JP2008179791A - Epoxy resin composition for use in semiconductor sealing and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition for use in semiconductor sealing that is excellent in low stress property, flowability and continuous moldability. <P>SOLUTION: The epoxy resin composition for use in the semiconductor sealing comprises (A) an epoxy resin having structure expressed by general formula (1), (B) a compound having 2 or more phenolic hydroxyl groups, (C) an inorganic filler, (D) a curing accelerator, and (E) oxidized polyethylene. In the general formula (1), Ar is an aromatic group, R1 and R2 are hydrocarbon groups, W1 is an oxygen atom or sulfur atom, R3 is a hydrogen, hydrocarbon group or aromatic group, and m and n represent a molar ratio. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device.

  In recent years, as electronic components such as integrated circuits (ICs), large scale integrated circuits (LSIs), and very large scale integrated circuits (VLSIs) and semiconductor devices have been increased in density and integration, their mounting methods have been changed from insertion mounting. It is changing to surface mounting. Along with this, there is a demand for a multi-pin lead frame and a narrow lead pitch. Surface mount type QFP (Quad Flat Package), which is small, light, and compatible with multi-pin use, is used in various semiconductor devices. It has been. And since the semiconductor device is excellent in balance of productivity, cost, reliability, etc., it is mainstream to seal using an epoxy resin composition. In addition, area mounting type semiconductor devices have been developed in response to further increase in the number of pins and higher speed, and the promotion of surface mounting of semiconductor devices. The reliability of these semiconductor devices has been severely demanded due to an increase in mounting temperature for solder used for connection. In particular, a more robust semiconductor device is required for an on-vehicle semiconductor device. Accordingly, low stress is an important issue as a characteristic required for the sealing material used.

In the case of the epoxy resin composition described above, it is composed of an epoxy resin, a curing agent, an inorganic filler, etc. In order to develop low stress properties, the resin structure is improved, and a resin component and an inorganic filler are blended. Various studies have been made such as optimization of the ratio and reduction of stress by additives. In particular, an epoxy resin composition having a specific structure has been proposed for improving the resin structure (see, for example, Patent Documents 1 and 2). However, these resins have a problem that the melt viscosity is high at the sealing temperature and the fluidity is lowered. This problem is limited when increasing the proportion of the inorganic filler added to the sealing material when it is necessary to reduce the coefficient of linear expansion as a means to improve reliability. It was a factor. Moreover, the epoxy resin composition using the resin or the hardening | curing agent shown by these literature had low sclerosis | hardenability, and had problems, such as causing the sticking at the time of shaping | molding, and a trouble in continuous moldability.
Japanese Patent Laid-Open No. 03-281623 JP-A-11-130944

  The present invention provides an epoxy resin composition for semiconductor encapsulation excellent in low-stress property, fluidity and continuous moldability, and a semiconductor device obtained by encapsulating a semiconductor element using the same.

The present invention
[1] (A) An epoxy resin having a structure represented by the following general formula (1), (B) a compound containing two or more phenolic hydroxyl groups, (C) an inorganic filler, and (D) curing acceleration An epoxy resin composition for semiconductor encapsulation, comprising an agent and (E) oxidized polyethylene,

（ただし、上記一般式（１）において、Ａｒは炭素数６〜２０の芳香族基であり、互いに同じであっても異なっていてもよい。Ｒ１は炭素数１〜６の炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ２は炭素数１〜４の炭化水素基で、Ｗ１は酸素原子又は硫黄原子である。Ｒ３は水素、炭素数１〜４の炭化水素基又は炭素数６〜２０の芳香族基であり、互いに同じであっても異なっていてもよい。ａは０〜１０の整数、ｂは１〜３の整数である。ｍ、ｎはモル比を表し、０≦ｍ＜１、０＜ｎ≦１で、ｍ＋ｎ＝１、かつ、ｍ／ｎの平均値は１／１０〜１／１である。）

(In the above general formula (1), Ar is an aromatic group having 6 to 20 carbon atoms, and may be the same or different from each other. R1 is a hydrocarbon group having 1 to 6 carbon atoms. And R2 is a hydrocarbon group having 1 to 4 carbon atoms, W1 is an oxygen atom or a sulfur atom, R3 is hydrogen, a hydrocarbon group having 1 to 4 carbon atoms, or An aromatic group having 6 to 20 carbon atoms, which may be the same or different from each other, a is an integer of 0 to 10, b is an integer of 1 to 3, and m and n represent molar ratios. 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and the average value of m / n is 1/10 to 1/1.)

[2] (A) The epoxy resin having the structure represented by the general formula (1) co-condenses the phenolic hydroxyl group-containing aromatics, aldehydes, and the compound represented by the following general formula (2). 2. The epoxy resin composition for semiconductor encapsulation according to claim 1, which is an epoxy resin obtained by glycidyl etherification of an epoxy resin obtained by epichlorohydrin,

（ただし、上記一般式（２）において、Ａｒは炭素数６〜２０の芳香族基である。Ｒ１は炭素数１〜６の炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ２は炭素数１〜４の炭化水素基で、Ｗ１は酸素原子又は硫黄原子である。ａは０〜１０の整数、ｂは１〜３の整数である。）

(However, in the said General formula (2), Ar is a C6-C20 aromatic group. R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 is a hydrocarbon group having 1 to 4 carbon atoms, W1 is an oxygen atom or a sulfur atom, a is an integer of 0 to 10, and b is an integer of 1 to 3).

[3] The item [1] or [3], wherein the epoxy resin (A) having the structure represented by the general formula (1) is an epoxy resin represented by the following general formula (3): 2] An epoxy resin composition for encapsulating a semiconductor according to item

（ただし、上記一般式（３）において、Ｒ１は炭素数１〜６の炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ２は炭素数１〜４の炭化水素基で、Ｗ１は酸素原子又は硫黄原子である。ｃは０〜５の整数、ｄは０〜３の整数である。ｍ、ｎはモル比を表し、０≦ｍ＜１、０＜ｎ≦１で、ｍ＋ｎ＝１、かつ、ｍ／ｎの平均値は１／１０〜１／１である。）
［４］ 前記一般式（３）で表されるエポキシ樹脂が、下記一般式（４）で表されるエポキシ樹脂であることを特徴とする第［３］項に記載の半導体封止用エポキシ樹脂組成物、

(However, in the said General formula (3), R1 is a C1-C6 hydrocarbon group and may mutually be same or different. R2 is a C1-C4 hydrocarbon group, W1 is an oxygen atom or a sulfur atom, c is an integer of 0 to 5, d is an integer of 0 to 3, m and n represent a molar ratio, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and the average value of m / n is 1/10 to 1/1.)
[4] The epoxy resin for semiconductor encapsulation according to item [3], wherein the epoxy resin represented by the general formula (3) is an epoxy resin represented by the following general formula (4) Composition,

（ただし、上記一般式（４）において、Ｒ１は炭素数１〜６の炭化水素基であり、互いに同じであっても異なっていてもよい。ｃは０〜５の整数、ｄは０〜３の整数である。ｍ、ｎはモル比を表し、０≦ｍ＜１、０＜ｎ≦１で、ｍ＋ｎ＝１、かつ、ｍ／ｎの平均値は１／１０〜１／１である。）

(However, in the said General formula (4), R1 is a C1-C6 hydrocarbon group and may mutually be same or different. C is an integer of 0-5, d is 0-3. M and n represent molar ratios, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and the average value of m / n is 1/10 to 1/1. )

[5] The curing accelerator (D) is a compound represented by the following general formula (5), a compound represented by the following general formula (6), a compound represented by the following general formula (7), and the following general formula The epoxy resin composition for semiconductor encapsulation according to any one of [1] to [4], which is at least one selected from compounds represented by formula (8):

（ただし、上記一般式（５）において、Ｐはリン原子を表す。Ｒ４、Ｒ５、Ｒ６及びＲ７は芳香族基又はアルキル基を表す。Ａはヒドロキシル基、カルボキシル基、チオール基か
ら選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸のアニオンを表す。ＡＨはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸を表す。ｘ、ｙは１〜３の整数、ｚは０〜３の整数であり、かつｘ＝ｙである。）

(However, in the said General formula (5), P represents a phosphorus atom. R4, R5, R6, and R7 represent an aromatic group or an alkyl group. A is a functional group chosen from a hydroxyl group, a carboxyl group, and a thiol group. Represents an anion of an aromatic organic acid having at least one of the following: AH is an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring X and y are integers of 1 to 3, z is an integer of 0 to 3, and x = y.

（ただし、上記一般式（６）において、Ｘ１は炭素数１〜３のアルキル基、Ｙ１はヒドロキシル基を表す。ｅ、ｆは０〜３の整数である。）

(However, in the said General formula (6), X1 represents a C1-C3 alkyl group, Y1 represents a hydroxyl group. E and f are integers of 0-3.)

（ただし、上記一般式（７）において、Ｐはリン原子を表す。Ｒ８、Ｒ９及びＲ１０は炭素数１〜１２のアルキル基又は炭素数６〜１２のアリール基を表し、互いに同一であっても異なっていてもよい。Ｒ１１、Ｒ１２及びＲ１３は水素原子又は炭素数１〜１２の炭化水素基を表し、互いに同一であっても異なっていてもよく、Ｒ１１とＲ１２が結合して環状構造となっていてもよい。）

(However, in the said General formula (7), P represents a phosphorus atom. R8, R9, and R10 represent a C1-C12 alkyl group or a C6-C12 aryl group, and they are mutually the same. R11, R12 and R13 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R11 and R12 are bonded to form a cyclic structure. May be.)

