JP2003277477A - Epoxy resin composition and resin-sealing type semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing with which reflow resistance and moisture proof reliability are improved while satisfying characteristics such as moldability and hardness. <P>SOLUTION: The epoxy resin composition comprises (A) an epoxy resin component, (B) a phenol resin curing agent, (C) a silane coupling agent and (D) an inorganic filler as essential components. The epoxy resin component (A) comprises an epoxy resin having a skeleton represented by the genera formula (1) (wherein n is an integer of 0 or ≥1) and the phenol resin curing agent component (B) comprises a phenol resin having a skeleton represented by the general formula (2) (wherein n is an integer of 0 or ≥1). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition used as a sealing material for electronic parts such as semiconductor elements and a resin-sealed semiconductor device using the same.

[0002]

2. Description of the Related Art Regarding electronic parts such as semiconductor elements,
Generally, a thermosetting resin is used for sealing. Epoxy resin is used as the base material for such encapsulation, and a composition in which a curing agent, a curing accelerator, and an inorganic filler such as silica powder or a pigment is added to the encapsulation material is reliable, formable, and inexpensive. It is often used from the point.

By the way, in recent years, in the field of semiconductor integrated circuits, along with the high integration of semiconductor devices, the size of the devices has been increased. On the other hand, regarding the package design, the conventional pin insertion mounting type DIP (Dual-In Li
ne Package), surface mount type SOP (Small Outlin)
e Package), QFP (Quad Flat Package), SOJ
(Small Outline J-lead Package), TSOP (Thin
SOP), LQFP (Large QFP), TQFP (Thin
QFP) and so on.

With such a change in the mounting method of the semiconductor package, a problem in the soldering process, which has not been a serious problem in the conventional pin insertion mounting type package, has become a problem. In other words, in the case of a surface mount type package, the entire package is directly immersed in solder when it is mounted on a printed circuit board, etc., and is rapidly exposed to a high temperature of 230 to 270 ° C. There are problems that cracks may occur and peeling may occur between the semiconductor element and the sealing resin portion or between the substrate such as the lead frame and the sealing resin portion. These are factors that reduce the manufacturing yield and reliability of semiconductor packages.

On the other hand, since the epoxy resin composition used for sealing electronic parts is very flammable as it is, it is required to impart flame retardancy according to UL standard in order to ensure safety. There is. In an epoxy resin composition, it is common to use a halogen-based flame retardant containing a halogen element such as chlorine or bromine and a flame retardant aid such as an antimony compound (for example, antimony trioxide) for flame retardation. .

However, these flame-retardant auxiliaries such as halogen-based flame retardants and antimony compounds, in addition to the problem of lowering the reliability of electronic parts, have become more environmentally friendly with the recent increasing awareness of environmental problems. The influence of is beginning to be seen as a problem. For example, it has been pointed out that some halogen-containing flame retardant-containing materials may generate highly toxic dioxin compounds when burned. In addition, antimony compounds are easily dissolved in water, which significantly affects the water quality environment. As described above, both the halogen-based flame retardant and the antimony compound have environmental hygiene problems.

Therefore, the use of phosphorus, metal oxides, hydroxides and the like as other flame retardants has been studied, but the addition of a small amount of phosphorus flame retardant can impart flame retardancy. On the other hand, it also has the problem of affecting the water quality environment. Further, flame retardants such as metal oxides and hydroxides have a low flame retardancy-imparting effect and need to be added in a large amount, which has a problem that the properties of the epoxy resin composition itself are adversely affected. . Further, when a phosphorus-based or inorganic flame-retardant is used, there is a problem that long-term moisture resistance reliability and high-temperature reliability are significantly inferior to the combined use of a halogen-based flame retardant and an antimony compound.

[0008]

As described above, since the surface mount type package is rapidly exposed to a high temperature during, for example, the soldering process, a package packaged with a conventional epoxy resin composition is sealed. There is a problem that cracks and peeling are likely to occur in the resin part. For this reason, when applied to a surface mount type package or the like, it is desired to develop an epoxy resin composition having excellent reliability that can suppress the occurrence of cracks or peeling during mounting, for example. Further, even in the epoxy resin composition for encapsulation, a highly reliable flame retardant technology capable of imparting good flame retardancy without using a halogen-based flame retardant or an antimony compound due to environmental considerations. Development is required.

