JPH06263839A - Production of epoxy resin, and epoxy resin composition and semiconductor-sealing material - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin having improved mechanical and electrical characteristics, moisture resistance. etc., by reacting an unsatd. cyclic hydrocarbon compd. with a hydroxylated fused polycyclic arom. compd. in the presence of an acid catalyst and reacting the resulting product with an epihalohydrin. CONSTITUTION:An epoxy resin is obtd. by reacting 1mol of an unsatd. cyclic hydrocarbon compd. with 0.8-12mol of a hydroxylated fused polycyclic arom compd. in the presence of an acid catalyst at 20-160 deg.C for 30min to 7hr to give a reactional product having a mol.wt. of 268-6,000 and reacting the product with an epihalohydrin in an amt. of 2-20 equivalents based on 1 equivalent of hydroxyl groups of the product in the presence of an aq. soln. of an alkali metal hydroxide at 40-120 deg.C. An epoxy resin compsn. is prepd. by compounding This epoxy resin with a curative and a cure accelerator. A semiconductor- sealing material is obtd. by compounding the resin with 50-90wt.% inorg. filler.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an epoxy resin useful as an epoxy resin for encapsulating materials and laminates, and further, mechanical properties, electrical properties, moisture resistance and heat resistance of which epoxy resin is an essential component. The present invention relates to an epoxy resin composition having excellent impact resistance and the like.

[0002]

2. Description of the Related Art Recently, science and technology have been rapidly advancing mainly in the electronics industry, and in particular, the semiconductor-related technology is advancing remarkably. In semiconductors, wiring has become finer and chips have been made thinner with the increase in the degree of integration of memories. With the improvement in the degree of integration, the mounting method is also shifting from through-hole mounting to surface mounting.

In the automated surface mounting line, the semiconductor package undergoes a rapid temperature change during soldering of the lead wires, which causes cracks in the resin molding portion and deterioration of the interface between the lead wire resins. As a result, there is a problem that the moisture resistance is lowered.

Epoxy resin is mainly used in the semiconductor resin composition, and orthocresol novolac type epoxy resin (ECN) is generally used as the epoxy resin. However, when the above-mentioned ECN is used, the hygroscopicity of the semiconductor package is strong, and as a result, there is a problem that the generation of cracks is unavoidable during immersion in the solder bath.

Therefore, conventionally, in order to improve the moisture resistance of the semiconductor sealing resin, for example, JP-A-61-293219 has been proposed.
The publication discloses an epoxidized product of a dicyclopentadiene-modified phenol resin (hereinafter abbreviated as "DCP resin").

[0006]

However, although the epoxidized product of the DCP resin has excellent moisture resistance, it cannot obtain sufficiently satisfactory heat resistance because of its low crosslink density.

The problem to be solved by the present invention is to provide an epoxy resin having excellent properties in both heat resistance and moisture resistance, and an epoxy resin composition having excellent heat resistance and moisture resistance when made into a cured product. To provide things.

Another object of the present invention is to provide a semiconductor encapsulating material which does not cause cracks and lead interface deterioration due to rapid temperature changes.

[0009]

Means for Solving the Problems As a result of intensive studies by the present inventors, an unsaturated cyclic hydrocarbon compound is reacted with a hydroxyl group-containing condensed polycyclic aromatic compound in the presence of an acid catalyst, and then this reaction product is formed. It was found that an epoxy resin having both excellent heat resistance and moisture resistance can be obtained by reacting a product with epihalohydrin, and the present invention has been completed.

That is, the present invention is characterized in that an unsaturated cyclic hydrocarbon compound is reacted with a hydroxyl group-containing condensed polycyclic aromatic compound under an acid catalyst, and then the obtained reaction product is reacted with epihalohydrin. Method for producing epoxy resin, epoxy resin, which is a reaction product of polyphenols having a structure in which a cycloaliphatic hydrocarbon group is bonded to a hydroxyl group-containing condensed polycyclic compound as a knot group, and an epihalohydrin, a curing agent, and a curing agent The present invention relates to an epoxy resin composition containing an accelerator as an essential component, and a semiconductor encapsulating material containing an inorganic filler further added to the epoxy resin composition.

The unsaturated cyclic hydrocarbon compound used in the present invention is not particularly limited, but among them, those having a cyclohexane ring or a cyclohexene ring in its skeleton are preferable from the viewpoint of excellent effect of improving the moisture resistance of the cured product. . Among these, this effect is particularly remarkable,
Specifically, 4-vinylcyclohexene, 5-vinylnorbona-2-ene, 3a, 4,7,7a-tetrahydroindene, dicyclopentadiene, α-pinene, β-pinene and limonene are preferable. These compounds may be used alone or in combination of two or more kinds. Further, among these, dicyclopentadiene is preferable because it can further improve the moisture resistance of the cured product.

