Epoxy resin composition

Abstract

To provide an epoxy resin composition which is excellent in curability, has high surface hardness of a cured coating film, is excellent in adhesion of the cured coating film, has good appearance of the cured coating film, prevents occurrence of sagging even when an uncured coating film is made into a vertical or inclined state, and is useful as an insulation paste.SOLUTION: An epoxy resin composition contains the following (A) to (C): (A) a urethane modified epoxy resin and / or a polyether modified epoxy resin having an epoxy equivalent of less than 400 g / eq; (B) an imidazole-based compound; and (C) organic modified clay mineral.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an epoxy resin composition. In particular, it relates to an epoxy resin composition useful as an insulating paste or the like.

Background Art

[0002] In the manufacture of electronic devices, electronic components, etc., as a method for forming an insulating layer, a method of applying an insulating paste to a predetermined region on a substrate and drying and curing it is known. As an insulating paste used for such applications, it is required to have excellent curability, excellent surface hardness, excellent adhesion to the substrate, and be able to form a coating film with excellent coating film appearance without problems such as sagging, peeling, and dripping. Patent Document 1 discloses an insulating paste having excellent adhesion strength to a substrate and excellent storage stability. Patent Document 2 discloses an insulating paste having excellent adhesion to a substrate and suppressing bleed-out of the resin component.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] After applying the insulating paste, drying and curing the base material in its original state is disadvantageous in terms of the working space and the like. Therefore, after applying the insulating paste, the base material is dried and cured in a non-horizontal state, for example, in a state where the coating surface is vertical. However, when the coating surface is made vertical after applying the insulating paste to the base material, with conventionally known insulating pastes, sagging occurs and problems arise in the appearance of the coating film, so improvement has been demanded. To suppress the occurrence of sagging, means such as reducing the amount of solvent used and adding a thixotropic agent have been studied, but a satisfactory insulating paste has not been obtained.

[0005] The problem to be solved by the present invention is to provide an epoxy resin composition that is excellent in curability, has a high surface hardness of the cured coating film, has excellent adhesion of the cured coating film, has a good appearance of the cured coating film, does not sag even when the uncured coating film is in a vertical or inclined state, and is useful as an insulating paste or the like.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by an epoxy resin composition having a specific composition, and have completed the present invention. Specifically, it is as follows. [Item 1] The following (A) to (C); (A) A urethane-modified epoxy resin and / or a polyether-modified epoxy resin having an epoxy equivalent of less than 400 g / eq, (B) An imidazole-based compound, (C) An organically modified clay mineral, An epoxy resin composition containing the same. [Item 2] Further, (D) One or more epoxy resins selected from the group consisting of bisphenol-type epoxy resins, triphenylmethane-type epoxy resins, fluorene-type epoxy resins, naphthalene-type epoxy resins, and phenol novolak-type epoxy resins, The epoxy resin composition according to Item 1, containing the same.

Effects of the Invention

[0007] According to the present invention, there is provided an epoxy resin composition which has excellent curability, a high surface hardness of the cured coating film, excellent adhesion of the cured coating film, a good appearance of the cured coating film, no sagging even when the uncured coating film is in a vertical or inclined state, and is useful as an insulating paste or the like.

Mode for Carrying Out the Invention

[0008] The epoxy resin composition of the present invention is an epoxy resin composition containing (A) a urethane-modified epoxy resin and / or a polyether-modified epoxy resin having an epoxy equivalent of less than 400 g / eq, (B) an imidazole-based compound, and (C) an organically modified clay mineral. The epoxy resin composition of the present invention may further contain (D) one or more epoxy resins selected from the group consisting of bisphenol type epoxy resins, triphenylmethane type epoxy resins, fluorene type epoxy resins, naphthalene type epoxy resins, and phenol novolak type epoxy resins. Hereinafter, the epoxy resin composition of the present invention will be described in detail.

[0009] [Component (A)] Component (A), which is a constituent component of the epoxy resin composition of the present invention, is a urethane-modified epoxy resin and / or a polyether-modified epoxy resin having an epoxy equivalent of less than 400 g / eq.

[0010] [Urethane-Modified Epoxy Resin] The urethane-modified epoxy resin is not particularly limited as long as it is an epoxy resin having one or more urethane skeletons and epoxy groups in the molecule. The urethane skeleton has the formula (a1); -O-C(=O)-NH- ···(a1) and is a structure represented by the above formula. The urethane-modified epoxy resin may be used alone or in combination of two or more.

[0011] The urethane-modified epoxy resin can be obtained, for example, by reacting a compound containing a group reactive with an isocyanate group and an epoxy group, a hydroxy group-containing compound, and an isocyanate group-containing compound. Further, it can be obtained by reacting a compound containing a group reactive with an isocyanate group and an epoxy group with a urethane prepolymer containing an isocyanate group. Preferably, it is obtained by reacting a hydroxy group-containing epoxy compound with a urethane prepolymer containing an isocyanate group obtained by reacting a polyhydroxy compound and a polyisocyanate compound.

[0012] Examples of the hydroxy group-containing epoxy resin include hydroxy group-containing bisphenol A type epoxy resins, hydroxy group-containing bisphenol F type epoxy resins, and hydroxy group-containing bisphenol S type epoxy resins, such as hydroxy group-containing bisphenol type epoxy resins; hydroxy group-containing biphenyl type epoxy resins and hydroxy group-containing tetramethylbiphenyl type epoxy resins, such as hydroxy group-containing biphenyl type epoxy resins; hydroxy group-containing naphthalene type epoxy resins; hydroxy group-containing cyclohexanedimethanol type epoxy resins and hydroxy group-containing hydrogenated bisphenol type epoxy resins, such as hydroxy group-containing alicyclic epoxy resins; hydroxy group-containing phenol novolac type epoxy resins, hydroxy group-containing cresol novolac type epoxy resins, hydroxy group-containing bisphenol A novolac type epoxy resins, and hydroxy group-containing biphenyl novolac type epoxy resins, such as novolac type epoxy resins; hydroxy group-containing dicyclopentadiene type epoxy resins; hydroxy group-containing triphenylmethane type epoxy resins; hydroxy group-containing tetraphenylethane type epoxy resins; hydroxy group-containing phenol aralkyl type epoxy resins; and the like. The hydroxy group-containing epoxy resin may be used alone or in combination of two or more.

[0013] The polyhydroxy compound constituting the isocyanate group-containing urethane prepolymer is not particularly limited as long as it is a compound having two or more hydroxy groups. For example, polymer polyols such as polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyolefin polyol, polycarbonate polyol; diols such as ethylene glycol, propylene glycol, 1,4-butylene glycol (tetramethylene glycol), neopentyl glycol; triols such as glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol and trimethylolpropane; polyols such as erythritol, pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,3,5-pentanetetrol and 1,3,4,5-hexanetetrol, arabite, xylitol, sorbitol, mannitol; etc. may be mentioned. The weight average molecular weight of the polymer polyol is not particularly limited, for example, it is 300 or more, preferably 500 or more, and for example, it is 10,000 or less, preferably 5,000 or less.

[0014] The polyisocyanate compound constituting the isocyanate group-containing urethane prepolymer is not particularly limited as long as it is a compound having two or more isocyanate groups. For example, aliphatic polyisocyanate compounds such as methylene diisocyanate, 1,2-dimethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2-methyl-1,5-pentyldiisocyanate, 3-methyl-1,5-pentyldiisocyanate, 1,18-octadecylene diisocyanate, 1,10-decamethylene diisocyanate, bis(2-isocyanatoethyl) fumarate, lysine diisocyanate (2,6-diisocyanatohexanoic acid), 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate;Aromatic polyisocyanate compounds such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, 4,4'-diphenyl ether diisocyanate, 2,4'-diphenyl ether diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 2,6-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, dianisidine diisocyanate, o-phenyl diisocyanate, m-phenyl diisocyanate, p-phenyl diisocyanate, halogenated phenyl diisocyanate, cumene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 5,6-dimethyl-1,3-phenylene diisocyanate, benzidine diisocyanate, 1,4-anthracene diisocyanate, 9,10-anthracene diisocyanate, 4,4'-diisocyanate benzyl; Alicyclic polyisocyanate compounds such as methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,4-(isocyanatomethyl)cyclohexane, 1,3-(isocyanatomethyl)cyclohexane, 1,2-(isocyanatomethyl)cyclohexane, isophorone diisocyanate, dimer acid diisocyanate, bicycloheptane triisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornyl diisocyanate, norbornene methane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, hydrides of the above aromatic polyisocyanates;Examples of these polyisocyanate compounds include biuret compounds, allophanate compounds, adduct compounds, urethane compounds, carbodiimide compounds, polyisocyanate derivatives that are multimers, and the like.

[0015] Examples of urethane-modified epoxy resins include the Adeka Resin series (EPU-6, EPU-7N, EPU-11F, EPU-15F, EPU-1395, EPU-73B, EPU-17, EPU-17T-6, etc.) manufactured by ADEKA Corporation; the Epoxy series (802-30CX, 803, 820-40CX, 830, 834, 840, 810ST, etc.) manufactured by Mitsui Chemicals, Inc.; the EPICLON series (TSR-300, etc.) manufactured by DIC Corporation, and the like.

[0016] The epoxy equivalent of the urethane-modified epoxy resin is not particularly limited. For example, it can be 100 g / eq or more, preferably 150 g / eq or more, more preferably 175 g / eq or more, and can be 1,000 g / eq or less, preferably 700 g / eq or less, more preferably 500 g / eq or less. The epoxy equivalent is the number of grams (g / eq) of an epoxy resin containing 1 equivalent of epoxy groups.

