WO2015093136A1

WO2015093136A1 - Resin paste composition and semiconductor device

Info

Publication number: WO2015093136A1
Application number: PCT/JP2014/077712
Authority: WO
Inventors: 愉加吏井上; 山田　和彦; 賢藤田
Original assignee: 日立化成株式会社
Priority date: 2013-12-16
Filing date: 2014-10-17
Publication date: 2015-06-25
Also published as: TWI640567B; JP6405867B2; JP2015135805A; TW201527389A; CN105814093A; CN105814093B

Abstract

The present invention is a resin paste composition which contains (A) a (meth)acrylic compound, (B) a binder resin, (C) an amine compound, (D) a polymerization initiator, (E) a flexibility-imparting agent, (F) a silver powder and (G) an aluminum powder. The silver powder (F) contains a silver powder (F-1) that is coated with stearic acid and has a tap density of 4.0 g/cm³ or less. The content of the silver powder (F) is 42% by mass or less, and the content of the silver powder (F-1) is 11% by mass or more. The mass ratio of the content of the aluminum powder (G) to the content of the silver powder (F) is 0.3-2.3. The present invention is able to provide a low-cost resin paste composition that exhibits excellent electrical conductivity, excellent thermal conductivity and excellent adhesiveness, while reducing the amount of silver used therein, which is rare and expensive. This resin paste composition is suitable for use in bonding of a conductor element such as a semiconductor chip with a supporting member such as a lead frame. The present invention is also able to provide a semiconductor device which uses this resin paste composition.

Description

Resin paste composition and semiconductor device

The present invention relates to a resin paste composition suitable for die bonding of semiconductor elements and a semiconductor device in which a semiconductor element is bonded to a support member using the resin paste.

Au-Si eutectic, solder, resin paste composition, and the like are known as die bonding materials used for semiconductor devices. Among these, resin paste compositions are widely used from the viewpoint of workability and cost.

Generally, a semiconductor device is manufactured by bonding a semiconductor element to a support member such as a lead frame using a die bonding material. The die bonding material is required to have high adhesive strength, but absorbs stress caused by the difference between the thermal expansion coefficient of the element and the thermal expansion coefficient of the support member in order to reduce the warpage of the support member to which the semiconductor device is bonded. Performance is also required. As a resin paste having high adhesive strength and the ability to absorb the stress, a hybrid resin resin paste composition of an epoxy resin and an acrylic resin has been proposed (for example, see Patent Document 1).

With high integration and miniaturization of semiconductor elements, semiconductor elements are required to have high reliability in characteristics such as electrical conductivity and thermal conductivity. Therefore, the resin paste composition used for the die bonding material is required to have high reliability in characteristics such as electrical conductivity and thermal conductivity in addition to the adhesive strength. In order to impart such performance to the resin paste composition, a conductive filler is added to the resin paste composition. As the conductive filler used in the resin paste composition, it is considered to use metal powder such as gold powder, silver powder, and copper powder, and silver powder is mainly used at present. Silver powder is not as rare as gold powder, it is easily oxidized like copper powder, is not inferior in storage stability, has further excellent workability and mechanical properties, and is required as a conductive filler for resin paste compositions. Various characteristics are also excellent.

However, although not as much as gold powder, silver powder is also a precious metal, a rare and expensive material. For this reason, as a conductive filler used in the resin paste composition, a combination of silver powder and another conductive filler that is more easily available and inexpensive has been developed.

Aluminum powder has been studied as another conductive filler to be used together with silver powder from the viewpoints of availability and low cost, and stability and conductivity (see, for example, Patent Document 2 and Patent Document 3). However, the metal-containing paste described in Patent Document 2 has a volume ratio of 5:95 to 40:60 between the metal powder of aluminum and the metal powder such as silver, so that the amount of the metal powder such as silver is sufficient. It cannot be said that it is decreasing. In the resin paste composition described in Patent Document 3, the mass ratio of aluminum powder and silver powder is 2/8 to 8/2. However, when the ratio of the silver powder in the conductive filler is extremely reduced, characteristics such as volume resistance and viscosity may be inferior to those of a conventional resin paste composition containing silver powder. Thus, the resin paste composition which reduced the ratio of the silver powder in an electroconductive filler and has the characteristic more than the conventional resin paste composition containing many silver powders is not obtained.

JP 2002-179769 A Japanese Patent Laid-Open No. 2005-197118 International Publication No. 2012/124527 Pamphlet

The present invention is suitably used for adhesion between a semiconductor element and a support member, and uses a resin paste composition having a small amount of silver used and having excellent electrical conductivity, thermal conductivity and adhesiveness, and the resin paste composition. An object is to provide a semiconductor device used.

As a result of intensive studies to solve the above problems, the present inventors have found that the problem can be solved by the following invention. That is, the present invention provides the following resin paste composition and a semiconductor device using the resin paste composition.

[1] (Meth) acrylic compound (A), binder resin (B), amine compound (C), polymerization initiator (D), flexible agent (E), silver powder (F) and aluminum powder (G) A resin paste composition comprising:
Silver powder (F) includes silver powder (F-1) coated with stearic acid and having a tap density of 4.0 g / cm ³ or less,
The content of the silver powder (F) is 42% by mass or less and the content of the silver powder (F-1) is 10% by mass or more with respect to the total mass of the components (A) to (G).
The resin paste composition has a mass ratio of aluminum powder (G) content / silver powder (F) content of 0.3 to 2.3.
[2] The resin paste composition according to [1], wherein the silver powder (F) is in the form of flakes having an average particle diameter of 1 to 15 μm.
[3] The resin paste composition according to [1], wherein the silver powder (F-1) is in the form of flakes having an average particle diameter of 1 to 15 μm.
[4] The resin paste composition according to any one of the above [1] to [3], wherein the aluminum powder (G) is granular with an average particle diameter of 1 to 6 μm.
[5] The resin paste composition according to any one of [1] to [4], wherein the (meth) acrylic compound (A) is a (meth) acrylic acid ester compound.
[6] The resin paste composition according to any one of [1] to [5], wherein the binder resin (B) is an epoxy resin.
[7] The resin paste composition according to any one of [1] to [6], wherein the amine compound (C) is at least one selected from a polyamine compound and an imidazole compound.
[8] The resin paste composition according to any one of [1] to [7], wherein the flexible agent (E) is a rubber compound.
[9] The resin paste composition according to any one of [1] to [8], further including a coupling agent (H).
[10] Any one of the above [1] to [9], further comprising at least one selected from the group consisting of oleic acid (I), stearic acid (J), lauric acid (K) and dispersant (L) The resin paste composition described in 1.
[11] A semiconductor device comprising a semiconductor element and a support member, wherein the semiconductor element is joined to the support member by a cured product of the resin paste composition according to any one of [1] to [10] .
[12] The semiconductor device according to [11], wherein the semiconductor element and at least a part of the support member are sealed with a sealant.

