Two-part curable resin composition and its cured product

Abstract

[Topic] The purpose of this invention is to provide a two-component curing resin composition with excellent room temperature curing properties and the ability to inhibit staining of the cured material. [Solution] A two-component curable resin composition comprising agent A and agent B as follows: Agent A: A composition comprising (a) and (b) components. (a) Composition: An epoxy resin having two or more epoxy groups in one molecule; and (b) Ingredients: Aluminum alkoxide catalyst; Agent B: A composition containing components (c) and (d). (c) Ingredients: Organic polymers containing two or more hydrolyzable silyl groups; and (d) Ingredients: (a) Ingredients are used as hardeners.

Description

Technical Field

[0001] This invention relates to a two-component curable resin composition. Prior Technology

[0002] Traditionally, epoxy resins have been used in various applications, such as adhesives, sealants, potting compounds, coatings, and conductive pastes, due to their excellent adhesive strength, sealing properties, high strength, heat resistance, electrical properties, and chemical resistance. However, while cured epoxy resins exhibit strong mechanical strength, they suffer from poor ductility.

[0003] Therefore, to impart ductility to epoxy resin, a method of mixed modification of organosilicon resin is adopted. As such a technology, Patent Document 1 discloses a two-component curable resin composition containing epoxy resin, a titanium chelate as a curing catalyst, a modified organosilicon polymer, and an epoxy resin curing agent. [Previous Technical Documents] [Patent Literature]

[0004] Patent Document 1: Japanese Patent Application Publication No. 2007-270010 Summary of the Invention

[0005] [The problem this invention aims to solve]

[0006] However, as shown in Comparative Example 1 of this application, although the two-component curable resin composition disclosed in Patent Document 1 has good room temperature curing properties, it has the problem that it is originally white before curing but turns yellow after curing.

[0007] The purpose of this invention is to provide a two-component curable resin composition that exhibits good room temperature curing properties and can inhibit staining of the cured product. [Methods for solving the problem]

[0008] The main points of this invention are explained below. The embodiments of this invention overcome the aforementioned problems of the past.

[0009] [1] A two-component curable resin composition comprising the following agent A and agent B: Agent A: A composition comprising (a) and (b) components. (a) Composition: An epoxy resin having two or more epoxy groups per molecule; and (b) Ingredients: Aluminum alkoxide catalyst; Agent B: A composition containing components (c) and (d). (c) Ingredients: Organic polymers containing two or more hydrolyzable silane groups; and (d) Ingredients: (a) Ingredients are used as hardeners.

[0010] [2] The two-component curable resin composition as described in [1], wherein component (a) is a hydrogenated epoxy resin having two or more epoxy groups in one molecule of component (a-1) and / or a bisphenol epoxy resin having two or more epoxy groups in one molecule of component (a-2).

[0011] [3] A two-component curable resin composition as described in [1] or [2], wherein the hydrolyzable silyl group of the component (c) is dimethoxysilyl or trimethoxysilyl.

[0012] [4] A two-component curable resin composition as described in any one of [1] to [3], wherein, when the B agent is mixed in the range of 10 to 300 parts by weight relative to 100 parts by weight of the A agent, the (c) agent is 10 to 250 parts by weight relative to 100 parts by weight of the (a) component.

[0013] [5] A two-liquid curable resin composition as described in any one of [1] to [4], wherein the (d) component is an amine compound that is liquid at 25°C.

[0014] [6] A two-component curable resin composition as described in any one of [2] to [5], wherein the mass ratio of component (a-1) to component (a-2) is 20:80 to 80:20.

[0015] [7] A cured material formed by curing a two-component curable resin composition described in any one of [1] to [6]. [The effects of the invention]

[0016] The two-component curable resin composition of the present invention exhibits good curing properties at room temperature and can inhibit staining of the cured product. Implementation

[0017] The present invention will now be described in detail. Furthermore, in this specification, "X~Y" is used to encompass the meaning of the values ​​(X and Y) recorded before and after it as lower and upper limits, respectively, signifying "above X and below Y". When multiple "X~Y" are recorded, such as "X1~Y1 or X2~Y2", then all permutations and combinations of these values ​​as upper and lower limits are revealed (that is, they become the legal basis for correction). Specifically, corrections to above X1, below Y2, below X1, above Y2, from X1 to X2, and from X1 to Y2, etc., should all be considered legal. Furthermore, it goes without saying that "selecting at least one from the group consisting of A, B, C... and..." means that, apart from "only A, only B, only C, A and B, B and C, A and C, A and B and C...", if at least one of A, B, and C... has a subordinate concept, then it is not necessary to select all the subordinate concepts of A, B, and C...; selecting only the subordinate concept of any one of them is sufficient. Additionally, unless otherwise stated, measurements of operation and physical properties are performed at room temperature (20 to 25°C) and relative humidity 40 to 50% RH.

