Two-component curable resin composition for hydrogen sealing and cured product thereof

Abstract

The purpose of the present invention is to provide a two-component curable resin composition with which it is possible to obtain a cured product having excellent hydrogen barrier properties, high elongation, and high strength. The present invention provides a two-component curable resin composition for hydrogen sealing, the two-component curable resin composition comprising the following agent A and agent B, the cured product of the two-component curable resin composition having a sea-island structure: agent A: a composition containing an epoxy resin as component (a) and a catalyst as component (b); and agent B: a composition containing, as component (c), an organic polymer having two or more hydrolyzable silyl groups in one molecule, and containing, as component (d), a curing agent for epoxy resins.

Description

Technical Field

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

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

[0003] Therefore, in order to impart elongation to epoxy resin, modified silicone resin is added. As such a technology, Japanese Patent Publication No. 2007-099806 discloses a two-component curable resin composition comprising liquid A and liquid B, wherein liquid A contains epoxy resin and a curing catalyst for a modified silicone polymer, and liquid B contains a modified silicone polymer having an alkoxysilyl group at the end and a curing agent for the epoxy resin. Summary of the invention

[0004] However, the cured product of the two-component curable resin composition disclosed in Japanese Patent Application Laid-Open No. 2007-099806 has a problem of poor hydrogen gas barrier properties.

[0005] Therefore, an object of the present invention is to provide a two-component curable resin composition for hydrogen gas sealing, which can obtain a cured product having excellent hydrogen gas barrier properties, high elongation, and high strength.

[0006] The gist of the present invention will be described below. The embodiments of the present invention overcome the above-mentioned conventional problems.

[0007] [1] A two-component curable resin composition for hydrogen sealing, comprising the following agent A and agent B, wherein the cured product thereof has a sea-island structure,

[0008] Agent A: a composition containing an epoxy resin as component (a) and a catalyst as component (b),

[0009] Agent B: A composition containing an organic polymer having two or more hydrolyzable silyl groups in one molecule as the component (c) and a curing agent for an epoxy resin as the component (d).

[0010] [2] The two-component curable resin composition for hydrogen gas sealing according to [1], wherein the component (a) contains a hydrogenated epoxy resin as the component (a-1).

[0011] [3] The two-component curable resin composition for hydrogen gas sealing according to [1] or [2], wherein the component (b) is contained in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the component (c).

[0012] [4] The two-component curable resin composition for hydrogen gas sealing according to any one of [1] to [3], wherein the hydrolyzable silyl group includes a trimethoxysilyl group.

[0013] [5] The two-component curable resin composition for hydrogen gas sealing according to any one of [1] to [4], wherein the component (d) is an amine compound that is liquid at 25°C.

[0014] [6] The two-component curable resin composition for hydrogen gas sealing according to any one of [1] to [5], wherein the agent A and / or the agent B further contains a silane coupling agent as the component (e).

[0015] [7] The two-component curable resin composition for hydrogen gas sealing according to any one of [1] to [6], wherein the component (a) comprises a hydrogenated epoxy resin as the component (a-1) and an aromatic epoxy resin as the component (a-2).

[0016] [8] A two-component curable resin composition for hydrogen gas sealing according to any one of [1] to [7], wherein the cured product is obtained by mixing the agent A and the agent B and then aging the mixture at 20°C to 30°C and 40% RH to 60% RH for more than 12 hours.

[0017] [9] A two-component curable resin composition for hydrogen sealing, comprising the following agent A and agent B,

[0018] Agent A: a composition comprising an epoxy resin as component (a) and a catalyst as component (b), wherein the component (a) comprises a hydrogenated epoxy resin as component (a-1);

[0019] Agent B: A composition containing an organic polymer having two or more hydrolyzable silyl groups in one molecule as the component (c) and a curing agent for an epoxy resin as the component (d).

[0020]

[10] A cured product obtained by curing the two-component curable resin composition for hydrogen gas sealing according to any one of [1] to [9].

[0021]

[11] A method for producing a cured product having a sea-island structure, wherein the following agent A and agent B are mixed, and the mixture is aged at 20°C to 30°C and 40% RH to 60% RH.

[0022] Agent A: a composition comprising an epoxy resin as component (a) and a catalyst as component (b), wherein the component (a) comprises a hydrogenated epoxy resin as component (a-1);

[0023] Agent B: A composition containing an organic polymer having two or more hydrolyzable silyl groups in one molecule as the component (c) and a curing agent for an epoxy resin as the component (d).

[0024] The two-component curable resin composition for hydrogen gas sealing of the present invention can obtain a cured product having excellent hydrogen gas barrier properties, high elongation and high strength. DETAILED DESCRIPTION

[0025] Hereinafter, the embodiments of the present invention will be described. It should be noted that the present invention is not limited to the following embodiments. Throughout this specification, as far as the expression in singular form is concerned, unless otherwise specified, it should be understood that the expression in singular form also includes the concept of its plural form. Therefore, unless otherwise specified, it should be understood that the singular article (for example, "a", "an", "the", etc. in English) also includes the concept of its plural form. In addition, for the terms used in this specification, unless otherwise specified, it should be understood that they are used with the meaning commonly used in the field. Therefore, unless otherwise defined, all professional terms and scientific terms used in this specification have the same meaning as those commonly understood by those skilled in the art in the field to which the present invention belongs. In the event of a conflict, this specification (including definitions) takes precedence. The present invention is not limited to the following embodiments, and various changes can be made within the scope of the claims. In addition, in this specification, "X~Y" is used with the meaning of including the numerical values ​​(X and Y) recorded before and after as the lower limit and upper limit, which means "above X and below Y". In addition, unless otherwise specified, the concentration "%" represents the mass concentration "mass %", and unless otherwise specified, the ratio is set as the mass ratio. In addition, unless otherwise specified, the operation and measurement of physical properties were carried out under the conditions of room temperature (20°C to 25°C) / relative humidity 40%RH to 50%RH.

[0026] The two-component curable resin composition for hydrogen gas sealing according to one embodiment of the present invention is a two-component curable resin composition for hydrogen gas sealing comprising an agent A and an agent B, wherein the agent A is a composition comprising the components (a) and (b) described later, and the agent B is a composition comprising the components (c) and (d) described later. Furthermore, the agent A and / or the agent B of the two-component curable resin composition for hydrogen gas sealing according to one embodiment of the present invention may further comprise the component (e) described later, and the agent A and / or the agent B may further comprise an arbitrary component.

