TW202244101A - Conductive resin composition, high thermal conductive material and semiconductor device - Google Patents

Abstract

This electrically conductive resin composition contains (A) silver-containing particles, (B) a (meth)acrylic compound, and (C) at least one polyfunctional epoxy compound selected from compounds represented by general formula (1).

Description

Conductive resin composition, high thermal conductivity material and semiconductor device

The invention relates to a conductive resin composition, a high thermal conductivity material and a semiconductor device.

In the manufacture of semiconductor devices, conductive resin compositions having conductivity and adhesive properties are sometimes used. As a conductive resin composition having conductivity and adhesiveness, various compositions have been developed so far.

Patent Document 1 discloses a thermally conductive and electrically conductive adhesive composition comprising a conductive filler composed of silver powder having a predetermined average particle size, an epoxy resin, and epoxypropylene having one or more aliphatic hydrocarbon chains. Reactive diluent and hardener for functional groups. In this document, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, and the like are exemplified as the reactive diluent.

Patent Document 2 discloses a conductive adhesive containing a predetermined glycidyl ether compound, a predetermined phenolic resin-based hardener, a curing accelerator, and a conductive filler in a predetermined amount relative to the glycidyl ether compound. Contains the aforementioned phenolic resin-based hardener. In this document, 1,4-cyclohexanedimethanol diglycidyl ether and neopentylthritol tetraglycidyl ether are exemplified as the aforementioned glycidyl ether compound.

Patent Document 3 discloses a thermally conductive and conductive adhesive composition, which contains a conductive filler, an epoxy resin, a reactive diluent having two or more glycidyl ether functional groups on the aliphatic hydrocarbon chain, and a curing agent. agent. In this document, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, and the like are exemplified as the reactive diluent. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2018/225773 [Patent Document 2] Japanese Patent Laid-Open No. 2015-160932 [Patent Document 3] Japanese Patent Laid-Open No. 2015-224329

[Problem to be Solved by the Invention]

However, the conductive resin compositions described in Patent Documents 1 to 3 have room for improvement in terms of thermal conductivity, product reliability, and adhesion to substrates. [Technical means to solve the problem]

The inventors of the present invention found that the above-mentioned problems can be solved by using a (meth)acrylic compound and a specific polyfunctional epoxy compound in combination, and completed the present invention. That is, the present invention can be as follows.

（通式（1）中，R表示羥基或碳數1～3的烷基，存在複數個之R可以相同，亦可以不同。 Q表示2～6價的有機基。 X表示碳數1～3的伸烷基，存在複數個之X可以相同，亦可以不同。 m表示0～2的整數，n表示2～4的整數。） According to the present invention, there is provided a conductive resin composition comprising: (A) silver-containing particles; (B) (meth)acrylic compound; and (C) one selected from the compounds represented by the following general formula (1). At least one polyfunctional epoxy compound.

(In the general formula (1), R represents a hydroxyl group or an alkyl group with 1 to 3 carbons, and multiple Rs may be the same or different. Q represents a 2 to 6-valent organic group. X represents a carbon number of 1 to 3 Alkylene groups, there are plural Xs that may be the same or different. m represents an integer of 0 to 2, and n represents an integer of 2 to 4.)

According to the present invention, a high thermal conductivity material is provided, which is obtained by sintering the aforementioned conductive resin composition.

According to the present invention, a semiconductor device is provided, which has: substrate; and A semiconductor element mounted on the aforementioned substrate via an adhesive layer, The aforementioned adhesive layer is formed by sintering the aforementioned conductive resin composition. [Effect of Invention]

The conductive resin composition of the present invention promotes the sintering of silver-containing particles through hardening shrinkage, and can obtain a high thermal conductivity material with excellent thermal conductivity, and furthermore has a low elastic modulus, the stress is relaxed, and the adhesion to the substrate and the like is also excellent. Therefore, a highly thermally conductive material excellent in product reliability can be obtained. In other words, it is possible to provide a conductive resin composition with an excellent balance of these properties.

Hereinafter, embodiments of the present invention will be described using the drawings. In addition, in all drawings, the same code|symbol is attached|subjected to the same component, and description is abbreviate|omitted suitably.

In this specification, unless otherwise specified, the expression "a to b" in the description of the numerical range means a or more and b or less. For example, "1 to 5% by mass" means "more than 1% by mass and less than 5% by mass".

In the expression of a group (atomic group) in the present specification, the expression not described as substituted or unsubstituted includes both an expression having no substituent and an expression having a substituent. For example, "alkyl" includes not only an alkyl group without a substituent (unsubstituted alkyl group), but also an alkyl group with a substituent (substituted alkyl group). The expression "(meth)acrylic acid" in this specification shows the concept including both acrylic acid and methacrylic acid. The same applies to similar expressions such as "(meth)acrylate" and "(meth)acryl".

The conductive resin composition of this embodiment contains: (A) silver-containing particles; (B) (meth)acrylic compounds; and (C) At least one polyfunctional epoxy compound selected from compounds represented by the following general formula (1). Thereby, the sintering of the silver-containing particles is promoted by hardening shrinkage, and a high thermal conductivity material with excellent thermal conductivity can be obtained. Furthermore, the elastic modulus is low, the stress is relaxed, and the adhesion with the substrate and the like is excellent, so product reliability can be obtained. Excellent high thermal conductivity material. Like conductive substances such as metals, when free electrons take up most of both thermal conductivity and electrical conductivity, according to the Wiedemann–Franz law (Wiedemann–Franz law), it can be evaluated by volume resistivity thermal conductivity. That is, the volume resistivity is a resistance value per unit volume, and when the resistance value is low, free electrons become carriers, indicating that electricity passes easily, and it also serves as an indicator of ease of heat transfer (thermal conductivity).

[Silver-containing particles (A)] The silver-containing particles (A) can be sintered (sintered) by appropriate heat treatment to form a particle connection structure (sintered structure).

In particular, by containing silver-containing particles in the conductive resin composition (especially, by containing silver particles with a relatively small particle size and a relatively large specific surface area), even if heat treatment is performed at a relatively low temperature (about 180°C), it is easy to form Sintered structure. The preferred particle size will be described later.

The shape of silver-containing particles is not particularly limited, and known shapes such as spherical shape, tree shape, rope shape, scale shape, aggregate shape, and polyhedral shape can be mentioned. In this embodiment, one or more kinds of silver-containing particles of these shapes can be included. It is preferable to contain 2 or more types of silver particles. Thereby, electrical conductivity becomes more excellent.

