Two-component curable resin composition and its cured product

Abstract

The present invention provides a two-part curable resin composition that does not use a dibutyltin catalyst, has exceptional storage stability, cures quickly upon mixing, and yields a cured product having high elongation and high strength.　Provided is a two-part curable resin composition comprising part A and part B below.　Part A: composition containing component (a) and component (b). Component (a): hydrogenated epoxy resin. Component (b): one or more compounds selected from the group consisting of titanium dialkoxybis(acetylacetonate), titanium tetraisopropoxide, tetra-tert-butyl titanate, and aluminum catalysts. Part B: composition containing component (c) and component (d). Component (c): organic polymer having two or more hydrolyzable silyl groups. Component (d): 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 adhesive strength, sealing properties, high strength, heat resistance, electrical properties, and chemical resistance. However, the cured products of such epoxy resins have a problem in that, although they exhibit strong mechanical strength, they have poor extensibility.

[0003] Therefore, in order to impart extensibility to epoxy resins, modified silicone-based polymers have been 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 for a modified silicone-based polymer, and a liquid B containing a modified silicone-based polymer having an alkoxysilyl group at its 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 uses a dibutyltin catalyst as a curing agent for the modified silicone resin. Since the dibutyltin catalyst has a large environmental load, there has been a movement to regulate its use in various countries. Therefore, an alternative catalyst for the dibutyltin catalyst is strongly desired.

[0005] Alternative catalysts to dibutyltin include zirconium catalysts and phosphoric acid. However, resin compositions using zirconium have the problem of poor storage stability, as shown in Comparative Example 3 of this specification. Furthermore, resin compositions using phosphoric acid have the problem that the catalyst is deactivated by the epoxy resin curing agent, as shown in Comparative Example 4 of this specification, resulting in impaired curability after two-component mixing.

[0006] The present invention aims to provide a two-component curable resin composition that does not use a dibutyltin catalyst, exhibits excellent storage stability, cures rapidly upon mixing, and yields a cured product with high elongation and high strength. [Means for solving the problem]

[0007] The gist of the present invention is described below. Embodiments of the present invention overcome the conventional problems described above. [1] A two-component curable resin composition comprising the following components A and B. Agent A: A composition containing component (a) and component (b). (a) Components: Hydrogenated epoxy resin (b) Components: One or more compounds selected from the group consisting of titanium dialkoxybis (acetylacetonate), titanium tetraisopropoxide, tetratert-butyl titanate, and aluminum catalysts. Agent B: A composition containing component (c) and component (d). (c) Components: Organic polymer having two or more hydrolyzable silyl groups (d) Components: 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 component (a) 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] A two-component curable resin composition according to any one of [1] to [6], wherein the component (b) is titanium dialkoxybis(acetylacetonate). [8] The two-component curable resin composition according to [7], wherein the titanium dialkoxybis (acetylacetonate) is titanium diisopropoxybis (acetylacetonate). [9] The two-component curable resin composition according to any one of [1] to [8], wherein agent A and / or agent B further comprises a silane coupling agent as component (e).

[10] The two-component curable resin composition according to any one of [1] to [9], wherein the agent A further comprises an aromatic epoxy resin as component (f). A cured product obtained by curing a two-component curable resin composition described in any of

[11] [1] to

[10] .

[12] A composite obtained by bonding adherends with a two-component curable resin composition described in any of [1] to

[10] . [Modes for carrying out the invention]

[0008] 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 greater 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.

[0009] A two-component curable resin composition according to one embodiment of the present invention comprises 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 of the two-component curable resin composition according to one embodiment of the present invention may contain any components other than components (a) and (b), and Agent B may contain any components other than components (c) and (d). For example, Agent A may contain component (e) and / or component (f), and Agent B may contain component (e).

[0010] <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.

[0011] Agent A: A composition containing component (a) and component (b). (a) Components: Hydrogenated epoxy resin (b) Components: One or more compounds selected from the group consisting of titanium dialkoxybis (acetylacetonate), titanium tetraisopropoxide, tetratert-butyl titanate, and aluminum catalysts. Agent B: A composition containing component (c) and component (d). (c) Components: Organic polymer having two or more hydrolyzable silyl groups (d) Components: Hardener for component (a) According to one embodiment of the present invention, it is possible to provide a two-component curable resin composition that does not use a dibutyltin catalyst, has excellent storage stability, cures rapidly upon mixing, and yields a cured product with high elongation and high strength.

