JP3147317B2 - Epoxy resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and useful epoxy resin composition. More specifically, the present invention relates to an epoxy resin composition which is excellent in heat resistance, moisture resistance, adhesiveness, mechanical properties and workability, and is suitable for applications such as casting, lamination, adhesion, molding, sealing, and composite materials. Specifically, as a practical example, a semiconductor integrated circuit (I
The present invention relates to the molding material for sealing C).

[0002]

2. Description of the Related Art There are many epoxy resins and curing agents conventionally used in epoxy resin compositions for such applications. For example, typical epoxy resins include various liquid to solid epoxy resins obtained from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), and epoxy resins obtained from novolak resins. 4,4'-diaminodiphenylmethane (MDA) as the reactive epoxy resin
From epoxy resins.

[0003] Typical curing agents are aliphatic or aromatic amine compounds such as diethylenetriamine, isophoronediamine, m-xylylenediamine, m-phenylenediamine, and 4,4'-diaminodiphenylsulfone;
Acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and maleic anhydride; phenol resins such as phenol novolak; other polyamides; modified polyamines; and imidazoles. These epoxy resins and curing agents have been cured in various combinations depending on the application, and have been used as resin compositions using inorganic fillers.

However, epoxy resin compositions obtained by using these conventionally used epoxy resins and hardeners have advantages and disadvantages in performance, and are inevitably required to be high with the improvement of technology in each application field. It is hard to say that it can satisfy the level of performance.

[0005] That is, there is a demand for an epoxy resin which has a high level of each property such as heat resistance, moisture resistance and mechanical strength in a well-balanced manner and is also excellent in workability. Many combinations of epoxy resin and phenol novolak obtained from novolak have been used, but the epoxy resin composition obtained from this combination has a relatively high level of mechanical strength, but has a problem in moisture resistance. Recent developments in various industries have pointed out problems related to the reliability of final products, such as generation of cracks due to poor moisture resistance and insufficient heat resistance due to an increase in generated heat.

In order to solve such problems, several epoxy resins and curing agents have recently been proposed for the purpose of improving the heat resistance and moisture resistance of the epoxy resin composition. For example, by using 4,4'-diaminodiphenylmethane or 4,4'-dihydroxydiphenylsulfone as a curing agent, or by using an epoxidized product thereof as an epoxy main agent, a highly heat-resistant epoxy resin composition can be obtained. What is possible is already known. However, these are structurally inferior in moisture resistance and do not solve the problem.

Further, an epoxy resin composition (a) used in the present invention, which comprises a naphthol aralkyl resin represented by the general formula (I) as a curing agent (JP-B-48-1096)
0), (b) a phenol represented by the general formula (III)
Epoxy resin composition using dicyclopentadiene resin as a curing agent (Japanese Patent Application Laid-Open Nos. 61-250300 and 61-2503)
01), (c) Epoxy resin compositions (trade name: MILEX XL225, manufactured by Mitsui Toatsu Chemicals, Inc.) using a phenol aralkyl resin represented by the general formula (IV) as a curing agent are found to be excellent in moisture resistance. Particularly, an epoxy resin composition obtained using a naphthol aralkyl resin represented by the general formula (I) of (a) and a phenol-dicyclopentadiene resin represented by the general formula (III) of (b) is: In addition, the naphthol aralkyl resin represented by the general formula (I) of (a) has excellent performance in terms of heat resistance.
Due to the high melt viscosity of the resin, it is difficult to mix, knead, etc. without excessive heating or use of an unnecessary solvent when used, and the phenol represented by the general formula (III) of (b) Dicyclopentadiene resin has heat resistance,
Although the moisture resistance is excellent, the mechanical properties are slightly inferior. The phenol aralkyl resin represented by the general formula (IV) of (c) has excellent moisture resistance and mechanical properties but is inferior in heat resistance.
Each has its drawbacks.

