Epoxy resin composition

Abstract

The present invention addresses the problem of providing 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. As a means for solving the abovementioned problem, the present invention provides an epoxy resin composition containing 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.

Description

Epoxy resin composition

[0001] The present invention relates to an epoxy resin composition, and in particular to an epoxy resin composition capable of forming a coating film that has low volume resistivity, good electrical conductivity, excellent solder wettability, and excellent solder corrosion resistance when formed.

[0002] A wide variety of epoxy resin compositions are known, and due to their properties, conductive powders are added to produce conductive epoxy resin compositions, which are used as conductive pastes, conductive inks, conductive paints, circuit connecting materials, conductive adhesives, etc. for various purposes, such as the formation of electronic circuits and the bonding of electronic components. For example, they are applicable to various printing methods and are used as conductive inks useful for producing flexible plastic substrates having conductive structures such as interconnections, traces, and electrodes. They are also used as circuit connecting materials for high-density mounting and high integration of various electronic components such as LED elements, semiconductor elements, and capacitors on the same circuit board in electronic devices such as computers and mobile phones.

[0003] However, films of conventional conductive resin compositions have had poor solder wettability and the risk of solder erosion (a phenomenon in which solder erodes and penetrates the film of the conductive resin composition), resulting in poor solderability. When bonding electronic components and circuits, sufficient adhesive strength is often not obtained, resulting in low reliability of the conductive connection. Furthermore, the dispersibility of the conductive powder in the conductive resin composition can be insufficient, resulting in a high volume resistivity of the film of the conductive resin composition and insufficient conductivity. Therefore, for electronic devices in which the spacing between wiring patterns is narrowed due to miniaturization of components and high circuit density, a conductive resin composition that has excellent film properties, suppresses the occurrence of short-circuit failures, and provides highly reliable conductive connections is needed.

[0004] In response to such needs, Patent Documents 1 to 3 describe conductive resin compositions containing a conductive powder and a resin component. However, these conductive resin compositions have room for improvement in one or more of volume resistivity, solder wettability, and solder corrosion resistance.

[0005] JP-A-10-162646 International Publication No. 2014 / 104053 JP-A-10-247419

[0006] Until now, no epoxy resin composition has been known that has low volume resistivity, excellent electrical conductivity, and also good solder wettability and solder corrosion resistance, resulting in excellent solderability. The problem to be solved by the present invention is to provide an epoxy resin composition that, when formed into a coating film, is capable of forming a coating film that has low volume resistivity, good electrical conductivity, excellent solder wettability, and excellent solder corrosion resistance.

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved by an epoxy resin composition having a specific composition, thereby completing the present invention. Specifically, the present invention 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) polyether-modified epoxy resins, urethane-modified epoxy resins, and epoxy resins containing -O-CH in the molecule, ２ CH(OH)CH ２ An epoxy resin composition comprising: (a) one or more epoxy resins selected from the group consisting of mesogen-modified epoxy resins having an -O- skeleton, 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 silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder, and gold-based powder.

[0008] The present invention provides an epoxy resin composition capable of forming a coating film that exhibits low volume resistivity, good electrical conductivity, excellent solder wettability, and excellent solder erosion resistance when formed, and that is useful as a conductive ink, circuit connecting material, etc.

[0009] The epoxy resin composition of the present invention comprises: (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) a polyether-modified epoxy resin, a urethane-modified epoxy resin, or a hydroxyl group-containing epoxy resin having —O—CH 2 —CH 3 — ... ２ CH(OH)CH ２ The epoxy resin composition of the present invention comprises: (a) one or more epoxy resins selected from the group consisting of mesogen-modified epoxy resins having an —O— skeleton, 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 silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder, and gold-based powder. The epoxy resin composition of the present invention will be described in detail below.

[0010] [Component (A)] The component (A), which is a constituent of the epoxy resin composition of the present invention, is 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.

[0011] <Triphenylmethane-type epoxy resin> The triphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin having one or more triphenylmethane skeletons and one or more epoxy groups in the molecule. Examples of the triphenylmethane-type epoxy resin include those represented by the formula (a1); In formula (a1), a1 is an integer of 0 to 4, a2 is an integer of 0 to 3, and when n is 2 or more and there are multiple a2s, they may be the same or different, and a3 is an integer of 0 to 4, and when n is 2 or more and there are multiple a3s, they may be the same or different. n is the number of repeating units and is an integer of 1 or more. R ｃ is a substituent, and R ｃ When there are a plurality of R, they may be the same or different. ｃExamples of the substituent include a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, and a cyano group. The substituent may be one type alone or two or more types. The triphenylmethane type epoxy resin preferably has three or more epoxy groups. The triphenylmethane type epoxy resin may be used one type alone or two or more types.

[0012] Examples of triphenylmethane type epoxy resins include the EPPN series (501H, 501HY, 502H, etc.) manufactured by Nippon Kayaku Co., Ltd.; FAE-2500, etc. manufactured by Nippon Kayaku Co., Ltd.; the jER series (1032S50, etc.) manufactured by Mitsubishi Chemical Corporation; and the Tactix series (742, etc.) manufactured by Huntsman Advanced Materials.

[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 resins, polyhydroxybinaphthalene-type epoxy resins, and epoxidized polyhydroxynaphthalene-aldehyde condensation reaction products.

[0014] Examples of polyhydroxynaphthalene type epoxy resins include 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, 2,3-diglycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, etc. Examples of polyhydroxybinaphthalene type epoxy resins include 1,1'-bi-(2-glycidyloxy)naphthyl, 1-(2,7-diglycidyloxy)-1'-(2'-glycidyloxy)binaphthyl, 1,1'-bi-(2,7-diglycidyloxy)naphthyl, etc. Examples of epoxidized polyhydroxynaphthalene-aldehyde condensation reaction products include 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxynaphthyl)-1'-(2'-glycidyloxynaphthyl)methane, 1,1'-bis(2-glycidyloxynaphthyl)methane, etc. Naphthalene-type epoxy resins may be used alone or in combination of two or more.

[0015] <Phenol Novolac Epoxy Resin> Phenol novolac epoxy resins contain a compound represented by the formula (a2) in the molecule; There are no particular limitations on the epoxy resin as long as it has one or more phenol novolac type skeletons represented by the formula (a2) and one or more epoxy groups. The phenol novolac type epoxy resin preferably has two or more epoxy groups. In formula (a2), a4 is an integer of 0 to 3, and R ｃ is a substituent, and R ｃ When there are a plurality of R, they may be the same or different. ｃ Examples of the substituent include a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, a cyano group, etc. The substituent may be one type alone or two or more types.

[0016] Examples of phenol novolac epoxy resins 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.; and the EOCN series (102, 102S, 103, 103S, 104, 105, 106, 107, 108, 109, 110A, 111B, 112B, 113B, 114B, 115B, 116B, 117B, 118B, 119B, 120B, 121B, 122B, 123B, 124B, 125B, 126B, 127B, 128B, 129B, 130B, 131B, 132B, 133B, 134B, 135B, 136B, 137B, 138B, 139B, 140B, 141B, 142B, 143B, 144B, 145B, 146B, 147B, 148B, 149B, 150B, 151B, 152B, 153B, 154B, 155B, 156B, 157B, 158B, 159B, 160B, 04S, 1012, 1020, 1025, 1027, etc.); RE series (305, 305S, 306, etc.) manufactured by Nippon Kayaku Co., Ltd.; DEN series (431, 438, 485, etc.) manufactured by Dow Chemical Company; YDCN series (700, 700-10, 701, 702, 703, 704, etc.) manufactured by Nippon Steel Chemical & Material Co., Ltd.; Araldite series (ECN1235, ECN1273, ECN1280) manufactured by Huntsman Chemicals, Inc., but are not limited to these. One type of phenol novolac epoxy resin may be used alone, or two or more types may be used in combination.

[0017] <Content of Component (A)> The content of component (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" in the epoxy resin composition is not particularly limited. It may be, for example, 0.5 parts by mass or more, preferably 1.0 parts by mass or more, and more preferably 1.2 parts by mass or more, relative to 100 parts by mass of components (A) to (D) combined. It may be, for example, 13.0 parts by mass or less, preferably 10.0 parts by mass or less, and more preferably 7.0 parts by mass or less, relative to 100 parts by mass of components (A) to (D) combined. If the content of component (A) is less than 0.5 parts by mass relative to 100 parts by mass of components (A) to (D), the epoxy resin composition may not form a film, the short-term heating bonding strength may be reduced, and heat resistance may be reduced. If the content exceeds 13.0 parts by mass, curing may take a long time and electrical conductivity may be reduced.