In this embodiment, it is preferable to contain at least two kinds of silver-containing particles selected from spherical, scaly, aggregated, and polyhedral shapes. One or more silver-containing particles (a2) in a polyhedral shape and polyhedral shape are more preferable, and spherical silver-containing particles (a1) and scaly silver-containing particles (a2-1) are particularly preferable. Thereby, since the contact ratio of the silver-containing particles is further improved, it is easy to form a network after the sintering of the conductive resin composition, and the thermal conductivity and electrical conductivity are further improved.

When the silver-containing particle (A) contains the silver-containing particle (a2), it is possible to suppress resin cracking of a molded article obtained from the conductive resin composition, or to suppress the linear expansion coefficient. In addition, in this embodiment, the "spherical shape" is not limited to a perfect true sphere, but also includes a shape with some unevenness on the surface. The circularity is, for example, not less than 0.90, preferably not less than 0.92, more preferably not less than 0.94.

The surface of the silver-containing particles (A) may also be treated with organic compounds such as carboxylic acid, saturated fatty acid with 4-30 carbon atoms, unsaturated fatty acid with monovalent carbon number 4-30, and long-chain alkyl nitrile.

The silver-containing particles (A) may be (i) particles substantially composed of only silver, or (ii) particles composed of silver and components other than silver. In addition, (i) and (ii) may be used together as the metal-containing particles.

In this embodiment, the silver-coated resin particle which the surface of silver-containing particle (A) contains resin particle and silver-coated is especially preferable. Thereby, it is possible to prepare a conductive resin composition capable of obtaining a cured product that is more excellent in thermal conductivity and has a low storage elastic modulus.

The surface of the silver-coated resin particle is silver, and the inside is resin, so it is considered that the thermal conductivity is good, and it is softer than the particle composed only of silver. Therefore, it is considered that it is easy to design the thermal conductivity or the storage elastic modulus to an appropriate value by using the silver-coated resin particles.

Generally, in order to improve thermal conductivity, it may be considered to increase the amount of silver-containing particles. However, generally, since the metal is "hard", if the amount of silver-containing particles is too large, the modulus of elasticity after sintering may become too large. When some or all of the silver-containing particles are silver-coated resin particles, it is possible to easily design a conductive resin composition capable of obtaining a hardened product having a desired thermal conductivity or storage elastic modulus. In the silver-coated resin particle, the silver layer only needs to cover at least a part of the surface of the resin particle. Of course, silver may also cover the entire surface of the resin particles.

Specifically, in the silver-coated resin particles, the silver layer covers preferably 50% or more of the surface of the resin particles, more preferably 75% or more, still more preferably 90% or more. In silver-coated resin particles, it is particularly preferable that the silver layer covers substantially the entire surface of the resin particles. As another point of view, when the silver-coated resin particle is cut in a certain cross-section, it is preferable that the silver layer can be confirmed all around the cross-section.

As yet another viewpoint, 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.

Examples of the "resin" in silver-coated resin particles include silicone resins, (meth)acrylic resins, phenol resins, polystyrene resins, melamine resins, polyamide resins, and polytetrafluoroethylene resins. . Of course, other resins may also be used. Moreover, only 1 type may be sufficient as resin, and 2 or more types of resin may be used together. From the viewpoint of elastic properties and heat resistance, it is preferable that the resin is a silicone resin or a (meth)acrylic resin.

The polysiloxane resin may be particles composed of organopolysiloxane obtained by polymerizing organochlorosilanes such as methylchlorosilane, trimethyltrichlorosilane, and dimethyldichlorosilane . Also, it may be a polysiloxane resin having a structure obtained by further three-dimensionally crosslinking an organopolysiloxane as a basic skeleton.

The (meth)acrylic resin may be a resin obtained by polymerizing a monomer containing (meth)acrylate as a main component (at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight). Examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth) 2-ethylhexyl acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2-Propyl ester, Chloro-2-hydroxyethyl (meth)acrylate, Diethylene glycol mono(meth)acrylate, Methoxyethyl (meth)acrylate, Glycidyl (meth)acrylate , dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate are at least one compound. In addition, the monomer component of the acrylic resin may contain a small amount of other monomers. Examples of such other monomer components include styrene-based monomers. Regarding the silver-coated (meth)acrylic resin, the description in JP-A-2017-126463 and the like can also be referred to.

Various functional groups can be introduced into silicone resin or (meth)acrylic resin. The functional group that can be introduced is not particularly limited. For example, an epoxy group, an amino group, a methoxy group, a phenyl group, a carboxyl group, a hydroxyl group, an alkyl group, a vinyl group, a mercapto group etc. are mentioned.

The part of the resin particles in the silver-coated resin particles may contain various additive components such as a low stress modifier and the like. Examples of low stress modifiers include butadiene styrene rubber, butadiene acrylonitrile rubber, polyurethane (polyurethane) rubber, polyisoprene rubber, acrylic rubber, fluororubber, liquid organopolysiloxane, Liquid synthetic rubber such as liquid polybutadiene, etc. In particular, when the polysiloxane resin is contained in a part of the resin particles, the elastic properties of the silver-coated resin particles can be made better by containing the low stress modifier.

The shape of the resin particle portion in the silver-coated resin particle is not particularly limited. A combination of a spherical shape and a non-spherical shape such as a flat shape, a plate shape, and a needle shape is preferable.

The specific gravity of the silver-coated resin particles is not particularly limited, and the lower limit is, for example, 2 or more, preferably 2.5 or more, more preferably 3 or more. Also, the upper limit of the specific gravity is, for example, 10 or less, preferably 9 or less, more preferably 8 or less. It is preferable that the specific gravity is appropriate from the viewpoint of the dispersibility of the silver-coated resin particles themselves, or the uniformity when the silver-coated resin particles and other silver-containing particles are used together.

When silver-coated resin particles are used, the ratio of the silver-coated resin particles in the whole silver-containing particles (A) is preferably 1 to 50% by mass, more preferably 3 to 45% by mass, still more preferably 5% by mass. ~40% by mass. By appropriately adjusting this ratio, it is possible to further improve heat dissipation while suppressing a decrease in adhesive force due to thermal cycles.

By the way, when the ratio of the silver-coated resin particles in the whole silver-containing particles (A) is not 100% by mass, the silver-containing particles other than the silver-coated resin particles are, for example, particles composed substantially only of silver. .

The median diameter D ₅₀ of the silver-containing particles (A) is, for example, 0.01-50 μm, preferably 0.1-20 μm, more preferably 0.5-10 μm. By setting D ₅₀ to an appropriate value, it is easy to maintain a balance of thermal conductivity, sinterability, resistance to thermal cycles, and the like. Moreover, by making _D50 into an appropriate value, the workability improvement of coating/bonding, etc. may be aimed at. The particle size distribution of the silver-containing particles (horizontal axis: particle size, vertical axis: frequency) may be unimodal or multimodal.