[0012] <(a) Components> The A component of the two-component curable resin composition of this embodiment contains a hydrogenated epoxy resin as component (a). By combining the hydrogenated epoxy resin with the other components of this embodiment, the two-component curable resin composition of this embodiment has excellent storage stability, cures rapidly upon mixing of component A and component B, and yields a cured product that is highly elongated and high-strength. Component (a) 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, and hydrogenated bisphenol A type epoxy resin is more preferred. Component (a) can be used individually or as a mixture of two or more of these components.

[0013] (a) Examples of commercially available components include, but are not limited to, YX8000 (hydrogenated bisphenol A epoxy resin), YX8034 (hydrogenated bisphenol A epoxy resin) (both manufactured by Mitsubishi Chemical Corporation), HBE-100 (hydrogenated bisphenol A epoxy resin) (manufactured by Shin-Nippon Rika Co., Ltd.), and ST-3000 (hydrogenated bisphenol A epoxy resin) (manufactured by Nippon Steel Chemical & Material Co., Ltd.). These can be used individually or in combination of two or more.

[0014] In the two-component curable resin composition of this embodiment, the content of component (a) is preferably 1 to 500 parts by mass, more preferably 10 to 300 parts by mass, even more preferably 50 to 200 parts by mass, and particularly preferably 70 to 150 parts by mass, per 100 parts by mass of component (c). Within the above range, the cured product of the two-component curable resin composition according to this embodiment will have higher elongation and higher strength.

[0015] <(b) Component> Component (b) in agent A of the two-component curable resin composition of this embodiment is one or more compounds selected from the group consisting of titanium dialkoxybis (acetylacetonate), titanium tetraisopropoxide, tetratert-butyl titanate, and aluminum catalyst. By combining these (b) components with the other components of this embodiment, the two-component curable resin composition of this embodiment yields a cured product that has excellent storage stability, cures rapidly upon mixing of agent A and agent B, and exhibits high elongation and high strength.

[0016] (b) component is preferably one or more compounds selected from the group consisting of titanium dialkoxybis(acetylacetonate), titanium tetraisopropoxide, and aluminum catalysts from the viewpoint of having better storage stability, curing rapidly upon mixing of Agent A and Agent B, and obtaining a cured product with higher elongation and higher strength. Further, from the viewpoint of curing even more rapidly upon mixing of Agent A and Agent B and obtaining a cured product with even more sufficient high elongation, it is more preferable that the (b) component contains titanium dialkoxybis(acetylacetonate). At this time, it is even more preferable that the titanium dialkoxybis(acetylacetonate) is titanium diisopropoxybis(acetylacetonate). These can be used alone or in combination of two or more kinds.

[0017] Commercially available products of the (b) component are not particularly limited. For example, as titanium tetraisopropoxide, TA-8 (manufactured by Matsumoto Fine Chemical Co., Ltd.) can be mentioned; as tetra-tert-butyl titanate, TA-80 (manufactured by Matsumoto Fine Chemical Co., Ltd.) can be mentioned; as titanium dialkoxybis(acetylacetonate), TC-100, TC-120 (manufactured by Matsumoto Fine Chemical Co., Ltd.) which are titanium diisopropoxybis(acetylacetonate) etc. can be mentioned; as aluminum catalysts, 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.) etc. can be mentioned.

[0018] Regarding the content of the (b) component in Agent A of this form, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, even more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass of the (b) component with respect to 100 parts by mass of the (a) component. By being within the above range, the cured product of the two-component curable resin composition according to this form becomes even more sufficient in high elongation and high strength.

[0019] As the content of component (b) in the two-component curable resin composition of this form, it is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 17 parts by mass, still more preferably 0.5 to 13 parts by mass, and particularly preferably 1 to 7 parts by mass with respect to 100 parts by mass of component (c) described later. By being within the above range, when the agent A and the agent B are mixed, they cure more rapidly and have excellent storage stability.

[0020] <Component (c)> Component (c) contained in the agent B of the two-component curable resin composition of this form 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 alone or in combination of two or more. Among them, 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 a combination of an organic polymer having a dimethoxysilyl group and an organic polymer having a trimethoxysilyl group, the storage stability of the agent B can be made more excellent without using a dibutyltin catalyst, and further, it can cure more rapidly when the agent A and the agent B are mixed.

[0021] Also, the hydrolyzable silyl group of component (c) may be bonded to the terminal 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 terminal of the organic polymer, and more preferable that the hydrolyzable silyl group is bonded to both terminals of the organic polymer. Also, component (c) is preferably liquid at 25°C from the viewpoint of handling. Also, component (c) may be used alone or in combination of two or more.

