Epoxy resin composition

Abstract

To provide an epoxy resin composition that has low volume resistivity and exhibits suitable conductivity when formed as a coating film, and that makes it possible to form a coating film having excellent solder wettability and solder erosion resistance.SOLUTION: An epoxy resin composition contains the following components (A) to (D): (A) one or more epoxy resins selected from the group consisting of triphenylmethane-type epoxy resins, naphthalene-type epoxy resins, and phenol novolac-type epoxy resins; (B) one or more epoxy resins selected from the group consisting of polyether-modified epoxy resins, urethane-modified epoxy resins, mesogen-modified epoxy resins having an -O-CH2CH(OH)CH2-O- skeleton in the molecule thereof, bisphenol-type epoxy resins, and dicyclopentadiene-type epoxy resins; (C) an imidazole-based compound and / or a phenol-based compound; and (D) one or more conductive powders selected from among silver-coated copper powders, silver-based powders, nickel-based powders, conductive carbon powders, copper-based powders, and gold-based powders.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 capable of forming a coating film having a low volume resistivity when the coating film is formed, exhibiting good conductivity, excellent solder wettability, and excellent solder erosion resistance.

Background Art

[0002] As epoxy resin compositions, those with various compositions are known. From their characteristics, etc., conductive powder is added to form a conductive epoxy resin composition, which is used as a conductive paste, conductive ink, conductive paint, circuit connection material, conductive adhesive, etc. for various applications such as the formation of electronic circuits and the adhesion of electronic components. For example, it is applicable to various printing methods and is used as a conductive ink useful for the production of flexible plastic substrates having conductive structures such as interconnections, traces, and electrodes. Also, for example, in electronic devices such as computers and mobile phones, it is used as a circuit connection material for high-density mounting and high integration of various electronic components such as LED elements, semiconductor elements, and capacitors on the same circuit board.

[0003] However, the films of conventional conductive resin compositions have poor solder wetting, and there is a risk of solder erosion (a phenomenon in which the solder erodes and penetrates the film of the conductive resin composition), and they are inferior in solderability. In many cases, sufficient adhesive strength cannot be obtained when adhering electronic components to a circuit, so the reliability of conductive connection is low. Also, the dispersibility of the conductive powder in the conductive resin composition may be insufficient, resulting in a high volume resistivity of the film of the conductive resin composition and insufficient conductivity. Therefore, there is a demand for a conductive resin composition that has excellent film characteristics, suppresses the occurrence of short-circuit failures, and has high reliability of conductive connection for electronic devices in which the wiring pattern interval is narrowed due to miniaturization of components and high density of circuits.

[0004] In response to such needs, Patent Documents 1 to 3 describe a conductive resin composition containing conductive powder and a resin component. However, these conductive resin compositions had points that needed to be improved in one or more of volume resistivity, solder wettability, and solder erosion resistance.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] Hitherto, an epoxy resin composition excellent in solderability has not been known because it has a low volume resistivity, excellent conductivity, and furthermore, good solder wettability and solder erosion resistance. The problem to be solved by the present invention is to provide an epoxy resin composition capable of forming a coating film having a low volume resistivity when forming a coating film, showing good conductivity, excellent solder wettability, and excellent solder erosion resistance.

Means for Solving the Problems

[0007] 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 (D); (A) One or more epoxy resins selected from the group consisting of triphenylmethane type epoxy resins, naphthalene type epoxy resins, and phenol novolac type epoxy resins, (B) One or more epoxy resins selected from the group consisting of polyether-modified epoxy resins, urethane-modified epoxy resins, mesogen-modified epoxy resins having an -O-CH2CH(OH)CH2-O- skeleton in the molecule, bisphenol-type epoxy resins, and dicyclopentadiene-type epoxy resins, (C) Imidazole-based compounds and / or phenolic compounds, (D) One or more conductive powders selected from silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder, and gold-based powder, An epoxy resin composition containing the above components. [Advantages of the Invention]

[0008] According to the present invention, a coating film having a low volume resistivity when formed, exhibiting good conductivity, excellent solder wettability, and excellent solder erosion resistance can be formed, and an epoxy resin composition useful as a conductive ink, a circuit connection material, etc. is provided. [Embodiments for Carrying Out the Invention]

[0009] The epoxy resin composition of the present invention (A) One or more epoxy resins selected from the group consisting of triphenylmethane-type epoxy resins, naphthalene-type epoxy resins, and phenol novolak-type epoxy resins, (B) One or more epoxy resins selected from the group consisting of polyether-modified epoxy resins, urethane-modified epoxy resins, mesogen-modified epoxy resins having an -O-CH2CH(OH)CH2-O- skeleton in the molecule, bisphenol-type epoxy resins, and dicyclopentadiene-type epoxy resins, (C) Imidazole-based compounds and / or phenolic compounds, (D) One or more conductive powders selected from silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder, and gold-based powder, is an epoxy resin composition containing the above components. Hereinafter, the epoxy resin composition of the present invention will be described in detail.

[0010] [Component (A)] Component (A), which is a constituent of the epoxy resin composition of the present invention, is at least one epoxy resin selected from the group consisting of triphenylmethane type epoxy resins, naphthalene type epoxy resins, and phenol novolac type epoxy resins.

[0011] <Triphenylmethane type epoxy resin> The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having at least one triphenylmethane skeleton and at least one epoxy group in the molecule. Examples of the triphenylmethane type epoxy resin include the formula (a1);

Chemical formula

[0012] Examples of the triphenylmethane type epoxy resin include, for example, 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.

[0013] <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 polyhydroxynaphthalene type epoxy resin, polyhydroxybinaphthalene type epoxy resin, polyhydroxynaphthalene-aldehyde condensation reaction product epoxidized product, and the like.

[0014] Examples of the polyhydroxynaphthalene 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'-bis(2-glycidyloxy)naphthyl, 1-(2,7-diglycidyloxy)-1'-(2'-glycidyloxy)binaphthyl, 1,1'-bis(2,7-diglycidyloxy)naphthyl, and the like. Examples of the polyhydroxynaphthalene-aldehyde condensation reaction product epoxidized 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.

[0015] <Phenol novolak type epoxy resin> The phenol novolak type epoxy resin is an epoxy resin having at least one phenol novolak type skeleton represented by the formula (a2) in the molecule; [Chemical formula] It is not particularly limited as long as it is an epoxy resin having at least one phenol novolak type skeleton represented by the formula (a2) and at least one epoxy group in the molecule. The phenol novolak type epoxy resin preferably has two or more epoxy groups. In the formula (a2), a4 is an integer from 0 to 3, and 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 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 substituent may be a single type or two or more types.

[0016] Examples of the phenol novolak type epoxy resin include 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.

[0017] <Content of component (A)> The content of component (A), "one or more epoxy resins selected from the group consisting of triphenylmethane type epoxy resin, naphthalene type epoxy resin, and phenol novolac type epoxy resin" in the epoxy resin composition is not particularly limited. With respect to 100 parts by mass in total of components (A) to (D), for example, it is 0.5 part by mass or more, preferably 1.0 part by mass or more, more preferably 1.2 part by mass or more, and for example, it can be 13.0 parts by mass or less, preferably 10.0 parts by mass or less, more preferably 7.0 parts by mass or less. When the content of component (A) is less than 0.5 part by mass with respect to 100 parts by mass in total of components (A) to (D), the epoxy resin composition may not form a film, the short-time heat bonding strength may decrease, and the heat resistance may decrease. When it exceeds 13.0 parts by mass, it may take a long time to cure and the conductivity may decrease.