From the viewpoint of the effects of the present invention, it is preferable that the silver-containing particles (A) contain spherical silver-containing particles (a1) and scaly silver-containing particles (a2-1). These silver-containing particles are more preferably silver particles substantially composed only of silver.

The median diameter D ₅₀ of the spherical silver-containing particles (a1) is, for example, 0.1 to 20 μm, preferably 0.5 to 10 μm, more preferably 0.5 to 5.0 μm. 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. The tap density of the spherical silver-containing particles (a1) is, for example, 1.5-6.0 g/cm ³ , preferably 2.5-5.8 g/cm ³ , more preferably 4.5-5.5 g/cm ³ . The circularity of the spherical silver-containing particles (a1) is, for example, 0.90 or more, preferably 0.92 or more, more preferably 0.94 or more. By satisfying these various characteristics, the balance of thermal conductivity, sinterability, resistance to thermal cycles, and the like is excellent.

The median diameter D ₅₀ of the scaly silver-containing particles (a2-1) is, for example, 0.1 to 20 μm, preferably 1.0 to 15 μm, more preferably 2.0 to 10 μm. The specific surface area of the scaly 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 1.2 m ² /g. The tap density of the scaly silver-containing particles (a2-1) is, for example, 1.5-6.0 g/cm ³ , preferably 2.5-5.9 g/cm ³ , more preferably 4.0-5.8 g/cm ³ . By satisfying these various characteristics, the balance of thermal conductivity, sinterability, resistance to thermal cycles, and the like is excellent.

In this embodiment, by combining spherical silver-containing particles (a1) satisfying at least one of the above-mentioned characteristics and scaly silver-containing particles (a2-1) satisfying at least one of the above-mentioned characteristics, thermal conductivity and electrical conductivity are improved. Especially improve.

The ratio (a1/a2-1) of the content of the spherical silver-containing particles (a1) to the content of the scaly silver-containing particles (a2-1) is preferably from 0.1 to 10, more preferably from 0.3 to 10. 5 or less, particularly preferably 0.5 or more and 3 or less. Thereby, since the contact ratio of the silver-containing particles is particularly increased, a network is easily formed after the sintering of the pasty polymerizable composition, and the thermal conductivity and 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 scaly 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. Thereby, since the spherical silver-containing particles are efficiently filled in the gaps between the scale-like silver-containing particles, the contact ratio of the silver-containing particles is particularly improved. Therefore, after sintering of the paste-like polymerizable composition It is easy to form a network, and the thermal conductivity and electrical conductivity are particularly improved.

The ratio (a1/a2-1) of the tap density of the spherical silver-containing particles (a1) to the tap density of the scaly silver-containing particles (a2-1) is preferably from 0.5 to 2.0, more preferably 0.7 or more and 1.2 or less. Thereby, since the filling rate of the silver-containing particles is increased, the contact ratio of the silver-containing particles is particularly increased, so that the network is easily formed after sintering of the paste-like polymerizable composition, and the thermal conductivity and electrical conductivity are particularly improved.

The median diameter D ₅₀ of the silver-coated resin particles is, for example, 5.0-25 μm, preferably 7.0-20 μm, more preferably 8.0-15 μm. Thereby, thermal conductivity can be further improved.

The median diameter D ₅₀ of the silver-containing particles (A) can be obtained, for example, by performing 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 wet measurement of the volume-based median diameter using this apparatus.

The ratio of the silver-containing particles (A) in the entire conductive resin composition is, for example, 1 to 98% by mass, preferably 30 to 96% by mass, more preferably 50 to 94% by mass. By setting the ratio of metal-containing particles to 1% by mass or more, it is easy to improve thermal conductivity. By making the ratio of silver-containing particle (A) into 98 mass % or less, the workability|operativity of coating/bonding can be improved.

Among the silver-containing particles (A), particles composed of substantially only silver can be obtained from, for example, DOWA HIGHTECH CO., LTD., Fukuda Metal Foil & Powder Co., Ltd., and the like. Moreover, the silver-coated resin particle can be acquired from Mitsubishi Materials Corporation, Sekisui Chemical Co., Ltd., Sanno Co., Ltd., etc., for example.

[(Meth)acrylic compound (B)] The (meth)acrylic compound (B) is not particularly limited, and examples thereof include monofunctional or bifunctional (meth)acrylic compounds, or trifunctional or higher polyfunctional (meth)acrylic compounds. In this embodiment, a (meth)acrylic compound means 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 acid groups. base.

In this embodiment, examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylic acid Isopropyl ester, Butyl (meth)acrylate, Isobutyl (meth)acrylate, Secondary butyl (meth)acrylate, Tertiary butyl (meth)acrylate, Butoxyethyl (meth)acrylate ester, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octylheptyl (meth)acrylate, (meth) Nonyl acrylate, Decyl (meth)acrylate, Undecyl (meth)acrylate, Lauryl (meth)acrylate, Tridecyl (meth)acrylate, Tetradecyl (meth)acrylate Pentadecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, (meth)acrylic acid 2 -Hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, phenoxy polyethylene glycol ( Aliphatic (meth)acrylates such as meth)acrylates; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, dicyclopentanyl (meth)acrylate, (meth)acrylic acid Dicyclopentenyl ester, isobornyl (meth)acrylate, 3-methyl-3-oxetanylmethyl (meth)acrylate, 1-adamantyl (meth)acrylate, etc. Alicyclic (meth)acrylates; Phenyl (meth)acrylate, nonylphenyl (meth)acrylate, p-cumylphenyl (meth)acrylate (meth)acrylate, o-biphenyl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy- 3-(o-phenylphenoxy)propyl (meth)acrylate, 2-hydroxy-3-(1-naphthyloxy)propyl (meth)acrylate, 2-hydroxy-3-(2- Aromatic (meth)acrylates such as naphthyloxy)propyl (meth)acrylate; 2-Tetrahydrofurfuryl (meth)acrylate, N-(meth)acryloxyethylhexahydrophthalimide, 2-(meth)acryloxyethyl-N- Heterocyclic (meth)acrylates such as carbazole.