[0018] [Component (B)] Component (B), which is a constituent of the epoxy resin composition of the present invention, is a polyether-modified epoxy resin, a urethane-modified epoxy resin, or a hydroxyl group having —O—CH ２ CH(OH)CH２ The epoxy resin is at least one selected from the group consisting of mesogen-modified epoxy resins having an —O— skeleton, bisphenol-type epoxy resins, and dicyclopentadiene-type epoxy resins.

[0019] <Polyether-modified epoxy resin> The polyether-modified epoxy resin is not particularly limited as long as it is an epoxy resin having a polyether skeleton and one or more epoxy groups in the molecule. The polyether skeleton is represented by the formula (b1); -(-R ｂ１ -O-)n- ... (b1) In formula (b1), R ｂ１ is a divalent organic group. ｂ１ Examples of the polyether-modified epoxy resin include an alkylene group and an aryl group which may be substituted, and preferably an alkylene group having from 2 to 6 carbon atoms. One type of polyether-modified epoxy resin may be used alone, or two or more types may be used in combination.

[0020] The epoxy resin constituting the polyether-modified epoxy resin is not particularly limited. Examples thereof include bisphenol-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, triphenylmethane-type epoxy resins, naphthalene-type epoxy resins, biphenyl-type epoxy resins, fluorene-type epoxy resins, resorcinol diglycidyl ether, triphenolmethane-type epoxy resins, dihydroxynaphthalene-type epoxy resins, hydrogenated bisphenol-type epoxy resins, hydrogenated biphenol-type epoxy resins, glycidyl ethers of aliphatic polyols, glycidylamine-type epoxy resins, and dicyclopentadiene-type epoxy resins. One type of epoxy resin may be used alone, or two or more types may be used.

[0021] Examples of polyether-modified epoxy resins include polyalkylene oxide-modified bisphenol-type epoxy resins, polyalkylene oxide-phenol novolac-type epoxy resins, polyalkylene oxide-modified biphenyl-type epoxy resins, polyalkylene oxide-modified dicyclopentadiene-type epoxy resins, polyalkylene oxide-modified naphthalene-type epoxy resins, polyalkylene oxide-modified fluorene-type epoxy resins, polyalkylene oxide-modified cresol novolac-type epoxy resins, etc. Examples of polyether-modified epoxy resins include the ADEKA RESIN series (EP-4000, EP-4000S, EP-4005, EP-7001, EP4080E, etc.) manufactured by ADEKA Corporation, the EPICLON series (EXA-4850-150, EXA-4850-1000, etc.) manufactured by DIC Corporation, and AER-9000 manufactured by Asahi Kasei Corporation.

[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 for example, it 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 one 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 a urethane skeleton and one or more epoxy groups in the molecule. The urethane skeleton has a structure represented by formula (b2): -O-C(=O)-NH- (b2). One type of urethane-modified epoxy resin may be used alone, or two or more types may be used.

[0024] The urethane-modified epoxy resin can be obtained, for example, by reacting a compound containing an epoxy group and a group reactive with an isocyanate group with a hydroxy group-containing compound and an isocyanate group-containing compound. Alternatively, the urethane-modified epoxy resin can be obtained by reacting a compound containing an epoxy group and a group reactive with an isocyanate group-containing urethane prepolymer. Preferably, the urethane-modified epoxy resin is obtained by reacting a hydroxy group-containing epoxy compound with an isocyanate group-containing urethane prepolymer obtained by reacting a polyhydroxy compound with a polyisocyanate compound.

[0025] Examples of hydroxyl-containing epoxy resins include hydroxyl-containing bisphenol-type epoxy resins such as hydroxyl-containing bisphenol A-type epoxy resins, hydroxyl-containing bisphenol F-type epoxy resins, and hydroxyl-containing bisphenol S-type epoxy resins; hydroxyl-containing biphenyl-type epoxy resins such as hydroxyl-containing biphenyl-type epoxy resins and hydroxyl-containing tetramethylbiphenyl-type epoxy resins; hydroxyl-containing naphthalene-type epoxy resins; hydroxyl-containing alicyclic epoxy resins such as hydroxyl-containing cyclohexanedimethanol-type epoxy resins and hydroxyl-containing hydrogenated bisphenol-type epoxy resins; novolac-type epoxy resins such as hydroxyl-containing phenol novolac-type epoxy resins, hydroxyl-containing cresol novolac-type epoxy resins, hydroxyl-containing bisphenol A novolac-type epoxy resins, and hydroxyl-containing biphenyl novolac-type epoxy resins; hydroxyl-containing dicyclopentadiene-type epoxy resins; hydroxyl-containing triphenylmethane-type epoxy resins; hydroxyl-containing tetraphenylethane-type epoxy resins; hydroxyl-containing phenol aralkyl-type epoxy resins; and the like. One or more types of hydroxyl-containing epoxy resins may be used alone or in combination.

[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. Examples thereof include polymer polyols such as polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyolefin polyols, and polycarbonate polyols; diols such as ethylene glycol, propylene glycol, 1,4-butylene glycol (tetramethylene glycol), and neopentane glycol; 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, and 2,3,4- Examples of the polymer polyol include triols such as 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; and 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, arabidopsis, xylitol, sorbitol, and mannitol. The weight-average molecular weight of the polymer polyol is not particularly limited, and is, for example, 300 or more, preferably 500 or more, and for example, 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, 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, and 2-methyl-1,5-pentyl diisocyanate. aliphatic polyisocyanate compounds such as 3-methyl-1,5-pentyl diisocyanate, 1,18-octadecylene diisocyanate, 1,10-decamethylene diisocyanate, bis(2-isocyanatoethyl) fumarate, lysine diisocyanate (hexanoic acid-2,6-diisocyanate), 1,6,11-undecane triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, and 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'-biphenyl 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- Aromatic polyisocyanate compounds such as 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, and 4,4'-diisocyanate benzyl; methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,4-(isocyanate methyl) alicyclic polyisocyanate compounds such as 1,3-(isocyanatomethyl)cyclohexane, 1,3-(isocyanatomethyl)cyclohexane, 1,2-(isocyanatomethyl)cyclohexane, isophorone diisocyanate, dimer acid diisocyanate, bicycloheptane triisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornyl diisocyanate, norbornenemethane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, and hydrogenated products of the above aromatic polyisocyanates;Examples of the polyisocyanate compounds include biuret, nurate, adduct, allophanate, carbodiimide, and polymeric polyisocyanate derivatives.

[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 EPOKY series (802-30CX, 803, 820-40CX, 830, 834, 840, 810ST, etc.) manufactured by Mitsui Chemicals, Inc.; and the EPICLON series (TSR-300, etc.) manufactured by DIC Corporation.

[0029] The epoxy equivalent of the urethane-modified epoxy resin is not particularly limited and can be, for example, 100 g / eq or more, preferably 150 g / eq or more, more preferably 200 g / eq or more, and can be, for example, 1,000 g / eq or less, preferably 700 g / eq or less, more preferably 500 g / eq or less.

[0030] <—O—CH in the molecule ２ CH(OH)CH ２ Mesogen-modified epoxy resin having an —O— skeleton> ２ CH(OH)CH ２ The mesogen-modified epoxy resin having an —O— skeleton has an —O—CH ２ CH(OH)CH ２ There are no particular restrictions on the epoxy resin, as long as it is an epoxy resin other than component (A) that has an —O— skeleton, a mesogenic skeleton, and one or more epoxy groups. ２ CH(OH)CH ２ The mesogen-modified epoxy resin having an —O— skeleton may be used alone or in combination of two or more.

[0031] Examples of mesogenic skeletons include skeletons that have rigidity and orientation and that facilitate the development of liquid crystallinity and / or crystallinity through intermolecular interactions. For example, they include rod-shaped or plate-shaped rigid aromatic or non-aromatic rings, and aromatic or non-aromatic rings that are bonded to a single bond and / or a non-single bond (e.g., -CH=CH-, -C≡C-, -CH ２ O-, -CH ２ CH ２ -, -COO-, -OCO-, -O-, -CH=N-, -N=CH-, -N=N-, -CH=C(CH ３ )-, -CH=N(→O)-, -N=N(→O)-, -CH=CH-CO-, -CH=C(CN)-, etc.) as the bond. One type of single bond and / or non-single bond may be used alone, or two or more types may be used. Examples of the aromatic ring or non-aromatic ring include phenyl, biphenyl, phenyl benzoate, azobenzene, stilbene, naphthalene, anthracene, phenanthrene, cyclohexylbenzene, phenylpyrimidine, biphenyl benzoate, cyclohexylbiphenyl, and terphenyl. One type of aromatic ring or non-aromatic ring may be used alone, or two or more types may be used.

