JP5625248B2 - Resin paste composition and semiconductor device - Google Patents

Description

  The present invention relates to a resin paste composition suitable for bonding a semiconductor element such as an IC or LSI to a lead frame, a glass epoxy wiring board or the like, and a semiconductor device using the resin paste composition.

Conventionally, Au-Si eutectic, solder, resin paste compositions, and the like are known as semiconductor die bonding materials, but resin paste compositions are widely used in terms of workability and cost.
In recent years, a lead frame called a pre-plating lead frame (hereinafter abbreviated as PPF) in which Ni-Pd-Au is plated on a copper lead frame in advance as a lead frame has been increasing from the viewpoint of simplifying the assembly process of a semiconductor package. However, the conventional acrylic resin / epoxy resin mixed paste (see, for example, Patent Document 1) has a low adhesive strength against the Au plating on the outermost surface of the PPF, and the semiconductor package is mounted on the substrate (reflow soldering). There is a problem that the resin paste layer is peeled off and the reliability of the semiconductor package (hereinafter referred to as “semiconductor device”) is lowered. Moreover, the resin paste of the resin described in Patent Document 1 has a disadvantage that the amount of outgas is large and the probability of wire bond failure is high.

JP 2002-179769 A

  When the resin paste of the resin described in Patent Document 1 is used, as a result of earnestly examining the cause of the increase in the outgas amount, it was found that the number average molecular weight of the epoxy resin contained in the resin paste is the main cause. It was. If the number average molecular weight of the epoxy resin is made larger, the outgas amount can be reduced. However, the viscosity of the resin paste increases accordingly, resulting in a problem that workability is lowered. As a method for controlling the viscosity of the resin paste, it is effective to add an organic solvent. However, when the organic solvent is contained, there is a concern that outgassing and wettability to the lead frame are inferior.

  The present invention is excellent in adhesive strength, can suppress outgassing, and can be adjusted in viscosity to improve workability. Particularly, even when PPF is used for the lead frame, the adhesive strength is large, and reflow is possible. It is an object of the present invention to provide a resin paste composition that can reduce the occurrence of peeling of a paste layer during soldering, and a semiconductor device that uses this and has high productivity and high reliability.

The above problems are solved by the present invention described below.
(1) (A) (meth) acrylic acid ester compound, (B) radical initiator, (C) epoxy resin having a number average molecular weight of 400 to 1000, (D) epoxy resin curing agent, and (E) inorganic filler A resin paste composition comprising:
A resin paste composition comprising a monofunctional (meth) acrylic acid ester compound represented by the following general formula (I) as the component (A).

(一般式（Ｉ）中、Ｒは水素原子又はメチル基を示し、Ｘは炭素数１〜５のアルキレン基を示し、Ｒ^１は、

を示し、ｎは０〜１０の整数である。)

(In general formula (I), R represents a hydrogen atom or a methyl group, X represents an alkylene group having 1 to 5 carbon atoms, and R ¹ represents

N is an integer of 0-10. )

(2) The resin paste composition according to (1), further including a monofunctional (meth) acrylic acid ester compound represented by the general formula (II) as the component (A).

(一般式（ＩＩ）中、Ｒは水素原子又はメチル基を示し、Ｙは炭素数１〜５のアルキレン基を示し、Ｒ^２〜Ｒ^６は炭素数１〜２０のアルキル基を示し、ｍは０〜１０の整数である。)

(In General Formula (II), R represents a hydrogen atom or a methyl group, Y represents an alkylene group having 1 to 5 carbon atoms, R ^{2 to} R ⁶ represent an alkyl group having 1 to 20 carbon atoms, and m represents (It is an integer from 0 to 10.)

(3) Furthermore, the resin paste composition as described in said (1) or (2) formed by adding a polyfunctional (meth) acrylic acid ester compound as said (A) component.

(4) The resin paste composition according to any one of (1) to (3), further comprising a flexible material.

(5) The resin paste composition according to (4), wherein the flexible material is a liquid rubber or a thermoplastic resin.

(6) The resin paste composition according to any one of (1) to (5), further comprising a coupling agent.

(7) A semiconductor device formed by bonding a semiconductor element to a support member using the resin paste composition according to any one of (1) to (6) and then sealing the semiconductor element.

According to the resin paste composition of the present invention, when used as a die bonding material of a semiconductor device, it is excellent in adhesive strength, can suppress the generation of outgas, and can adjust the viscosity to improve workability, In particular, even when PPF is used for the lead frame, the adhesive strength is high, and the occurrence of peeling of the paste layer during reflow soldering can be reduced.
Moreover, according to the semiconductor device of the present invention, a highly reliable semiconductor device with high productivity can be provided.

