ-isocyanapropyltrimethoxysilane, γ-isoxapropyltriethoxysilane, and γ-isocyanapropylmethyldimethoxysilane; γ-aminopropyltrimethoxy. Silane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2) -Amino group-containing silanes such as aminoethyl) aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane; N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1 -Ketimin-type silanes such as propaneamine; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane; γ-glycidoxypropyltrimethoxysilane , Γ-Glysidoxypropyltriethoxysilane, γ-Glysidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Epoxy group-containing silanes such as; isocyanurate silanes such as tris (3-trimethoxysilylpropyl) isocyanurate, and the like can be mentioned. Among these, epoxy group-containing silanes are preferable from the viewpoint of the adhesive strength of the cured product obtained.

　本明細書において、エポキシ基含有シラン類であるシランカップリング剤（Ｆ）を、「エポキシシランカップリング剤（Ｆ１）」と称する場合がある。 In the present specification, the silane coupling agent (F) which is an epoxy group-containing silane may be referred to as "epoxy silane coupling agent (F1)".

　（Ｆ）成分は第一成分のみに含有してもよく、第二成分のみに含有してもよく、第一成分と第二成分の双方に含有してもよい。硬化性樹脂組成物の貯安性の観点から、（ａ）（Ｆ）成分がイソシアネート基含有シラン類、エポキシ基含有シラン類（エポキシシランカップリング剤（Ｆ１））およびイソシアヌレートシラン類からなる群から選択される１種以上である場合は、第一成分のみに（Ｆ）成分を含有することが好ましく、（ｂ）（Ｆ）成分がアミノ基含有シラン類、ケチミン型シラン類およびメルカプト基含有シラン類からなる群から選択される１種以上である場合は、第二成分のみに（Ｆ）成分を含有することが好ましい。 The component (F) may be contained only in the first component, may be contained only in the second component, or may be contained in both the first component and the second component. From the viewpoint of the storage stability of the curable resin composition, the group (a) and (F) are composed of isocyanate group-containing silanes, epoxy group-containing silanes (epoxysilane coupling agent (F1)) and isocyanurate silanes. When it is one or more selected from, it is preferable that the component (F) is contained only in the first component, and the components (b) and (F) contain amino group-containing silanes, ketimine-type silanes and mercapto groups. When it is one or more selected from the group consisting of silanes, it is preferable that the component (F) is contained only in the second component.

　前記エポキシ樹脂（Ａ）１００重量部に対する前記シランカップリング剤（Ｆ）の配合量は、接着性の向上効果と保存安定性の観点から、０．１重量部以上２０重量部以下が好ましく、１重量部以上１５重量部以下がより好ましく、２重量部以上１０重量部以下が更に好ましく、３重量部以上７重量部以下が特に好ましい。 The blending amount of the silane coupling agent (F) with respect to 100 parts by weight of the epoxy resin (A) is preferably 0.1 part by weight or more and 20 parts by weight or less from the viewpoint of improving adhesiveness and storage stability. It is more preferably 2 parts by weight or more and 15 parts by weight or less, further preferably 2 parts by weight or more and 10 parts by weight or less, and particularly preferably 3 parts by weight or more and 7 parts by weight or less.

　得られる硬化性樹脂組成物が貯安性に優れ、かつ当該硬化性樹脂組成物を硬化してなる硬化物が接着強度に優れることから、硬化性樹脂組成物は、第一成分が、（Ｆ）成分として、エポキシシランカップリング剤（Ｆ１）を含有することがより好ましい。 Since the obtained curable resin composition has excellent storage stability and the cured product obtained by curing the curable resin composition has excellent adhesive strength, the curable resin composition contains (F) as the first component. ), It is more preferable to contain an epoxy silane coupling agent (F1).

　＜強化剤＞
　硬化性樹脂組成物は、靭性、耐衝撃性、接着強度（せん断接着性（せん断接着強さ））、及び、剥離接着性などの性能を更に向上させる目的で、強化剤として、ブロックドウレタンやエポキシ未変性ゴム系重合体を、必要に応じて含有してもよい。強化剤は、単独で用いても良く、２種以上を併用しても良い。 <Strengthening agent>
The curable resin composition can be used as a reinforcing agent such as blocked urethane for the purpose of further improving performance such as toughness, impact resistance, adhesive strength (shear adhesiveness (shear adhesive strength)), and peeling adhesiveness. An epoxy-unmodified rubber-based polymer may be contained, if necessary. The fortifier may be used alone or in combination of two or more.

　＜ブロックドウレタン＞
　ブロックドウレタンは、エラストマー型であって、ウレタン基および／または尿素基を含有し、かつ、末端にイソシアネート基を有する化合物の当該末端イソシアネート基の全部または一部が活性水素基を有する種々のブロック剤でキャップされた化合物である。特に、当該末端イソシアネート基の全部がブロック剤でキャップされた化合物が好ましい。このような化合物は、例えば、末端に活性水素含有基を有する有機重合体に、過剰のポリイソシアネート化合物を反応させて、主鎖中にウレタン基および／または尿素基を有し末端にイソシアネート基を有する重合体（ウレタンプレポリマー）とした後、あるいは同時に、該イソシアネート基の全部または一部に、活性水素基を有するブロック剤でキャップすることにより得られる。 <Blocked urethane>
Blocked urethane is an elastomer type, and is a variety of blocks containing a urethane group and / or a urea group, and all or part of the terminal isocyanate group of the compound having an isocyanate group at the terminal has an active hydrogen group. It is a compound capped with an agent. In particular, a compound in which all of the terminal isocyanate groups are capped with a blocking agent is preferable. For such a compound, for example, an organic polymer having an active hydrogen-containing group at the terminal is reacted with an excess polyisocyanate compound to have a urethane group and / or a urea group in the main chain and an isocyanate group at the terminal. It is obtained by capping all or a part of the isocyanate groups with a blocking agent having an active hydrogen group after making the polymer (urethane prepolymer) having the polymer (urethane prepolymer) or at the same time.

　ブロックドウレタンの具体例としては、国際公開２０１６／１６３４９１号に記載の化合物を挙げることができる。 Specific examples of blocked urethane include the compounds described in International Publication No. 2016/163491.

　ブロックドウレタンの数平均分子量は、ＧＰＣで測定したポリスチレン換算分子量にて、２０００～４００００が好ましく、３０００～３００００がより好ましく、４０００～２００００が特に好ましい。分子量分布（重量平均分子量と数平均分子量との比）は、１～４が好ましく、１．２～３がより好ましく、１．５～２．５が特に好ましい。 The number average molecular weight of the blocked urethane is preferably 2000 to 40,000, more preferably 3000 to 30000, and particularly preferably 4000 to 20000 in terms of polystyrene-equivalent molecular weight measured by GPC. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 1 to 4, more preferably 1.2 to 3, and particularly preferably 1.5 to 2.5.

　ブロックドウレタンは、単独でまたは２種以上を組み合わせて使用することができる。 Blocked urethane can be used alone or in combination of two or more.

　ブロックドウレタンの量は、エポキシ樹脂（Ａ）１００重量部に対して、１～５０重量部が好ましく、２～４０重量部がより好ましく、５～３０重量部が特に好ましい。１重量部以上で、靱性、耐衝撃性、接着性などの改善効果が良好であり、５０重量部以下であると、得られる硬化物の弾性率が高くなる。 The amount of blocked urethane is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, and particularly preferably 5 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin (A). When it is 1 part by weight or more, the effect of improving toughness, impact resistance, adhesiveness and the like is good, and when it is 50 parts by weight or less, the elastic modulus of the obtained cured product is high.

　＜エポキシ未変性ゴム系重合体＞
　ゴム系重合体をエポキシ樹脂と反応させない未変性のまま、硬化性樹脂組成物中に、必要に応じて含有（配合）してもよい。 <Epoxy unmodified rubber polymer>
If necessary, the rubber-based polymer may be contained (blended) in the curable resin composition without being modified so as not to react with the epoxy resin.

　前記ゴム系重合体としては、アクリロニトリルブタジエンゴム（ＮＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、水素添加ニトリルゴム（ＨＮＢＲ）、エチレンプロピレンゴム（ＥＰＤＭ）、アクリルゴム（ＡＣＭ）、ブチルゴム（ＩＩＲ）、ブタジエンゴム、ポリプロピレンオキシドやポリエチレンオキシドやポリテトラメチレンオキシド等のポリオキシアルキレン、などのゴム系重合体を挙げることができる。該ゴム系重合体は、アミノ基、ヒドロキシ基、またはカルボキシル基等の反応性基を末端に有するものが好ましい。これらの中でも、ＮＢＲや、ポリオキシアルキレンが、得られる硬化性樹脂組成物の接着性や耐衝撃剥離接着性の観点から好ましく、ＮＢＲがより好ましく、カルボキシル基末端ＮＢＲ（ＣＴＢＮ）が特に好ましい。 Examples of the rubber polymer include acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), hydrogenated nitrile rubber (HNBR), ethylene propylene rubber (EPDM), acrylic rubber (ACM), butyl rubber (IIR), and butadiene rubber. , Polyoxyalkylenes such as polypropylene oxide, polyethylene oxide and polytetramethylene oxide, and rubber-based polymers can be mentioned. The rubber-based polymer preferably has a reactive group such as an amino group, a hydroxy group, or a carboxyl group at the end. Among these, NBR and polyoxyalkylene are preferable from the viewpoint of adhesiveness and impact resistance peeling adhesiveness of the obtained curable resin composition, NBR is more preferable, and carboxyl group terminal NBR (CTBN) is particularly preferable.

　前記ゴム系重合体のガラス転移温度（Ｔｇ）は、特に制限は無いが、－２５℃以下が好ましく、－３５℃以下がより好ましく、－４０℃以下が更に好ましく、－５０℃以下が特に好ましい。 The glass transition temperature (Tg) of the rubber-based polymer is not particularly limited, but is preferably −25 ° C. or lower, more preferably −35 ° C. or lower, further preferably −40 ° C. or lower, and particularly preferably −50 ° C. or lower. ..

　前記ゴム系重合体の数平均分子量は、ＧＰＣで測定したポリスチレン換算分子量にて、１５００～４００００が好ましく、３０００～３００００がより好ましく、４０００～２００００が特に好ましい。分子量分布（重量平均分子量と数平均分子量との比）は、１～４が好ましく、１．２～３がより好ましく、１．５～２．５が特に好ましい。 The number average molecular weight of the rubber-based polymer is preferably 1500 to 40,000, more preferably 3000 to 30000, and particularly preferably 4000 to 20000 in terms of polystyrene-equivalent molecular weight measured by GPC. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 1 to 4, more preferably 1.2 to 3, and particularly preferably 1.5 to 2.5.

　ゴム系重合体は、単独でまたは２種以上を組み合わせて使用することができる。 The rubber polymer can be used alone or in combination of two or more.

　ゴム系重合体の量は、エポキシ樹脂（Ａ）１００重量部に対して、１～３０重量部が好ましく、２～２０重量部がより好ましく、５～１０重量部が特に好ましい。１重量部以上で、靱性、耐衝撃性、接着性などの改善効果が良好であり、５０重量部以下であると、得られる硬化物の弾性率が高くなる。 The amount of the rubber-based polymer is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, and particularly preferably 5 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin (A). When it is 1 part by weight or more, the effect of improving toughness, impact resistance, adhesiveness and the like is good, and when it is 50 parts by weight or less, the elastic modulus of the obtained cured product is high.

　＜（Ｃ）成分以外の無機充填材＞
　硬化性樹脂組成物は、水酸化アルミニウム（Ｃ）以外の無機充填材を含有することができる。（Ｃ）成分以外の無機充填材としては、例えばケイ酸および／またはケイ酸塩を使用することができ、その具体例としては、乾式シリカ、湿式シリカ、ケイ酸アルミニウム、ケイ酸マグネシウム、ケイ酸カルシウム、ウォラストナイト、タルク、などが挙げられる。 <Inorganic filler other than component (C)>
The curable resin composition can contain an inorganic filler other than aluminum hydroxide (C). As the inorganic filler other than the component (C), for example, silicic acid and / or silicate can be used, and specific examples thereof include dry silica, wet silica, aluminum silicate, magnesium silicate, and silicic acid. Calcium, wollastonite, talc, etc. can be mentioned.

　前記乾式シリカはヒュームドシリカとも呼ばれ、表面無処理の親水性ヒュームドシリカと、親水性ヒュームドシリカのシラノール基部分にシランやシロキサンで化学的に処理することによって製造した疎水性ヒュームドシリカが挙げられるが、（Ａ）成分や（Ｄ）成分への分散性の点から、疎水性ヒュームドシリカが好ましい。ヒュームドシリカは、第一成分や第二成分に添加することでチクソトロピー性を付与することができ、たれ防止効果を示す。 The dry silica is also called fumed silica, and is produced by chemically treating the surface-untreated hydrophilic fumed silica and the silanol group portion of the hydrophilic fumed silica with silane or siloxane. However, hydrophobic fumed silica is preferable from the viewpoint of dispersibility in the component (A) and the component (D). Humed silica can be imparted with thixotropic properties by being added to the first component and the second component, and exhibits a sagging prevention effect.

　（Ｃ）成分以外の無機充填材のその他の具体例としては、ドロマイトおよびカーボンブラックの如き補強性充填材；重質炭酸カルシウム、膠質炭酸カルシウム、ウォラストナイト、炭酸マグネシウム、酸化チタン、酸化第二鉄、アルミニウム微粉末、酸化亜鉛、活性亜鉛華等が挙げられる。 Other specific examples of inorganic fillers other than the component (C) include reinforcing fillers such as dolomite and carbon black; heavy calcium carbonate, collagen carbonate, wollastonite, magnesium carbonate, titanium oxide, second oxide. Examples thereof include iron, fine aluminum powder, zinc oxide, and active zinc flower.

　（Ｃ）成分以外の無機充填材は、表面処理剤により表面処理していることが好ましい。表面処理により、（Ｃ）成分以外の無機充填材の硬化性樹脂組成物中の分散性が向上し、その結果、得られる硬化物の各種物性が向上する。 It is preferable that the inorganic filler other than the component (C) is surface-treated with a surface treatment agent. By the surface treatment, the dispersibility of the inorganic filler other than the component (C) in the curable resin composition is improved, and as a result, various physical properties of the obtained cured product are improved.

　（Ｃ）成分以外の無機充填材は１種を単独で用いても良く、２種以上を併用しても良い。 As the inorganic filler other than the component (C), one type may be used alone, or two or more types may be used in combination.

　（Ｃ）成分以外の無機充填材の含有量（使用量）は、（Ａ）成分１００重量部に対して、１～１００重量部が好ましく、２～７０重量部がより好ましく、５～４０重量部が更に好ましく、７～２０重量部が特に好ましい。 The content (usage amount) of the inorganic filler other than the component (C) is preferably 1 to 100 parts by weight, more preferably 2 to 70 parts by weight, and 5 to 40 parts by weight with respect to 100 parts by weight of the component (A). Parts are more preferable, and 7 to 20 parts by weight are particularly preferable.

　＜モノエポキシド＞
　硬化性樹脂組成物は、必要に応じて、モノエポキシドを含有することができる。モノエポキシドは反応性希釈剤として機能しうる。モノエポキシドの具体例としては、例えばブチルグリシジルエーテルなどの脂肪族グリシジルエーテル、あるいは例えばフェニルグリシジルエーテル、クレジルグリシジルエーテルなどの芳香族グリシジルエーテル、例えば２－エチルヘキシルグリシジルエーテルなどの炭素数８～１０のアルキル基とグリシジル基とからなるエーテル、例えばｐ－ｔｅｒｔブチルフェニルグリシジルエーテルなどの炭素数２～８のアルキル基で置換され得る炭素数６～１２のフェニル基とグリシジル基とからなるエーテル、例えばドデシルグリシジルエーテルなどの炭素数１２～１４のアルキル基とグリシジル基とからなるエーテル；例えばグリシジル（メタ）アクリレート、グリシジルマレエートなどの脂肪族グリシジルエステル；バーサチック酸グリシジルエステル、ネオデカン酸グリシジルエステル、ラウリン酸グリシジルエステルなどの炭素数８～１２の脂肪族カルボン酸のグリシジルエステル；ｐ－ｔ－ブチル安息香酸グリシジルエステルなどが挙げられる。 <Mono epoxide>
The curable resin composition can contain a monoepoxide, if necessary. The monoepoxide can function as a reactive diluent. Specific examples of the monoepoxide include an aliphatic glycidyl ether such as butyl glycidyl ether, an aromatic glycidyl ether such as phenyl glycidyl ether and cresyl glycidyl ether, and an aromatic glycidyl ether such as 2-ethylhexyl glycidyl ether having 8 to 10 carbon atoms. An ether consisting of an alkyl group and a glycidyl group, for example, an ether composed of a phenyl group having 6 to 12 carbon atoms and a glycidyl group which can be replaced with an alkyl group having 2 to 8 carbon atoms such as p-tert butylphenyl glycidyl ether, for example, dodecyl. Ether consisting of an alkyl group having 12 to 14 carbon atoms such as glycidyl ether and a glycidyl group; for example, an aliphatic glycidyl ester such as glycidyl (meth) acrylate and glycidyl maleate; versatic acid glycidyl ester, neodecanoic acid glycidyl ester, glycidyl laurate. Examples thereof include glycidyl esters of aliphatic carboxylic acids having 8 to 12 carbon atoms such as esters; and pt-butyl benzoic acid glycidyl esters.

　モノエポキシドを使用する場合、硬化性樹脂組成物中のモノエポキシドの含有量（使用量）は、（Ａ）成分１００重量部に対して、０．１～２０重量部が好ましく、０．５～１０重量部がより好ましく、１～５重量部が特に好ましい。０．１重量部以上で低粘度化効果が良好であり、２０重量部以下であると、接着性等の物性が良好となる。 When monoepoxide is used, the content (usage) of monoepoxide in the curable resin composition is preferably 0.1 to 20 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the component (A). 10 parts by weight is more preferable, and 1 to 5 parts by weight is particularly preferable. When it is 0.1 part by weight or more, the effect of reducing the viscosity is good, and when it is 20 parts by weight or less, the physical properties such as adhesiveness are good.

　＜その他の配合成分＞
　硬化性樹脂組成物は、必要に応じて、その他の配合成分（添加剤）を含有することができる。その他の配合成分としては、ラジカル硬化性樹脂、熱ラジカル重合開始剤、光硬化性樹脂、光重合開始剤、アゾタイプ化学的発泡剤、熱膨張性マイクロバルーンなどの膨張剤、アラミド系パルプなどの繊維パルプ、顔料や染料等の着色剤、体質顔料、紫外線吸収剤、酸化防止剤、安定化剤（ゲル化防止剤）、可塑剤、レベリング剤、消泡剤、帯電防止剤、滑剤、減粘剤、低収縮剤、有機質充填剤、熱可塑性樹脂、乾燥剤、分散剤、溶剤等が挙げられる。 <Other ingredients>
The curable resin composition may contain other compounding components (additives), if necessary. Other compounding components include radical curable resins, thermoplastic initiators, photocurable resins, photopolymerization initiators, azotype chemical foaming agents, expanders such as heat-expandable microballoons, and fibers such as aramid-based pulp. Pulps, colorants such as pigments and dyes, extender pigments, UV absorbers, antioxidants, stabilizers (antigels), plastics, leveling agents, defoaming agents, antistatic agents, lubricants, thickeners. , Low shrinkage agent, organic filler, thermoplastic resin, desiccant, dispersant, solvent and the like.

　硬化性樹脂組成物における、各成分の「含有量」は、各成分の「配合量」と読み替えてもよい。 The "content" of each component in the curable resin composition may be read as the "blending amount" of each component.

　＜硬化性樹脂組成物の製造方法＞
　硬化性樹脂組成物の製造方法としては特に限定されない。硬化性樹脂組成物の第一成分が、硬化性樹脂であるエポキシ樹脂（Ａ）と、（Ｂ）成分としてコアシェルポリマー粒子を含有する組成物（以下、「ポリマー粒子含有組成物」とも称する）を含む場合、該ポリマー粒子含有組成物は、コアシェルポリマー粒子（Ｂ）が１次粒子の状態で分散した組成物であることが好ましい。 <Manufacturing method of curable resin composition>
The method for producing the curable resin composition is not particularly limited. A composition containing an epoxy resin (A) as a curable resin as the first component of the curable resin composition and core-shell polymer particles as the component (B) (hereinafter, also referred to as “polymer particle-containing composition”). When included, the polymer particle-containing composition is preferably a composition in which the core-shell polymer particles (B) are dispersed in the state of primary particles.

　このような、コアシェルポリマー粒子（Ｂ）を１次粒子の状態で分散させた組成物（ポリマー粒子含有組成物）を得る方法は、種々の方法が利用できるが、例えば水性ラテックス状態で得られたコアシェルポリマー粒子（Ｂ）を（Ａ）成分と接触させた後、水等の不要な成分を除去する方法、コアシェルポリマー粒子（Ｂ）を一旦有機溶剤に抽出後に、抽出されたコアシェルポリマー粒子（Ｂ）と（Ａ）成分とを混合してから有機溶剤を除去する方法等が挙げられるが、国際公開第２００５／０２８５４６号に記載の方法を利用することが好ましい。ポリマー粒子含有組成物の具体的な製造方法は、順に、コアシェルポリマー粒子（Ｂ）を含有する水性ラテックス（詳細には、乳化重合によってコアシェルポリマー粒子（Ｂ）を製造した後の反応混合物）を、２０℃における水に対する溶解度が５重量％以上４０重量％以下の有機溶媒と混合した後、得られた混合物とさらに過剰の水とを混合して、コアシェルポリマー粒子（Ｂ）を凝集させる第１工程と、凝集したコアシェルポリマー粒子（Ｂ）を液相から分離・回収した後、得られたコアシェルポリマー粒子（Ｂ）の凝集体を再度有機溶媒と混合して、コアシェルポリマー粒子（Ｂ）の有機溶媒分散液を得る第２工程と、有機溶媒分散液をさらに（Ａ）成分と混合した後、得られた混合物から前記有機溶媒を留去する第３工程と、を含んで調製されることが好ましい。 As a method for obtaining such a composition (polymer particle-containing composition) in which the core-shell polymer particles (B) are dispersed in the state of primary particles, various methods can be used, for example, the composition was obtained in the state of an aqueous latex. A method of removing unnecessary components such as water after contacting the core-shell polymer particles (B) with the component (A), the core-shell polymer particles (B) extracted after once extracting the core-shell polymer particles (B) into an organic solvent. ) And the component (A) are mixed and then the organic solvent is removed. However, it is preferable to use the method described in International Publication No. 2005/0284546. Specific methods for producing the polymer particle-containing composition include, in order, an aqueous latex containing the core-shell polymer particles (B) (specifically, a reaction mixture after producing the core-shell polymer particles (B) by emulsification polymerization). First step of mixing with an organic solvent having a solubility in water at 20 ° C. of 5% by weight or more and 40% by weight or less, and then mixing the obtained mixture with an excess of water to aggregate the core-shell polymer particles (B). After separating and recovering the aggregated core-shell polymer particles (B) from the liquid phase, the obtained aggregates of the core-shell polymer particles (B) are mixed with the organic solvent again, and the organic solvent of the core-shell polymer particles (B) is obtained. It is preferably prepared by including a second step of obtaining a dispersion liquid and a third step of further mixing the organic solvent dispersion liquid with the component (A) and then distilling off the organic solvent from the obtained mixture. ..

　（Ａ）成分は、２３℃で液状であると、前記第３工程が容易となるため好ましい。「２３℃で液状」とは、軟化点が２３℃以下であることを意味し、２３℃で流動性を示すものである。 It is preferable that the component (A) is liquid at 23 ° C. because the third step is facilitated. "Liquid at 23 ° C" means that the softening point is 23 ° C or lower, and shows fluidity at 23 ° C.

　上記の工程を経て得た、（Ａ）成分にコアシェルポリマー粒子（Ｂ）が１次粒子の状態で分散した組成物（ポリマー粒子含有組成物）に対し、（Ｃ）成分、並びに、必要に応じて追加の（Ａ）成分およびその他の成分（（Ｅ）成分および／または（Ｆ）成分など）をプラネタリーミキサー等の撹拌機を用いて混合することにより、コアシェルポリマー粒子（Ｂ）が１次粒子の状態で分散した硬化性樹脂組成物の第一成分を得ることができる。また、（Ｄ）成分、（Ｃ）成分、及び、必要に応じてその他の成分（（Ｂ）成分、（Ｅ）成分および／または（Ｆ）成分など）をプラネタリーミキサー等の撹拌機を用いて混合することにより、硬化性樹脂組成物の第二成分を得ることができる。 In contrast to the composition (polymer particle-containing composition) in which the core-shell polymer particles (B) are dispersed in the component (A) obtained through the above steps in the state of primary particles, the component (C) and, if necessary, are required. By mixing the additional component (A) and other components (such as component (E) and / or component (F)) using a stirrer such as a planetary mixer, the core-shell polymer particles (B) are primary. The first component of the curable resin composition dispersed in the state of particles can be obtained. Further, the component (D), the component (C), and other components (such as the component (B), the component (E) and / or the component (F)), if necessary, are mixed with a stirrer such as a planetary mixer. The second component of the curable resin composition can be obtained by mixing the mixture.

　なお、上記では、コアシェルポリマー粒子（Ｂ）を含む第一成分を調製した後、当該第一成分と、コアシェルポリマー粒子（Ｂ）を含むか、または含まない第二成分とを混合して硬化性樹脂組成物を製造する態様について説明した。しかしながら、コアシェルポリマー粒子（Ｂ）を含まない第一成分を調製した後、当該第一成分と、コアシェルポリマー粒子（Ｂ）を含む第二成分とを混合して硬化性樹脂組成物を製造してもよい。 In the above, after preparing the first component containing the core-shell polymer particles (B), the first component and the second component containing or not containing the core-shell polymer particles (B) are mixed and curable. An embodiment of producing a resin composition has been described. However, after preparing the first component not containing the core-shell polymer particles (B), the first component and the second component containing the core-shell polymer particles (B) are mixed to produce a curable resin composition. May be good.

　上述したように、エポキシ樹脂（Ａ）を含む第一成分と、エポキシ硬化剤（Ｄ）を含む第二成分とは別体として調製されることが好ましい。第一成分と第二成分とは、使用直前（被接着体の接着操作直前、または硬化性樹脂組成物の硬化直前、ともいえる）に、混合されることが好ましい。 As described above, it is preferable that the first component containing the epoxy resin (A) and the second component containing the epoxy curing agent (D) are prepared separately. It is preferable that the first component and the second component are mixed immediately before use (which can be said to be immediately before the bonding operation of the adherend or immediately before the curing of the curable resin composition).

　一方、塩析等の方法により凝固させた後に乾燥させて得た、粉体状のコアシェルポリマー粒子（Ｂ）を、３本ペイントロール、ロールミル及びニーダー等の高い機械的せん断力を有する分散機を用いて、（Ａ）成分中または（Ｄ）成分中に再分散することが可能である。この際、高温で機械的せん断力を与えることで、効率良く、（Ｂ）成分の再分散を可能にする。（Ｂ）成分を（Ａ）成分中または（Ｄ）成分中に再分散させる際の温度は、５０～２００℃が好ましく、７０～１７０℃がより好ましく、８０～１５０℃が更に好ましく、９０～１２０℃が特に好ましい。 On the other hand, a disperser having a high mechanical shearing force, such as a three-paint roll, a roll mill, and a kneader, is used to obtain powdery core-shell polymer particles (B) obtained by solidifying by a method such as salting out and then drying. It can be used to redisperse in component (A) or in component (D). At this time, by applying a mechanical shearing force at a high temperature, the component (B) can be efficiently redispersed. The temperature at which the component (B) is redispersed in the component (A) or the component (D) is preferably 50 to 200 ° C, more preferably 70 to 170 ° C, further preferably 80 to 150 ° C, and 90 to 90 to. 120 ° C. is particularly preferable.

　＜硬化物＞
　硬化性樹脂組成物の第一成分と第二成分とをスタティックミキサーなどを用いて均一に混合し、得られた混合物を、後述する硬化温度で硬化させることで硬化物を得ることができる。上述した方法で得られた第一成分中では、コアシェルポリマー粒子（Ｂ）が均一に分散していると考えられるため、そのような第一成分を用いて得られた硬化物中では、コアシェルポリマー粒子（Ｂ）が均一に分散していると考えられる。 <Curing product>
A cured product can be obtained by uniformly mixing the first component and the second component of the curable resin composition using a static mixer or the like, and curing the obtained mixture at a curing temperature described later. Since it is considered that the core-shell polymer particles (B) are uniformly dispersed in the first component obtained by the above-mentioned method, the core-shell polymer is considered to be uniformly dispersed in the cured product obtained by using such a first component. It is considered that the particles (B) are uniformly dispersed.

　硬化性樹脂組成物が硬化してなる硬化物もまた、本発明の一実施形態（例えば第１実施形態～第３実施形態）である。本発明の一実施形態（例えば第１実施形態～第３実施形態）に係る硬化物は、接着強度に優れるという利点を有する。本発明の一実施形態（例えば第１実施形態～第３実施形態）に係る硬化物は、耐衝撃剥離接着性に優れるという利点も有する。 A cured product obtained by curing the curable resin composition is also an embodiment of the present invention (for example, the first to third embodiments). The cured product according to one embodiment of the present invention (for example, the first to third embodiments) has an advantage of being excellent in adhesive strength. The cured product according to one embodiment of the present invention (for example, the first to third embodiments) also has an advantage of being excellent in impact resistance peeling adhesiveness.

　＜塗布方法＞
　硬化性樹脂組成物は、任意の方法によって基材に塗布可能である。好適な実施形態によると、室温程度の低温で塗布可能であり、必要に応じて加温して塗布することも可能である。 <Applying method>
The curable resin composition can be applied to the substrate by any method. According to a preferred embodiment, it can be applied at a low temperature of about room temperature, and it can also be heated and applied if necessary.

　硬化性樹脂組成物の第一成分と第二成分とは、定量吐出装置から吐出された後、装置の先端に接続されたスタティックミキサーで均一混合されながら施工することが可能である。また、スタティックミキサーが先端に接続されたダブルカートリッジ型コーキングガンの各カートリッジに、硬化性樹脂組成物の第一成分と第二成分とを充填し、手動で押し出して塗布することも可能である。塗布ロボットを使用してビード状またはモノフィラメント状またはスワール（ｓｗｉｒｌ）状に基材上へ押出すこともできる。なお、硬化性樹脂組成物の塗布温度での粘度は、特に限定は無く、押出しビード法では、１５０～６００Ｐａ・ｓ程度が好ましく、渦巻き（ｓｗｉｒｌ）塗布法では、１００Ｐａ・ｓ程度が好ましく、高速度流動装置を用いた高体積塗布法では、２０～４００Ｐａ・ｓ程度が好ましい。 The first component and the second component of the curable resin composition can be applied while being uniformly mixed by a static mixer connected to the tip of the device after being discharged from the fixed quantity discharge device. It is also possible to fill each cartridge of the double cartridge type caulking gun to which the static mixer is connected to the tip with the first component and the second component of the curable resin composition, and manually extrude and apply the curable resin composition. It can also be extruded onto the substrate in the form of beads, monofilaments or swirls using a coating robot. The viscosity of the curable resin composition at the coating temperature is not particularly limited, and is preferably about 150 to 600 Pa · s in the extruded bead method and preferably about 100 Pa · s in the swirl coating method. In the high volume coating method using a speed flow device, about 20 to 400 Pa · s is preferable.

　＜接着剤＞
　硬化性樹脂組成物は、得られる硬化物の接着強度と耐衝撃性が優れる為、接着剤の一材料として用いることが好ましい。硬化性樹脂組成物を含む接着剤もまた、本発明の一実施形態（例えば第１実施形態～第３実施形態）である。本発明の一実施形態（例えば第１実施形態～第３実施形態）に係る接着剤は、速硬化性に優れ、かつ、得られる硬化物（接着層）が接着強度および耐衝撃性に優れるという利点を有する。 <Adhesive>
The curable resin composition is preferably used as a material for an adhesive because the obtained cured product has excellent adhesive strength and impact resistance. An adhesive containing a curable resin composition is also an embodiment of the present invention (for example, first to third embodiments). The adhesive according to one embodiment of the present invention (for example, the first to third embodiments) is said to have excellent quick-curing properties, and the obtained cured product (adhesive layer) has excellent adhesive strength and impact resistance. Has advantages.

　硬化性樹脂組成物を接着剤として使用して、様々な基材同士を接着させる場合、例えば、アルミニウム板や鋼板などの金属、木材、プラスチック、ガラス等の基材を接合することができる。基材としては、冷間圧延鋼や溶融亜鉛メッキ鋼などの鋼材、アルミニウムや被覆アルミニウムなどのアルミニウム材、汎用プラスチック、エンジニアリングプラスチック、ＣＦＲＰやＧＦＲＰ等の複合材料、等の各種のプラスチック系基板が挙げられる。 When various base materials are bonded to each other by using the curable resin composition as an adhesive, for example, a metal such as an aluminum plate or a steel plate, a base material such as wood, plastic, or glass can be bonded. Examples of the base material include various plastic substrates such as steel materials such as cold rolled steel and hot-dip zinc-plated steel, aluminum materials such as aluminum and coated aluminum, general-purpose plastics, engineering plastics, and composite materials such as CFRP and GFRP. Be done.

　また、硬化性樹脂組成物の硬化物は、熱伝導性と難燃性に優れる為、ＥＶバッテリーセルをモジュールケースに固定するための接着剤として使用することが好ましい。換言すれば、本発明の一実施形態（例えば第１実施形態～第３実施形態）に係る接着剤は、二次電池用接着剤であることが好ましい。硬化性樹脂組成物を含有する接着剤を用いたバッテリーモジュールの製造方法、並びに、該モジュールへの当該接着剤の塗布部位及び塗布方法については、国際公開２０１６／１３７３０３号に記載の方法を挙げることができる。 Further, since the cured product of the curable resin composition is excellent in thermal conductivity and flame retardancy, it is preferable to use it as an adhesive for fixing the EV battery cell to the module case. In other words, the adhesive according to one embodiment of the present invention (for example, the first to third embodiments) is preferably an adhesive for a secondary battery. The method described in International Publication No. 2016/137303 will be given as a method for manufacturing a battery module using an adhesive containing a curable resin composition, and a site and method for applying the adhesive to the module. Can be done.