[0027] <Two-component curable resin composition for hydrogen sealing>

[0028] One embodiment of the present invention is a two-component curable resin composition for hydrogen sealing, comprising the following agent A and agent B, wherein a cured product thereof has a sea-island structure.

[0029] Agent A: a composition containing an epoxy resin as component (a) and a catalyst as component (b),

[0030] Agent B: A composition containing an organic polymer having two or more hydrolyzable silyl groups in one molecule as the component (c) and a curing agent for an epoxy resin as the component (d).

[0031] According to one embodiment of the present invention, there is provided a two-component curable resin composition for hydrogen gas sealing, which can produce a cured product having excellent hydrogen gas barrier properties, high elongation, and high strength.

[0032] Another embodiment of the present invention is a two-component curable resin composition for hydrogen gas sealing, comprising the following agent A and agent B.

[0033] Agent A: a composition comprising an epoxy resin as component (a) and a catalyst as component (b), wherein the component (a) comprises a hydrogenated epoxy resin as component (a-1);

[0034] Agent B: A composition containing an organic polymer having two or more hydrolyzable silyl groups in one molecule as the component (c) and a curing agent for an epoxy resin as the component (d).

[0035] <(a)Component>

[0036] The component (a) contained in the agent A of the two-component curable resin composition for hydrogen gas sealing of the present embodiment contains an epoxy resin.

[0037] In a preferred embodiment, the epoxy resin as the component (a) includes a hydrogenated epoxy resin as the component (a-1), or an aromatic epoxy resin as the component (a-2). Among them, by including the hydrogenated epoxy resin as the component (a-1), it is easier to form a sea-island structure in the cured product. In addition, by including the hydrogenated epoxy resin as the component (a-1), a cured product with further excellent hydrogen barrier properties, high elongation, and high strength can be obtained, which is preferred.

[0038] As the hydrogenated epoxy resin of the component (a-1), for example, a compound obtained by nuclear hydrogenation of the aromatic ring of the aromatic epoxy resin of the component (a-2) described later can be used. As the hydrogenated epoxy resin of the component (a-1), for example, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol E type epoxy resin and other hydrogenated bisphenol type epoxy resins; hydrogenated cresol novolac type epoxy resin; hydrogenated phenol novolac type epoxy resin, etc. Among them, from the aspect of being able to obtain a cured product with excellent hydrogen barrier properties, high elongation, and high strength, the hydrogenated epoxy resin of the component (a-1) is preferably a hydrogenated bisphenol type epoxy resin, and particularly preferably a hydrogenated bisphenol A type epoxy resin. These components as the component (a-1) can be used alone or in combination of two or more.

[0039] Commercially available products of the component (a-1) include, for example, YX8000, YX8034 (all manufactured by Mitsubishi Chemical Corporation), RIKARESIN (registered trademark) HBE-100 (manufactured by Shin Nippon Chemical Co., Ltd.), ST-3000 (manufactured by Nippon Steel Chemical Materials Co., Ltd.), etc., but are not limited thereto. These may be used alone or in combination of two or more.

[0040] The aromatic epoxy resin as component (a-2) is not particularly limited, and examples thereof include bisphenol-type epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol AD ​​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-phenylenediamine; naphthalene-type epoxy resin; biphenyl-type epoxy resin, etc. Among them, the aromatic epoxy resin as component (a-2) is preferably a bisphenol-type epoxy resin, and particularly preferably a bisphenol A-type epoxy resin, from the perspective of obtaining a cured product having high elongation and high strength. These compounds may be used alone or in combination of two or more.

[0041] Commercially available products of component (a-2) include, for example, 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); ADEKA RESIN (registered trademark) EP4100, EP4400 (manufactured by ADEKA Corporation), but are not limited thereto. These may be used alone or in combination of two or more.

[0042] In addition, in this specification, the glycidyl group-containing silane coupling agent is not included in the (d) component but is handled as the (e) component mentioned later.

[0043] The two-component curable resin composition for hydrogen sealing of this embodiment can obtain a cured product with even higher strength by using the components (a-1) and (a-2) together. The mass ratio of the components (a-1) and (a-2) (parts by mass of the component (a-1):parts by mass of the component (a-2)) is not particularly limited, and is, for example, in the range of 20:80 to 80:20, more preferably in the range of 25:75 to 75:25, further preferably in the range of 30:70 to 70:30, and particularly preferably in the range of 35:65 to 65:35. By being within the above range, a cured product with even better hydrogen barrier properties, high elongation, and high strength can be obtained.

[0044] In one embodiment, the above-mentioned two-component curable resin composition for hydrogen sealing uses only component (a-1) as component (a). As a result, a cured product with further excellent hydrogen barrier properties, high elongation, and high strength can be obtained. In particular, compared with the case of using component (a-2) in combination, a cured product with higher elongation can be obtained.

[0045] The viscosity of the above-mentioned component (a) is not particularly limited, but is preferably 0.1 to 50 Pa·s, more preferably 0.3 to 30 Pa·s, and most preferably 0.5 to 10 Pa·s. When the components (a-1) and (a-2) are used in combination, the viscosity of the component (a-1) is preferably 0.1 to 50 Pa·s, more preferably 0.3 to 30 Pa·s, and most preferably 0.5 to 10 Pa·s. The viscosity of the component (a-2) is preferably 0.1 to 50 Pa·s, more preferably 0.3 to 30 Pa·s, further more preferably 1 to 15 Pa·s, and most preferably 5 to 15 Pa·s. By having the component (a-1) be 0.1 to 50 Pa·s and the component (a-2) be 0.1 to 50 Pa·s, a cured product having excellent hydrogen barrier properties can be obtained. The viscosity of the component (a) of the present invention is a value measured at 25°C using a cone and plate viscometer.

