JP2009227733A - Epoxy resin composition for sealing semiconductor, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing a semiconductor, which is excellent in flame resistance as well as in the balance of fluidity and soldering resistance although the composition is inexpensive without using a brominated epoxy resin or antimony compounds. <P>SOLUTION: The epoxy resin composition for sealing a semiconductor comprises: (A) an epoxy resin having a structure including a naphthalene structure having glycidyl ether and a benzene ring structure, in which a repeating unit of the specified naphthalene structure and a repeating unit of the benzene ring structure are present each in a specified range; (B) a hardening agent; and (C) an inorganic filler. A semiconductor device is obtained by sealing a semiconductor element with a hardened product of the epoxy resin composition for sealing a semiconductor. <P>COPYRIGHT: (C)2010,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 the balance of productivity, cost, reliability and the like, it is mainly sealed with an epoxy resin composition.

  Conventionally, bromine-containing epoxy resins and antimony oxide have generally been used for epoxy resin compositions for semiconductor encapsulation for the purpose of imparting flame retardancy. There is a growing movement to regulate the use of halogen-containing compounds that are likely to occur and highly toxic antimony compounds. Under these circumstances, metal oxides such as aluminum hydroxide and magnesium hydroxide have been used as flame retardants to replace brominated epoxy resins and antimony compounds. There has been a problem in that continuous formability and solder resistance are lowered due to the deterioration of the solder.

  From the above situation, an epoxy resin composition using a phenol aralkyl type epoxy resin having a biphenylene skeleton is proposed as a semiconductor epoxy resin composition that can obtain good flame retardancy without adding a flame retardant imparting agent. (For example, refer to Patent Documents 1 and 2). Although these epoxy resin compositions have the advantages of being able to obtain a highly reliable semiconductor device with low water absorption, low elastic modulus at heat, high adhesion, excellent flame retardancy, Manufacturing is expensive, and there is a problem that fluidity may not be sufficient when a thin semiconductor device is sealed.

JP 2004-203911 A Japanese Patent Application Laid-Open No. 2004-155841

  The present invention relates to an epoxy resin composition for semiconductor encapsulation, which does not use a brominated epoxy resin or an antimony compound, has excellent flame resistance at a low cost, and has a good balance of fluidity, continuous moldability and solder resistance. And the semiconductor device excellent in the reliability formed by sealing a semiconductor element with the hardened | cured material is provided.

（ただし、上記一般式（１）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、Ｒ３は炭素数１〜６の炭化水素基又は水素原子であり、互いに同じであっても異なっていてもよい。Ｒ４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。ａは０〜５の整数、ｂは０〜４の整数である。ｍは２〜２０の整数、ｎは０〜１９の整数であり、（ｍ−ｎ）は１以上の整数である。グリシジルエーテル基を有するナフタレン環のｍ個の繰り返し単位とベンゼン環を有するｎ個の繰り返し単位は、それぞれが連続で並んでいても、お互いが交互もしくはランダムに並んでいてもよいが、それぞれの間には必ず−ＣＲ２Ｒ３−を有する。）と、
（Ｂ）硬化剤と、
（Ｃ）無機充填剤とを含み、
前記エポキシ樹脂（Ａ）が、前記一般式（１）において（ｍ−ｎ）≧２、かつｎ≠０である成分（Ａ−１）と、ｎ＝０である成分（Ａ−２）と、を含むことを特徴とする。 The epoxy resin composition for semiconductor encapsulation of the present invention is (A) an epoxy resin having a structure represented by the following general formula (1)

(However, in the said General formula (1), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2, R3 is a C1-C6 hydrocarbon group. Or a hydrogen atom, which may be the same or different from each other, R4 is a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different from each other. An integer, b is an integer of 0 to 4. m is an integer of 2 to 20, n is an integer of 0 to 19, and (mn) is an integer of 1 or more, a naphthalene ring having a glycidyl ether group. The m repeating units and the n repeating units having a benzene ring may be arranged in succession, or may be alternately or randomly arranged with each other. And)
(B) a curing agent;
(C) an inorganic filler,
The epoxy resin (A) is a component (A-1) in which (mn) ≧ 2 and n ≠ 0 in the general formula (1), and a component (A-2) in which n = 0, It is characterized by including.

  The epoxy resin composition for semiconductor encapsulation of the present invention is a content ratio (A-1) / (A-2) of the component (A-1) and the component (A-2) in the epoxy resin (A). May be in the range of 1/9 to 9/1 by mass ratio.

  The epoxy resin composition for semiconductor encapsulation of the present invention further comprises a component (A-3) in which the epoxy resin (A) is (mn) = 1 and n ≠ 0 in the general formula (1). Can be included.

  In the epoxy resin composition for semiconductor encapsulation of the present invention, the content ratio of the component (A-3) in the epoxy resin (A) is the total amount of the component (A-1) and the component (A-2). It can be in the range of 1 to 300 parts by mass with respect to 100 parts by mass.

  The epoxy resin composition for semiconductor encapsulation of this invention can contain the said inorganic filler (C) 80 to 93 mass% of the said whole resin composition.

  In the epoxy resin composition for semiconductor encapsulation of the present invention, the curing agent (B) may be a phenol resin curing agent.

  The epoxy resin composition for semiconductor encapsulation of the present invention may further contain (D) a curing accelerator.

  In the epoxy resin composition for semiconductor encapsulation of the present invention, the curing accelerator (D) is an addition of a tetra-substituted phosphonium compound, a phosphobetaine compound, a phosphine compound and a quinone compound, and an addition of a phosphonium compound and a silane compound. It may contain a curing accelerator having at least one latency selected from those.

  The epoxy resin composition for semiconductor encapsulation of the present invention may further include a compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring.

  The semiconductor device of the present invention is characterized in that a semiconductor element is sealed with a cured product of the above-described epoxy resin composition for semiconductor sealing.

  According to the present invention, a brominated epoxy resin and an antimony compound are used, and the epoxy resin composition for semiconductor encapsulation has an excellent balance of fluidity, continuous moldability, and solder resistance while being low in cost and excellent in flame resistance. It is possible to obtain a semiconductor device having excellent properties and reliability.

  The present invention includes (A) an epoxy resin having a structure represented by the general formula (1), (B) a curing agent, and (C) an inorganic filler. In addition, an epoxy resin composition for semiconductor encapsulation excellent in the balance of fluidity, continuous moldability and solder resistance and a semiconductor device excellent in reliability can be obtained. Hereinafter, the present invention will be described in detail.

  First, the epoxy resin composition for semiconductor encapsulation will be described. In the epoxy resin composition for semiconductor encapsulation of 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) has a naphthalene structure in the molecule, which has effects such as improving the flame resistance of the resin composition, reducing the water absorption rate, and reducing the thermal expansion coefficient. The benzene structure having no substituent has an effect of improving the flame resistance of the resin composition in combination with the naphthalene structure and reducing the elastic modulus. As a result, an epoxy resin using the epoxy resin (A) is used. The resin composition has the feature of being excellent in flame resistance and solder resistance.

（ただし、上記一般式（１）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、Ｒ３は炭素数１〜６の炭化水素基又は水素原子であり、互いに同じであっても異なっていてもよい。Ｒ４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。ａは０〜５の整数、ｂは０〜４の整数である。ｍは２〜２０の整数、ｎは０〜１９の整数であり、（ｍ−ｎ）は１以上の整数である。グリシジルエーテル基を有するナフタレン環のｍ個の繰り返し単位とベンゼン環を有するｎ個の繰り返し単位は、それぞれが連続で並んでいても、お互いが交互もしくはランダムに並んでいてもよいが、それぞれの間には必ず−ＣＲ２Ｒ３−を有する。）

(However, in the said General formula (1), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2, R3 is a C1-C6 hydrocarbon group. Or a hydrogen atom, which may be the same or different from each other, R4 is a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different from each other. An integer, b is an integer of 0 to 4. m is an integer of 2 to 20, n is an integer of 0 to 19, and (mn) is an integer of 1 or more, a naphthalene ring having a glycidyl ether group. The m repeating units and the n repeating units having a benzene ring may be arranged in succession, or may be alternately or randomly arranged with each other. Have)

M in the general formula (1) is an integer of 2 to 20, n is an integer of 0 to 19, and (mn) is an integer of 1 or more, but the epoxy resin (A) is represented by the general formula (1). It is essential that the component (A-1) in which (mn) ≧ 2 and n ≠ 0 and the component (A-2) in which n = 0 are included in the epoxy resin (A) ( The content ratio (A-1) / (A-2) of the component (A-1) and the component (A-2) is preferably in the range of 1/9 to 9/1 in terms of mass ratio, and 1/6 to A range of 5/1 is more preferable. Thereby, the epoxy resin composition excellent in balance of curability, fluidity, and solder resistance can be obtained. In addition, the epoxy resin (A) may further include a component (A-3) in which (mn) = 1 and n ≠ 0 in the general formula (1). 3) The component is contained in the range of 1 to 300 parts by mass, more preferably in the range of 15 to 200 parts by mass with respect to 100 parts by mass of the total amount of the components (A-1) and (A-2). May be. The component (A-3) may be generated at the same time when the epoxy resin (A) containing the component (A-1) and the component (A-2) is synthesized. For example, there is little fear of impairing the balance of curability, fluidity, and solder resistance in the epoxy resin composition obtained by including the component (A-1) and the component (A-2).