Further, the properties of the epoxy resin as the main component also affect the performance of the finally obtained resin composition. For this reason, improvement in moisture resistance and heat resistance by using these curing agents cannot always be said to be sufficient to meet the development of technology in each industrial field and the required performance accompanying the development. In addition, the resin part, which is inevitably required to be thinner due to product miniaturization and higher integration, is required to have greater strength against changes in cooling and heat, and has a lower coefficient of thermal expansion and lower distortion due to changes in cooling and heat. There is a strong demand for improvements in epoxy base agents and curing agents.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an epoxy resin composition having a good balance of properties such as moisture resistance, heat resistance, adhesiveness, mechanical strength and workability.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention provides an epoxy resin composition comprising an epoxy resin and a curing agent, wherein (A) an epoxy resin component represented by the general formula (I):
1)

Embedded image (Where n represents an integer from 0 to 100) to a naphthol aralkyl resin represented by the formula (II):
2)

Embedded image An epoxy resin obtained by reacting epichlorohydrin represented by the following formula: (B) As a curing agent, (a) a general formula (I)

Embedded image (Where n represents an integer from 0 to 100), and (b) a naphthol aralkyl resin represented by the following general formula (III):

Embedded image (Wherein, r represents an integer of 0 to 10, and R ₁ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, or a phenyl group), or a phenol-dicyclopentadiene resin represented by the general formula: Formula (IV)

Embedded image (Where m represents an integer of 0 to 100), a phenol aralkyl resin represented by the formula:
Is an epoxy resin composition excellent in heat resistance, moisture resistance, adhesiveness, mechanical properties and workability obtained by using in combination with an epoxy resin composition further containing an inorganic filler. .

In the present invention, the naphthol aralkyl resin used as an epoxy resin raw material or a curing agent is:
It is manufactured by Japanese Patent Application No. 47-15111 and Japanese Patent Application No. 3-165923. This naphthol aralkyl resin is represented by the general formula (V):

Embedded image (In the formula, R ₂ is a halogen atom, a hydroxyl group, or a group having 1 carbon atom.
And represents lower alkoxy groups 4 to 4. The aralkyl halide or aralkyl alcohol derivative represented by the formula (1) is reacted with α-naphthol or β-naphthol in an amount of 1.1 times or more in the presence of an acid catalyst, and unreacted naphthol is distilled off, if necessary. Can be obtained by

In the present invention, a method for epoxidizing a naphthol aralkyl resin of the general formula (I) is disclosed in
Known and conventional methods are used, as indicated by 90075. That is, a naphthol aralkyl resin is reacted with epihalohydrin in an amount of 1 to 20 moles, preferably 2 to 10 moles, more preferably 3 to 8 moles, based on the hydroxyl group thereof in the presence of a base. As a form, for example, 100 to 115 ° C
A method in which an aqueous solution of sodium hydroxide is dropped into a mixture of a naphthol aralkyl resin and an epihalohydrin heated to a temperature above, but other methods can also be used. The use of a phase transfer catalyst such as a quaternary ammonium salt during the reaction is not limited.

The curing agent in the present invention uses two kinds of phenol resins in combination. The method of using the curing agent may be a method in which it is simply compounded at the same time as curing, but preferably it is previously kneaded uniformly at an arbitrary ratio. It is more preferable to use an object. That is, by mixing a naphthol aralkyl resin represented by the general formula (I) and a phenol-dicyclopentadiene resin represented by the general formula (III) or a phenol aralkyl resin represented by the general formula (IV), the melt viscosity is increased. In addition to being excellent in the above-mentioned performances, it is also possible to achieve superiority in workability.

A phenol-dicyclopentadiene resin used as another curing agent is disclosed in
14099, JP-A-47-35000, 61-1686
24, 62-4720, 63-99224, U.S. Pat. No. 3,336,398, and the like. According to these methods, 1 mol of dicyclopentadiene is reacted with the compound represented by the general formula (VI).

