JPH0713179B2 - Epoxy resin composition and resin-encapsulated semiconductor device - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an epoxy resin composition having improved heat resistance and toughness of an epoxy resin.
The present invention relates to a resin-sealed semiconductor device using this epoxy resin composition.

[0002]

2. Description of the Related Art Epoxy resins have hitherto been used as a resin for a sealing material for coating a base material for constituting an electronic device or an electronic component typified by an adhesive, a laminated board, a transistor, an IC or the like. It has been. In particular, demand is expanding as a sealing material for ICs. The epoxy resin has a very wide range of use because of its excellent electrical properties, adhesiveness, thermal properties, cost and the like. However, the epoxy resin is generally brittle, and there is a problem that cracks easily occur due to stress distortion during curing or use, heat or mechanical impact. To solve this problem, use a curing agent with long-chain aliphatic groups and rubber-like properties, add compounds with elastomeric properties, add plasticizers such as asphalt substances and glycols, and add rubber elasticity to the epoxy compound itself. The toughness of the resin is being improved by introducing the molecular groups shown, or introducing a thermoplastic polymer having high toughness. (Koichi Ochi, polymer 38
(3), 200, 1989).

On the other hand, as a sealing method for electronic circuit parts such as semiconductor devices, sealing with metal or ceramics or resin sealing with phenol resin, silicon resin or epoxy resin has been proposed. Among these, an epoxy resin composition based on a cresol novolac type epoxy resin from the viewpoint of economic efficiency, productivity and physical properties, and a novolac type phenol resin as a curing agent for this epoxy resin and silica powder as a filler. The main focus is resin sealing with objects. Further, recently, in the field of semiconductor integrated circuits, along with technological development of high integration and high reliability, automation of a process of mounting a semiconductor on a circuit board has been promoted. For example, when a flat package type semiconductor device is attached to a circuit board, conventionally, each lead pin is soldered, but recently, due to the development of surface mounting technology, the flat package type semiconductor device is connected to an infrared ray or the like. There are widely adopted a method of soldering by exposing the solder to vaporized (hereinafter referred to as VPS), and a method of dipping in a solder bath or the like for soldering.

[0004]

However, these substances are not sufficiently compatible with the epoxy resin, the sea-island structure size formed by mixing is large, and sufficient compounding characteristics cannot be obtained. Further, there are problems such as impairing properties such as heat resistance and adhesiveness, and extremely high cost. In particular, the encapsulating resin made of a cured product of an epoxy resin composition encapsulating semiconductor components and electronic components is required not only to have heat resistance to withstand soldering when mounted on a printed circuit board, In recent years, ICs are required to have a strong encapsulating resin that is strong against bending and the like even though the ICs are thin. However, a conventional semiconductor device sealed with a resin composition composed of an epoxy resin, a novolac-type phenol resin and silica powder has an external crack or heat resistance when the entire device is immersed in a solder bath or exposed to VPS. It has the problem of being insufficient. In particular, when a semiconductor device that has absorbed moisture is dipped in a solder bath or exposed to VPS, the sealing resin is peeled off from the semiconductor chip and the lead frame, resulting in a significant deterioration in moisture resistance, resulting in disconnection and cracking due to corrosion of the electrodes. There has been a problem that long-term reliability cannot be guaranteed due to cutting of the gold wire and generation of leakage current due to water. For this reason, the entire semiconductor device is immersed in a solder bath or V
There has been a strong demand for the development of an epoxy resin composition that has sufficient heat resistance so that external cracks do not occur even when exposed to PS, and that has little deterioration in moisture resistance. The present invention is intended to solve the above-mentioned problems, particularly when the epoxy resin composition excellent in heat resistance and toughness and this epoxy resin composition is applied for semiconductor encapsulation, in the soldering step. It has excellent heat resistance and moisture resistance. It is intended to provide an epoxy resin composition.

