Two-component curable resin composition and its cured product

Abstract

The present invention provides a two-part curable resin composition that, while maintaining the adhesive strength with respect to metals, can provide a cured product having high strength and high elongation.　Provided is a two-part curable resin composition comprising agent A and agent B. Agent A: A composition containing component (a), which includes (a-1) a hydrogenated epoxy resin and (a-2) a bisphenol-type epoxy resin, and component (b), which is a curing catalyst for component (c). Agent B: A composition containing component (c), which is an organic polymer having two or more hydrolysable silyl groups, and component (d), which is a curing agent for component (a).

Description

Technical Field

[0001] The present invention relates to a two-component curable resin composition and a cured product thereof.

Background Art

[0002] Conventionally, epoxy resins have been used in various applications such as adhesives, sealants, potting agents, coating agents, and conductive pastes because of their excellent adhesion, sealing properties, high strength, heat resistance, electrical properties, and chemical resistance. However, the cured products of such epoxy resins have a problem in that they have poor extensibility although they exhibit strong mechanical strength.

[0003] Therefore, in order to impart extensibility to epoxy resins, modified silicone resins are blended. As such a technique, Japanese Patent Application Laid-Open No. 2007-099806 discloses a two-component curable resin composition comprising a liquid A containing an epoxy resin and a curing catalyst of a modified silicone-based polymer, and a liquid B containing a modified silicone-based polymer having an alkoxysilyl group at the terminal and an epoxy resin curing agent.

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the two-component curable resin composition disclosed in Japanese Patent Application Laid-Open No. 2007-099806 has excellent adhesion to metals, but it has not been possible to obtain a cured product having high elongation and high strength.

[0005] An object of the present invention is to provide a two-component curable resin composition capable of obtaining a cured product having high elongation and high strength while maintaining the adhesion to metals.

Means for Solving the Problems

[0006] The gist of the present invention will be described below. Embodiments of the present invention overcome the above-described conventional problems. [1] A two-component curable resin composition comprising the following Agent A and Agent B; Agent A: A composition containing component (a) and component (b). (a) Components: (a-1) Hydrogenated epoxy resin and (a-2) Bisphenol-type epoxy resin (b) Component: Curing catalyst for component (c) Agent B: A composition containing component (c) and component (d). (c) Components: Organic polymer having two or more hydrolyzable silyl groups (d) Component: Hardener for component (a). [2] The two-component curable resin composition according to [1], comprising 0.1 to 20 parts by mass of component (b) per 100 parts by mass of component (c). [3] The two-component curable resin composition according to [1] or [2], wherein the (a-1) component is a hydrogenated bisphenol type epoxy resin. [4] The two-component curable resin composition according to any one of [1] to [3], wherein the component (c) comprises an organic polymer having a trimethoxysilyl group. [5] The two-component curable resin composition according to [4], wherein the component (c) further comprises an organic polymer having a dimethoxysilyl group. [6] The two-component curable resin composition according to any one of [1] to [5], wherein the component (d) is an amine compound that is liquid at 25°C. [7] The two-component curable resin composition according to any one of [1] to [6], wherein the mass ratio of component (a-1) to component (a-2) is in the range of 20:80 to 80:20. [8] The two-component curable resin composition according to any one of [1] to [7], wherein agent A and / or agent B further comprises a silane coupling agent as component (e). [9] A two-component curable resin composition according to any one of [1] to [8], wherein the (a-2) component is a bisphenol A type epoxy resin. A cured product obtained by curing a two-component curable resin composition described in any of

[10] [1] to [9].

[11] A composite obtained by bonding adhesives with a two-component curable resin composition described in any of [1] to [9]. [Modes for carrying out the invention]

[0007] Embodiments of the present invention are described below. However, this disclosure is not limited to the embodiments described below. Throughout this specification, singular expressions should be understood to include the concept of their plural form unless otherwise specified. Therefore, singular articles (e.g., "a," "an," "the," etc. in English) should be understood to include the concept of their plural form unless otherwise specified. Furthermore, terms used in this specification should be understood to have the meaning commonly used in the art unless otherwise specified. Therefore, unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by those skilled in the art to which the present invention pertains. In case of any conflict, this specification (including definitions) shall prevail. The present invention is not limited to the embodiments described below and can be modified in various ways within the scope of the claims. Furthermore, in this specification, "X~Y" means a range including the numerical values ​​(X and Y) described before and after it as the lower and upper limits, and means "X or more and Y or less." Furthermore, unless otherwise specified, concentrations in "%" represent mass concentrations ("mass%"), and ratios represent mass ratios unless otherwise specified. In addition, unless otherwise noted, operations and measurements of physical properties are performed under room temperature (20-25°C) and relative humidity of 40-50%RH.