Moreover, examples of bifunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate ester, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate base) 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 base) acrylate, 1,6-hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9-nonanediol Fats such as di(meth)acrylate, 1,10-decanediol di(meth)acrylate, glycerol di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate family of (meth)acrylates; Cyclohexane dimethanol (meth)acrylate, tricyclodecane dimethanol (meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, etc. Alicyclic (meth)acrylates; Bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate, bisphenol AF di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, fennel type Aromatic (meth)acrylates such as di(meth)acrylates; Heterocyclic (meth)acrylates such as isocyanuric acid di(meth)acrylate, etc.

Trimethylolpropane tri(meth)acrylate, neopentylthritol tri(meth)acrylate, ditrimethylolpropane Tetra(meth)acrylate, Neopentylthritol tetra(meth)acrylate, Dineopentaerythritol penta(meth)acrylate, Dineopentaerythritol hexa(meth)acrylate, Ethoxylated Aliphatic (meth)acrylates such as glycerol tri(meth)acrylate; heterocyclic (meth)acrylates such as isocyanuric acid tri(meth)acrylate, etc.

The (meth)acrylic compound (B) may contain at least 1 sort(s) selected from these, and may contain a monofunctional (meth)acrylate or a bifunctional (meth)acrylate.

From the viewpoint of the effects of the present invention, 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, More preferably, it is 1.0-10 mass %.

[Polyfunctional epoxy compound (C)] A polyfunctional epoxy compound (C) contains at least 1 sort(s) chosen from the compound represented by following General formula (1). The compound represented by the following general formula (1) contained in the polyfunctional epoxy compound (C) has a plurality of 2-6 valent organic groups bonded to groups containing epoxy groups, has excellent reactivity and is cross-linked Since the density is increased, the sintering of the silver-containing particles is promoted by curing shrinkage when the resin is obtained from this compound, and a high thermal conductivity material excellent in thermal conductivity can be obtained. Furthermore, since the obtained cured product (high thermal conductivity material) has a low modulus of elasticity and is excellent in flexibility, semiconductor devices and the like including the cured product have excellent product reliability due to stress relaxation. Furthermore, the obtained hardened|cured material (high thermal conductivity material) is also excellent in adhesiveness with a board|substrate etc., and it is excellent in product reliability. In other words, it is possible to provide a conductive resin composition with an excellent balance of these properties.

In the general formula (1), 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, and more preferably a hydroxyl group or an alkyl group having 1 carbon atoms. Plural R's 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 atoms. Plural Xs may be the same or different.

m represents an integer of 0-2, preferably 0 or 1. n represents an integer of 2-4, preferably 2 or 3. Q represents a 2-6 valent organic group.

As the divalent to hexavalent organic group in Q, known organic groups can be used within the range in which the effects of the present invention can be exhibited, and examples thereof include organic groups represented by the following general formulas (a) to (h).

Examples of compounds in which Q of the general formula (1) is an organic group of the general formula (a) include DENACOL EX-321 (manufactured by Nagase ChemteX Corporation), PETG (manufactured by Showa Denko K.K.), and the like. Examples of the compound in which Q of the general formula (1) is an organic group of the general formula (b) include CDMDG (manufactured by Showa Denko K.K.). Examples of the compound in which Q of the general formula (1) is an organic group of the general formula (c) include DENACOL EX-313 (manufactured by Nagase ChemteX Corporation) and the like. Examples of the compound in which Q of the general formula (1) is an organic group of the general formula (d) include DENACOL EX-810 (manufactured by Nagase ChemteX Corporation) and the like. In general formula (e), p represents the integer of 1-30, Preferably it is the integer of 10-25. Examples of the compound in which Q of the general formula (1) is an organic group of the general formula (e) include DENACOL EX-861 (manufactured by Nagase ChemteX Corporation) and the like.

In the general formula (f), Q ₁ and Q ₂ represent an alkylene group with 1 to 3 carbons or a cycloalkylene group with 3 to 8 carbons, preferably an alkylene group with 1 to 2 carbons Or a cycloalkylene group having 5 to 8 carbon atoms. R ¹ and R ² represent an alkylene group having 1 to 3 carbons, preferably an alkylene group having 1 to 2 carbons. Examples of compounds in which Q of the general formula (1) is an organic group of the general formula (f) include DENACOL EX-211 and EX-252 (manufactured by Nagase ChemteX Corporation) and the like. Examples of the compound in which Q of the general formula (1) is an organic group of the general formula (g) include DENACOL EX-512 (manufactured by Nagase ChemteX Corporation) and the like. Examples of the compound in which Q of the general formula (1) is an organic group of the general formula (h) include DENACOL EX-614B (manufactured by Nagase ChemteX Corporation) and the like. In the general formulas (a) to (h), * represents a bonding bond.

From the viewpoint of the effects of the present invention, the polyfunctional epoxy compound (C) contains at least one compound selected from the group consisting of organic groups represented by the general formulas (a), (b) and (c) above. Preferably, it contains at least one compound selected from the organic groups represented by the general formulas (a) and (b), more preferably contains at least one compound selected from the organic groups represented by the general formula (a). At least one type is further preferred.

The polyfunctional epoxy compound (C) is compound a (Q of general formula (1) is an organic group represented by general formula (a), and n is 3) and compound b (Q of general formula (1) is represented by In the case of a mixture of an organic group represented by general formula (a) and n is 2), the ratio of compound a to the total amount of compound a and compound b (a/(a+b)) can be set to 0.01 to 5 , preferably 0.05-3, more preferably 0.1-1.

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.

The (meth)acrylic compound (B) can contain 10-85 mass parts with respect to 100 mass parts of polyfunctional epoxy compounds (C), Preferably it is 15-60 mass parts, More preferably, it is 20-50 mass parts. In this embodiment, by using the polyfunctional epoxy compound (C) and the (meth)acrylic compound (B) in combination, the conductive resin composition further promotes the sintering of the silver-containing particles through hardening shrinkage, and can obtain heat conduction. High thermal conductivity material with better performance. Furthermore, since the obtained cured product (high thermal conductivity material) has a lower modulus of elasticity and is more excellent in flexibility, semiconductor devices and the like having the cured product are more excellent in product reliability due to stress relaxation. Furthermore, the obtained hardened|cured material (high thermal conductivity material) is also excellent in adhesiveness with a board|substrate etc., and it is excellent in product reliability. In other words, it is possible to provide a conductive resin composition with a better balance of these characteristics.

[Hardener (D)] The conductive resin composition of the present embodiment may further contain a curing agent (D). Examples of the curing agent (D) include a curing agent 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 hardeners are particularly preferred when the thermosetting component contains an epoxy group. The phenolic curing agent may be a low-molecular compound or a high-molecular compound (that is, a phenolic resin).