[0018] This invention relates to a two-component curable resin composition comprising agent A, which contains components (a) and (b) described below, and agent B, which contains components (c) and (d) described below. The components are as follows.

[0019] (a)Ingredients Component (a) of the present invention is an epoxy resin having two or more epoxy groups per molecule. Each molecule of the epoxy resin may have six or fewer, four or fewer, or three or fewer epoxy groups.

[0020] The above-mentioned component (a) is not particularly limited, but for example, hydrogenated epoxy resin having two or more epoxy groups in one molecule as component (a-1), or bisphenol epoxy resin having two or more epoxy groups in one molecule as component (a-2), etc., preferably includes component (a-1), more preferably uses components (a-1) and (a-2) together, and can be combined with other components of the present invention to have excellent room temperature curing properties and the effect of inhibiting staining of the cured product. When components (a-1) and (a-2) are used together in the present invention, it may further include "epoxy resin having two or more epoxy groups in one molecule other than components (a-1) and (a-2)".

[0021] The above-mentioned component (a-1) is not particularly limited, but for example, it can be hydrogenated bisphenol type epoxy resins such as hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol E type epoxy resin; hydrogenated cresol phenolic type epoxy resin; hydrogenated phenolic type epoxy resin, etc. Among them, hydrogenated bisphenol type epoxy resin is preferred because it has excellent room temperature curing properties and can inhibit staining of the cured product. Component (a-1) can be used alone or in combination of two or more.

[0022] In one embodiment of the present invention, the total content (mass%) of hydrogenated bisphenol type epoxy resin in component (a-1) can be 80% or more by mass, 85% or more by mass, 90% or more by mass, 95% or more by mass, 98% or more by mass, or 100% by mass.

[0023] Commercially available products containing the above-mentioned ingredient (a-1) include, for example, YX8000, YX8034 (manufactured by Mitsubishi Chemical Corporation), HBE-100 (manufactured by New Nippon Rikka Corporation), ST-3000 (manufactured by Nippon Steel Chemical Materials Co., Ltd.), etc., but are not limited to these. These ingredients may be used individually or in combination of two or more.

[0024] The aforementioned component (a-2) is not particularly limited, but examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD ​​type epoxy resin. Among these, bisphenol A type epoxy resin is preferred because it can inhibit staining of the cured product. These components can be used individually or in combination of two or more. According to an embodiment of the present invention, the bisphenol type epoxy resin as component (a-2) is not hydrogenated.

[0025] The total content (mass%) of bisphenol A type epoxy resin in the above (a-2) components can be 80% or more by mass, 85% or more by mass, 90% or more by mass, 95% or more by mass, 98% or more by mass, or 100% by mass.

[0026] Commercially available products containing the above-mentioned (a-2) ingredients include, for example, JER825, 827, 828, 828US, 834, 1001, 806, and 807 (manufactured by Mitsubishi Chemical Corporation); Epiclon 840, 850, 830LVP, EXA850CRP, 835, and EXA835LV (manufactured by DIC Corporation); EP4100 and EP4400 (manufactured by ADEKA Corporation), etc., but are not limited to the above. These ingredients can be used individually or in combination of two or more.

[0027] There are no particular limitations on the mass ratio of component (a-1) to component (a-2) mentioned above, but for example, a range of 20:80 to 80:20 is preferred, a range of 25:75 to 75:25 is more preferred, and a range of 35:75 to 75:35 is more preferred. Within the above ranges, hardened materials with higher ductility and higher strength can be obtained.

[0028] In one embodiment of the present invention, the proportion (by mass%) of a molecule of hydrogenated epoxy resin having two or more epoxy groups and / or a molecule of bisphenol type epoxy resin having two or more epoxy groups (total if there are two or more) of the component (a) may be 80% by mass or more, 85% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass.