[0005]

As a result of intensive studies to solve the above problems, the present inventor has found that a resin having a imide or amide skeleton in the molecule and containing a phenolic hydroxyl group, and an epoxy resin. By reacting with resin,
It was found that an epoxy resin having excellent heat resistance and toughness can be obtained, and excellent characteristics as an epoxy resin for semiconductor encapsulation can be obtained, and the present invention has been completed. That is, the present invention is an epoxy resin represented by the following general formula phenolic hydroxyl group-containing polyamide Imi earthen others general formula (II) modified epoxy resin obtained by reacting a phenolic hydroxyl group-containing polyamide indicated in indicated in (I) Is an epoxy resin composition characterized by being contained in an epoxy resin, and further, the epoxy resin composition, a semiconductor chip is encapsulated with a composition containing a novolac-type phenol resin and an inorganic filler as a curing agent. The resin-encapsulated semiconductor device.

[Chemical 5] (In the formula, m = 1 to 400 integer, n = 0 to 400 integer, m / (m + n) = 0.01 to 1.0, Ar ¹ is a tetravalent aromatic organic group, and Each carbonyl group is directly bonded to a different carbon atom, and each pair of carbonyl groups is bonded to an adjacent carbon atom in the Ar ¹ group, R is an aromatic or alicyclic divalent organic group, and Ar ³ is A divalent aromatic group,
Ar ² represents a divalent aromatic group containing a phenolic hydroxyl group)

[Chemical 6] (In the formula, m = 1 to an integer of 400, n = 0 to an integer of 400, m / (m + n) = 0.01 to 1.0, Ar ⁵ , Ar
⁶ is a divalent aromatic group, Ar ⁴ is a divalent aromatic group containing a phenolic hydroxyl group)

The epoxy resin used in the present invention has two or more epoxy groups in one molecule. Examples of such epoxy resins include glycidyl ethers, glycidyl esters, glycidyl amines,
Examples of the resin include linear aliphatic epoxides, alicyclic epoxides, hydantoin type epoxies, and the like.
Examples of the glycidyl ethers include glycidyl ether of bisphenol, polyglycidyl ether of phenolvolac, alkylene glycol or glycidyl ether of polyalkylene glycol. As the glycidyl ether of bisphenol, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, tetramethylbisphenol A type, tetramethylbisphenol F type,
Diglycidyl ethers of dihydric phenols such as tetramethylbisphenol AD type, tetramethylbisphenol S type, tetrachlorobisphenol A type, tetrabromobisphenol A type, and polyglycidyl ethers of phenol novolac include, for example, phenol novolac and cresol. Novolaks, polyglycidyl ethers of novolac resins such as brominated phenol novolacs, and diglycidyl ethers of alkylene glycols or polyalkylene glycols include, for example, polyethylene glycol, polypropylene glycol, butanediol, and other glycol diglycidyl ethers. To be Examples of the glycidyl esters include glycidyl ester of hexahydrophthalic acid and glycidyl ester of dimer acid.
Examples of glycidyl amines include triglycidyl aminodiphenylmethane, triglycidyl aminophenol, triglycidyl isocyanate, and the like. Further, as the linear aliphatic epoxides, for example,
Examples thereof include epoxidized polybutadiene and epoxidized soybean oil. Examples of alicyclic epoxides include 3,4
-Epoxy-6-methylcyclohexylmethylcarboxylate, 3,4-epoxycyclohexylmethylcarboxylate, hydrogenated bisphenol epoxy and the like. Examples of hydantoin-type epoxies include diglycidylhydantoin and glycidylglycidoxyalkylhydantoin.

Examples of the curing agent for the epoxy resin used in the present invention include bis (4-aminophenyl) sulfone, bis (4-aminophenyl) methane, 1,5-diaminonaphthalene, p-phenylenediamine and m. Aromatic compounds such as phenylenediamine, o-phenylenediamine, 2,6-dichloro-1,4-benzenediamine, 1,3-di (p-aminophenyl) propane, m-xylylenediamine, ethylenediamine, Diethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, menthenediamine, isophoronediamine, bis (4-amino-
Aliphatic amine compounds such as 3-methyldicyclohexyl) methane, polymethylene diamine, polyether diamine, polyaminoamide compounds, aliphatic acid anhydrides such as dodecyl succinic anhydride, polyadipic acid anhydride, polyazelaic acid anhydride, etc., Aromatics such as alicyclic acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bistrimellitate, and glycerol tris trimellitate Group aromatic acid anhydrides, phenolic resins, amino resins, urea resins, melamine resins, dicyandiamide and dihydrazine compounds, imidazole compounds, Lewis acids and Bronsted acid salts, polymercaptan compounds, isocyanates and bromo compounds. Click isocyanate compounds and the like, but not limited thereto.