　硬化性樹脂組成物は、接着性に優れる。それ故、硬化性樹脂組成物は、２枚の基材の接着（接合）のための接着剤として使用することが好ましい。そのようにして得られる積層体は、２枚の基材と、該２枚の基材の間に、硬化性樹脂組成物を含む接着剤が硬化してなる接着層と、を含む。当該接着層もまた、本発明の一実施形態（例えば第１実施形態～第３実施形態）である。本発明の一実施形態（例えば第１実施形態～第３実施形態）に係る積層体は、例えば以下の方法により得ることができる：（１）硬化性樹脂組成物を含む接着剤を、一方または両方の基材へ塗布する；（２）接合しようとする２枚の基材間に当該接着剤が配置されるよう基材同士を接触させる；（３）その状態で接着剤を硬化させて２枚の基材を接合する。このようにして得られる本発明の一実施形態（例えば第１実施形態～第３実施形態）に係る積層体は、高い接着強度を示すため好ましい。 The curable resin composition has excellent adhesiveness. Therefore, it is preferable to use the curable resin composition as an adhesive for adhering (bonding) two substrates. The laminate thus obtained includes two substrates and an adhesive layer in which an adhesive containing a curable resin composition is cured between the two substrates. The adhesive layer is also an embodiment of the present invention (for example, first to third embodiments). The laminate according to one embodiment of the present invention (for example, the first embodiment to the third embodiment) can be obtained by, for example, the following method: (1) An adhesive containing a curable resin composition, one of them or Apply to both substrates; (2) contact the substrates so that the adhesive is placed between the two substrates to be joined; (3) cure the adhesive in that state 2 Join the sheets of substrate. The laminate according to one embodiment of the present invention (for example, the first embodiment to the third embodiment) thus obtained is preferable because it exhibits high adhesive strength.

　硬化性樹脂組成物、及び当該硬化性樹脂組成物を含む接着剤は、靭性に優れるため、線膨張係数の異なる異種基材間の接合に適している。 Since the curable resin composition and the adhesive containing the curable resin composition are excellent in toughness, they are suitable for joining dissimilar substrates having different linear expansion coefficients.

　また、硬化性樹脂組成物、及び当該硬化性樹脂組成物を含む接着剤は、航空宇宙用の構成材、特に、外装金属構成材の接合にも使用できる。 Further, the curable resin composition and the adhesive containing the curable resin composition can also be used for joining components for aerospace, particularly exterior metal components.

　＜硬化温度＞
　硬化性樹脂組成物の硬化温度は、特に限定はないが、常温付近で容易に硬化できる観点から、５℃～６０℃が好ましく、１０℃～５０℃がより好ましく、１５℃～４０℃が更に好ましく、２０℃～３０℃が特に好ましい。 <Curing temperature>
The curing temperature of the curable resin composition is not particularly limited, but is preferably 5 ° C to 60 ° C, more preferably 10 ° C to 50 ° C, and further preferably 15 ° C to 40 ° C from the viewpoint of easy curing near room temperature. It is preferable, and 20 ° C to 30 ° C is particularly preferable.

　＜用途＞
　硬化性樹脂組成物は、車両や航空機向けの構造用接着剤、ＥＶバッテリーセル等の二次電池用接着剤、風力発電用構造接着剤などの接着剤、塗料、複合材料を得るためにガラス繊維および／または炭素繊維と積層するための材料、プリント配線基板用材料、ソルダーレジスト、層間絶縁膜、ビルドアップ材料、ＦＰＣ用接着剤、半導体・ＬＥＤ等電子部品用封止材等の電気絶縁材料、ダイボンド材料、アンダーフィル、半導体（例えばＡＣＦ、ＡＣＰ、ＮＣＦ、ＮＣＰ等）の実装材料、表示機器（例えば液晶パネルおよびＯＬＥＤディスプレイなど）および照明機器（例えばＯＬＥＤ照明など）用の封止材、コンクリート補修用複合材、などの用途に好ましく用いられる。硬化性樹脂組成物は、特に、二次電池用接着剤として有用である。 <Use>
The curable resin composition is a structural adhesive for vehicles and aircraft, an adhesive for secondary batteries such as EV battery cells, an adhesive such as a structural adhesive for wind power generation, a paint, and a glass fiber for obtaining a composite material. And / or materials for laminating with carbon fibers, materials for printed wiring boards, solder resists, interlayer insulating films, build-up materials, adhesives for FPCs, electrical insulating materials such as encapsulants for electronic parts such as semiconductors and LEDs, Diebond materials, underfills, mounting materials for semiconductors (eg ACF, ACP, NCF, NCP, etc.), encapsulants for display equipment (eg liquid crystal panels and OLED displays) and lighting equipment (eg OLED lighting), concrete repair It is preferably used for applications such as composite materials. The curable resin composition is particularly useful as an adhesive for a secondary battery.

　硬化性樹脂組成物を複合材に使用する場合、特に制限なく幅広い成形法に使用することができる。具体的には、ハンドレイアップ法、スプレーアップ法、プルトルージョン法、フィラメントワインディング法、マッチドダイ法、プリプレグ法、遠心成形法、リキッドモールディング法、ホットプレス法、キャスティング法、インジェクションモールディング法、コンティニュアスラミネーション法、レジントランスファーモールディング（ＲＴＭ）法、バキュームバッグ成型法、コールドプレス法等の公知の成型方法で成形可能である。硬化性樹脂組成物はガラス繊維や炭素繊維との複合材料、ＢＭＣ（バルクモールディングコンパウンド）やＳＭＣ（シートモールディングコンパウンド）の原材料として好適である。また、適用部位も特に制限はないが、具体的には、キッチンカウンターや洗面ボウル、浴槽、壁材等の人造大理石用途、レジンコンクリート、タンク、圧力容器、工業用パイプ、工場配管、継手、パイプ、波板、ヘルメット、ポール、風力発電用ブレード、サッカーロッド・ポンプなどの油田のポンプ採油システムの配管、電機部品、自動車部品、鉄道車両部品、船舶部品、航空機部品、産業機械部品、建設資材、家具、楽器等の構造部材、化粧板や装飾シート等のシート材として好適である。 When the curable resin composition is used as a composite material, it can be used in a wide range of molding methods without any particular limitation. Specifically, the hand lay-up method, spray-up method, pull-fusion method, filament winding method, matched die method, prepreg method, centrifugal molding method, liquid molding method, hot press method, casting method, injection molding method, continuous method. It can be molded by a known molding method such as a lamination method, a resin transfer molding (RTM) method, a vacuum bag molding method, or a cold press method. The curable resin composition is suitable as a composite material with glass fiber or carbon fiber, and as a raw material for BMC (bulk molding compound) or SMC (sheet molding compound). The application site is not particularly limited, but specifically, artificial marble applications such as kitchen counters, wash bowls, bathtubs, and wall materials, resin concrete, tanks, pressure vessels, industrial pipes, factory pipes, joints, and pipes. , Corrugated sheet, helmet, pole, blade for wind power generation, piping of pump oil sampling system of oil field such as soccer rod pump, electrical parts, automobile parts, railroad vehicle parts, ship parts, aircraft parts, industrial machinery parts, construction materials, It is suitable as a structural member for furniture, musical instruments, etc., and as a sheet material for decorative boards, decorative sheets, etc.

　〔ＩＩ．第２実施形態〕
　第２実施形態は、エポキシ樹脂を含む二成分型の硬化性樹脂組成物、及び、それを含む接着剤に関する。 [II. 2nd Embodiment]
The second embodiment relates to a two-component curable resin composition containing an epoxy resin and an adhesive containing the same.

　加熱硬化型の一成分型硬化性樹脂組成物は塗布時の温度を高くすることで組成物粘度を低くすることが可能であるが、低温で硬化し得る二成分型硬化性樹脂組成物は塗布時の温度も低くすることが望ましく、低粘度で作業性の良好な二成分型硬化性樹脂組成物が望まれている。 The thermosetting one-component curable resin composition can reduce the viscosity of the composition by raising the temperature at the time of application, but the two-component curable resin composition that can be cured at a low temperature is applied. It is desirable to lower the temperature at the time, and a two-component curable resin composition having a low viscosity and good workability is desired.

　電気デバイスからの放熱性を高めるために、デバイスに使用する硬化性樹脂組成物に水酸化アルミやアルミナなどの熱伝導性フィラーを添加して熱伝導性を高める検討がされている。しかしながら、熱伝導性フィラーの添加に伴って、硬化性樹脂組成物の粘度が高くなり作業性が低下する場合がある。更に、電気デバイスに幅広く使用されているエポキシ樹脂の硬化物は破壊靭性が小さく、非常に脆性的な性質を示すという問題がある。 In order to improve the heat dissipation from the electric device, it is being studied to add a heat conductive filler such as aluminum hydroxide or alumina to the curable resin composition used for the device to improve the heat conductivity. However, with the addition of the thermally conductive filler, the viscosity of the curable resin composition may increase and the workability may decrease. Further, a cured product of an epoxy resin widely used in electric devices has a problem that it has a low fracture toughness and exhibits a very brittle property.

　特許文献１に記載の樹脂組成物は、耐衝撃性が十分ではなく改善の余地があった。また、特許文献２～３には、エポキシ樹脂と多量の水酸化アルミニウムを組合わせたエポキシ系硬化性樹脂組成物における、作業性の改善技術について記載されていない。 The resin composition described in Patent Document 1 did not have sufficient impact resistance and had room for improvement. Further, Patent Documents 2 to 3 do not describe a technique for improving workability in an epoxy-based curable resin composition in which an epoxy resin and a large amount of aluminum hydroxide are combined.

　第２実施形態に係る発明は、上記現状に鑑み、エポキシ樹脂と水酸化アルミニウムを配合しながらも粘度が低く作業性が良好で、かつ、優れた熱伝導性、難燃性、及び接着強度を示す硬化物を与え、室温または室温に近い低温でも硬化し得る二成分型の硬化性樹脂組成物を提供することを目的とする。 In view of the above situation, the invention according to the second embodiment has low viscosity and good workability while blending an epoxy resin and aluminum hydroxide, and has excellent thermal conductivity, flame retardancy, and adhesive strength. It is an object of the present invention to provide a curable resin composition of a two-component type which gives a cured product as shown and can be cured at room temperature or a low temperature close to room temperature.

　本発明者らは上記課題を解決するために鋭意研究を重ねた結果、エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分、を含む二成分型の硬化性樹脂組成物に、特定の平均粒子径と特定の組成を有するコアシェル構造を有するポリマー粒子（Ｂ）と、水酸化アルミニウム（Ｃ）を特定の重量比で配合することで、硬化前の組成物が低粘度で、優れた熱伝導性、難燃性、及び接着強度を示す硬化物が得られることを見出した。 As a result of diligent research to solve the above problems, the present inventors have made a two-component type containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D). By blending the polymer particles (B) having a core-shell structure having a specific average particle size and a specific composition and aluminum hydroxide (C) in a specific weight ratio into the curable resin composition of the above, before curing. It has been found that the composition has a low viscosity, and a cured product showing excellent thermal conductivity, flame retardancy, and adhesive strength can be obtained.

　すなわち、第２実施形態に係る発明は、エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含む二成分型の硬化性樹脂組成物であって、前記硬化性樹脂組成物は、更に、コアシェル構造を有するポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）を含有し、前記硬化性樹脂組成物の総重量に対する前記水酸化アルミニウム（Ｃ）の総重量が、５５重量％以上８５重量％以下であり、前記コアシェル構造を有するポリマー粒子（Ｂ）の平均粒子径が、０．１５μｍ以上０．３０μｍ以下であり、前記コアシェル構造を有するポリマー粒子（Ｂ）のコア層／シェル層の重量比が、６５／３５～９２／８であり、前記コアシェル構造を有するポリマー粒子（Ｂ）が、シェル層が炭素数１～４のアルキル（メタ）アクリレートを５５ｗｔ％以上含有するモノマー成分の共重合体であり、前記シェル層を構成するモノマー成分として、炭素数１のアルキル（メタ）アクリレートを１０～１００ｗｔ％、炭素数４のアルキル（メタ）アクリレートを０～８０ｗｔ％含有する、硬化性樹脂組成物に関する。 That is, the invention according to the second embodiment is a two-component curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D). The curable resin composition further contains the polymer particles (B) having a core-shell structure and the aluminum hydroxide (C), and the aluminum hydroxide (C) with respect to the total weight of the curable resin composition. The total weight of the polymer particles (B) having the core-shell structure is 55% by weight or more and 85% by weight or less, and the average particle size of the polymer particles (B) having the core-shell structure is 0.15 μm or more and 0.30 μm or less. The weight ratio of the core layer / shell layer of (B) is 65/35 to 92/8, and the polymer particles (B) having the core-shell structure have an alkyl (meth) acrylate having a shell layer having 1 to 4 carbon atoms. It is a copolymer of a monomer component containing 55 wt% or more of, and as a monomer component constituting the shell layer, an alkyl (meth) acrylate having 1 carbon atom is used in an amount of 10 to 100 wt% and an alkyl (meth) acrylate having 4 carbon atoms is used. The present invention relates to a curable resin composition containing 0 to 80 wt%.

　上記のように構成された本発明の硬化性樹脂組成物によれば、エポキシ樹脂と高添加量の水酸化アルミニウムにより得られる硬化物は優れた熱伝導性、難燃性、及び接着強度を発現できる。更に、特定の平均粒子径と特定の組成を有するコアシェル構造を有するポリマー粒子を用いることで、硬化性樹脂組成物の粘度を低くすることができる。すなわち、第２実施形態によると、優れた熱伝導性、難燃性、及び接着強度を示す硬化物を与えることができ、粘度が低く作業性が良好であり、かつ室温または室温に近い低温でも硬化し得る二成分型の硬化性樹脂組成物を提供することができる。 According to the curable resin composition of the present invention configured as described above, the cured product obtained by the epoxy resin and a high amount of aluminum hydroxide exhibits excellent thermal conductivity, flame retardancy, and adhesive strength. can. Further, by using polymer particles having a core-shell structure having a specific average particle size and a specific composition, the viscosity of the curable resin composition can be lowered. That is, according to the second embodiment, a cured product exhibiting excellent thermal conductivity, flame retardancy, and adhesive strength can be provided, the viscosity is low, the workability is good, and even at room temperature or a low temperature close to room temperature. It is possible to provide a curable resin composition of a two-component type that can be cured.

　別の表現をすれば、第２実施形態は、少なくとも、エポキシ樹脂（Ａ）、コアシェル構造を有するポリマー粒子（Ｂ）、水酸化アルミニウム（Ｃ）、およびエポキシ硬化剤（Ｄ）を含有する硬化性樹脂組成物である。第２実施形態に係る硬化性樹脂組成物は、エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分とを必須成分として含み、更には、必要に応じてカラートナーや硬化性調整剤など、その他の成分を、使用直前に混合して用いる二成分型の硬化性樹脂組成物である。また第２実施形態に係る硬化性樹脂組成物は、更に、コアシェル構造を有するポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）を含有する。コアシェル構造を有するポリマー粒子（Ｂ）および水酸化アルミニウム（Ｃ）は、各々、第一成分および／または第二成分に含有されることが好ましい。第２実施形態に係る硬化性樹脂組成物は、第一成分および第二成分以外に、必要に応じて別の成分を含んでいても良い。 In other words, the second embodiment is curable containing at least an epoxy resin (A), polymer particles (B) having a core-shell structure, aluminum hydroxide (C), and an epoxy curing agent (D). It is a resin composition. The curable resin composition according to the second embodiment contains a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D) as essential components, and further, if necessary. It is a two-component curable resin composition in which other components such as a color toner and a curability adjusting agent are mixed and used immediately before use. Further, the curable resin composition according to the second embodiment further contains polymer particles (B) having a core-shell structure and aluminum hydroxide (C). The polymer particles (B) and aluminum hydroxide (C) having a core-shell structure are preferably contained in the first component and / or the second component, respectively. The curable resin composition according to the second embodiment may contain another component, if necessary, in addition to the first component and the second component.

　第２実施形態に係る硬化性樹脂組成物によれば、エポキシ樹脂と高添加量の水酸化アルミニウムにより得られる硬化物は優れた熱伝導性、難燃性、及び接着強度を発現できる。更に、第２実施形態に係る硬化性樹脂組成物では、特定の平均粒子径と特定の組成を有するコアシェル構造を有するポリマー粒子を用いることで、硬化性樹脂組成物の粘度を低くすることができる。 According to the curable resin composition according to the second embodiment, the cured product obtained by the epoxy resin and a high amount of aluminum hydroxide can exhibit excellent thermal conductivity, flame retardancy, and adhesive strength. Further, in the curable resin composition according to the second embodiment, the viscosity of the curable resin composition can be lowered by using polymer particles having a core-shell structure having a specific average particle diameter and a specific composition. ..

　以下、第２実施形態に関する各態様について説明するが、以下に詳説した事項以外は、適宜、第１実施形態の記載を援用する。 Hereinafter, each aspect of the second embodiment will be described, but the description of the first embodiment will be appropriately incorporated except for the matters described in detail below.

　＜エポキシ樹脂（Ａ）＞
　第２実施形態におけるエポキシ樹脂（Ａ）の各態様（種類、含有量およびそれらの好ましい態様など）については、第１実施形態における＜エポキシ樹脂（Ａ）＞の項で説明したものと同じであるため、当該記載を援用し、ここでは説明を省略する。 <Epoxy resin (A)>
Each aspect (type, content, preferred embodiment thereof, etc.) of the epoxy resin (A) in the second embodiment is the same as that described in the section <Epoxy resin (A)> in the first embodiment. Therefore, the description is used and the description is omitted here.

　＜コアシェル構造を有するポリマー粒子（Ｂ）＞
　第２実施形態の硬化性樹脂組成物は、第一成分および／または前記第二成分中に、（Ｂ）成分として、コアシェル構造を有するポリマー粒子を含有する。 <Polymer particles (B) having a core-shell structure>
The curable resin composition of the second embodiment contains polymer particles having a core-shell structure as the component (B) in the first component and / or the second component.

　第２実施形態において、コアシェルポリマー粒子（Ｂ）の平均粒子径は、工業的生産性と硬化性樹脂組成物の作業性の観点から０．１５μｍ以上０．３０μｍ以下であることが必須であり、０．１６μｍ以上０．２８μｍ以下であることが好ましく、０．１７μｍ以上０．２７μｍ以下であることがより好ましく、０．１８μｍ以上０．２５μｍ以下であることが更に好ましい。第２実施形態において、コアシェルポリマー粒子（Ｂ）の平均粒子径を、（ａ）０．１５μｍ以上とすることで、硬化性樹脂組成物の粘度はより低くなるため、作業性がより良好となり、（ｂ）０．３０μｍ以下とすることで、（Ｂ）成分の重合時間がより短くなり、工業的生産性がより高くなる。 In the second embodiment, it is essential that the average particle size of the core-shell polymer particles (B) is 0.15 μm or more and 0.30 μm or less from the viewpoint of industrial productivity and workability of the curable resin composition. It is preferably 0.16 μm or more and 0.28 μm or less, more preferably 0.17 μm or more and 0.27 μm or less, and further preferably 0.18 μm or more and 0.25 μm or less. In the second embodiment, when the average particle size of the core-shell polymer particles (B) is (a) 0.15 μm or more, the viscosity of the curable resin composition becomes lower, so that the workability becomes better. (B) When the thickness is 0.30 μm or less, the polymerization time of the component (B) becomes shorter and the industrial productivity becomes higher.

　第２実施形態のコアシェルポリマー粒子（Ｂ）において、シェル層の重量に対するコア層の重量の比（コア層の重量／シェル層の重量）は、硬化性樹脂組成物の作業性がより良好となり、かつ硬化物の耐衝撃接着性がより良好となることから、６５／３５～９２／８であることが必須であり、６８／３２～９１／９であることが好ましく、７０／３０～９０／１０であることがより好ましい。 In the core-shell polymer particles (B) of the second embodiment, the ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer / weight of the shell layer) makes the workability of the curable resin composition better. Moreover, since the impact resistance of the cured product becomes better, it is essential that the content is 65/35 to 92/8, preferably 68/32 to 91/9, and 70/30 to 90 /. It is more preferably 10.

　第２実施形態のコアシェルポリマー粒子（Ｂ）は、硬化性樹脂組成物の作業性が良好となることから、シェル層が、モノマー成分（シェル層形成用モノマー）１００重量％中、炭素数１～４のアルキル（メタ）アクリレートを５５重量％以上含有するモノマー成分（シェル層形成用モノマー）を重合してなる共重合体であることが必須であり、６５重量％以上含有するモノマー成分を重合してなる共重合体であることが好ましく、７５重量％以上含有するモノマー成分を重合してなる共重合体であることがより好ましく、７８重量％以上含有するモノマー成分を重合してなる共重合体であることが更に好ましく、８３重量％以上含有するモノマー成分を重合してなる共重合体であることが特に好ましい。 Since the core-shell polymer particles (B) of the second embodiment have good workability of the curable resin composition, the shell layer has 1 to 1 carbon atoms in 100% by weight of the monomer component (monomer for forming the shell layer). It is essential that the copolymer is obtained by polymerizing a monomer component (monomer for forming a shell layer) containing 55% by weight or more of the alkyl (meth) acrylate of 4, and the monomer component containing 65% by weight or more is polymerized. It is preferably a copolymer obtained by polymerizing a monomer component containing 75% by weight or more, and more preferably a copolymer obtained by polymerizing a monomer component containing 78% by weight or more. Is more preferable, and a copolymer formed by polymerizing a monomer component containing 83% by weight or more is particularly preferable.

　換言すれば、第２実施形態のシェル層は、シェル層１００重量％中、炭素数１～４のアルキル（メタ）アクリレートに由来する構成単位を５５重量％以上含有することが必須であり、６５重量％以上含有することが好ましく、７５重量％以上含有することがより好ましく、７８重量％以上含有することが更に好ましく、８３重量％以上含有することが特に好ましい。 In other words, it is essential that the shell layer of the second embodiment contains 55% by weight or more of a structural unit derived from an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of the shell layer. It is preferably contained in an amount of 7% by weight or more, more preferably 75% by weight or more, further preferably 78% by weight or more, and particularly preferably 83% by weight or more.

　第２実施形態では、コアシェルポリマー粒子（Ｂ）のシェル層を構成するモノマー成分（シェル層形成用モノマー）は、当該モノマー成分１００重量％中、炭素数１のアルキル（メタ）アクリレートを１０重量％～１００重量％含有することが必須であり、１１重量％～９５重量％含有することが好ましく、１２重量％～９２重量％含有することがより好ましく、１３重量％～５５重量％含有することが更に好ましく、１４重量％～５０重量％含有することが特に好ましい。また、第２実施形態では、コアシェルポリマー粒子（Ｂ）のシェル層を構成するモノマー成分（シェル層形成用モノマー）は、当該モノマー成分１００重量％中、炭素数４のアルキル（メタ）アクリレートを０重量％～８０重量％含有することが必須であり、１重量％～８９重量％含有することが好ましく、１重量％～８８重量％含有することがより好ましく、１重量％～８７重量％含有することが好ましく、１重量％～８６重量％含有することが好ましく、１重量％～７８重量％含有することがより好ましく、２重量％～７６重量％含有することがより好ましく、５重量％～７６重量％含有することがより好ましく、８重量％～７６重量％含有することがより好ましく、２０重量％～７４重量％含有することがより好ましく、３５重量％～７２重量％含有することがより好ましく、３５重量％～６０重量％含有することがさらに好ましく、３５重量％～５０重量％含有することが特に好ましい。コアシェルポリマー粒子（Ｂ）のシェル層を構成するシェル層形成用モノマーが、炭素数１のアルキル（メタ）アクリレートおよび／または炭素数４のアルキル（メタ）アクリレートを上述した範囲で含む場合、コアシェルポリマー粒子（Ｂ）と（Ｃ）成分との相互作用を適切にコントロールできるため、硬化性樹脂組成物の粘度が低く抑えられ、作業性が良好となるという利点を有する。 In the second embodiment, the monomer component (monomer for forming the shell layer) constituting the shell layer of the core-shell polymer particles (B) contains 10% by weight of an alkyl (meth) acrylate having 1 carbon atom in 100% by weight of the monomer component. It is essential to contain ~ 100% by weight, preferably 11% by weight to 95% by weight, more preferably 12% by weight to 92% by weight, and preferably 13% by weight to 55% by weight. It is more preferably contained in an amount of 14% by weight to 50% by weight, and particularly preferably contained in an amount of 14% by weight to 50% by weight. Further, in the second embodiment, the monomer component (monomer for forming the shell layer) constituting the shell layer of the core-shell polymer particles (B) contains no alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the monomer component. It is essential to contain 1% by weight to 80% by weight, preferably 1% by weight to 89% by weight, more preferably 1% by weight to 88% by weight, and 1% to 87% by weight. It is preferably 1% by weight to 86% by weight, more preferably 1% by weight to 78% by weight, more preferably 2% by weight to 76% by weight, and 5% by weight to 76% by weight. It is more preferably contained in an amount of% by weight, more preferably 8% by weight to 76% by weight, more preferably 20% by weight to 74% by weight, and even more preferably 35% by weight to 72% by weight. , 35% by weight to 60% by weight is more preferable, and 35% by weight to 50% by weight is particularly preferable. When the shell layer forming monomer constituting the shell layer of the core-shell polymer particles (B) contains an alkyl (meth) acrylate having 1 carbon atom and / or an alkyl (meth) acrylate having 4 carbon atoms in the above range, the core-shell polymer Since the interaction between the particles (B) and the component (C) can be appropriately controlled, the curable resin composition has an advantage that the viscosity is suppressed to a low level and the workability is improved.

　第２実施形態において、硬化性樹脂組成物中の水酸化アルミニウム（Ｃ）の含有量は、後述のように、硬化性樹脂組成物の総重量１００重量％中５５重量％以上８５重量％以下と非常に高く、それ故、（Ｂ）成分は（Ｃ）成分と接触する確率が高い。そのため、第２実施形態において、（Ｂ）成分の前記シェルポリマーは、極性の高い（Ｃ）成分の表面との相互作用が小さくなるようなモノマー組成とすることで、硬化性樹脂組成物の粘度を低く抑え作業性を良好にすることが肝要である。第２実施形態において、コアシェルポリマー粒子（Ｂ）のシェル層は、上述したように特定の構成を有する。エポキシ樹脂と混合するコアシェルポリマー粒子（Ｂ）のシェル層は、エポキシ樹脂との相溶性を高める組成とすることが一般的であるが、第２実施形態における上記の様な（Ｂ）成分の特定の平均粒子径および特定の組成は、水酸化アルミニウム（Ｃ）を多量に含有する第２実施形態の配合組成との組み合わせで最適化された特異な設計であると考えられる。第２実施形態における上述した（Ｂ）成分の特定の平均粒子径および特定の組成は、本発明者が第２実施形態に関する鋭意検討中に見出した、独自の構成である。 In the second embodiment, the content of aluminum hydroxide (C) in the curable resin composition is 55% by weight or more and 85% by weight or less in 100% by weight of the total weight of the curable resin composition, as described later. It is very high and therefore the component (B) has a high probability of coming into contact with the component (C). Therefore, in the second embodiment, the shell polymer of the component (B) has a monomer composition such that the interaction with the surface of the highly polar component (C) is small, so that the viscosity of the curable resin composition is small. It is important to keep it low and improve workability. In the second embodiment, the shell layer of the core-shell polymer particles (B) has a specific configuration as described above. The shell layer of the core-shell polymer particles (B) to be mixed with the epoxy resin generally has a composition that enhances compatibility with the epoxy resin, but the above-mentioned component (B) is specified in the second embodiment. The average particle size and the specific composition of the above are considered to be a unique design optimized in combination with the compounding composition of the second embodiment containing a large amount of aluminum hydroxide (C). The specific average particle size and the specific composition of the component (B) described above in the second embodiment are unique configurations found by the present inventor during the diligent study on the second embodiment.

　硬化性樹脂組成物の作業性をより良好にする観点から、第２実施形態のシェル層形成用モノマーは、炭素数１のアルキル（メタ）アクリレートおよび炭素数４のアルキル（メタ）アクリレートの両方を有することが好ましく、炭素数１のアルキル（メタ）アクリレートを１３重量％～５５重量％、および炭素数４のアルキル（メタ）アクリレートを２０重量％～７４重量％含有することがより好ましい。換言すれば、第２実施形態のシェル層は、炭素数１のアルキル（メタ）アクリレートに由来する構成単位及び炭素数４のアルキル（メタ）アクリレートに由来する構成単位の両方を有することが好ましく、炭素数１のアルキル（メタ）アクリレートに由来する構成単位を１３重量％～５５重量％、および炭素数４のアルキル（メタ）アクリレートに由来する構成単位を２０重量％～７４重量％含有することが好ましい。 From the viewpoint of improving the workability of the curable resin composition, the shell layer forming monomer of the second embodiment contains both an alkyl (meth) acrylate having 1 carbon atom and an alkyl (meth) acrylate having 4 carbon atoms. It is preferable to have, and it is more preferable to contain 13% by weight to 55% by weight of the alkyl (meth) acrylate having 1 carbon atom and 20% by weight to 74% by weight of the alkyl (meth) acrylate having 4 carbon atoms. In other words, the shell layer of the second embodiment preferably has both a structural unit derived from an alkyl (meth) acrylate having 1 carbon atom and a structural unit derived from an alkyl (meth) acrylate having 4 carbon atoms. It may contain 13% by weight to 55% by weight of a structural unit derived from an alkyl (meth) acrylate having 1 carbon atom and 20% by weight to 74% by weight of a structural unit derived from an alkyl (meth) acrylate having 4 carbon atoms. preferable.

　なお、第２実施形態のモノマー成分は、モノマー成分１００重量％中、炭素数１のアルキル（メタ）アクリレートおよび炭素数４のアルキル（メタ）アクリレートの合計が１００重量％となる必要はない。換言すれば、第２実施形態のモノマー成分は、モノマー成分１００重量％中、（ａ）炭素数１のアルキル（メタ）アクリレート、（ｂ）炭素数４のアルキル（メタ）アクリレート、並びに（ｃ）炭素数１のアルキル（メタ）アクリレートおよび炭素数４のアルキル（メタ）アクリレート以外のモノマーの合計が１００重量％となればよい。すなわち、第２実施形態のモノマー成分は、炭素数１のアルキル（メタ）アクリレートおよび炭素数４のアルキル（メタ）アクリレート以外のモノマーを含んでいてもよい。 The monomer component of the second embodiment does not need to have a total of 100% by weight of the alkyl (meth) acrylate having 1 carbon atom and the alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the monomer component. In other words, the monomer component of the second embodiment is (a) an alkyl (meth) acrylate having 1 carbon atom, (b) an alkyl (meth) acrylate having 4 carbon atoms, and (c) in 100% by weight of the monomer component. The total of the monomers other than the alkyl (meth) acrylate having 1 carbon atom and the alkyl (meth) acrylate having 4 carbon atoms may be 100% by weight. That is, the monomer component of the second embodiment may contain a monomer other than the alkyl (meth) acrylate having 1 carbon atom and the alkyl (meth) acrylate having 4 carbon atoms.

　コアシェルポリマー粒子（Ｂ）の硬化性樹脂組成物中での相溶性及び分散性が良好となることから、第２実施形態では、シェル層形成モノマーとして、例えば、芳香族ビニルモノマー、および／またはビニルシアンモノマーをさらに有していてもよい。（Ｂ）成分と（Ｃ）成分との相互作用を小さくすることにより、硬化性樹脂組成物の作業性を良好にできるから、第２実施形態において、シェル層形成用モノマー１００重量％中の芳香族ビニルモノマーの含有量は３０重量％以下が好ましく、２０重量％以下がより好ましく、１０重量％以下がより好ましく、８重量％以下がより好ましく、６重量％以下がより好ましく、５重量％以下が更に好ましく、０重量％以下である（すなわち芳香族ビニルモノマーを含有しない）ことが特に好ましい。同様に、硬化性樹脂組成物の作業性を良好にする観点から、第２実施形態において、シェル層形成用モノマー１００重量％中のビニルシアンモノマーの含有量は１０重量％以下が好ましく、８重量％以下がより好ましく、５重量％以下がより好ましく、４重量％以下がより好ましく、３重量％以下がより好ましく、２重量％以下がさらに好ましく、１重量％以下がよりさらに好ましく、０重量％以下である（すなわちビニルシアンモノマーを含有しない）ことが特に好ましい。 Since the compatibility and dispersibility of the core-shell polymer particles (B) in the curable resin composition are good, in the second embodiment, the shell layer-forming monomer is, for example, an aromatic vinyl monomer and / or vinyl. It may further have a cyan monomer. By reducing the interaction between the component (B) and the component (C), the workability of the curable resin composition can be improved. Therefore, in the second embodiment, the fragrance in 100% by weight of the monomer for forming the shell layer The content of the group vinyl monomer is preferably 30% by weight or less, more preferably 20% by weight or less, more preferably 10% by weight or less, more preferably 8% by weight or less, still more preferably 6% by weight or less, and 5% by weight or less. Is more preferable, and it is particularly preferable that the content is 0% by weight or less (that is, it does not contain an aromatic vinyl monomer). Similarly, from the viewpoint of improving the workability of the curable resin composition, in the second embodiment, the content of the vinyl cyan monomer in 100% by weight of the monomer for forming the shell layer is preferably 10% by weight or less, preferably 8% by weight. % Or less is more preferable, 5% by weight or less is more preferable, 4% by weight or less is more preferable, 3% by weight or less is more preferable, 2% by weight or less is further preferable, 1% by weight or less is further preferable, and 0% by weight is used. It is particularly preferable that the following (that is, it does not contain a vinyl cyan monomer).

　第２実施形態では、例えば、（ａ）炭素数１のアルキル（メタ）アクリレートモノマー（特にメチルメタクリレート）１０～１００重量％（好ましくは１１～９５重量％、特に好ましくは１４～５０重量％）、（ｂ）炭素数４のアルキル（メタ）アクリレートモノマー（特にブチルアクリレート）０～８０重量％（好ましくは１～７８重量％、特に好ましくは３５～７２重量％）、（ｃ）芳香族ビニルモノマー（特にスチレン）３０重量％以下（好ましくは２０重量％以下、より好ましくは１０重量％以下、より好ましくは８重量％以下、より好ましくは６重量％以下、さらに好ましくは５重量％以下、特に好ましくは０重量％）、（ｄ）ビニルシアンモノマー（特にアクリロニトリル）１０重量％以下（好ましくは８重量％以下、より好ましくは５重量％以下、より好ましくは４重量％以下、より好ましくは３重量％以下、より好ましくは２重量％以下、さらに好ましくは１重量％以下、特に好ましくは０重量％）、および（ｅ）エポキシ基を有するモノマー（特にグリシジルメタクリレート）０～４５重量％（好ましくは０～２５重量％、より好ましくは３～２０重量％）を組み合わせたシェル層形成用モノマー（合計１００重量％）を重合してなる共重合体をシェル層とすることが好ましい。これにより、所望の靱性を改良させる効果と作業性をバランス良く実現することができる。 In the second embodiment, for example, (a) an alkyl (meth) acrylate monomer having 1 carbon atom (particularly methyl methacrylate) in an amount of 10 to 100% by weight (preferably 11 to 95% by weight, particularly preferably 14 to 50% by weight). (B) 0 to 80% by weight (preferably 1 to 78% by weight, particularly preferably 35 to 72% by weight) of an alkyl (meth) acrylate monomer (particularly butyl acrylate) having 4 carbon atoms, (c) aromatic vinyl monomer (c) Especially styrene) 30% by weight or less (preferably 20% by weight or less, more preferably 10% by weight or less, more preferably 8% by weight or less, more preferably 6% by weight or less, still more preferably 5% by weight or less, particularly preferably. 0% by weight), (d) Vinyl cyanomer monomer (particularly acrylonitrile) 10% by weight or less (preferably 8% by weight or less, more preferably 5% by weight or less, more preferably 4% by weight or less, more preferably 3% by weight or less. , More preferably 2% by weight or less, still more preferably 1% by weight or less, particularly preferably 0% by weight), and (e) a monomer having an epoxy group (particularly glycidyl methacrylate) 0 to 45% by weight (preferably 0 to 25%). It is preferable that the shell layer is a copolymer formed by polymerizing a shell layer forming monomer (100% by weight in total) in which (% by weight, more preferably 3 to 20% by weight) is combined. Thereby, the effect of improving the desired toughness and the workability can be realized in a well-balanced manner.