[0029] In one embodiment of the present invention, the amount of component (a) added above, relative to component (c) below as 100 parts by mass, may be 80-120 parts by mass, 85-115 parts by mass, 90-110 parts by mass, or 95-105 parts by mass.

[0030] In one embodiment of the present invention, the content (mass %) of component (a) in agent A can be 85% by mass or more, 90% by mass or more, 92% by mass or more, or 94% by mass or more. The content (mass %) of component (a) in agent A can be 99% by mass or less, 98% by mass or less, or 97% by mass or less. The content (mass %) of component (a) in agent A can be 85-99% by mass, 90-98% by mass, or 94-97% by mass.

[0031] (b) Components Component (b) of this invention is an alkoxide-based aluminum compound (i.e., an alkoxide-based aluminum catalyst). In the catalyst, by selecting component (b) of this invention and combining it with other components of this invention, excellent room temperature curing properties and a significant effect in inhibiting staining of the cured product can be obtained.

[0032] Furthermore, chelated aluminum catalysts are not considered part (b) of this invention. Examples of such chelated aluminum catalysts include, for instance, alkyl aluminum acetate diisopropyl ester. In one embodiment of this invention, alkoxide-based aluminum catalysts do not include chelated aluminum catalysts.

[0033] In one embodiment of the present invention, the alkoxide-based aluminum catalyst has the general formula: Al(OR 1)(OR 2)(OR 3), wherein R 1, R 2, and R 3 are each independently a straight-chain, branched, or cyclic alkyl group. The number of carbon atoms in the alkyl group can be, for example, 1-10, 2-9, 3-8, 4-7, 4-6, 4, or 5. Preferably, R 1, R 2, and R 3 are each independently a branched alkyl group. The branched alkyl group can improve its compatibility with component (A) and enhance its storage stability. Examples of alkyl groups having 1-10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, c-pentyl (cyclopentyl), n-hexyl, c-hexyl (cyclohexyl), n-heptyl, n-octyl, n-nonyl, n-decyl, etc. Among them, branched alkyl groups such as tert-butyl are preferred.

[0034] The components in (b) above are not particularly limited, but for example, they may include aluminum tri-sec-butoxide, aluminum diisopropoxide mono-sec-butoxide, aluminum isopropoxide, and aluminum ethoxide, among which aluminum tri-sec-butoxide, aluminum isopropoxide, and aluminum ethoxide are preferred, and aluminum tri-sec-butoxide and aluminum isopropoxide are even more preferred. They can be used alone or in combination of two or more. Furthermore, commercially available products containing components in (b) above include, but are not limited to, Organiatics AL-3001 (manufactured by Matsumoto Fine Chemicals), AMD, ASBD, AIPD, PADM, and aluminum ethoxide (Kawaken Fine Chemicals).

[0035] The amount of component (b) added relative to component (c) below, per 100 parts by weight, can be 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, and particularly preferably 1 to 10 parts by weight, 2 to 9 parts by weight, 3 to 8 parts by weight, 3 to 7 parts by weight, 3 to 6 parts by weight, or 3 to 5 parts by weight. Within the above range, products with better room temperature curing properties and the ability to inhibit staining of cured products can be obtained.

[0036] In one embodiment of the present invention, the content (mass %) of component (b) in agent A may be 15% by mass or less, 10% by mass or less, 8% by mass or less, or 6% by mass or less. The content (mass %) of component (b) in agent A may be 1% by mass or more, 2% by mass or more, or 3% by mass. The content (mass %) of component (b) in agent A may be 1 to 10% by mass, 2 to 8% by mass, or 3 to 6% by mass.

[0037] In one embodiment of the present invention, the total content (mass%) of component (a) and component (b) in agent A may be 80% or more by mass, 85% or more by mass, 90% or more by mass, 95% or more by mass, 98% or more by mass, or 100% by mass.

[0038] (c) Components The component (c) of this invention is an organic polymer having two or more hydrolyzable silyl groups. In one embodiment of this invention, the component (c) is an organic polymer having six or fewer, four or fewer, or three or fewer hydrolyzable silyl groups.

[0039] In one embodiment of the present invention, the hydrolyzable silyl group is a group consisting of one, two, or three hydrolyzable groups bonded to silicon atoms. In one embodiment of the present invention, the hydrolyzable groups include, for example, hydrogen atoms, halogen atoms, alkoxy groups, acetoxy groups, ketoximate groups, amino groups, acetamino groups, aminooxy groups, mercapto groups, and alkenoxy groups. In one embodiment of the present invention, preferably, an alkoxysilyl group is used as the hydrolyzable silyl group.

