WO2022186316A1 - 硬化性樹脂組成物及び接着剤 - Google Patents

硬化性樹脂組成物及び接着剤 Download PDF

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WO2022186316A1
WO2022186316A1 PCT/JP2022/009037 JP2022009037W WO2022186316A1 WO 2022186316 A1 WO2022186316 A1 WO 2022186316A1 JP 2022009037 W JP2022009037 W JP 2022009037W WO 2022186316 A1 WO2022186316 A1 WO 2022186316A1
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weight
parts
resin composition
curable resin
core
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PCT/JP2022/009037
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French (fr)
Japanese (ja)
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敏彦 岡本
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株式会社カネカ
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    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • 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
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present invention relates to a curable resin composition and an adhesive containing the same.
  • Vehicle noise and vibration countermeasures are important characteristics of vehicle body design that have been studied for some time. Noise propagating through partition walls, gaps, and the like through air has been dealt with by installing various soundproofing materials, sound absorbing materials, and sound insulating materials. In addition, noise and vibration propagating from the driving system such as the engine, tires and transmission through various parts of the vehicle body have been solved by using damping materials such as asphalt sheets. However, the problem is that these additional parts lead to an increase in vehicle weight. There is a need for a method of controlling vehicle noise and vibration while limiting the increase in vehicle weight.
  • Patent Document 1 studies are being conducted to reduce the weight of the vehicle body by applying a high elastic modulus epoxy-based structural adhesive to the vehicle body structure such as the center pillar.
  • Patent Document 2 discloses a technique for improving damping properties of vehicle body vibration without increasing vehicle weight by using an epoxy-based one-liquid type thermosetting adhesive composition that has a high elastic modulus and excellent vibration damping properties. ing.
  • Patent Document 3 discloses a technique for improving the toughness and impact resistance of the resulting cured product by dispersing fine polymer particles in a curable resin composition containing a curable resin such as an epoxy resin as a main component. ing.
  • thermosetting adhesive composition in order to improve the damping property of vehicle vibration near room temperature, a compounding agent that lowers the heat resistance (Tg) of the epoxy resin is used. (such as dimer acid-modified epoxy and rubber-modified epoxy) are added. Therefore, in the conventional one-liquid type thermosetting adhesive composition as described in Patent Document 2, the high elastic modulus (rigidity) inherent in the epoxy resin may be greatly reduced at high temperatures. In the case of automobiles, heat resistance of 80° C. or higher is required.
  • An object of one embodiment of the present invention is to provide a curable epoxy resin composition that maintains a high elastic modulus even at high temperatures and can give a cured product exhibiting excellent damping properties.
  • Crosslinked polymer particles having a specific composition ( A curable epoxy resin composition containing B) can maintain a high elastic modulus even at high temperatures and provide a cured product exhibiting excellent damping properties.
  • the curable resin composition according to one embodiment of the present invention is a curable resin composition containing 100 parts by weight of epoxy resin (A) and 1 to 100 parts by weight of crosslinked polymer particles (B), ,
  • the crosslinked polymer particles (B) are composed of crosslinked polymer particles (B-1), crosslinked polymer particles (B-2), and crosslinked polymer particles (B-3) described in (1) to (3) below. comprising one or more crosslinked polymer particles selected from the group;
  • the crosslinked polymer particle (B-1) has a core-shell structure and/or a single layer structure including a core layer and a shell layer, and the core layer and/or the single layer contains a crosslinkable monomer.
  • the crosslinked polymer particles (B-2) have a core-shell structure including a core layer and a shell layer, and the core layer contains a monomer mixture (m-2) containing no crosslinkable monomer.
  • the crosslinked polymer particles (B-3) have a core-shell structure including a core layer and a shell layer, and the shell layer has a glass transition temperature of ⁇ 20° C. or higher and 30° C. or lower as determined by the Fox formula ( It contains a meth)acrylate polymer (M-3′), and the content of the shell layer is 30% by weight or more and 90% by weight or less with respect to the total amount of the crosslinked polymer particles (B-3).
  • the curable resin composition according to one embodiment of the present invention configured as described above contains an epoxy resin and crosslinked polymer particles having a specific composition. Therefore, the cured product obtained from the curable resin composition maintains a high elastic modulus even at high temperatures and exhibits excellent damping properties.
  • weight is synonymous with “mass” and intends “mass”. Therefore, “weight” may be replaced with “mass” in the description of this specification.
  • a cured product obtained by curing the curable adhesive composition disclosed in Patent Document 2 exhibits a good modulus of elasticity at room temperature, but the modulus of elasticity decreases at high temperatures, and the rigidity at high temperatures may not be sufficient. there were.
  • the reason for this is that non-crosslinked elastomers such as dimer acid-modified epoxy resins and CTBN-modified epoxy resins used as components for imparting damping properties in Patent Document 2 partially or completely remain even after curing of the curable adhesive composition. continues to be compatible with the epoxy resin, lowering the high glass transition temperature characteristic of the epoxy resin. For example, in the case of automobiles, heat resistance of 80° C. or higher is required assuming summertime.
  • the present inventors have made intensive studies with the aim of providing a cured product that is excellent in rigidity and damping properties at room temperature and whose rigidity does not easily decrease even at high temperatures (elastic modulus does not easily decrease even at high temperatures). rice field.
  • the present inventor has newly discovered that the crosslinked polymer particles do not dissolve in the epoxy resin even after curing, and that the heat resistance of the cured epoxy resin is not substantially reduced. Based on such findings, the present inventors conducted extensive studies with the idea of achieving both high-temperature rigidity and damping performance by introducing a damping polymer component into the crosslinked polymer particles. As a result, the present inventors have found a curable resin composition containing crosslinked polymer particles containing a (meth)acrylate polymer (hereinafter also referred to as a "damping polymer”) having a glass transition temperature of ⁇ 20° C. or higher and 30° C. or lower. It was newly discovered that the cured product obtained by curing has a high attenuation property near room temperature.
  • a (meth)acrylate polymer hereinafter also referred to as a "damping polymer”
  • the present inventors have also newly discovered that the lower the degree of cross-linking of the "damping polymer” (the less the cross-linking monomer constituting the damping polymer), the better the damping property.
  • the present inventors have also newly discovered that the greater the content of the "damping polymer", the better the damping property.
  • the present inventor designed crosslinked polymer particles having the following three compositions (1) to (3) as crosslinked polymer particles containing a damping polymer, thereby achieving both rigidity and damping performance at high temperatures.
  • a curable resin composition was provided and the present invention was completed.
  • the crosslinked polymer particles (B-1) are obtained by adding a low-crosslinked (containing 0.1% by weight or more and 10% by weight or less of a crosslinkable monomer) attenuation polymer in the core layer to (B-1).
  • (B-1) may be a single-layer crosslinked polymer particle of the low-crosslinking damping polymer alone (100% by weight of the low-crosslinking damping polymer).
  • the crosslinked polymer particles (B-2) contain a non-crosslinked (containing no crosslinkable monomer) attenuation polymer in the core layer, and a low to highly crosslinked (with 1 crosslinkable monomer) in the shell layer.
  • the crosslinked polymer particles (B-3) are crosslinked polymer particles having a core-shell structure containing 30% by weight or more and 90% by weight or less of the damping polymer in the shell layer.
  • a curable resin composition capable of providing a cured product with excellent rigidity at high temperatures in addition to damping properties has not been reported so far, and it can be said to be a surprising discovery.
  • Such a curable resin composition is extremely useful as an adhesive, especially as an attenuating adhesive.
  • the curable resin composition according to one embodiment of the present invention can provide a cured product having excellent vibration damping properties and rigidity at high temperatures, and also has excellent adhesiveness. newly found.
  • Conventional attenuating adhesives such as those described in Patent Document 2 also have low adhesiveness, and from this point as well, the curable resin composition according to one embodiment of the present invention is extremely useful as an attenuating adhesive. is.
  • the curable resin composition according to one embodiment of the present invention (hereinafter, “the curable resin composition according to one embodiment of the present invention” may be referred to as the “main curable resin composition”) is epoxy A curable resin composition containing 100 parts by weight of a resin (A) and 1 to 100 parts by weight of crosslinked polymer particles (B), wherein the crosslinked polymer particles (B) are the following (1) to (3) Crosslinked polymer particles (B-1), crosslinked polymer particles (B-2), and crosslinked polymer particles (B-3) according to 1 or more selected from the group consisting of crosslinked polymer particles; (1)
  • the crosslinked polymer particle (B-1) has a core-shell structure or a single layer structure including a core layer and a shell layer, and the core layer and/or the single layer contains 0.00 of a crosslinkable monomer.
  • the crosslinked polymer particles (B-2) have a core-shell structure including a core layer and a shell layer, and the core layer contains a monomer mixture (m-2) containing no crosslinkable monomer.
  • Polymerized (meth)acrylate polymer (M-2) having a glass transition temperature of ⁇ 20° C. or higher and 30° C.
  • the crosslinked polymer particles (B-3) have a core-shell structure including a core layer and a shell layer, and the shell layer has a glass transition temperature of ⁇ 20° C. or higher and 30° C. or lower as determined by the Fox formula ( It contains a meth)acrylate polymer (M-3′), and the content of the shell layer is 30% by weight or more and 90% by weight or less with respect to the total amount of the crosslinked polymer particles (B-3).
  • the present curable resin composition has the above structure, it is possible to provide a cured product that maintains a high elastic modulus even at high temperatures and exhibits excellent damping properties.
  • the cured product can be obtained by curing the present curable resin composition by a known method.
  • cured material can also be called an "adhesion layer.”
  • Epoxy resin (A) and “crosslinked polymer particles (B)” are hereinafter sometimes referred to as “(A) component” and “(B) component”, respectively.
  • a curable resin composition of one embodiment of the present invention contains an epoxy resin (A) as a curable resin.
  • Various epoxy resins can be used as the epoxy resin.
  • epoxy resins include 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, glycidyl amine type epoxy resin, novolac type epoxy resin, bisphenol A Glycidyl ether type epoxy resin of propylene oxide adduct, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, fluorinated epoxy resin, flame retardant epoxy resin such as glycidyl ether of tetrabromobisphenol A, p-oxy Benzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, various alicyclic epoxy resins, N,N-diglycidy
  • polyalkylene glycol diglycidyl ether examples 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. be done.
  • diglycidyl esters of aliphatic polybasic acids include diglycidyl dimer, diglycidyl adipate, diglycidyl sebacate, and diglycidyl maleate.
  • the glycidyl ethers of dihydric or higher polyhydric aliphatic alcohols include trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil-modified polyglycidyl ether, propoxylated glycerol triglycidyl ether, and sorbitol. polyglycidyl ether and the like.
  • the polyalkylene glycol diglycidyl ether, the glycol diglycidyl ether, the diglycidyl ester of the aliphatic polybasic acid, and the glycidyl ether of the dihydric or higher polyhydric aliphatic alcohol are epoxy resins having relatively low viscosity. . Epoxy resins with these relatively low viscosities are sometimes referred to as "polyepoxides.” When other epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin are used in combination with polyepoxide, the polyepoxide functions as a reactive diluent to improve the balance between the viscosity of the composition and the physical properties of the cured product. can.
  • the epoxy resin (A) preferably contains polyepoxide as a reactive diluent.
  • monoepoxide functions as a reactive diluent as described later, but is not included in epoxy resin (A).
  • the content of these epoxy resins (for example, polyepoxides) that function as reactive diluents is preferably 0.5% to 30% by weight, more preferably 2% to 20% by weight, based on 100% by weight of component (A). , 5% to 15% by weight is more preferred.
  • the chelate-modified epoxy resin is a reaction product of an epoxy resin and a compound containing a chelate functional group (chelate ligand).
  • a chelate-modified epoxy resin When the curable resin composition contains a chelate-modified epoxy resin, it is possible to improve the adhesiveness (adhesive strength) to the surface of a metal substrate contaminated with an oily substance, and the curable resin composition is particularly suitable as an adhesive for vehicle components. become a thing.
  • a chelate functional group is a functional group of a compound having multiple coordination sites in the molecule that can coordinate to a metal ion. CO 2 H), sulfur-containing acid groups (eg —SO 3 H), amino groups and hydroxyl groups (especially hydroxyl groups adjacent to each other on an aromatic ring), and the like.
  • Chelating ligands include ethylenediamine, bipyridine, ethylenediaminetetraacetic acid, phenanthroline, porphyrin, crown ether, and the like.
  • a commercially available chelate-modified epoxy resin can also be used as the chelate-modified epoxy resin.
  • Commercially available chelate-modified epoxy resins include ADEKA ADEKA ADEKA RESIN EP-49-10N.
  • the amount (content) of the chelate-modified epoxy resin used in 100 wt % of component (A) is preferably 0.1 wt % to 10 wt %, more preferably 0.5 wt % to 3 wt %.
  • Examples of epoxy compounds obtained by addition reaction of polybasic acids and the like to epoxy resins include, for example, a dimer of tall oil fatty acid (dimer acid) and bisphenol A, as described in International Publication No. 2010-098950.
  • addition reaction products dimer acid-modified epoxy resins
  • type epoxy resins type epoxy resins.
  • the amount (content) of the dimer acid-modified epoxy resin used is preferably 60% by weight or less, more preferably 50% by weight or less, more preferably 50% by weight or less, based on 100% by weight of component (A), from the viewpoint of the heat resistance of the resulting cured product. Weight % or less is more preferable.
  • the rubber-modified epoxy resin is intended to be a reaction product obtained by reacting rubber with an epoxy group-containing compound.
  • the rubber-modified epoxy resin preferably has 1.1 or more, more preferably 2 or more, epoxy groups on average per molecule.
  • examples of rubber include acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), hydrogenated nitrile rubber (HNBR), carboxyl group-terminated NBR (CTBN), ethylene propylene rubber (EPDM), acrylic rubber (ACM), butyl rubber (IIR ), butadiene rubber, and polyoxyalkylenes such as polypropylene oxide, polyethylene oxide, and polytetramethylene oxide.
  • NBR acrylonitrile butadiene rubber
  • SBR styrene butadiene rubber
  • HNBR hydrogenated nitrile rubber
  • CBN carboxyl group-terminated NBR
  • EPDM ethylene propylene rubber
  • ACM acrylic rubber
  • IIR but
  • the rubber-based polymer preferably has a reactive group such as an amino group, a hydroxyl group, or a carboxyl group at its terminal.
  • a rubber-modified epoxy resin is a reaction product obtained by reacting these rubber-based polymers and an epoxy resin at an appropriate compounding ratio by a known method.
  • rubber-modified epoxy resins acrylonitrile-butadiene rubber-modified epoxy resins and polyoxyalkylene-modified epoxy resins are preferable from the viewpoint of adhesiveness (adhesive strength) and impact resistance of the resulting curable resin composition, and acrylonitrile-butadiene Rubber-modified epoxy resins are more preferred.
  • the acrylonitrile-butadiene rubber-modified epoxy resin can be obtained, for example, by reacting a carboxyl-terminated NBR (CTBN) with a bisphenol A type epoxy resin.
  • CBN carboxyl-terminated NBR
  • the content of the component derived from the acrylonitrile monomer in the acrylonitrile-butadiene rubber is (i) the adhesiveness (adhesive strength) of the resulting curable resin composition.
  • the adhesiveness adheresive strength
  • the resulting curable resin composition 20% by weight to 30% by weight is particularly preferable from the viewpoint of workability of the product.
  • the workability of the curable resin composition can be evaluated, for example, by the viscosity of the curable resin composition. For example, when the viscosity of the curable resin composition is low, it can be said that the curable resin composition is excellent in workability.
  • addition reaction products of amino group-terminated polyoxyalkylenes and epoxy resins are also included in rubber-modified epoxy resins.
  • the addition reaction product can be easily produced by known methods, for example, as described in US Pat. No. 5,084,532 and US Pat. No. 6,015,865.
  • Examples of the epoxy resin used in producing the addition reaction product include specific examples of the component (A) described above, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable, type epoxy resins are more preferred.
  • Examples of the commercially available amino group-terminated polyoxyalkylene used in producing the addition reaction product include Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000 and Jeffamine manufactured by Huntsman. D-4000, Jeffamine T-5000 and the like.
  • the average number of epoxide-reactive terminal groups per molecule in the rubber is preferably 1.5 to 2.5, more preferably 1.8 to 2.2.
  • the number average molecular weight of the rubber is preferably 1,000 to 10,000, more preferably 2,000 to 8,000, and particularly preferably 3,000 to 6,000 in terms of polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the method for producing the rubber-modified epoxy resin 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 the epoxy group-containing compound. Specifically, it is preferable to react two or more equivalents of an epoxy group-containing compound with one equivalent of epoxy-reactive terminal groups in the rubber. It is more preferable to react a sufficient amount of the epoxy group-containing compound with the rubber so that the resulting addition reaction product is a mixture of the adduct of the rubber and the epoxy group-containing compound and the free epoxy group-containing compound. .
  • rubber-modified epoxy resins are produced by heating a mixture of an epoxy group-containing compound with rubber to a temperature of 100° C. to 250° C.
  • the epoxy group-containing compound used in producing the rubber-modified epoxy resin is not particularly limited, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferred, and bisphenol A type epoxy resin is more preferred. If an excessive amount of the epoxy group-containing compound is used during the production of the rubber-modified epoxy resin, unreacted epoxy group-containing compound may remain in the reaction product obtained after the reaction. The unreacted epoxy group-containing compound remaining in this way is not included in the rubber-modified epoxy resin referred to in this specification.
  • the rubber-modified epoxy resin can be modified by pre-reacting the bisphenol component and the rubber-modified epoxy resin.
  • the bisphenol component used for modification is preferably 3 to 35 parts by weight, more preferably 5 to 25 parts by weight, per 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 adhesion durability after exposure to high temperatures, 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, still more 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 1,500 to 40,000, more preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000 in terms of polystyrene equivalent molecular weight measured by GPC.
  • This configuration has the advantage that the resulting curable resin composition is excellent in adhesiveness (adhesive strength) and workability.
  • the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight (weight average molecular weight/number average molecular weight)) of the rubber-modified epoxy resin is preferably 1.0 to 4.0, more preferably 1.2 to 3.0. , 1.5 to 2.5 are particularly preferred.
  • This configuration has the advantage that the resulting curable resin composition has excellent workability.
  • the rubber-modified epoxy resins can be used singly or in combination of two or more.
  • the amount (content) of the rubber-modified epoxy resin used in 100% by weight of component (A) is preferably 1% to 50% by weight, more preferably 2% to 40% by weight. Preferably, 5% to 30% by weight is more preferable, and 10% to 20% by weight is particularly preferable.
  • the urethane-modified epoxy resin is a reaction product obtained by reacting a compound containing a group reactive with an isocyanate group and an epoxy group with a urethane prepolymer containing an isocyanate group.
  • the urethane-modified epoxy resin preferably has 1.1 or more epoxy groups, more preferably 2 or more, on average per molecule.
  • 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 1,500 to 40,000, more preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000 in terms of polystyrene equivalent molecular weight measured by GPC.
  • This configuration has the advantage that the resulting curable resin composition is excellent in adhesiveness (adhesive strength) and workability.
  • the molecular weight distribution of the urethane-modified epoxy resin (the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight)) is preferably 1.0 to 4.0, more preferably 1.2 to 3.0. , 1.5 to 2.5 are particularly preferred.
  • This configuration has the advantage that the resulting curable resin composition has excellent workability.
  • the urethane-modified epoxy resins can be used singly or in combination of two or more.
  • the amount (content) of the urethane-modified epoxy resin used in 100% by weight of component (A) is preferably 1% to 50% by weight, more preferably 2% to 40% by weight. Preferably, 5% to 30% by weight is more preferable, and 10% to 20% by weight is particularly preferable.
  • the total amount of dimer acid-modified epoxy resin, rubber-modified epoxy resin, and urethane-modified epoxy resin is preferably 70% by weight or less, preferably 60% by weight, based on 100% by weight of component (A), from the viewpoint of the heat resistance of the resulting cured product.
  • the following is more preferable, 50% by weight or less is even more preferable, and 40% by weight or less is particularly preferable.
  • an epoxy resin having at least two epoxy groups in one molecule has high curability, and the cured product after curing is highly flexible. It is preferable from the viewpoint of being excellent in the effect of improving impact peel resistance.
  • the epoxy resin (A) a compound having two epoxy groups in one molecule (epoxy resin) is particularly preferable.
  • the epoxy resin (A) preferably contains an epoxy resin (A1) having an epoxy equivalent of 90 g/eq or more and less than 200 g/eq, more preferably 100 g/eq or more and less than 195 g/eq. more preferably 120 g/eq or more and less than 191 g/eq of the epoxy resin (A1), more preferably 150 g/eq or more and less than 190 g/eq of the epoxy resin (A1) Especially preferred.
  • the "epoxy resin (A1)" may be referred to as "(A1) component".
