JP2001040067A - Epoxy resin composition and resin sealing type semiconductor apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having low viscosity, excellent high fluidity and bond strength of cured material by making the composition include a glycidyl ether-based epoxy resin and a glycidylamine-based epoxy resin. SOLUTION: This composition comprises (A) a glycidyl ether-based epoxy resin (except one having a glycidylamine structure) obtained by subject a tri- or polyhydric phenol such as a tris(hydroxyphenyl)alkane to a glycidyl formation reaction and (B) a glycidylamine-based epoxy resin preferably obtained by subjecting an aromatic amine (e.g. aminophenol, etc.), to a glycidyl formation reaction. In the composition, 1-400 pts.wt. of the component A is preferably used based on 100 pts.wt. of the component B. The composition may contain an epoxy resin curing agent [e.g. tris(hydroxyphenyl)alkane, etc.], if required.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an epoxy resin composition. More specifically, the present invention relates to an epoxy resin composition containing a glycidyl ether-based epoxy resin and a glycidylamine-based epoxy resin, and a resin-sealed semiconductor device using the epoxy resin composition.

[0002]

2. Description of the Related Art Epoxy resin compositions are mainly used for sealing semiconductor elements in the manufacture of semiconductor devices such as ICs and LSIs from the viewpoint of economy and the like. In recent years, as electronic devices have become smaller and higher in density, surface mounting of semiconductor devices on printed wiring boards has become mainstream, and there has been a demand for smaller, thinner semiconductor devices. I have. Therefore, there is a demand for improved properties of the epoxy resin composition used as the sealing material. Therefore, besides general-purpose novolak type epoxy resin,
For example, a biphenyl type epoxy resin or a stilbene type epoxy resin is used for the purpose of improving the low viscosity of the composition, and a tris (hydroxyphenyl) alkane type epoxy resin is used for the purpose of improving the heat resistance of the cured product. Also,
A combination of a novolak type epoxy resin and a biphenyl type epoxy resin (Japanese Patent Publication No. 4-7365) or a combination of a biphenyl type epoxy resin and tris (hydroxyphenyl)
Combination with alkane type epoxy resin (Japanese Patent Publication No. 3-1)
No. 24758) has also been studied. However, conventional epoxy resin compositions are unsatisfactory in terms of low viscosity, high fluidity, and adhesive strength of a cured product.For example, when used as a sealing material, ease of high-density filling, transfer molding Operability, adhesiveness with a die pad, etc. were not always sufficient.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an epoxy resin composition which is excellent in low viscosity and high fluidity and whose cured product is excellent in adhesive strength, and a resin-sealed semiconductor using the same. It is to provide a device.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that an epoxy resin composition containing a specific epoxy resin achieves the above-mentioned objects. The invention has been completed. That is, the present invention relates to [1]. The present invention relates to an epoxy resin composition containing a glycidyl ether-based epoxy resin and a glycidylamine-based epoxy resin. In addition, the present invention relates to [2]. A resin-encapsulated semiconductor device, wherein a semiconductor element is encapsulated with the epoxy resin composition according to the above [1].

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a glycidyl ether-based epoxy resin means an epoxy resin having one or more glycidyl ether structures, except for those having a glycidylamine structure. The glycidyl ether-based epoxy resin can be usually obtained by subjecting a polyhydric phenol to a glycidylation reaction with an epihalohydrin such as epichlorohydrin. Examples of the polyhydric phenols include novolaks such as phenol novolak and cresol novolak; dihydric phenols such as bisphenol A, bisphenol F, bisphenol S, dihydroxystilbene and dihydroxybiphenyl; phenol, cresol; -T-butyl-5-
Tris (hydroxyphenyl) alkanes obtained by the condensation reaction of phenols such as methylphenol and hydroxyphenylcarbonyl compounds such as hydroxybenzaldehydes and hydroxyphenyl ketones; phenols and glyoxal, glutaraldehyde, butanedione, hexane Tetrakis (hydroxyphenyl) alkanes obtained by a condensation reaction with a dicarbonyl compound such as dione; phenols obtained by an addition reaction of phenols with dialkenylbenzenes such as divinylbenzene and dipropenylbenzene Aralkyl resins; phenol alkyl resins obtained by the addition reaction of phenols with dienes such as dicyclopentadiene, terpenes, etc .; polyvinylphenol, polyisopropenylphenol Vinyl polymerization type polyhydric phenols and the like; and the like. One or more glycidyl ether epoxy resins can be used.

As the glycidyl ether-based epoxy resin, from the viewpoint of heat resistance of the cured product, an epoxy resin obtained by glycidylation of a phenol having a valency of 3 or more is preferable. Tris (hydroxyphenyl) alkanes are glycidylated. Epoxy resins obtained by the reaction are more preferred.