The hydroxyl group-containing condensed polycyclic aromatic compound used in the present invention is a compound having a hydroxyl group in the molecular skeleton and a plurality of benzene rings sharing a π electron cloud, and is particularly limited. However, α-naphthol, β-naphthol, 1,1-bis (hydroxynaphthyl) methane, dihydroxynaphthalene and the like are preferably mentioned because they have a remarkable effect of improving the heat resistance of the cured product. Dihydroxynaphthalene is 1,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,
Any isomer of 6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene can be used. These compounds may be used alone or in combination of two or more kinds.

The charging ratio when the unsaturated cyclic hydrocarbon compound is reacted with the hydroxyl group-containing condensed polycyclic aromatic compound is determined by the amount of the hydroxyl group-containing condensed polycyclic aromatic compound charged. By adjusting the amount of the cyclic hydrocarbon compound to be 0.8 to 12 times the molar equivalent, the molecular weight of the obtained polyphenols can be adjusted to an appropriate range, and the melt viscosity of the finally obtained epoxy resin can be reduced. It is preferable from the point. Above all, a range of 1 to 5 times the molar equivalent is preferable from the viewpoint that this effect becomes remarkable.

In the present invention, in addition to the above unsaturated cyclic hydrocarbon compound and the hydroxyl group-containing condensed polycyclic aromatic compound, phenol, cresol or the like may be used in combination.

As the acid catalyst used in the present invention, boron trifluoride, boron trifluoride ether, boron trifluoride complex such as phenol or alcohol complex, aluminum trichloride, aluminum compound such as diethylaluminum monochloride. , Iron chloride, titanium tetrachloride, sulfuric acid, hydrogen fluoride, trifluoromethanesulfonic acid, p-toluenesulfonic acid, zeolite catalyst, various metals such as magnesium, calcium, strontium, barium, boron, aluminum, gallium, selenium, platinum, A solid acid composed of rhenium, nickel, cobalt, iron, copper, germanium, rhodium, osmium, iridium, molybdenum, tungsten, silver and a mixture thereof and a solid acid composed of zeolite and a mixture thereof and the like can be preferably used. In particular, from the viewpoint of activity and easy removal of catalyst, boron trifluoride, boron trifluoride / ether complex, boron trifluoride / phenol complex, boron trifluoride / water complex, boron trifluoride / alcohol complex, Boron fluoride / amine complex is preferable, and boron trifluoride and boron trifluoride / phenol complex are most preferable.

Although the amount of the acid catalyst used is not particularly limited, it is usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the unsaturated cyclic hydrocarbon compound, but an appropriate reaction rate is obtained. Therefore, 0.5 to 10 parts by weight is more preferable from the viewpoint of easy reaction control and easy removal of the catalyst after completion of the reaction.

In the reaction of the above unsaturated cyclic hydrocarbon compound and the hydroxyl group-containing condensed polycyclic aromatic compound, a solvent is usually used, but any solvent may be used as long as it does not inhibit the reaction. Although not particularly limited, for example, aromatic hydrocarbon compounds such as benzene, toluene and xylene can be preferably mentioned. On this occasion,
The amount of the solvent used is preferably in the range of 20 to 300 parts by weight with respect to 100 parts by weight of the cyclic hydrocarbon. The reaction temperature in the reaction is usually 20 to 160 ° C., and particularly preferably 60 to 120 ° C. from the viewpoint of easy reaction control. The reaction time is usually in the range of 30 minutes to 7 hours, preferably 2 to 4 hours.

In order to make the reaction proceed smoothly in the above-mentioned method for producing polyphenols, it is preferable to reduce the water content in the system as much as possible, and it is particularly preferable to keep the water content at 100 ppm by weight or less. Further, since this reaction is accompanied by remarkable heat generation, it is preferable to carry out the method of continuously or intermittently adding the cyclic hydrocarbon compound from the viewpoint of safety.

After the reaction is completed, the catalyst is removed from the reaction solution, and then the reaction solution is concentrated to obtain the polynaphthols. The method of removing the catalyst differs depending on the type of the catalyst used.
In the case of a phenol complex, it is preferable to add calcium hydroxide, magnesium hydroxide and / or hydrotalcites in an amount of 1 to 10 times the molar amount of the catalyst to deactivate it, and then filter the catalyst. In filtration, it is desirable to improve workability by adding a solvent or performing treatment such as raising the temperature of the filtrate. Further, a method of deactivating and washing with an alkaline aqueous solution such as caustic soda water is also preferable.