The phenolic hydroxyl group-containing polyamideimide used in the present invention is a resin represented by the general formula (I), and the phenolic hydroxyl group-containing polyamide is a resin represented by the general formula (II).

[Chemical 7]

[Chemical 8]

The phenolic hydroxyl group-containing polyamideimide or the phenolic hydroxyl group-containing polyamide in the present invention can be easily produced by the following method. That is, the resin of the general formula (I) is prepared by using an aromatic tetracarboxylic dianhydride, an aromatic diamine containing a phenolic hydroxyl group and an aromatic diamine containing no phenolic hydroxyl group as an organic solvent such as N-methyl-2-pyrrolidone. It is obtained by subjecting a tetracarboxylic acid group and an amino group to polycondensation to synthesize an amic acid, and then subjecting this amic acid group to imidation by performing a heat dehydration cyclization reaction. On the other hand, the resin of the general formula (II) is prepared by mixing an aromatic diamine, a phenolic hydroxyl group-containing aromatic dicarboxylic acid and a phenolic hydroxyl group-free aromatic dicarboxylic acid in an organic solvent such as N-methyl-2-pyrrolidone, for example, It can be produced by polycondensing a carboxylic acid group and an amino group in the presence of a phosphite ester and a pyridine derivative as a catalyst.

Examples of the aromatic tetracarboxylic acid anhydride used in the production of the resin of the general formula (I) in the present invention include pyromellitic dianhydride and 2,3,6,7-naphthalenetetracarboxylic acid. Dianhydride, 3,4,3 ',
4'-biphenyltetracarboxylic dianhydride, 2,3
2 ', 3'-biphenyltetracarboxylic dianhydride,
3,4,3 ′, 4′-biphenylsulfone tetracarboxylic dianhydride, bis (3,4-dicarboxylphenyl) methane anhydride, bis (3,4-dicarboxylphenyl) ether anhydride, 2,2 -Bis (3,4-dicarboxylphenyl) propane dianhydride, 3,4,3 ',
4'-dibenzophenone tetracarboxylic dianhydride,
4,4'-Biphthalic dianhydride, 2,2-bis (3,4
-Dicarboxyphenyl) hexafluoropropane dianhydride, etc., which can be used alone or in combination.

As the Ar ² -containing aromatic diamine having a phenolic hydroxyl group used for the production of the resin of the general formula (I), N, N'-bis (2-, 3- or 4-aminophenyl) -5 is used. -Hydroxyisophthalamide, N,
N'-bis (2-, 3- or 4-aminophenyl) -5
-Hydroxyterephthalamide, N, N'-bis (2
-, 3- or 4-aminophenyl) -2-hydroxyphthalamide, N, N'-bis (2-, 3- or 4-aminophenyl) -2-hydroxyisophthalamide, N,
N'-bis (2-, 3- or 4-aminophenyl) -3
-Hydroxyphthalamide, N, N'-bis (4-amino-3,5'-dimethylphenyl) -5-hydroxyisophthalamide, N, N'-bis (4-amino-3,
5'-Dimethylphenyl) -2-hydroxyphthalamide, N, N'-bis (4-amino-3,5'-dimethylphenyl) -3-hydroxyphthalamide, N, N'-
Bis (4-amino-n-butyl) -5-hydroxyisophthalamide, N, N'-bis (4-amino-n-hexyl) -5-hydroxyisophthalamide, N, N'-bis [4- (4- Aminophenoxy) phenyl] -5-hydroxyisophthalamide, N, N'-bis [4- (4
-Aminophenylsulfonyl) phenyl] -5-hydroxyisophthalamide, etc., which can be used alone or in combination.

