JP3214756B2 - Epoxy resin composition, cured product thereof, and semiconductor device - Google Patents

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 excellent in heat resistance and moisture resistance for casting, laminating, bonding, molding, encapsulating, composite materials and the like, and a cured product thereof. The present invention relates to an epoxy resin composition suitable for device sealing, a cured product thereof, and a semiconductor device using the same.

[0002]

2. Description of the Related Art The use of phenolic resins in matrix resins for heat-resistant composite materials and heat-resistant molding materials is difficult.
In recent years, it has become increasingly diverse and industrially important. In these advanced fields, high performance is required for the phenolic resin itself. For example, in the field of IC encapsulants, it is used as an epoxy resin or as a curing agent thereof, and as a whole, high performance is required in adhesiveness, heat resistance, moisture resistance, and the like. Conventionally, as a phenolic resin in this field, a combination of an ortho-cresol novolak type epoxy resin and a phenol novolak resin as a curing agent has been the mainstream.

[0003] In recent years, as electronic components have been mounted on a printed wiring board at a high density, electronic components have become more prevalent than conventional pin insertion type packages, but surface mount type packages. Surface mount ICs such as ICs and LSIs are becoming thinner and smaller packages in order to increase the mounting density and lower the mounting height. The thickness has become very thin. Furthermore, these packages are different in mounting from the conventional pin insertion type. That is, in the pin insertion type package, since the pins are inserted into the wiring board and then soldered from the back surface of the wiring board, the package is not directly exposed to a high temperature. However, the surface mount IC is temporarily exposed to the soldering temperature because it is temporarily fixed to the surface of the wiring board and is processed by a solder bath or a reflow device. At present, when an IC package is mounted on a wiring board, a method using IR reflow is mainly used.
The application temperature by this method is generally about 215 ° C. However, with the improvement of productivity, the soldering temperature is required to be higher than 240 ° C. to 265 ° C., and in such a high temperature range, the moisture resistance of the base resin and the Heat resistance is extremely important.

[0004] In an epoxy resin composition as a base resin, generally, moisture resistance and heat resistance have an opposite relationship. That is, if the crosslink density is increased to improve the heat resistance, the hygroscopicity increases, and if the crosslink density is reduced to reduce the hygroscopicity, there remains a problem in the heat resistance. At present, the phenol novolak structure, which is currently the mainstream of semiconductor encapsulants, has excellent heat resistance, but has high moisture absorption, so if it is used at high temperatures as described above, if the package absorbs moisture, it will absorb moisture during soldering. Moisture expands rapidly and cracks the package. At present, this phenomenon has become a major problem relating to surface mount ICs. To solve such a problem, several methods for improving the resin structure itself have been attempted. For example, a method using a phenol resin having a xylylene bond represented by the general formula (II) (Chemical Formula 2) (JP-A-59-105018, JP-B-62-28165, JP-A-3-90075) No., JP-A-4-933
No. 20).

[0005]

Embedded image (In the formula, A represents phenol, naphthol, etc., and l represents an integer.)

However, the sealing materials using these phenolic resins have low hygroscopicity as compared with the novolak structure, but still have insufficient glass transition temperature (Tg) of 150 to 160 ° C. indicating heat resistance. is there. That is, 240
Problems such as blistering of the package at a soldering temperature of ２６265 ° C. cannot be solved. On the other hand, from the viewpoint of improving heat resistance at the expense of a little sacrifice of hygroscopicity, a method of improving the crosslink density by introducing an amino group into a phenol novolak structure has been attempted (JP-A-5-105734). However, in this method, only the heat resistance is improved, and the hygroscopicity is increased, so that the occurrence of the package crack cannot be suppressed.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to find an epoxy resin composition for achieving a further improvement in heat resistance without impairing the hygroscopicity of the base resin composition. Another object of the present invention is to provide a highly reliable semiconductor device by using the semiconductor device.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems. As a result, in the epoxy resin composition, it was found that the object can be achieved by using, as a curing agent, a phenol resin structure having a xylylene bond with an amino group introduced, and completed the present invention. . That is, the present invention
(A) an epoxy resin having two or more epoxy groups in one molecule; and (B) a softening point of 40 to 120 ° C., an average molecular weight of 300 to 5000, and an amine value represented by the general formula (I). An epoxy resin composition containing a curing agent containing an amino group-containing phenol resin of 150 to 2000 g / eq; and 50% by weight of the epoxy resin composition.
The present invention relates to an epoxy resin composition for semiconductor encapsulation containing the above-mentioned inorganic filler, and further relates to a semiconductor device encapsulated by a cured product containing these cured products and the above-mentioned inorganic filler. is there.