[0046] The content of component (a) in the two-component curable resin composition for hydrogen sealing of the present embodiment is preferably 1 to 500 parts by mass, more preferably 10 to 300 parts by mass, further preferably 50 to 200 parts by mass, and particularly preferably 70 to 150 parts by mass, relative to 100 parts by mass of component (c). By being within the above range, the cured product of the two-component curable resin composition for hydrogen sealing described in the present embodiment becomes a cured product with higher elongation and higher strength. Preferably, the content of component (a) is within the above range when mixing agent A and agent B.

[0047] <(b) Components>

[0048] The component (b) contained in the A component of the two-component curable resin composition for hydrogen sealing of this embodiment is a catalyst. Preferably, the component (b) is a curing catalyst of the component (c). The component (b) is not particularly limited, but is preferably a catalyst for crosslinking the component (c) described later. Specific examples of the catalyst for crosslinking the component (c) include dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin distearate, dibutyltin laurate oxide, dibutyltin diacetylacetonate, dibutyltin dioleylmalate, dibutyltin octoate and other dibutyltin compounds, dioctyltin oxide, dioctyltin dilaurate and other dioctyltin compounds, and a reaction product of dioctyltin salt and silicate; titanium catalysts such as titanium tetraisopropoxide, diisopropyl di(acetylacetonato)titanate, tetraisopropyl titanate, tetraisopentyl titanate, tetra-n-butoxy titanate, tetra-tert-butyl titanate; aluminum catalysts; bismuth catalysts; zirconium catalysts; zinc catalysts; amine salts; organic phosphoric acid compounds, and the like. Among them, from the viewpoint of excellent hydrogen barrier property of the cured product, tin catalyst, titanium catalyst, aluminum catalyst, zinc catalyst are preferred, titanium catalyst is more preferred, and titanium tetraisopropoxide, di(acetylacetonato)titanate diisopropyl, and tetra-tert-butyl titanate are most preferred. They can be used alone or in combination of two or more. In addition, from the viewpoint of more effectively forming a cured product having a sea island structure, component (b) preferably contains a titanium catalyst, and most preferably contains only a titanium catalyst.

[0049] There are no particular limitations on commercially available products of the component (b). Examples of tin catalysts include NEOSTANN (registered trademark) U-100, U-130, U-200, and U-303 (manufactured by Nitto Kasei Co., Ltd.). Examples of titanium catalysts include ORGATIX (registered trademark) TA-8, TA-10, TA-21, TA-23, TA-30, TA-80, TC-100, TC-120, and TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.). Examples of bismuth catalysts include K-KAT348 (manufactured by King Industries, Inc.). Examples of zirconium catalysts include ORGATIX (registered trademark) ZA-45 (manufactured by Matsumoto Fine Chemical Co., Ltd.). Co., Ltd.), etc., 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 (Kawaken Fine Chemicals Co., Ltd.), ORGATIX (registered trademark) AL-3001, AL-3100, AL-3200, AL-3215 (Matsumoto Fine Chemical Co., Ltd.), K-KAT5218 (King Industries, Inc.), etc., as the zinc catalyst, for example, K-KAT670 (King Industries, Inc.), etc.

[0050] As the content of component (b), relative to 100 parts by mass of component (c) described later, component (b) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 17 parts by mass, further 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 having further excellent hydrogen barrier properties, high elongation, and high strength can be obtained. It is preferred that the content of component (b) is within the above range when mixing agent A and agent B.

[0051] As the content of the component (b) relative to 100 parts by mass of the component (a), the component (b) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, further preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass. By being within the above range, the two-component curable resin composition for hydrogen sealing described in this embodiment can obtain a cured product with further excellent hydrogen barrier properties, high elongation, and high strength. Preferably, when mixing agent A and agent B, the content of component (b) is within the above range.

[0052] <(c) Components>

[0053] The component (c) contained in the B agent of the two-component curable resin composition for hydrogen sealing of this embodiment is an organic polymer having two or more hydrolyzable silyl groups in one molecule. As the hydrolyzable silyl group, an alkoxysilyl group is preferred, and examples thereof include methyldimethoxysilyl, trimethoxysilyl, methyldiethoxysilyl, triethoxysilyl, etc. Among them, the hydrolyzable silyl group preferably includes a trimethoxysilyl group. The two or more hydrolyzable silyl groups contained in one molecule of the organic polymer may be the same as or different from each other. The number of hydrolyzable silyl groups contained in one molecule of the organic polymer is preferably 2 to 6, more preferably 2 to 3, and further preferably 2.

[0054] As component (c), for example, an organic polymer having a methyldimethoxysilyl group, an organic polymer having a trimethoxysilyl group, an organic polymer having a methyldiethoxysilyl group, or an organic polymer having a triethoxysilyl group can be cited. These compounds can be used alone or in combination of two or more. Among them, component (c) preferably includes an organic polymer having a trimethoxysilyl group, and more preferably uses an organic polymer having a methyldimethoxysilyl group and an organic polymer having a trimethoxysilyl group. By using an organic polymer having a methyldimethoxysilyl group and an organic polymer having a trimethoxysilyl group, the hydrogen barrier property of the cured product of the two-component curing type resin composition for hydrogen sealing is more excellent.

[0055] The mass ratio of the organic polymer having a methyldimethoxysilyl group and the organic polymer having a trimethoxysilyl group when used together is not particularly limited, and preferably the organic polymer having a methyldimethoxysilyl group: the organic polymer having a trimethoxysilyl group = 9:1 to 1:9, more preferably 8:2 to 2:8, further preferably 7:3 to 3:7, further more preferably 6:4 to 4:6, and particularly preferably 5.5:4.5 to 4.5:5.5. If the above mass ratio is 9:1 to 1:9, a cured product with better hydrogen barrier properties can be obtained.

[0056] In addition, the hydrolyzable silyl group may be bonded to the end or side chain of the organic polymer. From the viewpoint of obtaining a cured product with high elongation and high strength, it is preferred that the hydrolyzable silyl group is bonded to the end of the organic polymer, and more preferably the hydrolyzable silyl group is bonded to both ends of the organic polymer. In addition, from the viewpoint of handling, the component (c) is preferably liquid at 25° C. The component (c) may be used alone or in combination of two or more.