[0040] In one embodiment of the invention, the alkoxy group in the alkoxysilyl group can be linear, branched, or cyclic, and from the viewpoint of room temperature curing, a linear group is preferred. The number of carbon atoms in the alkoxy group can be, for example, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1, or 2.

[0041] As an example of component (c) above, it may be an organic polymer having dimethoxysilyl groups, an organic polymer having trimethoxysilyl groups, an organic polymer having diethoxysilyl groups, or an organic polymer having triethoxysilyl groups. Among these, an organic polymer having trimethoxysilyl groups is preferred.

[0042] In one embodiment of the present invention, an organic polymer having two or more hydrolyzable silyl groups containing one or two hydrolyzable groups (e.g., alkoxy groups) and an organic polymer having two or more hydrolyzable silyl groups containing three or more hydrolyzable groups (e.g., alkoxy groups) are used in combination. From the viewpoint of obtaining a product with better room temperature curing properties and better inhibition of staining of the cured product, it is preferable to use an organic polymer having trimethylsilyl groups, or to use a combination of an organic polymer having dimethoxysilyl groups and an organic polymer having trimethoxysilyl groups. In such a combination, the mass ratio between an organic polymer having two or more hydrolyzable silyl groups containing one or two hydrolyzable groups (e.g., alkoxy groups) and an organic polymer having two or more hydrolyzable silyl groups containing three hydrolyzable groups (e.g., alkoxy groups) is not particularly limited, but for example, it can be in the range of 20:80 to 80:20, more preferably in the range of 25:75 to 75:25, and even more preferably in the range of 35:65 to 65:35.

[0043] The hydrolyzable silyl group of component (c) above can be bonded to the end or side chain of the organic polymer, but from the viewpoint of obtaining a cured product with high ductility and high strength, it is preferable to bond to the end. Furthermore, from an operability viewpoint, component (c) is preferably liquid at 25°C. Component (c) can be used alone or in combination of two or more.

[0044] The structure of the organic polymer in component (c) above is not particularly limited, but examples include structures such as polyoxyethylene, polyester, polycarbonate, polyurethane, polyamide, polyurea, polyimide, polyethylene, polypropylene, polyisobutylene, (meth)acrylic acid polymer, polystyrene, polyvinyl chloride, polybutadiene, polyisoprene, polyvinyl butyral, and polyvinyl ether. From the viewpoint of obtaining products with better room temperature curing properties and better inhibition of staining of cured products, a structure of polyoxyethylene, polyisobutylene, and (meth)acrylic acid polymer is preferred. Alternatively, a mixture of two or more of these components may also be used.

[0045] In one embodiment of the present invention, when it is a mixture of two or more organic polymers containing two or more hydrolyzable silyl groups and organic polymers other than polyoxyethylene containing two or more hydrolyzable silyl groups, the content (mass %) of the polyoxyethylene containing two or more hydrolyzable silyl groups (total if there are two or more) is 80% by mass or more, 85% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass.

[0046] Commercially available products containing two or more hydrolyzable silyl groups as components in (c) above include, for example, SAT010, SAX115, SAT030, SAT030, SAT200, SAT350, SAT400, SAX220, SAX510, SAX530, SAX575, SAX580, SAX710, SAX720, SAX510, SAX530, SAX575, SAX580, SAX710, SAX720, SAX725, SAX750, and SAX7 70, S203, S303, S203H, S303H, S943S, S911S, MA440, MA447, MA451, MA903, MA903M, MA904, S943, MAX923, MAX951, SAX510, SAX520, SAX530, SAX580, etc. (manufactured by Kaneka Corporation), ES-S2410, ES-S2420, ES-S3430, ES-S3610, and ES-S3630 (manufactured by Asahi Glass Corporation). Commercially available products containing the (meth)acrylic acid polymers of component (c) above include, for example, SA100S, SA310S, and OR100S (manufactured by Kaneka Corporation). Commercially available products containing two or more hydrolyzable silyl groups of polyisobutylene, which are also components of (c) above, include, for example, EP100S, EP103S, EP303S and EP505S (manufactured by Kaneka Corporation).

