Two-component resin composition and cured product thereof

Abstract

Conventional two-component resin compositions containing a crosslinkable silyl group-containing organic polymer and an epoxy resin have problems, such as long gel times due to slow reaction times, resin dripping when used on surfaces other than flat surfaces, and long tack times for preventing an adherend from moving during processes. The present disclosure addresses the problem of providing a two-component resin composition having excellent gel time and compatibility at 25°C. The problem is solved by a two-component resin composition containing the following components (A) to (E). Component (A): an epoxy resin. Component (B): a chelate-based metal catalyst. Component (C): a crosslinkable silyl group-containing organic polymer. Component (D): a polyether skeleton-containing thiol compound. Component (E): an amine compound. (Components (A)-(E) are not silane coupling agents.)

Description

Two-component resin composition and cured product thereof

[0001] The present invention relates to a two-component resin composition and a cured product thereof, which are excellent in gel time and compatibility at 25°C (short gel time and excellent compatibility when two liquids are mixed).

[0002] Conventionally, a two-component resin composition containing a crosslinkable silyl group-containing organic polymer and an epoxy resin has been used as an adhesive or a sealant for members and parts that cannot be heated because it can be cured at room temperature (about 25°C). However, the reaction of the two-component resin composition is slow, and the time until it loses fluidity (hereinafter also referred to as "gel time") is long. Therefore, when used other than on a flat surface, there are problems such as resin dripping, and it is necessary to suppress the movement of the adherend during work, resulting in a long tact time (working time). To solve such problems, a method of adding water to the two-component resin composition is known to shorten the gel time (International Publication No. 2006 / 075482 (corresponding to US Patent Application Publication No. 2008 / 200607)).

[0003] However, conventional two-component resin compositions that can achieve a short gel time have problems such that the components separate after mixing and a uniform cured product cannot be obtained, or unevenness occurs in the gel time due to separation.

[0004] An object of the present invention is to provide a two-component resin composition having a short gel time and excellent compatibility at 25°C.

[0005] The gist of the present invention is described below. The present invention overcomes the conventional problems described above. [1] A two-component resin composition comprising the following components (A) to (E): (A) component: epoxy resin (B) component: chelate metal catalyst (C) component: crosslinkable silyl group-containing organic polymer (D) component: polyether skeleton-containing thiol compound (E) component: amine compound (However, components (A) to (E) are not silane coupling agents.) [2] The two-component resin composition according to [1], comprising agent A and agent B, wherein agent A is a composition containing component (A) and component (B), and agent B is a composition containing components (C) to (E). [3] The two-component resin composition according to [1] or [2], wherein component (A) is an epoxy resin having two or more epoxy groups. [4] The two-component resin composition according to any one of [1] to [3], wherein component (A) is (a1) a bisphenol-type epoxy resin and / or (a2) a hydrogenated epoxy resin. [5] A two-component resin composition according to any one of [1] to [4], wherein the component (B) comprises a chelate-type titanium catalyst. [6] A two-component resin composition according to any one of [1] to [5], wherein the component (C) comprises an organic polymer having a dimethoxysilyl group. [7] A two-component resin composition according to any one of [1] to [6], wherein the component (C) comprises an organic polymer having a polyether structure. [8] A cured product obtained by curing a two-component resin composition according to any one of [1] to [7].

[0006] The present invention will now be described in detail. The two-component resin composition according to the present invention comprises the following components (A) to (E): (A) Component: epoxy resin (B) Component: chelate metal catalyst (C) Component: crosslinkable silyl group-containing organic polymer (D) Component: polyether skeleton-containing thiol compound (E) Component: amine compound (However, components (A) to (E) are not silane coupling agents.) The two-component resin composition of the present invention exhibits excellent gel time and compatibility at 25°C. In this specification, "X to Y" means including numerical values ​​(X and Y) as lower and upper limits, and means "X or more and Y or less". In this specification, the term (meth)acrylic means both acrylic and methacrylic. In addition, "A and / or B" means including A, B, and combinations thereof.

[0007] Component (A) of the present invention is an epoxy resin. Component (A) is a compound having one or more epoxy groups, and may be solid or liquid, and is not particularly limited. The epoxy groups may be present in the form of glycidyl groups. In terms of excellent gel time and adhesive strength at 25°C, component (A) preferably contains an epoxy resin having two or more epoxy groups, and more preferably contains an epoxy resin having two epoxy groups. Furthermore, in terms of the workability of the two-component resin composition, component (A) is preferably liquid, and more preferably liquid at 25°C. In this specification, "liquid" means a state in which it has fluidity (liquid) at 25°C. Specifically, "liquid at 25°C" means that at 25°C, the shear rate is 10 s using a cone-plate rotational viscometer. －１This refers to epoxy resins whose viscosity, as measured, is 100 Pa·s or less. As an example, the viscosity of the epoxy resin used as component (A) at 25°C is preferably 0.01 Pa·s or more and less than 100 Pa·s, more preferably 0.1 to 50 Pa·s, even more preferably 0.3 to 10 Pa·s, and particularly preferably 0.5 to 5 Pa·s. Examples of component (A) include bisphenol-type epoxy resins, hydrogenated epoxy resins obtained by hydrogenating epoxy resins having aromatic rings, 1,2-butanediol diglycidyl ether, 1,3-butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, (poly)ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 2,3-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol. Examples include alkylene glycol-type epoxy resins such as diglycidyl ether and 1,4-cyclohexanedimethanol diglycidyl ether, novolac-type epoxy resins such as phenol novolac-type epoxy resin and cresol novolac-type epoxy resin; glycidylamine compounds such as N,N-diglycidyl-4-glycidyloxyaniline, 4,4'-methylenebis(N,N-diglycidylaniline), tetraglycidyldiaminodiphenylmethane, and tetraglycidyl-m-xylylenediamine; and naphthalene-type epoxy resins having four glycidyl groups. These may be used individually or in combination of two or more. From the viewpoint of excellent adhesive strength, component (A) preferably contains (a1) a bisphenol-type epoxy resin and / or (a2) a hydrogenated epoxy resin, more preferably both a bisphenol-type epoxy resin and a hydrogenated epoxy resin, and most preferably only a bisphenol-type epoxy resin and a hydrogenated epoxy resin. Furthermore, silane coupling agents, as described later, will not be treated as component (A) even if they have an epoxy group, but as optional components.