（ただし、上記一般式（２）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、Ｒ３は炭素数１〜６の炭化水素基又は水素原子であり、互いに同じであっても異なっていてもよい。Ｒ４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。ａは０〜５の整数、ｂは０〜４の整数である。ｐは０〜１９の整数、ｑは０〜１９の整数であるが、ｐ＝ｑ＝０は除く。ｐ個の繰り返し単位とｑ個の繰り返し単位は、それぞれが連続で並んでいても、お互いが交互もしくはランダムに並んでいてもよい。） The epoxy resin having the structure represented by the general formula (1) can also be represented by the following general formula (2). In the following general formula (2), the component having p> 0 and q> 0 is (A− 1) Component, component with p = 0, q> 0 corresponds to component (A-2), component with p> 0, q = 0 corresponds to component (A-3). Here, p and q in the following general formula (2) and m and n in the general formula (1) have a relationship as shown in the following formula.
p = n
q = mn-1

(However, in the said General formula (2), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2, R3 is a C1-C6 hydrocarbon group. Or a hydrogen atom, which may be the same or different from each other, R4 is a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different from each other. Integer, b is an integer from 0 to 4. p is an integer from 0 to 19, q is an integer from 0 to 19, except for p = q = 0, p repeating units and q repeating units May be arranged one after the other or alternately or randomly.)

  The lower limit value of the content ratio of the component (A-1) where (mn) ≧ 2 and n ≠ 0 in the epoxy resin (A) having the structure represented by the general formula (1) is not particularly limited. Is preferably 10% by mass or more, and more preferably 15% by mass or more. When the lower limit value is within the above range, the effect of improving the curability and the solder resistance of the resin composition can be obtained. Further, the upper limit of the content ratio of the component (A-1) in which (mn) ≧ 2 and n ≠ 0 is not particularly limited, but is preferably 45% by mass or less, and 40% by mass or less. It is more preferable that When the upper limit is within the above range, a resin composition having low epoxy resin viscosity and excellent fluidity can be obtained.

  The lower limit of the content ratio of the component (A-2) where n = 0 in the epoxy resin (A) having the structure represented by the general formula (1) is not particularly limited, but is 10% by mass or more. It is preferable that it is 25% by mass or more. When the lower limit value of the content ratio of the n = 0 component (A-2) is within the above range, the effect of improving the fluidity and solder resistance of the resin composition can be obtained. Although it does not specifically limit as an upper limit of the content rate of the component (A-2) which is n = 0, It is preferable that it is 55 mass% or less, and it is more preferable that it is 45 mass% or less. A resin composition can show favorable sclerosis | hardenability as the upper limit of the content rate of the component (A-2) which is n = 0 is in the said range.

  The epoxy resin (A) having a structure represented by the general formula (1) includes a component (A-1) in which (mn) ≧ 2 and n ≠ 0, and a component in which n = 0 (A− 2), the reason why the curability and solder resistance of the resin composition are improved is not clear, but the following reasons are conceivable. As an example of the component (A-1) in which (mn) ≧ 2 and n ≠ 0 in the general formula (1), for example, the following general formula (m−n) = 2 and n ≠ 0 The compound represented by 3) can be mentioned, but compared with the compound represented by the following general formula (4) corresponding to the component (A-3) in which (mn) = 1 and n ≠ 0. It is considered that the density of the epoxy group is locally increased, thereby improving the reactivity with the curing agent component and improving the adhesion to the metal interface. In addition, a compound represented by the following general formula (5) corresponding to the component (A-2) where n = 0 in the epoxy resin (A), particularly a component (general formula (m) where m = 2 and n = 0. In 5), it is presumed that the fact that the thermal elastic modulus of the resin composition is reduced due to the fact that not only a small amount of component (q = 1) is included is also a factor in improving the solder resistance.

（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、Ｒ３は炭素数１〜６の炭化水素基又は水素原子であり、互いに同じであっても異なっていてもよい。Ｒ４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。ａは０〜５の整数、ｂは０〜４の整数である。）

(However, in the said General formula (3), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2, R3 is a C1-C6 hydrocarbon group. Or a hydrogen atom, which may be the same or different from each other, R4 is a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different from each other. Integer, b is an integer of 0-4.)

（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。Ｒ２、Ｒ３は炭素数１〜６の炭化水素基又は水素原子であり、互いに同じであっても異なっていてもよい。Ｒ４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。ａは０〜５の整数、ｂは０〜４の整数である。ｐは１〜１９の整数である。）

(However, in the said General formula (4), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2, R3 is a C1-C6 hydrocarbon group. Or a hydrogen atom, which may be the same or different from each other, R4 is a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different from each other. An integer, b is an integer of 0 to 4. p is an integer of 1 to 19.)

（ただし、上記一般式（５）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、Ｒ３は炭素数１〜６の炭化水素基又は水素原子であり、互いに同じであっても異なっていてもよい。ａは０〜５の整数である。ｑは１〜１９の整数である。）

(However, in the said General formula (5), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2, R3 is a C1-C6 hydrocarbon group. Or a hydrogen atom, which may be the same or different from each other, a is an integer of 0 to 5, and q is an integer of 1 to 19.)

  Among the epoxy resins (A) having the structure represented by the general formula (1), the general formula (4) corresponding to the component (A-3) in which (mn) = 1 and n ≠ 0 As an example of the compound represented, the compound represented by the following formula (6) is commercially available as ESN-185 from Nippon Steel Chemical Co., Ltd., but this is (A-3) Since it is composed of only components, the epoxy resin composition using this composition has a certain level of properties in flame resistance and solder resistance, but the curability and fluidity may be insufficient. As a result, the continuous formability and productivity of the semiconductor device may become a problem, which is not preferable.

（ただし、上記式（６）において、ｐは１〜１９の整数である。）

(However, in said formula (6), p is an integer of 1-19.)

  Moreover, the epoxy containing the compound represented by the general formula (5) corresponding to the component (A-2) in which n = 0 among the epoxy resins (A) having the structure represented by the general formula (1) As patent documents relating to the resin composition, there are JP-A-2-227418, JP-A-5-287052, and the like, and it is expected that characteristics such as flame resistance, fluidity, and solder resistance will be improved to some extent. However, in the case of only the component (A-2), the curability in the resin composition is not sufficient, and therefore solder resistance may not be sufficiently exhibited, which is not preferable.

  On the other hand, in the general formula (1), it includes a component (A-1) in which (mn) ≧ 2 and n ≠ 0 and an n = 0 component (A-2), more preferably both components If the content ratio of the epoxy resin (A) is within the above-mentioned preferable range, the epoxy resin composition for semiconductor encapsulation has excellent flame resistance and good balance of curability, fluidity, and solder resistance at a low cost. As a result, a semiconductor device having excellent flame resistance and solder resistance can be continuously produced. In order to make the content ratio of the component (A-1) and the component (A-2) in the epoxy resin (A) having the structure represented by the general formula (1) within the above-described preferable range, a method described later. Can be synthesized and adjusted.

  The content ratio of the component (A-1), the component (A-2), and the component (A-3) in the epoxy resin (A) having the structure represented by the general formula (1) is calculated as follows. be able to. The gel permeation chromatography (GPC) measurement of the epoxy resin (A) is performed to determine the PS-converted molecular weight of each component corresponding to the detected peak, and corresponds to the detected peak from the ratio of the detected peak areas. The content ratio (% by mass) of each component is calculated. Moreover, the FD-MS measurement of an epoxy resin (A) is performed, and the value of m and n for each component corresponding to the detected peak is obtained by identifying the molecular weight and structure of the component corresponding to the detected peak. . By comparing the molecular weight obtained by GPC measurement with the PS-converted molecular weight and the molecular weight obtained by FD-MS, the structure, molecular weight, m, n value and content ratio for each component corresponding to the detected peak are determined. In (1), (mn) ≧ 2 and n ≠ 0 component (A-1), n = 0 component (A-2), (mn) = 1, and n ≠ 0. The content ratio of a certain component (A-3) can be calculated. Here, GPC measurement needs to have a high resolution and is measured by the method described later. In the high molecular weight region where (m + n) exceeds 7, the separation of peaks, the values of m, n Verification / identification may be difficult. Such a high molecular weight component is divided into a half (A-1) component and a (A-3) component for convenience in consideration of the assumed structure.