[0022] 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.

[0023] 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. In particular, from the viewpoint of obtaining a cured product that hardens quickly upon mixing of agent A and agent B, and that also has high elongation and high 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.

[0024] 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 AGC Inc.). 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).

[0025] In the two-component curable resin composition of this embodiment, the content of component (c) is preferably 0.1 to 200 parts by mass, more preferably 1 to 150 parts by mass, and even more preferably in the range of 10 to 120 parts by mass, per 100 parts by mass of component (a). Furthermore, if the two-component curable resin composition of this embodiment contains component (f), which will be described later, then the content of component (c) is preferably 30 to 200 parts by mass, more preferably 50 to 150 parts by mass, and even more preferably in the range of 70 to 120 parts by mass, per 100 parts by mass of the total amount of components (a) and (f). Within the above range, the mixture of agent A and agent B cures quickly, and a cured product with high elongation and high strength is obtained.

[0026] <(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 capable of curing the hydrogenated epoxy resin, which is component (a) 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 mercaptans, and acid anhydrides. Furthermore, component (d) may be used alone or in combination of two or more.

[0027] 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 include ethylenediamine, diethylenetriamine, triethylenetetramine, and hexamethylenediamine. Alicyclic primary amines are not particularly limited, but include mensendiamine, isophoronediamine, N-aminoethylpiperazine, diaminodicyclohexylmethane, and norbornanediamine. Aromatic primary amines are not particularly limited, but include 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.

[0028] The secondary and tertiary amines are not particularly limited, but examples include 2,4,6-tris(dimethylaminomethyl)phenol, piperidine, pyridine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, triethylenediamine, dimethylcyclohexylamine, dimethylbenzylamine, dimethylhexylamine, dimethylaminomethylphenol, bis(dimethylaminomethyl)phenol, dimethylaminophenol, and dimethylamino p-cresol. A commercially available example is Ankamin K54 (Air Products Japan Co., Ltd.). From the viewpoint of excellent curability, compounds having an aromatic ring are preferred as secondary and tertiary amines.

[0029] (d) Component is preferably an amine compound that is liquid at 25°C from the viewpoint of curability after mixing agent A and agent B and workability. Examples of compounds that are liquid at 25°C include 2,4,6-trisdimethylaminomethylphenol, polyamidoamine, and dimeramine.

[0030] Furthermore, there are no particular restrictions on the imidazole, 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 Examples include -2-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.

[0031] 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)-trione, 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. When polymercaptan is used as a curing agent, it is preferable to use it in combination with tertiary amines, etc., as this significantly improves curability.

[0032] 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.

[0033] In the two-component curable resin composition of this embodiment, the content of component (d) 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, per 100 parts by mass of component (a). Furthermore, if the two-component curable resin composition of this embodiment contains component (f), which will be described later, 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, per 100 parts by mass of the total amount of components (a) and (f). Being within the above range results in good curability after mixing agent A and agent B, and excellent storage stability.

[0034] Furthermore, the content of component (d) in component B of 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). Being within the above range results in good curability after mixing component A and component B, and also excellent storage stability of component B.

[0035] <(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, the storage stability is improved and a cured product with higher elongation can be obtained. Furthermore, it is preferable to include component (e) in both component A and component B.

[0036] 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.

[0037] 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 in the range of 0.3 to 10 parts by mass, per 100 parts by mass of component (a). By being within the above range, the storage stability of agent A is further improved, and a cured product with even greater elongation can be obtained.

[0038] The content of component (e) in agent B is preferably 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and particularly preferably 0.3 to 10 parts by mass, per 100 parts by mass of component (c). By being within the above range, the storage stability of agent B is further improved, and a cured product with sufficiently high elongation can be obtained.

[0039] <(f) component> Furthermore, the two-component curable resin composition of this embodiment may contain an aromatic epoxy resin as component (f) in component A. By including component (f) in component A, the mixture of component A and component B cures rapidly, resulting in a cured product with significantly higher elongation and strength, and a two-component curable resin composition with excellent adhesion to metals.

[0040] (f) The components are not particularly limited, but examples include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD ​​type epoxy resin; novolac type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin; glycidylamine compounds such as N,N-diglycidyl-4-glycidyloxyaniline, 4,4'-methylenebis(N,N-diglycidylaniline), tetraglycidyldiaminodiphenylmethane, and tetraglycidyl-m-xylylenediamine; and naphthalene type epoxy resins. These compounds may be used individually or in combination of two or more.