  • the content of the epoxy resin (A1) in the total amount of the epoxy resin (A) in the present curable resin composition in other words, the content of the epoxy resin (A1) in 100% by weight of the epoxy resin (A) explain.
  • the content is preferably 25% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, and particularly preferably 60% by weight or more, from the viewpoints of elastic modulus and heat resistance of the resulting cured product.
  • the number average molecular weight of the epoxy resin (A) is preferably 180 or more and less than 400, more preferably 300 or more and less than 390.
  • the epoxy resin (A) preferably contains a bisphenol A type epoxy resin (A2) and/or a bisphenol F type epoxy resin (A2), and particularly preferably contains a bisphenol A type epoxy resin (A2).
  • A2 bisphenol A type epoxy resin
  • A2 bisphenol F type epoxy resin
  • (A2) component may be referred to as "(A2) component".
  • the content of bisphenol A type epoxy resin (A2) and/or bisphenol F type epoxy resin (A2) in the total amount of epoxy resin (A) in the present curable resin composition in other words epoxy resin (A) 100
  • the content (total content) of the bisphenol A type epoxy resin (A2) and/or the bisphenol F type epoxy resin (A2) in wt% will be explained.
  • the content (total content) is preferably 25% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, and 60% by weight, from the viewpoint of the elastic modulus and heat resistance of the resulting cured product. The above are particularly preferred.
  • a bisphenol A type epoxy resin (A3) having an epoxy equivalent of 90 g/eq or more and less than 200 g/eq and/or an epoxy equivalent of 90 g/eq.
  • a bisphenol F type epoxy resin (A3) having a content of 200 g/eq or more is used.
  • the total amount of the component (A1) and the component (A2) is, from the viewpoint of the elastic modulus and heat resistance of the resulting cured product, in 100% by weight of the component (A) 25% by weight or more is preferable, 40% by weight or more is more preferable, 50% by weight or more is still more preferable, and 60% by weight or more is particularly preferable.
  • a bisphenol A type epoxy resin having an epoxy equivalent weight of less than 200 g/eq and a bisphenol F type epoxy resin having an epoxy equivalent weight of less than 200 g/eq are liquid at room temperature, and the resulting curable resin composition has good handleability. Therefore, it is preferable.
  • the epoxy resin (A) is a bisphenol A type epoxy resin having an epoxy equivalent of 200 g/eq or more and less than 5000 g/eq and/or an epoxy equivalent of 200 g/eq or more and less than 5000 g/eq. of the bisphenol F type epoxy resin, more preferably 40% by weight or less, more preferably 20% by weight or less, based on 100% by weight of component (A).
  • the curable resin composition according to one embodiment of the present invention can provide a cured product with excellent damping properties due to the damping property improving effect of the component (B). Furthermore, the curable resin composition according to one embodiment of the present invention has excellent toughness and adhesiveness due to the toughness improving effect of the component (B), and further has a high Tg and good heat resistance and elastic modulus (rigidity). A cured product can be provided. In the curable resin composition according to one embodiment of the present invention, the component (B) exerts an effect of improving toughness and does not substantially reduce the heat resistance of the cured epoxy resin, so that the elastic modulus (rigidity) can provide a cured product that is good.
  • the curable resin composition according to one embodiment of the present invention contains 1 to 100 parts by mass of crosslinked polymer particles (B) per 100 parts by mass of component (A).
  • the present curable resin composition preferably contains 3 parts by mass to 70 parts by mass, more preferably 5 parts by mass to 50 parts by mass, of component (B) with respect to 100 parts by mass of component (A). It is more preferable to contain 10 parts by mass to 40 parts by mass.
  • a (meth)acrylate polymer having a glass transition temperature (Tg) of ⁇ 20° C. or higher and 30° C. or lower is included as an attenuation property imparting component (hereinafter also referred to as “attenuation polymer”). It contains one or more crosslinked polymer particles selected from the group consisting of crosslinked polymer particles (B-1) to (B-3) having specific compositions having the configurations (1) to (3).
  • Component (B) in one embodiment of the present invention is more preferably one or more crosslinked polymer particles selected from the group consisting of crosslinked polymer particles (B-1) to (B-3).
  • (meth)acrylate means acrylate and/or methacrylate.
  • the glass transition temperature (Tg) of the (meth)acrylate polymer is calculated in Kelvin temperature by the following FOX formula (Formula 1) and converted into Celsius temperature. From the viewpoint of damping properties of the cured product, the glass transition temperature of the (meth)acrylate polymer (damping polymer) must be ⁇ 20° C. or higher and 30° C. or lower, and ⁇ 15° C. or higher and 25° C. or lower. It is preferably -10°C or higher and 20°C or lower, more preferably -5°C or higher and 18°C or lower, and particularly preferably 0°C or higher and 15°C or lower.
  • the crosslinked polymer particles (B-1) have a core-shell structure including a core layer and a shell layer, or have a single-layer structure.
  • a crosslinked polymer particle having a core-shell structure and a crosslinked polymer particle having a monolayer structure may be used in combination.
  • the crosslinked polymer particles (B-1) are obtained by polymerizing a monomer mixture (m-1) containing 0.1% by weight or more and 10% by weight or less of a crosslinkable monomer, and the glass transition obtained by the Fox formula A (meth)acrylate polymer (M-1) having a temperature of -20°C or higher and 30°C or lower is contained in an amount of 60% or more and 100% or less by weight based on the total amount of (B-1).
  • the (meth)acrylate polymer (M-1) corresponds to the damping polymer described above.
  • crosslinked polymer particles having a core-shell structure including a core layer and a shell layer may be referred to as “core-shell polymer” or “core-shell polymer particles”.
  • core-shell polymer or “core-shell polymer particles”.
  • crosslinked polymer particles having a single-layer structure may be referred to as “single-layer polymer” or “single-layer polymer particles.”
  • the core layer and/or the single layer preferably contain (M-1), and more preferably consist of (M-1) only.
  • the core layer and/or the single layer are more preferably formed of (M-1).
  • "X is composed only of Y” can also be said to be "X is Y”.
  • (M-1) is contained in an amount of 60% by weight or more and less than 100% by weight with respect to the total amount of (B-1). be done.
  • the shell layer preferably contains a (meth)acrylate polymer (M-1′) obtained by graft-polymerizing the monomer mixture (m-1′) to the core layer, and only (M-1′) It is more preferable to consist of
  • the (meth)acrylate polymer (M-1′) is not particularly limited, and those described in ((meth)acrylate polymer) described later can be used.
  • the (meth)acrylate polymer (M-1′) contains a (meth)acrylate polymer (M-1′-a) having a glass transition temperature of ⁇ 20° C. or higher and 30° C. or lower as determined by the Fox formula. is preferred, and it is more preferred that it consists only of (M-1′-a). According to this configuration, there is an advantage that a cured product obtained by curing the obtained curable resin composition has excellent vibration damping properties.
  • the content of the epoxy group in the (meth)acrylate polymer (M-1′) is, from the viewpoint of improving the vibration damping properties and adhesiveness of the cured product obtained by curing the curable resin composition, (M- 1′) with respect to the total amount is preferably 0.0 mmol/g or more and 2.0 mmol/g or less, more preferably 0.1 mmol/g or more and 1.0 mmol/g or less, and 0.2 mmol/g More than 0.7 mmol/g and less than 0.7 mmol/g are particularly preferable.
  • the content of epoxy groups in (M-1′) being 0.0 mmol/g with respect to the total amount of (M-1′) means that (M-1′) does not contain epoxy groups. intended to (M-1') may not contain an epoxy group.
  • the monolayer in the crosslinked polymer particles having a monolayer structure is formed by (M-1)
  • the monolayer polymer (B-1) is added to the total amount of (B-1) (M- 1) is contained in an amount of 100% by weight. That is, if the single layer is formed from (M-1), the single layer (B-1) is formed from (M-1) only.
  • the crosslinked polymer particles (B-1) may be monolayer crosslinked polymer particles composed only of the (meth)acrylate polymer (M-1). This configuration has the advantage of shortening the time required to produce the crosslinked polymer particles (B-1) and improving productivity.
  • the crosslinked polymer particles (B-1) may be a combination of crosslinked polymer particles having a core-shell structure and crosslinked polymer particles having a monolayer structure. That is, the (meth)acrylate polymer (M-1) may be used for both the core layer of the core-shell structure and the single layer of the single layer structure. As long as the function (effect) according to one embodiment of the present invention is not impaired, the core layer of the core-shell polymer may have another component other than (M-1), and the single layer of the single-layer polymer ( It may have another component other than M-1). Also, (B-1) may have a component other than (M-1).
  • the content of component (M-1) in component (B-1) is, when (B-1) is a crosslinked polymer particle having a core-shell structure, in the total amount (100% by weight) of (B-1), 60% by weight or more.
  • the content of component (M-1) in the total amount (100% by weight) of component (B-1) is 70% by weight or more from the viewpoint of improving the damping properties of the cured product obtained by curing the curable resin composition. is preferred, 75% by weight or more is more preferred, 80% by weight or more is even more preferred, and 85% by weight or more is particularly preferred.
  • the upper limit of the content of component (M-1) in the total amount (100% by weight) of component (B-1) may be less than 100% by weight, preferably 99 parts by weight or less, more preferably 95 parts by weight or less. , is more preferably 93 parts by weight or less, and particularly preferably 90 parts by weight or less.
  • (B-1) is a crosslinked polymer particle having a single layer structure
  • the single layer polymer (B-1) has another component other than the component (M-1) as described above. may be used, but it is preferred that no other ingredients are included. That is, when (B-1) is a crosslinked polymer particle having a single-layer structure, the (M-1) component in the total amount (100% by weight) of the single-layer polymer (B-1) component is 100% by weight. is preferably
  • the content of the crosslinkable monomer in the monomer mixture (m-1) is 0.1% by weight or more and 10.0% by weight or less in 100% by weight of the monomer mixture (m-1), 0.2 wt% or more and 8.0 wt% or less is preferable, 0.3 wt% or more and 7.0 wt% or less is more preferable, 0.4 wt% or more and 6.0 wt% or less is still more preferable, and 0.5 wt% or more is preferable. More than 5.0% by weight and less than 5.0% by weight are particularly preferable.
  • the content of the crosslinkable monomer in 100% by weight of the monomer mixture (m-1) is 0.1% by weight or more (a) to swell the component (B-1) to form a curable resin composition. (b) 10.0% by weight or less can improve the damping properties of a cured product obtained by curing the curable resin composition.
  • crosslinkable monomer in (m-1) a crosslinkable monomer described in ((meth)acrylate-based polymer) described later can be used.
  • Crosslinked polymer particles (B-2) have a core-shell structure including a core layer and a shell layer, and the core layer does not contain a crosslinkable monomer (0.0% by weight of the crosslinkable monomer).
  • the shell layer comprises a (meth)acrylate polymer (M-2) obtained by polymerizing the monomer mixture (m-2) and having a glass transition temperature of ⁇ 20° C. or higher and 30° C. or lower as determined by the Fox formula.
  • M-2' is a (meth)acrylate polymer (M-2') obtained by graft-polymerizing a monomer mixture (m-2') containing 1% by weight or more and 100% by weight or less of a crosslinkable monomer to the core layer including.
  • the (meth)acrylate polymer (M-2) corresponds to the damping polymer described above.
  • the core layer of the crosslinked polymer particles (B-2) preferably contains (M-2), and more preferably consists of (M-2) only.
  • the core layer of the crosslinked polymer particles (B-2) is more preferably formed of (M-2).
  • the core layer of the core-shell polymer may contain another component other than (M-2) as long as the function (effect) according to one embodiment of the present invention is not impaired.
  • (B-2) may have a component other than (M-2).
  • the content of the (M-2) component which is the core layer in the (B-2) component, is the curable resin composition
  • 50 parts by weight or more and 95 parts by weight in the total amount (100 parts by weight) of (B-2) parts by weight or less more preferably 60 to 95 parts by weight, more preferably 70 to 93 parts by weight, still more preferably 80 to 91 parts by weight, and 85 to 90 parts by weight Especially preferred.
  • the content of the core layer in the component (B-2) is, from the viewpoint of lowering the viscosity of the curable resin composition and improving the damping properties of a cured product obtained by curing the curable resin composition, ( In the total amount (100% by weight) of B-2), preferably 50% by weight or more and 95% by weight or less, more preferably 60% by weight or more and 95% by weight or less, more preferably 70% by weight or more and 93% by weight or less, 80% by weight % or more and 91 weight % or less is more preferable, and 85 weight % or more and 90 weight % or less is particularly preferable.
  • the content of the component (M-2) in the component (B-2) is from the viewpoint of reducing the viscosity of the curable resin composition and improving the vibration damping properties of the cured product obtained by curing the curable resin composition.
  • the total amount (100% by weight) of (B-2) is preferably 50% by weight or more and 95% by weight or less, more preferably 60% by weight or more and 95% by weight or less, and more preferably 70% by weight or more and 93% by weight or less. It is preferably 80% by weight or more and 91% by weight or less, and particularly preferably 85% by weight or more and 90% by weight or less.
  • the shell layer of the crosslinked polymer particles (B-2) preferably contains a (meth)acrylate polymer (M-2') obtained by graft-polymerizing the monomer mixture (m-2') onto the core layer. , (M-2′) only.
  • the (meth)acrylate polymer (M-2') is not particularly limited, and those described in ((meth)acrylate polymer) below can be used.
  • the (meth)acrylate polymer (M-2') contains a (meth)acrylate polymer (M-2'-a) having a glass transition temperature of ⁇ 20° C. or higher and 30° C. or lower as determined by the Fox formula. is preferred, and it is more preferred that it consists only of (M-2'-a). According to this configuration, there is an advantage that a cured product obtained by curing the obtained curable resin composition has excellent vibration damping properties.
  • the content of the crosslinkable monomer in the monomer mixture (m-2') is 1.0% by weight or more and 100% by weight or less based on 100% by weight of the monomer mixture (m-2'), 1.3 wt% or more and 80 wt% or less is preferable, 1.5 wt% or more and 60 wt% or less is more preferable, 1.7 wt% or more and 40 wt% or less is still more preferable, 2.0 wt% or more and 20 wt% or less.
  • Storage of the curable resin composition due to swelling of the component (B-2) by setting the content of the crosslinkable monomer in 100% by weight of the monomer mixture (m-2′) to 1.0% by weight or more Stability can be improved. That is, the crosslinked polymer particles (B-2) preferably have a non-crosslinked core layer and a shell layer having a predetermined degree of crosslinking, as described above.
  • crosslinkable monomer in (m-2') As a specific example of the crosslinkable monomer in (m-2'), the crosslinkable monomer described in ((meth)acrylate-based polymer) described later can be used.
  • the content of the epoxy group in the (meth)acrylate polymer (M-2′) is, from the viewpoint of improving the vibration damping properties and adhesiveness of the cured product obtained by curing the curable resin composition, (M- 2′) with respect to the total amount is preferably 0.0 mmol/g or more and 2.0 mmol/g or less, more preferably 0.1 mmol/g or more and 1.0 mmol/g or less, and 0.2 mmol/g More than 0.7 mmol/g and less than 0.7 mmol/g are particularly preferable.
  • the content of epoxy groups in (M-2′) being 0.0 mmol/g with respect to the total amount of (M-2′) means that (M-2′) does not contain epoxy groups. intended to (M-2') may not contain an epoxy group.
  • the crosslinked polymer particles (B-3) have a core-shell structure including a core layer and a shell layer, and the shell layer is a (meth)acrylate having a glass transition temperature of ⁇ 20° C. or higher and 30° C. or lower as determined by the Fox formula.
  • the content of the shell layer with respect to the total amount of the crosslinked polymer particles (B-3) is 30% by weight or more and 90% by weight or less.
  • the shell layer may contain other components than (M-3') as long as the functions of the present invention are not impaired.
  • the (meth)acrylate polymer (M-3') corresponds to the attenuation polymer described above.
  • the shell layer of the crosslinked polymer particles (B-3) preferably contains (M-3'), and more preferably consists of (M-3') only.
  • the shell layer of the crosslinked polymer particles (B-3) is more preferably formed by (M-3').
  • the content of the component (M-3′) in the component (B-3) is from the viewpoint of reducing the viscosity of the curable resin composition and improving the damping properties of the cured product obtained by curing the curable resin composition.
  • the total amount (100% by weight) is preferably 30% by weight or more and 90% by weight or less, preferably 35% by weight or more and 85% by weight or less, and more preferably 40% by weight or more and 82% by weight or less.
  • it is more than 40% by weight and 82% by weight or less, more preferably 45% by weight or more and 80% by weight or less, and particularly preferably 50% by weight or more and 78% by weight or less.
  • the content of the shell layer in the component (B-3) is In the total amount (100% by weight) of B-3), 30% by weight or more and 90% by weight or less, preferably 35% by weight or more and 85% by weight or less, more preferably 40% by weight or more and 82% by weight or less, 40% by weight 82% by weight or less is more preferable, 45% by weight or more and 80% by weight or less is still more preferable, and 50% by weight or more and 78% by weight or less is particularly preferable.
  • the (meth)acrylate polymer (M-3') comprises a monomer mixture (m-3') having a crosslinkable monomer content of 0.0% by weight or more and 2.0% by weight or less as a core. It is preferable that the layer contains a polymer obtained by graft polymerization, and it is more preferable that the layer is composed only of the polymer.
  • (M-3') contains a polymer obtained by grafting (m-3') to the core layer or is composed only of the polymer, the resulting curable resin composition is cured. It has the advantage that the cured product is more excellent in damping properties.
  • the (meth)acrylate polymer (M-3') has a crosslinkable monomer content of 0.0% by weight, that is, a monomer mixture (m-3'-a) containing no crosslinkable monomer. is preferably included in the core layer, and it is more preferable that the core layer is composed only of the polymer.
  • (M-3') contains a polymer obtained by grafting (m-3'-a) to the core layer or is composed only of the polymer, the resulting curable resin composition is cured. It has the advantage that the resulting cured product is more excellent in damping properties.
  • crosslinkable monomer in (m-3') As a specific example of the crosslinkable monomer in (m-3'), the crosslinkable monomer described in ((meth)acrylate-based polymer) described later can be used.
  • the content of epoxy groups in the (meth)acrylate polymer (M-3′) is, from the viewpoint of improving the damping properties of a cured product obtained by curing the curable resin composition, (M-3′) is preferably 0.0 mmol/g or more and 2.0 mmol/g or less, more preferably 0.0 mmol/g or more and 1.5 mmol/g or less, and 0.0 mmol/g or more and 1.5 mmol/g or less with respect to the total amount of It is more preferably 0 mmol/g or less.
  • the content of epoxy groups in (M-3′) being 0.0 mmol/g with respect to the total amount of (M-3′) means that (M-3′) does not contain epoxy groups.
  • the (meth)acrylate polymer (M-3′) does not contain an epoxy group (in other words, (M-3 ') is 0.0 mmol/g with respect to the total amount of (M-3')).
  • the crosslinked polymer particles (B-3) include at least one core layer selected from the group consisting of diene polymers, (meth)acrylate polymers (M-3), and organosiloxane polymers (e.g. crosslinked core layer).
  • the effect of improving the impact resistance of the resulting cured product is high, and the affinity with the epoxy resin (A) is low, so the increase in viscosity over time due to the swelling of the core layer due to the component (A) is unlikely to occur.
  • the core layer (B-3) more preferably contains a diene-based polymer, and more preferably consists of only a diene-based polymer (in other words, is a diene-based polymer).
  • the core layer of (B-3) more preferably contains a (meth)acrylate polymer (M-3), and only (M-3) (In other words, (M-3)) is more preferable.
  • the diene-based polymer, (meth)acrylate-based polymer (M-3), and organosiloxane-based polymer have good productivity in emulsion polymerization.
  • the core layer (B-3) is a monomer mixture (m-3- It is more preferable to contain a (meth)acrylate polymer (M-3-a) obtained by polymerizing a), and is composed only of (M-3-a) (in other words, (M-3- a) is more preferred.
  • the core layer (B-3) contains 0.1% by weight or more of the crosslinkable monomer.
  • a (meth)acrylate polymer (M-3-) it is further preferred that it comprises b) (ie the damping polymer), and it is especially preferred that it consists solely of (M-3-b) (in other words is (M-3-b)).
  • the (meth)acrylate polymer (M-3-a) has a glass transition determined by the Fox formula. It is more preferable to contain a (meth)acrylate polymer (M-3-b) (ie, attenuation polymer) having a temperature of ⁇ 20° C. or higher and 30° C. or lower, and is composed only of (M-3-b) (in other words (M-3-b)) is particularly preferred.
  • a (meth)acrylate polymer (M-3-b) ie, attenuation polymer having a temperature of ⁇ 20° C. or higher and 30° C. or lower, and is composed only of (M-3-b) (in other words (M-3-b)) is particularly preferred.