Further, the above general formula (I) or general formula (I
As an Ar ³ or Ar ⁶ -containing aromatic diamine containing no phenolic hydroxyl group, which is used for producing the resin of I), m
-Phenylenediamine, p-phenylenediamine, metatolylenediamine, 4,4'-diaminodiphenylene-
Ter, 3,3′-dimethyl-4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4 ′
-Diaminodiphenylthioether, 3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,
3'-diethoxy-4,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3 '
-Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (4- Aminophenyl) propane, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl , P
-Xylylenediamine, m-xylylenediamine, 1,
4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 1,4-bis (p-
Aminophenylisopropylidene) benzene, 1,3-
There are bis (p-aminophenylisopropylidene) benzene, 1,3-bis (p-aminophenoxy) benzene and the like, and these can be used alone or in combination.

In the present invention, as the Ar ⁴ -containing aromatic dicarboxylic acid having a phenolic hydroxyl group used for producing the resin of the general formula (II), 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid and 2-hydroxyphthalic acid are used. Acids, 3-hydroxyphthalic acid, 2-hydroxyterephthalic acid, etc., but are not limited to these.

Further, as the Ar ⁵ -containing aromatic dicarboxylic acid having no phenolic hydroxyl group used for the production of the resin of the general formula (II), phthalic acid, isophthalic acid, terephthalic acid and 4,4'-biphenyldicarboxylic acid can be used. Acid, 3,3'-
Methylene dibenzoic acid, 4,4'-methylene dibenzoic acid,
4,4'-oxydibenzoic acid, 4,4'-thiodibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid,
Examples thereof include 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid, but are not limited thereto.

The epoxy resin composition of the present invention can be produced by the following two methods. After the general formula (I) or (II) in a phenolic hydroxyl group-containing polyamide Lee Mi de or phenolic hydroxyl group-containing polyamide and epoxy resin are reacted illustrated a modified epoxy resin synthesized, accordingly, the modified epoxy resin Mix with unreacted epoxy resin. Proper formulation amount of the epoxy resin in this case is 1 to 20 equivalents to the phenolic hydroxyl group-containing polyamide Lee Mi de or polyamide represented by the general formula (I) or formula (II), preferably 5 to
It is 15 times equivalent. This reaction is carried out at a reaction temperature of 50 ° C. or higher, preferably 70 ° C. or higher in the presence of a catalyst such as an alkali metal hydroxide, a tertiary amine, a quaternary ammonium salt, imidazoles, phosphines and phosphonium salts.
By carrying out for 30 hours, the epoxy resin composition of the present invention can be manufactured.

The phenolic hydroxyl group-containing polyamideimide or polyamide of the general formula (I) or the general formula (II) is mixed with a large excess amount of the epoxy resin in excess of the above-described appropriate compounding amount to prepare an excess amount of the epoxy resin. A part of them can be produced by reacting with the above resin to form a modified epoxy resin, and the rest being contained as an unreacted epoxy resin.

The phenolic hydroxyl group-containing polyamideimide or polyamide represented by the general formula (I) or general formula (II) contained in the epoxy resin composition of the present invention is an epoxy resin which contributes to the reaction or an unreacted epoxy resin. 0.1 to 30% by weight based on the total epoxy resin including
Is. If the content of the polyamideimide or polyamide is 0.1% by weight or less, the effect of adding the polyamideimide or polyamide cannot be obtained, and if the content of the polyamideimide or polyamide is 30% by weight or more, transfer molding becomes difficult, that is, the epoxy resin. The composition has a high contact viscosity and is difficult to inject into the mold, which is not preferable.

In the production process for obtaining the epoxy resin composition of the present invention, the epoxy resin and the phenolic hydroxyl group-containing polyamideimide or polyamide represented by the general formula (I) or the general formula (II) are mixed with a mixer or the like. after thorough mixing uniformly, using, for example, hot roll, may be reacted by molten kneading, or may be reacted by mixing the two components in a solvent such as an amide solvent. Especially,
The latter method is preferable because it allows more uniform complexing with the phenolic hydroxyl group-containing polyamideimide or polyamide represented by the general formula (I) or general formula (II), which has poor compatibility with the epoxy resin. In this case, as the amide solvent, N, N-dimethylformamide,
N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like are used.