[0057] As an organic polymer having a methyldimethoxysilyl group, for example, polyoxyalkylene containing a methyldimethoxysilyl group at both ends, (meth) acrylic polymer containing a methyldimethoxysilyl group at both ends, polyisobutylene containing a methyldimethoxysilyl group at both ends, and polyurethane containing a methyldimethoxysilyl group at both ends can be cited. As an organic polymer having a trimethoxysilyl group, for example, polyoxyalkylene containing a trimethoxysilyl group at both ends, (meth) acrylic polymer containing a trimethoxysilyl group at both ends, polyisobutylene containing a trimethoxysilyl group at both ends, and polyurethane containing a trimethoxysilyl group at both ends can be cited. As an organic polymer having a methyldiethoxysilyl group, for example, (meth) acrylic polymer containing a methyldiethoxysilyl group at both ends, polyisobutylene containing a methyldiethoxysilyl group at both ends, and polyurethane containing a methyldiethoxysilyl group at both ends can be cited. Examples of the organic polymer having a triethoxysilyl group include a (meth)acrylic polymer containing a triethoxysilyl group at both terminals, a polyisobutylene containing a triethoxysilyl group at both terminals, and a polyurethane containing a triethoxysilyl group at both terminals.

[0058] The structure of the organic polymer is not particularly limited, and examples thereof include structures such as polyoxyalkylene, polyester, polycarbonate, polyurethane, polyamide, polyurea, polyimide, polyethylene, polypropylene, polyisobutylene, (meth) acrylic polymer, polystyrene, polyvinyl chloride, polybutadiene, polyisoprene, polyvinyl butyral, and polyvinyl ether. Among them, from the viewpoint of obtaining a cured product with further excellent hydrogen barrier properties, high elongation, and high strength, the structure of the organic polymer is preferably a structure such as polyoxyalkylene, polyisobutylene, and (meth) acrylic polymer, and more preferably polyoxyalkylene. In addition, the structure of the organic polymer may be a single type or a mixture of two or more types.

[0059] Examples of commercially available polyoxyalkylenes having two or more hydrolyzable silyl groups in one molecule include SAX010, SAX115, SAT030, SAT200, SAT350, SAT400, SAX220, SAX510, SAX530, SAX575, SAX580, SAX710, SAX720, SAX720A, SAX725, and SAX750. , SAX770, S203, S303, S203H, S303H, S943S, S911S, MA440, MA440A, MA447, MA451, MA490, MA903, MA903M, MA904, S943, MAX923, MAX951, SAX510, SAX520, SAX530, SAX580, etc. (manufactured by KANEKA CORPORATION), ES-S2410, ES-S2420, ES-S3430, ES-S3610, ES-S3630 (manufactured by AGC Co., Ltd.). Commercially available products of (meth)acrylic acid polymers having two or more hydrolyzable silyl groups in one molecule as component (c) include, for example, SA100S, SA310S, OR100S, etc. (manufactured by KANEKA CORPORATION). Examples of commercially available products of the polyisobutylene having two or more hydrolyzable silyl groups in one molecule of the component (c) include EP100S, EP103S, EP303S, and EP505S (manufactured by KANEKA CORPORATION).

[0060] In addition, in this specification, the silane coupling agent which has two or more hydrolyzable silyl groups in one molecule is not included in (c) component, but is handled as (e) component mentioned later.

[0061] The viscosity of the component (c) is not particularly limited, and is preferably 10 to 100 Pa·s at 23°C, more preferably 20 to 80 Pa·s, further preferably 30 to 70 Pa·s, and further preferably 40 to 60 Pa·s. By making the viscosity of the component (c) 10 Pa·s to 100 Pa·s, it is possible to easily form an island structure when mixed with the component (a), thereby obtaining a cured product having excellent hydrogen barrier properties, high elongation, and high strength. The viscosity of the component (c) in the present invention is a value measured using a B-type viscometer at 23°C. It should be noted that when two or more compounds are used in combination as the component (c), it is more preferred that the viscosity of any one of the compounds is within the above range.

[0062] Regarding the content of component (c) in the two-component curable resin composition for hydrogen sealing of this embodiment, relative to 100 parts by mass of component (a), component (c) is preferably 30 to 250 parts by mass, more preferably 50 to 200 parts by mass, further preferably 70 to 150 parts by mass, and further preferably 90 to 110 parts by mass. By being within the above range, a cured product with further excellent hydrogen barrier properties, high elongation, and high strength can be obtained. Preferably, when mixing agent A and agent B, the content of component (c) is within the above range.

[0063] <(d) Component>

[0064] The component (d) contained in the B agent of the two-component curing resin composition for hydrogen sealing of this mode is a curing agent for epoxy resin, which is a compound that can cure the component (a) contained in the A agent, i.e., the epoxy resin. As the component (d), there is no particular restriction as long as the epoxy resin as the component (a) can be cured, and examples thereof include amine compounds, polythiol compounds, acid anhydride compounds, organic phosphorus compounds, etc. As the above-mentioned amine compounds, primary amines, secondary amines, tertiary amines, polyamide compounds, imidazole compounds, epoxy adduct compounds (compounds that stop the reaction midway by adding tertiary amines to compounds or epoxy resins having an imidazole skeleton), etc. can be cited. Among them, from the viewpoint of having high elongation and high strength and achieving hydrogen barrier properties, the component (d) preferably contains tertiary amines, and most preferably contains only tertiary amines. In addition, from the viewpoint of more effectively forming a cured product having an island structure, the component (d) preferably contains tertiary amines, and most preferably contains only tertiary amines. In addition, the component (d) can be used alone or in combination of two or more. The component (d) is preferably liquid at 25°C from the viewpoint of curability and workability after mixing.

[0065] There are no particular restrictions on the primary amine, and examples thereof include aliphatic primary amines, alicyclic primary amines, and primary amines containing aromatic groups. There are no particular restrictions on the aliphatic primary amine, and examples thereof include ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, and dimer diamine. In addition, there are no particular restrictions on the alicyclic primary amine, and examples thereof include menthenediamine, isophoronediamine, N-aminoethylpiperazine, diaminodicyclohexylmethane, and norbornanediamine. In addition, there are no particular restrictions on the primary amine containing an aromatic group, and examples thereof include dimethylaminomethylphenol, meta-xylenediamine, meta-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and diaminodiethyldiphenylmethane. It should be noted that in this specification, the amino group-containing silane coupling agent is not included in the component (d), but is disposed of as the component (e) described later.