[0032] -O-CH ２ CH(OH)CH ２ An example of a mesogen-modified epoxy resin having an —O— structure is LCE-2615 manufactured by Nippon Kayaku Co., Ltd.

[0033] <Bisphenol-Type Epoxy Resin> A bisphenol-type epoxy resin contains a compound represented by the formula (b3) in the molecule; There are no particular limitations on the epoxy resin as long as it has one or more bisphenol-type skeletons represented by the formula (b3) and one or more epoxy groups. In formula (b3), b11 is an integer of 0 to 4, and b12 is an integer of 0 to 4. R ｃ is a substituent, and R ｃ When there are a plurality of R, they may be the same or different. ｃExamples of the substituent include a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, and a cyano group. The substituent may be one type or two or more types. X is -CR ａ４１ R ａ４２ -, -S(=O) ２ A group selected from -, -O-, and -C(=O)-, wherein R ａ４１ and R ａ４２ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, and may be the same or different, and may be bonded to each other to form a ring. In the present invention, X in formula (b1) represents -C(CH ３ ) ２ -, -CH ２ -, -C(CF ３ ) ２ -, -S(=O) ２ -, -O-, -C(=O)-, -C(CH ３ )(Ph)-,-C(Ph) ２ -, -C(CH ３ ) (C ２ H ５ ) -, -CH(C ２ H ５ ) -, =C(CH ２ ) ５ Preferably, it is a group selected from the following (wherein Ph is a phenyl group).

[0034] Examples of bisphenol type epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD ​​type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, bisphenol B type epoxy resins, bisphenol BP type epoxy resins, bisphenol AP type epoxy resins, bisphenol E type epoxy resins, bisphenol Z type epoxy resins, etc. In the present invention, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol BP type epoxy resins, and bisphenol Z type epoxy resins are preferred, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol AD ​​type epoxy resins are more preferred, and bisphenol A type epoxy resins are even more preferred.

[0035] Examples of bisphenol-type epoxy resins include 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.); and Epotohto manufactured by Nippon Steel Chemical & Material Co., Ltd. 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.); Epotote manufactured by Nippon Steel Chemical & Material Co., Ltd. YDF series (170, 170N, 2001, 2004, etc.); DER series (301, 330, 361, etc.) manufactured by Dow Chemical Company; 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, 705) manufactured by DIC Corporation EP-4300, EP-4300E, EP-4400, EP-4520S, EP-4530, EP-4504, EP-4700, EP-4901, EP-4901E, EP-4901HF, etc.); and the ADEKA RESIN EP series manufactured by ADEKA Corporation (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.); but are not limited to these. Bisphenol-type epoxy resins may be used alone or in combination of two or more.

[0036] <Dicyclopentadiene-Type Epoxy Resin> Dicyclopentadiene-type epoxy resins contain a compound represented by the formula (b4) in the molecule; There are no particular limitations on the epoxy resin as long as it has one or more dicyclopentadiene skeletons represented by the following formula and one or more epoxy groups. The dicyclopentadiene epoxy resin preferably has two or more epoxy groups.

[0037] Examples of dicyclopentadiene type epoxy resins include dicyclopentadiene phenol epoxy resins obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound, dicyclopentadiene epoxy resins obtained by epoxidizing a dicyclopentadiene polyol, etc. One type of dicyclopentadiene type epoxy resin may be used alone, or two or more types may be used.

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

[0039] <Content of Component (B)> Component (B) in the epoxy resin composition “polyether-modified epoxy resin, urethane-modified epoxy resin, —O—CH ２ CH(OH)CH ２The content of the "one or more epoxy resins selected from the group consisting of mesogen-modified epoxy resins having an -O- skeleton, bisphenol-type epoxy resins, and dicyclopentadiene-type epoxy resins" is not particularly limited. It may be, for example, 0.2 parts by mass or more, preferably 0.4 parts by mass or more, and more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the total of components (A), (B), and (C), and may be, for example, 10.0 parts by mass or less, preferably 7.0 parts by mass or less, and more preferably 5.0 parts by mass or less. If the content of component (B) is less than 0.2 parts by mass relative to 100 parts by mass of the total of components (A), (B), and (C), the epoxy resin composition may not form a film, the short-term heating bonding strength may be reduced, and heat resistance may be reduced. If the content exceeds 10.0 parts by mass, curing may take a long time and electrical conductivity may be reduced.

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

[0041] <Imidazole-Based Compounds> Examples of imidazole-based compounds include imidazole compounds, clathrate imidazoles, microencapsulated imidazoles, imidazole adducts, and stabilizer-coordinated imidazoles. Among these, imidazole adducts, clathrate imidazoles, microencapsulated imidazoles, and stabilizer-coordinated imidazoles are preferably used because they have high curing and curing-accelerating capabilities and excellent pot life. In the present invention, imidazole-based compounds are preferably imidazole compounds and / or clathrate imidazoles. One type of imidazole-based compound may be used alone, or two or more types may be used.

[0042] Among the imidazole compounds, examples of the 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, and 1-cyanoethyl-2-ethylimidazole. 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Among these, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole are preferred from the viewpoint of storage stability and the like. The imidazole compound may be a commercially available product. For example, the Curezol series (2E4MZ, 2P4MZ, 2P4MHZ, 2PZ-CN, C11Z-CNS, C11Z-A, 2MZA-PW, 2MA-OK, 2P4MHZ-PW, 2PHZ-PW, etc.) manufactured by Shikoku Chemicals Corporation may be mentioned.

[0043] Among imidazole compounds, clathrate imidazole is an imidazole compound that has been subjected to a clathration 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. Of these, dicarboxylic acid compounds and tetrakisphenol compounds are preferred.

[0044] Examples of dicarboxylic acid compounds that are host compounds constituting the clathrate imidazole include isophthalic acid compounds such as 5-t-butylisophthalic acid, 5-nitroisophthalic acid, and 5-hydroxyisophthalic acid, 2,3-pyridinedicarboxylic acid, and 2,6-pyridinedicarboxylic acid. From the viewpoint of storage stability, etc., 5-nitroisophthalic acid and 5-hydroxyisophthalic acid are preferred.

[0045] Examples of tetrakisphenol compounds that are host compounds constituting the clathrate 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, etc. From the viewpoint of storage stability, etc., 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane is preferred.

[0046] Examples of the inclusion imidazole include 5-hydroxyisophthalic acid inclusion 2-methylimidazole, 5-hydroxyisophthalic acid inclusion 2-ethyl-4-methylimidazole, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane inclusion 2-methylimidazole, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane inclusion 2-ethyl-4-methylimidazole, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane inclusion 1-benzyl-2-methylimidazole, and 1,1,2,2- Examples of the clathrate imidazole include tetrakis(4-hydroxyphenyl)ethane 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1,1,2,2-tetrakis(3-methyl-4-hydroxyphenyl)ethane 1-benzyl-2-methylimidazole, 1,1,2,2-tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane 1-benzyl-2-methylimidazole, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane 1-isopropyl-2-methylimidazole. Commercially available clathrate imidazoles may be used, and examples thereof include NISSOCURE TIC-188, KM-188, HIPA-2P4MHZ, NIPA-2P4MHZ, TEP-2E4MZ, HIPA-2E4MZ, and NIPA-2E4MZ, all manufactured by Nippon Soda Co., Ltd.

[0047] Among the imidazole-based compounds, microencapsulated imidazole is the imidazole-based compound encapsulated in an encapsulation material that is destroyed by heating, such as a vinyl compound, a urea compound, a phenolic resin, a urethane resin, an epoxy resin, polyethylene, polypropylene, polystyrene, nylon, polyester, polyvinyl chloride, polyvinylidene chloride, or a thermoplastic resin.

[0048] The average particle size of the microencapsulated imidazole is not particularly limited. From the viewpoint of dispersibility in the epoxy resin composition, it can be, for example, 20 μm or less, preferably 12 μm or less. The average particle size refers to the average particle size defined by the median diameter. More specifically, it refers to the Stokes diameter measured by a laser diffraction / light scattering method using a particle size distribution analyzer.

[0049] Commercially available microencapsulated imidazole products include the Novacure series (HX3721, HX3722, HX3742, HX3748, HXA3792, etc.) manufactured by Asahi Kasei Corporation; LC-80 manufactured by A&C Catalysts; and the like.