As the curing agent used in the resin-sealed semiconductor device of the present invention, a novolac type phenol resin obtained by reacting phenols such as phenol and alkylphenol with formaldehyde or paraformaldehyde, and modified resins thereof. Examples thereof include ethylated or butylated novolac type phenolic resin and silicon-modified phenolic resin. Further, in the present invention, these novolac type phenol resins can be used alone or in combination. The compounding amount of the above curing agent component of the composition used for the resin-encapsulated semiconductor device of the present invention is not particularly limited, but usually the molar ratio of the phenolic hydroxyl group to the epoxy resin is 0.8 to 1.2. It is preferably in the range of.

As the inorganic filler used in the composition for a resin-encapsulated semiconductor device of the present invention, commercially available ones are generally used. Among them, fused silica having a low impurity content is preferable. The average particle size of the inorganic filler is 3
It is preferably 0 μm or less, and when it is 30 μm or more, the moisture resistance and the moldability are adversely affected. The mixing ratio of the inorganic filler in the range of 70 to 85% by weight relative to the epoxy resins composition. If this proportion is less than 70% by weight, the amount of moisture absorbed by the epoxy resin composition of the present invention will increase and the solder heat resistance will decrease, such being undesirable. Further, if it exceeds 85% by weight, the fluidity is extremely deteriorated and the moldability is deteriorated, which is not preferable.

The composition for a resin-encapsulated semiconductor device of the present invention contains, if necessary, a curing accelerator, a coloring agent such as a dye or a pigment,
An oxidation stabilizer, a light stabilizer, a coupling agent, a release agent, a stress relaxation agent, a flame retardant and the like can also be added. Examples of the curing accelerator include phosphorus-based compounds such as triphenylphosphine, and tertiary amine-based compounds such as triethylamine, tetraethanolamine and 1,8-diaza-bicyclo [5,5.
4,0] -7-undecene (DBU), N, N-dimethylbenzylamine, 1,1,3,3-tetramethylguanidine, 2-ethyl-4-methylimidazole, N-methylpiperazine, etc., boron-based, For example, 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate and the like are used. As the release agent, natural waxes, synthetic waxes and metal salts of long chain fatty acids can be used. Furthermore, as a stress relaxation agent, silicone rubber, nitrile rubber, butadiene rubber,
Polysiloxanes and the like can be used.

The epoxy resin composition for semiconductor encapsulation of the present invention is manufactured by the following method. That is, an epoxy resin composition containing a modified epoxy resin and an unreacted epoxy resin obtained by reacting an epoxy resin with a phenolic hydroxyl group-containing polyamideimide or polyamide represented by the general formula (I) or the general formula (II). In the product, a novolac type phenolic resin and an inorganic filler and other additives are appropriately blended as necessary, sufficiently mixed with a mixer or the like, and then melt-kneaded with a hot roll or the like, followed by rapid cooling to room temperature, followed by normal It is crushed by a crushing means and further classified to obtain a sealing resin composition.

[0023]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Synthesis Example 1 10.9 g (30 mmol) of N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide and m-
13.2 g (120 mmol) of phenylenediamine and 48 g (150 mmol) of 3,4,3 ', 4'-benzophenone tetracarboxylic dianhydride were added to N-methyl-2-.
It was dissolved in 450 ml of pyrrolidone and reacted at room temperature for 6 hours in a nitrogen atmosphere to obtain a polyamic acid. This polyamic acid solution was heated at 200 ° C. for 2 hours to carry out a dehydration cyclization reaction. After allowing to cool, the polymer solution was poured into a large amount of methanol. The precipitated solid is filtered off, washed and dried to give an intrinsic viscosity of 0.55 dl / g (dimethylacetamide solution,
A polyamideimide containing a phenolic hydroxyl group at 30 ° C. was obtained.

Synthesis Example 2 20 g (120 mmol) of isophthalic acid, 26.4 g (132 mmol) of 3,4'-oxydianiline, 2.6 g (20 mmol) of 5-hydroxyisophthalic acid, 3.9 g of lithium chloride, 12.1 g of calcium chloride, 240 ml of N-methyl-2-pyrrolidone, 54 ml of pyridine
Put in a 4-neck round flask of No. 1 and stir to dissolve, then add 74 g of triphenyl phosphite,
After reacting for a time, a solution containing a phenolic hydroxyl group-containing aramid oligomer was obtained. After this solution was cooled to room temperature, it was poured into methanol 201 to precipitate the phenolic hydroxyl group-containing polyamide used in the present invention. The precipitated polymer was further washed with methanol and further refluxed with methanol for purification. The intrinsic viscosity of the obtained phenolic hydroxyl group-containing polyamide was 0.85 dl / g (dimethylacetamide solution, 30 ° C.).