The polyphenols obtained as described above are not particularly limited in their molecular weight, but usually 2
It is preferably 68 to 6000, and more preferably 268 to 2,000 from the viewpoint that the melt viscosity of the epoxy resin can be lowered.

The polyphenols thus obtained are then reacted with epihalohydrin to give the desired epoxy resin. The method for epoxidizing these polyphenols may be carried out according to known means, for example, the following method.

That is, the hydroxyl group 1 of the above polynaphthols
2 to 20 equivalents of epihalohydrin were added to the equivalent weight and dissolved, and then an alkali metal hydroxide aqueous solution was added to 40 to 120 equivalent weight.
The water content in the system is distilled off azeotropically with epihalohydrin at the same time. After cooling and aggregation, the epihalohydrin and water are allowed to stand and separate, and the reaction is carried out while returning only epihalohydrin into the system. Examples of epihalohydrin at this time include epichlorohydrin, epibromhydrin, epiiodohydrin, β-methylepichlorohydrin, and the like, but epichlorohydrin is preferable because of its easy availability. After completion of the reaction, excess epihalohydrin is distilled and recovered, and a solvent such as MIBK and toluene is added to the obtained crude resin, followed by washing with water, dehydration, filtration and desolvation to obtain the desired epoxy resin. .

The epoxy resin composition of the present invention comprises an epoxy resin which is a reaction product of a polyphenol having a structure in which a cycloaliphatic hydrocarbon group is bonded to a hydroxyl group-containing condensed polycyclic compound as a knot group and epihalohydrin. The curing agent and the curing accelerator are essential components.

The epoxy resin used in the resin composition is not particularly limited, and for example, one having a cyclohexane ring in the skeleton as a cyclic aliphatic hydrocarbon group which is a knot group has a moisture resistance of a cured product. Although it is mentioned as a preferable thing from the viewpoint of being excellent in the improvement effect, the epoxy resin obtained by the above-mentioned production method is particularly preferable. That is, the cyclic aliphatic hydrocarbon group is 4-vinylcyclohexene, 5-vinylnorborna-2-ene, 3a, 4,7,
7a-tetrahydroindene, dicyclopentadiene,
A divalent hydrocarbon group derived from α-pinene, β-pinene or limonene, and the hydroxyl group-containing condensed polycyclic compound is α-naphthol, β-naphthol,
Preferred are those selected from the group consisting of 1,1-bis (hydroxynaphthyl) methane and dihydroxynaphthalene.

When the epoxy resin is obtained by the above-mentioned production method, the polyphenols which are intermediates of the epoxy resin are one kind of unsaturated cyclic hydrocarbon compound and one kind of condensed polycyclic aromatic compound containing hydroxyl group. It is needless to say that not only the reaction product with the above but also the reaction product obtained by using two or more kinds respectively.

As the curing agent used in the present invention, all compounds commonly used as curing agents for epoxy resins can be used. For example, aliphatic amines such as diethylenetriamine and triethylenetetramine, metaphenylenediamine, Aromatic amines such as diaminodiphenylmethane and diaminodiphenyl sulfone, phenol novolac resins, orthocresol novolac resins, bisphenol A novolac resins, bisphenol F novolac resins, phenols-dicyclopentadiene addition type resins, dihydroxynaphthalene novolac resins, and other aromatic amines Hydrocarbon-formaldehyde resin, polyamide resin and modified products thereof, acid anhydride curing such as maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride , Dicyandiamide, imidazole, BF3 - amine complex latent curing agent such as guanidine derivatives. Among these, an aromatic hydrocarbon-formaldehyde resin is particularly preferable for a semiconductor sealing material.

As the curing accelerator, known curing accelerators for epoxy resins can be used, for example, tertiary phosphines, imidazoles, tertiary amines and the like can be used. Specifically, examples of the tertiary phosphines preferably include triethylphosphine, tributylphosphine, triphenylphosphine, and the like. Preferred examples of the tertiary amines include dimethylethanolamine, dimethylbenzylamine, 2,4,6-tris (dimethylamino) phenol and 1,8 diazabicyclo [5,4,0] undecene. it can. Examples of imidazoles include 2-ethyl-4-methylimidazole,
2,4-dimethylimidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-vinyl-2-methylimidazole, 1
-Propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -Phenylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Examples thereof include hydroxymethylimidazole. Among these, 2-methylimidazole, diazabicycloundecene (DBU), triphenylphosphine, dimethylbenzylamine and the like are excellent in heat resistance, water resistance, electrical characteristics and the like, and also excellent in stability as a semiconductor encapsulating material. Mixtures of these are preferred.