The present invention has been made in order to cope with such a conventional problem, and satisfies basic characteristics such as moldability and moisture resistance reliability and, at the same time, high temperature reliability (thermal shock resistance) such as reflow resistance. Reliability), an epoxy resin composition with good flame retardancy without using a halogen-based flame retardant or an antimony compound in consideration of the influence on the environment. An object of the present invention is to provide a resin-encapsulated semiconductor device using the epoxy resin composition.

[0010]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that an epoxy resin having a specific structure containing a biphenylene group and a specific structure of a dioxynaphthalene type are selected. By using the phenolic resin hardeners we have, we can enhance the high temperature reliability (thermal shock reliability) such as reflow resistance while satisfying the characteristics such as moldability and moisture resistance reliability. It has been found that the moisture resistance reliability and reflow resistance can be further improved by using an aminosilane coupling agent having a nitrogen atom therein. Furthermore, in addition to the use of an epoxy resin and a phenol resin having a specific structure, by controlling the compounding amount of an inorganic filler, it is possible to impart excellent flame retardancy to an epoxy resin composition without using a flame retardant. Found that is possible.

The present invention has been made on the basis of such findings, and the epoxy resin composition of the present invention has, as described in claim 1, (A) epoxy resin component, (B) phenol resin curing agent, An epoxy resin composition containing (C) a silane coupling agent and (D) an inorganic filler as essential components, wherein the epoxy resin component of component (A) is

[Chemical 3] The phenol resin curing agent as the component (B), which contains an epoxy resin having a skeleton represented by

[Chemical 4] It is characterized by containing a phenol resin having a skeleton represented by

The epoxy resin composition of the present invention is further characterized in that the silane coupling agent as the component (C) contains an aminosilane coupling agent having a nitrogen atom in the skeleton. . In addition, claim 5
As described above, the inorganic filler as the component (D) is contained in the range of 83 to 90% by mass with respect to the total amount of the composition, and the flame retardant is not substantially contained.

The resin-encapsulated semiconductor device of the present invention uses the above-mentioned epoxy resin composition of the present invention as an encapsulating material, and as described in claim 6, the epoxy resin composition of the present invention is used. It is characterized by comprising a semiconductor chip sealed with a cured product. In such a resin-encapsulated semiconductor device, since the moisture resistance reliability and high temperature reliability of the resin encapsulation portion can be improved, highly reliable mounting is realized even when various mounting methods are adopted. It becomes possible.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Modes for carrying out the present invention will be described below.

The epoxy resin composition of the present invention comprises (A) an epoxy resin component, (B) a phenol resin curing agent, and (C).
It contains a silane coupling agent and (D) an inorganic filler as essential components. Of these essential components, the epoxy resin component of component (A) is

[Chemical 5] An epoxy resin having a skeleton represented by (hereinafter referred to as a biphenylene group-containing epoxy resin) is included.

The biphenylene group-containing epoxy resin whose skeleton is represented by the above formula (1) maintains basic properties such as moldability of the epoxy resin composition and, on the basis of its skeleton structure, moisture resistance reliability and It is a component that contributes to improvement of thermal shock reliability such as reflow resistance, and further improvement of flame retardancy of the epoxy resin composition. As such a biphenylene group-containing epoxy resin, those having an epoxy equivalent of 200 to 350 are preferably used, and further an epoxy equivalent of 250 to 3 is used.
The range of 20 is more preferable. Also, the softening temperature is 40 ~
It is preferably in the range of 100 ° C, and further 50 to 75 ° C.
The range is more preferably. Furthermore, regarding the resin melt viscosity, the resin melt viscosity measured by an ICI viscometer (cone and plate type) at 150 ° C. is 0.1.
It is preferably in the range of up to 3.0 poise.