[0008] The bisphenol-type epoxy resin is not particularly limited as long as it is an epoxy resin having a bisphenol skeleton. Examples of bisphenol-type epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, urethane-modified bisphenol-type epoxy resin, rubber-modified bisphenol-type epoxy resin, and polyoxyalkylene-modified bisphenol-type epoxy resin. These may be used individually or in combination of two or more. Bisphenol A type epoxy resin and / or bisphenol F type epoxy resin are preferred, and bisphenol A type epoxy resin is more preferred, in terms of excellent gel time.

[0009] Commercially available bisphenol-type epoxy resins are not particularly limited, but examples include jER® 828, 834, 1000, 1001, 806, 807 (manufactured by Mitsubishi Chemical Corporation), Epiclon® 830, 850, 830LVP, 850CRP, 835LV, 860, 1050 (manufactured by DIC Corporation), Adeka Resin® EP4100, EP4400, EP4901, EP4000, EP4000S (manufactured by ADEKA Corporation), D.E.R.®-331, 332, 334 (manufactured by Dow Chemical Company), YD-115, YD-127, YDF-170, YDF-2001 (manufactured by Nippon Steel Chemical & Material Co., Ltd.). These may be used individually or in combination of two or more types.

[0010] The hydrogenated epoxy resin is not particularly limited, but examples include 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 novolac type epoxy resin; and hydrogenated phenol novolac type epoxy resin. Among these, hydrogenated bisphenol type epoxy resin is preferred due to its excellent adhesive strength, and hydrogenated bisphenol A type epoxy resin is more preferred. These may be used individually or in combination of two or more types.

[0011] Examples of commercially available hydrogenated epoxy resins include, but are not limited to, YX8000, YX8034 (manufactured by Mitsubishi Chemical Corporation), RikaResin® HBE-100 (manufactured by Shin-Nippon Rika Co., Ltd.), EP-4080E (manufactured by ADEKA Corporation), ST-3000 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), and Denacol® EX-252 (manufactured by Nagase ChemteX Corporation). These may be used individually or in combination of two or more.

[0012] In the present invention, it is preferable to use a combination of a bisphenol-type epoxy resin and a hydrogenated epoxy resin as component (A). The mass ratio of the bisphenol-type epoxy resin to the hydrogenated epoxy resin is not particularly limited, but for example, it is 20:80 to 80:20, preferably 30:70 to 70:30, and more preferably 40:60 to 60:40. By being within the above range, a two-component resin composition with even better adhesive strength can be obtained.

[0013] When component (A) of the present invention includes (a1) a bisphenol-type epoxy resin and / or (a2) a hydrogenated epoxy resin, from the viewpoint of further improving the effects of the present invention (gel time at 25°C and compatibility), a higher proportion of component (a1) and / or (a2) in component (A) is preferable. That is, the proportion of the mass of (a1) bisphenol-type epoxy resin and / or (a2) hydrogenated epoxy resin (the total mass if two or more are included) to the total mass of component (A) is preferably more than 50% by mass, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass (i.e., the two-component resin composition according to the present invention does not contain epoxy resins other than (a1) bisphenol-type epoxy resin and / or (a2) hydrogenated epoxy resin).

[0014] Component (B) used in the present invention is a chelate metal catalyst. A chelate metal catalyst is a compound having a cyclic structure formed by the covalent and / or coordinate bonding of a ligand to a metal species. Component (B) may contain any metal species as long as it is a chelate metal catalyst that hardens component (A). Examples of metal species for component (B) include tin, titanium, zirconium, zinc, and aluminum. Titanium, zirconium, and aluminum are preferred, with titanium being more preferred, in terms of excellent gel time. These may be used individually or in combination of two or more. Examples of ligands include, but are not limited to, acetylacetone, ethyl acetoethyl, octanediol, and phosphate esters.