  The gel permeation chromatography (GPC) measurement of the present invention is performed as follows. The GPC device is composed of a pump, an injector, a guard column, a column, and a detector, and tetrahydrofuran (THF) is used as a solvent. The pump flow rate is 0.5 ml / min. A flow rate higher than this is not preferable because the detection accuracy of the target molecular weight is lowered. In order to accurately measure at the above flow rate, it is necessary to use a pump with good flow rate accuracy, and the flow rate accuracy is preferably 0.10% or less. A commercially available guard column (for example, TSK GUARDCOLUMN HHR-L: diameter 6.0 mm, tube length 40 mm) manufactured by Tosoh Corporation, and a commercially available polystyrene gel column (TSK-GEL GMHHR- manufactured by Tosoh Corporation) are used for the guard column. L: diameter 7.8 mm, tube length 30 mm) are connected in series. A differential refractometer (RI detector, for example, a differential refractive index (RI) detector W2414 manufactured by WATERS) is used as the detector. Prior to the measurement, the guard column, the column and the inside of the detector are stabilized at 40 ° C. As a sample, a THF solution of an epoxy resin (A) adjusted to a concentration of 3 to 4 mg / ml is prepared, and this is injected from an about 50 to 150 μl injector to perform measurement. In analyzing the sample, a calibration curve prepared from a monodisperse polystyrene (hereinafter referred to as PS) standard sample is used. For the calibration curve, a logarithmic value of the molecular weight of PS and the peak detection time (retention time) of PS are plotted, and a regression of the cubic equation is used. As standard PS samples for preparing calibration curves, Shodex Standard SL-105 series product numbers S-1.0 (peak molecular weight 1060), S-1.3 (peak molecular weight 1310), S-2 manufactured by Showa Denko K.K. 0.0 (peak molecular weight 1990), S-3.0 (peak molecular weight 2970), S-4.5 (peak molecular weight 4490), S-5.0 (peak molecular weight 5030), S-6.9 (peak molecular weight 6930) ), S-11 (peak molecular weight 10700), S-20 (peak molecular weight 19900) were used.

  The epoxy resin (A) having the structure represented by the general formula (1) used in the epoxy resin composition for semiconductor encapsulation according to the present invention includes naphthols, aldehydes, and a fragrance represented by the following general formula (7). It can be obtained by glycidyl etherification with epichlorohydrin using a naphthol resin obtained by reacting a group compound as a precursor.

（ただし、上記一般式（７）において、Ｒ２、Ｒ３は炭素数１〜６の炭化水素基又は水素原子であり、互いに同じであっても異なっていてもよい。Ｒ４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。Ｘは、ハロゲン基、水酸基又は炭素数１〜６のアルコキシ基である。Ｒ５、Ｒ６は炭素数１〜５の炭化水素基又は水素原子であり、互いに同じであっても異なっていてもよい。）

(However, in the said General formula (7), R2 and R3 are C1-C6 hydrocarbon groups or a hydrogen atom, and may mutually be same or different. R4 is C1-C6. A hydrocarbon group, which may be the same or different from each other, X is a halogen group, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, and R5 and R6 are hydrocarbon groups having 1 to 5 carbon atoms. Or a hydrogen atom, which may be the same or different.

  Although it does not specifically limit as naphthols used for manufacture of the naphthol resin which is a precursor of an epoxy resin (A), For example, (alpha)-naphthol, (beta) -naphthol, 2-methyl- 1-naphthol, 3-methyl-1-naphthol, 4-methyl-1-naphthol, 6-methyl-1-naphthol, 7-methyl-1-naphthol, 8-methyl-1-naphthol, 9-methyl-1-naphthol, 3- Methyl-2-naphthol, 5-methyl-1-naphthol, 6,7-dimethyl-1-naphthol, 5,7-dimethyl-1-naphthol, 2,5,8-trimethyl-1-naphthol, 2,6- Dimethyl-1-naphthol, 2,3-dimethyl-1-naphthol, 2-methyl-3-phenyl-1-naphthol, 2-methyl-3-ethyl-1-naphthol, Rasinylene A, 7-hydroxycadalene, 1,6-di-tert-butylnaphthalen-2-ol, 6-hexyl-2-naphthol and the like can be mentioned. Among these, α-naphthol and β-naphthol are preferable from the viewpoint of curability of the resin composition, and further, raw material costs are low, and β-naphthol is more preferable from the viewpoint of viscosity of the epoxy resin and fluidity of the resin composition. . These may be used alone or in combination of two or more.

  Examples of aldehydes used in the production of naphthol resins that are precursors of the epoxy resin (A) include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde. Among these, formaldehyde and paraformaldehyde are preferable from the viewpoints of curability of the resin composition and raw material costs. These may be used alone or in combination of two or more.

As an aromatic compound represented by General formula (7) used for manufacture of the naphthol resin which is a precursor of an epoxy resin (A), it is a structure of General formula (7), R2, R3 is C1-C1 6 hydrocarbon group or hydrogen atom, R4 is a hydrocarbon group having 1 to 6 carbon atoms, X is a halogen atom, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, R5 and R6 are hydrocarbon groups having 1 to 5 carbon atoms Or if it is a hydrogen atom, there will be no restriction | limiting in particular. Examples of the hydrocarbon having 1 to 6 carbon atoms in R2 and R3 include methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-methylbutyl group, 3 -Methylbutyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2,2-dimethylbutyl group, 2,3- Dimethylbutyl group, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, 3,4-dimethylbutyl group, 4,4-dimethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, cyclohexyl group and phenyl Examples of the hydrocarbon having 1 to 6 carbon atoms in R4 include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, and a t-butyl group. n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2 , 2-dimethylbutyl group, 2,3-dimethylbutyl group, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, 3,4-dimethylbutyl group, 4,4-dimethylbutyl group, 2-ethylbutyl Group, 1-ethylbutyl group, cyclohexyl group, phenyl group and the like. Examples of X include halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom, methoxy group, ethoxy group, propoxy, n-butoxy. Group, isobutoxy group, t-butoxy group, n-pentoxy group, 2-methylbutoxy group, 3-methylbutoxy group, t-pentoxy group, n- Chitoxy group, 1-methylpentoxy group, 2-methylpentoxy group, 3-methylpentoxy group, 4-methylpentoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, 2,4 -Dimethylbutoxy group, 3,3-dimethylbutoxy group, 3,4-dimethylbutoxy group, 4,4-dimethylbutoxy group, 2-ethylbutoxy group, 1-ethylbutoxy group, hydroxyl group and the like, and = CR5R6 ( Examples of alkylidene groups include methylidene, ethylidene, propylidene, n-butylidene, isobutylidene, t-butylidene, n-pentylidene, 2-methylbutylidene, 3-methylbutylidene, t -Pentylidene group, n-hexylidene group, 1-methylpentylidene group, 2-methylpentylidene group, 3-methylpentylidene group 4-methylpentylidene group, 2,2-dimethylbutylidene group, 2,3-dimethylbutylidene group, 2,4-dimethylbutylidene group, 3,3-dimethylbutylidene group, 3,4-dimethylbutyride Examples include a lidene group, a 4,4-dimethylbutylidene group, a 2-ethylbutylidene group, a 1-ethylbutylidene group, and a cyclohexylidene group. The aromatic compound represented by General formula (7) may be used individually by 1 type, or may use 2 or more types together. The m-form and p-form of xylylene glycol can be synthesized at a relatively low temperature, and the reaction by-products can be easily distilled off and handled.

  The method for synthesizing the naphthol resins that are precursors of the epoxy resin (A) used in the epoxy resin composition for semiconductor encapsulation of the present invention is not particularly limited, but the synthesis method is, for example, 1 mol of naphthols. On the other hand, the aromatic compound represented by the general formula (7) and aldehydes in total 0.2 to 0.8 mol, formic acid, oxalic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, Lewis Obtained by reacting 0.01 to 0.05 mol of an acid catalyst such as an acid at a temperature of 50 to 200 ° C. for 2 to 20 hours, and then distilling off the remaining monomer by a method such as vacuum distillation or steam distillation. Can do. In the reaction, an organic solvent such as toluene, benzene, methanol, ethanol, or ethylene glycol may be used. As the reaction operation, an naphthol and an aromatic compound represented by the general formula (7) are used in an acidic catalyst. Alternatively, an aldehyde may be added to the reaction system for co-condensation while the condensation reaction is performed.