Specific examples of the biphenylene group-containing epoxy resin as described above include NC-manufactured by Nippon Kayaku Co., Ltd.
3000P (trade name; epoxy equivalent = 277, softening temperature = 61
℃, resin melt viscosity = 1.1 poise), NC-3000S (trade name; epoxy equivalent = 282, softening temperature = 59 ℃, resin melt viscosity = 0.9 poise) and the like. These biphenylene group-containing epoxy resins may be used alone or in combination of two or more.

In the epoxy resin component of component (A), in addition to the above-mentioned biphenylene group-containing epoxy resin, other epoxy resin may be used in combination if necessary.
Examples of the epoxy resin used in combination include novolac type epoxy resin, cresol novolac type epoxy resin, triphenol methane type epoxy resin, biphenyl type epoxy resin, heterocyclic epoxy resin, naphthalene ring-containing epoxy resin, bisphenol A type epoxy resin, bisphenol. Examples thereof include F-type epoxy resins, stilbenzene-type epoxy resins, condensed polycyclic aromatic hydrocarbon-modified epoxy resins and the like, and one or more of these can be used in combination.

When the other epoxy resin as described above is used in combination, the compounding amount thereof is based on the total amount of the epoxy resin (total mass of epoxy resin components = mass of biphenylene group-containing epoxy resin + mass of other epoxy resin). It is preferably less than 50% by mass. In other words, it is preferable that the biphenylene group-containing epoxy resin having a skeleton represented by the formula (1) is contained in an amount of 50% by mass or more based on the total amount of the epoxy resin. When the blending amount of the biphenylene group-containing epoxy resin is less than 50% by mass with respect to the total amount of the epoxy resin, the above-mentioned effects of improving the moisture resistance reliability and reflow resistance may not be sufficiently obtained. The blending amount of the biphenylene group-containing epoxy resin is more preferably 80% by mass or more based on the total amount of epoxy resin.

The (B) component phenol resin curing agent is
(A) Component which is cured by reacting with an epoxy group in the epoxy resin component,

[Chemical 6] A phenol resin having a skeleton represented by (hereinafter referred to as a dioxynaphthalene type phenol resin) is included.
This dioxynaphthalene-type phenol resin is a component that contributes to the improvement of the moisture resistance reliability and the thermal shock reliability such as the reflow resistance of the cured product based on its skeleton structure, and further enhances the flame retardancy.

As such a dioxynaphthalene type phenol resin, one having a phenolic hydroxyl group equivalent in the range of 90 to 120 is preferably used, and further the hydroxyl equivalent is 95.
Those in the range of to 115 are more preferable. Regarding the resin melt viscosity, the resin melt viscosity measured by an ICI viscometer (cone and plate type) at 150 ° C. is 0.5.
It is preferably in the range of -10.0 poise, more preferably in the range of 1.0-8.0 poise. Specific examples of the dioxynaphthalene type phenol resin include SN-375 (trade name; hydroxyl group equivalent = 106, resin melt viscosity = 1.0 poise) manufactured by Nippon Steel Chemical Co., Ltd., SN-385 (trade name; hydroxyl group equivalent =). 105, resin melt viscosity = 3.1 poise) SN-3
Examples include the 00 series.

In the phenol resin curing agent as the component (B), in addition to the above-mentioned dioxynaphthalene type phenol resin, other phenol resin may be used in combination if necessary. Examples of the phenol resin to be used in combination include, for example, phenol novolac resin, cresol novolac resin, dicyclopentadiene modified phenol resin, paraxylene modified phenol resin, condensate of phenol and benzaldehyde or naphthyl aldehyde, triphenol methane compound, phenol biphenyl aralkyl resin. And the like, and one or more of these may be used in combination.

When the other phenolic resin as described above is used in combination, the compounding amount of the dioxynaphthalene type phenolic resin whose skeleton is represented by the formula (2) is such that the total phenolic resin amount (total mass of phenolic resin component = diethyl resin It is preferably 5% by mass or more based on the mass of the oxynaphthalene type phenolic resin + the mass of the other phenolic resin). If the amount of the dioxynaphthalene-type phenol resin compounded is less than 5% by mass with respect to the total amount of the phenol resin, it may not be possible to sufficiently obtain the above-described effects of improving the moisture resistance reliability and reflow resistance.