[0015] Examples of chelate-type titanium catalysts include titanium diisopropoxybis(acetylacetonate), titanium tetraacetylacetonate, titanium diisopropoxybis(ethylacetoacetate), and titanium octylene glycolate. Titanium diisopropoxybis(acetylacetonate) and / or titanium diisopropoxybis(ethylacetoacetate) are preferred due to their excellent gel time, and titanium diisopropoxybis(acetylacetonate) is more preferred. Commercially available chelate-type titanium catalysts include TC-100, TC-245, TC-401, TC-710, and TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.). These may be used individually or in combination of two or more.

[0016] Examples of chelate-type zirconium catalysts include zirconium tetraacetylacetonate, zirconium dibutoxybis(ethylacetoacetate), and zirconium triputoxymonoacetylacetonate. Commercially available examples include ZC-150, ZC-540, ZC-580, and ZC-700 (manufactured by Matsumoto Fine Chemical Co., Ltd.). These may be used individually or in combination of two or more.

[0017] Examples of chelate aluminum catalysts include aluminum trisacetylacetonate and aluminum bisethylacetoacetate monoacetylacetonate. Commercially available examples include AL-3100 and AL-3200 (manufactured by Matsumoto Fine Chemical Co., Ltd.), and aluminum chelate M, aluminum chelate D, and aluminum chelate A (manufactured by Kawaken Fine Chemical Co., Ltd.). These may be used individually or in combination of two or more.

[0018] The amount of component (B) added is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, even more preferably 0.5 to 10 parts by mass, particularly preferably 0.7 to 5 parts by mass, and most preferably 1 to 3 parts by mass, relative to 100 parts by mass of component (A). By adding 0.01 to 30 parts by mass of component (B) relative to 100 parts by mass of component (A), a two-component resin composition with excellent gel time and adhesive strength can be obtained. Furthermore, the amount of component (B) added is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, even more preferably 0.5 to 10 parts by mass, particularly preferably 0.7 to 7 parts by mass, and most preferably 1 to 4 parts by mass, relative to 100 parts by mass of component (C), which will be described later.

[0019] When component (B) of the present invention contains a chelate-type titanium catalyst, from the viewpoint of further improving the effects of the present invention (gel time and compatibility at 25°C), a higher proportion of the chelate-type titanium catalyst in component (B) is preferable. That is, the proportion of the mass of the chelate-type titanium catalyst (total mass if two or more types are included) to the total mass of component (B) is preferably more than 50% by mass, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass (i.e., the two-component resin composition according to the present invention does not contain any chelate-type metal catalysts other than the chelate-type titanium catalyst). Furthermore, from the viewpoint of further improving the effects of the present invention (gel time and compatibility at 25°C), it is preferable that the two-component resin composition according to the present invention does not contain any metal catalysts other than the chelate-type titanium catalyst.

[0020] Component (C) used in the present invention is a crosslinkable silyl group-containing organic polymer. Component (C) is not particularly limited as long as it is an organic polymer having a crosslinkable silyl group in its molecule, but from the viewpoint of excellent adhesive strength, an organic polymer having two or more crosslinkable silyl groups is preferred, and an organic polymer having a crosslinkable silyl group at its terminus is more preferred. In one preferred embodiment, component (C) is an organic polymer having two crosslinkable silyl groups at both ends. Examples of crosslinkable silyl groups include dimethoxysilyl group, trimethoxysilyl group, diethoxysilyl group, and triethoxysilyl group, but from the viewpoint of excellent gel time, dimethoxysilyl group and / or trimethoxysilyl group are preferred. These may be used alone or two or more may be used in combination, but from the viewpoint of excellent gel time, it is preferable to include an organic polymer having a dimethoxysilyl group. Furthermore, from the viewpoint of handling, component (C) is preferably liquid at 25°C. Furthermore, the silane coupling agents and preservative stabilizers described later will not be treated as component (C), but as optional components.

[0021] The structure of the organic polymer of component (C) above is not particularly limited, but examples include polyether, polyester, polycarbonate, polyurethane, polyamide, polyurea, polyimide, polyethylene, polypropylene, polyisobutylene, poly(meth)acrylate, polystyrene, polyvinyl chloride, polybutadiene, polyisoprene, polyvinyl butyral, and polyvinyl ether. From the viewpoint of excellent gel time and adhesive strength, the polyether structure is preferred, and the polyoxyalkylene structure is more preferred. These may be used individually or in combination of two or more.

[0022] Examples of commercially available crosslinkable silyl group-containing organic polymers of component (C) include SAT010, SAX115, SAT030, SAT200, SAT350, SAT400, SAX220, SAX510, SAX530, SAX575, SAX580, SAX710, SAX720, SAX725, SAX750, SAX770, S203, S303, and S203. Examples include H, S303H, S943S, S911S, MA440, MA447, MA451, MA903, MA903M, MA904, S943, MAX923, MAX951, SAX520, etc. (manufactured by Kaneka Corporation), and ES-S2410, ES-S2420, ES-S3430, ES-S3610, ES-S3630, etc. (manufactured by Asahi Glass Co., Ltd.).