[0017] <Polyether-modified epoxy resin with an epoxy equivalent of less than 400 g / eq> The polyether-modified epoxy resin with an epoxy equivalent of less than 400 g / eq is an epoxy resin having one or more polyether skeletons and epoxy groups in the molecule, and is not particularly limited as long as the epoxy equivalent is less than 400 g / eq. The polyether skeleton has the formula (a2); -(-R a21 -O-)n- ···(a2) In the formula (a2), R a21 is a divalent organic group. Examples of R a21 include an alkylene group and an optionally substituted aryl group, and preferably an alkylene group having 2 to 6 carbon atoms. The polyether-modified epoxy resin may be used alone or in combination of two or more.

[0018] The epoxy resin constituting the polyether-modified epoxy resin is not particularly limited. For example, bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, resorcinol diglycidyl ether, triphenolmethane type epoxy resin, dihydroxynaphthalene type epoxy resin, hydrogenated bisphenol type epoxy resin, hydrogenated biphenyl type epoxy resin, glycidyl ether of aliphatic polyol, glycidylamine type epoxy resin, dicyclopentadiene type epoxy resin, etc. may be mentioned. The epoxy resin may be used alone or in combination of two or more.

[0019] The epoxy equivalent of the polyether-modified epoxy resin is less than 400 g / eq, preferably 390 g / eq or less, and can be, for example, 100 g / eq or more, preferably 200 g / eq or more.

[0020] Examples of the polyether-modified epoxy resin include polyalkylene oxide-modified bisphenol type epoxy resin, polyalkylene oxide phenol novolac type epoxy resin, polyalkylene oxide-modified biphenyl type epoxy resin, polyalkylene oxide-modified dicyclopentadiene type epoxy resin, polyalkylene oxide-modified naphthalene type epoxy resin, polyalkylene oxide-modified fluorene type epoxy resin, polyalkylene oxide-modified cresol novolac type epoxy resin, etc. Examples of the polyether-modified epoxy resin include Adeka Resin series (EP-4000, EP-4000S, EP-4005, EP-7001, EP4080E, etc.) manufactured by ADEKA; EPICLON series (EXA-4850-150, EXA-4850-1000, etc.) manufactured by DIC; AER-9000 manufactured by Asahi Kasei Co., Ltd.; etc.

[0021] <Content of component (A)> The content of component (A) "urethane-modified epoxy resin and / or polyether-modified epoxy resin with an epoxy equivalent of less than 400 g / eq" in the epoxy resin composition is not particularly limited. Taking the total amount of the epoxy resin composition as 100% by mass, it can be, for example, 10.0% by mass or more, preferably 15.0% by mass or more, more preferably 20.0% by mass or more, and can be, for example, 93.0% by mass or less, preferably 90.0% by mass or less, more preferably 87.0% by mass or less.

[0022] [Component (B)] Component (B), which is a component of the epoxy resin composition of the present invention, is an imidazole-based compound. The imidazole-based compound functions as a curing agent and / or a curing accelerator for the epoxy resin.

[0023] Examples of the imidazole-based compound include imidazole compounds, clathrate imidazoles, microcapsule-type imidazoles, imidazole adducts, stabilizer-coordinated imidazoles, etc. Among these, imidazole adducts, clathrate imidazoles, microcapsule-type imidazoles, and stabilizer-coordinated imidazoles are preferably used because they have high curing and curing acceleration ability and excellent pot life. In the present invention, as the imidazole-based compound, an imidazole compound and / or a clathrate imidazole is preferred. The imidazole-based compound may be used alone or in combination of two or more.

[0024] Among imidazole compounds, examples of imidazole compounds include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 1-isopropyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and the like. Among these, from the viewpoint of storage stability and the like, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole are preferable. The imidazole compound may be a commercially available product. For example, the Curezol series (2E4MZ, 2P4MZ, 2PZ-CN, C11Z-CNS, C11Z-A, 2MZA-PW, 2MA-OK, 2P4MHZ-PW, 2PHZ-PW, etc.) manufactured by Shikoku Kasei Kogyo Co., Ltd. and the like can be mentioned.

[0025] Among imidazole compounds, inclusion imidazole is obtained by subjecting an imidazole compound to an inclusion treatment with a host compound, and is an inclusion complex in which the imidazole compound is included in the host compound. Examples of the host compound include dicarboxylic acid compounds, tetrakisphenol compounds, pyridine derivatives, 4,4’,4’’-trihydroxytriphenylmethane, tris(2-hydroxyethyl)isocyanurate, 2,2’,4,4’-tetrahydroxybenzophenone, and the like. Among these, dicarboxylic acid compounds and tetrakisphenol compounds are preferred.

[0026] Examples of the dicarboxylic acid compound, which is the host compound constituting the inclusion imidazole, include isophthalic acid compounds such as 5-t-butylisophthalic acid, 5-nitroisophthalic acid, and 5-hydroxyisophthalic acid, and 2,3-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, and the like. From the viewpoint of storage stability and the like, 5-nitroisophthalic acid and 5-hydroxyisophthalic acid are preferred.

[0027] Examples of the tetrakisphenol compound, which is the host compound constituting the inclusion imidazole, include 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-chloro-4-hydroxyphenyl)ethane, and the like. From the viewpoint of storage stability and the like, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane is preferred.

[0028] Examples of the clathrate imidazole include 5-hydroxyisophthalic acid clathrate 2-methylimidazole, 5-hydroxyisophthalic acid clathrate 2-ethyl-4-methylimidazole, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane clathrate 2-methylimidazole, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane clathrate 2-ethyl-4-methylimidazole, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane clathrate 1-benzyl-2-methylimidazole, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane clathrate 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1,1,2,2-tetrakis(3-methyl-4-hydroxyphenyl)ethane clathrate 1-benzyl-2-methylimidazole, 1,1,2,2-tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane clathrate 1-benzyl-2-methylimidazole, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane clathrate 1-isopropyl-2-methylimidazole, and the like. Commercially available products may be used as the clathrate imidazole. Examples include NISSOCURE TIC-188, KM-188, HIPA-2P4MHZ, NIPA-2P4MHZ, TEP-2E4MZ, HIPA-2E4MZ, NIPA-2E4MZ, etc. manufactured by Nippon Soda Co., Ltd.

[0029] Among the imidazole compounds, the microcapsule-type imidazole is obtained by encapsulating the imidazole compound with a capsule material that is destroyed by heating, such as vinyl compounds, urea compounds, phenol resins, urethane resins, epoxy resins, polyethylene, polypropylene, polystyrene, nylon, polyester, polyvinyl chloride, polyvinylidene chloride, and thermoplastic resins.

[0030] The average particle diameter of the microcapsule-type imidazole is not particularly limited. From the viewpoint of dispersibility in the epoxy resin composition and the like, it can be, for example, 20 μm or less, preferably 12 μm or less. The average particle diameter means the average particle diameter defined by the median diameter. More specifically, it refers to the Stokes diameter measured by the laser diffraction / scattering method using a particle size distribution analyzer.

[0031] Examples of commercially available microcapsule-type imidazoles include the Novacure series (HX3721, HX3722, HX3742, HX3748, HXA3792, etc.) manufactured by Asahi Kasei Corporation; LC-80, etc. manufactured by A&C Catalysts; and the like.

[0032] Among imidazole-based compounds, imidazole adducts are obtained by reacting an imidazole compound with a compound that can react with the imidazole compound to subject the imidazole compound to adduct treatment. Examples thereof include compounds obtained by subjecting an epoxy group-containing compound and an imidazole compound to a ring-opening addition reaction. Commercially available products may be used for imidazole adducts. For example, the Amicure series (PN-23, PN-H, PN-31, PN-40, PN-50, PN-F, PN-23J, PN-31J, PN-40J, PN-50J, etc.) manufactured by Ajinomoto Fine-Techno Co., Inc.; the Cureduct series (e.g., P0505, etc.) manufactured by Shikoku Kasei Kogyo Co., Ltd.; the Adeka Hardener series (EH-3293S, EH-5011S, EH-5046S) manufactured by ADEKA Corporation; the Fujicure series (FXR-1121, etc.) manufactured by T&K TOKA Co., Ltd.; and the like.

[0033] Among imidazole-based compounds, stabilizer-coordinated imidazoles are obtained by subjecting an imidazole-based compound to coordination treatment with a stabilizer. Examples of imidazole-based compounds include various imidazole compounds and imidazole adducts. Examples of stabilizers include epoxy-phenol-borate ester blends and the like. For example, there is an example in which an epoxy-phenol-borate ester blend (e.g., L-07L manufactured by Shikoku Kasei Kogyo Co., Ltd.) is coordinated as a stabilizer to an imidazole adduct (e.g., Cureduct P0505 manufactured by Shikoku Kasei Kogyo Co., Ltd.).

[0034] The content of component (B), the "imidazole-based compound", in the epoxy resin composition is not particularly limited. When the total of component (A), component (D), and the epoxy component as other components in the epoxy resin composition is 100% by mass, as the imidazole compound in the imidazole-based compound, for example, it can be 0.5% by mass or more, preferably 1.0% by mass or more, more preferably 1.5% by mass or more, and for example, it can be 25.0% by mass or less, preferably 20.0% by mass or less, more preferably 16.0% by mass or less. For example, when using an imidazole compound as the imidazole-based compound, the "content of the imidazole compound in the imidazole-based compound" is the same as the amount of the imidazole compound used. On the other hand, when using those containing components other than the imidazole compound, such as clathrate imidazole, microcapsule-type imidazole, and stabilizer-coordinated imidazole as the imidazole-based compound, the amount excluding the components other than the imidazole compound is the "content of the imidazole compound in the imidazole-based compound".