[0041] The content of component (f) in agent A is not particularly limited, but for example, it is preferably 5 to 95 parts by mass, more preferably 10 to 80 parts by mass, and even more preferably 20 to 70 parts by mass, based on 100 parts by mass of the total amount of components (a) and (f). Similarly, the content of component (f) in the two-component curable resin composition of this embodiment is not particularly limited, but for example, it is preferably 5 to 95 parts by mass, more preferably 10 to 80 parts by mass, and even more preferably 20 to 70 parts by mass, based on 100 parts by mass of component (c). Within the above ranges, the two-component curable resin composition can adhere more sufficiently to substrates such as metals.

[0042] <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.

[0043] 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.

[0044] 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.

[0045] 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 included in component A, it is preferably 0.1 to 300 parts by mass per 100 parts by mass of component (a), and when included in component B, it is preferably 0.1 to 300 parts by mass per 100 parts by mass of component (c). Within the above ranges, a cured product with high elongation and high strength can be obtained, and the workability of the two-component curable resin composition can be improved.

[0046] 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. More preferably, fumed silica surface-treated with dimethylsilane, trimethylsilane, alkylsilane, methacryloxysilane, organochlorosilane, polydimethylsiloxane, hexamethyldisilazane, etc. can be used as fumed silica. 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).

[0047] 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.

[0048] 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 be manufactured by mixing them by a well-known method. Then, when using, agent A and agent B can be mixed by a well-known method and used.

[0049] 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, more preferably 30 to 200 parts by mass, and even more preferably 50 to 150 parts by mass, when agent A is 100 parts by mass.

[0050] <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.

[0051] <Application> One embodiment of the present invention is a two-component curable resin composition that does not use a dibutyltin catalyst, has excellent storage stability, cures rapidly upon mixing of component A and component B, and yields a cured product with high elongation and high strength. Therefore, it is preferably used in various applications such as adhesives, sealants, potting agents, coatings, lining materials, heat dissipation materials, and conductive pastes. Among these, it is particularly suitable for use as a structural adhesive because it has a cured product with high elongation and high strength while also possessing excellent adhesive strength to adherends such as metals. Specific applications of this structural adhesive 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.

[0052] <complex> Another embodiment of the present invention is a composite obtained by bonding adherends with a two-component curable resin composition.

[0053] The adherends to be bonded with the two-component curable resin composition, which is one embodiment of the present invention, are not particularly limited, but examples include metals to metals, metals and plastics, metals and rubbers, metals and glass, plastics and rubbers, plastics and glass, plastics to plastics, rubbers to rubbers, rubbers and glass, and glass to glass. Among these, metals to metals, metals and plastics, and plastics to plastics are preferred.

[0054] 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]

[0055] 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).

[0056] <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.

[0057] <(a) Components> a1: Hydrogenated bisphenol A epoxy resin (manufactured by Shin-Nippon Rika Co., Ltd., RikaResin® HBE-100) <Component (b) and component (b'), which is a comparison component of component (b)> 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: Aluminum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., DX-9740) b'1: Dibutyltin compound (manufactured by Nitto Kasei Co., Ltd., Neostan® U-100) b'2: Titanium diisopropoxybis(ethylacetoacetate) (manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics® TC-750, ingredient concentration 95% by mass or higher) b'3: Zirconium octylate compound (manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics® ZC-200, component concentration 80% by mass or higher) b'4: Tetra-n-butyl titanate (manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics® TA-25) b'5: Phosphate catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., X-40-2309A) <(c) component> c1: Polyoxyalkylene containing trimethoxysilyl groups at both ends (manufactured by Kaneka Corporation, SAX-575, liquid at 25°C) c2: Polyoxyalkylene containing dimethoxysilyl groups at both ends (manufactured by Kaneka Corporation, SAX-750, 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 Industries, Ltd., DOWSIL (trademark registered) Z-6094 Silane) <(f) component> f1: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER (trademark) 828) The test methods used in the examples and comparative examples in Table 1 are as follows:

[0058] <(1) Storage stability test of component A of a two-component curable resin composition> Each of the above-prepared Agent A was filled into a glass container, sealed with a lid, and stored at 25°C for one month. After that, the container was opened, tilted, and visually checked for fluidity, and evaluated according to the following criteria. The results are shown in Table 1.