（ただし、上記一般式（８）において、Ｐはリン原子を表し、Ｓｉは珪素原子を表す。Ｒ１４、Ｒ１５、Ｒ１６及びＲ１７は、それぞれ、芳香環又は複素環を有する有機基、あるいは脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｘ２は、基Ｙ２及びＹ３と結合する有機基である。式中Ｘ３は、基Ｙ４及びＹ５と結合する有機基である。Ｙ２及びＹ３は、プロトン供与性置換基がプロトンを放出してなる基を表し、同一分子内の基Ｙ２及びＹ３が珪素原子と結合してキレート構造を形成するものである。Ｙ４及びＹ５はプロトン供与性置換基がプロトンを放出してなる基を表し、同一分子内の基Ｙ４及び
Ｙ５が珪素原子と結合してキレート構造を形成するものである。Ｘ２、及びＸ３は互いに同一でも異なっていてもよく、Ｙ２、Ｙ３、Ｙ４、及びＹ５は互いに同一であっても異なっていてもよい。Ｚ１は芳香環又は複素環を有する有機基、あるいは脂肪族基である。）

(However, in the said General formula (8), P represents a phosphorus atom and Si represents a silicon atom. R14, R15, R16, and R17 are respectively an organic group or an aliphatic group which has an aromatic ring or a heterocyclic ring. X2 is an organic group bonded to the groups Y2 and Y3, where X3 is an organic group bonded to the groups Y4 and Y5. And Y3 represent a group formed by releasing a proton from a proton-donating substituent, and groups Y2 and Y3 in the same molecule are combined with a silicon atom to form a chelate structure. The functional substituent represents a group formed by releasing a proton, and the groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure, and X2 and X3 may be the same or different from each other. Often Y2, Y3, Y4, and Y5 is .Z1 which may be the same or different from each other is an organic group or an aliphatic group, an aromatic ring or a heterocyclic ring.)

[6] Further, (F) a butadiene-acrylonitrile copolymer (F1) having a carboxyl group and / or a reaction product (F2) of a butadiene-acrylonitrile copolymer (F1) having a carboxyl group and an epoxy resin. An epoxy resin composition for semiconductor encapsulation according to any one of items [1] to [5], comprising:
[7] The method further comprises (G) an organopolysiloxane having a carboxyl group (G1) and / or a reaction product (G2) of an organopolysiloxane having a carboxyl group (G1) and an epoxy resin. The epoxy resin composition for semiconductor encapsulation according to any one of items [1] to [6],
[8] The semiconductor according to any one of [1] to [7], wherein the inorganic filler (C) is contained in an amount of 80% by weight to 92% by weight based on the entire resin composition. Epoxy resin composition for sealing,
[9] A semiconductor device comprising a semiconductor element sealed with a cured product of the epoxy resin composition for semiconductor sealing according to any one of [1] to [8],
It is.

  According to the present invention, it is possible to obtain an epoxy resin composition for semiconductor encapsulation and a semiconductor device that are excellent in low stress, fluidity, and continuous moldability.

The present invention includes (A) an epoxy resin having a structure represented by the general formula (1), (B) a compound containing two or more phenolic hydroxyl groups, (C) an inorganic filler, and (D) curing acceleration. By including an agent and (E) oxidized polyethylene, an epoxy resin composition having excellent low stress properties and excellent fluidity and continuous moldability can be obtained.
Hereinafter, each component will be described in detail.

  In the present invention, an epoxy resin (A) having a structure represented by the following general formula (1) is used as the epoxy resin. The epoxy resin (A) having the structure represented by the following general formula (1) has many aromatic ring carbons in the molecule, and the cured product of the epoxy resin composition using this has excellent low-stress property and flame resistance. The water absorption rate is low. Further, it has a characteristic that it has excellent fluidity as compared with a naphthol aralkyl type epoxy resin having a phenylene skeleton that has been known to be excellent in low stress. The average value of the ratio m / n between m and n in the epoxy resin (A) having the structure represented by the following general formula (1) is preferably 1/10 to 1/1. More preferably, the ratio is / 5 to 2/5. When the average value of m / n is within the above range, an effect of improving low stress property, flame resistance, low water absorption and the like can be obtained. Moreover, if it is in the said range, there is little possibility of causing the fall of the fluidity | liquidity of the resin composition by the melt viscosity of this epoxy resin becoming high.

（ただし、上記一般式（１）において、Ａｒは炭素数６〜２０の芳香族基であり、互いに同じであっても異なっていてもよい。Ｒ１は炭素数１〜６の炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ２は炭素数１〜４の炭化水素基で、Ｗ１は酸素原子又は硫黄原子である。Ｒ３は水素、炭素数１〜４の炭化水素基又は炭素数６〜２０の芳香族基であり、互いに同じであっても異なっていてもよい。ａは０〜１０の整数、ｂは１〜３の整数である。ｍ、ｎはモル比を表し、０≦ｍ＜１、０＜ｎ≦１で、ｍ＋ｎ＝１、かつ、ｍ／ｎの平均値は１／１０〜１／１である。）

(In the above general formula (1), Ar is an aromatic group having 6 to 20 carbon atoms, and may be the same or different from each other. R1 is a hydrocarbon group having 1 to 6 carbon atoms. And R2 is a hydrocarbon group having 1 to 4 carbon atoms, W1 is an oxygen atom or a sulfur atom, R3 is hydrogen, a hydrocarbon group having 1 to 4 carbon atoms, or An aromatic group having 6 to 20 carbon atoms, which may be the same or different from each other, a is an integer of 0 to 10, b is an integer of 1 to 3, and m and n represent molar ratios. 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and the average value of m / n is 1/10 to 1/1.)

  Although it does not specifically limit as an epoxy resin (A) which has a structure represented by General formula (1) used by this invention, For example, the epoxy resin which has a structure represented by following General formula (4) , An epoxy resin having a structure represented by the following general formula (9), an epoxy resin having a structure represented by the following general formula (10), a compound having a structure represented by the following general formula (11), and the like. It is done. From the viewpoints of low stress and flame resistance, an epoxy resin having a structure represented by the following general formula (4) in which Ar in the general formula (1) is a naphthalene ring, a structure represented by the following general formula (10) An epoxy resin having is more preferable.

（ただし、上記一般式（４）において、Ｒ１は炭素数１〜６の炭化水素基であり、互いに同じであっても異なっていてもよい。ｃは０〜５の整数、ｄは０〜３の整数である。ｍ、ｎはモル比を表し、０≦ｍ＜１、０＜ｎ≦１で、ｍ＋ｎ＝１、かつ、ｍ／ｎの平均値は１／１０〜１／１である。）

(However, in the said General formula (4), R1 is a C1-C6 hydrocarbon group and may mutually be same or different. C is an integer of 0-5, d is 0-3. M and n represent molar ratios, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and the average value of m / n is 1/10 to 1/1. )

（ただし、上記一般式（９）において、Ｒ１は炭素数１〜６の炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ２は炭素数１〜４の炭化水素基である。ｄは０〜３の整数である。ｍ、ｎはモル比を表し、０≦ｍ＜１、０＜ｎ≦１で、ｍ＋ｎ＝１、かつ、ｍ／ｎの平均値は１／１０〜１／１である。）

(However, in the said General formula (9), R1 is a C1-C6 hydrocarbon group and may mutually be same or different. R2 is a C1-C4 hydrocarbon group. D is an integer of 0 to 3. m and n represent molar ratios, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and the average value of m / n is 1/10 to 10 1/1.)

（ただし、上記一般式（１０）において、Ｒ１は炭素数１〜６の炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ２は炭素数１〜４の炭化水素基である。ｃは０〜５の整数、ｄは０〜３の整数である。ｍ、ｎはモル比を表し、０≦ｍ＜１、０＜ｎ≦１で、ｍ＋ｎ＝１、かつ、ｍ／ｎの平均値は１／１０〜１／１である。）

(However, in the said General formula (10), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 is a C1-C4 hydrocarbon group. C is an integer of 0 to 5, d is an integer of 0 to 3. m and n are molar ratios, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and m / n The average value is 1/10 to 1/1.)

（ただし、上記一般式（１１）において、Ｒ１は炭素数１〜６の炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ２は炭素数１〜４の炭化水素基である。ｄは０〜３の整数である。ｍ、ｎはモル比を表し、０≦ｍ＜１、０＜ｎ≦１で、ｍ＋ｎ＝１、かつ、ｍ／ｎの平均値は１／１０〜１／１である。）

(However, in the said General formula (11), R1 is a C1-C6 hydrocarbon group and may mutually be same or different. R2 is a C1-C4 hydrocarbon group. D is an integer of 0 to 3. m and n represent molar ratios, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and the average value of m / n is 1/10 to 10 1/1.)