[0023] The amount of component (C) added is, for example, 20 to 150 parts by mass, more preferably 30 to 120 parts by mass, even more preferably 40 to 110 parts by mass, particularly preferably 45 to 100 parts by mass, and most preferably 50 to 90 parts by mass, per 100 parts by mass of component (A). A two-component resin composition with excellent adhesive strength can be obtained by adding 20 parts by mass or more of component (C) per 100 parts by mass of component (A), and with excellent gel time by adding 150 parts by mass or less. In particular, from the viewpoint of excellent gel time, the amount of component (C) added is preferably 60 to 90 parts by mass, and more preferably 65 to 85 parts by mass, per 100 parts by mass of component (A). Furthermore, in particular from the viewpoint of excellent adhesive strength, the amount of component (C) added is preferably 45 to 60 parts by mass, per 100 parts by mass of component (A).

[0024] When component (C) of the present invention includes an organic polymer having a polyether structure (backbone) (particularly an organic polymer having a polyether structure and a dimethoxysilyl group), from the viewpoint of further improving the effects of the present invention (gel time at 25°C and compatibility), a higher proportion of the organic polymer having a polyether structure (particularly an organic polymer having a polyether structure and a dimethoxysilyl group) in component (C) is preferable. That is, the proportion of the mass of the organic polymer having a polyether structure (particularly an organic polymer having a polyether structure and a dimethoxysilyl group) (or the total mass if two or more types are included) in the total mass of component (C) is preferably more than 50% by mass, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass (i.e., the two-component resin composition according to the present invention does not contain any component (C) other than the organic polymer having a polyether structure (particularly an organic polymer having a polyether structure and a dimethoxysilyl group)).

[0025] Component (D) used in the present invention is a polyether skeleton-containing thiol compound. Here, "polyether skeleton" refers to the main chain of a polymer in which ether bonds are repeatedly linked. Also, "thiol compound" refers to a compound having a thiol group (SH group). Component (D) is not particularly limited as long as it is a thiol compound having a polyether skeleton, but from the viewpoint of excellent curability, it is preferable to have 1 to 3 thiol groups in the molecule, and more preferably a trifunctional thiol compound. Examples of polyether skeletons include polyoxymethylene skeletons, polyoxyethylene skeletons, polyoxypropylene skeletons, and polyoxybutylene skeletons, but from the viewpoint of excellent adhesive strength, the polyoxypropylene skeleton is preferred. Also from the viewpoint of excellent adhesive strength, it is preferable to have 1 to 5 hydroxyl groups, more preferably 1 to 3, and particularly preferably 3. Furthermore, it is preferable that the hydroxyl groups are located in the side chains. However, compounds that fall under the category of crosslinkable silyl group-containing organic polymers are treated as component (C), even if they are compounds having a polyether skeleton and thiol groups. Furthermore, the silane coupling agents described later, even if they are compounds having a polyether skeleton and thiol groups, will not be treated as component (D) but as optional components.

[0026] (D) Commercially available products of component (D) include, but are not limited to, Polythiol® QE-340M and Thiokol LP® series (manufactured by Toray Fine Chemicals Co., Ltd.).

[0027] The amount of component (D) added is preferably 10 to 100 parts by mass, more preferably 15 to 80 parts by mass, even more preferably 20 to 70 parts by mass, and particularly preferably 25 to 65 parts by mass, per 100 parts by mass of component (A). A two-component resin composition with excellent gel time can be obtained by adding 10 parts by mass or more of component (D) per 100 parts by mass of component (A), and with excellent compatibility can be obtained by adding 100 parts by mass or less of component (D).

[0028] When component (D) of the present invention contains a trifunctional thiol compound (particularly a trifunctional thiol compound having a polyoxypropylene skeleton and hydroxyl groups), from the viewpoint of further improving the effects of the present invention (gel time at 25°C and compatibility), a higher proportion of the trifunctional thiol compound (particularly a trifunctional thiol compound having a polyoxypropylene skeleton and hydroxyl groups) in component (D) is preferable. That is, the proportion of the mass of the trifunctional thiol compound (particularly a trifunctional thiol compound having a polyoxypropylene skeleton and hydroxyl groups) (total mass if two or more types are included) in the total mass of component (D) is preferably more than 50% by mass, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass (i.e., the two-component resin composition according to the present invention does not contain any component (D) other than the trifunctional thiol compound (particularly a trifunctional thiol compound having a polyoxypropylene skeleton and hydroxyl groups)).

[0029] Component (E) used in the present invention is an amine compound. Component (E) acts as an accelerator for the reaction between component (D) and component (A), and also acts as a curing agent for component (A). From the viewpoint of compatibility, component (E) is preferably liquid at 25°C. These can be used individually or in mixtures of two or more. Note that the silane coupling agent described later, even if it is an amine compound, will not be treated as component (E) but as an optional component.

[0030] Examples of amine compounds include primary amines, secondary amines, tertiary amines, amine adduct compounds, polyamide compounds, and imidazole compounds. From the viewpoint of excellent gel time, primary amines, secondary amines, and tertiary amines are preferred, secondary amines and tertiary amines are more preferred, and tertiary amines are most preferred. These can be used individually or in combination of two or more.

[0031] Examples of primary amines include aliphatic primary amines, alicyclic primary amines, and aromatic primary amines. Examples of aliphatic primary amines are not particularly limited, but include ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, and 2-ethylhexylamine. Examples of alicyclic primary amines include mensendiamine, isophoronediamine, N-aminoethylpiperazine, diaminodicyclohexylmethane, and norbornanediamine. Examples of aromatic primary amines include dimethylaminomethylphenol, metaxylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and diaminodiethyldiphenylmethane.

