JPH05140261A - Epoxy resin mixture, epoxy resin composition and cured product thereof - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin compsn. excellent in workability because of its low resin viscosity, and capable of giving a cured product excellent in humidity resistance, heat resistance and adhesion by blending a specific polyfunctional epoxy resin with a specific bifunctional epoxy resin. CONSTITUTION:The objective epoxy resin compsn. comprises a polyfunctional epoxy resin (1) of formula I and a bifunctional epoxy resin (2) of formula II at a wt. ratio of (50-95):(50-5). In the formula I, Ep is a group of formula III; R1 is 1-4C alkyl, aryl or a halogen atom; R2 is H, 1-4C alkyl or a halogen atom; and (n) is 0 to 5. Esp. preferable curing agents usable in producing this epoxy resin compsn. include phenolic novolaks and cresolic novolaks. Any curing promoter used in common epoxy resins can be used for smoothly carrying out the curing reaction.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition which gives a cured product having a low resin viscosity, excellent workability, and excellent moisture resistance, heat resistance, adhesiveness, etc., and particularly for sealing or laminating electronic parts. TECHNICAL FIELD The present invention relates to an epoxy resin composition useful as a material for a resin, a cured product thereof, and an epoxy resin mixture useful as a component of the epoxy resin composition.

[0002]

2. Description of the Related Art Generally, epoxy resins are widely used as adhesives, paints, electrical insulating materials and the like because they are excellent in heat resistance, adhesiveness, chemical resistance, electrical characteristics and mechanical characteristics. Above all, in the field of electric / electronic parts, conventional epoxy resins are often used as electric insulating materials.

However, ICs accompanying the development of electronic materials in recent years
Due to the higher density and higher integration, the sealing agent is required to have higher heat resistance and lower water absorption. Especially under the harsh conditions of solder bath immersion in high-density mounting, the requirements for high heat resistance, low water absorption, and high adhesiveness are becoming stronger for cured products.

When a cresol-novolak type epoxy resin which is generally used as an epoxy resin is used, a cured product which can withstand a harsh condition such as immersion in a solder bath in heat resistance without problems has not been obtained. Further, it has been proposed to provide a cured product having heat resistance.
The epoxy compound of polyphenol described in Japanese Patent No. 264622 is inferior to a cured product of a cresol novolac type epoxy resin in terms of water absorption.

Further, Japanese Unexamined Patent Publication (Kokai) No. 62-20206 proposes polyglycidyl ether which is a condensate of 1-naphthol and formaldehyde, but this one improves the heat resistance of the cured product. However, there is a drawback that workability is impaired due to increase in softening point or increase in melt viscosity.

[0006]

DISCLOSURE OF THE INVENTION The present invention is excellent in high heat resistance, low water absorption, high adhesiveness, etc. that can withstand even more severe conditions while lowering the viscosity of the resin and improving workability. The present invention provides an epoxy resin composition giving a cured product, a cured product thereof, and an epoxy resin mixture useful as a component of the epoxy resin composition.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that when an epoxy resin mixture containing a combination of specific compounds is used, the cured product has heat resistance and water absorption. The inventors have found that the adhesiveness is significantly improved, the resin viscosity is low, and the workability is good, and the present invention has been completed.

That is, the present invention is based on the formula (1) (1)

[0009]

[Chemical 4]

(In the equation, Ep is the equation (E)

[0011]

[Chemical 5]

And R ₁ independently has 1 to 4 carbon atoms.
, An alkyl group, an aryl group or a halogen atom, R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and n is a value of 0 to 5). Polyfunctional epoxy resin and formula (2)

[0013]

[Chemical 6]

An epoxy resin mixture containing a bifunctional epoxy resin represented by: and the ratio of the polyfunctional epoxy resin (1) and the bifunctional epoxy resin (2) is 50 to 95:50 to 5 by weight.

(2) The epoxy resin mixture of (1) above,
An epoxy resin composition containing a curing agent and a curing accelerator,
(3) A cured product of the epoxy resin composition according to (2) above.