[0009]

Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, a hydroxyl group, or a C _{1 to} C ₁₂ alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, an alkoxy group, or an aryloxy group. at best, _{R 1} and R
₂ may form a ring, and R ₃ and R ₄ represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a C _{1 to} C ₁₂ alkyl group, an aryl group, a cycloalkyl group, an aralkyl group,
An amino-substituted aralkyl group, a hydroxy-substituted aralkyl group, an alkoxy group, an aryloxy group, an amino-substituted aryloxy group, or a hydroxy-substituted aryloxy group, which may be the same or different, and R ₃ and R ₄ represent a ring It may be formed. m and n each represent an integer of 1 to 20, and the terminal is a phenol compound and / or an aromatic amine compound, and the bonding order of the phenol compound and the aromatic amine compound is not limited.

The epoxy resin composition of the present invention is excellent in both heat resistance and moisture resistance and excellent in mechanical strength such as impact resistance, so that it is suitable for a matrix resin for a heat-resistant composite material as an advanced material, and especially a semiconductor. As a sealing material, a material that has not been used in a heat cycle of a soldering device or a heat cycle in a mounting device can be used without any problem, so that a highly reliable resin sealing device can be obtained. In the epoxy resin composition of the present invention, the amino group-containing phenol resin used as a curing agent has a xylylene bond in the linking group, so that it has excellent oxidation resistance, low softening point and low melt viscosity, and low workability. It is also characterized by being excellent. In the epoxy resin composition of the present invention, a phenol resin containing an amino group represented by the general formula (I) or a part of the phenol resin containing the amino group is used as a curing agent. In this case, the proportion of the amino group-containing phenol resin may be 15% by weight or more, preferably 30% by weight or more of the entire curing agent, and the other may be used in combination with one or more known curing agents for epoxy resins. Can be.

The amino group-containing phenolic resin represented by the general formula (I) has been newly discovered by the present inventors, and a method for producing the same will be described below. That is, the molar ratio of the phenol compound represented by the general formula (III) (formula 4) and the aromatic amine compound represented by the general formula (IV) (formula 5) is 0.97: 0.03 to 0.2: By reacting 1 mol of the mixture of 0.8 with 0.1 to 0.95 mol of the aralkyl compound represented by the general formula (V) (Formula 6), the amino group-containing phenol resin of the formula (I) To manufacture.

[0012]

Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, a hydroxyl group, or a C ₁ -C ₁₂ alkyl group, an aryl group, a cycloalkyl group, an aralkyl group , an alkoxy group, an aryl group,
Represents an oxy group and may be the same or different, and R ₁ and R ₂
May form a ring. )

[0013]

Embedded image (Wherein, R ₃ and R ₄ represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a C ₁ -C ₁₂ alkyl group, an aryl group,
A cycloalkyl group, an aralkyl group, an amino-substituted aralkyl group, a hydroxy-substituted aralkyl group, an alkoxy group, an aryloxy group, an amino-substituted aryloxy group, or a hydroxy-substituted aryloxy group, which may be the same or different; ₃ and R ₄ may form a ring. )

[0014]

Embedded image (In the formula, X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms.)

The phenolic compounds of the formula (III) which can be used in this method include monohydric or dihydric phenols, bisphenol, trisphenol and the like. Specifically, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, o-isopropylphenol, p-se
c-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, p
-Bromophenol, 2,4-xylenol, 2,6-
Xylenol, pt-butylphenol, p-octylphenol, p-nonylphenol, p-cumylphenol, p-phenylphenol, o-phenylphenol, p-phenoxyphenol, o-methoxyphenol, p-methoxyphenol, resorcinol, catechol , Hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, dihydroxydiphenylmethane, α
-Naphthol, β-naphthol and the like.