Examples of low-molecular compound phenolic hardeners include bisphenol compounds (phenol resins having a bisphenol F skeleton) such as bisphenol A and bisphenol F (dihydroxydiphenylmethane); 4,4'-bisphenol Compounds having a biphenylene skeleton, such as phenol, etc.

Specific examples of the phenolic resin include novolak-type phenolic resins such as phenol novolac resin, cresol novolac resin, bisphenol novolak resin, and phenol-biphenyl novolac resin; polyvinylphenol; triphenylmethane Polyfunctional phenol resins such as polyphenol resins; modified phenol resins such as terpene-modified phenol resins and dicyclopentadiene-modified phenol resins; phenol aralkyl groups with phenylene skeleton and/or biphenylene skeleton Resins, phenol aralkyl type phenol resins such as naphthol aralkyl resins having a phenylene and/or biphenylene skeleton, and the like. When using a hardening agent (D), only 1 type may be used, and 2 or more types may be used together.

In the case where the conductive resin composition of this embodiment contains the curing agent (D), when the amount of the polyfunctional epoxy compound (C) is 100 parts by mass, the amount is, for example, 10 to 120 parts by mass, which is relatively Preferably, it is 20-80 mass parts.

[Polymer (E) Containing Polyrotaxane] The conductive resin composition of this embodiment can further contain a polymer (E) containing a polyrotaxane.

A polyrotaxane generally includes a cyclic molecule forming an opening, a linear molecular chain penetrating the opening of the cyclic molecule, and end-capping groups respectively bonded to both ends of the linear molecular chain. The end-capping group prevents the cyclic molecule from detaching from the linear molecular chain. One linear molecular chain can pass through one or two or more openings of the cyclic molecule.

The cyclic molecule in the polyrotaxane is not particularly limited as long as it forms an opening through which a linear molecular chain can pass. As long as the linear molecular chain passing through the opening does not break away from the cyclic molecule, the ring may not be completely closed by a covalent bond.

Examples of cyclic molecules include cyclodextrins, crown ethers, benzocrowns, dibenzocrowns, dicyclohexylcrowns, and derivatives or modified forms thereof. Cyclic molecules are preferably cyclodextrins or their derivatives or modified bodies from the viewpoint of the occlusion energy of linear molecular chains.

When the cyclic molecule is cyclodextrin or their derivatives or modified products, it is preferable that some or all of the hydroxyl groups in the cyclodextrin are substituted with hydrophobic groups. By substituting the hydroxyl groups with hydrophobic groups, the solubility of polyrotaxanes in organic solvents is improved.

When the cyclic molecule is penetrated by the linear molecular chain, under the condition that the maximum amount of occlusion of the cyclic molecule by the linear molecular chain is set to 1, the relative amount of the occluded cyclic molecule (molar ratio ) 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 or less. By setting the occlusion amount of the cyclic molecule within the above range, it is easy to maintain the mobility of the cyclic molecule on the linear molecular chain.

The linear molecular chain in the polyrotaxane is a molecular chain that can pass through a cyclic molecule, and is not particularly limited as long as the cyclic molecule can move on the linear molecular chain. A linear molecular chain may have a branched or cyclic substituent, etc., as long as it substantially includes a linear portion. The length and molecular weight of the linear portion are not particularly limited.

Examples of linear molecular chains include alkylene chains, polyester chains, polyether chains, polyamide chains, and polyacrylate chains. Among them, from the viewpoint of the flexibility of the linear molecular chain itself, a polyester chain or a polyether chain is preferable, and a polyether chain is more preferable. As the polyether chain, polyethylene glycol chain (polyoxyethylene chain) and the like can be preferably mentioned.

The terminal capping group in the polyrotaxane is not particularly limited as long as it is a group arranged at both ends of the linear molecular chain and capable of maintaining a state in which the linear molecular chain penetrates the cyclic molecule. Examples of the end-blocking group include groups having a structure larger than the opening of the cyclic molecule, groups that cannot pass through the opening of the cyclic molecule due to ionic interaction, and the like. Specific examples of the end-blocking group include adamantyl groups, groups containing cyclodextrins, anthracenyl groups, terphenylenyl groups, pyrenyl groups, trityl groups, and their isomers and derivatives. .

In polyrotaxanes, the combination of cyclic molecules and linear molecular chains is preferably α-cyclodextrin or its derivatives as cyclic molecules and polyethylene glycol chains or its derivatives as linear molecular chains. combination of things. With this combination, the cyclic molecule moves easily on the linear molecular chain. In addition, this combination also has the advantage of being relatively easy to synthesize. The polyrotaxane preferably has a crosslinkable group. Since the polyrotaxane has a crosslinkable group, the thermosetting properties, adhesiveness, and the like of the conductive resin composition are improved.

When the polyrotaxane has a crosslinkable group, it is preferable that the cyclic molecule in the polyrotaxane has a crosslinkable group. Since the cyclic molecule has a crosslinkable group, even after the composition is thermally hardened (crosslinked), the state in which the cyclic molecule can slide along the linear molecular chain is maintained. Therefore, the flexibility and elongation property of the thermosetting film can be further improved.

The crosslinkable group is preferably a cationic crosslinkable group or a radical crosslinkable group, more preferably a radical crosslinkable group. The crosslinkable group is preferably a group containing an ethylenic carbon-carbon double bond such as a (meth)acryl group. As an aspect different from the (meth)acryl group, the crosslinkable group may contain an epoxy group and/or an oxetanyl group.

Polyrotaxanes may be synthesized by referring to known methods, or may be commercially available. Examples of commercially available products include "SeRM" (registered trademark, SeRM in the alphabet) series sold by ASM Inc. The conductive resin composition of this embodiment may contain only one type of polyrotaxane, or may contain two or more types.

The polymer (E) may contain known resins other than polyrotaxanes within the range in which the effects of the present invention are exhibited. Examples of such resins include silicone resins, (meth)acrylic resins, phenol resins, polystyrene resins, melamine resins, polyamide resins, and polytetrafluoroethylene resins.

In this embodiment, the content of the aforementioned 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. % by mass, particularly preferably 95% by mass to 100% by mass. By including the polyrotaxane in the above-mentioned amount in the polymer (E), the thermal conductivity and the storage modulus of elasticity are further improved, and the adhesiveness to the base material and the like is also further improved.

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.