  In order to adjust the content ratio of the component (A-1) in which (mn) ≧ 2 and n ≠ 0 in the epoxy resin (A) having the structure represented by the general formula (1) to a more preferable range. In addition, when synthesizing naphthol resins, the ratio of (the amount of aldehydes) / (the amount of the aromatic compound represented by the general formula (7)) is increased, and the ratio of adding aldehydes to the reaction system is The content ratio of the precursor of the component (A-1) can be increased by taking a method such as increasing from the initial stage to the middle stage of the reaction and decreasing from the middle stage to the late stage of the reaction. In addition, a compound represented by the following general formula (8), which is commercially available or synthesized separately, corresponding to the precursor of the component (A-3) is added to the naphthol resin precursor obtained by synthesis. Thus, a method such as relatively reducing the content ratio of the precursor of the component (A-1) may be taken. In addition, the naphthol resins precursors obtained by synthesis can be adjusted by appropriately combining known purification techniques such as column chromatography fractionation, molecular distillation, steam distillation, and recrystallization.

（ただし、上記一般式（８）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、Ｒ３は炭素数１〜６の炭化水素基又は水素原子であり、互いに同じであっても異なっていてもよい。Ｒ４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。ａは０〜５の整数、ｂは０〜４の整数である。ｒは１〜１９の整数である。）

(However, in the said General formula (8), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2, R3 is a C1-C6 hydrocarbon group. Or a hydrogen atom, which may be the same or different from each other, R4 is a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different from each other. An integer, b is an integer of 0 to 4. r is an integer of 1 to 19.)

  In order to make the content ratio of the component (A-2) where n = 0 in the epoxy resin (A) having the structure represented by the general formula (1) into a more preferable range, Increase the ratio of (aldehyde content) / (aromatic compound represented by formula (7)), increase the amount of naphthols, add aldehydes later in the reaction, synthesis The compound represented by the following general formula (9) obtained commercially or separately synthesized, corresponding to the precursor of the component (A-2) itself, is added to the naphthol resin precursor obtained as described above, etc. By taking this method, the content ratio of the precursor of the component (A-2) can be increased. Moreover, the compound represented by the general formula (8) obtained commercially or separately synthesized, corresponding to the precursor of the component (A-3), is added to the naphthol resin precursor obtained by synthesis. A method such as relatively reducing the content of the precursor of the component (A-2) may be taken. In addition, the naphthol resins precursor obtained by synthesis can be adjusted by appropriately combining known purification techniques such as column chromatography fractionation, molecular distillation, steam distillation and recrystallization.

（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、Ｒ３は炭素数１〜６の炭化水素基又は水素原子であり、互いに同じであっても異なっていてもよい。ａは０〜５の整数である。ｓは１〜１９の整数である。）

(However, in the said General formula (9), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2, R3 is a C1-C6 hydrocarbon group. Or a hydrogen atom, which may be the same or different from each other, a is an integer of 0 to 5, and s is an integer of 1 to 19.)

Although it does not specifically limit about the synthesis | combining method of the epoxy resin (A) which has the structure represented by General formula (1) used with the epoxy resin composition for semiconductor sealing of this invention, For example, the precursor of an epoxy resin (A) After the naphthol resin as a body is dissolved in excess epichlorohydrin, the reaction is carried out at 50 to 150 ° C., preferably 60 to 120 ° C. for 1 to 10 hours in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. And the like. 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 epoxy resin ( A) can be obtained.

In the epoxy resin composition for semiconductor encapsulation of the present invention, another epoxy resin is used in combination as long as the effect of using the epoxy resin (A) having the structure represented by the general formula (1) is not impaired. Can do. Examples of epoxy resins that can be used in combination include crystalline epoxy resins such as biphenyl type epoxy resins, bisphenol type epoxy resins, and stilbene type epoxy resins; novolak type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; Type epoxy resin, polyfunctional epoxy resin such as alkyl-modified triphenol methane type epoxy resin; phenol aralkyl type epoxy resin having phenylene skeleton, aralkyl type epoxy resin such as phenol aralkyl type epoxy resin having biphenylene skeleton; dihydroxynaphthalene type epoxy resin Naphthol-type epoxy resins such as epoxy resins obtained by glycidyl etherification of dihydroxynaphthalene dimers; triglycidyl isocyanurate , Triazine nucleus-containing epoxy resins such as monoallyl diglycidyl isocyanurate; dicyclopentadiene-modified phenol type bridged cyclic hydrocarbon compound-modified phenol type epoxy resin having an epoxy resin. Considering moisture resistance reliability as an epoxy resin composition for semiconductor encapsulation, it is preferable that Na ⁺ ions and Cl ⁻ ions as ionic impurities are 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 40% by mass or more based on the total epoxy resin, 45 The content is more preferably at least mass%, particularly preferably at least 60 mass%. The effect which improves a flame resistance, a low water absorption, etc. can be acquired as a compounding ratio exists in the said range.

  Although it does not specifically limit about the lower limit of the compounding ratio of the whole epoxy resin, It is preferable that it is 2 mass% or more in the epoxy resin composition for whole semiconductor sealing, and it is more preferable that it is 4 mass% or more. When the lower limit of the blending ratio is within the above range, there is little possibility of causing a decrease in fluidity. Further, the upper limit value of the blending ratio of the entire epoxy resin is not particularly limited, but is preferably 15% by mass or less and more preferably 13% by mass or less in the total epoxy resin composition for semiconductor encapsulation. preferable. When the upper limit of the blending ratio is within the above range, there is little possibility of causing a decrease in solder resistance.

  In the epoxy resin composition for semiconductor encapsulation of the present invention, a curing agent (B) is used. The curing agent that can be used in the epoxy resin composition for semiconductor encapsulation of the present invention can be roughly classified into three types, for example, a polyaddition type curing agent, a catalyst type curing agent, and a condensation type curing agent. .

  Examples of polyaddition type curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylene diamine (MXDA), diaminodiphenylmethane (DDM), and m-phenylenediamine (MPDA). In addition to aromatic polyamines such as diaminodiphenylsulfone (DDS), polyamine compounds including dicyandiamide (DICY), organic acid dihydrazide, and the like; alicyclics such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA) Acid anhydrides, including acid anhydrides, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), aromatic anhydrides such as benzophenone tetracarboxylic acid (BTDA), etc .; novolac-type phenolic resin, phenol Polyphenol compounds such as Rimmer; polysulfide, thioester, polymercaptan compounds such as thioethers; isocyanate prepolymer, isocyanate compounds such as blocked isocyanate; and organic acids such as carboxylic acid-containing polyester resins.

  Examples of the catalyst-type curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2-ethyl-4 -Imidazole compounds such as methylimidazole (EMI24); Lewis acids such as BF3 complexes.

  Examples of the condensation type curing agent include phenolic resin-based curing agents such as novolak type phenolic resin and resol type phenolic resin; urea resin such as methylol group-containing urea resin; and melamine resin such as methylol group-containing melamine resin. Can be mentioned.

  Among these, a phenol resin-based curing agent is preferable from the viewpoint of balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like. The phenol resin-based curing agent 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 Novolak resins such as resins; polyfunctional phenol resins such as triphenolmethane phenol resins; modified phenol resins such as terpene-modified phenol resins and dicyclopentadiene-modified phenol resins; phenol aralkyl resins having a phenylene skeleton and / or a biphenylene skeleton Aralkyl-type resins such as naphthol aralkyl resins having a phenylene and / or biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F, and the like. It may be used in combination or more. Among these, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.

  Although it does not specifically limit about the lower limit of the compounding ratio of the whole hardening | curing agent (B), It is preferable that it is 0.8 mass% or more in the epoxy resin composition for whole semiconductor sealing, and it is 1.5 mass% or more. More preferably. When the lower limit value of the blending ratio is within the above range, sufficient fluidity can be obtained. Also, the upper limit of the blending ratio of the entire curing agent (B) is not particularly limited, but it is preferably 10% by mass or less, and 8% by mass or less in the total epoxy resin composition for semiconductor encapsulation. It is more preferable. When the upper limit of the blending ratio is within the above range, good solder resistance can be obtained.

  In the case of using a phenol resin curing agent as the curing agent, the blending ratio of the entire epoxy resin and the entire phenol resin curing agent is the number of epoxy groups (EP) of the entire epoxy resin and the entire phenol resin curing agent. The equivalent ratio (EP) / (OH) to the number of phenolic hydroxyl groups (OH) is preferably 0.8 or more and 1.3 or less. When the equivalent ratio is within this range, sufficient curability can be obtained during molding of the epoxy resin composition for semiconductor encapsulation. Moreover, when the equivalent ratio is within this range, good physical properties in the resin cured product can be obtained.

  In the epoxy resin composition for semiconductor encapsulation of the present invention, (C) an inorganic filler is used. As the inorganic filler (C) used for the epoxy resin composition for semiconductor encapsulation of the present invention, those generally used for resin compositions for semiconductor encapsulation can be used, for example, fused silica, spherical silica, Examples thereof include crystalline silica, alumina, silicon nitride, and 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 into the mold cavity.