[0047] The amount of component (c) added relative to component (a) is 10-250 parts by weight per 100 parts by weight, preferably 50-200 parts by weight, more preferably 70-150 parts by weight, and may also be 80-140 parts by weight, 85-130 parts by weight, or 95-110 parts by weight. Within the above ranges, products with better room temperature curing properties and better inhibition of staining of cured products can be obtained.

[0048] (d) Components The (d) component of this invention is a curing agent for component (a), and is a compound capable of curing component (a). Specific examples of component (d) include, for instance, amine compounds, polythiol compounds, acid anhydride compounds, etc. Among these, amine compounds are preferred due to their excellent room-temperature curing properties. Furthermore, mixtures of two or more can also be used. From the viewpoint of curing and processability after mixing, component (d) is preferably liquid at 25°C. It can be used alone or in mixtures of two or more.

[0049] Examples of the aforementioned amine compounds include primary amines, secondary amines, tertiary amines, amine adducts, polyamide compounds, and imidazole compounds. Examples of primary amines include aliphatic primary amines, alicyclic primary amines, and aromatic primary amines. There are no particular limitations on the aliphatic primary amines, but examples include ethylenediamine, diethylenetriamine, triethylenetetramine, and hexamethylenediamine. Examples of alicyclic primary amines include menthene diamine, isophorone diamine, N-aminoethylpiperazine, diaminodicyclohexylmethane, and norbornene diamine. Examples of aromatic primary amines include dimethylaminomethylphenol, m-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylamine, and diaminodiethyldiphenylmethane.

[0050] In one embodiment of the present invention, the amine compound may be an aromatic amine having an aromatic ring. In one embodiment of the present invention, the amine compound may be a secondary or tertiary amine. In one embodiment of the present invention, the amine compound may be an aromatic secondary or aromatic tertiary amine. The number of carbon atoms in the alkyl group of the secondary amine (aromatic secondary amine) or tertiary amine (aromatic tertiary amine) is independently 1 to 5, 1 to 4, 1 to 3, 1, or 2. The aromatic ring may contain at least one selected from the group consisting of hydroxyl, carboxyl, halogen atoms, and alkyl groups. In one embodiment of the present invention, the aromatic ring may have an alkylaminoalkylene group. The number of carbon atoms in the alkylaminoalkylene group is 1 to 5, 1 to 4, 1 to 3, 1, or 2. The number of carbon atoms in the alkylaminoalkylene group is 1 to 5, 1 to 4, 1 to 3, 1, or 2.

[0051] There are no particular limitations on the aforementioned secondary or tertiary amines, but examples include piperidine, pyridine, benzyl dimethylamine, 2-(dimethylaminomethyl)phenol, triethylenediamine, dimethylcyclohexylamine, dimethylbenzylamine, dimethylhexylamine, dimethylaminophenol, dimethylaminop-cresol, piperidine, 1,4-diazabicyclo[2.2.2]octane, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]undecene-1, etc. There are no particular limitations on the imidazoles mentioned above, but examples include 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecanylimidazole, 1-isobutyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-undecylimidazole. Imidazoles, 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, etc. Commercially available products include, for example, K-54 (manufactured by Air Products Japan Co., Ltd.). From the viewpoint of excellent curability, compounds with aromatic rings are preferred among the aforementioned secondary and tertiary amines.

[0052] In one embodiment of the present invention, the curing agent used for component (a) is an aromatic compound having an alkylaminoalkylene group. In one embodiment of the present invention, the curing agent used for component (a) may be a phenolic compound having an alkylaminoalkylene group. In one embodiment of the present invention, the phenolic compound may have 1, 2, or 3 alkylaminoalkylene groups. The number of carbon atoms of the alkyl and alkylene groups in the alkylaminoalkylene group is the same as described above.

[0053] In one embodiment of the present invention, when an amine compound is used as component (d), the content ratio (mass%) of the tertiary amine in the amine compound is 80% or more by mass, 85% or more by mass, 90% or more by mass, 95% or more by mass, 98% or more by mass, or 100% by mass.

[0054] In one embodiment of the present invention, the content (mass %) of the above-mentioned amine compound (aromatic compound having alkylaminoalkylene group) in component (d) is 80% or more by mass, 85% or more by mass, 90% or more by mass, 95% or more by mass, 98% or more by mass, or 100% by mass.