[0018] [Component (B)] Component (B) which is a constituent component of the epoxy resin composition of the present invention is one or more epoxy resins selected from the group consisting of polyether-modified epoxy resin, urethane-modified epoxy resin, mesogen-modified epoxy resin having an -O-CH2CH(OH)CH2-O- skeleton in the molecule, bisphenol type epoxy resin, and dicyclopentadiene type epoxy resin.

[0019] [Polyether-modified epoxy resin] The polyether-modified epoxy resin is not particularly limited as long as it is an epoxy resin having one or more polyether skeletons and epoxy groups in the molecule. The polyether skeleton is represented by the formula (b1); -(-R b1 -O-)n- ···(b1) It is a structure represented by. In the formula (b1), R b1 is a divalent organic group. Examples of R b1 include, for example, an alkylene group and an optionally substituted aryl group, and preferably an alkylene group having 2 or more and 6 or less carbon atoms. The polyether-modified epoxy resin may be used alone or in combination of two or more.

[0020] The epoxy resin constituting the polyether-modified epoxy resin is not particularly limited. For example, bisphenol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, resorcinol diglycidyl ether, triphenol methane 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.

[0021] Examples of the polyether-modified epoxy resin include polyalkylene oxide-modified bisphenol type epoxy resin, polyalkylene oxide phenol novolak 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 novolak type epoxy resin, etc. Examples of the polyether-modified epoxy resin include the Adeka Resin series (EP-4000, EP-4000S, EP-4005, EP-7001, EP4080E, etc.) manufactured by ADEKA; the EPICLON series (EXA-4850-150, EXA-4850-1000, etc.) manufactured by DIC; AER-9000 manufactured by Asahi Kasei Co., Ltd.; etc.

[0022] The epoxy equivalent of the polyether-modified epoxy resin is not particularly limited. For example, it can be 100 g / eq or more, preferably 200 g / eq or more, more preferably 300 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.

[0023] <Urethane-modified epoxy resin> The urethane-modified epoxy resin is not particularly limited as long as it is an epoxy resin having at least one urethane skeleton and epoxy group in the molecule. The urethane skeleton is represented by the formula (b2); -O-C(=O)-NH- ···(b2) It is a structure represented by. The urethane-modified epoxy resin may be used alone or in combination of two or more.

[0024] 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. It can also 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 an isocyanate group-containing urethane prepolymer obtained by reacting a polyhydroxy compound and a polyisocyanate compound.

[0025] Examples of the hydroxy group-containing epoxy resin include hydroxy group-containing bisphenol type epoxy resins such as hydroxy group-containing bisphenol A type epoxy resin, hydroxy group-containing bisphenol F type epoxy resin, and hydroxy group-containing bisphenol S type epoxy resin; hydroxy group-containing biphenyl type epoxy resins such as hydroxy group-containing biphenyl type epoxy resin and hydroxy group-containing tetramethylbiphenyl type epoxy resin; hydroxy group-containing naphthalene type epoxy resin; hydroxy group-containing alicyclic epoxy resins such as hydroxy group-containing cyclohexanedimethanol type epoxy resin and hydroxy group-containing hydrogenated bisphenol type epoxy resin; novolak type epoxy resins such as hydroxy group-containing phenol novolak type epoxy resin, hydroxy group-containing cresol novolak type epoxy resin, hydroxy group-containing bisphenol A novolak type epoxy resin, and hydroxy group-containing biphenyl novolak type epoxy resin; hydroxy group-containing dicyclopentadiene type epoxy resin; hydroxy group-containing triphenylmethane type epoxy resin; hydroxy group-containing tetraphenylethane type epoxy resin; hydroxy group-containing phenol aralkyl type epoxy resin; etc. The hydroxy group-containing epoxy resin may be used alone or in combination of two or more.

[0026] 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.

[0027] 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;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 and other aromatic polyisocyanate compounds; 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, hydrogenated products of the above aromatic polyisocyanates and other alicyclic polyisocyanate compounds;Polyisocyanate derivatives such as biuret, allophanate, adduct, urethane, carbodiimide, and polyisocyanate compounds such as polymers; etc. can be mentioned.

[0028] 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; etc.

[0029] 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 200 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.

[0030] <Mesogen-modified epoxy resin having an -O-CH2CH(OH)CH2-O- skeleton in the molecule> The mesogen-modified epoxy resin having an -O-CH2CH(OH)CH2-O- skeleton in the molecule is an epoxy resin having an -O-CH2CH(OH)CH2-O- skeleton, a mesogen skeleton, and one or more epoxy groups in the molecule, and is not particularly limited as long as it is an epoxy resin other than the component (A). The mesogen-modified epoxy resin having an -O-CH2CH(OH)CH2-O- skeleton in the molecule may be used alone or in combination of two or more.

[0031] Examples of the mesogen skeleton include skeletons that have rigidity and orientation and are likely to exhibit liquid crystallinity and / or crystallinity due to intermolecular interactions. For example, rod-shaped or plate-shaped rigid aromatic or non-aromatic rings, or skeletons in which aromatic or non-aromatic rings are bonded by single bonds and / or non-single bonds (e.g., -CH=CH-, -C≡C-, -CH2O-, -CH2CH2-, -COO-, -OCO-, -O-, -CH=N-, -N=CH-, -N=N-, -CH=C(CH3)-, -CH=N(→O)-, -N=N(→O)-, -CH=CH-CO-, -CH=C(CN)-, etc.). The single bond and / or non-single bond may be used alone or in combination of two or more. Examples of the aromatic or non-aromatic ring include phenyl, biphenyl, phenyl benzoate, azobenzene, stilbene, naphthalene, anthracene, phenanthrene, cyclohexylbenzene, phenylpyrimidine, biphenyl benzoate, cyclohexylbiphenyl, terphenyl, etc. The aromatic or non-aromatic ring may be used alone or in combination of two or more.

[0032] Examples of the mesogen-modified epoxy resin having an -O-CH2CH(OH)CH2-O- skeleton in the molecule include LCE-2615 manufactured by Nippon Kayaku Co., Ltd.

[0033] <Bisphenol type epoxy resin> The bisphenol type epoxy resin is not particularly limited as long as it is an epoxy resin having one or more bisphenol type skeletons represented by the formula (b3) in the molecule; [Chemical formula] In the formula (b3), b11 is an integer from 0 to 4, and b12 is an integer from 0 to 4. R is a substituent, and when there are a plurality of R c they may be the same or different from each other. R c When there are a plurality of them, they may be the same or different from each other. R cExamples thereof 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, a cyano group and the like. The substituents may be single or in combination of two or more. X is -CR a41 R a42 -, -S(=O)2-, -O-, -C(=O)-, which is a group selected from, and R a41 and R a42 are 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 (b1) 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).

[0034] 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 and the like. 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.

[0035] Examples of bisphenol type epoxy resins include, for example, the jER series manufactured by Mitsubishi Chemical Corporation (e.g., 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 EP 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.

[0036] <Dicyclopentadiene type epoxy resin> The dicyclopentadiene type epoxy resin has the formula (b4) in the molecule;

Chemical formula

[0037] Examples of the dicyclopentadiene-type epoxy resin include a dicyclopentadiene-phenol epoxy resin obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound, a dicyclopentadiene epoxy resin obtained by epoxidizing dicyclopentadiene polyol, and the like. The dicyclopentadiene-type epoxy resin may be used alone or in combination of two or more.