[0066] As the secondary amine or tertiary amine, there is no particular limitation, and examples thereof include secondary amines such as piperidine, pyridine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, triethylenediamine, dimethylcyclohexylamine, dimethylbenzylamine, dimethylhexylamine, dimethylaminophenol, dimethylamino-p-cresol, 1,4-diazabicyclo〔2.2.2〕octane, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo〔5.4.0〕undecene-1 and other tertiary amines. As commercially available products, for example, K54 (manufactured by Air Products Japan Co., Ltd.) and the like can be cited. From the viewpoint of excellent curability, as secondary amines and tertiary amines, compounds having an aromatic ring are preferred.

[0067] Examples of the polyamide compound include polyamidoamine and the like.

[0068] In addition, from the viewpoint of curability and workability after mixing Agent A and Agent B, the component (d) is preferably an amine compound that is liquid at 25° C. Examples of the amine compound that is liquid at 25° C. include 2,4,6-tris(dimethylaminomethyl)phenol, polyamidoamine, and dimer diamine.

[0069] The imidazole compound is not particularly limited, and examples thereof 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, 1-cyanoethyl-2-undecylimidazole, and 1-isobutyl-2-methylimidazole. imidazole, 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, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the like.

[0070] The polythiol compound is not particularly limited, and examples thereof include 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dimercaptoacetate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (TEMPIC), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine- Alkyl polythiols such as 2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate) (TMMP), pentaerythritol tetrakis(3-mercaptopropionate) (PEMP), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptopropionate) (DPMP), 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol; polythioethers containing terminal thiol groups, etc.

[0071] The acid anhydride compound is not particularly limited, and examples thereof include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendoethylenetetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylnadic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and maleic anhydride.

[0072] Regarding the content of component (d) in the two-component curable resin composition for hydrogen sealing of this embodiment, relative to 100 parts by mass of component (a), component (d) is preferably 1 to 180 parts by mass, more preferably 3 to 140 parts by mass, further preferably 5 to 100 parts by mass, and further preferably 5 to 15 parts by mass. By being within the above range, a cured product with further excellent hydrogen barrier properties, high elongation, and high strength can be obtained. Preferably, when mixing agent A and agent B, the content of component (d) is within the above range.

[0073] In addition, regarding the content of component (d) in the two-component curable resin composition for hydrogen sealing of this embodiment, relative to 100 parts by mass of component (c), component (d) is preferably 1 to 150 parts by mass, more preferably 1 to 100 parts by mass, further preferably 3 to 50 parts by mass, and further preferably 5 to 15 parts by mass. By being within the above range, a cured product with further excellent hydrogen barrier properties, high elongation, and high strength can be obtained. Preferably, when mixing agent A and agent B, the content of component (d) is within the above range.

[0074] <(e) Ingredients>

[0075] The A agent and / or B agent of the two-component curable resin composition for hydrogen sealing described in this embodiment may further contain a silane coupling agent as the (e) component. The silane coupling agent mentioned in the present invention refers to a compound containing reactive functional groups other than alkoxysilyl and alkoxysilyl in the molecule. The reactive functional groups mentioned here can include glycidyl, vinyl, amino, (meth)acryloyl, isocyanate, sulfide groups, etc. By making the A agent and / or B agent contain a silane coupling agent, a cured product with further excellent hydrogen barrier properties, high elongation, and high strength can be obtained, so it is preferred.

[0076] Examples of the silane coupling agent 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 silanes such as vinyltri(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane. Coupling agent; silane coupling agent containing (meth)acryloyl group such as γ-methacryloxypropyltrimethoxysilane; silane coupling agent containing amino group such as 3-(2-aminoethylamino)propyltrimethoxysilane (N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane), γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, styrylsilane, urea silane, sulfide silane, isocyanate silane, etc. Among them, as a silane coupling agent, a glycidyl-containing silane coupling agent, a vinyl-containing silane coupling agent, and an amino-containing silane coupling agent are preferred. In addition, from the viewpoint of hydrogen barrier properties, agent A preferably contains a silane coupling agent that reacts with component (d). As a specific example, it is more preferred to include a glycidyl-containing silane coupling agent, and the glycidyl-containing silane coupling agent is further preferably glycidylpropyltrimethoxysilane. In addition, from the viewpoint of hydrogen barrier properties, agent B preferably includes a silane coupling agent that reacts with component (a). As a specific example, it is more preferred to include an amino-containing silane coupling agent, and the amino-containing silane coupling agent is further preferably 3-(2-aminoethylamino)propyltrimethoxysilane. The silane coupling agent can be used alone or in combination of two or more.

[0077] The content of the component (e) in the 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, further preferably 0.3 to 10 parts by mass, and further preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the component (a). By being within the above range, a cured product having further excellent hydrogen barrier properties, high elongation, and high strength can be obtained.

[0078] 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, further preferably 0.3 to 10 parts by mass, and further preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of component (c). By being within the above range, the hydrogen barrier property is further improved.

[0079] <Optional Ingredients>

[0080] The two-component curable resin composition for hydrogen gas sealing according to one embodiment of the present invention may contain additives such as curing accelerators, various elastomers such as styrene copolymers, fillers, storage stabilizers, antioxidants, flame retardant imparting agents, light stabilizers, heavy metal deactivators, plasticizers, defoamers, pigments, rust inhibitors, leveling agents, dispersants, rheology modifiers, flame retardants, and surfactants within the range that does not impair the purpose of the present invention. Each of these components may be contained in either agent A or agent B, or in both.

[0081] The two-component curable resin composition for hydrogen gas sealing according to one embodiment of the present invention may contain a filler for the purpose of improving the elastic modulus, fluidity, etc. of the cured product. Specific examples of the filler include inorganic powders, organic powders, and the like.