ADVANTAGE OF THE INVENTION According to this invention, it is used suitably for adhesion | attachment of a semiconductor element and a supporting member, The usage-amount of silver is small, The resin paste composition which was excellent in electrical conductivity, heat conductivity, and adhesiveness, and its resin paste composition A semiconductor device using an object can be provided.

FIGS. 1A to 1E are plan views for explaining a volume resistivity measuring method.

The resin paste composition of the present invention comprises (meth) acrylic compound (A), binder resin (B), amine compound (C), polymerization initiator (D), flexible agent (E), silver powder (F) and Contains aluminum powder (G). Hereinafter, the resin paste composition of the present invention will be described in detail.

[(Meth) acrylic compound (A)]
The (meth) acrylic compound (A) used in the present invention is not particularly limited as long as it is a compound having a (meth) acryloyl group. The (meth) acrylic compound (A) is excellent in electrical conductivity, adhesiveness and thermal conductivity when used in combination with specific silver powder (F) and aluminum powder (G), and is suitably used for die bonding. It is preferable that the resin paste composition which can be obtained is obtained. Moreover, it is preferable that a (meth) acrylic compound (A) can suppress isolation | separation with resin and fillers, such as silver powder and aluminum powder. From such a viewpoint, a preferable (meth) acrylic compound (A) is a (meth) acrylic acid ester compound having one or more (meth) acryloyloxy groups. Preferable (meth) acrylic acid ester compounds include, for example, compounds represented by the following general formulas (I) to (X). These may be used alone or in combination of two or more.

(In general formula (I), R ¹ represents hydrogen or a methyl group, and R ² represents a divalent aliphatic or cyclic hydrocarbon group having 1 to 100 carbon atoms, preferably 1 to 36 carbon atoms. )

(In general formula (II), R ¹ and R ² are the same as R ¹ and R ² above, respectively)

(In general formula (III), R ¹ is the same as R ¹ above, R ³ represents hydrogen, a methyl group or a phenoxymethyl group, R ⁴ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a phenyl group, Or represents a benzoyl group, and n represents an integer of 1 to 50)

(In the general formula (IV), R ¹ is the same as R ¹ above, R ⁵ represents a phenyl group, a cyano group, —Si (OR ⁶ ) ₃ (R ⁶ represents an alkyl group having 1 to 6 carbon atoms). Or a monovalent group represented by the following formula, m represents the number of 0, 1, 2, or 3)

(Wherein R ⁷ , R ⁸ and R ⁹ each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ¹⁰ represents hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group)

(In general formula (V), R ¹ and R ² are the same as R ¹ and R ² , respectively)

(In the general formula (VI), R ¹ , R ³ and n are the same as R ¹ , R ³ and n, respectively, provided that n is not 1 when R ³ is hydrogen or a methyl group).

(In general formula (VII), R ¹ is the same as R ¹ above, and R ¹¹ and R ¹² each independently represents hydrogen or a methyl group)

(In the general formula (VIII), R ¹ , R ¹¹ and R ¹² are the same as R ¹ , R ¹¹ and R ¹² , respectively, R ¹³ and R ¹⁴ each independently represent hydrogen or a methyl group; And q each independently represents an integer of 1 to 20)

(In the general formula (IX), R ¹ represents the above R ¹ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent hydrogen or a methyl group, and x represents an integer of 1 to 20)

(In general formula (X), R ¹ represents the above R ¹ , r, s, t and u are each independently a number of 0 or more indicating the average number of repetitions, and r + t is 0.1 or more, Preferably it is 0.3-5, and s + u is 1 or more, preferably 1-100)

Examples of the (meth) acrylic acid ester compound represented by the general formula (I) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl. (Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, hexadecyl (meth) acrylate, Lil (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclo [5.2.1.0 ^{2, 6]} decyl (meth) acrylate, 2- (tricyclo) [5.2.1.0 ^2,6 ] dec-3-en-8 or 9-yloxyethyl (meth) acrylate and the like. Among the (meth) acrylic acid ester compounds, a more preferred (meth) acrylic acid ester compound is ethyl acrylate.

Examples of the (meth) acrylic acid ester compound represented by the general formula (II) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and dimer diol mono (meth) acrylate. It is done.

Examples of the (meth) acrylic acid ester compound represented by the general formula (III) include diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) Acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-benzoyloxyethyl (meth) acrylate, and 2-hydroxy-3-pheno Shipuropiru (meth) acrylate. Among the (meth) acrylic acid ester compounds, a more preferred (meth) acrylic acid ester is 2-phenoxyethyl acrylate.

Examples of the (meth) acrylic acid ester compound represented by the general formula (IV) include benzyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, glycidyl (meta) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, tetrahydropyranyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidinyl ( (Meth) acrylate, 2,2,6,6-tetramethylpiperidinyl (meth) acrylate, (meth) acryloxyethyl phosphate, (meth) acryloxyethyl phenyl acid phosphate, β- (meth) acryloyloxyethyl hydrogen Examples thereof include phthalate, β- (meth) acryloyloxyethyl hydrogen succinate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. Among the (meth) acrylic acid ester compounds, a more preferred (meth) acrylic acid ester is dicyclopentenyloxyethyl acrylate.

Examples of the (meth) acrylic acid ester compound represented by the general formula (V) include ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth) ) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dimer diol di (meth) acrylate, and dimethylol tricyclode Examples include candi (meth) acrylate. Among the (meth) acrylic acid ester compounds, a more preferable (meth) acrylic acid ester is neopentyl glycol diacrylate.

Examples of the (meth) acrylic acid ester compound represented by the general formula (VI) include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di ( Examples include meth) acrylate, tripropylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. Among the (meth) acrylic acid ester compounds, a more preferable (meth) acrylic acid ester is polyethylene glycol diacrylate.

Examples of the (meth) acrylic acid ester compound represented by the general formula (VII) include a di (meth) acrylate compound obtained by reacting 1 mol of bisphenol A, bisphenol F or bisphenol AD with 2 mol of glycidyl (meth) acrylate, and the like. Is mentioned.

Examples of the (meth) acrylic acid ester compound represented by the general formula (VIII) include di (meth) acrylate compounds of polyethylene oxide adducts of bisphenol A, bisphenol F or bisphenol AD. Examples of the bisphenol A include ethoxylated bisphenol A, hydrogenated bisphenol A, and halogenated bisphenol A.