However, when the dioxynaphthalene type phenol resin is used alone, the moldability and the like may be slightly deteriorated. Therefore, the amount of other phenol is less than 50% by mass based on the total amount of the phenol resin. It is preferable to use a resin together. From this point of view, the amount of the dioxynaphthalene-type phenol resin compounded is preferably in the range of 5 to 50 mass% with respect to the total amount of the phenol resin. As for the other phenol resin used in combination, it is particularly preferable to use a para-xylene-modified phenol resin. Specific examples of the para-xylene-modified phenol resin include XL-225-3L, XLC-LL, and XL manufactured by Mitsui Chemicals, Inc.
C-3L, XLC-4L (trade name), MEH-7800M, MEH-7800S, MEH manufactured by Meiwa Kasei Co., Ltd.
-7800SS (trade name), HE-100C-10, HE-100C-15, HE- manufactured by Sumikin Chemical Co., Ltd.
100C-30 (trade name) and the like.

The mixing ratio of the epoxy resin component of the component (A) and the phenol resin curing agent of the component (B) is not particularly limited, but in order to suppress each unreacted component to a small amount, the component (A) is It is preferable to set the compounding ratio represented by the ratio (the number of phenolic hydroxyl groups / the number of epoxy groups) of the number of phenolic hydroxyl groups of the total phenolic resin of the component (B) to the number of epoxy groups of the total epoxy resin of 0.5 to 1.2. , And more preferably 0.7 to 1.0.

The silane coupling agent as the component (C) includes
For example, various silane coupling agents such as aminosilane-based, epoxysilane-based, vinylsilane-based, alkylsilane-based, and mercaptosilane-based can be used. Among these, it is particularly preferable to use an aminosilane coupling agent having a nitrogen atom in the skeleton. Aminosilane coupling agent, by using in combination with a biphenylene group-containing epoxy resin whose skeleton is represented by the above formula (1) and a dioxynaphthalene type phenolic resin whose skeleton is represented by the above formula (2), an epoxy resin composition Further improve the thermal shock reliability such as moisture resistance reliability and reflow resistance.

Examples of the aminosilane coupling agent include N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane and γ-aminopropyltriethoxysilane. , N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane and the like, and particularly N-phenyl-γ-aminopropyltrimethoxysilane and γ-ureidopropyltriethoxysilane and the like are preferable. These aminosilane coupling agents are used alone or as a mixture of two or more.

Further, in the silane coupling agent as the component (C), other silane coupling agent may be used in combination with the aminosilane coupling agent. Other silane coupling agents used in combination include epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. System, γ- (methacryloxypropyl) trimethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane and other vinylsilane systems, methyltrimethoxysilane, methyltriethoxysilane and other alkylsilane systems, γ-mercaptopropyltrimethoxysilane, Examples thereof include mercaptosilane-based compounds such as γ-mercaptopropylmethyldimethoxysilane and imidazolesilane.

When the aminosilane coupling agent and another silane coupling agent are used in combination, the amount of the aminosilane coupling agent is the total amount of silane coupling agents (total weight of silane coupling agent = weight of aminosilane coupling agent). + Mass of other silane coupling agent) is preferably 70% by mass or more. It is more preferable that the amount of the aminosilane coupling agent is 90% by mass or more based on the total amount of silane coupling agents.

The inorganic filler as the component (D) is added for the purpose of improving properties such as thermal expansion coefficient, thermal conductivity, water absorption, elastic modulus and flame retardancy of the cured product. Powders such as silica, crystalline silica, alumina, talc, titanium white, red iron oxide, and silicon carbide, beads obtained by sphering these, single crystal fibers, glass fibers, and the like can be given.These are one kind or a mixture of two or more kinds. used. Of these inorganic fillers, for example, fused silica is preferably used from the viewpoint of reducing thermal expansion, and crystalline silica or alumina is preferred from the viewpoint of high thermal conductivity. Further, fused silica and crystalline silica are preferably used from the viewpoint of imparting flame retardancy.

