JPH05170875A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition excellent in heat resistance, moisture resistance, adhesiveness, mechanical properties and workability by incorporating specified curing agents into an epoxy resin made by reacting a naphtholaralkyl resin with epichlorohydrin. CONSTITUTION:An epoxy resin composition containing an epoxy resin and curing agents, wherein the epoxy resin is one obtained by reacting a naphtholaralkyl resin of formula I with epichlorohydrin of formula II and the curing agents are a naphtholaralkyl resin of formula I and a phenol- dichloropentadiene resin of formula III or a phenolaralkyl resin of formula IV. In the formulas, n is 0 to 100; r is 0 to 10; and R1 is H, 1-9C alkyl or phenyl.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful epoxy resin composition. More specifically, the present invention relates to an epoxy resin composition having excellent heat resistance, moisture resistance, adhesiveness, mechanical properties and workability, which is suitable for applications such as casting, lamination, adhesion, molding, sealing, and composite materials. As a concrete example of what can be actually used, a semiconductor integrated circuit (I
The present invention relates to C) a molding material for sealing.

[0002]

2. Description of the Related Art There are many epoxy resins or 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), epoxy resins obtained from novolac resins, and the like, and high heat resistance. 4,4'-diaminodiphenylmethane (MDA)
There are epoxy resins and the like obtained from

Typical curing agents are aliphatic or aromatic amine compounds such as diethylenetriamine, isophoronediamine, m-xylylenediamine, m-phenylenediamine and 4,4'-diaminodiphenylsulfone.
Examples thereof include acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride and maleic anhydride, phenolic resins such as phenol novolac, other polyamides, modified polyamines and imidazoles. These epoxy resins and curing agents have been cured in various combinations depending on their respective uses, and have been used as resin compositions using inorganic fillers.

However, the epoxy resin compositions obtained by using these conventionally used epoxy resins and curing agents have advantages and disadvantages in performance and are inevitably required as the technology in each application field is improved. It is hard to say that the standard performance can be satisfied.

That is, there is a demand for an epoxy resin having a well-balanced and high level of each performance such as heat resistance, moisture resistance, mechanical strength, etc., and also excellent workability. For example, conventional o-cresol. A combination of an epoxy resin obtained from novolac and a phenol novolac has been often used, but an epoxy resin composition obtained from this combination has a relatively high level of mechanical strength, but has a problem in moisture resistance. With the development of each industry in recent years, problems related to the final reliability of the product, such as the occurrence of cracks due to poor moisture resistance and the lack of heat resistance due to an increase in the amount of heat generated, have been pointed out.

To address such problems, in recent years, several epoxy resins and curing agents have been proposed for the purpose of improving the heat resistance and moisture resistance of the epoxy resin composition. For example, a highly heat-resistant epoxy resin composition can be obtained 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. What is possible is already known. However, these are structurally inferior in moisture resistance and have not solved the problem.

Further, an epoxy resin composition using the naphthol aralkyl resin represented by the general formula (I) (a) used in the present invention as a curing agent (Japanese Patent Publication No. 48-1096).
0), (b) phenol represented by the general formula (III)
Epoxy resin composition using dicyclopentadiene resin as a curing agent (JP-A-61-250300, 61-2503)
01), (c) Epoxy resin composition using phenol aralkyl resin represented by the general formula (IV) as a curing agent (manufactured by Mitsui Toatsu Chemical Co., Inc .: trade name Milex XL225) and the like are found to have excellent moisture resistance. In particular, an epoxy resin composition obtained by using the naphthol aralkyl resin represented by the general formula (I) of (a) and the phenol-dicyclopentadiene resin represented by the general formula (III) of (b) is Although it also shows very excellent heat resistance, the naphthol aralkyl resin represented by the general formula (I) of (a) is excellent in performance,
Since the resin has a high melt viscosity, it is difficult to carry out work such as compounding and kneading unless excessive heating or an originally unnecessary solvent is used during use. Dicyclopentadiene resin is heat resistant,
Moisture resistance is excellent, but mechanical properties are slightly inferior, and the phenol aralkyl resin represented by the general formula (IV) of (c) is excellent in moisture resistance and mechanical properties, but inferior in heat resistance,
Each has its drawbacks.