[0032] The secondary or tertiary amine is not particularly limited, but examples include piperidine, pyridine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, triethylenediamine, dimethylcyclohexylamine, dimethylbenzylamine, dimethylhexylamine, dimethylaminophenol, dimethylamino p-cresol, 1,4-diazadicyclo[2.2.2]octane, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]undecene-1, etc. From the viewpoint of excellent gel time, compounds having an aromatic ring are preferred as secondary and tertiary amines, and 2,4,6-tris(dimethylaminomethyl)phenol is more preferred. Examples of commercially available products include Ankamin® K-54 (Air Products Japan Co., Ltd.).

[0033] The amount of component (E) added is 0.01 to 50 parts by mass, more preferably 0.05 to 20 parts by mass, even more preferably 0.1 to 15 parts by mass, and most preferably 1 to 10 parts by mass, per 100 parts by mass of component (A). Adding 0.01 to 50 parts by mass of component (E) per 100 parts by mass of component (A) yields a two-component resin composition with excellent gel time. Alternatively, the amount of component (E) added is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, even more preferably 2 to 25 parts by mass, and most preferably 5 to 20 parts by mass, per 100 parts by mass of component (D). Adding 0.1 to 50 parts by mass of component (E) per 100 parts by mass of component (D) yields a two-component resin composition with excellent gel time.

[0034] When component (E) of the present invention contains a tertiary amine, a higher proportion of the tertiary amine in component (E) is preferable from the viewpoint of further improving the effects of the present invention (gel time and compatibility at 25°C). That is, the proportion of the mass of the tertiary amine (total mass if two or more types are included) to the total mass of component (E) is preferably more than 50% by mass, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass (i.e., the two-component resin composition according to the present invention does not contain any component (E) other than the tertiary amine).

[0035] In the present invention, additives such as curing accelerators, fillers, various elastomers such as styrene copolymers, reactive diluents, silane coupling agents, preservative stabilizers, antioxidants, light stabilizers, heavy metal deactivators, defoamers, pigments, dyes, solvents, rust inhibitors, leveling agents, dispersants, rheology modifiers, flame retardants, and surfactants may or may not be included (they may not contain any additives), as long as they do not impair the objectives of the present invention.

[0036] In the present invention, fillers may be added for the purpose of improving adhesive strength and resin strength, and imparting functionalities such as heat dissipation and flame retardancy. Examples of fillers include organic powders, inorganic powders, and metallic powders. Examples of inorganic powder fillers include glass powder, talc powder, fumed silica powder, mica powder, ceramic powder, silicone rubber powder, calcium carbonate powder, boron nitride powder, silicon nitride powder, carbon powder, kaolin clay, dried clay minerals, and dried diatomaceous earth. Examples of organic powder fillers include polyethylene, polypropylene, nylon, crosslinked acrylic, crosslinked polystyrene, polyester, polyvinyl alcohol, polyvinyl butyral, and polycarbonate. Examples of metallic powder fillers include gold powder, silver powder, copper powder, alumina powder, aluminum nitride powder, aluminum hydroxide powder, magnesium oxide powder, and magnesium nitride powder. The amount of filler added is not particularly limited, but is preferably 0.1 to 90% by mass, more preferably 0.5 to 85% by mass, and most preferably 1 to 80% by mass, relative to the total amount of the two-component resin composition. An amount of 0.1 to 90% by mass can improve adhesive strength and resin strength, and impart functionalities such as heat dissipation and flame retardancy.

[0037] Fumed silica is added to two-component resin compositions for the purpose of adjusting the viscosity or improving the resin strength of the cured product. Preferably, fumed silica surface-treated with dimethylsilane, trimethylsilane, alkylsilane, methacryloxysilane, organochlorosilane, polydimethylsiloxane, hexamethyldisilazane, etc. is used. Examples of commercially available fumed silica include Aerosil® R972, R972V, R972CF, R974, R976, R976S, R9200, RX50, NAX50, NX90, RX200, RX300, R812, R812S, R8200, RY50, NY50, RY200S, RY200, RY300, R104, R106, R202, R805, R816, R711, RM50, R7200, etc. (manufactured by Nippon Aerosil Co., Ltd.), and TS720 (Cabot Corporation).

[0038] A preservative stabilizer is an additive that prevents the components of a two-component resin composition from reacting during storage. For example, a preservative stabilizer for component (C) is a silane compound having only a hydrolyzable alkoxy group as a reactive group (preferably a compound with a molecular weight of 1000 or less). Typically, it is of formula R １ ｎ -Si-(O-R ２ ) ４－ｎ (In the formula, R １ Each of these is an alkyl group having 1 to 4 carbon atoms, and R ２ Each of the elements is an alkyl group having 1 to 4 carbon atoms, and n is an integer from 0 to 3. A silane compound represented by ( ) is preferred. Examples of such preservative stabilizers include tetrafunctional alkoxysilanes such as tetramethoxysilane, tetraethoxysilane (ethyl silicate), tetrapropoxysilane (propyl silicate), and tetrabutoxysilane (butyl silicate), and alkylalkoxysilanes represented by methyltrimethoxysilane and methyltriethoxysilane. These may be used alone or in combination of two or more. The above preservative stabilizers are not treated as component (C) or as silane coupling agents as described later.