[0008] A two-component curable resin composition according to one embodiment of the present invention is a two-component curable resin composition comprising agent A, which is a composition containing components (a) and (b) described later, and agent B, which is a composition containing components (c) and (d) described later. Furthermore, agent A and / or agent B of the two-component curable resin composition according to one embodiment of the present invention may contain component (e), and agent A and / or agent B may further contain any optional components.

[0009] <Two-component curable resin composition> A two-component curable resin composition according to one embodiment of the present invention comprises the following components A and B.

[0010] Agent A: A composition containing component (a) and component (b). (a) Components: (a-1) Hydrogenated epoxy resin and (a-2) Bisphenol-type epoxy resin (b) Component: Curing catalyst for component (c) Agent B: A composition containing component (c) and component (d). (c) Components: Organic polymer having two or more hydrolyzable silyl groups (d) Component: Hardener for component (a).

[0011] According to one embodiment of the present invention, it is possible to provide a two-component curable resin composition that yields a cured product with high elongation and high strength while maintaining adhesive strength to metals.

[0012] <(a) Components> The component (a) contained in agent A of the two-component curable resin composition of this embodiment is (a-1) a hydrogenated epoxy resin and (a-2) a bisphenol-type epoxy resin. By using components (a-1) and (a-2) in combination with the other components of this embodiment, a cured product with high elongation and high strength can be obtained while maintaining adhesion to metal.

[0013] The hydrogenated epoxy resin of component (a-1) is not particularly limited, but examples include hydrogenated bisphenol type epoxy resins such as hydrogenated bisphenol A type epoxy resin (also called hydrogenated bisphenol A type epoxy resin; in this specification, "hydrogenated" is also referred to as "hydrogenated"), hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol E type epoxy resin; hydrogenated cresol novolac type epoxy resin; and hydrogenated phenol novolac type epoxy resin. Among these, hydrogenated bisphenol type epoxy resin is preferred for component (a-1) because it yields a cured product with high elongation and high strength. These components as component (a-1) can be used individually or in combination of two or more.

[0014] (a-1) Examples of commercially available components include, but are not limited to, YX8000, YX8034 (both manufactured by Mitsubishi Chemical Corporation), HBE-100 (manufactured by Shin-Nippon Rika Co., Ltd.), and ST-3000 (manufactured by Nippon Steel Chemical & Material Co., Ltd.). These can be used individually or in combination of two or more.

[0015] (a-2) The component is not particularly limited, but examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD ​​type epoxy resin. Among these, bisphenol A type epoxy resin is preferred because it yields a cured product with particularly excellent elongation properties. These compounds may be used individually or in combination of two or more types.

[0016] (a-2) Examples of commercially available components include, but are not limited to, jER(registered trademark) 825, 827, 828, 828US, 834, 1001, 806, 807 (manufactured by Mitsubishi Chemical Corporation); Epiclon(registered trademark) 840, 850, 830LVP, EXA850CRP, 835, EXA835LV (manufactured by DIC Corporation); and Adeka Resin(registered trademark) EP4100, EP4400 (manufactured by ADEKA Corporation). These can be used individually or in combination of two or more.

[0017] The mass ratio of component (a-1) to component (a-2) in the two-component curable resin composition of this embodiment (parts by mass of component (a-1):parts by mass of component (a-2)) is not particularly limited, but is preferably in the range of 20:80 to 80:20, more preferably in the range of 25:75 to 75:25, even more preferably in the range of 30:70 to 70:30, particularly preferably in the range of 35:75 to 75:35, and most preferably in the range of 40:60 to 60:40. By being within the above range, a cured product with even higher elongation and strength can be obtained.