Embedded image (Wherein, R ₁ represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms), and can be obtained by reacting 1 to 20 mol of a phenol or an alkylphenol. At this time, if the reaction is carried out under a high temperature and a high pressure in the absence of a catalyst, the obtained resin may not be a complete alternating copolymerization, and a Lewis acid catalyst, particularly boron trifluoride and its complex may be used. In the method used, there are problems such as the material of the reaction vessel, the mixing of the catalyst into the resin, and the elimination of wastewater after washing the resin with water.
Technology that solved these problems, Japanese Patent Application No. 2-29187.
2, 2-291873, 2-295489, 2-295
According to 490, it is desirably manufactured using an alkanesulfonic acid, a perfluoroalkanesulfonic acid, a perfluoroalkanesulfonic acid type ion exchange resin, or a sulfonic acid type strongly acidic ion exchange resin as a catalyst.

Similarly, the phenol aralkyl resin used in the present invention is produced by JP-B-47-15111, JP-A-62-70282, and the like. That is, similar to the naphthol aralkyl resin described above, the compound represented by the general formula (III)
Can be obtained by reacting an aralkyl halide or an aralkyl alcohol derivative represented by the formula with phenols in an amount of 1.1 times or more in the presence of an acid catalyst, and optionally distilling off unreacted phenols.

The amounts of the epoxy resin and the curing agent used in the present invention are based on the epoxy groups of the epoxy resin.
It is used so that the hydroxyl groups in the curing agent are approximately equivalent. That is, the hydroxyl group in the curing agent is 0.5 to 1.5 equivalents, preferably 0.8 to 1.5 equivalents to 1 equivalent of the epoxy group.
It is adjusted to be in the range of 1.2 equivalents. The ratio of the naphthol aralkyl resin to the phenol-dicyclopentadiene resin or the phenol aralkyl resin of the curing agent used in the present invention can be selected at an arbitrary ratio.
If the ratio exceeds 5%, the melt viscosity increases, and if the ratio is 5% by weight or less, the performance is not sufficiently exhibited. Therefore, the proportion of the naphthol aralkyl resin in the curing agent is in the range of 5% by weight to 95% by weight. However, the selection of this ratio may be determined in view of the required performance for the purpose of use.

Further, the epoxy resin of the present invention can be used by blending an inorganic filler. As the inorganic filler used, silica, alumina, silicon nitride, silicon carbide,
Talc, calcium silicate, calcium carbonate, mica,
Examples thereof include powders such as clay and titanium white, and fibrous bodies such as glass fiber and carbon fiber. Among these, crystalline silica and / or fusible silica are preferred from the viewpoint of the coefficient of thermal expansion and thermal conductivity. Further, considering the fluidity during molding of the resin composition, the shape is preferably spherical, or a mixture of spherical and irregular. The amount of the inorganic filler is 100 to 900% by weight based on the total weight of the epoxy resin and the curing agent.
And preferably 200 to 600% by weight.

In 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 adhesion 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. 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 most preferable. Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N
-(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-
Methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane 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.

In the present invention, in curing the resin composition, it is desirable to use a curing accelerator.
As such a curing accelerator, 2-methylimidazole,
Imidazoles such as 2-methyl-4-ethylimidazole and 2-heptadecylimidazole; amines such as triethanolamine, triethylenediamine and N-methylmorpholine; tributylphosphine, triphenylphosphine and tolylphosphine; Organic phosphines,
Tetraphenylphosphonium tetraphenylborate,
There are tetraphenylborons such as triethylammonium tetraphenylborate, 1,8-diaza-bicyclo (5,4,0) undecene-7 and derivatives thereof. The above-mentioned curing accelerators may be used alone or in combination of two or more. Further, these curing accelerators may be added in an amount of 0.1 to 100 parts by weight of the total amount of the epoxy resin and the curing agent.
It is used in the range of 01 to 10 parts by weight.

The resin composition may contain, in addition to the above components, a releasing agent such as a fatty acid, a fatty acid salt, or a wax, a flame retardant such as a bromo compound, antimony, and phosphorus, and a coloring such as carbon black. Agent, various silicone oils, etc.
It can be mixed and kneaded to obtain a molding material.

[0021]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
The composition of the resin by high performance liquid chromatography is indicated by area%.