[0039] Silane coupling agents are compounds that have both a crosslinkable silyl group (e.g., trifunctional alkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, and tris(β-methoxyethoxy)silyl groups; monofunctional or bifunctional alkylalkoxysilyl groups such as methyldimethoxysilyl and methyldiethoxysilyl groups) and a reactive group other than a crosslinkable silyl group (e.g., glycidyl, vinyl, acryloxy, methacryloxy, amino, mercapto, and chloro groups). Examples of silane coupling agents include glycidyl group-containing silane coupling agents such as 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane; vinyl group-containing silane coupling agents such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane; (meth)acrylic group-containing silane coupling agents such as 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-acryloxypropyltrimethoxysilane; and 3-aminopropyl Examples of amino group-containing silane coupling agents include ropiltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and their oligomers. However, glycidyl group-containing silane coupling agents and amino group-containing silane coupling agents are preferred in terms of improving adhesive strength, and it is even more preferable to use a glycidyl group-containing silane coupling agent and an amino group-containing silane coupling agent in combination, with the most preferable being the combination of 3-glycidoxypropyltrimethoxysilane and 3-(2-aminoethyl)aminopropyltrimethoxysilane. These may be used individually or in combination of two or more, but it is more preferable to use a glycidyl group-containing silane coupling agent and an amino group-containing silane coupling agent in combination in terms of improving adhesive strength.From the viewpoint of excellent storage stability, the glycidyl group-containing silane coupling agent is preferably contained in a liquid different from the component (E), and the amino group-containing silane coupling agent is preferably contained in a liquid different from the component (A). Further, the silane coupling agent is not treated as the components (A) to (E), and the silane compound contained in the storage stabilizer is not treated as the silane coupling agent.

[0040] Commercially available products of the silane coupling agent are not particularly limited. For example, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-403, KBM-502, KBE-502, KBM-503, KBE-503, KBM-5103, KBM-1403, KBM-602, KBM-603, KBM-903, KBE-903 (manufactured by Shin-Etsu Chemical Co., Ltd.), Z-6610, Z-6044, Z-6825, Z-6033, Z-6062, Z-6094 (manufactured by Toray Dow Corning Co., Ltd.), etc. can be mentioned.

[0041] The content of the silane coupling agent is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and most preferably 0.1 to 5% by mass with respect to the whole two-component resin composition. Further, the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and most preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (A). By setting the content of the silane coupling agent with respect to the whole two-component resin composition to be 0.01 to 10% by mass, a cured product excellent in adhesive strength can be obtained.

[0042] The two-component resin composition of the present invention is preferably a two-component mixed curable resin composition composed of two liquids, namely Agent A and Agent B. It is preferable that component (A) and component (E) are contained in different liquids, and it is also preferable that component (B) and component (C) are contained in different liquids. Since component (A) and component (E), and component (B) and component (C) will gradually react and cure when present in the same liquid, by separating them into separate liquids, unnecessary reactions during storage can be suppressed, and the storage stability can be enhanced. That is, according to a preferred form, Agent A is a composition containing component (A) and component (B), and Agent B is a composition containing component (C) and component (E). Component (D) may be contained in either Agent A or Agent B, but since there is a concern that it may react with component (A) and cure, it is preferably contained in a liquid different from component (A). That is, according to the most preferred form, Agent A is a composition containing component (A) and component (B), and Agent B is a composition containing component (C), component (D), and component (E). Optional components such as silane coupling agents and fillers may be contained in either Agent A or Agent B.

[0043] The addition amount of component (B) in Agent A is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass, based on 100 parts by mass of component (A).

[0044] The addition amount of component (D) in Agent B is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, and most preferably 20 to 120 parts by mass, based on 100 parts by mass of component (C). Also, the addition amount of component (E) in Agent B is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and most preferably 5 to 20 parts by mass, based on 100 parts by mass of component (C).

[0045] Two-component resin compositions are used by mixing the two liquids together. The mixing ratio of component A to component B is 95:5 to 5:95 by mass, more preferably 90:10 to 10:90, particularly preferably 80:20 to 20:80, and most preferably 80:20 to 50:50. A ratio of 95:5 to 5:95 yields a two-component resin composition with excellent gel time and adhesive strength.

[0046] A cured product obtained by curing the two-component resin composition of the present invention is also an embodiment of the invention. The curing method involves mixing the two components in predetermined ratios and then allowing them to stand at room temperature (preferably 20 to 30°C, more preferably 25°C) for, for example, 12 to 240 hours. The curing time is preferably 24 to 240 hours, more preferably 48 to 192 hours. With such a curing time, the adhesive strength of the two-component resin composition can be fully realized.

[0047] The two-component resin composition of the present invention is preferably used in various applications such as adhesives, encapsulants, sealants, potting agents, coatings, lining materials, heat dissipation materials, conductive pastes, and structural bonding applications. The adherend is not particularly limited, but examples include metals, magnets, plastics, rubber, glass, and wood.

