Conductive resin composition

Abstract

To provide a conductive resin composition that has low volume resistivity, can sufficiently cure even with low temperature and short heating time, can form a cured film with high bonding strength to various substrates, has excellent workability and storage stability, and a conductive adhesive containing the conductive resin composition. [Solution] (A)~(C): (A) Epoxy resin having a bisphenol skeleton, (B) Amine-based epoxy resin curing agent having a bisphenol skeleton, (C) Conductive powder containing one or more selected from silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder, and gold-based powder. A conductive resin composition containing [the specified ingredient].

Description

Technical Field

[0001] The present invention relates to a conductive resin composition and a conductive adhesive. In particular, the present invention relates to a conductive resin composition and a conductive adhesive that have low volume resistivity, excellent conductivity, excellent workability, a long pot life, can be cured by heating at a low temperature in a short time, have high bonding strength, and suppress an increase in volume resistance under high temperature and high pressure conditions. Background Art

[0002] Conductive resin compositions with a wide variety of compositions are known, and are used in various applications such as formation of electronic circuits and adhesion of electronic components as conductive adhesives, conductive inks, circuit connection materials, conductive pastes, and the like. For example, in the production of circuits for electrical and electronic devices, there is a demand for conductive adhesives and circuit connection materials that are used for conductive connection (adhesion) of electrical and electronic components instead of solder. Such conductive adhesives and circuit connection materials are used 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. There is also a demand for conductive inks that are applicable to various printing methods and are useful for producing flexible plastic substrates having conductive structures such as interconnections, traces, and electrodes. In response to such needs, Patent Documents 1 to 3 describe conductive resin compositions containing a conductive powder and a resin component. Prior Art Documents Patent Documents

[0003] Patent Document 1 Japanese Unexamined Patent Application Publication No. 2024-119271 Patent Document 2 Japanese Patent No. 7249473 Patent Document 3 Japanese Unexamined Patent Application Publication No. 2022-102442 Summary of the Invention [Problems that the invention aims to solve]

[0004] When fabricating circuits for electrical and electronic equipment such as printed circuit boards, and when mounting components in other electrical and electronic devices, soldering and bonding with conductive resin compositions are used. However, soldering requires temperatures exceeding 160°C during joining, making it unsuitable for low-heat-resistant substrates. Furthermore, forming bonds with materials such as ITO and glass was difficult using soldering. On the other hand, bonding with conductive resin compositions is difficult to apply to low-heat-resistant substrates because the curing temperature is high or the curing time is long, and overall heating is required using a heating furnace such as an oven. If the conductive resin composition is cured at a low temperature for application to low-heat-resistant substrates, it may not cure sufficiently, potentially resulting in low bonding strength. Furthermore, if the conductive resin composition contains a microencapsulated curing agent, it becomes highly viscous, making mechanical stirring difficult and requiring manual stirring, resulting in poor workability and problems such as increased volume resistivity due to reduced dispersibility. In addition, improvements were needed regarding the storage stability of conductive resin compositions.

[0005] One of the problems that the present invention aims to solve is to provide a conductive resin composition that has low volume resistivity, can sufficiently cure even with low temperature and short heating time, can form a cured film with high bonding strength to various substrates, has excellent workability, and has excellent storage stability. One of the problems that the present invention aims to solve is to provide a conductive adhesive containing a conductive resin composition that has low volume resistivity, can sufficiently cure even with low temperature and short heating time, can form a cured film with high bonding strength to various substrates, has excellent workability, and has excellent storage stability. [Means for solving the problem]

[0006] The inventors of the present invention conducted diligent research to solve the above problems and, as a result, discovered that the above problems can be solved by a conductive resin composition and a conductive adhesive of a specific composition, thus completing the present invention. Specifically, the invention is as follows. [Section 1] (A)~(C): (A) Epoxy resin having a bisphenol skeleton, (B) Amine-based epoxy resin curing agent having a bisphenol skeleton, (C) Conductive powder containing one or more selected from silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder, and gold-based powder. A conductive resin composition containing [the specified ingredient]. [Section 2] The conductive resin composition according to claim 1, wherein (A) comprises an epoxy resin having a bisphenol E skeleton and / or a bisphenol F skeleton. [Section 3] The conductive resin composition according to claim 1 or 2, wherein (B) comprises an amine-based epoxy resin curing agent having a bisphenol A skeleton. [Section 4] The conductive resin composition according to any one of claims 1 to 3, wherein (B) comprises a polyamine-based epoxy resin curing agent having a bisphenol skeleton and having an aromatic ring and / or heterocycle within the molecule. [Section 5] The conductive resin composition according to any one of claims 1 to 4, wherein (C) comprises silver powder and / or silver alloy powder. [Section 6] The conductive resin composition according to any one of claims 1 to 5, wherein (C) comprises plate-shaped, flake-shaped, or granular silver powder. [Section 7] The conductive resin composition according to any one of claims 1 to 6, wherein the content of (C) is 66% by mass or more, with the total amount of solids of (A) to (C) being 100% by mass. [Section 8] (D) A conductive resin composition according to any one of items 1 to 7, comprising a coupling agent. [Section 9] A conductive adhesive comprising a conductive resin composition as described in any one of items 1 to 8. [Effects of the Invention]

[0007] The present invention provides a conductive resin composition that has low volume resistivity, can be sufficiently cured even with low temperature and short heating time, can form a cured film with high bonding strength to various substrates, has excellent workability and storage stability. The present invention provides a conductive adhesive comprising a conductive resin composition that has low volume resistivity, can sufficiently cure even with low temperature and short heating time, can form a cured film with high bonding strength to various substrates, has excellent workability, and has excellent storage stability.

[0008] The conductive resin composition and conductive adhesive of the present invention are useful for applications where conductive bonding is performed by curing using induction heating (IH), low-temperature, short-duration heating methods such as ovens, lasers, microwaves, etc., as they can sufficiently cure even with low-temperature, short-duration heating and form a cured film with high bonding strength to various substrates. [Modes for carrying out the invention]

[0009] The conductive resin composition and conductive adhesive according to the present invention will be described in detail below. In this specification, numerical ranges can be constructed by arbitrarily combining the upper and lower limits exemplified.

[0010] [Conductive resin composition] The conductive resin composition of the present invention is (A) Epoxy resin having a bisphenol skeleton, (B) Amine-based epoxy resin curing agent having a bisphenol skeleton, (C) Conductive powder containing one or more selected from silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder, and gold-based powder. This is a conductive resin composition containing [a specific substance].

[0011] The conductive resin composition of the present invention may also include an epoxy resin having a bisphenol E skeleton and / or a bisphenol F skeleton in (A). The conductive resin composition of the present invention may contain, in which (B) above, an amine-based epoxy resin curing agent having a bisphenol A skeleton, or it may contain a polyamine-based epoxy resin curing agent having a bisphenol skeleton and whose intramolecular rings are aromatic rings and / or heterocycles. The conductive resin composition of the present invention may be a conductive powder in which (C) contains silver powder and / or silver alloy powder, or a conductive powder containing plate-shaped, flake-shaped, or granular silver powder. Furthermore, the conductive resin composition of the present invention may contain (C) in an amount of 66% by mass or more, with the total solid content of (A) to (C) being 100% by mass. The conductive resin composition of the present invention may contain (D) a coupling agent.

[0012] The conductive resin composition of the present invention, by containing specific (A) to (C), has low volume resistivity, can be sufficiently cured even with low temperature and short heating time, and can form a cured film with high bonding strength to various substrates, and has excellent workability and storage stability.

[0013] <(A) component> Component (A), which is a component of the conductive resin composition of the present invention, is an epoxy resin having a bisphenol skeleton.

[0014] Epoxy resins having a bisphenol skeleton contain formula (A1): [ka] The epoxy resin is not particularly limited as long as it has one or more bisphenol skeletons represented by and one or more epoxy groups. One type of epoxy resin having a bisphenol skeleton may be used alone, or two or more types may be used.

[0015] In Formula (A1), n1 is an integer from 0 to 4, and n2 is an integer from 0 to 4. R 1 and R 2 are substituents. When there are plural R 1 and / or R 2 groups, they may be the same as or different from each other. Examples of R 1 and R 2 include a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, and a cyano group. The substituent may be one type alone or two or more types. X is a group selected from -CR 11 R 12 -, -S(=O)2-, -O-, and -C(=O)-, wherein R 11 and R 12 are hydrogen or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other, and may be bonded to each other to form a ring. In the present invention, X in Formula (A1) is preferably a group selected from -CH(CH3)-, -C(CH3)2-, -CH2-, -C(CF3)2-, -S(=O)2-, -O-, -C(=O)-, -C(CH3)(Ph)-, -C(Ph)2-, -C(CH3)(C2H5)-, -CH(C2H5)-, and =C(CH2)5, wherein Ph is a phenyl group. More preferably, X is a group selected from -CH(CH3)-, -C(CH3)2-, -CH2-, -C(CF3)2-, -C(CH3)(Ph)-, -C(Ph)2-, -C(CH3)(C2H5)-, and -CH(C2H5)-, wherein Ph is a phenyl group. Still more preferably, X is selected from -CH(CH3)-, -C(CH3)2-, -CH2-, -C(CF3)2-, and -C(CH3)(Ph)-. Particularly preferably, X is -CH(CH 3 )- or -CH2-. In Formula (A1), the skeleton in which X is -CH(CH3)- and n1 and n2 are 0 is a bisphenol E skeleton, and the skeleton in which X is -CH2- and n1 and n2 are 0 is a bisphenol F skeleton.

[0016] Epoxy resins having a bisphenol skeleton preferably have two or more epoxy groups. The epoxy equivalent of the epoxy resin having a bisphenol skeleton is not particularly limited. For example, it can be 100 g / eq or more, preferably 150 g / eq or more, for example 5,000 g / eq or less, preferably 2,000 g / eq or less, for example 100 g / eq or more and 5,000 g / eq or less, for example 100 g / eq or more and 2,000 g / eq or less, for example 150 g / eq or more and 5,000 g / eq or less, for example 150 g / eq or more and 2,000 g / eq or less. Epoxy equivalent is the number of grams (g / eq) of epoxy resin containing one equivalent of epoxy groups.

[0017] Examples of epoxy resins having a bisphenol skeleton include bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol AD ​​type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol AP type epoxy resin, and bisphenol Z type epoxy resin. In the present invention, as the epoxy resin having a bisphenol skeleton, bisphenol E type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol BP type epoxy resin, and bisphenol Z type epoxy resin are preferred, bisphenol E type epoxy resin, bisphenol A type epoxy resin, and bisphenol F type epoxy resin are more preferred, and bisphenol E type epoxy resin and / or bisphenol F type epoxy resin are even more preferred.

[0018] The content of epoxy resin having a bisphenol skeleton, which is component (A), in the conductive resin composition is not particularly limited. Taking the total of components (A) to (C) as 100% by mass, it can be, for example, 5.0% by mass or more, preferably 7.0% by mass or more, more preferably 10.0% by mass or more, for example, 35.0% by mass or less, preferably 33.0% by mass or less, more preferably 28.0% by mass or less, for example, 5.0% by mass or more and 35.0% by mass or less, for example, 5.0% by mass or more and 33.0% by mass or less, for example, 5.0% by mass or more and 28.0% by mass or less, for example, 7.0% by mass or more and 35.0% by mass or less, for example, 7.0% by mass or more and 33.0% by mass or less, for example, 7.0% by mass or more and 28.0% by mass or less, for example, 10.0% by mass or more and 35.0% by mass or less, for example, 10.0% by mass or more and 33.0% by mass or less, for example, 10.0% by mass or more and 28.0% by mass or less. Assuming the total of components (A) to (C) is 100% by mass, if the content of component (A) is less than 5.0% by mass, workability may decrease and bonding strength may decrease. If it exceeds 35.0% by mass, workability may decrease, curing time may be longer, and the volume resistivity may increase, reducing conductivity.