As a lower limit of the content rate of an inorganic filler (C), it is preferable that it is 80 mass% or more of the whole epoxy resin composition for semiconductor sealing, It is more preferable that it is 83 mass% or more, 86 mass% or more It is particularly preferred that When the lower limit of the content ratio of the inorganic filler (C) is within the above range, the moisture absorption amount does not increase or the strength does not decrease as the cured product physical property of the epoxy resin composition for semiconductor encapsulation. Good solder crack resistance can be obtained. Moreover, as an upper limit of the content rate of an inorganic filler (C), it is preferable that it is 93 mass% or less of the whole epoxy resin composition for semiconductor sealing, It is more preferable that it is 91 mass% or less, 90 mass % Or less is particularly preferable. When the upper limit value of the content ratio of the inorganic filler (C) is within the above range, the flowability is not impaired and good moldability can be obtained.

  In the epoxy resin composition for semiconductor encapsulation of the present invention, a curing accelerator (D) can be further used. The curing accelerator (D) may be any as long as it has an action of promoting the crosslinking reaction between the epoxy resin and the curing agent, and it is possible to use those used in general epoxy resin compositions for semiconductor encapsulation. it can. Specific examples include phosphorus atom-containing curing accelerators such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; 1,8-diazabicyclo Nitrogen atom-containing curing accelerators such as (5,4,0) undecene-7, benzyldimethylamine, 2-methylimidazole and the like can be mentioned. Among these, phosphorus atom-containing curing accelerators can obtain preferable curability. . However, when the epoxy resin (A) having a structure represented by the general formula (1), the curing agent (B), and the inorganic filler (C) is blended with a phosphorus atom-containing curing accelerator having no latency, the resin During melt kneading of the composition, the composition viscosity increases and cures due to an exothermic reaction, and the production of the sealing resin composition may become extremely unstable. The details of the mechanism are unknown, but the epoxy resin (A) has a structure in which the density of the glycidyl ether group bonded to the naphthalene skeleton is locally high in the molecule, so that the effect of promoting the curing of phosphorus atoms is remarkably exhibited. It is possible to do. From the viewpoint of avoiding the above-mentioned production problems, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds have a latent phosphorus atom-containing curing. By using an accelerator, the reaction during melt-kneading can be suppressed, and a resin composition for semiconductor encapsulation can be obtained stably. Further, even when a phosphorus atom-containing curing accelerator having no latency is used, a compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring described later is used in combination. Thus, the reaction during melt-kneading can be similarly suppressed, and the resin composition for semiconductor encapsulation can be obtained stably. In addition, from the viewpoint of balance between fluidity and curability, phosphorus atoms having latency such as tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds, etc. A contained curing accelerator is more preferred. Tetra-substituted phosphonium compounds are particularly preferred when emphasizing the point of fluidity, and phosphobetaine compounds, phosphine compounds when emphasizing the point of low elastic modulus when cured of the epoxy resin composition for semiconductor encapsulation. An adduct with a quinone compound is particularly preferred, and an adduct with a phosphonium compound and a silane compound is particularly preferred when importance is attached to latent curing properties.

  Examples of the organic phosphine that can be used in the semiconductor sealing epoxy resin composition of the present invention include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; trimethylphosphine, triethylphosphine, Third phosphine such as tributylphosphine and triphenylphosphine can be used.

  Examples of the tetra-substituted phosphonium compound that can be used in the semiconductor sealing epoxy resin composition of the present invention include compounds represented by the following general formula (10).

（ただし、上記一般式（１０）において、Ｐはリン原子を表す。Ｒ７、Ｒ８、Ｒ９及びＲ１０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 (10), P represents a phosphorus atom. R7, R8, R9, and R10 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 (10) 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 (10) can be precipitated. In the compound represented by the general formula (10), R7, R8, R9 and R10 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（１１）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。ｆは０〜５の整数であり、ｇは０〜３の整数である。） Examples of the phosphobetaine compound that can be used in the epoxy resin composition for semiconductor encapsulation of the present invention include compounds represented by the following general formula (11).

(However, in the said General formula (11), X1 represents a C1-C3 alkyl group, Y1 represents a hydroxyl group. F is an integer of 0-5, g is an integer of 0-3.)

  The compound represented by the general formula (11) 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（１２）において、Ｐはリン原子を表す。Ｒ１１、Ｒ１２及びＲ１３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。Ｒ１４、Ｒ１５及びＲ１６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、Ｒ１４とＲ１５が結合して環状構造となっていてもよい。） Examples of the adduct of a phosphine compound and a quinone compound that can be used in the epoxy resin composition for semiconductor encapsulation of the present invention include compounds represented by the following general formula (12).

(However, in the said General formula (12), P represents a phosphorus atom. R11, R12, and R13 represent a C1-C12 alkyl group or a C6-C12 aryl group, and they are mutually the same. R14, R15 and R16 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 R14 and R15 are bonded to form a cyclic structure. May be.)

  Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. Those having a substituent such as a substituent or an alkyl group or an alkoxyl group are preferred, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. 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 (12), R11, R12 and R13 bonded to the phosphorus atom are phenyl groups, and R14, R15 and R16 are hydrogen atoms, that is, 1,4-benzoquinone and triphenyl A compound to which phosphine is added is preferable in that it reduces the thermal elastic modulus of the cured product of the epoxy resin composition for semiconductor encapsulation.

（ただし、上記一般式（１３）において、Ｐはリン原子を表し、Ｓｉは珪素原子を表す。Ｒ１７、Ｒ１８、Ｒ１９及びＲ２０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は互いに同一であって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 a phosphonium compound and a silane compound that can be used in the epoxy resin composition for semiconductor encapsulation of the present invention include compounds represented by the following general formula (13).

(In the general formula (13), P represents a phosphorus atom and Si represents a silicon atom. R17, R18, R19 and R20 are each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. 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 group, and groups Y2 and Y3 in the same molecule are bonded to a silicon atom to form a chelate structure, and Y4 and Y5 are proton donating groups. The group represents a group formed by releasing a proton, and the groups Y4 and Y5 in the same molecule are bonded to a silicon atom to form a chelate structure.X2 and X3 are the same or different from each other. Well 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 (13), examples of R17, R18, R19, and R20 include phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, n-butyl group, n-octyl group, cyclohexyl group, and the like. Among these, an aromatic group having a substituent such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, or the like. A substituted aromatic group is more preferred.

  Moreover, in General formula (13), 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 groups releasing protons, and groups Y2 and Y3 in the same molecule are combined with a silicon atom to form a chelate structure. Similarly, Y4 and Y5 are groups formed by proton-donating groups releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure. The groups X2 and X3 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 (13) 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 (13) 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 such as aliphatic hydrocarbon groups such as octyl group and aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxypropyl group, mercaptopropyl group, aminopropyl group and vinyl group 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 proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol and dissolved, and then room temperature. Sodium methoxide-methanol solution is added dropwise with stirring. 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.

The blending ratio of the curing accelerator (D) that can be used in the epoxy resin composition for semiconductor encapsulation of the present invention is more preferably 0.1% by mass or more and 1% by mass or less in the total epoxy resin composition. . When the blending ratio of the curing accelerator (D) is within the above range, sufficient curability can be obtained. Moreover, sufficient fluidity | liquidity can be obtained as the mixture ratio of a hardening accelerator (D) exists in the said range.

  In the present invention, a compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring can be used. A compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring (hereinafter also referred to as “compound (E)”) can be used in the general formula (1). Even when a phosphorus atom-containing curing accelerator having no latent property is used as a curing accelerator that promotes the crosslinking reaction between the epoxy resin (A) having the structure represented and the curing agent (B), the resin The reaction during melt kneading of the composition can be suppressed, and a resin composition for semiconductor encapsulation can be obtained stably. The compound (E) also has an effect of lowering the melt viscosity of the resin composition for semiconductor encapsulation and improving the fluidity. As the compound (E), a monocyclic compound represented by the following general formula (14) or a polycyclic compound represented by the following general formula (15) can be used. It may have a substituent.

（ただし、上記一般式（１４）において、Ｒ２１、Ｒ２５はどちらか一方が水酸基であり、片方が水酸基のとき他方は水素原子、水酸基又は水酸基以外の置換基である。Ｒ２２、Ｒ２３及びＲ２４は水素原子、水酸基又は水酸基以外の置換基である。）

(In the general formula (14), one of R21 and R25 is a hydroxyl group, and when one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group. R22, R23 and R24 are hydrogen atoms) An atom, a hydroxyl group or a substituent other than a hydroxyl group.)

（ただし、上記一般式（１５）において、Ｒ２６、Ｒ３２はどちらか一方が水酸基であり、片方が水酸基のとき他方は水素原子、水酸基又は水酸基以外の置換基である。Ｒ２７、Ｒ２８、Ｒ２９、Ｒ３０及びＲ３１は水素原子、水酸基又は水酸基以外の置換基である。）

(However, in the general formula (15), one of R26 and R32 is a hydroxyl group, and when one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group. R27, R28, R29, R30) And R31 is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group.)