[0050] Among imidazole compounds, imidazole adducts are those obtained by reacting an imidazole compound with a compound reactive with the imidazole compound and then subjecting the imidazole compound to adduct treatment. Examples include compounds obtained by subjecting an epoxy group-containing compound to a ring-opening addition reaction with an imidazole compound. Commercially available imidazole adducts may be used, including 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., Ltd., and the Cureduct series (e.g., P0505, etc.) manufactured by Shikoku Chemicals Corporation.

[0051] Among imidazole compounds, stabilizer-coordinated imidazole is an imidazole compound that has been subjected to a stabilizer coordination treatment. Examples of imidazole compounds include various imidazole compounds and imidazole adducts. Examples of stabilizers include epoxy-phenol-boric acid ester compounds. For example, an imidazole adduct (e.g., Cureduct P0505 manufactured by Shikoku Chemical Industry Co., Ltd.) coordinated with an epoxy-phenol-boric acid ester compound (e.g., L-07L manufactured by Shikoku Chemical Industry Co., Ltd.) as a stabilizer is exemplified.

[0052] <Phenol-based Compound> The phenol-based compound is not particularly limited as long as it is a compound having one or more, preferably two or more, phenolic hydroxyl groups capable of reacting with an epoxy group in its molecular structure. Examples thereof include bisphenols such as bisphenol A, bisphenol B, bisphenol F, bisphenol AD, and bisphenol S; biphenols such as biphenol and tetramethylbiphenol; phenols such as hydroxyphenol and bis(4-hydroxyphenyl)ether; alkylphenols; phenol novolacs such as 2,6-bis[(2-hydroxyphenyl)methyl]-phenol and phenol biphenylene novolac (biphenyl aralkylphenol); cresol novolacs such as o-cresol novolac, m-cresol novolac, and p-cresol novolac; triphenylmethanes; tetrakisphenols; phenols; phenol resins; phenol novolac resins; biphenyl aralkyl phenol resins; phenol biphenylene novolac resins; tetrakisphenol 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, and 4,4',4'',4''''-methanetetrayltetraphenol.

[0053] The phenolic compound may be a commercially available product, and examples thereof include MEH-8005 manufactured by Meiwa Chemical Industry Co., Ltd., the KAYAHARD series (GPH-65, GPH-103, etc.) manufactured by Nippon Kayaku Co., Ltd., BRG-555, BRG-556, BRG-557, BRG-558, CRG-951, and TAM-005 manufactured by Aica Kogyo Co., Ltd., and TEP-DF and PAPS series (BPAN, PN2, etc.) manufactured by Asahi Organic Chemicals Co., Ltd. One type of phenolic compound may be used alone, or two or more types may be used.

[0054] <Content of Component (C)> The content of the “imidazole compound and / or phenolic compound” (component (C)) in the epoxy resin composition is not particularly limited. When the total amount of the epoxy components (A), (B), and other components in the epoxy resin composition is 100 parts by mass, the total amount of the imidazole compound and phenolic compound in the “imidazole compound and / or phenolic compound” can be, for example, 1.0 part by mass or more, preferably 3.0 parts by mass or more, and 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, and more preferably 30.0 parts by mass or less. If the content of the “imidazole compound and / or phenolic compound” (component (C))” is less than 0.1 parts by mass, the curability of the epoxy resin composition may be reduced, and curing may take a long time. If the content 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 compound and / or phenol compound," the total amount of the imidazole compound and the phenol compound in the "imidazole compound and / or phenol compound" is the same as the amount of the imidazole compound used. On the other hand, when an "imidazole compound and / or phenol compound" containing components other than the imidazole compound and the phenol compound, such as clathrate imidazole, microencapsulated imidazole, or stabilizer-coordinated imidazole, is used as the "imidazole compound and / or phenol compound," the amount excluding 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 compound and / or phenol compound'."

[0055] [Component (D)] Component (D), a constituent 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 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," 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" from the viewpoints of cost, conductivity, migration properties, etc., and it is more preferable to use silver-coated copper powder.

[0056] The shape 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" is not particularly limited. Shapes such as spherical, approximately spherical (for example, with a length-to-width aspect ratio of 1.5 or less), dendritic, flat, block-like, plate-like, polygonal pyramidal, polyhedral, flake (scale-like), rod-like, fibrous, needle-like, and irregular shapes can be used depending on the application. In the present invention, spherical, approximately spherical, dendritic, flat, or flake (scale-like) shapes are preferred from the viewpoints of oxidation resistance, volume resistivity, dispersibility, and handleability.

[0057] <Silver-Coated Copper Powder> The silver-coated copper powder is not particularly limited as long as it is copper powder whose surface is coated with silver. By coating the copper powder with silver, it is possible to improve oxidation resistance, reduce the volume resistivity, and improve the storage stability of the epoxy resin composition. The method for producing the silver-coated copper powder is not particularly limited. For example, any silver-coated copper powder may be used, such as silver-plated copper powder or silver-coated copper powder produced by a substitution reaction between copper and silver.

[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, to enable printing of the epoxy resin composition, particularly application by screen printing or dispenser method, a volume-average particle diameter of 0.5 μm or more and 10 μm or less is preferable. Here, the average particle diameter of the silver-coated copper powder in the present invention is the volume-cumulative particle diameter D50 value at 50% by volume of cumulative volume measured by a laser diffraction / scattering particle size distribution measurement method. If the average particle diameter of the silver-coated copper powder is larger than 10 μm, the leveling ability of the conductive paste may be reduced or the wiring pattern may be prone to breakage, making it difficult to form a narrow wiring pattern. Furthermore, if the average particle diameter of the silver-coated copper powder is smaller than 0.5 μm, the copper core may be exposed, oxidizing from this portion, and the resistivity of the wiring pattern may increase over time. The thickness of the flake-shaped silver-coated copper powder is not particularly limited, and is, for example, 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 silver-coated copper powders include 10% Ag-coated Cu-HWQ5μm, 10% Ag-coated FCC-2000, 10% Ag-coated FCC-115, 10% Ag-coated 2L3 (all manufactured by Fukuda Metal Foil & Powder Co., Ltd.), 10% Ag / 1100Y, 10% Ag / 1100YP, ACFY-2, ACAX-225, ACBY-2, 10% Ag / 05KP (all manufactured by Mitsui Mining & Smelting Co., Ltd.), TFM-C02P, TFM-C05P, TFM-C05F, TFM-C15F (all manufactured by Toyo Aluminum KK), etc. One type of silver-coated copper powder may be used alone, or two or more types may be used.

[0060] The silver content of 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 copper core may be exposed, and the resistivity of the wiring pattern may increase over time. If the silver content is more than 30% by mass, the possibility of ion migration may increase.

[0061] <Silver-based powder> The silver-based powder is not particularly limited as long as it is a powder other than silver-coated copper and contains metallic silver. Examples include metallic silver powder, silver alloy powder, and silver-coated powder other than silver-coated copper. One type of silver-based powder may be used alone, or two or more types may be used.

[0062] The metallic silver powder is obtained by powdering metallic silver. The silver content of 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 determined appropriately from the viewpoint of the melting point of the silver alloy powder, and is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and is, for example, less than 97% by mass. The silver content in the silver-containing powder can be easily measured using an X-ray fluorescence analysis (XRF) device or the like. Examples of silver alloy powders include silver-copper alloys, silver-platinum alloys, and silver-palladium alloys.

[0064] Silver-coated powders other than silver-coated copper powders are particles in which at least a portion of the particle surface is coated with metallic silver. Examples of particles that form the silver-coated powder include one or more of metal particles (e.g., palladium particles, aluminum particles, nickel particles, alloy particles, etc.), organic polymer particles, and non-metallic inorganic particles (e.g., silica particles, alumina particles, carbon particles, potassium titanate particles, glass particles, ceramic particles, mineral-based particles, etc.). Examples of methods for coating the metallic silver include plating and vapor deposition. The thickness of the metallic silver coating is not particularly limited, but is preferably in the range of 0.01 μm to 5 μm.

[0065] The silver-based powder may further contain other atoms as long as the properties of the silver-based powder are not impaired. Examples of other atoms include 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, and S. The content of other atoms is, for example, 3% by mass or less, preferably 1% by mass or less, in the silver-based powder.

[0066] The volume average particle size of the silver-based powder is not particularly limited. It can be appropriately determined taking into consideration dispersibility and ease of handling. 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, it can be 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 is 0.30 m ２ / g or more, preferably 0.50m ２ / g or more, more preferably 0.70m ２ / g or more, for example, 2.5m ２ / g or less, preferably 2.1m ２ / g or less, more preferably 1.6m 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. Examples include metallic nickel powder, nickel alloy powder, and nickel-coated powder. One type of nickel-based powder may be used alone, or two or more types may be used.