[0019] <(B) component> Component (B), which is a component of the conductive resin composition of the present invention, is an amine-based epoxy resin curing agent having a bisphenol skeleton.

[0020] Amine-based epoxy resin curing agents having a bisphenol skeleton have formula (B1) in their molecule: [ka] The epoxy resin curing agent is not particularly limited as long as it has one or more bisphenol skeletons represented by and one or more amino groups. The amine-based epoxy resin curing agent having a bisphenol skeleton preferably has two or more primary amino groups and / or secondary amino groups. The number of amino groups in one molecule of the amine-based epoxy resin curing agent having a bisphenol skeleton is not particularly limited; for example, it may be two or more. The epoxy resin curing agent having a bisphenol skeleton may be used alone or in combination of two or more types.

[0021] In equation (B1), n3 is an integer from 0 to 4, and n4 is an integer from 0 to 4. 3 and R 4 is a substituent, R 3 and / or R 4 If there are multiple instances, they may be identical or different from one another. 3 and R 4 Examples of substituents include halogen atoms, hydrocarbon groups, alkoxy groups, cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, alkylthio groups, cycloalkylthio groups, arylthio groups, aralkylthio groups, acyl groups, nitro groups, cyano groups, etc. The substituent may be a single type or two or more types. X is -CR 31 R 32 A group selected from -, -S(=O)2-, -O-, and -C(=O)-, R 31 and R 32 These are hydrogen atoms and optionally substituted hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different from each other, and may be bonded to each other to form a ring. In the present invention, X in formula (B1) is preferably a group selected from -C(CH3)2-, -CH2-, -CH(CH3)-, -C(CF3)2-, -S(=O)2-, -O-, -C(=O)-, -C(CH3)(Ph)-, -C(Ph)2-, -C(CH3)(C2H5)-, -CH(C2H5)-, and =C(CH2)5 (Ph is a phenyl group). More preferably, the group is selected from -C(CH3)2-, -CH2-, -CH(CH3)-, -C(CF3)2-, -C(CH3)(Ph)-, -C(Ph)2-, -C(CH3)(C2H5)- and -CH(C2H5)- (Ph is a phenyl group), even more preferably -C(CH3)2-, -CH2-, -CH(CH3)-, -C(CF3)2-, -C(CH3)(Ph)-, and particularly preferably -C(CH3)2- or -CH2-. In formula (B1), the skeleton in which X is -C(CH3)2- and n3 and n4 are 0 is the bisphenol A skeleton, and the skeleton in which X is -CH2- and n3 and n4 are 0 is the bisphenol F skeleton.

[0022] Examples of amine-based epoxy resin curing agents having a bisphenol skeleton include (i) an epoxy resin curing agent containing an amine compound having a bisphenol skeleton, (ii) an epoxy resin curing agent containing a reaction product obtained by reacting at least a primary amino group-containing amine compound with an epoxy resin (epoxy adduct) having a bisphenol skeleton, and (iii) a compound modified from the epoxy resin curing agent of (i) or (ii) that has active hydrogen such as a phenol compound.

[0023] Examples of amine compounds having a bisphenol skeleton include formula (B2): [ka] Examples include compounds represented by formula (B2) and modified polyamines, polyamidoamines, etc., obtained by epoxy adducting, Michael addition, Mannich reaction, etc. These may be used individually or in combination of two or more types. In formula (B2), R 3 n3, R4 n4 and n4 are, respectively, R in equation (B1). 3 n3, R 4 And it is similar to n4, R 5 and R 6 These are divalent organic groups, and they may be the same or different from each other, R 7 and R 8 These are hydrogen or an optionally substituted alkyl group having 1 to 12 carbon atoms, and may be the same or different from each other.

[0024] In the reaction product obtained by reacting a primary amino group-containing amine compound with an epoxy resin (epoxy adduct) having a bisphenol skeleton, examples of primary amino group-containing compounds include diethylenetriamine, triethylenetetramine, diethylaminopropylamine, menthanediamine, isophoronediamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, m-xylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiethyldiphenylmethane, and one or more modified polyamines and polyamidoamines obtained by modifying the primary amino group-containing compound portion of these by Michael addition, Mannich reaction, etc. In a reaction product obtained by reacting a primary amino group-containing amine compound with at least one epoxy resin having a bisphenol skeleton (epoxy adduct), the epoxy resin having a bisphenol skeleton (epoxy adduct) can be, for example, one or more of the epoxy resins having a bisphenol skeleton listed as <component (A)> above, or adducts of these epoxy resins.

[0025] Examples of amine-based epoxy resin curing agents having a bisphenol skeleton include those containing epoxy resin curing agents having a bisphenol A skeleton. Preferably, these include polyamine-based epoxy resin curing agents having a bisphenol skeleton and whose intramolecular rings are aromatic rings and / or heterocyclic rings; more preferably, these include polyamine-based epoxy resin curing agents having a bisphenol A skeleton and whose intramolecular rings are aromatic rings and / or heterocyclic rings; even more preferably, these include polyamine-based epoxy resin curing agents obtained by reacting a polyamine having two or more amino groups with an epoxy resin having a bisphenol A skeleton or its adduct, and whose intramolecular rings are aromatic rings and / or heterocyclic rings; particularly preferably, these include polyamine-based epoxy resin curing agents obtained by reacting a polyamine having two or more amino groups with an epoxy resin having a bisphenol A skeleton or its adduct, and a phenol compound, and whose intramolecular rings are aromatic rings and / or heterocyclic rings.

[0026] The content of the amine-based epoxy resin curing agent having a bisphenol skeleton, which is component (B) in the conductive resin composition is not particularly limited. Taking the total epoxy resin in the conductive resin composition as 100% by mass, it can be, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, for example 65.0% by mass or less, preferably 60.0% by mass or less, more preferably 58.0% by mass or less, for example 0.1% by mass or more and 65.0% by mass or less, for example 0.1% by mass or more and 60.0% by mass or less, for example 0.1% by mass or more and 58.0% by mass or less, for example 0.5% by mass or more and 65.0% by mass or less, for example 0.5% by mass or more and 60.0% by mass or less, for example 0.5% by mass or more and 58.0% by mass or less, for example 1.0% by mass or more and 65.0% by mass or less, for example 1.0% by mass or more and 60.0% by mass or less, for example 1.0% by mass or more and 58.0% by mass or less. With the total epoxy resin content in the conductive resin composition being 100% by mass, if the content of component (B) is less than 0.1% by mass, the curability of the conductive adhesive may decrease, curing may take longer, and the bonding strength may decrease. If it exceeds 65.0% by mass, the conductive adhesive may not solidify and a film may not form, workability may decrease, and the volume resistivity may increase, resulting in decreased conductivity.

[0027] <(C) component> Component (C), which is a component of the conductive 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.

[0028] (C) The shape of component is not particularly limited. Spherical, nearly spherical (for example, with an aspect ratio of 1.5 or less), dendritic, flattened, block-shaped, plate-shaped, polygonal pyramidal, polyhedral, flake-shaped (scale-like), rod-shaped, fibrous, needle-shaped, irregularly shaped, etc., can be used depending on the application. In the present invention, spherical, nearly spherical, dendritic, flattened, or flake-shaped (scale-like) components are preferred from the viewpoint of oxidation resistance, volume resistivity, dispersibility, and handling.

[0029] In the present invention, as component (C), 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 viewpoint of conductivity, migration characteristics, etc., more preferably silver-based powder, and even more preferably silver powder and / or silver alloy powder.

[0030] (Silver-coated copper powder) Silver-coated copper powder is not particularly limited as long as the surface of the copper powder is coated with silver. By silver-coating the copper powder, excellent oxidation resistance can be achieved, the volume resistivity can be reduced, and the storage stability of the conductive resin composition can be improved. The method for producing silver-coated copper powder is not particularly limited. For example, silver-coated copper powder produced by silver plating, silver-coated copper powder produced by a copper-silver substitution reaction, etc., can all be used.

[0031] The volume-average particle size 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, for example, 100 μm or less, preferably 50 μm or less, more preferably 20 μm or less, for example, 0.1 μm to 100 μm, for example, 0.1 μm to 50 μm, for example, 0.1 μm to 20 μm, for example, 0.3 μm to 100 μm, for example, 0.3 μm to 50 μm, for example, 0.3 μm to 20 μm, for example, 0.5 μm to 100 μm, for example, 0.5 μm to 50 μm, for example, 0.5 μm to 20 μm. For example, in order to enable the conductive resin composition to be printable, particularly by screen printing or dispenser application, it is preferable that the particle size be 0.5 μm to 10 μm. Here, the volume-average particle size of the silver-coated copper powder in this invention is the value of the volume-cumulative particle size D50 at a cumulative volume of 50% as measured by laser diffraction scattering particle size distribution analysis. If the volume-average particle size of the silver-coated copper powder is larger than 10 μm, the leveling properties of the conductive paste will decrease, and the wiring pattern will be more prone to breakage, making it difficult to form narrow wiring patterns. Also, if the volume-average particle size of the silver-coated copper powder is smaller than 0.5 μm, the copper in the core will be exposed, and the copper in this area will oxidize, potentially increasing the resistivity of the wiring pattern over time.

[0032] Furthermore, the thickness of the flake-shaped silver-coated copper powder is not particularly limited. For example, it may be 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.

[0033] Specific examples of silver-coated copper powder include 10%Ag coated Cu-HWQ 5μm, 10%Ag coated FCC-2000, 10%Ag coated FCC-115, 10%Ag coated 2L3 (all manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd.), 10%Ag / 1100Y, 10%Ag / 1100YP, 10%Ag / 05KP, ACFY-2, ACAX-225, ACBY-2 (all manufactured by Mitsui Mining & Smelting Co., Ltd.), TFM-C02P, TFM-C05P, TFM-C05F, TFM-C15F (all manufactured by Toyo Aluminum Co., Ltd.), and others. Silver-coated copper powder may be used alone or in combination of two or more types.

[0034] The silver content in 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 exceeds 30% by mass, the likelihood of ion migration may increase.

[0035] (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 powders other than silver-coated copper. The silver-based powder may be used alone or in combination of two or more types.

[0036] Metallic silver powder is obtained by pulverizing metallic silver. The silver content in 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.

[0037] The silver alloy powder is not particularly limited as long as it is an alloy powder containing silver. The silver content in the silver alloy powder can be appropriately determined from the viewpoint of the melting point of the silver alloy powder, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and for example, less than 97% by mass. The silver content in silver-containing powder can be easily measured using an X-ray fluorescence (XRF) analyzer or similar device. Examples of silver alloy powders include silver-copper alloys, silver-platinum alloys, and silver-palladium alloys.

[0038] Silver-coated powders other than silver-coated copper powder are those in which at least a portion of the particle surface is coated with metallic silver. Examples of particles that form silver-coated powder include one or more 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 particles, etc.). Methods for coating with metallic silver include plating and vapor deposition. The thickness of the metallic silver coating is not particularly limited, but it is preferably in the range of 0.01 μm to 5 μm.

[0039] The silver-based powder may contain other atoms to the extent that they do not impair the properties of the silver-based powder. Examples of other atoms include one or more of the following: 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, Ge, Bi, C, B, N, P, S, etc. The content of other atoms is, for example, 3% by mass or less, preferably 1% by mass or less, in the silver-based powder.