[0038] Examples of the dicyclopentadiene-type epoxy resin include the EPICLON series (HP7200L, HP7200, HP7200H, HP7200HH, HP7200HHH, HP-7200H-75M, etc.) manufactured by DIC Corporation; the Tactix series (556, 558, etc.) manufactured by Huntsman Advanced Materials; the XD series (1000, 1000-1L, 1000-2L, 1000-H, etc.) manufactured by Nippon Kayaku Co., Ltd.; the Adeka Resin series (EP-4088S, EP-4088L, etc.) manufactured by ADEKA Corporation; and the like.

[0039] <Content of component (B)> The content of component (B) "one or more epoxy resins selected from the group consisting of polyether-modified epoxy resins, urethane-modified epoxy resins, mesogen-modified epoxy resins having an -O-CH2CH(OH)CH2-O- skeleton in the molecule, bisphenol-type epoxy resins, and dicyclopentadiene-type epoxy resins" in the epoxy resin composition is not particularly limited. With respect to 100 parts by mass in total of components (A) to (D), it can be, for example, 0.2 parts by mass or more, preferably 0.4 parts by mass or more, more preferably 0.5 parts by mass or more, and can be, for example, 10.0 parts by mass or less, preferably 7.0 parts by mass or less, more preferably 5.0 parts by mass or less. When the content of component (B) is less than 0.2 parts by mass with respect to 100 parts by mass in total of components (A) to (D), the epoxy resin composition may not form a film, the short-time heat bonding strength may decrease, and the heat resistance may decrease. When it exceeds 10.0 parts by mass, the curing may take a long time and the conductivity may decrease.

[0040] [Component (C)] Component (C), which is a constituent component of the epoxy resin composition of the present invention, is an imidazole-based compound and / or a phenol-based compound. The imidazole-based compound functions as a curing agent and / or a curing accelerator for the epoxy resin, and the phenol-based compound functions as a curing agent for the epoxy resin.

[0041] [Imidazole-based compound] Examples of the imidazole-based compound include imidazole compounds, inclusion imidazoles, microcapsule-type imidazoles, imidazole adducts, stabilizer-coordinated imidazoles, and the like. Among these, imidazole adducts, inclusion 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 an inclusion imidazole is preferable. The imidazole-based compound may be used alone or in combination of two or more.

[0042] 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 viewpoints 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, Curezol series (2E4MZ, 2P4MZ, 2P4MHZ, 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] Examples of the clathrate imidazoles 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 imidazoles. Examples thereof include NISSOCURE TIC-188, KM-188, HIPA-2P4MHZ, NIPA-2P4MHZ, TEP-2E4MZ, HIPA-2E4MZ, NIPA-2E4MZ, etc. manufactured by Nippon Soda Co., Ltd.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] Among imidazole-based compounds, imidazole adducts are obtained by reacting an imidazole compound with a compound capable of reacting with the imidazole compound and subjecting the imidazole compound to adduct treatment. For example, compounds obtained by subjecting an epoxy group-containing compound and an imidazole compound to a ring-opening addition reaction can be mentioned. 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 (for example, P0505, etc.) manufactured by Shikoku Kasei Kogyo Co., Ltd.; and the like.

[0051] Among imidazole-based compounds, stabilizer-coordinated imidazoles are those 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-boric acid ester blends and the like. For example, an imidazole adduct (for example, Cureduct P0505 manufactured by Shikoku Kasei Kogyo Co., Ltd.) coordinated with an epoxy-phenol-boric acid ester blend (for example, L-07L manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a stabilizer can be mentioned.

[0052] <Phenolic compound> The phenolic compound is not particularly limited as long as it has one or more, preferably two or more phenolic hydroxyl groups capable of reacting with an epoxy group in the molecular structure. For example, bisphenols such as bisphenol A, bisphenol B, bisphenol F, bisphenol AD, and bisphenol S; biphenyls such as biphenyl and tetramethylbiphenyl; phenols such as hydroxyphenol and bis(4-hydroxyphenyl) ether; alkylphenols; phenol novolacs such as 2,6-bis[(2-hydroxyphenyl)methyl]-phenol and phenol biphenylene novolak (biphenyl aralkylphenol); cresol novolacs such as o-cresol novolak, m-cresol novolak, and p-cresol novolak; triphenylmethanes; tetrakisphenols; phenolic resins; phenol novolak resin; biphenyl aralkyl type phenolic resin; phenol biphenylene novolak resin; tetrakisphenolic compounds 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, and 1,1,2,2-tetrakis(3-chloro-4-hydroxyphenyl)ethane; 4,4’,4’’-trihydroxytriphenylmethane, 4,4’,4’’,4’’’-methanetetrayltetraphenol, etc. are mentioned.

[0053] Commercially available products may be used for the phenolic compound. For example, MEH-8005 manufactured by Meiwa Kasei Co., Ltd., KAYAHARD series (GPH-65, GPH-103, etc.) manufactured by Nippon Kayaku Co., Ltd., BRG-555, BRG-556, BRG-557, BRG-558, CRG-951, TAM-005 manufactured by Aica Kogyo Co., Ltd., TEP-DF, PAPS series (BPAN, PN2, etc.) manufactured by Asahi Organic Chemicals Industry Co., Ltd., etc. are mentioned. The phenolic compound may be used alone or in combination of two or more.

[0054] <Content of component (C)> The content of component (C), "imidazole-based compound and / or phenol-based compound", in the epoxy resin composition is not particularly limited. When the total of component (A), component (B) and the epoxy component as other components in the epoxy resin composition is 100 parts by mass, the total amount of the imidazole compound and the phenol compound in the "imidazole-based compound and / or phenol-based compound" can be, for example, 1.0 part by mass or more, preferably 3.0 parts by mass or more, more preferably 5.0 parts by mass or more, and can be, for example, 40.0 parts by mass or less, preferably 35.0 parts by mass or less, more preferably 30.0 parts by mass or less. When the content of component (C), "imidazole-based compound and / or phenol-based compound", is less than 0.1 part by mass, the curability of the epoxy resin composition may decrease and the curing may take a long time. When it exceeds 40.0 parts by mass, the epoxy resin composition may not solidify and may not form a film. For example, when an imidazole compound is used as the "imidazole-based compound and / or phenol-based compound", the total amount of the imidazole compound and the phenol compound in the "imidazole-based compound and / or phenol-based compound" is the same as the amount of the imidazole compound used. On the other hand, when a material containing components other than the imidazole compound and the phenol compound, such as clathrate imidazole, microcapsule-type imidazole and stabilizer-coordinated imidazole, is used as the "imidazole-based compound and / or phenol-based compound", the amount excluding the components other than the imidazole compound and the phenol compound is the "total amount of the imidazole compound and the phenol compound in the 'imidazole-based compound and / or phenol-based compound'".

[0055] [Component (D)] Component (D), which is a constituent component of the epoxy resin composition of the present invention, is one or more conductive powders selected from silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder and gold-based powder. In the present invention, as the component (D) "one or more conductive powders selected from silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder, and gold-based powder", from the viewpoints of cost, conductivity, migration characteristics, etc., it is preferable to use "one or more conductive powders selected from silver-coated copper powder, silver-based powder, nickel-based powder, and conductive carbon powder", and it is more preferable to use silver-coated copper powder.