[0082] As fillers for inorganic powders, glass, fumed silica, mica, ceramics, silicone rubber powder, calcium carbonate, carbon powder, kaolin, dry clay minerals, dry diatomaceous earth, metallic powders, etc. can be cited. As fillers for metallic powders, gold, silver, copper, aluminum oxide, aluminum nitride, etc. can be cited. In addition, as fillers for organic powders, for example, polyethylene, polypropylene, nylon, cross-linked acrylic acid, cross-linked polystyrene, polyester, polyvinyl alcohol, polyvinyl butyral, and polycarbonate can be cited. In addition, the content of the filler is not particularly limited. When it is combined with agent A, it is preferably 0.1 to 300 parts by mass relative to 100 parts by mass of component (a), and when it is combined with agent B, it is preferably 0.1 to 300 parts by mass relative to 100 parts by mass of component (c). By being within the above range, a cured product with higher elongation and higher strength can be obtained, and the operability of the two-component curing resin composition for hydrogen sealing can be excellent.

[0083] Among the fillers of inorganic powders, fumed silica can be preferably used from the viewpoint of adjusting the viscosity of the two-component curable resin composition for hydrogen sealing or improving the mechanical strength of the cured product. As fumed silica, fumed silica surface-treated with dimethylsilane, trimethylsilane, alkylsilane, methacryloxysilane, organochlorosilane, polydimethylsiloxane, hexamethyldisilazane, etc. can be more preferably used. Examples of commercially available products of fumed silica include AEROSIL (registered trademark) 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 (manufactured by Cabot Corp.).

[0084] Examples of the storage stabilizer include tetrafunctional alkoxysilanes such as tetramethoxysilane and tetraethoxysilane, silicate compounds represented by methyltrimethoxysilane, methyltriethoxysilane, ethyl silicate, propyl silicate, and butyl silicate, etc. These may be used alone or in combination of two or more.

[0085] The two-component curing type resin composition for hydrogen sealing described in one embodiment of the present invention contains the above-mentioned A agent and B agent, and is preferably composed of A agent and B agent. A agent is a composition containing (a) component and (b) component, and B agent is a composition containing (c) component and (d) component. In this way, by dividing the components into two compositions of A agent and B agent, it is possible to suppress useless reactions during storage and improve storage stability. It should be noted that in such a two-component curing type resin composition for hydrogen sealing, A agent and B agent can be manufactured by mixing each component by a known method respectively. Moreover, when in use, A agent and B agent can be mixed and used by a known method.

[0086] In the two-component curable resin composition for hydrogen gas sealing according to one embodiment of the present invention, the amount of the 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, based on 100 parts by mass of the agent A.

[0087] <Cured product>

[0088] Another embodiment of the present invention is a cured product obtained by curing the above-mentioned two-component curable resin composition for hydrogen sealing (cured product of the two-component curable resin composition for hydrogen sealing). As for the cured product as another embodiment of the present invention, it is obtained by mixing the A agent and the B agent constituting the two-component curable resin composition for hydrogen sealing, and curing the mixed two-component curable resin composition for hydrogen sealing.

[0089] The cured product of the two-component curable resin composition for hydrogen sealing of the present invention has an island structure. By making the above-mentioned cured product have an island structure, a cured product with excellent hydrogen barrier properties, high elongation and high strength can be obtained. It should be noted that in the present invention, the above-mentioned "island structure" means a structure in which the phase constituting the island (equivalent to the island) is dispersed in another phase (equivalent to the sea). The above-mentioned island structure can be confirmed by observing at a magnification of 2000 to 10,000 times using a CCD camera, a scanning electron microscope (SEM), etc. In addition, as a method for confirming that the cured product has an island structure, a method for confirming the appearance can be cited. Specifically, when the appearance is immediately transparent after the A agent and the B agent of the present invention are mixed, and the appearance of the cured product is turbid, it can be judged that an island structure is formed. It should be noted that in the present invention, the cured product used to confirm whether it has an island structure is: after mixing the A agent and the B agent of each hydrogen sealing two-component curable resin composition, it is cured for 168 hours under an environment of 25°C and 50%RH. In order to achieve excellent hydrogen barrier properties, high elongation and high strength in the cured product, it is preferred that the sea contains component (c) and the islands contain component (a). The area ratio of the sea to the islands is preferably 95:5 to 40:60.

[0090] There is no particular limitation on the method for making the cured product have an island structure. For example, after mixing the agent A and the agent B of the two-component curable resin composition for hydrogen sealing of the present method, the mixture is cured and cured at 20°C to 30°C and 40%RH to 60%RH, thereby obtaining a cured product having an island structure.

[0091] At this time, for example, by including a hydrogenated epoxy resin as component (a-1) in component (a), it is easier to obtain a cured product having an island structure, so it is preferred. In addition, when a titanium catalyst is used as component (b), it is easy to properly control the curing rate, so it is easier to obtain a cured product having an island structure, so it is preferred. In addition, when a tertiary amine is used as component (d), it is easy to properly control the curing rate, so it is easier to obtain a cured product having an island structure, so it is preferred. In a preferred embodiment, for the above-mentioned two-component curing resin composition for hydrogen sealing, in agent A, component (a) includes a hydrogenated epoxy resin as component (a-1), component (b) includes a titanium catalyst, and in agent B, component (d) includes a tertiary amine.

[0092] The hydrogen permeability coefficient of the cured product of the two-component curable resin composition for hydrogen sealing of the present embodiment is preferably 1.0×10 -14 mol·m / (m 2 ·s·Pa) or less, more preferably 0.9×10 -14 mol·m / (m 2 ·s·Pa) or less, more preferably 0.8×10 -14 mol·m / (m 2 ·s·Pa) or less. The hydrogen permeability coefficient of the solidified material is 1.0×10 -14 mol·m / (m 2 When the hydrogen permeability coefficient of the cured product is less than 1.0×10·s·Pa), it can be suitably used as an adhesive for hydrogen sealing. The lower limit of the hydrogen permeability coefficient of the cured product is not particularly limited, but the lower the value, the better. For example, 1.0×10 -17 mol·m / (m 2 ·s·Pa) or more. It should be noted that the hydrogen permeability coefficient of the solidified material is a value measured by the method described in the Examples described later.

[0093] <Method for producing cured product>

[0094] A method for producing a cured product having a sea-island structure is also one embodiment of the present invention, wherein the following agent A and agent B are mixed and the resulting mixture is aged in an environment of 20° C. to 30° C. and 40% RH to 60% RH.

[0095] Agent A: A composition comprising an epoxy resin as component (a) and a catalyst as component (b), wherein the component (a) comprises a hydrogenated epoxy resin as component (a-1).