Further, the properties of the epoxy resin, which is the main component, affect the performance of the resin composition finally obtained. Therefore, it cannot be said that the improvement of moisture resistance and heat resistance by using these curing agents can sufficiently meet the development of technology in each industrial field and the required performance accompanying it. In addition, the resin portion, which is inevitably required to be thin due to the miniaturization and high integration of products, is required to have further strength against changes in cold heat. There is a strong demand for improvements in epoxy base and curing agents.

[0009]

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

[0010]

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

[Chemical 11] (However, in the formula, n represents an integer of 0 to 100.) The naphthol aralkyl resin represented by the formula (II)
2)

[Chemical 12] An epoxy resin obtained by reacting epichlorohydrin represented by: (B) as a curing agent, (a) general formula (I)

[Chemical 13] (However, n represents an integer of 0 to 100 in the formula), and (b) the general formula (III) (Chemical formula 14)

[Chemical 14] (However, in the formula, 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 general formula Formula (IV) (Chemical Formula 15)

[Chemical 15] (However, m represents an integer of 0 to 100 in the formula),
Is an epoxy resin composition excellent in heat resistance, moisture resistance, adhesiveness, mechanical properties and workability obtained by using in combination, and an epoxy resin composition further containing an inorganic filler. .

The naphthol aralkyl resin used as the epoxy resin raw material or the curing agent in the present invention is
It is manufactured according to Japanese Patent Publication No. Sho 47-15111 and Japanese Patent Application No. 3-165923. This naphthol aralkyl resin has the general formula (V)

[Chemical 16] (In the formula, R ₂ is a halogen atom, a hydroxyl group, or 1 carbon atom.
4 shows a lower alkoxy group. ) In the presence of an acid catalyst, an aralkyl halide or an aralkyl alcohol derivative represented by) is reacted with 1.1 times or more moles of α-naphthol or β-naphthol, and if necessary, unreacted naphthol is distilled off. Can be obtained by

In the present invention, a method for epoxidizing a naphthol aralkyl resin of the general formula (I) is disclosed in JP-A-3-
Known and conventional methods are used as indicated by 90075. That is, the naphthol aralkyl resin is reacted with 1 to 20 times mol, preferably 2 to 10 times mol, and more preferably 3 to 8 times mol of epihalohydrin in the presence of a base. The form is, for example, 100 to 115 ° C.
A method in which an aqueous sodium hydroxide solution is added dropwise to a mixture of the naphthol aralkyl resin and epihalohydrin heated to 1, but other methods can also be used. Also, the use of a phase transfer catalyst such as a quaternary ammonium salt in the reaction is not limited.

The curing agent used in the present invention is a combination of two types of phenolic resins. The method of use may be a method of simply blending them at the time of curing, but it is preferable that the curing agents have been uniformly kneaded in an arbitrary ratio in advance. It is more preferable to use a product. That is, the naphthol aralkyl resin represented by the general formula (I) and the phenol-dicyclopentadiene resin represented by the general formula (III) or the phenol aralkyl resin represented by the general formula (IV) are mixed to obtain a melt viscosity. In addition to being excellent in each of the above performances, it is possible to achieve superiority in workability.