The aromatic amine compound of the formula (IV) includes aniline, 2-methylaniline, 2-chloroaniline, 2-ethylaniline, m-phenylenediamine,
-Phenylenediamine, 2,6-diaminotoluene,
3,5-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 1,3,5-triaminobenzene, p-aminophenol, m-aminophenol, 4-amino-
4'-hydroxydiphenyl ether, 4-amino-
4'-hydroxypropane, 2-amino-1,3-resorcin, 4-amino-1,3-resorcin, 2-aminohydroquinone, 2-methoxyaniline, 4-methoxyaniline, 2-isopropoxyaniline, 2,4 -Dimethoxyaniline, o-isopropylaniline, m-isopropylaniline, p-isopropylaniline, on-
Propylaniline, o-tert-butylaniline, p
-Tert-butylaniline, p-sec-butylaniline, 2,3-xylidine, 2,4-xylidine, 2,
6-xylidine, 3,4-xylidine, 3,5-xylidine, 2-methyl-3-ethylaniline, 2-methyl-
4-isopropylaniline, 2,6-diethylaniline, 2-ethyl-5-tert-butylaniline, 2,4-
Diisopropylaniline, 2,4,6-trimethylaniline, 4-chloroaniline, 4-bromoaniline, 4-
Fluoroaniline, 3-chloroaniline, 3-bromoaniline, 3,4-dichloroaniline, 3-chloro-o
-Toluidine, 3-chloro-p-toluidine, 2,6-
Dimethyl-4-chloroaniline, 2-amino-4-cresol, 4-amino-2-tert-butylphenol,
2,6-dimethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-amino-1,3-
Resorcinol, 4-amino-1,3-resorcinol, 1,1
-Dimethyl-4-aminoindane, o-phenylenediamine, 2,4-diaminotoluene, 2,4-diaminoethylbenzene, 2,6-diaminoethylbenzene, 2,
4-diaminoisopropylbenzene, 2,4-diamino-tert-butylbenzene, 2,6-diamino-te
rt-butylbenzene, 2,4-diamino-1,3-dimethylbenzene, 1,1-dimethyl-4-aminoindan, 1,1-dimethyl-4,6-diaminoindan and the like. A preferred compound is aniline.

The aralkyl compound is a compound represented by the formula (V), wherein X is a halogen atom such as a chlorine atom, a bromine atom and a fluorine atom, a hydroxyl group, and an alkoxy group having 1 to 4 carbon atoms. For example, α, α′-dihydroxy-o-xylene, α, α′-dihydroxy-m-xylene, α, α ′
-Dihydroxy-p-xylene, α, α'-dimethoxy-m-xylene, α, α'-dimethoxy-p-xylene, α, α'-diethoxy-o-xylene, α, α'-
Diethoxy-m-xylene, α, α'-diethoxy-p
-Xylene, α, α′-diisopropoxy-o-xylene, α, α′-diisopropoxy-m-xylene, α,
α′-diisopropoxy-p-xylene, α, α′-di-n-propoxy-p-xylene, α, α′-di-n-
Butoxy-m-xylene, α, α′-di-n-butoxy-p-xylene, α, α′-di-sec-butoxy-p-
Xylene, α, α'-diisobutoxy-p-xylene,
α, α′-dichloro-o-xylene, α, α′-dichloro-m-xylene, α, α′-dichloro-p-xylene, α, α′-dibromo-o-xylene, α, α′-dibromo -M-xylene, α, α′-dibromo-p-xylene, α, α′-difluoro-o-xylene, α, α ′
-Difluoro-m-xylene, α, α'-difluoro-
p-xylene, α, α'-jodo-o-xylene,
α, α′-Jodo-m-xylene, α, α′-Jodo-p-xylene and the like can be mentioned. Suitable compounds include α, α′-dihydroxy-p-xylene,
α, α'-dichloro-p-xylene and the like.