Synthesis Example 1 α, α′-Dimethoxy- was added to a reactor equipped with a stirrer, a thermometer, a Dean-Stark azeotropic trap, and a cooler.
249 g (1.5 mol) of p-xylene, 648 g (4.5 mol) of β-naphthol, and 0.45 g of trifluoromethanesulfonic acid were charged, and 150 to 160 were added while stirring.
The reaction was performed at 4 ° C. for 4 hours. The generated methanol was sequentially trapped and removed out of the system. After completion of the reaction, unreacted naphthol was removed by distillation under reduced pressure to obtain 465 g of β-naphthol aralkyl resin having a structure of the general formula (I).
The composition of the resin by high performance liquid chromatography is n =
0 is 51.0%, n = 1 is 25.7%, and n = 2 is 12.
7% and n ≧ 3 were 10.6%. The hydroxy equivalent of this resin was 232.5 g / eq. The softening point is 98 ° C. and the ICI melt viscosity (150 ° C.) is 1
0.2 Poise.

Synthesis Example 2 150 g of the naphthol aralkyl resin produced in Synthesis Example 1 and epichlorohydrin 2 in a reactor equipped with a stirrer, a thermometer, a Dean-Stark azeotropic trap, and a cooler.
98.4 g (3.23 mol) was charged, and the mixture was heated to 115 ° C. with stirring to completely dissolve the mixture. While continuously stirring, 71.0 g of a 40% aqueous sodium hydroxide solution
Was added dropwise over 2 hours. During dropping, the reaction temperature is 100 to 11
While keeping the temperature at 5 ° C., the azeotropic epichlorohydrin was returned to the system, and water was removed from the system. After the completion of the dropwise addition of the 40% aqueous sodium hydroxide solution, the reaction was continued until the distillation of water stopped. After the completion of the reaction, the mixture was cooled to room temperature, and the by-produced inorganic salt was filtered. Epichlorohydrin was distilled from the filtrate under reduced pressure to obtain a crude epoxidized naphthol aralkyl resin.
32.1 g was obtained. This crude epoxidized product was dissolved in 700 g of methyl isobutyl ketone, 50 g of a 5% aqueous sodium hydroxide solution was added, and the mixture was stirred at 60 ° C. for 30 minutes.
After standing, the lower aqueous layer was drained, and the organic layer was neutralized with 100 g of a 1% aqueous solution of sodium dihydrogen phosphate.
g of water were washed three times, and methyl isobutyl ketone was distilled off under reduced pressure. In this way, 228.5 g of a pure naphthol aralkyl resin epoxy resin was obtained. The epoxy equivalent thereof was 303.7 g / eq and the softening point was 6
9 ° C.

Synthesis Example 3 α, α'-Dimethoxy- was added to a reactor equipped with a stirrer, a thermometer, a Dean-Stark azeotropic trap, and a cooler.
249 g (1.5 mol) of p-xylene, 432 g (3.0 mol) of α-naphthol, and 0.15 g of trifluoromethanesulfonic acid were charged, and 150 to 160 were added while stirring.
The reaction was performed at 4 ° C. for 4 hours. The generated methanol was sequentially trapped and removed out of the system. After completion of the reaction, unreacted naphthol was removed by distillation under reduced pressure to obtain 454 g of an α-naphthol aralkyl resin having a structure of the general formula (I).
The composition of the resin by high performance liquid chromatography is n =
0 is 32.8%, n = 1 is 23.5%, and n = 2 is 15.
2% and n ≧ 3 were 28.5%. The hydroxy equivalent of this resin was 234.1 g / eq. The softening point is 96 ° C., and the ICI melt viscosity (150 ° C.) is 1
It was 4.7 Poise.