Regarding the shape of the inorganic filler, fluidity,
From the viewpoint of moldability and mold wear resistance, a spherical shape or a shape close to a spherical shape is preferable. Furthermore, the maximum particle size of the inorganic filler is
It is preferable to use a powder of 100 μm or less, and further 75 μm or less. This is because if the maximum particle size of the inorganic filler exceeds 100 μm, the moldability tends to deteriorate due to a decrease in the filling property into the narrow portion. The average particle size of the inorganic filler is preferably in the range of 5 to 50 μm. If the average particle size of the inorganic filler powder is less than 5 μm, the viscosity of the epoxy resin composition increases, while if it exceeds 50 μm, the dispersibility of the resin component and the filler decreases, and, for example, the molded product becomes uneven. In addition, there are problems such as deterioration of the filling property in narrow details. The average particle size of the inorganic filler powder is 10-30μ
More preferably, it is in the range of m.

The blending amount of the inorganic filler as the component (D) is preferably 70 to 92% by mass, more preferably 78 to 91% by mass, based on the total amount of the composition. The inorganic filler improves the properties such as the thermal expansion coefficient, the thermal conductivity, the water absorption, the elastic modulus, and the flame retardancy of the cured product as described above, and the compounding amount of such an inorganic filler is 70 mass. If it is less than%, the effect of improving the characteristics as described above cannot be sufficiently obtained. On the other hand, if the blending amount of the inorganic filler exceeds 92% by mass, the flowability of the epoxy resin composition will be significantly reduced and the moldability will be poor, such being unsuitable for practical use.

In the epoxy resin composition of the present invention,
In particular, as the inorganic filler of the component (D), a filler having a high flame retardancy-imparting property such as fused silica or crystalline silica is selected.
It is desirable to use one kind or two or more kinds and to make the blending amount within the range of 83 to 90 mass% with respect to the total amount of the composition. That is, 83% by mass of the inorganic filler as described above
By blending in the above range, good flame retardancy can be imparted to the epoxy resin composition without substantially blending the flame retardant. The content of the inorganic filler is preferably 90% by mass or less in order to keep the moldability better.

In addition to the above-mentioned essential components (A) to (D), other additives may be added to the epoxy resin composition of the present invention, if necessary, within a range that does not impair the effects of the present invention. You can Other additives commonly used in compositions of this type are phosphorus-based, amine-based, imidazole-based,
Organic phosphine-based and tetraphenylboron salt-based curing accelerators, carbon black, cobalt blue and other coloring agents, alkyl titanate and other surface treatment agents, natural wax, synthetic wax and other release agents, silicone oil and silicone rubber, etc. The stress reducing agents of

As a general method for producing the epoxy resin composition of the present invention, the above-mentioned essential components (A) to (D) and, if necessary, other additive components are sufficiently homogeneously mixed with a mixer or the like ( Dry blend) and then heat roll,
Examples thereof include a method of melt-kneading with a kneader or an extruder, cooling and then pulverizing.

The epoxy resin composition of the present invention thus obtained is useful as a sealing material for electronic parts such as semiconductor elements. That is, the epoxy resin component (A) containing the biphenylene group-containing epoxy resin whose skeleton is represented by the above formula (1) and the dioxynaphthalene type phenol resin whose skeleton is represented by the above formula (2) are included ( B) When used in combination with a phenolic resin curing agent, basic characteristics such as moldability are maintained based on the skeleton structure of these resin components, and reliability against heat shock such as moisture resistance and reflow resistance is maintained. Can be improved. Properties such as moisture resistance reliability and reflow resistance can be further enhanced by using an aminosilane coupling agent as the component (C).

As described above, by improving the thermal shock reliability such as the reflow resistance of the epoxy resin composition,
For example, when an epoxy resin composition is used as a sealing material for a surface mount type package, cracks in the sealing resin portion of the package during the soldering process, and the sealing resin portion and a substrate such as a semiconductor element or a lead frame It is possible to suppress the occurrence of peeling between them. That is, regardless of the package mounting method, the mounting process (soldering process)
The reliability of time can be greatly improved.

Further, the epoxy resin composition of the present invention is
Since it is possible to include a relatively large amount of an inorganic filler while maintaining properties such as its moldability, it is possible to obtain a favorable result without using a flame retardant aid such as a halogen-based flame retardant or an antimony compound. Flame resistance can be imparted.
The skeleton structure of the resin component also contributes to the improvement of the flame retardancy of the epoxy resin composition. As previously mentioned,
Since halogen-based flame retardants and antimony compounds have begun to be regarded as environmentally problematic, the significance of imparting good flame retardancy to epoxy resin compositions without the use of such flame retardants Is big.