Specific examples of the monocyclic compound represented by the general formula (14) include catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof. Specific examples of the polycyclic compound represented by the general formula (15) include 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. Among these, a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting an aromatic ring is preferable because of easy control of fluidity and curability. In consideration of volatilization in the kneading step, it is more preferable that the mother nucleus is a compound having a low volatility and a highly stable weighing naphthalene ring. In this case, specifically, the compound (E) can be a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof. These compounds (E) may be used individually by 1 type, or may use 2 or more types together.

  The compounding ratio of the compound (E) is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.03% by mass or more, 0.8% in the total semiconductor sealing resin composition. It is 0.05 mass% or less, Most preferably, it is 0.05 mass% or more and 0.5 mass% or less. When the lower limit value of the compounding ratio of the compound (E) is within the above range, a sufficient viscosity reduction and fluidity improvement effect of the resin composition for semiconductor encapsulation can be obtained. Moreover, there is little possibility of causing the fall of sclerosis | hardenability of a resin composition for semiconductor sealing, and the fall of physical property of hardened | cured material as the upper limit of the compounding ratio of a compound (E) is in the said range.

  In the epoxy resin composition for semiconductor encapsulation of the present invention, an adhesion assistant (F) such as a silane coupling agent can be added in order to improve the adhesion between the epoxy resin and the inorganic filler (C). . 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. Moreover, a silane coupling agent can also raise the effect of the compound (E) of reducing the melt viscosity of the resin composition for semiconductor sealing, and improving fluidity | liquidity by using together with the above-mentioned compound (E). 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.

  The blending ratio of the adhesion aid (F) such as a silane coupling agent that can be used in the epoxy resin composition for semiconductor encapsulation of the present invention is 0.01% by mass or more and 1% by mass in the total epoxy resin composition. The following is preferable, more preferably 0.05% by mass or more and 0.8% by mass or less, and particularly preferably 0.1% by mass or more and 0.6% by mass or less. If the blending ratio of the adhesion aid (F) such as a silane coupling agent is not less than the above lower limit value, the interface strength between the epoxy resin and the inorganic filler will not decrease, and good solder crack resistance in the semiconductor device Can be obtained. Moreover, if the blending ratio of the adhesion assistant (F) such as a silane coupling agent is within the above range, the water absorption of the cured product of the epoxy resin composition does not increase, and good solder crack resistance in the semiconductor device. Sex can be obtained.

In the epoxy resin composition for semiconductor encapsulation of the present invention, in addition to the components described above, colorants such as carbon black, bengara and titanium oxide; natural wax such as carnauba wax; synthetic wax such as polyethylene wax; stearic acid and stearic acid Release agents such as higher fatty acids such as zinc and metal salts thereof or paraffin; low-stress additives such as silicone oil and silicone rubber; inorganic ion exchangers such as bismuth oxide hydrate; aluminum hydroxide and magnesium hydroxide Additives such as metal hydroxides and flame retardants such as zinc borate, zinc molybdate, phosphazene, and antimony trioxide may be appropriately blended.

  The epoxy resin composition for semiconductor encapsulation of the present invention is obtained by uniformly mixing the components (A) to (C) and other additives at room temperature using, for example, a mixer, and then a heating roll. In addition, it is possible to use a material in which the degree of dispersion, the fluidity, and the like are appropriately adjusted as necessary, such as melt kneading using a kneader such as a kneader or an extruder, followed by cooling and pulverization.

  Next, the semiconductor device of the present invention will be described. 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 mounted with a semiconductor element, a circuit board or the like is placed in a mold cavity. Then, what is necessary is just to shape-harden the epoxy resin composition for semiconductor sealing by shaping | molding methods, such as a transfer mold, a compression mold, and an injection mold.

  The semiconductor element sealed with the semiconductor device of 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 low profile package, and the like. Quad Flat Package (LQFP), Small Outline Package (SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Examples include a tape carrier package (TCP), a ball grid array (BGA), and a chip size package (CSP).

  The semiconductor device of the present invention in which a semiconductor element is encapsulated with a cured product of an epoxy resin composition for encapsulating a semiconductor by a molding method such as transfer molding is used as it is or at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours. After being fully cured over a period of time, it is mounted on an electronic device or the like.

  FIG. 1 is a view showing a cross-sectional structure of an example of a semiconductor device using the epoxy resin composition for semiconductor encapsulation 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 an epoxy resin composition for semiconductor sealing.

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

FIG. 2 shows an FD-MS chart of the epoxy resin 1, and this FD-MS measurement was performed under the following conditions. After adding 1 g of the solvent dimethyl sulfoxide (DMSO) to 10 mg of the epoxy resin 1 sample and dissolving it sufficiently, it was applied to the FD emitter and subjected to measurement. FD-
The MS system uses MS-FD15A manufactured by JEOL Ltd. as the ionization unit and the MS-700 model name double-convergent mass spectrometer manufactured by JEOL Ltd. as the detector, and uses a detection mass range (m / m z) Measured at 50-2000.

  Moreover, although the gel permeation chromatography (GPC) chart of the epoxy resin 1 is shown in FIG. 3, this gel permeation chromatography (GPC) measurement was performed on the following conditions. 6 ml of solvent tetrahydrofuran (THF) was added to 20 mg of a sample of epoxy resin 1 and sufficiently dissolved, and subjected to GPC measurement. The GPC system includes WATERS module W2695, Tosoh Corporation TSK GUARDCOLUMN HHR-L (diameter 6.0 mm, pipe length 40 mm, guard column), Tosoh Corporation TSK-GEL GMHHR-L (diameter 7.8 mm, A tube having a tube length of 30 mm and two polystyrene gel columns) and a differential refractive index (RI) detector W2414 manufactured by WATERS, in series, was used. The flow rate of the pump was 0.5 ml / min, the temperature in the column and the differential refractometer was 40 ° C., and measurement was performed by injecting the measurement solution from a 100 μl injector. In analyzing the sample, a calibration curve prepared from a monodisperse polystyrene (hereinafter referred to as PS) standard sample is used. For the calibration curve, a logarithmic value of the molecular weight of PS and the peak detection time (retention time) of PS are plotted, and a regression of the cubic equation is used. As standard PS samples for preparing calibration curves, Shodex Standard SL-105 series product numbers S-1.0 (peak molecular weight 1060), S-1.3 (peak molecular weight 1310), S-2 manufactured by Showa Denko K.K. 0.0 (peak molecular weight 1990), S-3.0 (peak molecular weight 2970), S-4.5 (peak molecular weight 4490), S-5.0 (peak molecular weight 5030), S-6.9 (peak molecular weight 6930) ), S-11 (peak molecular weight 10700), S-20 (peak molecular weight 19900) were used.

  FIG. 4 is a plot of the molecular weight obtained by FD-MS of the epoxy resin 1 and the PS-converted peak molecular weight obtained by GPC. 2, 3 and 4, each peak is numbered. In FIG. 4, the plotted point is on a straight line passing through the vicinity of the origin, and the tendency of each peak intensity in FIGS. 2 and 3 is It almost agreed. From the above, the content ratio of the component (A-1), the component (A-2), and the component (A-3) can be calculated by associating the result of FD-MS and the result of GPC. The details of the calculation are shown in Table 1 for an example of the epoxy resin 1. Epoxy resins 1 to 3 are epoxy resins that satisfy the conditions of epoxy resin (A), but for high molecular weight components that are difficult to separate and identify and identify m and n, consider the assumed structure. For the sake of convenience, the calculation was performed by halving the component (A-1) and the component (A-3).