[0056] The shape of the component (D) "one or more conductive powders selected from silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder, and gold-based powder" is not particularly limited. Spherical, substantially spherical (for example, the aspect ratio of length to width is 1.5 or less), dendritic, flat, block-shaped, plate-shaped, polyhedral pyramid-shaped, polyhedral-shaped, flake-shaped (scaly), rod-shaped, fibrous, needle-shaped, irregular-shaped, etc. can be used according to the application and the like. In the present invention, from the viewpoints of oxidation resistance, volume resistivity, dispersibility, handleability, etc., spherical, substantially spherical, dendritic, flat or flake-shaped (scaly) ones are preferable.

[0057] <Silver-coated copper powder> The silver-coated copper powder is not particularly limited as long as the surface of the copper powder is coated with silver. By silver-coating the copper powder, it has excellent oxidation resistance, can lower the volume resistivity, and can improve the storage stability of the epoxy resin composition, etc. The production method of the silver-coated copper powder is not particularly limited. For example, any silver-coated copper powder such as silver-coated copper powder by silver plating, silver-coated copper powder by the substitution reaction of copper and silver, etc. can be used.

[0058] The volume average particle diameter of the silver-coated copper powder is not particularly limited. For example, it can be 0.1 μm or more, preferably 0.3 μm or more, more preferably 0.5 μm or more, and can be 100 μm or less, preferably 50 μm or less, more preferably 20 μm or less. For example, in order to be able to print an epoxy resin composition, particularly to enable coating by a screen printing method or a dispenser method, it is preferably 0.5 μm or more and 10 μm or less. Here, the average particle diameter of the silver-coated copper powder in the present invention is the value of the volume cumulative particle diameter D50 at a cumulative volume of 50% by volume measured by a laser diffraction scattering particle size distribution measurement method. This is because if the average particle diameter of the silver-coated copper powder is larger than 10 μm, the leveling property of the conductive paste deteriorates, and disconnection of the wiring pattern is likely to occur, making it difficult to form a narrow wiring pattern. Also, if the average particle diameter of the silver-coated copper powder is smaller than 0.5 μm, the core copper is exposed and copper oxidizes from this part, which may increase the specific resistance of the wiring pattern over time. In addition, in the case of flaky silver-coated copper powder, its thickness is not particularly limited. For example, it is 0.01 μm or more, preferably 0.05 μm or more, and for example, 20.0 μm or less, preferably 10.0 μm or less.

[0059] Specific examples of the silver-coated copper powder include 10% Ag-coated Cu-HWQ5μm, 10% Ag-coated FCC-2000, 10% Ag-coated FCC-115, 10% Ag-coated 2L3 (manufactured by Fukuda Metal Foil & Powder Co., Ltd.), 10% Ag / 1100Y, 10% Ag / 1100YP, ACFY-2, ACAX-225, ACBY-2, 10% Ag / 05KP (manufactured by Mitsui Mining & Smelting Co., Ltd.), TFM-C02P, TFM-C05P, TFM-C05F, TFM-C15F (manufactured by Toyo Aluminum Co., Ltd.), etc. The silver-coated copper powder may be used alone or in combination of two or more.

[0060] The silver content in the silver-coated copper powder is preferably 5% by mass or more and 30% by mass or less. If the silver content is less than 5% by mass, the core copper may be exposed, and the specific resistance of the wiring pattern may increase over time. Also, if the silver content exceeds 30% by mass, there is a high possibility that ion migration may occur.

[0061] <Silver-based powder> The silver-based powder is a powder other than silver-coated copper, and is not particularly limited as long as it is a powder containing metallic silver. For example, metallic silver powder, silver alloy powder, silver-coated powder other than silver-coated copper, etc. may be mentioned. The silver-based powder may be used alone or in combination of two or more.

[0062] The metallic silver powder is obtained by pulverizing metallic silver. The silver content in the metallic silver powder is not particularly limited. For example, it is 97% by mass or more, preferably 98% by mass or more, and more preferably 99% by mass or more.

[0063] The silver alloy powder is not particularly limited as long as it is an alloy powder containing silver. The silver content in the silver alloy powder can be appropriately determined from the viewpoints of the melting point properties of the silver alloy powder, etc. For example, it is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and for example, less than 97% by mass. The silver content in the silver-containing powder can be easily measured by using a fluorescent X-ray analysis (XRF) apparatus or the like. Examples of the silver alloy powder include silver-copper-based alloys, silver-platinum-based alloys, silver-palladium-based alloys, etc.

[0064] The silver-coated powder other than the silver-coated copper powder is one in which at least a part of the particle surface is coated with metallic silver. Examples of the particles forming the silver-coated powder include one or more of metallic particles (for example, palladium particles, aluminum particles, nickel particles, alloy particles, etc.), organic polymer particles, non-metallic inorganic particles (for example, silica particles, alumina particles, carbon particles, potassium titanate particles, glass particles, ceramic particles, mineral-based particles, etc.). As the means for coating with metallic silver, means such as plating and vapor deposition can be mentioned. The thickness of the metallic silver coating is not particularly limited, but it is preferably in the range of 0.01 μm or more and 5 μm or less.

[0065] The silver-based powder may further contain other atoms as long as the properties of the silver-based powder are not inhibited. Examples of other atoms include one or more of Ni, Mn, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Al, Zr, W, Mo, Ti, Co, Sn, Au, Hf, Nb, Ta, Cr, Fe, Ru, Rh, Ir, Pd, Pt, Cu, Ga, In, Si, Ge, Bi, C, B, N, P, S, etc. The content rate of other atoms is, for example, 3 mass% or less, preferably 1 mass% or less in the silver-based powder.

[0066] The volume average particle diameter of the silver-based powder is not particularly limited. It can be appropriately determined in consideration of dispersibility and handleability. For example, it can be 0.1 μm or more, preferably 0.4 μm or more, more preferably 0.7 μm or more, and for example, 100.0 μm or less, preferably 50.0 μm or less, more preferably 20.0 μm or less.

[0067] The specific surface area of the silver-based powder is not particularly limited. For example, it can be 0.30 m 2 / g or more, preferably 0.50 m 2 / g or more, more preferably 0.70 m 2 / g or more, and for example, 2.5 m 2 / g or less, preferably 2.1 m 2 / g or less, more preferably 1.6 m 2 / g or less.

[0068] <Nickel-based powder> The nickel-based powder is not particularly limited as long as it is a powder containing metallic nickel. For example, metallic nickel powder, nickel alloy powder, nickel-coated powder, etc. can be mentioned. The nickel-based powder may be used alone or in combination of two or more.

[0069] The metallic nickel powder is obtained by pulverizing metallic nickel. The nickel content in the metallic nickel powder is not particularly limited. For example, it is 95% by mass or more, preferably 97% by mass or more, and more preferably 99% by mass or more.

[0070] The nickel alloy powder is not particularly limited as long as it is an alloy powder containing nickel. The nickel content in the nickel alloy powder can be appropriately determined from viewpoints such as the melting point of the nickel alloy powder. For example, it is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and preferably less than 95% by mass. The nickel content rate in the nickel-containing powder can be easily measured by using a fluorescent X-ray analysis (XRF) apparatus or the like. Examples of the nickel alloy powder include nickel-iron alloys (such as Ni-58Fe), nickel-copper alloys (such as Ni-75Cu), nickel-copper-zinc alloys (such as Ni-6Cu-20Zn), nickel-chromium alloys, nickel-chromium-silver alloys, and the like.

[0071] The nickel-coated powder is one in which at least a part of the particle surface is coated with metallic nickel. Examples of the particles forming the nickel-coated powder include one or more of metallic particles (such as palladium particles, aluminum particles, nickel particles, alloy particles, etc.), organic polymer particles, non-metallic inorganic particles (such as carbon particles, potassium titanate particles, glass particles, ceramic particles, mineral-based particles, etc.). Examples of the coating means of metallic nickel include means such as plating and vapor deposition. The thickness of the metallic nickel coating is not particularly limited, but it is preferably in the range of 0.01 μm or more and 5 μm or less.

[0072] The nickel-based powder may further contain other atoms as long as the properties of the nickel-based powder are not inhibited. Examples of the other atoms include one or more of Ag, Mn, Sb, Si, K, Na, Li, Ba, Sr, Ca, Mg, Be, Zn, Pb, Cd, Tl, V, Al, Zr, W, Mo, Ti, Co, Sn, Au, Hf, Nb, Ta, Cr, Fe, Ru, Rh, Ir, Pd, Pt, Cu, Ga, In, Si, Ge, Bi, C, B, N, P, S, etc. The content of the other atoms is, for example, 3% by mass or less, preferably 1% by mass or less in the nickel-containing powder.

[0073] The volume average particle diameter of the nickel-based powder is not particularly limited and can be appropriately determined in consideration of dispersibility and handleability. For example, it can be 0.5 μm or more, preferably 1.0 μm or more, more preferably 3.0 μm or more, and for example, it can be 100.0 μm or less, preferably 50.0 μm or less, more preferably 20.0 μm or less.

[0074] <Conductive carbon powder> The conductive carbon powder is not particularly limited as long as it is a carbon powder composed of carbon atoms. Examples include carbon black, activated carbon, carbon fiber, carbon nanotube, graphene, etc. Preferably, carbon black, carbon nanotube, and graphene are included. The conductive carbon powder may be used alone or in combination of two or more.

[0075] Examples of the carbon black include acetylene black, furnace black, ketjen black, channel black, lamp black, thermal black, etc.

[0076] The primary particle diameter of the carbon black is not particularly limited. For example, it can be 5 nm or more, preferably 10 nm or more, and for example, it can be 700 nm or less, preferably 500 nm or less. The primary particle diameter can be the arithmetic average of the particle diameters of 100 particles observed and measured by an electron microscope (SEM or TEM).

[0077] A carbon nanotube is a cylindrical hollow fibrous material composed of carbon, and it may be either a multi-walled carbon nanotube or a single-walled carbon nanotube. From the viewpoint of conductivity, multi-walled carbon nanotubes are preferred. The carbon nanotubes may be, for example, those produced by an arc discharge method, a chemical vapor deposition method (CVD method), or a laser ablation method. Commercially available carbon nanotubes may also be used.

[0078] The average diameter of the carbon nanotubes can be, for example, 1 nm or more, preferably 3 nm or more, more preferably 5 nm or more, and can be, for example, 30 nm or less, preferably 25 nm or less, more preferably 20 nm or less. The average length of the carbon nanotubes can be, for example, 0.1 μm or more, preferably 0.5 μm or more, and can be, for example, 100 μm or less, preferably 70 μm or less. The average diameter and average length of the carbon nanotubes are the arithmetic means of the average diameters and average lengths of 100 carbon nanotubes observed and measured by an electron microscope (SEM, TEM), respectively.

[0079] The BET specific surface area of the carbon nanotubes is, for example, 50 m 2 / g or more, preferably 100 m 2 / g or more, more preferably 150 m 2 / g or more, and can be, for example, 800 m 2 / g or less, preferably 600 m 2 / g or less, more preferably 500 m 2 / g or less.

[0080] Graphene is a material with a dense two-dimensional crystal structure having a carbon six-membered ring structure and has quantized conduction characteristics (ballistic conduction characteristics).

[0081] <Copper-based powder> The copper-based powder is a powder containing metallic copper, and is not particularly limited as long as it is a powder other than silver-coated copper powder, silver-based powder, and nickel-based powder. For example, metallic copper powder, copper alloy powder, copper-coated powder, etc. may be mentioned. The copper-based powder may be used alone or in combination of two or more.

[0082] <Gold-based powder> The gold-based powder is a powder containing metallic gold, and is not particularly limited as long as it is a powder other than silver-coated copper powder, silver-based powder, nickel-based powder, and copper-based powder. For example, metallic gold powder, gold alloy powder, gold-coated powder, etc. may be mentioned. The gold-based powder may be used alone or in combination of two or more.

[0083] The content of component (D) "one or more conductive powders selected from silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder, and gold-based powder" in the epoxy resin composition is not particularly limited. Taking the total amount of the cured product of the epoxy resin composition as 100% by mass, for example, it is 75% by mass or more, preferably 80% by mass or more, more preferably 82% by mass or more, and for example, 97% by mass or less, preferably 95% by mass or less, more preferably 93% by mass or less. When the content of component (D) is less than 75% by mass with the total amount of the cured product of the epoxy resin composition being 100% by mass, the conductivity of the obtained cured product (coating film) of the epoxy resin composition may be insufficient (the volume resistivity increases), and when it exceeds 97% by mass, the bonding strength of the epoxy resin composition may be insufficient.

[0084] [Other components] The epoxy resin composition of the present invention may contain, as necessary and within a range where the performance is not deteriorated, a solvent, a resin other than the epoxy resin, an epoxy resin other than the component (A) and the component (B), a coupling agent, a wetting and dispersing agent, a filler, an epoxy resin curing agent other than the component (C), a curing accelerator (curing catalyst) other than the component (C), an adhesion promoter, a viscoelasticity modifier, a reactive diluent, a conductive powder other than the component (D), an antioxidant, a gap regulator (spacer; interval controller), an organic acid compound, a pigment, a corrosion inhibitor, a surfactant, an antifoaming agent, a dispersant, a viscosity regulator (thixotropy regulator), an adhesion-imparting agent, an anti-settling agent, etc., a pH regulator, a leveling agent, an ultraviolet absorber, a flame retardant, a heavy metal inactivator, a gap regulator, etc., "other components". The other components may be used singly or in combination of two or more.

[0085] <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 workability, coatability, handleability, etc. can be improved. 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 becomes a viscosity that can be appropriately applied, printed, etc. on a substrate and / or a viscosity that can be appropriately impregnated into an impregnated material such as a non-woven fabric or a porous body.

[0086] 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, isopalmitol, 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; and the like, 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.

[0087] <Resins other than epoxy resins> The epoxy resin composition of the present invention may contain a resin other than the epoxy resin. The resin other than the epoxy resin may be either a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include polyvinyl acetal resins, 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, and the like. Examples of the thermosetting resin include resol type phenol resins, polyimide resins, xylene resins, polyurethane resins, melamine resins, urea resins, furan resins, isocyanate resins, urea resins, blocked urethane resins, and the like. In the present invention, as the resin other than the epoxy resin, polyurethane resins, blocked urethane resins, polyvinyl acetal resins, resol type phenol resins, acrylic resins, polyester resins, phenoxy resins, polyimide resins, and xylene resins are preferable. Among these, from the viewpoints of film-forming state, connection reliability, adhesion to the substrate, etc., polyurethane resins, blocked urethane resins, polyester resins, polyvinyl acetal resins, and acrylic resins are more preferable. The resin other than the epoxy resin may be used alone or in combination of two or more.