A semiconductor device of the present invention uses the above-mentioned epoxy resin composition of the present invention as a sealing material, and comprises a semiconductor chip sealed with a cured product of the epoxy resin composition of the present invention. To do. The semiconductor element that constitutes the semiconductor device is not particularly limited, and is applicable to various semiconductor elements such as an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, and a diode. As described above, since the epoxy resin composition of the present invention is excellent in moisture resistance reliability and thermal shock reliability, in addition to improvement in long-term reliability of the package itself,
It is possible to suppress the occurrence of defects and the decrease in reliability during the package mounting process. As a result, it is possible to improve the manufacturing yield and reliability of package components such as semiconductor packages.

As a method of sealing the semiconductor element, a low pressure transfer molding method is generally used, but it is also possible to seal it by injection molding, compression molding, casting or the like. After sealing with the epoxy resin composition and heating and curing, a semiconductor device finally sealed with the cured product is obtained. The curing by heating is preferably heat curing at a temperature of 150 ° C. or higher. Furthermore, examples of the substrate on which the semiconductor element is mounted include a ceramic substrate, a plastic substrate, a polyimide film, a lead frame and the like, but the substrate is not particularly limited thereto.

[0041]

EXAMPLES Next, specific examples of the present invention and evaluation results thereof will be described. However, the present invention is not limited to these examples.

Example 1 First, a parabiphenylene group-containing epoxy resin having the structural formula (3) below, NC-3000P (trade name, manufactured by Nippon Kayaku Co., Ltd .; epoxy equivalent = 277 g / eq, softening temperature = 61). ℃, resin melt viscosity = 1.1 poise) 9.50 mass%, and dioxynaphthalene type phenol resin having the following structural formula (4)
SN-375 (trade name, manufactured by Nippon Steel Chemical Co .; hydroxyl equivalent = 1)
04g / eq, resin melt viscosity = 1.1 poise) 3.50% by mass and silane coupling agent γ-aminopropyltriethoxysilane (aminosilane coupling agent 1) 1.0% by mass
And fused spherical silica powder as the inorganic filler (maximum particle size
= 75 μm, average particle size = 16 μm, specific surface area = 4.6 m ² / g) 85 mass%
And triphenylphosphine (TP
P) 0.15 mass%, carnauba wax 0.35 mass% and carbon black 0.5 mass% are mixed at room temperature, and then 70
The mixture was melt-kneaded by heating at ~ 90 ° C. After cooling, it was pulverized to an appropriate size to obtain the desired epoxy resin composition. In addition,
The compounding ratio of epoxy resin and phenol resin (number of phenolic hydroxyl groups / number of epoxy groups) is 0.98.

[0043]

[Chemical 7]

[Chemical 8]

Examples 2 to 26 As the epoxy resin, the parabiphenylene group-containing epoxy resin NC-3000P (epoxy equivalent = 277 g / eq) used in Example 1 and biphenyl having the structural formula (5) below. Type Epoxy Resin YX-4000H (trade name, JE
R company; epoxy equivalent = 193 g / eq) and orthocresol novolac type epoxy resin having the structural formula (6) below: EOCN-1020-55 (trade name, manufactured by Nippon Kayaku Co .; epoxy equivalent = 198 g) / eq) was prepared respectively.

[0045]

[Chemical 9]

[Chemical 10]

For the phenol resin, the dioxynaphthalene type phenol resin SN-37 used in Example 1 was used.
5 (hydroxyl equivalent = 104 g / eq) and para-xylene-modified phenol resin having the structural formula (7) below: MEH-78
00SS (Brand name, manufactured by Meiwa Kasei Co .; hydroxyl equivalent = 175g / e
q), and a biphenyl-modified phenolic resin MEH-7851SS (trade name, manufactured by Meiwa Kasei Co .; hydroxyl equivalent = 198 g / eq) having the structural formula of the following formula (8) and the structural formula of the following formula (9). Naphthol type phenolic resin having SN-180
(Trade name, manufactured by Nippon Steel Chemical Co .; hydroxyl equivalent = 196 g / eq) were prepared.