<Production of Polyamideimide Modified Epoxy Resin (A)> Polyamideimide 24 containing 0.2 mol% of the phenolic hydroxyl group obtained in Synthesis Example 1 in 200 g of dimethylformamide.
After dissolving g, epoxy resin (cresol novolac type epoxy resin, Sumiepoxy ESCN-220H
H, epoxy equivalent: 205 g / eq, manufactured by Sumitomo Chemical Co., Ltd.) 112 g, and triphenylphosphine 0.08 g which is a curing accelerator were added and reacted at 90 ° C. for 2 hours. After completion of the reaction, the reaction solution is poured into water to precipitate a resin, washing with hot water is repeated, and tetrahydrofuran is further added to azeotrope these solvents under reduced pressure for purification, followed by vacuum drying and polyamide. An imide-modified epoxy resin was obtained.
To the solution obtained by dissolving 3 mg of the obtained epoxy resin in about 30 ml of pyridine, 1 g of an indicator solution of a phenolic hydroxyl group (1 g of anhydrous iron (III) chloride was dissolved in 100 ml of chloroform, and further 8 ml of pyridine was added, followed by precipitation. Was obtained by adjusting a red solution by filtration) and stirred, but no discoloration was observed, and all phenolic hydroxyl groups in this resin reacted with glycidyl groups, and unreacted phenolic It was confirmed that no hydroxyl group was contained.

<Preparation of Polyamide Modified Epoxy Resin (B)> Synthesis Example 2
24 g of polyamide containing 14 mol% of the phenolic hydroxyl group obtained in 1., 148 g of epoxy resin (cresol novolac type epoxy resin, Sumiepoxy ESCN-220H
H, epoxy equivalent: 205 g / eq, manufactured by Sumitomo Chemical Co., Ltd.), triphenylphosphine 0.6 which is a curing accelerator.
Dissolve 4 g in 200 g of dimethylformamide,
The same operation as in Example 1 was performed to obtain a polyamide-modified epoxy resin. About 30 mg of the obtained epoxy resin
To a solution dissolved in ml of pyridine, a color indicator of phenolic hydroxyl group (1 g of anhydrous iron (III) chloride is dissolved in 100 ml of chloroform, and 8 ml of pyridine is further added.
The precipitate was filtered and a red solution was prepared to obtain a few drops) and stirred, but no discoloration was observed, and all phenolic hydroxyl groups in this resin reacted with the glycidyl group, and unreacted. It was confirmed that no phenolic hydroxyl group was contained.

Examples 1 to 4 The components were mixed at a mixing ratio shown in Table 1 (numbers represent parts by weight) at room temperature using a mixer, and further 90 to 10
The mixture was kneaded with a hot roll set at 0 ° C. for about 3 hours and cooled to room temperature to prepare a mixed mass of the resin composition, which was then pulverized and classified to obtain the epoxy resin composition for semiconductor encapsulation of the present invention. This epoxy resin composition was transfer-injected into a mold heated to 175 ° C., and the resulting molded product was evaluated for bending strength and solder heat resistance. The results are shown in Table-1.

Comparative Example Similar to the example, the compounding components shown in Table 1 were kneaded with a solvent and then pulverized through a pulverizer to obtain a comparative epoxy resin composition for semiconductor encapsulation.

The contents of each component in Table-1 and the evaluation method are as follows. <Contents of each component> (A) Epoxy resin: cresol novolac type epoxy resin (Sumiepoxy ESCN-220HH, epoxy equivalent: 205 g / eq, manufactured by Sumitomo Chemical Co., Ltd.) (B) Novolac type phenol resin: phenol equivalent:
107 g / eq, manufactured by Sumitomo Bakelite Co., Ltd. (C) Inorganic filler: ground fused silica having an average particle size of 10 μm or less (FS-30, manufactured by Denki Kagaku Kogyo Co., Ltd.) (D) Resin represented by the general formula (I) or (II) A: A composition containing a product obtained by reacting the phenolic hydroxyl group-containing polyamideimide obtained in Synthesis Example 1 with an epoxy resin corresponding to the general formula (I) B: Synthesized corresponding to the general formula (II) Composition containing a product obtained by reacting the phenolic hydroxyl group-containing polyamide obtained in Example 2 with an epoxy resin (E) Curing accelerator: 2-methylimidazole (F) Wax: Ester wax (Hoechst wax E)

