JPH0873564A - Epoxy resin composition and resin-encapsulated semiconductor device - Google Patents

Abstract

(57) [Summary] [Object] To provide an epoxy resin composition having low viscosity, low hygroscopicity, and high adhesion, and a resin-sealed semiconductor device using the same. [Structure] (A) General formula (1) (In the formula, R ₁ represents a hydrogen atom, a chain or cyclic alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group or a halogen atom, and R ₁ may be the same or different from each other. Good, n represents an integer value of 0 to 4.)
An epoxy resin composition characterized by containing an epoxy resin and a curing agent as main components, and a resin-encapsulated semiconductor device obtained by encapsulating a semiconductor element using the epoxy resin composition.

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 particularly useful for encapsulating electronic parts and a resin encapsulation type semiconductor device using the same.

[0002]

2. Description of the Related Art Recently, LSIs, ICs, transistors, etc.
Transfer molding of an economically useful epoxy resin composition is performed for sealing a semiconductor. In particular, recently, surface mounting of LSIs has been carried out, and the number of cases in which they are directly immersed in a solder bath is increasing. At that time, the sealing material is 20
Since the sealant is exposed to a high temperature of 0 ° C. or higher, the moisture absorbed in the encapsulant expands, causing cracks or peeling at the interface with the die pad.

Therefore, the epoxy resin encapsulant is required to have improved low hygroscopicity, crack resistance and adhesion. Further, for the purpose of obtaining low hygroscopicity, a low-viscosity epoxy resin that can be filled with a filler at a high density is desired. At present, a sealant using glycidyl ether of o-cresol novolac as the epoxy resin and phenol novolac as the curing agent is the mainstream, but there is the above problem when moisture is absorbed during storage, and in order to avoid this, practically Is used in a moisture-proof package.

[0004]

The encapsulant mainly composed of glycidyl ether of o-cresol novolac has a good balance in terms of heat resistance and moldability, but at the high level as described above. There is a problem in solder cracking properties because it is not always sufficient in applications where low hygroscopicity is required. An object of the present invention is to provide an epoxy resin composition having low viscosity, low hygroscopicity and high adhesion, and a resin-sealed semiconductor device using the same.

[0005]

In view of the above circumstances, the inventors of the present invention have made earnest studies, and as a result, found that a specific epoxy resin composition meets the above object, and completed the present invention. That is, the present invention provides (A) general formula (1)

[0006]

Embedded image (In the formula, R ₁ represents a hydrogen atom, a chain or cyclic alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group or a halogen atom, and R ₁ may be the same or different from each other. Good, n represents an integer value of 0 to 4.)
And an epoxy resin composition containing a curing agent as main components, and a resin-encapsulated semiconductor characterized by encapsulating a semiconductor element using the epoxy resin composition. It relates to the device.

Specific examples of the substituent R ₁ of the epoxy resin which is the component (A) represented by the general formula (1) used in the present invention include methyl group, ethyl group, propyl group, butyl group, and Examples thereof include an amyl group, a hexyl group, a cyclohexyl group, a phenyl group, a tolyl group, a xylyl group (including each isomer), a chlorine atom and a bromine atom.

The epoxy resin used in the present invention can be obtained by a known method of converting phenols into glycidyl ether. That is, it is a method of reacting phenols with epihalohydrin in the presence of an alkali such as caustic soda. In particular, when a high-purity product is obtained,
As described in 60-31517, the reaction in an aprotic solvent is preferable.

The phenols used here are represented by the general formula (2)

[Chemical 3] (In the formula, the meanings of R ₁ and n are the same as those of the general formula (1).) As specific examples of the phenols represented by the general formula (2), the following compounds can be mentioned. To be

[0010]

[Chemical 4]

[0011]

[Chemical 5]