(Epoxy resin)
Epoxy resin 1: β-naphthol (Tokyo Chemical Industry 2-naphthol, melting point 122 ° C., molecular weight 144, purity 99.3%) 100 parts by mass, p-xylylene glycol (Tokyo Chemical Industry p-xylylene glycol, melting point) 118.degree. C., molecular weight 138, purity 98%) 38.3 parts by weight, p-toluenesulfonic acid (Wako Pure Chemical Industries, Ltd., p-toluenesulfonic acid, molecular weight 172.3, purity 99%) 0.2 parts by weight. Weigh in a bull flask, heat while replacing with nitrogen, and start stirring as melting begins. After confirming that the system reached 150 ° C., 5.7 parts by mass of a 37% aqueous solution of formaldehyde (formalin 37% manufactured by Wako Pure Chemical Industries, Ltd.) was added over 30 minutes. After reacting for 60 minutes as it was, 5.7 parts by mass of 37% formaldehyde aqueous solution (formalin 37% manufactured by Wako Pure Chemical Industries, Ltd.) was added to the system over 30 minutes, and further reacted for 60 minutes. From the start of heating / melting until the end of the reaction, the temperature in the system is maintained in the range of 145 ° C. to 155 ° C., and the moisture generated in the system due to the reaction or mixed into the system due to the addition of formalin. Was discharged out of the system by a nitrogen stream. After completion of the reaction, 200 parts by mass of toluene is added and uniformly dissolved, then transferred to a separatory funnel, 150 parts by mass of distilled water is added and shaken, and then the operation of rinsing the aqueous layer (washing with water) After repeating until it became neutral, volatile components such as toluene and residual monomer components were distilled off by subjecting the oil layer to a reduced pressure at 125 ° C. to obtain a brown solid (precursor naphthol resin). To 100 parts by mass of the naphthol resin thus obtained, 263.4 parts by mass of epichlorohydrin and 200 parts by mass of dimethyl sulfoxide are added and dissolved, and then heated to 40 ° C. to obtain sodium hydroxide (solid fine particle, purity 99% reagent) 20 .1 part by mass was added over 2 hours, the temperature was raised to 50 ° C. for 2 hours, and the temperature was further raised to 70 ° C. for 2 hours. After the reaction, after adding 150 parts by mass of distilled water and shaking, the operation (water washing) of discarding the aqueous layer was repeated until the washing water became neutral, and then the epichlorohydrin and Dimethyl sulfoxide was distilled off. 260 parts by mass of toluene was added to the obtained solid to dissolve it, heated to 70 ° C., 9.3 parts by mass of a 20% by mass aqueous sodium hydroxide solution was added over 1 hour, reacted for another 1 hour, and then allowed to stand. The water layer was discarded. After adding 260 parts by mass of distilled water to the oil layer and performing a washing operation, the same washing operation was repeated until the washing water became neutral, and then methyl isobutyl ketone was distilled off by heating under reduced pressure. Epoxy resin 1 (epoxy equivalent 256, softening point 68 ° C., ICI viscosity 1.50 dPa · s at 150 ° C. (A-1) component content 19 mass%, (A-2) component content 30 mass% (A-3) component content ratio 51% by mass). FIG. 2 shows the FD-MS chart, FIG. 3 shows the GPC chart, and Table 1 shows the calculation results of the content ratios of the components (A-1), (A-2), and (A-3).

Epoxy resin 2: In the synthesis of epoxy resin 1, 38.3 parts by mass of p-xylylene glycol (p-xylylene glycol manufactured by Tokyo Chemical Industry Co., Ltd., melting point 118 ° C., molecular weight 138, purity 98%) was changed to 19.2. The addition amount of 5.7 parts by mass of the first formaldehyde 37% aqueous solution (formalin 37% manufactured by Wako Pure Chemical Industries, Ltd.) to 4.3 parts by mass is added to the mass part by the second formaldehyde 37% aqueous solution (Wako Pure Chemical Industries, Ltd.). The amount of 5.7 parts by mass of industrial formalin 37%) was changed to 1.9 parts by mass, and an operation for recovering unreacted monomer by steam distillation was added after the reaction was completed. (16) epoxy resin 2 (epoxy equivalent 252, softening point 76 ° C., ICI viscosity 2.2 dPa · s at 150 ° C., (A-1) component content 34.5% by mass, (A 2) component content 21 mass%, to obtain a component (A-3) content of 44.5 wt%.).

Epoxy resin 3: In the synthesis of epoxy resin 1, 28.3 parts by mass of 38.3 parts by mass of p-xylylene glycol (p-xylylene glycol manufactured by Tokyo Chemical Industry Co., Ltd., melting point 118 ° C., molecular weight 138, purity 98%) was used. The addition amount of 5.7 parts by mass of the first formaldehyde 37% aqueous solution (formalin 37% manufactured by Wako Pure Chemical Industries, Ltd.) to 4.3 parts by mass is added to the mass part by the second formaldehyde 37% aqueous solution (Wako Pure Chemical Industries, Ltd.). The addition amount of 5.7 parts by mass of industrial formalin 37%) is 4.3 parts by mass, the reaction time after the second addition of the 37% aqueous formaldehyde solution is 60 minutes, and p-xylylene glycol (Tokyo Kasei) is added. 21.5 parts by mass of industrial p-xylylene glycol, melting point 118 ° C., molecular weight 138, purity 98%) was added to the system over 30 minutes, and the reaction was continued for 60 minutes. I adapted it. An epoxy resin 3 represented by the formula (16) (epoxy equivalent 253, softening point 72 ° C., 150 ° C.) except that an operation for recovering unreacted monomer by steam distillation was added after completion of the reaction. ICI viscosity at 1.7 dPa · s (A-1) component content 13.2% by mass, (A-2) component content 25.0% by mass, (A-3) component content 61.8% by mass .)

  Epoxy resin 4: 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.)

  Epoxy resin 5: biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., jER (registered trademark) YX4000K. Epoxy equivalent 185, melting point 105 ° C.)

  Epoxy resin 6: Bisphenol F type epoxy resin (Nippon Steel Chemical Co., Ltd., YSLV-80XY. Epoxy equivalent 190, melting point 80 ° C.)

  Epoxy resin 7: Orthocresol novolac type epoxy resin (manufactured by Dainippon Ink Co., Ltd., N660. Epoxy equivalent 210, softening point 62 ° C.)

Epoxy resin 8: α-naphthol (Tokyo Chemical Industry 1-naphthol, melting point 96 ° C., molecular weight 144, purity 99.6%) 15 parts by mass, β-naphthol (Tokyo Chemical Industry 2-naphthol, melting point 122 ° C., molecular weight) 144, purity 99.3%) 85 parts by mass, methyl isobutyl ketone (Tokyo Chemical Industry Co., Ltd. special grade reagent, purity 99.5%) 100 parts by mass was weighed into a separable flask, and the solid content was stirred. It melt | dissolved and 2.8 mass parts of 49 mass% sodium hydroxide aqueous solution was added. When the temperature inside the system reached 100 ° C. while purging with nitrogen, 36.6 parts by mass of 37% formaldehyde aqueous solution (formalin 37% manufactured by Wako Pure Chemical Industries, Ltd.) was gradually added. The reaction was carried out at 120 ° C. for 120 minutes. During the period from the start of heating / melting to the end of the reaction, the temperature in the system is maintained in the range of 95 ° C. to 105 ° C., and water generated / mixed in the system due to the reaction or addition of formalin is added to the system by a nitrogen stream. Discharged outside. After completion of the reaction, the mixture was transferred to a separatory funnel, and after adding 150 parts by mass of distilled water and shaking, the operation of discarding the aqueous layer (washing) was repeated until the washing water became neutral, and then the oil layer was 125 ° C. By carrying out the reduced pressure treatment, volatile components such as methyl isobutyl ketone and residual monomer components were distilled off to obtain a brown solid (precursor naphthol resin). 291.2 parts by mass of epichlorohydrin and 200 parts by mass of dimethyl sulfoxide are added to 100 parts by mass of the obtained naphthol resin, dissolved, heated to 40 ° C., and sodium hydroxide (solid fine granular, 99% purity reagent) 22 2 parts by mass were added over 2 hours, the temperature was raised to 50 ° C. for 2 hours, and the temperature was further raised to 70 ° C. for 2 hours. After the reaction, after adding 150 parts by mass of distilled water and shaking, the operation (water washing) of discarding the aqueous layer was repeated until the washing water became neutral, and then the epichlorohydrin and Dimethyl sulfoxide was distilled off. 260 parts by mass of toluene was added to the obtained solid and dissolved, heated to 70 ° C., 10.2 parts by mass of a 20% by mass aqueous sodium hydroxide solution was added over 1 hour, reacted for another 1 hour, and then allowed to stand. The water layer was discarded. After adding 260 parts by mass of distilled water to the oil layer and performing a water washing operation, the same water washing operation was repeated until the washing water became neutral, and then methyl isobutyl ketone was distilled off by heating under reduced pressure. Epoxy resin 8 (epoxy equivalent 231, softening point 80 ° C., ICI viscosity at 150 ° C. 0.8 dPa · s. (A-2) equivalent to component content of 100% by mass) was obtained.

  Epoxy resin 9: naphthol aralkyl type epoxy resin represented by the following formula (6) (Nippon Steel Chemical Co., Ltd., ESN-185, epoxy equivalent 280, softening point 80 ° C., ICI viscosity 4.5 ° C. at 150 ° C.) (Equivalent to 100% by mass of component (A-3))

  In Comparative Example 4, the epoxy resin 7 and the epoxy resin 8 are blended in a mass ratio of 2.71 parts by mass, 5.42 parts by mass, that is, 1: 2, respectively. This epoxy resin mixture can be represented by the general formula (1): (A-1) component content 0 mass%, (A-2) component content 33.3 mass%, (A-3) component content This corresponds to a ratio of 66.7% by mass.