[0035] [Component (C)] Component (C), which is a constituent component of the epoxy resin composition of the present invention, is an organically modified clay mineral. The organically modified clay mineral is a hydrophobicized product obtained by treating a clay mineral with an organic treating agent.

[0036] Examples of the clay mineral constituting the organically modified clay mineral include diatomaceous earth, calcined clay, clay, talc, titanium oxide, kaolinite, bentonite, laponite, hectorite, montmorillonite, magnesium aluminum silicate, phyllosilicate, calcite, dolomite, feldspar, quartz, zeolite, attapulgite, sepiolite, palygorskite, allophane, smectite, etc. As the clay mineral constituting the organically modified clay mineral, one kind may be used alone, or two or more kinds may be used.

[0037] The shape of the clay mineral constituting the organically modified clay mineral is not particularly limited. Examples of the shape include those selected from the group consisting of plate-like, scaly, layered, rod-like, chain-like, needle-like, and fibrous shapes. It is preferable to include clay minerals other than layered ones, and it is more preferable to include rod-like, needle-like, fibrous, and chain-like clay minerals.

[0038] The average particle size (volume average primary particle size) of the clay mineral constituting the organically modified clay mineral is not particularly limited. For example, it can be 0.1 μm or more, preferably 0.2 μm or more, more preferably 0.3 μm or more, and for example, it can be 50 μm or less, preferably 25 μm or less, more preferably 15 μm or less. The average particle size (volume average primary particle size) of the clay mineral can be obtained by measuring it by the laser diffraction method (volume basis) after performing a redispersion treatment such as ultrasonic treatment.

[0039] The organic modifier for organically treating and hydrophobizing the clay mineral constituting the organically modified clay mineral is not particularly limited as long as it can hydrophobize the clay mineral. Examples include quaternary ammonium salt compounds, amine compounds, phosphonium compounds, sulfonium compounds, and the like. The organic modifier may be used alone or in combination of two or more. As the organic modifier, it is preferable to use a quaternary ammonium salt. Examples of the quaternary ammonium salt include alkyl and / or arylalkyl quaternary ammonium salts containing at least one linear or branched saturated or unsaturated alkyl group having 1 to 30 carbon atoms in the molecule. Examples of the anion of the quaternary ammonium salt include chloride, bromide, methyl sulfate, nitrate, hydroxide, acetate, phosphate, and mixtures thereof, and preferably those selected from the group consisting of chloride, bromide, and methyl sulfate.

[0040] In the preparation of the organically modified clay mineral, the amount of the organic modifier used is not particularly limited. For example, it can be 5 mg or more per 100 g of the clay mineral, and for example, it can be 200 mg or less, preferably 100 mg or less.

[0041] The content of the (C) component "organically modified clay mineral" in the epoxy resin composition is not particularly limited. It can be, for example, 1.0% by mass or more, preferably 1.5% by mass or more, more preferably 2.0% by mass or more, and can be, for example, 20.0% by mass or less, preferably 15.0% by mass or less, more preferably 10.0% by mass or less, based on 100% by mass of the total amount of the epoxy resin composition.

[0042] [(D) component] The epoxy resin composition of the present invention may contain, as component (D), one or more epoxy resins selected from the group consisting of bisphenol-type epoxy resins, triphenylmethane-type epoxy resins, fluorene-type epoxy resins, naphthalene-type epoxy resins, and phenol novolac-type epoxy resins, preferably bisphenol-type epoxy resins and / or triphenylmethane-type epoxy resins. In the present invention, the epoxy resin of component (D) is an epoxy resin other than component (A) (urethane-modified epoxy resin, polyether-modified epoxy resin having an epoxy equivalent of less than 400 g / eq).

[0043] <Bisphenol-type epoxy resin> Bisphenol type epoxy resins have the formula (d1) in the molecule; [ka] There are no particular limitations on the epoxy resin, so long as it has one or more bisphenol-type skeletons represented by the following formula and one or more epoxy groups: In formula (d1), d1 is an integer from 0 to 4, and d2 is an integer from 0 to 4. R c is a substituent, R c When there are multiple R, they may be the same or different. c Examples of the substituent include a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, and a cyano group. The substituent may be one type alone or two or more types. X is -CRd11 R d12 -、 -S(=O)2-、 -O-、 -C(=O)-, a group selected from, R d11 and R d12 is hydrogen, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, may be the same or different from each other, and may be bonded to each other to form a ring. In the present invention, X in the formula (d1) is preferably a group selected from -C(CH3)2-, -CH2-, -C(CF3)2-, -S(=O)2-, -O-, -C(=O)-, -C(CH3)(Ph)-, -C(Ph)2-, -C(CH3)(C2H5)-, -CH(C2H5)-, =C(CH2)5 (Ph is a phenyl group).

[0044] Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol AP type epoxy resin, bisphenol E type epoxy resin, bisphenol Z type epoxy resin, etc. Further, a polyether-modified bisphenol type epoxy resin having an epoxy equivalent of 400 g / eq or more may also be used. In the present invention, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol BP type epoxy resin, bisphenol Z type epoxy resin are preferred, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin are more preferred, and bisphenol A type epoxy resin is even more preferred.

[0045] Examples of bisphenol type epoxy resins include, for example, the jER series manufactured by Mitsubishi Chemical Corporation (such as 806, 806H, 807, 825, 827, 828, 828EL, 828US, 828XA, 801N, 811, 813, 816, 819, 1001, 10010, 1002, 1002F, 1003, 1003F, 1004, 1004F, 1004AF, 1005, 1005F, 1007, 1055, 1256, 1256B40, 1255HX30, 1750, 4005P, 4007P, 4010P, YL6810, YL980, YL983U, etc.); the Epotote YD series (011, 012, 013, 014, 017, 019, 020G, 115, 115CA, 127, 128, 128S, 128CA, 134, 825GS, 901, 902, 903N, 904, 907, 7910, 8125, etc.) manufactured by Nippon Steel Chemical & Material Co., Ltd.; the Epotote YDF series (170, 170N, 2001, 2004, etc.) manufactured by Nippon Steel Chemical & Material Co., Ltd.; the DER series (301, 330, 361, etc.) manufactured by Dow Chemical Company; the EPICLON series (830, 830-S, EXA830CRP, EXA830LVP, 835, EXA-835LV, 840, 840-S, 850, 850-S, EXA-850-CP, 850-LC, 855, 857, 860, 1050, 1055, 3050, 4050, 7050, N-865, N-885, N-890, etc.) manufactured by DIC Corporation; the Adeka Resin series (EP-4100, EP-4100G, EP-4100E, EP-4100TX, EP-4100HF, EP-4300, EP-4300E, EP-4400, EP-4520S, EP-4530, EP-4504, EP-4700, EP-4901, EP-4901E, EP-4901HF, etc.) manufactured by ADEKA Corporation; etc., but are not limited thereto. The bisphenol type epoxy resin may be used alone or in combination of two or more.

[0046] <Triphenylmethane type epoxy resin> The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having one or more triphenylmethane skeletons and one or more epoxy groups in the molecule. Examples of the triphenylmethane type epoxy resin include the formula (d2); [Chemical formula] The epoxy resin represented by is mentioned. In formula (d2), d3 is an integer from 0 to 4, d4 is an integer from 0 to 3. When n is 2 or more and there are a plurality of d4, they may be the same or different from each other. d5 is an integer from 0 to 4. When n is 2 or more and there are a plurality of d5, they may be the same or different from each other. n is the number of repeating units and is an integer of 1 or more. R c is a substituent. When there are a plurality of R c , they may be the same or different from each other. Examples of R c include, for example, a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, a cyano group, etc. The substituents may be one kind alone or two or more kinds. The triphenylmethane type epoxy resin preferably has three or more epoxy groups. The triphenylmethane type epoxy resin may be used alone or in combination of two or more.

[0047] Examples of the triphenylmethane type epoxy resin include the EPPN series (501H, 501HY, 502H, etc.) manufactured by Nippon Kayaku Co., Ltd.; FAE-2500, etc. manufactured by Nippon Kayaku Co., Ltd.; the jER series (for example, 1032S50, etc.) manufactured by Mitsubishi Chemical Corporation; the Tactix series (742, etc.) manufactured by Huntsman Advanced Material.

[0048] [Fluorene type epoxy resin] The fluorene type epoxy resin has the formula (d3) in the molecule; [Chemistry] There is no particular limitation as long as it is an epoxy resin having one or more 9,9-bisarylfluorene skeletons represented by the formula and one or more epoxy groups. The fluorene-type epoxy resin preferably has two or more epoxy groups.

[0049] In formula (d3), Ar 1 and Ar 2 are each independently an aromatic hydrocarbon ring which may have a substituent. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a biphenyl ring, a binaphthyl ring; a 1-phenylnaphthalene ring, a 2-phenylnaphthalene ring, a terphenyl ring and the like. Among these aromatic hydrocarbon rings, a benzene ring, a naphthalene ring and a biphenyl ring are preferable, and a benzene ring is more preferable. Ar 1 and Ar 2 The substituents which may be possessed include, for example, a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, a cyano group and the like. The substituents may be a single kind or two or more kinds. In formula (d3), d6 is an integer from 0 to 8, R c is a substituent, and when there are a plurality of R c , they may be the same or different from each other, and the substituents are the same groups as the substituents in the above Ar 1 and Ar 2 .