Synthesis Example 4 150 g of the naphthol aralkyl resin produced in Synthesis Example 3 and epichlorohydrin 2 in a reactor equipped with a stirrer, a thermometer, a Dean-Stark azeotropic trap, and a cooler
96.4 g (3.20 mol) was charged, and the mixture was heated to 115 ° C. while stirring to completely dissolve it. While stirring continuously, 70.5 g of 40% aqueous sodium hydroxide solution
Was added dropwise over 2 hours. During dropping, the reaction temperature is 100 to 11
While keeping the temperature at 5 ° C., the azeotropic epichlorohydrin was returned to the system, and water was removed from the system. After the completion of the dropwise addition of the 40% aqueous sodium hydroxide solution, the reaction was continued until the distillation of water stopped. After the completion of the reaction, the mixture was cooled to room temperature, and the by-produced inorganic salt was filtered. Epichlorohydrin was distilled from the filtrate under reduced pressure to obtain a crude epoxidized naphthol aralkyl resin.
29.7 g were obtained. This crude epoxidized product was dissolved in 700 g of methyl isobutyl ketone, 50 g of a 5% aqueous sodium hydroxide solution was added, and the mixture was stirred at 60 ° C. for 30 minutes.
After standing, the lower aqueous layer was drained, and the organic layer was neutralized with 100 g of a 1% aqueous solution of sodium dihydrogen phosphate.
After washing three times with 00 g of water, methyl isobutyl ketone was distilled off under reduced pressure. In this way, 228.5 g of a pure naphthol aralkyl resin epoxy resin was obtained. The epoxy equivalent was 305.1 g / eq and the softening point was 66.5 ° C.

Synthesis Example 5 423 g (4.5 mol) of phenol and 0.45 g of methanesulfonic acid were inserted into a reactor equipped with a stirrer, a thermometer, and a cooler, and stirred at 40 to 50 ° C. 198 g (1.5 mol) of dicyclopentadiene
Was dropped in 3.5 hours. After continuing stirring at the same temperature for 1 hour, the temperature was raised to 140 ° C in 1 hour, and the reaction was carried out at 140 to 150 ° C for 3 hours. After the completion of the reaction, unreacted phenol is removed by distillation under reduced pressure, and the phenol having the structure of general formula (I) 41
0 g of phenol-dicyclopentadiene resin was obtained.
The composition of the resin by high performance liquid chromatography is n =
0 is 49.7%, n = 1 is 26.5%, and n = 2 is 10.
8% and n ≧ 3 were 13.0%. The hydroxy equivalent of this resin was 172.5 g / eq. The softening point was 121 ° C. and the ICI melt viscosity (150 ° C.) was 3.2 Poise.

Synthesis Example 6 α, α'-Dimethoxy- was added to a reactor equipped with a stirrer, a thermometer, a Dean-Stark azeotropic trap, and a cooler.
249 g (1.5 mol) of p-xylene and phenol 42
5 g (4.5 mol) and 0.34 g of methanesulfonic acid were inserted, and the mixture was reacted at 140 to 150 ° C. for 4 hours while stirring. The generated methanol was sequentially trapped and removed out of the system. After the completion of the reaction, unreacted phenol is removed by distillation under reduced pressure, and 303 having the structure of general formula (III) is obtained.
g of phenol aralkyl resin was obtained. Is 50.8% for n = 0, 24.3% for n = 1, and n =
2 was 11.6% and n ≧ 3 was 13.3%. The hydroxy equivalent of this resin was 168.5 g / eq.
The softening point is 52 ° C. and the ICI melt viscosity (150
C) was 3.8 Poise.

Example 1 85 parts of the β-naphthol aralkyl resin synthesized in Synthesis Example 1 and phenol synthesized in Synthesis Example 5
15 parts of dicyclopentadiene resin was melt mixed at 150 ° C. The ICI melt viscosity of the obtained mixed resin (1
(50 ° C.) was 6.2 Poise. This mixed resin was blended at the ratio shown in Table 1 as a curing agent for the epoxy resin of β-naphthol aralkyl resin synthesized in Synthesis Example 2, and the physical properties of the cured product obtained by casting the mixture were determined. It was measured. (Table 1) shows the results.

Example 2 70 parts of the β-naphthol aralkyl resin synthesized in Synthesis Example 1 and 30 parts of the phenol aralkyl resin synthesized in Synthesis Example 6 were melt-mixed at 150 ° C. The ICI melt viscosity (150 ° C.) of the obtained mixed resin was 5.8 Poise. As a curing agent for the epoxy resin of the α-naphthol aralkyl resin synthesized in Synthesis Example 4, this mixed resin was blended in the ratio shown in Table 1 and the physical properties of the cured product obtained by casting the mixture were determined. It was measured. (Table 1) shows the results.