（ただし、上記一般式（２）において、Ａｒは炭素数６〜２０の芳香族基である。Ｒ１は炭素数１〜６の炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ２は炭素数１〜４の炭化水素基で、Ｗ１は酸素原子又は硫黄原子である。ａは０〜１０の整数、ｂは１〜３の整数である。） The epoxy resin (A) having a structure represented by the general formula (1) used in the present invention comprises a phenolic hydroxyl group-containing aromatic, an aldehyde, and a compound (J) represented by the following general formula (2). The phenol resins obtained by co-condensation can be obtained by glycidyl etherification with epichlorohydrin. Compound (J) represented by the following general formula (2) has an aromatic ring to which a glycidyl ether group is not bonded, W1R2 (W1 is an oxygen atom or a sulfur atom, and R2 is a hydrocarbon group having 1 to 4 carbon atoms. ) Are connected to each other. Since W1R2 is bonded, the compound (J) represented by the following general formula (2) has polarity, and this improves the reactivity. Therefore, a novolak comprising a phenolic hydroxyl group-containing aromatic or aldehyde The structure of the compound (J) can be introduced into the resin structure.

(However, in the said General formula (2), Ar is a C6-C20 aromatic group. R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 is a hydrocarbon group having 1 to 4 carbon atoms, W1 is an oxygen atom or a sulfur atom, a is an integer of 0 to 10, and b is an integer of 1 to 3).

  Although it does not specifically limit as phenolic hydroxyl group containing aromatics used for manufacture of the epoxy resin (A) which has a structure represented by General formula (1), For example, phenol, catechol, resorcinol, hydroquinone , O-cresol, p-cresol, m-cresol, phenylphenol, ethylphenol, n-propylphenol, iso-propylphenol, t-butylphenol, xylenol, methylpropylphenol, methylbutylphenol, dipropylphenol, dibutylphenol, nonylphenol , Phenols such as mecitol, 2,3,5-trimethylphenol and 2,3,6-trimethylphenol, and naphthols such as 1-naphthol, 2-naphthol and methylnaphthol. Among these, phenol, o-cresol, 1-naphthol and 2-naphthol are preferable, and o-cresol is more preferable. These may be used alone or in combination of two or more.

  Although it does not specifically limit as aldehydes used for manufacture of the epoxy resin (A) which has a structure represented by General formula (1), For example, aliphatic aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde Aromatic aldehydes such as benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, 4-biphenylaldehyde, naphthylaldehyde, and salicylaldehyde. Among these, formaldehyde, benzaldehyde, and naphthylaldehyde are preferable, and formaldehyde is more preferable. These may be used alone or in combination of two or more.

The compound (J) represented by the general formula (2) used for the production of the epoxy resin (A) having the structure represented by the general formula (1) is particularly limited as long as it is a structure of the general formula (2). For example, methoxybenzene, ethoxybenzene, methylphenyl sulfide, ethylphenyl sulfide, 1-methoxynaphthalene, 2-methoxynaphthalene, 1-methyl-2-methoxynaphthalene, 1-methoxy-2-methylnaphthalene 1,3,5-trimethyl-2-methoxynaphthalene, 1-ethoxynaphthalene, 2-ethoxynaphthalene, 1-t-butoxynaphthalene, methyl naphthyl sulfide, ethyl naphthyl sulfide, 1,4-dimethoxynaphthalene, 2,6- Dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 1-methoxya Anthracene, and the like. Among these, low stress,
In view of flame resistance, low water absorption and the like, a compound represented by the following formula (12) is preferable, and a methoxynaphthalene compound represented by the following formula (13) is more preferable.

（ただし、上記一般式（１２）において、Ｒ１は炭素数１〜６の炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ２は炭素数１〜４の炭化水素基で、Ｗ１は酸素原子又は硫黄原子である。ｃは０〜５の整数である。）

(However, in the said General formula (12), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 is a C1-C4 hydrocarbon group, W1 is an oxygen atom or a sulfur atom, and c is an integer of 0 to 5.)

（ただし、上記一般式（１３）において、Ｒ１は炭素数１〜６の炭化水素基であり、互いに同じであっても異なっていてもよい。ｃは０〜５の整数である。）

(However, in the said General formula (13), R1 is a C1-C6 hydrocarbon group and may mutually be same or different. C is an integer of 0-5.)

  The method for synthesizing the phenol resin which is a precursor of the epoxy resin (A) having the structure represented by the general formula (1) used in the present invention is not particularly limited. For example, the phenolic hydroxyl group-containing aromatics and Examples include a method in which an aldehyde and a compound (J) represented by the general formula (2) are co-condensed using an acidic catalyst in the coexistence.

  The method for synthesizing the epoxy resin (A) having a structure represented by the general formula (1) used in the present invention is not particularly limited. For example, an epoxy resin having a structure represented by the general formula (1) (A ) In the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, dissolved in excess epichlorohydrin, and then dissolved in an excess of epichlorohydrin. Examples include a method of reacting at 120 ° C. or lower for 1 to 10 hours. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is evaporated to remove the target general An epoxy resin (A) having a structure represented by the formula (1) can be obtained.

In this invention, it can use together with another epoxy resin in the range by which the effect by using the epoxy resin (A) which has a structure represented by General formula (1) is not impaired. Examples of epoxy resins that can be used in combination include biphenyl type epoxy resins, bisphenol type epoxy resins, stilbene type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenolmethane type epoxy resins, and phenol aralkyl type epoxy resins having a phenylene skeleton. Examples thereof include a resin, a phenol aralkyl type epoxy resin having a biphenylene skeleton, a naphthol type epoxy resin, an alkyl-modified triphenol methane type epoxy resin, a triazine nucleus-containing epoxy resin, and a dicyclopentadiene-modified phenol type epoxy resin. In consideration of moisture resistance reliability as an epoxy resin composition for semiconductor encapsulation, it is preferable that Na ions and Cl ions, which are ionic impurities, be as small as possible. From the viewpoint of curability, the epoxy equivalent is 100 g / eq or more and 500 g / eq or less is preferable.

  The blending ratio of the epoxy resin (A) having the structure represented by the general formula (1) when other epoxy resins are used in combination is preferably 10% by weight or more, more preferably based on the total epoxy resin. Is 30% by weight or more, particularly preferably 50% by weight or more. When the blending ratio is within the above range, an effect of improving low stress properties, flame resistance, low water absorption, and the like can be obtained.

  In the present invention, a compound (B) containing two or more phenolic hydroxyl groups is used as a curing agent from the viewpoints of flame resistance, moisture resistance, electrical properties, curability, storage stability, and the like. The compound (B) containing two or more phenolic hydroxyl groups is a monomer, oligomer or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak resin, triphenolmethane type phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin having phenylene skeleton and / or biphenylene skeleton, phenylene and / or biphenylene skeleton A naphthol aralkyl resin, a bisphenol compound, etc. are mentioned, These may be used individually by 1 type, or may use 2 or more types together. Among these, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.

  As the inorganic filler (C) used in the present invention, those generally used for semiconductor sealing resin compositions can be used, for example, fused silica, spherical silica, crystalline silica, alumina, silicon nitride, Examples thereof include aluminum nitride. The particle size of the inorganic filler (C) is preferably 0.01 μm or more and 150 μm or less in consideration of the filling property to the mold. Further, the content of the inorganic filler (C) is preferably 80% by weight or more and 92% by weight or less, more preferably 82% by weight or more and 91% by weight or less, and particularly preferably 84% by weight of the entire epoxy resin composition. % To 90% by weight. When the content of the inorganic filler (C) is within the above range, the amount of water absorption of the cured product of the epoxy resin composition is increased and there is little possibility of causing a decrease in solder crack resistance due to a decrease in strength. Further, when the content of the inorganic filler (C) is within the above range, there is little possibility of causing defects on the molding surface due to the loss of fluidity.

  The curing accelerator (D) used in the present invention is not limited as long as it accelerates the reaction between the epoxy group of the epoxy resin and the phenolic hydroxyl group of the compound containing two or more phenolic hydroxyl groups. What is used for the resin composition can be utilized. Specific examples include organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, phosphorus atom-containing compounds such as adducts of phosphine compounds and quinone compounds, 1,8-diazabicyclo (5,4,0) undecene-7, benzyl Nitrogen atom-containing compounds such as dimethylamine and 2-methylimidazole can be mentioned. Among these, a phosphorus atom-containing compound is preferable, and a tetra-substituted phosphonium compound is particularly preferable in consideration of fluidity, and a phosphobetaine compound and a phosphine compound in consideration of a low elastic modulus when cured of an epoxy resin composition. An adduct of quinone compound and a quinone compound is preferable, and an adduct of a phosphonium compound and a silane compound is preferable in consideration of latent curing property.

Examples of the organic phosphine used in the present invention include a first phosphine such as ethylphosphine and phenylphosphine, a second phosphine such as dimethylphosphine and diphenylphosphine, and a third phosphine such as trimethylphosphine, triethylphosphine, tributylphosphine, and triphenylphosphine. Is mentioned.

  Examples of the tetra-substituted phosphonium compound used in the present invention include compounds represented by the following general formula (5).

（ただし、上記一般式（５）において、Ｐはリン原子を表す。Ｒ４、Ｒ５、Ｒ６及びＲ７は芳香族基又はアルキル基を表す。Ａはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸のアニオンを表す。ＡＨはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸を表す。ｘ、ｙは１〜３の整数、ｚは０〜３の整数であり、かつｘ＝ｙである。）

(However, in the said General formula (5), P represents a phosphorus atom. R4, R5, R6, and R7 represent an aromatic group or an alkyl group. A is a functional group chosen from a hydroxyl group, a carboxyl group, and a thiol group. Represents an anion of an aromatic organic acid having at least one of the following: AH is an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring X and y are integers of 1 to 3, z is an integer of 0 to 3, and x = y.