[Organic solvent (F)] The conductive resin composition of this embodiment can further contain an organic solvent (F). Examples of the organic solvent (F) include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Alcohol 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, α-terpineol , β-terpineol, hexanediol, benzyl alcohol, 2-phenylethanol, isopalmityl alcohol, isostearyl alcohol, lauryl alcohol, ethylene glycol, propylene glycol, butylglycerol, glycerin and other alcohols; Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3,5 ,5-trimethyl-2-cyclohexen-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone) and other ketones; Ethyl acetate, Butyl acetate, Diethyl phthalate, Dibutyl phthalate, Acetyloxyethane, Methyl butyrate, Methyl caproate, Methyl caprylate, Methyl caprate, Methyl celluloid acetate, Ethylene glycol monobutyl ether acetate, Propylene glycol monomethyl ether acetate, 1,2-Diacetyloxyethane, Tributyl phosphate, Tricresyl phosphate, Tripentyl phosphate and other esters; Tetrahydrofuran, 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)ethyl ether Alkanes, 1,2-bis(2-methoxyethoxy)ethane and other ethers; Ester ethers such as 2-(2-butoxyethoxy)ethane acetic acid; 2-(2-methoxyethoxy)ethanol and other ether alcohols; Toluene, xylene, normal alkanes, isoalkanes, dodecylbenzene, turpentine, kerosene, light oil and other hydrocarbons; Nitriles such as acetonitrile or propionitrile; Amides such as acetamide and N,N-dimethylformamide; Low molecular weight volatile silicone oil, volatile organic modified silicone oil and other silicone oils; Monofunctional (meth)acrylic compounds, etc. When using an organic solvent (F), only 1 type of solvent may be used, and 2 or more types of solvents may be used together.

When using the organic solvent (F), the amount thereof is not particularly limited. What is necessary is just to adjust the usage-amount suitably according to desired fluidity etc. As an example, the organic solvent (F) is used in such an amount that the non-volatile matter concentration of the conductive resin composition is 50 to 95% by mass.

[hardening accelerator] The conductive resin composition of this embodiment can further contain a hardening accelerator. Hardening accelerators typically accelerate the reaction of the polyfunctional epoxy compound (C) with the hardener (D).

Examples of the hardening accelerator include, specifically, imidazole compounds, organic phosphines, tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds, etc. Phosphorous atom-containing compounds such as finished products; Amidines such as dimethylamine, tertiary amines; nitrogen atom-containing compounds such as amidines or quaternary ammonium salts of the above-mentioned tertiary amines, etc. When using a hardening accelerator, only 1 type may be used, and 2 or more types may be used together.

[Radical polymerization initiator] The conductive resin composition of this embodiment can further contain a hardening accelerator. By using the radical polymerization initiator, for example, insufficient curing can be suppressed, or the curing reaction can be sufficiently advanced at a relatively low temperature (for example, 180° C.), or the adhesive force can be further improved. As a radical polymerization initiator, a peroxide, an azo compound, etc. are mentioned.

Examples of peroxides include organic peroxides such as diacyl peroxides, dialkyl peroxides, and peroxyketals, and more specifically, methyl ethyl ketone peroxide and cyclohexanone peroxide. Peroxides such as ketone peroxides; Oxidized ketal; p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tertiary butyl hydroperoxide oxides and other hydroperoxides; Bis(2-tertiary butylperoxyisopropyl)benzene, diisophenylpropyl peroxide, 2,5-dimethyl-2,5-bis(tertiary butylperoxy)hexane, tri Grade butylisopropylphenyl peroxide, di-tertiary hexyl peroxide, 2,5-dimethyl-2,5-di(tertiary butylperoxy)hexyne-3, di-tertiary Grade butyl peroxide and other dialkyl peroxides; Dibenzoyl peroxide, di(4-methylbenzoyl) peroxide and other diacyl peroxides; Di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate and other peroxydicarbonates; 2,5-Dimethyl-2,5-bis(benzoylperoxy)hexane, tertiary hexylperoxybenzoate, tertiary butylperoxybenzoate, tertiary butylperoxybenzoate Peroxyesters such as oxy-2-ethylhexanoate, etc.

Examples of azo compounds include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile) ), 2,2'-azobis(2,4-dimethylvaleronitrile), etc. When using a radical polymerization initiator, only 1 type may be used, and 2 or more types may be used together.

[other ingredients] The conductive resin composition of this embodiment can contain a hardening accelerator, a silane coupling agent, a plasticizer, an adhesiveness imparting agent, etc. as other components.

The adhesive force can be further improved by containing a silane coupling agent, and the storage modulus of elasticity can be reduced by containing a plasticizer. In addition, it is easy to further suppress the decrease in adhesive force due to thermal cycles.

＜Conductive resin composition＞ The conductive resin composition of the present embodiment is preferably paste-like at 20°C. That is, it is preferable that the conductive resin composition (paste composition) of this embodiment can be applied to a substrate or the like at 20° C. like a paste. Thereby, the conductive resin composition of this embodiment can be used suitably as an adhesive agent of a semiconductor element, etc. Of course, according to the applied manufacturing process, etc., the conductive resin composition of this embodiment may also be in the form of a relatively low-viscosity varnish or the like. The conductive resin composition of the present embodiment can be obtained by mixing the above-mentioned components and other components as necessary by a conventionally known method.

＜High thermal conductivity material＞ A high thermal conductivity material can be obtained by sintering the conductive resin composition of this embodiment. By changing the shape of high thermal conductivity materials, it can be applied to various parts that require heat dissipation in the fields of automobiles and motors.

＜Semiconductor Devices＞ A semiconductor device can be manufactured using the conductive resin composition of this embodiment. For example, a semiconductor device can be manufactured by using the conductive resin composition of this embodiment as an "adhesive" between a base material and a semiconductor element.

In other words, the semiconductor device of the present embodiment includes, for example: a base material; and a semiconductor element on which an adhesive layer obtained by sintering the above-mentioned conductive resin composition by heat treatment is mounted on the base material.

In the semiconductor device of the present embodiment, the stress is relaxed, and furthermore, the adhesiveness of the adhesive layer and the like are less likely to be lowered even through a heat cycle. That is, the reliability of the semiconductor device of this embodiment is high. Examples of semiconductor elements include ICs, LSIs, semiconductor elements for electric power (power semiconductors), and various other elements. Examples of the substrate include various semiconductor wafers, lead frames, BGA substrates, mounting substrates, heat spreaders, heat sinks, and the like.

Hereinafter, an example of a semiconductor device will be described with reference to the drawings. 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 through an adhesive layer 10 (die attach material) which is a heat-treated body of a conductive resin composition.

The semiconductor element 20 and the base material 30 are electrically connected, for example, via a bonding wire 40 or the like. Also, the semiconductor element 20 is sealed with, for example, a sealing resin 50 .