The epoxy resin composition of the present invention contains the above-mentioned epoxy resin, curing agent and curing accelerator as essential components, and if necessary, fillers such as silica powder, glass fiber, carbon fiber and calcium carbonate, and bromine. Epoxy resin, antimony trioxide, flame retardant such as hexabromobenzene, carbon black, colorant such as red iron oxide, natural wax,
It can be obtained by appropriately blending a release agent such as a synthetic wax and various additives such as a low stress additive such as silicone oil and rubber.

In order to prepare a molding material from the epoxy resin composition of the present invention, the epoxy resin, the curing agent, the curing accelerator, and other additives are sufficiently and uniformly mixed with a mixer or the like, and then the heat roll is further added. Alternatively, it can be obtained by melt-kneading with a kneader or the like, pulverizing after injection or cooling.

The semiconductor encapsulating material of the present invention is the epoxy resin composition of the present invention containing the above-mentioned epoxy resin, curing agent and curing accelerator as essential components, and further containing an inorganic filler as an essential component. .

As the inorganic filler used in the semiconductor encapsulating material of the present invention, silica powder filler or the like can be generally preferably used. The compounding ratio of the inorganic filler used in the epoxy resin composition for encapsulant of the present invention is usually 50 to 90 wt% with respect to the entire semiconductor encapsulating material, and in particular 65 to
A range of 85% by weight is preferred.

The epoxy resin composition for encapsulant of the present invention is
If necessary, an epoxy resin other than the above-mentioned epoxy resin (hereinafter abbreviated as “other epoxy resin”) can be used. Examples of the other epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, BPA novolac type epoxy resin, naphthol novolac type epoxy resin, biphenol type epoxy resin,
Brominated phenol novolac type epoxy resin, brominated B
PA type epoxy resin, glycidyl amine type 4 functional epoxy resin, etc. can be mentioned. The amount of the other epoxy resin used is preferably 100 parts by weight or less, particularly 50 parts by weight or less, relative to 100 parts by weight of the epoxy resin as an essential component in order to maintain excellent moisture resistance of the cured product.

In the semiconductor encapsulating material of the present invention, in addition to the above components, a silane coupling agent, a brominated epoxy resin,
Flame retardants such as antimony trioxide and hexabromobenzene,
Coloring agents such as carbon black and red iron oxide, releasing agents such as natural wax and synthetic wax, and various additives such as low stress additives such as silicone oil and rubber can be appropriately added.

In order to prepare a molding material using the semiconductor encapsulating material of the present invention, the above components are sufficiently and uniformly mixed with a mixer or the like, and then the mixture is melted and kneaded with a hot roll, a kneader or the like, and then injected or injected. It can be obtained by pulverizing after cooling.

[0035]

The present invention will be described in detail below with reference to specific examples, but the present invention is not limited thereto.

Example 1 In a 5 liter reactor equipped with a reflux condenser and a Liebig condenser, 1442 g of α-naphthol and 7 parts of toluene were added.
00 g was charged, the mixture was heated to 160 ° C., and azeotropically distilled with toluene to dehydrate the water in the system to 60 ppm, and 250 g of toluene was distilled off. Then, the system was cooled to 100 ° C., 20 g of boron trifluoride / phenol complex was added and homogenized, and then 330 g of dicyclopentadiene having a water content of 20 ppm at a reaction temperature of 100 ° C.
Was gradually added dropwise over 1.5 hours, and the mixture was further heated and stirred for 2.5 hours after completion of the addition. After the reaction, toluene 60
After adding 0 g and 80 g of magnesium compound "KW-1000" (trade name; manufactured by Kyowa Chemical Industry Co., Ltd.) and stirring for 30 minutes to deactivate the catalyst, the reaction solution was filtered. The obtained transparent filtrate was distilled under reduced pressure at 240 ° C. using a thin film distillation apparatus to obtain 910 g of naphthol resin.

The resulting naphthol resin has a softening point of 11
It was 0 ° C. The equivalent of phenolic hydroxyl group determined by reverse titration after acetylation with acetic anhydride was 225 g / equivalent. Furthermore, gel permeation chromatography
The number average molecular weight of this resin was found to be 580 by analysis (hereinafter referred to as GPC).