In the present invention, the glycidylamine epoxy resin means an epoxy resin having at least one glycidylamine structure (monoglycidylamine structure or diglycidylamine structure), and may have a glycidylether structure. A glycidylamine-based epoxy resin can be usually obtained by subjecting an amine to a glycidylation reaction with an epihalohydrin such as epichlorohydrin. As the amines, aromatic amines are preferable from the viewpoint of glycidylation reaction and the like, and from the viewpoint of availability,
Aminophenols such as aminophenol and aminocresol, and bis (aminophenyl) alkanes such as bis (aminophenyl) methane are more preferred. One or more glycidylamine-based epoxy resins can be used.

The glycidylamine epoxy resin is used in an amount of usually 1 to 400 parts by weight, preferably 5 to 300 parts by weight, per 100 parts by weight of the glycidyl ether epoxy resin.
Parts by weight, more preferably 10 to 100 parts by weight.
If the amount is less than 1 part by weight, the adhesion between the cured product and the metal may not be sufficient. If the amount exceeds 400 parts by weight, the softening point of the composition may be low and the handleability may be poor.

In the present invention, the glycidyl ether-based epoxy resin and the glycidylamine-based epoxy resin are usually separately prepared and used, but the respective precursors are mixed with polyhydric phenols and amines. Thereafter, an epoxy resin obtained by a glycidylation reaction may be used.

The epoxy resin composition of the present invention may contain an epoxy resin curing agent from the viewpoint of the balance between heat resistance and low moisture absorption of the cured product. Examples of the epoxy resin curing agent include the above-mentioned novolaks, dihydric phenols, tris (hydroxyphenyl) alkanes, tetrakis (hydroxyphenyl) alkanes, phenol aralkyl resins, phenol alkyl resins, and vinyl polymerization type Polyhydric phenolic curing agents such as polyhydric phenols; amine curing agents such as dicyandiamide, bis (aminophenyl) methane, bis (aminophenyl) sulfone; pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic acid Acid anhydride-based curing agents such as acid dianhydride; and the like, and one or more of them can be used.

As the epoxy resin curing agent, a polyhydric phenol curing agent is preferable from the viewpoint of low moisture absorption of the cured product.
Above all, novolaks are used from the viewpoint of handling properties, and tris (hydroxyphenyl) is used from the viewpoint of heat resistance of the cured product.
Alkanes are more preferably phenol aralkyl resins from the viewpoint of low viscosity of the composition.

The amount of the epoxy resin curing agent used is, for example, when a polyhydric phenol curing agent is used, the hydroxyl groups in the polyhydric phenol curing agent are 0.7 to 1.2 molar equivalents relative to the epoxy groups of all epoxy resins. It is preferred that 0.
If it is less than 7 equivalents, or if it exceeds 1.2 equivalents, curing may be incomplete.

The epoxy resin composition of the present invention may contain an inorganic filler from the viewpoint of low moisture absorption and low thermal expansion of the cured product. As the inorganic filler, for example, silica,
Alumina, titanium white, aluminum hydroxide, talc, clay, glass fiber and the like can be mentioned, and at least one of them can be used. These can be used by increasing the filling amount by mixing different shapes (spherical or crushed types) or sizes.

Further, the epoxy resin composition of the present invention comprises:
If necessary, a curing accelerator may be contained. As the curing accelerator, for example, organic phosphine compounds such as triphenylphosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine, tri-2-cyanoethylphosphine, and the like; Triphenylborane complexes; quaternary phosphonium salts such as tetraphenylphosphonium tetraphenylborate and tetrabutylphosphonium tetraphenylborate; tributylamine;
Tertiary amines such as triethylamine, 1,8-diazabicyclo (5,4,0) undecene-7, triamylamine; quaternary ammonium such as benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, triethylammonium tetraphenylborate, etc. Salts; imidazoles; and the like, and at least one of them can be used.

Further, the epoxy resin composition of the present invention may contain a flame retardant, a silane coupling agent, a liquid rubber, a coloring agent, a solvent, etc., depending on the use and purpose of use. Examples of the flame retardant include brominated epoxy resin and antimony trioxide.

The mixing of each component of the epoxy resin composition of the present invention may be carried out while the epoxy resin is in a molten state,
After dissolving and mixing in a solvent, the solvent may be removed by concentration or the like. For the mixing, a kneader such as a kneader or an extruder may be used, or a two-roll or three-roll may be used.

The epoxy resin composition of the present invention may be used, for example, as electric and electronic parts materials such as sealing materials and laminate materials; sports equipment (racquets, clubs, etc.) materials;
Composite materials such as leisure goods (such as fishing rods) materials, structural materials for aircraft, etc .; adhesive materials, paint materials, and the like.
Among them, the epoxy resin composition of the present invention has low viscosity, excellent fluidity, and the cured product thereof has excellent adhesive strength. Therefore, the epoxy resin composition is suitably used as a sealing material. By sealing, a useful resin-sealed semiconductor device can be obtained. As a molding method at the time of resin sealing, compression molding method, transfer molding method,
Although an injection molding method and the like can be mentioned, a transfer molding method is usually employed.