<Evaluation method> Bending strength: 12.7x obtained by transfer molding
ASTM for 127 x 6.35 mm bending test piece
Solder heat resistance measured by the method described in D-790: Silicon chips bonded to a normal 42 alloy frame were transfer-molded with the sealing resin composition shown in Table 1 at 175 ° C. for 90 seconds to obtain 16 × 16 ×.
A 1.8-pin 44-pin flat package molded product was obtained. This was cured at 180 ° C. for 5 hours. The 16 molded articles thus obtained were subjected to moisture absorption treatment at 85 ° C., 85% RH for 168 hours, and then exposed to a solder vapor phase (VPS) at 215 ° C. for 90 seconds. The number of occurrences is displayed.

Evaluation of the transfer cast product thus obtained showed that the epoxy resin composition of the present invention had high bending strength and solder heat resistance, as shown in Table 1.

[0032]

[Table 1]

[0033]

INDUSTRIAL APPLICABILITY The epoxy resin composition of the present invention is excellent in solder heat resistance and has excellent characteristics of preventing cracking from chip surface peeling and chip edges, and thus is useful as a molding material for semiconductor encapsulation. is there.

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Claims (3)

[Claims] And 1. A epoxy resin, a phenolic hydroxyl group-containing polyamide-imide or the following general formula (II) phenolic hydroxyl group-containing polyamide and a modified epoxy resin obtained by reacting represented by the general formula (I) And an epoxy resin composition contained in an epoxy resin. [Chemical 1] (In the formula, m = 1 to 400 integer, n = 0 to 400 integer, m / (m + n) = 0.01 to 1.0, Ar ¹ is a tetravalent aromatic organic group, and Each carbonyl group is directly bonded to a different carbon atom, and each pair of carbonyl groups is bonded to an adjacent carbon atom in the Ar ¹ group, R is an aromatic or alicyclic divalent organic group, and Ar ³ is A divalent aromatic group,
Ar ² represents a divalent aromatic group containing a phenolic hydroxyl group) (In the formula, m = 1 to an integer of 400, n = 0 to an integer of 400, m / (m + n) = 0.01 to 1.0, Ar ⁵ , Ar
⁶ is a divalent aromatic group, Ar ⁴ is a divalent aromatic group containing a phenolic hydroxyl group) 2. A phenolic hydroxyl group-containing polyamideimide represented by the general formula (I) or the general formula (II).
The epoxy resin composition according to claim 1, characterized in that the phenolic hydroxyl group-containing polyamide represented by the formula (1) is contained in an amount of 0.1 to 30% by weight based on the total epoxy resin. 3. A epoxy resin, a phenolic hydroxyl group-containing polyamide-imide or the following general formula (II) phenolic hydroxyl group-containing polyamide and a modified epoxy resin obtained by reacting represented by the general formula (I) A resin-encapsulated semiconductor device, wherein a semiconductor chip is encapsulated with an epoxy resin composition contained in an epoxy resin, a resin composition containing a novolac type phenol resin and an inorganic filler as main components. [Chemical 3] (In the formula, m = 1 to 400 integer, n = 0 to 400 integer, m / (m + n) = 0.01 to 1.0, Ar ¹ is a tetravalent aromatic organic group, and Each carbonyl group is directly bonded to a different carbon atom, and each pair of carbonyl groups is bonded to an adjacent carbon atom in the Ar ¹ group, R is an aromatic or alicyclic divalent organic group, and Ar ² is A divalent aromatic group containing a phenolic hydroxyl group, Ar ³ represents a divalent aromatic group) (In the formula, m = 1 to 400, n = 0 to 400, m / (m + n) = 0.01 to 1.0, Ar ⁴ is a divalent aromatic group containing a phenolic hydroxyl group, Ar ⁵ , A
r ⁶ represents a divalent aromatic group)