　＜水酸化アルミニウム（Ｃ）＞
　第２実施形態の硬化性樹脂組成物は、第一成分および／または前記第二成分中に、（Ｃ）成分として、水酸化アルミニウムを含有する。第２実施形態の硬化性樹脂組成物が（Ｃ）成分を含む場合、得られる硬化物は熱伝導性および難燃性（例えば垂直燃焼試験（ＵＬ９４）で評価される難燃性）に優れるという利点を有する。 <Aluminum hydroxide (C)>
The curable resin composition of the second embodiment contains aluminum hydroxide as the component (C) in the first component and / or the second component. When the curable resin composition of the second embodiment contains the component (C), the obtained cured product is said to be excellent in thermal conductivity and flame retardancy (for example, flame retardancy evaluated by a vertical combustion test (UL94)). Has advantages.

　第２実施形態において、硬化性樹脂組成物の総重量に対する水酸化アルミニウム（Ｃ）の総重量は、５５重量％以上８５重量％以下であることが必須である。 In the second embodiment, it is essential that the total weight of aluminum hydroxide (C) with respect to the total weight of the curable resin composition is 55% by weight or more and 85% by weight or less.

　第２実施形態において、（Ｃ）成分の平均粒子径は、特に限定されない。第２実施形態において、（Ｃ）成分の平均粒子径は、得られる硬化物の耐衝撃性と接着強度との両立の観点と、硬化前の硬化性樹脂組成物中での（Ｅ）成分の経時での沈降を抑制する観点から、１１μｍ以上２００μｍ以下であることが好ましく、１２μｍ以上１５０μｍ以下がより好ましく、１３μｍ以上１００μｍ以下がさらに好ましく、１５μｍ以上５０μｍ以下が更により好ましく、１７μｍ以上３０μｍ以下が特に好ましい。 In the second embodiment, the average particle size of the component (C) is not particularly limited. In the second embodiment, the average particle size of the component (C) is determined from the viewpoint of achieving both impact resistance and adhesive strength of the obtained cured product, and the component (E) in the curable resin composition before curing. From the viewpoint of suppressing sedimentation over time, it is preferably 11 μm or more and 200 μm or less, more preferably 12 μm or more and 150 μm or less, further preferably 13 μm or more and 100 μm or less, further preferably 15 μm or more and 50 μm or less, and 17 μm or more and 30 μm or less. Especially preferable.

　第２実施形態において、硬化性樹脂組成物の総重量に対する水酸化アルミニウム（Ｃ）の総重量は、得られる硬化物特性（熱伝導性、難燃性、接着強度、及び耐衝撃性）を向上させる観点と、硬化前の組成物の作業性を向上させる観点から、５５重量％以上８５重量％以下であることが必須であり、５７重量％以上８０重量％以下が好ましく、６０重量％以上７６重量％以下がより好ましく、６２重量％以上７３重量％以下が更に好ましく、６５重量％以上７０重量％以下が特に好ましい。 In the second embodiment, the total weight of the aluminum hydroxide (C) with respect to the total weight of the curable resin composition improves the obtained cured product properties (heat conductivity, flame retardancy, adhesive strength, and impact resistance). From the viewpoint of improving the workability of the composition before curing, it is essential that the composition is 55% by weight or more and 85% by weight or less, preferably 57% by weight or more and 80% by weight or less, and 60% by weight or more and 76% by weight. By weight% or less is more preferable, 62% by weight or more and 73% by weight or less is further preferable, and 65% by weight or more and 70% by weight or less is particularly preferable.

　第２実施形態の水酸化アルミニウム（Ｃ）について、上述した事項以外の態様については、適宜、第１実施形態の記載を援用する。 Regarding the aluminum hydroxide (C) of the second embodiment, the description of the first embodiment is appropriately incorporated for aspects other than the above-mentioned matters.

　第２実施形態の硬化性樹脂組成物は、水酸化アルミニウム以外（（Ｃ）成分以外）の熱伝導性フィラーおよび／または水酸化アルミニウム以外（（Ｃ）成分以外）の難燃剤を含有することができる。第２実施形態における「水酸化アルミニウム以外の熱伝導性フィラー」および「水酸化アルミニウム以外の難燃剤」の各態様（種類、含有量およびそれらの好ましい態様など）については、第１実施形態における＜水酸化アルミニウム以外の熱伝導性フィラー＞および＜水酸化アルミニウム以外の難燃剤＞の項で説明したものと同じであるため、当該記載を援用し、ここでは説明を省略する。 The curable resin composition of the second embodiment may contain a heat conductive filler other than aluminum hydroxide (other than component (C)) and / or a flame retardant other than aluminum hydroxide (other than component (C)). can. Regarding each aspect (type, content, preferred embodiment thereof, etc.) of "heat conductive filler other than aluminum hydroxide" and "flame retardant other than aluminum hydroxide" in the second embodiment, < Since it is the same as that described in the sections of the heat conductive filler other than aluminum hydroxide> and the <flame retardant other than aluminum hydroxide>, the description is incorporated and the description thereof is omitted here.

　＜エポキシ硬化剤（Ｄ）＞
　第２実施形態の硬化性樹脂組成物は、第二成分中に（Ｄ）成分として、エポキシ硬化剤を含有する。第２実施形態における「エポキシ硬化剤（Ｄ）」の各態様（種類、含有量およびそれらの好ましい態様など）については、第１実施形態における＜エポキシ硬化剤（Ｄ）＞の項で説明したものと同じであるため、当該記載を援用し、ここでは説明を省略する。 <Epoxy curing agent (D)>
The curable resin composition of the second embodiment contains an epoxy curing agent as the component (D) in the second component. Each embodiment of the "epoxy curing agent (D)" in the second embodiment (type, content, preferred embodiments thereof, etc.) is described in the section <Epoxy curing agent (D)> in the first embodiment. Since it is the same as the above, the description is incorporated and the description is omitted here.

　＜（Ｄ）成分以外の高温で活性を示すエポキシ硬化剤＞
　低温でエポキシ樹脂と反応し得る活性水素基を含有するエポキシ硬化剤（上記のアミン系硬化剤やメルカプタン系硬化剤など）以外の、高温で活性を示すエポキシ硬化剤を、第２実施形態の硬化性樹脂組成物の硬化速度を損なわない範囲で含有することが可能である。第２実施形態における「（Ｄ）成分以外の高温で活性を示すエポキシ硬化剤」の各態様（種類、含有量およびそれらの好ましい態様など）については、第１実施形態における＜（Ｄ）成分以外の高温で活性を示すエポキシ硬化剤＞の項で説明したものと同じであるため、当該記載を援用し、ここでは説明を省略する。 <Epoxy curing agent that exhibits activity at high temperatures other than component (D)>
An epoxy curing agent exhibiting activity at a high temperature other than an epoxy curing agent containing an active hydrogen group that can react with an epoxy resin at a low temperature (such as the above-mentioned amine-based curing agent and mercaptan-based curing agent) can be used for curing the second embodiment. It can be contained within a range that does not impair the curing rate of the sex resin composition. Regarding each aspect (type, content, preferred embodiment thereof, etc.) of the "epoxy curing agent exhibiting activity at a high temperature other than the component (D)" in the second embodiment, <(D) component other than the component (D) in the first embodiment. Since it is the same as that described in the section of "Epoxy curing agent exhibiting activity at high temperature", the description thereof is incorporated, and the description thereof is omitted here.

　＜エポキシ硬化促進剤（Ｅ）＞
　第２実施形態の硬化性樹脂組成物は、第一成分および／または前記第二成分中に、エポキシ硬化促進剤（Ｅ）を含有することができる。第２実施形態における「エポキシ硬化促進剤（Ｅ）」の各態様（種類、含有量およびそれらの好ましい態様など）については、第１実施形態における＜エポキシ硬化促進剤（Ｅ）＞の項で説明したものと同じであるため、当該記載を援用し、ここでは説明を省略する。 <Epoxy curing accelerator (E)>
The curable resin composition of the second embodiment can contain an epoxy curing accelerator (E) in the first component and / or the second component. Each aspect (type, content, preferred embodiment thereof, etc.) of the "epoxy curing accelerator (E)" in the second embodiment will be described in the section <Epoxy curing accelerator (E)> in the first embodiment. Since it is the same as the one described above, the description is used and the description is omitted here.

　＜シランカップリング剤（Ｆ）＞
　第２実施形態の硬化性樹脂組成物は、第一成分および／または前記第二成分中に、シランカップリング剤（Ｆ）を含有することができる。第２実施形態における「シランカップリング剤（Ｆ）」の各態様（種類、含有量およびそれらの好ましい態様など）については、第１実施形態における＜シランカップリング剤（Ｆ）＞の項で説明したものと同じであるため、当該記載を援用し、ここでは説明を省略する。 <Silane coupling agent (F)>
The curable resin composition of the second embodiment can contain a silane coupling agent (F) in the first component and / or the second component. Each aspect (type, content, preferred embodiment thereof, etc.) of the "silane coupling agent (F)" in the second embodiment will be described in the section <Silane coupling agent (F)> in the first embodiment. Since it is the same as the one described above, the description is used and the description is omitted here.

　〔ＩＩＩ．第３実施形態〕
　第３実施形態は、硬化性樹脂組成物、硬化物、接着剤及び積層体に関する。 [III. Third Embodiment]
A third embodiment relates to a curable resin composition, a cured product, an adhesive and a laminate.

　脂肪族アミン系硬化剤を用いる二成分型エポキシ樹脂組成物は、低温で硬化する。それ故、二成分型エポキシ樹脂組成物は、硬化のために加熱設備などが不要である。二成分型エポキシ樹脂組成物を硬化して得られる硬化物は、強度、耐熱性、耐水性、耐薬品性および電気絶縁性などに優れることから、工業用及び土木建築用等の幅広い用途で用いられている。現在、二成分型エポキシ樹脂組成物として、様々なものが開発されている（例えば、特許文献４など）。 The two-component epoxy resin composition using an aliphatic amine-based curing agent cures at a low temperature. Therefore, the two-component epoxy resin composition does not require heating equipment or the like for curing. The cured product obtained by curing a two-component epoxy resin composition is excellent in strength, heat resistance, water resistance, chemical resistance, electrical insulation, etc., and is therefore used in a wide range of applications such as industrial and civil engineering and construction. Has been done. Currently, various two-component epoxy resin compositions have been developed (for example, Patent Document 4).

　上述したように、二成分型エポキシ樹脂組成物を硬化して得られる硬化物は強度に優れるものであるが、二成分型エポキシ樹脂組成物には、硬化速度が遅い傾向にあるという課題がある。 As described above, the cured product obtained by curing the two-component epoxy resin composition has excellent strength, but the two-component epoxy resin composition has a problem that the curing rate tends to be slow. ..

　特に、自動車などの生産性（タクトタイム）を重視する分野では、二成分型接着剤の速硬化性が重要である。また、電気自動車（ＥＶ）のバッテリー固定に用いられる二成分型接着剤にも、速硬化性が要求されている。 In particular, in fields such as automobiles where productivity (tact time) is important, the quick-curing property of the two-component adhesive is important. In addition, a two-component adhesive used for fixing a battery of an electric vehicle (EV) is also required to have quick curing property.

　しかしながら、上述のような従来技術（例えば特許文献４に記載の技術）は、速硬化性の観点からは、十分なものでなく、さらなる改善の余地があった。 However, the above-mentioned conventional technique (for example, the technique described in Patent Document 4) is not sufficient from the viewpoint of quick curing, and there is room for further improvement.

　第３実施形態は、前記問題点に鑑みなされたものであり、その目的は、速硬化性に優れる、二成分型または多成分型の新規の硬化性樹脂組成物を提供することである。 The third embodiment has been made in view of the above problems, and an object thereof is to provide a novel two-component or multi-component curable resin composition having excellent quick-curing properties.

　本発明者らは、前記課題を解決するため鋭意検討した結果、第３実施形態に係る発明を完成させるに至った。 As a result of diligent studies to solve the above problems, the present inventors have completed the invention according to the third embodiment.

　本発明者らは、前記課題を解決するため鋭意検討した結果、以下の知見を独自にかつ新規に見出し、第３実施形態に係る本発明を完成させるに至った：エポキシ樹脂（Ａ）と、特定のエポキシ硬化剤と、に加えて、１分子中に１個の芳香環、および少なくとも２個のフェノール性水酸基を有し、また、当該フェノール性水酸基に対してオルト位に位置する第三級アルキル基の個数が、１分子中に０個又は１個である化合物、を組み合わせて用いることにより、速硬化性に優れる二成分型または多成分型の硬化性樹脂組成物とすることができる。 As a result of diligent studies to solve the above problems, the present inventors have independently and newly found the following findings, and have completed the present invention according to the third embodiment: epoxy resin (A) and. In addition to the specific epoxy curing agent, it has one aromatic ring in one molecule and at least two phenolic hydroxyl groups, and is a tertiary located at the ortho position with respect to the phenolic hydroxyl groups. By using a compound in which the number of alkyl groups is 0 or 1 in one molecule, a two-component type or multi-component type curable resin composition having excellent rapid curability can be obtained.

　第３実施形態に係る硬化性樹脂組成物は、エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含む二成分型または多成分型の硬化性樹脂組成物であって、前記硬化性樹脂組成物は、更に、コア層とシェル層とを含むコアシェル構造を有するポリマー粒子（Ｂ）と、１分子中に（ｉ）１個の芳香環、および（ｉｉ）少なくとも２個のフェノール性水酸基を有する化合物（Ｇ）と、を含有し、前記化合物（Ｇ）において、前記フェノール性水酸基に対してオルト位に位置する第三級アルキル基の個数は、１分子中に０個又は１個であり、前記エポキシ硬化剤（Ｄ）が、前記エポキシ硬化剤（Ｄ）が、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上である。 The curable resin composition according to the third embodiment is a two-component type or a multi-component type containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D). The curable resin composition is a polymer particle (B) having a core-shell structure including a core layer and a shell layer, and (i) one aromatic ring in one molecule. , And (ii) a compound (G) having at least two phenolic hydroxyl groups, and in the compound (G), the number of tertiary alkyl groups located at the ortho position with respect to the phenolic hydroxyl group. Is 0 or 1 in one molecule, and the epoxy curing agent (D) and the epoxy curing agent (D) are aliphatic amines, alicyclic amines, amidamines, amine-terminated polyethers, and amine-terminated. At least one selected from the group consisting of butadiene nitrile rubber, modified aliphatic amines, modified alicyclic amines, modified amidamines, modified amine-terminated polyethers and modified amine-terminated butadiene nitrile rubbers. That is all.

　「第３実施形態に係る硬化性樹脂組成物」を「第３の硬化性樹脂組成物」と称する場合がある。 The "curable resin composition according to the third embodiment" may be referred to as a "third curable resin composition".

　第３実施形態によれば、速硬化性に優れる、二成分型または多成分型の硬化性樹脂組成物を提供することができるという効果を奏する。 According to the third embodiment, there is an effect that it is possible to provide a two-component type or a multi-component type curable resin composition having excellent quick-curing properties.

　以下、第３実施形態に関する各態様について説明するが、以下に詳説した事項以外は、適宜、第１実施形態および第２実施形態の記載を援用する。 Hereinafter, each aspect of the third embodiment will be described, but the description of the first embodiment and the second embodiment will be appropriately incorporated except for the matters described in detail below.

　第３の硬化性樹脂組成物は、前述した構成を有するため、優れた速硬化性を示すことができるという利点を有する。なお、本明細書において「速硬化性」とは、室温付近（例えば、５℃～５０℃）において、短時間（例えば、数分間から数時間程度）で硬化することができる性質を意図する。すなわち、第３の硬化性樹脂組成物は、５０℃超の高温下での熱処理を必要とせずに、５℃から５０℃以下の温度にて、短時間（例えば、数分間から数時間程度）で硬化することができるという利点を有する。 Since the third curable resin composition has the above-mentioned structure, it has an advantage that it can exhibit excellent quick-curing property. In addition, in this specification, "fast curing property" is intended to be a property that can be cured in a short time (for example, about several minutes to several hours) at around room temperature (for example, 5 ° C to 50 ° C). That is, the third curable resin composition does not require heat treatment at a high temperature of more than 50 ° C., and is used at a temperature of 5 ° C. to 50 ° C. or lower for a short time (for example, about several minutes to several hours). It has the advantage that it can be cured with.

　第３の硬化性樹脂組成物は、第一成分にエポキシ樹脂（Ａ）を含んでおり、換言すれば、二成分型エポキシ樹脂組成物または多成分型エポキシ樹脂組成物ともいえる。それ故、第３の硬化性樹脂組成物は、接着強度に優れるという利点も有する。 The third curable resin composition contains the epoxy resin (A) as the first component, and in other words, it can be said to be a two-component epoxy resin composition or a multi-component epoxy resin composition. Therefore, the third curable resin composition also has an advantage of being excellent in adhesive strength.

　二成分型接着剤としては、二成分型エポキシ樹脂組成物の他に、ウレタン樹脂を主成分とする二成分型ウレタン系組成物も知られている。二成分型ウレタン系組成物は、二成分型エポキシ樹脂組成物と比べて、短時間で硬化し得る速硬化性を有する。しかしながら、二成分型ウレタン系組成物は、二成分型エポキシ樹脂組成物と比べて、得られる硬化物の強度および耐熱性などが不十分な傾向にあるという課題がある。 As the two-component adhesive, in addition to the two-component epoxy resin composition, a two-component urethane-based composition containing a urethane resin as a main component is also known. The two-component urethane-based composition has a fast-curing property that can be cured in a short time as compared with the two-component epoxy resin composition. However, the two-component urethane-based composition has a problem that the strength and heat resistance of the obtained cured product tend to be insufficient as compared with the two-component epoxy resin composition.

　電気自動車（ＥＶ）のバッテリー固定に用いられる二成分型接着剤には、速硬化性および強度の両立が求められる場合も多い。 The two-component adhesive used to fix the battery of an electric vehicle (EV) is often required to have both quick curing and strength.

　上述したように、第３の硬化性樹脂組成物は、接着強度に優れるとともに、速硬化性に優れるものである。それ故、第３の硬化性樹脂組成物は、電気自動車（ＥＶ）のバッテリー固定用の二成分型接着剤として、特に好適に利用することができる。 As described above, the third curable resin composition has excellent adhesive strength and quick curability. Therefore, the third curable resin composition can be particularly preferably used as a two-component adhesive for fixing a battery of an electric vehicle (EV).

　また、第３の硬化性樹脂組成物は、コア層とシェル層とを含むコアシェル構造を有するポリマー粒子（Ｂ）を含んでおり、そのため、第３の硬化性樹脂組成物は、耐衝撃剥離接着性に優れるという利点も有する。 Further, the third curable resin composition contains polymer particles (B) having a core-shell structure including a core layer and a shell layer, so that the third curable resin composition is impact-resistant and peel-bonded. It also has the advantage of being excellent in sex.

　＜エポキシ樹脂（Ａ）＞
　第３実施形態におけるエポキシ樹脂（Ａ）の各態様（種類、含有量およびそれらの好ましい態様など）については、第１実施形態における＜エポキシ樹脂（Ａ）＞の項で説明したものと同じであるため、当該記載を援用し、ここでは説明を省略する。 <Epoxy resin (A)>
Each aspect (type, content, preferred embodiment thereof, etc.) of the epoxy resin (A) in the third embodiment is the same as that described in the section <Epoxy resin (A)> in the first embodiment. Therefore, the description is used and the description is omitted here.

　＜コアシェル構造を有するポリマー粒子（Ｂ）＞
　第３実施形態の硬化性樹脂組成物は、第一成分および／または前記第二成分中に、（Ｂ）成分として、コアシェル構造を有するポリマー粒子を含有する。第３実施形態におけるコアシェル構造を有するポリマー粒子（Ｂ）の各態様（例えば、コア層の組成、シェル層の組成およびそれらの好ましい態様など）については、第１実施形態における＜コアシェル構造を有するポリマー粒子（Ｂ）＞の項で説明したものと同じであるため、当該記載を援用し、ここでは説明を省略する。 <Polymer particles (B) having a core-shell structure>
The curable resin composition of the third embodiment contains polymer particles having a core-shell structure as the component (B) in the first component and / or the second component. For each aspect of the polymer particles (B) having a core-shell structure in the third embodiment (for example, the composition of the core layer, the composition of the shell layer and their preferred embodiments, etc.), the <polymer having a core-shell structure in the first embodiment, etc.). Since it is the same as that described in the section of particle (B)>, the description thereof is incorporated, and the description thereof is omitted here.

　＜化合物（Ｇ）＞
　第３実施形態の硬化性樹脂組成物は、第一成分中および／または前記第二成分中に、（Ｇ）成分として、１分子中に（ｉ）１個の芳香環、および（ｉｉ）少なくとも２個のフェノール性水酸基を有する化合物（Ｇ）を含有する。当該化合物（Ｇ）において、フェノール性水酸基に対してオルト位に位置する第三級アルキル基の個数は、１分子中に０個又は１個である。 <Compound (G)>
The curable resin composition of the third embodiment has (i) one aromatic ring in one molecule as (G) component in the first component and / or the second component, and (ii) at least. It contains a compound (G) having two phenolic hydroxyl groups. In the compound (G), the number of tertiary alkyl groups located at the ortho position with respect to the phenolic hydroxyl group is 0 or 1 in one molecule.

　化合物（Ｇ）は、ポリマー粒子（Ｂ）および後述のエポキシ硬化剤（Ｄ）と併用することにより、良好な接着強度を維持したまま、硬化性樹脂組成物の硬化速度を向上させる効果を有する。また、第３実施形態の硬化性樹脂組成物は、ポリマー粒子（Ｂ）および後述のエポキシ硬化剤（Ｄ）と共に、化合物（Ｇ）を含むことにより、５０℃超の高温下での熱処理を必要とせずに、優れた速硬化性を示し、化合物（Ｇ）を含まない硬化性樹脂組成物に比べて、短時間で硬化することができる。 The compound (G) has an effect of improving the curing rate of the curable resin composition while maintaining good adhesive strength when used in combination with the polymer particles (B) and the epoxy curing agent (D) described later. Further, the curable resin composition of the third embodiment needs to be heat-treated at a high temperature of more than 50 ° C. by containing the compound (G) together with the polymer particles (B) and the epoxy curing agent (D) described later. It exhibits excellent fast-curing properties and can be cured in a short time as compared with a curable resin composition containing no compound (G).

　（Ｇ）成分は第一成分のみに含有してもよく、第二成分のみに含有してもよく、第一成分と第二成分の双方に含有してもよい。硬化性樹脂組成物の貯安性の観点から、（Ｇ）成分は、第二成分のみに含有することが好ましい。 The component (G) may be contained only in the first component, may be contained only in the second component, or may be contained in both the first component and the second component. From the viewpoint of the storage stability of the curable resin composition, the component (G) is preferably contained only in the second component.

　本明細書において、芳香環とは、ヒュッケル則を満たす環状炭化水素および複素環式化合物を意味する。芳香環の具体例としては、ベンゼン、ナフタレン、アズレン、アントラセン、ピロール、ピリジン、フラン、チオフェンなどが挙げられる。速硬化性向上効果および入手のしやすさなどの観点から、これらの中でも、ベンゼンが特に好ましい。 In the present specification, the aromatic ring means a cyclic hydrocarbon and a heterocyclic compound satisfying Hückel's rule. Specific examples of the aromatic ring include benzene, naphthalene, azulene, anthracene, pyrrole, pyridine, furan, thiophene and the like. Among these, benzene is particularly preferable from the viewpoints of the effect of improving the quick-curing property and the availability.

　本明細書において、フェノール性水酸基とは、芳香環の炭素原子に結合した水酸基を意味する。化合物（Ｇ）において、２個のフェノール性水酸基の位置は特に限定されず、芳香環のいずれの炭素原子上に位置していてもよい。 In the present specification, the phenolic hydroxyl group means a hydroxyl group bonded to a carbon atom of an aromatic ring. In compound (G), the positions of the two phenolic hydroxyl groups are not particularly limited and may be located on any carbon atom of the aromatic ring.

　芳香環がベンゼンである場合、２個のフェノール性水酸基は、互いに、オルト位、メタ位、またはパラ位のいずれの位置関係にあってもよいが、優れた速硬化性向上効果を発揮することから、オルト位またはメタ位の位置関係にあることがより好ましく、メタ位の位置関係にあることがさらに好ましい。 When the aromatic ring is benzene, the two phenolic hydroxyl groups may be in any positional relationship of the ortho-position, the meta-position, or the para-position with respect to each other, but exhibit an excellent effect of improving fast-curing property. Therefore, it is more preferable to have an ortho-position or a meta-position positional relationship, and it is further preferable to have a meta-position positional relationship.

　化合物（Ｇ）は、本発明の一実施形態に係る効果を阻害しない範囲で、芳香環上に、２個のフェノール性水酸基以外に、少なくとも１つのさらなる置換基を有していてもよい。さらなる置換基としては、特に限定されないが、例えば、炭素数８以下のアルキル基（メチル基、エチル基、プロピル基、１－メチルエチル基（イソプロピル基）、ブチル基、１，１－ジメチルエチル基（ｔｅｒｔ－ブチル基）など）、ハロゲン（塩素、臭素、ヨウ素）、などが挙げられる。 Compound (G) may have at least one additional substituent on the aromatic ring in addition to the two phenolic hydroxyl groups, as long as the effect according to the embodiment of the present invention is not impaired. The further substituent is not particularly limited, but is, for example, an alkyl group having 8 or less carbon atoms (methyl group, ethyl group, propyl group, 1-methylethyl group (isopropyl group), butyl group, 1,1-dimethylethyl group). (Tart-butyl group) and the like), halogens (chlorine, bromine, iodine) and the like.

　ただし、化合物（Ｇ）がさらなる置換基として第三級アルキル基（例えば、ｔｅｒｔ－ブチル基など）を有する場合、フェノール性水酸基に対してオルト位に位置する第三級アルキル基の個数は、１分子中に０個または１個である。化合物（Ｇ）１分子中に、フェノール性水酸基に対してオルト位に位置する第三級アルキル基の個数が２個以上である場合、速硬化性向上効果が得られず、硬化にかかる時間が増大するため好ましくない。この理由は定かではないが、第三級アルキル基による立体障害により、速硬化性向上効果が阻害されるためと推測され得る。 However, when the compound (G) has a tertiary alkyl group (for example, tert-butyl group) as a further substituent, the number of tertiary alkyl groups located at the ortho position with respect to the phenolic hydroxyl group is 1. There are 0 or 1 in the molecule. When the number of tertiary alkyl groups located at the ortho position with respect to the phenolic hydroxyl group is two or more in one molecule of compound (G), the effect of improving quick curability cannot be obtained and the time required for curing is not obtained. It is not preferable because it increases. The reason for this is not clear, but it can be presumed that the steric hindrance caused by the tertiary alkyl group hinders the effect of improving the fast curability.

　化合物（Ｇ）は、芳香環上に、２個のフェノール性水酸基以外の置換基を有さないことが好ましい。当該構成により、速硬化性向上効果が高まるという利点を有する。 It is preferable that the compound (G) has no substituent other than the two phenolic hydroxyl groups on the aromatic ring. The configuration has an advantage that the effect of improving the quick curing property is enhanced.

　化合物（Ｇ）としては、１，３－ジヒドロキシベンゼン（別名；レゾルシノール）、１，２－ジヒドロキシベンゼン（別名；カテコール）、１，４－ジヒドロキシベンゼン（別名；ヒドロキノン）、４－ｔｅｒｔ－ブチルカテコール、メチルヒドロキノン、ｔｅｒｔ－ブチルヒドロキノン、クロロヒドロキノン、２，５－ジクロロヒドロキノン、２，５－ジブロモヒドロキノン、ピロガロール、ヒドロキシキノール、フロログルシノールなどが挙げられる。優れた速硬化性向上効果を発揮することから、これらの中でも、レゾルシノール、カテコール、ヒドロキノンおよびメチルヒドロキノンがより好ましく、レゾルシノール、およびカテコールがさらに好ましく、レゾルシノールが特に好ましい。 Examples of the compound (G) include 1,3-dihydroxybenzene (also known as resorcinol), 1,2-dihydroxybenzene (also known as catechol), 1,4-dihydroxybenzene (also known as hydroquinone), 4-tert-butylcatechol, and the like. Examples thereof include methylhydroquinone, tert-butylhydroquinone, chlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dibromohydroquinone, pyrogallol, hydroxyquinone, fluororesorcinol and the like. Among these, resorcinol, catechol, hydroquinone and methylhydroquinone are more preferable, resorcinol and catechol are more preferable, and resorcinol is particularly preferable, because they exhibit an excellent effect of improving fast curing property.

　化合物（Ｇ）は、１種類を単独で用いてもよく２種以上を組み合わせて用いてもよい。 The compound (G) may be used alone or in combination of two or more.

　第３実施形態の硬化性樹脂組成物は、エポキシ樹脂（Ａ）１００重量部に対して、化合物（Ｇ）を、１～２５重量部を含有することが好ましく、２～２０重量部を含有することがより好ましく、３～１５重量部を含有することがさらに好ましく、４～１０重量部を含有することが特に好ましい。化合物（Ｇ）の含有量が、エポキシ樹脂（Ａ）１００重量部に対して、（ａ）１重量部以上である場合、化合物（Ｇ）の速硬化性向上効果が良好に発揮され、（ｂ）２５重量部以下である場合、硬化性樹脂組成物の貯蔵安定性が良好となり、取り扱い易いという利点を有する。 The curable resin composition of the third embodiment preferably contains 1 to 25 parts by weight of the compound (G) with respect to 100 parts by weight of the epoxy resin (A), and contains 2 to 20 parts by weight. It is more preferable to contain 3 to 15 parts by weight, and particularly preferably 4 to 10 parts by weight. When the content of the compound (G) is 1 part by weight or more with respect to 100 parts by weight of the epoxy resin (A), the effect of improving the quick curability of the compound (G) is satisfactorily exhibited (b). ) When the amount is 25 parts by weight or less, the curable resin composition has an advantage that the storage stability is good and it is easy to handle.

　なお、後述するエポキシ硬化剤（Ｄ）による硬化速度を加速する硬化助剤として、ビスフェノールＡおよび２，４，６－トリス（ジメチルアミノメチル）フェノール等のフェノール性水酸基を有する化合物が知られている。ビスフェノールＡなどの、１分子中に２個の芳香環と２個のフェノール性水酸基を有する化合物は、環境規則等で使用が規制されている為に取り扱いが難しい。それ故、第３実施形態の硬化性樹脂組成物において、１分子中に２個の芳香環と２個のフェノール性水酸基を有する化合物（ビスフェノールＡ）の含有量は少ないほど好ましく、例えばエポキシ樹脂（Ａ）１００重量部に対して３重量部以下であることが好ましい。しかしながら、本発明の一実施形態に係る効果を損なわない範囲内において、第３実施形態の硬化性樹脂組成物は、１分子中に２個の芳香環と２個のフェノール性水酸基を有する化合物（例えばビスフェノールＡ）を含んでいてもよい。 As a curing aid for accelerating the curing rate with the epoxy curing agent (D) described later, compounds having a phenolic hydroxyl group such as bisphenol A and 2,4,6-tris (dimethylaminomethyl) phenol are known. .. Compounds having two aromatic rings and two phenolic hydroxyl groups in one molecule, such as bisphenol A, are difficult to handle because their use is regulated by environmental regulations and the like. Therefore, in the curable resin composition of the third embodiment, the smaller the content of the compound (bisphenol A) having two aromatic rings and two phenolic hydroxyl groups in one molecule is preferable, for example, an epoxy resin (epoxy resin). A) It is preferably 3 parts by weight or less with respect to 100 parts by weight. However, the curable resin composition of the third embodiment is a compound having two aromatic rings and two phenolic hydroxyl groups in one molecule, as long as the effect according to the embodiment of the present invention is not impaired. For example, it may contain bisphenol A).

　第３実施形態の硬化性樹脂組成物において、１分子中に２個の芳香環と２個のフェノール性水酸基を有する化合物（ビスフェノールＡ）の含有量は、エポキシ樹脂（Ａ）１００重量部に対して、２重量部以下であってもよく、１重量部以下であってもよく、０．５重量部以下であってもよく、０．１重量部未満であってもよい。 In the curable resin composition of the third embodiment, the content of the compound (bisphenol A) having two aromatic rings and two phenolic hydroxyl groups in one molecule is 100 parts by weight of the epoxy resin (A). It may be 2 parts by weight or less, 1 part by weight or less, 0.5 parts by weight or less, or less than 0.1 parts by weight.

　また、第３実施形態において、本発明者が、後述するエポキシ硬化剤（Ｄ）の代わりに、硬化剤として２，４，６－トリス（ジメチルアミノメチル）フェノール等の１分子中に１個のフェノール性水酸基を有する化合物を使用したところ、速硬化性の改善効果が十分ではないということを、独自に見出した。しかしながら、本発明の一実施形態に係る効果を損なわない範囲内において、第３実施形態の硬化性樹脂組成物は、１分子中に１個のフェノール性水酸基を有する化合物（例えば２，４，６－トリス（ジメチルアミノメチル）フェノール）を含んでいてもよい。 Further, in the third embodiment, the present inventor uses one molecule of 2,4,6-tris (dimethylaminomethyl) phenol or the like as a curing agent instead of the epoxy curing agent (D) described later. It was independently found that the effect of improving the quick-curing property was not sufficient when a compound having a phenolic hydroxyl group was used. However, as long as the effect according to the embodiment of the present invention is not impaired, the curable resin composition of the third embodiment is a compound having one phenolic hydroxyl group in one molecule (for example, 2, 4, 6). -Tris (dimethylaminomethyl) phenol) may be contained.