Example 3 20 parts of the α-naphthol aralkyl resin synthesized in Synthesis Example 3 and the phenol synthesized in Synthesis Example 6
80 parts of dicyclopentadiene resin was melt mixed at 150 ° C. The ICI melt viscosity of the obtained mixed resin (1
(50 ° C.) was 3.8 Poise. This mixed resin was blended at the ratio shown in Table 1 as a curing agent for the epoxy resin of β-naphthol aralkyl resin synthesized in Synthesis Example 2, and the physical properties of the cured product obtained by casting the mixture were determined. It was measured. (Table 1) shows the results.

Example 4 50 parts of the α-naphthol aralkyl resin synthesized in Synthesis Example 3 and 50 parts of the phenol aralkyl resin synthesized in Synthesis Example 6 were melt-mixed at 150 ° C. The ICI melt viscosity (150 ° C.) of the obtained mixed resin was 4.7 Poise. As a curing agent for the epoxy resin of the α-naphthol aralkyl resin synthesized in Synthesis Example 4, this mixed resin was blended in the ratio shown in Table 1 and the physical properties of the cured product obtained by casting the mixture were determined. It was measured. (Table 1) shows the results.

Examples 5 to 8 The same resins as in Examples 1 to 4 were used, and an inorganic filler
Various other additives were blended at the ratios as shown in Table 2 and the physical properties of a cured product obtained by casting the mixture were measured. (Table 2) shows the results.

Comparative Example 1 Bisphenol A type epoxy resin (trade name; Epicoat 828, manufactured by Yuka Shell Chemical) as an epoxy resin, and phenol novolak resin (trade name; BRG) as a curing agent
# 558, manufactured by Showa Polymer Co., Ltd.), and the physical properties of a cured product obtained by casting the mixture were measured. (Table 1) shows the results.

Comparative Example 2 The curing agent in Comparative Example 1 was replaced with 4,4'-diaminodiphenylsulfone (trade name; Sumicure S, manufactured by Sumitomo Chemical Co., Ltd.).
(Table 1) shows the results.

Comparative Example 3 The epoxy resin in Comparative Example 1 was replaced with an o-cresol novolak type epoxy resin (trade name: EOCN-102S,
(Nippon Kayaku Co., Ltd.), and the physical properties of the cured product obtained in the same manner were measured. (Table 1) shows the results.

Comparative Examples 4 to 6 The same resins as in Comparative Examples 1 to 3 were used.
Various other additives were blended at the ratios as shown in Table 2 and the physical properties of a cured product obtained by casting the mixture were measured. (Table 2) shows the results.

Comparative Example 7 In Example 5, the amount of the inorganic filler was adjusted to be 80% of the total weight of the epoxy resin and the curing agent, and the physical properties of the obtained cured product were measured. However, the blending amount was adjusted so that the total weight became equal. (Table 2) shows the results.

A test piece (10 mm × 10 mm square) was mounted on the element mounting portion of a flat package type semiconductor device lead frame using a resin mixture.
After mounting, transfer molding (180 ° C, 30k
g / cm2, 3 min). This was used as a test semiconductor device.

As shown in Table 1, the epoxidized naphthol aralkyl resin and the naphthol aralkyl resin obtained in the present invention, and the cured product obtained from the phenol-dicyclopentadiene resin or the phenol aralkyl resin are heat-resistant. Therefore, it can be said that moisture resistance and mechanical properties are at a high level, and the performance is balanced. On the other hand, the cured products obtained from the combination of the conventional epoxy resin and the curing agent shown in Comparative Examples 1 to 3 were inferior in each performance, and particularly, as in Comparative Examples 1 and 2, heat resistance and moisture resistance Is often obtained at the expense of the other.