[0088] <Epoxy resin other than component (A) and component (B)> The epoxy resin composition of the present invention may contain an epoxy resin other than component (A) and component (B). The epoxy resin other than component (A) and component (B) is not particularly limited as long as it is an epoxy resin other than triphenylmethane type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, polyether-modified epoxy resin, urethane-modified epoxy resin, mesogen-modified epoxy resin having an -O-CH2CH(OH)CH2-O- skeleton in the molecule, bisphenol type epoxy resin, and dicyclopentadiene type epoxy resin. Epoxy resins other than component (A) and component (B) 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, alkyl-modified triphenolmethane type epoxy resin, phenol aralkyl type epoxy resin having a phenylene skeleton; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated biphenol type epoxy resin, epoxy resins having an alicyclic structure such as glycidyl ethers of polyols having an alicyclic structure such as cyclohexanediol, cyclohexanedimethanol, and cyclohexanedietanol; glycidyl ethers of aliphatic polyols such as butanediol, hexanediol, octanediol, nonanediol, decanediol, pentaerythritol, glycerin, and trimethylolpropane; aromatic glycidylamine type epoxy resins such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diamino diphenylmethane type glycidylamine, and aminophenol type glycidylamine; etc. The epoxy resin other than component (A) and component (B) may be used alone or in combination of two or more.

[0089] <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 γ-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, titanium dodecylbenzenesulfonate 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 zirconium coupling agents 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 silane coupling agent may be used alone or in combination of two or more.

[0090] <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, Solsperse series (9000, 12000, 17000, 20000, 21000, 24000, 26000, 27000, 28000, 32000, 35100, 54000, etc.) manufactured by Lubrizol Japan, 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, Ajisper series (PA111, PB711, PB821, PB822, PN411, etc.) manufactured by Ajinomoto Fine-Techno Co., Ltd., 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.

[0091] <Filler> The epoxy resin composition of the present invention may contain a filler. Examples of the filler include fused silica, fumed silica, precipitated silica, crystalline silica, carbon black, dolomite, silicic anhydride, hydrous silicic acid, heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, glass powder, zinc oxide, silas balloon, glass balloon, phenolic resin microballoon, vinylidene chloride resin microballoon, vinyl chloride resin, acrylic resin powder, styrene resin powder, urethane resin powder, polyamide resin powder, glass fiber, potassium titanate fiber, and the like. The filler may be used alone or in combination of two or more.

[0092] <Epoxy resin curing agent other than component (C)> The epoxy resin composition of the present invention may contain an epoxy resin curing agent other than component (C) (imidazole-based compound and / or phenolic-based compound). Examples of such an epoxy resin curing agent include acid anhydride-based curing agents, amine-based curing agents, thiol-based curing agents, amide-based curing agents, and thermal cationic polymerization initiators. The epoxy resin curing agent other than component (C) may be used alone or in combination of two or more.

[0093] The acid anhydride-based curing agent is not particularly limited as long as it is a compound having one or more carboxylic acid anhydride groups (-C(=O)-O-C(=O)-) in its 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, 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 among the organic carboxylic acids are included. Examples include aliphatic monocarboxylic acid anhydrides, aliphatic polycarboxylic acid anhydrides, alicyclic polycarboxylic acid anhydrides, aromatic polycarboxylic acid anhydrides, and the like.

[0094] 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 the 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. are particularly mentioned, and SB-20AH, IPU-22AH, and ST-2PAH are especially mentioned. The acid anhydride-based curing agent may be used alone or in combination of two or more.

[0095] Examples of the thiol-based curing agent include thiol compounds 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.

[0096] 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.

[0097] 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.

[0098] 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 its 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, polyamideamines, etc. obtained by modifying these by 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.

[0099] The thermal cationic polymerization initiator is not particularly limited as long as it is a compound that generates cations by heat. For example, an onium salt composed of at least one cation selected from aromatic sulfonium, aromatic iodonium, aromatic diazonium, pyridinium, etc., and at least one anion selected from BF4-, PF6-, SbF6-, AsF6-, CF3SO3-, (CF3SO2)2N-, B(C6F5)4-, etc.; an aluminum complex; etc. are mentioned. For example, TA-100, TA-100FG, IK-1, IK-1FG, etc. manufactured by San-Apro; 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 mentioned. The thermal cationic polymerization initiator may be used alone or in combination of two or more.

[0100] <Curing accelerator (curing catalyst) other than component (C)> The epoxy resin composition of the present invention may contain a curing accelerator (curing catalyst) other than the component (C) (imidazole-based compound and / or phenol-based compound) in order to accelerate the curing of the epoxy resin and the curing agent. Such curing accelerators are not particularly limited, but examples include amine-based curing accelerators, guanidine-based curing accelerators, phosphonium-based curing accelerators, transition metal-based curing accelerators, etc. 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).

[0101] 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-tetrapyrrolo[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. As the curing accelerator (curing catalyst) other than the component (C), one kind may be used alone or two or more kinds may be used.

[0102] <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, and hydroxyl groups), and salts thereof. Examples of the adhesion promoter include the BYK series (4509, 4510, 4512, etc.) manufactured by BYK Chemie Japan. As the adhesion promoter, one kind may be used alone or two or more kinds may be used.

[0103] <Viscoelasticity modifier> The epoxy resin composition of the present invention may contain a viscoelasticity regulator (rheology control agent). Thereby, the viscoelasticity (rheology) of the epoxy resin composition can be adjusted, contributing to the improvement of workability and the like. Examples of the viscoelasticity regulator (rheology control agent) include polyamide-based, aminoplast-based, polycarboxylic acid-based, urethane-based, cellulose-based, and inorganic layered compound-based viscoelasticity regulators (rheology control agents). For example, RHEOBYK series (H370, H400, H600, H600VF, 100, 405, 410, 411, 415, 430, 431, 440, 7410ET, etc.) manufactured by BYK Japan; DISPARON series (AQ-600, AQH-800, 3600N, 3900EF, etc.) manufactured by Kusumoto Chemicals, Ltd.; SN thickener series (613, 617, 618, 630, 634, 636, 621N, 623N, etc.) manufactured by San Nopco Ltd.; ADEKA NOL series (UH-814N, UH-752, UH-750, UH-462, etc.), HEC Daicel series (SP600N, etc.) manufactured by Daicel Corporation; BENTONE HD manufactured by Elementis Japan, etc. The viscoelasticity regulator may be used alone or in combination of two or more.

[0104] <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. The reactive diluent may be used alone or in combination of two or more.

[0105] <Conductive powder other than component (D)> The epoxy resin composition of the present invention may contain a conductive powder other than the component (D) "one or more conductive powders selected from silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder, and gold-based powder". Examples of the conductive powder other than the component (D) include lead-free solder powder, tin powder, zinc powder, aluminum powder, iron powder, metal alloy powders other than silver-based, nickel-based, copper-based, and gold-based, resin particles coated with a metal other than silver, nickel, copper, and gold, etc. (D) The shape of the conductive powder other than the component is not particularly limited. It can be spherical, substantially spherical (for example, the aspect ratio of length to width is 1.5 or less), flat, block-shaped, plate-shaped, polyhedral pyramid-shaped, polyhedral-shaped, scaly, rod-shaped, fibrous, needle-shaped, irregular-shaped, etc. From the viewpoints of oxidation resistance, volume resistivity, dispersibility, handleability, etc., spherical, substantially spherical, flat or scaly ones are preferred. (D) The conductive powder other than the component may be used alone or in combination of two or more.

[0106] <Antioxidant> The epoxy resin composition of the present invention may contain an antioxidant. This can contribute to the improvement of 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.