[0096] Agent B: A composition containing an organic polymer having two or more hydrolyzable silyl groups in one molecule as the component (c) and a curing agent for an epoxy resin as the component (d).

[0097] It is preferred that after mixing the above-mentioned agent A and agent B, the obtained mixture is aged in an environment of 25° C. and 50% RH.

[0098] The aging time is not particularly limited, but is preferably 12 hours or more, more preferably 24 hours or more, and most preferably 72 hours or more. The upper limit of the aging time is also not particularly limited, but is, for example, 300 hours or less, preferably 200 hours or less, and more preferably 180 hours or less.

[0099] <Purpose>

[0100] The two-component curable resin composition for hydrogen sealing of one embodiment of the present invention can obtain a cured product having excellent hydrogen barrier properties, high elongation, and high strength, and therefore can be preferably used in various applications such as adhesives, sealants, sealing agents, potting agents, coating agents, and lining materials. Examples of hydrogen sealing include sealants / adhesives used for valve peripheral components of hydrogen storage tanks, fuel cells, gas piping, and gas cylinders.

[0101] Therefore, one embodiment of the present invention is use of a two-component curable resin composition comprising the following agent A and agent B for hydrogen sealing, wherein a cured product of the composition has a sea-island structure:

[0102] Agent A: a composition containing an epoxy resin as component (a) and a catalyst as component (b);

[0103] Agent B: A composition containing an organic polymer having two or more hydrolyzable silyl groups in one molecule as the component (c) and a curing agent for an epoxy resin as the component (d).

[0104] In addition, one embodiment of the present invention is use of a two-component curable resin composition comprising the following agent A and agent B for hydrogen gas sealing:

[0105] Agent A: a composition comprising an epoxy resin as component (a) and a catalyst as component (b), wherein the component (a) comprises a hydrogenated epoxy resin as component (a-1);

[0106] Agent B: A composition containing an organic polymer having two or more hydrolyzable silyl groups in one molecule as the component (c) and a curing agent for an epoxy resin as the component (d).

[0107] Another embodiment of the present invention is use of the two-component curable resin composition for hydrogen sealing of valve peripheral members of hydrogen tanks, fuel cells, gas piping, or gas cylinders.

[0108] Example

[0109] Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. It should be noted that in the following Examples, the operations were performed at room temperature (25° C.) unless otherwise specified.

[0110] <Preparation of two-component curable resin composition for hydrogen sealing>

[0111] The following components were collected at the ratio (parts by mass) shown in Table 1 and mixed in a mixer at room temperature for 60 minutes to prepare Part A and Part B corresponding to the two-component curable resin composition for hydrogen sealing. The details of each component are as follows.

[0112] <(a)Component>

[0113] a-1-1: Hydrogenated bisphenol A type epoxy resin (RIKARESIN (registered trademark) HBE-100 manufactured by Shin Nippon Rika Co., Ltd.), viscosity (25° C.) 2 Pa·s

[0114] a-2-1: bisphenol A type epoxy resin (jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation), viscosity (25° C.) 13 Pa·s

[0115] a-2-2: bisphenol F type epoxy resin (jER (registered trademark) 807 manufactured by Mitsubishi Chemical Corporation), viscosity (25° C.): 4 Pa·s.

[0116] <(b) Components>

[0117] b1: Titanium tetraisopropoxide (manufactured by Matsumoto Fine Chemical Co., Ltd., ORGATIX (registered trademark) TA-8, component concentration 99 mass % or more)

[0118] b2: diisopropyl di(acetylacetonato)titanate (ORGATIX (registered trademark) TC-100 manufactured by Matsumoto Fine Chemical Co., Ltd., component concentration 75 mass % or more)

[0119] b3: Tetra-tert-butyl titanate (ORGATIX (registered trademark) TA-80 manufactured by Matsumoto Fine Chemical Co., Ltd., component concentration 83% by mass or more).

[0120] <(c) Components>

[0121] c1: Polyoxyalkylene containing trimethoxysilyl groups at both ends (SAX575 manufactured by KANEKA CORPORATION, liquid at 25°C, viscosity (23°C) 50 Pa·s)

[0122] c2: Polyoxyalkylene containing methyldimethoxysilyl groups at both ends (SAX750 manufactured by KANEKA CORPORATION, liquid at 25°C, viscosity (23°C) 46 Pa·s).

[0123] <(d) Component>

[0124] d1: 2,4,6-tris(dimethylaminomethyl)phenol (manufactured by Air Products Japan Co., Ltd., ANCAMINE (registered trademark) K54, liquid at 25°C).

[0125] <(e) Ingredients>

[0126] e1: Glycidylpropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)

[0127] e2: 3-(2-aminoethylamino)propyltrimethoxysilane (DOWSIL (registered trademark) Z-6094 Silane manufactured by Dow Toray Co., Ltd.) (not handled as component (d) in the present invention).

[0128] The test methods in the Examples and Comparative Examples in Table 1 are as follows.

[0129] <(1) Hydrogen permeability test of cured product>

[0130] 100 g of agent A and 100 g of agent B of each two-component curing resin composition for hydrogen sealing in the examples and comparative examples were mixed at 25°C. Next, the thickness of the mixed resin composition was set to 1 mm, and it was aged for 168 hours at 25°C and 50% RH to cure it and produce a sheet-like cured product. Next, the sheet-like cured product was used to measure the hydrogen permeability coefficient in accordance with JIS K7126-1: 2006 (Plastics-Film and sheeting-Determination of gas-transmission rate-Part 1: Differential-pressure method). It should be noted that the type of test is the pressure sensor method, and the conditions are that the test gas (hydrogen) on the high-pressure side is measured at 23°C and 100 kPa. The results are shown in Table 1. In the present invention, in order to be used for hydrogen sealing, the hydrogen permeability coefficient is preferably 1.0×10 -14 mol·m / (m 2 ·s·Pa) or less.