[0069] The metallic nickel powder is obtained by powdering metallic nickel. The nickel content of 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 determined appropriately from the viewpoint of the melting point of the nickel alloy powder, and is, for example, 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 in the nickel-containing powder can be easily measured using an X-ray fluorescence analysis (XRF) device or the like. Examples of nickel alloy powders 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, and nickel-chromium-silver alloys.

[0071] The nickel-coated powder is a particle in which at least a portion of the particle surface is coated with metallic nickel. Examples of particles that form the nickel-coated powder include one or more of metal particles (e.g., palladium particles, aluminum particles, nickel particles, alloy particles, etc.), organic polymer particles, and non-metallic inorganic particles (e.g., carbon particles, potassium titanate particles, glass particles, ceramic particles, mineral-based particles, etc.). Examples of methods for coating the metallic nickel include plating and vapor deposition. The thickness of the metallic nickel coating is not particularly limited, but is preferably in the range of 0.01 μm to 5 μm.

[0072] The nickel-based powder may further contain other atoms to the extent that the properties of the nickel-based powder are not impaired. Examples of other atoms include 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, and S. The content of other atoms in the nickel-containing powder is, for example, 3% by mass or less, preferably 1% by mass or less.

[0073] The volume average particle size of the nickel-based powder is not particularly limited. It can be appropriately determined taking into consideration dispersibility and ease of handling. For example, it can be 0.5 μm or more, preferably 1.0 μm or more, more preferably 3.0 μm or more, and 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 nanotubes, graphene, etc. Preferred are carbon black, carbon nanotubes, and graphene. One type of conductive carbon powder may be used alone, or two or more types may be used.

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

[0076] The primary particle size 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 size can be the arithmetic average of the particle sizes of 100 particles observed and measured using an electron microscope (SEM or TEM).

[0077] Carbon nanotubes are cylindrical hollow fibrous materials made of carbon, and may be either multi-walled carbon nanotubes or single-walled carbon nanotubes. Multi-walled carbon nanotubes are preferred from the viewpoint of electrical conductivity. Examples of carbon nanotubes include those produced by arc discharge, chemical vapor deposition (CVD), and laser ablation. 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 diameter and average length of 100 carbon nanotubes observed and measured using an electron microscope (SEM, TEM).

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

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

[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. Examples include metallic copper powder, copper alloy powder, copper-coated powder, etc. One type of copper-based powder may be used alone, or two or more types may be used.

[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. Examples include metallic gold powder, gold alloy powder, and gold-coated powder. One type of gold-based powder may be used alone, or two or more types may be used.

[0083] The content of component (D) in the epoxy resin composition, "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. It can be, for example, 75% by mass or more, preferably 80% by mass or more, and more preferably 82% by mass or more, and for example, 97% by mass or less, preferably 95% by mass or less, and more preferably 93% by mass or less, based on 100% by mass of the total amount of the cured epoxy resin composition. If the content of component (D) is less than 75% by mass, based on 100% by mass of the total amount of the cured epoxy resin composition, the electrical conductivity of the resulting cured epoxy resin composition (coating film) may be insufficient (the volume resistivity may be high), whereas if 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 optionally contain "other components" such as solvents, resins other than epoxy resins, epoxy resins other than component (A) and component (B), coupling agents, wetting and dispersing agents, fillers, epoxy resin curing agents other than component (C), curing accelerators (curing catalysts) other than component (C), adhesion promoters, viscoelasticity modifiers, reactive diluents, conductive powders other than component (D), antioxidants, gap adjusters (spacers; spacing control agents), organic acid compounds, pigments, corrosion inhibitors, surfactants, defoamers, dispersants, viscosity modifiers (thixotropy modifiers), adhesion promoters, anti-settling agents, pH adjusters, leveling agents, UV absorbers, flame retardants, heavy metal deactivators, and gap adjusters, provided that such components do not impair performance. These other components may be used alone or in combination of two or more.

[0085] <Solvent> The epoxy resin composition of the present invention may contain a solvent. This makes it possible to adjust the fluidity of the epoxy resin composition and improve workability, applicability, handleability, etc. The content of the solvent, when used, is not particularly limited, and may be appropriately adjusted so that the viscosity of the epoxy resin composition is such that it can be appropriately applied or printed on a substrate and / or can be appropriately impregnated into a material to be impregnated, such as a nonwoven fabric or a porous body.

[0086] The solvent may be any one or more selected from the group consisting of water and various organic solvents. Examples of the organic solvent include 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, isopalmin alcohols such as ethyl alcohol, isostearyl alcohol, lauryl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and glycerin; ketone-based 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), and diisobutyl ketone (2,6-dimethyl-4-heptanone); ester-based 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, and 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, etc.; acetic acid 2-(2-butoxyethoxy)ethane, methyl cellosolve acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether Examples of the solvent include one or more solvents selected from the group consisting of ether ester solvents such as acetate and 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, and light oil; nitrile solvents such as acetonitrile and propionitrile; nitrogen-containing polar solvents such as dimethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone; and silicone oil solvents. One solvent may be used alone, or two or more solvents may be used.

[0087] <Resins Other Than Epoxy Resins> The epoxy resin composition of the present invention may contain a resin other than an epoxy resin. The resin other than an epoxy resin may be either a thermoplastic resin or a thermosetting resin. Examples of thermoplastic resins 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, polyvinylpyrrolidone resins, and terpene resins. Examples of thermosetting resins include resol-type phenolic resins, polyimide resins, xylene resins, polyurethane resins, melamine resins, urea resins, furan resins, isocyanate resins, urea resins, and block urethane resins. In the present invention, preferred resins other than epoxy resins are polyurethane-based resins, block urethane-based resins, polyvinyl acetal-based resins, resol-type phenolic resins, acrylic resins, polyester-based resins, phenoxy resins, polyimide-based resins, and xylene-based resins. Among these, polyurethane-based resins, block urethane-based resins, polyester-based resins, polyvinyl acetal-based resins, and acrylic resins are more preferred from the viewpoints of film formation state, connection reliability, adhesion to substrates, etc. One type of resin other than epoxy resin may be used alone, or two or more types may be used.

[0088] <Epoxy Resins 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). Examples of epoxy resins other than component (A) and component (B) include triphenylmethane-type epoxy resins, naphthalene-type epoxy resins, phenol novolac-type epoxy resins, polyether-modified epoxy resins, urethane-modified epoxy resins, and epoxy resins containing —O—CH ２ CH(OH)CH ２There are no particular limitations on the epoxy resin, as long as it is other than a mesogen-modified epoxy resin having an —O— skeleton, a bisphenol-type epoxy resin, or a dicyclopentadiene-type epoxy resin. The epoxy resin other than components (A) and (B) may be any of a monomer, oligomer, or polymer having two or more glycidyl groups in one molecule, and the molecular weight is not particularly limited. Examples thereof include alkyl-modified triphenolmethane-type epoxy resins, phenol aralkyl-type epoxy resins having a phenylene skeleton; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; epoxy resins having an alicyclic structure such as hydrogenated bisphenol A-type epoxy resins, hydrogenated bisphenol F-type epoxy resins, hydrogenated biphenol-type epoxy resins, and glycidyl ethers of polyols having an alicyclic structure such as cyclohexanediol, cyclohexanedimethanol, and cyclohexanediethanol; glycidyl ethers of aliphatic polyols such as butanediol, hexanediol, octanediol, nonanediol, decanediol, pentaerythritol, glycerin, and trimethylolpropane; and aromatic glycidylamine-type epoxy resins such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane-type glycidylamine, and aminophenol-type glycidylamine. The epoxy resins other than the components (A) and (B) may be used singly or in combination of two or more.

[0089] <Coupling Agent> The epoxy resin composition of the present invention may contain a coupling agent. This can improve the short-time heating bonding strength of the epoxy resin composition. Examples of coupling agents include silane coupling agents, titanium coupling agents, aluminum coupling agents, and zirconium coupling agents. Examples of silane coupling agents 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; and isocyanate group-containing silane compounds such as γ-isocyanatopropyltrimethoxysilane. Examples of titanium coupling agents include tetraisopropyl titanate, tetra-normal butyl titanate, butyl titanate, tetraoctyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, dodecylbenzenesulfonic acid titanium compound, titanium octylene glycolate, titanium ethylacetoacetate, titanium lactate ammonium salt, titanium lactate, titanium triethanolamine, tetraisopropyl titanate, tetratertiary butyl titanate, tetrastearyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium isostearate, titanium diethanolamine, titanium aminoethylaminoethanolate, and titanium oligomers. Examples of aluminum coupling agents 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 tributoxyethylacetoacetate, zirconium butoxyacetylacetonate bis(ethylacetoacetate), tetrakis(2,4-pentanedionate)zirconium, etc. Silane coupling agents may be used alone or in combination of two or more.