<Resin paste composition>
The resin paste composition of the present invention comprises (A) (meth) acrylic acid ester compound, (B) radical initiator, (C) an epoxy resin having a number average molecular weight of 400 to 1000, (D) an epoxy resin curing agent, And (E) a resin paste composition containing an inorganic filler, wherein the component (A) contains a monofunctional (meth) acrylic acid ester compound represented by the general formula (I). .
Here, “(meth) acrylic acid ester compound” means an acrylic acid ester compound or a methacrylic acid ester compound.
Hereinafter, the resin paste composition of the present invention will be described in detail.

[(A) (Meth) acrylic ester compound]
(Compound represented by formula (I))
The resin paste composition of the present invention contains a monofunctional (meth) acrylic acid ester compound represented by the following general formula (I) as the component (A). The resin paste composition of this invention can improve the adhesive force with respect to PPF by containing the (meth) acrylic acid ester compound represented by the said general formula (I), and prevents peeling of the resin paste layer. be able to.

(一般式（Ｉ）中、Ｒは水素原子又はメチル基を示し、Ｘは炭素数１〜５のアルキレン基を示し、Ｒ^１は

を示し、ｎは０〜１０の整数である)

(In general formula (I), R represents a hydrogen atom or a methyl group, X represents an alkylene group having 1 to 5 carbon atoms, and R ¹ represents

And n is an integer of 0 to 10)

  Examples of the (meth) acrylic acid ester compound represented by the general formula (I) include dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyloxyethyl acrylate, and dicyclopentanyloxyethyl methacrylate. , Dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, and the like. Dicyclopentenyl acrylate as FA-511A, dicyclopentenyloxyethyl acrylate as FA-512A, dicyclopentenyl acrylate as FA-513A, dicyclopentenyloxyethyl methacrylate as FA-512M, dicyclopentanyl methacrylate Are commercially available as FA-513M (all manufactured by Hitachi Chemical Co., Ltd.).

(Compound represented by formula (II))
Moreover, it is preferable that the monofunctional (meth) acrylic acid ester compound represented with the following general formula (II) is further included as (A) component from a viewpoint which can improve adhesive strength more.

(一般式（ＩＩ）中、Ｒは水素原子又はメチル基を示し、Ｙは炭素数１〜５のアルキレン基を示し、Ｒ^２〜Ｒ^６は炭素数１〜２０のアルキル基を示し、ｍは０〜１０の整数である)

(In General Formula (II), R represents a hydrogen atom or a methyl group, Y represents an alkylene group having 1 to 5 carbon atoms, R ^{2 to} R ⁶ represent an alkyl group having 1 to 20 carbon atoms, and m represents (It is an integer from 0 to 10)

  Examples of the (meth) acrylic acid ester compound represented by the general formula (II) include pentamethylpiperidyl methacrylate and tetramethylpiperidyl methacrylate. Pentamethylpiperidyl methacrylate is commercially available as FA-711MM, and tetramethylpiperidyl methacrylate is commercially available as FA-712HM (both manufactured by Hitachi Chemical Co., Ltd.).

In the resin paste composition of the present invention, a monofunctional (meth) acrylic acid ester compound other than the above general formula (I) and general formula (II) may be used in combination as the component (A).
Examples of monofunctional (meth) acrylic acid ester compounds other than the above general formula (I) and general formula (II) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t -Butyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, tridecyl acrylate, hexadecyl acrylate, stearyl acrylate, isostearyl Acrylate, cyclohexyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl Methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, isodecyl methacrylate , Lauryl methacrylate, tridecyl methacrylate, hexadecyl methacrylate, stearyl methacrylate, isostearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, dimer diol monoacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimer diol monomethacrylate, diethylene glycol acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, methoxydiethylene glycol acrylate, Methoxypolyethylene glycol acrylate, 2-phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxypolyethylene glycol acrylate, 2-benzoyloxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, diethylene glycol methacrylate, polyethylene glycol Coal methacrylate, polypropylene glycol methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, 2-phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxypolyethylene glycol methacrylate, 2 -Benzoyloxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, benzyl acrylate, 2-cyanoethyl acrylate, γ-acryloxypropyltrimethoxysilane, glycidyl acrylate, tetrahydrofurfuryl acrylate, tetrahydropyranyl acrylate , Dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acryloxyethyl phosphate, acryloxyethyl phenyl acid phosphate, β-acryloyloxyethyl hydrogen phthalate, β-acryloyloxyethyl hydrogen succinate, benzyl methacrylate, 2-cyanoethyl methacrylate, γ-methacryloxypropyltrimethoxysilane, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydropyranyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacryloxyethyl phosphate, methacryloxyethyl phenyl acid phosphate, β-methacryloyloxyethyl hydrogen lid Over DOO, beta-methacryloyloxyethyl hydrogen succinate, and the like.