Phenol-dicyclopentadiene resins used as other curing agents are disclosed in JP-B-41-
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 used to prepare a compound represented by the general formula (VI):

[Chemical 17] (However, in the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.) It can be obtained by reacting 1 to 20 mol of a phenol or an alkylphenol. At this time, in the method of carrying out the reaction at a high temperature and a high pressure without a catalyst, the obtained resin may not be a complete alternating copolymerization, and a Lewis acid catalyst, especially boron trifluoride and its complex may be used. In the method used, there are problems such as the material of the reaction vessel, the mixture of the catalyst in the resin, and the pollution of the wastewater after washing the resin with water.
Techniques for solving these problems, Japanese Patent Application No. 2-29187
2, 2-2918773, 2-295489, 2-295
490 is preferably produced 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 manufactured according to Japanese Patent Publication No. 47-15111 and Japanese Patent Application No. 62-70282. That is, similar to the above-mentioned naphthol aralkyl resin, the compound represented by the general formula (III)
It can be obtained by reacting an aralkyl halide or an aralkyl alcohol derivative represented by the above with 1.1 times or more moles of phenols in the presence of an acid catalyst, and distilling off unreacted phenols if necessary.

The amount of the epoxy resin and the curing agent used in the present invention is as follows, based on the epoxy group of the epoxy resin.
It is used so that the hydroxyl groups in the curing agent are almost equivalent. That is, the hydroxyl group in the curing agent is 0.5 to 1.5 equivalents, preferably 0.8 to 1 equivalent to the epoxy group.
It is adjusted to be in the range of 1.2 equivalents. Further, the curing agent used in the present invention, the ratio of the naphthol aralkyl resin and the phenol-dicyclopentadiene resin or the phenol aralkyl resin can be selected at any ratio, but the naphthol aralkyl resin is 95% by weight.
If it exceeds 5% by weight, the melt viscosity will increase, and if it becomes less than 5% by weight, its performance will not be exhibited sufficiently. Therefore, the proportion of the naphthol aralkyl resin in the curing agent should be in the range of 5% by weight to 95% by weight. However, the selection of this ratio may be made in consideration of the performance required for the purpose of use.

Furthermore, 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 fiber bodies such as glass fibers and carbon fibers. Among these, crystalline silica and / or fusible silica are preferable from the viewpoint of thermal expansion coefficient and thermal conductivity. Further, considering the fluidity of the resin composition at the time of molding, its shape is preferably spherical or a mixture of spherical and amorphous. The content of the inorganic filler is 100 to 900% by weight based on the total weight of the epoxy resin and the curing agent.
It is necessary to be, and preferably 200 to 600% by weight.

In the present invention, it is desirable to add various additives from the viewpoints 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. As such a coupling agent, a silane-based, titanate-based, aluminate-based, and zircoaluminate-based coupling agent is used. Can be used. Among them, silane coupling agents are preferable, and silane coupling agents having a functional group that reacts with an epoxy resin are 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. These silane coupling agents are preferably immobilized in advance on the surface of the inorganic filler by adsorption or reaction.

In the present invention, it is desirable to use a curing accelerator when curing the resin composition.
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, tritolylphosphine and the like. Organic phosphines,
Tetraphenylphosphonium tetraphenylborate,
There are tetraphenylborones such as triethylammonium tetraphenylborate, 1,8-diaza-bicyclo (5,4,0) undecene-7 and its derivatives. The above-mentioned curing accelerators may be used alone or in combination of two or more kinds, and the mixing ratio of these curing accelerators may be 0.
It is used in the range of 01 to 10 parts by weight.

In addition to the above-mentioned components, the resin composition may optionally contain a releasing agent such as a fatty acid, a fatty acid salt or a wax, a bromine compound, a flame retardant such as antimony or phosphorus, and a coloring such as carbon black. Agent, various silicone oils, etc.,
A molding material can be obtained by mixing and kneading.

[0021]

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

Synthesis Example 1 α, α'-dimethoxy-in a reactor equipped with a stirrer, a thermometer, a Dean Stark azeotropic trap, and a condenser.
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 the mixture was stirred at 150 to 160.
The reaction was carried out at ℃ for 4 hours. The produced methanol was sequentially trapped and removed from the system. After the reaction was completed, unreacted naphthol was removed by distillation under reduced pressure to obtain 465 g of β-naphthol aralkyl resin having the structure of 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 was 10.6%. The hydroxy equivalent weight of this resin was 232.5 g / eq. The softening point is 98 ° C, and the ICI melt viscosity (150 ° C) is 1
It was 0.2 Poise.

Synthesis Example 2 150 g of 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 condenser.
98.4 g (3.23 mol) was charged and the mixture was heated to 115 ° C. with stirring to completely dissolve it. While continuing to stir, 71.0 g of 40% aqueous sodium hydroxide solution
Was added dropwise over 2 hours. During the dropping, the reaction temperature is 100 to 11
The temperature was kept at 5 ° C., the azeotropically distilled epichlorohydrin was returned to the system, and water was removed to the outside of the system. After the dropping of the 40% aqueous sodium hydroxide solution was completed, the reaction was continued until the water was not distilled off. After the reaction was completed, the reaction 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 epoxide of naphthol aralkyl resin.
32.1 g was obtained. The crude epoxide 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 discharged, and the organic layer was neutralized with 100 g of a 1% sodium dihydrogen phosphate aqueous solution and then 100
After washing 3 times with g of water, methyl isobutyl ketone was distilled off under reduced pressure. In this way, 228.5 g of a pure epoxy resin of naphthol aralkyl resin was obtained. This product has an epoxy equivalent of 303.7 g / eq and a softening point of 6
It was 9 ° C.

Synthesis Example 3 α, α'-dimethoxy-in a reactor equipped with a stirrer, a thermometer, a Dean Stark azeotropic trap, and a condenser.
Charge 249 g (1.5 mol) of p-xylene, 432 g (3.0 mol) of α-naphthol and 0.15 g of trifluoromethanesulfonic acid, and stir 150-160.
The reaction was carried out at ℃ for 4 hours. The produced methanol was sequentially trapped and removed from the system. After the completion of the reaction, unreacted naphthol was removed by distillation under reduced pressure to obtain 454 g of α-naphthol aralkyl resin having the structure of 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 was 28.5%. The hydroxy equivalent weight 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.

Synthetic Example 4 150 g of naphthol aralkyl resin produced in Synthetic Example 3 and epichlorohydrin 2 in a reactor equipped with a stirrer, a thermometer, a Dean Stark azeotropic trap, and a condenser.
96.4 g (3.20 mol) was charged, and the mixture was heated to 115 ° C. with stirring to completely dissolve it. While continuing to stir, 40% aqueous sodium hydroxide solution 70.5 g
Was added dropwise over 2 hours. During the dropping, the reaction temperature is 100 to 11
The temperature was kept at 5 ° C., the azeotropically distilled epichlorohydrin was returned to the system, and water was removed to the outside of the system. After the dropping of the 40% aqueous sodium hydroxide solution was completed, the reaction was continued until the water was not distilled off. After the reaction was completed, the reaction 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 epoxide of naphthol aralkyl resin.
29.7 g was obtained. The crude epoxide 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 discharged, the organic layer was neutralized with 100 g of a 1% sodium dihydrogen phosphate aqueous solution, and then 1
It was washed 3 times with 00 g of water and methyl isobutyl ketone was distilled off under reduced pressure. In this way, 228.5 g of a pure epoxy resin of naphthol aralkyl resin was obtained. The epoxy equivalent of this product 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 condenser, and the mixture was stirred at 40 to 50 ° C. 198 g (1.5 mol) of dicyclopentadiene
Was added dropwise over 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 reaction is completed, unreacted phenol is removed by distillation under reduced pressure to obtain a compound having the structure of general formula (I).
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 was 13.0%. The hydroxy equivalent weight 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-in a reactor equipped with a stirrer, a thermometer, a Dean Stark azeotropic trap, and a condenser.
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 reaction was carried out at 140 to 150 ° C. for 4 hours while stirring. The produced methanol was sequentially trapped and removed from the system. After completion of the reaction, unreacted phenol is removed by distillation under reduced pressure to obtain 303 having the structure of general formula (III).
g of phenol aralkyl resin was obtained. The composition of the resin by n = 0 is 50.8%, n = 1 is 24.3%, and n =
2 was 11.6% and n ≧ 3 was 13.3%. The hydroxy equivalent weight 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 β-naphthol aralkyl resin synthesized in Synthesis Example 1 and phenol synthesized in Synthesis Example 5
15 parts of dicyclopentadiene resin were melt mixed at 150 ° C. The ICI melt viscosity (1
50 ° C) was 6.2 Poise. This mixed resin was mixed as a curing agent for the epoxy resin of the β-naphthol aralkyl resin synthesized in Synthesis Example 2 in the proportions shown in (Table 1), and the mixture was cast to obtain the physical properties of the cured product obtained. It was measured. The results are shown in (Table 1).

Example 2 70 parts of β-naphthol aralkyl resin synthesized in Synthesis Example 1 and 30 parts of 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. This mixed resin was blended as a curing agent for the epoxy resin of α-naphthol aralkyl resin synthesized in Synthesis Example 4 in the proportions shown in (Table 1), and the mixture was cast to obtain the physical properties of the cured product obtained. It was measured. The results are shown in (Table 1).

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

Example 4 50 parts of α-naphthol aralkyl resin synthesized in Synthesis Example 3 and 50 parts of 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. This mixed resin was blended as a curing agent for the epoxy resin of α-naphthol aralkyl resin synthesized in Synthesis Example 4 in the proportions shown in (Table 1), and the mixture was cast to obtain the physical properties of the cured product obtained. It was measured. The results are shown in (Table 1).

Examples 5 to 8 Using the same resins as in Examples 1 to 4, an inorganic filler,
Various other additives were blended in the proportions as shown in (Table 2), and the mixture was cast to measure the physical properties of the cured product. The results are shown in (Table 2).

Comparative Example 1 A bisphenol A type epoxy resin (trade name; Epicoat 828, manufactured by Yuka Shell Chemical Co., Ltd.) as an epoxy resin, and a phenol novolac resin (trade name: BRG) as a curing agent.
# 558, manufactured by Showa High Polymer Co., Ltd., was blended in the proportions as shown in (Table 1), and the mixture was cast-processed to measure the physical properties of the cured product. The results are shown in (Table 1).

Comparative Example 2 The curing agent in Comparative Example 1 was replaced with 4,4′-diaminodiphenyl sulfone (trade name; Sumicure S, manufactured by Sumitomo Chemical Co., Ltd.), and the physical properties of a cured product obtained in the same manner were measured.
The results are shown in (Table 1).

Comparative Example 3 The epoxy resin used in Comparative Example 1 was replaced by an o-cresol novolac type epoxy resin (trade name: EOCN-102S,
Instead of Nippon Kayaku), the physical properties of the cured product obtained in the same manner were measured. The results are shown in (Table 1).

Comparative Examples 4 to 6 The same resins as in Comparative Examples 1 to 3 were used, and an inorganic filler,
Various other additives were blended in the proportions as shown in (Table 2), and the mixture was cast to measure the physical properties of the cured product. The results are shown in (Table 2).

Comparative Example 7 In Example 5, the inorganic filler was blended in an amount of 80% of the total weight of the epoxy resin and the curing agent, and the physical properties of the resulting cured product were measured. However, the blending amount was adjusted so that the total weight was equal. The results are shown in (Table 2).

A test piece for measuring physical properties was prepared by using a resin mixture, and a test element (10 mm × 10 mm square) was mounted on an element mounting portion of a lead frame for a flat package type semiconductor device.
After mounting, transfer molding (180 ℃, 30k
g / cm2, 3 min). This was used as a test semiconductor device.

As shown in (Table 1), the epoxidized product of the 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. It has a high level of moisture resistance and mechanical properties and can be said to have balanced performance. 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 are inferior in each performance. Especially, as in Comparative Examples 1 and 2, the heat resistance and the moisture resistance are high. Is often obtained at the expense of the other.