Examples of the (meth) acrylic acid ester compound represented by the general formula (IX) include bis ((meth) acryloxypropyl) polydimethylsiloxane and bis ((meth) acryloxypropyl) methylsiloxane-dimethylsiloxane copolymer. Etc.

The (meth) acrylic acid ester compound represented by the general formula (X) includes, for example, a reaction product obtained by reacting polybutadiene to which maleic anhydride is added and 2-hydroxyethyl (meth) acrylate, and hydrogen thereof. There are additives, for example, MM-1000-80, MAC-1000-80 (both are JX Nippon Mining & Energy Co., Ltd., trade name) and the like.

As the (meth) acrylic compound (A) used in the present invention, the above compound, preferably the above (meth) acrylic acid ester compound may be used alone or in combination of two or more.

Total mass of (meth) acrylic compound (A), binder resin (B), amine compound (C), polymerization initiator (D), flexible agent (E), silver powder (F) and aluminum powder (G) ( Hereinafter, the content of the (meth) acrylic compound (A) in the resin paste composition is preferably 18 to 24% by mass relative to the total mass of the components (A) to (G). More preferably, it is 19 to 23% by mass. When the content of the (meth) acrylic compound (A) is 18% by mass or more, high adhesive strength is exhibited, and when it is 24% by mass or less, high adhesive strength is maintained without generating voids during curing.

[Binder resin (B)]
Examples of the binder resin (B) used in the present invention include an epoxy resin, a silicone resin, a urethane resin, and an acrylic resin. Among these resins, when combined with the above (meth) acrylic compound (A), a preferable binder resin (B) is an epoxy resin from the viewpoint of excellent adhesiveness and suppression of separation between the resin and the filler. .

A preferred epoxy resin is an epoxy resin having two or more epoxy groups in one molecule. Examples of such epoxy resins include bisphenol A type epoxy resins (for example, AER-X8501 (Asahi Kasei Corporation, trade name), R-301 (Mitsubishi Chemical Corporation, trade name), YL-980 (Mitsubishi). Chemical Co., Ltd., trade name)), bisphenol F type epoxy resin (for example, YDF-170 (Toto Kasei Co., Ltd., trade name)), bisphenol AD type epoxy resin (for example, R-1710 (Mitsui Chemicals, Inc.) ), Phenol novolac type epoxy resin (eg, N-730S (DIC Corporation, trade name), Quatrex-2010 (Dow Chemical Co., trade name)), cresol novolac type epoxy resin (eg, N -665-EXP (DIC Corporation, trade name), YDCN-702S (Toto Kasei Co., trade name), EOCN-100 (Nippon Kayaku) Co., Ltd., trade name)), polyfunctional epoxy resin (for example, EPPN-501 (Nippon Kayaku Co., Ltd., trade name), TACTIX-742 (Dow Chemical Co., trade name), VG-3010 (Mitsui Chemicals, Inc.) Co., Ltd., trade name), 1032S (Mitsubishi Chemical Corporation, trade name)), epoxy resin having a naphthalene skeleton (for example, HP-4032 (DIC Corporation, trade name)), alicyclic epoxy resin (for example, , CEL-3000 (Daicel Corporation, trade name)), epoxidized polybutadiene (for example, PB-3600 (Daicel Corporation, trade name), E-1000-6.5 (JX Nippon Oil & Energy Corporation) ), Amine type epoxy resin (for example, ELM-100 (Sumitomo Chemical Co., Ltd., trade name), YH-434L (Toto Kasei Co., Ltd., trade name)), resorcinol type epoxy resin ( For example, Denacol EX-201 (Nagase ChemteX Corporation, trade name)), neopentyl glycol type epoxy resin (for example, Denacol EX-211 (Nagase ChemteX Corporation, trade name)), hexane diner glycol type Epoxy resin (for example, Denacol EX-212 (Nagase ChemteX Corporation, trade name)), ethylene / propylene glycol type epoxy resin (for example, Denacol EX-810, 811, 850, 851, 821, 830, 832, 841) 861 (Nagase ChemteX Corporation, trade name)), epoxy resin represented by the following general formula (XI) (for example, E-XL-24, E-XL-3L (Mitsui Chemicals, trade name) )) And the like.

(In general formula (XI), v represents an integer of 0 to 5)

Among these epoxy resins, more preferable epoxy resins are bisphenol F type epoxy resin, epoxidized polybutadiene, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. When these resins are used as the binder resin (B), they are excellent in electrical conductivity, adhesiveness and thermal conductivity, and are excellent in coating workability and mechanical properties, and can be more suitably used for die bonding. A paste composition can be obtained. Moreover, these epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

The number average molecular weight of the binder resin (B) used in the present invention, particularly an epoxy resin, is preferably 160 to 3000. The number average molecular weight is a value measured by gel permeation chromatography using a standard polystyrene calibration curve (hereinafter referred to as GPC method). When the number average molecular weight of the binder resin (B) is 160 or more, the resin paste composition has excellent adhesiveness, and when it is 3000 or less, the viscosity of the resin paste composition does not increase excessively and good workability is obtained. can get.

The epoxy equivalent of the epoxy resin used as the binder resin (B) is preferably 80 to 1000, more preferably 100 to 500. When the epoxy equivalent of the epoxy resin is 80 or more, the resin paste composition has excellent adhesiveness. It can suppress that unreacted hardened | cured material remains at the time of hardening of a resin paste composition as the epoxy equivalent of an epoxy resin is 1000 or less. Thereby, generation | occurrence | production of the outgas of the hardened | cured material of the resin paste composition produced with the heat history after hardening can be suppressed.

The content of the binder resin (B) in the resin paste composition with respect to the total mass of the components (A) to (G) is preferably 0.1 to 2.0% by mass, more preferably 0.00. It is 5 to 1.5% by mass. When the content of the binder resin (B) is 0.1% by mass or more, the resin paste composition has excellent adhesiveness, and when it is 2.0% by mass or less, the viscosity of the resin paste composition is excessively increased. Good workability can be obtained without any problems.

The epoxy resin used as the binder resin (B) may contain a monofunctional epoxy compound (reactive diluent) that is a compound having one epoxy group in one molecule. Examples of such monofunctional epoxy compounds include phenyl glycidyl ether (for example, PGE (Nippon Kayaku Co., Ltd., trade name)), alkylphenol monoglycidyl ether (for example, PP-101 (Toto Kasei Co., Ltd.), Name)), aliphatic monoglycidyl ether (eg (ED-502, ADEKA, trade name)), alkylphenol monoglycidyl ether (eg ED-509 (ADEKA, trade name)), alkylphenol mono Glycidyl ether (for example, YED-122 (Mitsubishi Chemical Corporation, trade name)), 3-glycidoxypropyltrimethoxysilane (for example, KBM-403 (Shin-Etsu Chemical Co., Ltd., trade name)), 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane 1- (3-glycidoxypropyl) -1,1,3,3,3-pentamethyldisiloxane (eg, TSL-8350, TSL-8355, TSL-9905 (all Momentive Performance Materials)・ Japan, trade name)), etc.