  • crosslinkable monomer in (m-3-a) As a specific example of the crosslinkable monomer in (m-3-a), the crosslinkable monomer described in ((meth)acrylate polymer) described later can be used.
  • the curable resin composition according to one embodiment of the present invention has a core-shell structure having a diene polymer core layer and a shell layer, and is a crosslinked polymer particle (B-3) different from the crosslinked polymer particle (B-3). 4) can be further included. That is, the crosslinked polymer particles (B) are one or more selected from the group consisting of crosslinked polymer particles (B-1), (B-2), and (B-3), and further (B-4). You may have Due to the toughness-improving effect of the component (B-4), the resulting cured product has excellent impact resistance.
  • the glass transition temperature of the core layer of the crosslinked polymer particles (B-4) is preferably 0° C. or lower, more preferably ⁇ 20° C. or lower, and ⁇ 40° C. or lower in order to increase the toughness of the resulting cured product. is more preferred, and -60°C or lower is particularly preferred.
  • the ratio of the core layer in the crosslinked polymer particles (B-4) is preferably 40% by weight to 97% by weight, more preferably 60% by weight to 95% by weight, based on 100% by weight of the component (B-4). % to 93% by weight is more preferred, and 80% to 90% by weight is particularly preferred.
  • the proportion of the core layer in 100% by weight of component (B-4) is 40% by weight or more, the impact resistance of the resulting cured product can be improved.
  • the proportion of the core layer in 100% by weight of component (B-4) is 97% by weight or less, the core-shell polymer particles are less likely to aggregate, the viscosity of the curable resin composition becomes lower, and the workability becomes better. obtain.
  • the shell layer of the crosslinked polymer particles (B-4) contains, for example, an aromatic vinyl monomer (particularly preferably styrene) at 0 to 50% by weight (preferably 1 to 50% by weight, more preferably 2 to 48% by weight), Vinyl cyan monomer (particularly preferably acrylonitrile) 0-50% by weight (preferably 0-30% by weight, more preferably 10-25% by weight), (meth)acrylate monomer (particularly preferably methyl methacrylate) 0-100% by weight (preferably 5 to 100 wt%, more preferably 15 to 95 wt%), a monomer having an epoxy group (particularly preferably glycidyl methacrylate) 1 to 50 wt% (preferably 2 to 35 wt%, more preferably 3 to 20% by weight) and a shell layer-forming monomer (100% by weight in total).
  • an aromatic vinyl monomer particularly preferably styrene
  • Vinyl cyan monomer particularly preferably acrylonitrile
  • (meth)acrylate monomer particularly preferably
  • the crosslinked polymer particles (B-4) may not have an epoxy group in the shell layer, but preferably have an epoxy group in the shell layer.
  • the content of epoxy groups in the shell layer with respect to the total amount of the shell layer of the crosslinked polymer particles (B-4) determines the impact resistance of the resulting cured product. from the viewpoint of , it is preferably 0.1 mmol/g or more and 2.0 mmol/g or less, and more preferably 0.3 mmol/g or more and 1.5 mmol/g or less.
  • crosslinked polymer particles (B-4) As a result, aggregation of the crosslinked polymer particles (B-4) is suppressed, and the crosslinked polymer particles (B-4) can be dispersed in the state of primary particles in the cured product, resulting in improved impact resistance of the cured product. can be improved.
  • the amount of (B-4) is, from the viewpoint of the balance between the effect of improving the toughness of the resulting cured product and the improvement of damping properties, per 100 parts by weight of the total amount of component (B). , preferably 1 to 80 parts by weight, more preferably 5 to 70 parts by weight, still more preferably 10 to 60 parts by weight, and particularly preferably 20 to 55 parts by weight.
  • (B-4) is 1 part by weight or more (a) with respect to 100 parts by weight of the total amount of component (B), the effect of improving toughness, impact resistance, adhesion, etc. is good, and (b) When it is 80 parts by weight or less, the obtained cured product has high damping properties.
  • the (meth)acrylate polymer is used as a core layer of the crosslinked polymer particles (B-1, B-2, B-3), and (B-1, B-2, B-3, B-4 ) and can contribute to the improvement of the vibration damping properties of the cured product.
  • (meth)acrylate-based polymer refers to a monomer containing 30% by weight or more of at least one monomer selected from the group consisting of (meth)acrylate-based monomers in 100% by weight of the mixture. A polymer obtained by polymerizing a mixture is intended.
  • the (meth)acrylate polymer contains at least one monomer selected from the group consisting of (meth)acrylate monomers in an amount of 30% to 100% by weight (more preferably 40% to 100% by weight, more preferably 50 wt% to 100 wt%), and 0 wt% to 70 wt% (more preferably 0 wt% to 60 wt%, still more preferably It is preferably a polymer obtained by polymerizing a monomer mixture containing 0% by weight to 50% by weight).
  • the (meth)acrylate polymer may consist only of at least one monomer selected from the group consisting of (meth)acrylate monomers.
  • the (meth)acrylate polymer polymerizes a monomer mixture containing 0% to 100% by weight of a non-crosslinkable monomer and 0% to 100% by weight of a crosslinkable monomer. It is a polymer obtained by In other words, the (meth)acrylate polymer may have only structural units derived from non-crosslinkable monomers, or may have only structural units derived from crosslinkable monomers. It may have both a structural unit derived from a non-crosslinkable monomer and a structural unit derived from a crosslinkable monomer.
  • Examples of the (meth)acrylate monomer include (i) methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, ) Alkyl (meth)acrylates such as acrylate, stearyl (meth)acrylate and behenyl (meth)acrylate; (ii) Aromatic ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate; ( iii) hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; (iv) glycidyl (meth)acrylates such as glycidyl (meth)acrylate and glycidylalkyl (
  • (meth)acrylate monomers may be used singly or in combination of two or more.
  • Ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred as (meth)acrylate monomers.
  • Examples of other vinyl monomers copolymerizable with (meth)acrylate monomers include (i) vinyl arenes such as styrene, ⁇ -methylstyrene, monochlorostyrene and dichlorostyrene; (ii) acrylic acid and methacrylic acid.
  • vinyl cyanides such as acrylonitrile and methacrylonitrile
  • vinyl halides such as vinyl chloride, vinyl bromide and chloroprene
  • vinyl acetate ethylene and propylene alkenes such as , butylene and isobutylene
  • multifunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and divinylbenzene;
  • vinyl monomers may be used singly or in combination of two or more.
  • styrene is particularly preferred because it can easily increase the refractive index.
  • the crosslinkable monomer does not include conjugated diene-based monomers such as butadiene.
  • Acrylates ; (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 ( Polyfunctional (meth)acrylates having two or more meth)acrylic groups; diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, etc., preferably allyl methacrylate, triallyl isocyanurate .
  • One type of these crosslinkable monomers may be used alone, or two or more types may be used in combination.
  • the particle size of the crosslinked polymer particles (B) is not particularly limited, but considering industrial productivity, the volume average particle size (Mv) is preferably 10 nm to 2000 nm, more preferably 30 nm to 600 nm, and even more preferably 50 nm to 500 nm. , 100 nm to 400 nm are particularly preferred.
  • the volume average particle diameter (Mv) of the polymer particles can be measured using Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.) for the latex of the polymer particles.
  • the crosslinked polymer particles (B) in the curable resin composition have a half-value width of 0.5 times or more and 1 time or less of the volume average particle size in the number distribution of the particle size. It is preferable because the flexible resin composition has a low viscosity and is easy to handle.
  • the number distribution of the particle size of the crosslinked polymer particles (B) has two or more maximum values, and from the viewpoint of labor and cost during production. , more preferably 2 to 3 maxima, and more preferably 2 maxima.
  • the crosslinked polymer particles (B) are particularly composed of 10% to 90% by weight of crosslinked 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 crosslinked polymer particles having a volume average particle diameter of 150 nm or more and 2000 nm or less. % by weight.
  • the crosslinked polymer particles (B) are preferably dispersed in the curable resin composition in the form of primary particles.
  • the crosslinked polymer particles are dispersed in the state of primary particles means that the crosslinked polymer particles are substantially independently dispersed (without contact).
  • the dispersion state is obtained by, for example, dissolving a part of the curable resin composition in a solvent such as methyl ethyl ketone, and measuring the particle size with a particle size measuring device using laser light scattering. can be confirmed by
  • volume average particle size (Mv)/number average particle size (Mn) measured by particle size 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 size (Mv)/number average particle size (Mn) is 3.0 or less, it is considered that the crosslinked polymer particles (B) are well dispersed, and the resulting cured product has impact resistance and Physical properties such as adhesion (adhesion strength) are improved.
  • volume average particle size (Mv)/number average particle size (Mn) can be measured using Microtrac UPA (manufactured by Nikkiso Co., Ltd.) and obtained by dividing Mv by Mn.
  • the "stable dispersion" of the crosslinked polymer particles means that the crosslinked polymer particles do not agglomerate, separate, or precipitate in the continuous layer, and can be continuously dispersed under normal conditions for a long period of time. It means a state that is distributed over In addition, the distribution of the crosslinked polymer particles in the continuous layer does not substantially change, and even if these compositions are heated to a non-hazardous range to lower the viscosity and stirred, the "stable It is preferable to be able to retain the "dispersion".
  • the crosslinked polymer particles (B) may be used singly or in combination of two or more.
  • the structure of the crosslinked polymer particles (B-1) may be a single layer structure or a two or more layer structure, and is not particularly limited.
  • the crosslinked polymer particles (B-1) preferably have a structure of two or more layers, more preferably a core-shell structure including a core layer and a shell layer.
  • crosslinked polymer particles (B-1 to B-3) when they have a core-shell structure, they should 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. is also possible.
  • the "core layer” includes a core layer of crosslinked polymer particles having a core-shell structure among (B-1), a core layer of (B-2), a core layer of (B-3), and All of the core layers of (B-4) are intended.
  • the “intermediate layer” includes an intermediate layer of crosslinked polymer particles having a core-shell structure among (B-1), an intermediate layer of (B-2), an intermediate layer of (B-3), and an intermediate layer of (B-4). ) are intended to be all intermediate layers of the intermediate layer.
  • the “shell layer” includes (B-1) a shell layer of crosslinked polymer particles having a shell-shell structure, (B-2) a shell layer, (B-3) a shell layer, and (B- All shell layers of the shell layers of 4) are intended.
  • the core layers of the crosslinked polymer particles (B-1), (B-3), and (B-4) preferably have a gel content of 60% by weight or more, more preferably 80% by weight or more. It is preferably 90% by weight or more, more preferably 95% by weight or more, and particularly preferably 95% by weight or more.
  • the gel content referred to in this specification means the amount obtained by immersing 0.5 g of the crumbs obtained by coagulating and drying in 100 g of toluene, standing at 23° C. for 24 hours, and then separating the insolubles and solubles. , means the ratio of insolubles to the total amount of insolubles and solubles.
  • the core layer contains at least one selected from the group consisting of diene-based polymers, (meth)acrylate-based polymers, and organosiloxane-based polymers, as shown below. preferably included.
  • the diene polymer is a polymer that can be used as the core layer of the crosslinked polymer particles (B-3) and (B-4), and can improve the impact resistance of the resulting cured product.
  • conjugated diene monomer constituting the diene polymer examples include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, 2-methyl-1,3-butadiene and the like. . These conjugated diene 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 of the core layer, more preferably in the range of 70 to 100% by weight, and in the range of 90 to 100% by weight. It is even more preferable to have When the content of the conjugated diene-based monomer is 50% by weight or more, the resulting cured product may have better impact resistance.
  • Vinyl monomers copolymerizable with conjugated diene monomers include, for example, vinyl arenes such as styrene, ⁇ -methylstyrene, monochlorostyrene and dichlorostyrene; vinylcarboxylic acids such as acrylic acid and methacrylic acid; vinyl cyanides 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; 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 preferred.
  • 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 of the core layer, more preferably in the range of 0 to 30% by weight. Preferably, it is 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 resulting cured product may have better impact resistance.
  • a diene rubber is highly effective in improving impact resistance, and since it has a low affinity with the epoxy resin (A), it is difficult for the viscosity to increase over time due to swelling of the core layer.
  • Butadiene rubber using 3-butadiene and/or butadiene-styrene rubber which is a copolymer of 1,3-butadiene and styrene are preferred, and butadiene rubber is more preferred.
  • 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 copolymer is a polymer that can be used as the core layer of the crosslinked polymer particles (B-1), (B-2), and (B-3), and The same polymers as the (meth)acrylate copolymers exemplified in are exemplified.
  • the (meth)acrylate polymer (M-1 to 3) that can be used as the core layer of the crosslinked polymer particles (B-1 to 3) is the vibration damping property of the cured product obtained by curing the curable resin composition. From the viewpoint of improvement, a (meth)acrylate polymer (M-1 to 3) are preferable.
  • the content of the styrenic monomer in 100% by weight of the monomer mixture (m-1 to 3) is more preferably 20% by weight or more and 60% by weight or less, still more preferably 25% by weight or more and 55% by weight or less. More than 50% by weight and less than 50% by weight are particularly preferable.
  • Crosslinked polymer particles (B-1 to 3) are any one or more of crosslinked polymer particles (B-1), crosslinked polymer particles (B-2) and crosslinked polymer particles (B-3).
  • intended to (Meth)acrylate polymers (M-1 to 3) include (meth)acrylate polymer (M-1), (meth)acrylate polymer (M-2) and (meth)acrylate polymer ( Among M-3), any one or more (meth)acrylate-based polymers are intended.
  • Monomer mixtures (m-1 to 3) are any one or more of monomer mixture (m-1), monomer mixture (m-2) and monomer mixture (m-3) is intended as a monomer mixture of
  • styrenic monomer examples include styrene, ⁇ -methylstyrene, and monochlorostyrene.
  • the (meth)acrylate polymers (M-1 to M-3) are used from the viewpoint of improving the vibration damping property of a cured product obtained by curing the curable resin composition, and from the viewpoint of improving the workability of the curable resin composition.
  • (Meth)acrylate polymers (M-1 to 3) obtained by polymerizing
  • "unsubstituted alkyl (meth)acrylate having 3 to 20 carbon atoms in the alkyl group” is referred to as "unsubstituted alkyl (meth)acrylate having 3 to 20 carbon atoms” or "C3-C20 free It may be referred to as "substituted alkyl (meth)acrylate”.
  • the content of unsubstituted alkyl (meth)acrylate having 3 to 20 carbon atoms in 100% by weight of the monomer mixture (m-1 to 3) is more preferably 51% by weight or more and 80% by weight or less, more preferably 52% by weight or more. 70% by weight or less is more preferable, and 53% by weight or more and 65% by weight or less is particularly preferable.
  • unsubstituted alkyl (meth)acrylates having 3 to 20 carbon atoms examples include n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, ) acrylate, stearyl (meth)acrylate and the like.
  • organosiloxane polymer examples include (i) composed of disubstituted alkyl or aryl silyloxy units such as dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, dimethylsilyloxy-diphenylsilyloxy, etc. (ii) polysiloxane polymers composed of alkyl- or aryl-monosubstituted silyloxy units such as organohydrogensilyloxy in which some of the alkyl side chains are substituted with hydrogen atoms; be done.
  • polysiloxane-based polymers may be used singly or in combination of two or more.
  • dimethylsilyloxy, methylphenylsilyloxy, and dimethylsilyloxy-diphenylsilyloxy are preferable because they can impart heat resistance to the cured product, and dimethylsilyloxy is most preferable because it is easily available.
  • the polysiloxane polymer portion is 80% by weight or more (more preferably 90% by weight or more).
  • the volume average particle size of the core layer is preferably 0.03 ⁇ m to 2 ⁇ m, more preferably 0.05 ⁇ m to 1 ⁇ m. Within this range, stable production can be achieved, and the cured product can have good heat resistance and impact resistance.
  • the volume average particle size can be measured using Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.).
  • the core layer often has a single-layer structure, but it may have a multi-layer structure. Also, 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. For example, when crosslinked polymer particles are used and the core layer is multi-layered in (B-1), all layers in the core layer are preferably damping polymers.
  • An intermediate layer may be formed between the core layer and the shell layer, if necessary.
  • the following surface crosslinked layer may be formed as the intermediate layer.
  • the intermediate layer When the intermediate layer is formed, it may cover at least a part of the core layer, or may cover the entire core 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, and even more preferably 0.5 to 10 parts by weight. , 1 to 5 parts by weight are particularly preferred.
  • the surface cross-linking layer is formed by polymerizing a surface cross-linking layer component comprising 30 to 100% by weight of a crosslinkable monomer having two or more radically polymerizable double bonds in one molecule and 0 to 70% by weight of another vinyl monomer. It has the effect of lowering the viscosity of the curable resin composition and the effect of improving the dispersibility of the crosslinked 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.
  • crosslinkable monomer having two or more radically polymerizable double bonds include the same monomers as the above-mentioned crosslinkable monomers, but allyl methacrylate and triallyl isocyanurate are preferred. .
  • the shell layer present on the outermost side of the crosslinked polymer particles is obtained by polymerizing the shell layer-forming monomers, and improves the compatibility between the crosslinked polymer particles (B) and the component (A), thereby forming a curable resin composition. , or a shell polymer that plays a role in enabling the crosslinked polymer particles (B) to be dispersed in the state of primary particles in the cured product.
  • Such a shell polymer is preferably grafted onto the core layer and/or intermediate layer.
  • the term "grafted to the core layer” includes a mode of grafting to the intermediate layer when the intermediate layer is formed on the core layer.
  • the monomer component used to form the shell layer is the core polymer forming the core layer (when the intermediate layer is formed, the core polymer also includes the intermediate layer polymer forming the intermediate layer. , the same) to substantially chemically bond the shell polymer and the core polymer (when the intermediate layer is formed, the shell polymer and the intermediate layer polymer are chemically bonded). is also preferred).
  • the shell polymer is formed by graft-polymerizing the shell layer-forming monomer in the presence of the core polymer. partially or wholly covered.
  • This polymerization operation can be carried out by adding a monomer for forming a shell polymer layer to a latex of a core polymer prepared in the form of an aqueous polymer latex and polymerizing it.
  • the shell layer-forming monomer may be, for example, an aromatic vinyl monomer, a vinyl cyanide monomer, or a (meth)acrylate monomer. can be used, but (meth)acrylate monomers are more preferred.
  • the shell layer-forming monomer preferably contains methyl methacrylate and/or butyl (meth)acrylate. These shell layer-forming monomers may be used alone or in combination as appropriate.
  • the shell layer may cover at least a portion of the core layer and/or the intermediate layer, or may cover the entirety of the core layer and/or the intermediate layer.
  • the (meth)acrylate polymer (M-1' to 3') that can be used as the shell layer of the crosslinked polymer particles (B-1 to 3) is used from the viewpoint of improving the T-peel adhesion of the curable resin composition.
  • Polymerized (meth)acrylate polymers (M-1′ to 3′) are preferred.
  • alkyl (meth)acrylate having 1 or 2 carbon atoms in the alkyl group is referred to as "alkyl (meth)acrylate having 1 or 2 carbon atoms" or "C1-C2 alkyl (meth)acrylate”.
  • the content of alkyl (meth)acrylate having 1 or 2 carbon atoms in 100% by weight of the monomer mixture (m-1′ to 3′) is more preferably 71% by weight or more and 99% by weight or less, and more preferably 72% by weight or more and 98% by weight. % by weight or less is more preferable, and 75% by weight or more and 95% by weight or less is particularly preferable.
  • (Meth)acrylate polymers (M-1′ to 3′) include (meth)acrylate polymer (M-1′), (meth)acrylate polymer (M-2′) and (meth)acrylate Any one or more (meth)acrylate polymers are intended among the polymer (M-3′).
  • the monomer mixture (m-1' to 3') is the monomer mixture (m-1'), the monomer mixture (m-2') and the monomer mixture (m-3'), Any one or more monomer mixtures are contemplated.
  • alkyl (meth)acrylates having 1 or 2 carbon atoms examples include methyl (meth)acrylate and ethyl (meth)acrylate. Among these, methyl acrylate and ethyl acrylate are more preferable from the viewpoint of improving the workability of the curable resin composition.
  • epoxy is used as the shell layer-forming monomer. group, an oxetane group, a hydroxyl group, an amino group, an imide group, a carboxylic acid group, a carboxylic anhydride group, a cyclic ester, a cyclic amide, a benzoxazine group, and a cyanate ester group.
  • a reactive group-containing monomer may be contained, a monomer having an epoxy group is particularly preferred.
  • the monomer having an epoxy group is preferably contained in an amount of 0% to 90% by weight, preferably 1% to 1% by weight, based on 100% by weight of the monomer for forming the shell layer. 50% by weight is more preferred, 2% to 35% by weight is even more preferred, and 3% to 20% by weight is particularly preferred.