[0050] Examples of the fluorene-type epoxy resin include, but are not limited to, 9,9-bis(glycidyloxyphenyl)fluorenes, 9,9-bis(polyglycidyloxyphenyl)fluorenes, 9,9-bis(glycidyloxynaphthyl)fluorenes, 9,9-bis(glycidyloxy(poly)alkoxyphenyl)fluorenes, 9,9-bis(polyglycidyloxy(poly)alkoxyphenyl)fluorenes, 9,9-bis(glycidyloxy(poly)alkoxynaphthyl)fluorenes, etc. The fluorene-type epoxy resin may be used alone or in combination of two or more kinds.

[0051] Examples of 9,9-bis(glycidyloxyphenyl)fluorenes include, but are not limited to, 9,9-bis(4-glycidyloxyphenyl)fluorene such as 9,9-bis(glycidyloxyphenyl)fluorene; 9,9-bis(3-methyl-4-glycidyloxyphenyl)fluorene, 9,9-bis(3,5-dimethyl-4-glycidyloxyphenyl)fluorene and other 9,9-bis(mono- or di-C1-C4 alkyl-glycidyloxyphenyl)fluorenes; 9,9-bis(3-phenyl-4-glycidyloxyphenyl)fluorene and other 9,9-bis(mono- or di-C6-C 10 aryl-glycidyloxyphenyl)fluorenes; etc.

[0052] Examples of 9,9-bis(polyglycidyloxyphenyl)fluorenes include, but are not limited to, 9,9-bis(3,4-diglycidyloxyphenyl)fluorene, 9,9-bis(3,5-diglycidyloxyphenyl)fluorene and other 9,9-bis(di- or triglycidyloxyphenyl)fluorenes; etc.

[0053] Examples of 9,9-bis(glycidyloxynaphthyl)fluorenes include, but are not limited to, 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene, 9,9-bis(5-glycidyloxy-1-naphthyl)fluorene and other 9,9-bis(glycidyloxynaphthyl)fluorenes; etc.

[0054] Examples of 9,9-bis(glycidyloxy(poly)alkoxyphenyl)fluorenes include 9,9-bis(glycidyloxy(poly)C2-C4 alkoxy-phenyl)fluorenes such as 9,9-bis[4-(2-glycidyloxyethoxy)phenyl]fluorene; 9,9-bis(mono or di C1-C4 alkyl-glycidyloxy(poly)C2-C4 alkoxy-phenyl)fluorenes such as 9,9-bis[4-(2-glycidyloxyethoxy)-3-methylphenyl]fluorene and 9,9-bis[4-(2-glycidyloxyethoxy)-3,5-dimethylphenyl]fluorene; 9,9-bis(mono or di C6-C 10 Aryl-glycidyloxy(poly)C2-C4 alkoxy-phenyl)fluorene; and the like, but are not limited thereto.

[0055] Examples of 9,9-bis(polyglycidyloxy(poly)alkoxyphenyl)fluorenes include 9,9-bis(di or triglycidyloxy(poly)C2-C4 alkoxy-phenyl)fluorenes such as 9,9-bis(3,4-di(2-glycidyloxyethoxy)phenyl)fluorene and 9,9-bis(3,5-di(2-glycidyloxyethoxy)phenyl)fluorene; and the like, but are not limited thereto.

[0056] Examples of 9,9-bis(glycidyloxy(poly)alkoxynaphthyl)fluorenes include 9,9-bis(glycidyloxy(poly)alkoxynaphthyl)fluorenes such as 9,9-bis[6-(2-glycidyloxyethoxy)-2-naphthyl]fluorene and 9,9-bis[5-(2-glycidyloxyethoxy)-1-naphthyl]fluorene; and the like, but are not limited thereto.

[0057] <Naphthalene-type epoxy resin> The naphthalene-type epoxy resin is not particularly limited as long as it is a compound having one or more naphthalene rings which may be substituted in the molecule and one or more epoxy groups. Examples of the naphthalene-type epoxy resin include dihydroxynaphthalene-type epoxy resin, polyhydroxybinaphthalene-type epoxy resin, and epoxy compounds of polyhydroxynaphthalene-aldehyde condensation reaction products.

[0058] Examples of the dihydroxynaphthalene-type epoxy resin include 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, 2,3-diglycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, and the like. Examples of the polyhydroxybinaphthalene-type epoxy resin include 1,1'-bi-(2-glycidyloxy)naphthyl, 1-(2,7-diglycidyloxy)-1'-(2'-glycidyloxy)binaphthyl, 1,1'-bi-(2,7-diglycidyloxy)naphthyl, and the like. Examples of the epoxy compound of the polyhydroxynaphthalene-aldehyde condensation reaction product include 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxynaphthyl)-1'-(2'-glycidyloxynaphthyl)methane, 1,1'-bis(2-glycidyloxynaphthyl)methane, and the like. The naphthalene-type epoxy resin may be used alone or in combination of two or more.

[0059] <Phenol novolac-type epoxy resin> The phenol novolac-type epoxy resin is not particularly limited as long as it is an epoxy resin having one or more phenol novolac-type skeletons represented by the formula (d4) in the molecule and one or more epoxy groups. It is preferable that the phenol novolac-type epoxy resin has two or more epoxy groups.

Chemical formula

[0060] Examples of the phenol novolak type epoxy resin include, for example, the jER series (152, 154, 157H65, etc.) manufactured by Mitsubishi Chemical Corporation; the EPICLON series (N-660, N-665, N-680, N-695, N-730A, N-740, N-770, N-775, N-500P-10, etc.) manufactured by DIC Corporation; the EPPN series (201, 202, etc.) manufactured by Nippon Kayaku Co., Ltd.; the EOCN series (102, 102S103, 103S, 104, 104S, 1012, 1020, 1025, 1027, etc.) manufactured by Nippon Kayaku Co., Ltd.; the RE series (305, 305S, 306, etc.) manufactured by Nippon Kayaku Co., Ltd.; the DEN series (431, 438, 485, etc.) manufactured by Dow Chemical Company; the YDCN series (700, 700-10, 701, 702, 703, 704, etc.) manufactured by Nippon Steel Chemical & Material Co., Ltd.; the Araldite series (ECN1235, ECN1273, ECN1280) manufactured by Huntsman Corporation; etc., but are not limited thereto. The phenol novolak type epoxy resin may be used alone or in combination of two or more.

[0061] <(Content of component (D))> The content of component (D) "one or more epoxy resins selected from the group consisting of bisphenol type epoxy resin, triphenylmethane type epoxy resin, fluorene type epoxy resin, naphthalene type epoxy resin and phenol novolak type epoxy resin" in the epoxy resin composition is not particularly limited. The epoxy resin composition of the present invention may or may not contain component (D). The content of component (D) can be 0% by mass or more, for example, 70% by mass or less, preferably 65% by mass or less, and more preferably 60% by mass or less, with the total amount of the epoxy resin composition being 100% by mass.

[0062] [Other Components] The epoxy resin composition of the present invention may, if necessary and within a range where the performance does not deteriorate, contain epoxy resin curing agents other than component (B), resins other than epoxy resins, coupling agents, solvents, wetting and dispersing agents, reactive diluents, antioxidants, epoxy resins other than components (A) and (D), curing accelerators (curing catalysts) other than component (B), fillers other than component (C), adhesion imparting agents, viscoelasticity modifiers, organic acid compounds, pigments, corrosion inhibitors, surfactants, defoaming agents, dispersants, viscosity modifiers (thixotropy modifiers), adhesion imparting agents, anti-settling agents, etc., pH adjusters, leveling agents, ultraviolet absorbers, flame retardants, heavy metal inactivators, gap adjusters, etc., which are "other components". These other components may be used alone or in combination of two or more.

[0063] <Epoxy Resin Curing Agent Other than Component (B)> The epoxy resin composition of the present invention may contain an epoxy resin curing agent other than component (B). Examples of such epoxy resin curing agents include phenolic curing agents, acid anhydride curing agents, thiol curing agents, amine curing agents, amide curing agents, and thermal cationic polymerization initiators. These epoxy resin curing agents may be used in the form of the compound itself, or may be adducts, microencapsulated products, etc. In the present invention, it is preferable to contain a phenolic curing agent. The epoxy resin curing agent other than component (B) may be used alone or in combination of two or more.

[0064] The phenolic curing agent is not particularly limited as long as it is a compound having one or more, preferably two or more phenolic hydroxyl groups capable of reacting with epoxy groups in the molecular structure. For example, bisphenols such as bisphenol A, bisphenol B, bisphenol F, bisphenol AD, bisphenol S; biphenyls such as biphenyl, tetramethylbiphenyl; phenols such as hydroxyphenol, bis(4-hydroxyphenyl) ether; alkylphenols; phenol novolacs such as 2,6-bis[(2-hydroxyphenyl)methyl]-phenol, phenol biphenylene novolak (biphenyl aralkylphenol); cresol novolacs such as o-cresol novolak, m-cresol novolak, p-cresol novolak; triphenylmethanes such as 4,4’,4’’-trihydroxytriphenylmethane; tetrakisphenols such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-chloro-4-hydroxyphenyl)ethane; phenolic resins; phenol novolak resins; biphenyl aralkyl type phenolic resins; 4,4’,4’’,4’’’-methanetetrayltetraphenol, 4,4’,4’’-trihydroxytriphenylmethane, MEH-8005 manufactured by Meiwa Kasei Co., Ltd., KAYAHARD GPH-65, KAYAHARD GPH-103 manufactured by Nippon Kayaku Co., Ltd., TEP-DF, PAPS series (BPAN, PN2, etc.) manufactured by Asahi Organic Materials Industry Co., Ltd., BRG-555, BRG-556, BRG-557, BRG-558, CRG-951, TAM-005, etc. manufactured by Aica Industries Co., Ltd. The phenolic curing agent may be used alone or in combination of two or more.

[0065] The acid anhydride curing agent is not particularly limited as long as it is a compound having one or more carboxylic anhydride groups (-C(=O)-O-C(=O)-) in the molecular structure. The acid anhydride-based curing agent is obtained by dehydration between two molecules of an organic carboxylic acid and / or dehydration in the molecular structure of one molecule of an organic carboxylic acid. In the present invention, for example, among the above-mentioned organic carboxylic acids, one or more selected from the group consisting of those obtained by intermolecular dehydration of an organic monocarboxylic acid and those obtained by intramolecular dehydration and / or intermolecular dehydration of an organic polycarboxylic acid can be mentioned. For example, aliphatic monocarboxylic acid anhydrides, aliphatic polycarboxylic acid anhydrides, alicyclic polycarboxylic acid anhydrides, aromatic polycarboxylic acid anhydrides, etc. can be mentioned.

[0066] Examples of the acid anhydride-based curing agent include acetic anhydride, propionic anhydride, oxalic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, succinic anhydride, 2-methylsuccinic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, (poly)adipic anhydride, (poly)azelaic anhydride, (poly)sebacic anhydride, norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, polyacid polyanhydride, etc. Here, the polyacid polyanhydride is obtained by intermolecular dehydration condensation reaction of a long-chain aliphatic dicarboxylic acid. For example, SL-12AH, SL-20AH, SB-20AH, IPU-22AH, ST-2PAH, etc. manufactured by Okamura Oil Co., Ltd. can be mentioned, and in particular, SB-20AH, IPU-22AH, and ST-2PAH can be mentioned. The acid anhydride-based curing agent may be used alone or in combination of two or more.

[0067] The thiol-based curing agent is not particularly limited as long as it is a thiol compound having one or more, preferably two or more, thiol groups capable of reacting with an epoxy group in the molecular structure. As the thiol compound, a polyfunctional thiol compound having 2 to 6 (bifunctional to hexafunctional) thiol groups in the molecular structure is preferable, and a polyfunctional thiol compound having 3 to 6 (trifunctional to hexafunctional) thiol groups is more preferable. The thiol equivalent is not particularly limited. In the case of a low molecular weight thiol compound having a molecular weight of less than 500, it can be, for example, 50 g / eq or more, preferably 70 g / eq or more, and can be, for example, 200 g / eq or less, preferably 150 g / eq or less. In the case of a high molecular weight thiol compound having a weight average molecular weight of 500 or more, it can be, for example, 250 g / eq or more, preferably 400 g / eq or more, and can be, for example, 5,000 g / eq or less, preferably 3,000 g / eq or less.

[0068] Examples of thiol-based curing agents include thiol compounds (polyfunctional thiol compounds) such as trimethylolpropane tris(3-mercaptopropionate) (abbreviation: TMTP), pentaerythritol tetrakis(3-mercaptopropionate) (abbreviation: PEMP), dipentaerythritol hexakis(3-mercaptopropionate) (abbreviation: DPMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (abbreviation: TEMPIC), tris(3-mercaptopropyl) isocyanurate (abbreviation: TMPIC), ethylene glycol bisthioglycolate (abbreviation: EGTG), trimethylolpropane tristthioglycolate (abbreviation: TMTG), pentaerythritol tetrakisthioglycolate (abbreviation: PETG), pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate) (abbreviation: TPMB), trimethylolethane tris(3-mercaptobutyrate) (abbreviation: TEMB), 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril, 1,3,4,6-tetrakis(2-mercaptopropyl) glycoluril, 4,4’-isopropylidene bis[(3-mercaptopropoxy)benzene], 1,3,5-triazine-2,4,6-trithiol, and polysulfide polymers having a thiol group.

[0069] Specifically, for example, polyfunctional thiols manufactured by SC Organic Chemicals Co., Ltd. (TMMP-LV, PEMP-LV, DPMP, TEMPIC, PEMP, etc.), polyfunctional thiols manufactured by Toray Fine Chemical Co., Ltd. (QE-340M, LP-2, LP-3, LP-55, LP-31, etc.), polyfunctional thiols manufactured by Shikoku Kasei Kogyo Co., Ltd. (TS-G, C3TS-G, etc.), polyfunctional thiols manufactured by Resonac Co., Ltd. (Karenz MT series (PE-1, BD-1, NR-1, TPMB, TEMB, etc.)), polyfunctional thiols manufactured by Yodo Chemical Co., Ltd. (OTG, EGTG, TMTG, PETG, 3-MPA, TMTP, PETP, etc.), polyfunctional thiols manufactured by Asahi Chemical Industry Co., Ltd. (G-2S, PE-2S, PE-3S, PE-4S, TMP-3S, etc.) and the like can be mentioned. The thiol-based curing agent may be used alone or in combination of two or more kinds.

[0070] The amine-based curing agent is not particularly limited as long as it is a compound having one or more amino groups capable of reacting with an epoxy group in the molecular structure. For example, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, methanediamine, isophoronediamine, bis[4-amino-3-methyldicyclohexyl]methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, m-xylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiethyldiphenylmethane, and modified polyamines and polyamideamines obtained by modifying these by an epoxy adduct, Michael addition, Mannich reaction, etc. can be mentioned. The amine-based curing agent may be used alone or in combination of two or more kinds.

[0071] The thermal cationic polymerization initiator is not particularly limited as long as it is a compound that generates a cation by heat. For example, at least one cation selected from aromatic sulfonium, aromatic iodonium, aromatic diazonium, pyridinium, etc., and BF4 - 、PF6 - 、SbF6 - 、AsF6 - 、CF3SO3 - 、(CF3SO2)2N - and B(C6F5)4 -An onium salt composed of at least one anion selected from the group consisting of...; an aluminum complex; etc. are exemplified. For example, TA-100, TA-100FG, IK-1, IK-1FG, etc. manufactured by San Apro Ltd.; SI-60, SI-80, SI-100, SI-150, etc. manufactured by Sanshin Chemical Industry Co., Ltd.; K-PURE TAG series, K-PURE CXC series, etc. manufactured by KING INDUSTRIES; etc. are exemplified. The thermal cationic polymerization initiator may be used alone or in combination of two or more kinds.

[0072] <Resins other than epoxy resins> The epoxy resin composition of the present invention may contain a resin other than the epoxy resin. As the resin other than the epoxy resin, either a thermoplastic resin or a thermosetting resin may be used. Also, it may be in the form of powder (bead), flake, etc. For example, resin powder (resin beads) having a volume average particle diameter of 0.1 μm or more, preferably 0.2 μm or more, and 50 μm or less, preferably 30 μm or less can be used.

[0073] Examples of the thermoplastic resin include polyvinyl acetal resins, (meth)acrylic resins, polyester resins, phenoxy resins, polyimide resins, polyolefin resins, polyurethane resins, polyamide resins, polycarbonate resins, polyphenylene ether resins, polyvinyl ether resins, polyvinyl alcohol resins, polyvinyl acetate resins, ionomer resins, polyvinyl pyrrolidone resins, terpene resins, etc. Examples of the thermosetting resin include resol type phenol resins, blocked urethane resins, polyimide resins, xylene resins, polyurethane resins, melamine resins, urea resins, furan resins, isocyanate resins, urea resins, etc. In the present invention, as the resin other than the epoxy resin, a blocked urethane resin, a polyurethane resin, a polyvinyl acetal resin, a resol type phenol resin, a (meth)acrylic resin, a polyester resin, a phenoxy resin, a polyimide resin, and a xylene resin are preferable. Among these, a blocked urethane resin, a polyurethane resin, a blocked urethane resin, a polyester resin, a polyvinyl acetal resin, and a (meth)acrylic resin are more preferable, and a (meth)acrylic resin is even more preferable. The resin other than the epoxy resin may be used alone or in combination of two or more.

[0074] The content of the "resin other than the epoxy resin" in the epoxy resin composition is not particularly limited. The epoxy resin composition may or may not contain the "resin other than the epoxy resin". Taking the total amount of the epoxy resin composition as 100% by mass, for example, it can be 20.0% by mass or less, preferably 15.0% by mass or less, and more preferably 10.0% by mass or less.

[0075] <Coupling agent> The epoxy resin composition of the present invention may contain a coupling agent. Thereby, the short-time heat bonding strength of the epoxy resin composition can be improved. Examples of the coupling agent include silane coupling agents, titanium coupling agents, aluminum coupling agents, and zirconium coupling agents. Examples of the silane coupling agent include amino group-containing silane compounds such as aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, and aminoethylaminopropylmethylmethoxysilane; vinyl group-containing silane compounds such as vinyltrimethoxysilane; epoxy group-containing silane compounds such as 3-glycidoxypropyltrimethoxysilane; (meth)acryloyl group-containing silane compounds such as γ-methacryloxypropyltrimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane; isocyanate group-containing silane compounds such as γ-isocyanatopropyltrimethoxysilane; and the like. Examples of the titanium coupling agent include tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate, tetraoctyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, dodecylbenzenesulfonic acid titanium compound, titanium octylene glycolate, titanium ethylacetoacetate, titanium lactate ammonium salt, titanium lactate, titanium triethanolamineate, tetraisopropyl titanate, tetra-t-butyl titanate, tetrastearyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium isostearate, titanium diethanolamineate, titanium aminoethylaminoethanolate, titanium oligomer, and the like. Examples of the aluminum coupling agent include aluminate compounds having an alkoxide group such as alkylacetoacetate aluminum diisopropylate, and aluminate compounds having an acetylacetonate group such as aluminum trisacetylacetonate.Examples of the zirconium coupling agent include tetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis(acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis(ethyl acetoacetate), tetrakis(2,4-pentanedionate)zirconium, and the like. The coupling agent may be used alone or in combination of two or more.

[0076] The content of the "coupling agent" in the epoxy resin composition is not particularly limited. The epoxy resin composition may or may not contain the "coupling agent". Taking the total amount of the epoxy resin composition as 100% by mass, it can be, for example, 5.0% by mass or less, preferably 3.0% by mass or less.

[0077] <Solvent> The epoxy resin composition of the present invention may contain a solvent. Thereby, it is possible to adjust the fluidity of the epoxy resin composition, and improve workability, coatability, handleability, etc. When using a solvent, the content is not particularly limited, and it may be appropriately adjusted so that the viscosity of the epoxy resin composition is such that it can be appropriately applied, printed, etc. on the substrate and / or such that it can be appropriately impregnated into an impregnated material such as a non-woven fabric or a porous body.

[0078] As the solvent, any one or more selected from the group consisting of water and various organic solvents can be used. Examples of the organic solvent include alcohols such as ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, 2-ethyl-1,3-hexanediol, methyl methoxybutanol, α-terpineol, β-terpineol, hexylene glycol, benzyl alcohol, 2-phenylethyl alcohol, isopalmitoyl alcohol, isostearyl alcohol, lauryl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3,5,5-trimethyl-2-cyclohexen-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone); ester solvents such as ethyl acetate, butyl acetate, diethyl phthalate, dibutyl phthalate, acetoxyethane, methyl butyrate, methyl hexanoate, methyl octanoate, methyl decanoate, methyl cellosolve acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethyl diglycol acetate, 1,2-diacetoxyethane;Ether solvents such as tetrahydrofuran, dimethyl ether, diethyl ether, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, ethoxyethyl ether, 1,2-bis(2-diethoxy)ethane, 1,2-bis(2-methoxyethoxy)ethane; ether ester solvents such as 2-(2-butoxyethoxy)ethyl acetate, methyl cellosolve acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; ether alcohol solvents such as 2-(2-methoxyethoxy)ethanol; hydrocarbon solvents such as benzene, toluene, xylene, n-paraffin, isoparaffin, dodecylbenzene, turpentine oil, kerosene, light oil; nitrile solvents such as acetonitrile, propionitrile; nitrogen-containing polar solvents such as dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone; silicone oil solvents, etc., and one or more selected from the group consisting thereof are mentioned.; The solvent may be used alone or in combination of two or more kinds.;

[0079] The content of the "solvent" in the epoxy resin composition is not particularly limited. The epoxy resin composition may or may not contain the "solvent". Taking the total amount of the epoxy resin composition as 100% by mass, for example, it can be 40.0% by mass or less, preferably 30.0% by mass or less.;

[0080] <Wetting dispersant> The epoxy resin composition of the present invention may contain a wetting dispersant as necessary to prevent aggregation of the components of the epoxy resin composition.; Specific examples of the wetting dispersant include, for example, the Solsperse series (9000, 12000, 17000, 20000, 21000, 24000, 26000, 27000, 28000, 32000, 35100, 54000, etc.) manufactured by Lubrizol Japan, the EFKA series (4008, 4009, 4010, 4015, 4046, 4047, 4060, 4080, 7462, 4020, 4050, 4055, 4400, 4401, 4402, 4403, 4300, 4330, 4340, 6220, 6225, 6700, 6780, 6782, 8503, etc.) manufactured by BASF, the Ajisper series (PA111, PB711, PB821, PB822, PN411, etc.) manufactured by Ajinomoto Fine-Techno Co., Ltd., the DISPERBYK series (101, 106, 108, 116, 130, 140, 145, 161, 163, 166, 168, 171, 180, 192, 2000, 2001, 2020, 2025, 2070, 2152, 2155, 2164, 220S, 300, 320, 340, 378, 380N, 410, 425, 430, etc.) manufactured by BYK-Chemie Japan, and the like. The wetting dispersant may be used alone or in combination of two or more.

[0081] <Reactive diluent> The epoxy resin composition of the present invention may contain a reactive diluent for viscosity adjustment, curability adjustment, etc. The reactive diluent is not particularly limited, and examples thereof include one or more compounds having one epoxy group in the molecular structure, compounds having one or more oxetane groups in the molecular structure, etc. For example, glycidyl phenyl ether, glycidyl lauryl ether, 2-phenylphenol glycidyl ether, tolyl glycidyl ether, allyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, N-glycidyl phthalimide, 2-ethylhexyl glycidyl ether, 2-ethylhexyl glycidyl ether, YED111N, YED111AN, YED188 manufactured by Mitsubishi Chemical Corporation, Adeka Glycerol ED-502, Adeka Glycerol ED-502S, Adeka Glycerol ED-509E, Adeka Glycerol ED-509S, Adeka Glycerol ED-529 manufactured by Adeka Corporation, Denacol EX-145, Denacol EX-171, Denacol EX-192 manufactured by Nagase ChemteX Corporation, Epolite M-1230, Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd., Aron Oxetane OXT-101, Aron Oxetane OXT-212, Aron Oxetane OXT-121, Aron Oxetane OXT-221 manufactured by Toagosei Co., Ltd., ETERNACOLL EHO, ETERNACOLL HBOX, ETERNACOLL OXMA, ETERNACOLL OXBP manufactured by UBE Corporation, etc. In the present invention, the boiling point of the reactive diluent is, for example, 150°C or higher, preferably 200°C or higher, more preferably 250°C or higher. The reactive diluent may be used alone or in combination of two or more.

[0082] <Antioxidant> The epoxy resin composition of the present invention may contain an antioxidant. This can contribute to improving the heat resistance, yellowing resistance, etc. of the cured product of the epoxy resin composition. The antioxidant is not particularly limited as long as it is a compound having an antioxidant function, and known or commonly used antioxidants can be used. For example, phenolic antioxidants such as hindered phenol compounds, quinone antioxidants such as hydroquinone, phosphorus antioxidants, sulfur antioxidants, hindered amine antioxidants such as hindered amine compounds, etc. can be mentioned.

[0083] Examples of antioxidants include 2,2 - methylene - bis(4 - methyl - 6 - tert - butylphenol), catechol, tert - butylcatechol, 2 - butyl - 4 - hydroxyanisole, 2,6 - di - tert - butyl - p - cresol, 2,4 - di - tert - butyl - 6 - methylphenol, 2 - tert - butyl - 4 - methylphenol, 2,4 - di - tert - butylphenol, 2,4 - di - tert - pentylphenol, bis - [3,3 - bis - (4’ - hydroxy - 3’ - tert - butylphenyl) - butanoic acid] - glycol ester, 2 - tert - butyl - 6 - (3 - tert - butyl - 2 - hydroxy - 5 - methylbenzyl) - 4 - methylphenyl acrylate, 2 - [1 - (2 - hydroxy - 3,5 - di - tert - pentylphenyl)ethyl] - 4,6 - di - tert - pentylphenyl acrylate, 4,4’ - butylidenebis(6 - tert - butyl - 3 - methylphenol), 2,2’ - butylidenebis(4,6 - di - tert - butylphenol), 4,4’ - thiobis(6 - tert - butyl - 3 - methylphenol), 3,9 - bis[2 - [3 - (3 - tert - butyl - 4 - hydroxy - 5 - methylphenyl)propionyloxy] - 1,1 - dimethylethyl] - 2,4,8,10 - tetraoxaspiro[5,5]undecane, pentaerythritol tetrakis[3 - (3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionate], thiodiethylene bis[3 - (3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionate], octadecyl - 3 - (3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionate, N,N’ - hexane - 1,6 - diylbis[3 - (3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionamide], benzenepropanoic acid - 3,5 - bis(1,1 - dimethylethyl) - 4 - hydroxy - C7 - C9 branched alkyl ester, 2,4 - dimethyl - 6 - (1 - methylpentadecyl)phenol, diethyl[[3,5 - bis(1,1 - dimethylethyl) - 4 - hydroxyphenyl]methyl]phosphonate, 3,3’,3’’,5,5’,5’’ - hexa - tert - butyl - a,a’,a’’ - (mesitylene - 2,4,6-Tril)tri-p-cresol, calcium diethyl bis[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, reaction product of N-phenylbenzeneamine and 2,4,6-trimethylpentene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, phenolic antioxidants such as picric acid, citric acid; quinone antioxidants such as β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di-tert-butyl-p-benzoquinone; phosphite antioxidants such as tris(2,4-di-tert-butylphenyl)phosphite, tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphefin-6-yl]oxy]ethyl]amine, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,Phosphorus-based antioxidants such as 4'-diylbisphosphonite and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepine; sulfur-based antioxidants such as dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis(3-laurylthiopropionate), and 2-mercaptobenzimidazole; amine-based antioxidants such as phenothiazine; lactone-based antioxidants; vitamin E-based antioxidants; and the like can be mentioned., Commercially available products may be used as the antioxidant. For example, IRGANOX series manufactured by BASF, ADEKA STAB series manufactured by ADEKA, NONFLEX series manufactured by Seiko Chemical Co., Ltd., Sumilizer series manufactured by Sumitomo Chemical Co., Ltd., and the like can be mentioned., The antioxidant may be used alone or in combination of two or more.,

[0084] <Epoxy resin other than component (A) and component (D)> The epoxy resin composition of the present invention may contain an epoxy resin other than component (A) and component (D). The epoxy resin other than component (A) and component (D) is not particularly limited as long as it is an epoxy resin other than "urethane-modified epoxy resin, polyether-modified epoxy resin having an epoxy equivalent of less than 400 g / eq, bisphenol type epoxy resin, triphenylmethane type epoxy resin, fluorene type epoxy resin, naphthalene type epoxy resin, and phenol novolac type epoxy resin". Epoxy resins other than component (A) and component (D) may be any monomer, oligomer, or polymer having two or more glycidyl groups in one molecule, and the molecular weight is not particularly limited. For example, polyether-modified epoxy resins with an epoxy equivalent of 400 g / eq or more; biphenyl-type epoxy resins; chelate-modified epoxy resins; hydroquinone-type epoxy resins; stilbene-type epoxy resins; resorcinol diglycidyl ether; triphenolmethane-type epoxy resins, alkyl-modified triphenolmethane-type epoxy resins, phenol aralkyl-type epoxy resins having a phenylene skeleton; naphthol-type epoxy resins such as dihydroxynaphthalene-type epoxy resins and epoxy resins obtained by epoxidizing a dimer of dihydroxynaphthalene; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; hydrogenated bisphenol A-type epoxy resins, hydrogenated bisphenol F-type epoxy resins, hydrogenated biphenyl-type epoxy resins, epoxy resins having an alicyclic structure such as glycidyl ethers of polyols having an alicyclic structure such as cyclohexanediol, cyclohexanedimethanol, and cyclohexanediethanol; glycidyl ethers of aliphatic polyols such as butanediol, hexanediol, octanediol, nonanediol, decanediol, pentaerythritol, and glycerin; aromatic glycidylamine-type epoxy resins such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diamino diphenylmethane-type glycidylamine, and aminophenol-type glycidylamine; dicyclopentadiene-type epoxy resins; etc. The epoxy resin other than component (A) and component (D) may be used alone or in combination of two or more.

[0085] <Accelerator for curing (curing catalyst) other than component (B)> The epoxy resin composition of the present invention may contain a curing accelerator (curing catalyst) other than the component (B) for accelerating the curing of the epoxy resin and the curing agent. The curing accelerator (curing catalyst) is not particularly limited, and examples thereof include amine-based curing accelerators, guanidine-based curing accelerators, phosphonium-based curing accelerators, transition metal-based curing accelerators, and the like. In the epoxy resin composition of the present invention, from the viewpoints of workability, handleability, and manufacturing suitability, etc., it is preferable to contain a curing accelerator (curing catalyst) that is liquid at room temperature (25 °C ± 5 °C). (The curing accelerator (curing catalyst) other than the component (B) may be used alone or in combination of two or more kinds.)

[0086] Examples of the curing accelerator (curing catalyst) include amine-based curing accelerators such as triethylamine, tripropylamine, tributylamine, dimethylbutylamine, dimethylpentylamine, dimethylcyclohexylamine, triethylenediamine, dimethylbenzylamine, 2-(dimethylaminomethyl)phenol, dimethylamino-p-cresol, piperidine, N,N-dimethylpiperazine, α-picoline, pyridine, 4-dimethylaminopyridine, 2,4,6-tris(dimethylaminomethyl)phenol, 3,4,5-tris(dimethylaminomethyl)phenol, N-aminoethylpiperazine, 1,3,6-trisaminomethylhexane, m-xylenediamine, p-xylenediamine, N-(2-aminoethyl)piperazine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, methylenedianiline, 2,4-toluenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylamine, 4,4'-methylenedianiline, 1,3-diaminocyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraazapentacyclo[5,5]undecane, 1,8-diazabicyclo[5,4,0]undecene-7, 1,5-diazabicyclo[4,3,0]-nonene, polyamine, polyamideamine, polyamide, modified polyamine, modified polyamideamine, modified polyamide; guanidine-based curing accelerators such as dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, di(o-tolyl)guanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4,4,0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4,4,0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide;Tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, butyltriphenylphosphonium bromide, tetraphenylphosphonium iodide, tetrabutylphosphonium iodide, butyltriphenylphosphonium iodide, tetraphenylphosphonium tetraphenylborate, tetrabutylphosphonium tetraphenylborate, butyltriphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrabutylborate, tetrabutylphosphonium tetrabutylborate, butyltriphenylphosphonium tetrabutylborate, tetraphenylphosphonium acetate, tetrabutylphosphonium acetate, butyltriphenylphosphonium acetate, tetrabutylphosphonium tetrafluoroborate, tetrabutylphosphonium hexafluorophosphate, methyltributylphosphonium dimethylphosphate, tetrabutylphosphonium acetate, tetrabutylphosphonium hydroxide and other phosphonium-based curing accelerators; transition metal-based curing accelerators containing transition metals such as titanium and cobalt; and the like. The curing accelerator (curing catalyst) may be used alone or in combination of two or more.

[0087] <Filler other than component (C)> The epoxy resin composition of the present invention may contain a filler other than component (C). Examples of the filler other than component (C) include fused silica, fumed silica, precipitated silica, crystalline silica, carbon black, dolomite, anhydrous silicic acid, hydrous silicic acid, heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, ferric oxide, glass powder, zinc oxide, silas balloon, glass balloon, phenol resin microballoon, vinylidene chloride resin microballoon, glass fiber, potassium titanate fiber and the like. The filler other than component (C) may be used alone or in combination of two or more.

[0088] <Adhesion promoter> The epoxy resin composition of the present invention may contain an adhesion promoter. Thereby, when the epoxy resin composition is applied to a substrate, the adhesion to the substrate and the like can be improved. Examples of the adhesion promoter include triazole compounds, thiazole compounds, triazine compounds, polymers having functional groups (such as carboxylic acid groups, amino groups, hydroxyl groups), and salts thereof. Examples of the adhesion promoter include the BYK series (4509, 4510, 4512, etc.) manufactured by BYK Chemie Japan. The adhesion promoter may be used alone or in combination of two or more.

[0089] <Viscoelasticity modifier> The epoxy resin composition of the present invention may contain a viscoelasticity modifier (rheology control agent). Thereby, the viscoelasticity (rheology) of the epoxy resin composition can be adjusted, which can contribute to the improvement of workability and the like. Examples of the viscoelasticity modifier (rheology control agent) include viscoelasticity modifiers (rheology control agents) such as polyamide-based, aminoplast-based, polycarboxylic acid-based, urethane-based, cellulose-based, and inorganic layered compound-based. For example, the RHEOBYK series (H370, H400, H600, H600VF, 100, 405, 410, 411, 415, 430, 431, 440, 7410ET, etc.) manufactured by BYK Chemie Japan; the Disparon series (AQ-600, AQH-800, 3600N, 3900EF, etc.) manufactured by Namboku Kasei Co., Ltd.; the SN thickener series (613, 617, 618, 630, 634, 636, 621N, 623N, etc.) manufactured by San Nopco Ltd.; the Adekanol series (UH-814N, UH-752, UH-750, UH-462, etc.) manufactured by ADEKA Corporation, the HEC Daicel series (SP600N, etc.) manufactured by Daicel Corporation; BENTONE HD manufactured by Elementis Japan, etc. The viscoelasticity modifier may be used alone or in combination of two or more.

[0090] [Method for preparing epoxy resin composition] The method for preparing the epoxy resin composition of the present invention is not particularly limited. For example, there is a method of preparing by adding the essential components (A) to (C) and the component (D) and / or other components used as required to a mixing container in any order and mixing and stirring. When mixing and stirring, for example, a ball mill, a roll mill, a bead mill, a planetary mixer, a tumbler, a stirrer, a stirrer, a mechanical homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a V-type blender, a Nauta mixer, a Banbury mixer, a rotary mixer, a kneading roll, a single-screw or twin-screw extruder, etc. can be used for mixing and stirring.

[0091] The temperature when preparing the epoxy resin composition (the temperature when mixing each component) is not particularly limited. If necessary, heating etc. can be carried out, and for example, it can be set to 10 to 40°C. The atmosphere when preparing the epoxy resin composition is not particularly limited. It can be carried out in the air, or it can also be carried out under an inert atmosphere.