The monofunctional epoxy compound is used as long as the properties of the resin paste composition of the present invention are not impaired. The content of the monofunctional epoxy compound is preferably 10% by mass or less, more preferably 1 to 5% by mass with respect to the mass of the binder resin (B). When the content of the monofunctional epoxy compound in the binder resin (B) is 10% by mass or less, good workability can be obtained without excessive increase in the viscosity of the resin paste composition.

[Amine compound (C)]
The amine compound (C) used in the present invention functions as a curing agent for the binder resin (B) when the binder resin (B), particularly the binder resin (B) is an epoxy resin. Preferred amine compounds (C) include dicyandiamide and dibasic acid dihydrazide represented by the following general formula (XII) (for example, ADH, PDH, SDH (all from Nippon Finechem Co., Ltd., trade name)), epoxy resin A microcapsule type curing agent (for example, NOVACURE (Asahi Kasei Co., Ltd., trade name)), and diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, urea, urea Examples thereof include polyamine compounds such as derivatives and melamine.

(In the general formula (XII), R ¹⁹ represents a divalent aromatic group such as an m-phenylene group or a p-phenylene group, or a linear or branched alkylene group having 2 to 12 carbon atoms)

Other preferred amine compounds (C) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methyl- Examples include imidazole compounds such as 5-hydroxymethylimidazole.

The above amine compounds (C) may be used alone or in combination of two or more.

The compounding amount of the amine compound (C) is preferably 0.05 to 0.5% by mass, more preferably 0.1 to 0.5% by mass with respect to the total mass of the components (A) to (G). %. When the compounding amount of the amine compound (C) is 0.05% by mass or more, the curability of the resin paste composition is good, and when it is 0.5% by mass or less, the stability of the resin paste composition is good. .

[Polymerization initiator (D)]
A polymerization initiator (D) is used in order to accelerate | stimulate hardening of the resin paste composition of this invention. The polymerization initiator (D) is preferably a radical polymerization initiator. From the viewpoint of suppressing void formation during the curing of the resin paste composition, the radical polymerization initiator is preferably a peroxide radical polymerization initiator. Further, from the viewpoint of curability and viscosity stability of the resin paste composition, a preferable radical polymerization initiator is one having a decomposition temperature of 70 to 170 ° C. in a rapid heating test.

Preferred peroxide radical polymerization initiators used as the polymerization initiator (D) include, for example, 1,1,3,3-tetramethylperoxy 2-ethylhexanoate, 1,1-bis (t-butyl) Peroxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, di-t-butylperoxyisophthalate, t-butylperbenzoate, dicumyl peroxide, t-butylcumyl peroxide, 2, Examples include 5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, cumene hydroperoxide, and the like.

The blending amount of the polymerization initiator (D) is preferably 0.1 to 5% by mass, more preferably 0.6 to 3% by mass with respect to the total mass of the components (A) to (G). . When the blending amount of the polymerization initiator (D) is 0.1% by mass or more, the curability of the resin paste composition is not lowered, and the blending amount of the polymerization initiator (D) is 5% by mass or less. Then, the volatile content does not increase, and voids called voids are hardly generated in the cured product.

[Flexible agent (E)]
The flexible agent (E) is used for imparting flexibility to the cured product of the resin paste composition of the present invention. Preferable flexible agents (E) include, for example, rubber compounds and thermoplastic resins.

A preferable rubber-based compound used as the flexible agent (E) is preferably a butadiene-based rubber having a butadiene skeleton. Preferred butadiene rubbers include, for example, liquid rubbers such as epoxidized polybutadiene rubber, maleated polybutadiene, acrylonitrile butadiene rubber, carboxy terminal acrylonitrile butadiene rubber, amino terminal acrylonitrile butadiene rubber, vinyl terminal acrylonitrile butadiene rubber, and styrene butadiene rubber. Can be mentioned.

The number average molecular weight of the rubber compound used as the flexible agent (E) is preferably 500 to 10,000, more preferably 1,000 to 5,000. When the number average molecular weight of the rubber compound is 500 or more, good flexibility can be imparted to the cured product of the resin paste composition of the present invention, and when the number average molecular weight of the rubber compound is 10,000 or less, the resin. Good workability of the resin paste composition can be obtained without increasing the viscosity of the paste composition. The number average molecular weight is a value measured by the vapor pressure infiltration method or a value measured by the GPC method.

The blending amount of the flexible agent (E) is preferably 1 to 10% by mass, more preferably 6 to 10% by mass with respect to the total mass of the components (A) to (G). When the blending amount of the flexible agent (E) is 1% by mass or more, warpage of the cured product of the resin paste composition of the present invention can be reduced, and the blending amount of the flexible agent (E) is 10% by mass or less. When it exists, the favorable workability | operativity of a resin paste composition is obtained, without the viscosity of a resin paste composition increasing.

[Silver powder (F)]
Silver powder (F) imparts electrical conductivity and thermal conductivity to the resin paste composition of the present invention. The average particle diameter of the silver powder (F) is preferably 1 to 15 μm, more preferably 2 to 8 μm, and further preferably 3 to 6 μm. When the average particle diameter of the silver powder (F) is 1 to 15 μm, the silver powder in the resin paste composition is difficult to settle, and it is possible to suppress clogging in the needle when the resin paste composition is dispensed. In addition, the average particle diameter of silver powder (F) can be calculated | required as a median diameter with the particle size distribution measuring apparatus (for example, Microtrac X100, Nikkiso Co., Ltd.) using a laser beam diffraction method. The median diameter is a value of the particle diameter (D50) at which the cumulative ratio in the number-based particle size distribution is 50%.

The silver powder (F) preferably has a shape such as a granular shape, a flake shape, a spherical shape, a needle shape, and an irregular shape, and more preferably has a flake shape. When the silver powder (F) has a flaky shape, contact between individual silver powders easily occurs, and the electrical conductivity and thermal conductivity of the resin paste can be further increased. Moreover, the resin paste composition which was further excellent in electrical conductivity, adhesiveness, storage stability, coating workability | operativity, and mechanical characteristics can be obtained by using in combination with the below-mentioned aluminum powder (G).

Silver powder (F) is preferably coated with stearic acid. By coating the silver powder (F) with stearic acid, the viscosity of the resin paste composition can be stabilized for a long time. Furthermore, separation of the resin and the filler in the resin paste composition can be suppressed.