[0055] Examples of amine adducts include those obtained by adding a tertiary amine or imidazole compound to an epoxy resin and stopping the reaction midway. Considering storage stability and curing properties, it is best to use a fine powder obtained by pulverizing the epoxy adduct. Commercially available epoxy adducts include, for example, the Amicure series manufactured by Ajinomoto Fine-Techno Co., Ltd., the Fujicure series manufactured by T&K TOKA Co., Ltd., and the Novacure series manufactured by Asahi Kasei Chemicals Co., Ltd.

[0056] There are no particular limitations on the polythiol compounds mentioned above, but examples include 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetra(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyroxyl)butane, tris[(3-mercaptopropyroxyl)-ethyl]-isocyanurate (TEMPIC), 1,3,5-tris(3-mercaptobutyroxyl)-1,3,5- Alkyl polythiols such as triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate) (TMMP), pentaerythritol tetra(3-mercaptopropionate) (PEMP), pentaerythritol tetra(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptopropionate) (DPMP), 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, and polysulfides containing terminal thiol groups.

[0057] There are no particular limitations on the aforementioned acid anhydride compounds, but examples include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylene ethyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylnaphthalic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and maleic anhydride, etc.

[0058] The amount of component (d) added, relative to component (a) as 100 parts by weight, is 1 to 180 parts by weight, more preferably 3 to 140 parts by weight, particularly preferably 5 to 100 parts by weight, and may also be 6 to 50 parts by weight, 7 to 40 parts by weight, 8 to 30 parts by weight, 9 to 20 parts by weight, or 9 to 15 parts by weight. Within the above range, a product with excellent room temperature curing properties and the ability to inhibit staining of the cured product can be obtained.

[0059] Any component In this invention, various elastomers such as curing accelerators, fillers, and styrene copolymers, reactive diluents (monofunctional epoxy monomers), silane coupling agents, fillers, storage stabilizers, antioxidants, flame retardants, light stabilizers, heavy metal passivators, plasticizers, defoamers, pigments, rust inhibitors, leveling agents, dispersants, rheology modifiers, flame retardants, and surfactants may be added within a range that does not impair the purpose of this invention.

[0060] In one embodiment of the present invention, a two-component curable resin composition is provided, comprising Agent A and Agent B as described below, and comprising at least one additive selected from the group consisting of curing accelerators, fillers, elastomers (such as styrene copolymers), reactive diluents (monofunctional epoxy monomers), silane coupling agents, fillers, storage stabilizers, antioxidants, flame retardants, light stabilizers, heavy metal passivators, plasticizers, defoamers, pigments, rust inhibitors, leveling agents, dispersants, rheology modifiers, flame retardants, and surfactants: Agent A: A composition comprising (a) and (b) components. (a) Composition: Epoxy resin with two or more epoxy groups per molecule; (b) Ingredients: Aluminum alkoxide catalyst; Agent B: A composition containing components (c) and (d). (c) Ingredients: Organic polymers containing two or more hydrolyzable silyl groups; (d) Ingredients: (a) Ingredients are used as hardeners.

[0061] In this invention, fillers may be added to improve the elastic modulus and flowability of the hardened material. Specific examples include organic powders, inorganic powders, and metal powders.

[0062] Examples of fillers for inorganic powders include glass, fumed silica, mica, ceramics, silicone rubber powder, calcium carbonate, carbon powder, kaolin, dried clay minerals, and dried diatomaceous earth. Examples of fillers for the aforementioned organic powders include polyethylene, polypropylene, nylon, cross-linked acrylic acid, cross-linked polystyrene, polyester, polyvinyl alcohol, polyvinyl butyral, and polycarbonate. Examples of fillers for metallic powders include gold, silver, copper, alumina, and aluminum nitride. There are no particular limitations on the amount of filler used, but when combined with agent A, it should be 0.1 to 300 parts by weight relative to component (a) when it is 100 parts by weight; when combined with agent B, it should be 0.1 to 300 parts by weight relative to component (c) when it is 100 parts by weight. Within these ranges, hardened materials with high ductility and high strength, and excellent processability, can be obtained.

[0063] The aforementioned fumed silica is added to adjust the viscosity of the two-component curable resin composition and improve the mechanical strength of the cured product. Preferably, fumed silica surface-treated with dimethylsilane, trimethylsilane, alkylsilane, methacryloyloxysilane, organochlorosilane, polydimethylsiloxane, or hexamethyldisilazane is used. Commercially available products of 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 (manufactured by Nippon Aerosil Inc.), and TS720 (Cabonet Corporation).