　＜水酸化アルミニウム（Ｃ）＞
　第３実施形態の硬化性樹脂組成物は、さらに、水酸化アルミニウム（Ｃ）を含有してもよく、含有しなくてもよい。第３実施形態の硬化性樹脂組成物は、第一成分および／または前記第二成分中に、水酸化アルミニウム（Ｃ）を含有することが好ましい。第３実施形態の硬化性樹脂組成物が（Ｃ）成分を含む場合、得られる硬化物は熱伝導性及び難燃性（例えば垂直燃焼試験（ＵＬ９４）で評価される難燃性）に優れるという利点を有する。 <Aluminum hydroxide (C)>
The curable resin composition of the third embodiment may or may not further contain aluminum hydroxide (C). The curable resin composition of the third embodiment preferably contains aluminum hydroxide (C) in the first component and / or the second component. When the curable resin composition of the third embodiment contains the component (C), the obtained cured product is said to be excellent in thermal conductivity and flame retardancy (for example, flame retardancy evaluated by a vertical combustion test (UL94)). Has advantages.

　第３実施形態において、（Ｃ）成分の平均粒子径は、特に限定されない。第３実施形態において、（Ｃ）成分の平均粒子径は、得られる硬化物の耐衝撃性と接着強度との両立の観点と、硬化前の硬化性樹脂組成物中での（Ｃ）成分の経時での沈降を抑制する観点から、１１μｍ以上２００μｍ以下であることが好ましく、１２μｍ以上１５０μｍ以下がより好ましく、１３μｍ以上１００μｍ以下がさらに好ましく、１５μｍ以上５０μｍ以下が更により好ましく、１７μｍ以上３０μｍ以下が特に好ましい。 In the third embodiment, the average particle size of the component (C) is not particularly limited. In the third embodiment, the average particle size of the component (C) is determined from the viewpoint of achieving both impact resistance and adhesive strength of the obtained cured product, and the component (C) in the curable resin composition before curing. From the viewpoint of suppressing sedimentation over time, it is preferably 11 μm or more and 200 μm or less, more preferably 12 μm or more and 150 μm or less, further preferably 13 μm or more and 100 μm or less, further preferably 15 μm or more and 50 μm or less, and 17 μm or more and 30 μm or less. Especially preferable.

　第３実施形態において、硬化性樹脂組成物の総重量に対する水酸化アルミニウム（Ｃ）の総重量は、特に限定されない。第３実施形態において、硬化性樹脂組成物の総重量に対する水酸化アルミニウム（Ｃ）の総重量は、得られる硬化物特性（熱伝導性、難燃性、接着強度、及び耐衝撃性）を向上させる観点と、硬化前の組成物の作業性を向上させる観点から、５５重量％以上８５重量％以下であることが好ましく、５７重量％以上８０重量％以下がより好ましく、６０重量％以上７６重量％以下がより好ましく、６２重量％以上７３重量％以下が更に好ましく、６５重量％以上７０重量％以下が特に好ましい。 In the third embodiment, the total weight of aluminum hydroxide (C) with respect to the total weight of the curable resin composition is not particularly limited. In the third embodiment, the total weight of the aluminum hydroxide (C) with respect to the total weight of the curable resin composition improves the obtained cured product properties (heat conductivity, flame retardancy, adhesive strength, and impact resistance). From the viewpoint of improving the workability of the composition before curing, it is preferably 55% by weight or more and 85% by weight or less, more preferably 57% by weight or more and 80% by weight or less, and 60% by weight or more and 76% by weight. % Or less is more preferable, 62% by weight or more and 73% by weight or less is further preferable, and 65% by weight or more and 70% by weight or less is particularly preferable.

　第３実施形態の水酸化アルミニウム（Ｃ）について、上述した事項以外の態様については、適宜、第１実施形態の記載を援用する。 Regarding the aluminum hydroxide (C) of the third embodiment, the description of the first embodiment is appropriately incorporated for aspects other than the above-mentioned matters.

　第３実施形態の硬化性樹脂組成物は、水酸化アルミニウム以外（（Ｃ）成分以外）の熱伝導性フィラーおよび／または水酸化アルミニウム以外（（Ｃ）成分以外）の難燃剤を含有することができる。第３実施形態における「水酸化アルミニウム以外の熱伝導性フィラー」および「水酸化アルミニウム以外の難燃剤」の各態様（種類、含有量およびそれらの好ましい態様など）については、第１実施形態における＜水酸化アルミニウム以外の熱伝導性フィラー＞および＜水酸化アルミニウム以外の難燃剤＞の項で説明したものと同じであるため、当該記載を援用し、ここでは説明を省略する。 The curable resin composition of the third embodiment may contain a heat conductive filler other than aluminum hydroxide (other than component (C)) and / or a flame retardant other than aluminum hydroxide (other than component (C)). can. Regarding each aspect (type, content, preferred embodiment thereof, etc.) of "heat conductive filler other than aluminum hydroxide" and "flame retardant other than aluminum hydroxide" in the third embodiment, < Since it is the same as that described in the sections of the heat conductive filler other than aluminum hydroxide> and the <flame retardant other than aluminum hydroxide>, the description is incorporated and the description thereof is omitted here.

　＜エポキシ硬化剤（Ｄ）＞
　第３実施形態の硬化性樹脂組成物は、第二成分中に（Ｄ）成分として、エポキシ硬化剤を含有する。第３実施形において、エポキシ硬化剤（Ｄ）としては、アミン系硬化剤が好適に使用される。 <Epoxy curing agent (D)>
The curable resin composition of the third embodiment contains an epoxy curing agent as the component (D) in the second component. In the third embodiment, as the epoxy curing agent (D), an amine-based curing agent is preferably used.

　第３実施形において、アミン系硬化剤は、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上である。第３実施形において、エポキシ硬化剤（Ｄ）は、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上であってもよく、当該群より選択される少なくとも１種以上のみからなってもよい。エポキシ硬化剤（Ｄ）が上述した群から選択される少なくとも１種以上であるか、または当該群から選択される１種以上のみからなる場合、硬化性樹脂組成物が室温での硬化性（速硬化性）に優れるという利点を有する。第３実施形において、エポキシ硬化剤（Ｄ）は、１種類を単独で用いてもよく２種以上を組み合わせて用いてもよい。 In the third embodiment, the amine-based curing agent is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified aliphatic amine, a modified alicyclic amine, or an amidoamine. At least one selected from the group consisting of a modified product of an amine-terminated polyether, a modified product of an amine-terminated butadiene nitrile rubber, and a modified product of an amine-terminated butadiene nitrile rubber. In the third embodiment, the epoxy curing agent (D) is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified product of an aliphatic amine, or a modified product of an alicyclic amine. , At least one selected from the group consisting of a modified product of amidoamine, a modified product of an amine-terminated polyether and a modified product of an amine-terminated butadiene nitrile rubber, and only one or more selected from the group. It may consist of. When the epoxy curing agent (D) is at least one selected from the above-mentioned group, or is composed of only one selected from the group, the curable resin composition is curable (fast) at room temperature. It has the advantage of being excellent in curability). In the third embodiment, the epoxy curing agent (D) may be used alone or in combination of two or more.

　第３実施形態のエポキシ硬化剤（Ｄ）は、アミン系硬化剤の中でも、（ａ）得られる硬化物の耐衝撃性の観点から、（ａ－１）アミン末端ポリエーテルおよびアミン末端ブタジエンニトリルゴムからなる群から選択される１種以上を含むことが好ましく、（ａ－２）アミン末端ポリエーテルおよびアミン末端ブタジエンニトリルゴムからなる群から選択される１種以上であることがより好ましく、（ｂ）更に硬化性の観点からアミン末端ブタジエンニトリルゴムを含むことがより好ましく、アミン末端ブタジエンニトリルゴムであることがさらに好ましい。第３実施形態のエポキシ硬化剤（Ｄ）は、アミン系硬化剤の中でも、（ａ）得られる硬化物の接着強度の観点から、（ａ－１）脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される１種以上を含むことが好ましく、（ａ－２）脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される１種以上であることがより好ましく、（ｂ）更に硬化性の観点から、（ｂ－１）脂環族アミンおよびアミン末端ブタジエンニトリルゴムからなる群より選択される１種以上を含むことがより好ましく、（ｂ－２）脂環族アミンおよびアミン末端ブタジエンニトリルゴムからなる群より選択される１種以上であることがより好ましい。第３実施形態のエポキシ硬化剤（Ｄ）は、得られる硬化物の接着強度および硬化性の観点から、脂環族アミン、アミン末端ブタジエンニトリルゴム、脂環族アミンの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上を含むことがより好ましく、脂環族アミン、アミン末端ブタジエンニトリルゴム、脂環族アミンの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上であることがさらに好ましい。 Among the amine-based curing agents, the epoxy curing agent (D) of the third embodiment is (a-1) an amine-terminated polyether and an amine-terminated butadiene nitrile rubber from the viewpoint of (a) impact resistance of the obtained cured product. It is preferable to contain one or more selected from the group consisting of (a-2) amine-terminated polyether and amine-terminated butadiene nitrile rubber, and more preferably one or more selected from the group consisting of (b). ) Further, from the viewpoint of curability, it is more preferable to contain an amine-terminated butadiene nitrile rubber, and further preferably an amine-terminated butadiene nitrile rubber. Among the amine-based curing agents, the epoxy curing agent (D) of the third embodiment is (a-1) alicyclic amine, amidoamine, amine-terminated polyether from the viewpoint of (a) adhesive strength of the obtained cured product. , Amine-terminated butadiene nitrile rubber, modified alicyclic amine, modified amidamine, modified amine-terminated polyether and modified amine-terminated butadiene nitrile rubber may contain one or more selected from the group. Preferably, (a-2) alicyclic amines, amidamines, amine-terminated polyethers, amine-terminated butadiene nitrile rubbers, modified alicyclic amines, modified amidamines, modified amine-terminated polyethers and amine-terminated butadiene nitriles. It is more preferably one or more selected from the group consisting of modified rubbers, and (b-1) from the viewpoint of curability, (b-1) from the group consisting of alicyclic amines and amine-terminated butadiene nitrile rubbers. It is more preferable to contain one or more selected species, and more preferably one or more selected from the group consisting of (b-2) alicyclic amines and amine-terminated butadiene nitrile rubbers. The epoxy curing agent (D) of the third embodiment has an alicyclic amine, an amine-terminated butadiene nitrile rubber, a modified alicyclic amine, and an amine-terminated butadiene nitrile from the viewpoint of adhesive strength and curability of the obtained cured product. It is more preferable to contain at least one selected from the group consisting of modified rubbers, from alicyclic amines, amine-terminated butadiene nitrile rubbers, modified alicyclic amines and modified amine-terminated butadiene nitrile rubbers. It is more preferable that the number is at least one selected from the group.

　第３実施形態のエポキシ硬化剤（Ｄ）について、上述した事項以外の態様については、適宜、第１実施形態の記載を援用する。 Regarding the epoxy curing agent (D) of the third embodiment, the description of the first embodiment is appropriately incorporated for aspects other than the above-mentioned matters.

　＜（Ｄ）成分以外の高温で活性を示すエポキシ硬化剤＞
　低温でエポキシ樹脂と反応し得る活性水素基を含有するエポキシ硬化剤（上記のアミン系硬化剤やメルカプタン系硬化剤など）以外の、高温で活性を示すエポキシ硬化剤を、第３実施形態の硬化性樹脂組成物の硬化速度を損なわない範囲で含有することが可能である。第３実施形態における「（Ｄ）成分以外の高温で活性を示すエポキシ硬化剤」の各態様（種類、含有量およびそれらの好ましい態様など）については、第１実施形態における＜（Ｄ）成分以外の高温で活性を示すエポキシ硬化剤＞の項で説明したものと同じであるため、当該記載を援用し、ここでは説明を省略する。 <Epoxy curing agent that exhibits activity at high temperatures other than component (D)>
An epoxy curing agent exhibiting activity at a high temperature other than an epoxy curing agent containing an active hydrogen group that can react with an epoxy resin at a low temperature (such as the above-mentioned amine-based curing agent and mercaptan-based curing agent) can be used to cure the third embodiment. It can be contained within a range that does not impair the curing rate of the sex resin composition. Regarding each aspect (type, content, preferred embodiment thereof, etc.) of the "epoxy curing agent exhibiting activity at a high temperature other than the component (D)" in the third embodiment, the components other than the <(D) component in the first embodiment are used. Since it is the same as that described in the section of "Epoxy curing agent exhibiting activity at high temperature", the description thereof is incorporated, and the description thereof is omitted here.

　＜化合物（Ｇ）以外のエポキシ硬化促進剤（Ｈ）＞
　第３実施形態の硬化性樹脂組成物は、第一成分および／または前記第二成分が、化合物（Ｇ）以外のエポキシ硬化促進剤（Ｈ）（以下、「（Ｈ）成分」と称する場合もある。）を含有していてもよい。 <Epoxy curing accelerator (H) other than compound (G)>
In the curable resin composition of the third embodiment, the first component and / or the second component may be referred to as an epoxy curing accelerator (H) other than the compound (G) (hereinafter, referred to as “(H) component”). Yes.) May be contained.

　（Ｈ）成分は、エポキシ樹脂（Ａ）と反応して架橋を形成することが困難な化合物であるが、エポキシ樹脂（Ａ）とエポキシ硬化剤（Ｄ）による硬化反応を加速することができる。特に（Ｈ）成分は、前記（Ｄ）成分、すなわち室温での硬化性が高いエポキシ硬化剤との併用により、顕著な硬化加速効果を示すものが好ましい。 The component (H) is a compound that is difficult to form a crosslink by reacting with the epoxy resin (A), but the curing reaction between the epoxy resin (A) and the epoxy curing agent (D) can be accelerated. In particular, the component (H) is preferably a component (D) that exhibits a remarkable curing acceleration effect when used in combination with the component (D), that is, an epoxy curing agent having high curability at room temperature.

　（Ｈ）成分は第一成分のみに含有してもよく、第二成分のみに含有してもよく、第一成分と第二成分の双方に含有してもよい。硬化性樹脂組成物の貯安性の観点から、（Ｈ）成分は、第二成分のみに含有することが好ましい。 The component (H) may be contained only in the first component, may be contained only in the second component, or may be contained in both the first component and the second component. From the viewpoint of the storage stability of the curable resin composition, the component (H) is preferably contained only in the second component.

　（Ｈ）成分としては、例えば、アルキレンの炭素数が１から１２（Ｃ１－Ｃ１２）のアルキレンイミダゾール、Ｎ－アリールイミダゾール、２－メチルイミダゾール、２－エチル－２－メチルイミダゾール、Ｎ－ブチルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾリウム・トリメリテート、エポキシ樹脂とイミダゾールとの付加生成物、などのイミダゾール類；Ｎ，Ｎ－ジメチルピペラジン、ジアザビシクロウンデセン、ジアザビシクロノネン、トリエチレンジアミン、ベンジルジメチルアミン、トリエチルアミンなどの３級アミン類；２－（ジメチルアミノメチル）フェノール、２，４，６－トリス（ジメチルアミノメチル）フェノール、ポリ（ｐ－ビニルフェノール）マトリックスに組み込まれた２，４，６－トリス（ジメチルアミノメチル）フェノール、ｐ－ｔ－ブチルフェノール、フェノール、４－メトキシフェノールなどのフェノール類；等が挙げられる。これらの中でも、硬化性改善効果の観点からイミダゾール類およびフェノール類が好ましく、２，４，６－トリス（ジメチルアミノメチル）フェノールなどのフェノール類がより好ましい。（Ｈ）成分は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the component (H) include alkylene imidazole having 1 to 12 (C1-C12) carbon atoms, N-aryl imidazole, 2-methyl imidazole, 2-ethyl-2-methyl imidazole, and N-butyl imidazole. Imidazoles such as 1-cyanoethyl-2-undecylimidazolium trimellitate, an addition product of epoxy resin and imidazole; N, N-dimethylpiperazine, diazabicycloundecene, diazabicyclononen, triethylenediamine, benzyl. Tertiary amines such as dimethylamine and triethylamine; 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4 incorporated into poly (p-vinylphenol) matrix Examples thereof include phenols such as 6-tris (dimethylaminomethyl) phenol, pt-butylphenol, phenol, and 4-methoxyphenol; and the like. Among these, imidazoles and phenols are preferable from the viewpoint of the effect of improving curability, and phenols such as 2,4,6-tris (dimethylaminomethyl) phenol are more preferable. As the component (H), one type may be used alone, or two or more types may be used in combination.

　第３実施形態の硬化性樹脂組成物における、前記エポキシ樹脂（Ａ）１００重量部に対する前記エポキシ硬化促進剤（Ｈ）の含有量は、硬化性の向上効果および保存安定性の両立の観点から、０．１重量部以上３０重量部以下が好ましく、１重量部以上２０重量部以下がより好ましく、２重量部以上１５重量部以下が更に好ましく、３重量部以上１０重量部以下が特に好ましい。 The content of the epoxy curing accelerator (H) with respect to 100 parts by weight of the epoxy resin (A) in the curable resin composition of the third embodiment is from the viewpoint of achieving both the effect of improving curability and the storage stability. 0.1 part by weight or more and 30 parts by weight or less are preferable, 1 part by weight or more and 20 parts by weight or less are more preferable, 2 parts by weight or more and 15 parts by weight or less are further preferable, and 3 parts by weight or more and 10 parts by weight or less are particularly preferable.

　本発明の一実施形態は、以下のような構成であってもよい。 One embodiment of the present invention may have the following configuration.

　〔Ａ１〕エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含む二成分型の硬化性樹脂組成物であって、
前記硬化性樹脂組成物は、更に、コアシェル構造を有するポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）を含有し、前記硬化性樹脂組成物の総重量に対する前記水酸化アルミニウム（Ｃ）の総重量が、５５重量％以上８５重量％以下であり、前記水酸化アルミニウム（Ｃ）の平均粒子径が、１１μｍ以上２００μｍ以下である、硬化性樹脂組成物。 [A1] A two-component curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
The curable resin composition further contains polymer particles (B) having a core-shell structure and aluminum hydroxide (C), and the total weight of the aluminum hydroxide (C) with respect to the total weight of the curable resin composition. However, the curable resin composition is 55% by weight or more and 85% by weight or less, and the average particle size of the aluminum hydroxide (C) is 11 μm or more and 200 μm or less.

　〔Ａ２〕前記コアシェル構造を有するポリマー粒子（Ｂ）および前記水酸化アルミニウム（Ｃ）は、各々、前記第一成分および／または前記第二成分に含有される、〔Ａ１〕に記載の硬化性樹脂組成物。 [A2] The curable resin according to [A1], wherein the polymer particles (B) having the core-shell structure and the aluminum hydroxide (C) are contained in the first component and / or the second component, respectively. Composition.

　〔Ａ３〕前記エポキシ樹脂（Ａ）が有するエポキシ基のモル数／前記エポキシ硬化剤（Ｄ）が有する活性水素基のモル数の比が、０．５以上１．５以下である、〔Ａ１〕または〔Ａ２〕に記載の硬化性樹脂組成物。 [A3] The ratio of the number of moles of the epoxy group of the epoxy resin (A) to the number of moles of the active hydrogen group of the epoxy curing agent (D) is 0.5 or more and 1.5 or less [A1]. Alternatively, the curable resin composition according to [A2].

　〔Ａ４〕前記エポキシ樹脂（Ａ）が、ビスフェノールＡ型エポキシ樹脂および／またはビスフェノールＦ型エポキシ樹脂である、〔Ａ１〕～〔Ａ３〕のいずれか１つに記載の硬化性樹脂組成物。 [A4] The curable resin composition according to any one of [A1] to [A3], wherein the epoxy resin (A) is a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin.

　〔Ａ５〕前記エポキシ硬化剤（Ｄ）が、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、からなる群より選択される１種以上のアミン硬化剤またはその変性物である、〔Ａ１〕～〔Ａ４〕のいずれか１つに記載の硬化性樹脂組成物。 [A5] One or more amine curing agents selected from the group consisting of an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, and an amine-terminated butadiene nitrile rubber, or a curing agent thereof. The curable resin composition according to any one of [A1] to [A4], which is a modified product.

　〔Ａ６〕前記エポキシ樹脂（Ａ）１００重量部に対する前記コアシェルポリマー粒子（Ｂ）の配合量が、１重量部以上１００重量部以下である、〔Ａ１〕～〔Ａ５〕のいずれか１つに記載の硬化性樹脂組成物。 [A6] Described in any one of [A1] to [A5], wherein the blending amount of the core-shell polymer particles (B) with respect to 100 parts by weight of the epoxy resin (A) is 1 part by weight or more and 100 parts by weight or less. Curable resin composition.

　〔Ａ７〕前記エポキシ樹脂（Ａ）１００重量部に対する前記水酸化アルミニウム（Ｃ）の配合量が、２５０重量部以上７５０重量部以下である、〔Ａ１〕～〔Ａ６〕のいずれか１つに記載の硬化性樹脂組成物。 [A7] Described in any one of [A1] to [A6], wherein the blending amount of the aluminum hydroxide (C) with respect to 100 parts by weight of the epoxy resin (A) is 250 parts by weight or more and 750 parts by weight or less. Curable resin composition.

　〔Ａ８〕前記エポキシ樹脂（Ａ）１００重量部に対する前記エポキシ硬化剤（Ｄ）の配合量が、１５重量部以上３００重量部以下である、〔Ａ１〕～〔Ａ７〕のいずれか１つに記載の硬化性樹脂組成物。 [A8] Described in any one of [A1] to [A7], wherein the blending amount of the epoxy curing agent (D) with respect to 100 parts by weight of the epoxy resin (A) is 15 parts by weight or more and 300 parts by weight or less. Curable resin composition.

　〔Ａ９〕前記第一成分および／または前記第二成分に、更に、エポキシ硬化促進剤（Ｅ）を含有する、〔Ａ１〕～〔Ａ８〕のいずれか１つに記載の硬化性樹脂組成物。 [A9] The curable resin composition according to any one of [A1] to [A8], which further contains an epoxy curing accelerator (E) in the first component and / or the second component.

　〔Ａ１０〕前記第一成分および／または前記第二成分に、更に、シランカップリング剤（Ｆ）を含有する、〔Ａ１〕～〔Ａ９〕のいずれか１つに記載の硬化性樹脂組成物。 [A10] The curable resin composition according to any one of [A1] to [A9], which further contains a silane coupling agent (F) in the first component and / or the second component.

　〔Ａ１１〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、ジエン系ゴム、（メタ）アクリレート系ゴム、及びオルガノシロキサン系ゴムからなる群より選択される１種以上のコア層を有する、〔Ａ１〕～〔Ａ１０〕のいずれか１つに記載の硬化性樹脂組成物。 [A11] The polymer particles (B) having a core-shell structure have one or more core layers selected from the group consisting of a diene-based rubber, a (meth) acrylate-based rubber, and an organosiloxane-based rubber [A1]. The curable resin composition according to any one of [A10].

　〔Ａ１２〕前記コアシェル構造を有するポリマー粒子（Ｂ）がジエン系ゴムを有し、前記ジエン系ゴムが、ブタジエンゴム、および／または、ブタジエン－スチレンゴムである、〔Ａ１１〕に記載の硬化性樹脂組成物。 [A12] The curable resin according to [A11], wherein the polymer particles (B) having the core-shell structure have a diene-based rubber, and the diene-based rubber is a butadiene rubber and / or a butadiene-styrene rubber. Composition.

　〔Ａ１３〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、芳香族ビニルモノマー、ビニルシアンモノマー、及び（メタ）アクリレートモノマーからなる群より選択される１種以上のモノマー成分を、コア層にグラフト重合してなるシェル層を有する、〔Ａ１〕～〔Ａ１２〕のいずれか１つのいずれか１項に記載の硬化性樹脂組成物。 [A13] The polymer particles (B) having the core-shell structure are graft-polymerized on the core layer with one or more monomer components selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth) acrylate monomers. The curable resin composition according to any one of [A1] to [A12], which has a shell layer made of.

　〔Ａ１４〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、シェル層にエポキシ基を有する、〔Ａ１〕～〔Ａ１３〕のいずれか１つに記載の硬化性樹脂組成物。 [A14] The curable resin composition according to any one of [A1] to [A13], wherein the polymer particles (B) having the core-shell structure have an epoxy group in the shell layer.

　〔Ａ１５〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、エポキシ基を有するモノマー成分を、コア層にグラフト重合してなるシェル層を有する、〔Ａ１〕～〔Ａ１４〕のいずれか１つに記載の硬化性樹脂組成物。 [A15] Described in any one of [A1] to [A14], wherein the polymer particles (B) having a core-shell structure have a shell layer obtained by graft-polymerizing a monomer component having an epoxy group onto the core layer. Curable resin composition.

　〔Ａ１６〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、シェル層にエポキシ基を有し、前記シェル層の総量に対する、前記シェル層が有する前記エポキシ基の含有量が０．１～２．０ｍｍｏｌ／ｇ以下である、〔Ａ１〕～〔Ａ１５〕のいずれか１つに記載の硬化性樹脂組成物。 [A16] The polymer particles (B) having the core-shell structure have an epoxy group in the shell layer, and the content of the epoxy group in the shell layer is 0.1 to 2.0 mmol with respect to the total amount of the shell layer. The curable resin composition according to any one of [A1] to [A15], which is / g or less.

　〔Ａ１７〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、シェル層にエポキシ基を含有しない、〔Ａ１〕～〔Ａ１３〕のいずれか１つに記載の硬化性樹脂組成物。 [A17] The curable resin composition according to any one of [A1] to [A13], wherein the polymer particles (B) having the core-shell structure do not contain an epoxy group in the shell layer.

　〔Ａ１８〕〔Ａ１〕～〔Ａ１７〕のいずれか１つに記載の硬化性樹脂組成物が硬化した硬化物。 [A18] A cured product obtained by curing the curable resin composition according to any one of [A1] to [A17].

　〔Ａ１９〕〔Ａ１〕～〔Ａ１７〕のいずれか１つに記載の硬化性樹脂組成物を含む接着剤。 [A19] An adhesive containing the curable resin composition according to any one of [A1] to [A17].

　〔Ａ２０〕前記接着剤が二次電池用接着剤である、〔Ａ１９〕に記載の接着剤。 [A20] The adhesive according to [A19], wherein the adhesive is an adhesive for a secondary battery.

　〔Ａ２１〕２枚の基材と、該２枚の基材を接合する、〔Ａ１９〕又は〔Ａ２０〕に記載の接着剤が硬化した接着層とを含む、積層体。 [A21] A laminate comprising two base materials and an adhesive layer obtained by joining the two base materials and having the adhesive according to [A19] or [A20] cured.

　本発明の一実施形態は、以下のような構成であってもよい。 One embodiment of the present invention may have the following configuration.

　〔Ｂ１〕エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含む二成分型の硬化性樹脂組成物であって、前記硬化性樹脂組成物は、更に、コアシェル構造を有するポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）を含有し、前記硬化性樹脂組成物の総重量に対する前記水酸化アルミニウム（Ｃ）の総重量が、５５重量％以上８５重量％以下で前記コアシェル構造を有するポリマー粒子（Ｂ）の平均粒子径が、０．１５μｍ以上０．３０μｍ以下であり、前記コアシェル構造を有するポリマー粒子（Ｂ）のコア層／シェル層の重量比が、６５／３５～９２／８であり、前記コアシェル構造を有するポリマー粒子（Ｂ）が、シェル層が炭素数１～４のアルキル（メタ）アクリレートを５５ｗｔ％以上含有するモノマー成分の共重合体であり、前記シェル層を構成するモノマー成分として、炭素数１のアルキル（メタ）アクリレートを１０～１００ｗｔ％、炭素数４のアルキル（メタ）アクリレートを０～８０ｗｔ％含有する、硬化性樹脂組成物。 [B1] A two-component curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D). The product further contains polymer particles (B) having a core-shell structure and aluminum hydroxide (C), and the total weight of the aluminum hydroxide (C) is 55% by weight based on the total weight of the curable resin composition. The average particle size of the polymer particles (B) having the core-shell structure of 85% by weight or less is 0.15 μm or more and 0.30 μm or less, and the core layer / shell layer of the polymer particles (B) having the core-shell structure. The weight ratio is 65/35 to 92/8, and the polymer particles (B) having the core-shell structure include a monomer component in which the shell layer contains 55 wt% or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms. A curable resin which is a polymer and contains 10 to 100 wt% of an alkyl (meth) acrylate having 1 carbon atom and 0 to 80 wt% of an alkyl (meth) acrylate having 4 carbon atoms as a monomer component constituting the shell layer. Composition.

　〔Ｂ２〕前記コアシェル構造を有するポリマー粒子（Ｂ）および前記水酸化アルミニウム（Ｃ）は、各々、前記第一成分および／または前記第二成分に含有される、〔Ｂ１〕に記載の硬化性樹脂組成物。 [B2] The curable resin according to [B1], wherein the polymer particles (B) having the core-shell structure and the aluminum hydroxide (C) are contained in the first component and / or the second component, respectively. Composition.

　〔Ｂ３〕前記エポキシ樹脂（Ａ）が有するエポキシ基のモル数／前記エポキシ硬化剤（Ｄ）が有する活性水素基のモル数の比が、０．５以上１．５以下である、〔Ｂ１〕または〔Ｂ２〕に記載の硬化性樹脂組成物。 [B3] The ratio of the number of moles of the epoxy group of the epoxy resin (A) to the number of moles of the active hydrogen group of the epoxy curing agent (D) is 0.5 or more and 1.5 or less [B1]. Alternatively, the curable resin composition according to [B2].

　〔Ｂ４〕前記エポキシ樹脂（Ａ）が、ビスフェノールＡ型エポキシ樹脂および／またはビスフェノールＦ型エポキシ樹脂である、〔Ｂ１〕～〔Ｂ３〕のいずれか１つに記載の硬化性樹脂組成物。 [B4] The curable resin composition according to any one of [B1] to [B3], wherein the epoxy resin (A) is a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin.

　〔Ｂ５〕前記エポキシ硬化剤（Ｄ）が、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、からなる群より選択される１種以上のアミン硬化剤またはその変性物である、〔Ｂ１〕～〔Ｂ４〕のいずれか１つに記載の硬化性樹脂組成物。 [B5] One or more amine curing agents selected from the group consisting of an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, and an amine-terminated butadiene nitrile rubber, or a curing agent thereof. The curable resin composition according to any one of [B1] to [B4], which is a modified product.

　〔Ｂ６〕前記エポキシ樹脂（Ａ）１００重量部に対する前記コアシェルポリマー粒子（Ｂ）の配合量が、１重量部以上１００重量部以下である、〔Ｂ１〕～〔Ｂ５〕のいずれか１つに記載の硬化性樹脂組成物。 [B6] Described in any one of [B1] to [B5], wherein the blending amount of the core-shell polymer particles (B) with respect to 100 parts by weight of the epoxy resin (A) is 1 part by weight or more and 100 parts by weight or less. Curable resin composition.

　〔Ｂ７〕前記エポキシ樹脂（Ａ）１００重量部に対する前記水酸化アルミニウム（Ｃ）の配合量が、２５０重量部以上７５０重量部以下である、〔Ｂ１〕～〔Ｂ６〕のいずれか１つに記載の硬化性樹脂組成物。 [B7] Described in any one of [B1] to [B6], wherein the blending amount of the aluminum hydroxide (C) with respect to 100 parts by weight of the epoxy resin (A) is 250 parts by weight or more and 750 parts by weight or less. Curable resin composition.

　〔Ｂ８〕前記エポキシ樹脂（Ａ）１００重量部に対する前記エポキシ硬化剤（Ｄ）の配合量が、１５重量部以上３００重量部以下である、〔Ｂ１〕～〔Ｂ７〕のいずれか１つに記載の硬化性樹脂組成物。 [B8] Described in any one of [B1] to [B7], wherein the blending amount of the epoxy curing agent (D) with respect to 100 parts by weight of the epoxy resin (A) is 15 parts by weight or more and 300 parts by weight or less. Curable resin composition.

　〔Ｂ９〕前記第一成分および／または前記第二成分に、更に、エポキシ硬化促進剤（Ｅ）を含有する、〔Ｂ１〕～〔Ｂ８〕のいずれか１つに記載の硬化性樹脂組成物。 [B9] The curable resin composition according to any one of [B1] to [B8], which further contains an epoxy curing accelerator (E) in the first component and / or the second component.

　〔Ｂ１０〕前記第一成分および／または前記第二成分に、更に、シランカップリング剤（Ｆ）を含有する、〔Ｂ１〕～〔Ｂ９〕のいずれか１つに記載の硬化性樹脂組成物。 [B10] The curable resin composition according to any one of [B1] to [B9], which further contains a silane coupling agent (F) in the first component and / or the second component.

　〔Ｂ１１〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、ジエン系ゴム、（メタ）アクリレート系ゴム、及びオルガノシロキサン系ゴムからなる群より選択される１種以上のコア層を有する、〔Ｂ１〕～〔Ｂ１０〕のいずれか１つに記載の硬化性樹脂組成物。 [B11] The polymer particles (B) having a core-shell structure have one or more core layers selected from the group consisting of a diene-based rubber, a (meth) acrylate-based rubber, and an organosiloxane-based rubber [B1]. The curable resin composition according to any one of [B10].

　〔Ｂ１２〕前記コアシェル構造を有するポリマー粒子（Ｂ）がジエン系ゴムを有し、前記ジエン系ゴムが、ブタジエンゴム、および／または、ブタジエン－スチレンゴムである、〔Ｂ１１〕に記載の硬化性樹脂組成物。 [B12] The curable resin according to [B11], wherein the polymer particles (B) having the core-shell structure have a diene-based rubber, and the diene-based rubber is a butadiene rubber and / or a butadiene-styrene rubber. Composition.

　〔Ｂ１３〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、芳香族ビニルモノマー、ビニルシアンモノマー、及び（メタ）アクリレートモノマーからなる群より選択される１種以上のモノマー成分を、コア層にグラフト重合してなるシェル層を有する、〔Ｂ１〕～〔Ｂ１２〕のいずれか１つに記載の硬化性樹脂組成物。 [B13] The polymer particles (B) having the core-shell structure are graft-polymerized with one or more monomer components selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth) acrylate monomers on the core layer. The curable resin composition according to any one of [B1] to [B12], which has a shell layer made of.

　〔Ｂ１４〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、シェル層にエポキシ基を有する、〔Ｂ１〕～〔Ｂ１３〕のいずれか１つに記載の硬化性樹脂組成物。 [B14] The curable resin composition according to any one of [B1] to [B13], wherein the polymer particles (B) having the core-shell structure have an epoxy group in the shell layer.

　〔Ｂ１５〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、エポキシ基を有するモノマー成分を、コア層にグラフト重合してなるシェル層を有する、〔Ｂ１〕～〔Ｂ１４〕のいずれか１つに記載の硬化性樹脂組成物。 [B15] Described in any one of [B1] to [B14], wherein the polymer particles (B) having a core-shell structure have a shell layer obtained by graft-polymerizing a monomer component having an epoxy group onto the core layer. Curable resin composition.

　〔Ｂ１６〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、シェル層にエポキシ基を有し、前記シェル層の総量に対する、前記シェル層が有する前記エポキシ基の含有量が０．１～２．０ｍｍｏｌ／ｇ以下である、〔Ｂ１〕～〔Ｂ１５〕のいずれか１つに記載の硬化性樹脂組成物。 [B16] The polymer particles (B) having the core-shell structure have an epoxy group in the shell layer, and the content of the epoxy group in the shell layer is 0.1 to 2.0 mmol with respect to the total amount of the shell layer. The curable resin composition according to any one of [B1] to [B15], which is / g or less.