A specific method for producing this amino group-containing phenolic resin is to prepare a mixture of a phenolic compound represented by the formula (III) and an aromatic amine compound represented by the formula (IV) by the formula (V) Is reacted with an aralkyl compound represented by the formula (1) using an acid catalyst. Examples of the acid catalyst include inorganic or organic acids such as hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, Friedel-Crafts catalysts such as zinc chloride, stannic chloride, aluminum chloride and ferric chloride, methanesulfonic acid And super strong acids such as Nafion H (trade name, manufactured by DuPont), which may be used alone or in combination. Activated clay, zeolite solid acid catalysts and heteropolyacids can also be used. Industrially preferred is inexpensive hydrochloric acid. The amount of the catalyst used is 3 mol% or more, preferably 5 to 80 mol%, based on the total of the phenol compound and the aromatic amine compound. In the case of a solid acid catalyst, the amount is 1 to 100 wt%, preferably 5 wt% or more, based on all raw materials. Above this range, there is no problem in the reaction, but it is not economical. When a bishalogenomethyl derivative is used as the aralkyl compound represented by the formula (V), the reaction can be performed in the absence of a catalyst, but an acid catalyst may be used for the purpose of accelerating the reaction. As the acid catalyst, any of the aforementioned acid catalysts can be used, and industrially preferred is inexpensive hydrochloric acid.

In this method, the reaction between the aromatic amine compound and the aralkyl compound of the formula (V) is obtained by a two-step reaction. That is, in the first-stage reaction, a resin containing a secondary amine is generated, and this secondary amine can be led to a primary amine resin by a transfer reaction (second-stage reaction). The transfer reaction is achieved using the above-mentioned acid as a catalyst, but when a bishalogenomethyl derivative is used as the aralkyl compound, the transfer reaction is achieved using hydrogen halide generated when a secondary amine resin is formed as a catalyst. Is done. In order to accelerate this transfer reaction, there are means such as (a) increasing the amount of the same or different type of catalyst, (b) increasing the reaction temperature, and (c) increasing the reaction time, compared with the reaction conditions under which the secondary amine resin is formed. It is performed by Even when a reaction is carried out by a self-catalyst using a bishalogenomethyl derivative as an aralkyl compound, the reaction can be accelerated by using the above-mentioned acid catalyst as described above. In this method, a reaction between the phenol compound and the aralkyl compound occurs simultaneously during the reaction between the first and second steps. As a result, an amino group-containing phenol resin used as a curing agent in the present application is produced. Note that the molar ratio of the phenol compound to the aromatic amine compound is 0.97: 0.03 to 0.2: 0.8.

The reaction temperature is from 0 to 220 for the whole reaction.
° C, but in the first stage reaction,
C., preferably 20 to 110 ° C., and in the second stage reaction, 150 to 220 ° C. In order to shorten the reaction time of the second stage as much as possible, a reaction temperature of 170 ° C. or higher is desirable. The reaction time is 1 to 1 in the first stage reaction.
5 hours and 3-20 hours for the second stage reaction.

In the phenol resin as the curing agent of the present invention, by changing the molar ratio of the aralkyl compound to the total of the phenol compound and the aromatic amine compound, phenol resins of various forms from low molecular weight resin to high molecular weight resin can be used. It can be manufactured according to the application. That is, liquid-
A phenol resin having a low softening point can be obtained by increasing the total molar ratio of a phenol compound and an aromatic amine compound to an aralkyl compound during the condensation reaction. On the other hand, an aromatic amine resin having a high softening point can be obtained by making the total molar ratio of the phenol compound and the aromatic amine compound to the aralkyl compound close to the theoretical amount during the condensation reaction. That is, by reacting the aralkyl compound in a range of 0.1 to 0.95 mol with respect to a total of 1 mol of the phenol compound and the aromatic amine compound,
The molecular weight range of the resulting phenolic resin is 300-500
0 and the amine value is 150 to 2000 g / eq.
The softening point range of the resin is about 40 to 120 ° C.

In the present invention, the other curing agent used in combination with the above-mentioned amino group-containing phenol resin as the component (B) includes, for example, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and the like. And formaldehyde,
Novolak-type phenol resins obtained by subjecting acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc. to a condensation reaction in the presence of an acidic catalyst, aralkyl resins by xylylene bonds such as phenol, phenol-dicyclopentadiene resins, and the like. Or two or more of them may be used in combination.

The epoxy resin having two or more epoxy groups in one molecule, which is the component (A) used in the present invention, may be any epoxy resin generally used as an epoxy resin, for example, phenol novolak type. Epoxy resin, epoxidized novolak resin obtained from phenols and aldehydes including o-cresol novolak type epoxy resin, phenol, epoxidized aralkyl resin by xylylene bond of naphthols, phenol-dicyclopentadiene resin Epoxidized product, bisphenol A, bisphenol F,
Bisphenol S, thiodiphenol, bisphenol, substituted bisphenol, diglycidyl ethers such as dihydroxynaphthalene, phthalic acid, glycidyl ester type epoxy resin obtained by the reaction of polybasic acid such as dimer acid and epichlorohydrin, diaminodiphenylmethane, diaminodiphenylsulfone, There is a glycidylamine type epoxy resin obtained by the reaction of a polyamine such as isocyanuric acid and epichlorohydrin, and any number of these can be used in combination. The equivalent ratio between the epoxy resin and the total curing agent is not particularly limited, but is preferably 0.5 to 1.5.