The thickness of the subsequent layer 10 is preferably at least 5 μm, more preferably at least 10 μm, and still more preferably at least 20 μm. Thereby, the stress absorbing ability of the conductive resin composition can be improved, and the heat cycle resistance can be improved. The thickness of the subsequent layer 10 is, for example, less than 100 μm, preferably less than 50 μm.

In FIG. 1 , the substrate 30 is, for example, a lead frame. At this time, the semiconductor element 20 is mounted on a die pad 32 or a base material 30 via an adhesive layer 10 . Moreover, the semiconductor element 20 is electrically connected to the outer lead 34 (base material 30 ) via, for example, a bonding wire 40 . The base material 30 as a lead frame is made of, for example, a 42 alloy, a Cu frame, or the like.

The substrate 30 may be an organic substrate or a ceramic substrate. Examples of organic substrates include those made of epoxy resins, cyanate resins, maleimide resins, and the like. The surface of the substrate 30 may be coated with metal such as silver or gold, for example. Thereby, the adhesiveness of the adhesive layer 10 and the base material 30 is improved.

FIG. 2 is a cross-sectional view showing an example of a semiconductor device 100 different from FIG. 1 . In the semiconductor device 100 of FIG. 2 , the substrate 30 is, for example, an interposer. For example, a plurality of solder balls 52 are formed on the surface of the substrate 30 serving as an interposer, which is opposite to the surface on which the semiconductor element 20 is mounted. At this time, the semiconductor device 100 is connected to another wiring board via the solder balls 52 .

An example of a method of manufacturing a semiconductor device will be described. First, the conductive resin composition is coated on the substrate 30, 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 coating the conductive resin composition is not particularly limited. Specifically, a dispensing method (dispensing), a printing method, an inkjet method, etc. are mentioned.

Next, the conductive resin composition is thermally cured. Thermal hardening is preferably performed by pre-hardening and post-hardening. By thermosetting, the conductive resin composition becomes a heat-treated body (cured product). By thermosetting (heat treatment), the metal-containing particles in the conductive resin composition are aggregated to form a structure in which the interface between the plurality of metal-containing particles disappears in the adhesive layer 10 . Thereby, the base material 30 and the semiconductor element 20 are bonded via the bonding layer 10 . Next, the semiconductor element 20 is electrically connected to the base material 30 using the bonding wire 40 . Next, the semiconductor element 20 is sealed with a sealing resin 50 . In this way, a semiconductor device can be manufactured.

As mentioned above, although embodiment of this invention was described, these are only the example of this invention, and various structures other than the above can be employ|adopted. In addition, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope of achieving the object of the present invention are included in the present invention. [Example]

Hereinafter, the present invention will be described in further detail by way of examples, but the present invention is not limited thereto. The components used in the examples are as follows.

(Epoxy resin) ・Aliphatic polyfunctional epoxy compound 1: Trimethylolpropane polyglycidyl ether (mixture of compounds represented by the following chemical formula, DENACOL EX-321L, manufactured by Nagase ChemteX Corporation)

・Aliphatic polyfunctional epoxy compound 2: Epoxidation reaction product of neopentylitol tetraallyl ether and hydrogen peroxide (compound represented by the following chemical formula, Show free PETG, manufactured by SHOWA DENKO KK)

・Aliphatic polyfunctional epoxy compound 3: Epoxidation reaction product of neopentylitol tetraallyl ether and hydrogen peroxide (compound represented by the following chemical formula, Show free CDMDG, manufactured by SHOWA DENKO KK)

・Epoxy resin 4: Bisphenol F type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., RE-303S) ・Epoxy resin 5: Aminophenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER630)

((Meth)acrylic compound) • Acrylic monomer 1: Ethylene glycol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER EG) • Acrylic monomer 2: 1,4-cyclohexanedimethanol monoacrylate (manufactured by NIHONKASEI Co., Ltd., CHDMMA, monofunctional acrylic acid)

(polyrotaxane)

・Polyrotaxane 1: SA1305P-20: 50% by mass solution of ethyl acetate of polyrotaxane sold by ASM Inc. The cyclic molecule in the polyrotaxane contains acryl group, overall weight average molecular weight (representative value): 1 million, methacrylic acid equivalent (representative value): 1500g/eq

(hardener) • Hardener 1: Phenol resin having a bisphenol F skeleton (manufactured by DIC Corporation, DIC-BPF)

(radical polymerization initiator) • Radical polymerization initiator 1: dicumyl peroxide (manufactured by Kayaku Akzo Corporation, Perkadox BC)

(hardening accelerator) • Hardening accelerator 1: 2-phenyl-1H-imidazole-4,5-dimethanol (manufactured by Shikoku Chemicals Corporation., 2PHZ-PW)

(Contains silver particles) ・Silver filler 1: manufactured by DOWA Electronics Materials Co., Ltd., AG-DSB-114, spherical, D ₅₀ : 0.7μm, specific surface area: 1.05m ² /g, tap density 5.25g/ cm ³ , circularity: 0.953 ・Silver filler 2: manufactured by Fukuda Metal Foil & Powder Co., Ltd., HKD-12, scaly, median particle diameter D ₅₀ : 7.6 μm, specific surface area: 0.315 m ² /g , Tap density: 5.5g/cm ³

(solvent) ・Solvent 1: Tripropylene glycol mono-n-butyl ether (BFTG, manufactured by NIPPON NYUKAZAI CO., LTD., boiling point 274°C)

[Examples 1-8, Comparative Examples 1-2] According to the compounding quantity shown in Table 1, each raw material component was mixed, and the varnish was obtained. Next, using the obtained varnish, it blended in the compounding quantity shown in Table 1, and kneaded with the 3-roll mill at normal temperature. Thereby, a conductive resin composition was produced.

(volume resistivity) The conductive resin composition was coated on a glass plate, and the temperature was raised from 30° C. to 200° C. in a nitrogen atmosphere for 60 minutes, followed by heat treatment at 200° C. for 120 minutes. Thereby, 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 DC four-electrode method based on a milliohm meter (manufactured by HIOKI E.E. CORPORATION) with electrodes having an electrode interval of 40 mm.

(storage elastic modulus)

Using the heat-treated body of the conductive resin composition, it was cut into about 0.1 mm×about 10 mm×about 4 mm to obtain a strip-shaped sample for evaluation. Using this sample, the storage elastic modulus (E') at 25°C was measured by DMA (dynamic viscoelasticity measurement, tensile mode) at a heating rate of 5°C/min and a frequency of 10Hz.