  Although the compound represented by General formula (5) used by this invention is obtained as follows, for example, it is not limited to this. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Then, when water is added, the compound represented by the general formula (5) can be precipitated. In the compound represented by the general formula (5), R3, R4, R5 and R6 bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols, and A Is preferably an anion of the phenol.

（ただし、上記一般式（６）において、Ｘ１は炭素数１〜３のアルキル基、Ｙ１はヒドロキシル基を表す。ｅ、ｆは０〜３の整数である。） Examples of the phosphobetaine compound used in the present invention include compounds represented by the following general formula (6).

(However, in the said General formula (6), X1 represents a C1-C3 alkyl group, Y1 represents a hydroxyl group. E and f are integers of 0-3.)

  The compound represented by the general formula (6) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt and replacing the triaromatic substituted phosphine with a diazonium group of the diazonium salt. However, the present invention is not limited to this.

（ただし、上記一般式（７）において、Ｐはリン原子を表す。Ｒ８、Ｒ９及びＲ１０は炭素数１〜１２のアルキル基又は炭素数６〜１２のアリール基を表し、互いに同一であっても異なっていてもよい。Ｒ１１、Ｒ１２及びＲ１３は水素原子又は炭素数１〜１２の炭化水素基を表し、互いに同一であっても異なっていてもよく、Ｒ１１とＲ１２が結合して環状構造となっていてもよい。） Examples of the adduct of the phosphine compound and quinone compound used in the present invention include compounds represented by the following general formula (7).

(However, in the said General formula (7), P represents a phosphorus atom. R8, R9, and R10 represent a C1-C12 alkyl group or a C6-C12 aryl group, and they are mutually the same. R11, R12 and R13 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R11 and R12 are bonded to form a cyclic structure. May be.)

The phosphine compound used as an adduct of a phosphine compound and a quinone compound has no substitution on aromatic rings such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, tris (benzyl) phosphine, etc. Or what has substituents, such as an alkyl group and an alkoxyl group, is preferable, and what has 1-6 carbon atoms is mentioned as an organic group of an alkyl group and an alkoxyl group. From the viewpoint of availability, triphenylphosphine is preferable.
In addition, examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include o-benzoquinone, p-benzoquinone, and anthraquinones. Among them, p-benzoquinone is preferable from the viewpoint of storage stability.
As a method for producing an adduct of a phosphine compound and a quinone compound, the adduct can be obtained by contacting and mixing in a solvent capable of dissolving both organic tertiary phosphine and benzoquinone. The solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct. However, the present invention is not limited to this.
In the compound represented by the general formula (7), R8, R9 and R10 bonded to the phosphorus atom are phenyl groups, and R11, R12 and R13 are hydrogen atoms, that is, 1,4-benzoquinone and triphenyl A compound to which phosphine has been added is preferable in that it reduces the elastic modulus of the cured epoxy resin composition when heated.

（ただし、上記一般式（８）において、Ｐはリン原子を表し、Ｓｉは珪素原子を表す。Ｒ１４、Ｒ１５、Ｒ１６及びＲ１７は、それぞれ、芳香環又は複素環を有する有機基、あるいは脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｘ２は、基Ｙ２及
びＹ３と結合する有機基である。式中Ｘ３は、基Ｙ４及びＹ５と結合する有機基である。Ｙ２及びＹ３は、プロトン供与性置換基がプロトンを放出してなる基を表し、同一分子内の基Ｙ２及びＹ３が珪素原子と結合してキレート構造を形成するものである。Ｙ４及びＹ５はプロトン供与性置換基がプロトンを放出してなる基を表し、同一分子内の基Ｙ４及びＹ５が珪素原子と結合してキレート構造を形成するものである。Ｘ２、及びＸ３は互いに同一でも異なっていてもよく、Ｙ２、Ｙ３、Ｙ４、及びＹ５は互いに同一であっても異なっていてもよい。Ｚ１は芳香環又は複素環を有する有機基、あるいは脂肪族基である。） Examples of the adduct of the phosphonium compound and the silane compound used in the present invention include compounds represented by the following general formula (8).

(However, in the said General formula (8), P represents a phosphorus atom and Si represents a silicon atom. R14, R15, R16, and R17 are respectively an organic group or an aliphatic group which has an aromatic ring or a heterocyclic ring. X2 is an organic group bonded to the groups Y2 and Y3, where X3 is an organic group bonded to the groups Y4 and Y5. And Y3 represent a group formed by releasing a proton from a proton-donating substituent, and groups Y2 and Y3 in the same molecule are combined with a silicon atom to form a chelate structure. The functional substituent represents a group formed by releasing a proton, and the groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure, and X2 and X3 may be the same or different from each other. Often Y2, Y3, Y4, and Y5 is .Z1 which may be the same or different from each other is an organic group or an aliphatic group, an aromatic ring or a heterocyclic ring.)

  In the general formula (8), examples of R14, R15, R16, and R17 include a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, a hydroxynaphthyl group, a benzyl group, a methyl group, an ethyl group, An n-butyl group, an n-octyl group, a cyclohexyl group, and the like can be given. Among these, aromatic groups such as a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, and a hydroxynaphthyl group are more preferable.

  Moreover, in General formula (8), X2 is an organic group couple | bonded with Y2 and Y3. Similarly, X3 is an organic group bonded to the groups Y4 and Y5. Y2 and Y3 are groups formed by proton-donating substituents releasing protons, and groups Y2 and Y3 in the same molecule are bonded to a silicon atom to form a chelate structure. Similarly, Y4 and Y5 are groups formed by proton-donating substituents releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure. The groups Y2 and Y3 may be the same or different from each other, and the groups Y2, Y3, Y4, and Y5 may be the same or different from each other. The groups represented by -Y2-X2-Y3- and -Y4-X3-Y5- in general formula (8) are composed of groups in which a proton donor releases two protons. Examples of proton donors include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 1,1′-bi-2-naphthol, and salicylic acid. 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol and glycerin. Among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable.

  Z1 in the general formula (8) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Reactions of aliphatic hydrocarbon groups such as octyl and octyl groups, aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl and biphenyl, glycidyloxypropyl, mercaptopropyl, aminopropyl and vinyl Among them, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are more preferable from the viewpoint of thermal stability.

  As a method for producing an adduct of a phosphonium compound and a silane compound, a silane compound such as phenyltrimethoxysilane and a bivalent or higher proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol and dissolved. Then, a sodium methoxide-methanol solution is added dropwise with stirring at room temperature. Furthermore, when a solution prepared by dissolving a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide in methanol in methanol is added dropwise with stirring at room temperature, crystals are precipitated. The precipitated crystals are filtered, washed with water, and vacuum dried to obtain an adduct of a phosphonium compound and a silane compound. However, it is not limited to this.

As for the compounding quantity of the hardening accelerator (D) used for this invention, 0.1 to 1 weight% is preferable in all the epoxy resin compositions. There is little possibility of causing curability fall that the compounding quantity of a hardening accelerator (D) exists in the said range. Moreover, there is little possibility of causing a fluid fall as the compounding quantity of a hardening accelerator (D) exists in the said range.

  The polyethylene oxide (E) used in the present invention has a polar group composed of carboxylic acid and the like and a nonpolar group composed of a long carbon chain, and is used as a release agent (wax). As an example, a commercially available product can be obtained, and the particle size can be adjusted if necessary. Among them, preferred examples include polyethylene oxide produced by a low pressure polymerization method, polyethylene oxide produced by a high pressure polymerization method, and oxide of a high density polyethylene polymer.

  A characteristic of the oxidized polyethylene (E) used in the present invention includes a dropping point (according to ASTM-D127; a temperature at which a molten wax is first dropped through a metal nipple), and the range thereof is 60 ° C. or more and 140 ° C. or less. Is more preferable, and it is 100 degreeC or more and 130 degrees C or less. When the dropping point is within the above range, the oxidized polyethylene (E) is excellent in thermal stability, and the oxidized polyethylene (E) is hardly seized at the time of molding. Therefore, it is excellent in the mold release property of the hardened | cured material from a metal mold | die, and is excellent also in continuous moldability. Furthermore, when it is within the above range, the polyethylene oxide (E) is sufficiently melted when the epoxy resin composition is cured. Thereby, polyethylene oxide (E) disperses | distributes substantially uniformly in hardened | cured material. Therefore, segregation of polyethylene oxide (E) on the surface of the cured product is suppressed, and the deterioration of the appearance of the mold surface and the resin cured product can be reduced.

  The acid value of the oxidized polyethylene (E) is preferably 10 mgKOH / g or more and 50 mgKOH / g or less, more preferably 15 mgKOH / g or more and 40 mgKOH / g or less. The acid value affects the compatibility between the cured resin and the acid value polyethylene (E). The acid value can be measured by a method based on JIS K 3504. Specifically, it is measured as the number of milligrams of potassium hydroxide required to neutralize free fatty acids contained in 1 g of waxes. In the following examples, it can be measured by the same method. When the acid value is within the above range, polyethylene oxide (E) is in a compatible state with the epoxy resin matrix in the cured product. Thereby, a polyethylene oxide (E) and an epoxy resin matrix do not raise | generate phase separation. Therefore, segregation of polyethylene oxide (E) on the cured product surface is suppressed, and deterioration of the appearance of the mold and the cured product can be reduced. Furthermore, since the oxidized polyethylene (E) is present on the surface of the cured product, the release property of the cured product from the mold is excellent. On the other hand, if the compatibility between the oxidized polyethylene (E) and the epoxy resin matrix is too high, the oxidized polyethylene (E) cannot be oozed out on the surface of the cured product, and sufficient releasability may not be ensured. is there.