In the epoxy resin composition for semiconductor encapsulation, an inorganic filler (C) is used as an essential component. The amount of the inorganic filler used is 50% by weight or more of the total epoxy resin composition, but is preferably 70% by weight or more from the viewpoint of improving moisture resistance and mechanical strength. As the inorganic filler, silica,
Examples thereof include powders such as alumina, silicon nitride, silicon carbide, talc, calcium silicate, calcium carbonate, mica, clay, and titanium white, and fibrous bodies such as glass fibers and carbon fibers. Among these, from the point of thermal expansion coefficient and thermal conductivity,
Crystalline silica and / or fusible silica are preferred.
Further, considering the fluidity during molding of the resin composition, the shape is preferably spherical, or a mixture of spherical and amorphous.

In the present invention, in curing the resin composition, it is desirable to use a curing accelerator. Examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-methyl-4-ethylimidazole and 2-heptadecylimidazole; amines such as triethanolamine, triethylenediamine and N-methylmorpholine; tributylphosphine; Phenylphosphine,
Organic phosphines such as tolyl phosphine; tetraphenylborons such as tetraphenylphosphonium tetraphenylborate and triethylammonium tetraphenylborate; and 1,8-diaza-bicyclo (5,4,
0) Undecene-7 and its derivatives. These curing accelerators may be used alone or in combination of two or more. The curing accelerator is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the epoxidized product or epoxy compound and the curing agent.

In the epoxy resin composition of the present invention,
It is desirable to add various additives in view of mechanical strength and heat resistance. That is, it is preferable to use a coupling agent in combination for the purpose of improving the adhesiveness between the resin and the inorganic filler. Examples of such a coupling agent include silane-based, titanate-based, aluminate-based and zircoaluminate-based coupling agents. Agents can be used. Among them, a silane coupling agent is preferable, and a silane coupling agent having a functional group that reacts with an epoxy resin is particularly preferable. Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N
-(2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Silane and the like can be mentioned, and these can be used alone or in combination. It is preferable that these silane coupling agents are previously fixed to the surface of the inorganic filler by adsorption or reaction.

Further, a silicone compound may be added to the epoxy resin composition for semiconductor encapsulation of the present invention in order to reduce internal stress. Examples of the silicone compound include polysiloxanes having an amino group, an epoxy group, a carboxy group, a hydroxyl group or a cyclohexene oxide group at the terminal and the branched terminal as disclosed in JP-A-4-155940. The addition amount of such a silicone compound is at most 5% by weight based on the whole composition, and is usually in the range of 0.5 to 3% by weight. Further, in addition to the above components, the resin composition of the present invention may further comprise, if necessary, a release agent such as a fatty acid, a fatty acid group and a wax, a brominated compound, a flame retardant such as antimony and phosphorus, and a coloring agent such as carbon black. Can be mixed, kneaded and kneaded to obtain a molding material for IC encapsulation. The method of sealing a semiconductor element using the epoxy resin composition of the present invention is not particularly limited, and can be performed by a known molding method such as ordinary transfer molding. A semiconductor device obtained by such a method has excellent crack resistance during solder immersion, and is stable over a long period of use as a highly integrated IC, so that high reliability is obtained.

[0028]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Synthesis Example 1 193.0 g of phenol and 181.5 g of aniline were placed in a glass reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser.
And the internal temperature was raised to 105 ° C. Next, 175.0 g of p-xylylene dichloride was charged, and stirring was continued for 2.5 hours while maintaining the internal temperature at the same temperature.
The temperature was raised to 0 ° C., and stirring was continued for another 9.5 hours. After completion of the reaction, the internal temperature was gradually cooled to 60 ° C., and 280 g of 28% aqueous ammonia was charged for neutralization. Then, water, unreacted phenol and aniline were removed by vacuum distillation, and toluene and water were added to the residue and washed with water to remove ammonium chloride. After washing with water, toluene and a trace amount of water were removed by distillation under reduced pressure, and the resulting red-brown transparent resin was discharged when hot.
The yield was 215 g and the softening point (JIS-K-2548) was 62.4 ° C. The hydroxyl equivalent (g / e) of this resin
q) was 201 and the amine value (g / eq) was 820. The average molecular weight of the resin measured by GPC was 620.