(Curing agent)
Curing agent 1: Phenol aralkyl resin having a phenylene skeleton (manufactured by Mitsui Chemicals, XLC-4L. Hydroxyl equivalent 168, softening point 62 ° C.)
Curing agent 2: Phenol novolak resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-HF-3, hydroxyl equivalent 104, softening point 80 ° C.)
Curing agent 3: Phenol aralkyl resin having a biphenylene skeleton (Maywa Kasei Co., Ltd., MEH-7851SS. Hydroxyl equivalent 203, softening point 67 ° C.)

(Inorganic filler)
Inorganic filler 1: 100 parts by mass of fused spherical silica FB560 (average particle size 30 μm) manufactured by Denki Kagaku Kogyo, 6.5 parts by mass of synthetic spherical silica SO-C2 (average particle size 0.5 μm) manufactured by Admatex, synthesized by Admatex A blend of 7.5 parts by mass of spherical silica SO-C5 (average particle size 30 μm) in advance.

(Curing accelerator)
Curing accelerator 1: Curing accelerator represented by the following formula (18)

Curing accelerator 2: Curing accelerator represented by the following formula (19)

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

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

  Curing accelerator 5: Triphenylphosphine (manufactured by Hokuko Chemical Co., Ltd., TPP)

(Compound (E))
Compound E1: Compound represented by the following formula (22) (manufactured by Tokyo Chemical Industry Co., Ltd., 2,3-naphthalenediol, purity 98%)

(Silane coupling agent)
Silane coupling agent 1: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
Silane coupling agent 2: γ-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803)

(Coloring agent)
Colorant 1: Carbon black (Mitsubishi Chemical Industry Co., Ltd., MA600)

(Release agent)
Mold release agent 1: Carnauba wax (Nikko Fine Co., Ltd., Nikko Carnauba, melting point 83 ° C.)

Example 1
Epoxy resin 1 8.06 parts by mass Curing agent 1 5.04 parts by mass Inorganic filler 1 86.00 parts by mass Curing accelerator 1 0.30 parts by mass Silane coupling agent 1 0.10 parts by mass Silane coupling agent 2 0 .10 parts by weight Colorant 1 0.30 parts by weight Release agent 1 0.10 parts by weight are mixed at room temperature using a mixer, melt-kneaded with a heating roll at 80 to 100 ° C., cooled and pulverized, and epoxy resin composition Got. It evaluated by the following method using the obtained epoxy resin composition. The evaluation results are shown in Table 2.

  Spiral flow: Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a spiral flow measurement mold according to EMMI-1-66 was applied at 175 ° C., injection pressure 6.9 MPa, holding pressure The epoxy resin composition was injected under the condition of time 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.

  Flame resistance: Epoxy resin using a low pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.) under conditions of a mold temperature of 175 ° C., an injection time of 15 seconds, a curing time of 120 seconds, and an injection pressure of 9.8 MPa. The composition was injection molded to produce a 3.2 mm thick flame proof test piece. About the obtained test piece, the flame resistance test was done according to the specification of UL94 vertical method. The table shows Fmax, ΣF and the fire resistance rank after the determination. The epoxy resin composition obtained in Example 1 exhibited good flame resistance such as Fmax: 7 seconds, ΣF: 24 seconds, and flame resistance rank: V-0.

  Curing torque ratio: Using a curast meter (manufactured by Orientec Co., Ltd., JSR curast meter IVPS type), the mold temperature was 175 ° C., the torque after 90 seconds from the start of heating, and after 300 seconds, the curing torque ratio: ( Torque after 90 seconds) / (torque after 300 seconds) × 100 (%) was calculated. The torque in the curast meter is a parameter of thermal rigidity, and a larger curing torque ratio is better from the viewpoint of fast curing. Units%.

  Solder resistance test 1: Epoxy resin composition using a low pressure transfer molding machine (Daiichi Seiko Co., Ltd., GP-ELF) under conditions of a mold temperature of 180 ° C., an injection pressure of 7.4 MPa, and a curing time of 120 seconds. A lead frame or the like on which a semiconductor element (silicon chip) is mounted is sealed by molding, and 80 pQFP (Cu lead frame, the size is 14 × 20 mm × thickness 2.00 mm, the semiconductor element is 7 × 7 mm × A semiconductor device having a thickness of 0.35 mm and the semiconductor element and the inner lead portion of the lead frame are bonded with a gold wire having a diameter of 25 μm. Six semiconductor devices heat-treated at 175 ° C. for 4 hours as post-cure were humidified for 120 hours at 60 ° C. and 60% relative humidity, and then IR reflow treatment (260 ° C., according to JEDEC Level 3 conditions) was performed. The presence or absence of peeling and cracks inside these semiconductor devices was observed with an ultrasonic flaw detector (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., mi-scope 10), and the occurrence of either peeling or cracking was regarded as defective. The number of defective semiconductor devices in n = 6 is displayed. The epoxy resin composition obtained in Example 1 showed a good reliability with a defective number of 0/6.

  Solder resistance test 2: A test was performed in the same manner as the solder resistance test 1 except that the humidification treatment conditions of the solder resistance test 1 described above were humidified at 85 ° C. and a relative humidity of 60% for 168 hours. The epoxy resin composition obtained in Example 1 showed a good reliability with a defective number of 0/6.

Examples 2-12, Comparative Examples 1-4
According to the formulations shown in Tables 2 and 3, epoxy resin compositions were 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 Tables 2 and 3.

  Examples 1-12 contain the epoxy resin (A) which has a structure represented by General formula (1), a hardening | curing agent (B), an inorganic filler (C), and the kind of epoxy resin (A) Or a mixture ratio changed, a type of curing agent (B) changed, a type of curing accelerator (D) changed or a compound (E) added, In addition, the fluidity (spiral flow), flame resistance, curability and solder resistance were excellent.

  According to the present invention, a brominated epoxy resin and an antimony compound are used, and an epoxy resin composition and a cured product thereof, which are excellent in flame resistance at a low cost and have a good balance of fluidity, curability and solder resistance. Thus, a semiconductor device formed by sealing a semiconductor element having excellent productivity and reliability can be obtained. Therefore, the semiconductor device is suitable for sealing a semiconductor device, particularly for a surface mounting type semiconductor device.

It is the figure which showed the cross-section about an example of the semiconductor device using the epoxy resin composition for semiconductor sealing which concerns on this invention. 2 is an FD-MS chart of epoxy resin 1. 2 is a GPC chart of epoxy resin 1. It is the figure which showed the relationship between the molecular weight obtained by FD-MS of the epoxy resin 1, and the PS conversion peak molecular weight obtained by GPC.

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 epoxy resin composition for semiconductor sealing

Claims (10)

(A) Epoxy resin having a structure represented by the following general formula (1)

(However, in the said General formula (1), R1 is a C1-C6 hydrocarbon group, and may mutually be same or different. R2, R3 is a C1-C6 hydrocarbon group. Or a hydrogen atom, which may be the same or different from each other, R4 is a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different from each other. An integer, b is an integer of 0 to 4. m is an integer of 2 to 20, n is an integer of 0 to 19, and (mn) is an integer of 1 or more, a naphthalene ring having a glycidyl ether group. The m repeating units and the n repeating units having a benzene ring may be arranged in succession, or may be alternately or randomly arranged with each other. And)
(B) a curing agent;
(C) an inorganic filler,
The epoxy resin (A) is a component (A-1) in which (mn) ≧ 2 and n ≠ 0 in the general formula (1), and a component (A-2) in which n = 0, An epoxy resin composition for encapsulating a semiconductor, comprising:   The content ratio (A-1) / (A-2) of the component (A-1) and the component (A-2) in the epoxy resin (A) is in the range of 1/9 to 9/1 by mass ratio. The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein:   3. The epoxy resin (A) further comprises a component (A-3) in which (mn) = 1 and n ≠ 0 in the general formula (1). The epoxy resin composition for semiconductor encapsulation as described in 2.   The content ratio of the component (A-3) in the epoxy resin (A) is in the range of 1 to 300 parts by mass with respect to 100 parts by mass of the total amount of the component (A-1) and the component (A-2). The epoxy resin composition for semiconductor encapsulation according to claim 3, wherein:   5. The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the inorganic filler (C) is contained in an amount of 80% by mass or more and 93% by mass or less based on the entire resin composition. .   The epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 5, wherein the curing agent (B) is a phenol resin-based curing agent.   The epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 6, further comprising (D) a curing accelerator. The curing accelerator (D) has at least one latency selected from a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound. The epoxy resin composition for semiconductor encapsulation according to claim 7, further comprising a curing accelerator.   9. The epoxy resin for semiconductor encapsulation according to claim 1, further comprising a compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring. Composition.   A semiconductor device, wherein a semiconductor element is sealed with a cured product of the epoxy resin composition for sealing a semiconductor according to any one of claims 1 to 9.

Images