　〔Ｂ１７〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、シェル層にエポキシ基を含有しない、〔Ｂ１〕～〔Ｂ１３〕のいずれか１つに記載の硬化性樹脂組成物。 [B17] The curable resin composition according to any one of [B1] to [B13], wherein the polymer particles (B) having the core-shell structure do not contain an epoxy group in the shell layer.

　〔Ｂ１８〕〔Ｂ１〕～〔Ｂ１７〕のいずれか１つに記載の硬化性樹脂組成物が硬化した硬化物。 A cured product obtained by curing the curable resin composition according to any one of [B18], [B1] to [B17].

　〔Ｂ１９〕〔Ｂ１〕～〔Ｂ１７〕のいずれか１つに記載の硬化性樹脂組成物を含む接着剤。 An adhesive containing the curable resin composition according to any one of [B19] and [B1] to [B17].

　〔Ｂ２０〕前記接着剤が二次電池用接着剤である、〔Ｂ１９〕に記載の接着剤。 [B20] The adhesive according to [B19], wherein the adhesive is an adhesive for a secondary battery.

　〔Ｂ２１〕２枚の基材と、該２枚の基材を接合する、〔Ｂ１９〕又は〔Ｂ２０〕に記載の接着剤が硬化した接着層とを含む、積層体。 [B21] A laminate comprising two base materials and an adhesive layer obtained by joining the two base materials and having the adhesive according to [B19] or [B20] cured.

　本発明の一実施形態は、以下のような構成であってもよい。 One embodiment of the present invention may have the following configuration.

　〔Ｃ１〕エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含む二成分型または多成分型の硬化性樹脂組成物であって、前記硬化性樹脂組成物は、更に、コア層とシェル層とを含むコアシェル構造を有するポリマー粒子（Ｂ）と、１分子中に（ｉ）１個の芳香環、および（ｉｉ）少なくとも２個のフェノール性水酸基を有する化合物（Ｇ）と、を含有し、前記化合物（Ｇ）において、前記フェノール性水酸基に対してオルト位に位置する第三級アルキル基の個数は、１分子中に０個又は１個であり、前記エポキシ硬化剤（Ｄ）が、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上である、硬化性樹脂組成物。 [C1] A two-component or multi-component curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D). The curable resin composition further comprises a polymer particle (B) having a core-shell structure including a core layer and a shell layer, (i) one aromatic ring in one molecule, and (ii) at least two phenols. The number of tertiary alkyl groups contained in the compound (G) having a sex hydroxyl group and located at the ortho position with respect to the phenolic hydroxyl group in the compound (G) is 0 or 1 in one molecule. The epoxy curing agent (D) is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified product of an aliphatic amine, or a modified product of an alicyclic amine. A curable resin composition which is at least one selected from the group consisting of a modified product of amidamine, a modified product of an amine-terminated polyether, and a modified product of an amine-terminated butadiene nitrile rubber.

　〔Ｃ２〕前記エポキシ樹脂（Ａ）が有するエポキシ基のモル数と前記エポキシ硬化剤（Ｄ）が有する活性水素基のモル数との比（前記エポキシ基のモル数／前記活性水素基のモル数）が、０．５以上１．６以下である、〔Ｃ１〕に記載の硬化性樹脂組成物。 [C2] The ratio of the number of moles of the epoxy group of the epoxy resin (A) to the number of moles of the active hydrogen group of the epoxy curing agent (D) (number of moles of the epoxy group / number of moles of the active hydrogen group). ) Is 0.5 or more and 1.6 or less, the curable resin composition according to [C1].

　〔Ｃ３〕前記エポキシ樹脂（Ａ）が、ビスフェノールＡ型エポキシ樹脂および／またはビスフェノールＦ型エポキシ樹脂である、〔Ｃ１〕または〔Ｃ２〕に記載の硬化性樹脂組成物。 [C3] The curable resin composition according to [C1] or [C2], wherein the epoxy resin (A) is a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin.

　〔Ｃ４〕前記エポキシ硬化剤（Ｄ）が、脂環族アミン、アミン末端ブタジエンニトリルゴム、脂環族アミンの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上である、〔Ｃ１〕～〔Ｃ３〕のいずれか１つに記載の硬化性樹脂組成物。 [C4] The epoxy curing agent (D) is at least one selected from the group consisting of alicyclic amines, amine-terminated butadiene nitrile rubbers, modified alicyclic amines, and modified amine-terminated butadiene nitrile rubbers. The curable resin composition according to any one of [C1] to [C3].

　〔Ｃ５〕前記エポキシ樹脂（Ａ）１００重量部に対する前記ポリマー粒子（Ｂ）の含有量が、１重量部以上１００重量部以下である、〔Ｃ１〕～〔Ｃ４〕のいずれか１つに記載の硬化性樹脂組成物。 [C5] The invention according to any one of [C1] to [C4], wherein the content of the polymer particles (B) with respect to 100 parts by weight of the epoxy resin (A) is 1 part by weight or more and 100 parts by weight or less. Curable resin composition.

　〔Ｃ６〕前記第一成分および／または前記第二成分が、更に、水酸化アルミニウム（Ｃ）を含有する、〔Ｃ１〕～〔Ｃ５〕のいずれか１つに記載の硬化性樹脂組成物。 [C6] The curable resin composition according to any one of [C1] to [C5], wherein the first component and / or the second component further contains aluminum hydroxide (C).

　〔Ｃ７〕前記硬化性樹脂組成物における、前記エポキシ樹脂（Ａ）１００重量部に対する前記エポキシ硬化剤（Ｄ）の含有量が、１５重量部以上３００重量部以下である、〔Ｃ１〕～〔Ｃ６〕のいずれか１つに記載の硬化性樹脂組成物。 [C7] The content of the epoxy curing agent (D) in 100 parts by weight of the epoxy resin (A) in the curable resin composition is 15 parts by weight or more and 300 parts by weight or less, [C1] to [C6]. ] The curable resin composition according to any one of.

　〔Ｃ８〕前記硬化性樹脂組成物における、前記エポキシ樹脂（Ａ）１００重量部に対する前記水酸化アルミニウム（Ｃ）の含有量が、２５０重量部以上７５０重量部以下である、〔Ｃ６〕に記載の硬化性樹脂組成物。 [C8] The content of the aluminum hydroxide (C) in 100 parts by weight of the epoxy resin (A) in the curable resin composition is 250 parts by weight or more and 750 parts by weight or less, according to [C6]. Curable resin composition.

　〔Ｃ９〕前記第一成分および／または前記第二成分が、更に、シランカップリング剤（Ｆ）を含有する、〔Ｃ１〕～〔Ｃ８〕のいずれか１つに記載の硬化性樹脂組成物。 [C9] The curable resin composition according to any one of [C1] to [C8], wherein the first component and / or the second component further contains a silane coupling agent (F).

　〔Ｃ１０〕前記第一成分が、更に、エポキシシランカップリング剤（Ｆ１）を含有する、〔Ｃ１〕～〔Ｃ９〕のいずれか１つに記載の硬化性樹脂組成物。 [C10] The curable resin composition according to any one of [C1] to [C9], wherein the first component further contains an epoxysilane coupling agent (F1).

　〔Ｃ１１〕前記シェル層がエポキシ基を有する、〔Ｃ１〕～〔Ｃ１０〕のいずれか１つに記載の硬化性樹脂組成物。 [C11] The curable resin composition according to any one of [C1] to [C10], wherein the shell layer has an epoxy group.

　〔Ｃ１２〕前記シェル層が、エポキシ基を有するモノマー成分を、前記コア層にグラフト重合してなる重合体である、〔Ｃ１〕～〔Ｃ１１〕のいずれか１つに記載の硬化性樹脂組成物。 [C12] The curable resin composition according to any one of [C1] to [C11], wherein the shell layer is a polymer obtained by graft-polymerizing a monomer component having an epoxy group onto the core layer. ..

　〔Ｃ１３〕前記シェル層がエポキシ基を有し、
　前記シェル層の総重量に対する、前記シェル層が有する前記エポキシ基の含有量が０ｍｍｏｌ／ｇを超えて２．０ｍｍｏｌ／ｇ以下である、〔Ｃ１〕～〔Ｃ１２〕のいずれか１つに記載の硬化性樹脂組成物。 [C13] The shell layer has an epoxy group and has an epoxy group.
The invention according to any one of [C1] to [C12], wherein the content of the epoxy group contained in the shell layer with respect to the total weight of the shell layer is more than 0 mmol / g and 2.0 mmol / g or less. Curable resin composition.

　〔Ｃ１４〕前記シェル層がエポキシ基を有しない、〔Ｃ１〕～〔Ｃ１３〕のいずれか１つに記載の硬化性樹脂組成物。 [C14] The curable resin composition according to any one of [C1] to [C13], wherein the shell layer does not have an epoxy group.

　〔Ｃ１５〕前記化合物（Ｇ）は、前記芳香環上に前記フェノール性水酸基以外の置換基を有さない、〔Ｃ１〕～〔Ｃ１４〕のいずれか１つに記載の硬化性樹脂組成物。 [C15] The curable resin composition according to any one of [C1] to [C14], wherein the compound (G) has no substituent other than the phenolic hydroxyl group on the aromatic ring.

　〔Ｃ１６〕〔Ｃ１〕～〔Ｃ１５〕のいずれか１つに記載の硬化性樹脂組成物が硬化してなる、硬化物。 [C16] A cured product obtained by curing the curable resin composition according to any one of [C1] to [C15].

　〔Ｃ１７〕〔Ｃ１〕～〔Ｃ１５〕のいずれか１つに記載の硬化性樹脂組成物を含む、接着剤。 An adhesive containing the curable resin composition according to any one of [C17] [C1] to [C15].

　〔Ｃ１８〕前記接着剤が二次電池用接着剤である、〔Ｃ１７〕に記載の接着剤。 [C18] The adhesive according to [C17], wherein the adhesive is an adhesive for a secondary battery.

　〔Ｃ１９〕２枚の基材と、該２枚の基材の間に、〔Ｃ１７〕又は〔Ｃ１８〕に記載の接着剤が硬化してなる接着層と、を含む、積層体。 [C19] A laminate comprising two base materials and an adhesive layer obtained by curing the adhesive according to [C17] or [C18] between the two base materials.

　本発明の一実施形態は、以下のような構成であってもよい。 One embodiment of the present invention may have the following configuration.

　〔Ｘ１〕二成分型の硬化性樹脂組成物であって、エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含み、前記硬化性樹脂組成物は、更に、コア層とシェル層とを含むコアシェル構造を有するポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）とを含有し、前記硬化性樹脂組成物の総重量１００重量％における前記水酸化アルミニウム（Ｃ）の総重量が、５５重量％以上８５重量％以下であり、前記水酸化アルミニウム（Ｃ）の平均粒子径が、１１μｍ以上２００μｍ以下である、硬化性樹脂組成物。 [X1] A two-component curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D), and the curable resin. The composition further contains polymer particles (B) having a core-shell structure including a core layer and a shell layer, and aluminum hydroxide (C), and the water in 100% by weight of the total weight of the curable resin composition. A curable resin composition having a total weight of aluminum oxide (C) of 55% by weight or more and 85% by weight or less, and an average particle size of aluminum hydroxide (C) of 11 μm or more and 200 μm or less.

　〔Ｘ２〕前記ポリマー粒子（Ｂ）の平均粒子径が、０．１５μｍ以上０．３０μｍ以下であり、前記ポリマー粒子（Ｂ）における、前記シェル層の重量に対する前記コア層の重量の比（前記コア層の重量／前記シェル層の重量）が、６５／３５～９２／８であり、前記ポリマー粒子（Ｂ）の前記シェル層が、モノマー成分１００重量％中炭素数１～４のアルキル（メタ）アクリレートを５５ｗｔ％以上含有する当該モノマー成分を重合してなる共重合体であり、前記モノマー成分は、当該モノマー成分１００重量％中、炭素数１のアルキル（メタ）アクリレートを１０～１００ｗｔ％および炭素数４のアルキル（メタ）アクリレートを０～８０ｗｔ％含有する、〔Ｘ１〕に記載の硬化性樹脂組成物。 [X2] The average particle size of the polymer particles (B) is 0.15 μm or more and 0.30 μm or less, and the ratio of the weight of the core layer to the weight of the shell layer in the polymer particles (B) (the core). The weight of the layer / the weight of the shell layer) is 65/35 to 92/8, and the shell layer of the polymer particles (B) is an alkyl (meth) having 100% by weight of the monomer component and 1 to 4 carbon atoms in the monomer component. It is a copolymer obtained by polymerizing the monomer component containing 55 wt% or more of acrylate, and the monomer component contains 10 to 100 wt% of an alkyl (meth) acrylate having 1 carbon atom and carbon in 100% by weight of the monomer component. The curable resin composition according to [X1], which contains 0 to 80 wt% of an alkyl (meth) acrylate of number 4.

　〔Ｘ３〕前記エポキシ硬化剤（Ｄ）が、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される１種以上である、〔Ｘ１〕または〔Ｘ２〕に記載の硬化性樹脂組成物。 [X3] The epoxy curing agent (D) contains an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified aliphatic amine, a modified alicyclic amine, and an amidoamine. The curable resin composition according to [X1] or [X2], which is one or more selected from the group consisting of a modified product of an amine-terminated polyether, a modified product of an amine-terminated butadiene nitrile rubber, and a modified product of an amine-terminated butadiene nitrile rubber.

　〔Ｘ４〕前記硬化性樹脂組成物は、更に、１分子中に（ｉ）１個の芳香環、および（ｉｉ）少なくとも２個のフェノール性水酸基を有する化合物（Ｇ）、を含有し、前記化合物（Ｇ）において、前記フェノール性水酸基に対してオルト位に位置する第三級アルキル基の個数は、１分子中に０個又は１個であり、前記エポキシ硬化剤（Ｄ）が、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上である、〔Ｘ１〕または〔Ｘ２〕に記載の硬化性樹脂組成物。 [X4] The curable resin composition further contains (i) one aromatic ring and (ii) a compound (G) having at least two phenolic hydroxyl groups in one molecule, and the compound. In (G), the number of tertiary alkyl groups located at the ortho position with respect to the phenolic hydroxyl group is 0 or 1 in one molecule, and the epoxy curing agent (D) is an aliphatic amine. , Alicyclic amines, amidamines, amine-terminated polyethers, amine-terminated butadiene nitrile rubbers, modified aliphatic amines, modified alicyclic amines, modified amidamines, modified amine-terminated polyethers and amine-terminated butadiene The curable resin composition according to [X1] or [X2], which is at least one selected from the group consisting of modified products of nitrile rubber.

　〔Ｘ５〕前記エポキシ硬化剤（Ｄ）が有する活性水素基のモル数に対する前記エポキシ樹脂（Ａ）が有するエポキシ基のモル数の比（前記エポキシ樹脂（Ａ）が有するエポキシ基のモル数／前記エポキシ硬化剤（Ｄ）が有する活性水素基のモル数）が、０．５以上１．５以下である、〔Ｘ１〕～〔Ｘ４〕のいずれか１つに記載の硬化性樹脂組成物。 [X5] The ratio of the number of moles of the epoxy group of the epoxy resin (A) to the number of moles of the active hydrogen group of the epoxy curing agent (D) (the number of moles of the epoxy group of the epoxy resin (A) / the said The curable resin composition according to any one of [X1] to [X4], wherein the epoxy curing agent (D) has a molar number of active hydrogen groups of 0.5 or more and 1.5 or less.

　〔Ｘ６〕前記ポリマー粒子（Ｂ）が、前記コア層にジエン系ゴムを有し、前記ジエン系ゴムが、ブタジエンゴム、および／または、ブタジエン－スチレンゴムである、〔Ｘ１〕～〔Ｘ５〕のいずれか１つに記載の硬化性樹脂組成物。 [X6] Of [X1] to [X5], the polymer particles (B) have a diene-based rubber in the core layer, and the diene-based rubber is a butadiene rubber and / or a butadiene-styrene rubber. The curable resin composition according to any one.

　〔Ｘ７〕前記コアシェル構造を有するポリマー粒子（Ｂ）が、シェル層にエポキシ基を有する、〔Ｘ１〕～〔Ｘ６〕のいずれか１つに記載の硬化性樹脂組成物。 [X7] The curable resin composition according to any one of [X1] to [X6], wherein the polymer particles (B) having the core-shell structure have an epoxy group in the shell layer.

　〔Ｘ８〕前記ポリマー粒子（Ｂ）が、前記シェル層にエポキシ基を有し、前記シェル層の総量に対する、前記シェル層が有する前記エポキシ基の含有量が０．１～２．０ｍｍｏｌ／ｇ以下である、〔Ｘ１〕～〔Ｘ７〕のいずれか１つに記載の硬化性樹脂組成物。 [X8] The polymer particles (B) have an epoxy group in the shell layer, and the content of the epoxy group in the shell layer is 0.1 to 2.0 mmol / g or less with respect to the total amount of the shell layer. The curable resin composition according to any one of [X1] to [X7].

　〔Ｘ９〕前記ポリマー粒子（Ｂ）が、前記シェル層にエポキシ基を含有しない、〔Ｘ１〕～〔Ｘ６〕のいずれか１つに記載の硬化性樹脂組成物。 [X9] The curable resin composition according to any one of [X1] to [X6], wherein the polymer particles (B) do not contain an epoxy group in the shell layer.

　〔Ｘ１０〕〔Ｘ１〕～〔Ｘ９〕のいずれか１つに記載の硬化性樹脂組成物を硬化してなる、硬化物。 A cured product obtained by curing the curable resin composition according to any one of [X10] [X1] to [X9].

　〔Ｘ１１〕〔Ｘ１〕～〔Ｘ９〕のいずれか１つに記載の硬化性樹脂組成物を含む、接着剤。 An adhesive containing the curable resin composition according to any one of [X11] [X1] to [X9].

　〔Ｘ１２〕前記接着剤が二次電池用接着剤である、〔Ｘ１１〕に記載の接着剤。 [X12] The adhesive according to [X11], wherein the adhesive is an adhesive for a secondary battery.

　〔Ｘ１３〕２枚の基材と、〔Ｘ１２〕に記載の接着剤を硬化してなる接着層とを含み、前記接着層は、前記２枚の基材を接合している、積層体。 [X13] A laminated body containing two base materials and an adhesive layer obtained by curing the adhesive according to [X12], wherein the adhesive layer is a bonding of the two base materials.

　〔Ｘ１４〕二成分型の硬化性樹脂組成物であって、
　エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含み、
　前記硬化性樹脂組成物は、更に、コア層とシェル層とを含むコアシェル構造を有するポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）とを含有し、前記硬化性樹脂組成物の総重量１００重量％における前記水酸化アルミニウム（Ｃ）の総重量が、５５重量％以上８５重量％以下であり、前記ポリマー粒子（Ｂ）の平均粒子径が、０．１５μｍ以上０．３０μｍ以下であり、前記ポリマー粒子（Ｂ）における、前記シェル層の重量に対する前記コア層の重量の比（前記コア層の重量／前記シェル層の重量）が、６５／３５～９２／８であり、前記ポリマー粒子（Ｂ）の前記シェル層が、モノマー成分１００重量％中炭素数１～４のアルキル（メタ）アクリレートを５５ｗｔ％以上含有する当該モノマー成分を重合してなる共重合体であり、前記モノマー成分は、当該モノマー成分１００重量％中、炭素数１のアルキル（メタ）アクリレートを１０～１００ｗｔ％および炭素数４のアルキル（メタ）アクリレートを０～８０ｗｔ％含有する、硬化性樹脂組成物。 [X14] A two-component curable resin composition.
It contains a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
The curable resin composition further contains polymer particles (B) having a core-shell structure including a core layer and a shell layer and aluminum hydroxide (C), and the total weight of the curable resin composition is 100 weight. The total weight of the aluminum hydroxide (C) in% is 55% by weight or more and 85% by weight or less, the average particle size of the polymer particles (B) is 0.15 μm or more and 0.30 μm or less, and the polymer. The ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer / weight of the shell layer) in the particles (B) is 65/35 to 92/8, and the polymer particles (B) The shell layer is a copolymer obtained by polymerizing the monomer component containing 55 wt% or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of the monomer component, and the monomer component is the monomer. A curable resin composition containing 10 to 100 wt% of an alkyl (meth) acrylate having 1 carbon atom and 0 to 80 wt% of an alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the component.

　〔Ｘ１５〕二成分型または多成分型の硬化性樹脂組成物であって、エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含み、前記硬化性樹脂組成物は、更に、コア層とシェル層とを含むコアシェル構造を有するポリマー粒子（Ｂ）と、１分子中に（ｉ）１個の芳香環、および（ｉｉ）少なくとも２個のフェノール性水酸基を有する化合物（Ｇ）と、を含有し、前記化合物（Ｇ）において、前記フェノール性水酸基に対してオルト位に位置する第三級アルキル基の個数は、１分子中に０個又は１個であり、前記エポキシ硬化剤（Ｄ）が、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上である、硬化性樹脂組成物。 [X15] A two-component or multi-component curable resin composition containing a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D). The curable resin composition further comprises a polymer particle (B) having a core-shell structure including a core layer and a shell layer, (i) one aromatic ring in one molecule, and (ii) at least two. The number of tertiary alkyl groups contained in the compound (G) having a phenolic hydroxyl group and located at the ortho position with respect to the phenolic hydroxyl group in the compound (G) is 0 or 0 in one molecule. The epoxy curing agent (D) is one, and the epoxy curing agent (D) is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified product of an aliphatic amine, or a modified product of an alicyclic amine. , A curable resin composition which is at least one selected from the group consisting of a modified product of an amidamine, a modified product of an amine-terminated polyether and a modified product of an amine-terminated butadiene nitrile rubber.

　〔実施例Ａ〕
　以下に実施例Ａを掲げて第１実施形態をさらに詳細に説明するが、本発明はこれら実施例Ａに限定されるものではない。 [Example A]
The first embodiment will be described in more detail below with reference to Example A, but the present invention is not limited to these Examples A.

　（体積平均粒子径の測定）
　製造例に記載されたポリブタジエンゴムラテックス中のポリブタジエンゴム粒子、及び、コアシェルポリマーラテックス中のコアシェルポリマー粒子（Ｂ）について、以下の方法により、それぞれの平均粒子径を測定した。水性ラテックスに分散している粒子の体積平均粒子径（Ｍｖ）は、マイクロトラックＵＰＡ１５０（日機装株式会社製）を用いて測定した。脱イオン水で希釈したものを測定試料として用いた。測定は、水の屈折率、およびそれぞれのコアシェルポリマー粒子（Ｂ）の屈折率を入力し、計測時間６００秒、Ｓｉｇｎａｌ　Ｌｅｖｅｌが０．６～０．８の範囲内になるように試料濃度を調整して行った。 (Measurement of volume average particle size)
The average particle size of each of the polybutadiene rubber particles in the polybutadiene rubber latex described in the production example and the core-shell polymer particles (B) in the core-shell polymer latex was measured by the following method. The volume average particle diameter (Mv) of the particles dispersed in the aqueous latex was measured using Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.). A sample diluted with deionized water was used as a measurement sample. For the measurement, input the refractive index of water and the refractive index of each core-shell polymer particle (B), and adjust the sample concentration so that the measurement time is 600 seconds and the Signal Level is in the range of 0.6 to 0.8. I went there.

　Ａ１．コア層の形成
　製造例Ａ１；ポリブタジエンゴムラテックス（Ｒ－２）の調製
　耐圧重合機中に、水２００重量部、リン酸三カリウム０．０３重量部、エチレンジアミン四酢酸二ナトリウム（ＥＤＴＡ）０．００２重量部、硫酸第一鉄・７水和塩（ＦＥ）０．００１重量部、及び、ドデシルベンゼンスルホン酸ナトリウム（ＳＤＢＳ）１．５５重量部を投入し、撹拌しつつ十分に窒素置換を行なって酸素を除いた後、ブタジエン（Ｂｄ）１００重量部を系中に投入し、４５℃に昇温した。パラメンタンハイドロパーオキサイド（ＰＨＰ）０．０３重量部、続いてナトリウムホルムアルデヒドスルホキシレート（ＳＦＳ）０．１０重量部を投入し重合を開始した。重合開始から３、５、７時間目それぞれに、ＰＨＰ０．０２５重量部を投入した。また、重合開始４、６、８時間目それぞれに、ＥＤＴＡ０．０００６重量部、及びＦＥ０．００３重量部を投入した。重合１５時間目に減圧下残存モノマーを脱揮除去して重合を終了し、ポリブタジエンゴムを主成分とするポリブタジエンゴムラテックス（Ｒ－１）を得た。得られたラテックスに含まれるポリブタジエンゴム粒子の体積平均粒子径は８０ｎｍであった。 A1. Formation of core layer Production example A1; Preparation of polybutadiene rubber latex (R-2) 200 parts by weight of water, 0.03 parts by weight of tripotassium phosphate, 0.002 parts of disodium ethylenediamine tetraacetate (EDTA) in a pressure-resistant polymerizer. Add 0.001 part by weight of ferrous sulfate heptahydrate (FE) and 1.55 part by weight of sodium dodecylbenzene sulfonate (SDBS), and sufficiently replace with nitrogen while stirring. After removing oxygen, 100 parts by weight of butadiene (Bd) was added to the system and the temperature was raised to 45 ° C. 0.03 part by weight of paramentan hydroperoxide (PHP) and then 0.10 part by weight of sodium formaldehyde sulfoxylate (SFS) were added to initiate polymerization. 0.025 parts by weight of PHP was added at 3, 5 and 7 hours after the start of polymerization. Further, 0.0006 parts by weight of EDTA and 0.003 parts by weight of FE were added at 4, 6 and 8 hours after the start of polymerization, respectively. At the 15th hour of the polymerization, the residual monomer was volatilized and removed under reduced pressure to complete the polymerization, and a polybutadiene rubber latex (R-1) containing a polybutadiene rubber as a main component was obtained. The volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 80 nm.

　耐圧重合機中に、ポリブタジエンゴムラテックス（Ｒ－１）を２１重量部（ポリブタジエンゴム７重量部を含む）、脱イオン水１８５重量部、リン酸三カリウム０．０３重量部、ＥＤＴＡ０．００２重量部、及びＦＥ０．００１重量部を投入し、撹拌しつつ十分に窒素置換を行なって酸素を除いた後、Ｂｄ９３重量部を系中に投入し、４５℃に昇温した。ＰＨＰ０．０２重量部、続いてＳＦＳ０．１０重量部を投入し重合を開始した。重合開始から２４時間目まで３時間おきに、それぞれ、ＰＨＰ０．０２５重量部、及びＥＤＴＡ０．０００６重量部、及びＦＥ０．００３重量部を投入した。重合３０時間目に減圧下残存モノマーを脱揮除去して重合を終了し、ポリブタジエンゴムを主成分とするポリブタジエンゴムラテックス（Ｒ－２）を得た。得られたラテックスに含まれるポリブタジエンゴム粒子の体積平均粒子径は２００ｎｍであった。 21 parts by weight of polybutadiene rubber latex (R-1) (including 7 parts by weight of polybutadiene rubber), 185 parts by weight of deionized water, 0.03 parts by weight of tripotassium phosphate, 0.002 parts by weight of EDTA in a pressure-resistant polymerizer. , And 0.001 part by weight of FE was added, and after sufficient nitrogen substitution was performed while stirring to remove oxygen, 93 parts by weight of Bd was added into the system and the temperature was raised to 45 ° C. 0.02 part by weight of PHP and then 0.10 part by weight of SFS were added to initiate polymerization. From the start of polymerization to the 24th hour, 0.025 parts by weight of PHP, 0.0006 parts by weight of EDTA, and 0.003 parts by weight of FE were added every 3 hours, respectively. At the 30th hour of the polymerization, the residual monomer was volatilized and removed under reduced pressure to complete the polymerization, and a polybutadiene rubber latex (R-2) containing a polybutadiene rubber as a main component was obtained. The volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 200 nm.

　Ａ２．コアシェルポリマーラテックスの調製（シェル層の形成）
　製造例Ａ２－１；コアシェルポリマーラテックス（ＡＬ－１）の調製
　温度計、撹拌機、還流冷却器、窒素流入口、及びモノマーの添加装置を有するガラス反応器に、製造例Ａ１で調製したポリブタジエンゴムラテックス（Ｒ－２）２６２重量部（ポリブタジエンゴム粒子８７重量部を含む）、及び、脱イオン水５７重量部を仕込み、窒素置換を行いながら６０℃で撹拌した。ＥＤＴＡ０．００４重量部、ＦＥ０．００１重量部、及びＳＦＳ０．２重量部を加えた後、シェルモノマー（メチルメタクリレート（ＭＭＡ）４重量部、スチレン（ＳＴ）６重量部、アクリロニトリル（ＡＮ）２重量部、グリシジルメタクリレート（ＧＭＡ）１重量部）、及び、クメンヒドロパーオキサイド（ＣＨＰ）０．０４重量部の混合物を１２０分間かけて連続的に添加した。添加終了後、ＣＨＰ０．０４重量部を添加し、さらに２時間撹拌を続けて重合を完結させ、コアシェルポリマー粒子を含む水性ラテックス（ＡＬ－１）を得た。モノマー成分の重合転化率は９９％以上であった。水性ラテックス（ＡＬ－１）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は０．５ｍｍｏｌ／ｇである。 A2. Preparation of core-shell polymer latex (formation of shell layer)
Production Example A2-1; Preparation of core-shell polymer latex (AL-1) Polybutadiene rubber prepared in Production Example A1 in a glass reactor equipped with a thermometer, agitator, reflux condenser, nitrogen inlet, and monomer addition device. 262 parts by weight of latex (R-2) (including 87 parts by weight of polybutadiene rubber particles) and 57 parts by weight of deionized water were charged and stirred at 60 ° C. while performing nitrogen substitution. After adding 0.004 parts by weight of EDTA, 0.001 part by weight of FE, and 0.2 parts by weight of SFS, shell monomer (4 parts by weight of methyl methacrylate (MMA), 6 parts by weight of styrene (ST), 2 parts by weight of acrylonitrile (AN)). , 1 part by weight of glycidyl methacrylate (GMA)) and 0.04 part by weight of cumenhydroperoxide (CHP) were continuously added over 120 minutes. After completion of the addition, 0.04 part by weight of CHP was added, and the mixture was further stirred for 2 hours to complete the polymerization to obtain an aqueous latex (AL-1) containing core-shell polymer particles. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (AL-1) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0.5 mmol / g.

　製造例Ａ２－２；コアシェルポリマーラテックス（ＡＬ－２）の調製
　シェルモノマーをＭＭＡ５重量部、ＳＴ６重量部、ＡＮ２重量部に変えた以外は製造例Ａ２－１と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＡＬ－２）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＡＬ－２）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は０．０ｍｍｏｌ／ｇである。 Production Example A2-2; Preparation of Core-Shell Polymer Latex (AL-2) The same as Production Example A2-1 except that the shell monomer was changed to 5 parts by weight of MMA, 6 parts by weight of ST, and 2 parts by weight of AN, and an aqueous solution containing core-shell polymer particles. Latex (AL-2) was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (AL-2) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0.0 mmol / g.

　製造例Ａ２－３；コアシェルポリマーラテックス（ＡＬ－３）の調製
　シェルモノマーをＭＭＡ３重量部、ＳＴ６重量部、ＡＮ２重量部、ＧＭＡ２重量部に変えた以外は製造例Ａ２－１と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＡＬ－３）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＡＬ－３）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は１．１ｍｍｏｌ／ｇである。 Production Example A2-3; Preparation of Core-Shell Polymer Latex (AL-3) The same as Production Example A2-1 except that the shell monomer was changed to 3 parts by weight of MMA, 6 parts by weight of ST, 2 parts by weight of AN, and 2 parts by weight of GMA, and the core-shell polymer was used. An aqueous latex (AL-3) containing particles was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (AL-3) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.

　製造例Ａ２－４；コアシェルポリマーラテックス（ＡＬ－４）の調製
　シェルモノマーをＭＭＡ１重量部、ＳＴ６重量部、ＡＮ２重量部、ＧＭＡ４重量部に変えた以外は製造例Ａ２－１と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＡＬ－４）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＡＬ－４）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は２．２ｍｍｏｌ／ｇである。 Production Example A2-4; Preparation of Core-Shell Polymer Latex (AL-4) The same as Production Example A2-1 except that the shell monomer was changed to 1 part by weight of MMA, 6 parts by weight of ST, 2 parts by weight of AN, and 4 parts by weight of GMA, and the core-shell polymer was used. An aqueous latex (AL-4) containing particles was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (AL-4) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 2.2 mmol / g.

　製造例Ａ２－５；コアシェルポリマーラテックス（ＡＬ－５）の調製
　シェルモノマーをＭＭＡ１３重量部に変えた以外は製造例Ａ２－１と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＡＬ－５）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＡＬ－５）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は０．０ｍｍｏｌ／ｇである。 Production Example A2-5; Preparation of Core-Shell Polymer Latex (AL-5) The same as in Production Example A2-1 except that the shell monomer was changed to 13 parts by weight of MMA to obtain an aqueous latex (AL-5) containing core-shell polymer particles. rice field. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (AL-5) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0.0 mmol / g.

　Ａ３．硬化性樹脂中にコアシェルポリマー粒子（Ｂ）が分散した分散物（Ｍ）の調製
　製造例Ａ３－１；分散物（ＡＭ－１）の調製
　２５℃の１Ｌ混合槽にメチルエチルケトン（ＭＥＫ）１３２ｇを導入し、撹拌しながら、製造例Ａ２－１で得たコアシェルポリマーラテックス（ＡＬ－１）を１３２ｇ（コアシェルポリマー粒子４０ｇ相当）投入した。均一に混合後、水２００ｇを８０ｇ／分の供給速度で投入した。供給終了後、速やかに撹拌を停止したところ、浮上性の凝集体および有機溶媒を一部含む水相からなるスラリー液を得た。次に、一部の水相を含む凝集体を残し、水相３６０ｇを槽下部の払い出し口より排出させた。得られた凝集体にＭＥＫ９０ｇを追加して均一に混合し、コアシェルポリマー粒子を均一に分散した分散体を得た。この分散体に、（Ａ）成分であるエポキシ樹脂（Ａ－１；三菱化学社製、ＪＥＲ８２８：液状ビスフェノールＡ型エポキシ樹脂）６０ｇを混合した。この混合物から、回転式の蒸発装置で、ＭＥＫを除去した。このようにして、エポキシ樹脂にコアシェルポリマー粒子が分散した分散物（ＡＭ－１）を得た。 A3. Preparation of dispersion (M) in which core-shell polymer particles (B) are dispersed in a curable resin Production Example A3-1; Preparation of dispersion (AM-1) 132 g of methyl ethyl ketone (MEK) is introduced into a 1 L mixing tank at 25 ° C. Then, while stirring, 132 g (corresponding to 40 g of core-shell polymer particles) of the core-shell polymer latex (AL-1) obtained in Production Example A2-1 was added. After mixing uniformly, 200 g of water was added at a supply rate of 80 g / min. When the stirring was immediately stopped after the end of the supply, a slurry liquid consisting of a floating aggregate and an aqueous phase partially containing an organic solvent was obtained. Next, 360 g of the aqueous phase was discharged from the discharge port at the bottom of the tank, leaving an agglomerate containing a part of the aqueous phase. 90 g of MEK was added to the obtained aggregate and mixed uniformly to obtain a dispersion in which the core-shell polymer particles were uniformly dispersed. 60 g of an epoxy resin (A-1; manufactured by Mitsubishi Chemical Corporation, JER828: liquid bisphenol A type epoxy resin) as a component (A) was mixed with this dispersion. MEK was removed from this mixture with a rotary evaporator. In this way, a dispersion (AM-1) in which core-shell polymer particles were dispersed in an epoxy resin was obtained.