Further, Table 2 shows the physical properties of a cured product obtained by using an inorganic filler and other additives. Examples 5 to 8 and Comparative Examples 4 and 6 correspond to Examples 1 to 4 and Comparative Examples 1 to 3 in (Table 1), respectively. It can be seen that the water resistance and mechanical properties are greatly improved. In Comparative Example 7, when the amount of the inorganic filler used is 100% or less of the total weight of the resin within the range of the present invention, it is understood that the effect is almost equal. From these facts, according to the present invention, it is possible to obtain an epoxy resin composition having excellent heat resistance, moisture resistance, mechanical strength, etc., and a well-balanced performance.

The symbols, substances and measuring methods used in Tables 1 and 2 are shown below.・ Epicoat 828; bisphenol A type epoxy resin (manufactured by Yuka Shell Chemical) ・ EOCN-102S; o-cresol novolak type epoxy resin (manufactured by Nippon Kayaku) ・ BRG # 558; phenol novolak resin (manufactured by Showa Kogaku) S: 4,4'-diaminodiphenyl sulfone (manufactured by Sumitomo Chemical) C11Z; 2-undecylimidazole (manufactured by Shikoku Fine Chemical) Inorganic filler: spherical fused silica (Halimic S-CO,
50 parts by weight and amorphous fused silica (Hughes Rex RD)
-8 Mixture with 50 parts by weight of Tatsumori Corp.-Silane coupling agent; (SZ-6083, manufactured by Toray Dow Corning Silicone Co., Ltd.)-Glass transition temperature; TMA method (Shimadzu TMA-System DT-30)・ Bending strength and elastic modulus; JIS K-6911 ・ Boiled water absorption: Measured for weight increase after boiling for 2 hours in boiling water at 100 ° C. * V. P. S test: Test semiconductor device at 65 ° C, 9
Immediately after leaving for 168 hours in a 5% constant temperature and humidity chamber,
5 ° C Fronate solution (manufactured by Sumitomo 3M Limited, FC-
70), and the number of semiconductor devices 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.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

The epoxy resin composition provided by the present invention is excellent in heat resistance and moisture resistance, and is also excellent in mechanical properties, adhesiveness, crack resistance and workability, so that it is extremely useful as a matrix resin. It is highly useful. This provides an ideal material especially in the field of a semiconductor encapsulant, which has been conventionally limited in use because of its strengths and weaknesses in performance, and greatly contributes to it.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-67704 (JP, A) JP-A-5-97973 (JP, A) JP-A-5-140260 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08G 59/20 C08G 59/62 C08L 63/00-63/10

Claims (2)

(57) [Claims] An epoxy resin composition comprising an epoxy resin and a curing agent, wherein (A) an epoxy resin component represented by the general formula (I): (Where n represents an integer from 0 to 100) to a naphthol aralkyl resin represented by the formula (II): An epoxy resin obtained by reacting epichlorohydrin represented by the following formula: (B) as a curing agent, (a) a general formula (I) (Where n represents an integer from 0 to 100), and (b) a naphthol aralkyl resin represented by the following general formula (III): (Wherein, r represents an integer of 0 to 10, and R ₁ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, or a phenyl group), or a phenol-dicyclopentadiene resin represented by the general formula: Formula (IV) (Where m represents an integer of 0 to 100), a phenol aralkyl resin represented by the formula:
An epoxy resin composition obtained from the composition. 2. An epoxy resin composition containing an epoxy resin, a curing agent and an inorganic filler, wherein (A) an epoxy resin component represented by the general formula (I): (Where n represents an integer from 0 to 100) to a naphthol aralkyl resin represented by the formula (II): An epoxy resin obtained by reacting epichlorohydrin represented by the following formula: (B) As a curing agent, (a) a general formula (I) (Wherein, n represents an integer from 0 to 100), and (b) a general formula (III). (Wherein, r represents an integer of 0 to 10, and R ₁ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, or a phenyl group), or a phenol-dicyclopentadiene resin represented by the general formula: Formula (IV) (Wherein, m represents an integer of 0 to 100) An epoxy resin composition obtained by using a phenol aralkyl resin represented by the following formula (C): an inorganic filler.