  The number average molecular weight of the oxidized polyethylene (E) is preferably 500 or more and 5000 or less, more preferably 1000 or more and 4000 or less. The number average molecular weight can be calculated by polystyrene conversion using a GPC apparatus such as HLC-8120 manufactured by Tosoh Corporation. In the following examples, it can be measured by the same method. When the number average molecular weight is within the above range, polyethylene oxide (E) and the epoxy resin matrix are in a preferable affinity state. Therefore, the cured product is excellent in releasability from the mold. On the other hand, if the compatibility between the oxidized polyethylene (E) and the epoxy resin matrix is high, sufficient releasability may not be obtained. On the other hand, if the compatibility is low, phase separation occurs, which may cause mold stains and deterioration of the appearance of the cured resin.

The density of the oxidized polyethylene (E) is preferably 0.94 g / cm ³ or more and 1.03 g / cm ³ or less, more preferably 0.97 g / cm ³ or more and 0.99 g / cm ³ or less. The density can be calculated by density measurement at 20 ° C. by a floating method based on ASTM D1505. In the following examples, it can be measured by the same method. When the density is within the above range, the oxidized polyethylene (E) is excellent in thermal stability, and the oxidized polyethylene (E) is hardly seized at the time of molding. Therefore, it is excellent in the mold release property of the cured product from the mold and also in the continuous moldability. Furthermore, when it is within the above range, the polyethylene oxide (E) is sufficiently melted when the epoxy resin composition is cured. Thereby, the polyethylene oxide (E) is uniformly dispersed in the cured product. Therefore, segregation of polyethylene oxide (E) on the cured product surface is suppressed, and deterioration of the appearance of the mold and the cured product can be reduced.

  The average particle diameter of the oxidized polyethylene (E) is preferably 0.1 μm or more and 100 μm or less, more preferably 30 μm or more and 60 μm or less. The average particle diameter can be measured by using a laser diffraction particle size distribution measuring device such as SALD-7000 manufactured by Shimadzu Corporation as a solvent and water, and a weight-based 50% particle diameter as an average particle diameter. it can. When the average particle diameter is within the above range, the polyethylene oxide (E) is in a compatible state with the epoxy resin matrix in the cured product. Thereby, polyethylene oxide (E) exists in the cured | curing material surface, and it is excellent in the mold release property of the cured | curing material from a metal mold | die. On the other hand, if the compatibility with the epoxy resin matrix is too high, the cured product surface cannot be oozed out and sufficient releasability cannot be ensured. Furthermore, since the polyethylene oxide (E) and the epoxy resin matrix are in a preferable compatible state, segregation of the polyethylene oxide (E) on the surface of the cured product is suppressed, and the mold surface is soiled and the appearance of the resin cured product is deteriorated. Can be reduced. Furthermore, when it exists in the said range, when hardening an epoxy resin composition, polyethylene oxide (E) will fully fuse | melt. Therefore, the epoxy resin composition is excellent in fluidity.

  The content ratio of particles having a particle size of 106 μm or more in the total oxidized polyethylene (E) is preferably 0.1% by weight or less. This content ratio can be measured using a standard sieve having an opening of 106 μm according to JIS Z8801. In the following examples, it can be measured by the same method. If it is said content ratio, a polyethylene oxide (E) will disperse | distribute uniformly and it can suppress the deterioration of the external appearance of the stain | pollution | contamination of a metal mold | die, or resin cured material. In addition, when the epoxy resin composition is cured, the polyethylene oxide is sufficiently melted, and thus has excellent fluidity.

  The content of polyethylene oxide (E) is preferably 0.01% by weight or more and 1% by weight or less in the epoxy resin composition, more preferably 0.03% by weight or more and 0.5% by weight or less. preferable. It is excellent in the mold release property of the hardened | cured material from a metal mold | die within the said range. Within the above range, the adhesiveness to the lead frame member or the circuit board is further excellent, so that the peeling between the lead frame member or the circuit board and the cured resin can be suppressed during the soldering process. In addition, it is possible to suppress deterioration of the mold surface during molding and deterioration of the appearance of the cured resin.

  By using a combination of the epoxy resin (A) having the structure represented by the general formula (1) and the oxidized polyethylene (E) used in the present invention, further improvement in low-stress property and continuous moldability are included. The moldability can be greatly improved. Although the reason why the low-stress property is improved by using in combination is not clear, the synergistic effect can be confirmed by comparing an example described later and a comparative example. Moreover, about the great improvement of the moldability including continuous moldability, the epoxy resin (A) having the structure represented by the general formula (1) and the polyethylene oxide (E) exhibit appropriate compatibility, It is considered that the mold surface contamination and the deterioration of the appearance of the cured resin can be greatly reduced, and the moldability including continuous moldability can be greatly improved.

In addition, in this invention, if it is a range which does not impair the effect which adds polyethylene oxide (E), another mold release agent can be used together other than that. As a release agent that can be used in combination, for example,
Examples thereof include natural waxes such as carnauba wax, metal salts of higher fatty acids such as zinc stearate, and fatty acid esters.

  In the present invention, (F) a butadiene / acrylonitrile copolymer (F1) having a carboxyl group and / or a reaction product (F2) of a butadiene / acrylonitrile copolymer (F1) having a carboxyl group and an epoxy resin. Can be used. The butadiene-acrylonitrile copolymer (F1) having a carboxyl group (hereinafter, also simply referred to as “butadiene-acrylonitrile copolymer (F1)”) is a copolymer of butadiene and acrylonitrile, and has an epoxy resin composition for sealing. It has the effect of improving the low stress property of the object. In addition, since the carboxyl group and acrylonitrile group in the butadiene-acrylonitrile copolymer (F1) having a carboxyl group have polarity, the compatibility with the epoxy resin contained as a raw material of the epoxy resin composition for sealing is high. It becomes an appropriate state, and the dispersibility of the butadiene-acrylonitrile copolymer (F1) in the epoxy resin composition for sealing becomes good. For this reason, the butadiene-acrylonitrile copolymer (F1) having a carboxyl group can suppress the progress of dirt on the mold surface and the surface of the cured resin product during molding, and also has an effect of improving continuous moldability. It is what you have.

  Furthermore, by using a reaction product (F2) obtained by previously melting and reacting the whole or a part of the butadiene-acrylonitrile copolymer (F1) having a carboxyl group with an epoxy resin and a curing accelerator, an epoxy for sealing is used. The dispersibility of the butadiene-acrylonitrile copolymer (F1) in the resin composition can be further improved, the mold surface after continuous molding is less likely to be stained, and the continuous moldability is extremely good. Can do. The method for producing the reaction product (F2) of the butadiene-acrylonitrile copolymer (F1) having a carboxyl group and the epoxy resin that can be used in the present invention is not particularly limited. A butadiene-acrylonitrile copolymer (F1) and an epoxy resin can be obtained by melting and reacting in the presence of a curing accelerator. The term “epoxy resin” as used herein refers to monomers, oligomers, and polymers in general having two or more epoxy groups in one molecule. The molecular weight and molecular structure thereof are not particularly limited, and are represented by the general formula (1). As the epoxy resin (A) having a structure or an epoxy resin that can be used in combination with the epoxy resin (A), the same ones as described above can be used. The curing accelerator referred to here may be any accelerator that promotes the curing reaction between the carboxyl group in the butadiene-acrylonitrile copolymer and the epoxy group in the epoxy resin. The same thing as the hardening accelerator which accelerates | stimulates hardening reaction with the phenolic hydroxyl group of the compound containing 2 or more of a functional hydroxyl group can also be used.

（ただし、上記一般式（１４）において、ｉは１未満の正数、ｊは１未満の正数で、かつｉ＋ｊ＝１。ｋは５０〜８０の整数。） Although it does not specifically limit as a butadiene acrylonitrile copolymer (F1) which has a carboxyl group which can be used by this invention, The compound which has a carboxyl group at the both ends of the structure is preferable, and following General formula (14) The compound represented by these is more preferable.

(However, in the general formula (14), i is a positive number less than 1, j is a positive number less than 1, and i + j = 1. K is an integer of 50 to 80.)

In the general formula (14), i is a positive number less than 1, j is a positive number less than 1, and i + j = 1. k is an integer of 50-80. The acrylonitrile content j in the compound represented by the general formula (14) is preferably 0.05 or more and 0.30 or less, more preferably 0.10 or more and 0.25 or less. The acrylonitrile content j affects the compatibility with the epoxy resin matrix. If the acrylonitrile content y is within the above range, the butadiene-acrylonitrile copolymer (F1) is in an appropriate compatible state with the epoxy resin matrix, and the mold There is little risk of causing surface contamination or deterioration of the appearance of the cured resin. In addition, when the acrylonitrile content y is within the above range, there is little possibility of causing a defective filling due to a decrease in fluidity and a disadvantage such as a gold wire flow in the electronic component device due to an increase in viscosity.