[0048] The metals used are not particularly limited, but examples include gold, silver, iron, steel, aluminum, magnesium, copper, stainless steel, and titanium. The plastics used are not particularly limited, but examples include fiber-reinforced plastics (FRP), carbon fiber reinforced plastics (CFRP), polyacrylic, polyester, polyamide, acrylonitrile-butadiene-styrene, nylon 6, polycarbonate, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyphenylene ether, polyether ether ketone, polyethylene, and polypropylene. The rubbers used are not particularly limited, but examples include nitrile rubber, butyl rubber, urethane rubber, silicone rubber, and EPDM. The two-component resin composition of the present invention is suitably used for bonding two or more adherends selected from these. The surfaces of the adherends may be pre-treated before bonding, or they may be subjected to bonding without treatment.

[0049] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples (hereinafter, a mixture of two-component resin compositions will also be simply referred to as "composition"). In addition, in the following examples, unless otherwise specified, the operations were carried out under conditions of a temperature of 25°C and a relative humidity of 55% RH.

[0050] <Preparation of Two-Part Resin Compositions> The raw materials used in Examples 1-3 and Comparative Examples 1-6 are as follows. Each component was taken in parts by mass as shown in Table 1 and mixed in a mixer at room temperature for 60 minutes to prepare component A and component B, respectively. The detailed preparation amounts are as shown in Table 1, and all values ​​are expressed in parts by mass.

[0051] (A) Components: Epoxy resin - jER828 (Bisphenol A type epoxy resin epoxy group: bifunctional, liquid at 25°C, manufactured by Mitsubishi Chemical Corporation) - Ricarezin HBE-100 (Hydrogenated bisphenol A type epoxy resin epoxy group: bifunctional, liquid at 25°C, manufactured by Shin Nippon Rika Co., Ltd.) (B) Components: Chelate metal catalyst - TC-100 (Titanium diisopropoxybis(acetylacetonate), manufactured by Matsumoto Fine Chemical Co., Ltd.) (B') Components: Non-chelate metal catalyst - TA-80 (Tetraisopropyl titanate, manufactured by Matsumoto Fine Chemical Co., Ltd.) (C) Components: Crosslinkable silyl group-containing organic polymer - SAX-750 (Polyoxyalkylene containing dimethoxysilyl groups at both ends, liquid at 25°C, manufactured by Kaneka Corporation) (D) Component: Polyether skeleton-containing thiol compound - Polythiol QE-340M (a thiol compound having a polypropylene oxide skeleton and three hydroxyl groups in the side chain, SH functional group: trifunctional, manufactured by Toray Industries, Inc.) (D') Component: Thiol compound without a polyether skeleton - PEMP (pentaerythritol tetrakis(3-mercaptopropionate), SH functional group: tetrafunctional, manufactured by Sakai Chemical Industry Co., Ltd.) (E) Component: Amine compound - Ankamin K-54 (2,4,6-tris(dimethylaminomethyl)phenol, manufactured by Air Products Japan Co., Ltd.) Optional components - Aerosil R805 (fumed silica surface-treated with alkylsilane filler, manufactured by Nippon Aerosil Co., Ltd.) - KBM-403 (silane coupling agent, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) - Z-6094 (silane coupling agent) 3-(2-aminoethyl)aminopropyltrimethoxysilandau (manufactured by Toray Industries, Inc.)

[0052] <Compatibility> Agents A and B listed in Table 1 were placed in an ointment container in an equal mass ratio and mixed for 1 minute using a wooden stick at 25°C and 55% RH. The mixed composition was left to stand at 25°C for 5 minutes, and the state of the composition after 5 minutes was visually checked to see if separation had occurred. If no separation was observed, it could be judged that the compatibility was excellent. Compatibility was judged according to the following evaluation criteria, and "○" is preferable. [Compatibility Evaluation Criteria] ○: No separation was observed ×: Separation was observed

[0053] <Gel Time> Agents A and B, as listed in Table 1, were placed in an ointment container in equal mass ratios and mixed for 1 minute using a wooden stick at 25°C and 55% RH. The container containing the mixed composition was placed on a flat surface, and the composition was lifted with the wooden stick every minute. The time it took for the liquid surface of the composition in the container to become flat was then measured. If it took 10 seconds or more for the liquid surface to become flat, it was judged that fluidity had been lost, and this time was recorded as the "gel time". From the viewpoint of shortening the cycle time, a gel time of less than 20 minutes is preferable, 15 minutes or less is more preferable, and 12 minutes or less is most preferable. In addition, there is no particular lower limit to the gel time, but from the viewpoint of workability, 1 minute or more is preferable, 3 minutes or more is more preferable, and 5 minutes or more is most preferable. For Comparative Examples 4 and 6, which showed "×" for compatibility, the gel time was not measured. In the table, not measured is indicated with "-". Also, in this test, if fluidity was observed at the measurement after 60 minutes, no further measurements were taken, and it was indicated as "60 or more".