　製造例Ａ３－２；分散物（ＡＭ－２）の調製
　製造例Ａ３－１において、コアシェルポリマーラテックスとして（ＡＬ－１）の代わりに、製造例Ａ２－２で得た（ＡＬ－２）を用いたこと以外は製造例Ａ３－１と同様にして、エポキシ樹脂にコアシェルポリマー粒子が分散した分散物（ＡＭ－２）を得た。 Production Example A3-2; Preparation of Dispersion (AM-2) In Production Example A3-1, (AL-2) obtained in Production Example A2-2 was used instead of (AL-1) as the core-shell polymer latex. A dispersion (AM-2) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example A3-1 except for the above.

　製造例Ａ３－３；分散物（ＡＭ－３）の調製
　製造例Ａ３－１において、コアシェルポリマーラテックスとして（ＡＬ－１）の代わりに、製造例Ａ２－３で得た（ＡＬ－３）を用いたこと以外は製造例Ａ３－１と同様にして、エポキシ樹脂にコアシェルポリマー粒子が分散した分散物（ＡＭ－３）を得た。 Production Example A3-3; Preparation of Dispersion (AM-3) In Production Example A3-1, (AL-3) obtained in Production Example A2-3 was used instead of (AL-1) as the core-shell polymer latex. A dispersion (AM-3) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example A3-1 except for the above.

　製造例Ａ３－４；分散物（ＡＭ－４）の調製
　製造例Ａ３－１において、コアシェルポリマーラテックスとして（ＡＬ－１）の代わりに、製造例Ａ２－４で得た（ＡＬ－４）を用いたこと以外は製造例Ａ３－１と同様にして、エポキシ樹脂にコアシェルポリマー粒子が分散した分散物（ＡＭ－４）を得た。 Production Example A3-4; Preparation of Dispersion (AM-4) In Production Example A3-1, (AL-4) obtained in Production Example A2-4 was used instead of (AL-1) as the core-shell polymer latex. A dispersion (AM-4) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example A3-1 except for the above.

　製造例Ａ３－５；分散物（ＡＭ－５）の調製
　製造例Ａ３－１において、コアシェルポリマーラテックスとして（ＡＬ－１）の代わりに、製造例Ａ２－５で得た（ＡＬ－５）を用い、エポキシ樹脂（Ａ－１）６０ｇの代わりに、エポキシ樹脂（Ａ－２；Ｈｅｘｉｏｎ製、ＥＰＯＮ８６３：液状ビスフェノールＦ型エポキシ樹脂）６０ｇを用いたこと以外は製造例Ａ３－１と同様にして、エポキシ樹脂にコアシェルポリマー粒子が分散した分散物（ＡＭ－５）を得た。 Production Example A3-5; Preparation of Dispersion (AM-5) In Production Example A3-1, (AL-5) obtained in Production Example A2-5 was used instead of (AL-1) as the core-shell polymer latex. , Epoxy in the same manner as in Production Example A3-1 except that 60 g of epoxy resin (A-2; manufactured by Hexion, EPON863: liquid bisphenol F type epoxy resin) was used instead of 60 g of epoxy resin (A-1). A dispersion (AM-5) in which core-shell polymer particles were dispersed in a resin was obtained.

　（実施例Ａ１～１７、比較例Ａ１～８）
　表１～表３に示す処方にしたがって、各成分をそれぞれ計量し、よく混合して二成分型硬化性樹脂組成物の第一成分と第二成分を得た。 (Examples A1 to 17, Comparative Examples A1 to 8)
Each component was weighed according to the formulations shown in Tables 1 to 3 and mixed well to obtain the first component and the second component of the two-component curable resin composition.

　表１～表３の各二成分型硬化性樹脂組成物について、以下の方法で、動的割裂抵抗力（耐衝撃剥離接着性）、せん断接着強さ、熱伝導性、難燃性（ＵＬ－９４）、の評価を行った。 For each of the two-component curable resin compositions shown in Tables 1 to 3, the dynamic split resistance (impact peeling adhesiveness), shear adhesive strength, thermal conductivity, and flame retardancy (UL-) are used by the following methods. 94), was evaluated.

　＜動的割裂抵抗力（耐衝撃剥離接着性）＞
　表１～表３の第一成分と第二成分をよく混合して得た各組成物を、２枚の冷間圧延鋼板（ＳＰＣＣ－ＳＤ）に塗布し、接着層厚み０．２５ｍｍとなるように重ね合せ、２３℃×７日の条件で硬化させて積層体を得た。この積層体を用いて、ＩＳＯ　１１３４３に従って、２３℃で動的割裂抵抗力（耐衝撃剥離接着性）を測定した。結果を表１～表３に示す。 <Dynamic split resistance (impact peeling adhesiveness)>
Each composition obtained by mixing the first component and the second component of Tables 1 to 3 well is applied to two cold-rolled steel sheets (SPCC-SD) so that the adhesive layer thickness is 0.25 mm. And cured under the condition of 23 ° C. × 7 days to obtain a laminated body. Using this laminate, the dynamic split resistance (impact peeling adhesiveness) was measured at 23 ° C. according to ISO 11343. The results are shown in Tables 1 to 3.

　＜せん断接着強さ＞
　表２の第一成分と第二成分をよく混合して得た各組成物を、幅２５ｍｍ×長さ１００ｍｍ×厚み１．６ｍｍの２枚の冷間圧延鋼板（ＳＰＣＣ－ＳＤ）またはアルミニウム板（Ａ－５０５２Ｐ）に塗布し、接着層が幅２５ｍｍ×長さ１２．５ｍｍ×厚み０．１３ｍｍとなるように貼りあわせ、２３℃×７日の条件で硬化させて積層体を得た。 <Shear adhesion strength>
Each composition obtained by thoroughly mixing the first component and the second component in Table 2 is obtained by combining two cold-rolled steel plates (SPCC-SD) or aluminum plates (SPCC-SD) having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm. It was applied to A-5052P), bonded so that the adhesive layer had a width of 25 mm × a length of 12.5 mm × a thickness of 0.13 mm, and cured under the conditions of 23 ° C. × 7 days to obtain a laminated body.

　測定温度を２３℃、テストスピードを１．３ｍｍ／ｍｉｎとした測定条件で、単位をＭＰａとしたせん断接着強さを測定した。結果を表２に示す。 The shear adhesion strength was measured with MPa as the unit under the measurement conditions where the measurement temperature was 23 ° C and the test speed was 1.3 mm / min. The results are shown in Table 2.

　＜熱伝導率＞
　表３の第一成分と第二成分を混合後、脱泡して得た各組成物を、厚み３ｍｍのスペーサーを挟んだ２枚のガラス板の間に注ぎ込み、２３℃×７日の条件で硬化させ、厚み３ｍｍの硬化板を得た。この硬化板を切削し、直径２０ｍｍの円盤状サンプルを２枚得た。ホットディスク法熱伝導率測定装置ＴＰＡ－５０１（京都電子工業（株）製）を用い、４φサイズのセンサーを２枚の試料で挟む方法にて、硬化物の熱伝導率を測定した。 <Thermal conductivity>
After mixing the first component and the second component in Table 3, each composition obtained by defoaming was poured between two glass plates sandwiching a spacer having a thickness of 3 mm, and cured under the conditions of 23 ° C. × 7 days. , A cured plate having a thickness of 3 mm was obtained. This hardened plate was cut to obtain two disk-shaped samples having a diameter of 20 mm. The thermal conductivity of the cured product was measured by a method of sandwiching a 4φ size sensor between two samples using a hot disk method thermal conductivity measuring device TPA-501 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.).

　＜難燃性＞
　表３の第一成分と第二成分を混合後、脱泡して得た各組成物を、厚み３ｍｍのスペーサーを挟んだ２枚のガラス板の間に注ぎ込み、２３℃×７日の条件で硬化させ、厚み３ｍｍの硬化板を得た。この硬化板を１２７ｍｍ×１２．７ｍｍ×３ｍｍ厚みの短冊型に切削し、ＵＬ－９４　２０ｍｍ垂直燃焼試験（Ｖ試験）に準じて評価した。試験結果は難燃性が良好な方から「Ｖ－０」、「Ｖ－１」、「Ｖ－２」の順で表され、ＵＬ－９４　Ｖ試験に合格しないものは「規格外」とした。 <Flame retardant>
After mixing the first component and the second component in Table 3, each composition obtained by defoaming was poured between two glass plates sandwiching a spacer having a thickness of 3 mm, and cured under the conditions of 23 ° C. × 7 days. , A cured plate having a thickness of 3 mm was obtained. This hardened plate was cut into strips having a thickness of 127 mm × 12.7 mm × 3 mm, and evaluated according to the UL-94 20 mm vertical combustion test (V test). The test results are shown in the order of "V-0", "V-1", and "V-2" from the one with the best flame retardancy, and those that do not pass the UL-94 V test are classified as "non-standard". ..

　なお、表１～表３中の各種配合剤は、以下に示すものを使用した。
＜エポキシ樹脂（Ａ）＞
Ａ－１：ＪＥＲ８２８（三菱化学製、常温で液状のビスフェノールＡ型エポキシ樹脂、エポキシ当量：１８４～１９４）
Ａ－２：ＥＰＯＮ８６３（Ｈｅｘｉｏｎ製、常温で液状のビスフェノールＦ型エポキシ樹脂、エポキシ当量：１６５～１７４）
Ａ－３：ＹＥＤ２１６Ｍ（三菱化学製、アルキルジグリシジルエーテル、エポキシ当量：１４０～１６０）
＜エポキシ樹脂（Ａ）中にポリマー粒子（Ｂ）が分散した分散物（Ｍ）＞
ＡＭ－１～５：前記製造例Ａ３－１～５で得られた分散物
＜水酸化アルミニウム（Ｃ）＞
Ｃ－１：Ｂ３０３（日本軽金属製、無処理水酸化アルミニウム、平均粒子径（Ｄｐ５０）：２６μｍ）
Ｃ－２：Ｂ３０３ＳＴＥ（日本軽金属製、エポキシシランカップリング剤処理水酸化アルミニウム、平均粒子径（Ｄｐ５０）：１７μｍ）
Ｃ－３：Ｂ５３（日本軽金属製、無処理水酸化アルミニウム、平均粒子径（Ｄｐ５０）：５７μｍ）
Ｃ－４：ＳＢ９３（日本軽金属製、無処理水酸化アルミニウム、平均粒子径（Ｄｐ５０）：１１４μｍ）
Ｃ－５：ＢＥ０３３（日本軽金属製、無処理水酸化アルミニウム、平均粒子径（Ｄｐ５０）：３．２μｍ）
Ｃ－６：ＢＥ０４３ＳＴＥ（日本軽金属製、エポキシシランカップリング剤処理水酸化アルミニウム、平均粒子径（Ｄｐ５０）：３．７μｍ）
Ｃ－７：ＢＦ０１３（日本軽金属製、無処理水酸化アルミニウム、平均粒子径（Ｄｐ５０）：１．２μｍ）
Ｃ－８：ＢＦ０１３ＳＴ（日本軽金属製、エポキシシランカップリング剤処理水酸化アルミニウム、平均粒子径（Ｄｐ５０）：１．２μｍ）
＜エポキシ硬化剤（Ｄ）＞
Ｄ－１：１，３－ビス(アミノメチル)シクロヘキサン（富士フイルム和光純薬製、活性水素等量：３５．５ｇ／ｅｑ）
Ｄ－２：Ｊｅｆｆａｍｉｎｅ　Ｔ－５０００（Ｈｕｎｔｓｍａｎ製、グリセリルポリ（オキシプロピレン）トリアミン、分子量：約５０００、活性水素等量：９５２ｇ／ｅｑ）
Ｄ－３：Ｈｙｐｒｏ　ＡＴＢＮ　１３００ｘ１６（Ｈｕｎｔｓｍａｎ製、アミン末端ブタジエン－アクリロニトリル共重合体、分子量：約３８００、活性水素等量：８００～１０００ｇ／ｅｑ）
Ｄ－４：イソホロンジアミン（富士フイルム和光純薬製、活性水素等量：４１ｇ／ｅｑ）
＜エポキシ硬化促進剤（Ｅ）＞
Ｅ－１：レゾルシノール（富士フイルム和光純薬製）
＜エポキシシランカップリング剤（Ｆ）＞
Ｆ－１：ＤＯＷＳＩＬ　Ｚ－６０４０　Ｓｉｌａｎｅ（東レ・ダウコーニング製） As the various compounding agents in Tables 1 to 3, the ones shown below were used.
<Epoxy resin (A)>
A-1: JER828 (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin liquid at room temperature, epoxy equivalent: 184 to 194)
A-2: EPON863 (manufactured by Hexion, bisphenol F type epoxy resin liquid at room temperature, epoxy equivalent: 165 to 174)
A-3: YED216M (Mitsubishi Chemical, alkyl diglycidyl ether, epoxy equivalent: 140-160)
<Dispersion (M) in which polymer particles (B) are dispersed in epoxy resin (A)>
AM-1 to 5: Dispersion obtained in Production Examples A3-1 to 5 <Aluminum hydroxide (C)>
C-1: B303 (Nippon Light Metal, untreated aluminum hydroxide, average particle size (Dp50): 26 μm)
C-2: B303STE (Nippon Light Metal, epoxy silane coupling agent treated aluminum hydroxide, average particle size (Dp50): 17 μm)
C-3: B53 (Nippon Light Metal, untreated aluminum hydroxide, average particle size (Dp50): 57 μm)
C-4: SB93 (Nippon Light Metal, untreated aluminum hydroxide, average particle size (Dp50): 114 μm)
C-5: BE033 (Nippon Light Metal, untreated aluminum hydroxide, average particle size (Dp50): 3.2 μm)
C-6: BE043STE (Nippon Light Metal, epoxy silane coupling agent treated aluminum hydroxide, average particle size (Dp50): 3.7 μm)
C-7: BF013 (Nippon Light Metal, untreated aluminum hydroxide, average particle size (Dp50): 1.2 μm)
C-8: BF013ST (Nippon Light Metal, epoxy silane coupling agent treated aluminum hydroxide, average particle size (Dp50): 1.2 μm)
<Epoxy curing agent (D)>
D-1: 1,3-bis (aminomethyl) cyclohexane (manufactured by Wako Pure Chemical Industries, Ltd., equivalent amount of active hydrogen: 35.5 g / eq)
D-2: Jeffamine T-5000 (manufactured by Huntsman, glycerylpoly (oxypropylene) triamine, molecular weight: about 5000, active hydrogen equivalent: 952 g / eq)
D-3: Hyper ATBN 1300x16 (manufactured by Huntsman, amine-terminated butadiene-acrylonitrile copolymer, molecular weight: about 3800, active hydrogen equivalent: 800-1000 g / eq)
D-4: Isophorone diamine (manufactured by Wako Pure Chemical Industries, Ltd., active hydrogen equivalent: 41 g / eq)
<Epoxy curing accelerator (E)>
E-1: Resorcinol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
<Epoxy silane coupling agent (F)>
F-1: DOWNSIL Z-6040 Silane (manufactured by Toray Dow Corning)

Figure JPOXMLDOC01-appb-T000001
　表１から、第一成分に（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分を含有し、第二成分に（Ｃ）成分及び（Ｄ）成分を含有する実施例Ａ１～８の二成分型硬化性樹脂組成物は、得られる硬化物の動的割裂抵抗力の値が大きく、耐衝撃剥離接着性が良好であることが分かる。
Figure JPOXMLDOC01-appb-T000001
 From Table 1, Examples A1 to 8-2 in which the first component contains the (A) component, the (B) component, and the (C) component, and the second component contains the (C) component and the (D) component. It can be seen that the component-type curable resin composition has a large value of the dynamic split resistance of the obtained cured product and has good impact-resistant peeling adhesiveness.

　実施例Ａ１、３～８と比較例Ａ１～５の組成物は、添加した（Ｃ）成分の種類が異なるだけで（Ｃ）成分以外は全て同一配合組成である。実施例Ａ１、３～８の組成物は用いた水酸化アルミニウムの平均粒子径が大きいのに対して、比較例Ａ１～５の組成物では用いた水酸化アルミニウムの平均粒子径が小さく、実施例Ａ１、３～８と比較して、耐衝撃剥離接着性が低い。 The compositions of Examples A1 and 3 to 8 and Comparative Examples A1 to 5 all have the same composition except for the component (C) added, only the type of the component (C) is different. The compositions of Examples A1 to 3 to 8 have a large average particle size of aluminum hydroxide used, whereas the compositions of Comparative Examples A1 to 5 have a small average particle size of aluminum hydroxide, and the examples have a large average particle size. Compared with A1, 3-8, the impact resistance peeling adhesiveness is low.

　実施例Ａ２の組成物は、実施例Ａ１の組成物にエポキシ硬化促進剤（Ｅ）を添加した配合組成であり、耐衝撃剥離接着性も優れることが分かる。 It can be seen that the composition of Example A2 is a compounding composition in which the epoxy curing accelerator (E) is added to the composition of Example A1, and the impact resistance peeling adhesiveness is also excellent.

Figure JPOXMLDOC01-appb-T000002
　表２から、第一成分に（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分を含有し、第二成分に（Ｃ）成分及び（Ｄ）成分を含有する実施例Ａ９～１４の二成分型硬化性樹脂組成物は、鋼板やアルミニウム板へのせん断接着性を高く維持しながら、得られる硬化物の耐衝撃剥離接着性が良好であることが分かる。
Figure JPOXMLDOC01-appb-T000002
 From Table 2, Examples A9 to 14-2 in which the first component contains the (A) component, the (B) component, and the (C) component, and the second component contains the (C) component and the (D) component. It can be seen that the component-type curable resin composition has good impact-resistant peeling adhesiveness of the obtained cured product while maintaining high shear adhesiveness to steel plates and aluminum plates.

　実施例Ａ９～１１と比較例Ａ６の組成物は、添加した（Ｃ）成分の種類が異なるだけで（Ｃ）成分以外は全て同一配合組成である。実施例Ａ９～１１の組成物は用いた水酸化アルミニウムの平均粒子径が大きいのに対して、比較例Ａ６の組成物では用いた水酸化アルミニウムの平均粒子径が小さく、実施例Ａ９～１１と比較して、耐衝撃剥離接着性が低い。 The compositions of Examples A9 to 11 and Comparative Example A6 all have the same composition except for the component (C) added, only the type of the component (C) is different. The compositions of Examples A9 to 11 have a large average particle size of aluminum hydroxide used, whereas the composition of Comparative Example A6 has a small average particle size of aluminum hydroxide, which is the same as that of Examples A9 to 11. In comparison, the impact resistance peeling adhesiveness is low.

　実施例Ａ９、１２～１４の組成物は、添加した（Ｂ）成分が異なるだけで（Ｂ）成分以外は全て同一配合組成である。実施例Ａ９、１２～１４の組成物で用いた（Ｂ）成分は、シェル層のエポキシ基含量が異なる。シェル層にエポキシ基を含有しない場合（実施例Ａ１２）と、シェル層のエポキシ基含量が０．５ｍｍｏｌ／ｇ（実施例Ａ９）と、１．１ｍｍｏｌ／ｇ（実施例Ａ１３）の場合に、比較的良好な耐衝撃剥離接着性を示した。 The compositions of Examples A9 and 12 to 14 all have the same composition except for the component (B) added, except for the component (B). The components (B) used in the compositions of Examples A9 and 12 to 14 differ in the epoxy group content of the shell layer. Comparison between the case where the shell layer does not contain an epoxy group (Example A12), the case where the epoxy group content of the shell layer is 0.5 mmol / g (Example A9), and the case where the shell layer contains 1.1 mmol / g (Example A13). It showed good impact resistance and peeling adhesiveness.

Figure JPOXMLDOC01-appb-T000003
　表３から、第一成分に（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分を含有し、第二成分に（Ｃ）成分及び（Ｄ）成分を含有する実施例Ａ１５～１７の二成分型硬化性樹脂組成物は、熱伝導率が高く、難燃性に優れ、得られる硬化物の耐衝撃剥離接着性が良好であることが分かる。
Figure JPOXMLDOC01-appb-T000003
 From Table 3, Examples A15 to 17-2 in which the first component contains the (A) component, the (B) component, and the (C) component, and the second component contains the (C) component and the (D) component. It can be seen that the component-type curable resin composition has high thermal conductivity, excellent flame retardancy, and good impact-resistant peeling adhesiveness of the obtained cured product.

　実施例Ａ１５～１７と比較例Ａ７の組成物は、添加した（Ｃ）成分量が異なるだけで（Ｃ）成分量以外は全て同一配合組成である。硬化性樹脂組成物の総重量に対する（Ｃ）成分の総重量が少ない比較例Ａ７では、熱伝導率が比較的低く、ＵＬ－９４難燃性試験で不合格（規格外）となった。同様に（Ｃ）成分を含有しない比較例Ａ８では、熱伝導率が低く、ＵＬ－９４難燃性試験で不合格（規格外）となった。 The compositions of Examples A15 to 17 and Comparative Example A7 all have the same composition except for the amount of the added component (C) but the amount of the component (C). In Comparative Example A7, in which the total weight of the component (C) was small with respect to the total weight of the curable resin composition, the thermal conductivity was relatively low, and the UL-94 flame retardancy test failed (non-standard). Similarly, in Comparative Example A8 containing no component (C), the thermal conductivity was low, and the UL-94 flame retardancy test failed (non-standard).

　〔実施例Ｂ〕
　以下に実施例Ｂを掲げて第２実施形態をさらに詳細に説明するが、本発明はこれら実施例Ｂに限定されるものではない。 [Example B]
The second embodiment will be described in more detail with reference to Example B below, but the present invention is not limited to these Examples B.

　（体積平均粒子径の測定）
　製造例Ｂに記載されたポリブタジエンゴムラテックス中のポリブタジエンゴム粒子、及び、コアシェルポリマーラテックス中のコアシェルポリマー粒子の平均粒子径の測定方法は、前記〔実施例Ａ〕の（体積平均粒子径の測定）の項に記載の方法と同じである。そのため、前記〔実施例Ａ〕の（体積平均粒子径の測定）の項の記載を援用し、ここでは説明を省略する。 (Measurement of volume average particle size)
The method for measuring the average particle size of the polybutadiene rubber particles in the polybutadiene rubber latex and the core-shell polymer particles in the core-shell polymer latex described in Production Example B is the above-mentioned [Measurement of volume average particle size] in [Example A]. It is the same as the method described in the section. Therefore, the description in the section (Measurement of volume average particle size) in [Example A] is referred to, and the description thereof is omitted here.

　Ｂ１．コア層の形成
　実施例Ｂにおいて、コア層としては、前記〔実施例Ａ〕の「製造例Ａ１；ポリブタジエンゴムラテックス（Ｒ－２）の調製」の項に記載の方法で得られたＲ－２を使用した。そのため、前記〔実施例Ａ〕の「製造例Ａ１；ポリブタジエンゴムラテックス（Ｒ－２）の調製」の項の記載を援用し、ここでは説明を省略する。 B1. Formation of core layer In Example B, the core layer is R-2 obtained by the method described in the above-mentioned "Production Example A1; Preparation of Polybutadiene Rubber Latex (R-2)" in [Example A]. It was used. Therefore, the description in the section "Production Example A1; Preparation of Polybutadiene Rubber Latex (R-2)" in [Example A] is referred to, and the description thereof is omitted here.

　Ｂ２．コアシェルポリマーラテックスの調製（シェル層の形成）
　製造例Ｂ２－１；コアシェルポリマーラテックス（ＢＬ－１）の調製
　温度計、撹拌機、還流冷却器、窒素流入口、及びモノマーの添加装置を有するガラス反応器に、製造例Ａ１で調製したポリブタジエンゴムラテックス（Ｒ－２）２７１重量部（ポリブタジエンゴム粒子９０重量部を含む）、及び、脱イオン水５１重量部を仕込み、窒素置換を行いながら６０℃で撹拌した。ＥＤＴＡ０．００４重量部、ＦＥ０．００１重量部、及びＳＦＳ０．２重量部を加えた後、シェルモノマー（メチルメタクリレート（ＭＭＡ）９重量部、グリシジルメタクリレート（ＧＭＡ）１重量部）、及び、クメンヒドロパーオキサイド（ＣＨＰ）０．１４重量部の混合物を１２０分間かけて連続的に添加した。添加終了後、ＣＨＰ０．０４重量部を添加し、さらに２時間撹拌を続けて重合を完結させ、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－１）を得た。モノマー成分の重合転化率は９９％以上であった。水性ラテックス（ＢＬ－１）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は０．７ｍｍｏｌ／ｇである。 B2. Preparation of core-shell polymer latex (formation of shell layer)
Production Example B2-1; Preparation of core-shell polymer latex (BL-1) The polybutadiene rubber prepared in Production Example A1 was placed in a glass reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet, and monomer addition device. 271 parts by weight of latex (R-2) (including 90 parts by weight of polybutadiene rubber particles) and 51 parts by weight of deionized water were charged and stirred at 60 ° C. while performing nitrogen substitution. After adding 0.004 part by weight of EDTA, 0.001 part by weight of FE, and 0.2 part by weight of SFS, shell monomers (9 parts by weight of methyl methacrylate (MMA), 1 part by weight of glycidyl methacrylate (GMA)), and cumenhydroper. A mixture of 0.14 parts by weight of oxide (CHP) was added continuously over 120 minutes. After completion of the addition, 0.04 part by weight of CHP was added, and stirring was continued for another 2 hours to complete the polymerization to obtain an aqueous latex (BL-1) containing core-shell polymer particles. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-1) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0.7 mmol / g.

　製造例Ｂ２－２；コアシェルポリマーラテックス（ＢＬ－２）の調製
　温度計、撹拌機、還流冷却器、窒素流入口、及びモノマーの添加装置を有するガラス反応器に、製造例Ａ１で調製したポリブタジエンゴムラテックス（Ｒ－２）２６２重量部（ポリブタジエンゴム粒子８７重量部を含む）、及び、脱イオン水５７重量部を仕込み、窒素置換を行いながら６０℃で撹拌した。ＥＤＴＡ０．００４重量部、ＦＥ０．００１重量部、及びＳＦＳ０．２重量部を加えた後、シェルモノマー（ＭＭＡ１１重量部、ＧＭＡ２重量部）、及び、ＣＨＰ０．０６重量部の混合物を１２０分間かけて連続的に添加した。添加終了後、ＣＨＰ０．０４重量部を添加し、さらに２時間撹拌を続けて重合を完結させ、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－２）を得た。モノマー成分の重合転化率は９９％以上であった。水性ラテックス（ＢＬ－２）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は１．１ｍｍｏｌ／ｇである。 Production Example B2-2; Preparation of Core-Shell Polymer Latex (BL-2) The polybutadiene rubber prepared in Production Example A1 was placed in a glass reactor equipped with a thermometer, agitator, reflux condenser, nitrogen inlet, and a monomer addition device. 262 parts by weight of latex (R-2) (including 87 parts by weight of polybutadiene rubber particles) and 57 parts by weight of deionized water were charged and stirred at 60 ° C. while performing nitrogen substitution. After adding 0.004 part by weight of EDTA, 0.001 part by weight of FE, and 0.2 part by weight of SFS, a mixture of shell monomer (11 parts by weight of MMA, 2 parts by weight of GMA) and 0.06 part by weight of CHP was continuously added over 120 minutes. Was added. After completion of the addition, 0.04 part by weight of CHP was added, and stirring was continued for another 2 hours to complete the polymerization to obtain an aqueous latex (BL-2) containing core-shell polymer particles. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-2) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.

　製造例Ｂ２－３；コアシェルポリマーラテックス（ＢＬ－３）の調製
　シェルモノマーをＭＭＡ２重量部、ブチルアクリレート（ＢＡ）９重量部、ＧＭＡ２重量部に変えた以外は製造例Ｂ２－２と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－３）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＢＬ－３）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は１．１ｍｍｏｌ／ｇである。 Production Example B2-3; Preparation of Core-Shell Polymer Latex (BL-3) The same as Production Example B2-2 except that the shell monomer was changed to 2 parts by weight of MMA, 9 parts by weight of butyl acrylate (BA), and 2 parts by weight of GMA, and the core shell was used. An aqueous latex (BL-3) containing polymer particles was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-3) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.

　製造例Ｂ２－４；コアシェルポリマーラテックス（ＢＬ－４）の調製
　温度計、撹拌機、還流冷却器、窒素流入口、及びモノマーの添加装置を有するガラス反応器に、製造例Ａ１で調製したポリブタジエンゴムラテックス（Ｒ－２）２２３重量部（ポリブタジエンゴム粒子７４重量部を含む）、及び、脱イオン水８３重量部を仕込み、窒素置換を行いながら６０℃で撹拌した。ＥＤＴＡ０．００４重量部、ＦＥ０．００１重量部、及びＳＦＳ０．２重量部を加えた後、シェルモノマー（ＭＭＡ４重量部、ＢＡ１８重量部、ＧＭＡ４重量部）、及び、ＣＨＰ０．１２重量部の混合物を１２０分間かけて連続的に添加した。添加終了後、ＣＨＰ０．０４重量部を添加し、さらに２時間撹拌を続けて重合を完結させ、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－４）を得た。モノマー成分の重合転化率は９９％以上であった。水性ラテックス（ＢＬ－４）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２２μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は１．１ｍｍｏｌ／ｇである。 Production Example B2-4; Preparation of Core-Shell Polymer Latex (BL-4) Polybutadiene rubber prepared in Production Example A1 in a glass reactor equipped with a thermometer, agitator, reflux condenser, nitrogen inlet, and monomer addition device. 223 parts by weight of latex (R-2) (including 74 parts by weight of polybutadiene rubber particles) and 83 parts by weight of deionized water were charged and stirred at 60 ° C. while performing nitrogen substitution. After adding 0.004 part by weight of EDTA, 0.001 part by weight of FE, and 0.2 part by weight of SFS, 120 parts by weight of the shell monomer (4 parts by weight of MMA, 18 parts by weight of BA, 4 parts by weight of GMA) and 0.12 parts by weight of CHP are mixed. It was added continuously over a minute. After completion of the addition, 0.04 part by weight of CHP was added, and the mixture was further stirred for 2 hours to complete the polymerization to obtain an aqueous latex (BL-4) containing core-shell polymer particles. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-4) was 0.22 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.

　製造例Ｂ２－５；コアシェルポリマーラテックス（ＢＬ－５）の調製
　シェルモノマーをＢＡ１１重量部、ＧＭＡ２重量部に変えた以外は製造例Ｂ２－２と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－５）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＢＬ－５）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は１．１ｍｍｏｌ／ｇである。 Production Example B2-5; Preparation of Core-Shell Polymer Latex (BL-5) The same as Production Example B2-2 except that the shell monomer was changed to BA11 parts by weight and GMA2 parts by weight, and the aqueous latex (BL-) containing core-shell polymer particles was used. 5) was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-5) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.

　製造例Ｂ２－６；コアシェルポリマーラテックス（ＢＬ－６）の調製
　シェルモノマーをＭＭＡ１重量部、ＳＴ６重量部、ＡＮ２重量部、ＧＭＡ４重量部に変えた以外は製造例Ｂ２－２と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－６）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＢＬ－６）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は２．２ｍｍｏｌ／ｇである。 Production Example B2-6; Preparation of Core-Shell Polymer Latex (BL-6) The same as Production Example B2-2 except that the shell monomer was changed to 1 part by weight of MMA, 6 parts by weight of ST, 2 parts by weight of AN, and 4 parts by weight of GMA, and the core-shell polymer was used. An aqueous latex (BL-6) containing particles was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-6) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 2.2 mmol / g.

　製造例Ｂ２－７；コアシェルポリマーラテックス（ＢＬ－７）の調製
　シェルモノマーをＭＭＡ８重量部、ＧＭＡ２重量部に変えた以外は製造例Ｂ２－１と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－７）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＢＬ－７）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は１．４ｍｍｏｌ／ｇである。 Production Example B2-7; Preparation of Core-Shell Polymer Latex (BL-7) The same as Production Example B2-1 except that the shell monomer was changed to 8 parts by weight of MMA and 2 parts by weight of GMA, and an aqueous latex containing core-shell polymer particles (BL- 7) was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-7) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.4 mmol / g.

　製造例Ｂ２－８；コアシェルポリマーラテックス（ＢＬ－８）の調製
　シェルモノマーをＭＭＡ６重量部、ＧＭＡ４重量部に変えた以外は製造例Ｂ２－１と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－８）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＢＬ－８）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は２．８ｍｍｏｌ／ｇである。 Production Example B2-8; Preparation of Core-Shell Polymer Latex (BL-8) The same as Production Example B2-1 except that the shell monomer was changed to 6 parts by weight of MMA and 4 parts by weight of GMA, and an aqueous latex containing core-shell polymer particles (BL- 8) was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-8) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 2.8 mmol / g.

　製造例Ｂ２－９；コアシェルポリマーラテックス（ＢＬ－９）の調製
　シェルモノマーをＭＭＡ６重量部、ＢＡ７重量部に変えた以外は製造例Ｂ２－２と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－９）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＢＬ－９）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は０ｍｍｏｌ／ｇである。 Production Example B2-9; Preparation of Core-Shell Polymer Latex (BL-9) The same as Production Example B2-2 except that the shell monomer was changed to 6 parts by weight of MMA and 7 parts by weight of BA, and the aqueous latex containing core-shell polymer particles (BL- 9) was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-9) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0 mmol / g.

　製造例Ｂ２－１０；コアシェルポリマーラテックス（ＢＬ－１０）の調製
　シェルモノマーをＭＭＡ５重量部、ＢＡ６重量部、ＧＭＡ２重量部に変えた以外は製造例Ｂ２－２と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－１０）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＢＬ－１０）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は１．１ｍｍｏｌ／ｇである。 Production Example B2-10; Preparation of Core-Shell Polymer Latex (BL-10) The same as Production Example B2-2 except that the shell monomer was changed to 5 parts by weight of MMA, 6 parts by weight of BA, and 2 parts by weight of GMA, and an aqueous solution containing core-shell polymer particles. Latex (BL-10) was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-10) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.