  The total blending amount of the component (F) that can be used in the present invention is a blending amount as a butadiene-acrylonitrile copolymer (F1) having a carboxyl group, and is 0.01% by weight or more in the total epoxy resin composition. % By weight or less is preferable, 0.05% by weight or more and 0.5% by weight or less is more preferable, and 0.1% by weight or more and 0.3% by weight or less is particularly preferable. By setting it as the said range, generation | occurrence | production of malfunctions, such as generation | occurrence | production of the filling failure at the time of shaping | molding by fall of fluidity | liquidity, and the wire flow by high viscosity can be suppressed.

  The number average molecular weight of the butadiene-acrylonitrile copolymer (F1) having a carboxyl group is preferably 2000 or more and 5000 or less, and more preferably 3000 or more and 4000 or less. By making it within the above range, it is possible to suppress the occurrence of defective filling during molding due to a decrease in fluidity and the occurrence of defects such as gold wire flow due to increased viscosity.

  Further, the carboxyl group equivalent of the butadiene-acrylonitrile copolymer (F1) having a carboxyl group is preferably 1200 or more and 3000 or less, and more preferably 1700 or more and 2500 or less. By making it within the above range, the mold and the cured resin are less likely to be stained without lowering the fluidity and releasability at the time of molding the resin composition, and the effect that the continuous moldability is particularly good. Is obtained.

  The amount of sodium ions and the amount of chlorine ions contained in the component (F) used in the present invention are preferably 10 ppm or less and 450 ppm or less, respectively, with respect to the (F1) equivalent. The amount of sodium ions and the amount of chloride ions can be determined by the following method. Component (F) is subjected to dry decomposition and ashing and then dissolved in acid, and the amount of sodium ions is measured by ICP emission analysis. Chlorine ion content is measured by the combustion tube oxygen method-IC method. When the amount of sodium ions or chlorine ions is within the above range, the corrosion resistance of the solder receiving circuit due to sodium ions or chlorine ions easily proceeds, and there is little possibility of causing a decrease in the moisture resistance reliability of the solder receiving device.

  In the present invention, (G) a carboxyl group-containing organopolysiloxane (G1) and / or a reaction product (G2) of a carboxyl group-containing organopolysiloxane (G1) and an epoxy resin can be used. . (G) When molding a resin composition by using an organopolysiloxane (G1) having a carboxyl group and / or a reaction product (G2) of an organopolysiloxane (G1) having a carboxyl group and an epoxy resin. Without lowering the fluidity and releasability in the mold, stains on the mold surface and the cured resin surface are less likely to occur, and the effect that the continuous moldability is particularly good is obtained.

Furthermore, by using a reaction product (G2) obtained by previously melting and reacting all or part of the carboxyl group-containing organopolysiloxane (G1) with an epoxy resin and a curing accelerator, Dirt is less likely to occur and the continuous formability can be made extremely good. The method for producing the reaction product (G2) of the organopolysiloxane (G1) having a carboxyl group and the epoxy resin that can be used in the present invention is not particularly limited. For example, the organopolysiloxane having a carboxyl group is used. (G1) and an epoxy resin can be obtained by melting and reacting in the presence of a curing accelerator. The term “epoxy resin” as used herein refers to monomers, oligomers, and polymers in general having two or more epoxy groups in one molecule. The molecular weight and molecular structure thereof are not particularly limited, and are represented by the general formula (1). As the epoxy resin (A) having a structure or an epoxy resin that can be used in combination with the epoxy resin (A), the same ones as described above can be used. The curing accelerator referred to here may be any accelerator that promotes the curing reaction between the carboxyl group in the organopolysiloxane and the epoxy group in the epoxy resin. The same thing as the hardening accelerator which accelerates | stimulates hardening reaction with the phenolic hydroxyl group of the compound containing 2 or more can also be used.

（ただし、上記一般式（１５）において、Ｒ１８は少なくとも１つ以上がカルボキシル基を有する炭素数１〜４０の有機基であり、残余の基は水素、フェニル基、又はメチル基から選ばれる基であり、互いに同一であっても異なっていてもよい。ｈの平均値は、１以上、５０以下の正数である。） The organopolysiloxane (G1) having a carboxyl group that can be used in the present invention (hereinafter also simply referred to as “organopolysiloxane (G1)”) is an organopolysiloxane having one or more carboxyl groups in one molecule. Although not particularly limited, organopolysiloxanes represented by the following general formula (15) are desirable.

(However, in the general formula (15), R18 is an organic group having 1 to 40 carbon atoms, at least one of which has a carboxyl group, and the remaining group is a group selected from hydrogen, a phenyl group, or a methyl group. Yes, they may be the same or different, and the average value of h is a positive number of 1 or more and 50 or less.)

  In the general formula (15), R18 is an organic group having 1 to 40 carbon atoms, at least one of which has a carboxyl group, and the remaining groups are groups selected from hydrogen, a phenyl group, or a methyl group, and are identical to each other. Or different. In addition, the carbon number of the organic group having a carboxyl group of the organopolysiloxane represented by the general formula (15) refers to a sum of the hydrocarbon group in the organic group and the carbon number of the carboxyl group. By making the carbon number of the organic group having a carboxyl group within the above range, deterioration of the appearance of the cured resin surface due to a decrease in compatibility with the resin can be suppressed. Moreover, in General formula (15), the average value of h is a positive number of 1 or more and 50 or less. By setting the average value of h within the above range, it is possible to suppress a decrease in fluidity due to an increase in the viscosity of a single oil. When the organopolysiloxane represented by the general formula (15) is used, the fluidity is not lowered and the appearance of the resin cured product surface is particularly good.

  The total blending amount of the component (G) that can be used in the present invention is the blending amount as the organopolysiloxane (G1) having a carboxyl group, and is 0.01% by weight or more and 3% by weight or less in the total epoxy resin composition. It is preferably 0.03% by weight or more and 2% by weight or less, more preferably 0.05% by weight or more and 1% by weight or less. By setting the blending amount in the above range, it is possible to suppress stains on the surface of the cured resin due to the release agent and excess organopolysiloxane and to obtain good continuous moldability.

  Moreover, in this invention, the effect of adding the reaction product (G2) of the organopolysiloxane (G1) which has (G) carboxyl group, and / or the organopolysiloxane (G1) which has a carboxyl group, and an epoxy resin. Other organopolysiloxanes can be used in combination as long as the above is not impaired.

In this invention, in order to improve the adhesiveness of an epoxy resin and an inorganic filler, adhesion assistants, such as a silane coupling agent, can be added. Examples thereof include, but are not limited to, epoxy silane, amino silane, ureido silane, mercapto silane, etc., which react between the epoxy resin and the inorganic filler to improve the interfacial strength between the epoxy resin and the inorganic filler. If it is.
More specifically, examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and β- (3,4 epoxy). (Cyclohexyl) ethyltrimethoxysilane and the like. Examples of the aminosilane include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-aminopropyl. Methyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3 -Aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, etc. In addition, examples of ureidosilane include γ-ureidopropyltriethoxysilane, hexa Methyl disilazane, etc. In addition, mercap Examples of tosilane include γ-mercaptopropyltrimethoxysilane, etc. These silane coupling agents may be used alone or in combination of two or more.

  As a compounding quantity of the silane coupling agent which can be used for this invention, 0.01 weight% or more and 1 weight% or less are preferable in all the epoxy resin compositions, More preferably, 0.05 weight% or more, 0.8 % By weight or less, particularly preferably 0.1% by weight or more and 0.6% by weight or less. If the blending amount of the silane coupling agent is within the above range, there is little possibility of causing a decrease in solder crack resistance in the semiconductor device due to a decrease in the interface strength between the epoxy resin and the inorganic filler. Moreover, if the compounding quantity of a silane coupling agent exists in the said range, there is little possibility of causing the fall of solder crack resistance by the water absorption of the hardened | cured material of an epoxy resin composition increasing.

  In the present invention, in addition to the components described above, colorants such as carbon black, bengara, titanium oxide; low stress additives such as silicone oil and silicone rubber; inorganic ion exchangers such as bismuth oxide hydrate; aluminum hydroxide; Additives such as metal hydroxides such as magnesium hydroxide, flame retardants such as zinc borate, zinc molybdate, and phosphazene may be appropriately blended.

  The epoxy resin composition for semiconductor encapsulation of the present invention is obtained by uniformly mixing the components of the present invention and other additives at room temperature using, for example, a mixer, and then heating roll, kneader or extrusion. It is possible to use a material that has been appropriately adjusted in dispersity, fluidity, etc., if necessary, such as melt kneaded using a kneader such as a machine, followed by cooling and pulverization.

  To manufacture a semiconductor device by sealing a semiconductor element with a cured product of the epoxy resin composition for semiconductor sealing of the present invention, for example, a lead frame, a circuit board, etc. mounted with the semiconductor element are placed in a mold cavity. Then, the epoxy resin composition for semiconductor encapsulation may be molded and cured by a molding method such as transfer molding, compression molding, or injection molding.

The semiconductor element that performs sealing in the present invention is not particularly limited, and examples thereof include an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element.
The form of the semiconductor device of the present invention is not particularly limited. For example, the dual in-line package (DIP), the plastic lead chip carrier (PLCC), the quad flat package (QFP), the small outline, and the like. package(
SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Tape Carrier Package (TCP), Ball Grid Array ( BGA), chip size package (CSP) and the like.
A semiconductor device sealed by a molding method such as the above transfer mold is mounted on an electronic device or the like as it is or after being completely cured at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours. Is done.