In addition, Table 2 shows the physical properties of the cured product obtained by using the inorganic filler and other additives. Examples 5 to 8 and Comparative Examples 4 to 6 correspond to Examples 1 to 4 and Comparative Examples 1 to 3 in (Table 1), respectively. From this (Table 2), an inorganic filler should be added. It can be seen that the water resistance and mechanical properties are significantly improved. In Comparative Example 7, it can be seen that 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, the effect is insignificant. From these facts, the present invention makes it possible to obtain an epoxy resin composition which is excellent in heat resistance, moisture resistance, mechanical strength and the like and has 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 (Yuka Kagaku Kagaku) ・ EOCN-102S; o-cresol novolac type epoxy resin (Nippon Kayaku) ・ BRG # 558; Phenol novolac resin (Showa High Polymer) ・ Sumikyua S; 4,4'-diaminodiphenyl sulfone (Sumitomo Chemical Co., Ltd.)-C11Z; 2-undecyl imidazole (Shikoku Fine Chemicals Co., Ltd.)-Inorganic filler; spherical fused silica (Harimic S-CO,
Micron Co., Ltd. 50 parts by weight and amorphous fused silica (Hugh Rex RD)
-8 Mixture with 50 parts by weight of Tatsumori Co., Ltd.-Silane coupling agent; (SZ-6083, Toray Dow Corning Silicone Co., Ltd.)-Glass transition temperature; TMA method (Shimadzu TMA-System DT-30)・ Bending strength, elastic modulus; JIS K-6911 ・ Boiling water absorption rate: Measure the weight increase after boiling for 2 hours in boiling water at 100 ° C.・ V. P. S test; test semiconductor device at 65 ° C, 9
After leaving it in a 5% constant temperature and humidity chamber for 168 hours, immediately
Fronato liquid at 5 ° C (Sumitomo 3M, FC-
70), and the number of semiconductor devices in which the package resin had cracks was counted. The test value is shown by a fraction, the numerator is the number of semiconductor devices in which a crack has occurred, and the denominator is the number of semiconductor devices used in the test.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

The epoxy resin composition provided by the present invention has excellent heat resistance and moisture resistance, and further has excellent mechanical properties, adhesiveness, crack resistance and workability, and therefore is extremely useful as various matrix resins. It is highly useful. This provides an ideal material particularly in the field of semiconductor encapsulants, which has been limited in use because of its advantages and disadvantages in performance, and its contribution is great.

Claims (2)

[Claims] 1. An epoxy resin composition containing an epoxy resin and a curing agent, wherein (A) the epoxy resin component is represented by the general formula (I) (However, in the formula, n represents an integer of 0 to 100.) The naphthol aralkyl resin represented by the formula (II) (Chemical Formula 2) An epoxy resin obtained by reacting epichlorohydrin represented by: (B) as a curing agent, (a) general formula (I) (chemical formula 3) (However, n represents an integer of 0 to 100 in the formula), and (b) the general formula (III) (Chemical Formula 4) (However, in the formula, 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 general formula Formula (IV) (Chemical Formula 5) (However, m represents an integer of 0 to 100 in the formula),
The obtained epoxy resin composition. 2. An epoxy resin composition containing an epoxy resin, a curing agent and an inorganic filler, wherein the epoxy resin component (A) is represented by the general formula (I) (Chemical Formula 6): (However, in the formula, n represents an integer of 0 to 100.) The naphthol aralkyl resin represented by the formula (II) (Chemical formula 7) An epoxy resin obtained by reacting epichlorohydrin represented by: (B) As a curing agent, (a) General formula (I) (Chemical formula 8) (Wherein n represents an integer from 0 to 100), and (b) the general formula (III) (Chemical Formula 9) (However, in the formula, 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 general formula Formula (IV) (Chemical Formula 10) (However, in the formula, m represents an integer of 0 to 100.) An epoxy resin composition obtained by using a phenol aralkyl resin represented by the formula (C) and an inorganic filler.