　製造例Ｂ２－１１；コアシェルポリマーラテックス（ＢＬ－１１）の調製
　シェルモノマーをＭＭＡ１３重量部に変えた以外は製造例Ｂ２－２と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－１１）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＢＬ－１１）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２１μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は０ｍｍｏｌ／ｇである。 Production Example B2-11; Preparation of Core-Shell Polymer Latex (BL-11) Similar to Production Example B2-2 except that the shell monomer was changed to 13 parts by weight of MMA to obtain an aqueous latex (BL-11) containing core-shell polymer particles. rice field. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-11) was 0.21 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0 mmol / g.

　製造例Ｂ２－１２；コアシェルポリマーラテックス（ＢＬ－１２）の調製
　シェルモノマーをＭＭＡ４重量部、ＢＡ８重量部、ブチルメタクリレート（ＢＭＡ）１０重量部、ＧＭＡ４重量部に変えた以外は製造例Ｂ２－４と同様にし、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－１２）を得た。モノマー成分の転化率は９９％以上であった。水性ラテックス（ＢＬ－１２）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２２μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は１．１ｍｍｏｌ／ｇである。 Production Example B2-12; Preparation of Core-Shell Polymer Latex (BL-12) Production Example B2-4 except that the shell monomer was changed to 4 parts by weight of MMA, 8 parts by weight of BA, 10 parts by weight of butyl methacrylate (BMA), and 4 parts by weight of GMA. Similarly, an aqueous latex (BL-12) containing core-shell polymer particles was obtained. The conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-12) was 0.22 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.

　製造例Ｂ２－１３；コアシェルポリマーラテックス（ＢＬ－１３）の調製
　温度計、撹拌機、還流冷却器、窒素流入口、及びモノマーの添加装置を有するガラス反応器に、製造例Ａ１で調製したポリブタジエンゴムラテックス（Ｒ－１）２４１重量部（ポリブタジエンゴム粒子８０重量部を含む）、及び、脱イオン水７１重量部を仕込み、窒素置換を行いながら６０℃で撹拌した。ＥＤＴＡ０．００４重量部、ＦＥ０．００１重量部、及びＳＦＳ０．２重量部を加えた後、シェルモノマー（ＭＭＡ２０重量部）、及び、ＣＨＰ０．０９重量部の混合物を１２０分間かけて連続的に添加した。添加終了後、ＣＨＰ０．０４重量部を添加し、さらに２時間撹拌を続けて重合を完結させ、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－１３）を得た。モノマー成分の重合転化率は９９％以上であった。水性ラテックス（ＢＬ－１３）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．０９μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は０ｍｍｏｌ／ｇである。 Production Example B2-13; Preparation of Core Shell Polymer Latex (BL-13) Polybutadiene rubber prepared in Production Example A1 in a glass reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet, and monomer addition device. 241 parts by weight of latex (R-1) (including 80 parts by weight of polybutadiene rubber particles) and 71 parts by weight of deionized water were charged and stirred at 60 ° C. while performing nitrogen substitution. After adding 0.004 part by weight of EDTA, 0.001 part by weight of FE, and 0.2 part by weight of SFS, a mixture of shell monomer (20 parts by weight of MMA) and 0.09 part by weight of CHP was continuously added over 120 minutes. .. After completion of the addition, 0.04 part by weight of CHP was added, and the mixture was further stirred for 2 hours to complete the polymerization to obtain an aqueous latex (BL-13) containing core-shell polymer particles. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-13) was 0.09 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 0 mmol / g.

　製造例Ｂ２－１４；コアシェルポリマーラテックス（ＢＬ－１４）の調製
　温度計、撹拌機、還流冷却器、窒素流入口、及びモノマーの添加装置を有するガラス反応器に、製造例Ａ１で調製したポリブタジエンゴムラテックス（Ｒ－２）１４５重量部（ポリブタジエンゴム粒子４８重量部を含む）、及び、脱イオン水１３５重量部を仕込み、窒素置換を行いながら６０℃で撹拌した。ＥＤＴＡ０．００４重量部、ＦＥ０．００１重量部、及びＳＦＳ０．３重量部を加えた後、シェルモノマー（ＭＭＡ８重量部、ＢＡ１６重量部、ＢＭＡ２０重量部、ＧＭＡ８重量部）、及び、ＣＨＰ０．２４重量部の混合物を２４０分間かけて連続的に添加した。添加終了後、ＣＨＰ０．０４重量部を添加し、さらに２時間撹拌を続けて重合を完結させ、コアシェルポリマー粒子を含む水性ラテックス（ＢＬ－１４）を得た。モノマー成分の重合転化率は９９％以上であった。水性ラテックス（ＢＬ－１４）に含まれるコアシェルポリマー粒子の体積平均粒子径は０．２４μｍであった。該コアシェルポリマー粒子のシェル層の総量に対するエポキシ基の含有量は１．１ｍｍｏｌ／ｇである。 Production Example B2-14; Preparation of Core-Shell Polymer Latex (BL-14) The polybutadiene rubber prepared in Production Example A1 was placed in a glass reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet, and monomer addition device. 145 parts by weight of latex (R-2) (including 48 parts by weight of polybutadiene rubber particles) and 135 parts by weight of deionized water were charged and stirred at 60 ° C. while performing nitrogen substitution. After adding 0.004 parts by weight of EDTA, 0.001 parts by weight of FE, and 0.3 parts by weight of SFS, shell monomers (8 parts by weight of MMA, 16 parts by weight of BA, 20 parts by weight of BMA, 8 parts by weight of GMA), and 0.24 parts by weight of CHP. The mixture was added continuously over 240 minutes. After completion of the addition, 0.04 part by weight of CHP was added, and the mixture was further stirred for 2 hours to complete the polymerization to obtain an aqueous latex (BL-14) containing core-shell polymer particles. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-14) was 0.24 μm. The content of the epoxy group with respect to the total amount of the shell layer of the core-shell polymer particles is 1.1 mmol / g.

　Ｂ３．硬化性樹脂中にコアシェルポリマー粒子（Ｂ）が分散した分散物（Ｍ）の調製
　製造例Ｂ３－１；分散物（ＢＭ－１）の調製
　２５℃の１Ｌ混合槽にメチルエチルケトン（ＭＥＫ）１３２ｇを導入し、撹拌しながら、製造例Ｂ２－１で得たコアシェルポリマーラテックス（ＢＬ－１）を１３２ｇ（コアシェルポリマー粒子４０ｇ相当）投入した。均一に混合後、水２００ｇを８０ｇ／分の供給速度で投入した。供給終了後、速やかに撹拌を停止したところ、浮上性の凝集体および有機溶媒を一部含む水相からなるスラリー液を得た。次に、一部の水相を含む凝集体を残し、水相３６０ｇを槽下部の払い出し口より排出させた。得られた凝集体にＭＥＫ９０ｇを追加して均一に混合し、コアシェルポリマー粒子を均一に分散した分散体を得た。この分散体に、（Ａ）成分であるエポキシ樹脂（三菱化学社製、ＪＥＲ８２８：液状ビスフェノールＡ型エポキシ樹脂）６０ｇを混合した。この混合物から、回転式の蒸発装置で、ＭＥＫを除去した。このようにして、エポキシ樹脂にコアシェルポリマー粒子が分散した分散物（ＢＭ－１）を得た。 B3. Preparation of dispersion (M) in which core-shell polymer particles (B) are dispersed in a curable resin Production Example B3-1; Preparation of dispersion (BM-1) 132 g of methyl ethyl ketone (MEK) is introduced into a 1 L mixing tank at 25 ° C. Then, while stirring, 132 g (corresponding to 40 g of core-shell polymer particles) of the core-shell polymer latex (BL-1) obtained in Production Example B2-1 was added. After mixing uniformly, 200 g of water was added at a supply rate of 80 g / min. When the stirring was immediately stopped after the end of the supply, a slurry liquid consisting of a floating aggregate and an aqueous phase partially containing an organic solvent was obtained. Next, 360 g of the aqueous phase was discharged from the discharge port at the bottom of the tank, leaving an agglomerate containing a part of the aqueous phase. 90 g of MEK was added to the obtained aggregate and mixed uniformly to obtain a dispersion in which the core-shell polymer particles were uniformly dispersed. 60 g of an epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER828: liquid bisphenol A type epoxy resin) as a component (A) was mixed with this dispersion. MEK was removed from this mixture with a rotary evaporator. In this way, a dispersion (BM-1) in which core-shell polymer particles were dispersed in an epoxy resin was obtained.

　製造例Ｂ３－２～３－１４；分散物（ＢＭ－２）～（ＢＭ－１４）の調製
　製造例Ｂ３－１において、コアシェルポリマーラテックスとして（ＢＬ－１）の代わりに、製造例Ｂ２－２～２－１４で得た（ＢＬ－２）～（ＢＬ－１４）を用いたこと以外は製造例Ｂ３－１と同様にして、エポキシ樹脂にコアシェルポリマー粒子が分散した分散物（ＢＭ－２）～（ＢＭ－１４）を得た。 Production Examples B3-2 to 3-14; Preparation of Dispersions (BM-2) to (BM-14) In Production Example B3-1, instead of (BL-1) as the core-shell polymer latex, Production Example B2-2 A dispersion (BM-2) in which core-shell polymer particles were dispersed in an epoxy resin in the same manner as in Production Example B3-1 except that (BL-2) to (BL-14) obtained in 2-14 were used. -(BM-14) was obtained.

　（実施例Ｂ１～１７、比較例Ｂ１～６）
　表４～表７に示す処方にしたがって、各成分をそれぞれ計量し、よく混合して二成分型硬化性樹脂組成物の第一成分と第二成分を得た。 (Examples B1 to 17, Comparative Examples B1 to 6)
Each component was weighed according to the formulations shown in Tables 4 to 7 and mixed well to obtain the first component and the second component of the two-component curable resin composition.

　表４～表７の各二成分型硬化性樹脂組成物について、以下の方法で、粘度、せん断接着強さ、動的割裂抵抗力（耐衝撃剥離接着性）、熱伝導性、及び難燃性（ＵＬ－９４）、の評価を行った。 For each of the two-component curable resin compositions shown in Tables 4 to 7, the viscosity, shear adhesive strength, dynamic splitting resistance (impact peeling adhesiveness), thermal conductivity, and flame retardancy were obtained by the following methods. (UL-94), was evaluated.

　＜粘度＞
　レオメーターを使用し、表４～表７の第一成分または第二成分の２５℃での粘度を、せん断速度５ｓ－１で測定した。粘度の値が小さいほど作業性に優れることを意味する。 <Viscosity>
Using a leometer, the viscosities of the first or second components of Tables 4-7 at 25 ° C. were measured at a shear rate of 5s -1 . The smaller the viscosity value, the better the workability.

　＜せん断接着強さ＞
　表４～表６の第一成分と第二成分をよく混合して得た各組成物を、幅２５ｍｍ×長さ１００ｍｍ×厚み１．６ｍｍの２枚のＳＰＣＣ鋼板またはアルミニウム板（Ａ－５０５２Ｐ）に塗布し、接着層が幅２５ｍｍ×長さ１２．５ｍｍ×厚み０．１３ｍｍとなるように貼りあわせ、２３℃×７日の条件で硬化させて積層体を得た。 <Shear adhesion strength>
Each composition obtained by mixing the first component and the second component of Tables 4 to 6 well is obtained by combining two SPCC steel plates or aluminum plates (A-5052P) having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm. The adhesive layer was bonded so as to have a width of 25 mm, a length of 12.5 mm, and a thickness of 0.13 mm, and was cured under the conditions of 23 ° C. × 7 days to obtain a laminated body.

　　測定温度を２３℃、テストスピードを１．３ｍｍ／ｍｉｎとした測定条件で、単位をＭＰａとしたせん断接着強さを測定した。 Shear adhesion strength was measured with MPa as the unit under measurement conditions with a measurement temperature of 23 ° C and a test speed of 1.3 mm / min.

　＜動的割裂抵抗力（耐衝撃剥離接着性）＞
　表５～表６の第一成分と第二成分をよく混合して得た各組成物を、２枚のＳＰＣＣ鋼板に塗布し、接着層厚み０．２５ｍｍとなるように重ね合せ、２３℃×７日の条件で硬化させて積層体を得た。この積層体を用いて、ＩＳＯ　１１３４３に従って、２３℃で動的割裂抵抗力（耐衝撃剥離接着性）を測定した。 <Dynamic split resistance (impact peeling adhesiveness)>
Each composition obtained by mixing the first component and the second component of Tables 5 to 6 well was applied to two SPCC steel sheets and superposed so as to have an adhesive layer thickness of 0.25 mm. It was cured under the condition of 7 days to obtain a laminated body. Using this laminate, the dynamic split resistance (impact peeling adhesiveness) was measured at 23 ° C. according to ISO 11343.

　＜熱伝導率＞
　表７の第一成分と第二成分を混合後、脱泡して得た各組成物を、厚み３ｍｍのスペーサーを挟んだ２枚のガラス板の間に注ぎ込み、２３℃×７日の条件で硬化させ、厚み３ｍｍの硬化板を得た。この硬化板を切削し、直径２０ｍｍの円盤状サンプルを２枚得た。ホットディスク法熱伝導率測定装置ＴＰＡ－５０１（京都電子工業（株）製）を用い、４φサイズのセンサーを２枚の試料で挟む方法にて、硬化物の熱伝導率を測定した。 <Thermal conductivity>
After mixing the first component and the second component in Table 7, each composition obtained by defoaming was poured between two glass plates sandwiching a spacer having a thickness of 3 mm, and cured under the conditions of 23 ° C. × 7 days. , A cured plate having a thickness of 3 mm was obtained. This hardened plate was cut to obtain two disk-shaped samples having a diameter of 20 mm. The thermal conductivity of the cured product was measured by a method of sandwiching a 4φ size sensor between two samples using a hot disk method thermal conductivity measuring device TPA-501 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.).

　＜難燃性＞
　表７の第一成分と第二成分を混合後、脱泡して得た各組成物を、厚み３ｍｍのスペーサーを挟んだ２枚のガラス板の間に注ぎ込み、２３℃×７日の条件で硬化させ、厚み３ｍｍの硬化板を得た。この硬化板を１２７ｍｍ×１２．７ｍｍ×３ｍｍ厚みの短冊型に切削し、ＵＬ－９４　２０ｍｍ垂直燃焼試験（Ｖ試験）に準じて評価した。試験結果は難燃性が良好な方から「Ｖ－０」、「Ｖ－１」、「Ｖ－２」の順で表され、ＵＬ－９４　Ｖ試験に合格しないものは「規格外」とした。 <Flame retardant>
After mixing the first component and the second component in Table 7, each composition obtained by defoaming was poured between two glass plates sandwiching a spacer having a thickness of 3 mm, and cured under the conditions of 23 ° C. × 7 days. , A cured plate having a thickness of 3 mm was obtained. This hardened plate was cut into strips having a thickness of 127 mm × 12.7 mm × 3 mm, and evaluated according to the UL-94 20 mm vertical combustion test (V test). The test results are shown in the order of "V-0", "V-1", and "V-2" from the one with the best flame retardancy, and those that do not pass the UL-94 V test are classified as "non-standard". ..

　なお、表４～表７中の各種配合剤は、以下に示すものを使用した。
＜エポキシ樹脂（Ａ）＞
Ａ－１：ＪＥＲ８２８（三菱化学製、常温で液状のビスフェノールＡ型エポキシ樹脂、エポキシ当量：１８４～１９４）
Ａ－２：ＹＥＤ２１６Ｍ（三菱化学製、アルキルジグリシジルエーテル、エポキシ当量：１４０～１６０）
＜エポキシ樹脂（Ａ）中にポリマー粒子（Ｂ）が分散した分散物（Ｍ）＞
ＢＭ－１～１４：前記製造例Ｂ３－１～１４で得られた分散物
＜水酸化アルミニウム（Ｃ）＞
Ｃ－１：Ｂ３０３（日本軽金属製、無処理水酸化アルミニウム、平均粒子径（Ｄｐ５０）：２６μｍ）
Ｃ－２：ＢＥ０３３（日本軽金属製、無処理水酸化アルミニウム、平均粒子径（Ｄｐ５０）：３．２μｍ）
＜エポキシ硬化剤（Ｄ）＞
Ｄ－１：１，３－ビス(アミノメチル)シクロヘキサン（富士フイルム和光純薬製）
Ｄ－２：Ｊｅｆｆａｍｉｎｅ　Ｔ－５０００（Ｈｕｎｔｓｍａｎ製、グリセリルポリ（オキシプロピレン）トリアミン、分子量：約５０００、活性水素等量：９５２ｇ／ｅｑ）
Ｄ－３：Ｈｙｐｒｏ　ＡＴＢＮ　１３００ｘ１６（Ｈｕｎｔｓｍａｎ製、アミン末端ブタジエン－アクリロニトリル共重合体、分子量：約３８００、活性水素等量：８００～１０００ｇ／ｅｑ）
＜エポキシ硬化促進剤（Ｅ）＞
Ｅ－１：レゾルシノール（富士フイルム和光純薬製）
＜エポキシシランカップリング剤（Ｆ）＞
Ｆ－１：ＤＯＷＳＩＬ　Ｚ－６０４０　Ｓｉｌａｎｅ（東レ・ダウコーニング製） As the various compounding agents in Tables 4 to 7, those shown below were used.
<Epoxy resin (A)>
A-1: JER828 (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin liquid at room temperature, epoxy equivalent: 184 to 194)
A-2: YED216M (Mitsubishi Chemical, alkyl diglycidyl ether, epoxy equivalent: 140-160)
<Dispersion (M) in which polymer particles (B) are dispersed in epoxy resin (A)>
BM-1 to 14: Dispersion obtained in Production Examples B3-1 to 14 <Aluminum hydroxide (C)>
C-1: B303 (Nippon Light Metal, untreated aluminum hydroxide, average particle size (Dp50): 26 μm)
C-2: BE033 (Nippon Light Metal, untreated aluminum hydroxide, average particle size (Dp50): 3.2 μm)
<Epoxy curing agent (D)>
D-1: 1,3-bis (aminomethyl) cyclohexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
D-2: Jeffamine T-5000 (manufactured by Huntsman, glycerylpoly (oxypropylene) triamine, molecular weight: about 5000, active hydrogen equivalent: 952 g / eq)
D-3: Hyper ATBN 1300x16 (manufactured by Huntsman, amine-terminated butadiene-acrylonitrile copolymer, molecular weight: about 3800, active hydrogen equivalent: 800-1000 g / eq)
<Epoxy curing accelerator (E)>
E-1: Resorcinol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
<Epoxy silane coupling agent (F)>
F-1: DOWNSIL Z-6040 Silane (manufactured by Toray Dow Corning)

Figure JPOXMLDOC01-appb-T000004
　表４から、第一成分に（Ａ）成分、（Ｂ）成分及び（Ｃ）成分を含有し、第二成分に（Ｃ）成分及び（Ｄ）成分を含有する実施例Ｂ１～４の二成分型硬化性樹脂組成物は、粘度が低くて作業性に優れ、得られる硬化物のせん断接着性が良好であることが分かる。
Figure JPOXMLDOC01-appb-T000004
 From Table 4, the two components of Examples B1 to 4 containing the component (A), the component (B) and the component (C) in the first component and the components (C) and (D) in the second component. It can be seen that the mold-curable resin composition has a low viscosity and is excellent in workability, and the obtained cured product has good shear adhesiveness.

　実施例Ｂ１～４と比較例Ｂ１～２の組成物は、添加した（Ｂ）成分が異なるだけで（Ｂ）成分以外は全て同一配合組成である。実施例Ｂ１～４の組成物で用いた（Ｂ）成分は、シェル層を構成するモノマー成分として、炭素数１～４のアルキル（メタ）アクリレートを主成分（５５重量％以上）とし、かつ、炭素数４のアルキル（メタ）アクリレートの含量は８０重量％以下である。一方、炭素数４のアルキル（メタ）アクリレートの含量が８５重量％であるシェル層の比較例Ｂ１は、粘度が非常に高く、作業性が悪い為せん断接着強さを測定しなかった。また炭素数１～４のアルキル（メタ）アクリレートが８重量％と少なく他のモノマー成分を主成分とするシェル層の比較例Ｂ２の組成物は、実施例Ｂ１～４と比較して、第一成分の粘度が高く、得られる硬化物のせん断接着性も低い値を示した。 The compositions of Examples B1 to 4 and Comparative Examples B1 to 2 have the same composition except for the added component (B) but the component (B). The component (B) used in the compositions of Examples B1 to B4 contains an alkyl (meth) acrylate having 1 to 4 carbon atoms as a main component (55% by weight or more) as a monomer component constituting the shell layer, and The content of the alkyl (meth) acrylate having 4 carbon atoms is 80% by weight or less. On the other hand, Comparative Example B1 of the shell layer having an alkyl (meth) acrylate having 4 carbon atoms having a content of 85% by weight did not measure the shear adhesive strength because the viscosity was very high and the workability was poor. Further, the composition of Comparative Example B2 of the shell layer having a small amount of alkyl (meth) acrylate having 1 to 4 carbon atoms as a main component of 8% by weight and containing other monomer components as a main component was first compared with Examples B1 to 4. The viscosity of the components was high, and the shear adhesion of the obtained cured product was also low.

Figure JPOXMLDOC01-appb-T000005
　表５から、実施例Ｂ５～１０の二成分型硬化性樹脂組成物は、表４の実施例Ｂ１～４と同様に、粘度が低くて作業性に優れることがわかる。
Figure JPOXMLDOC01-appb-T000005
 From Table 5, it can be seen that the two-component curable resin compositions of Examples B5 to 10 have a low viscosity and are excellent in workability, as in Examples B1 to 4 of Table 4.

　実施例Ｂ１と２は、第一成分が同一であるが、実施例Ｂ２の第二成分は実施例Ｂ１の第二成分の各配合剤の添加量を０．７５倍に減量したものである。これにより、実施例Ｂ２は、（Ａ）成分中のエポキシ基のモル数／（Ｄ）成分中の活性水素基のモル数の比が高く、エポキシ過剰の組成物となり、せん断接着性が低い値を示した。 Examples B1 and 2 have the same first component, but the second component of Example B2 is obtained by reducing the addition amount of each combination of the second component of Example B1 by 0.75 times. As a result, in Example B2, the ratio of the number of moles of epoxy groups in the component (A) / the number of moles of active hydrogen groups in the component (D) is high, the composition has an excess of epoxy, and the shear adhesiveness is low. showed that.

　実施例Ｂ５、７～１０の組成物は、添加した（Ｂ）成分が異なるだけで（Ｂ）成分以外は全て同一配合組成である。（Ｂ）成分のシェル層中のエポキシ基の含有量が多い実施例Ｂ８の組成物は、耐衝撃剥離接着性が低い値を示した。また、（Ｂ）成分のシェル層にエポキシ基を含有しない実施例Ｂ９の組成物も、耐衝撃剥離接着性が比較的低い値を示した。この結果より、（Ａ）成分中のエポキシ基のモル数／（Ｄ）成分中の活性水素基のモル数の比がせん断接着強さに効いており、（Ｂ）成分のシェル層中のエポキシ基の量が耐衝撃剥離接着性に効いていると考えられる。 The compositions of Examples B5 and 7 to 10 all have the same composition except for the added component (B) but different from the component (B). The composition of Example B8 having a large content of epoxy groups in the shell layer of the component (B) showed a value of low impact resistance peeling adhesiveness. Further, the composition of Example B9, which does not contain an epoxy group in the shell layer of the component (B), also showed a value of relatively low impact resistance peeling adhesiveness. From this result, the ratio of the number of moles of the epoxy group in the component (A) / the number of moles of the active hydrogen group in the component (D) is effective for the shear adhesion strength, and the epoxy in the shell layer of the component (B). It is considered that the amount of the group is effective for the impact resistance peeling adhesiveness.

Figure JPOXMLDOC01-appb-T000006
　表６から、実施例Ｂ１１～１４の二成分型硬化性樹脂組成物は、粘度が低くて作業性に優れ、得られる硬化物のせん断接着性と耐衝撃剥離接着性が良好であることが分かる。
Figure JPOXMLDOC01-appb-T000006
 From Table 6, it can be seen that the two-component curable resin compositions of Examples B11 to 14 have low viscosity and excellent workability, and the obtained cured product has good shear adhesiveness and impact-resistant peeling adhesiveness. ..

　実施例Ｂ１１～１４と比較例Ｂ３～５の組成物は、添加した（Ｂ）成分が異なるだけで（Ｂ）成分以外は全て同一配合組成である。実施例Ｂ１１～１４の組成物で用いた（Ｂ）成分は、平均粒子径が０．１５～０．３０μｍで、コア層／シェル層の重量比が６５／３５～９２／８で、シェル層を構成するモノマー成分が炭素数１～４のアルキル（メタ）アクリレートを主成分（５５重量％以上）である。一方、炭素数１～４のアルキル（メタ）アクリレートが８重量％と少ない比較例Ｂ３の組成物や、（Ｂ）成分の平均粒子径が０．０９μｍと小さい比較例Ｂ４の組成物や、コア層／シェル層の重量比が４８／５２でコア層の少ない比較例Ｂ５の組成物は、いずれも、第一成分の粘度が高く、作業性が悪い。更に、比較例Ｂ５の組成物の耐衝撃剥離接着性が低い値を示したことから、（Ｂ）成分のコア層／シェル層の重量比が耐衝撃剥離接着性に効いていると考えられる。また、（Ｂ）成分のシェル層にエポキシ基を含有しない実施例Ｂ１２と比較例Ｂ４の組成物も、耐衝撃剥離接着性が比較的低い値を示した。この結果より、（Ｂ）成分のシェル層中のエポキシ基の量が耐衝撃剥離接着性に効いていると考えられる。 The compositions of Examples B11 to 14 and Comparative Examples B3 to 5 have the same composition except for the added component (B) but the component (B). The component (B) used in the compositions of Examples B11 to 14 has an average particle size of 0.15 to 0.30 μm, a core layer / shell layer weight ratio of 65/35 to 92/8, and a shell layer. The monomer component constituting the above is mainly composed of an alkyl (meth) acrylate having 1 to 4 carbon atoms (55% by weight or more). On the other hand, the composition of Comparative Example B3 in which the amount of alkyl (meth) acrylate having 1 to 4 carbon atoms is as small as 8% by weight, the composition of Comparative Example B4 in which the average particle size of the component (B) is as small as 0.09 μm, and the core. In each of the compositions of Comparative Example B5 having a layer / shell layer weight ratio of 48/52 and a small core layer, the viscosity of the first component is high and the workability is poor. Further, since the composition of Comparative Example B5 showed a low impact-resistant peeling adhesiveness, it is considered that the weight ratio of the core layer / shell layer of the component (B) is effective for the impact-resistant peeling adhesiveness. Further, the compositions of Example B12 and Comparative Example B4, which do not contain an epoxy group in the shell layer of the component (B), also showed a value of relatively low impact resistance peeling adhesiveness. From this result, it is considered that the amount of the epoxy group in the shell layer of the component (B) is effective for the impact resistance peeling adhesiveness.

Figure JPOXMLDOC01-appb-T000007
　表７から、第一成分に（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分を含有し、第二成分に（Ｃ）成分及び（Ｄ）成分を含有する実施例Ｂ１５～１７の二成分型硬化性樹脂組成物は、熱伝導率が高く、難燃性に優れ、低粘度で作業性に優れることが分かる。
Figure JPOXMLDOC01-appb-T000007
 From Table 7, 2 of Examples B15 to 17 containing the component (A), the component (B), and the component (C) in the first component, and the components (C) and (D) in the second component. It can be seen that the component-type curable resin composition has high thermal conductivity, excellent flame retardancy, low viscosity, and excellent workability.

　実施例Ｂ１５～１７と比較例Ｂ６の組成物は、添加した（Ｃ）成分量が異なるだけで（Ｃ）成分量以外は全て同一配合組成である。硬化性樹脂組成物の総重量に対する（Ｃ）成分の総重量が少ない比較例Ｂ６では、熱伝導率が比較的低く、ＵＬ－９４難燃性試験で不合格（規格外）となった。 The compositions of Examples B15 to 17 and Comparative Example B6 all have the same composition except for the amount of the added component (C) but the amount of the component (C). In Comparative Example B6 in which the total weight of the component (C) was small with respect to the total weight of the curable resin composition, the thermal conductivity was relatively low, and the UL-94 flame retardancy test failed (non-standard).

　〔実施例Ｃ〕
　以下に実施例Ｃを掲げて第２実施形態をさらに詳細に説明するが、本発明はこれら実施例Ｃに限定されるものではない。 [Example C]
The second embodiment will be described in more detail below with reference to Example C, but the present invention is not limited to these Examples C.

　（体積平均粒子径の測定）
　製造例Ｃに記載されたポリブタジエンゴムラテックス中のポリブタジエンゴム粒子、及び、コアシェルポリマーラテックス中のコアシェルポリマー粒子の平均粒子径の測定方法は、前記〔実施例Ａ〕の（体積平均粒子径の測定）の項に記載の方法と同じである。そのため、前記〔実施例Ａ〕の（体積平均粒子径の測定）の項の記載を援用し、ここでは説明を省略する。 (Measurement of volume average particle size)
The method for measuring the average particle size of the polybutadiene rubber particles in the polybutadiene rubber latex and the core-shell polymer particles in the core-shell polymer latex described in Production Example C is the above-mentioned (Measurement of volume average particle size) in [Example A]. It is the same as the method described in the section. Therefore, the description in the section (Measurement of volume average particle size) in [Example A] is referred to, and the description thereof is omitted here.

　Ｃ１．コア層の形成
　実施例Ｃにおいて、コア層としては、前記〔実施例Ａ〕の「製造例Ａ１；ポリブタジエンゴムラテックス（Ｒ－２）の調製」の項に記載の方法で得られたＲ－２を使用した。そのため、前記〔実施例Ａ〕の「製造例Ａ１；ポリブタジエンゴムラテックス（Ｒ－２）の調製」の項の記載を援用し、ここでは説明を省略する。 C1. Formation of core layer In Example C, the core layer is R-2 obtained by the method described in the above-mentioned "Production Example A1; Preparation of Polybutadiene Rubber Latex (R-2)" in [Example A]. It was used. Therefore, the description in the section "Production Example A1; Preparation of Polybutadiene Rubber Latex (R-2)" in [Example A] is referred to, and the description thereof is omitted here.

　Ｃ２．コアシェルポリマーラテックスの調製（シェル層の形成）
　製造例Ｃ２－１；コアシェルポリマーラテックス（ＣＬ－１）の調製
　温度計、撹拌機、還流冷却器、窒素流入口、及びモノマーの添加装置を有するガラス反応器に、製造例Ａ１で調製したポリブタジエンゴムラテックス（Ｒ－２）２６２重量部（ポリブタジエンゴム粒子８７重量部を含む）、及び、脱イオン水５７重量部を仕込み、窒素置換を行いながら６０℃で撹拌した。ＥＤＴＡ０．００４重量部、ＦＥ０．００１重量部、及びＳＦＳ０．２重量部を加えた後、シェルモノマー（メチルメタクリレート（ＭＭＡ）３重量部、スチレン（ＳＴ）６重量部、アクリロニトリル（ＡＮ）２重量部、グリシジルメタクリレート（ＧＭＡ）２重量部）、及び、クメンヒドロパーオキサイド（ＣＨＰ）０．０４重量部の混合物を１２０分間かけて連続的に添加した。添加終了後、ＣＨＰ０．０４重量部を添加し、さらに２時間撹拌を続けて重合を完結させ、コアシェルポリマー粒子（Ｂ）を含む水性ラテックス（ＣＬ－１）を得た。モノマー成分の重合転化率は９９％以上であった。水性ラテックス（ＣＬ－１）に含まれるコアシェルポリマー粒子（Ｂ）の体積平均粒子径は０．２１μｍであった。 C2. Preparation of core-shell polymer latex (formation of shell layer)
Production Example C2-1; Preparation of core-shell polymer latex (CL-1) The polybutadiene rubber prepared in Production Example A1 was placed in a glass reactor equipped with a thermometer, agitator, reflux condenser, nitrogen inlet, and a monomer addition device. 262 parts by weight of latex (R-2) (including 87 parts by weight of polybutadiene rubber particles) and 57 parts by weight of deionized water were charged and stirred at 60 ° C. while performing nitrogen substitution. After adding 0.004 part by weight of EDTA, 0.001 part by weight of FE, and 0.2 part by weight of SFS, 3 parts by weight of shell monomer (methyl methacrylate (MMA), 6 parts by weight of styrene (ST), 2 parts by weight of acrylonitrile (AN)). , 2 parts by weight of glycidyl methacrylate (GMA)) and 0.04 part by weight of cumenhydroperoxide (CHP) were continuously added over 120 minutes. After completion of the addition, 0.04 part by weight of CHP was added, and the mixture was further stirred for 2 hours to complete the polymerization to obtain an aqueous latex (CL-1) containing core-shell polymer particles (B). The polymerization conversion rate of the monomer component was 99% or more. The volume average particle diameter of the core-shell polymer particles (B) contained in the aqueous latex (CL-1) was 0.21 μm.

　Ｃ３．硬化性樹脂中にコアシェルポリマー粒子（Ｂ）が分散した分散物（Ｍ）の調製
　製造例Ｃ３－１；分散物（Ｍ－１）の調製
　２５℃の１Ｌ混合槽にメチルエチルケトン（ＭＥＫ）１３２ｇを導入し、撹拌しながら、製造例Ｃ２－１で得たコアシェルポリマーラテックス（ＣＬ－１）を１３２ｇ（コアシェルポリマー粒子（Ｂ）４０ｇ相当）投入した。均一に混合後、水２００ｇを８０ｇ／分の供給速度で投入した。供給終了後、速やかに撹拌を停止したところ、浮上性の凝集体および有機溶媒を一部含む水相からなるスラリー液を得た。次に、一部の水相を含む凝集体を残し、水相３６０ｇを槽下部の払い出し口より排出させた。得られた凝集体にＭＥＫ９０ｇを追加して均一に混合し、コアシェルポリマー粒子（Ｂ）を均一に分散した分散体を得た。この分散体に、（Ａ）成分であるエポキシ樹脂（Ａ－１；三菱化学製、ＪＥＲ８２８：液状ビスフェノールＡ型エポキシ樹脂、エポキシ当量：１８４～１９４ｇ／ｅｑ）６０ｇを混合した。この混合物から、回転式の蒸発装置で、ＭＥＫを除去した。このようにして、エポキシ樹脂にコアシェルポリマー粒子（Ｂ）が分散した分散物（Ｍ－１）を得た。 C3. Preparation of dispersion (M) in which core-shell polymer particles (B) are dispersed in a curable resin Production Example C3-1; Preparation of dispersion (M-1) 132 g of methyl ethyl ketone (MEK) is introduced into a 1 L mixing tank at 25 ° C. Then, while stirring, 132 g (corresponding to 40 g of the core-shell polymer particles (B)) of the core-shell polymer latex (CL-1) obtained in Production Example C2-1 was added. After mixing uniformly, 200 g of water was added at a supply rate of 80 g / min. When the stirring was immediately stopped after the end of the supply, a slurry liquid consisting of a floating aggregate and an aqueous phase partially containing an organic solvent was obtained. Next, 360 g of the aqueous phase was discharged from the discharge port at the bottom of the tank, leaving an agglomerate containing a part of the aqueous phase. 90 g of MEK was added to the obtained aggregate and mixed uniformly to obtain a dispersion in which the core-shell polymer particles (B) were uniformly dispersed. This dispersion was mixed with 60 g of an epoxy resin (A-1; manufactured by Mitsubishi Chemical Corporation, JER828: liquid bisphenol A type epoxy resin, epoxy equivalent: 184 to 194 g / eq) as a component (A). MEK was removed from this mixture with a rotary evaporator. In this way, a dispersion (M-1) in which the core-shell polymer particles (B) were dispersed in the epoxy resin was obtained.