[0064] Examples of the aforementioned preservation stabilizers include tetrafunctional alkoxysilanes such as tetramethoxysilane and tetraethoxysilane; and silicate compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyl silicate, propyl silicate, and butyl silicate. These can be used alone or in combination of two or more.

[0065] The two-component curable resin composition of the present invention comprises agent A and agent B. Agent A is a composition containing components (a) and (b), and agent B is a composition containing components (c) and (d). Separating the components into separate liquids avoids unnecessary reactions during storage and improves storage stability. In this two-component curable resin composition, individual liquids can be manufactured by mixing them using the method described above. The two liquids are then mixed before use. Furthermore, relative to 100 parts by weight of agent A, agent B ranges from 10 to 300 parts by weight, preferably 30 to 200 parts by weight, and particularly preferably 50 to 150 parts by weight.

[0066] hardened material The cured product obtained by curing the two-component curable resin composition of the present invention is also an embodiment of the present invention.

[0067] use The two-component curable resin composition of this invention has good room temperature curing properties and can inhibit staining of the cured material. Therefore, it can be used in various applications such as adhesives, sealants, potting compounds, coatings, lining materials, heat dissipation materials, and conductive pastes. Among these, it is preferred for use as a structural adhesive. The specific applications of the structural adhesive are not particularly limited, but examples include bonding panels to each other in automobile doors, pillars, and roofs; bonding the body to the roof; and bonding motor magnets.

[0068] complex The composite bonded using the two-component curable resin composition of the present invention is also an embodiment of the present invention.

[0069] The two-component curable resin composition of the present invention is suitable as an adhesive. There are no particular limitations on the adhered materials, but examples include metal-to-metal, metal-to-plastic, metal-to-rubber, metal-to-glass, plastic-to-rubber, plastic-to-glass, plastic-to-plastic, rubber-to-rubber, rubber-to-glass, and glass-to-glass, among which metal-to-metal, metal-to-plastic, and plastic-to-plastic are preferred.

[0070] The aforementioned metals are not particularly limited, but examples include gold, silver, iron, aluminum, magnesium, copper, stainless steel, and titanium. Similarly, the aforementioned plastics are not particularly limited, but examples include fiber-reinforced plastics (FRP), carbon fiber-reinforced plastics (CFRP), polyacrylic acid, polyester, polyamide, acrylonitrile-butadiene-styrene, nylon 6, polycarbonate, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyphenylene ether, polyetheretherketone, polyethylene, and polypropylene. Furthermore, the aforementioned rubbers are not particularly limited, but examples include nitrile rubber, butyl rubber, polyurethane rubber, silicone rubber, and ethylene propylene diene monomer (EPDM). For example, adhesion between at least two of these materials is permitted. The surfaces of the aforementioned materials may be pre-treated or left untreated. [Example]

[0071] The following embodiments are provided to illustrate the invention in more detail, but the invention is not limited to these embodiments.

[0072] The test methods used in the embodiments and comparative examples are described below.

[0073] Preparation of two-component curable resin composition Sample each component according to the mass parts shown in Table 1, and mix them in a mixer at room temperature for 60 minutes to prepare Agent A and Agent B equivalent to the two-component curing resin composition. Furthermore, detailed preparation amounts are as shown in Table 1, and all values ​​are expressed in parts by mass.

[0074] (a) Ingredients: a1-1 (equivalent to component (a-1)): Hydrogenated bisphenol A type epoxy resin (HBE-100 manufactured by Shin Nippon Rikan Ka Co., Ltd.) a2-1 (equivalent to component (a-2)): Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER828). (b) Components and Comparative Components: b1: Aluminum tri-sec-butoxide with an active ingredient content of 99% or more (manufactured by Matsumoto Fine Chemicals Co., Ltd., AL-3001) b'1: Aluminum-based chelation catalyst (Shin-Etsu Chemical Co., Ltd., DX-9740) b'2: Diisopropoxydititanium (acetylacetone) with an active ingredient content of 75% by mass or higher (manufactured by Matsumoto Fine Chemicals Co., Ltd. TC-100) b'3: Tetra-n-butoxide titanium (manufactured by Matsumoto Fine Chemicals Co., Ltd., TA-21) with an active ingredient content of 99% or more by mass. b'4: Phosphoric acid catalyst (Shin-Etsu Chemical Co., Ltd., X-40-2309A) (c) Ingredients: c1: A polyoxyethylene compound that is liquid at 25°C and contains dimethoxysilyl groups at both ends (manufactured by Kaneka Corporation, SAX-750). c2: A polyoxyethylene compound that is liquid at 25°C and contains trimethoxysilyl groups at both ends (manufactured by Kaneka Corporation, SAX-575). (d) Ingredients: d1: 2,4,6-Tris(dimethylamino)methylphenol (manufactured by Air Products Japan Co., Ltd., K-54) is liquid at 25°C.