[0018]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. The following were used as each component of the epoxy resin composition. Epoxy resin-1: An epoxy resin obtained by subjecting a condensate of 2-t-butyl-5-methylphenol and p-hydroxybenzaldehyde to a glycidylation reaction [viscosity:
3.2 poise (150 ° C.), softening point: 86 ° C., epoxy equivalent: 218 g / equivalent, synthesized according to Reference Example 2 of Japanese Patent Publication No. 7-121979] Epoxy resin-2: 4-amino-m-cresol Epoxy resin obtained by glycidylation reaction [viscosity:
0.1 poise (150 ° C.), liquid at room temperature, epoxy equivalent: 106 g / equivalent, synthesized according to Example 1 of JP-B-6-27176] Epoxy resin-3: bis (4-aminophenyl) methane is glycidyl Epoxy resin obtained by a chemical reaction [viscosity: 0.3 poise (150 ° C.), liquid at room temperature, epoxy equivalent: 116 g / equivalent, synthesized according to Examples in JP-B-6-27176] Curing agent: Tris (hydroxyphenyl) methane Hardening accelerator: Triphenylphosphine Filler: Fused silica (crushed silica (trade name: FS-891 manufactured by Denki Kagaku Kogyo Co., Ltd.) / Spherical silica (Denki Kagaku Kogyo Co., Ltd. Product name: FB-60) = 20/80
(Use by mixing in weight ratio)]-Release agent: carnauba wax-Silane coupling agent (Toray Dow Corning Silicone, trade name: SH-6040)

The following methods were used to evaluate the epoxy resin composition and its cured product. Epoxy equivalent: After dissolving a sample in dioxane and adding a hydrochloric acid / dioxane solution to react with an epoxy group, excess hydrochloric acid was titrated with a sodium hydroxide / methanol solution to obtain an epoxy equivalent, which was measured by a hydrochloric acid-dioxane method. . -Softening point: Measured by the ring and ball method according to JIS K7234.・ ICI viscosity: 150 ° C. (50 ° C.) using an ICI viscometer.
(Hz).・ Spiral flow: 175 ℃ / 70kg / cm according to EMMI-1-66
^{Performed under} the conditions of ² . -Glass transition temperature: measured using TMA.・ Pull-out adhesive strength: After forming a molded product in which 42 alloy is embedded with a transfer molding machine (175 ° C./70 kg / cm ² ), a sample after-cured in an oven (180 ° C./5h)
It was measured with a tensile tester (SHIMADZU IS-10T) (measuring temperature: 240 ° C).

Examples 1 to 4 and Comparative Example 1 Each component was placed in a four-necked flask having the composition (parts by weight) shown in Table 1 and purged with nitrogen. Then, the resin was melted in an oil bath at 150 ° C. The mixture was stirred until it became uniform to obtain an epoxy resin composition. Table 1 shows the evaluation results of the composition.

[0021]

[Table 1]

Examples 5 to 8, Comparative Example 2 The epoxy resin compositions and the components obtained in Examples 1 to 4 and Comparative Example 1 were mixed in the composition (weight ratio) shown in Table 2 and rolled. After heating and kneading to obtain an epoxy resin composition, transfer molding was performed to obtain a cured product. Table 2 shows the evaluation results of the composition and the cured product.

[0023]

[Table 2]

[0024]

The epoxy resin composition of the present invention is excellent in low viscosity and high fluidity, and the cured product thereof has excellent adhesive strength without impairing the conventional heat resistance. Therefore, by sealing a semiconductor element with the composition, a useful resin-sealed semiconductor device is provided.

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Claims (8)

[Claims] 1. An epoxy resin composition comprising a glycidyl ether epoxy resin and a glycidylamine epoxy resin. 2. The epoxy resin composition according to claim 1, wherein the glycidyl ether epoxy resin is an epoxy resin obtained by subjecting a phenol having a valency of 3 or more to glycidylation. 3. The epoxy resin composition according to claim 2, wherein the trivalent or higher phenol is a tris (hydroxyphenyl) alkane. 4. The epoxy resin composition according to claim 1, wherein the glycidylamine-based epoxy resin is an epoxy resin obtained by subjecting an aromatic amine to a glycidylation reaction. 5. The aromatic amines are bis (aminophenyl)
The epoxy resin composition according to claim 4, which is an alkane or an aminophenol. 6. The epoxy resin composition according to claim 1, further comprising an epoxy resin curing agent. 7. The method according to claim 1, further comprising an inorganic filler.
7. The epoxy resin composition according to any one of 6. 8. A resin-encapsulated semiconductor device, wherein a semiconductor element is encapsulated by using the epoxy resin composition according to claim 1.