[0059] [Evaluation Criteria] ○: The fluidity of the composition was confirmed. ×: The composition had gelled and was no longer fluid.

[0060] <(2) Storage stability test of component B of two-component curable resin composition> Each of the B agents prepared above was filled into a glass container, sealed with a lid, and stored at 25°C for one month. Afterward, the containers were opened and evaluated according to the following criteria. The results are shown in Table 1.

[0061] [Evaluation Criteria] ○: The fluidity of the composition was confirmed. ×: The composition had gelled and was no longer fluid.

[0062] <(3) Curing properties after mixing of Agent A and Agent B> 10g each of agent A and agent B were mixed at 25°C. The mixed resin composition was then left to stand for 1, 2, 3, 5, and 7 days at 25°C and 50% RH. Hardening was confirmed by touching the surface with a metal rod and checking for stickiness. The results were evaluated based on the following criteria. The results are shown in Table 1. [Evaluation Criteria] ◎: Confirmed to have hardened after 1 day. ○: Confirmed to have hardened after 2-7 days. ×: Confirmed to be uncured after 7 days. <(4) 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 for 168 hours at 25°C and 50% RH 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 5.0 MPa or higher is preferable, and 6.0 MPa or higher is more preferable. Note that "-" in Table 1 means that the test was not performed.

[0063] <(5) 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.

[0064] 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 200% or more is preferable, 300% or more is more preferable, and 350% or more is even preferable for sufficient elongation to withstand its intended use. Note that "-" in Table 1 means that the test was not performed.

[0065] <(6) Shear bond strength test for metals> A resin composition prepared by mixing 100g of agent A and 100g of agent B from Examples 1, 2, and 4 at 25°C was applied to a SUS304 test piece measuring 25mm wide x 100mm long x 1.6mm thick. Then, test pieces of SUS304 of the same size were bonded together so that the bonding surface was 25mm wide x 10mm long and secured with clips. Finally, the two-component curable resin composition was cured at 25°C x 50%RH for 168 hours to prepare test specimens.

[0066] 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. The results were 7.4 MPa for Example 1, 8.0 MPa for Example 2, and 12.0 MPa for Example 4. It should be noted that, from the viewpoint of superior adhesive strength to metal, the present invention preferably has an adhesive strength of 6.0 MPa or higher, and more preferably 10 MPa or higher. A "-" in Table 1 indicates that the experiment was not performed.

[0067] [Table 1]

[0068] The results from Examples 1-4 in Table 1 confirm that the two-component curable resin composition of this embodiment exhibits excellent storage stability for components A and B, and that it cures rapidly upon mixing of components A and B. Furthermore, it was confirmed that a cured product with high elongation and high strength can be obtained from this two-component curable resin composition.

[0069] Reference Example 1 is a resin composition that exhibits excellent curability after mixing and storage stability of each component constituting the two-component curable resin composition, but is undesirable considering its environmental impact due to the inclusion of a dibutyltin catalyst. Comparative Examples 1 to 4 are resin compositions in which the (b') component b'2 to b'5 catalyst is used instead of the (b) component of the present invention in component A of the two-component curable resin composition. However, Comparative Examples 1 to 3 show that the storage stability of component A is inferior. Furthermore, Comparative Example 4 shows that the curability after mixing is inferior. Comparative Example 5 is a resin composition that does not contain component (a) of component A of the present invention, but uses f1 instead, but the cured product had inferior elongation and strength. [Industrial applicability]

[0070] The two-component curable resin composition of the present invention exhibits excellent storage stability without the use of a dibutyltin catalyst, cures rapidly upon mixing of component A and component B, and yields a cured product with 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.

[0071] This application is based on Japanese Patent Application No. 2021-65803, 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: Hydrogenated epoxy resin (b) Component: One or more compounds selected from the group consisting of titanium dialkoxybis (acetylacetonate), titanium tetraisopropoxide, tetratert-butyl titanate, and aluminum catalyst. Here, component (a) 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 component (b) comprises titanium dialkoxybis (acetylacetonate).

7. The two-component curable resin composition according to claim 6, wherein the titanium dialkoxybis (acetylacetonate) is titanium diisopropoxybis (acetylacetonate).

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

9. The two-component curable resin composition according to any one of claims 1 to 8, wherein the agent A further comprises an aromatic epoxy resin as component (f).

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

11. A composite obtained by bonding adherends with a two-component curable resin composition according to any one of claims 1 to 9.

Images