　製造例Ｃ３－２；分散物（Ｍ－２）の調製
　製造例Ｃ３－１において、エポキシ樹脂（Ａ－１）６０ｇの代わりに、エポキシ樹脂（Ａ－２；ヘキシオン製、ＥＰＯＮ８６３：ビスフェノールＦ型エポキシ樹脂、エポキシ当量：１６５～１７４ｇ／ｅｑ）６０ｇを用いたこと以外は製造例Ｃ３－１と同様にして、エポキシ樹脂にコアシェルポリマー粒子（Ｂ）が分散した分散物（Ｍ－２）を得た。 Production Example C3-2; Preparation of Dispersion (M-2) In Production Example C3-1, instead of 60 g of epoxy resin (A-1), epoxy resin (A-2; manufactured by Hexion, EPON863: bisphenol F type epoxy) Resin, epoxy equivalent: 165 to 174 g / eq) 60 g) was used in the same manner as in Production Example C3-1 to obtain a dispersion (M-2) in which core-shell polymer particles (B) were dispersed in an epoxy resin. ..

　（実施例Ｃ１～２３、比較例Ｃ１～７）
　表８～表１２に示す処方にしたがって、各成分をそれぞれ計量し、よく混合して二成分型硬化性樹脂組成物の第一成分及び第二成分を得た。実施例Ｃ１～２３で得られた二成分型硬化性樹脂組成物は、第３実施形態に係る硬化性樹脂組成物（二成分型硬化性樹脂組成物）である。 (Examples C1 to 23, Comparative Examples C1 to 7)
Each component was weighed according to the formulations shown in Tables 8 to 12 and mixed well to obtain the first component and the second component of the two-component curable resin composition. The two-component curable resin composition obtained in Examples C1 to 23 is the curable resin composition (two-component curable resin composition) according to the third embodiment.

　表８または９の各二成分型硬化性樹脂組成物について、以下の方法で、硬化時間の評価を行った。 The curing time of each of the two-component curable resin compositions shown in Table 8 or 9 was evaluated by the following method.

　＜硬化時間＞
　表８または９の第一成分と第二成分とをよく混合して得た各二成分型硬化性樹脂組成物の５０℃での粘度の経時変化を、Ｍａｌｖｅｒｎ社製「ＢｏｈｌｉｎＣＶＯレオメーター」を用い、ＰＰ２５を使用し、プレートギャップ０．２ｍｍにて、ずり速度５ｓ－１で測定した。粘度測定は１０秒ごとに行い、第一成分と第二成分とを混合した直後の粘度を初期粘度とし、初期粘度の１０倍の粘度に達するまでの時間を計測して、これを硬化時間とした。硬化時間が短い程、硬化性に優れる。 <Curing time>
The change in viscosity of each two-component curable resin composition obtained by mixing the first component and the second component in Table 8 or 9 at 50 ° C. with time was measured using a "Bohlin CVO leometer" manufactured by Malvern. , PP25 was used, and the measurement was performed at a plate gap of 0.2 mm and a shear rate of 5s -1 . Viscosity measurement is performed every 10 seconds, the viscosity immediately after mixing the first component and the second component is taken as the initial viscosity, and the time until the viscosity reaches 10 times the initial viscosity is measured, and this is called the curing time. did. The shorter the curing time, the better the curing property.

　表８～表１２の各二成分型硬化性樹脂組成物について、以下の方法で、せん断接着強さの評価を行った。 The shear adhesive strength of each of the two-component curable resin compositions shown in Tables 8 to 12 was evaluated by the following method.

　＜せん断接着強さ＞
　表８～表１２の第一成分と第二成分とをよく混合して得た各二成分型硬化性樹脂組成物を、幅２５ｍｍ×長さ１００ｍｍ×厚み１．６ｍｍの２枚のアルミニウム板（Ａ－５０５２Ｐ）または冷間圧延鋼板に塗布し、塗布された二成分型硬化性樹脂組成物（接着層）が幅２５ｍｍ×長さ１２．５ｍｍ×厚み０．２５ｍｍとなるように貼りあわせ、２３℃×７日の条件で硬化させて積層体を得た。 <Shear adhesion strength>
Each of the two-component curable resin compositions obtained by mixing the first component and the second component of Tables 8 to 12 well was formed into two aluminum plates having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm. A-5052P) or cold-rolled steel sheet is coated, and the applied two-component curable resin composition (adhesive layer) is bonded so as to have a width of 25 mm, a length of 12.5 mm, and a thickness of 0.25 mm. A laminate was obtained by curing under the conditions of ° C. × 7 days.

　　測定温度を２３℃、テストスピードを１．３ｍｍ／ｍｉｎとした測定条件で、単位をＭＰａとしたせん断接着強さを測定した。結果を表８～表１２に示す。 Shear adhesion strength was measured with MPa as the unit under measurement conditions with a measurement temperature of 23 ° C and a test speed of 1.3 mm / min. The results are shown in Tables 8 to 12.

　表１０の各二成分型硬化性樹脂組成物について、以下の方法で、動的割裂抵抗力（耐衝撃剥離接着性）の評価を行った。 The dynamic split resistance (impact peeling adhesiveness) was evaluated for each two-component curable resin composition in Table 10 by the following method.

　＜動的割裂抵抗力（耐衝撃剥離接着性）＞
　表１０の第一成分と第二成分をよく混合して得た各組成物を、２枚の冷間圧延鋼板に塗布し、接着層厚み０．２５ｍｍとなるように重ね合せ、２３℃×７日の条件で硬化させて積層体を得た。この積層体を用いて、ＩＳＯ　１１３４３に従って、２３℃で動的割裂抵抗力（耐衝撃剥離接着性）を測定した。結果を表１０に示す。 <Dynamic split resistance (impact peeling adhesiveness)>
Each composition obtained by mixing the first component and the second component in Table 10 well was applied to two cold-rolled steel sheets and superposed so as to have an adhesive layer thickness of 0.25 mm, and 23 ° C. × 7 It was cured under the conditions of the day to obtain a laminated body. Using this laminate, the dynamic split resistance (impact peeling adhesiveness) was measured at 23 ° C. according to ISO 11343. The results are shown in Table 10.

　なお、表８～表１２中の各種配合剤は、以下に示すものを使用した。
＜エポキシ樹脂（Ａ）＞
Ａ－１：ＪＥＲ８２８（三菱化学製、常温で液状のビスフェノールＡ型エポキシ樹脂、エポキシ当量：１８４～１９４）
Ａ－２：ＥＰＯＮ８６３（ヘキシオン製、ビスフェノールＦ型エポキシ樹脂、エポキシ当量：１６５～１７４）
＜エポキシ樹脂（Ａ）中にコアシェルポリマー粒子（Ｂ）が分散した分散物（Ｍ）＞
ＣＭ－１～２：前記製造例Ｃ３－１～２で得られた分散物
＜化合物（Ｇ）＞
レゾルシノール（富士フィルム和光純薬工業製）
カテコール（富士フィルム和光純薬工業製）
4-tert-ブチルカテコール（富士フィルム和光純薬工業製）
メチルヒドロキノン（東京化成製）
tert-ブチルヒドロキノン（東京化成製）
＜（Ｇ）成分と異なる、フェノール性水酸基を有する化合物＞
2,5-ジ-tert-ブチルヒドロキノン（東京化成製）
2,4,6-トリス（ジメチルアミノメチル）フェノール（東京化成製）
4-tert-ブチルフェノール（東京化成製）
フェノール（富士フィルム和光純薬工業製）
4-メトキシフェノール（富士フィルム和光純薬工業製）
＜エポキシ硬化剤（Ｄ）＞
Ｄ－１（脂環族アミン）：１，３－ビス(アミノメチル)シクロヘキサン（富士フイルム和光純薬製）
Ｄ－２（アミン末端ポリエーテル）：Ａｎｃａｍｉｎｅ　１９２２Ａ（Ｅｖｏｎｉｋ製、３，３’－（Ｏｘｙｂｉｓ（２，１－ｅｔｈａｎｅ－ｄｉｙｌｏｘｙ））ｂｉｓ－１－ｐｏｐａｎａｍｉｎｅ、活性水素等量：５５ｇ／ｅｑ）
Ｄ－３（アミン末端ブタジエンニトリルゴム）：Ｈｙｐｒｏ　ＡＴＢＮ　１３００ｘ１６（Ｈｕｎｔｓｍａｎ製、アミン末端ブタジエン－アクリロニトリル共重合体、分子量：約３８００、活性水素等量：８００～１０００ｇ／ｅｑ）
Ｄ－４（アミドアミン）：ベジケムグリーン　Ｖ１４０（築野食品製、ダイマー酸や脂肪酸とポリアミンとの縮合物、活性水素等量：９７ｇ／ｅｑ）
Ｄ－５（アミン末端ポリエーテル）：Ｊｅｆｆａｍｉｎｅ　Ｔ－５０００（Ｈｕｎｔｓｍａｎ製、グリセリルポリ（オキシプロピレン）トリアミン、分子量：約５０００、活性水素等量：９５２ｇ／ｅｑ）
＜水酸化アルミニウム（Ｃ）＞
Ｃ－１：Ｂ３０３（日本軽金属製、無処理水酸化アルミニウム、平均粒子径（Ｄｐ５０）：２６μｍ）
Ｃ－２：ＢＥ０３３（日本軽金属製、無処理水酸化アルミニウム、平均粒子径（Ｄｐ５０）：３．２μｍ）
＜エポキシシランカップリング剤（Ｆ）＞
Ｆ－１：ＤＯＷＳＩＬ　Ｚ－６０４０　Ｓｉｌａｎｅ（東レ・ダウコーニング製、３－グリシドキシプロピルトリメトキシシラン）
Ｆ－２：ＫＢＭ　６０３　Ｓｉｌａｎｅ（信越シリコーン製、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン）
＜重質炭酸カルシウム＞
ホワイトンＳＢ（白石カルシウム製、平均粒子径：１．８μｍ）
＜カーボンブラック＞
ＭＯＮＡＲＣＨ　２８０（Ｃａｂｏｔ製）
＜ヒュームドシリカ＞
ＣＡＢ－Ｏ－ＳＩＬ　ＴＳ－７２０（ＣＡＢＯＴ製、ポリジメチルシロキサンで表面処理されたヒュームドシリカ）、

Figure JPOXMLDOC01-appb-T000008
As the various compounding agents in Tables 8 to 12, those shown below were used.
<Epoxy resin (A)>
A-1: JER828 (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin liquid at room temperature, epoxy equivalent: 184 to 194)
A-2: EPON863 (made by hexion, bisphenol F type epoxy resin, epoxy equivalent: 165 to 174)
<Dispersion (M) in which core-shell polymer particles (B) are dispersed in epoxy resin (A)>
CM-1 to 2: Dispersion obtained in Production Examples C3-1 to 2 <Compound (G)>
Resorcinol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
Catechol (manufactured by Fuji Film Wako Pure Chemical Industries)
4-tert-Butylcatechol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
Methyl hydroquinone (manufactured by Tokyo Kasei)
tert-Butylhydroquinone (manufactured by Tokyo Kasei)
<Compound having a phenolic hydroxyl group different from the component (G)>
2,5-Di-tert-Butylhydroquinone (manufactured by Tokyo Kasei)
2,4,6-Tris (dimethylaminomethyl) phenol (manufactured by Tokyo Kasei)
4-tert-Butylphenol (manufactured by Tokyo Kasei)
Phenol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
4-methoxyphenol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
<Epoxy curing agent (D)>
D-1 (alicyclic amine): 1,3-bis (aminomethyl) cyclohexane (manufactured by Wako Pure Chemical Industries, Ltd.)
D-2 (amine-terminated polyether): Ancamine 1922A (manufactured by Evonik, 3,3'-(Oxybis (2,1-ethane-dyloxy)) bis-1-popanamine, active hydrogen equal amount: 55 g / eq)
D-3 (amine-terminated butadiene nitrile rubber): Hyper ATBN 1300x16 (manufactured by Huntsman, amine-terminated butadiene-acrylonitrile copolymer, molecular weight: about 3800, active hydrogen equal amount: 800 to 1000 g / eq)
D-4 (Amidamine): Vegechem Green V140 (manufactured by Tsukino Foods Co., Ltd., a condensate of dimer acid or fatty acid and polyamine, equivalent amount of active hydrogen: 97 g / eq)
D-5 (amine-terminated polyether): Jeffamine T-5000 (manufactured by Huntsman, glycerylpoly (oxypropylene) triamine, molecular weight: about 5000, active hydrogen equivalent: 952 g / eq)
<Aluminum hydroxide (C)>
C-1: B303 (Nippon Light Metal, untreated aluminum hydroxide, average particle size (Dp50): 26 μm)
C-2: BE033 (Nippon Light Metal, untreated aluminum hydroxide, average particle size (Dp50): 3.2 μm)
<Epoxy silane coupling agent (F)>
F-1: DOWNSIL Z-6040 Silane (manufactured by Toray Dow Corning, 3-glycidoxypropyltrimethoxysilane)
F-2: KBM 603 Silane (manufactured by Shinetsu Silicone, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane)
<Heavy calcium carbonate>
Whiten SB (made of Shiraishi calcium, average particle size: 1.8 μm)
<Carbon black>
MONARCH 280 (manufactured by Cabot)
<Humeed silica>
CAB-O-SIL TS-720 (CABOT, surface-treated fumed silica with polydimethylsiloxane),
Figure JPOXMLDOC01-appb-T000008

Figure JPOXMLDOC01-appb-T000009
　表８から、第一成分に（Ａ）成分～（Ｂ）成分を含有し、第二成分に（Ｇ）成分および（Ｄ）成分を含有する実施例Ｃ１～１２の二成分型硬化性樹脂組成物は、硬化時間が短く硬化性に優れることが分かる。
Figure JPOXMLDOC01-appb-T000009
 From Table 8, the two-component curable resin composition of Examples C1 to 12 containing the components (A) to (B) in the first component and the components (G) and (D) in the second component. It can be seen that the product has a short curing time and excellent curability.

　特に、芳香環上にフェノール性水酸基以外の置換基を有さない（Ｇ）成分を用いた実施例Ｃ１、２、７～１２の二成分型硬化性樹脂組成物は、得られる硬化物のせん断接着強度が高く、接着性にも優れることが分かる。 In particular, the two-component curable resin composition of Examples C1, 2, 7 to 12 using the component (G) having no substituent other than the phenolic hydroxyl group on the aromatic ring is the shearing of the obtained cured product. It can be seen that the adhesive strength is high and the adhesiveness is also excellent.

　また、（Ｆ）成分として、エポキシシランカップリング剤を含有する実施例Ｃ９～１０の二成分型硬化性樹脂組成物は、得られる硬化物のせん断接着強度が特に高く、接着性に優れることが分かる。 Further, the two-component curable resin composition of Examples C9 to 10 containing an epoxysilane coupling agent as the component (F) has a particularly high shear adhesive strength of the obtained cured product and is excellent in adhesiveness. I understand.

　一方、表９から、（Ｇ）成分を含有しない比較例Ｃ１、２個のフェノール性水酸基とそのオルト位に２個の第三級アルキル基を有する化合物を含有する比較例Ｃ２、及び、１個のフェノール性水酸基を有する化合物を含有する比較例Ｃ３～６の二成分型硬化性樹脂組成物は、硬化時間が長く硬化性に劣ることが分かる。

Figure JPOXMLDOC01-appb-T000010
On the other hand, from Table 9, Comparative Example C1 containing no component (G), Comparative Example C2 containing two phenolic hydroxyl groups and a compound having two tertiary alkyl groups at the ortho position thereof, and one. It can be seen that the two-component curable resin compositions of Comparative Examples C3 to C6 containing the compound having a phenolic hydroxyl group have a long curing time and are inferior in curability.
Figure JPOXMLDOC01-appb-T000010

Figure JPOXMLDOC01-appb-T000011
　表１１から、第一成分に（Ａ）成分～（Ｂ）成分を含有し、第二成分に（Ｇ）成分および（Ｄ）成分を含有する実施例Ｃ１４～１９の二成分型硬化性樹脂組成物は、得られる硬化物のせん断接着強さが良好であることが分かる。
Figure JPOXMLDOC01-appb-T000011
 From Table 11, the two-component curable resin composition of Examples C14 to 19 containing the components (A) to (B) in the first component and the components (G) and (D) in the second component. It can be seen that the product has good shear adhesion strength of the obtained cured product.

　なお、前記モル数の比が１．１～１．６の範囲である実施例Ｃ１５～１７の二成分型硬化性樹脂組成物は、前記モル数の比が１．０である実施例Ｃ１４の二成分型硬化性樹脂組成物と比較して、得られる硬化物のせん断接着強さが高い値を示し、前記モル数の比が１．１～１．６である二成分型硬化性樹脂組成物の接着性が特に優れることが分かる。 The two-component curable resin composition of Examples C15 to 17 in which the ratio of the number of moles is in the range of 1.1 to 1.6 is the same as that of Example C14 in which the ratio of the number of moles is 1.0. Compared with the two-component curable resin composition, the obtained cured product shows a high value in shear adhesive strength, and the ratio of the number of moles is 1.1 to 1.6. It can be seen that the adhesiveness of the object is particularly excellent.

　また、（Ｆ）成分として、エポキシシランカップリング剤を含有する実施例Ｃ１８～１９の二成分型硬化性樹脂組成物は、得られる硬化物のせん断接着強度が特に高く、接着性に優れることが分かる。 Further, the two-component curable resin composition of Examples C18 to 19 containing an epoxysilane coupling agent as the component (F) has a particularly high shear adhesive strength of the obtained cured product and is excellent in adhesiveness. I understand.

Figure JPOXMLDOC01-appb-T000012
　表１２から、第一成分に（Ａ）成分、（Ｂ）成分および（Ｇ）成分を含有し、第二成分に（Ｇ）成分および（Ｄ）成分、または（Ｄ）成分を含有する実施例Ｃ２０～２３の二成分型硬化性樹脂組成物は、得られる硬化物のせん断接着強さが良好であることが分かる。
Figure JPOXMLDOC01-appb-T000012
 From Table 12, an example in which the first component contains the component (A), the component (B) and the component (G), and the second component contains the component (G) and the component (D), or the component (D). It can be seen that the two-component curable resin compositions of C20 to 23 have good shear adhesion strength of the obtained cured product.

　一方、第一成分にも第二成分にも（Ｇ）成分を含有しない比較例Ｃ７の二成分型硬化性樹脂組成物は、実施例Ｃ２０～２３の二成分型硬化性樹脂組成物と比較して、（ｉ）硬化時間が非常に長く、かつ（ｉｉ）せん断接着強さが低い値を示した。 On the other hand, the two-component curable resin composition of Comparative Example C7 containing neither the first component nor the second component (G) is compared with the two-component curable resin compositions of Examples C20 to 23. Therefore, (i) the curing time was very long and (ii) the shear adhesive strength was low.

　なお、（Ｇ）成分以外の成分（例えば、（Ｄ）成分、（Ｅ）成分、（Ｆ）成分および（Ｅ）以外の無機充填材）は、硬化時間にはほぼ影響を与えない。そのため、実施例Ｃ１３～２３の二成分型硬化性樹脂組成物は、実施例Ｃ１または２と同程度の硬化時間を示す蓋然性が高く、すくなくとも比較例Ｃ１～７の二成分型硬化性樹脂組成物の硬化時間よりも短いものである。 It should be noted that the components other than the component (G) (for example, the component (D), the component (E), the component (F) and the inorganic filler other than the component (E)) have almost no effect on the curing time. Therefore, the two-component curable resin compositions of Examples C13 to 23 are highly likely to show a curing time similar to that of Examples C1 or 2, and at least the two-component curable resin compositions of Comparative Examples C1 to C7. It is shorter than the curing time of.

　本発明の一態様によると、二成分型または多成分型のエポキシ樹脂組成物として従来と比して優れた、新規の硬化性樹脂組成物を提供することができる。例えば、第１実施形態によると、優れた熱伝導性、難燃性、接着強度、及び耐衝撃剥離接着性を示す硬化物を与えることができ、かつ、室温または室温に近い低温でも硬化し得る二成分型の硬化性樹脂組成物を提供することができる。例えば、第２実施形態によると、優れた熱伝導性、難燃性、及び接着強度を示す硬化物を与えることができ、粘度が低く作業性が良好であり、かつ室温または室温に近い低温でも硬化し得る二成分型の硬化性樹脂組成物を提供することができる。例えば、第３実施形態によると、速硬化性に優れる、二成分型または多成分型の硬化性樹脂組成物を提供することができる。それ故、本発明の一実施形態に係る硬化性樹脂組成物は、車両や航空機向けの構造用接着剤、ＥＶバッテリーセル等の二次電池用接着剤、風力発電用構造接着剤などの接着剤、塗料、複合材料を得るためにガラス繊維および／または炭素繊維と積層するための材料、プリント配線基板用材料、ソルダーレジスト、層間絶縁膜、ビルドアップ材料、ＦＰＣ用接着剤、半導体・ＬＥＤ等電子部品用封止材等の電気絶縁材料、ダイボンド材料、アンダーフィル、半導体（例えばＡＣＦ、ＡＣＰ、ＮＣＦ、ＮＣＰ等）の実装材料、表示機器（例えば液晶パネルおよびＯＬＥＤディスプレイなど）および照明機器（例えばＯＬＥＤ照明など）用の封止材、コンクリート補修用複合材、などの用途に好ましく用いることができ、特に、二次電池用接着剤として好適に用いることができる。

  According to one aspect of the present invention, it is possible to provide a novel curable resin composition which is superior to the conventional one as a two-component type or multi-component type epoxy resin composition. For example, according to the first embodiment, it is possible to provide a cured product exhibiting excellent thermal conductivity, flame retardancy, adhesive strength, and impact-resistant peeling adhesiveness, and it can be cured at room temperature or a low temperature close to room temperature. A two-component curable resin composition can be provided. For example, according to the second embodiment, it is possible to provide a cured product exhibiting excellent thermal conductivity, flame retardancy, and adhesive strength, having a low viscosity and good workability, and even at room temperature or a low temperature close to room temperature. It is possible to provide a curable resin composition of a two-component type that can be cured. For example, according to the third embodiment, it is possible to provide a two-component type or a multi-component type curable resin composition having excellent fast-curing properties. Therefore, the curable resin composition according to one embodiment of the present invention is an adhesive for structural adhesives for vehicles and aircraft, adhesives for secondary batteries such as EV battery cells, and structural adhesives for wind power generation. , Paints, materials for laminating with glass fibers and / or carbon fibers to obtain composite materials, materials for printed wiring boards, solder resists, interlayer insulating films, build-up materials, adhesives for FPCs, semiconductors, LEDs, etc. Electrical insulation materials such as encapsulants for parts, die bond materials, underfills, mounting materials for semiconductors (eg ACF, ACP, NCF, NCP, etc.), display equipment (eg liquid crystal panels and OLED displays, etc.) and lighting equipment (eg OLED). It can be preferably used as a sealing material for lighting, etc.), a composite material for repairing concrete, and the like, and in particular, it can be preferably used as an adhesive for a secondary battery.

Claims (15)

　二成分型の硬化性樹脂組成物であって、
　エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含み、
　前記硬化性樹脂組成物は、更に、コア層とシェル層とを含むコアシェル構造を有するポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）とを含有し、
　前記硬化性樹脂組成物の総重量１００重量％における前記水酸化アルミニウム（Ｃ）の総重量が、５５重量％以上８５重量％以下であり、
　前記水酸化アルミニウム（Ｃ）の平均粒子径が、１１μｍ以上２００μｍ以下である、硬化性樹脂組成物。 A two-component curable resin composition
It contains a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
The curable resin composition further contains polymer particles (B) having a core-shell structure including a core layer and a shell layer, and aluminum hydroxide (C).
The total weight of the aluminum hydroxide (C) in 100% by weight of the total weight of the curable resin composition is 55% by weight or more and 85% by weight or less.
A curable resin composition having an average particle size of the aluminum hydroxide (C) of 11 μm or more and 200 μm or less. 　前記ポリマー粒子（Ｂ）の平均粒子径が、０．１５μｍ以上０．３０μｍ以下であり、
　前記ポリマー粒子（Ｂ）における、前記シェル層の重量に対する前記コア層の重量の比（前記コア層の重量／前記シェル層の重量）が、６５／３５～９２／８であり、
　前記ポリマー粒子（Ｂ）の前記シェル層が、モノマー成分１００重量％中炭素数１～４のアルキル（メタ）アクリレートを５５ｗｔ％以上含有する当該モノマー成分を重合してなる共重合体であり、
　前記モノマー成分は、当該モノマー成分１００重量％中、炭素数１のアルキル（メタ）アクリレートを１０～１００ｗｔ％および炭素数４のアルキル（メタ）アクリレートを０～８０ｗｔ％含有する、請求項１に記載の硬化性樹脂組成物。 The average particle size of the polymer particles (B) is 0.15 μm or more and 0.30 μm or less.
The ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer / weight of the shell layer) in the polymer particles (B) is 65/35 to 92/8.
The shell layer of the polymer particles (B) is a copolymer obtained by polymerizing the monomer component containing 55 wt% or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of the monomer component.
The first aspect of the present invention, wherein the monomer component contains 10 to 100 wt% of an alkyl (meth) acrylate having 1 carbon atom and 0 to 80 wt% of an alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the monomer component. Curable resin composition. 　前記エポキシ硬化剤（Ｄ）が、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される１種以上である、請求項１または２に記載の硬化性樹脂組成物。 The epoxy curing agent (D) is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified aliphatic amine, a modified alicyclic amine, or a modified amidamine. The curable resin composition according to claim 1 or 2, which is one or more selected from the group consisting of a modified product of an amine-terminated polyether and a modified product of an amine-terminated butadiene nitrile rubber. 　前記硬化性樹脂組成物は、更に、１分子中に（ｉ）１個の芳香環、および（ｉｉ）少なくとも２個のフェノール性水酸基を有する化合物（Ｇ）、を含有し、
　前記化合物（Ｇ）において、前記フェノール性水酸基に対してオルト位に位置する第三級アルキル基の個数は、１分子中に０個又は１個であり、
　前記エポキシ硬化剤（Ｄ）が、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上である、請求項１または２に記載の硬化性樹脂組成物。 The curable resin composition further contains (i) one aromatic ring and (ii) the compound (G) having at least two phenolic hydroxyl groups in one molecule.
In the compound (G), the number of tertiary alkyl groups located at the ortho position with respect to the phenolic hydroxyl group is 0 or 1 in one molecule.
The epoxy curing agent (D) is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified aliphatic amine, a modified alicyclic amine, or a modified amidamine. The curable resin composition according to claim 1 or 2, which is at least one selected from the group consisting of a modified product of an amine-terminated polyether and a modified product of an amine-terminated butadiene nitrile rubber. 　前記エポキシ硬化剤（Ｄ）が有する活性水素基のモル数に対する前記エポキシ樹脂（Ａ）が有するエポキシ基のモル数の比（前記エポキシ樹脂（Ａ）が有するエポキシ基のモル数／前記エポキシ硬化剤（Ｄ）が有する活性水素基のモル数）が、０．５以上１．５以下である、請求項１～４のいずれか１項に記載の硬化性樹脂組成物。 The ratio of the number of moles of the epoxy group of the epoxy resin (A) to the number of moles of the active hydrogen group of the epoxy curing agent (D) (the number of moles of the epoxy group of the epoxy resin (A) / the epoxy curing agent) The curable resin composition according to any one of claims 1 to 4, wherein the active hydrogen group (the number of moles of the active hydrogen group (D)) is 0.5 or more and 1.5 or less. 　前記ポリマー粒子（Ｂ）が、前記コア層にジエン系ゴムを有し、前記ジエン系ゴムが、ブタジエンゴム、および／または、ブタジエン－スチレンゴムである、請求項１～５のいずれか１項に記載の硬化性樹脂組成物。 The one according to any one of claims 1 to 5, wherein the polymer particles (B) have a diene-based rubber in the core layer, and the diene-based rubber is a butadiene rubber and / or a butadiene-styrene rubber. The curable resin composition according to the above. 　前記コアシェル構造を有するポリマー粒子（Ｂ）が、シェル層にエポキシ基を有する、請求項１～６のいずれか１項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 6, wherein the polymer particles (B) having a core-shell structure have an epoxy group in the shell layer. 　前記ポリマー粒子（Ｂ）が、前記シェル層にエポキシ基を有し、前記シェル層の総量に対する、前記シェル層が有する前記エポキシ基の含有量が０．１～２．０ｍｍｏｌ／ｇ以下である、請求項１～７のいずれか１項に記載の硬化性樹脂組成物。 The polymer particles (B) have an epoxy group in the shell layer, and the content of the epoxy group in the shell layer is 0.1 to 2.0 mmol / g or less with respect to the total amount of the shell layer. The curable resin composition according to any one of claims 1 to 7. 　前記ポリマー粒子（Ｂ）が、前記シェル層にエポキシ基を含有しない、請求項１～６のいずれか１項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 6, wherein the polymer particles (B) do not contain an epoxy group in the shell layer. 　請求項１～９のいずれか１項に記載の硬化性樹脂組成物を硬化してなる、硬化物。 A cured product obtained by curing the curable resin composition according to any one of claims 1 to 9. 　請求項１～９のいずれか１項に記載の硬化性樹脂組成物を含む、接着剤。 An adhesive containing the curable resin composition according to any one of claims 1 to 9. 　前記接着剤が二次電池用接着剤である、請求項１１に記載の接着剤。 The adhesive according to claim 11, wherein the adhesive is an adhesive for a secondary battery. 　２枚の基材と、請求項１２に記載の接着剤を硬化してなる接着層とを含み、
　前記接着層は、前記２枚の基材を接合している、積層体。 It comprises two substrates and an adhesive layer obtained by curing the adhesive according to claim 12.
The adhesive layer is a laminated body in which the two base materials are joined. 　二成分型の硬化性樹脂組成物であって、
　エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含み、
　前記硬化性樹脂組成物は、更に、コア層とシェル層とを含むコアシェル構造を有するポリマー粒子（Ｂ）と水酸化アルミニウム（Ｃ）とを含有し、
　前記硬化性樹脂組成物の総重量１００重量％における前記水酸化アルミニウム（Ｃ）の総重量が、５５重量％以上８５重量％以下であり、
　前記ポリマー粒子（Ｂ）の平均粒子径が、０．１５μｍ以上０．３０μｍ以下であり、
　前記ポリマー粒子（Ｂ）における、前記シェル層の重量に対する前記コア層の重量の比（前記コア層の重量／前記シェル層の重量）が、６５／３５～９２／８であり、
　前記ポリマー粒子（Ｂ）の前記シェル層が、モノマー成分１００重量％中炭素数１～４のアルキル（メタ）アクリレートを５５ｗｔ％以上含有する当該モノマー成分を重合してなる共重合体であり、
　前記モノマー成分は、当該モノマー成分１００重量％中、炭素数１のアルキル（メタ）アクリレートを１０～１００ｗｔ％および炭素数４のアルキル（メタ）アクリレートを０～８０ｗｔ％含有する、硬化性樹脂組成物。 A two-component curable resin composition
It contains a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
The curable resin composition further contains polymer particles (B) having a core-shell structure including a core layer and a shell layer, and aluminum hydroxide (C).
The total weight of the aluminum hydroxide (C) in 100% by weight of the total weight of the curable resin composition is 55% by weight or more and 85% by weight or less.
The average particle size of the polymer particles (B) is 0.15 μm or more and 0.30 μm or less.
The ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer / weight of the shell layer) in the polymer particles (B) is 65/35 to 92/8.
The shell layer of the polymer particles (B) is a copolymer obtained by polymerizing the monomer component containing 55 wt% or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100% by weight of the monomer component.
The monomer component is a curable resin composition containing 10 to 100 wt% of an alkyl (meth) acrylate having 1 carbon atom and 0 to 80 wt% of an alkyl (meth) acrylate having 4 carbon atoms in 100% by weight of the monomer component. .. 　二成分型または多成分型の硬化性樹脂組成物であって、
　エポキシ樹脂（Ａ）を含有する第一成分と、エポキシ硬化剤（Ｄ）を含有する第二成分と、を含み、
　前記硬化性樹脂組成物は、更に、コア層とシェル層とを含むコアシェル構造を有するポリマー粒子（Ｂ）と、１分子中に（ｉ）１個の芳香環、および（ｉｉ）少なくとも２個のフェノール性水酸基を有する化合物（Ｇ）と、を含有し、
　前記化合物（Ｇ）において、前記フェノール性水酸基に対してオルト位に位置する第三級アルキル基の個数は、１分子中に０個又は１個であり、
　前記エポキシ硬化剤（Ｄ）が、脂肪族アミン、脂環族アミン、アミドアミン、アミン末端ポリエーテル、アミン末端ブタジエンニトリルゴム、脂肪族アミンの変性物、脂環族アミンの変性物、アミドアミンの変性物、アミン末端ポリエーテルの変性物およびアミン末端ブタジエンニトリルゴムの変性物からなる群より選択される少なくとも１種以上である、硬化性樹脂組成物。 A two-component or multi-component curable resin composition,
It contains a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D).
The curable resin composition further comprises polymer particles (B) having a core-shell structure including a core layer and a shell layer, (i) one aromatic ring in one molecule, and (ii) at least two. Containing a compound (G) having a phenolic hydroxyl group,
In the compound (G), the number of tertiary alkyl groups located at the ortho position with respect to the phenolic hydroxyl group is 0 or 1 in one molecule.
The epoxy curing agent (D) is an aliphatic amine, an alicyclic amine, an amidoamine, an amine-terminated polyether, an amine-terminated butadiene nitrile rubber, a modified aliphatic amine, a modified alicyclic amine, or a modified amidamine. , A curable resin composition which is at least one selected from the group consisting of a modified product of an amine-terminated polyether and a modified product of an amine-terminated butadiene nitrile rubber.
PCT/JP2021/047831 2020-12-25 2021-12-23 Curable resin composition and adhesive agent Ceased WO2022138807A1 (en)

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WO2025249411A1 (en) * 2024-05-29 2025-12-04 株式会社カネカ Curable resin composition, use of curable resin composition, cured product, and method for producing cured product

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