[0090] <Wetting and dispersing agent> The epoxy resin composition of the present invention may contain a wetting and dispersing agent as needed to prevent aggregation of the components of the epoxy resin composition. Specific examples of wetting and dispersing agents include the Solsperse series (9000, 12000, 17000, 20000, 21000, 24000, 26000, 27000, 28000, 32000, 35100, 54000, etc.) manufactured by Lubrizol Japan Corporation, and the EFKA series (4008, 4009, 4010, 4015, 4046, 4047, 4060, 4080, 7462, 4020, 4050, 4055, 4400, 4401, 4402, 4403, 4300, 4330, 4340, 6220, 6225, 670 ... 780, 6782, 8503, etc.), 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 Japan Co., Ltd. One type of wetting and dispersing agent may be used alone, or two or more types may be used.

[0091] <Filler> The epoxy resin composition of the present invention may contain a filler. Examples of fillers include fused silica, fumed silica, precipitated silica, crystalline silica, carbon black, dolomite, silicic acid anhydride, hydrated 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, shirasu balloons, glass balloons, phenolic resin microballoons, vinylidene chloride resin microballoons, vinyl chloride resin, acrylic resin powder, styrene resin powder, urethane resin powder, polyamide resin powder, glass fiber, and potassium titanate fiber. One type of filler may be used alone, or two or more types may be used in combination.

[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 phenol-based compound). Examples of such epoxy resin curing agents include acid anhydride-based curing agents, amine-based curing agents, thiol-based curing agents, amide-based curing agents, and thermal cationic polymerization initiators. One type of epoxy resin curing agent other than component (C) may be used alone, or two or more types may be used in combination.

[0093] The acid anhydride 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 curing agent is obtained by intermolecular dehydration of two organic carboxylic acid molecules and / or dehydration within the molecular structure of one organic carboxylic acid molecule. In the present invention, for example, among the organic carboxylic acids, one or more selected from the group consisting of those obtained by intermolecular dehydration of organic monocarboxylic acids and those obtained by intramolecular dehydration and / or intermolecular dehydration of organic polycarboxylic acids can be used. Examples of the organic carboxylic acids include aliphatic monocarboxylic acid anhydrides, aliphatic polycarboxylic acid anhydrides, alicyclic polycarboxylic acid anhydrides, and aromatic polycarboxylic acid anhydrides.

[0094] Examples of acid anhydride curing agents 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, and polyacid polyanhydrides. Here, the polyacid polyanhydride is obtained by an intermolecular dehydration condensation reaction of a long-chain aliphatic dicarboxylic acid, and examples thereof include SL-12AH, SL-20AH, SB-20AH, IPU-22AH, ST-2PAH, and the like, particularly SB-20AH, IPU-22AH, and ST-2PAH, manufactured by Okamura Oil Mills, Ltd. One type of acid anhydride curing agent may be used alone, or two or more types may be used.

[0095] Examples of thiol-based curing agents include thiol compounds having one or more, preferably two or more, thiol groups in their molecular structure that can react with epoxy groups. As thiol compounds, polyfunctional thiol compounds having 2 to 6 (difunctional to hexafunctional) thiol groups in their molecular structure are preferred, and polyfunctional thiol compounds having 3 to 6 (trifunctional to hexafunctional) thiol groups are more preferred. The thiol equivalent is not particularly limited. For low-molecular-weight thiol compounds with a molecular weight of less than 500, the thiol equivalent 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. For high-molecular-weight thiol compounds with a weight-average molecular weight of 500 or more, the thiol equivalent 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 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 tristhioglycolate (abbreviation: TMTG), pentaerythritol tetrakisthioglycolate (abbreviation: PETG), and pentaerythritol tetrakis(3-mercaptobutylate). thiol compounds (polyfunctional thiol compounds) such as 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 1,3,4,6-tetrakis(2-mercaptopropyl)glycoluril, 4,4'-isopropylidenebis[(3-mercaptopropoxy)benzene] and 1,3,5-triazine-2,4,6-trithiol, and polysulfide polymers having a thiol group.

[0097] Specific examples include polyfunctional thiols manufactured by SC Organic Chemicals (TMMP-LV, PEMP-LV, DPMP, TEMPIC, PEMP, etc.), polyfunctional thiols manufactured by Toray Fine Chemicals Co., Ltd. (QE-340M, LP-2, LP-3, LP-55, LP-31, etc.), polyfunctional thiols manufactured by Shikoku Chemical Industry Co., Ltd. (TS-G, C3TS-G, etc.), polyfunctional thiols manufactured by Resonac Corporation (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.), and polyfunctional thiols manufactured by Asahi Chemical Industry Co., Ltd. (G-2S, PE-2S, PE-3S, PE-4S, TMP-3S, etc.). The thiol-based curing agent may be used alone or in combination of two or more.

[0098] The amine curing agent is not particularly limited as long as it is a compound having one or more amino groups in its molecular structure that can react with epoxy groups. Examples include diethylenetriamine, triethylenetetramine, diethylaminopropylamine, menthanediamine, isophoronediamine, bis[4-amino-3-methyldicyclohexyl]methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, m-xylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiethyldiphenylmethane, and modified polyamines and polyamidoamines obtained by modifying these through epoxy adducts, Michael addition, Mannich reaction, or the like. One type of amine curing agent may be used alone, or two or more types may be used.

[0099] The thermal cationic polymerization initiator is not particularly limited as long as it is a compound that generates cations by heat. For example, a compound containing at least one cation selected from aromatic sulfonium, aromatic iodonium, aromatic diazonium, and pyridinium, and BF ４ -, PF ６ -, SbF ６ -, AsF ６ -, CF ３ SO ３ -, (CF ３ SO ２ ) ２ N- and B(C ６ F５ ) ４ and aluminum complexes. Examples include TA-100, TA-100FG, IK-1, IK-1FG, etc. manufactured by San-Apro Co., Ltd.; SI-60, SI-80, SI-100, SI-150, etc. manufactured by Sanshin Chemical Industry Co., Ltd.; K-PURE TAG series, K-PURE CXC series, etc. manufactured by KING INDUSTRIES. One type of thermal cationic polymerization initiator may be used alone, or two or more types may be used in combination.

[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 component (C) (imidazole compound and / or phenolic compound) in order to accelerate the curing of the epoxy resin and curing agent. Examples of such curing accelerators include, but are not limited to, amine-based curing accelerators, guanidine-based curing accelerators, phosphonium-based curing accelerators, and transition metal-based curing accelerators. From the viewpoints of workability, handleability, and manufacturability, the epoxy resin composition of the present invention preferably contains a curing accelerator (curing catalyst) that is liquid at room temperature (25°C ± 5°C).

[0101] Examples of the curing accelerator (curing catalyst) include 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, and 3,4,5-tris(dimethylaminomethyl)phenol. 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, Amine-based curing accelerators such as 10-tetrapyro[5,5]undecane, 1,8-diazabicyclo[5,4,0]undecene-7,1,5-diazabicyclo[4,3,0]-nonene, polyamines, polyamidoamines, polyamides, modified polyamines, modified polyamidoamines, and modified polyamides; dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, di(o-tolyl)guanidine, trimethyl guanidine-based curing accelerators such as butyl guanidine, tetramethyl guanidine, pentamethyl guanidine, 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, and 1-(o-tolyl)biguanide;Examples of suitable curing accelerators include phosphonium-based curing accelerators such as 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, and tetrabutylphosphonium hydroxide; transition metal-based curing accelerators containing transition metals such as titanium and cobalt; and the like. The curing accelerators (curing catalysts) other than component (C) may be used singly or in combination of two or more.

[0102] <Adhesion Imparting Agent> The epoxy resin composition of the present invention may contain an adhesion imparting agent. This can improve adhesion to a substrate when the epoxy resin composition is applied to the substrate. Examples of the adhesion imparting agent include triazole compounds, thiazole compounds, triazine compounds, polymers having a functional group (carboxylic acid group, amino group, hydroxyl group, etc.) and salts thereof. Examples of the adhesion imparting agent include the BYK series (4509, 4510, 4512, etc.) manufactured by BYK Japan. One type of adhesion imparting agent may be used alone, or two or more types may be used.