Synthesis Example 2 259.6 g of α-naphthol and 111.aniline were placed in a glass reactor equipped with a stirrer, thermometer and reflux condenser.
7 g was charged, and the internal temperature was raised to 95 ° C. Next, 105.1 g of p-xylylene dichloride was charged, and Example 1 was added.
The reaction was carried out in the same manner as described above. After the completion of the reaction, the internal temperature was gradually cooled to 60 ° C., and neutralized by charging 157.7 g of 28% aqueous ammonia. Next, water and toluene were added thereto, and the mixture was separated and washed with water to remove ammonium chloride. Toluene, remaining unreacted α-naphthol and traces of water were removed by distillation under reduced pressure, and the resulting dark brown resin was discharged hot. Yield 15
6g, softening point (JIS-K-2548) 94.0 ° C
Met. The hydroxyl equivalent (g / eq) of this resin is 390
And the amine value (g / eq) was 1190. Also,
The average molecular weight of the resin measured by GPC was 760.

Synthesis Example 3 138.1 g of α, α'-dihydroxy-p-xylene, 94.1 g of phenol, p-amino were placed in a glass reactor equipped with a stirrer, thermometer, reflux condenser and water separator. Phenol 109.1 and 68.3 g of activated clay (Galeonite # 136, manufactured by Mizusawa Chemical Co., Ltd.) were charged, and the internal temperature was raised to 180 ° C. The internal temperature was kept at the same temperature, and stirring was continued for 13 hours. Water generated during the reaction was removed by a water separator. After completion of the reaction, the reaction solution was cooled to 110 ° C., and then activated clay was removed by filtration. The remaining phenol and p-aminophenol were removed by distillation under reduced pressure, and the resulting dark brown resin was discharged while hot. Yield 2
With 30 g, the softening point (JIS-K-2548) was 81 ° C. The hydroxyl equivalent (g / eq) of this resin is 175
And the amine value (g / eq) was 435. The average molecular weight of the resin by GPC was 2,300.

Examples 1 to 4 An o-cresol novolak type epoxy resin (trade name: EOCN-102S, manufactured by Nippon Kayaku Co., Ltd.) was used as the epoxy resin.
And biphenyl type epoxy resin (trade name: YX-40)
00H, manufactured by Yuka Shell Epoxy Co., Ltd.), and as the curing agent, the amino group-containing phenol resin and phenol novolak resin (trade name BRG) obtained in Synthesis Examples 1 to 3
# 558, manufactured by Showa Kogyo Co., Ltd.), spherical fused silica (Halimic S-CO, manufactured by Micron Corporation) and amorphous fused silica (Hughex RD-8,
50/50 (weight ratio) mixture of Tatsumori Co., Ltd.) and other additives were added in the proportions (parts by weight) shown in Table 1 (Table 1), and mixed with a mixing roll machine at a temperature of 100 ° C. for 3 minutes. Kneading was performed to obtain an epoxy resin composition. The composition was cast and the physical properties of the obtained cured product were measured. The test piece for measuring physical properties was transfer molded (180 ° C, 30Kg / c
m ² , 3 min) and post-cured under the conditions shown in Table 1. Further, after the semiconductor element (10 mm × 10 mm square) is mounted on the element mounting portion of the flat package type lead frame for a semiconductor device using the epoxy resin composition, transfer molding (180 ° C., 30 kg) is performed.
/ Cm ² , 3 min) to obtain a semiconductor device. About this semiconductor device, P. An S test (crack generation test) was performed. The results are shown in Table 1.

Comparative Example 1 A phenol novolak resin (trade name BR) was used as a curing agent.
G # 558, manufactured by Showa Polymer Co., Ltd.) and Xyloc resin (trade name: MILEX XL-225-3L, manufactured by Mitsui Toatsu Chemicals, Inc.) were used in the same manner as in Examples, except that epoxy resin compositions were used. And a semiconductor device. The evaluation results are shown in Table 1.