The content of silver powder (F) is 42% by mass or less, preferably 3 to 40% by mass, more preferably 10 to 40% by mass with respect to the total mass of components (A) to (G). is there. When the content of the silver powder (F) is 40% by mass or less, an inexpensive resin paste composition excellent in application workability and mechanical properties in addition to electric conductivity, thermal conductivity and adhesiveness can be obtained.

The BET specific surface area of the silver powder (F) is preferably 0.5 to 2.1 m ² / g. Here, the specific surface area of the silver powder (F) is a value measured by the BET method N ₂ gas adsorption one point method. When the BET specific surface area of the silver powder (F) is 0.5 to 2.1 m ² / g, the cured product of the resin paste composition having excellent electrical conductivity without excessively increasing the viscosity of the resin paste composition. Can be obtained.

Silver powder (F) contains silver powder (F-1) having a tap density of 4.0 g / cm ³ or less. Here, the tap density of the silver powder is a value obtained by measuring with a tap density measuring device according to JIS Z 2512. Specifically, 100 g of silver powder is gently dropped onto a 100 ml graduated cylinder using a funnel. Measure the volume of the compressed silver powder by dropping the cylinder 600 times at a drop distance of 20 mm and a speed of 60 times / minute by placing it on a tap density measuring device (model number: KRS-406, manufactured by Kuramochi Scientific Instruments). To do. The tap value calculated by dividing the mass of the silver powder by the volume of the compressed silver powder is the tap density. The tap density of the silver powder (F-1) is more preferably 1.0 to 4.0 g / cm ³ .

In the case where the tap density of the silver powder has a range of constant by variation of the measured values, when the range includes the value of 4.0 g / cm ^3, or, within the scope that range of 4.0 g / cm ³ or less The tap density of the silver powder is 4.0 g / cm ³ or less. Further, when the tap density of the silver powder has a certain range due to variations in the measured value, the range includes a value of 4.0 g / cm ^{3 and} a value of 1.0 g / cm ³ , or the range Is included in the range of 1.0 to 4.0 g / cm ³ , the tap density of the silver powder is assumed to be 1.0 to 4.0 g / cm ³ .

The average particle diameter of the silver powder (F-1) is preferably 1 to 15 μm, more preferably 2 to 8 μm, and further preferably 3 to 6 μm. When the average particle size of the silver powder (F-1) is 1 to 15 μm, it is difficult for the silver powder in the resin paste composition to settle, and the occurrence of clogging in the needle is suppressed when the resin paste composition is dispensed. it can. The average particle diameter of the silver powder (F-1) can be obtained as the median diameter with a particle size distribution measuring apparatus (for example, Microtrack X100) using a laser light diffraction method. The median diameter is a value of the particle diameter (D50) at which the cumulative ratio in the number-based particle size distribution is 50%.

The silver powder (F-1) preferably has a granular shape, a flake shape, a spherical shape, a needle shape, an irregular shape, or the like, and more preferably has a flake shape. When the silver powder (F-1) has a flaky shape, contact between the individual silver powders is likely to occur, and the electrical conductivity and thermal conductivity of the resin paste can be further increased. Moreover, the resin paste composition which was further excellent in electrical conductivity, adhesiveness, storage stability, coating workability | operativity, and mechanical characteristics can be obtained by using in combination with the below-mentioned aluminum powder (G).

Silver powder (F-1) is coated with stearic acid. By coating silver powder (F-1) with stearic acid, the viscosity of the resin paste composition can be stabilized for a long time. Furthermore, separation of the resin and the filler in the resin paste composition can be suppressed.

The silver powder (F) may further contain silver powder (F-2) having a tap density larger than 4.0 g / cm ³ . The tap density of the silver powder (F-2) is more preferably more than 4.0 g / cm ^{3 and not} more than 6.0 g / cm ³ .

To the total mass of (meth) acrylic compound (A), binder resin (B), amine compound (C), polymerization initiator (D), flexible agent (E), silver powder (F) and aluminum powder (G) On the other hand, the content of silver powder (F-1) is 10% by mass or more, preferably 10 to 40% by mass. When the content of the silver powder (F-1) is 10% by mass or more, excellent electrical conductivity is obtained, and the viscosity of the resin paste composition is increased with a small amount of silver powder, and good coating workability is obtained. .

[Aluminum powder (G)]
Aluminum powder (G) imparts excellent electrical conductivity, thermal conductivity, adhesiveness and viscosity stability to the resin paste composition of the present invention. Thereby, even if it reduces content of silver powder (F), the electrical conductivity and heat conductivity of a resin paste composition can be made high. And by containing aluminum powder (G), since content of silver powder (F) can be decreased, the resin paste composition of this invention can be made cheap.

The aluminum powder (G) preferably has an average particle diameter of 1 to 6 μm, more preferably 2 to 5 μm, and still more preferably 2 to 4 μm. When the average particle size of the aluminum powder (G) is 1 to 6 μm, it is possible to suppress a decrease in wet spreadability of the resin paste composition. Therefore, the semiconductor element is mounted on the support member using the resin paste composition. When the semiconductor element is tilted, it can be suppressed. In addition, the average particle diameter of aluminum powder (G) can be calculated | required as a median diameter with the particle size distribution measuring apparatus (for example, microtrack X100) using a laser beam diffraction method. The median diameter is a value of the particle diameter (D50) at which the cumulative ratio in the number-based particle size distribution is 50%.

Apparent density of aluminum powder (G) is preferably 0.40 ~ 1.20g / cm ^3, more preferably 0.55 ~ 1.00g / cm ^3.

The aluminum powder (G) preferably has a shape such as granular, flaky, spherical, acicular or irregular, and more preferably has a granular shape.

The value of content of aluminum powder (G) / content of silver powder (F) is 0.3 to 2.3, preferably 1.0 to 2.0 in terms of mass ratio. When the value of the content of the aluminum powder (G) / the content of the silver powder (F) is 0.3 to 2.3, the workability, electrical conductivity and adhesiveness of the resin paste composition can be further increased. it can.

[Coupling agent (H)]
The resin paste composition of the present invention may further contain a coupling agent (H). Thereby, the adhesiveness of the resin paste composition with respect to a supporting member further improves. Although there is no restriction | limiting in particular in the silane coupling agent (H) used for this invention, As a preferable coupling agent (H), a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate, for example And a coupling agent and a zircoaluminate coupling agent.

Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyl-tris (2- Methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, methyltri (methacryloxyethoxy) silane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- ( -Vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, 3- (4,5-dihydroimidazolyl) Propyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiisopro Penoxysilane, methyltriglycidoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, trimethylsilyl isocyanate, dimethylsilyl Isocyanate, phenyl triisocyanate, tetraisocyanate silane, methyl triisocyanate, and vinyl triisocyanate, and silane triisocyanate and the like. Among the above silane coupling agents, more preferable silane coupling agents are γ-glycidoxypropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane.

Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl Titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl (dioctyl phosphate) Taneto, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, and diisostearoyl ethylene titanate. Among the titanate coupling agents, more preferred titanate coupling agents are isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl trioctanoyl titanate, isopropyl tricumylphenyl titanate and isopropyl tri (N-aminoethyl). -Aminoethyl) isopropyl trititanate such as titanate.

The aluminum coupling agent is, for example, acetoalkoxyaluminum diisopropionate.

Zirconate coupling agents include, for example, tetrapropyl zirconate, tetrabutyl zirconate, tetra (triethanolamine) zirconate, tetraisopropyl zirconate, zirconium acetylacetonate, acetylacetone zirconium butyrate, and zirconium stearate butyrate. Is mentioned.

Examples of the zircoaluminate coupling agent include monoalkoxyzircoaluminate, trialkoxyzircoaluminate, and tetraalkoxyzircoaluminate.

Among the above silane coupling agents, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane are exemplified as monofunctional epoxy compounds (reactive diluents) that can be contained in an epoxy resin. It is. These compounds have both the function of a silane coupling agent and the function of a reactive diluent.

100 of the total of (meth) acrylic compound (A), binder resin (B), amine compound (C), polymerization initiator (D), flexible agent (E), silver powder (F) and aluminum powder (G) The blending amount of the coupling agent (H) is preferably 0.5 to 6.0 parts by mass, more preferably 1.0 to 5.0 parts by mass with respect to parts by mass. When the blending amount of the coupling agent (H) is 0.5 parts by mass or more, the adhesive strength of the resin paste composition is further improved, and when it is 6.0 parts by mass or less, the volatile content of the resin paste composition is increased. In other words, voids called voids are hardly generated in the cured product.

[Oleic acid (I), stearic acid (J), lauric acid (K), dispersant (L)]
The resin paste composition of the present invention may further include at least one selected from the group consisting of oleic acid (I), stearic acid (J), lauric acid (K), and dispersant (L). By adding at least one selected from the group consisting of oleic acid (I), stearic acid (J), lauric acid (K) and dispersant (L), only the resin component in the paste composition is separated. The phenomenon of bleeding on the substrate surface (bleed out) can be suppressed. At least one selected from the group consisting of oleic acid (I), stearic acid (J), lauric acid (K), and dispersant (L) is adsorbed on the surface of the filler, making it easy to wet the resin. By improving the dispersion of the filler, the separation of the resin is suppressed, and the bleed-out, which is a seepage of the resin, can be reduced. 100 of the total of (meth) acrylic compound (A), binder resin (B), amine compound (C), polymerization initiator (D), flexible agent (E), silver powder (F) and aluminum powder (G) The blending amount of at least one selected from the group consisting of oleic acid (I), stearic acid (J), lauric acid (K) and dispersant (L) is preferably 0.3 to 1.0 part by mass, and more preferably 0.5 to 1.0 part by mass. Resin of the present invention when the blending amount of at least one selected from the group consisting of oleic acid (I), stearic acid (J), lauric acid (K) and dispersant (L) is 0.3 parts by mass or more Bleed-out of the paste composition can be reduced, and when the amount of oleic acid is 1.0 part by mass or less, good workability of the resin paste composition can be obtained without the viscosity of the resin paste composition being too low. .

[Other ingredients]
If necessary, the resin paste composition of the present invention further includes a moisture absorbent such as calcium oxide and magnesium oxide, a wet surfactant such as a fluorosurfactant, a nonionic surfactant and a higher fatty acid, and a silicone oil. Various additives such as a foaming agent and an ion trapping agent such as an inorganic ion exchanger can be appropriately added singly or in combination of several kinds.

Moreover, the resin paste composition of the present invention may further contain conductive particles other than silver powder (F) and aluminum powder (G). As such conductive particles, conductive particles having an average particle diameter of less than 10 μm are preferable. Examples of the conductive particles include gold powder, copper powder, nickel powder, iron powder, and stainless steel powder.

[Resin paste composition]
The resin paste composition of the present invention can be produced, for example, as follows. Prepare the above-mentioned components constituting the resin paste of the present invention, and various additives to be added as desired, and batch or divide them into a stirrer, a hybrid mixer, a likai machine, a three roll, a planetary mixer The mixture is put into an apparatus capable of dispersing, stirring and kneading, and heated as necessary, and mixed, dissolved, granulated, kneaded and / or dispersed to produce a uniform paste-like composition. This composition is the resin paste composition of the present invention.

In the obtained resin paste composition, the amount of silver that is a rare and expensive material is reduced. Nevertheless, the resin paste composition is excellent in electrical conductivity, thermal conductivity and adhesiveness. Moreover, separation of the resin and filler in the resin paste composition is suppressed, and the resin and filler are rarely separated even if the resin paste composition is stored for a long period of time. The resin paste composition of the present invention is used, for example, as a resin paste composition for bonding semiconductor elements. More specifically, the resin paste composition of the present invention is suitably used for bonding a conductor element such as a semiconductor chip and a support member such as a lead frame.

[Semiconductor device]
The semiconductor device of the present invention includes a semiconductor element and a support member, and the semiconductor element is bonded to the support member by a cured product of the resin paste composition of the present invention. In the semiconductor device of the present invention, it is preferable that the semiconductor element and at least a part of the support member are sealed with a sealant.

Examples of the support member include a lead frame such as a copper lead frame, a glass epoxy substrate (a substrate made of glass fiber reinforced epoxy resin), and a BT substrate (a BT resin-use substrate made of cyanate monomer and its oligomer and bismaleimide). An organic substrate etc. are mentioned.

In the semiconductor device of the present invention, the semiconductor element and the support member are joined by the cured product of the resin paste composition of the present invention. In order to adhere the semiconductor element to a support member such as a lead frame, for example, a resin paste composition is applied onto the support member by a dispensing method, and then the semiconductor element is pressure-bonded, and then a heating device such as an oven or a heat block is used. By heating and curing. Next, a wire bonding process or the like is performed to obtain the semiconductor device of the present invention. Thereafter, the semiconductor element and at least a part of the support member may be further sealed with a sealant by a normal method.

The heat curing conditions of the resin paste composition are different for the case of long-time curing at a low temperature and the case of rapid curing at a high temperature. For example, in the case of rapid curing at a high temperature, the heat curing conditions for the resin paste composition are generally preferably 150 to 220 ° C., more preferably 180 to 200 ° C., and preferably 30 seconds to 2 hours, more preferably. Is a heating time of 10 minutes to 2 hours, more preferably 1 hour to 1 hour 30 minutes.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Evaluation methods)
The resin paste compositions of Examples and Comparative Examples were evaluated by the following evaluation methods.
(1) Measurement of viscosity, measurement of viscosity stability and evaluation of coating workability:
a) Measurement of viscosity Viscosity after 3 minutes of 0.5 rpm at 25 ° C. using the resin paste composition of each Example and Comparative Example using an EHD type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd., 3 ° cone). (Pa · s) was measured.
b) Measurement of viscosity stability The resin paste compositions of the examples and comparative examples were stored at 23 ° C. for 7 days and then EHD type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd., 3 ° cone) was used. The viscosity (Pa · s) after 3 minutes at 0.5 rpm at ℃ was measured.
c) Evaluation of coating workability When continuous hitting (4225 points) was performed with a dispenser (manufactured by Musashi Engineering Co., Ltd.), the state between the hitting points was visually confirmed and evaluated according to the following criteria.
A No 4225 points where stringing occurred B B2252 points where threading occurred 1-211 points C 4225 points where stringing occurred 2113-4225 points

(2) Measurement of shear adhesive strength About 0.5 mg of the resin paste composition of each example and comparative example was placed on a Ni / Au plated copper frame, an Ag ring plated copper lead frame, and an Ag spot plated copper lead frame. It is coated, and a 2 mm x 2 mm Si chip (thickness: about 0.4 mm) is pressure-bonded thereon. Further, the temperature is raised to 180 ° C in 30 minutes in an oven and heated at 180 ° C for 1 hour to cure the resin paste composition. It was. This was measured for shear adhesive strength (MPa) when held at 260 ° C. for 20 seconds using an automatic adhesive strength tester (BT4000, manufactured by Dage). In addition, about each Example and a comparative example, the shear bond strength was measured about ten test pieces, and the average value was made into the shear bond strength (MPa) of each Example and a comparative example.

(3) Measurement of volume resistivity The volume resistivity of the cured product of the resin paste composition was measured by the procedure shown in FIG. FIG. 1 is a plan view illustrating a method for measuring volume resistivity. Three paper tapes 2 (Nitto Denko CS System) on the surface of a slide glass 1 (manufactured by Tokyo Glass Equipment Co., Ltd., dimensions = 76 × 26 mm, thickness = 0.9 to 1.2 mm) (FIG. 1A) No.7210F, manufactured by Co., Ltd., dimension width = 18 mm, thickness = 0.10 mm) is attached in parallel with an interval between each other, thereby exposing the surface of the slide glass 1 between these three paper tapes 2. Two sections 1a (width 2 mm) were formed (FIG. 1B). The resin paste composition 3 was placed on these exposed portions 1a (FIG. 1 (c)) and stretched flat with another slide glass or the like (FIG. 1 (d)). Next, the paper tape 2 was peeled off, and heated in an oven at 200 ° C. for 1 hour to cure the resin paste composition, thereby obtaining two linear cured products 4 parallel to the surface of the slide glass 1 (see FIG. 1 (e)). The volume resistivity (Ω · cm) of these cured products 4 was measured at a temperature of 23 ° C. using a digital multimeter (TR6846, manufactured by ADVANTEST).

(4) Measurement of thermal conductivity Specific heat, specific gravity, and thermal diffusivity of the cured product obtained in the same manner as (3) above were measured under the following conditions. The thermal conductivity was determined by specific heat × specific gravity × thermal diffusivity.
a) Measurement of specific heat Specific heat was measured at a temperature of 25 ° C. using a specific heat measuring device: a differential scanning calorimeter (DSC manufactured by Parking-Elmer).
b) Measurement of specific gravity Specific gravity was measured at room temperature (Archimedes method) using a density meter (a density meter manufactured by Alpha Mirage).
c) Measurement of thermal diffusivity Thermal diffusivity: Thermal diffusivity was measured under the condition of temperature: 25 ° C. using a xenon flash analyzer (LFA447, manufactured by NETZSCH).

(5) Measurement of warpage About 0.5 mg of the resin paste composition of each example and comparative example was applied on a copper lead frame with Ag ring plating, and a 5 mm × 5 mm Si chip (thickness of about 0.00 mm) was formed thereon. 4 mm), and further heated to 180 ° C. in 30 minutes in an oven and heated at 180 ° C. for 1 hour to cure the resin paste composition. This was measured for warpage of the chip surface at a scanning distance of 6.5 mm using a specific contact film thickness meter (KS-1100, manufactured by Keyence Corporation). In addition, about each Example and the comparative example, the curvature of 10 test pieces was measured and the average value was made into the curvature of each Example and the comparative example.

(6) Measurement of bleed out About 0.5 mg of the resin paste composition of each example and comparative example was applied on a copper lead frame with Ag spot plating, stored at room temperature, and visually checked for bleed out after 10 minutes. confirmed.

Moreover, the silver powder used for the resin paste composition of an Example and a comparative example was evaluated with the following evaluation methods.
(7) Measurement of tap density The tap density of silver powder is a value obtained by measuring with a tap density measuring device in accordance with JIS Z 2512 (established in 2006). Specifically, 100 g of silver powder was measured and gently dropped into a 100 ml graduated cylinder with a funnel. The measuring cylinder was placed on a tap density measuring device, dropped 600 times at a falling distance of 20 mm and a speed of 60 times / minute, and the volume of the compressed silver powder was measured. The tap density was calculated by dividing the sample amount by the volume of the compressed silver powder.

(8) Measurement of average particle diameter Take 1 or 2 cups of silver powder with a microspatella, add about 60 ml of isopropyl alcohol, and disperse with an ultrasonic homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd., model number: US-150) for 1 minute. . This was continuously measured twice with a laser diffraction particle size analyzer (Microtrack, X100) at a measurement time of 30 seconds, and the average value of 50% cumulative diameter was defined as the average particle diameter.

(Production of resin paste compositions of Examples 1 to 14 and Comparative Examples 1 to 5)
Each material was mixed at the blending ratio shown in Tables 1 to 3 and kneaded using a planetary mixer (manufactured by PRIMIX Corporation, model number: TK HIVIS MIX 2P-06), and then 666. A defoaming treatment was performed at 61 Pa (5 Torr) or less for 10 minutes to obtain a resin paste composition. The properties (viscosity and viscosity stability, coating workability, shear adhesive strength, volume resistivity, etc.) of the obtained resin paste composition were examined by the method described above. The results are shown in Tables 1 to 3.

Abbreviations in Tables 1 to 3 are as follows.
(1) (A) (Meth) acrylic compound ((meth) acrylic ester compound)
SR-349 (product name of ethoxylated bisphenol A diacrylate, manufactured by Sartomer)
FA-512AS (product name of dicyclopentenyloxyethyl acrylate, manufactured by Hitachi Chemical Co., Ltd.)
FA-512M (product name of dicyclopentenyloxyethyl methacrylate, manufactured by Hitachi Chemical Co., Ltd.)
FA-513AS (manufactured by Hitachi Chemical Co., Ltd., trade name of dicyclopentanyl acrylate)
FA-513M (product name of dicyclopentanyl methacrylate, manufactured by Hitachi Chemical Co., Ltd.)
(2) (B) Binder resin N-665-EXP (product name of cresol novolac type epoxy resin manufactured by DIC Corporation, epoxy equivalent: 198-208)
(3) (C) Amine compound Dicy (manufactured by Mitsubishi Chemical Corporation, dicyandiamide)
(4) (D) Polymerization initiator Trigonox 22-70E (manufactured by Kayaku Akzo Co., Ltd., 1,1-bis (t-butylperoxy) cyclohexane, 10 hour half-life temperature: 91 ° C.)
(5) (E) Flexible agent Epolide PB-4700 (manufactured by Daicel Corporation, trade name of epoxidized polybutadiene, epoxy equivalent: 152.4 to 177.8, number average molecular weight = 3500)
(6) (F) Silver powder TC-20E-L (manufactured by Tokuru Honten Co., Ltd., shape: flake, average particle size: 3.5 to 5.5 μm, tap density: 3.0 to 4.0 g / cm ³ Specific surface area: 1.4 to 2.1 m ² / g, surface coating material: stearic acid)
TCG-11N (manufactured by Tokuru Honten Co., Ltd., shape: flake shape, average particle size: 4.5 to 6.5 μm, tap density: 3.9 to 4.5 g / cm ³ , specific surface area: 0.9 to 1 .2m ² / g, surface coating material: stearic acid)
TCG-1 (manufactured by Tokuroku Honten Co., Ltd., shape: flake shape, average particle size: 4.0 to 5.0 μm, tap density: 2.7 to 3.3 g / cm ³ , surface coating material: stearic acid)
TC-204B (manufactured by Tokuru Honten Co., Ltd., shape: flake shape, average particle diameter: 2.0 to 4.0 μm, tap density: 2.0 to 3.0 g / cm ³ , surface coating material: stearic acid)
TC-505CS (manufactured by Tokuru Honsha Co., Ltd., shape: flake shape, average particle size: 1.0 to 3.0 μm, tap density: 5.0 to 6.0 g / cm ³ , surface coating material: stearic acid)
TC-106 (manufactured by Tokuru Honten Co., Ltd., shape: flake shape, average particle size: 6.0 to 8.0 μm, tap density: 1.6 to 2.2 g / cm ³ , specific surface area: 0.8 to 2 .4m ² / g, surface coating material: oleic acid)
(7) (G) Aluminum powder 12-0086 (product name of aluminum powder manufactured by Toyo Aluminum Co., Ltd., shape: granular, average particle diameter: 3.5 to 4.2 μm)
(8) (H) Coupling agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd., γ-glycidoxypropyltrimethoxysilane)
(9) (I) oleic acid oleic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
(10) (J) Stearic acid powder stearic acid 300 (manufactured by Shin Nippon Rika Co., Ltd.)
(11) (K) Lauric acid Lauric acid (manufactured by Wako Pure Chemical Industries, Ltd.)
(12) (L) Dispersant Esliem AD-374M (polyalkylene glycol derivative) (manufactured by NOF Corporation)

As shown in Tables 1 and 2, it was confirmed that the resin paste composition of the present invention had good viscosity stability and excellent adhesive strength, electrical conductivity, and thermal conductivity. Thus, according to the resin paste composition of the present invention, a resin paste composition having good properties such as viscosity stability, adhesive strength and volume resistivity can be obtained without using a large amount of silver having a high rare value. It was confirmed that Moreover, the resin paste composition of this invention can suppress a bleed-out by containing a dispersing agent or a fatty acid.

According to the present invention, it is suitably used for adhesion between a conductor element such as a semiconductor chip and a support member such as a lead frame, while reducing the amount of silver used, which is a rare and expensive material, electric conductivity, An inexpensive resin paste composition that is excellent in thermal conductivity and adhesiveness and suppresses separation between the resin and the filler, and a semiconductor device using the resin paste composition are obtained.

DESCRIPTION OF SYMBOLS 1 Slide glass 1a Exposed part 2 Paper tape 3 Resin paste composition 4 Hardened | cured material

Claims

Resin containing (meth) acrylic compound (A), binder resin (B), amine compound (C), polymerization initiator (D), flexible agent (E), silver powder (F) and aluminum powder (G) A paste composition comprising:
The silver powder (F) includes silver powder (F-1) coated with stearic acid and having a tap density of 4.0 g / cm 3 or less.
The content of the silver powder (F) is 42% by mass or less with respect to the total mass of the components (A) to (G), and the content of the silver powder (F-1) is 10% by mass or more,
The resin paste composition having a mass ratio of the content of the aluminum powder (G) / the content of the silver powder (F) is 0.3 to 2.3.
The resin paste composition according to claim 1, wherein the silver powder (F) is in the form of flakes having an average particle diameter of 1 to 15 µm.
The resin paste composition according to claim 1, wherein the silver powder (F-1) is in the form of flakes having an average particle diameter of 1 to 15 µm.
The resin paste composition according to any one of claims 1 to 3, wherein the aluminum powder (G) is in the form of granules having an average particle diameter of 1 to 6 µm.
The resin paste composition according to any one of claims 1 to 4, wherein the (meth) acrylic compound (A) is a (meth) acrylic acid ester compound.
The resin paste composition according to any one of claims 1 to 5, wherein the binder resin (B) is an epoxy resin.
The resin paste composition according to any one of claims 1 to 6, wherein the amine compound (C) is at least one selected from a polyamine compound and an imidazole compound.
The resin paste composition according to any one of claims 1 to 7, wherein the flexible agent (E) is a rubber compound.
The resin paste composition according to any one of claims 1 to 8, further comprising a coupling agent (H).
The resin according to any one of claims 1 to 9, further comprising at least one selected from the group consisting of oleic acid (I), stearic acid (J), lauric acid (K), and dispersant (L). Paste composition.
A semiconductor device comprising a semiconductor element and a support member,
A semiconductor device in which the semiconductor element is bonded to the support member by a cured product of the resin paste composition according to any one of claims 1 to 10.
The semiconductor device according to claim 11, wherein the semiconductor element and at least a part of the support member are sealed with a sealant.