[0092] [Use of Epoxy Resin Composition] The epoxy resin composition of the present invention can be used as an insulating paste etc. used for forming an insulating layer when manufacturing electronic devices, electronic components, etc. The shape etc. of the epoxy resin composition are not particularly limited, but it is preferably liquid (paste-like or varnish-like), film-like or powdery at room temperature (25°C ± 5°C). The liquid epoxy resin composition can, for example, be directly used as the epoxy resin composition by stirring and mixing the constituent components of the epoxy resin composition, and if necessary, a solvent such as an organic solvent can be mixed. The film-like epoxy resin composition can be obtained, for example, by stirring and mixing the constituent components of the epoxy resin composition, and if necessary, mixing a solvent such as an organic solvent to obtain a liquid epoxy resin composition, casting and coating it on a release substrate to form a film, drying to remove the solvent to form a film, and peeling it from the release substrate. Further, the film-like epoxy resin composition can be obtained by impregnating a nonwoven fabric or the like, forming it on a release substrate, drying to remove the solvent, and then peeling it off from the release substrate.

[0093] The substrate to which the epoxy resin composition of the present invention is applied is not particularly limited. For example, it can be applied to inorganic substances such as semiconductors, glass, and ceramics, organic substances such as polyimide and polycarbonate, composites such as glass / epoxy, and combinations thereof.

[0094] The epoxy resin composition of the present invention can be applied to various substrates by any printing or coating method such as casting method, dipping method, bar coating method, dispenser method, roll coating method, gravure coating method, screen printing method, metal mask printing method, flexographic printing method, spray coating method, spin coating method, inkjet method, etc., and heated and dried at a temperature of 300°C or lower to form a coating film. The atmosphere during drying includes one or more selected from the group consisting of air, inert gas, vacuum, reduced pressure, etc. The film thickness of the formed coating film can be made appropriate according to various uses. For example, it can be 5 μm or more, preferably 7.5 μm or more, more preferably 10 μm or more, and can be 100 μm or less, for example.

Examples

[0095] Examples and comparative examples are given below to explain the present invention in more detail. The present invention is not limited to these examples. Unless otherwise specified, “%” means “mass %” and “part” means “part by mass”. Also, all numerical values regarding the blending amounts of the respective components in Tables 1 to 4 are in “parts” (parts by mass).

[0096] [Components Used] The components used in Examples 1 to 18 and Comparative Examples 1 to 19 are as follows. In each structural formula, n is the number of repeating units and is a value that gives a predetermined epoxy equivalent.

[0097] <Component (A)> ·UM-EP: Urethane-modified epoxy resin ("EPICLON TSR-300" manufactured by DIC Corporation; epoxy equivalent 191 g / eq) ·EM-EP1: Polyether-modified epoxy resin ("EP-4000S" manufactured by ADEKA Corporation; epoxy equivalent 260 g / eq) ·EM-EP2: Polyether-modified epoxy resin ("AER-9000" manufactured by Asahi Kasei Corporation; epoxy equivalent 370 g / eq) ·EM-EP3: Polyether-modified epoxy resin ("EPICLON EXA-4850-1000" manufactured by DIC Corporation; epoxy equivalent 350 g / eq)

[0098] <Component (B)> ·IMD-TPE: 2-Phenyl-4-methyl-5-hydroxymethylimidazole-1,1,2,2-tetrakis(4-hydroxyphenyl)ethane inclusion compound ·IMD: 2-Phenyl-4-methyl-5-hydroxymethylimidazole

[0099] <Component (C)> ·OM-CM: Organically modified phyllosilicate ("GARAMITE1958" manufactured by BYK)

[0100] <Component (D)> ·BPA-EP1: Bisphenol A type epoxy resin (epoxy equivalent 190 g / eq)

Chem.

Chem.

Chem.

[0101] [Other components] ·ACB1: Poly(meth)acrylate resin particles (average particle size 0.3 μm) ·ACB2: Polymethacrylate resin particles (average particle size 2.0 μm) ·ACB3: Poly(meth)acrylate resin particles (average particle size 0.5 μm) ·TPE: 1,1,2,2-Tetrakis(4-hydroxyphenyl)ethane ·ESiCA1: 3-Glycidoxypropyltrimethoxysilane ·ESiCA2: Multifunctional silane coupling agent ("X-12-981S" manufactured by Shin-Etsu Silicone Co., Ltd.) ·BC: Diethylene glycol monobutyl ether

[0102] [Measurement and evaluation of properties of epoxy resin composition] In the examples, the measurement and evaluation of the properties ("curability", "surface hardness", "adhesion", and "coating film appearance") of the epoxy resin composition were carried out as follows.

[0103] [Curability] Using the epoxy resin composition obtained in each example / comparative example, it was applied onto a glass plate by the screen printing method and dried for 30 minutes in a standing state in a hot air circulation drying furnace set at 150 °C to prepare a coating film with a thickness of 30 μm to 60 μm. Then, regarding the coating film returned to room temperature, the state of the coating film was confirmed by finger touch, and the curability was evaluated according to the following criteria. In the present invention, A is qualified and D is unqualified. (Curability evaluation criteria) A: There is no tackiness or stickiness on the coating film surface, and curing and drying are complete. D: There is tackiness or stickiness on the coating film surface, and curing and drying are not complete.

[0104] <Surface hardness> Using the epoxy resin compositions obtained in each example / comparative example, they were applied onto a glass plate by the screen printing method, and dried for 30 minutes in a standing state in a hot air circulation drying oven set at 150°C to produce a coating film with a thickness of 30 μm to 60 μm. Then, for the coating film returned to room temperature, based on the pencil hardness method specified in JIS K 5600, the pencil hardness of the coating film surface was measured. In the present invention, H to 10H are considered qualified.

[0105] <Adhesion> Using the epoxy resin compositions obtained in each example / comparative example, they were applied onto a glass plate by the screen printing method, and dried for 30 minutes in a standing state in a hot air circulation drying oven set at 150°C to produce a coating film with a thickness of 30 μm to 60 μm. Then, for the coating film returned to room temperature, based on the cross-cut method specified in JIS K 5600, after making six grid-shaped cuts at 1 mm intervals reaching the substrate into the coating film, cellophane tape (registered trademark) was pasted and peeled off, and the adhesion was evaluated according to the following criteria based on the degree of film peeling. In the present invention, S is considered qualified, and A to E are considered unqualified. (Adhesion evaluation criteria) S: Classification 0 (The edges of the cuts are completely smooth, and there is no peeling at any of the grid meshes.) A: Classification 1 (Small peeling of the coating film at the intersections of the cuts. The influence at the cross-cut part is clearly not more than 5%.) B: Classification 2 (The coating film is peeling along the edges of the cuts and / or at the intersections. The influence at the cross-cut part is clearly more than 5% but not more than 15%.) C: Classification 3 (The coating film is partially or completely peeling off along the edges of the cuts, and / or various parts of the meshes are partially or completely peeling off. The influence at the cross-cut part is clearly more than 15% but not more than 35%.) D: Classification 4 (The coating film has partially or completely peeled off along the edge of the cut, and / or several places have partially or completely peeled off. The affected area in the cross-cut part does not clearly exceed 35%.) E: Classification 5 (Any degree of peeling that cannot be classified as Classification 4.)

[0106] <Appearance of Coating Film> Using the epoxy resin compositions obtained in each example / comparative example, they were applied onto a glass plate by the screen printing method and dried in a hot air circulation type drying oven set at 150°C for 30 minutes while standing upright to produce a coating film with a thickness of 30 μm to 60 μm. Thereafter, the appearance of the coating film at room temperature was visually observed and evaluated according to the following criteria. In the present invention, A is considered qualified and D is considered unqualified. A: There are no bubbles generated on the surface of the coating film and it is smooth. D: Bubbles are generated and / or sagging is generated on the surface of the coating film, and it is not smooth.

[0107] [Example 1] 23.2 parts of UM-EP (urethane-modified epoxy resin), 3.7 parts of IMD (2-phenyl-4-methyl-5-hydroxymethylimidazole), 4.1 parts of OM-CM (organically modified phyllosilicate), 54.2 parts of BPA-EP1 (bisphenol A type epoxy resin) and 14.8 parts of ACB1 (poly(meth)acrylate resin particles) were mixed and stirred to prepare an epoxy resin composition. Using the obtained epoxy resin composition, evaluations were made on curability, surface hardness, adhesion and the appearance of the coating film. The results are shown in Table 1.

[0108] [Examples 2 to 18, Comparative Examples 1 to 19] Epoxy resin compositions were prepared in the same manner as in Example 1, except that the constituent components and their amounts used of the epoxy resin compositions were as shown in Tables 1 to 4. Using the obtained epoxy resin compositions, evaluations were made on curability, surface hardness, adhesion and the appearance of the coating film in the same manner as in Example 1. The results are shown together in Tables 1 to 4.

[0109]

Table 1

[0110]

Table 2

[0111]

Table 3

[0112]

Table 4

[0113] From the results of Examples 1 to 18 and Comparative Examples 1 to 19, it can be seen that the epoxy resin composition of the present invention is excellent in curability, has a high surface hardness of the cured coating film, excellent adhesion of the cured coating film, good appearance of the cured coating film, and no sagging even when the uncured coating film is in a vertical or inclined state, and is an epoxy resin composition useful as an insulating paste or the like.

Claims

1. The following (A) to (C); (A) A urethane-modified epoxy resin and / or a polyether-modified epoxy resin having an epoxy equivalent of less than 400 g / eq, (B) An imidazole-based compound, (C) An organically modified clay mineral, An epoxy resin composition containing the same.

2. Furthermore, (D) One or more epoxy resins selected from the group consisting of bisphenol type epoxy resins, triphenylmethane type epoxy resins, fluorene type epoxy resins, naphthalene type epoxy resins, and phenol novolac type epoxy resins, The epoxy resin composition according to Claim 1, containing the same.

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