[0075] The test methods for the embodiments and comparative examples in Table 1 are described below.

[0076] (1) Visual confirmation of the hardened material 100 g of agent A and 100 g of agent B of each two-component curing resin composition were mixed at 25°C. The mixed resin composition was visually confirmed to be white. Next, the mixed resin composition was placed in a polyethylene container and allowed to stand at 25°C and 50% RH for 168 hours to prepare the cured product. The appearance of the cured product was visually evaluated based on the following evaluation criteria. The results are shown in Table 1.

[0077] Evaluation criteria ◎: A transparent or white hardened substance, with no visible yellow or brown color throughout. ○: A transparent or white hardened substance, but some parts may appear yellow or brown. ×: Hardened material that is yellow or brown in color.

[0078] (2) Confirmation of room temperature curing properties (surface drying time) 100 g of component A and 100 g of component B of each two-component curable resin were mixed at 25°C. The mixed curable resin composition was then coated onto a 250 μm thick glass slide. At 25°C and 50% RH, the surface of the mixed curable resin composition was touched with a wooden stick every 5 minutes, and curing was evaluated by the disappearance of tackiness. The curing time was defined as the tack-free time (in minutes). The results are shown in Table 1. The preferred tack-free time was 3–140 minutes, particularly preferred was 5–65 minutes, even more preferred was 5–50 minutes, and optimal was 7–25 minutes.

[0079] (3) Visual inspection of Agent A before curing and (4) Visual inspection of Agent B before curing The appearance of Agent A and Agent B before hardening was evaluated visually.

[0080] Table 1

[0081] Based on the results of Examples 1 to 5 in Table 1, it can be confirmed that the two-component curable resin composition of the present invention has excellent room temperature curing properties and can suppress staining of the cured material.

[0082] Comparative Examples 1-4 are two-component curable resin compositions using comparative components b'1-b'4 other than component (b) of this application, but they are inferior in terms of room temperature curing properties or the appearance of the cured product. [Industrial Utilization]

[0083] The two-component curable resin composition of this invention exhibits excellent room-temperature curing properties and inhibits staining of the cured material, making it suitable for various applications such as adhesives, sealants, potting compounds, coatings, lining materials, heat dissipation materials, and conductive pastes. Therefore, it has wide applicability and is industrially useful.

[0084] This application is based on Japanese Patent Application No. 2021-206146, filed on December 20, 2021, the entire contents of which are incorporated herein by reference.

Claims

1. A two-component curable resin composition comprising the following A agent and B agent: A agent: a composition comprising component (a) and component (b): (a) component: an epoxy resin having two or more epoxy groups in one molecule; and (b) component: an aluminum alkoxide catalyst; B agent: a composition comprising component (c) and component (d): (c) component: an organic polymer having two or more hydrolyzable silyl groups; and (d) component: a curing agent for component (a).

2. The two-component curable resin composition as described in claim 1, wherein, The component (a) is a hydrogenated epoxy resin having two or more epoxy groups in one molecule of component (a-1) and / or a bisphenol type epoxy resin having two or more epoxy groups in one molecule of component (a-2).

3. The two-component curable resin composition as described in claim 1 or 2, wherein, The hydrolyzable silyl group of component (c) is dimethoxysilyl or trimethoxysilyl.

4. A two-component curable resin composition as described in claim 1 or 2, wherein, When the B agent is mixed in the range of 10 to 300 parts by mass relative to 100 parts by mass of the A agent, the (c) agent is 10 to 250 parts by mass relative to 100 parts by mass of the (a) agent.

5. A two-component curable resin composition as described in claim 1 or 2, wherein, The (d) component is an amine compound that is liquid at 25°C.

6. The two-component curable resin composition as described in claim 2, wherein, The mass ratio of component (a-1) to component (a-2) is 20:80 to 80:

20.

7. A cured material formed by curing a two-component curable resin as described in claim 1 or 2.