The present invention will be described in detail below. Formula (1)
In R ₁ of, as the alkyl group having 1 to 4 carbon atoms,
Examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group, and a methyl group and a t-butyl group are particularly preferable. Examples of the aryl group include a phenyl group, a 4-methylphenyl group and a 2-methylphenyl group, and a phenyl group is particularly preferable. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom, but a chlorine atom and a bromine atom are particularly preferable.

Examples of the alkyl group having 1 to 4 carbon atoms in R ₂ of the formula (1) include a methyl group, an ethyl group and a t-butyl group. Examples of the halogen atom include chlorine atom, fluorine atom, bromine atom, iodine atom and the like. Preferred R ₂ is a hydrogen atom, a methyl group, a t-butyl group,
A bromine atom etc. are mentioned. The polyfunctional epoxy resin of the formula (1) can be produced, for example, as follows. That is, equation (3)

[0018]

[Chemical 7]

(Wherein R ₁ has the same meaning as described above)
A dimethylol compound represented by the formula (4)

[0020]

[Chemical 8]

(Wherein R ₂ has the same meaning as described above)
It can be produced by dehydration condensation with a naphthol represented by the formula (3) in the presence of an acid catalyst and further epoxidation.

The dimethylol compound represented by the formula (3) is 4,6-dimethylol-2-methylphenol.
2,6-dimethylol-4-methylphenol,
4,6-Dimethyl-2-ethylphenol, 2,6
-Dimethylol-4-n-propylphenol, 4,6
-Dimethyl-2-t-butylphenol, 2,6-
Dimethyl-4-phenylphenol or 2,6
Examples include, but are not limited to, dimethylroll-4-chlorophenol, 2,6-dimethylol-4-bromophenol and the like.

The naphthols represented by the formula (4) include 1-naphthol, 2-naphthol and 1-methyl-2.
-Naphthol, 2-methyl-1-naphthol and the like. As the acid catalyst, hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, oxalic acid or the like can be used, and the acid catalyst is 0.1 to 30% by weight of the dimethylol compound represented by the formula (3). Is preferred. The naphthols are 2 to 15 relative to the dimethylol compound represented by the formula (3).
It is preferable to use a molar amount.

The reaction can be carried out without solvent or in a solvent such as benzene, toluene or methyl isobutyl ketone. The reaction temperature is preferably in the range of 20 to 150 ° C.
After completion of the reaction, the catalyst used is removed by washing with water, and the solvent and excess naphthols are distilled off under reduced pressure,
A dehydration condensate is obtained. Next, the dehydration condensate thus obtained was added with the formula (5)

[0025]

[Chemical 9]

By reacting an epihalohydrin compound represented by the formula (wherein X represents a halogen atom) in the presence of a basic compound, a polyfunctional epoxy resin represented by the formula (1) can be easily obtained. ..

In the formula (5), the halogen atom represented by X includes Cl, Br, I and the like, and the compound of the formula (5) is specifically epichlorohydrin, epibromhydrin, Examples include epiyodohydrin and the like, and a mixture thereof can be used, but epichlorohydrin is preferably used industrially.

The reaction between the dehydrated condensate and the epihalohydrin compound can be carried out by a known method. For example, the dehydration condensate and an epihalohydrin compound in an excess molar amount relative to the hydroxyl equivalent thereof are treated with a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or triethylammonium chloride, or sodium hydroxide or potassium hydroxide. When a quaternary ammonium salt or the like is used by reacting in the presence of an alkali metal hydroxide or the like, the reaction stops at the stage of the ring-opening addition reaction, so the above alkali metal hydroxide is added to close the ring. ..

When the alkali metal hydroxide is added and reacted from the beginning, the ring-opening addition reaction and the ring-closing reaction are carried out at once. The ratio of the epirohalohydrin compound used is usually 1 to 50 mol, preferably 3 to 15 mol, per 1 equivalent of the hydroxyl group of the dehydrated condensate. At this time, alcohols such as methanol, in order to smoothly carry out the reaction,
Alternatively, an aprotic polar solvent such as acetone or dimethyl sulfoxide, dimethyl sulfone, or dimethylformamide can be used, and it is particularly preferable to use dimethyl sulfoxide.

The alkali metal hydroxide can be added in the form of an aqueous solution or in the form of a solid, and the amount thereof is usually 0.8 to 1 with respect to 1 equivalent of the hydroxyl group of the dehydration condensation product.
5 moles, preferably 0.9 to 1.3 moles,
When a quaternary ammonium salt is used, its amount is usually 0.001 to 1 equivalent of the hydroxyl group of the dehydration condensation product.
The amount is 1 mol, preferably 0.005 to 0.5 mol.

The reaction temperature is usually 30 to 130 ° C, preferably 40 to 120 ° C. It is also possible to proceed the reaction while removing the water generated in the reaction from the reaction system. After the completion of the reaction, the salt produced as a by-product is removed by washing with water, filtration and the like, and the excess epihalohydrin compound is distilled off to obtain the polyfunctional epoxy resin represented by the formula (1).

In the polyfunctional epoxy resin represented by the formula (1), the preferable value of n is 0 to 3, and the formula (6)

[0033]

[Chemical 10]

It is preferable that the trinuclear epoxy compound represented by the formula (wherein R ₁ and R ₂ have the same meanings as described above) is contained in an amount of 30% by weight or more, and particularly preferably 35% by weight or more.

Examples of the bifunctional epoxy resin represented by the formula (2) include bisphenol F type epoxy resin (for example, RE-304S manufactured by Nippon Kayaku Co., Ltd.). The epoxy resin mixture of the present invention can be obtained by mixing the polyfunctional epoxy resin of the formula (1) and the bifunctional epoxy resin of the formula (2). The mixing ratio of the polyfunctional epoxy resin of the formula (1) and the bifunctional epoxy resin of the formula (2) is 50 by weight.
~ 95: 50-5, but especially 60-90: 40-10
(Weight ratio) is preferable.

The epoxy resin composition of the present invention will be described below. The epoxy resin composition of the present invention can be obtained by uniformly mixing the respective components. At this time, the polyfunctional epoxy resin of the formula (1) and the difunctional epoxy resin of the formula (2) are preliminarily mixed with each other. May be mixed to form an epoxy resin mixture and then mixed with other components, or both may not be mixed in advance and mixed together with other components.

Other functional epoxy resin of formula (1) and formula (2)
The proportion of the bifunctional epoxy resin used is as described above. If the proportion of the polyfunctional epoxy resin of the formula (1) is too large, the viscosity of the epoxy resin composition will be high and the workability will be poor. The heat resistance of the cured product decreases and the moisture resistance also deteriorates.

As the curing agent used in the epoxy resin composition of the present invention, various ones can be used and are not particularly limited. For example, polyamine curing agents such as aliphatic polyamines, aromatic polyamines and polyamide polyamines, acid anhydride curing agents such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, and novolak resins such as phenol novolac and cresol novolac. Examples thereof include hardeners, Lewis acids such as boron trifluoride or salts thereof, dicyandiamide, and the like.

Particularly preferred curing agents include novolac resins such as phenol novolac and cresol novolac. The amount of the curing agent used is preferably 0.3 to 2 equivalents, and more preferably 0.5 to 1.5 equivalents, relative to 1 equivalent of epoxy groups of all epoxy resins.

As the curing accelerator for smoothly carrying out the curing reaction, any of those used for ordinary epoxy resins can be used, for example, 2-methylimidazole.
, 2-ethyl-4-methylimidazole, 2-phenylimidazole and other imidazoles, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl)
Tertiary amines such as phenol, phosphines such as triphenylphosphine and salts thereof, 1,8-diaza-bicyclo (5,4,0) undecene-7 (DBU) and salts thereof, aluminum compounds, titanium A compound etc. are mentioned.

The amount of the curing accelerator used is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the total amount of the epoxy resin used.
If the amount of the curing accelerator is too large, the time until gelation may be short, which may cause a problem in workability, and if it is too small, a problem of insufficient curing may occur.

To the epoxy resin composition of the present invention, a flame retardant, a surface treatment agent such as an inorganic or organic filler or a silane coupling agent, a release agent, a compounding agent such as a pigment is added as an optional component. be able to. The epoxy resin composition of the present invention is prepared by uniformly mixing and kneading the respective components by means of a mixer, a roll, a kneader or the like.

A cured product is obtained by curing the epoxy resin composition of the present invention by a conventional method. For example, it can be cured by pre-curing and post-curing. Pre-curing is possible at the softening temperature of the epoxy resin composition or higher,
Usually, it is carried out at a temperature of 150 to 180 ° C. The curing time varies greatly depending on the amount, type and curing temperature of the curing accelerator, but it is usually performed in a transfer molding machine in the range of 30 to 300 seconds. The obtained pre-cured product does not have sufficient heat resistance in practical use because the curing is still insufficient, and it is usually 160 to 1
Post-cure at 80 ° C. for 4-8 hours.

The epoxy resin composition of the present invention has a low resin viscosity and is excellent in workability, and the cured product thereof is excellent in moisture resistance, heat resistance and adhesiveness, so that it is used as a material for sealing or laminating electronic parts. It is suitable.

[0045]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples. Synthesis example 1 162 g (1.5 mol) of para-cresol, 90 g (3 mol) of paraformaldehyde and 100 ml of water were thermometered.
A 1 liter flask equipped with a cooling tube, a dropping funnel and a stirrer was charged, and while stirring under a nitrogen atmosphere, 120 g of a 15% aqueous sodium hydroxide solution (0.45 mol as sodium hydroxide) was heated at room temperature. Carefully, the liquid temperature was slowly added dropwise so as not to exceed 50 ° C. Then, the mixture was heated to 50 ° C. in a hot water bath and reacted for 10 hours. After completion of the reaction, 300 ml of water was added, the mixture was cooled to room temperature, neutralized with 10% hydrochloric acid aqueous solution while paying attention to heat generation, and the precipitated crystals were collected by filtration. The filtrate was washed with water until neutral and the crystals were dried under reduced pressure (10 mmHg) at 50 ° C. to give white crystals (A1) 20
2 g was obtained.

168 g (1.0 mol) of the white crystals (A1) and 576 g (4.0 mol) of 1-naphthol were placed in a glass container equipped with a thermometer and a stirrer, and 1500 ml of methyl isobutyl ketone was used as a solvent. While stirring at room temperature under a nitrogen atmosphere, 1.7 g of p-toluenesulfonic acid was gradually added thereto while paying attention to heat generation so that the liquid temperature did not exceed 50 ° C. After the addition, the mixture was heated to 50 ° C in a hot water bath and reacted for 2 hours, and then methylisobutylketone 500 was added.
After adding ml, the mixture was transferred to a separating funnel and washed with water until the washing water showed neutrality. After washing with water, unreacted raw materials and solvent were removed from the organic layer under reduced pressure to obtain 368 g of a pale yellow viscous substance (A2). The softening temperature (JIS K2425 ring and ball method measurement) of the product (A2) is 117 ° C., and the hydroxyl group equivalent (g / mol) is 13.
It was 7.

137 g of the product (A2) was transferred to a 1 liter reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a water separator for production, and then 460 g of epichlorohydrin was charged and the atmosphere was replaced with nitrogen. 85 g of 48% aqueous sodium hydroxide solution was added dropwise over 5 hours. Reaction temperature 6 during dropping
The produced water and the water of the sodium hydroxide aqueous solution were continuously removed from the reaction system by azeotropic distillation with epichlorohydrin at 0 ° C. under a reduced pressure of 100 to 150 mmHg, and epichlorohydrin was returned to the system. Then, excess unreacted epichlorohydrin was recovered under reduced pressure, 500 ml of methyl isobutyl ketone was added, and the mixture was washed with 100 ml of water until the aqueous layer became neutral. Methyl isobutyl ketone was removed from the methyl isobutyl ketone layer under reduced pressure to give a pale yellow viscous substance (A3)
172 g were obtained. The product (A3) has a softening temperature (JIS
K2425 ring and ball method measurement) 89 ° C, epoxy equivalent (g /
mol) 215 of the epoxy resin of the formula (1) [the formula (1)
In the above, R ₁ represents a methyl group bonded to the para position with respect to Ep, R ₂ represents a hydrogen atom, and the average value of n is 1.14]. Further, the product (A3) contained 37% by weight of the trinuclear epoxy compound corresponding to the formula (6).

Synthesis Example 2 222 g (1.5 mol) of 4-t-butylphenol, 90 g (3 mol) of paraformaldehyde and 100 ml of water.
Was charged into a 1-liter flask equipped with a thermometer, a cooling tube, a dropping funnel and a stirrer, and 120 g of a 15% sodium hydroxide aqueous solution at room temperature while stirring under a nitrogen atmosphere.
(0.45 mol of sodium hydroxide) was slowly added dropwise while paying attention to heat generation so that the liquid temperature did not exceed 50 ° C. Then, the mixture was heated to 50 ° C. in a hot water bath and reacted for 10 hours. After completion of the reaction, add 300 ml of water and cool to room temperature.
It was neutralized with 10% aqueous hydrochloric acid while paying attention to the heat generation. Chloroform (500 ml) was added for extraction, the oil layer was separated, and this was separated with a water-methanol solution (water: methanol-8).
It was washed with 0:20 (wt%)), and anhydrous sodium sulfate was added to dry it. Chloroform was removed under reduced pressure to obtain 256 g of yellow-green sticky liquid (B1).

254 g of the liquid (B1) thus obtained and 576 g (4.0 mol) of 1-naphthol were placed in a glass container equipped with a thermometer and a stirrer, 1500 ml of methyl isobutyl ketone was added as a solvent, and the mixture was placed under a nitrogen atmosphere. While stirring at room temperature, 1.7 g of p-toluenesulfonic acid was gradually added thereto while paying attention to heat generation so that the liquid temperature did not exceed 50 ° C. After the addition, the mixture was heated to 50 ° C. in a hot water bath and reacted for 2 hours. Then, 500 ml of methyl isobutyl ketone was added and the mixture was transferred to a separating funnel and washed with water until the washing water showed neutrality. After washing with water, unreacted raw materials and solvent were removed from the organic layer under reduced pressure to obtain 414 g of a product (B2). Product (B
The softening temperature of 2) (measured by JIS K2425 ring and ball method) is 1
The hydroxyl equivalent (g / mol) was 151 at 21 degreeC.

In Synthesis Example 1, 151 g of the above product (B2) was used in place of the product (A2), and epoxidation was carried out in the same manner as in the other to obtain 186 g of the product (B3). The product (B3) has a softening temperature (JIS K2425).
Ring and ball method measurement) 89 ° C, epoxy equivalent (g / mol) 24
An epoxy resin of the formula (1) of 0 [in the formula (1), R ₁
Is a t-butyl group bound to the para position with respect to Ep, R ₂
Represents a hydrogen atom, and the average value of n is 1.06]. Further, the product (B3) contained 35% by weight of the trinuclear epoxy compound corresponding to the formula (6).

Synthesis Example 3 255 g (1.5 mol) of 4-phenylphenol, 90 g (3 mol) of paraformaldehyde and 100 ml of water were added to a 1 liter flask equipped with a thermometer, a condenser, a dropping funnel and a stirrer. And 15 g of a 15% aqueous sodium hydroxide solution at room temperature with stirring under a nitrogen atmosphere.
(0.45 mol of sodium hydroxide) was slowly added dropwise while paying attention to heat generation so that the liquid temperature did not exceed 50 ° C. Then, the mixture was heated to 50 ° C. in a hot water bath and reacted for 20 hours. After completion of the reaction, 300 ml of water was added, the mixture was cooled to room temperature, and neutralized with 10% hydrochloric acid aqueous solution while paying attention to heat generation.
Chloroform (500 ml) was added for extraction, the oil layer was separated, and this was separated with a water-methanol solution (water: methanol = 8).
It was washed with 0:20 (wt%)), and anhydrous sodium sulfate was added to dry it. Chloroform was removed under reduced pressure to obtain 305 g of a yellow viscous liquid (Cl).

The viscous liquid (C
l) 295 g and 1-naphthol 576 g (4.0 mol) were charged into a glass container equipped with a thermometer and a stirrer,
1500 ml of methyl isobutyl ketone was added as a solvent, and 1.7 g of p-toluenesulfonic acid was added to this while stirring at room temperature under a nitrogen atmosphere.
Was added gradually so as not to exceed. 50 on the hot water after addition
After warming to 0 ° C. and reacting for 2 hours, 500 ml of methyl isobutyl ketone was added and the mixture was transferred to a separating funnel and washed with water until the washing water showed neutrality. After washing with water, unreacted raw materials and solvent were removed from the organic layer under reduced pressure to obtain 415 g of the product (C2).
Obtained. The softening temperature (JIS K2425 ring and ball method measurement) of the product (C2) is 128 ° C., and the hydroxyl group equivalent (g / mol) is 1.
It was 59.

In Synthesis Example 1, 159 g of the above product (C2) was used in place of the product (A2), and epoxidation was performed in the same manner as in the other, to obtain 194 g of the product (C3). The product (C3) has a softening temperature (JIS K2425).
Ring and ball method measurement) 95 ° C., epoxy equivalent (g / mol) 23
Epoxy resin of the formula (1) of 3 [in the formula (1), R ₁ is a phenyl group bonded to the para position with respect to Ep, R ₂ is a hydrogen atom, and the average value of n is 0.97] Met. The product (C3) contained 42% by weight of the trinuclear epoxy compound corresponding to the formula (6).

Synthesis Example 4 193 g (1.5 mol) of 4-chlorophenol, 90 g (3 mol) of paraformaldehyde and 100 ml of water were placed in a 1 liter flask equipped with a thermometer, a condenser, a dropping funnel and a stirrer. Charge, stirring under a nitrogen atmosphere,
At room temperature, 120 g of a 15% aqueous sodium hydroxide solution (0.45 mol of sodium hydroxide) was slowly added dropwise while paying attention to heat generation so that the liquid temperature did not exceed 50 ° C.
Then, the mixture was heated to 50 ° C. in a hot water bath and reacted for 10 hours.
After completion of the reaction, 300 ml of water was added, the mixture was cooled to room temperature, and neutralized with 10% hydrochloric acid aqueous solution while paying attention to heat generation. afterwards,
The deposited crystals were collected by filtration, washed until the pH of the filtrate became 6 to 7, and dried under reduced pressure (10 mmHg) at 50 ° C to obtain 226 g of white crystals (D1).

White crystals (D1) 189 thus obtained
and 576 g (4.0 mol) of 1-naphthol were charged in a glass container equipped with a thermometer and a stirrer, 1500 ml of methyl isobutyl ketone was added as a solvent, and p was added to this while stirring at room temperature under a nitrogen atmosphere. -Toluenesulfonic acid (1.7 g) Gradually taking care not to generate heat, the solution temperature was gradually added so as not to exceed 50 ° C. After the addition, warm to 50 ° C on a hot water bath 2
After reacting for an hour, 500 ml of methyl isobutyl ketone
Was added, and the mixture was transferred to a separating funnel and washed with water until the washing water showed neutrality. After washing with water, unreacted raw materials and solvent were removed from the organic layer under reduced pressure to obtain 388 g of a product (D2). Softening temperature of product (D2) (measured by JIS-K2425 ring and ball method)
Was 118 ° C. and the hydroxyl group equivalent (g / mol) was 142.

In Synthesis Example 1, 142 g of the product (D2) was used in place of the product (A2), and epoxidation was performed in the same manner as in the other to obtain 176 g of the product (D3). The product (D3) has a softening temperature (JIS-K2425).
Ring and ball method measurement) 95 ° C., epoxy equivalent (g / mol) 23
An epoxy resin of the formula (1) of 0 [in the formula (1), R ₁
Is a chlorine atom bonded to the para position with respect to Ep, R ₂ is a hydrogen atom, and the average value of n is 1.03]. Further, the product (D3) contained 37% by weight of the trinuclear epoxy compound corresponding to the formula (6).

Examples 1-5. In the case shown in Table 1, the products (A3) to (D3) and RE-304S [methylene group in the formula (2) bound to the glycidyloxy group in the para position] were mixed to form an epoxy resin mixture. Obtained. The solution viscosity and epoxy equivalent of this mixture are shown in Table 1. The melt viscosity of the product (A3) itself is 10.5 poise (150
℃).

Examples 6 to 10 and Comparative Examples 1 to 2 The respective components were blended in the proportions shown in Table 2, and 30 to 60 were added.
Kneading was carried out uniformly with a roll kneader heated to ℃. After that, the mixture was cooled, pulverized with a pulverizer, and tabletted with a tablet machine to obtain a molding material. This tablet was preheated with a high-frequency preheater and was pressed and molded under the condition of 150 ° C. for 200 seconds using a transfer molding machine, which was further heated at 160 ° C. for 2 hours and 180 ° C. for 6 hours. Post curing was carried out using an oven to obtain a cured molded product test piece. Table 2 shows the results of measuring heat resistance (glass transition temperature) and moisture absorption rate using this test piece.

Further, the respective components were blended in the proportions shown in Table 2,
This was kneaded uniformly with a roll kneader heated to 30 to 60 ° C. Thereafter, the product that was cooled and pulverized with a pulverizer was heated and cured at 150 ° C. for 10 minutes under an adhesive pressure of 1 kgf / cm ² . This was further post-cured with an open under conditions of 160 ° C. for 2 hours and 180 ° C. for 6 hours to obtain a cured molded product test piece. The results of measuring the adhesive strength using this test piece are shown in Table 2.

The measurement conditions are as follows. (Heat resistance) Thermomechanical measuring device (TM
A); Vacuum Riko Co., Ltd. TM-7000 temperature rising rate; 2 ° C /
It was measured at min. (Hygroscopicity) The rate of weight increase after standing for 24 hours in an atmosphere of 85 ° C. and 85% was determined. The test piece is JIS-K691.
1 is the dimension shown. (Adhesive strength) The tensile adhesive shear strength was measured based on the JIS-K6850 test.

Table 1 Example 1 2 3 4 5 Product (A3) (wt%) 90 70 Product (B3) (wt%) 90 Product (C3) (wt%) 70 Product (D3) (wt %) 80 RE-304S (wt%) 10 30 10 30 20 Melt viscosity (poise / 150 ° C) 3.3 0.7 3.0 0.9 1.5 Epoxy equivalent (g / mol) 205 199 231 208 213

Table 2 (in Table 2, the numbers of each component indicate parts by weight) Example Comparative Example 6 7 8 9 10 1 2 Mixture 150 of Example 1 Mixture 150 of Example 2 Mixture 150 of Example 3 Mixture of Example 4 150 Mixture of Example 5 150 Product (A3) 150 EOCN-1020 * 1 150 Phenol novolac * 2 77.6 79.9 68.8 76.4 74.6 74.0 79.5 Curing accelerator * 3 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Glass transition temperature (℃) 162 159 161 158 160 165 153 Moisture absorption rate (wt%) 0.63 0.65 0.62 0.67 0.64 0.60 0.85 Adhesive strength * 4 ○ ◎ ○ ◎ ◎ △ ○ * 1 Nippon Kayaku Co., Ltd. 0-cresol novolac epoxy Resin, epoxy equivalent 200g / mol, melt viscosity 3.2 poise (150 ° C) * 2 Nippon Kayaku Co., Ltd., hydroxyl equivalent 106, softening temperature 83 ° C * 3 triphenylphosphine * 4 tensile adhesive shear strength, 40kg / cm ² or less △, the ^{40~60kg / cm 2 ○, 60kg /} cm 2 The above is marked with ◎.

[0063]

The epoxy resin composition of the present invention has a low resin viscosity and is excellent in workability, and its cured product has moisture resistance, heat resistance,
It has excellent adhesive strength and is extremely useful in industry.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location H01L 23/31

Claims (3)

[Claims] 1. A formula (1): (Where Ep is the formula (E) , R ₁ is independently an alkyl group having 1 to 4 carbon atoms, an aryl group or a halogen atom, and R ₂ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, n represents a value of 0 to 5) and a polyfunctional epoxy resin represented by the formula (2) An epoxy resin mixture containing a bifunctional epoxy resin represented by, and the weight ratio of the polyfunctional epoxy resin (1) to the bifunctional epoxy resin (2) is 50 to 95:50 to 5. 2. An epoxy resin composition containing the epoxy resin mixture according to claim 1, a curing agent and a curing accelerator. 3. A cured product of the epoxy resin composition according to claim 2.