[0033]

[Table 1] The epoxy resin composition using the amino group-containing phenol resin of the present invention has a significantly improved glass transition temperature with respect to a phenol resin having a similar skeleton as can be seen by comparing Example 1 and Comparative Example 1, Hygroscopicity hardly changes.
Further, it has low hygroscopicity as compared with a novolak type phenol resin.

Test methods for various physical properties and the like are as follows. -Glass transition temperature: TMA method (Shimadzu, TMA-DRW
(Measured by DT-30) Boiling water absorption: Measure the weight increase after boiling for 2 hours in boiling water at 100 ° C. P. S test: Test semiconductor device at 65 ° C, 9
Immediately after leaving for 168 hours in a 5% constant temperature and humidity chamber,
40 ° C Freonart liquid (manufactured by Sumitomo 3M, FC-7
0), and the number of semiconductors having cracks in the package resin was counted. The test value is indicated by a fraction, the numerator is the number of semiconductor devices having cracks, and the denominator is the number of semiconductor devices subjected to the test. The additives, epoxidized products, and curing agents used in the test are as follows. -C11Z: undecyl imidazole (manufactured by Shikoku Fine Chemical)-Inorganic filler: spherical fused silica (Halimic S-CO,
A mixture of 50 parts by weight of Micron Co., Ltd. and 50 parts by weight of amorphous fused silica (Hughes Rex RD-8, manufactured by Tatsumori Co., Ltd.) • Silane coupling agent: (SZ-6083, manufactured by Toray Dow Corning Silicone) EOCN-102S: o-cresol novolak type epoxy resin, Nippon Kayaku Co., Ltd., epoxy equivalent 214 · BRG # 558: phenol novolak resin
Showa Polymer, hydroxyl equivalent 102 * YX-4000H: Biphenyl epoxy resin
Made of Yuka Shell Epoxy, epoxy equivalent 190g / eq. XL-225-3L: Xyloc resin [Formula (VI) below
(Chemical formula 7)] 174 g of hydroxyl equivalent, manufactured by Mitsui Toatsu Chemicals, Inc.
/ Eq

[0035]

Embedded image (Where p represents an integer of 0 to 20)

[0036]

The epoxy resin composition using the amino group-containing phenolic resin of the present invention has a significantly improved glass transition temperature and substantially no change in hygroscopicity as compared with a phenolic resin having a similar skeleton. On the other hand, on the other hand, its hygroscopicity is lower than that of a novolak type phenol resin. For this reason, the epoxy resin composition of the present invention is suitable as a semiconductor encapsulating material, and a device encapsulated with the epoxy resin composition has high reliability.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. −29390 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/62 C08L 63/00-63/10 H01L 23/29

Claims (5)

(57) [Claims] (A) an epoxy resin having two or more epoxy groups in one molecule; (B) an epoxy resin represented by the general formula (I) (Chemical Formula 1) having a softening point of 40 to 120 ° C. and an average molecular weight of 1. 300
An epoxy resin composition comprising a curing agent containing an amino group-containing phenolic resin having an amine value of 150 to 2000 g / eq. Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, a hydroxyl group, or a C _{1 to} C ₁₂ alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, an alkoxy group, or an aryloxy group. at best, _{R 1} and R
₂ may form a ring, and R ₃ and R ₄ represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a C _{1 to} C ₁₂ alkyl group, an aryl group, a cycloalkyl group, an aralkyl group,
An amino-substituted aralkyl group, a hydroxy-substituted aralkyl group, an alkoxy group, an aryloxy group, an amino-substituted aryloxy group, or a hydroxy-substituted aryloxy group, which may be the same or different, and R ₃ and R ₄ represent a ring It may be formed. m and n each represent an integer of 1 to 20, and the terminal is a phenol compound and / or an aromatic amine compound, and the bonding order of the phenol compound and the aromatic amine compound is not limited. 2. The epoxy resin composition according to claim 1,
An epoxy resin composition for semiconductor encapsulation, comprising 50% by weight or more of an inorganic filler. 3. A cured product obtained by curing the epoxy resin composition according to claim 1. 4. A cured product obtained by curing the epoxy resin composition according to claim 2. 5. A semiconductor device sealed with the cured product according to claim 4.