(Evaluation of peeling after constant temperature moisture absorption treatment) A predetermined amount of the obtained conductive resin composition was coated on the plated Ag of the Ag-plated Cu lead frame, and an Au-coated chip on the back surface of 5×7 mm square was mounted on it so that the Au-coated surface was in contact with it. It was cured at 200° C. for 2 hours in a nitrogen atmosphere to produce a semiconductor device for evaluation. The presence or absence of delamination after treating the obtained semiconductor device under the conditions of a temperature of 60° C. and a humidity of 60% for 48 hours was evaluated using an ultrasonic testing machine (SAT). The device in which peeling was confirmed was marked as x, and the device that was not peeled was marked as 0.

(adhesion strength after constant temperature moisture absorption treatment) The semiconductor device for evaluation prepared above was treated for 48 hours under the conditions of a temperature of 60° C. and a humidity of 60% in the same manner as above, to obtain an evaluation sample. For the die adhesion strength, using a 4000 universal bonding tester (manufactured by Nordson Dage), the strength when shearing at a position of 50 μm from the lead frame at a tool speed of 500 μm/s while heating at 260° C. was taken as the die adhesion strength did an evaluation.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative example 1 Comparative example 2 Composition epoxy resin Aliphatic polyfunctional epoxy compound 1 parts by mass 50 34 50 50 50 Aliphatic polyfunctional epoxy compound 2 20 50 Aliphatic polyfunctional epoxy compound 3 30 50 epoxy compound 4 50 Epoxy compound 5 50 (meth)acrylic compounds Acrylic Monomer 1 20 20 20 20 20 Acrylic Monomer 2 20 10 20 20 20 polyrotaxane Polyrotaxane 1 10 hardener Hardener 1 20 20 20 20 20 20 20 20 20 20 Free Radical Polymerization Initiator Free radical polymerization initiator 1 3.5 1.2 1.2 1.2 1.2 1.2 1.2 1.2 2.5 2.5 hardening accelerator hardening accelerator 1 1 1 1 1 1 1 1 1 1 1 total parts by mass 94.5 92.2 92.2 92.2 92.2 92.2 92.2 92.2 93.5 93.5 conductive resin composition Composition The above composition parts by mass 10.6 10.6 10.6 10.6 10.6 10.6 10.6 10.6 10.6 10.6 silver particles Silver Filler 1 45 45 45 45 45 45 45 45 45 45 Silver filler 2 40 40 40 40 40 40 40 40 40 40 solvent Solvent 1 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 total parts by mass 100 100 100 100 100 100 100 100 100 100 volume resistivity μΩ･cm 8.9 8.6 7.1 8.6 8.3 8.6 13.3 9.8 10.8 20.2 Storage modulus of elasticity (E') GPa 16 15 15 14 15 15 18 13 20 18 Adhesive strength after constant temperature moisture absorption treatment N 54 56 67 83 78 - 73 54 33 twenty two Whether there is peeling after constant temperature moisture absorption treatment determination ○ ○ ○ ○ ○ ○ ○ ○ x x

From the results described in Table 1, it can be seen that the cured product obtained from the conductive resin composition containing a polyfunctional epoxy compound has a low volume resistivity and excellent thermal conductivity, and has a low storage elastic modulus and relaxed stress. After the constant temperature moisture absorption test, the adhesion strength is also high and peeling is also suppressed, so the reliability of semiconductor devices and the like having cured products is excellent, in other words, the balance of these characteristics is excellent.

This application claims priority based on Japanese Patent Application No. 2021-048261 filed on March 23, 2021 and Japanese Patent Application No. 2021-163521 filed on October 4, 2021, and the entire disclosure thereof is incorporated herein.

100: Semiconductor device 10: Next layer 20: Semiconductor components 30: Substrate 32: wafer pad 34: Outer lead 40: Bonding wire 50: sealing resin 52: solder ball

[ Fig. 1 ] is a cross-sectional view schematically showing an example of a semiconductor device. [ Fig. 2 ] is a cross-sectional view schematically showing an example of a semiconductor device.

10: Next layer

20: Semiconductor components

30: Substrate

32: wafer pad

34: Outer lead

40: Bonding wire

50: sealing resin

100: Semiconductor device

Claims (11)

A conductive resin composition comprising: (A) silver-containing particles; (B) a (meth)acrylic compound; and (C) at least one polyfunctional compound selected from compounds represented by the following general formula (1): epoxy compound,

In the general formula (1), R represents a hydroxyl group or an alkyl group with 1 to 3 carbons, and multiple Rs may be the same or different, Q represents a 2-6 valent organic group, and X represents an organic group with 1 to 3 carbons. In the alkylene group, plural Xs may be the same or different, m represents an integer of 0-2, and n represents an integer of 2-4. The conductive resin composition according to claim 1, wherein the polyfunctional epoxy compound (C) contains a compound selected from the general formula (1) in which the aforementioned Q is an organic group represented by the general formulas (a) to (h) at least 1 of them,

In the general formula (e), p represents an integer of 1 to 30. In the general formula (f), Q ₁ and Q ₂ represent an alkylene group with 1 to 3 carbons or a cycloalkylene group with 3 to 8 carbons. group), R ¹ and R ² represent an alkylene group having 1 to 3 carbon atoms, and in general formulas (a) to (h), * represents a bond. The conductive resin composition according to claim 1 or 2, wherein, A polyfunctional epoxy compound (C) contains at least 1 sort(s) chosen from the compound which said Q is an organic group represented by general formula (a), (b), and (c). The conductive resin composition according to claim 1 or 2, wherein, A polyfunctional epoxy compound (C) contains at least 1 sort(s) chosen from the compound which said Q is an organic group represented by general formula (a) and (b). The conductive resin composition according to claim 1 or 2, wherein, 10-85 mass parts of (meth)acrylic compounds (B) are contained with respect to 100 mass parts of polyfunctional epoxy compounds (C). The conductive resin composition according to claim 1 or 2, wherein, The silver-containing particles (A) contain two or more types of silver-containing particles selected from spherical, dendritic, rope-shaped, scaly, aggregated, and polyhedral-shaped silver-containing particles. The conductive resin composition according to claim 1 or 2, further comprising a hardener (D). The conductive resin composition according to claim 1 or 2, further comprising a polymer (E) containing polyrotaxane. The conductive resin composition according to claim 1 or 2, which further contains an organic solvent (F). A high thermal conductivity material obtained by sintering the conductive resin composition according to any one of claims 1 to 9. A semiconductor device comprising: substrate; and A semiconductor element mounted on the aforementioned substrate via an adhesive layer, The aforementioned adhesive layer is formed by sintering the conductive resin composition according to any one of claims 1 to 9.

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