(Polyfunctional (meth) acrylic acid ester compound)
Moreover, it is preferable that the resin paste composition of this invention contains a polyfunctional (meth) acrylic acid ester compound further as (A) component. The polyfunctional compound preferably includes a compound having two acryloyloxy groups or methacryloyloxy groups in one molecule. By including the compound, it is possible to reduce the generation of bubbles in the resin paste that causes a decrease in reflow resistance during thermosetting.

  Examples of the compound having two acryloyloxy groups or methacryloyloxy groups in one molecule include ethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and 1,9-nonane. Diacrylate compounds such as diol diacrylate, 1,3-butanediol diacrylate, neopentyl glycol diacrylate, dimer diol diacrylate, dimethylol tricyclodecane diacrylate; ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol dimethacrylate, dimer Dimethacrylate compounds such as all dimethacrylate, dimethylol tricyclodecane dimethacrylate; diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, etc. Dimethacrylate compounds; diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, etc .; bisphenol A, bisphenol F or bi Reaction product of 1 mol of phenol AD and 2 mol of glycidyl acrylate; reaction product of 1 mol of bisphenol A, bisphenol F or bisphenol AD and 2 mol of glycidyl methacrylate; A, diacrylate of polypropylene oxide adduct of bisphenol F or bisphenol AD; dimethacrylate of polyethylene oxide adduct of bisphenol A, bisphenol F or bisphenol AD; dimethacrylate of polypropylene oxide adduct of bisphenol A, bisphenol F or bisphenol AD; Bis (acryloxypropyl) polydimethylsiloxane, bis (acryloxypro) Pyr) methylsiloxane-dimethylsiloxane copolymer, bis (methacryloxypropyl) polydimethylsiloxane, bis (methacryloxypropyl) methylsiloxane-dimethylsiloxane copolymer, and the like.

  Among these (meth) acrylic acid ester compounds having two acryloyloxy groups or methacryloyloxy groups in one molecule, adhesion to PPF can be improved and peeling of the resin paste layer can be prevented. From the viewpoint that it can be used, it is preferable to use a compound represented by the following general formula (III).

（一般式（ＩＩＩ）中、Ｒは水素原子又はメチル基を示し、Ｒ^６〜Ｒ^７はそれぞれ独立に水素原子又はメチル基を示し、Ｚ^１及びＺ^２はそれぞれ独立に炭素数１〜５のアルキレン基を示し、ｐ及びｑはそれぞれ独立に１〜２０の整数を示す。）

(In the general formula (III), R represents a hydrogen atom or a methyl group, R ^{6 to} R ⁷ each independently represents a hydrogen atom or a methyl group, and Z ¹ and Z ² each independently represent 1 to 5 carbon atoms. An alkylene group, and p and q each independently represent an integer of 1 to 20.)

  As the polyfunctional (meth) acrylic acid ester compound, a compound having three or more acryloyloxy groups or methacryloyloxy groups in one molecule can be used.

  Examples of the compound having three or more acryloyloxy groups or methacryloyloxy groups in one molecule include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, and ethylene oxide. Propylene oxide modified trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, ethylene oxide modified trimethylolpropane Trimethacrylate, propire Examples include oxide-modified trimethylolpropane trimethacrylate, ethylene oxide / propylene oxide-modified trimethylolpropane trimethacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, pentaerythritol trimethacrylate, etc. It is done.

  (A) As a (meth) acrylic acid ester compound of a component, said monofunctional thing and polyfunctional thing can be used individually or in combination of 2 or more types.

The content of the monofunctional (meth) acrylic acid ester compound as the component (A) is preferably 10 to 80% by weight, and preferably 25 to 75% by weight, based on the total amount of the total solid content excluding the (E) inorganic filler. More preferred is 40 to 70% by weight. When the content is 10 to 80% by weight, sufficient adhesive strength can be obtained with respect to Ni—Pd—Au plating, the volatile content is small, and voids called voids are hardly generated in the cured product.
In particular, in the present invention, the content of the compound represented by the general formula (I) which is an essential component in the component (A) is preferably 40% by weight or more in the component (A).

[(B) Radical initiator]
The radical initiator of the component (B) used in the present invention is not particularly limited, but a peroxide is preferable from the viewpoint of suppressing generation of voids and the like, and the curability and viscosity stability of the resin paste composition. Therefore, it is preferable that the decomposition temperature of the peroxide in the rapid heating test is 70 to 170 ° C.

  Specific examples of the (B) component radical initiator include 1,1,3,3-tetramethylperoxy 2-ethylhexanoate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1 -Bis (t-butylperoxy) cyclododecane, di-t-butylperoxyisophthalate, t-butylperbenzoate, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5- Examples include di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, cumene hydroperoxide, and the like.

  The content of the radical initiator (B) is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 10% by weight, based on the total amount of the total solid content excluding (E) the inorganic filler. When the blending ratio is 0.1 to 20% by weight, the curability is excellent, shrinkage at the time of curing is small, and the occurrence of warpage of the semiconductor element can be suppressed. .

[(C) Epoxy resin having a number average molecular weight of 400 to 1000]
As an epoxy resin whose number average molecular weight of (C) component used for this invention is 400-1000, phenol novolak type epoxy resin [N-730S, N-740 (Dainippon Ink Chemical Co., Ltd., brand name) ), Cresol novolac type epoxy resin [YDCN-700-7, N-665-EXP (Toto Kasei Co., Ltd., trade name), EOCN-100 (Nippon Kayaku Co., Ltd., trade name)], polyfunctional epoxy resin [EPPN-501 (Nippon Kayaku Co., Ltd., trade name), TACTIX-742 (Dow Chemical Co., trade name), VG-3010 (Mitsui Chemicals, trade name), 1032S (Oilized Shell Epoxy ( Co., Ltd., trade name)], epoxy resin having a naphthalene skeleton [HP-4032 (Dainippon Ink Chemical Co., Ltd., trade name)], YH-434L (Tohto Kasei) Co., Ltd.), trade name)] and the like. Among these, novolac type epoxy resins are preferable. 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 is in the range of 400 to 1000, but is more preferably 500 to 800 from the viewpoint of suppression of outgas and workability.
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). The content of the epoxy resin as the component (C) is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, and more preferably 3 to 10% by weight based on the total amount of the total solid content excluding the (E) inorganic filler. Particularly preferred. When the content is 1 to 30% by weight, sufficient adhesive strength can be obtained, and since the viscosity is low, the workability during production and the coating workability during use are excellent.

[(D) Epoxy resin curing agent]
The epoxy resin curing agent used as the component (D) of the present invention is not particularly limited, but dicyandiamide, represented by the following general formula (IV)

（一般式（ＩＶ）中、Ｒ^８はｍ−フェニレン基、ｐ−フェニレン基等の２価の芳香族基、炭素数２〜１２の直鎖又は分岐鎖のアルキレン基を示す）で表される二塩基酸ジヒドラジド［ＡＤＨ、ＰＤＨ、ＳＤＨ（いずれも日本ヒドラジン工業（株）、商品名）］、エポキシ樹脂とアミン化合物の反応物からなるマイクロカプセル型硬化剤［ノバキュア（旭化成工業（株）、商品名）］等が挙げられる。

(In the general formula (IV), R ⁸ 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). Dibasic acid dihydrazide [ADH, PDH, SDH (Nippon Hydrazine Kogyo Co., Ltd., trade name)], microcapsule type curing agent consisting of a reaction product of epoxy resin and amine compound [Novacure (Asahi Kasei Kogyo Co., Ltd., product) Name)] and the like.

  Moreover, these epoxy resin hardening | curing agents may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the epoxy resin curing agent as component (D) is preferably 0.1 to 50% by weight, more preferably 1 to 20% by weight, based on the epoxy resin. When the content of the epoxy resin curing agent is 0.1 to 50% by weight, the curability and the viscosity stability of the resin paste composition are excellent.

  Furthermore, a curing accelerator can be added to the resin paste composition of the present invention as necessary. Examples of the curing accelerator include organic boron salt compounds [EMZ · K, TPPK (trade name, manufactured by Hokuko Chemical Co., Ltd.)], tertiary amines or salts thereof [DBU, U-CAT102, 106, 830, 840. , 5002 (both are trade names of San Apro Co., Ltd.), etc.] and imidazoles [Cureazole, 2P4MHZ, C17Z, 2PZ-OK (both are trade names of Shikoku Kasei Co., Ltd.)] and the like. In general, the amount of the curing accelerator is preferably 20 parts by weight or less based on the epoxy resin. The hardening accelerator added as needed may be used individually by 1 type, and may be used in combination of multiple types of hardening accelerator suitably.

[(E) Inorganic filler]
The inorganic filler of the component (E) used in the present invention is not particularly limited as long as the number average particle diameter is less than 10 μm, and various types can be used. For example, gold, silver, copper, nickel, iron, aluminum , Powders of stainless steel, silicon oxide, boron nitride, aluminum oxide, aluminum borate, aluminum nitride, silicon nitride, silicon carbide and the like. When the number average particle size of the filler is less than 10 μm, the paste uniformity and various physical properties can be maintained. The preferred number average particle diameter is 0.5 to 7 μm, and more preferably 0.8 to 5 μm. Examples of the shape include a scale shape, a spherical shape, a block shape, a dendritic shape, and a plate shape, and a scale shape and a spherical shape are preferable.

  (E) Although content of the inorganic filler of a component is not specifically limited, 20 to 90 weight% is preferable with respect to the resin paste composition total amount, and 40 to 85 weight% is more preferable. When the content is 20 to 90% by weight, sufficient adhesive strength can be obtained when heated, and since the viscosity is low, the workability during production and the coating workability during use are excellent.

[Flexible material]
Although there is no restriction | limiting in particular in the flexible material used for the resin paste composition of this invention, It is preferable to use liquid rubber or a thermoplastic resin. Each will be described below.

(Liquid rubber)
Examples of the liquid rubber include liquid rubbers such as polybutadiene, epoxidized butadiene, maleated polybutadiene, acrylonitrile butadiene rubber, acrylonitrile butadiene rubber having a carboxy group, amino terminal acrylonitrile butadiene rubber, vinyl terminal acrylonitrile butadiene rubber, and styrene butadiene rubber. It is done.

Among these flexible materials, epoxidized polybutadiene or acrylonitrile butadiene rubber having a carboxy group is preferable from the viewpoint of further reducing the elastic modulus of the cured resin paste.
The epoxidized polybutadiene can be easily obtained by epoxidizing a commercially available polybutadiene with a hydrogen peroxide solution and peracids.

Examples of the epoxidized polybutadiene include B-1000, B-3000, G-1000, G-3000 (manufactured by Nippon Soda Co., Ltd.), B-1000, B-2000, B-3000, B-4000 ( (Nippon Oil Co., Ltd.), R-15HT, R-45HT, R-45M (Idemitsu Oil Co., Ltd.), Epolide PB-3600, Epolide PB-4700 (Made by Daicel Chemical Industries), etc. Is commercially available.
The oxirane oxygen concentration of the epoxidized polybutadiene is preferably 3% to 18%, and more preferably 5% to 15%.

  Further, from the viewpoint of further improving the adhesive strength, acrylonitrile butadiene rubber having a carboxy group is more preferable. As the acrylonitrile butadiene rubber having a carboxy group, a compound represented by the general formula (V) is particularly preferable.

〔一般式（Ｖ）中、ｘ／ｙは９５／５〜５０／５０であり、ｎは５〜５０の整数である。〕

[In general formula (V), x / y is 95 / 5-50 / 50, and n is an integer of 5-50. ]

  Examples of the butadiene-acrylonitrile copolymer having a carboxyl group represented by the general formula (V) include Hycar CTBN-2009 × 162, CTBN-1300 × 31, CTBN-1300 × 8, CTBN-1300 × 13, CTBN-1009SP-S and CTBNX-1300 × 9 (both manufactured by Ube Industries, Ltd.) are available as commercial products.

  From the viewpoint of workability and adhesive strength, it is preferable to use epoxidized polybutadiene and acrylonitrile butadiene rubber having a carboxy group in combination.

The liquid rubber preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. When the number average molecular weight is within the range, a sufficient flexibility effect is obtained, and the viscosity of the resin paste composition is not increased and the workability is excellent.
The number average molecular weight is a value measured by the GPC method. The thermoplastic resin preferably has a number average molecular weight of 10,000 to 300,000, more preferably 20,000 to 200,000.

(Thermoplastic resin)
Examples of the thermoplastic resin include polyvinyl acetate, polymethyl acrylate, ε-caprolactone-modified polyester, phenoxy resin, polyimide, and thermoplastic resins such as a copolymer represented by the following general formula (VI). It is done.

〔一般式（ＶＩ）中、Ｒ^１はそれぞれ独立に水素原子又はメチル基であり、ｒ、ｓ、ｔ及びｕはそれぞれ独立に繰り返し数の平均値を示す０以上の数であり、ｒ＋ｔは０．１以上、好ましくは０．３〜５であり、ｓ＋ｕは１以上、好ましくは１〜１００である。〕

[In General Formula (VI), R ¹ is each independently a hydrogen atom or a methyl group, 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 0.1 or more, preferably 0.3 to 5, and s + u is 1 or more, preferably 1 to 100. ]

  As content of a flexible material, it is preferable to use 5 to 50 weight% with respect to the total amount of the total solid except (E) inorganic filler, It is more preferable to use 10 to 40 weight%, and 20 to 20 weight% is preferable. It is particularly preferable to use 30% by weight. When this content is 5 to 50% by weight, a sufficient flexibility effect can be obtained, and since the viscosity is low, the application workability of the resin paste composition is excellent.

[Coupling agent]
A coupling agent can be added to the resin paste composition of the present invention. The coupling agent used in the present invention is not particularly limited, and various types such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, and a zircoaluminate coupling agent. Is used.

  Specific examples of the 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- (N- Nylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, 3- (4,5-dihydroimidazolyl) propyl Triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiisopropeno Xysilane, methyltriglycidoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, trimethylsilyl isocyanate, dimethylsilyliso Silane coupling agents such as anate, phenylsilyl triisocyanate, tetraisocyanate silane, methylsilyl triisocyanate, vinylsilyl triisocyanate, ethoxysilane triisocyanate, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyro) Phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (Dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ) Ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethylaminoethyl) titanate, dicumylphenyloxyacetate titanate, Titanate coupling agents such as diisostearoylethylene titanate, aluminum coupling agents such as acetoalkoxyaluminum diisopropionate, tetrapropyl zirconate, tetrabutyl zirconate, tetra (triethanolamine) zirconate, tetraisopropyl zirconate , Zirconium acetylacetonate acetylacetone zirconium butyrate, There are zirconate-based coupling agents such as stearic acid zirconium butyrate.

  The content of the coupling agent is preferably from 0.1 to 20% by weight, more preferably from 0.5 to 10% by weight, more preferably from 1 to 6% by weight based on the total amount of the total solid content excluding (E) the inorganic filler. Is particularly preferred. When the content is 0.1 to 20% by weight, the effect of improving the adhesive strength is obtained, and the volatile content is small, and the generation of voids in the cured product is suppressed.

[Other additive components]
If necessary, the resin paste composition of the present invention further includes a moisture absorbent such as calcium oxide and magnesium oxide, a fluorosurfactant, a nonionic surfactant, a wetting improver such as a higher fatty acid, and a silicone oil. Solvents for viscosity adjustment, such as foaming agents and ion trapping agents such as inorganic ion exchangers, can be added as appropriate, alone or in combination of several kinds. In addition, when adding a solvent, it is preferable to set it as 3 weight% or less with respect to the total amount of a resin paste composition from the point of a void.

In order to produce the resin paste composition of the present invention, (A) a compound represented by the general formula (I), (B) a radical initiator, (C) an epoxy resin having a number average molecular weight of 400 to 1000, ( D) Epoxy resin curing agent, (E) Inorganic filler, together with various additives used as needed, or batch or divided to disperse / dissolve equipment such as stirrer, lyric apparatus, three rolls, planetary mixer, etc. What is necessary is just to put into the apparatus combined suitably and to heat and mix, melt | dissolve, pulverize knead | mix, or disperse | distribute as needed, and you may make it a uniform paste form.
The viscosity (25 ° C.) of the resin paste of the present invention is preferably 30 to 100 Pa · s, more preferably 40 to 90 Pa · s, and 50 to 80 Pa · s from the viewpoint of workability. Is particularly preferred.

<Semiconductor device>
The semiconductor device of the present invention is characterized in that a semiconductor element is bonded to a support member using the above resin paste composition of the present invention and then sealed.
As support members, for example, lead frames such as 42 alloy lead frames and copper lead frames, glass epoxy substrates (substrates made of glass fiber reinforced epoxy resin), BT substrates (cyanate monomers and their oligomers and BT resins made of bismaleimide) Organic substrate such as a substrate).

  In order to adhere a semiconductor element to a support member such as a lead frame using the resin paste composition of the present invention, first, after applying the resin paste composition on the support member by a dispensing method, a screen printing method, a stamping method, It can be performed by pressure-bonding the semiconductor element and then heat-curing using a heating device such as an oven or a heat block. Furthermore, it can be set as the completed semiconductor device by sealing by a normal method after passing through a wire bond process.

  The heat curing is different depending on the case of long-time curing at a low temperature or the case of rapid curing at a high temperature, but is usually 100 to 300 ° C, preferably 130 to 220 ° C, preferably 5 seconds to 3 hours, preferably It is preferable to carry out for 15 seconds to 1 hour.

  Since the semiconductor device of the present invention obtained as described above uses the resin paste composition of the present invention described above, it is possible to reduce defects during wire bonding and to improve the adhesion strength to PPF, Since the occurrence of peeling of the paste layer during reflow soldering can be reduced, the reliability of the semiconductor device can be improved.

  EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not restrict | limited by this.

First, the compounds used in Examples and Comparative Examples are exemplified below.
(1) Acrylic ester compound / FA-512A (dicyclopentenyloxyethyl acrylate, manufactured by Hitachi Chemical Co., Ltd., trade name, compound represented by the following structure)

・ FA-711MM (Pentamethylpiperidyl methacrylate, manufactured by Hitachi Chemical Co., Ltd., trade name, compound represented by the following structure)

・ FA-513A (Dicyclopentanyl acrylate, Hitachi Chemical Co., Ltd., trade name, compound represented by the following structure)

SR-339A (2-phenoxyethyl acrylate, manufactured by Sartomer, trade name, compound represented by the following structure)

・ Lauryl acrylate (compound represented by the following structure)

SR-349 (EO modified bisphenol A diacrylate, manufactured by Sartomer, trade name, compound represented by the following structure)

(2) Radical initiator, dicumyl peroxide (3) Epoxy resin, N-665-EXP (trade name, cresol novolac type epoxy resin, epoxy equivalent = 200, number average molecular weight = 600, manufactured by Toto Kasei Co., Ltd.)
YDF-170 (manufactured by Toto Kasei Co., Ltd., trade name, bisphenol F type epoxy resin, epoxy equivalent = 170, number average molecular weight = 340)
Epicoat 1055 (manufactured by Japan Epoxy Resin Co., Ltd., trade name, bisphenol A type epoxy resin, epoxy equivalent = 800, number average molecular weight = 1600)
(4) Epoxy resin curing agent, dicyandiamide (5) flexible material, CTBN 1300 × 31 (trade name of carboxyl group-containing acrylonitrile polybutadiene copolymer, number average molecular weight: 3500, acrylonitrile content: manufactured by Ube Industries, Ltd. 10% by weight)
PB-4700 (trade name of epoxidized polybutadiene manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent = 152.4 to 177.8, number average molecular weight = 3500)
(6) Coupling agent γ-glycidoxypropyltrimethoxysilane (7) Filler AgC-239 (trade name and shape of silver powder manufactured by Fukuda Metal Foil Industry Co., Ltd.)
SF-65LV (trade name of silver powder manufactured by Ferro Japan, shape: scale-like)

  In each Example / Comparative Example, the above materials were mixed at the blending ratio shown in Table 1 and kneaded using three rolls, and then defoamed for 10 minutes at 666.61 Pa (5 Torr) or less. The resin paste compositions of the examples and comparative examples were obtained. The characteristics (viscosity, adhesive strength, outgas amount, reflow resistance) of these resin paste compositions were examined by the following methods. The results are shown in Table 1.

(1) Viscosity: Viscosity (Pa · s) at 25 ° C. and 0.5 rpm was measured using an EHD type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.).
(2) Adhesive strength: about 0.2 mg of the resin paste composition is applied on PPF (Ni-Pd-Au plated copper lead frame), and a 2 mm × 2 mm Si chip (thickness: about 0.4 mm) is formed thereon. Then, the temperature was increased in an oven to 180 ° C. in 30 minutes and cured at 180 ° C. for 1 hour. This was measured for room-temperature shear adhesive strength (kgf / chip) using an automatic adhesive strength tester (BT100, manufactured by Dage). The adhesive strength was measured for 20 test pieces.
(3) Outgas amount: A resin paste composition of 30 mm × 30 mm × 0.2 mm was applied on a silicon wafer, heated in an oven to 180 ° C. in 30 minutes, and cured at 180 ° C. for 1 hour. A spacer having a thickness of 0.4 mm was placed around the cured product, and a glass plate (40 mm × 40 mm × 0.2 mm) was placed thereon. Subsequently, the weight change of the glass plate after this sample was left on a hot plate at 240 ° C. for 30 minutes was measured. And the amount of outgas was computed by the following formula | equation. In the following formula, “weight of the cured resin paste” is a weight after curing at 180 ° C. for 1 hour and before leaving at 240 ° C. for 30 minutes.
Outgas amount (wt%) =
(Increase in weight of glass plate after heat treatment / weight of cured resin paste) × 100
(4) Reflow resistance: Using the resin paste compositions obtained in Examples and Comparative Examples, the following lead frame and Si chip were cured and bonded under the following curing conditions. Thereafter, it was sealed with an epoxy sealing material (trade name CEL-4620) manufactured by Hitachi Chemical Co., Ltd. to obtain a solder reflow test package. The package was moisture-absorbed for 96 hours in a constant temperature and high humidity bath set at 85 ° C. and 85% humidity, respectively. Thereafter, solder reflow was performed under a reflow condition of 260 ° C./10 seconds, and the number of occurrences of peeling of the paste layer inside the package was observed with a scanning ultrasonic microscope. The number of samples in which peeling occurred for 10 samples is shown.
Chip size: 4.9mm x 9.5mm
Package size: 8mm x 18mm x 2.7mm
Support member: PPF (Ni-Pd-Au plated copper lead frame)
Curing conditions: temperature rise to 180 ° C in 30 minutes, cure at 180 ° C for 1 hour

  From the results shown in Table 1, the resin paste compositions of the present invention (Examples 1 to 4) have higher adhesive strength than the conventional resin paste compositions (Comparative Examples 1 and 5), excellent reflow resistance, and outgas. The amount is also small. Moreover, compared with the conventional resin paste composition (Comparative Examples 2 and 4), the adhesive strength is high and the reflow resistance is excellent. Further, the amount of outgas is small as compared with the conventional resin paste composition (Comparative Example 3). From this, according to the resin paste composition of the present invention, it is possible to reduce the amount of outgas at the time of wire bonding, and further reduce the occurrence of peeling of the paste layer during reflow soldering by improving the adhesive strength to PPF. It was confirmed that it was possible.

Claims (6)

(A) (meth) acrylic acid ester compound, (B) a peroxide having a decomposition temperature in a rapid heating test of 70 to 170 ° C., (C) an epoxy resin having a number average molecular weight of 400 to 1000, (D) A resin paste composition comprising dicyandiamide and (E) an inorganic filler,
As the component (A), (A1) a polyfunctional (meth) acrylate compound represented by the following general formula (III) and (A2) a (meth) acrylate compound other than (A1) Including
The component (A2) contains a monofunctional (meth) acrylic acid ester compound represented by the following general formula (I):
Said component (A1), the (E) 4/25 × 100 ~12 / 25 × that it contains 100% by weight relative to the total amount of the total solid content excluding the inorganic filler,
The component (A2) is the (E) 2/25 × 100 ~12 / 25 × that it contains 100% by weight relative to the total amount of the total solid content excluding the inorganic filler,
The (B) component, the (E) that it contains 0.1 to 20% by weight relative to the total amount of the total solid content excluding the inorganic filler,
The component (C), wherein (E) that it contains 1 to 30 wt% based on the total amount of the total solids excluding inorganic filler,
The component (D) is contained in an amount of 1 to 20% by weight based on the component (C); and
The component (E) is contained in an amount of 40 to 85% by weight based on the total amount of the resin paste composition;
A resin paste composition characterized by the above.

(In general formula (I), R represents a hydrogen atom or a methyl group, X represents an alkylene group having 1 to 5 carbon atoms, and R ¹ represents

N is an integer of 0-10. )

(In the general formula (III), R represents a hydrogen atom or a methyl group, R ^{6 to} R ⁷ each independently represents a hydrogen atom or a methyl group, and Z ¹ and Z ² each independently represent 1 to 5 carbon atoms. An alkylene group, and p and q each independently represent an integer of 1 to 20.) The resin paste composition according to claim 1, further comprising a monofunctional (meth) acrylic acid ester compound represented by the general formula (II) as the component ( A2 ).

(In General Formula (II), R represents a hydrogen atom or a methyl group, Y represents an alkylene group having 1 to 5 carbon atoms, R ^{2 to} R ⁶ represent an alkyl group having 1 to 20 carbon atoms, and m represents (It is an integer from 0 to 10.) Furthermore, the resin paste composition of Claim 1 or 2 formed by adding a flexible material. The resin paste composition according to claim 3 , wherein the flexible material is a liquid rubber or a thermoplastic resin. Furthermore, the resin paste composition of any one of Claims 1-4 formed by adding a coupling agent. After bonding the semiconductor element to a supporting member by using a resin paste composition according to any one of claims 1 to 5 semiconductor device obtained by encapsulating.