[0107] Examples of the antioxidant 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 side - chain 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 diethylbis[[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-phenylbenzenamine 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; phosphites 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; etc. can be mentioned., Commercially available products may be used as the antioxidant. For example, the IRGANOX series manufactured by BASF, the ADEKA STAB series manufactured by ADEKA, the NONFLEX series manufactured by Seiko Chemical Co., Ltd., the Sumilizer series manufactured by Sumitomo Chemical Co., Ltd., etc. can be mentioned., The antioxidant may be used alone or in combination of two or more.,

[0108] <Gap adjuster (spacer; interval controller)> The epoxy resin composition of the present invention may contain a gap adjuster (spacer; interval controller). The gap adjuster (spacer; interval controller) is used to control the thickness between adherends (the thickness of the adhesive layer). The gap adjuster (spacer; interval controller) is not particularly limited as long as it has a hardness that can withstand use and a desired particle size and aspect ratio. For example, silica fine particles (spherical silica), glass beads, ground glass fibers, resin beads, etc. can be mentioned., The resin beads are not particularly limited. For example, various (meth)acrylates such as polyethylene, polypropylene, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polymethyl methacrylate, polyimide, polyamide, polyester, polyvinyl chloride, polyvinylidene chloride, polydivinylbenzene, fluororesin, polyphenylene oxide, polyphenylene sulfide, polymethylpentene, urea resin, melamine resin, phenol resin, epoxy resin, benzoguanamine resin, polyacetal resin, xylene resin, furan resin, polyisocyanate resin, phenoxy resin, silicone resin, etc. can be mentioned. The resin beads may have their surfaces coated with a conductive metal such as Ag, Cu, Au, Pt, Ni, Al, Sn, Zn or its oxide, alloy, etc. As the gap adjuster (spacer; interval controller), commercially available products may be used. For example, the High-Presica series manufactured by Ube Eximer Co., Ltd., the Micro Pearl series manufactured by Sekisui Chemical Co., Ltd., the Tech Polymer series manufactured by Sekisui Chemical Products Co., Ltd., the Uni Beads series manufactured by Unitika Glass Beads Co., Ltd., etc. can be mentioned. The gap adjuster (spacer; interval controller) may be used alone or in combination of two or more.

[0109] [Conductivity of the cured film of the epoxy resin composition] The epoxy resin composition of the present invention has a cured film with a low volume resistivity and excellent conductivity. As the volume resistivity of the cured film of the epoxy resin composition, for example, it can be less than 1.0×10 -3 Ω·cm, preferably less than 8.0×10 -4 Ω·cm, more preferably less than 6.0×10 -4 Ω·cm. The volume resistivity of the cured film can be determined, for example, by casting or coating the epoxy resin composition on a peelable substrate, heating and curing at 150°C for 30 minutes to form a cured film with a thickness of 30 to 50 μm, and measuring it with a resistivity meter (for example, "Loresta GP-MCP T610" (manufactured by Nitto Seiko Analytic Co., Ltd.), etc.).

[0110] [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 (D) and other components used as necessary to a mixing container in an arbitrary order and mixing and stirring them. 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 rotating and revolving mixer, a kneading roll, a single-screw or twin-screw extruder, etc. can be used for mixing and stirring.

[0111] The temperature when preparing the epoxy resin composition (the temperature when mixing each component) is not particularly limited. If necessary, heating or the like can be performed, 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.

[0112] [Uses of Epoxy Resin Composition] The epoxy resin composition of the present invention can be used as a conductive paste or the like used for forming a conductive layer in the manufacture of 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 powder-like at room temperature (25°C ± 5°C). The liquid epoxy resin composition can be, for example, a composition obtained by simply stirring and mixing the constituent components of the epoxy resin composition as 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 peelable substrate to form a film, drying to remove the solvent to form a film, and peeling it from the peelable substrate. Further, the film-like epoxy resin composition can be obtained by impregnating a nonwoven fabric or the like, forming it on a releasable substrate, drying to remove the solvent, and then peeling it off from the releasable substrate.

[0113] 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.

[0114] The epoxy resin composition of the present invention can be applied to various substrates by any printing and 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. In particular, from the viewpoint of preventing oxidation of the conductive powder, an inert gas atmosphere such as nitrogen or argon is preferable. The film thickness of the formed coating film can be set to an appropriate thickness according to various applications. For example, it can be 7 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and can be 100 μm or less, for example.

[0115] The epoxy resin composition of the present invention can be used as a conductive material. Examples of the conductive material include conductive ink, circuit connection material, conductive adhesive, conductive paste, conductive film, conductive fiber, conductive paint, conductive material for semiconductor packages, conductive material for microelectronic devices, antistatic material, electromagnetic wave shielding material, die attach paste, actuator, sensor, conductive resin molded body, etc.

[0116] For example, the epoxy resin composition 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 then heated and dried at a temperature of 300°C or lower to form a conductive coating film. The atmosphere during drying includes one or more selected from the group consisting of air, inert gas, vacuum, reduced pressure, etc. In particular, from the viewpoint of suppressing deterioration of the coating film (such as preventing oxidation of conductive powder), an inert gas atmosphere such as nitrogen or argon is preferable.

[0117] The epoxy resin composition of the present invention can also be used, for example, as a conductive material for printing for forming a coating film such as wiring by printing on a substrate. Examples of the printing and coating methods include screen printing method, inkjet printing method, flexographic printing method, gravure printing method, etc. In the present invention, since it has excellent printability and shape retention, it is preferable to use one or more printing methods selected from the group consisting of screen printing method, metal mask printing method, inkjet printing method, etc. The mesh during screen printing can be appropriately selected, and it is preferable to adopt a mesh such that the conductive powder is not excessively removed. The film thickness of the conductive coating film formed by printing can be set to an appropriate thickness according to various applications. For example, it is 7μm or more, preferably 10μm or more, more preferably 15μm or more, and for example, 100μm or less.

Examples

[0118] Examples are given below to explain the present invention in more detail. Note that the present invention is not limited to these examples. Unless otherwise specified, “%” means “mass %” and “part” means “part by mass”. Also, all the numerical values regarding the blending amounts of the respective components in Tables 1 and 2 are “parts” (parts by mass).

[0119] [Components Used] In Examples 1 to 15 and Comparative Examples 1 to 7, the components used are as follows. In each structural formula, n is the number of repeating units and is a value that gives a predetermined epoxy equivalent or hydroxyl equivalent. MG is a mesogenic group. The hydroxyl equivalent is the molecular weight per hydroxyl group and can be determined, for example, from the following formula. Hydroxyl equivalent = number average molecular weight / number of hydroxyl groups per molecule

[0120] <Component (A)> · NAPH-EP: Naphthalene-type epoxy resin (epoxy equivalent 142 g / eq) [Chemical formula] · PN-EP: Phenol novolac-type epoxy resin (epoxy equivalent 173 g / eq) [Chemical formula] · TPM-EP1: Triphenylmethane-type epoxy resin (epoxy equivalent 164 g / eq) [Chemical formula] · TPM-EP2: Triphenylmethane-type epoxy resin (epoxy equivalent 167 g / eq) [Chemical formula]

[0121] <Component (B)> · PEM-EP1: Polyether-modified epoxy resin (epoxy equivalent 436 g / eq, "EPICLON EXA-4850-150" manufactured by DIC Corporation) · PEM-EP2: Polyether-modified epoxy resin (epoxy equivalent 370 g / eq, "AER-9000" manufactured by Asahi Kasei Corporation) · PUM-EP: Urethane-modified epoxy resin (epoxy equivalent 245 g / eq, "ADEKA RESIN EPU-73B" manufactured by ADEKA Corporation) ·MGM-EP: Mesogen-modified epoxy resin having an -O-CH2CH(OH)CH2-O- skeleton in the molecule (epoxy equivalent: 504 g / eq, "LCE-2615" manufactured by Nippon Kayaku Co., Ltd.)