[0018] As the content of the component (a) in the two-component curable resin composition of this form, it is preferably 1 to 500 parts by mass, more preferably 10 to 300 parts by mass, still more preferably 50 to 200 parts by mass, and particularly preferably 70 to 150 parts by mass with respect to 100 parts by mass of the component (c). By being within the above range, the cured product of the two-component curable resin composition according to this form becomes higher in elongation and strength. <Component (b)> The component (b) contained in the agent A of the two-component curable resin composition of this form is a curing catalyst for the component (c). The component (b) is not particularly limited as long as it is a catalyst for crosslinking the component (c) described later. Specifically, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin distearate, dibutyltin laurate oxide, dibutyltin diacetylacetonate, dibutyltin dioleyl maleate, dibutyltin octoate and other dibutyltin compounds, dioctyltin oxide, dioctyltin dilaurate and other dioctyltin compounds, tin catalysts such as the reaction product of dioctyltin salt and silicate; titanium catalysts such as titanium tetraisopropoxide, titanium diisopropoxide bis(acetylacetonate), tetraisopropyl titanate, tetraisopentyl titanate, tetra-n-butoxy titanate; aluminum catalysts; bismuth catalysts; zirconium catalysts; zinc catalysts; amine salts; organic phosphoric acid compounds and the like can also be mentioned. Among these, tin catalysts, titanium catalysts, aluminum catalysts, and zinc catalysts are preferred because cured products with particularly excellent high extensibility can be obtained. These may be used alone or in combination of two or more.

[0019] (b) As a commercially available product of the component, there is no particular limitation. As the tin catalyst, for example, Neo-Stann (registered trademark) U-100, U-130, U-200, U-303 (manufactured by Nitto Kasei Co., Ltd.) and the like can be mentioned. As the titanium catalyst, for example, Organix (registered trademark) TA-8, TA-10, TA-21, TA-23, TA-30, TA-80, TC-100, TC-120, TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) and the like can be mentioned. As the bismuth catalyst, for example, K-KAT348 (manufactured by King Industries) and the like can be mentioned. As the zirconium catalyst, Organix (registered trademark) ZA-45 (manufactured by Matsumoto Fine Chemical Co., Ltd.) and the like can be mentioned. As the aluminum catalyst, for example, DX-9740 (Shin-Etsu Chemical Co., Ltd.), AMD, ASBD, AIPD, ALCH, ALCH-TR, aluminum chelate M, aluminum chelate D, aluminum chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.) and the like can be mentioned. As the zinc catalyst, for example, K-KAT670 (manufactured by King Industries) and the like can be mentioned.

[0020] As the content of the (b) component, with respect to 100 parts by mass of the (c) component described later, the (b) component is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 17 parts by mass, still more preferably in the range of 1 to 13 parts by mass, and particularly preferably 2 to 5 parts by mass. By being within the above range, a cured product with even higher elongation and higher strength can be obtained.

[0021] As the content of the (b) component with respect to 100 parts by mass of the (a) component, the (b) component is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, still more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass. By being within the above range, the cured product of the two-component curable resin composition according to this embodiment becomes even more highly extensible and high-strength.

[0022] <(c) component> Component (c) in agent B of the two-component curable resin composition of this embodiment is an organic polymer having two or more hydrolyzable silyl groups. Examples of component (c) include an organic polymer having a dimethoxysilyl group, an organic polymer having a trimethoxysilyl group, an organic polymer having a diethoxysilyl group, or an organic polymer having a triethoxysilyl group. These compounds can be used individually or in combination of two or more. In particular, component (c) preferably contains an organic polymer having a trimethoxysilyl group, and more preferably a combination of an organic polymer having a dimethoxysilyl group and an organic polymer having a trimethoxysilyl group. By using an organic polymer having a dimethoxysilyl group and an organic polymer having a trimethoxysilyl group in combination, the two-component curable resin composition can produce a cured product that maintains better adhesion to metal while exhibiting higher elongation and strength.

[0023] Furthermore, the hydrolyzable silyl group of component (c) may be bonded to the end or side chain of the organic polymer, but from the viewpoint of obtaining a cured product with high elongation and high strength, it is preferable that the hydrolyzable silyl group is bonded to the end of the organic polymer, and it is more preferable that the hydrolyzable silyl group is bonded to both ends of the organic polymer. Also, from the viewpoint of handling, it is preferable that component (c) is liquid at 25°C. Component (c) may be used alone or as a mixture of two or more types.

[0024] Examples of organic polymers having dimethoxysilyl groups include polyoxyalkylenes containing dimethoxysilyl groups at both ends, (meth)acrylic polymers containing dimethoxysilyl groups at both ends, polyisobutylenes containing dimethoxysilyl groups at both ends, and polyurethanes containing dimethoxysilyl groups at both ends. Examples of organic polymers having trimethoxysilyl groups include polyoxyalkylenes containing trimethoxysilyl groups at both ends, (meth)acrylic polymers containing trimethoxysilyl groups at both ends, polyisobutylenes containing trimethoxysilyl groups at both ends, and polyurethanes containing trimethoxysilyl groups at both ends. Examples of organic polymers having diethoxysilyl groups include (meth)acrylic polymers containing diethoxysilyl groups at both ends, polyisobutylenes containing diethoxysilyl groups at both ends, and polyurethanes containing diethoxysilyl groups at both ends. Examples of organic polymers having triethoxysilyl groups include (meth)acrylic polymers containing triethoxysilyl groups at both ends, polyisobutylenes containing triethoxysilyl groups at both ends, and polyurethanes containing triethoxysilyl groups at both ends.