[0054] <Tensile Shear Adhesion> Using the two-component resin compositions prepared in Examples 1-3 and Comparative Examples 1-3 and 5, test specimens were prepared under the following conditions, and tensile shear adhesion tests were conducted. Components A and B of the Examples and Comparative Examples were mixed in equal mass ratios to obtain the compositions. Then, the compositions were applied to SPCC-SD test pieces measuring 25 mm wide x 100 mm long x 1.6 mm thick. Another SPCC-SD test piece measuring 25 mm wide x 100 mm long x 1.6 mm thick was bonded to the SPCC-SD test piece with an overlap of 25 mm x 10 mm and secured with clips. In this test, the time from mixing to securing with clips was less than 1 minute. The specimens were then left to stand for 168 hours at 25°C and 55% RH to obtain the test specimens. For the test specimens, the maximum strength [MPa] was measured at 25°C using a universal tensile testing machine (tensile speed 10 mm / min.) in accordance with JIS K 6850:1999, and this was defined as the tensile shear adhesive strength (SPCC-SD) [MPa]. The above test was also performed on a polybutylene terephthalate (PBT) test piece measuring 25 mm wide x 100 mm long x 1.0 mm thick, and the tensile shear adhesive strength (PBT) [MPa] was recorded. The tensile shear adhesive strength is preferably 1.0 MPa or higher, more preferably 1.5 MPa or higher, and most preferably 2.0 MPa or higher. In particular, the tensile shear adhesive strength (SPCC-SD) is preferably 2.3 MPa or higher, more preferably 2.5 MPa or higher, even more preferably 3.0 MPa or higher, and especially preferably 3.2 MPa or higher. Furthermore, the tensile shear bond strength (PBT) is preferably 2.4 MPa or higher, more preferably 2.5 MPa or higher, and even more preferably 2.7 MPa or higher. While there is no particular upper limit, it is preferably 20 MPa or lower, more preferably 15 MPa or lower, and most preferably 10 MPa or lower. In addition, the tensile shear bond strength was not measured for Comparative Examples 4 and 6, which were found to have poor compatibility ("×"). In the table, "-" indicates that measurement was not performed.

[0055] <Confirmation of Failure State> The failure state was visually confirmed using test specimens after measurement of tensile shear adhesion strength (SPCC-SD). While cohesive failure and interfacial failure are possible failure states, when the cured material undergoes interfacial failure, its adhesive strength is affected by the surface condition of the adherend, whereas when it undergoes cohesive failure, it does not depend much on the surface condition of the adherend, and a stable adhesive strength can be obtained. It is preferable for the failure state of the cured material to be cohesive failure. The failure state is judged according to the following evaluation criteria, and it is preferable to be "○". [Evaluation Criteria for Failure State] ○: Cohesive failure across the entire surface ×: Partial interfacial failure or interfacial failure across the entire surface.

[0056]

[0057] The results from Examples 1 to 3 in Table 1 confirm that the two-component resin composition of the present invention exhibits excellent resin compatibility and gel time. Furthermore, regarding adhesive strength, it was confirmed that sufficient strength was achieved with both SPCC-SD and PBT materials, and stable adhesive strength was obtained as the fracture state was cohesive failure. On the other hand, Comparative Example 1, which did not contain component (D) compared to Example 1, showed a long gel time and interfacial fracture. Comparative Example 2, which did not contain component (D) compared to Example 3, showed a very long gel time of over 60 minutes. Comparative Examples 3 and 5 were obtained by replacing component (B) of Example 1 or Comparative Example 1 with component (B'), respectively, and these also showed a very long gel time of over 60 minutes. Comparative Example 4 was obtained by replacing component (B) of Example 2 with component (B'), but it was confirmed that the compatibility between agent A and agent B was low, resulting in separation. Comparative Example 6 is obtained by replacing component (D) of Example 1 with component (D'), but it was confirmed that the compatibility between agent A and agent B was low and separation occurred.

[0058] The two-component resin composition of the present invention exhibits excellent gel time and compatibility at 25°C, thereby shortening the cycle time of work. Therefore, the two-component resin composition of the present invention can be suitably used in various applications such as adhesives, encapsulants, sealants, potting agents, coatings, conductive pastes, heat dissipation materials, and flame retardants, and is industrially useful as it can be applied to a wide range of fields.

[0059] This application is based on Japanese Patent Application No. 2024-227585, filed on 24 December 2024, the disclosures of which are referenced and incorporated in whole.

Claims

1. A two-component resin composition comprising the following components (A) to (E): (A) Component: epoxy resin (B) Component: chelate metal catalyst (C) Component: crosslinkable silyl group-containing organic polymer (D) Component: polyether skeleton-containing thiol compound (E) Component: amine compound (However, components (A) to (E) are not silane coupling agents.) 2. The two-component resin composition according to claim 1, comprising agent A and agent B, wherein agent A is a composition containing component (A) and component (B), and agent B is a composition containing components (C) to (E).

3. The two-component resin composition according to claim 1 or 2, wherein component (A) comprises an epoxy resin having two or more epoxy groups.

4. The two-component resin composition according to claim 1 or 2, wherein component (A) comprises (a1) a bisphenol-type epoxy resin and / or (a2) a hydrogenated epoxy resin.

5. The two-component resin composition according to claim 1 or 2, wherein component (B) comprises a chelate-type titanium catalyst.

6. The two-component resin composition according to claim 1 or 2, wherein the (C) component comprises an organic polymer having a dimethoxysilyl group.

7. The two-component resin composition according to claim 1 or 2, wherein the (C) component comprises an organic polymer having a polyether structure.

8. A cured product obtained by curing the two-component resin composition according to claim 1 or 2.

Images