[0047]

[Chemical 11]

[Chemical 12]

[Chemical 13]

Regarding the silane coupling agent,
In addition to γ-aminopropyltriethoxysilane (aminosilane coupling agent 1) used in Example 1, N-phenyl-γ-aminopropyltrimethoxysilane (aminosilane coupling agent 2) and γ-glycidoxypropyltrisilane were used. Methoxysilane (epoxysilane coupling agent)
Prepared. Further, as in Example 1, fused spherical silica powder (maximum particle size = 75 μm, average particle size = 16 μm, specific surface area =
4.6 m ² / g), triphenylphosphine (TPP), carnauba wax, and carbon black were prepared.

The above components were mixed at room temperature based on the compounding ratios shown in Tables 1 and 2, and then 70-90 ° C.
It was heated, melted and kneaded. After cooling, each was crushed to an appropriate size to obtain the desired epoxy resin composition.

[0050]

[Table 1]

[0051]

[Table 2]

Comparative Examples 1 to 8 As shown in Table 2, an epoxy resin composition outside the scope of the present invention was prepared in the same manner as in Example 1, using the same components as those in the above-mentioned examples. The phenol novolac resin used in Comparative Examples 3 and 5 has the following structural formula (10), and the phenol novolac resin TEH-1085 (trade name; hydroxyl equivalent = 104) manufactured by Meiwa Kasei Co., Ltd.
g / eq) was used.

[0053]

[Chemical 14]

Examples 1 to 26 and Comparative Example 1 described above
The properties of each epoxy resin composition obtained in Example 8, ie, water absorption, hardness, moldability, moisture resistance reliability, reflow resistance, and flame retardancy were measured and evaluated as follows. The results of these measurements are shown in Tables 3, 4, and 5, respectively.

Regarding the water absorption rate, first, each epoxy resin composition was transfer molded at 175 ° C. for 60 seconds to form a molded product having a diameter of 50 mm and a thickness of 3 mm, and post-cured at 175 ° C. for 8 hours. After that, these cured products were allowed to stand in saturated steam at 127 ° C. and 2.5 atm for 24 hours. The water absorption rate (%) was calculated based on the mass increased after standing.

Regarding the hardness, each epoxy resin composition
Transfer molding at 175 ° C for 60 seconds, diameter 5
A 0 mm x 3 mm thick molded product was prepared, and the hot hardness of the molded product was measured by a Barcol hardness meter immediately after the mold was opened. Regarding moldability, a mold conforming to the EMMI standard was used, and the spiral flow (mm) was measured under the conditions of 175 ° C. and 120 seconds.

Regarding the moisture resistance reliability, first, a silicon chip having two aluminum wirings was adhered to a 42 alloy frame, transfer molding was carried out using each epoxy resin composition at 175 ° C. for 90 seconds, and then 175 ° C. And post-cured for 8 hours. A moisture resistance reliability test (PCT) was performed on each of the molded products thus obtained in saturated steam at 127 ° C. and 2.5 atm to evaluate the time at which 50% disconnection (defect occurrence) due to aluminum corrosion occurred.

Regarding the reflow resistance, first, a dummy chip (6.0 × 6.0 mm) is placed in a QFP package (14 × 14 × 1.0 mm).
/ Cu frame), transfer molding was performed at 175 ° C. for 90 seconds using each epoxy resin composition, and post-curing was performed at 175 ° C. for 8 hours. Each resin-encapsulated semiconductor device (QFP type semiconductor package) obtained in this manner was subjected to a predetermined time (48
h, 72h, 96h, 168h), after 260 ℃ (ma
IR reflow (x) was performed three times, and after cooling to room temperature, the presence or absence of cracks and peeling was observed with a stereoscopic microscope and an ultrasonic flaw detector. After each moisture absorption treatment time, the defect occurrence rate due to the occurrence of cracks and peeling was examined.