In the composition of the present invention, the epoxy resin may be used in combination with the other epoxy resin. As these epoxy resins, known ones can be used, but if these are exemplified,
Novolac-based epoxy resin, which is a reaction product of phenols such as phenol and o-cresol, with formaldehyde, phloroglysin, tris- (4-hydroxyphenyl) -methane, 1,1,2,2, -tetrakis (4-hydroxy) Glycidyl ether compound derived from trivalent or higher phenols such as phenyl) ethane, bisphenol A,
Dihydric phenols such as bisphenol F, tetramethylbiphenol, hydroquinone, resorcin, 4,4′-thiodi (2,6-dimethylphenol), dihydroxynaphthalene, bis (hydroxyphenyl) dicyclopentane and bis (hydroxyphenyl) menthane Or a diglycidyl ether compound derived from halogenated bisphenols such as tetrabromobisphenol A,
Glycidyl ether compounds of polyhydric phenols obtained by condensation reaction of phenols and aromatic carbonyl compounds, p-aminophenol, m-aminophenol,
4-aminometacresol, 6-aminometacresol, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis ( 4-aminophenoxy) benzene, 1,4-bis (3-
Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexanebis (methylamine), 1,3-cyclohexanebis (methyl Amine-based epoxy resins, glycidyl ester-based compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalic acid, 5,5-dimethylhydantoin Hydantoin-based epoxy compounds derived from, etc., 2,2-bis (3,4
-Epoxycyclohexyl) propane, 2,2-bis [4
Alicyclic epoxy resin such as-(2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, N, N-
There is diglycidyl aniline and the like, and one or more of these epoxy resins are used.

As the epoxy resin curing agent which is the component (B) used in the present invention, known ones can be used. Examples of these include polyphenols such as phenol novolac, dicyandiamide, diaminodiphenylmethane, amine-based curing agents such as diaminodiphenylsulfone, pyromellitic dianhydride, trimellitic anhydride, acid anhydride curing agents such as benzophenonetetracarboxylic acid. From the viewpoint of moisture resistance, polyhydric phenols are preferably used.

To further exemplify the above-mentioned polyhydric phenols, one or more phenols such as phenol, various alkylphenols and naphthol, and formaldehyde, acetaldehyde, acrolein, glyoxal, benzaldehyde, naphthaldehyde, hydroxybenzaldehyde and the like can be mentioned. Polycondensates with aldehydes or ketones such as cyclohexanone and acetophenone, vinyl-polymerized polyphenols such as polyvinylphenol and polyisopropenylphenol, and phenols and formulas

[0015]

[Chemical 6] Diols such as compounds represented by

[0016]

[Chemical 7] A dialkoxy compound such as a compound represented by or a formula

[0017]

Embedded image The compound is a Friedel-Crafts type reaction product of a dihalogen such as a compound or a phenol with a diolefin such as dicyclopentadiene or diisopropenylbenzene, but from the viewpoint of workability and curability, phenol novolak Is particularly preferable. In addition, these curing agents may be used alone or in combination of two or more.

The mixing ratio of the epoxy resin as the component (A) and the curing agent for the epoxy resin as the component (B) is usually preferably 0.7 to 1.2 equivalents relative to the epoxy group. If the amount is less than 0.7 equivalent or more than 1.2 equivalent to the epoxy group, the curing will be incomplete.

When curing the resin composition of the present invention, a known curing accelerator may be used. Examples of such a curing accelerator include triphenylphosphine and tri-
Organic phosphine compounds such as 4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine and tri-2-cyanoethylphosphine and their tetraphenylborate salts, tributylamine, triethylamine, 1,8
Examples include tertiary amines such as diazabicyclo (5,4,0) undecene-7, triamylamine, quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, triethylammonium tetraphenylborate, and imidazoles. However, the present invention is not limited to these. Among these, organic phosphine compounds, 1,8-diazabicyclo (5,4,0) undecene-7, and imidazoles are preferable from the viewpoint of moisture resistance and curability, and triphenylphosphine is particularly preferable.