[0025] The structure of the organic polymer of component (c) is not particularly limited, but examples include polyoxyalkylene, polyester, polycarbonate, polyurethane, polyamide, polyurea, polyimide, polyethylene, polypropylene, polyisobutylene, (meth)acrylic polymers, polystyrene, polyvinyl chloride, polybutadiene, polyisoprene, polyvinyl butyral, and polyvinyl ether. Among these, from the viewpoint of obtaining a cured product with higher elongation and higher strength, the structure of the organic polymer of component (c) is preferably polyoxyalkylene, polyisobutylene, or (meth)acrylic polymers, and more preferably polyoxyalkylene. Furthermore, the structure of the organic polymer of component (c) may be a single type or a mixture of two or more types.

[0026] Commercially available polyoxyalkylenes include SAT010, SAX115, SAT030, SAT200, SAT350, SAT400, SAX220, SAX510, SAX530, SAX575, SAX580, SAX710, SAX720, SAX725, SAX750, SAX770, S203, S303, S203H, S303H, and S943. Examples include S, S911S, MA440, MA447, MA451, MA903, MA903M, MA904, S943, MAX923, MAX951, SAX510, SAX520, SAX530, SAX580, etc. (manufactured by Kaneka Corporation), and ES-S2410, ES-S2420, ES-S3430, ES-S3610, ES-S3630 (manufactured by Asahi Glass Co., Ltd.). In addition, commercially available (meth)acrylic polymers of component (c) include SA100S, SA310S, OR100S, etc. (manufactured by Kaneka Corporation). In addition, commercially available polyisobutylene of component (c) includes EP100S, EP103S, EP303S, EP505S, etc. (manufactured by Kaneka Corporation).

[0027] In the two-component curable resin composition of this embodiment, the content of component (c) is preferably 30 to 250 parts by mass, more preferably 50 to 200 parts by mass, and even more preferably 70 to 150 parts by mass, of component (a) per 100 parts by mass. Within the above range, a cured product with higher elongation and higher strength can be obtained.

[0028] <(d) component> Component (d) in component B of the two-component curable resin composition of this embodiment is a curing agent for component (a), and is a compound that can cure component (a) contained in component A. Component (d) is not particularly limited as long as it can cure component (a), but examples include primary amines, secondary amines, tertiary amines, polyamides, imidazoles, polymer captans, and acid anhydrides. Furthermore, component (d) may be used alone or in combination of two or more. From the viewpoint of curability and workability after mixing, component (d) is preferably liquid at 25°C.

[0029] Primary amines are not particularly limited, but include aliphatic primary amines, alicyclic primary amines, and aromatic primary amines. Aliphatic primary amines are not particularly limited, but examples include ethylenediamine, diethylenetriamine, triethylenetetramine, and hexamethylenediamine. Alicyclic primary amines are not particularly limited, but examples include mensendiamine, isophoronediamine, N-aminoethylpiperazine, diaminodicyclohexylmethane, and norbornanediamine. Aromatic primary amines are not particularly limited, but examples include dimethylaminomethylphenol, metaxylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and diaminodiethyldiphenylmethane. In this specification, amino group-containing silane coupling agents are not included in component (d) and are treated as component (e) described later.

[0030] The secondary or tertiary amine is not particularly limited, but examples include piperidine, pyridine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, triethylenediamine, dimethylcyclohexylamine, dimethylbenzylamine, dimethylhexylamine, dimethylaminophenol, dimethylamino p-cresol, piperidine, 1,4-diazadicyclo[2.2.2]octane, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]undecene-1, etc. A commercially available example is K54 (Air Products Japan Co., Ltd.). From the viewpoint of excellent curability, compounds having an aromatic ring are preferred as secondary and tertiary amines.

[0031] Furthermore, component (d) is preferably an amine compound that is liquid at 25°C, from the viewpoint of curability after mixing agents A and B, and workability. Examples of compounds that are liquid at 25°C include 2,4,6-trisdimethylaminomethylphenol, polyamidoamine, and dimeramine.