[0131] <(2) Measurement of tensile strength of cured product>

[0132] 100 g of agent A and 100 g of agent B of each two-component curing resin composition for hydrogen sealing in the embodiment and comparative example were mixed at 25°C. Next, the thickness of the mixed resin composition was set to 1 mm, and it was aged for 168 hours at 25°C and 50% RH to cure it and produce a sheet-like cured product. The cured product was punched out with a No. 3 dumbbell to produce a test piece. The two ends of the test piece were fixed to the chuck in such a way that the long axis of the test piece and the center of the chuck were in a straight line. The test piece was stretched at a tensile speed of 500 mm / min to determine the maximum load. The strength at the maximum load is referred to as "tensile strength (MPa)". The results are shown in Table 1. The details are in accordance with JIS K6251 (2010). It should be noted that in the present invention, in order to be used for hydrogen sealing, the tensile strength is preferably above 5 MPa, and more preferably above 8 MPa.

[0133] <(3) Method for measuring elongation of cured product>

[0134] 100 g of the A component and 100 g of the B component of each hydrogen gas sealing two-component curing resin composition of the embodiment and the comparative example were mixed at 25°C. Then, the mixed resin composition was set to a thickness of 1 mm and aged for 168 hours at 25°C and 50% RH to cure the composition and prepare a sheet-shaped cured product. The cured product was punched out with a No. 3 dumbbell to prepare a test piece, and the test piece was marked with marking lines at intervals of 20 mm.

[0135] Fix it to the chuck in the same manner as the measurement of tensile strength, and stretch it at a tensile speed of 500mm / min until the test piece breaks. During the measurement, the test piece stretches and the spacing between the markings expands, so the spacing between the markings is measured with a vernier caliper until the test piece breaks. By dividing the spacing between the markings (mm) just before the break by the initial spacing between the markings (20mm), the elongation ratio is calculated as "elongation (%)" (elongation (%) = (spacing between the markings just before the break / initial spacing between the markings) × 100). The results are shown in Table 1. It should be noted that in order to be used for hydrogen sealing, the elongation is preferably 300% or more, more preferably 400% or more, and particularly preferably 430% or more.

[0136] <(4) Confirmation test of the presence or absence of sea-island structure in the solidified material>

[0137] 100 g of the A component and 100 g of the B component of each hydrogen gas sealing two-component curable resin composition of the example and the comparative example were mixed at 25° C. Then, the mixed resin composition was cured to a thickness of 1 mm at 25° C. and 50% RH for 168 hours to prepare a sheet-shaped cured product.

[0138] The surface of the obtained cured product was observed at a magnification of 2000 times using a CCD camera to confirm the presence or absence of a sea-island structure. The results are shown in Table 1. The cured product formed from the two-component curable resin composition for hydrogen sealing of the present invention has a sea-island structure.

[0139] [Table 1]

[0140] Table 1

[0141]

[0142] According to the results of Examples 1 to 3 in Table 1, it can be confirmed that the two-component curable resin composition for hydrogen sealing of the present invention forms an island structure in the cured product, and a cured product with excellent hydrogen barrier properties, high elongation, and high strength can be obtained. Comparative Examples 1 and 2 are compositions that do not have an island structure in the cured product, and have poor hydrogen barrier properties and are not cured products with high elongation. From the above, it can be seen that by making the cured product have an island structure, excellent hydrogen barrier properties, high elongation, and high strength can be achieved.

[0143] Industrial Applicability

[0144] The two-component curable resin composition for hydrogen sealing of the present invention can obtain a cured product having excellent hydrogen barrier properties, high elongation, and high strength, and is therefore suitable for various uses such as adhesives, sealants, sealing agents, potting agents, and coating agents. Therefore, it can be applied to a wide range of fields and is therefore useful in industry.

[0145] This application is based on Japanese Patent Application No. 2022-148374 filed on September 16, 2022, the disclosure of which is referenced and cited in the present specification in its entirety.

Claims

1. A two-component curable resin composition for hydrogen sealing, comprising the following agent A and agent B, wherein the cured product thereof has a sea-island structure, Agent A: a composition containing an epoxy resin as component (a) and a catalyst as component (b), Agent B: A composition containing an organic polymer having two or more hydrolyzable silyl groups in one molecule as the component (c) and a curing agent for an epoxy resin as the component (d).

2. The two-component curable resin composition for hydrogen sealing according to claim 1, wherein: The component (a) contains a hydrogenated epoxy resin as the component (a-1).

3. The two-component curable resin composition for hydrogen sealing according to claim 1 or 2, wherein: The component (b) is contained in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the component (c).

4. The two-component curable resin composition for hydrogen sealing according to claim 1 or 2, wherein: The hydrolyzable silyl group includes a trimethoxysilyl group.

5. The two-component curable resin composition for hydrogen sealing according to claim 1 or 2, wherein: The component (d) is an amine compound that is liquid at 25°C.

6. The two-component curable resin composition for hydrogen sealing according to claim 1 or 2, wherein: The agent A and / or the agent B further contains a silane coupling agent as a component (e).

7. The two-component curable resin composition for hydrogen sealing according to claim 1 or 2, wherein: The component (a) includes a hydrogenated epoxy resin as a component (a-1) and an aromatic epoxy resin as a component (a-2).

8. The two-component curable resin composition for hydrogen sealing according to claim 1 or 2, wherein: The cured product is obtained by mixing the agent A and the agent B, and then aging the mixture under an environment of 20° C. to 30° C. and 40% RH to 60% RH for 12 hours or more.

9. A two-component curable resin composition for hydrogen sealing, comprising the following agent A and agent B, Agent A: A composition comprising an epoxy resin as component (a) and a catalyst as component (b), wherein: The component (a) comprises a hydrogenated epoxy resin as the component (a-1); Agent B: A composition containing an organic polymer having two or more hydrolyzable silyl groups in one molecule as the component (c) and a curing agent for an epoxy resin as the component (d). 10 . A cured product obtained by curing the two-component curable resin composition for hydrogen gas sealing according to claim 1 or 9 .

11. A method for producing a solidified product having a sea-island structure, wherein: Mix the following A and B, and age the mixture at 20°C to 30°C and 40% RH to 60% RH. Agent A: a composition comprising an epoxy resin as component (a) and a catalyst as component (b), wherein component (a) comprises a hydrogenated epoxy resin as component (a-1); Agent B: A composition containing an organic polymer having two or more hydrolyzable silyl groups in one molecule as the component (c) and a curing agent for an epoxy resin as the component (d).

Images