[0040] The volume-average particle size of the silver-based powder is not particularly limited. It can be determined appropriately considering dispersibility and handling. For example, it can be 0.1 μm or more, preferably 0.4 μm or more, more preferably 0.7 μm or more; for example, 100.0 μm or less, preferably 50.0 μm or less, more preferably 20.0 μm or less; for example, 0.1 μm or more and 100.0 μm or less; for example, 0.1 μm or more and 50.0 μm or less; for example, 0.1 μm or more and 20.0 μm or less; for example, 0.4 μm or more and 100.0 μm or less; for example, 0.4 μm or more and 50.0 μm or less; for example, 0.4 μm or more and 20.0 μm or less; for example, 0.7 μm or more and 100.0 μm or less; for example, 0.7 μm or more and 50.0 μm or less; for example, 0.7 μm or more and 20.0 μm or less.

[0041] Furthermore, the thickness of the flake-shaped silver powder is not particularly limited. For example, it may be 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.

[0042] The specific surface area of ​​the silver-based powder is not particularly limited. For example, 0.3 m². 2 / g or more, preferably 0.5m 2 / g or more, more preferably 0.7m 2 It can be set to 2.5m or more, for example. 2 Less than or equal to / g, preferably 2.1m 2 / g or less, more preferably 1.6m 2 It can be less than / g, for example, 0.3m 2 / g or more 2.5m 2 Less than / g, for example, 0.3m 2 / g or more 2.1m 2 Less than / g, for example, 0.3m 2 / g or more 1.6m 2 Less than / g, for example, 0.5m 2 / g or more 2.5m 2 Less than / g, for example, 0.5m 2 / g or more 2.1m 2Less than / g, for example, 0.5m 2 / g or more 1.6m 2 Less than / g, for example, 0.7m 2 / g or more 2.5m 2 Less than / g, for example, 0.7m 2 / g or more 2.1m 2 Less than / g, for example, 0.7m 2 / g or more 1.6m 2 It can be less than / g.

[0043] (Nickel-based powder) Nickel-based powders are powders containing metallic nickel, and are not particularly limited as long as they are not silver-based powders. Examples include metallic nickel powder, nickel alloy powder, nickel-coated powder, and the like. Nickel-based powders may be used individually or in combination of two or more types.

[0044] Metallic nickel powder is obtained by pulverizing metallic nickel. The nickel content in 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.

[0045] Nickel alloy powder is not particularly limited as long as it is an alloy powder containing nickel. The nickel content in the nickel alloy powder can be appropriately determined from the viewpoint of the melting point of the nickel alloy powder, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and for example, less than 95% by mass. The nickel content in nickel-containing powder can be easily measured using an X-ray fluorescence (XRF) analyzer or similar device. 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.

[0046] Nickel-coated powder is a powder in which at least a portion of the particle surface is coated with metallic nickel. Examples of particles that form nickel-coated powder include one or more 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 particles, etc.). Methods for coating with metallic nickel include plating and vapor deposition. The thickness of the metallic nickel coating is not particularly limited, but it is preferably in the range of 0.01 μm to 5 μm.

[0047] Nickel-based powders may contain other atoms to the extent that they do not impair the properties of the nickel-based powder. Examples of other atoms include one or more of the following: 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, Ge, Bi, C, B, N, P, S, etc. The content of other atoms is, for example, 3% by mass or less, preferably 1% by mass or less, in the nickel-containing powder.

[0048] The volume-average particle size of the nickel-based powder is not particularly limited. It can be determined as appropriate, taking into consideration dispersibility and handling. For example, it can be 0.5 μm or larger, preferably 1.0 μm or larger, more preferably 3.0 μm or larger, and for example, 100.0 μm or smaller, preferably 50.0 μm or smaller, more preferably 20.0 μm or smaller.

[0049] (Conductive carbon powder) The conductive carbon powder is not particularly limited as long as it is a carbon powder composed of carbon atoms and is not coated with silver, nickel, copper, or gold. Examples include carbon black, activated carbon, carbon fiber, carbon nanotubes, and graphene. Preferably, carbon black, carbon nanotubes, and graphene are used. The conductive carbon powder may be used alone or in combination of two or more types.

[0050] Examples of carbon black include acetylene black, furnace black, Ketjen black, channel black, lamp black, and thermal black.

[0051] The primary particle size of carbon black is not particularly limited. For example, it can be 5 nm or larger, preferably 10 nm or larger, and for example, 700 nm or smaller, preferably 500 nm or smaller. The primary particle size can be defined as the arithmetic mean of the particle sizes of 100 particles observed and measured with an electron microscope (SEM or TEM).

[0052] Carbon nanotubes are cylindrical, hollow, fibrous materials composed of carbon, and can be either multi-walled or single-walled carbon nanotubes. From the viewpoint of conductivity, multi-walled carbon nanotubes are preferred. Carbon nanotubes can be manufactured by methods such as arc discharge, chemical vapor deposition (CVD), or laser ablation. Commercially available carbon nanotubes may also be used.

[0053] 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 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 for example, 100 μm or less, preferably 70 μm or less. The average diameter and average length of carbon nanotubes are the arithmetic mean of the average diameter and average length of 100 carbon nanotubes observed and measured using an electron microscope (SEM, TEM).

[0054] The BET specific surface area of ​​carbon nanotubes is, for example, 50 m², based on the relationship between viscosity and conductivity.2 / g or more, preferably 100m 2 / g or more, comfortable 150m 2 It can be 800m or more, for example. 2 Less than or equal to / g, preferably 600m 2 Less than / g, more preferably 500m 2 It can be less than / g.

[0055] Graphene is a dense, two-dimensional crystalline material with a carbon six-membered ring structure, and it possesses quantized conductivity (ballistic conductivity).

[0056] (Copper-based powder) Copper-based powders are powders containing metallic copper, and are not particularly limited as long as they are powders other than silver-coated copper powder, silver-based powder, and nickel-based powder. Examples include metallic copper powder, copper alloy powder, and copper-coated powder. Copper-based powders may be used individually or in combination of two or more types.

[0057] (Gold-based powder) Gold-based powders are powders containing metallic gold, and are not particularly limited as long as they are powders 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. Gold-based powders may be used individually or in combination of two or more types.

[0058] (Content) The content of component (C) in the conductive resin composition is not particularly limited. Taking the total amount of the conductive resin composition as 100% by mass, it can be, for example, 45.0% by mass or more, preferably 50.0% by mass or more, more preferably 55.0% by mass or more, and even more preferably 66% by mass or more. It can also be, for example, 97.0% by mass or less, preferably 95.0% by mass or less, and more preferably 93.0% by mass or less. For example, 45.0% by mass or more and 97.0% by mass or less, for example, 45.0% by mass or more and 95.0% by mass or less, for example, 45.0% by mass or more and 93.0% by mass or less. For example, it can be 50.0% by mass or more and 97.0% by mass or less, for example, 50.0% by mass or more and 95.0% by mass or less, for example, 50.0% by mass or more and 93.0% by mass or less, for example, 55.0% by mass or more and 97.0% by mass or less, for example, 55.0% by mass or more and 95.0% by mass or less, for example, 55.0% by mass or more and 93.0% by mass or less, for example, 66.0% by mass or more and 97.0% by mass or less, for example, 66.0% by mass or more and 95.0% by mass or less, for example, 66.0% by mass or more and 93.0% by mass or less. If the content of component (C) is less than 45.0% by mass when the total amount of the conductive resin composition is 100% by mass, the conductivity of the obtained conductive resin composition (conductive film) may be insufficient (volume resistivity may be high), and if it exceeds 97.0% by mass, the bonding strength of the conductive resin composition may be insufficient.

[0059] <(D) component> The conductive resin composition of the present invention may contain (D) a coupling agent. Examples of coupling agents include those containing one or more silane coupling agents, titanium coupling agents, aluminum coupling agents, and zirconium coupling agents. Preferably, the product contains a silane coupling agent, and more preferably, it contains an epoxy group-containing silane coupling agent and / or an amino group-containing silane coupling agent. The conductive resin composition of the present invention, by incorporating a coupling agent as a component, can form a film on various substrates that exhibits excellent long-term reliability in terms of bonding strength.

[0060] Examples of silane coupling agents include amino group-containing silane compounds such as aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropylmethylmethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane; vinyl group-containing silane compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy group-containing silane compounds such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane; (meth)acryloyl group-containing silane compounds such as γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; and isocyanate group-containing silane compounds such as γ-isocyanatetopropyltrimethoxysilane and γ-isocyanatetopropyltriethoxysilane.

[0061] Examples of titanium coupling agents include tetraisopropyl titanate, tetran-butyl titanate, butyl titanate, tetraoctyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium dodecylbenzenesulfonate compounds, titanium octylene glycolate, titanium ethylacetoacetate, titanium lactate ammonium salt, titanium lactate, titanium triethanolamine, tetraisopropyl titanate, tetratashery-butyl titanate, tetrastearyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium isostearate, titanium diethanolamine, titanium aminoethylaminoethanolate, and titanium oligomers.

[0062] Examples of aluminum coupling agents include aluminate compounds having an alkoxy group, such as alkylacetacetate aluminum diisopropylate, and aluminate compounds having an acetylacetonate group, such as aluminum trisacetylacetonate.

[0063] Examples of zirconium coupling agents include tetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis(acetylacetonate), zirconium triputoxyethylacetoacetate, zirconium butoxyacetylacetonate bis(ethylacetoacetate), and tetrakis(2,4-pentanedione)zirconium. The coupling agent may be used alone or in combination of two or more types.

[0064] The content of the coupling agent, which is component (D), in the conductive resin composition is not particularly limited. Taking the total of components (A) to (D) as 100% by mass, it can be, for example, 0% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. It can also be, for example, 10.0% by mass or less, preferably 5.0% by mass or less, and more preferably 3.0% by mass or less. For example, 0% by mass or more and 10.0% by mass or less, for example, 0% by mass or more and 5.0% by mass or less, and for example, 0% by mass or more and 3.0% by mass or less. For example, it can be 0.05% by mass or more and 10.0% by mass or less, for example 0.05% by mass or more and 5.0% by mass or less, for example 0.05% by mass or more and 3.0% by mass or less, for example 0.1% by mass or more and 10.0% by mass or less, for example 0.1% by mass or more and 5.0% by mass or less, for example 0.1% by mass or more and 3.0% by mass or less, for example 0.5% by mass or more and 10.0% by mass or less, for example 0.5% by mass or more and 5.0% by mass or less, for example 0.5% by mass or more and 3.0% by mass or less. If the total of components (A) to (D) is taken as 100% by mass, the content of component (D) may be less than 0.05% by mass, and if it exceeds 10.0% by mass, the workability may be reduced, the volume resistivity may increase and conductivity may decrease.

[0065] <Other ingredients> The conductive resin composition of the present invention may optionally contain "other components" such as epoxy resins other than component (A), resins other than epoxy resins, wetting and dispersing agents, fillers, solvents, epoxy resin curing agents other than component (B), adhesion promoters, viscoelastic modifiers, curing accelerators (curing catalysts), reactive diluents, conductive powders other than component (C), antioxidants, gap adjusters (spacers; spacing control agents), organic acid compounds, pigments, corrosion inhibitors, surfactants, defoamers, dispersants, viscosity modifiers (thixotropy modifiers), adhesion promoters, settling inhibitors, pH adjusters, leveling agents, ultraviolet absorbers, flame retardants, heavy metal deactivators, etc., to the extent that performance is not impaired. Other ingredients may be used individually or in combination of two or more.

[0066] (Epoxy resins other than component (A)) The conductive resin composition of the present invention may contain epoxy resins other than component (A). The epoxy resins other than component (A) are not particularly limited as long as they do not have a biphenyl skeleton. One epoxy resin other than component (A) may be used alone, or two or more may be used.

[0067] (A) Epoxy resins other than component (A), which do not have a biphenyl skeleton, may be monomers, oligomers, or polymers having two or more glycidyl groups in one molecule, and their molecular weight is not particularly limited. For example, chelate-modified epoxy resins; hydroquinone-type epoxy resins; stilbene-type epoxy resins; resorcinol diglycidyl ethers; triphenolmethane-type epoxy resins, alkyl-modified triphenolmethane-type epoxy resins, phenol aralkyl-type epoxy resins having a phenylene skeleton; naphthol-type epoxy resins such as dihydroxynaphthalene-type epoxy resins and epoxy resins obtained by epoxidizing a dimer of dihydroxynaphthalene; triazine-nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; dicyclopentadiene-type epoxy resins, hydrogenated bisphenol A-type epoxy resins, and hydrogenated bisphenol F-type epoxy resins. Examples include resins, hydrogenated biphenol-type epoxy resins, epoxy resins having an alicyclic structure such as glycidyl ethers of polyols having an alicyclic structure such as cyclohexanediol, cyclohexanedimethanol, and cyclohexanediethanol; glycidyl ethers of aliphatic polyols such as butanediol, hexanediol, octanediol, nonanediol, decanediol, trimethylolpropane, pentaerythritol, and glycerin; aromatic glycidylamine-type epoxy resins such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane-type glycidylamine, and aminophenol-type glycidylamine; and resorcinol diglycidyl ethers. Of these, one or more of the following are preferred: biphenyl-type epoxy resin, fluorene-type epoxy resin, phenol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, etc.

[0068] The biphenyl-type epoxy resin is not particularly limited as long as it is an epoxy resin having one or more biphenyl skeletons and one or more epoxy groups in its molecule. It is preferable that the biphenyl-type epoxy resin has two or more epoxy groups.

[0069] Examples of biphenyl-type epoxy resins include, but are not limited to, glycidyl ethers of biphenols that may be substituted (e.g., 3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl, 3,3',5,5'-tetra-tert-butyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl, 4,4'-bis(glycidyloxy)biphenyl, 3,3'-dimethyl-4,4'-bis(glycidyloxy)biphenyl, etc.), biphenyl aralkyl epoxy resins, and glycidyl ethers of alkylene oxide adducts of biphenols that may be substituted. Biphenyl-type epoxy resins may be used individually or in combination of two or more types.

[0070] Examples of biphenyl-type epoxy resins include, but are not limited to, NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, etc. from Nippon Kayaku Co., Ltd.; and the jER series (YX4000, YX4000K, YX4000H, YL6121H, YL6640, YL6677, etc.) from Mitsubishi Chemical Corporation.

[0071] The fluorene-type epoxy resin is not particularly limited as long as it is an epoxy resin having one or more 9,9-bisarylfluorene skeletons and one or more epoxy groups in its molecule. Preferably, the fluorene-type epoxy resin has two or more epoxy groups.

[0072] Examples of fluorene-type epoxy resins include, but are not limited to, 9,9-bis(glycidyloxyphenyl)fluorenes, 9,9-bis(polyglycidyloxyphenyl)fluorenes, 9,9-bis(glycidyloxynaphthyl)fluorenes, 9,9-bis(glycidyloxy(poly)alkoxyphenyl)fluorenes, 9,9-bis(polyglycidyloxy(poly)alkoxyphenyl)fluorenes, and 9,9-bis(glycidyloxy(poly)alkoxynaphthyl)fluorenes. One type of fluorene-type epoxy resin may be used alone, or two or more types may be used together.

[0073] Examples of 9,9-bis(glycidyloxyphenyl)fluorenes include 9,9-bis(glycidyloxyphenyl)fluorene such as 9,9-bis(4-glycidyloxyphenyl)fluorene; 9,9-bis(3-methyl-4-glycidyloxyphenyl)fluorene, 9,9-bis(3,5-dimethyl-4-glycidyloxyphenyl)fluorene, etc.; and 9,9-bis(mono or diC1~C4 alkyl-glycidyloxyphenyl)fluorene such as 9,9-bis(3-phenyl-4-glycidyloxyphenyl)fluorene, etc. 10 Examples include, but are not limited to, aryl-glycidyloxyphenyl ()fluorene; etc.

[0074] Examples of 9,9-bis(polyglycidyloxyphenyl)fluorenes include, but are not limited to, 9,9-bis(di or triglycidyloxyphenyl)fluorenes such as 9,9-bis(3,4-diglycidyloxyphenyl)fluorene and 9,9-bis(3,5-diglycidyloxyphenyl)fluorene.

[0075] Examples of 9,9-bis(glycidyloxynaphthyl)fluorenes include, but are not limited to, 9,9-bis(glycidyloxynaphthyl)fluorenes such as 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene and 9,9-bis(5-glycidyloxy-1-naphthyl)fluorene;

[0076] Examples of 9,9-bis(glycidyloxy(poly)alkoxyphenyl)fluorenes include 9,9-bis[4-(2-glycidyloxyethoxy)phenyl]fluorene, etc., 9,9-bis(glycidyloxy(poly)C2~C4alkoxyphenyl)fluorenes; 9,9-bis[4-(2-glycidyloxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-glycidyloxyethoxy)-3,5-dimethylphenyl]fluorene, etc., 9,9-bis(mono or diC1~C4alkyl-glycidyloxy(poly)C2~C4alkoxyphenyl)fluorenes; 9,9-bis[4-(2-glycidyloxyethoxy)-3-phenylphenyl]fluorene, etc., 9,9-bis(mono or diC6~C 10 Examples include, but are not limited to, aryl-glycidyloxy(poly)C2~C4 alkoxy-phenyl)fluorene; etc.

[0077] Examples of 9,9-bis(polyglycidyloxy(poly)alkoxyphenyl)fluorenes include, but are not limited to, 9,9-bis(di or triglycidyloxy(poly)C2~C4 alkoxyphenyl)fluorenes such as 9,9-bis(3,4-di(2-glycidyloxyethoxy)phenyl)fluorene and 9,9-bis(3,5-di(2-glycidyloxyethoxy)phenyl)fluorene; and others.

[0078] Examples of 9,9-bis(glycidyloxy(poly)alkoxynaphthyl)fluorenes include, but are not limited to, 9,9-bis[6-(2-glycidyloxyethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-glycidyloxyethoxy)-1-naphthyl]fluorene, and other 9,9-bis(glycidyloxy(poly)alkoxynaphthyl)fluorenes.

[0079] The phenol novolac type epoxy resin is not particularly limited as long as it is an epoxy resin having one or more phenol novolac type skeletons and one or more epoxy groups in its molecule. It is preferable that the phenol novolac type epoxy resin has two or more epoxy groups.

[0080] Examples of phenol novolac type epoxy resins include the jER series from Mitsubishi Chemical Corporation (152, 154, 157H65, etc.); the EPICLON series from DIC Corporation (N-660, N-665, N-680, N-695, N-730A, N-740, N-770, N-775, N-500P-10, etc.); the EPPN series from Nippon Kayaku Co., Ltd. (201, 202, etc.); and the EOCN series from Nippon Kayaku Co., Ltd. (102, 102S, 103, 103S, 104, Examples include, but are not limited to, the following: 104S, 1012, 1020, 1025, 1027, etc.; the RE series from Nippon Kayaku Co., Ltd. (305, 305S, 306, etc.); the DEN series from Dow Chemical Corporation (431, 438, 485, etc.); the YDCN series from Nippon Steel Chemical & Material Co., Ltd. (700, 700-10, 701, 702, 703, 704, etc.); and the Araldite series from Huntsman Ltd. (ECN1235, ECN1273, ECN1280). Phenol novolac type epoxy resins may be used individually or in combination of two or more types.

[0081] {Dicyclopentadiene type epoxy resin} The dicyclopentadiene-type epoxy resin is not particularly limited as long as it is an epoxy resin having one or more dicyclopentadiene-type skeletons and one or more epoxy groups in its molecule. Preferably, the dicyclopentadiene-type epoxy resin has two or more epoxy groups.

[0082] Examples of dicyclopentadiene-type epoxy resins include those obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound, and those obtained by epoxidizing a dicyclopentadiene polyol. Dicyclopentadiene-type epoxy resins may be used individually or in combination of two or more types.

[0083] Examples of dicyclopentadiene-type epoxy resins include the EPICLON series from DIC Corporation (HP7200L, HP7200, HP7200H, HP7200HHH, HP7200HHH, etc.); the Tactix series from Huntsman Advanced Materials (558, etc.); the XD series from Nippon Kayaku Co., Ltd. (1000, 1000-1L, 1000-2L, etc.); and the Adeka Resin series from ADEKA Corporation (EP-4088S, EP-4088L, etc.).

[0084] {Trimethylolpropane polyglycidyl ether} Trimethylolpropane polyglycidyl ether is not particularly limited as long as it is mainly composed of an epoxy resin in which the hydroxyl groups of trimethylolpropane, a trihydric alcohol, have been converted to a glycidyl ether. For example, it may contain trimethylolpropane triglycidyl ether and by-products contained during the production of trimethylolpropane triglycidyl ether. Alternatively, for example, it may be a mixture mainly composed of trimethylolpropane triglycidyl ether and containing one or more of the following: trimethylolpropane monoglycidyl ether, trimethylolpropane diglycidyl ether, or a condensation product of trimethylolpropane and epihalohydrin.

[0085] (Resins other than epoxy resins) The conductive resin composition of the present invention may contain resins other than epoxy resins. The resin other than 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, as resins other than epoxy resins, block urethane resins, polyurethane resins, polyvinyl acetal resins, resol-type phenolic resins, acrylic resins, polyester resins, phenoxy resins, polyimide resins, and xylene resins are preferred. Among these, block urethane resins, polyurethane resins, polyester resins, polyvinyl acetal resins, and acrylic resins are more preferred from the viewpoint of film formation state, connection reliability, and adhesion to the substrate. Resins other than epoxy resin may be used individually or in combination of two or more types.

[0086] (Wetting and dispersing agent) The conductive resin composition of the present invention may optionally contain a wetting and dispersing agent to prevent aggregation of the components of the conductive resin composition. Specific examples of wetting and dispersing agents include, for example, the Solspers series from Lubrizol Japan (9000, 12000, 17000, 20000, 21000, 24000, 26000, 27000, 28000, 32000, 35100, 54000, etc.); and the EFKA series from BASF (4008, 4009, 4010, 4015, 4046, 4047, 4060, 4080, 7462, 4020, 4050, 4055, 4400, 4401, 4402, 4403, 4300, 4330, 4340, 6220, 6225, 6700, 67 Examples include: 80, 6782, 8503, etc.; Ajinomoto Fine Techno's Ajisper series (PA111, PB711, PB821, PB822, PN411, etc.); and Bic Chemie Japan's 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.). The wetting and dispersing agent may be used individually or in combination of two or more types.

[0087] (Filler) The conductive resin composition of the present invention may contain fillers. Examples of fillers include fused silica, fumed silica, precipitated silica, crystalline silica, carbon black, dolomite, anhydrous silicic acid, hydrated silicic acid, heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium dioxide, 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 fibers, potassium titanate fibers, and the like. The filler may be used individually or in combination of two or more types.

[0088] (solvent) The conductive resin composition of the present invention may contain a solvent. This allows for adjustment of the fluidity of the conductive resin composition, thereby improving workability, applicability, handling, and other properties. The amount of solvent used is not particularly limited, and the viscosity of the conductive resin composition should be adjusted as appropriate so that it is suitable for coating, printing, etc., onto a substrate and / or for impregnating materials such as nonwoven fabrics and porous materials.

[0089] As a solvent, one or more can be selected from the group consisting of water and various organic solvents. Examples of organic solvents 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 monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, ethyl carbitol, butyl carbitol, 2-ethyl-1,3-hexanediol, methyl methoxybutanol, α-terpineol, β-terpineol, hexylene glycol, benzyl alcohol, 2-phenylethyl alcohol, isopalmi Alcohols such as ethyl alcohol, isostearyl alcohol, lauryl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and glycerin; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3,5,5-trimethyl-2-cyclohexen-1-one), and diisobutyl ketone (2,6-dimethyl-4-heptanone); Ester solvents such as ethyl acetate, butyl acetate, diethyl phthalate, dibutyl phthalate, acetoxyethane, methyl butyrate, methyl hexanoate, methyl octanoate, methyl decanoate, methyl cellosolve acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethyl diglycol acetate, and 1,2-diacetoxyethane;Ether-based 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; 2-(2-butoxyethoxy)ethane acetate, methyl cellosolve acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether 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 diesel fuel; 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. The solvent may be used alone or in combination of two or more types.

[0090] (Epoxy resin curing agents other than component (B)) The conductive resin composition of the present invention may contain epoxy resin curing agents other than component (B). Examples of such epoxy resin curing agents include acid anhydride-based curing agents, phenol-based curing agents, amine-based curing agents, imidazole-based curing agents, microencapsulated latent curing agents, thiol-based curing agents, thermal cationic polymerization initiators, amide-based curing agents, and the like. (B) The epoxy resin curing agents other than component (B) may be used individually or in combination of two or more types.

[0091] The acid anhydride-based curing agent is not particularly limited as long as it is a compound having one or more carboxylic acid anhydride groups (-C(=O)-OC(=O)-) in its molecular structure. Acid anhydride-based curing agents are obtained by intermolecular dehydration of two organic carboxylic acid molecules and / or intermolecular dehydration of one organic carboxylic acid molecule. In the present invention, for example, one or more organic carboxylic acids 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 are mentioned. Examples include aliphatic monocarboxylic acid anhydrides, aliphatic polycarboxylic acid anhydrides, alicyclic polycarboxylic acid anhydrides, aromatic polycarboxylic acid anhydrides, and the like.

[0092] Examples of acid anhydride-based 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 acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, and polyacid polyanhydride. Here, polyacid polyanhydride is obtained by an intermolecular dehydration condensation reaction of long-chain aliphatic dicarboxylic acids, and examples include SL-12AH, SL-20AH, SB-20AH, IPU-22AH, ST-2PAH, etc., manufactured by Okamura Oil Co., Ltd., with SB-20AH, IPU-22AH, and ST-2PAH being particularly noteworthy. The acid anhydride-based curing agent may be used alone or in combination of two or more types.

[0093] The phenolic curing agent is not particularly limited as long as it is a compound having one or more, preferably two or more, phenolic hydroxyl groups in its molecular structure that can react with epoxy groups. For example, 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 (biphenylaralkylphenol); cresol novolacs such as o-cresol novolac, m-cresol novolac, and p-cresol novolac; triphenylmethanes; tetrakisphenols; phenol resins; phenol novolac resins; biphenylaralkyl type phenol resins; 4,4',4''-trihydroxytriphenylmethane, 4,4',4'',4'''-methanetetrayltetraphenol, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, MEH-8005 manufactured by Meiwa Kasei Co., Ltd.; KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd., KAYAHARD Examples include GPH-103; TEP-DF and PAPS series (BPAN, PN2, etc.) manufactured by Asahi Organic Chemicals Industry Co., Ltd.; and BRG-555, BRG-556, BRG-557, BRG-558, CRG-951, and TAM-005 manufactured by Aica Industrial Co., Ltd. The phenolic curing agent may be used alone or in combination of two or more types.

[0094] The amine-based 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 triethylenediamine, diethylenetriamine, triethylenetetramine, α-picoline, 1,3,6-trisaminomethylhexane, m-xylenediamine, p-xylenediamine, N-(2-aminoethyl)piperazine, m-phenylenediamine, p-phenylenediamine, 2,4-toluenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 1,3-diaminocyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetrapyro[5.5]undecane, menthanediamine, isophoronediamine, bis[4-amino-3-methyldicyclohexyl]methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, m-xylylenediamine, metaphenylenediamine, polyamines, polyamidoamines, and modified polyamines and polyamidoamines obtained by epoxy adducting, Michael addition, Mannich reaction, etc. Amine-based curing agents may be used individually or in combination of two or more types.

[0095] The imidazole-based curing agent is not particularly limited as long as it is a compound having one or more imidazole rings in its molecule. Examples include 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and modified imidazole. The imidazole-based curing agent may be used alone or in combination of two or more.

[0096] Microencapsulated latent curing agents include curing agents such as imidazole compounds, polyhydric phenol compounds, acid anhydrides, amine compounds, hydrazide compounds, mercapto compounds, Lewis acid-amine complexes, and latent curing agents, encapsulated in heat-destroying capsule materials such as vinyl compounds, urea compounds, phenolic resins, urethane resins, epoxy resins, polyethylene, polypropylene, polystyrene, nylon, polyester, polyvinyl chloride, polyvinylidene chloride, and thermoplastic resins. Among these, microencapsulated latent curing agents obtained by treating amine adduct-type latent curing agents with isocyanates are preferred. Microencapsulated latent curing agents may be used individually or in combination of two or more types.

[0097] The average particle size of the microencapsulated latent curing agent is not particularly limited. From the viewpoint of dispersibility in conductive resin compositions, it is, 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 laser diffraction / light scattering using a particle size distribution analyzer.

[0098] Examples of thiol compounds include those having one or more, preferably two or more, thiol groups in their molecular structure that can react with epoxy groups. Polyfunctional thiol compounds with 2 to 6 (2-6 functional) thiol groups in their molecular structure are preferred, and polyfunctional thiol compounds with 3 to 6 (3-6 functional) 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, it can be, for example, 50 g / eq or more, preferably 70 g / eq or more, and 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, it can be, for example, 250 g / eq or more, preferably 400 g / eq or more, and for example, 5,000 g / eq or less, preferably 3,000 g / eq or less.

[0099] 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-mercaptopropyl) Examples include thiol compounds (polyfunctional thiol compounds) such as 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptobutyrate) (abbreviated as TPMB), trimethylolethanetris(3-mercaptobutyrate) (abbreviated as TEMB), 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluryl, 1,3,4,6-tetrakis(2-mercaptopropyl) glycoluryl, 4,4'-isopropylidenebis[(3-mercaptopropoxy)benzene], and 1,3,5-triazine-2,4,6-trithiol, as well as polysulfide polymers having thiol groups.

[0100] Specifically, examples include polyfunctional thiols from SC Organic Chemicals (TMMP-LV, PEMP-LV, DPMP, TEMPIC, PEMP, etc.); polyfunctional thiols from Toray Fine Chemicals (QE-340M, LP-2, LP-3, LP-55, LP-31, etc.); polyfunctional thiols from Shikoku Chemicals (TS-G, C3TS-G, etc.); polyfunctional thiols from Resonac (Karenz MT series (PE-1, BD-1, NR-1, TPMB, TEMB, etc.)); polyfunctional thiols from Yodo Chemical (OTG, EGTG, TMTG, PETG, 3-MPA, TMTP, PETP, etc.); and polyfunctional thiols from Asahi Chemical Industries (G-2S, PE-2S, PE-3S, PE-4S, TMP-3S, etc.). Thiol-based curing agents may be used individually or in combination of two or more types.

[0101] The thermal cationic polymerization initiator is not particularly limited as long as it is a compound that generates a cation upon heat. For example, at least one cation selected from aromatic sulfonium, aromatic iodonium, aromatic diazonium, and pyridinium, and BF4 - PF6 - SbF6 - AsF6 - CF3SO3 - , (CF3SO2)2N - and B(C6F5)4 - Examples include onium salts composed of at least one anion selected from the above; aluminum complexes; etc. Examples include TA-100, TA-100FG, IK-1, IK-1FG etc. from Sunapro Co., Ltd.; SI-60, SI-80, SI-100, SI-150 etc. from Sanshin Chemical Industry Co., Ltd.; K-PURE TAG series, K-PURE CXC series etc. from King Industries, Ltd., etc. The thermal cationic polymerization initiator may be used alone or in combination of two or more.

[0102] (Adhesion enhancer) The conductive resin composition of the present invention may contain an adhesion promoter. This improves the adhesion between the conductive resin composition and the substrate when the composition is applied to the substrate. Examples of adhesion promoters include triazole compounds, thiazole compounds, triazine compounds, polymers having functional groups (carboxylic acid groups, amino groups, hydroxyl groups, etc.) and salts thereof. Examples of adhesion-enhancing agents include the BYK series (4509, 4510, 4512, etc.) manufactured by BIC Chemie Japan. The adhesion-enhancing agent may be used alone or in combination of two or more types.

[0103] (Viscoelastic modifier) The conductive resin composition of the present invention may contain a viscoelastic modifier (rheology control agent). This allows for adjustment of the viscoelasticity (rheology) of the conductive resin composition, contributing to improvements in workability and other aspects. Examples of viscoelastic modifiers (rheology control agents) include polyamide-based, aminoplast-based, polycarboxylic acid-based, urethane-based, cellulose-based, and inorganic layered compound-based viscoelastic modifiers (rheology control agents). Examples include the RHEOBYK series from BIC Chemie Japan (H370, H400, H600, H600VF, 100, 405, 410, 411, 415, 430, 431, 440, 7410ET, etc.); the Disparon series from Kusumoto Chemical Co., Ltd. (AQ-600, AQH-800, 3600N, 3900EF, etc.); the SN Thickener series from Sunopco Corporation (613, 617, 618, 630, 634, 636, 621N, 623N, etc.); the Adekanol series from ADEKA Corporation (UH-814N, UH-752, UH-750, UH-462, etc.); the HEC Daicel series from Daicel Corporation (SP600N, etc.); and BENTONE HD from Elementis Japan Co., Ltd. The viscoelastic modifier may be used alone or in combination of two or more types.

[0104] (Curing accelerator (curing catalyst)) The conductive adhesive of the present invention may contain a curing accelerator (curing catalyst) for promoting the curing of the epoxy resin and curing agent. The curing accelerator is not particularly limited, but may be one or more selected from the group consisting of amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, phosphonium-based curing accelerators, transition metal-based curing accelerators, etc.

[0105] Examples of curing accelerators (curing catalysts) include amine-based curing accelerators such as triethylamine, tripropylamine, tributylamine, dimethylbutylamine, dimethylpentylamine, dimethylcyclohexylamine, dimethylbenzylamine, diethylaminopropylamine, 2-(dimethylaminomethyl)phenol, dimethylamino-p-cresol, piperidine, N,N-dimethylpiperazine, α-picoline, pyridine, 4-dimethylaminopyridine, 2,4,6-tris(dimethylaminomethyl)phenol, 3,4,5-tris(dimethylaminomethyl)phenol, N-aminoethylpiperazine, 1,3,6-trisaminomethylhexane, 1,8-diazabicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]-nonene, polyamines, polyamidoamines, polyamides, modified polyamines, modified polyamidoamines, modified polyamides, etc.; 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl -2-Undecylimidazole, 2-Heptadecylimidazole, 2-Ethyl-4-Methylimidazole, 2-Phenylimidazole, and 2-Phenyl-4-Methylimidazole, 1-Benzyl-2-Methylimidazole, 1-Cyanoethyl-2-Methylimidazole, 1-Cyanoethyl-2-Ethyl-4-Methylimidazole, 2-Phenyl-4-Methyl-5-Hydroxymethylimidazole, 2-Phenyl-4,5-Dihydroxymethylimidazole, Modified Imidazole Imidazole-based curing accelerators such as dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, di(o-tolyl)guanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.Guanidine-based curing accelerators such as dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide; tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, butyltriphenylphosphonium bromide, tetraphenylphosphonium iodide, tetrabutylphosphonium iodide, butyltriphenylphosphonium iodide, tetraphenylphosphonium tetraphenylborate, tetrabutylphosphonium tetraphenylborate, Examples include phosphonium-based curing accelerators such as 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; and transition metal-based curing accelerators containing transition metals such as titanium and cobalt. The curing accelerator (curing catalyst) may be used alone or in combination of two or more types.

[0106] (Reactive diluent) The conductive resin composition of the present invention may contain a reactive diluent for viscosity adjustment, curability adjustment, etc. The reactive diluent is not particularly limited, but examples include one or more compounds having one epoxy group in their molecular structure, or compounds having one or more oxetane groups in their molecular structure. For example, glycidylphenyl ether, glycidyl lauryl ether, 2-phenylphenol glycidyl ether, tolyl glycidyl ether, allyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, N-glycidylphthalimide, 2-ethylhexyl glycidyl ether, YED111N, YED111AN, YED188 from Mitsubishi Chemical Corporation; ADEKA glycyrrhizol ED-502, ADEKA glycyrrhizol ED-502S, ADEKA Examples include glycirol ED-509E, adekaglycirol ED-509S, adekaglycirol ED-529; Denacol EX-145, Denacol EX-171, Denacol EX-192 manufactured by Nagase ChemteX Corporation; Epolite M-1230, Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.; Aronoxetane OXT-101, Aronoxetane OXT-212, Aronoxetane OXT-121, Aronoxetane OXT-221 manufactured by Toagosei Co., Ltd.; and ETERNACOLL EHO, ETERNACOLL HBOX, ETERNACOLL OXMA, ETERNACOLL OXBP manufactured by UBE Corporation. In the present invention, the boiling point of the reactive diluent is, for example, 150°C or higher, preferably 200°C or higher, and more preferably 250°C or higher. The reactive diluent may be used alone or in combination of two or more types.

[0107] ((C) component other than conductive powder) The conductive resin composition of the present invention may contain conductive powders other than component (C), 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 (C) include lead-free solder powder, tin-based powder, zinc-based powder, aluminum-based powder, iron-based powder, metal alloy powders other than silver-based, nickel-based, copper-based, and gold-based powders, and resin particles coated with metals other than silver, nickel, copper, and gold.

[0108] The shape of the conductive powder other than component (C) is not particularly limited. It can be spherical, approximately spherical (for example, with an aspect ratio of 1.5 or less), flat, block-shaped, plate-shaped, polygonal pyramidal, polyhedral, flaky, rod-shaped, fibrous, needle-shaped, or irregularly shaped. From the viewpoint of oxidative properties, volume resistivity, dispersibility, and handling, spherical, approximately spherical, flat, or flaky shapes are preferred. The conductive powders other than component (C) may be used individually or in combination of two or more types.

[0109] (Antioxidant) The conductive resin composition of the present invention may contain an antioxidant. This can contribute to improving the heat resistance and resistance to yellowing of the cured product of the conductive resin composition. The antioxidant is not particularly limited as long as it is a compound having antioxidant function, and known or conventional antioxidants can be used. Examples include phenolic antioxidants such as hindered phenol compounds, quinone antioxidants such as hydroquinone, phosphorus antioxidants, sulfur antioxidants, and hindered amine antioxidants such as hindered amine compounds.

[0110] 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, and bis-[3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)-butanoic]. Acid glycol ester, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 2,2'-butylidenebis(4,6-di-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 3,9-Bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 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], benzenepropanoate-3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7~C9 side-chain alkyl ester, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-Tolyl)tri-p-cresol, calcium diethylbis[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydro [Xyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, N-phenylbenzeneamine and 2,4,6-trimethylpentene Reaction products with phenols, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, picric acid, citric acid, and other phenolic antioxidants; β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di-tert-butyl-p-benzo Quinone-based antioxidants such as phosphite; tris(2,4-di-tert-butylphenyl) phosphite, tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[df][1,3,2]dioxaphosphephine-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,Examples include phosphorus-based antioxidants such as 4'-diylbisphosphonate and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[df][1,3,2]dioxaphosphophene; sulfur-based antioxidants such as dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityltetrakis(3-laurylthiopropionate), and 2-mercaptobenzimidazole; amine-based antioxidants such as phenothiazine; lactone-based antioxidants; vitamin E-based antioxidants; and others. Commercial antioxidants may be used. Examples include the IRGANOX series from BASF, the ADEKA Stab series from ADEKA Corporation, the Nonflex series from Seiko Chemical Co., Ltd., and the Smilizer series from Sumitomo Chemical Co., Ltd. The antioxidant may be used alone or in combination of two or more types.

[0111] (Gap adjuster (spacer; gap control agent)) The conductive 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). The gap adjuster (spacer; spacing control agent) is not particularly limited as long as it has sufficient hardness for use and a desired particle size-aspect ratio. Examples include silica fine particles (spherical silica), glass beads, crushed glass fibers, resin beads, etc. The resin beads are not particularly limited and include, for example, 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, silicone resin, etc. The surface of the resin beads may be coated with conductive metals such as Ag, Cu, Au, Pt, Ni, Al, Sn, Zn, or their oxides, alloys, etc. Commercially available gap adjusters (spacers; gap control agents) may be used. Examples include the HighPresica series from Ube Eximo, the Micropearl series from Sekisui Chemical Co., Ltd., the Techpolymer series from Sekisui Chemicals Co., Ltd., and the UniBeads series from Unitika Glass Beads Co., Ltd. Gap adjusters (spacers; gap control agents) may be used individually or in combination of two or more types.

[0112] <Conductivity of the cured film of the conductive resin composition> The conductive resin composition of the present invention has a low volume resistivity of its cured film and excellent conductivity. For example, the volume resistivity of the cured film of the conductive resin composition is 1.0 × 10⁻⁶. -2 It is less than Ω·cm, preferably 8.0 × 10 -3 It is less than Ω·cm, and more preferably 7.0 × 10 -3 Less than Ω·cm, more preferably 6.0 × 10 -3 Less than Ω·cm, particularly preferably 1.0 × 10⁻⁶ -3The resistivity can be less than Ω·cm. The volume resistivity of the cured film can be determined, for example, by casting or coating a conductive resin composition onto a releaseable substrate, heating and curing it at 150°C for 30 minutes to form a cured film with a thickness of 80-100 μm, and measuring it with a resistivity meter (e.g., "Loresta GP-MCP T610" (manufactured by Nitto Seikou Analytech Co., Ltd.)).

[0113] <Method for preparing conductive resin compositions> The method for preparing the conductive resin composition of the present invention is not particularly limited. For example, one method is to add components (A) to (C), component (D) used as needed, and other components to a mixing container in any order and mix and stir. For example, one method is to add components (A) to (C), component (D) used as needed, and other components to a container and mix and stir, or to add components (A), (B), component (D) used as needed, and other components used as needed to a container, mix and stir, and then add component (C) and other components used as needed and mix and stir.

[0114] 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, Nauter mixer, Banbury mixer, rotational mixer, kneading roll, single-screw or twin-screw extruder, grinder, etc. can be used for mixing and stirring.

[0115] The temperature at which the conductive resin composition is prepared (the temperature at which each component is mixed) is not particularly limited. Heating may be performed as needed, for example, and the temperature can be set to 10 to 40°C. The atmosphere used when preparing the conductive resin composition is not particularly limited. It can be carried out in air or under an inert atmosphere.

[0116] <Applications of conductive resin compositions> The conductive resin composition of the present invention can be used as a conductive material. Examples of conductive materials include conductive inks, circuit connection materials, conductive pastes, conductive films, conductive fibers, conductive paints, conductive materials for semiconductor packages, conductive materials for microelectronic devices, antistatic materials, electromagnetic shielding materials, die attach pastes, actuators, sensors, and conductive resin molded articles.

[0117] The conductive resin composition of the present invention can be used for conductive connections between various electronic components and circuit boards, connections (adhesion) between electrical and electronic circuits, and the assembly of electronic components themselves. The shape of the conductive resin composition is not particularly limited, but it is preferably liquid (paste or varnish), film, or powder at room temperature (25°C ± 5°C). A liquid conductive resin composition can be obtained by, for example, stirring and mixing the components of a conductive resin composition as is, or by mixing in a solvent such as an organic solvent as needed. A film-like conductive resin composition can be obtained, for example, by stirring and mixing the components of a conductive resin composition, and if necessary, mixing in a solvent such as an organic solvent to obtain a liquid conductive resin composition, which is then cast or coated onto a releaseable substrate to form a film, dried to remove the solvent and form a film, and then peeled off from the releaseable substrate. Furthermore, the film-like conductive resin composition can be obtained by impregnating a nonwoven fabric or the like, forming it on a releaseable substrate, drying it to remove the solvent, and then peeling it off the releaseable substrate.

[0118] The electrical connection method using the conductive resin composition of the present invention is not particularly limited. For example, one method involves providing the conductive resin composition between an electrode of an electronic component or circuit and an electrode on a substrate facing it, and then heating and / or pressurizing it as needed to establish an electrical connection between the two electrodes and bond them together. The method for providing the conductive resin composition between opposing electrodes is not particularly limited. Examples include applying a liquid conductive resin composition or sandwiching a film-like conductive resin composition between them. Furthermore, when making a conductive connection between a pin on an electronic component and a circuit, one method involves applying a conductive resin composition to the base of the pin and butt-joining it to establish the conductive connection.

[0119] The conductive resin composition of the present invention can also be used as a substantially anisotropic conductive material. Furthermore, the conductive resin composition of the present invention can be used in an electrode connection method in which the conductive resin composition is formed between opposing electrodes on a substrate, and contact between the two electrodes and adhesion between the substrates are obtained by heating and pressurizing as needed. The substrate on which the electrodes are formed is not particularly limited. Examples include inorganic materials such as semiconductors, glass, and ceramics, organic materials such as polyimide and polycarbonate, composites such as glass / epoxy, and combinations thereof. Furthermore, since the conductive resin composition of the present invention can form a film at low temperatures, conductive connections can be made even at low temperatures, such as 200°C or below.

[0120] For example, a conductive 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 lower to form a conductive film. The drying atmosphere can be one or more selected from the group consisting of air, inert gas, vacuum, or reduced pressure. In particular, from the viewpoint of suppressing deterioration of the conductive film (prevention of oxidation of conductive powder, etc.), an inert gas atmosphere such as nitrogen or argon is preferred.

[0121] The conductive resin composition of the present invention can also be used as a conductive material for printing, for example, to form a coating film such as wiring on a substrate by printing. Examples of printing and coating methods include screen printing, metal mask printing, inkjet printing, flexographic printing, gravure printing, gravure offset printing, pad printing, and dispenser printing. In the present invention, it is preferable to use one or more printing methods selected from the group consisting of screen printing and inkjet printing, etc., because they have excellent printability and shape retention. The mesh used during screen printing can be appropriately selected, and it is preferable to use a mesh that does not excessively remove the conductive powder. The film thickness of the coating formed by printing can be set to an appropriate thickness depending on the application. For example, it can be 1 μm or more, preferably 2 μm or more, more preferably 5 μm or more, and for example, 100 μm or less.

[0122] <Method for heat curing conductive resin composition> The conductive resin composition of the present invention can form a cured film with excellent bonding strength even with short heating times. Therefore, since it is possible to suppress the temperature rise of the substrate, the conductive resin composition can be heat-cured even when applied to a substrate that does not have high heat resistance. The heating method used in the heat curing method for conductive resin compositions is not particularly limited. For example, one or more methods such as induction heating (IH), heating in a heating furnace (oven, etc.), irradiation with active energy rays (laser, microwave, etc.), and plasma irradiation can be used.

[0123] The substrates to which the conductive resin composition is applied are not particularly limited. Examples include ceramics, glass, polyimide resins, polyphenylene sulfide resins, polysulfone resins, polyetheretherketone resins, polyethersulfone resins, polyphenylene ether resins, polyacetal resins, polyoxymethylene resins, cycloolefin polymers, polybutylene terephthalate resins, polyamideimide resins, polyetherimide resins, polyethernitrile resins, polyarylate resins, liquid crystal polymers, polyethylene terephthalate resins, polyethylene naphthalate resins, acrylic resins, polycarbonate resins, polyvinyl chloride resins, fluororesins, acrylonitrile-butadiene-styrene resins, acrylonitrile-styrene resins, polyamide resins, polystyrene resins, phenolic resins, epoxy resins, urethane resins, maleimide resins, cyanate resins, urea resins, melamine resins, polyolefin resins, thermoplastic elastomers, paper, textiles, metals, and materials containing one or more composites and mixtures thereof. The form of the substrate is not particularly limited. For example, it can be in the form of a film, a sheet, a resin molded product such as a housing, etc.

[0124] The conductive resin composition of the present invention can be heat-cured using induction heating. Induction heating utilizes the phenomenon in which Joule heat is generated when eddy currents are passed through a conductive material. In the present invention, the conductive material (conductive powder or magnetic powder in the conductive resin composition or its cured product, a conductive layer on a component or substrate, etc.) is self-heated, thereby enabling the heat curing of the conductive resin composition at any location in a short time.

[0125] One method of induction heating involves interposing a conductive resin composition between a substrate and a component, and then heating and curing the conductive resin composition by induction heating, such as electromagnetic induction heating. In this case, a conductive connection can be formed by using a substrate with a conductive layer, a component having a conductive part, and interposing the conductive resin composition between the conductive layer and the conductive part and then applying induction heating. Furthermore, it is also possible to use a substrate and components that do not contain conductive materials, interpose a conductive resin composition between the substrate and the components, and heat-cur the conductive powder or magnetic particles in the conductive resin composition by induction heating, thereby bonding the non-conductive materials together.

[0126] The induction heating method is not particularly limited. For example, an induction heating (IH) method can be performed using an apparatus that includes, in a plan view, at least a coil having an internal space, a magnetic material that is movable perpendicular to the space of the coil, an adjustment mechanism for adjusting the distance (working distance WD) between the magnetic material and a conductor in the coil space, and a power supply that applies an AC voltage to the coil to produce a high-frequency current. By placing the magnetic material in the internal space of the coil, the magnetic flux φ generated in the internal space of the coil can be focused onto the conductor (a conductive layer provided on a substrate, etc.) without attenuation through the magnetic material. This makes it possible to efficiently use the magnetic flux φ for induction heating of the conductor, thereby enabling efficient adhesion by thermal curing of the conductive resin composition. Examples of magnetic materials include ferrite.

[0127] The position of the magnetic material placed in the internal space of this coil can be adjusted, and the heating efficiency can be adjusted by changing the distance from the conductor to be irradiated. The closer the distance, the more efficiently the magnetic flux φ focused by the magnetic material can be irradiated onto the conductor, thereby increasing the heating efficiency. Furthermore, by setting this distance to zero (pressing the magnetic material directly against the component), it is possible to prevent the conductor from moving due to the influence of the magnetic field generated during induction heating. When performing induction heating, the temperature of the magnetic material should preferably be 40°C or lower. This is because if the temperature exceeds 40°C, the permeability of the magnetic material decreases, and the heating efficiency decreases.

[0128] When a substrate is used in which an auxiliary heating conductive pad is provided on a surface of the substrate that does not have a conductive layer, or adjacent to a conductive layer, if the volume of the auxiliary heating conductive pad is made relatively large compared to the volume of the conductive layer or conductive resin composition, the amount of heat generated by induction heating can be increased, and the heat generated by the auxiliary heating conductive pad is transferred to the conductive resin composition, thereby enabling effective heat curing of the conductive resin composition. Furthermore, by reducing the volume resistivity of the auxiliary heating conductive pad, the amount of heat generated by dielectric heating can be increased, making it possible to effectively heat-cur the conductive resin composition. Specific methods of induction heating include, for example, a method of performing induction heating (IH) using an apparatus that comprises, in a plan view, a coil having an internal space, a plurality of ferrites arranged in the space of the coil along the transport direction of the substrate, an adjustment mechanism for independently adjusting the distance between each ferrite and the conductive layer formed on the substrate, and a power supply that applies an AC voltage to the coil to induction heat the conductive layer and / or conductive resin composition formed on the substrate.

[0129] The induction heating time in induction heating can be between 1 second and 300 seconds. The induction heating time is the time during which a high-frequency current is passed through the coil. If the induction heating time T is less than 1 second, the induction heating may be insufficient, resulting in inadequate heating of the conductive resin composition, making adhesion impossible or resulting in insufficient adhesive strength. If it exceeds 300 seconds, the induction heating may be excessive, potentially causing thermal damage to the substrate, components, or conductive resin composition. In induction heating, heating can be appropriately adjusted by considering factors such as the induction heating frequency (control of the amount of current), working distance WD (attenuated in proportion to the square of WD), conductive layer area, conductive layer thickness, volume resistivity of the conductive layer, thermal conductivity of the conductive layer, thermal conductivity of the substrate, substrate thickness, distance between the magnetic material and the object to be heated, magnetic material shape, coil height, coil shape, thermal conductivity of the environment, wind speed, temperature, humidity, and environmental atmosphere (vacuum, inert gas, reducing atmosphere, etc.).

[0130] In induction heating, the induction heating frequency (kHz) is the frequency of the high-frequency current flowing through the coil. The induction heating frequency can be, for example, in the range of 90 kHz to 900 kHz. Preferably, the induction heating frequency is in the range of 90 kHz to 270 kHz. By adjusting the induction heating frequency, it is possible to control the heating process in induction heating.

[0131] The working distance WD (mm) is the distance between a magnetic material that is movable perpendicular to the space inside a coil and a conductor within the space inside the coil. The working distance WD can be, for example, 3 mm or more, preferably 5 mm or more, and for example, 30 mm or less, preferably 20 mm or less. By adjusting the working distance WD, it is possible to control the heating in induction heating.

[0132] The conductive resin composition of the present invention can be heat-cured by heating in a short time, allowing for adhesion between the substrate and the component. Therefore, it can be applied even to substrates and components that do not have very high heat resistance.

[0133] The conductive resin composition of the present invention can be heat-cured using a heating furnace such as an oven. The heating temperature during heat curing in the heating furnace can be, for example, 150°C or less, and the heating time during heat curing in the heating furnace can be, for example, 1 hour or less.

[0134] [Conductive adhesive] The conductive adhesive of the present invention comprises the above-mentioned [conductive resin composition]. Details of the conductive resin composition are as described above in [conductive resin composition].

[0135] The conductive adhesive of the present invention is used to bond various substrates in a conductive state. For example, it can be used for conductive connections between various electronic components and circuit boards, and for connecting (bonding) electrical and electronic circuits to each other. The shape of the conductive adhesive is not particularly limited, but it is preferably in the form of a liquid, film, or powder. Liquid conductive adhesives can be obtained, for example, by constructing a conductive resin composition using components that are liquid at 25°C and 0.1 MPa. Alternatively, they can be obtained by mixing a solvent such as an organic solvent with a conductive resin composition that is liquid or solid at 25°C and 0.1 MPa. A film-like conductive adhesive can be obtained, for example, by directly casting or coating a conductive resin composition or a mixture thereof with a solvent such as an organic solvent onto a release substrate to form a film, drying to remove the solvent and form a film, and then peeling it off the release substrate. Alternatively, it can be obtained, for example, by partially curing (pre-curing) the conductive adhesive. Alternatively, it can be obtained, for example, by impregnating a nonwoven fabric or the like with the conductive resin composition of the present invention or a mixture thereof with a solvent such as an organic solvent, forming it on a release substrate, drying to remove the solvent and then peeling it off the release substrate.

[0136] The substrate used for bonding with conductive adhesives is not particularly limited. Examples include ceramics, glass, polyimide resins, polyphenylene sulfide resins, polysulfone resins, polyetheretherketone resins, polyethersulfone resins, polyphenylene ether resins, polyacetal resins, polyoxymethylene resins, cycloolefin polymers, polybutylene terephthalate resins, polyamideimide resins, polyetherimide resins, polyethernitrile resins, polyarylate resins, liquid crystal polymers, polyethylene terephthalate resins, polyethylene naphthalate resins, acrylic resins, polycarbonate resins, polyvinyl chloride resins, fluororesins, acrylonitrile-butadiene-styrene resins, acrylonitrile-styrene resins, polyamide resins, polystyrene resins, phenolic resins, epoxy resins, urethane resins, maleimide resins, cyanate resins, urea resins, melamine resins, polyolefin resins, thermoplastic elastomers, paper, textiles, metals, and materials containing one or more composites and mixtures of these materials. The form of the substrate is not particularly limited. For example, it can be in the form of a film, a sheet, a resin molded product such as a housing, etc.

[0137] The substrate may have a conductive material provided on a part of it. The conductive material can be a conductive layer partially laminated on the substrate by bonding, printing, etching, etc. The conductive layer may be an electrode in a circuit, etc. The conductive layer is usually composed of a metal, and examples of metals that make up the conductive layer include one or more selected from the group consisting of copper, silver, aluminum, gold, nickel, tin, solder, bismuth, zinc, iron, cobalt, titanium, silicon, carbon, alloys containing two or more of these, or oxides thereof. The substrate and conductive layer may be, for example, a circuit board with printed circuits formed on its surface, or an interposer with electrode pads formed on both sides, in which the substrate and conductive layer are integrated.

[0138] The conductive layer provided on the substrate typically has an area that can be heated by induction heating. For example, it is preferable to have an area of ​​0.2 mm × 0.2 mm or larger. If there are limitations on the area of ​​the conductive layer, an auxiliary heating conductive pad can be provided on the surface of the substrate where the conductive layer is not provided or adjacent to the conductive layer.

[0139] The components that can be bonded with the conductive adhesive of the present invention are not particularly limited, as long as they can be bonded to a substrate with the conductive adhesive. Preferably, the components are electrical or electronic components having conductive parts such as electrode parts / terminals. Examples of components include one or more selected from the group consisting of semiconductor elements, resistors, capacitors, LED elements, sensor elements, LSIs, ICs, inductors, transistors, liquid crystal display elements, piezoelectric elements, resistors, filters, crystal oscillators, crystal resonators, connectors, switches, motors, actuators, batteries, solar cells, microphones, camera modules, communication modules, heaters, heat sinks, vapor chambers, optical modules, etc.

[0140] The electrical connection method using the conductive adhesive of the present invention is not particularly limited. For example, one method involves providing a conductive adhesive between an electrode of an electronic component or circuit and an electrode on a substrate facing it, and then heating and / or pressurizing the adhesive as necessary to electrically connect the two electrodes and bond them together. The method for providing a conductive adhesive between opposing electrodes is not particularly limited. Examples include applying a liquid or powdered conductive adhesive, or sandwiching a film or powdered conductive adhesive between the electrodes. Another method for making a conductive connection between a pin on an electronic component and a circuit is to apply a conductive adhesive to the base of the pin and then butt-join the pin to create the conductive connection.

[0141] The conductive adhesive of the present invention can also be used as a substantially anisotropic conductive adhesive. Furthermore, it can be used in an electrode connection method in which a conductive adhesive with excellent adhesive properties is formed between opposing electrodes on a substrate, and contact between the two electrodes and adhesion between the substrates are obtained by heating and pressurizing as needed. Applicable substrates for forming the electrodes include inorganic materials such as semiconductors, glass, and ceramics, organic materials such as polyimide and polycarbonate, and various combinations of these such as glass / epoxy.

[0142] The conductive adhesive of the present invention can bond even with low-temperature, short-duration heating. Therefore, conductive connections can be formed even with oven heating at low temperatures and for short periods, such as 150°C or less for less than one hour. Furthermore, conductive connections can also be formed by induction heating. [Examples]

[0143] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples. Unless otherwise specified, "%" means "mass percent" and "parts" means "parts by mass". Furthermore, all numerical values ​​for the blending amounts of each component in Tables 1 and 2 are in "parts" (parts by mass).

[0144] [Ingredients used] The components used in the examples are as follows:

[0145] <(A) component> • BPE-EP: Bisphenol E type epoxy resin (Printec Co., Ltd. "EPOX MK R1710") • BPF-EP: Bisphenol F type epoxy resin (ADEKA Corporation "EP-4901") • BPA-EP: Bisphenol A type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., "YD-014")

[0146] <(B) component> • Hardener 1: Phenol-neutralizing bisphenol A skeleton-containing polyamine-based epoxy resin curing agent (ADEKA "ADEKA Hardener EH-5030S"). • Hardener 2: Tetrafunctional thiol compound-based epoxy resin curing agent (Shikoku Chemicals Co., Ltd. "C3TS-G") • Hardener 3: Acrylate imidazole adduct-type epoxy resin hardener (ADEKA "ADEKA Hardener EH-2021" manufactured by ADEKA Corporation) • Hardener 4: Imidazole-based epoxy resin hardener (ADEKA "ADEKA Hardener EH-5046S") • Hardener 5: Imidazole-based epoxy resin hardener (ADEKA "ADEKA Hardener EH-2110K") Hardener 6:2-ethyl-4-methylimidazole (Shikoku Chemicals Co., Ltd. "Curezol 2E4MZ") Hardener 7: 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine (manufactured by Shikoku Chemicals, Inc. as "2MZA-PW") Hardener 8: Epoxyimidazole adduct-type epoxy resin hardener (Shikoku Chemicals Co., Ltd. "CureDuct P-0505") • Hardener 9: Boric acid ester-based epoxy resin hardener (Shikoku Chemicals Co., Ltd. "CureDuct L-07N") • Hardener 10: Acid anhydride-based epoxy resin curing agent (Shin Nippon Rika Co., Ltd. "Ricacid MH-700G") • Hardener 11: Microencapsulated imidazole-based epoxy resin curing agent (Asahi Kasei Corporation's "NovaCure HXA-3792")

[0147] <(C) component> • Ag: Plate-shaped silver filler (TC-508 manufactured by Tokuriki Honten Co., Ltd., average particle size 5 μm by laser diffraction method, silver content 10% by mass) • Ag-Coat-Cu 1: Amorphous silver-coated copper (Mitsui Mining & Smelting Co., Ltd. "ACFY-2") • Ag-Coat-Cu 2: Spherical silver-coated copper (Mitsui Mining & Smelting Co., Ltd. "1100Y")

[0148] <(D) component> • GTMS: 3-Glycidoxypropyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd. "KBM-403") • GTES: 3-Glycidoxypropyltriethoxysilane (Shin-Etsu Silicone Co., Ltd. "KBE-403")

[0149] [Measurement and evaluation of the properties of conductive resin compositions] In the examples and comparative examples, the properties of the conductive resin compositions were measured and evaluated as follows.

[0150] <Volume resistivity> Using a metal mask with a pattern of 2 cm x 2 cm and a thickness of 100 microns, a conductive resin composition was hand-printed to create a 2 cm x 2 cm coating on a 5 cm x 5 cm glass substrate. Next, the coating was heat-cured at 150°C for 30 minutes to produce a conductive film (dried coating) for volume resistivity measurement. The volume resistivity of the obtained conductive film (dried coating film) was measured by the four-probe method using a resistivity meter "Loresta GP-MCP T610" (manufactured by Nitto Seiko Analytech Co., Ltd.) in two directions: a direction passing through the center of the coating film and parallel to the upper side of the coating film, and a direction perpendicular to the aforementioned direction. The average volume resistivity of the two measurements was calculated. Furthermore, two conductive films (dried coating films) were produced for each conductive resin composition, and the average volume resistivity of the two conductive films (dried coating films) was calculated and used as the volume resistivity. In the present invention, evaluation was performed according to the following criteria. Evaluations A and B are acceptable, and evaluation C is unacceptable. A: The volume resistivity is 1.0×10 -3 Ω·cm or less. B: The volume resistivity is 1.0×10 -3 Ω·cm or more and less than 1.0×10 -2 Ω·cm. C: The volume resistivity is 1.0×10 -2 Ω·cm or more (including insulation and unmeasurable cases).

[0151] <IH Bonding Strength> The conductive resin composition was coated on a glass substrate using a metal mask with a pattern of 2.3 mm × 1.1 mm and a thickness of 100 μm. Next, a surface mount connector HH-1-G (manufactured by McEight Corporation) was placed thereon, and induction heating (working distance (WD): 15 mm, output: 35%, duration: 3 seconds) was performed using an electromagnetic induction heating solder reflow (IH reflow) apparatus manufactured by Wonder Future Corporation. After induction heating, the product was allowed to stand at room temperature (25°C ± 5°C) for 1 hour, then the die shear bonding strength was measured 5 times using a bonding tester PTR1102 (manufactured by Rhesca Corporation), and the average value was taken as the IH bonding strength. In the present invention, evaluation was performed according to the following criteria. Evaluations A and B are acceptable, and evaluation C is unacceptable. A: IH bonding strength is 8,000 gf or more. B: IH bonding strength is 4,000 gf or more and less than 8,000 gf. C: IH bonding strength is less than 4,000 gf.

[0152] <Oven Bonding Strength> A conductive resin composition was applied to a glass substrate using a metal mask with a pattern of 2.3 mm × 1.1 mm and a thickness of 100 μm. The mixture was then heated in an 80°C oven for 15 minutes. After heating, the mixture was allowed to stand at room temperature (25°C ± 5°C) for 1 hour. The die-shear bond strength was then measured using a bonding tester PTR1102 (manufactured by Lesca Corporation) and defined as the oven bond strength. In this invention, evaluation was performed according to the following criteria. A and B ratings indicate a pass, and a C rating indicates a fail. A: Oven bonding strength of 8,000 gf or more. B: Oven bond strength is 4,000 gf or more and less than 8,000 gf. C: Oven bond strength is less than 4,000 gf.

[0153] <Viscosity> The viscosity of the conductive resin composition was measured using a rheometer (Rheometer DHR-2, TA Instruments). 20mm cone plate, 25°C, shear rate 10s. -1 Measurement was started, and the viscosity value was defined as the viscosity 120 seconds after the start of measurement.

[0154] <Storage stability> The conductive resin compositions were placed in containers and stored at 25°C or in a freezer (-24°C). The storage stability of each conductive resin composition was then evaluated according to the following evaluation items and criteria. A and B are considered pass, and C is considered fail. A: The initial viscosity value more than doubles after 30 days or more of storage. B: The initial viscosity value more than doubles after storage begins within 14 to 30 days. C: The initial viscosity value more than doubles in less than 14 days after the start of storage.

[0155] [Example 1] 60.5 parts BPE-EP, 33.5 parts Hardener 1, and 6.0 parts GTMS were added to a container, stirred, and mixed to prepare the varnish. A conductive resin composition was prepared by stirring and mixing 100.0 parts of the obtained varnish with 300.0 parts of Ag. The obtained conductive resin compositions were measured and evaluated for volume resistivity, IH bonding strength, and oven bonding strength. The results are shown in Table 1.

[0156] [Examples 2-4, Comparative Examples 1-8] A conductive resin composition was prepared in the same manner as in Example 1, except that the components of the conductive resin composition and their amounts used were as shown in Table 1. For each conductive resin composition obtained, the volume resistivity, IH bonding strength, and oven bonding strength were measured and evaluated. The results are shown in Table 1. * 1 indicates that measurement is not possible because it is not yet cured. * 2 represents insulation, * 3 indicates that it is impossible to measure because it peels off easily.

[0157] [Table 1]

[0158] [Examples 2, 5, 6, Comparative Example 9] A conductive resin composition was prepared in the same manner as in Example 1, except that the components of the conductive resin composition and their amounts used were as shown in Table 2. Viscosity, volume resistivity, and IH bonding strength were measured and evaluated for each of the obtained conductive resin compositions. Furthermore, storage stability evaluations (25°C) and storage stability evaluations (freezing) were performed for each of the obtained conductive resin compositions. The results are shown in Table 2.

[0159] [Table 2]

[0160] Tables 1 and 2 show that the conductive resin composition according to the present invention has low volume resistivity and excellent conductivity, hardens with short-time low-temperature heating, has excellent bonding strength and strong adhesion to various substrates, has a moderate viscosity for excellent workability, and has excellent storage stability.

Claims

1. (A) to (C): (A) Epoxy resin having a bisphenol skeleton, (B) Amine-based epoxy resin curing agent having a bisphenol skeleton, (C) Conductive powder containing one or more selected from silver-coated copper powder, silver-based powder, nickel-based powder, conductive carbon powder, copper-based powder, and gold-based powder. A conductive resin composition containing [the specified ingredient].

2. The conductive resin composition according to claim 1, wherein (A) comprises an epoxy resin having a bisphenol E skeleton and / or a bisphenol F skeleton.

3. The conductive resin composition according to claim 1 or 2, wherein (B) comprises an amine-based epoxy resin curing agent having a bisphenol A skeleton.

4. The conductive resin composition according to claim 1 or 2, wherein (B) comprises a polyamine-based epoxy resin curing agent having a bisphenol skeleton and having an aromatic ring and / or heterocycle within the molecule.

5. The conductive resin composition according to claim 1 or 2, wherein (C) comprises silver powder and / or silver alloy powder.

6. The conductive resin composition according to claim 1 or 2, wherein (C) comprises plate-shaped, flake-shaped, or granular silver powder.

7. The conductive resin composition according to claim 1 or 2, wherein the content of (C) is 66% by mass or more, with the total amount of solids of (A) to (C) being 100% by mass.

8. (D) The conductive resin composition according to claim 1 or 2, comprising a coupling agent.

9. A conductive adhesive comprising the conductive resin composition according to claim 1 or 2.

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