Further, (C) in the resin composition of the present invention
As the inorganic filler as a component, silica, alumina, titanium white, aluminum hydroxide, talc, clay,
Examples thereof include glass fiber, and silica and alumina are particularly preferable. These are their shapes (spherical or crushed),
Alternatively, different sizes may be mixed to increase the filling amount and used. The blending ratio of the inorganic filler needs to be 25 to 92% by weight, preferably 70 to 92% by weight, based on the total amount of the resin composition. If the amount of the filler is less than 70% by weight, the moisture resistance is inferior, and if it exceeds 92% by weight, there is a problem in moldability. In the present invention, a natural wax, a synthetic wax, a higher fatty acid and its metal salt, a release agent such as paraffin, a coloring agent such as carbon black, a surface treatment agent such as a silane coupling agent, etc., if necessary. May be added. Also,
A flame retardant such as antimony trioxide, a phosphorus compound and a brominated epoxy resin may be added. In order to have a flame retardant effect,
Brominated epoxy resins are especially preferred. Further, in order to reduce the stress, various elastomers may be added or reacted in advance and used. Specific examples thereof include addition-type or reaction-type elastomers such as polybutadiene, butadiene-acrylonitrile copolymer, silicone rubber and silicone oil. In order to produce a resin-encapsulated semiconductor device by encapsulating an electronic component such as a semiconductor using the resin composition according to the present invention, curing molding by a conventionally known molding method such as transfer molding, compression molding, injection molding, etc. do it.

[0021]

The epoxy resin composition of the present invention has lower hygroscopicity and is well-balanced in adhesiveness, especially as a sealing material for electronic parts. Moreover, the resin-sealed semiconductor device using this resin composition is excellent in solder crack resistance.

Further, since this composition has a lower viscosity than glycidyl ether of o-cresol novolac, it is possible to add a large amount of filler, the hygroscopicity is improved, and the reliability of the produced product is improved. Can be increased.

[0023]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. In the examples, the epoxy equivalent is defined as the molecular weight of the epoxy resin per epoxy group. Further, with hydrolyzable chlorine, an epoxy resin is dissolved in dioxane, an alcohol solution of potassium hydroxide is added, and chlorine ions desorbed when heated for 30 minutes under reflux are back-titrated with an aqueous silver nitrate solution, Ppm in compound
It is represented by.

The evaluation method of the kneaded product and the cured molded product is as follows.・ Gel time: 18 with a gelation tester manufactured by Nisshin Chemical Co., Ltd.
The measurement was performed at 0 ° C. -Burcol hardness: measured according to ASTM D-648 with a 935 type hardness meter at 175 ° C / 90 seconds.・ Glass transition temperature: Thermomechanical analyzer (SHIMADZU DT-3
0). Bending strength and flexural modulus: Measured with a tensile tester (SHIMADZU IS-10T) according to JIS K-6911.・ Moisture absorption rate: Constant temperature and humidity chamber (Advantech Toyo AGX-326)
Was used to measure the weight change under the conditions of 85 ° C./85% RH.・ Spiral flow: 175 ℃ / 70kg / according to EMMI-1-66
It was performed under the condition of cm ² .・ Frame pull-out strength: Copper and 42 as shown in FIG.
The molded product was transfer-molded on the alloy frame, and the pulling strength was evaluated.・ Solder cracking: Simulated IC (52-pin QFP package:
The number of IC chips with cracks after the package thickness 2.05 mm) was absorbed under the conditions of 85 ° C / 85% RH / 72 hours and immediately immersed in a solder bath at 240 ° C for 30 seconds. Number of test individuals 8
Individual.

Reference Example 1 Synthesis of Raw Material Phenol p-Hydroxybenzaldehyde 170. was added to a 3 liter four-necked flask equipped with a thermometer, a stirrer and a condenser.
97 g (1.40 mol), p-aminophenol 15
2.78 g (1.40 mol) and 971 g of tetrahydrofuran were charged and dissolved. Next, the reaction system is heated to 50 ° C.
The reaction solution was cooled to 5 ° C. and kept at this temperature for 1 hour. After separating the crystals by filtration, toluene 10
It was washed with 00 g and then vacuum dried at 80 ° C. for 5 hours to obtain 214.6 g of light-colored crystals (designated as DHAM).
The melting point of this product was 194 ° C. according to DSC measurement.