[0032] The imidazole is not particularly limited, but examples include 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-isobutyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2 Examples include undecylimidazole, 2,4-diamino-6(2′-methylimidazole(1′))ethyl-s-triazine, 2,4-diamino-6(2′-undecylimidazole(1′))ethyl-s-triazine, 2,4-diamino-6(2′-ethyl,4-methylimidazole(1′))ethyl-s-triazine, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole.

[0033] The polymercaptan is not particularly limited, but examples include 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (TEMPIC), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3 Examples include H,5H)-triones, trimethylolpropanetris(3-mercaptopropionate) (TMMP), pentaerythritoltetrakis(3-mercaptopropionate) (PEMP), pentaerythritoltetrakis(3-mercaptobutyrate), dipentaerythritolhexakis(3-mercaptopropionate) (DPMP), alkyl polythiols such as 1,4-butanedithiol, 1,6-hexanedithiol, and 1,10-decanedithiol; and polythioethers containing terminal thiol groups.

[0034] The acid anhydride compounds are not particularly limited, but examples include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendoethylenetetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylnadic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and maleic anhydride.

[0035] In the two-component curable resin composition of this embodiment, the content of component (d) is preferably 1 to 180 parts by mass, more preferably 3 to 140 parts by mass, and even more preferably 5 to 100 parts by mass, of component (d) per 100 parts by mass of component (a). Within this range, a cured product with higher elongation and higher strength can be obtained while maintaining better adhesion to metal.

[0036] Furthermore, the content of component (d) in the two-component curable resin composition of this embodiment is preferably 1 to 150 parts by mass, more preferably 1 to 100 parts by mass, and even more preferably 3 to 50 parts by mass, of component (d) per 100 parts by mass of component (c). Within the above range, a cured product with higher elongation and higher strength can be obtained while maintaining better adhesion to metal.

[0037] <(e) component> The two-component curable resin composition according to this embodiment may contain a silane coupling agent as component (e). By including a silane coupling agent in component A and / or B, a cured product can be obtained that has higher elongation and higher strength while maintaining better adhesion to metal. Furthermore, it is preferable to include component (e) in both component A and component B.

[0038] Examples of silane coupling agents include glycidyl group-containing silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, glycidylpropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane), and 3-glycidoxypropylmethyldiethoxysilane; vinyl group-containing silane coupling agents such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane; and γ- Examples of silane coupling agents include (meth)acrylic group-containing silane coupling agents such as methacryloxypropyltrimethoxysilane; amino group-containing silane coupling agents such as 3-(2-aminoethylamino)propyltrimethoxysilane (N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane), γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; and γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, styrylsilane, ureidosilane, sulfidosilane, and isocyanatesilane. Among these, glycidyl group-containing silane coupling agents, vinyl group-containing silane coupling agents, and amino group-containing silane coupling agents are preferred as silane coupling agents. Furthermore, it is more preferable that agent A contains a glycidyl group-containing silane coupling agent, and it is even more preferable that the glycidyl group-containing silane coupling agent is glycidylpropyltrimethoxysilane. Furthermore, it is more preferable that agent B contains an amino group-containing silane coupling agent, and it is even more preferable that the amino group-containing silane coupling agent is 3-(2-aminoethylamino)propyltrimethoxysilane. The silane coupling agent may be used alone or in combination of two or more types.

[0039] The content of component (e) in agent A is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and even more preferably 0.3 to 10 parts by mass, per 100 parts by mass of component (a). Within the above range, a two-component curable resin composition can be obtained in which a cured product with even higher elongation and strength can be obtained.

[0040] Furthermore, the content of component (e) in agent B is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and even more preferably 0.3 to 10 parts by mass, per 100 parts by mass of component (c). By being within the above range, a two-component curable resin composition can be obtained in which a cured product with even higher elongation and strength can be obtained.

[0041] <Optional ingredients> A two-component curable resin composition according to one embodiment of the present invention may contain additives such as curing accelerators, fillers, various elastomers such as styrene copolymers, fillers, storage stabilizers, antioxidants, flame retardants, light stabilizers, heavy metal deactivators, plasticizers, defoamers, pigments, rust inhibitors, leveling agents, dispersants, rheology modifiers, flame retardants, and surfactants, to the extent that the objectives of the present invention are not impaired.

[0042] A curing accelerator that may be included in a two-component curable resin composition according to one embodiment of the present invention is a curing accelerator that promotes the reaction between component (a) and component (d). The curing accelerator is preferably solid at room temperature, and it is more preferable, considering storage stability and curability, to use a compound having a solid imidazole skeleton or a fine powder obtained by pulverizing an epoxy adduct compound in which a tertiary amine has been added to an epoxy resin to stop the reaction midway. Examples of commercially available epoxy adduct compounds include the Amicure series from Ajinomoto Fine Techno Co., Ltd., the Fujicure series from T&K TOKA Corporation, and the Novacure series from Asahi Kasei Chemicals Corporation. In addition, organophosphorus compounds are known as liquid curing accelerators at room temperature. Furthermore, the curing accelerator may be used alone or in combination of multiple types.

[0043] A two-component curable resin composition according to one embodiment of the present invention may contain fillers for the purpose of improving the elastic modulus, fluidity, and other properties of the cured product. Specifically, these fillers include organic powders, inorganic powders, metallic powders, and the like.

[0044] Examples of inorganic powder fillers include glass, fumed silica, mica, ceramics, silicone rubber powder, calcium carbonate, carbon powder, kaolin clay, dried clay minerals, and dried diatomaceous earth. Examples of organic powder fillers include polyethylene, polypropylene, nylon, crosslinked acrylic, crosslinked polystyrene, polyester, polyvinyl alcohol, polyvinyl butyral, and polycarbonate. Examples of metallic powder fillers include gold, silver, copper, alumina, and aluminum nitride. The content of the filler is not particularly limited, but when blended with component A, it is preferably 0.1 to 300 parts by mass per 100 parts by mass of component (a), and when blended with component B, it is preferably 0.1 to 300 parts by mass per 100 parts by mass of component (c). By staying within the above range, a cured product with higher elongation and higher strength can be obtained, and the two-component curable resin composition may have excellent workability.

[0045] Among inorganic powder fillers, fumed silica can be suitably used from the viewpoint of adjusting the viscosity of two-component curable resin compositions or improving the mechanical strength of the cured product. As the fumed silica, fumed silica surface-treated with dimethylsilane, trimethylsilane, alkylsilane, methacryloxysilane, organochlorosilane, polydimethylsiloxane, hexamethyldisilazane, etc. can be more suitably used. Examples of commercially available fumed silica include Aerosil® R972, R972V, R972CF, R974, R976, R976S, R9200, RX50, NAX50, NX90, RX200, RX300, R812, R812S, R8200, RY50, NY50, RY200S, RY200, RY300, R104, R106, R202, R805, R816, T805, R711, RM50, R7200, etc. (manufactured by Nippon Aerosil Co., Ltd.), and TS720 (Cabonet Corporation).

[0046] Examples of preservative stabilizers include tetrafunctional alkoxysilanes such as tetramethoxysilane and tetraethoxysilane, silicate compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyl silicate, propyl silicate, and butyl silicate. These may be used individually or in combination of two or more.

[0047] A two-component curable resin composition according to one embodiment of the present invention contains agent A and agent B, wherein agent A is a composition containing component (a) and component (b), and agent B is a composition containing component (c) and component (d). By separating the components into two compositions, agent A and agent B, unnecessary reactions during storage can be suppressed, and storage stability can be improved. In such a two-component curable resin composition, agent A and agent B can also be manufactured by mixing them using the method described above. Then, when using, agent A and agent B can be mixed using a well-known method.

[0048] Furthermore, in a two-component curable resin composition according to one embodiment of the present invention, the amount of agent B is preferably in the range of 10 to 300 parts by mass, preferably 30 to 200 parts by mass, and more preferably 50 to 150 parts by mass, per 100 parts by mass of agent A.

[0049] <Cured product> Another embodiment of the present invention is a cured product (cured product of a two-component curable resin composition) obtained by curing the above-described two-component curable resin composition. The cured product, which is another embodiment of the present invention, is obtained by curing the two-component curable resin composition by mixing agent A and agent B that constitute the two-component curable resin composition.

[0050] <Application> One embodiment of the two-component curable resin composition of the present invention yields a cured product with high elongation and high strength, and is therefore preferably used in various applications such as adhesives, encapsulants, sealants, potting agents, coatings, lining materials, heat dissipation materials, and conductive pastes. In particular, one embodiment of the two-component curable resin composition of the present invention is suitably used as a structural adhesive because it yields a cured product with high elongation and high strength while maintaining adhesion to metals. Specific applications of structural adhesives are not particularly limited, but examples include bonding panels that make up automobile doors, pillars, and roofs to each other, bonding the body to the roof, and bonding magnets to motors.

[0051] <complex> Another embodiment of the present invention is a composite obtained by bonding adherends with the above-described two-component curable resin composition.

[0052] A two-component curable resin composition, one embodiment of the present invention, is suitable as an adhesive. The adherends are not particularly limited, but examples include metal to metal, metal to plastic, metal to rubber, metal to glass, plastic to rubber, plastic to glass, plastic to plastic, rubber to rubber, rubber to glass, and glass to glass. Among these, metal to metal, metal to plastic, and plastic to plastic are preferred.

[0053] The metals used are not particularly limited, but examples include gold, silver, iron, aluminum, magnesium, copper, stainless steel, and titanium. The plastics used are not particularly limited, but examples include fiber-reinforced plastics (FRP), carbon fiber reinforced plastics (CFRP), polyacrylic, polyester, polyamide, acrylonitrile-butadiene-styrene, nylon 6, polycarbonate, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyphenylene ether, polyether ether ketone, polyethylene, and polypropylene. The rubbers used are not particularly limited, but examples include nitrile rubber, butyl rubber, urethane rubber, silicone rubber, and EPDM. The bonding process involves adhering at least two or more substrates selected from these materials. The surface of the materials may be pre-treated or left untreated. [Examples]

[0054] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, the operations were carried out at room temperature (25°C).

[0055] <Preparation of two-component curable resin composition> Each of the components listed below was taken in the proportions (parts by mass) shown in Table 1 and mixed in a mixer at room temperature for 60 minutes to prepare two components, A and B, which correspond to a two-component curable resin composition. Details of each component are as follows.

[0056] <(a) Components and comparative components> a-1-1: Hydrogenated bisphenol A epoxy resin (manufactured by Shin-Nippon Rika Co., Ltd., RikaResin® HBE-100) a-2-1: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER (trademark registered) 828) a-2-2: Bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER (trademark registered) 807) a'1: Biphenyl-type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX4000) a'2: Tetraglycidyldiaminodimethylmethane (manufactured by Mitsubishi Chemical Corporation, jER (trademark registered) 604) (not treated as component (d) in this invention) <(b) Component> b1: Titanium tetraisopropoxide (manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics® TA-8, concentration of 99% by mass or higher) b2: Titanium diisopropoxybis(acetylacetonate) (manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics® TC-100, ingredient concentration 75% by mass or higher) b3: Dibutyltin compound (manufactured by Nitto Kasei Co., Ltd., Neostan® U-100) <(c) component> c1: Polyoxyalkylene containing trimethoxysilyl groups at both ends (SAX-575, manufactured by Kaneka Corporation, liquid at 25°C) c2: Polyoxyalkylene containing dimethoxysilyl groups at both ends (SAX-750, manufactured by Kaneka Corporation, liquid at 25°C) <(d) component> d1: 2,4,6-Tris(dimethylaminomethyl)phenol (manufactured by Air Products Japan Co., Ltd., Ankamin® registered trademark, K54, liquid at 25°C) <(e) component> e1: Glycidylpropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) e2:3-(2-aminoethylamino)propyltrimethoxysilane (manufactured by Dow Toray Corporation, DOWSIL (trademark registered), Z-6094 Silane) (not treated as component (d) in this invention) The test methods used in the examples and comparative examples in Table 1 are as follows:

[0057] <(1) Shear bond strength test for metals> A SUS304 test piece measuring 25mm wide x 100mm long x 1.6mm thick was coated with a mixture of 100g of component A and 100g of component B of each two-component curing resin composition, prepared at 25°C. Then, two SUS304 test pieces of similar size were bonded together so that the bonding surface was 25mm wide x 10mm long and secured with clips. Finally, the two-component curing resin composition was cured at 25°C and 50% RH for 168 hours to prepare a test specimen.

[0058] The test specimen was fixed at both ends and measured under a tensile speed of 10 mm / min. The strength at the maximum load was defined as the adhesive strength to metal (MPa). The measurement results are shown in Table 1. In this invention, from the viewpoint of excellent adhesive strength to metal, the adhesive strength is preferably 8.0 MPa or higher, and more preferably 9.0 MPa or higher.

[0059] <(2) Measurement of the tensile strength of the hardened material> 100g each of component A and component B of each two-component curable resin composition were mixed at 25°C to obtain the resin composition. Next, the thickness of the resin composition was set to 1 mm, and cured at 25°C and 50% RH for 168 hours to produce a sheet-like cured material. A test piece was made by punching out the cured material with a No. 3 dumbbell. Both ends of the test piece were fixed to the chuck so that the long axis of the test piece and the center of the chuck were in a straight line. The test piece was pulled at a tensile speed of 500 mm / min, and the maximum load was measured. The strength at this maximum load was defined as "tensile strength (MPa)". The results are shown in Table 1. Details follow JIS K 6251 (2010). Note that for a cured product of a two-component curable resin composition to be strong enough to withstand its intended use, a tensile strength of 8.0 MPa or higher is preferable, and 9.0 MPa or higher is more preferable.

[0060] <(3) Method for measuring the elongation of a cured product> 100g each of component A and component B of each two-component curing resin composition were mixed at 25°C to obtain a resin composition. Next, the thickness of the resin composition was set to 1 mm, and it was cured for 168 hours at 25°C and 50% RH to produce a sheet-like cured material. Test pieces were made by punching out the cured material with a No. 3 dumbbell, and marking lines were marked on the test pieces at 20 mm intervals.

[0061] The test specimen was fixed to a chuck in the same manner as for measuring tensile strength, and pulled at a tensile speed of 500 mm / min until it broke. During measurement, the test piece stretched and the gauge marks widened, so the gauge marks were measured with calipers until the test piece broke. The elongation rate (%) was calculated by dividing the gauge marks (mm) just before break by the initial gauge marks (20 mm) (Elongation rate (%) = (Gauge marks just before break / Initial gauge marks) × 100). The results are shown in Table 1. As a cured product of a two-component curable resin composition, an elongation rate of 470% or more is preferable, 480% or more is more preferable, and 500% or more is even preferable to have sufficient elongation for its intended use.

[0062] [Table 1]

[0063] The results from Examples 1-5 in Table 1 confirm that the two-component curable resin composition of the present invention can produce a cured product with high elongation and high strength while maintaining adhesion to metal.

[0064] Comparative Example 1 was a composition that did not contain component (a-2), but the adhesion to metal and the strength of the cured product were inferior. Comparative Examples 2 and 3 were compositions that did not contain component (a-1), but the adhesion to metal, the elongation of the cured product, and the strength were inferior. Comparative Example 4 was a composition that used component a'1 instead of component (a-2), but the adhesion to metal, the elongation of the cured product, and the strength were inferior. Comparative Example 5 was a composition that used component a'2 instead of component (a-2), but the elongation of the cured product was inferior. [Industrial applicability]

[0065] The two-component curable resin composition of the present invention yields a cured product that maintains adhesion to metals while exhibiting high elongation and high strength. Therefore, it is suitable for various applications such as adhesives, sealants, potting agents, coatings, and conductive pastes. Consequently, it is industrially useful as it can be applied to a wide range of fields.

[0066] This application is based on Japanese Patent Application No. 2021-65804, filed on April 8, 2021, the disclosures of which are referenced and incorporated in whole.

Claims

1. A two-component curable resin composition consisting of the following components A and B; Agent A: A composition containing component (a) and component (b). (a) Components: (a-1) Hydrogenated epoxy resin and (a-2) Bisphenol-type epoxy resin (b) Component: Curing catalyst for component (c), Here, component (a-1) is a hydrogenated bisphenol type epoxy resin. Agent B: A composition containing component (c) and component (d). (c) Component: Organic polymer having two or more hydrolyzable silyl groups (d) Component: Hardener for component (a).

2. The two-component curable resin composition according to claim 1, comprising 0.1 to 20 parts by mass of component (b) with respect to 100 parts by mass of component (c).

3. The two-component curable resin composition according to claim 1 or 2, wherein the component (c) comprises an organic polymer having a trimethoxysilyl group.

4. The two-component curable resin composition according to claim 3, wherein component (c) further comprises an organic polymer having a dimethoxysilyl group.

5. The two-component curable resin composition according to any one of claims 1 to 4, wherein the (d) component is an amine compound that is liquid at 25°C.

6. The two-component curable resin composition according to any one of claims 1 to 5, wherein the mass ratio of component (a-1) to component (a-2) is in the range of 20:80 to 80:

20.

7. The two-component curable resin composition according to any one of claims 1 to 6, wherein the agent A and / or the agent B further comprises a silane coupling agent as component (e).

8. The two-component curable resin composition according to any one of claims 1 to 7, wherein the (a-2) component is a bisphenol A type epoxy resin.

9. A cured product obtained by curing a two-component curable resin composition according to any one of claims 1 to 8.

10. A composite obtained by bonding adhesive bodies with the two-component curable resin composition described in any one of claims 1 to 8.

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