Chem.

Chem.

Chem.

Chem.

Chem.

[0122] <(C) Component> ·CA1: Inclusion imidazole compound ("NISSOCURE TIC-188" manufactured by Nippon Soda Co., Ltd.) ·CA2: 2-Phenyl-4-methyl-5-hydroxymethylimidazole ·CA3: 1,1,2,2-Tetrakis(4-hydroxyphenyl)ethane (hydroxyl equivalent: 100 g / eq) ·CA4: Phenol biphenylene novolak (hydroxyl equivalent: 199 g / eq)

Chem.

[0123] <(D) component> · SCC1: Silver-coated copper powder (volume average particle diameter 6 μm, silver content 20 mass% (manufactured by Toyo Aluminum Co., Ltd., "Toraytec Filler TFM-C05F")) · SCC2: Silver-coated copper powder (volume average particle diameter 6.6 μm, silver content 10 mass% (manufactured by Mitsui Mining & Smelting Co., Ltd., "10%Ag / 05KP"))

[0124] <Other components> · DGMEA: Diethylene glycol monoethyl ether acetate · DGMBE: Diethylene glycol monobutyl ether · TPOL: Terpineol · TGMBE: Tripropylene glycol monobutyl ether · IMDBP-EP: Imide group-containing bisphenol type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "WHR-991S"))

[0125] [Measurement and evaluation of properties of epoxy resin composition] In the examples, the measurement and evaluation of the properties ("volume resistivity", "solder wettability", and "solder erosion resistance") of the epoxy resin composition were carried out as follows.

[0126] <Volume resistivity> The epoxy resin composition was applied onto a glass plate by screen printing and heated at 150 °C for 30 minutes to prepare a coating film with a thickness of 30 to 50 μm. Then, after returning to room temperature, the volume resistivity of the obtained coating film at 25 °C was measured using a resistivity meter "Loresta GP-MCP T610" (manufactured by Nitto Seiko Analytic Co., Ltd.). In the present invention, those with a volume resistivity of the coating film less than 6.0×10 -4 Ω·cm are considered qualified.

[0127] <Solder wettability> The epoxy resin composition was applied onto a glass plate by screen printing, and heated at 150°C for 30 minutes to form a coating film with a thickness of 30 - 50 μm, thereby producing a sample. Using a metal mask, a solder paste (alloy composition: SnBi) was applied onto the formed coating film to have a diameter of 3 mm and a thickness of 100 μm, and the solder was melted for 5 minutes in an incubator set at 150°C, then taken out from the incubator and cooled. The front and back surfaces of the sample were observed, and the solder wettability was evaluated according to the following criteria. In the present invention, S and A are qualified.

[0128] (Solder Wettability Evaluation Criteria) S: The state where 95% or more of the area of the part where the solder paste was applied is in a wet state A: The state where 70% or more and less than 95% of the area of the part where the solder paste was applied is in a wet state B: The state where 50% or more and less than 70% of the area of the part where the solder paste was applied is in a wet state C: The state where 30% or more and less than 50% of the area of the part where the solder paste was applied is in a wet state D: The state where 5% or more and less than 30% of the area of the part where the solder paste was applied is in a wet state E: The state where less than 5% of the area of the part where the solder paste was applied is in a wet state or the solder paste becomes spherical

[0129] <Solder Erosion Resistance> The epoxy resin composition was applied onto a glass plate by screen printing, and heated at 150°C for 30 minutes to form a coating film with a thickness of 30 - 50 μm, thereby producing a sample. Using a metal mask, a solder paste (alloy composition: SnBi) was applied onto the formed coating film to have a diameter of 3 mm and a thickness of 100 μm, and the solder was melted for 5 minutes in an incubator set at 150°C, then taken out from the incubator and cooled. The front and back surfaces of the sample were observed, and the solder erosion resistance was evaluated according to the following criteria. In the present invention, S is qualified.

[0130] (Solder Erosion Resistance Evaluation Criteria) S: The state where solder erosion to the back surface is observed within a range of less than 5% of the area A: The state where solder erosion to the back surface is observed in the range of 5 area % or more and less than 10 area % B: The state where solder erosion to the back surface is observed in the range of 10 area % or more and less than 20 area % C: The state where solder erosion to the back surface is observed in the range of 20 area % or more and less than 80 area % D: The state where solder erosion to the back surface is observed in the range of 80 area % or more

[0131] [Example 1] 1.9 parts of NAPH-EP (naphthalene type epoxy resin), 1.9 parts of BPA-EP1 (bisphenol A type epoxy resin), 1.3 parts of DCPDPH-EP1 (dicyclopentadiene phenol type epoxy resin), 1.1 parts of CA1 (clathrate imidazole compound), and 82.6 parts of SCC1 (silver-coated copper powder), 5.6 parts of TPOL (terpineol) and 5.6 parts of TGMBE (tripropylene glycol monobutyl ether) were mixed and stirred to prepare an epoxy resin composition. Using the obtained epoxy resin composition, evaluation was carried out on volume resistivity, solder wettability and solder erosion resistance. The results are shown in Table 1.

[0132] [Examples 2 to 15, Comparative Examples 1 to 7] An epoxy resin composition was prepared in the same manner as in Example 1, except that the constituent components of the epoxy resin composition and their usage amounts were as shown in Tables 1 and 2. Using the obtained epoxy resin composition, evaluation was carried out on volume resistivity, solder wettability and solder erosion resistance in the same manner as in Example 1. The results are shown together in Tables 1 and 2. For Comparative Examples 1 to 4 and 6, since the solder wettability was poor and the measurement of solder erosion resistance could not be performed, “-” was used.

[0133]

Table 1

[0134]

Table 2

[0135] From Tables 1 and 2, it can be seen that the epoxy resin composition of the present invention containing the predetermined components (A) to (D) has a low volume resistivity and excellent conductivity, and further has good solder wettability and solder erosion resistance, so it is excellent in solderability. From Tables 1 and 2, it can be seen that the epoxy resin composition according to the comparative example that does not contain any one or more of the predetermined components (A) to (D) has a problem in solder wettability. In Comparative Examples 1 to 4 and 6, since the solder wettability was poor and the solder paste became ball-shaped, the solder erosion resistance could not be measured.

Claims

【Claim 1】 The following (A) to (D); (A) One or more epoxy resins selected from the group consisting of triphenylmethane type epoxy resins, naphthalene type epoxy resins, and phenol novolac type epoxy resins, (B) One or more epoxy resins selected from the group consisting of polyether-modified epoxy resins, urethane-modified epoxy resins, mesogen-modified epoxy resins having an -O-CH ２ CH(OH)CH ２ -O-skeleton, bisphenol-type epoxy resins, and dicyclopentadiene-type epoxy resins (C) Imidazole-based compounds and / or phenol-based compounds, (D) One or more conductive powders selected from silver-coated copper powders, silver-based powders, nickel-based powders, conductive carbon powders, copper-based powders, and gold-based powders, An epoxy resin composition containing the same.

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