[0103] <Viscoelasticity modifier> The epoxy resin composition of the present invention may contain a viscoelasticity modifier (rheology control agent). This can adjust the viscoelasticity (rheology) of the epoxy resin composition, contributing to improved workability, etc. Examples of the viscoelasticity modifier (rheology control agent) include polyamide-based, aminoplast-based, polycarboxylic acid-based, urethane-based, cellulose-based, and inorganic layered compound-based viscoelasticity modifiers (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; DISPARLON series (AQ-600, AQH-800, 3600N, 3900EF, etc.) manufactured by Kusumoto Chemicals Co., Ltd.; SN Thickener series (613, 617, 618, 630, 634, 636, 621N, 623N, etc.) manufactured by San Nopco; ADEKA NOL series (UH-814N, UH-752, UH-750, UH-462, etc.) manufactured by ADEKA; HEC Daicel series (SP600N, etc.) manufactured by Daicel; BENTONE manufactured by Elementis Japan Co., Ltd. HD, etc. One type of viscoelasticity modifier may be used alone, or two or more types may be used in combination.

[0104] <Reactive Diluent> The epoxy resin composition of the present invention may contain a reactive diluent for adjusting viscosity, curing properties, 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. Examples of the reactive diluent include 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, and YED188 manufactured by Mitsubishi Chemical Corporation, and ADEKA GLYCIROL ED-502 and ADEKA GLYCIROL E manufactured by ADEKA Corporation. D-502S, ADEKA GLYCIROL ED-509E, ADEKA GLYCIROL ED-509S, ADEKA GLYCIROL ED-529, DENACOL EX-145, DENACOL EX-171, DENACOL EX-192 manufactured by Nagase ChemteX Corporation, EPOLYTE M-1230 and EPOLYTE 100MF manufactured by Kyoeisha Chemical Co., Ltd., ARON OXETANE OXT-101, ARON OXETANE OXT-212, ARON OXT-121, ARON OXT-221 manufactured by Toagosei Co., Ltd., ETERNACOLL EHO, ETERNACOLL HBOX, ETERNACOLL OXMA, and ETERNACOLL OXBP manufactured by UBE Corporation, and the like. 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 component (D), which 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." Examples of conductive powders other than 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, and resin particles coated with metals other than silver, nickel, copper, and gold. The shape of the conductive powder other than component (D) is not particularly limited. It may be spherical, approximately spherical (e.g., having an aspect ratio of 1.5 or less), flat, block-like, plate-like, polygonal pyramidal, polyhedral, flaky, rod-like, fibrous, needle-like, or irregularly shaped. From the viewpoints of oxidation resistance, volume resistivity, dispersibility, handleability, and the like, spherical, approximately spherical, flat, or flaky shapes are preferred. The conductive powder other than the component (D) may be used alone or in combination of two or more kinds.

[0106] <Antioxidant> The epoxy resin composition of the present invention may contain an antioxidant. This can contribute to improving the heat resistance and yellowing resistance 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. Examples of the antioxidant include phenol-based antioxidants such as hindered phenol compounds, quinone-based antioxidants such as hydroquinone, phosphorus-based antioxidants, sulfur-based antioxidants, and hindered amine-based antioxidants such as hindered amine compounds.

[0107] Examples of antioxidants include 2,2-methylene-bis(4-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, 2-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2,4-di-tert-butyl-6-methylphenol, 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, bis-[3,3 -bis-(4'-hydroxy-3'-tert-butylphenyl)-butanoic acid]-glycol ester, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 4,4'-butylidenebis(6-tert-butyl-3-methylphenyl) phenol), 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-hydroxy bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[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-C ７ ~C ９Side 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-tolyl)tri-p-cresol, calcium diethyl bis[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 4,6-bis 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-hydroxyphenyl)propionate 1,3,5-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 products of N-phenylbenzenamine with 2,4,6-trimethylpentene, 2,6-di-tert-butyl-4-(4,6-bis(oxol) Phenol-based antioxidants such as (octylthio)-1,3,5-triazin-2-ylamino)phenol, picric acid, and citric acid; quinone-based 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, and 2,5-di-tert-butyl-p-benzoquinone;Tris(2,4-di-tert-butylphenyl)phosphite, tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphen-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-bisphenyl]-4,4'-diylbisphosphonite, 6-[3-(3-tert-butyl Examples of antioxidants include phosphorus-based antioxidants such as [(4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphene; 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; and vitamin E-based antioxidants. Commercially available antioxidants may be used. Examples include the IRGANOX series manufactured by BASF, the Adeka STAB series manufactured by ADEKA, the Non-Flex series manufactured by Seiko Chemical Co., Ltd., and the Sumilizer series manufactured by Sumitomo Chemical Co., Ltd. The antioxidants may be used alone or in combination of two or more.

[0108] <Gap Adjuster (Spacer; Spacing Control Agent)> The epoxy resin composition of the present invention may contain a gap adjuster (spacer; spacing control agent). The gap adjuster (spacer; spacing control agent) is used to control the thickness between adherends (thickness of the adhesive layer). There are no particular limitations on the gap adjuster (spacer; spacing control agent) as long as it has a hardness that can withstand use and the desired particle size and aspect ratio. Examples include silica fine particles (spherical silica), glass beads, ground glass fibers, resin beads, etc. The resin beads are not particularly limited, and examples thereof include polyethylene, polypropylene, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polycarbonate, various (meth)acrylates such as polymethyl methacrylate, polyimide, polyamide, polyester, polyvinyl chloride, polyvinylidene chloride, polydivinylbenzene, fluororesin, polyphenylene oxide, polyphenylene sulfide, polymethylpentene, urea resin, melamine resin, phenolic resin, epoxy resin, benzoguanamine resin, polyacetal resin, xylene resin, furan resin, polyisocyanate resin, phenoxy resin, and silicone resin. The surfaces of the resin beads may be coated with a conductive metal such as Ag, Cu, Au, Pt, Ni, Al, Sn, or Zn, or an oxide or alloy thereof. Commercially available gap adjusters (spacers; spacing control agents) may be used. Examples include the Highpressica series manufactured by Ube Exsymo Co., Ltd., the Micropearl series manufactured by Sekisui Chemical Co., Ltd., the Techpolymer series manufactured by Sekisui Plastics Co., Ltd., and the Unibeads series manufactured by Unitika Glass Beads Ltd. One type of gap adjuster (spacer; distance control agent) may be used alone, or two or more types may be used in combination.

[0109] [Conductivity of Cured Film of Epoxy Resin Composition] The epoxy resin composition of the present invention provides a cured film having low volume resistivity and excellent conductivity. The volume resistivity of a cured film of the epoxy resin composition is, for example, 1.0 × 10 －３ Less than Ω cm, preferably 8.0×10 －４ less than Ω cm, more preferably 6.0 × 10 －４The volume resistivity of the cured film can be determined, for example, by casting or applying the epoxy resin composition onto a release substrate, heating and curing at 150°C for 30 minutes to form a cured film having a thickness of 30 to 50 µm, and measuring the resistivity with a resistivity meter (for example, Loresta GP-MCP T610 (manufactured by Nitto Seiko Analytech Co., Ltd.)).

[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, the essential components (A) to (D) and other components used as needed can be added to a mixing vessel in any order and mixed and stirred. For mixing and stirring, for example, a ball mill, roll mill, bead mill, planetary mixer, tumbler, stirrer, agitator, mechanical homogenizer, ultrasonic homogenizer, high-pressure homogenizer, paint shaker, V-type blender, Nauta mixer, Banbury mixer, planetary mixer, kneading roll, single-screw or twin-screw extruder, etc. can be used.

[0111] The temperature at which the epoxy resin composition is prepared (the temperature at which the components are mixed) is not particularly limited. Heating or the like can be performed as necessary, and the temperature can be, for example, 10 to 40°C. The atmosphere at which the epoxy resin composition is prepared is not particularly limited. The preparation can be performed in air or in 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 to form a conductive layer in the manufacture of electronic devices, electronic components, etc. The form of the epoxy resin composition is not particularly limited, but it is preferably in a liquid (paste or varnish), film, or powder form at room temperature (25°C ± 5°C). For example, a liquid epoxy resin composition can be obtained by stirring and mixing the components of the epoxy resin composition, or by adding a solvent such as an organic solvent, if necessary. For example, a film-like epoxy resin composition can be obtained by stirring and mixing the components of the epoxy resin composition, and optionally adding a solvent such as an organic solvent, to obtain a liquid epoxy resin composition, which is then cast and applied onto a release substrate to form a film, dried to remove the solvent, and then peeled off from the release substrate. Alternatively, a film-like epoxy resin composition can be obtained by impregnating a nonwoven fabric or the like with the composition, forming the composition on a release substrate, drying to remove the solvent, and then peeling off from the release substrate.

[0113] The substrate to which the epoxy resin composition of the present invention is applied is not particularly limited, and may be, for example, an inorganic material such as a semiconductor, glass, or ceramic, an organic material such as a polyimide or polycarbonate, a composite such as glass / epoxy, or a combination thereof.

[0114] The epoxy resin composition of the present invention can be applied to various substrates by any printing or coating method, such as casting, dipping, bar coating, dispenser coating, roll coating, gravure coating, screen printing, metal mask printing, flexographic printing, spray coating, spin coating, or inkjet printing, and then dried by heating at a temperature of 300°C or less to form a coating film. The drying atmosphere can be one or more selected from the group consisting of air, inert gas, vacuum, reduced pressure, etc. In particular, an inert gas atmosphere such as nitrogen or argon is preferred from the viewpoint of preventing oxidation of the conductive powder. The thickness of the coating film formed can be adjusted appropriately depending on the application. For example, it can be 7 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and can be, for example, 100 μm or less.

[0115] The epoxy resin composition of the present invention can be used as a conductive material, for example, conductive ink, circuit connecting 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 product, etc.

[0116] For example, the epoxy resin composition can be applied to various substrates by any printing or coating method, such as casting, dipping, bar coating, dispenser coating, roll coating, gravure coating, screen printing, metal mask printing, flexographic printing, spray coating, spin coating, or inkjet printing, and then heated and dried at a temperature of 300° C. or less to form a conductive coating film. The atmosphere during drying can be one or more selected from the group consisting of air, inert gas, vacuum, reduced pressure, and the like. In particular, from the viewpoint of suppressing deterioration of the coating film (preventing oxidation of the conductive powder, etc.), an inert gas atmosphere such as nitrogen or argon is preferred.

[0117] The epoxy resin composition of the present invention can also be used as a printing conductive material for forming a coating film such as wiring by printing on a substrate. Examples of printing and coating methods include screen printing, inkjet printing, flexographic printing, and gravure printing. In the present invention, it is preferable to use one or more printing methods selected from the group consisting of screen printing, metal mask printing, and inkjet printing, because they provide excellent printability and shape retention. The mesh used in screen printing can be selected appropriately, and it is preferable to use a mesh that does not remove excessive conductive powder. The thickness of the conductive coating film formed by printing can be adjusted to an appropriate thickness depending on the application. For example, it is 7 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and for example, 100 μm or less.

[0118] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass." In addition, all numerical values ​​relating to the blending amount of each component in Tables 1 and 2 are in "parts by mass."

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

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

[0121] <Component (B)> PEM-EP1: polyether-modified epoxy resin (epoxy equivalent weight 436 g / eq, EPICLON EXA-4850-150 manufactured by DIC Corporation) PEM-EP2: polyether-modified epoxy resin (epoxy equivalent weight 370 g / eq, AER-9000 manufactured by Asahi Kasei Corporation) PUM-EP: urethane-modified epoxy resin (epoxy equivalent weight 245 g / eq, ADEKA RESIN EPU-73B manufactured by ADEKA Corporation) MGM-EP: -O-CH ２ CH(OH)CH ２ Mesogen-modified epoxy resin having an —O— skeleton (epoxy equivalent: 504 g / eq, "LCE-2615" manufactured by Nippon Kayaku Co., Ltd.) BPA-EP1: Bisphenol A epoxy resin (epoxy equivalent 190 g / eq) BPA-EP2: Bisphenol A type epoxy resin (epoxy equivalent: 8021 g / eq) DCPDPH-EP1: dicyclopentadiene type epoxy resin (epoxy equivalent 260 g / eq) DCPDPH-EP2: dicyclopentadiene type epoxy resin (epoxy equivalent 286 g / eq)

[0122] <Component (C)> CA1: clathrate 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 group equivalent 100 g / eq) CA4: phenol biphenylene novolak (hydroxyl group equivalent 199 g / eq)

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

[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 ("WHR-991S" manufactured by Nippon Kayaku Co., Ltd.)

[0125] [Measurement and Evaluation of Properties of Epoxy Resin Composition] In the examples, the properties of the epoxy resin composition ("volume resistivity," "solder wettability," and "solder corrosion resistance") were measured and evaluated as follows.

[0126] <Volume Resistivity> An epoxy resin composition was applied to a glass plate by screen printing and heated at 150°C for 30 minutes to form a coating film having a thickness of 30 to 50 μm. The coating film was then returned to room temperature and the volume resistivity at 25°C of the resulting coating film was measured using a resistivity meter "Loresta GP-MCP T610" (manufactured by Nitto Seiko Analytech Co., Ltd.). In the present invention, the volume resistivity of the coating film was 6.0 × 10 －４ A value of less than Ω·cm is acceptable.

[0127] <Solder Wettability> Samples were prepared by screen printing an epoxy resin composition onto a glass plate and heating it at 150°C for 30 minutes to form a coating film 30 to 50 μm thick. A metal mask was used to apply solder paste (alloy composition: SnBi) to the formed coating film to a diameter of 3 mm and a thickness of 100 μm. The solder was melted for 5 minutes in a heat-retaining chamber set to 150°C, then removed from the chamber 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 acceptable.

[0128] (Solder wettability evaluation criteria) S: 95% or more of the area where the solder paste was applied was wet. A: 70% or more but less than 95% of the area where the solder paste was applied was wet. B: 50% or more but less than 70% of the area where the solder paste was applied was wet. C: 30% or more but less than 50% of the area where the solder paste was applied was wet. D: 5% or more but less than 30% of the area where the solder paste was applied was wet. E: Less than 5% of the area where the solder paste was applied was wet, or the solder paste formed balls.

[0129] <Solder Corrosion Resistance> Samples were prepared by screen printing an epoxy resin composition onto a glass plate and heating it at 150°C for 30 minutes to form a coating film 30 to 50 μm thick. A metal mask was used to apply solder paste (alloy composition: SnBi) to the formed coating film to a diameter of 3 mm and a thickness of 100 μm. The solder was melted for 5 minutes in a heat-retaining chamber set to 150°C, then removed from the chamber and cooled. The front and back surfaces of the sample were observed, and the solder corrosion resistance was evaluated according to the following criteria. In the present invention, S is acceptable.

[0130] (Solder corrosion resistance evaluation criteria) S: Solder corrosion on the back surface is observed in an area of ​​less than 5% by area. A: Solder corrosion on the back surface is observed in an area of ​​5% to less than 10% by area. B: Solder corrosion on the back surface is observed in an area of ​​10% to less than 20% by area. C: Solder corrosion on the back surface is observed in an area of ​​20% to less than 80% by area. D: Solder corrosion on the back surface is observed in an area of ​​80% or more by area.

[0131] Example 1 An epoxy resin composition was prepared by mixing and stirring 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), 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). The resulting epoxy resin composition was evaluated for volume resistivity, solder wettability, and solder corrosion resistance. The results are shown in Table 1.

[0132] [Examples 2 to 15, Comparative Examples 1 to 7] Epoxy resin compositions were prepared in the same manner as in Example 1, except that the components of the epoxy resin compositions and the amounts used were as shown in Tables 1 and 2. Using the obtained epoxy resin compositions, evaluations of volume resistivity, solder wettability, and solder corrosion resistance were carried out in the same manner as in Example 1. The results are also shown in Tables 1 and 2. Note that for Comparative Examples 1 to 4 and 6, solder wettability was poor and solder corrosion resistance could not be measured, so they were marked with "-".

[0133]

[0134]

[0135] Tables 1 and 2 show that the epoxy resin compositions of the present invention containing the specified components (A) to (D) have low volume resistivity and excellent conductivity, and furthermore, good solder wettability and solder erosion resistance, and therefore excellent solderability. Tables 1 and 2 show that the epoxy resin compositions of the comparative examples that do not contain any one or more of the specified components (A) to (D) have problems with solder wettability. Note that in Comparative Examples 1 to 4 and 6, the solder wettability was poor and the solder paste formed balls, so it was not possible to measure solder erosion resistance.

Claims

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) Polyether-modified epoxy resins, urethane-modified epoxy resins, mesogen-modified epoxy resins having an -O-CH ２ CH(OH)CH ２ -O-skeleton, one or more epoxy resins selected from the group consisting of bisphenol type epoxy resins and dicyclopentadiene type epoxy resins, (C) Imidazole 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.

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