Regarding the flame retardancy, each epoxy resin composition was transfer molded under the conditions of 175 ° C. and 90 seconds, and 120 ×
12 × 0.8 mm and 120 × 12 × 3.2 mm molded products were made, and then post-cured at 175 ° C. for 8 hours. Each of these cured products was subjected to a combustion test based on the UL-94 flame resistance test standard to evaluate flame retardancy.

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

As is clear from Table 3, Table 4 and Table 5, the epoxy resin compositions according to the respective examples are excellent in hardness, moldability, moisture resistance reliability and reflow resistance, and further have a predetermined amount of inorganic filler. It can be seen that good flame retardancy is imparted by containing (fused spherical silica in the examples). Furthermore, by using the dioxynaphthalene type phenol resin having the structural formula (4) as a phenol resin curing agent and another phenol resin together, the moldability is further improved, and the moisture resistance reliability and reflow resistance are also improved. It can be seen that the moisture resistance reliability and the reflow resistance are further improved by the use of the aminosilane coupling agent. In addition, when the inorganic filler was blended in an amount exceeding 92 mass% in the composition ratio of Examples 5 to 7, a decrease in moldability (spiral flow) was observed, while the blending amount of the inorganic filler was less than 83 mass%. It was confirmed that the flame retardancy was lowered, and the moisture resistance reliability and the reflow resistance were slightly lowered.

On the other hand, in the epoxy resin compositions according to the respective comparative examples, Comparative Examples 1 and 2 using only the epoxy resin other than the parabiphenylene group-containing epoxy resin having the structural formula (3), were excellent in moisture resistance reliability and resistance. The reflowability and flame retardancy were inferior to those of the examples. In Comparative Examples 3 to 8 in which only the phenol resin other than the dioxynaphthalene type phenol resin having the structural formula (4) is used, moisture resistance reliability and reflow resistance are inferior depending on the phenol resin used, or It was inferior in basic properties such as hardness and incombustibility.

[0065]

As described above, according to the epoxy resin composition of the present invention, the characteristics such as hardness and moldability are satisfied, and the thermal shock reliability such as humidity resistance and reflow resistance is improved. It is possible to improve, and it is possible to impart good flame retardancy without using a flame retardant or the like. According to the resin-encapsulated semiconductor device of the present invention using such an epoxy resin composition as an encapsulating material, it is possible to improve the reliability at the time of mounting, the manufacturing yield, and the like.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 23/29 H01L 23/30 R 23/31 F term (reference) 4J002 CC032 CC042 CD041 CD061 CD201 CE002 DE117 DE137 DE147 DJ007 DJ017 DJ047 DL007 EX016 EX056 EX076 EX086 FA047 FD017 FD142 FD206 GQ05 4J036 AD12 AE07 FA01 FA03 FA05 FA13 FB08 JA07 4M109 AA01 EA02 EB03 EB06 EB13

Claims (6)

[Claims] 1. An epoxy resin composition containing (A) an epoxy resin component, (B) a phenol resin curing agent, (C) a silane coupling agent, and (D) an inorganic filler as essential components, wherein: The epoxy resin component of component (A) is as follows: The phenol resin curing agent of the component (B), which contains an epoxy resin having a skeleton represented by: An epoxy resin composition comprising a phenol resin having a skeleton represented by: 2. The component (B) phenolic resin curing agent contains 5% by mass or more of a phenolic resin having a skeleton represented by the formula (2), based on the total amount of phenolic resin. The epoxy resin composition according to claim 1. 3. The (B) component phenol resin curing agent contains a phenol resin having a skeleton represented by the formula (2) in an amount of 5 to 50 mass% with respect to the total amount of the phenol resin. An epoxy resin composition according to claim 1. 4. The epoxy according to any one of claims 1 to 3, wherein the silane coupling agent as the component (C) contains an aminosilane coupling agent having a nitrogen atom in the skeleton. Resin composition. 5. The inorganic filler as the component (D) is contained in the range of 83 to 90% by mass with respect to the total amount of the composition, and the flame retardant is not substantially contained. The epoxy resin composition according to claim 4. 6. A resin-encapsulated semiconductor device comprising a semiconductor element encapsulated with a cured product of the epoxy resin composition according to claim 1. Description: