WO2022202505A1 - 導電性樹脂組成物、高熱伝導性材料および半導体装置 - Google Patents

導電性樹脂組成物、高熱伝導性材料および半導体装置 Download PDF

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WO2022202505A1
WO2022202505A1 PCT/JP2022/011708 JP2022011708W WO2022202505A1 WO 2022202505 A1 WO2022202505 A1 WO 2022202505A1 JP 2022011708 W JP2022011708 W JP 2022011708W WO 2022202505 A1 WO2022202505 A1 WO 2022202505A1
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meth
resin composition
silver
conductive resin
acrylate
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PCT/JP2022/011708
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English (en)
French (fr)
Japanese (ja)
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智将 樫野
安澄 濱島
将人 吉田
直輝 渡部
真 高本
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住友ベークライト株式会社
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Priority to JP2023509054A priority Critical patent/JP7491463B2/ja
Priority to CN202280023168.7A priority patent/CN117098806A/zh
Priority to KR1020237035594A priority patent/KR20230159849A/ko
Publication of WO2022202505A1 publication Critical patent/WO2022202505A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver

Definitions

  • the present invention relates to a conductive resin composition, a highly thermally conductive material and a semiconductor device.
  • Patent Document 1 discloses a conductive filler made of silver powder having a predetermined average particle size, an epoxy resin, a reactive diluent having one or more glycidyl functional groups in an aliphatic hydrocarbon chain, and a thermally conductive filler containing a curing agent.
  • a conductive adhesive composition is disclosed. The document exemplifies cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, and the like as the reactive diluent.
  • Patent Document 2 discloses a composition containing a predetermined glycidyl ether compound, a predetermined phenolic resin curing agent, a curing accelerator, and a conductive filler, wherein a predetermined amount of the phenolic resin curing agent is added to the glycidyl ether compound.
  • a conductive adhesive is disclosed comprising: This document exemplifies 1,4-cyclohexanedimethanol diglycidyl ether and pentaerythritol tetraglycidyl ether as the glycidyl ether compound.
  • Patent Document 3 discloses a thermally conductive conductive adhesive composition containing a conductive filler, an epoxy resin, a reactive diluent having two or more glycidyl ether functional groups in an aliphatic hydrocarbon chain, and a curing agent. things are disclosed. The document exemplifies cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, and the like as the reactive diluent.
  • Patent Documents 1 to 3 have room for improvement in thermal conductivity, product reliability, and adhesion to substrates.
  • the present inventors have found that the above problems can be solved by using a combination of a (meth)acrylic compound and a specific polyfunctional epoxy compound, and have completed the present invention. That is, the present invention can be shown below.
  • a conductive resin composition is provided.
  • R represents a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and multiple Rs may be the same or different.
  • Q represents a divalent to hexavalent organic group.
  • X represents an alkylene group having 1 to 3 carbon atoms, and multiple X's may be the same or different.
  • m is an integer of 0-2, n is an integer of 2-4.
  • a high thermal conductivity material obtained by sintering the conductive resin composition is provided.
  • a substrate A semiconductor element mounted on the base material via an adhesive layer, A semiconductor device is provided in which the adhesive layer is formed by sintering the conductive resin composition.
  • the conductive resin composition of the present invention promotes sintering of the silver-containing particles by curing shrinkage to obtain a highly thermally conductive material with excellent thermal conductivity. It is possible to obtain a highly thermally conductive material with excellent product reliability because it also has excellent adhesion to. In other words, it is possible to provide a conductive resin composition having an excellent balance of these properties.
  • FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device
  • FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device
  • FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device
  • alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
  • (meth)acryl used herein represents a concept that includes both acryl and methacryl. The same applies to similar expressions such as "(meth)acrylate” and "(meth)acryloyl”.
  • the conductive resin composition of the present embodiment is (A) silver-containing particles; (B) a (meth) acrylic compound; (C) at least one polyfunctional epoxy compound selected from compounds represented by the following general formula (1).
  • the sintering of the silver-containing particles is promoted by curing shrinkage, and a high thermal conductivity material with excellent thermal conductivity is obtained.
  • the elastic modulus is low, the stress is relaxed, and the adhesiveness to the substrate etc. is excellent. Therefore, a high thermal conductivity material with excellent product reliability can be obtained.
  • thermal conductivity can be evaluated by volume resistivity according to the Wiedemann-Franz law. In other words, the volume resistivity is the electrical resistance value per unit volume. If the electrical resistance value is low, the free electrons become carriers and electricity easily passes through. .
  • the silver-containing particles (A) can be sintered by an appropriate heat treatment to form a particle connecting structure (sintering structure).
  • the inclusion of silver-containing particles in the conductive resin composition particularly the inclusion of silver particles having a relatively small particle size and a relatively large specific surface area, allows A sintered structure is likely to be formed even by heat treatment.
  • a preferred particle size will be described later.
  • the shape of the silver-containing particles is not particularly limited, and includes known shapes such as spherical, dendritic, string-like, scale-like, agglomerated, and polyhedral shapes. can include one or more, preferably two or more. Thereby, it is excellent by electroconductivity.
  • spherical silver-containing particles (a1) and scaly, aggregated, and one or more kinds of silver-containing particles (a2) selected from polyhedral shapes, more preferably containing spherical silver-containing particles (a1) and scale-like silver-containing particles (a2-1) is particularly preferred.
  • the contact ratio between the silver-containing particles is further improved, so that a network is easily formed after sintering the conductive resin composition, and the thermal conductivity and the electrical conductivity are further improved.
  • the term “spherical” is not limited to a perfect sphere, and includes a shape with some irregularities on the surface. Its circularity is, for example, 0.90 or more, preferably 0.92 or more, and more preferably 0.94 or more.
  • the surface of the silver-containing particles (A) is treated with an organic compound such as a carboxylic acid, a saturated fatty acid having 4 to 30 carbon atoms, a monovalent unsaturated fatty acid having 4 to 30 carbon atoms, or a long-chain alkylnitrile. good too.
  • an organic compound such as a carboxylic acid, a saturated fatty acid having 4 to 30 carbon atoms, a monovalent unsaturated fatty acid having 4 to 30 carbon atoms, or a long-chain alkylnitrile. good too.
  • the silver-containing particles (A) may be (i) particles consisting essentially of silver, or (ii) particles consisting of silver and a component other than silver. Moreover, (i) and (ii) may be used together as the metal-containing particles.
  • the silver-containing particles (A) particularly preferably contain silver-coated resin particles in which the surfaces of resin particles are coated with silver. Thereby, it is possible to prepare a conductive resin composition that gives a cured product having excellent thermal conductivity and a low storage elastic modulus.
  • the silver-coated resin particles have silver on the surface and a resin inside, they are considered to have good thermal conductivity and to be softer than particles made only of silver. Therefore, it is considered that the use of silver-coated resin particles facilitates designing appropriate values for thermal conductivity and storage elastic modulus.
  • the thermal conductivity it is considered to increase the amount of silver-containing particles.
  • metals are generally "hard", too much silver-containing particles may result in too high a modulus after sintering.
  • Part or all of the silver-containing particles are silver-coated resin particles, making it possible to easily design a conductive resin composition from which a cured product having desired thermal conductivity and storage elastic modulus can be obtained.
  • the silver-coated resin particles it is sufficient that at least a part of the surface of the resin particles is covered with a silver layer. Of course, the entire surface of the resin particles may be covered with silver.
  • the silver layer preferably covers 50% or more, more preferably 75% or more, and still more preferably 90% or more of the surface of the resin particles.
  • the silver layer covers substantially the entire surface of the resin particles. From another point of view, when the silver-coated resin particles are cut along a certain cross section, it is preferable that the silver layer is observed all around the cross section.
  • the mass ratio of resin/silver in the silver-coated resin particles is, for example, 90/10 to 10/90, preferably 80/20 to 20/80, more preferably 70/30 to 30/70. be.
  • the "resin" in the silver-coated resin particles examples include silicone resins, (meth)acrylic resins, phenol resins, polystyrene resins, melamine resins, polyamide resins, polytetrafluoroethylene resins, and the like. Of course, resins other than these may be used. Moreover, only one resin may be used, or two or more resins may be used in combination. From the viewpoint of elastic properties and heat resistance, the resin is preferably a silicone resin or a (meth)acrylic resin.
  • the silicone resin may be particles composed of organopolysiloxane obtained by polymerizing organochlorosilanes such as methylchlorosilane, trimethyltrichlorosilane, and dimethyldichlorosilane.
  • organochlorosilanes such as methylchlorosilane, trimethyltrichlorosilane, and dimethyldichlorosilane.
  • a silicone resin having a basic skeleton structure obtained by further three-dimensionally cross-linking an organopolysiloxane may be used.
  • the (meth)acrylic resin is a resin obtained by polymerizing a monomer containing (meth)acrylic acid ester as a main component (50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more). be able to.
  • (Meth)acrylic acid esters for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate , stearyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-propyl (meth)acrylate, chloro-2-hydroxyethyl (meth)acrylate, diethylene glycol mono (meth)acrylate, At least one compound selected from the group consisting of methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate and isoboronol (meth)acrylate can be mentioned.
  • the monomer component of the acrylic resin may contain a small amount of other monomers.
  • Such other monomer components include, for example, styrenic monomers.
  • silver-coated (meth)acrylic resin see also the description in JP-A-2017-126463.
  • Suitable functional groups may be introduced into silicone resins and (meth)acrylic resins.
  • Functional groups that can be introduced are not particularly limited. Examples thereof include epoxy group, amino group, methoxy group, phenyl group, carboxyl group, hydroxyl group, alkyl group, vinyl group and mercapto group.
  • the resin particle portion of the silver-coated resin particles may contain various additive components, such as low-stress modifiers.
  • low-stress modifiers include liquid synthetic rubbers such as butadiene styrene rubber, butadiene acrylonitrile rubber, polyurethane rubber, polyisoprene rubber, acrylic rubber, fluororubber, liquid organopolysiloxane, and liquid polybutadiene.
  • liquid synthetic rubbers such as butadiene styrene rubber, butadiene acrylonitrile rubber, polyurethane rubber, polyisoprene rubber, acrylic rubber, fluororubber, liquid organopolysiloxane, and liquid polybutadiene.
  • the resin particle portion contains a silicone resin
  • the inclusion of a low-stress modifier can make the elastic properties of the silver-coated resin particles preferable.
  • the shape of the resin particle portion of the silver-coated resin particles is not particularly limited. A combination of a spherical shape and an irregular shape other than a spherical shape, such as a flat shape, a plate shape, a needle shape, etc., is preferable.
  • the specific gravity of the silver-coated resin particles is not particularly limited, the lower limit is, for example, 2 or more, preferably 2.5 or more, and more preferably 3 or more. Further, the upper limit of the specific gravity is, for example, 10 or less, preferably 9 or less, more preferably 8 or less. Appropriate specific gravity is preferable in terms of dispersibility of the silver-coated resin particles themselves and uniformity when silver-coated resin particles and other silver-containing particles are used in combination.
  • the proportion of silver-coated resin particles in the total silver-containing particles (A) is preferably 1 to 50% by mass, more preferably 3 to 45% by mass, and still more preferably 5 to 40% by mass. is. By appropriately adjusting this ratio, it is possible to further improve heat dissipation while suppressing a decrease in adhesive strength due to heat cycles.
  • the silver-containing particles other than the silver-coated resin particles are, for example, particles consisting essentially of silver.
  • the median diameter D50 of the silver-containing particles (A) is, for example, 0.01-50 ⁇ m, preferably 0.1-20 ⁇ m, more preferably 0.5-10 ⁇ m.
  • D50 By setting D50 to an appropriate value, it is easy to balance thermal conductivity, sinterability, resistance to heat cycles, and the like. Also, by setting D50 to an appropriate value, it may be possible to improve the workability of application/adhesion.
  • the particle size distribution (horizontal axis: particle size, vertical axis: frequency) of the silver-containing particles may be unimodal or multimodal.
  • the silver-containing particles (A) contain spherical silver-containing particles (a1) and scale-like silver-containing particles (a2-1). These silver-containing particles are more preferably silver particles consisting essentially of silver.
  • the median diameter D 50 of the spherical silver-containing particles (a1) is, for example, 0.1-20 ⁇ m, preferably 0.5-10 ⁇ m, more preferably 0.5-5.0 ⁇ m.
  • the specific surface area of the spherical silver-containing particles (a1) is, for example, 0.1 to 2.5 m 2 /g, preferably 0.5 to 2.3 m 2 /g, more preferably 0.8 to 2.0 m 2 /g. is g.
  • the tap density of the spherical silver-containing particles (a1) is, for example, 1.5 to 6.0 g/cm 3 , preferably 2.5 to 5.8 g/cm 3 , more preferably 4.5 to 5.5 g/cm 3 .
  • the circularity of the spherical silver-containing particles (a1) is, for example, 0.90 or more, preferably 0.92 or more, and more preferably 0.94 or more. Satisfying each of these properties provides an excellent balance of thermal conductivity, sinterability, resistance to heat cycles, and the like.
  • the median diameter D50 of the scale-like silver-containing particles (a2-1) is, for example, 0.1 to 20 ⁇ m, preferably 1.0 to 15 ⁇ m, more preferably 2.0 to 10 ⁇ m.
  • the specific surface area of the scale-like silver-containing particles (a2-1) is, for example, 0.1 to 2.5 m 2 /g, preferably 0.2 to 2.0 m 2 /g, more preferably 0.25 to 1.0 m 2 /g. 2 m 2 /g.
  • the tap density of the scale-like silver-containing particles (a2-1) is, for example, 1.5 to 6.0 g/cm 3 , preferably 2.5 to 5.9 g/cm 3 , more preferably 4.0 to 5.0 g/cm 3 . 8 g/cm 3 . Satisfying each of these properties provides an excellent balance of thermal conductivity, sinterability, resistance to heat cycles, and the like.
  • the ratio (a1/a2-1) of the content of the spherical silver-containing particles (a1) to the content of the scale-like silver-containing particles (a2-1) is preferably 0.1 or more and 10 or less, more preferably 0.1. It can be 3 or more and 5 or less, particularly preferably 0.5 or more and 3 or less. As a result, the contact ratio between the silver-containing particles is particularly improved, so that a network is easily formed after sintering the paste-like polymerizable composition, and the thermal conductivity and the electrical conductivity are particularly improved.
  • the ratio (a1/a2-1) of the median diameter D50 of the spherical silver-containing particles (a1) to the median diameter D50 of the scale-like silver-containing particles (a2-1) is preferably 0.01 or more and 0.8 or less. , more preferably 0.05 or more and 0.6 or less.
  • the ratio (a1/a2-1) of the tap density of the spherical silver-containing particles (a1) to the tap density of the scale-like silver-containing particles (a2-1) is preferably 0.5 or more and 2.0 or less, more preferably It is 0.7 or more and 1.2 or less.
  • the filling rate of the silver-containing particles is improved, and the contact ratio between the silver-containing particles is particularly improved.
  • Conductivity is particularly improved.
  • the median diameter D50 of the silver-coated resin particles is, for example, 5.0-25 ⁇ m, preferably 7.0-20 ⁇ m, more preferably 8.0-15 ⁇ m. Thereby, thermal conductivity can be improved more.
  • the median diameter D 50 of the silver-containing particles (A) can be determined by, for example, particle image measurement using a flow type particle image analyzer FPIA (registered trademark)-3000 manufactured by Sysmex Corporation. More specifically, the particle diameter of the silver-containing particles (A) can be determined by measuring the volume-based median diameter in a wet manner using this device.
  • FPIA flow type particle image analyzer
  • the ratio of the silver-containing particles (A) in the entire conductive resin composition is, for example, 1-98% by mass, preferably 30-96% by mass, more preferably 50-94% by mass.
  • the ratio of the metal-containing particles By setting the ratio of the metal-containing particles to 1% by mass or more, it is easy to increase the thermal conductivity.
  • the ratio of the silver-containing particles (A) By setting the ratio of the silver-containing particles (A) to 98% by mass or less, the workability of coating/adhesion can be improved.
  • particles consisting essentially of silver can be obtained from, for example, DOWA Hi-Tech Co., Ltd., Fukuda Metal Foil & Powder Co., Ltd., and the like.
  • silver-coated resin particles can be obtained from, for example, Mitsubishi Materials Corporation, Sekisui Chemical Co., Ltd., Sanno Co., Ltd., and the like.
  • the (meth)acrylic compound (B) is not particularly limited, but includes, for example, a monofunctional or bifunctional (meth)acrylic compound, or a trifunctional or higher polyfunctional (meth)acrylic compound.
  • the (meth) acrylic compound represents an acrylic compound, a methacrylic compound, or a mixture thereof, and having a (meth) acrylic group means having one or more acrylic groups, or having one or more methacrylic groups.
  • the monofunctional (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth) Acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, butoxyethyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate , octylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (
  • bifunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,3 -butanediol di(meth)acrylate, 2-methyl-1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl- 1,5-pentanediol di(meth)acrylate, 1,6-hexane
  • trifunctional or higher polyfunctional (meth)acrylates examples include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, di aliphatic (meth)acrylates such as pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated glycerin tri(meth)acrylate; heterocyclic (meth)acrylates such as isocyanuric acid tri(meth)acrylate; ) acrylates and the like.
  • the (meth)acrylic compound (B) can contain at least one selected from these, and can contain a monofunctional (meth)acrylate or a bifunctional (meth)acrylate.
  • the ratio of the (meth)acrylic compound (B) in the entire conductive resin composition of the present embodiment is, for example, 0.1 to 15% by mass, preferably 0.5 to 12% by mass, from the viewpoint of the effects of the present invention. , more preferably 1.0 to 10% by mass.
  • the polyfunctional epoxy compound (C) contains at least one compound selected from compounds represented by the following general formula (1).
  • the compound represented by the following general formula (1) contained in the polyfunctional epoxy compound (C) has a divalent to hexavalent organic group to which a plurality of epoxy group-containing groups are bonded, and has excellent reactivity and crosslink density. increases, sintering of the silver-containing particles is promoted by curing shrinkage when a resin is obtained from the compound, and a highly thermally conductive material with excellent thermal conductivity can be obtained. Furthermore, since the resulting cured product (high thermal conductive material) has a low elastic modulus and excellent flexibility, a semiconductor device or the like provided with the cured product has excellent product reliability due to stress relaxation. Furthermore, the resulting cured product (high thermal conductivity material) is excellent in adhesion to substrates and the like, and is excellent in product reliability. In other words, it is possible to provide a conductive resin composition having an excellent balance of these properties.
  • R represents a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, preferably a hydroxyl group or an alkyl group having 1 to 2 carbon atoms, more preferably a hydroxyl group or an alkyl group having 1 carbon atom. Multiple R may be the same or different.
  • X represents an alkylene group having 1 to 3 carbon atoms, preferably an alkylene group having 1 to 2 carbon atoms, more preferably an alkylene group having 1 carbon atom. Multiple X's may be the same or different.
  • n represents an integer of 2 to 4, preferably 2 or 3;
  • Q represents a divalent to hexavalent organic group.
  • divalent to hexavalent organic group in Q known organic groups can be used as long as the effects of the present invention are exhibited. can be mentioned.
  • Examples of compounds in which Q in general formula (1) is an organic group in general formula (a) include Denacol EX-321 (manufactured by Nagase ChemteX Corporation) and PETG (manufactured by Showa Denko KK). Examples of compounds in which Q in general formula (1) is an organic group in general formula (b) include CDMDG (manufactured by Showa Denko KK). Examples of compounds in which Q in general formula (1) is an organic group in general formula (c) include Denacol EX-313 (manufactured by Nagase ChemteX Corporation).
  • Examples of compounds in which Q in general formula (1) is an organic group in general formula (d) include Denacol EX-810 (manufactured by Nagase ChemteX Corporation). In general formula (e), p represents an integer of 1-30, preferably an integer of 10-25. Examples of compounds in which Q in general formula (1) is an organic group in general formula (e) include Denacol EX-861 (manufactured by Nagase ChemteX Corporation).