Reference Example 2 Synthesis of Epoxy Resin 95.9 g of phenol DHAM obtained in Reference Example 1 was charged in a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel and a condenser with a separating tube, and epichlorohydrin 582.8.
g, and dissolved in 582.8 g of dimethyl sulfoxide. While maintaining the reaction system at 35 torr, at a temperature of 48 ° C, 4
74.53 g of 8.3% caustic soda was continuously added dropwise over 5 hours. During this period, while keeping the temperature at 48 ° C., the azeotropically distilled epichlorohydrin and water were cooled and liquefied, and the reaction was carried out while returning the organic layer into the reaction system. After completion of the reaction, unreacted epichlorohydrin was removed by concentration under reduced pressure, a glycidyl ether containing a by-product salt and dimethyl sulfoxide was dissolved in 341 g of methyl isobutyl ketone, and the by-product salt and dimethyl sulfoxide were removed by washing with water. 170 ℃,
Methyl isobutyl ketone was distilled off under reduced pressure at 10 torr to obtain the desired product (designated as DHAM-E). This product had a melting point of 107 ° C., a melt viscosity of 0.24 P (150 ° C.), and an epoxy equivalent of 201.5 g / eq.

Examples 1 and 2 and Comparative Examples 1 and 2 The glycidyl ether obtained in Reference Example 2 and the glycidyl ether of o-cresol novolac (trade name: Sumiepoxy)
ESCN-195, manufactured by Sumitomo Chemical Co., Ltd., melt viscosity 2.6p (150 ℃),
Softening point 65.6 ° C, Epoxy equivalent 195g / eq), Phenol novolac (trade name PSM-4261, manufactured by Gunei Chemical Industry) as a curing agent, triphenylphosphine as a curing accelerator, fused silica as filler (contents of each brand name) Is shown below),
Carnauba wax as a release agent, coupling agent (trade name SH-6040, made by Toray Dow Corning Silicone)
The amount (g) shown in Table 1 was blended, and the mixture was heated and kneaded with a roll, and then transfer molding was performed. In addition, in an oven at 180 ℃,
Post cure was carried out for 5 hours to obtain a cured molded product. The physical properties of this cured molded product were measured. The results are shown in Table 1.
The content of each trade name of fused silica is as follows. FS-891: Fractured silica (average particle size 13 μm), manufactured by Denki Kagaku Kogyo FS-20: Fractured silica (average particle size 5.6 μm), Denki Kagaku Kogyo FB-74: Spherical silica (Average particle size 30 μm), manufactured by Denki Kagaku Co., Ltd. Admafine SOC-2: Spherical silica (average particle size 10.8)
cisna Star MK-06 manufactured by Admatech Co., Ltd .: Spherical silica (average particle size 18μ
m), manufactured by Nippon Kagaku Kogyo Co., Ltd. Excelica SE-40: Spherical silica (average particle size 61.2μ)
m), manufactured by Tokuyama Soda Co., Ltd.

[0028]

[Table 1]

[Brief description of drawings]

FIG. 1 is a plan view of a pull-out strength measuring frame.

[Explanation of reference numerals] 1: Place where a resin cured product is formed (hatched portion) 2: Extraction piece 3, 4: Holding part for performing extraction operation

Continuation of front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location H01L 23/31 (72) Inventor Noriaki Saito 6 Kitahara, Tsukuba, Ibaraki Prefecture Sumitomo Chemical Co., Ltd. (72) Inventor Nao Morimoto 5-1, Soukai-cho, Niihama-shi, Ehime Sumitomo Chemical Co., Ltd.

Claims (4)

[Claims] 1. (A) General formula (1): (In the formula, R ₁ represents a chain or cyclic alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group or a halogen atom, and when R ₁ is the same or different in plural rings, they are the same. Or they may be different n
Indicates an integer value of 0 to 4, respectively. ) An epoxy resin composition comprising an epoxy resin represented by the formula (4) and an epoxy resin curing agent (B) as essential components. 2. The epoxy resin composition according to claim 1, wherein the epoxy resin curing agent as the component (B) is a polyphenol. 3. The epoxy resin composition according to claim 1, which further comprises (C) an inorganic filler in addition to the components (A) and (B). 4. A resin-encapsulated semiconductor device in which a semiconductor element is encapsulated with the epoxy resin composition according to claim 1.