  • the epoxy group-containing monomer is preferably used for forming the shell layer, and more preferably used only for the shell layer.
  • a crosslinkable monomer having two or more radically polymerizable double bonds is used as the shell layer-forming monomer, swelling of the core-shell polymer particles in the curable resin composition is prevented, and the curable resin It is preferable because the viscosity of the composition tends to be low and the handleability tends to be good.
  • a cross-linking monomer having two or more radically polymerizable double bonds is used as the shell layer-forming monomer. It is preferred not to use the body.
  • aromatic vinyl monomer examples include vinylbenzenes such as styrene, ⁇ -methylstyrene, p-methylstyrene, and divinylbenzene.
  • vinyl cyan monomer examples include acrylonitrile, methacrylonitrile, and the like.
  • (meth)acrylate monomers other than the alkyl (meth)acrylates having 1 or 2 carbon atoms include alkyl (meth)acrylates having 3 or more carbon atoms such as butyl (meth)acrylate; hydroxyalkyl (meth)acrylates; Ester etc. are mentioned.
  • the (meth)acrylic acid hydroxyalkyl ester include, for example, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxy linear alkyl (meth) Acrylates (particularly, hydroxy straight-chain C1-6 alkyl (meth)acrylates); caprolactone-modified hydroxy (meth)acrylates; hydroxy-branched alkyls such as methyl ⁇ -(hydroxymethyl)acrylate and ethyl ⁇ -(hydroxymethyl)acrylate ( Hydroxyl group-containing (meth)acrylates such as meth)acrylates, mono(meth)acrylates of polyester diols (especially saturated polyester diols) obtained from divalent carboxylic acids (phthalic acid, etc.) and dihydric alcohols (propylene glycol, etc.) etc.
  • epoxy group-containing monomer examples include glycidyl group-containing vinyl monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and allyl glycidyl ether.
  • crosslinkable monomer having two or more radically polymerizable double bonds include the same monomers as the above-mentioned crosslinkable monomers, but allyl methacrylate and triallyl isocyanurate are preferred. .
  • the shell layer may be formed by containing other monomer components in addition to the above monomer components.
  • the shell layer-forming monomer does not contain a structural unit containing an alkoxy group, a structural unit containing an aryloxy group, a structural unit containing an oxetane group, or a structural unit containing a hydroxyl group.
  • a (meth)acrylate polymer having a glass transition temperature of ⁇ 20° C. or higher and 30° C. or lower as determined by the Fox formula can be easily formed using a general-purpose monomer.
  • the graft ratio of the shell layer is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
  • the graft rate is 70% or more, the viscosity of the curable resin composition can be further lowered.
  • the method for calculating the graft rate is as follows. First, an aqueous latex containing core-shell polymer particles is coagulated and dewatered, and finally dried to obtain a powder of core-shell polymer particles. Next, 2 g of the powder of core-shell polymer particles is immersed in 100 g of methyl ethyl ketone (MEK) at 23° C. for 24 hours, and then MEK-soluble and MEK-insoluble are separated, and methanol-insoluble is separated from MEK-soluble. Then, the ratio of the MEK-insoluble matter to the total amount of the MEK-insoluble matter and the methanol-insoluble matter is calculated to calculate the graft ratio.
  • MEK methyl ethyl ketone
  • Formation of the core layer constituting the crosslinked polymer particles (B) can be produced by, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization, and the like, for example, WO 2005/028546 and WO 2006/070664. The method described in can be used.
  • the intermediate layer can be formed by polymerizing an intermediate layer-forming monomer by known radical polymerization in the presence of the core layer.
  • the polymerization of the intermediate layer-forming monomers is preferably carried out by emulsion polymerization.
  • a polymer formed by coating the core layer with the intermediate layer (by polymerizing the intermediate layer-forming monomer onto the core layer) may be referred to as a "polymer particle precursor".
  • the shell layer can be formed by polymerizing a shell layer-forming monomer by known radical polymerization in the presence of the core layer or polymer particle precursor.
  • the shell layer-forming monomer is preferably polymerized by an emulsion polymerization method, for example, according to the method described in WO 2005/028546. can be done.
  • Emulsifiers (dispersants) that can be used in emulsion polymerization include alkyl or aryl sulfonic acids typified by dioctylsulfosuccinic acid and dodecylbenzene sulfonic acid, alkyl or aryl ether sulfonic acids, and alkyl or aryl sulfonic acids typified 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 sarcosic acid represented by dodecyl sarcosic acid, alkyl or aryl ethers represented by oleic acid and stearic acid.
  • Anionic emulsifiers such as various acids such as arylcarboxylic acids, alkyl or aryl ether carboxylic acids, 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. These emulsifiers (dispersants) may be used alone or in combination of two or more.
  • the amount of emulsifier (dispersant) used is preferably small as long as it does not interfere with the dispersion stability of the aqueous latex of polymer particles. Further, the emulsifier (dispersant) is preferably as high in water solubility as possible. If 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.
  • thermal decomposition type initiators such as 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate and ammonium persulfate can be used. .
  • a chelating agent such as disodium ethylenediaminetetraacetate and, if necessary, a phosphorus-containing compound such as sodium pyrophosphate may be used in combination.
  • redox type initiators using organic peroxides such as cumene hydroperoxide, dicumyl peroxide and t-butyl hydroperoxide as peroxides are preferred.
  • the amount of the thermal decomposition type initiator used, the amount of the redox type initiator used, and the amounts of the reducing agent, transition metal salt and chelating agent used when the redox type initiator is used are within a known range. can be used. Further, when polymerizing a monomer having two or more radically polymerizable double bonds, a known chain transfer agent can be used within a known range. Surfactants can additionally be used and are within the known range.
  • Conditions such as polymerization temperature, pressure, deoxidation, etc. in the polymerization for forming each layer can be applied within a known range.
  • the polymerization of the intermediate layer-forming monomer may be carried out in one step or in two or more steps.
  • the elastic core layer is added to the reactor.
  • a method of adding an emulsion of the constituent rubber elastic body and then carrying out the polymerization can be adopted.
  • blocked urethane (C) can be used if desired.
  • blocked urethane (C) may be referred to as "(C) component”.
  • the present curable resin composition contains component (C)
  • the resulting cured product has excellent toughness and elongation properties due to the toughness-improving effect of component (C).
  • blocked urethane is an elastomer type compound containing a urethane group and/or a urea group, and having an isocyanate group at the end of a compound in which all or part of the terminal isocyanate group is an active hydrogen group.
  • a variety of blocking agent-capped compounds are contemplated. Particularly preferred is a compound in which all of the terminal isocyanate groups are capped with a blocking agent.
  • Such a compound can be produced, for example, by reacting an organic polymer having an active hydrogen-containing group at the terminal 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. All or part of the isocyanate groups are capped with a blocking agent having an active hydrogen group after or at the same time as a polymer (urethane prepolymer) having an active hydrogen group.
  • blocked urethane examples include compounds described in International Publication No. 2016/163491.
  • the number average molecular weight of the blocked urethane is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000 in terms of polystyrene equivalent molecular weight measured by GPC.
  • This configuration has the advantage that the resulting curable resin composition is excellent in adhesiveness (adhesive strength) and workability.
  • the molecular weight distribution of the blocked urethane (the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight)) is preferably 1.0 to 4.0, more preferably 1.2 to 3.0. 1.5 to 2.5 are particularly preferred.
  • This configuration has the advantage that the resulting curable resin composition has excellent spreadability and workability.
  • the blocked urethanes can be used singly or in combination of two or more.
  • the content of blocked urethane in the curable resin composition is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin (A). , more preferably 2 to 40 parts by weight, more preferably 5 to 30 parts by weight.
  • the content of blocked urethane in the curable resin composition is 1 part by weight or more of (a) with respect to 100 parts by weight of the epoxy resin (A), toughness, impact resistance, adhesion (adhesion strength), etc.
  • the improvement effect is good and (b) is 50 parts by weight or less, the resulting cured product has a high elastic modulus.
  • Epoxy resin curing agent (D) In one embodiment of the present invention, an epoxy resin hardener (D) can be used as needed.
  • epoxy resin curing agent (D) may be referred to as "(D) component”.
  • the present curable resin composition is tentatively used as a one-component composition (for example, a one-component curable resin composition)
  • a one-component curable resin composition for example, a one-component curable resin composition
  • component (D) and (E) described below are combined so that the curable resin composition cures very slowly, if at all, at room temperature (about 22°C) and temperatures up to at least 50°C.
  • the type and amount of ingredients are preferably selected.
  • Component (D) component a component that exhibits activity upon heating (sometimes referred to as a latent epoxy curing agent) can be used.
  • Nitrogen (N)-containing curing agents such as specific amine-based curing agents (including imine-based curing agents) can be used as such latent epoxy curing agents.
  • Component (D) includes, for example, boron trichloride/amine complex, boron trifluoride/amine complex, dicyandiamide, melamine, diallylmelamine, guanamine (e.g., acetoguanamine and benzoguanamine), aminotriazole (e.g., 3-amino- 1,2,4-triazoles), hydrazides (e.g.
  • adipic acid dihydrazide stearic acid dihydrazide, isophthalic acid dihydrazide, semicarbazide), cyanoacetamides, as well as aromatic polyamines (e.g. metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, etc.) is mentioned.
  • aromatic polyamines e.g. metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, etc.
  • dicyandiamide, dihydrazide isophthalate, dihydrazide adipic acid, and 4,4'-diaminodiphenylsulfone are more preferably used, and particularly preferably dicyandiamide, because of their excellent adhesion (adhesion strength). .
  • the latent epoxy curing agent is preferable because it enables the present curable resin composition to be used as a one-component curable resin composition.
  • amine-based curing agents including imine-based curing agents
  • mercaptan-based curing agents sometimes referred to as room-temperature-curing curing agents
  • D room temperature
  • component (D) that exhibits activity at relatively low temperatures such as room temperature
  • amines such as polyamidoamines, amine-terminated polyethers, amine-terminated rubbers, modified aliphatic polyamines, modified alicyclic polyamines and polyamides. system curing agents, and various compounds described in paragraph [0113] of the specification of WO2016-163491.
  • Amine-terminated polyethers containing a polyether backbone and having an average of 1 to 4 (preferably 1.5 to 3) amino and/or imino groups per molecule are also relatively stable at about room temperature. It can be used as the component (D) that exhibits activity at low temperatures.
  • Commercially available amine terminated polyethers include Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-5000 from Huntsman.
  • an amine-terminated rubber containing a conjugated diene-based polymer backbone and having an average of 1 to 4 (more preferably 1.5 to 3) amino groups and/or imino groups per molecule is also used at room temperature. It can be used as the component (D) that exhibits activity at a relatively low temperature of about.
  • the main chain of the rubber that is, the conjugated diene polymer main chain is preferably a homopolymer or copolymer of polybutadiene, more preferably a polybutadiene/acrylonitrile copolymer, and the acrylonitrile monomer content is 5 to 40% by mass (more preferably 10 to 35%). %, more preferably 15-30% by weight) are particularly preferred.
  • Commercially available amine-terminated rubbers include Hypro 1300X16 ATBN manufactured by CVC.
  • amine-based curing agents that are active at relatively low temperatures such as room temperature
  • polyamidoamines, amine-terminated polyethers, and amine-terminated rubbers are more preferable. It is particularly preferable to use together.
  • acid anhydrides and phenols can also be used as the latent epoxy curing agent.
  • Acid anhydrides and phenols require a higher temperature than amine curing agents, but they have a longer pot life, and the resulting cured product has a good balance of physical properties such as electrical, chemical, and mechanical properties. becomes good.
  • Examples of acid anhydrides include various compounds described in paragraph [0117] of the specification of WO2016-163491.
  • the component (D) may be used singly or in combination of two or more.
  • the (D) component can be used in an amount sufficient to cure the curable resin composition. Typically, a sufficient amount of component (D) can be used to consume at least 80% of the epoxide groups present in the curable resin composition. A large excess of component (D) over the amount required to consume the epoxide groups is usually not necessary.
  • the present curable resin composition preferably further contains 1 to 80 parts by mass of an epoxy curing agent (D), more preferably 2 to 40 parts by mass, relative to 100 parts by mass of the epoxy resin (A). It is more preferably contained in an amount of 3 to 30 parts by mass, and particularly preferably in an amount of 5 to 20 parts by mass.
  • D an epoxy curing agent
  • the content of component (D) is 1 part by mass or more of (a) with respect to 100 parts by mass of component (A)
  • the curability of the present curable resin composition is good, and (b) is 80 parts by mass.
  • the storage stability of this curable resin composition becomes favorable, and it has the advantage of being easy to handle.
  • a curing accelerator (E) can be used as needed.
  • hardening accelerator (E) may be referred to as "(E) component”.
  • the component (E) is a compound that functions as a catalyst that promotes the reaction between the epoxy group and the epoxide-reactive group possessed by the curing agent and components other than the epoxy resin (A) contained in the curable resin composition. be.
  • Component (E) is not particularly limited as long as it has the catalytic action described above.
  • Examples include (a) 3-(3,4-dichlorophenyl)-1,1-dimethylurea, p-chlorophenyl-N, N-dimethylurea (trade name: Monuron), 3-phenyl-1,1-dimethylurea (trade name: Fenuron), 3,4-dichlorophenyl-N,N-dimethylurea (trade name: Diuron), N-( 3-chloro-4-methylphenyl)-N',N'-dimethylurea (trade name: Chlortoluron), ureas such as 1,1-dimethylphenyl urea (trade name: Dyhard); (b) benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol incorporated in a poly
  • component (E) tertiary amines and imidazoles are used in combination with component (D) (for example, component (D) that exhibits activity at relatively low temperatures such as room temperature). It is possible to improve the speed and the physical properties and heat resistance of the resulting cured product.
  • the component (E) may be used singly or in combination of two or more.
  • This curable resin composition preferably contains 0.1 to 10.0 parts by mass of a curing accelerator (E) with respect to 100 parts by mass of the epoxy resin (A), and 0.2 parts by mass. parts to 5.0 parts by mass, more preferably 0.5 parts to 3.0 parts by mass, and particularly preferably 0.8 parts to 2.0 parts by mass.
  • a curing accelerator E
  • the content of component (E) is 0.1 parts by mass or more (a) with respect to 100 parts by mass of component (A)
  • the curability of the present curable resin composition is good
  • (b) 10 When it is 0 parts by mass or less, the present curable resin composition has an advantage of good storage stability and easy handling.
  • the curable resin composition of one embodiment of the present invention contains, for the purpose of further improving properties such as toughness, impact resistance, shear adhesion, and peel adhesion of the cured product, a reinforcing agent such as unmodified epoxy.
  • a reinforcing agent such as unmodified epoxy.
  • a rubber-based polymer may be contained as necessary.
  • the reinforcing agent may be used singly or in combination of two or more.
  • the unmodified epoxy rubber polymer means an unmodified rubber polymer that has not reacted with the epoxy resin (not modified with the epoxy resin). That is, the rubber-based polymer may be contained in the curable resin composition of one embodiment of the present invention as necessary without being modified without reacting with the epoxy resin.
  • unmodified epoxy rubber polymer examples include acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), hydrogenated nitrile rubber (HNBR), ethylene-propylene rubber (EPDM), acrylic rubber (ACM), and butyl rubber (IIR). , butadiene rubber, and polyoxyalkylenes such as polypropylene oxide, polyethylene oxide, and polytetramethylene oxide.
  • the epoxy unmodified rubber-based polymer preferably has a reactive group such as an amino group, a hydroxyl group, or a carboxyl group at its terminal.
  • NBR and polyoxyalkylene are preferable, NBR is more preferable, and NBR having a carboxyl group terminal ( CTBN) is particularly preferred.
  • the glass transition temperature (Tg) of the epoxy unmodified rubber polymer is not particularly limited.
  • the Tg of the unmodified epoxy rubber polymer is preferably ⁇ 25° C. or lower, more preferably ⁇ 35° C. or lower, still more preferably ⁇ 40° C. or lower, and particularly preferably ⁇ 50° C. or lower. This configuration has the advantage that the cured product has excellent adhesive strength and excellent impact resistance.
  • the number-average molecular weight of the epoxy-unmodified rubber-based polymer is preferably 1,500 to 40,000, more preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000 in terms of polystyrene equivalent molecular weight measured by GPC.
  • This configuration has the advantage that the resulting curable resin composition is excellent in adhesiveness (adhesive strength) and workability.
  • the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight (weight average molecular weight/number average molecular weight)) of the unmodified epoxy rubber polymer is preferably 1.0 to 4.0, more preferably 1.2 to 3.0. is more preferred, and 1.5 to 2.5 is particularly preferred.
  • This configuration has the advantage that the resulting curable resin composition has excellent workability.
  • the epoxy-unmodified rubber-based polymer can be used alone or in combination of two or more.
  • the amount (content) of the epoxy unmodified rubber polymer in the present curable resin composition is preferably 1 part by weight to 30 parts by weight, more preferably 2 parts by weight to 20 parts by weight, with respect to 100 parts by weight of the epoxy resin (A). parts are more preferred, and 5 to 10 parts by weight are particularly preferred. When it is 1 part by weight or more, the effect of improving toughness, impact resistance, adhesiveness, etc. is good, and when it is 50 parts by weight or less, the elastic modulus of the resulting cured product increases.
  • the curable resin composition of one embodiment of the present invention can contain an inorganic filler.
  • Silicic acid and/or silicates for example, can be used as inorganic fillers.
  • Specific examples of silicic acid and silicates include dry silica, wet silica, aluminum silicate, magnesium silicate, calcium silicate, wollastonite, talc, and the like.
  • Said fumed silica also called fumed silica, includes surface-untreated hydrophilic fumed silica and hydrophobic fumes prepared by chemically treating the silanol moiety of hydrophilic fumed silica with silane and/or siloxane. and dosilica.
  • hydrophobic fumed silica is preferable from the viewpoint of dispersibility in component (A).
  • Substances other than silicic acid and silicates may be used as inorganic fillers.
  • Inorganic fillers other than silicic acid and silicates include reinforcing fillers such as dolomite and carbon black; ground calcium carbonate; colloidal calcium carbonate; magnesium carbonate; Zinc; active zinc white and the like can be mentioned.
  • the inorganic filler is preferably surface-treated with a surface treatment agent.
  • the surface treatment improves the dispersibility of the inorganic filler in the curable resin composition, and as a result, various physical properties of the obtained cured product are improved.
  • Inorganic fillers may be used singly or in combination of two or more.
  • the amount (content) of the inorganic filler used in the present curable resin composition is preferably 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, per 100 parts by weight of component (A). , more preferably 10 to 100 parts by weight, particularly preferably 20 to 70 parts by weight.
  • the curable resin composition of one embodiment of the present invention can contain calcium oxide.
  • calcium oxide in the curable resin composition removes water from the curable resin composition by reaction with water in the curable resin composition, It is possible to solve various physical property problems caused by For example, calcium oxide in the curable resin composition functions as an anti-foaming agent by removing moisture, and can suppress a decrease in adhesive strength of the cured product.
  • Calcium oxide can be surface treated with a surface treatment agent.
  • the surface treatment improves the dispersibility of calcium oxide in the curable resin composition.
  • physical properties such as adhesive strength of the obtained cured product are improved as compared with the case of using calcium oxide that has not been surface-treated.
  • the surface treatment agent is not particularly limited, fatty acids are preferred.
  • the amount (content) of calcium oxide used in the present curable resin composition is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of component (A). is more preferable, 0.5 to 3 parts by weight is more preferable, and 1 to 2 parts by weight is particularly preferable.
  • the content of calcium oxide in the curable resin composition is 0.1 parts by weight or more (a) with respect to 100 parts by weight of component (A), the effect of removing water from the curable resin composition is good.
  • (b) When it is 10 parts by weight or less, the strength of the resulting cured product increases.
  • One type of calcium oxide may be used alone, or two or more types may be used in combination.
  • the curable resin composition of one embodiment of the present invention can optionally contain a radical curable resin having two or more double bonds in the molecule.
  • the curable resin composition of one embodiment of the present invention further contains a low-molecular-weight compound having at least one double bond in the molecule and having a molecular weight of less than 300, if necessary. can do.
  • the low-molecular-weight compound has the function of adjusting the viscosity, the physical properties of the cured product, and the curing speed when used in combination with the radical-curable resin, and functions as a so-called reactive diluent for the radical-curable resin. .
  • a radical polymerization initiator can be added to the curable resin composition of one embodiment of the present invention.
  • the radical polymerization initiator is preferably of latent type which is activated by raising the temperature (preferably from about 50° C. to about 150° C.).
  • radical-curable resin examples include unsaturated polyester resins, polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, polyether (meth)acrylates, and acrylated (meth)acrylates. These may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the radical-curable resin include compounds described in International Publication No. 2014-115778. Further, specific examples of the low-molecular compound and the radical polymerization initiator include compounds described in International Publication No. 2014-115778.
  • the radical polymerization initiator is activated at a temperature different from the curing temperature of the epoxy resin, selective polymerization of said radically curable resin results in partial curing of the curable resin composition. Curing is possible. This partial curing can increase the viscosity of the curable resin composition after application and improve wash-off resistance.
  • the curable resin composition in an uncured state may partially dissolve or scatter due to the water pressure of the shower during the washing shower process. Deformation may adversely affect the corrosion resistance of the steel plate in the coated portion, or reduce the rigidity of the steel plate.
  • this partial curing can provide a function of temporarily fixing (temporarily adhering) substrates together until the composition is completely cured. Therefore, the radical polymerization initiator is preferably activated by heating to 80°C to 130°C, more preferably activated by heating to 100°C to 120°C. preferable.
  • the curable resin composition of one embodiment of the invention can optionally contain a monoepoxide.
  • Monoepoxides can function as reactive diluents.
  • Specific examples of monoepoxides include aliphatic glycidyl ethers such as butyl glycidyl ether; aromatic glycidyl ethers such as phenyl glycidyl ether and cresyl glycidyl ether; alkyl groups having 8 to 10 carbon atoms such as 2-ethylhexyl glycidyl ether; and a glycidyl group; ethers consisting of a phenyl group having 6 to 12 carbon atoms and a glycidyl group, which may be substituted with an alkyl group having 2 to 8 carbon atoms, such as p-tertbutylphenyl glycidyl ether; for example, dodecyl glycidyl
  • the amount (content) of the monoepoxide used in the curable resin composition is 0.1 to 20 parts by weight per 100 parts by weight of component (A). parts are preferred, 0.5 to 10 parts by weight are more preferred, and 1 to 5 parts by weight are particularly preferred.
  • the content of the monoepoxide in the curable resin composition is 0.1 parts by weight or more of (a) with respect to 100 parts by weight of component (A), the viscosity-lowering effect is satisfactorily exhibited, and (b) 20 When it is not more than parts by weight, physical properties such as adhesiveness (adhesive strength) of the cured product are improved.
  • the curable resin composition may contain a photopolymerization initiator.
  • photopolymerization initiators include (i) onium salts such as aromatic sulfonium salts and aromatic iodonium salts with anions (hexafluoroantimonate, hexafluorophosphate, tetraphenylborate, etc.), (ii) Aromatic diazonium salts, and (iii) photocationic polymerization initiators (photoacid generators) such as metallocene salts with the above anions are included. These photopolymerization initiators may be used alone or in combination of two or more.
  • other formulation ingredients can be used as desired.
  • Other ingredients include expansion agents such as azo-type chemical blowing agents and thermally expandable microballoons; fiber pulps such as aramidic pulp; colorants such as pigments and dyes; extender pigments; Stabilizer (anti-gelling agent); plasticizer; leveling agent; antifoaming agent; silane coupling agent; antistatic agent; desiccant; dispersant and the like.
  • the curable resin composition of one embodiment of the present invention contains an epoxy resin (A) as a curable resin and a core-shell polymer as the component (B), the composition contains crosslinked polymer particles (B ) are dispersed in the form of primary particles.
  • the curable resin composition of one embodiment of the present invention contains an epoxy resin (A) as a curable resin and a monolayer polymer as the component (B), the composition contains crosslinked polymer particles ( It is preferred that B) is a composition dispersed in the form of primary particles.
  • the production method includes, for example, a method of contacting the core-shell polymer particles or monolayer polymer obtained in an aqueous latex state with the component (A) and then removing unnecessary components such as water, For example, the polymer is once extracted into an organic solvent, mixed with the component (A), and then the organic solvent is removed.
  • the production method it is preferable to use the method described in International Publication No. 2005/028546.
  • the present curable resin composition is preferably prepared by a manufacturing method including the following first to third steps in order. : (1) An aqueous latex containing crosslinked polymer particles (B) (specifically, a reaction mixture after producing crosslinked polymer particles (B) (core-shell polymer particles or monolayer polymer) by emulsion polymerization) at 20°C.
  • B crosslinked polymer particles
  • B core-shell polymer particles or monolayer polymer
  • the component (A) is in a liquid state at 23°C because the third step is facilitated.
  • liquid at 23°C means that the softening point is 23°C or lower and exhibits fluidity at 23°C.
  • the powdery crosslinked polymer particles (B) obtained by drying after being solidified by a method such as salting out are dispersed using a dispersing machine having a high mechanical shearing force such as a three-roll paint roll, a roll mill, or a kneader. can be used to redisperse in the (A) component.
  • a curable resin composition according to one embodiment of the present invention can be obtained by redispersing the crosslinked polymer particles (B).
  • the mixture of components (A) and (B) is subjected to mechanical shearing force at a high temperature to enable efficient dispersion of component (B).
  • the temperature at which component (B) is (re)dispersed in component (A) is preferably 50 to 200°C, more preferably 70 to 170°C, still more preferably 80 to 150°C, particularly 90 to 120°C. preferable.
  • the curable resin composition according to one embodiment of the present invention is used as a one-liquid curable resin composition that is sealed and stored after all the ingredients are blended in advance, and that is cured by heating and/or light irradiation after application. be able to.
  • (A) component is the main component, and further A solution containing (B) component and optionally (C) component is prepared, (D) component and (E) component are contained, and if necessary A liquid B containing the component (B) and/or the component (C) may be prepared separately from the liquid A.
  • the curable resin composition according to one embodiment of the present invention can also be used as a two-component or multi-component curable resin composition comprising the A liquid and the B liquid. Specifically, the A liquid and the B liquid can be mixed before use.
  • the curable composition according to one embodiment of the present invention is particularly useful when used as a one-part curable resin composition.
  • the components (B) and (C) are either liquid A or liquid B, respectively. or at least one of them, for example, it may be contained only in A liquid or only in B liquid, or may be contained in both A liquid and B liquid good.
  • a cured product can be obtained by curing the curable resin composition of one embodiment of the present invention.
  • the curable resin composition contains core-shell polymer particles as the component (B)
  • the crosslinked polymer particles (B) are uniformly dispersed in the cured product.
  • the curable resin composition has a low viscosity, and a cured product can be obtained with good workability.
  • the Young's modulus (elastic modulus) at 23°C of the cured product obtained by curing the curable resin composition of one embodiment of the present invention is preferably 50 MPa or more, more preferably 100 MPa or more, and 200 MPa or more. is more preferable, and 500 MPa or more is particularly preferable. If the Young's modulus is 50 MPa or more, it is possible to secure the rigidity and adhesive strength necessary for the structural adhesive. When the Young's modulus is converted into durometer A hardness, a Young's modulus of 50 MPa or more corresponds to a durometer A hardness of 95 or more.
  • the elastic modulus at high temperature of the cured product obtained from the curable resin composition of one embodiment of the present invention can be evaluated by the Young's modulus at 80°C and/or the storage elastic modulus at 80°C.
  • the Young's modulus at 80° C. of the cured product obtained by curing the curable resin composition of one embodiment of the present invention is preferably 50 MPa or more, more preferably 100 MPa or more, and 200 MPa or more. More preferably, it is particularly preferably 500 MPa or more. If the Young's modulus is 50 MPa or more, the rigidity and adhesive strength required for structural adhesives can be ensured even in a high-temperature environment.
  • the cured product obtained by curing the curable resin composition of one embodiment of the present invention has high heat resistance, the cured product exhibits sufficient elastic response. Therefore, as an approximate value of the Young's modulus, the storage elastic modulus in the tensile mode obtained by dynamic viscoelasticity measurement (frequency: 20 Hz) of the cured product can be utilized.
  • the storage elastic modulus at 23°C of the cured product obtained by curing the curable resin composition of one embodiment of the present invention is preferably 50 MPa or more.
  • the storage modulus (23° C.) is more preferably 100 MPa or more, still more preferably 200 MPa or more, and particularly preferably 500 MPa or more. If the storage elastic modulus (23° C.) is 50 MPa or more, it is possible to ensure the rigidity and adhesive strength necessary for structural adhesives.
  • the storage elastic modulus is a value obtained by measuring at a frequency of 20 Hz by dynamic viscoelasticity measurement.
  • the storage modulus (80°C) of the cured product obtained by curing the curable resin composition of one embodiment of the present invention at 80°C is preferably 50 MPa or more, more preferably 100 MPa or more, and 200 MPa. It is more preferably 500 MPa or more, and particularly preferably 500 MPa or more. If the storage elastic modulus (80° C.) is 50 MPa or more, it is possible to ensure the rigidity and adhesive strength necessary for a structural adhesive even in a high-temperature environment.
  • a cured product obtained by curing the curable resin composition of one embodiment of the present invention has a high loss tangent tan ⁇ at 40°C as attenuation performance.
  • the "vibration damping property" of the cured product can be evaluated by the loss tangent (tan ⁇ ) at 40°C of the cured product. That is, the cured product obtained by curing the curable resin composition of one embodiment of the present invention suppresses the decrease in Young's modulus at high temperatures, in other words, suppresses the decrease in storage elastic modulus (rigidity) at high temperatures. high loss tangent can be maintained.
  • Tan ⁇ is obtained by dynamic viscoelasticity measurements and can be measured at a frequency of, for example, 20 Hz.
  • the curable resin composition of one embodiment of the invention can be applied to the substrate by any method. According to a preferred embodiment, the curable resin composition can be applied at a low temperature of about room temperature, and if necessary, the curable resin composition can be heated and applied.
  • the curable resin composition of one embodiment of the present invention is excellent in storage stability, and therefore is particularly useful in a method of heating and applying the curable resin composition.
  • the curable resin composition of one embodiment of the present invention can be extruded onto a substrate in the form of beads, monofilaments, or swirls using a coating robot.
  • a mechanical application method such as a caulking gun or other manual application means can be used to apply the curable resin composition of one embodiment of the present invention.
  • the curable resin composition can also be applied to the substrate using a jet spray method or a streaming method.
  • the curable resin composition of one embodiment of the present invention is applied to one or both substrates, and the substrates are brought into contact so that the curable resin composition is disposed between the two substrates to be joined. The two substrates can be bonded together by curing the curable resin composition in this state.
  • the viscosity of the curable resin composition is not particularly limited, and is preferably about 150 Pa s to 600 Pa s at 45 ° C. in the extrusion bead method, and about 100 Pa s at 45 ° C. in the swirl coating method. is preferable, and in a high-volume coating method using a high-speed flow device, it is preferably about 20 Pa ⁇ s to 400 Pa ⁇ s at 45°C.
  • the temperature of the heated curable resin composition is preferably 30°C to 80°C, more preferably 40°C to 70°C, and 45°C. ⁇ 60°C is more preferred.
  • the curable resin composition of one embodiment of the present invention as an adhesive (that is, a structural adhesive) for joining structural members such as vehicles will be described.
  • the bonding between the members can be strengthened by appropriately spot-welding after applying the curable resin composition as a weld-bonding method.
  • the spot joints in the weld bond method may be formed by welding.
  • the spot joints in the weld bond construction method are not limited to welding, and may be a spot joint structure, for example, mechanical joints such as SPR (self-piercing riveting).
  • the joint portion may be formed by an appropriate combination of only an adhesive, a combination of an adhesive and spot welding, and a combination of an adhesive and mechanical bonding.
  • the interval between the spot joints is preferably 10 mm to 100 mm, more preferably 15 mm to 70 mm, even more preferably 25 mm to 50 mm.
  • the curable resin composition of one embodiment of the present invention When the curable resin composition of one embodiment of the present invention is used as a vehicle adhesive, it is effective to increase the thixotropy of the curable resin composition in order to improve the "hardness to be washed off". is. In general, thixotropy is improved by thixotropy-imparting agents such as fumed silica and amide wax. composition.
  • the curable resin composition of one embodiment of the present invention is preferable because it tends to have a low viscosity and thus tends to increase thixotropy.
  • a highly thixotropic curable resin composition can be adjusted to a viscosity that can be applied by heating.
  • the curable resin composition of one embodiment of the present invention is used as a structural adhesive for joining structural members such as vehicles, it is preferable to adjust the viscosity characteristics of the curable resin composition with a thixotropic agent or the like. .
  • the viscosity characteristics of the curable resin composition By adjusting the viscosity characteristics of the curable resin composition, the stringiness of the structural adhesive (curable resin composition) is reduced. Therefore, it is possible not only to apply the structural adhesive continuously in the form of beads, but also to apply it intermittently.
  • the adhesive can be applied while avoiding the site where spot welding is performed, and the adhesive can be applied. It is effective in suppressing the generation of smoke and/or combustion gases such as carbon dioxide due to burning, and reducing the amount of adhesive used.
  • a polymer compound having a crystalline melting point near the application temperature of the curable resin composition is added to the curable resin composition. Blending in the resin composition is preferred.
  • the curable resin composition containing the polymer compound has a low viscosity (easy to apply) at the application temperature, and becomes highly viscous at the temperature in the washing shower process, thereby improving "difficulty in washing off".
  • Examples of the polymer compound having a crystalline melting point near the application temperature include various polyester resins such as crystalline or semi-crystalline polyester polyols.
  • An adhesive according to one embodiment of the present invention includes a curable resin composition according to one embodiment of the present invention.
  • a curable resin composition according to one embodiment of the present invention.
  • substrates such as wood, metal, plastic, and glass can be bonded.
  • the curable resin composition of one embodiment of the present invention as an adhesive to join automobile parts. Bonding between automobile frames or bonding between automobile frames and other automobile parts using the curable resin composition of one embodiment of the present invention as an adhesive is more preferred.
  • Substrates include steel materials such as cold-rolled steel and hot-dip galvanized steel, aluminum materials such as aluminum and coated aluminum, general-purpose plastics, engineering plastics, composite materials such as CFRP and GFRP, and various plastic-based substrates. be done.
  • a cured product obtained by curing the present curable resin composition has excellent damping properties, so the present curable resin composition can be suitably used as a structural adhesive for weld bonding. That is, the structural adhesive for weld bonding according to one embodiment of the present invention contains the curable resin composition according to one embodiment of the present invention.
  • An adhesive containing a curable resin composition according to one embodiment of the present invention is applied to one or both of two substrates, and the curable according to one embodiment of the present invention is applied between the two substrates.
  • the two substrates are brought into contact with each other so that the adhesive containing the resin composition is arranged, and the curable resin composition according to one embodiment of the present invention is cured in that state, thereby bonding the two substrates.
  • Materials can be joined via a cured product according to one embodiment of the present invention. That is, in one embodiment of the present invention, two substrates and an adhesive containing the curable resin composition according to one embodiment of the present invention for joining the two substrates or structural adhesion for weld bonding and an adhesive layer in which the agent is cured.
  • a laminate according to one embodiment of the present invention can also be expressed as follows: A laminate obtained by laminating a first substrate, a cured product obtained by curing an adhesive containing the curable resin composition, and a second substrate in this order.
  • the curable resin composition of one embodiment of the present invention has excellent adhesion. Therefore, after laminating the curable resin composition of one embodiment of the present invention between a plurality of members containing an aluminum base material, the members obtained by curing the curable resin composition are joined. A laminate obtained by bonding is preferable because it exhibits high adhesive strength.
  • the curable resin composition of one embodiment of the present invention is excellent in toughness, so it is suitable for joining different types of base materials with different coefficients of linear expansion.
  • curable resin composition of one embodiment of the present invention can also be used to join components for aerospace applications, particularly exterior metal components.
  • curable resin composition of one embodiment of the present invention is described in WO2011/141148, WO2014/176512, WO2015/011686, WO2015/011687, and WO2017/176832.
  • the curable resin composition of one embodiment of the present invention JP-A-8-198995, WO2008/014053, WO2013/114195, and the filling described in JP-A-2015-147928 It can be used in the form of a reinforcing material, particularly an expandable filling reinforcing material, and is useful as a filling reinforcing material that fills and reinforces a closed cross-section structure described later and has damping properties (vibration damping properties).
  • the curing temperature of the curable resin composition of one embodiment of the present invention is not particularly limited, but is preferably 50 ° C. to 250 ° C., more preferably 80 ° C. to 220 ° C., further preferably 100 ° C. to 200 ° C., and 130 C. to 180.degree. C. are particularly preferred.
  • the curable resin composition of one embodiment of the present invention is used as an automotive adhesive, after applying the adhesive to an automotive member, a coating such as electrodeposition coating is then applied, and the coating is baked and cured. From the viewpoint of process shortening and simplification, it is preferable to cure the adhesive at the same time.
  • the application parts of the vehicle include roof rails, floor frames, A pillars (front pillars), B Structural parts such as pillars (center pillars), C pillars, D pillars, floor panels, rear floor panels, front side members, rear side members, side members, tunnel rains, floor cross members, wheel houses, side sills, outer sills, doors, It is useful for hemming the inner and outer panels of hoods and trunks.
  • the curable resin composition of one embodiment of the present invention has excellent damping properties (vibration damping properties), a member that receives vibration input due to road noise of a vehicle or the like and a vehicle body structure between the vehicle compartment of the vehicle When applied to the panel joints of members, it is effective in reducing vibration and noise levels in the cabin due to road noise and improving quietness. Specifically, it is a vibration transmission path from the suspension to the passenger compartment.
  • damping properties vibration damping properties
  • the curable resin composition of one embodiment of the present invention has excellent damping properties (vibration damping properties), a member that receives vibration input due to engine noise of a vehicle or the like and a vehicle body structure between the vehicle compartment of the vehicle When applied to the panel joints of members, it is effective in reducing vibration and noise levels in the cabin due to engine noise and improving quietness. Specifically, it is a vibration transmission path from the engine to the passenger compartment, and more specifically, for example, a joint around an engine mount.
  • the curable resin composition of one embodiment of the present invention has excellent damping properties, it is described in JP-A-2015-128942 and JP-A-2015-134536.
  • JP-A-2015-147501, JP-A-2018-184077, JP-A-2019-38926, JP-A-2019-38364, JP-A-2019-98897, JP-A-2019-98901 As an adhesive for vehicle body structural members described in Japanese Patent Laid-Open Publications, JP-A-2019-98902, JP-A-2019-98907, JP-A-2019-98908, JP-A-2019-98909, and WO2015/119054. Useful.
  • a vehicle member having closed cross-section structure in which two or more base materials each having a closed cross section and a joint flange formed at an end thereof are joined to each other,
  • a curable resin composition of one embodiment of the present invention as an adhesive or a structural adhesive for weld bonding between flanges and then curing the adhesive to join.
  • a vehicle member according to an embodiment of the present invention can also be expressed as follows: two or more base materials each having a closed cross section and a joint flange formed at the end thereof are attached to each other. After the adhesive according to one embodiment of the present invention or the structural adhesive for weld bonding according to one embodiment of the present invention is applied between the joint flange portions of the vehicle member to be joined, A vehicle member having a closed cross-sectional structure joined by curing an adhesive.
  • the joint flange portion means a plate-shaped collar or ear provided at the end of two or more substrates for reinforcing and connecting the joint between the substrates. (projection) intended.
  • the closed cross-section part is a hollow columnar member having a closed cross-section structure obtained by joining the flange parts, which is formed by joining two or more base materials, for example, two hat-shaped steel materials. Intended cross-section.
  • a vehicle member according to one embodiment of the present invention has a closed cross-sectional portion, and the closed cross-sectional portion includes two or more substrates having joint flange portions at the ends thereof, and a bonding method containing the curable resin composition. It is formed by bonding by curing the agent. Specifically, an adhesive containing the curable resin composition is applied to the joint flange portion of at least one of two or more substrates having joint flange portions at the ends, and the adhesive is applied. Two or more substrates can be bonded by bonding the bonding flange portion of another substrate to the surface thus formed and curing the adhesive. Thereby, a vehicle member having a closed cross section can be formed.
  • a laminated structure including a joint flange portion of two or more base materials and a cured product formed between the joint flange portions is also referred to as a closed cross-section structure.
  • the cured product obtained by curing the present curable resin composition or the adhesive according to one embodiment of the present invention exhibits high rigidity not only at room temperature but also in a high temperature environment such as 80 ° C.
  • the area of the joint flange portion is Even if it is made small, it is possible to maintain sufficient rigidity even in a high-temperature environment, resulting in a lighter vehicle member.
  • the cured product obtained by curing the present curable resin composition or the adhesive according to one embodiment of the present invention exhibits high damping properties, vibration transmission such as road noise through the vehicle member is small. As a result, it is possible to reduce the weight of the asphalt sheet used in the vehicle, such as sound absorbing materials and damping materials, leading to weight reduction of the vehicle.
  • the thickness of the base material used for the vehicle member is reduced, it is possible to compensate for the deterioration of the damping property due to the decrease in the rigidity of the vehicle member by the high vibration damping property of the cured product obtained by curing the adhesive. , and it is possible to achieve both excellent damping performance and weight reduction of the vehicle.
  • the curable resin composition of one embodiment of the present invention includes structural adhesives for vehicles and aircraft, adhesives such as structural adhesives for wind power generation, paints, materials for lamination with glass fibers, and printed wiring boards. Materials, solder resists, interlayer insulation films, build-up materials, adhesives for FPC, electrical insulating materials such as sealing materials for electronic parts such as semiconductors and LEDs, die bonding materials, underfill, semiconductors such as ACF, ACP, NCF, NCP It is preferably used for packaging materials, liquid crystal panels, OLED lighting, sealing materials for display devices and lighting devices such as OLED displays. In particular, it is useful as a structural adhesive for weld bonding.
  • An embodiment of the invention may relate to: A curable resin composition containing 100 parts by weight of an epoxy resin (A) and 1 to 100 parts by weight of crosslinked polymer particles (B), wherein the crosslinked polymer particles (B) contain the following (1) to (3 A curable resin composition which is one or more crosslinked polymer particles selected from the crosslinked polymer particles (B-1), crosslinked polymer particles (B-2), and crosslinked polymer particles (B-3) according to ). ; (1) The crosslinked polymer particle (B-1) has a core-shell structure and/or a single layer structure including a core layer and a shell layer, and the core layer and/or the single layer contains a crosslinkable monomer.
  • the crosslinked polymer particles (B-2) have a core-shell structure including a core layer and a shell layer, and the core layer contains a monomer mixture (m-2) containing no crosslinkable monomer.
  • the crosslinked polymer particles (B-3) have a core-shell structure including a core layer and a shell layer, and the shell layer has a glass transition temperature of ⁇ 20° C. or higher and 30° C. or lower as determined by the Fox formula
  • a meth)acrylate polymer (M-3′) wherein the content of the shell layer is 30% by weight or more and 90% by weight or less with respect to the total amount of the crosslinked polymer particles (B-3).
  • curable resin composition having a Young's modulus of 50 MPa or more at 23°C of a cured product obtained by curing the curable resin composition.
  • the epoxy resin (A) contains an epoxy resin (A1) having an epoxy equivalent of 90 g/eq or more and less than 200 g/eq, and the content of component (A1) in the total amount of component (A) is 25% by weight. It is preferable to use the curable resin composition described above.
  • the epoxy resin (A) contains a bisphenol A type epoxy resin and/or a bisphenol F type epoxy resin (A2), and the content of the component (A2) in the total amount of the component (A) is 25% by weight or more. It is preferable to use a certain curable resin composition.
  • crosslinked polymer particles (B-1) it is preferable to use a curable resin composition that is a monolayer crosslinked polymer particle of the (meth)acrylate polymer (M-1) only.
  • curable resin composition in which the content of the core layer of the crosslinked polymer particles (B-2) is 50 parts by weight or more and 95 parts by weight or less with respect to the total amount of the crosslinked polymer particles (B-2). preferable.
  • the (meth)acrylate polymer (M-3′) in the crosslinked polymer particles (B-3) is a monomer having a crosslinkable monomer content of 0.0% by weight or more and 2.0% by weight or less. It is preferable to use a curable resin composition obtained by polymerizing the mixture (m-3').
  • a curable resin composition in which the (meth)acrylate polymer (M-3′) is obtained by polymerizing a monomer mixture (m-3′-a) containing no crosslinkable monomer. is preferably used.
  • the crosslinked polymer particles (B-3) have at least one crosslinked core layer selected from the group consisting of diene polymers, (meth)acrylate polymers (M-3), and organosiloxane polymers. It is preferable to use a curable resin composition having
  • the core layer of the crosslinked polymer particles (B-3) is obtained by polymerizing a monomer mixture (m-3-a) containing 0.1% by weight or more and 10% by weight or less of a crosslinkable monomer (meta ) It is preferable to use a curable resin composition which is an acrylate polymer (M-3-a).
  • the (meth)acrylate polymer (M-3-a) is a (meth)acrylate polymer (M-3-b) having a glass transition temperature of ⁇ 20° C. or higher and 30° C. or lower as determined by the Fox formula. , it is preferable to use a curable resin composition.
  • the (meth)acrylate polymer (M-1' and/or M-2') is a (meth)acrylate polymer (M- 1′-a and/or M-2′-a) is preferably used in the curable resin composition.
  • the (meth)acrylate polymer (M-1 to 3) polymerizes a monomer mixture (m-1 to 3) having a styrene monomer content of 10% by weight or more and 70% by weight or less. It is preferable to use a curable resin composition that is a (meth)acrylate polymer (M-1 to 3).
  • the (meth)acrylate polymer (M-1 to 3) is a monomer mixture (m It is preferable to use a curable resin composition which is a (meth)acrylate polymer (M-1 to 3) obtained by polymerizing M-1 to 3).
  • a monomer mixture (m-) It is preferable to use a curable resin composition that is a (meth)acrylate polymer (M-1' to 3') obtained by polymerizing M-1' to 3').
  • curable resin composition that further contains 1 to 50 parts by mass of blocked urethane (C) with respect to 100 parts by mass of the epoxy resin (A).
  • curable resin composition that further contains 1 to 80 parts by mass of the epoxy curing agent (D) with respect to 100 parts by mass of the epoxy resin (A).
  • curable resin composition that further contains 0.1 to 10.0 parts by mass of a curing accelerator (E) with respect to 100 parts by mass of the epoxy resin (A).
  • a cured product obtained by curing the curable resin composition It is preferable to use a cured product obtained by curing the curable resin composition.
  • a laminate that includes two substrates and an adhesive layer that bonds the two substrates and is formed by curing the adhesive.
  • a vehicle member formed by joining two or more substrates each having a closed cross-sectional portion and joint flange portions formed at the ends thereof, wherein the adhesive is applied between the joint flange portions. It is preferable to use a vehicle member having a closed cross-sectional structure which is joined by curing the adhesive after the adhesive is applied.
  • the crosslinked polymer particles (B) are a group consisting of the crosslinked polymer particles (B-1), the crosslinked polymer particles (B-2), and the crosslinked polymer particles (B-3) described in (1) to (3) below.
  • a curable resin composition comprising one or more crosslinked polymer particles selected from; (1)
  • the crosslinked polymer particle (B-1) has a core-shell structure or a single layer structure including a core layer and a shell layer, and the core layer and/or the single layer contains 0.00 of a crosslinkable monomer.
  • the crosslinked polymer particles (B-2) have a core-shell structure including a core layer and a shell layer, and the core layer contains a monomer mixture (m-2) containing no crosslinkable monomer.
  • the shell layer contains a (meth)acrylate polymer (M-2) having a glass transition temperature of ⁇ 20° C. or higher and 30° C.
  • the crosslinked polymer particles (B-3) have a core-shell structure including a core layer and a shell layer, and the shell layer has a glass transition temperature of ⁇ 20° C. or higher and 30° C. or lower as determined by the Fox formula ( It contains a meth)acrylate polymer (M-3′), and the content of the shell layer is 30% by weight or more and 90% by weight or less with respect to the total amount of the crosslinked polymer particles (B-3).
  • a cured product obtained by curing the curable resin composition has a storage modulus at 23° C. of 50 MPa or more, and the storage modulus is obtained by measuring dynamic viscoelasticity at a frequency of 20 Hz.
  • the epoxy resin (A) contains an epoxy resin (A1) having an epoxy equivalent of 90 g/eq or more and less than 200 g/eq, and the epoxy resin (A1) in the total amount of the epoxy resin (A)
  • the curable resin composition according to any one of [1] to [3], wherein the content of is 25% by weight or more.
  • the epoxy resin (A) contains a bisphenol A type epoxy resin (A2) and/or a bisphenol F type epoxy resin (A2), and the bisphenol A type epoxy resin in the total amount of the epoxy resin (A)
  • the curable resin composition according to any one of [1] to [4], wherein the content of the resin (A2) and the bisphenol F type epoxy resin (A2) is 25% by weight or more.
  • crosslinked polymer particles (B-1) are monolayer crosslinked polymer particles composed only of the (meth)acrylate polymer (M-1).
  • the curable resin composition according to any one of the above.
  • the (meth)acrylate polymer (M-3′) in the crosslinked polymer particles (B-3) has a crosslinkable monomer content of 0.0% by weight or more and 2.0% by weight or less.
  • the (meth)acrylate polymer (M-3') includes a polymer obtained by polymerizing a monomer mixture (m-3'-a) containing no crosslinkable monomer, [ 8], the curable resin composition.
  • the content of epoxy groups in the (meth)acrylate polymer (M-3′) is 0.0 mmol/g or more and 2.0 mmol/g or less with respect to the total amount of (M-3′).
  • the curable resin composition according to any one of [1] to [9].
  • the crosslinked polymer particles (B-3) have at least one core selected from the group consisting of diene polymers, (meth)acrylate polymers (M-3), and organosiloxane polymers.
  • the curable resin composition according to any one of [1] to [11], which has a layer.
  • the (meth)acrylate polymer (M-3-a) is a (meth)acrylate polymer (M-3-b ), the curable resin composition according to [13].
  • the (meth)acrylate polymer (M-1′ and/or M-2′) is a (meth)acrylate polymer having a glass transition temperature of ⁇ 20° C. or higher and 30° C. or lower as determined by the Fox formula.
  • the (meth)acrylate polymer (M-1) is obtained by polymerizing a monomer mixture (m-1) having a styrene monomer content of 10% by weight or more and 70% by weight or less.
  • the (meth)acrylate polymer (M-2) is obtained by polymerizing a monomer mixture (m-2) having a styrene monomer content of 10% by weight or more and 70% by weight or less.
  • the (meth)acrylate polymer (M-3) is obtained by polymerizing a monomer mixture (m-3) having a styrene monomer content of 10% by weight or more and 70% by weight or less.
  • the (meth)acrylate polymer (M-1) is a monomer mixture (The curable resin composition according to any one of [1] to [18], which is a (meth)acrylate polymer (M-1) obtained by polymerizing m-1).
  • the (meth)acrylate polymer (M-2) is a monomer mixture (The curable resin composition according to any one of [1] to [19], which is a (meth)acrylate polymer (M-2) obtained by polymerizing m-2).
  • the (meth)acrylate polymer (M-3) is a monomer mixture (The curable resin composition according to any one of [1] to [20], which is a (meth)acrylate polymer (M-3) obtained by polymerizing m-3).
  • a monomer mixture (m- The curable resin composition according to any one of [1] to [21], which is a (meth)acrylate polymer (M-1′) obtained by polymerizing 1′).
  • a monomer mixture (m- The curable resin composition according to any one of [1] to [22], which is a (meth)acrylate polymer (M-2') obtained by polymerizing 2').
  • a monomer mixture (m- The curable resin composition according to any one of [1] to [23], which is a (meth)acrylate polymer (M-3') obtained by polymerizing 3').
  • the volume average particle size (Mv) of the crosslinked polymer particles dispersed in the aqueous latexes described in Production Examples was measured using Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.). A sample diluted with deionized water was used as a measurement sample. The measurement was performed by inputting the refractive index of water and the refractive index of each crosslinked polymer particle, adjusting the sample concentration so that the signal level was within the range of 0.6 to 0.8 with a measurement time of 600 seconds. rice field.
  • core layer monomers 47 parts by weight of methyl methacrylate (MMA), 40 parts by weight of butyl acrylate (BA), 0.43 parts by weight of allyl methacrylate (ALMA)) and 0.13 parts by weight of cumene hydroperoxide (CHP) was added dropwise over a period of 3 hours.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • ALMA allyl methacrylate
  • CHP cumene hydroperoxide
  • a mixture of graft monomers (9.5 parts by weight of MMA, 1.2 parts by weight of BA, 1 part by weight of glycidyl methacrylate (GMA), 1.3 parts by weight of ALMA) and 0.07 parts by weight of CHP was added thereto over 120 minutes. added continuously. After completion of the addition, 0.07 part by weight of CHP was added, and stirring was continued for 2 hours to complete the polymerization, thereby obtaining a latex (L-1) containing a core-shell polymer.
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.36 ⁇ m.
  • Production Example 1-2 Preparation of core-shell polymer latex (L-2) In Production Example 1-1, ⁇ MMA45 parts by weight, A core-shell polymer latex (L-2) was obtained in the same manner as in Production Example 1-1, except that 42 parts by weight of methoxyethyl acrylate (MEA) and 0.43 parts by weight of ALMA> were used. The volume average particle size of the core-shell polymer contained in the obtained latex was 0.33 ⁇ m.
  • Production Example 1-3 Preparation of Core-Shell Polymer Latex (L-3)
  • a core-shell polymer latex (L-3) was obtained in the same manner as in Production Example 1-1, except that 78 parts by weight of butyl methacrylate (BMA) and 0.43 parts by weight of ALMA> were used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.31 ⁇ m.
  • Production Example 1-4 Preparation of Core-Shell Polymer Latex (L-4)
  • a core-shell polymer latex (L-4) was obtained in the same manner as in Production Example 1-1, except that 1 part by weight of GMA, 1 part by weight of GMA, and 1.3 parts by weight of ALMA> were used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.33 ⁇ m.
  • Production Example 1-5 Preparation of core-shell polymer latex (L-5)
  • BA40 parts by weight, ALMA0.43 parts by weight> as core layer monomers
  • ⁇ MMA47 parts by weight, 40 parts by weight of BA, 4.3 parts by weight of ALMA>, and ⁇ MMA 2 parts by weight BA 10 parts by weight> instead of ⁇ MMA 9.5 parts by weight, BA 1.2 parts by weight, GMA 1 part by weight, ALMA 1.3 parts by weight> as a graft monomer
  • a core-shell polymer latex (L-5) was obtained in the same manner as in Production Example 1-1, except that , GMA 1 part by weight> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.37 ⁇ m.
  • Production Example 1-6 Preparation of Core-Shell Polymer Latex (L-6)
  • a core-shell polymer latex (L-6) was obtained in the same manner as in Production Example 1-1, except that , GMA 1 part by weight> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.29 ⁇ m.
  • Production Example 1-7 Preparation of Core-Shell Polymer Latex (L-7)
  • 0.4 parts by mass of SDS initially charged was used instead of 0.01 parts by mass, and ⁇ MMA47 weight was used as the core layer monomer.
  • Production Example 1-8 Preparation of core-shell polymer latex (L-8)
  • 0.1 parts by mass of SDS initially charged was changed to 0.01 parts by mass, and ⁇ MMA47 weight was used as the core layer monomer.
  • Production Example 1-9 Preparation of core-shell polymer latex (L-9)
  • 0.1 parts by mass of SDS initially charged was changed to 0.01 parts by mass, and ⁇ MMA47 weight was used as the core layer monomer.
  • Production Example 1-10 Preparation of Core-Shell Polymer Latex (L-10)
  • 0.1 part by mass of SDS initially charged was changed to 0.01 part by mass, and ⁇ MMA47 weight was used as the core layer monomer.
  • Production Example 1-11 Preparation of Core-Shell Polymer Latex (L-11)
  • 0.1 part by mass of SDS initially charged was changed to 0.01 part by mass, and ⁇ MMA47 weight was used as the core layer monomer.
  • Production Example 1-12 Preparation of core-shell polymer latex (L-12) In Production Example 1-1, ⁇ MMA 15 parts by weight, 72 parts by weight of BA, 0.43 parts by weight of ALMA>, and ⁇ 9.5 parts by weight of MMA, 1.2 parts by weight of BA, 1 part by weight of GMA, 1.3 parts by weight of ALMA> as graft monomers> ⁇ 9.5 parts by weight of MMA, BA2
  • a core-shell polymer latex (L-12) was obtained in the same manner as in Production Example 1-1, except that .5 parts by weight and 1 part by weight of GMA> were used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.31 ⁇ m.
  • Production Example 1-13 Preparation of core-shell polymer latex (L-13) In Production Example 1-1, ⁇ MMA72 parts by weight, 15 parts by weight of BA, 0.43 parts by weight of ALMA>, and ⁇ 9.5 parts by weight of MMA, 1.2 parts by weight of BA, 1 part by weight of GMA, 1.3 parts by weight of ALMA> as grafting monomers.
  • a core-shell polymer latex (L-13) was obtained in the same manner as in Production Example 1-1, except that .5 parts by weight and 1 part by weight of GMA> were used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.35 ⁇ m.
  • Production Example 1-14 Preparation of core-shell polymer latex (L-14) In Production Example 1-1, ⁇ MMA72 parts by weight, A core-shell polymer latex (L-14) was obtained in the same manner as in Production Example 1-1, except that 15 parts by weight of BA and 0.43 parts by weight of ALMA> were used. The volume average particle size of the core-shell polymer contained in the obtained latex was 0.35 ⁇ m.
  • Production Example 1-15 Preparation of Core-Shell Polymer Latex (L-15)
  • a core-shell polymer latex (L-15) was obtained in the same manner as in Production Example 1-1, except that 1 part by weight of GMA, 1.3 parts by weight of ALMA> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.34 ⁇ m.
  • Production Example 1-16 Preparation of Core-Shell Polymer Latex (L-16) In Production Example 1-1, ⁇ MMA72 parts by weight, A core-shell polymer latex (L-16) was obtained in the same manner as in Production Example 1-1, except that 15 parts by weight of MEA and 0.43 parts by weight of ALMA> were used. The volume average particle size of the core-shell polymer contained in the obtained latex was 0.35 ⁇ m.
  • Production Example 1-17 Preparation of Core-Shell Polymer Latex (L-17) 40 parts by weight of BA, 12.9 parts by weight of ALMA>, and ⁇ MMA 2 parts by weight, BA 10 parts by weight> instead of ⁇ MMA 9.5 parts by weight, BA 1.2 parts by weight, GMA 1 part by weight, ALMA 1.3 parts by weight> as a graft monomer
  • a core-shell polymer latex (L-17) was obtained in the same manner as in Production Example 1-1, except that , GMA 1 part by weight> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.33 ⁇ m.
  • Production Example 1-18 Preparation of core-shell polymer latex (L-18) In Production Example 1-1, ⁇ MMA45 parts by weight, MEA 42 parts by weight>, ⁇ MMA 9.5 parts by weight, BA 1.2 parts by weight, GMA 1 part by weight, ALMA 1.3 parts by weight> as a graft monomer instead of ⁇ MMA 4.7 parts by weight, BA 6 parts by weight, GMA 1 part by weight>
  • a core-shell polymer latex (L-18) was obtained in the same manner as in Production Example 1-1, except that , ALMA 1.3 parts by weight> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.35 ⁇ m.
  • Production Example 1-19 Preparation of Core-Shell Polymer Latex (L-19)
  • a core-shell polymer latex (L-19) was obtained in the same manner as in Production Example 1-1, except that , ALMA 0.3 parts by weight> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.34 ⁇ m.
  • Production Example 1-20 Preparation of core-shell polymer latex (L-20) In Production Example 1-1, ⁇ MMA45 parts by weight, MEA 42 parts by weight, ALMA 0.87 parts by weight> is used, and ⁇ MMA 9.5 parts by weight, BA 1.2 parts by weight, GMA 1 part by weight, ALMA 1.3 parts by weight> is replaced with ⁇ MMA 1.7 parts by weight, BA 10
  • a core-shell polymer latex (L-20) was obtained in the same manner as in Production Example 1-1, except that 1 part by weight of GMA, 0.3 part by weight of ALMA> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.33 ⁇ m.
  • Production Example 1-21 Preparation of Core-Shell Polymer Latex (L-21)
  • ⁇ MMA45 parts by weight, MEA 42 parts by weight, ALMA 1.74 parts by weight> is used, and ⁇ MMA 9.5 parts by weight, BA 1.2 parts by weight, GMA 1 part by weight, ALMA 1.3 parts by weight> is replaced with ⁇ MMA 1.7 parts by weight, BA 10
  • a core-shell polymer latex (L-21) was obtained in the same manner as in Production Example 1-1, except that 1 part by weight of GMA, 0.3 part by weight of ALMA> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.32 ⁇ m.
  • Production Example 1-1 ⁇ MMA45 parts by weight, MEA 42 parts by weight, ALMA 0.87 parts by weight>, ⁇ MMA 9.5 parts by weight, BA 1.2 parts by weight, GMA 1 part by weight, ALMA 1.3 parts by weight> instead of ⁇ MMA 2 parts by weight, BA 10 parts by weight> as a graft monomer
  • a core-shell polymer latex (L-22) was obtained in the same manner as in Production Example 1-1 except that , GMA 1 part by weight> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.33 ⁇ m.
  • Production Example 1-23 Preparation of core-shell polymer latex (L-23) Into a glass reactor equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a device for adding monomers and emulsifiers, 182 parts by weight of deionized water, 0.006 parts by weight of EDTA, 0.0015 parts by weight of FE, 1.5 parts by weight of SFS and 0.01 parts by weight of SDS were charged, and the temperature was raised to 60° C. while stirring in a nitrogen stream. Next, a mixture of core layer monomers (MMA 8 parts by weight, BA 40 parts by weight, ALMA 2.4 parts by weight) and CHP 0.07 parts by weight was added dropwise over 2 hours.
  • MMA 8 parts by weight, BA 40 parts by weight, ALMA 2.4 parts by weight a mixture of core layer monomers (MMA 8 parts by weight, BA 40 parts by weight, ALMA 2.4 parts by weight) and CHP 0.07 parts by weight was added dropwise over 2 hours.
  • a core-shell polymer latex (L-24) was obtained in the same manner as in Production Example 1-23, except that 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 0.94 parts by weight of CHP> were used. .
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.33 ⁇ m.
  • Production Example 1-25 Preparation of core-shell polymer latex (L-25) Into a glass reactor equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a device for adding monomers and emulsifiers, 182 parts by weight of deionized water, 0.006 parts by weight of EDTA, 0.0015 parts by weight of FE, 1.5 parts by weight of SFS and 0.01 parts by weight of SDS were charged, and the temperature was raised to 60° C. while stirring in a nitrogen stream. Next, a mixture of core layer monomers (12 parts by weight of MMA, 12 parts by weight of BA, 1.2 parts by weight of ALMA) and 0.04 parts by weight of CHP was added dropwise over 1 hour.
  • a mixture of core layer monomers (12 parts by weight of MMA, 12 parts by weight of BA, 1.2 parts by weight of ALMA) and 0.04 parts by weight of CHP was added dropwise over 1 hour.
  • Production Example 1-26 Preparation of core-shell polymer latex (L-26) In Production Example 1-25, instead of ⁇ MMA 38 parts by weight, BA 38 parts by weight, CHP 0.46 parts by weight> as the graft monomer and its initiator (CHP)
  • a core-shell polymer latex (L-30) was obtained in the same manner as in Production Example 1-25 except that ⁇ MMA 33 parts by weight, BA 33 parts by weight, GMA 10 parts by weight, CHP 0.46 parts by weight> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.32 ⁇ m.
  • Production Example 1-27 Preparation of core-shell polymer latex (L-27) Into a glass reactor equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a device for adding monomers and emulsifiers, 182 parts by weight of deionized water, 0.006 parts by weight of EDTA, 0.0015 parts by weight of FE, 1.5 parts by weight of SFS and 0.01 parts by weight of SDS were charged, and the temperature was raised to 60° C. while stirring in a nitrogen stream. Next, a mixture of core layer monomers (12 parts by weight of MMA, 12 parts by weight of BA, 1.2 parts by weight of ALMA) and 0.04 parts by weight of CHP was added dropwise over 1 hour.
  • a mixture of core layer monomers (12 parts by weight of MMA, 12 parts by weight of BA, 1.2 parts by weight of ALMA) and 0.04 parts by weight of CHP was added dropwise over 1 hour.
  • Production Example 1-28 Preparation of core-shell polymer latex (L-28) In Production Example 1-27, the graft monomer and its initiator (CHP) ⁇ MMA 33 parts by weight, BA 33 parts by weight, GMA 10 parts by weight, CHP 0.46 parts by weight A core-shell polymer latex (L -28) was obtained. The volume average particle size of the core-shell polymer contained in the obtained latex was 0.31 ⁇ m.
  • Production Example 1-29 Preparation of core-shell polymer latex (L-29) In Production Example 1-27, the graft monomer and its initiator (CHP) ⁇ MMA 33 parts by weight, BA 33 parts by weight, GMA 10 parts by weight, CHP 0.46 parts by weight A core-shell polymer latex (L -29) was obtained. The volume average particle size of the core-shell polymer contained in the obtained latex was 0.31 ⁇ m.
  • Production Example 1-30 Preparation of core-shell polymer latex (L-30)
  • the graft monomer and its initiator (CHP) were ⁇ 33 parts by weight of MMA, 33 parts by weight of BA, 10 parts by weight of GMA, and 0.46 parts by weight of CHP.
  • a core-shell polymer latex (L-30) was prepared in the same manner as in Production Example 1-27 except that ⁇ MMA 22 parts by weight, BA 24 parts by weight, BMA 30 parts by weight, CHP 1.37 parts by weight> was used instead of ⁇ Parts>. Obtained.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.31 ⁇ m.
  • Production Example 1-31 Preparation of core-shell polymer latex (L-31)
  • ⁇ 33 parts by weight of MMA, 33 parts by weight of BA, 10 parts by weight of GMA, 0.46 parts by weight of CHP as the graft monomer and its initiator (CHP) Parts> instead of ⁇ MMA 20 parts by weight, BA 24 parts by weight, BMA 30 parts by weight, acrylonitrile (AN) 2 parts by weight, CHP 1.37 parts by weight> was used in the same manner as in Production Example 1-27 to prepare a core-shell polymer.
  • latex (L-31) was obtained.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.31 ⁇ m.
  • Production Example 1-32 Preparation of core-shell polymer latex (L-32) Core-shell polymer latex (L -32) was obtained.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.36 ⁇ m.
  • Production Example 1-33 Preparation of core-shell polymer latex (L-33) Core-shell polymer latex (L-33) was prepared in the same manner as in Production Example 1-24 except that ⁇ MMA 26 parts by weight, BA 26 parts by weight, CHP 0.30 parts by weight> was used instead of CHP 0.94 parts by weight>. Obtained. The volume average particle size of the core-shell polymer contained in the obtained latex was 0.35 ⁇ m.
  • Production Example 1-34 Preparation of core-shell polymer latex (L-34)
  • 200 parts by weight of water, 0.03 parts by weight of tripotassium phosphate, 0.002 parts by weight of EDTA, 0.001 parts by weight of FE, and , and 1.55 parts by weight of SDS were added, and the mixture was sufficiently purged with nitrogen while stirring to remove oxygen.
  • 0.03 parts by weight of paramenthane hydroperoxide (PHP) and then 0.10 parts by weight of SFS were added to initiate polymerization.
  • 0.025 parts by weight of PHP was added at 3, 5 and 7 hours after the initiation of polymerization.
  • the residual monomer was devolatilized and removed under reduced pressure to complete the polymerization, thereby obtaining a polybutadiene rubber latex (R-2) containing polybutadiene rubber as a main component.
  • the volume average particle size of the polybutadiene rubber particles contained in the obtained latex was 0.20 ⁇ m.
  • aqueous latex (L-34) 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 (L-34) was 0.27 ⁇ m.
  • Production Example 1-35 Preparation of Core-Shell Polymer Latex (L-35) 256 parts by weight of polybutadiene rubber latex (R-2) (containing 85 parts by weight of polybutadiene rubber particles) and 61 parts by weight of deionized water were charged and stirred at 60° C. while replacing with nitrogen. After adding 0.004 parts by weight of EDTA, 0.001 parts by weight of FE, and 0.2 parts by weight of SFS, shell monomers (7 parts by weight of styrene (ST), 1.5 parts by weight of MMA, 2.5 parts by weight of AN, 4 parts by weight of GMA) , and 0.04 parts by weight of cumene hydroperoxide (CHP) were continuously added over 2 hours.
  • L-35 256 parts by weight of polybutadiene rubber latex (R-2) (containing 85 parts by weight of polybutadiene rubber particles) and 61 parts by weight of deionized water were charged and stirred at 60° C. while replacing with nitrogen. After adding 0.004 parts by
  • aqueous latex (L-35) containing core-shell polymer particles 0.04 part by weight of CHP was added, and the mixture was stirred for 2 hours to complete the polymerization, thereby obtaining an aqueous latex (L-35) 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 (L-35) was 0.21 ⁇ m.
  • Production Example 1-36 Preparation of core-shell polymer latex (L-36) In Production Example 1-23, the core layer monomer and its initiator (CHP) ⁇ MMA 8 parts by weight, BA 40 parts by weight, ALMA 2.4 parts by weight, CHP0 ⁇ MMA 12 parts by weight, BA 60 parts by weight, ALMA 3.6 parts by weight, CHP 0.10 parts by weight> instead of ⁇ MMA 8 parts by weight, BA 16 parts by weight> as the graft monomer and its initiator (CHP) , BMA 20 parts by weight, GMA 8 parts by weight, CHP 0.23 parts by weight> instead of ⁇ MMA 4 parts by weight, BA 8 parts by weight, BMA 10 parts by weight, GMA 4 parts by weight, CHP 0.12 parts by weight> Production Example 1 A core-shell polymer latex (L-36) was obtained in the same manner as for L-23. The volume average particle size of the core-shell polymer contained in the obtained latex was 0.33 ⁇ m.
  • Production Example 1-37 Preparation of core-shell polymer latex (L-37) Core-shell polymer latex (L -37) was obtained.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.33 ⁇ m.
  • Production Example 1-38 Preparation of core-shell polymer latex (L-38) Core-shell polymer latex (L -38) was obtained.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.35 ⁇ m.
  • Production Example 1-40 Preparation of core-shell polymer latex (L-40)
  • ⁇ MMA 16 parts by weight, 40 parts by weight of BA, 31 parts by weight of ST, 4.3 parts by weight of ALMA>, and ⁇ MMA 2 parts by weight instead of ⁇ MMA 9.5 parts by weight, BA 1.2 parts by weight, GMA 1 part by weight, ALMA 1.3 parts by weight> as a graft monomer , 10 parts by weight of BA, and 1 part by weight of GMA>
  • a core-shell polymer latex (L-40) was obtained in the same manner as in Production Example 1-1.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.15 ⁇ m.
  • Production Example 1-42 Preparation of core-shell polymer latex (L-42) In Production Example 1-1, ⁇ MMA 8 parts by weight, 40 parts by weight of BA, 39 parts by weight of ST, 4.3 parts by weight of ALMA>, and ⁇ MMA 7 parts by weight, instead of ⁇ MMA 9.5 parts by weight, BA 1.2 parts by weight, GMA 1 part by weight, ALMA 1.3 parts by weight> as a graft monomer , 5 parts by weight of BA, and 1 part by weight of GMA>, a core-shell polymer latex (L-42) was obtained in the same manner as in Production Example 1-1. The volume average particle size of the core-shell polymer contained in the obtained latex was 0.15 ⁇ m.
  • BA40 parts by weight, ALMA0.43 parts by weight> as core layer monomers
  • ⁇ MMA 7 parts by weight BA 5 parts by weight> instead of ⁇ MMA 9.5 parts by weight
  • a core-shell polymer latex (L-43) was obtained in the same manner as in Production Example 1-1, except that , GMA 1 part by weight> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.14 ⁇ m.
  • Production Example 1-45 Preparation of Core-Shell Polymer Latex (L-45) Using 4 parts by weight of BA, 26 parts by weight of MEA, 31 parts by weight of ST, 4.3 parts by weight of ALMA> as a graft monomer instead of ⁇ 9.5 parts by weight of MMA, 1.2 parts by weight of BA, 1 part by weight of GMA, 1.3 parts by weight of ALMA>
  • a core-shell polymer latex (L-45) was obtained in the same manner as in Production Example 1-1 except that ⁇ MMA 7 parts by weight, BA 5 parts by weight, GMA 1 part by weight> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.16 ⁇ m.
  • Production Example 1-46 Preparation of core-shell polymer latex (L-46) 12 parts by weight of BA, 18 parts by weight of 2-ethylhexyl acrylate (2EHA), 39 parts by weight of ST, and 4.3 parts by weight of ALMA>, and ⁇ 9.5 parts by weight of MMA, 1.2 parts by weight of BA, 1 part by weight of GMA, 1 part by weight of ALMA as graft monomers.
  • a core-shell polymer latex (L-46) was obtained in the same manner as in Production Example 1-1, except that ⁇ MMA 7 parts by weight, BA 5 parts by weight, GMA 1 part by weight> was used instead of ⁇ 3 parts by weight>.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.13 ⁇ m.
  • Production Example 1-47 Preparation of core-shell polymer latex (L-47) 18 parts by weight of BA, 12 parts by weight of 4-hydroxybutyl acrylate (4HBA), 31 parts by weight of ST, and 4.3 parts by weight of ALMA>, and ⁇ 9.5 parts by weight of MMA, 1.2 parts by weight of BA, 1 part by weight of GMA, and 1 part by weight of ALMA as graft monomers.
  • a core-shell polymer latex (L-47) was obtained in the same manner as in Production Example 1-1, except that ⁇ MMA 7 parts by weight, BA 5 parts by weight, GMA 1 part by weight> was used instead of .3 parts by weight>.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.16 ⁇ m.
  • Production Example 1-48 Preparation of core-shell polymer latex (L-48) In Production Example 1-1, instead of ⁇ MMA 47 parts by weight, BA 40 parts by weight, ALMA 0.43 parts by weight> as core layer monomers, ⁇ benzyl acrylate (BZA ) 26 parts by weight, 30 parts by weight of BA, 31 parts by weight of ST, 4.3 parts by weight of ALMA> as a graft monomer instead of ⁇ 9.5 parts by weight of MMA, 1.2 parts by weight of BA, 1 part by weight of GMA, 1.3 parts by weight of ALMA>
  • a core-shell polymer latex (L-48) was obtained in the same manner as in Production Example 1-1 except that ⁇ MMA 7 parts by weight, BA 5 parts by weight, GMA 1 part by weight> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.14 ⁇ m.
  • Production Example 1-49 Preparation of core-shell polymer latex (L-49) ) 21 parts by weight, 35 parts by weight of BA, 31 parts by weight of ST, 4.3 parts by weight of ALMA> instead of ⁇ 9.5 parts by weight of MMA, 1.2 parts by weight of BA, 1 part by weight of GMA, 1.3 parts by weight of ALMA> as graft monomers
  • a core-shell polymer latex (L-49) was obtained in the same manner as in Production Example 1-1 except that ⁇ MMA 7 parts by weight, BA 5 parts by weight, GMA 1 part by weight> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.13 ⁇ m.
  • Latex (L-50) Containing Crosslinked Polymer Particles Having Single Layer Structure 182 parts by weight of deionized water, 0.006 parts by weight of EDTA, 0.0015 parts by weight of FE, 0.6 parts by weight of SFS and 0.01 parts by weight of SDS were charged and heated to 60° C. while stirring in a nitrogen stream.
  • a mixture of core layer monomers 47 parts by weight of MMA, 40 parts by weight of BA, 4.3 parts by weight of ALMA
  • 0.13 parts by weight of CHP was added dropwise over 3 hours.
  • 20 parts by weight of a 5% by weight aqueous solution of SDS was continuously added over 3 hours.
  • a mixture of core layer monomers (33.5 parts by weight of BA, 41.5 parts by weight of ST, 3.8 parts by weight of ALMA) and 0.022 parts by weight of CHP was added dropwise over 3 hours.
  • 20 parts by weight of a 5% by weight aqueous solution of SDS was continuously added over 3 hours. Stirring was continued for 1 hour from the end of the addition of the monomer mixture to complete the polymerization, and a latex containing acrylic polymer particles was obtained.
  • an intermediate layer monomer 1.5 parts by weight of triallyl isocyanurate (TAIC)
  • TAIC triallyl isocyanurate
  • a mixture of grafting monomers (19.5 parts by weight of MMA, 0.5 parts by weight of BA, 5 parts by weight of GMA) and 0.34 parts by weight of CHP were added continuously over 150 minutes. After completion of the addition, 0.07 parts by weight of CHP was added, and the mixture was stirred for 2 hours to complete the polymerization, thereby obtaining a latex (L-51) containing a core-shell polymer.
  • the polymerization conversion rate of the monomer component was 99% or more.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.08 ⁇ m.
  • Production Example 1-52 Preparation of core-shell polymer latex (L-52) In Production Example 1-51, ⁇ Methyl acrylate ( A core-shell polymer latex (L-52) was obtained in the same manner as in Production Example 1-51, except that MA) 19.5 parts by weight, BA 0.5 parts by weight, and GMA 5 parts by weight> were used. The volume average particle size of the core-shell polymer contained in the obtained latex was 0.08 ⁇ m.
  • Production Example 1-53 Preparation of core-shell polymer latex (L-53)
  • ⁇ MMA 19.5 parts by weight, BA 0.5 parts by weight, GMA 5 parts by weight> was replaced with ⁇ MA 23.5 by weight.
  • a core-shell polymer latex (L-53) was obtained in the same manner as in Production Example 1-51, except that parts by weight of BA, 0.5 parts by weight of BA, and 1 part by weight of GMA> were used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.08 ⁇ m.
  • Production Example 1-54 Preparation of core-shell polymer latex (L-54)
  • Production Example 1-51 instead of ⁇ MMA 19.5 parts by weight, BA 0.5 parts by weight, GMA 5 parts by weight> as graft monomers, ⁇ MMA 6 parts by weight> , MA 12 parts by weight, BA 6 parts by weight, GMA 1 part by weight> was used in the same manner as in Production Example 1-51 to obtain a core-shell polymer latex (L-54).
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.08 ⁇ m.
  • Production Example 1-55 Preparation of core-shell polymer latex (L-55) In Production Example 1-51, instead of ⁇ BA33.5 parts by weight, ST41.5 parts by weight, ALMA3.8 parts by weight> as core layer monomers, BMA 22 parts by weight, BA 26 parts by weight, ST 27 parts by weight, ALMA 3.8 parts by weight>, and ⁇ MMA 19.5 parts by weight, BA 0.5 parts by weight, GMA 5 parts by weight> instead of ⁇ MMA 12.5 parts by weight> as a graft monomer , 11.5 parts by weight of BA, and 1 part by weight of GMA>, a core-shell polymer latex (L-55) was obtained in the same manner as in Production Example 1-51. The volume average particle size of the core-shell polymer contained in the obtained latex was 0.08 ⁇ m.
  • Production Example 1-56 Preparation of core-shell polymer latex (L-56) BMA 26 parts by weight, BA 22 parts by weight, ST 27 parts by weight, ALMA 3.8 parts by weight>, and ⁇ MMA 19.5 parts by weight, BA 0.5 parts by weight, GMA 5 parts by weight> instead of ⁇ MA 23.5 parts by weight> as a graft monomer , 0.5 parts by weight of BA, and 1 part by weight of GMA> were used in the same manner as in Production Example 1-51 to obtain a core-shell polymer latex (L-56).
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.08 ⁇ m.
  • Production Example 1-57 Preparation of core-shell polymer latex (L-57) BMA 26 parts by weight, BA 22 parts by weight, ST 27 parts by weight, ALMA 3.8 parts by weight>, and ⁇ MMA 19.5 parts by weight, BA 0.5 parts by weight, GMA 5 parts by weight> instead of ⁇ MA 20 parts by weight, ST4
  • a core-shell polymer latex (L-57) was obtained in the same manner as in Production Example 1-51, except that 1 part by weight of GMA> was used.
  • the volume average particle size of the core-shell polymer contained in the obtained latex was 0.08 ⁇ m.
  • Production Example 2-1 Preparation of Dispersion (K-1) 132 g of methyl ethyl ketone (MEK) was introduced into a 1 L mixing tank at 25° C., and the core-shell polymer latex obtained in Production Example 1-1 (L-1 ) was added (equivalent to 40 g of core-shell polymer particles). After mixing uniformly, 200 g of water was added at a feed rate of 80 g/min. After the supply was finished, the stirring was quickly stopped to obtain a slurry liquid consisting of an aqueous phase partially containing floating aggregates and an organic solvent. Next, 300 g of the water phase was discharged from the discharge port at the bottom of the tank, leaving the aggregates containing a part of the water phase.
  • K-1 methyl ethyl ketone
  • Production Example 2-2 Preparation of Dispersion (K-2) In Production Example 2-1, (L-2) obtained in Production Example 1-2 was used instead of (L-1) as the core-shell polymer latex.
  • a dispersion (K-2) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-1 except that the resin was added.
  • the viscosity of (K-2) was 29 Pa ⁇ s.
  • Production Example 2-3 Preparation of Dispersion (K-3) In Production Example 2-1, (L-3) obtained in Production Example 1-3 was used instead of (L-1) as the core-shell polymer latex.
  • a dispersion (K-3) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-1 except that the resin was added.
  • the viscosity of (K-3) was 29 Pa ⁇ s.
  • Production Example 2-4 Preparation of Dispersion (K-4) In Production Example 2-1, (L-4) obtained in Production Example 1-4 was used instead of (L-1) as the core-shell polymer latex.
  • the viscosity of (K-4) was 45 Pa ⁇ s.
  • Production Example 2-5 Preparation of Dispersion (K-5) In Production Example 2-1, (L-5) obtained in Production Example 1-5 was used instead of (L-1) as the core-shell polymer latex. A dispersion (K -5) was obtained. The viscosity of (K-5) was 12 Pa ⁇ s.
  • Production Example 2-6 Preparation of Dispersion (K-6) In Production Example 2-5, (L-6) obtained in Production Example 1-6 was used instead of (L-5) as the core-shell polymer latex.