  FIG. 1 is a view showing a cross-sectional structure of an example of a semiconductor device using the epoxy resin composition according to the present invention. The semiconductor element 1 is fixed on the die pad 3 via the die bond material cured body 2. The electrode pad of the semiconductor element 1 and the lead frame 5 are connected by a gold wire 4. The semiconductor element 1 is sealed with a cured body 6 of a sealing resin composition.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples. Hereinafter, the blending ratio is parts by weight.
The components used in Examples and Comparative Examples are shown below.

(Epoxy resin)
Epoxy resin 1: an epoxy resin having a structure represented by the following formula (16) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by co-condensing o-cresol, formaldehyde, and 2-methoxynaphthalene with epichlorohydrin) Equivalent 251 and softening point 58 ° C. In the following general formula (16), the average value of m / n is ¼.)
Epoxy resin 2: an epoxy resin having a structure represented by the following formula (16) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by co-condensing o-cresol, formaldehyde, and 2-methoxynaphthalene with epichlorohydrin) Equivalent 220, softening point 52 ° C. In the following general formula (16), the average value of m / n is 1/9.)
Epoxy resin 3: An epoxy resin having a structure represented by the following formula (16) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by co-condensing o-cresol, formaldehyde, and 2-methoxynaphthalene with epichlorohydrin) Equivalent 270, softening point 63 ° C. In the following general formula (16), the average value of m / n is 3/7.)

Epoxy resin 4: Epoxy resin having a structure represented by the following formula (17) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by cocondensation of phenol, formaldehyde and methylphenyl sulfide with epichlorohydrin. Epoxy equivalent 196, (Softening point 54 ° C. In the following general formula (17), the average value of m / n is ¼.)

Epoxy resin 5: An epoxy resin having a structure represented by the following formula (18) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by cocondensation of phenol, benzaldehyde and methylphenyl sulfide with epichlorohydrin. Epoxy equivalent 285, Softening point 74 ° C. In the following general formula (18), the average value of m / n is ¼.)

Epoxy resin 6: epoxy resin having a structure represented by the following formula (19) (an epoxy resin obtained by glycidyl etherification of a phenol resin obtained by cocondensing 1-naphthol, formaldehyde and methoxybenzene with epichlorohydrin. Epoxy equivalent 273) The softening point is 68 ° C. In the following general formula (19), the average value of m / n is ¼.)

Epoxy resin 7: β-naphthol aralkyl type epoxy resin having a phenylene skeleton (manufactured by Tohto Kasei Co., Ltd., ESN-175, epoxy equivalent 252 and softening point 58 ° C.)
Epoxy resin 8: Orthocresol novolak type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd., Sumiepoxy (registered trademark) ESCN195LA. Epoxy equivalent 196, softening point 62 ° C.)
(Compounds containing two or more phenolic hydroxyl groups)
Phenol resin 1: Phenol novolac resin (Sumitomo Bakelite Co., Ltd., Sumilite Resin (registered trademark) PR-HF-3, softening point 80 ° C., hydroxyl equivalent 104)
Phenol resin 2: Phenol aralkyl resin having a phenylene skeleton (Mitsui Chemicals, Millex (registered trademark) XLC-4L. Hydroxyl equivalent 165, softening point 65 ° C.)
(Inorganic filler)
Fused spherical silica (average particle size 30μm)
(Curing accelerator)
Curing accelerator 1: Triphenylphosphine Curing accelerator 2: 1,8-diazabicyclo (5,4,0) undecene-7

Curing accelerator 3: Curing accelerator represented by the following formula (20)

Curing accelerator 4: Curing accelerator represented by the following formula (21)

(Polyethylene oxide)
Polyethylene oxide 1 (drop point 120 ° C., acid value 20 mg KOH / g, number average molecular weight 2000, density 0.98 g / cm ³ , average particle size 45 μm, content of particles of 106 μm or more 0.0% by weight. Oxide.)
Polyethylene oxide 2 (drop point 110 ° C., acid value 12 mg KOH / g, number average molecular weight 1200, density 0.97 g / cm ³ , average particle size 40 μm, content of particles of 106 μm or more 0.0% by weight. Oxide.)
(Other release agents)
Carnauba wax (Nikko Rica Co., Ltd., Nikko Carnauba)
((F) component)
F1-1: butadiene-acrylonitrile copolymer having carboxyl groups at both ends (
CTBN-1008SP, manufactured by Ube Industries, Ltd. In the general formula (11), x = 0.82, y = 0.18, and the average value of z is 62. Number average molecular weight 3550, carboxyl group equivalent 2200 g / eq. Sodium ion amount 5ppm, chlorine ion amount 200ppm. )
F2-1: Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., YL
-6810 (epoxy equivalent: 172 g / eq, melting point: 45 ° C.) 65 parts by weight was heated and melted at 140 ° C., and 33 parts by weight of F1-1 and 0.8 parts by weight of triphenylphosphine were added. Molten reaction product obtained by melt mixing for 30 minutes

((G) component)
G1-1: Compound represented by the following formula (22) (Toray Dow Corning Co., Ltd., BY-750, molecular weight of about 1500)

G2-1: 12 parts by weight of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., jER (registered trademark) YL-6810 (epoxy equivalent 172 g / eq, melting point 45 ° C.) at 140 ° C. is heated and melted, and G1 6 parts by weight of -1 and 0.15 parts by weight of triphenylphosphine were added and melted reaction product obtained by melt mixing at 140 ° C. for 30 minutes (silane coupling agent)
Silane coupling agent 1: γ-glycidoxypropyltrimethoxysilane (coloring agent)
Carbon black

Example 1
Epoxy resin 1 8.80 parts by weight Phenolic resin 1 3.80 parts by weight Fused spherical silica 86.00 parts by weight Curing accelerator 1 0.20 parts by weight Polyethylene oxide 1 0.20 parts by weight F2-1 0.30 parts by weight G2 -1 0.10 parts by weight Silane coupling agent 1 0.30 parts by weight Carbon black 0.30 parts by weight is mixed at room temperature with a mixer, melted and kneaded with a heating roll at 80 to 100 ° C., cooled and crushed, A resin composition was obtained. It evaluated by the following method using the obtained epoxy resin composition. The evaluation results are shown in Table 1.

Spiral flow: Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a spiral flow measurement mold conforming to EMMI-1-66 was maintained at 175 ° C., injection pressure 6.9 MPa. The epoxy resin composition was injected under a pressure time of 120 seconds, and the flow length was measured. The spiral flow is a fluidity parameter, and the larger the value, the better the fluidity. The unit is cm.

-Wire flow rate: Using a low-pressure transfer molding machine (YKC, YKC40TA-M) under conditions of a mold temperature of 175 ° C, an injection pressure of 9.3 MPa, and a curing time of 90 seconds, After sealing and molding a silicon chip or the like to obtain 208 pin QFP (copper frame: 28 mm × 28 mm × 3.2 mm thickness, pad size: 11 mm × 11 mm, chip size 7 mm × 7 mm × 0.35 mm thickness), 175 Post-curing was performed at 4 ° C. for 4 hours. After cooling to room temperature, it was observed with a soft X-ray fluoroscope (PRO-TEST100, manufactured by Softex Corporation), and the flow rate of the gold wire was expressed as a ratio of (flow rate) / (gold wire length). The value of the gold wire part that becomes the largest is shown. Units%. When this value exceeds 5%, there is a high possibility that adjacent gold wires come into contact with each other. The criterion was ○ for less than 5% and x for 5% or more.

Continuous moldability: epoxy resin composition using a low-pressure transfer automatic molding machine (Daiichi Seiko Co., Ltd., GP-ELF) under conditions of a mold temperature of 175 ° C., an injection pressure of 9.6 MPa, and a curing time of 90 seconds. 80 pin QFP (Cu lead frame, package outer dimensions: 14 mm x 20 mm x 2.0 mm thickness, pad size: 8.0 mm x 8.0 mm, chip size 7.0 mm x 7 .0 mm × 0.35 mm thickness) was continuously performed up to 700 shots. Judgment criteria were ◎ for those that could be continuously molded up to 700 shots without any problems such as unfilled, ◯ for those that could be continuously molded up to 500 shots without any problems such as unfilled, and x otherwise.

  Package appearance and mold stain resistance: In the evaluation of the continuous moldability, the package surface and mold surface after 500 and 700 shot molding were visually evaluated for stain. The package appearance judgment and mold contamination criteria are indicated by ◎ for those that are not dirty up to 700 shots, ◯ for those that are not dirty up to 500 shots, and × that are dirty. Further, in the above-mentioned continuous formability, those that could not be formed without any problem up to 500 shots were judged based on the package appearance and mold contamination status when the continuous forming was abandoned.

Solder resistance: The package molded in the continuous moldability evaluation was post-cured at 175 ° C. for 8 hours. Ten packages obtained were humidified at 60 ° C. and 60% relative humidity for 168 hours, and then IR reflow treatment (maximum temperature 260 ° C.) was performed three times. After the treatment, the inside of the package and the presence or absence of cracks were observed with an ultrasonic scratching machine, and any of the peeling or cracking occurred was regarded as defective. When the number of defective packages is n, n / 10 is displayed.

・ Temperature cycle resistance: Ten packages obtained at the time of gold wire flow rate evaluation are repeatedly subjected to temperature cycle treatment in an environment of −60 ° C./30 minutes to 150 ° C./30 minutes to check for external cracks. Observed. The time when external cracks occurred in 50% or more of the evaluated packages was measured and indicated as “50% defect occurrence time”. The unit is hr. The longer the 50% defect occurrence time is, the more preferable.

Examples 2 to 21 and Comparative Examples 1 to 5
According to the composition of Table 1, Table 2, and Table 3, an epoxy resin composition was produced in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1, Table 2, and Table 3.

  In Examples 1 to 21, an epoxy resin (A) having a structure represented by the general formula (1), a compound (B) containing two or more phenolic hydroxyl groups, an inorganic filler (C), a curing accelerator (D ) And oxidized polyethylene (E), the type and amount of epoxy resin (A), the type of compound (B) containing two or more phenolic hydroxyl groups, the type and amount of oxidized polyethylene (E), A butadiene / acrylonitrile copolymer (F1) having a carboxyl group, or a butadiene / acrylonitrile copolymer having a carboxyl group, including those having different types of curing accelerators (D) and inorganic fillers (C). Reaction product (F2) of (F1) and epoxy resin, organopolysiloxane (G1) having a carboxyl group, and / or an organopom having a carboxyl group This includes the addition of the reaction product (G2) of siloxane (G1) and epoxy resin, but in all cases, fluidity (spiral flow), wire flow rate, continuous moldability, package appearance and mold contamination The results were excellent in the balance of solderability, solder resistance, and temperature cycle resistance.

On the other hand, in Comparative Example 1 using a β-naphthol aralkyl type epoxy resin (epoxy resin 5) having a phenylene skeleton in place of the epoxy resin (A) having a structure represented by the general formula (1), fluidity, The gold wire flow rate was inferior. In Comparative Example 2 using an ortho-cresol novolac type epoxy resin (epoxy resin 6) instead of the epoxy resin (A) having the structure represented by the general formula (1), the fluidity, solder resistance, The result was inferior temperature cycling. In Comparative Examples 3 and 4 using carnauba wax instead of polyethylene oxide (E), continuous moldability, package appearance and mold dirt, solder resistance, and temperature cycle resistance were inferior. Further, instead of the epoxy resin (A) having the structure represented by the general formula (1), an ortho cresol novolac type epoxy resin (epoxy resin 6) is used, and carnauba wax is used instead of polyethylene oxide (E). In Comparative Example 5 used, fluidity, continuous formability, package appearance and mold stain resistance, solder resistance, and temperature cycle resistance were inferior.

  The synergistic effect in low stress by using a combination of the epoxy resin (A) having the structure represented by the general formula (1) and the oxidized polyethylene (E) is as follows: Example 1 and Comparative Examples 2, 3, 5 It is clear by comparison. That is, the low-stress improvement effect only by using the epoxy resin (A) having the structure represented by the general formula (1) is as shown as a difference between Comparative Example 5 and Comparative Example 3 ( (Solder resistance: 10/10 → 5/10, temperature cycle resistance: 500 hours → 700 hours), the problem of the present invention cannot be solved. Moreover, the effect in the low stress property only by using the oxidized polyethylene (E) is as shown as a difference between the comparative example 5 and the comparative example 2 (solder resistance: 10/10 → 10/10, Temperature cycle resistance: 500 hours → 500 hours), almost no effect can be confirmed. On the other hand, the effect of improving low stress by using the epoxy resin (A) having the structure represented by the general formula (1) and the oxidized polyethylene (E) in combination is shown as a difference between Comparative Example 5 and Example 1. (Solder resistance: 10/10 → 0/10, temperature cycle resistance: 500 hours → 1000 hours or more) and an epoxy resin (A) having a structure represented by the general formula (1) The result showed a remarkable synergistic effect that could not be expected from the effect of using only and the effect of using only oxidized polyethylene (E).

  According to the present invention, an epoxy resin composition having excellent low stress properties and excellent fluidity and continuous moldability can be obtained, which is suitable for sealing a semiconductor device.

It is the figure which showed the cross-section about an example of the semiconductor device using the epoxy resin composition which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Die-bonding material hardening body 3 Die pad 4 Gold wire 5 Lead frame 6 Hardening body of resin composition for sealing

Claims (9)

(A) an epoxy resin having a structure represented by the following general formula (1);
(B) a compound containing two or more phenolic hydroxyl groups;
(C) an inorganic filler;
(D) a curing accelerator;
(E) The epoxy resin composition for semiconductor sealing characterized by including polyethylene oxide.

(In the above general formula (1), Ar is an aromatic group having 6 to 20 carbon atoms, and may be the same or different from each other. R1 is a hydrocarbon group having 1 to 6 carbon atoms. And R2 is a hydrocarbon group having 1 to 4 carbon atoms, W1 is an oxygen atom or a sulfur atom, R3 is hydrogen, a hydrocarbon group having 1 to 4 carbon atoms, or An aromatic group having 6 to 20 carbon atoms, which may be the same or different from each other, a is an integer of 0 to 10, b is an integer of 1 to 3, and m and n represent molar ratios. 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and the average value of m / n is 1/10 to 1/1.) (A) The epoxy resin having the structure represented by the general formula (1) co-condenses the phenolic hydroxyl group-containing aromatics, aldehydes, and the compound (J) represented by the following general formula (2). 2. The epoxy resin composition for semiconductor encapsulation according to claim 1, which is an epoxy resin obtained by glycidyl etherification of the phenol resin obtained in this way with epichlorohydrin.

(However, in the said General formula (2), Ar is a C6-C20 aromatic group. R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2 is a hydrocarbon group having 1 to 4 carbon atoms, W1 is an oxygen atom or a sulfur atom, a is an integer of 0 to 10, and b is an integer of 1 to 3). 3. The semiconductor according to claim 1, wherein the epoxy resin having a structure represented by the general formula (1) is an epoxy resin represented by the following general formula (3). An epoxy resin composition for sealing.

(However, in the said General formula (3), R1 is a C1-C6 hydrocarbon group and may mutually be same or different. R2 is a C1-C4 hydrocarbon group, W1 is an oxygen atom or a sulfur atom, c is an integer of 0 to 5, d is an integer of 0 to 3, m and n represent a molar ratio, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and the average value of m / n is 1/10 to 1/1.) The epoxy resin composition for semiconductor encapsulation according to claim 3, wherein the epoxy resin represented by the general formula (3) is an epoxy resin represented by the following general formula (4).

(However, in the said General formula (4), R1 is a C1-C6 hydrocarbon group and may mutually be same or different. C is an integer of 0-5, d is 0-3. M and n represent molar ratios, 0 ≦ m <1, 0 <n ≦ 1, m + n = 1, and the average value of m / n is 1/10 to 1/1. ) The curing accelerator (D) is a compound represented by the following general formula (5), a compound represented by the following general formula (6), a compound represented by the following general formula (7), and the following general formula (8). 5. The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the epoxy resin composition is at least one selected from compounds represented by the formula:

(However, in the said General formula (5), P represents a phosphorus atom. R4, R5, R6, and R7 represent an aromatic group or an alkyl group. A is a functional group chosen from a hydroxyl group, a carboxyl group, and a thiol group. Represents an anion of an aromatic organic acid having at least one of the following: AH is an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring X and y are integers of 1 to 3, z is an integer of 0 to 3, and x = y.

(However, in the said General formula (6), X1 represents a C1-C3 alkyl group, Y1 represents a hydroxyl group. E and f are integers of 0-3.)

(However, in the said General formula (7), P represents a phosphorus atom. R8, R9, and R10 represent a C1-C12 alkyl group or a C6-C12 aryl group, and they are mutually the same. R11, R12 and R13 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R11 and R12 are bonded to form a cyclic structure. May be.)

(However, in the said General formula (8), P represents a phosphorus atom and Si represents a silicon atom. R14, R15, R16, and R17 are respectively an organic group or an aliphatic group which has an aromatic ring or a heterocyclic ring. X2 is an organic group bonded to the groups Y2 and Y3, where X3 is an organic group bonded to the groups Y4 and Y5. And Y3 represent a group formed by releasing a proton from a proton-donating substituent, and groups Y2 and Y3 in the same molecule are combined with a silicon atom to form a chelate structure. The functional substituent represents a group formed by releasing a proton, and the groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure, and X2 and X3 may be the same or different from each other. Often Y2, Y3, Y4, and Y5 is .Z1 which may be the same or different from each other is an organic group or an aliphatic group, an aromatic ring or a heterocyclic ring.)   And (F) a butadiene / acrylonitrile copolymer (F1) having a carboxyl group and / or a reaction product (F2) of a butadiene / acrylonitrile copolymer (F1) having a carboxyl group and an epoxy resin. The epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 5, wherein the composition is an epoxy resin composition for semiconductor encapsulation.   Further, (G) an organopolysiloxane (G1) having a carboxyl group and / or a reaction product (G2) of an organopolysiloxane (G1) having a carboxyl group and an epoxy resin is included. The epoxy resin composition for semiconductor sealing in any one of thru | or 6.   The epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 7, wherein the inorganic filler (C) is contained in an amount of 80% by weight or more and 92% by weight or less of the entire resin composition. .   A semiconductor device comprising a semiconductor element sealed with a cured product of the epoxy resin composition for semiconductor sealing according to claim 1.

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