  • Q 1 and Q 2 represent an alkylene group having 1 to 3 carbon atoms or a cycloalkylene group having 3 to 8 carbon atoms, preferably an alkylene group having 1 to 2 carbon atoms or 5 to 8 carbon atoms.
  • Examples of compounds in which Q in general formula (1) is an organic group in general formula (f) include Denacol EX-211 and EX-252 (manufactured by Nagase ChemteX Corporation).
  • Examples of compounds in which Q in general formula (1) is an organic group in general formula (g) include Denacol EX-512 (manufactured by Nagase ChemteX Corporation). Examples of compounds in which Q in general formula (1) is an organic group in general formula (h) include Denacol EX-614B (manufactured by Nagase ChemteX Corporation). In general formulas (a) to (h), * indicates a bond.
  • the polyfunctional epoxy compound (C) is at least one compound selected from compounds in which Q is an organic group represented by general formulas (a), (b) and (c). It preferably contains at least one selected from compounds that are organic groups represented by general formulas (a) and (b), and more preferably contains an organic group represented by general formula (a) More preferably, it contains at least one selected from compounds.
  • the polyfunctional epoxy compound (C) is a compound a in which Q in the general formula (1) is an organic group represented by the general formula (a) and n is 3, and Q in the general formula (1) is the general formula
  • the ratio of compound a to the total amount of compound a and compound b (a/(a+b)) is 0.01 to 5, preferably 0.05 to 3, more preferably 0.1 to 1.
  • the proportion of the polyfunctional epoxy compound (C) in the entire conductive resin composition of the present embodiment is, for example, 0.1 to 20% by mass, preferably 0.2 to 17% by mass, more preferably 0.5 to 15% by mass. % by mass.
  • the conductive resin composition further promotes sintering of the silver-containing particles due to curing shrinkage. It is possible to obtain a highly thermally conductive material with even better thermal conductivity. Furthermore, since the resulting cured product (high thermal conductive material) has a lower elastic modulus and is more excellent in flexibility, a semiconductor device or the like provided with the cured product is more excellent in product reliability due to stress relaxation. Furthermore, the resulting cured product (high thermal conductivity material) is excellent in adhesion to substrates and the like, and is excellent in product reliability. In other words, it is possible to provide a conductive resin composition with a better balance of these properties.
  • the conductive resin composition of this embodiment can further contain a curing agent (D).
  • a curing agent (D) include those having a reactive group that reacts with the epoxy group contained in the polyfunctional epoxy compound (C).
  • the curing agent (D) preferably contains a phenolic curing agent. These curing agents are particularly preferred when the thermosetting component contains epoxy groups.
  • the phenol-based curing agent may be a low-molecular-weight compound or a high-molecular-weight compound (ie, phenolic resin).
  • phenolic resins include novolac-type phenolic resins such as phenol novolak resin, cresol novolak resin, bisphenol novolak resin, and phenol-biphenyl novolak resin; polyvinylphenol; polyfunctional phenolic resins such as triphenylmethane-type phenol resin; modified phenolic resins such as modified phenolic resins and dicyclopentadiene-modified phenolic resins; phenolic aralkyl-type phenolic resins such as phenolaralkyl resins having a phenylene skeleton and/or biphenylene skeleton and naphtholaralkyl resins having a phenylene and/or biphenylene skeleton; be able to.
  • the curing agent (D) only one type may be used, or two or more types may be used in combination.
  • the amount thereof is, for example, 10 to 120 parts by mass, preferably 20 parts by mass when the amount of the polyfunctional epoxy compound (C) is 100 parts by mass. ⁇ 80 parts by mass.
  • the conductive resin composition of the present embodiment can further contain a polymer (E) containing polyrotaxane.
  • a polyrotaxane usually comprises a cyclic molecule forming an opening, a linear molecular chain passing through the opening of the cyclic molecule, and blocking groups bonded to both ends of the linear molecular chain. Blocking groups prevent the cyclic molecule from leaving the linear chain.
  • a single linear molecular chain can pass through an opening in one or more cyclic molecules.
  • the cyclic molecule in the polyrotaxane is not particularly limited as long as it forms an opening through which the linear molecular chain can pass.
  • a cyclic molecule does not have to be completely closed by a covalent bond, as long as the linear molecular chain passing through the opening does not break off.
  • Cyclic molecules include, for example, cyclodextrin, crown ether, benzocrown, dibenzocrown, dicyclohexanocrown, and derivatives or modifications thereof. From the viewpoint of inclusion ability of linear molecular chains, the cyclic molecule is preferably cyclodextrin or a derivative or modified form thereof.
  • the cyclic molecule is cyclodextrin or a derivative or modified form thereof
  • part or all of the hydroxy groups in the cyclodextrin are preferably substituted with hydrophobic groups.
  • the solubility of the polyrotaxane in organic solvents is improved.
  • the relative amount of the cyclic molecule to be included is, for example, 0.001, preferably 0.01, more preferably 0.1 or more, and the upper limit is, for example, 0.7 or less, preferably 0.6 or less, more preferably 0.5 It is below.
  • the inclusion amount of the cyclic molecule is within the above range, the mobility of the cyclic molecule on the linear molecular chain is likely to be maintained.
  • the linear molecular chain in the polyrotaxane is not particularly limited as long as it is a molecular chain that can penetrate the cyclic molecule and the cyclic molecule can move on the linear molecular chain.
  • the straight-chain molecular chain only needs to contain a substantially straight-chain portion, and may have a branched chain or a cyclic substituent or the like.
  • the length and molecular weight of the linear portion are not particularly limited.
  • linear molecular chains examples include alkylene chains, polyester chains, polyether chains, polyamide chains, and polyacrylate chains. Among these, a polyester chain or a polyether chain is preferred, and a polyether chain is more preferred, from the viewpoint of the flexibility of the linear molecular chain itself.
  • Polyether chains are preferably polyethylene glycol chains (polyoxyethylene chains).
  • the blocking groups in the polyrotaxane are not particularly limited as long as they are groups arranged at both ends of the linear molecular chain and capable of maintaining the state in which the linear molecular chain penetrates the cyclic molecule.
  • the blocking group includes a group having a structure larger than the opening of the cyclic molecule, a group that cannot pass through the opening of the cyclic molecule due to ionic interaction, and the like.
  • Specific examples of blocking groups include adamantyl groups, groups containing cyclodextrin, anthracene groups, triphenylene groups, pyrene groups, trityl groups, and isomers and derivatives thereof.
  • the combination of a cyclic molecule and a linear molecular chain is preferably a combination of ⁇ -cyclodextrin or a derivative thereof as the cyclic molecule and a polyethylene glycol chain or derivative thereof as the linear molecular chain. .
  • This combination facilitates movement of the cyclic molecule on the linear molecular chain.
  • this combination also has the advantage of being relatively easy to synthesize.
  • the polyrotaxane preferably has crosslinkable groups. By having a crosslinkable group in the polyrotaxane, the thermosetting property, adhesiveness, etc. of the conductive resin composition are improved.
  • the cyclic molecule in the polyrotaxane preferably has a crosslinkable group. Since the cyclic molecule has a crosslinkable group, the cyclic molecule maintains a state in which it can slide along the linear molecular chain even after the composition is thermally cured (crosslinked). Therefore, it is possible to further enhance the flexibility and stretchability of the film after thermosetting.
  • the crosslinkable group is preferably a cationic crosslinkable group or a radical crosslinkable group, more preferably a radical crosslinkable group.
  • the crosslinkable groups are preferably ethylenic carbon-carbon double bond-containing groups such as (meth)acryloyl groups.
  • the crosslinkable group may contain an epoxy group and/or an oxetanyl group.
  • the polyrotaxane may be synthesized with reference to a known method, or may be a commercially available product. Commercially available products include the "Serum” (registered trademark, SeRM in the alphabet) series sold by ASM Corporation.
  • the conductive resin composition of the present embodiment may contain only one type of polyrotaxane, or may contain two or more types.
  • the polymer (E) can contain known resins other than polyrotaxane within the scope of the effects of the present invention.
  • resins include silicone resins, (meth)acrylic resins, phenol resins, polystyrene resins, melamine resins, polyamide resins, and polytetrafluoroethylene resins.
  • the content of the polyrotaxane in 100% by mass of the polymer (E) is 75% by mass to 100% by mass, preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, especially It is preferably 95% by mass to 100% by mass.
  • the proportion of the polymer (E) in the entire conductive resin composition of the present embodiment is, for example, 0.1 to 10% by mass, preferably 0.2 to 8% by mass, more preferably 0.3 to 5% by mass. be.
  • the conductive resin composition of the present embodiment can further contain an organic solvent (F).
  • organic solvent (F) examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, tripropylene glycol monobutyl ether, methyl methoxybutanol, ⁇ -terpineol, ⁇ -terpineol, hexylene glycol, benzyl alcohol, 2-phenyl Alcohols such as ethyl alcohol, isopalmityl alcohol, isostearyl alcohol, lauryl alcohol, ethylene glycol, propylene
  • the amount is not particularly limited.
  • the amount used may be appropriately adjusted based on the desired fluidity and the like.
  • the organic solvent (F) is used in such an amount that the nonvolatile component concentration of the conductive resin composition is 50 to 95% by mass.
  • the conductive resin composition of this embodiment can further contain a curing accelerator.
  • a curing accelerator typically accelerates the reaction between the polyfunctional epoxy compound (C) and the curing agent (D).
  • curing accelerators include phosphorus atom-containing compounds such as imidazole compounds, organic phosphines, tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; dicyandiamide, 1,8-diazabicyclo[5.4.0]undecene-7, amidines and tertiary amines such as benzyldimethylamine; nitrogen atom-containing compounds such as quaternary ammonium salts of the above amidines or the above tertiary amines; be done.
  • a hardening accelerator only 1 type may be used and 2 or more types may be used together.
  • the conductive resin composition of this embodiment can further contain a curing accelerator.
  • the radical polymerization initiator can, for example, prevent insufficient curing, allow the curing reaction to proceed sufficiently at a relatively low temperature (eg, 180° C.), or further improve the adhesive strength. sometimes it can be done.
  • Examples of radical polymerization initiators include peroxides and azo compounds.
  • peroxides examples include organic peroxides such as diacyl peroxide, dialkyl peroxide, and peroxyketals, more specifically, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; Peroxyketals such as 1,1-di(t-butylperoxy)cyclohexane and 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane; Hydroperoxides such as p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide; di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-buty
  • Azo compounds include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2, 4-dimethylvaleronitrile) and the like.
  • a radical polymerization initiator only one type may be used, or two or more types may be used in combination.
  • the conductive resin composition of the present embodiment can contain other components such as a curing accelerator, a silane coupling agent, a plasticizer, and an adhesion imparting agent.
  • the adhesive force can be further improved, and by including a plasticizer, the storage elastic modulus can be lowered. And it becomes easy to suppress the fall of the adhesive force by a heat cycle further.
  • the conductive resin composition of the present embodiment is preferably pasty at 20°C. That is, the conductive resin composition (paste composition) of the present embodiment can preferably be applied to a substrate or the like like a paste at 20°C. As a result, the conductive resin composition of the present embodiment can be preferably used as an adhesive for semiconductor elements or the like. Of course, depending on the applied process, the conductive resin composition of the present embodiment may be in the form of a relatively low-viscosity varnish.
  • the conductive resin composition of the present embodiment can be obtained by mixing each of the components described above and, if necessary, other components by a conventionally known method.
  • a highly thermally conductive material can be obtained by sintering the conductive resin composition of the present embodiment. By changing the shape of the high thermal conductivity material, it can be applied to various parts that require heat dissipation in the fields of automobiles and electrical machinery.
  • a semiconductor device can be manufactured using the conductive resin composition of the present embodiment.
  • a semiconductor device can be manufactured by using the conductive resin composition of the present embodiment as an "adhesive" between a substrate and a semiconductor element.
  • the semiconductor device of the present embodiment includes, for example, a substrate and a semiconductor element mounted on the substrate via an adhesive layer obtained by sintering the conductive resin composition by heat treatment. Prepare.
  • the stress is relaxed, and the adhesiveness of the adhesive layer is less likely to deteriorate due to heat cycles. That is, the reliability of the semiconductor device of this embodiment is high.
  • semiconductor devices include ICs, LSIs, power semiconductor devices (power semiconductors), and various other devices.
  • substrates include various semiconductor wafers, lead frames, BGA substrates, mounting substrates, heat spreaders, and heat sinks.
  • FIG. 1 is a cross-sectional view showing an example of a semiconductor device.
  • the semiconductor device 100 includes a base material 30 and a semiconductor element 20 mounted on the base material 30 via an adhesive layer 10 (die attach material) that is a heat-treated body of a conductive resin composition.
  • adhesive layer 10 die attach material
  • the semiconductor element 20 and the base material 30 are electrically connected, for example, via bonding wires 40 or the like. Also, the semiconductor element 20 is sealed with a sealing resin 50, for example.
  • the thickness of the adhesive layer 10 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 20 ⁇ m or more. Thereby, the stress absorption capacity of the conductive resin composition can be improved, and the heat cycle resistance can be improved.
  • the thickness of the adhesive layer 10 is, for example, 100 ⁇ m or less, preferably 50 ⁇ m or less.
  • the base material 30 is, for example, a lead frame.
  • the semiconductor element 20 is mounted on the die pad 32 or the base material 30 with the adhesive layer 10 interposed therebetween.
  • the semiconductor element 20 is electrically connected to the outer leads 34 (the base material 30) via bonding wires 40, for example.
  • the base material 30, which is a lead frame, is composed of, for example, 42 alloy, a Cu frame, or the like.
  • the substrate 30 may be an organic substrate or a ceramic substrate.
  • organic substrates include those made of epoxy resin, cyanate resin, maleimide resin, or the like.
  • the surface of the base material 30 may be coated with a metal such as silver or gold, for example. This improves the adhesiveness between the adhesive layer 10 and the substrate 30 .
  • FIG. 2 is a cross-sectional view showing another example of the semiconductor device 100 different from that in FIG.
  • the base material 30 is, for example, an interposer.
  • a plurality of solder balls 52 are formed on the surface of the substrate 30, which is the interposer, opposite to the surface on which the semiconductor element 20 is mounted. In this case, the semiconductor device 100 will be connected to another wiring board through the solder balls 52 .
  • the base material 30 is coated with a conductive resin composition, and then the semiconductor element 20 is arranged thereon. That is, the substrate 30, the conductive resin composition, and the semiconductor element 20 are laminated in this order.
  • the method of applying the conductive resin composition is not particularly limited. Specifically, a dispensing method, a printing method, an inkjet method, and the like can be mentioned.
  • the conductive resin composition is heat-cured.
  • Thermal curing is preferably carried out by pre-curing and post-curing.
  • thermosetting the conductive resin composition is made into a heat-treated body (cured product).
  • thermosetting heat treatment
  • the metal-containing particles in the conductive resin composition are aggregated, and a structure is formed in the adhesive layer 10 in which interfaces between a plurality of metal-containing particles have disappeared.
  • the substrate 30 and the semiconductor element 20 are adhered via the adhesive layer 10 .
  • the semiconductor element 20 and the base material 30 are electrically connected using bonding wires 40 .
  • the semiconductor element 20 is sealed with the sealing resin 50 .
  • a semiconductor device can be manufactured.
  • Aliphatic polyfunctional epoxy compound 1 trimethylolpropane polyglycidyl ether (a mixture of compounds represented by the following chemical formula, Denacol EX-321L, manufactured by Nagase Chemtech)
  • Aliphatic polyfunctional epoxy compound 2 epoxidation reaction product of pentaerythritol tetraallyl ether with hydrogen peroxide (compound represented by the following chemical formula, Showfree PETG, manufactured by Showa Denko)
  • Aliphatic polyfunctional epoxy compound 3 epoxidation reaction product of pentaerythritol tetraallyl ether with hydrogen peroxide (compound represented by the following chemical formula, Showfree CDMDG, manufactured by Showa Denko)
  • Epoxy resin 4 bisphenol F type epoxy resin (manufactured by Nippon Kayaku, RE-303S)
  • Epoxy resin 5 aminophenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER630)
  • Acrylic monomer 1 ethylene glycol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light Ester EG)
  • Acrylic monomer 2 1,4-cyclohexanedimethanol monoacrylate (manufactured by Nippon Kasei Co., Ltd., CHDMMA, monofunctional acrylic)
  • Polyrotaxane 1 SA1305P-20: 50% by mass solution of polyrotaxane ethyl acetate sold by ASM Co., Ltd., cyclic molecule in polyrotaxane contains acryloyl group, total weight average molecular weight (representative value): 1 million, methacrylic equivalent ( Representative value): 1500 g / eq
  • Curing agent Phenolic resin having a bisphenol F skeleton (DIC-BPF manufactured by DIC)
  • Radical polymerization initiator - Radical polymerization initiator 1: Dicumyl peroxide (manufactured by Kayaku Akzo Co., Ltd., Perkadox BC)
  • Curing accelerator 1 2-phenyl-1H-imidazole-4,5-dimethanol (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2PHZ-PW)
  • ⁇ Silver filler 1 Dowa Electronics Co., Ltd., AG-DSB-114, spherical, D 50 : 0.7 ⁇ m, specific surface area: 1.05 m 2 /g, tap density 5.25 g/cm 3 , circularity: 0.953 ⁇ Silver filler 2: HKD-12 manufactured by Fukuda Metal Foil & Powder Co., Ltd., scale-like, median diameter D 50 : 7.6 ⁇ m, specific surface area: 0.315 m 2 /g, tap density: 5.5 g/cm 3
  • Solvent 1 Tripropylene glycol mono-n-butyl ether (BFTG, manufactured by Nippon Emulsifier Co., Ltd., boiling point 274 ° C.)
  • Examples 1-8, Comparative Examples 1-2 Each raw material component was mixed according to the compounding amount shown in Table 1 to obtain a varnish. Next, the obtained varnish was blended according to the blending amounts shown in Table 1, and kneaded at room temperature in a three-roll mill. Thus, a conductive resin composition was produced.
  • the conductive resin composition was applied onto a glass plate, heated from 30° C. to 200° C. over 60 minutes in a nitrogen atmosphere, and then heat-treated at 200° C. for 120 minutes. As a result, a heat-treated body (cured product) of the conductive resin composition having a thickness of 0.05 mm was obtained.
  • the resistance value of the surface of the heat-treated body was measured using a direct current four-electrode method with a milliohmmeter (manufactured by Hioki Co., Ltd.) and electrodes with an electrode spacing of 40 mm.
  • the heat-treated body of the conductive resin composition was cut into pieces of about 0.1 mm x about 10 mm x about 4 mm to obtain strip-shaped samples for evaluation.
  • the storage modulus (E′) at 25° C. was measured by DMA (dynamic viscoelasticity measurement, tensile mode) under the conditions of a heating rate of 5° C./min and a frequency of 10 Hz.
  • the semiconductor device for evaluation produced as described above was treated in the same manner as described above at a temperature of 60° C. and a humidity of 60% for 48 hours to obtain an evaluation sample.
  • the chip adhesion strength using a 4000 universal bond tester (manufactured by Nordson Dage), the strength when shearing at a tool speed of 500 ⁇ m / s at a position of 50 ⁇ m in height from the lead frame when heating at 260 ° C. It was evaluated as strength.
  • the cured product obtained from the conductive resin composition containing the polyfunctional epoxy compound has low volume resistivity and excellent thermal conductivity, and has a low storage elastic modulus and is stress-relaxed. Furthermore, even after the constant temperature moisture absorption test, the adhesion strength is high and peeling is suppressed.
  • semiconductor device adhesive layer 20 semiconductor element 30 base material 32 die pad 34 outer lead 40 bonding wire 50 sealing resin 52 solder ball

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