  • a dispersion (K-6) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-5 except that the resin was added.
  • the viscosity of (K-6) was 11 Pa ⁇ s.
  • Production Example 2-7 Preparation of Dispersion (K-7) In Production Example 2-5, (L-7) obtained in Production Example 1-7 was used instead of (L-5) as the core-shell polymer latex.
  • a dispersion (K-7) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-5 except that the resin was added.
  • the viscosity of (K-7) was 27 Pa ⁇ s.
  • Production Example 2-8 Preparation of Dispersion (K-8) In Production Example 2-5, (L-8) obtained in Production Example 1-8 was used instead of (L-5) as the core-shell polymer latex.
  • a dispersion (K-8) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-5 except that the resin was added.
  • (K-8) had a viscosity of 19 Pa ⁇ s.
  • Production Example 2-9 Preparation of Dispersion (K-9) In Production Example 2-5, (L-9) obtained in Production Example 1-9 was used instead of (L-5) as the core-shell polymer latex.
  • a dispersion (K-9) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-5 except that the resin was added.
  • the viscosity of (K-9) was 25 Pa ⁇ s.
  • Production Example 2-10 Preparation of Dispersion (K-10) In Production Example 2-5, (L-10) obtained in Production Example 1-10 was used instead of (L-5) as the core-shell polymer latex.
  • a dispersion (K-10) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-5 except that the dispersion was added.
  • the viscosity of (K-10) was 73 Pa ⁇ s.
  • Production Example 2-11 Preparation of Dispersion (K-11) In Production Example 2-5, (L-11) obtained in Production Example 1-11 was used instead of (L-5) as the core-shell polymer latex.
  • a dispersion (K-11) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-5 except that the dispersion was added.
  • the viscosity of (K-11) was 45 Pa ⁇ s.
  • Production Example 2-12 Preparation of Dispersion (K-12) In Production Example 2-1, (L-12) obtained in Production Example 1-12 was used instead of (L-1) as the core-shell polymer latex.
  • a dispersion (K-12) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-1 except that the dispersion was added.
  • (K-12) had a viscosity of 150 Pa ⁇ s or more.
  • Production Example 2-13 Preparation of Dispersion (K-13) In Production Example 2-1, (L-13) obtained in Production Example 1-13 was used instead of (L-1) as the core-shell polymer latex.
  • a dispersion (K-13) in which the core-shell polymer particles were dispersed in the epoxy resin was obtained in the same manner as in Production Example 2-1 except that the dispersion was added.
  • the viscosity of (K-13) was 108 Pa ⁇ s.
  • Production Example 2-14 Preparation of Dispersion (K-14) In Production Example 2-1, (L-14) obtained in Production Example 1-14 was used instead of (L-1) as the core-shell polymer latex.
  • a dispersion (K-14) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-1 except that the dispersion was added.
  • the viscosity of (K-14) was 55 Pa ⁇ s.
  • Production Example 2-15 Preparation of Dispersion (K-15) In Production Example 2-1, (L-15) obtained in Production Example 1-15 was used instead of (L-1) as the core-shell polymer latex.
  • a dispersion (K-15) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-1 except that the dispersion was added.
  • the viscosity of (K-15) was 15 Pa ⁇ s.
  • Production Example 2-16 Preparation of Dispersion (K-16) In Production Example 2-1, (L-16) obtained in Production Example 1-16 was used instead of (L-1) as the core-shell polymer latex.
  • a dispersion (K-16) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-1 except that the dispersion was added.
  • the viscosity of (K-16) was 41 Pa ⁇ s.
  • Production Example 2-17 Preparation of Dispersion (K-17) In Production Example 2-1, (L-17) obtained in Production Example 1-17 was used instead of (L-1) as the core-shell polymer latex. A dispersion (K -17) was obtained. The viscosity of (K-17) was 10 Pa ⁇ s.
  • Production Example 2-18 Preparation of Dispersion (K-18) In Production Example 2-1, (L-2) obtained in Production Example 1-2 was used instead of (L-1) as the core-shell polymer latex.
  • epoxy resin (A-1) epoxy resin (A-2; manufactured by Mitsubishi Chemical Corporation, JER871: dimer acid-modified epoxy resin, epoxy equivalent is 410 g / eq, ⁇ (A1) component (A2)
  • a dispersion (K-18) in which core-shell polymer particles are dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-1, except that 60 g of the epoxy resin>) was used.
  • the viscosity of (K-18) was 19 Pa ⁇ s.
  • Production Example 2-19 Preparation of Dispersion (K-19) In Production Example 2-18, instead of (L-2) as the core-shell polymer latex, (L-3) obtained in Production Example 1-3 was used.
  • a dispersion (K-19) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-18, except that The viscosity of (K-19) was 15 Pa ⁇ s.
  • Production Example 2-20 Preparation of Dispersion (K-20) In Production Example 2-18, (L-18) obtained in Production Example 1-18 was used instead of (L-2) as the core-shell polymer latex.
  • a dispersion (K-20) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-18 except that the resin was added.
  • the viscosity of (K-20) was 5 Pa ⁇ s.
  • Production Example 2-21 Preparation of Dispersion (K-21) In Production Example 2-18, (L-19) obtained in Production Example 1-19 was used instead of (L-2) as the core-shell polymer latex.
  • a dispersion (K-21) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-18 except that the dispersion was added.
  • the viscosity of (K-21) was 7 Pa ⁇ s.
  • Production Example 2-22 Preparation of Dispersion (K-22) In Production Example 2-18, (L-20) obtained in Production Example 1-20 was used instead of (L-2) as the core-shell polymer latex.
  • a dispersion (K-22) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-18, except that The viscosity of (K-22) was 13 Pa ⁇ s.
  • Production Example 2-23 Preparation of Dispersion (K-23) In Production Example 2-18, (L-21) obtained in Production Example 1-21 was used instead of (L-2) as the core-shell polymer latex.
  • a dispersion (K-23) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-18 except that the dispersion was added.
  • the viscosity of (K-23) was 2 Pa ⁇ s.
  • Production Example 2-24 Preparation of Dispersion (K-24) In Production Example 2-18, (L-22) obtained in Production Example 1-22 was used instead of (L-2) as the core-shell polymer latex.
  • a dispersion (K-24) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-18 except that the dispersion was added.
  • (K-24) had a viscosity of 9 Pa ⁇ s.
  • Production Example 2-25 Preparation of Dispersion (K-25) In Production Example 2-18, (L-5) obtained in Production Example 1-5 was used instead of (L-2) as the core-shell polymer latex.
  • a dispersion (K-25) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-18 except that the dispersion was added.
  • the viscosity of (K-25) was 1 Pa ⁇ s.
  • Production Example 2-26 Preparation of Dispersion (K-26) In Production Example 2-18, (L-5) obtained in Production Example 1-5 was used instead of (L-2) as the core-shell polymer latex. , in the same manner as in Production Example 2-18, except that 26.7 g of epoxy resin (A-2) was used instead of 60 g of epoxy resin (A-2), to obtain a dispersion of core-shell polymer particles dispersed in epoxy resin. (K-26) was obtained. The viscosity of (K-26) was 7 Pa ⁇ s.
  • Production Example 2-27 Preparation of Dispersion (K-27) In Production Example 2-18, (L-19) obtained in Production Example 1-19 was used instead of (L-2) as the core-shell polymer latex. A dispersion (K -27) was obtained. (K-27) had a viscosity of 1 Pa ⁇ s.
  • Production Example 2-28 Preparation of Dispersion (K-28) In Production Example 2-17, (L-16) obtained in Production Example 1-16 was used instead of (L-2) as the core-shell polymer latex.
  • a dispersion (K-28) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-17 except that the dispersion was added.
  • the viscosity of (K-28) was 5 Pa ⁇ s.
  • Production Example 2-29 Preparation of Dispersion (K-29) 132 g of methyl ethyl ketone (MEK) was introduced into a 1 L mixing tank at 25° C., and the core-shell polymer latex obtained in Production Example 1-23 (L-23 ) was added (equivalent to 40 g of core-shell polymer particles). After mixing uniformly, 260 g of water was added at a feed rate of 80 g/min. After the supply was finished, the stirring was quickly stopped to obtain a slurry liquid consisting of an aqueous phase partially containing floating aggregates and an organic solvent. Next, 440 g of the water phase was discharged from the discharge port at the bottom of the tank, leaving the aggregates containing a part of the water phase.
  • K-29 methyl ethyl ketone
  • Production Example 2-30 Preparation of Dispersion (K-30) In Production Example 2-29, (L-24) obtained in Production Example 1-24 was used instead of (L-23) as the core-shell polymer latex.
  • a dispersion (K-30) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-29 except that the dispersion was added.
  • the viscosity of (K-30) was 14 Pa ⁇ s.
  • Production Example 2-31 Preparation of Dispersion (K-31) In Production Example 2-29, (L-25) obtained in Production Example 1-25 was used instead of (L-23) as the core-shell polymer latex.
  • a dispersion (K-31) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-29 except that the dispersion was added.
  • (K-31) had a viscosity of 150 Pa ⁇ s or more.
  • Production Example 2-33 Preparation of Dispersion (K-33) In Production Example 2-29, (L-27) obtained in Production Example 1-27 was used instead of (L-23) as the core-shell polymer latex.
  • a dispersion (K-33) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-29 except that the dispersion was added.
  • the viscosity of (K-33) was 140 Pa ⁇ s.
  • Production Example 2-34 Preparation of Dispersion (K-34) In Production Example 2-29, (L-28) obtained in Production Example 1-28 was used instead of (L-23) as the core-shell polymer latex.
  • a dispersion (K-34) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-29 except that the dispersion was added.
  • the viscosity of (K-34) was 49 Pa ⁇ s.
  • Production Example 2-35 Preparation of Dispersion (K-35) In Production Example 2-29, (L-29) obtained in Production Example 1-29 was used instead of (L-23) as the core-shell polymer latex.
  • a dispersion (K-35) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-29 except that the resin was added.
  • the viscosity of (K-35) was 16 Pa ⁇ s.
  • Production Example 2-36 Preparation of Dispersion (K-36) In Production Example 2-29, (L-30) obtained in Production Example 1-30 was used instead of (L-23) as the core-shell polymer latex.
  • a dispersion (K-36) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-29 except that the dispersion was added.
  • the viscosity of (K-36) was 11 Pa ⁇ s.
  • Production Example 2-37 Preparation of Dispersion (K-37) In Production Example 2-29, (L-31) obtained in Production Example 1-31 was used instead of (L-23) as the core-shell polymer latex.
  • a dispersion (K-37) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-29, except that The viscosity of (K-37) was 11 Pa ⁇ s.
  • Production Example 2-38 Preparation of Dispersion (K-38) In Production Example 2-29, (L-32) obtained in Production Example 1-32 was used instead of (L-23) as the core-shell polymer latex. A dispersion (K -38) was obtained. The viscosity of (K-38) was 111 Pa ⁇ s.
  • Production Example 2-39 Preparation of Dispersion (K-39) In Production Example 2-38, (L-33) obtained in Production Example 1-33 was used instead of (L-32) as the core-shell polymer latex.
  • a dispersion (K-39) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-38, except that (K-39) had a viscosity of 150 Pa ⁇ s or more.
  • Production Example 2-40 Preparation of Dispersion (K-40) In Production Example 2-38, (L-34) obtained in Production Example 1-34 was used instead of (L-32) as the core-shell polymer latex.
  • a dispersion (K-40) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-38, except that (K-40) had a viscosity of 150 Pa ⁇ s or more.
  • Production Example 2-41 Preparation of Dispersion (K-41) In Production Example 2-5, (L-35) obtained in Production Example 1-35 was used instead of (L-5) as the core-shell polymer latex.
  • a dispersion (K-41) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-5 except that the dispersion was added.
  • the viscosity of (K-41) was 25 Pa ⁇ s.
  • Production Example 2-42 Preparation of Dispersion (K-42) In Production Example 2-38, (L-36) obtained in Production Example 1-36 was used instead of (L-32) as the core-shell polymer latex.
  • a dispersion (K-42) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-38 except that the resin was added.
  • the viscosity of (K-42) was 24 Pa ⁇ s.
  • Production Example 2-43 Preparation of Dispersion (K-43) In Production Example 2-38, (L-37) obtained in Production Example 1-37 was used instead of (L-32) as the core-shell polymer latex.
  • the viscosity of (K-43) was 27 Pa ⁇ s.
  • Production Example 2-44 Preparation of Dispersion (K-44) In Production Example 2-38, (L-38) obtained in Production Example 1-38 was used instead of (L-32) as the core-shell polymer latex.
  • a dispersion (K-44) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-38, except that (K-44) had a viscosity of 150 Pa ⁇ s or more.
  • Production Example 2-45 Preparation of Dispersion (K-45) In Production Example 2-18, (L-19) obtained in Production Example 1-19 was used instead of (L-2) as the core-shell polymer latex. A dispersion (K -45) was obtained. The viscosity of (K-45) was 27 Pa ⁇ s.
  • Production Example 2-46 Preparation of Dispersion (K-46) In Production Example 2-1, (L-5) obtained in Production Example 1-5 was used instead of (L-1) as the core-shell polymer latex.
  • a dispersion (K-46) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 2-1 except that the dispersion was added.
  • Production Example 2-58 Preparation of Dispersion (K-58) In Production Example 2-1, (L-50) obtained in Production Example 1-50 was used instead of (L-1) as the core-shell polymer latex. A dispersion (K -58) was obtained.
  • Examples 1 to 62, Comparative Examples 1 to 18 According to the formulations shown in Tables 1 to 6, each component was weighed and thoroughly mixed to obtain a one-component curable resin composition.
  • Tables 1 to 6 show the storage modulus E' at 23°C and 80°C and the loss tangent (tan ⁇ ) at 40°C.
  • the curable resin composition is applied to two cold-rolled steel plates (SPCC steel plates) with dimensions: 25 x 100 x 1.6 mm, and the adhesive layer is 25 mm wide x 12.5 mm long x 0.13 mm thick. and cured under the conditions of 170° C. for 30 minutes to obtain a laminate.
  • SPCC steel plates cold-rolled steel plates
  • the adhesive layer is 25 mm wide x 12.5 mm long x 0.13 mm thick.
  • the shear bond strength was measured in units of MPa under the measurement conditions of a measurement temperature of 23°C and a test speed of 1.3 mm/min. Tables 4 and 6 show the results.
  • T-shaped peel adhesive strength The curable resin composition is applied to two SPCC steel plates with dimensions of 25 ⁇ 200 ⁇ 0.5 mm, superimposed so that the adhesive layer has a thickness of 0.25 mm, and cured under the conditions of 170 ° C. ⁇ 30 minutes, The T-peel adhesion strength at 23°C was measured according to JIS K6854. Test results are shown in Tables 4 and 6.
  • Tg of the core layer and the Tg of the shell layer in Tables 1 to 15 were calculated from the Fox formula using the Tg values of the homopolymers of the following monomers used.
  • Methyl methacrylate (MMA) 105°C
  • butyl acrylate (BA) -54°C
  • butyl methacrylate (BMA) 20°C
  • Methoxyethyl acrylate (MEA) -50°C
  • Styrene (St) 100°C
  • AN Acrylonitrile
  • AN Acrylonitrile
  • Glycidyl methacrylate 46°C
  • allyl methacrylate (ALMA) 52°C
  • butadiene (Bd) -85°C
  • 2-ethylhexyl acrylate (2EHA) -70°C
  • benzyl Acrylate (BZA) 6°C
  • the elastic modulus at 23° C. but also the elastic modulus at 80° C. is high, the heat resistance is excellent, and the rigidity at high temperatures is also high.
  • Comparative Example 1 containing no component (B-1), Comparative Example 2 containing crosslinked polymer particles having a core layer Tg of less than ⁇ 20° C., and containing crosslinked polymer particles having a core layer Tg of greater than 30° C.
  • the curable resin composition to which the component (B-2) is added has a higher tan ⁇ value than the curable resin composition to which the component (B-1) is added, even when the component is added in a small amount.
  • composition of Comparative Example 8 which does not contain the component (B)
  • composition of Comparative Example 9 which contains crosslinked polymer particles whose core layer has a Tg of greater than 30° C., have a small tan ⁇ value and a low damping property.
  • the crosslinked polymer particles (The curable resin compositions of Examples 24 to 35 to which B-3) was added had a high tan ⁇ value and excellent damping properties, and not only the elastic modulus at 23 ° C. but also the elastic modulus at 80 ° C. were high and heat resistant. It can be seen that it has excellent toughness and high rigidity at high temperatures.
  • the curable resin compositions of Examples 36 to 38 of the present invention have a high tan ⁇ value and excellent damping properties, and have a high elastic modulus not only at 23 ° C. but also at 80 ° C. It can be seen that it has excellent toughness and high rigidity at high temperatures. Furthermore, it can be seen that the shear adhesive strength and the T-shaped peel strength are both high, indicating excellent adhesiveness.
  • Example 37 which further contains diene-based core-shell polymer particles as the component (B-4), is found to be excellent in impact resistance peel adhesion.
  • Comparative Examples 15 and 16 which do not contain components (B-1 to 3), have small tan ⁇ values and low damping properties.
  • the curable resin compositions of Examples 40 to 50 in which the core layer is a polymer of a styrene monomer (10% by weight or more and 70% by weight or less), are core layers containing no styrene monomer.
  • the value of tan ⁇ is higher than that of the curable resin composition of Example 39.
  • the curable resin composition of Example 42 whose shell layer has a Tg of ⁇ 20° C. or more and 30° C. or less, has a higher tan ⁇ than the curable resin composition of Example 41, whose shell layer has a Tg of less than ⁇ 20° C. High value.
  • a curable resin composition of less than 50% by weight has a higher tan ⁇ value.
  • the curable resin composition of Example 51 to which the crosslinked polymer particles (B-1) of the present invention were added also had a high tan ⁇ value and excellent damping properties. It can be seen that the elastic modulus is high, the heat resistance is excellent, and the rigidity at high temperatures is high.
  • the curable resin compositions of Examples 53 to 62 in which the core layer is a polymer of a styrene monomer (10% by weight or more and 70% by weight or less), have high tan ⁇ values.
  • the curable resin composition of Example 54 whose shell layer has a Tg of ⁇ 20° C. or higher and 30° C. or lower, has a higher tan ⁇ value than the curable resin composition of Example 53, whose shell layer has a Tg of greater than 30° C. is high.
  • the shell layer is a polymer of a monomer mixture containing a large amount (70% by weight or more and 100% by weight or less) of an alkyl (meth)acrylate having 1 to 2 carbon atoms.
  • the curable resin composition has a large T-peel adhesive strength.
  • curable resin compositions of Examples 60 and 61 containing blocked urethane (C) have higher tan ⁇ values than the curable resin composition of Example 59, which does not contain blocked urethane (C). .

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  • Epoxy Resins (AREA)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024118584A1 (en) * 2022-11-29 2024-06-06 Certainteed Gypsum, Inc. Acoustic adhesive composition and laminated building board including same
WO2024203143A1 (ja) * 2023-03-30 2024-10-03 株式会社カネカ 積層体の製造方法
EP4498456A4 (en) * 2023-06-12 2025-06-25 Panac Co., Ltd. Resin composition for sealing material, sealing material with resin composition and solid polymer fuel cell and water electrolyzer sealing material

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JPH11181245A (ja) * 1997-12-22 1999-07-06 Dainippon Ink & Chem Inc 加熱圧縮成形材料組成物、シートモールディングコンパウンド及びバルクモールディングコンパウンド
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US20070100074A1 (en) * 2005-11-01 2007-05-03 Wayne Devonport Aqueous emulsion polymers comprising stable epoxy groups
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JPS62104888A (ja) * 1985-10-30 1987-05-15 Mitsubishi Rayon Co Ltd 接着剤組成物
JPH11181245A (ja) * 1997-12-22 1999-07-06 Dainippon Ink & Chem Inc 加熱圧縮成形材料組成物、シートモールディングコンパウンド及びバルクモールディングコンパウンド
JPH11263818A (ja) * 1998-03-17 1999-09-28 Nippon Shokubai Co Ltd 舗装工事用樹脂組成物、舗装構造体および施工方法
JP2001247743A (ja) * 2000-03-03 2001-09-11 Daicel Chem Ind Ltd 可逆記録表示媒体、液晶／高分子複合型記録表示層及びその製法、並びにそれに用いられるエポキシ含有樹脂
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024118584A1 (en) * 2022-11-29 2024-06-06 Certainteed Gypsum, Inc. Acoustic adhesive composition and laminated building board including same
WO2024203143A1 (ja) * 2023-03-30 2024-10-03 株式会社カネカ 積層体の製造方法
EP4498456A4 (en) * 2023-06-12 2025-06-25 Panac Co., Ltd. Resin composition for sealing material, sealing material with resin composition and solid polymer fuel cell and water electrolyzer sealing material

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