After 423 g of epichlorohydrin was added to 225 g of this naphthol resin and dissolved, the temperature was raised to 70 ° C.,
Adjust the system to azeotropic pressure and add 81 g of 49% NaOH aqueous solution to 3 g
It was suitable for a continuous period of time. At that time, an operation of returning only epichlorohydrin to the system while azeotropically distilling off epichlorohydrin and water was performed. After the end of the appropriate period, excess epichlorohydrin was recovered by distillation. To the obtained crude resin was added 422 g of methyl isobutyl ketone, dissolved, washed with 200 g of water, and then dehydrated, filtered and desolvated to obtain 265 g of the target epoxy resin (A). Epoxy equivalent of this 32
It was 3 g / eq.

Example 2 1442 g of β-naphthol instead of α-naphthol
Was reacted in the same manner as in Example 1 except that 270 g of 4-vinylcyclohexene was used instead of dicyclopentadiene to obtain 590 g of a naphthol resin.

The obtained naphthol resin has a softening point of 108.
The phenolic hydroxyl group equivalent at 211 ° C was 211 g / equivalent. The number average molecular weight of this resin was found to be 550 by GPC analysis.

When 211 g of this resin was epoxidized in exactly the same manner as in Example 1, the desired epoxy resin (B) 2 was obtained.
56 g were obtained. The epoxy equivalent of this was 300 g / eq.

Example 3 A reaction was carried out in the same manner as in Example 1, except that 1,1-bis (hydroxynaphthyl) methane (1800 g) was used instead of α-naphthol, and 5-vinylnorbornene (240 g) was used instead of dicyclopentadiene. After completion of the reaction, 1000 g of toluene and 60 g of slaked lime were added to the reaction solution and stirred to deactivate the catalyst, and then the reaction solution was filtered and concentrated by vacuum distillation at 240 ° C. to obtain a concentrate. In the concentrate, 840 g of unreacted 2,2-bis (hydroxynaphthyl) methane and 1162 g of an adduct with 5-vinylnorbornene were added.
Was included. The OH equivalent weight of the concentrate was 175 g / equivalent.

When 175 g of this resin was epoxidized in exactly the same manner as in Example 1, the desired epoxy resin (C) 2 was obtained.
19 g were obtained. The epoxy equivalent of this was 258 g / eq.

Example 4 1,600 g of 1,6-dihydroxynaphthalene was used instead of α-naphthol, and α was used instead of dicyclopentadiene.
-90 g of pinene, 90 g of β-pinene and 90 of limonene
The reaction was carried out in the same manner as in Example 1 using an unsaturated hydrocarbon solution consisting of g. After completion of the reaction, 1000 g of toluene was added, and the reaction solution was deactivated with 1000 g of a 2% aqueous potassium hydroxide solution. After washing with water, the reaction solution was concentrated by distillation under reduced pressure at 240 ° C. to obtain 965 g of a naphthol resin as an adduct with α-pinene, β-pinene and limonene. The OH equivalent of this naphthol resin was 125 g / equivalent.

When 250 g of this resin was epoxidized in exactly the same manner as in Example 1, the desired epoxy resin (D) 3
44 g was obtained. The epoxy equivalent of this was 203 g / eq.

Example 5 In the same manner as in Example 1, 1,600 g of 1,6-dihydroxynaphthalene was used instead of α-naphthol, and 300 g of tetrahydroindene was used instead of dicyclopentadiene. After completion of the reaction, 1000 g of toluene was added, and the reaction solution was deactivated with 1000 g of a 2% aqueous potassium hydroxide solution. After washing with water, the reaction solution was concentrated by vacuum distillation at 240 ° C. to obtain 890 g of a naphthol resin. The OH equivalent of this naphthol resin was 208 g / equivalent.

When 208 g of this resin was epoxidized in exactly the same manner as in Example 1, the desired epoxy resin (E) 2 was obtained.
38 g was obtained. The epoxy equivalent of this was 296 g / eq.

Examples 6 to 10 The epoxy resin produced in Examples 1 to 5, a phenol novolac resin, and triphenylphosphine as a curing accelerator were mixed, and the mixture was added at 150 ° C. for 2 hours and at 180 ° C. for 5 hours.
A test piece was obtained by heat curing at 200 ° C. for 2 hours. The mechanical properties of the test piece were measured according to JIS-K6911. The results are shown in Table 1.

Comparative Example 1 ECN, “EPICLON N-6”, was used as an epoxy resin.
65 (manufactured by Dainippon Ink and Chemicals, Inc.) "was used to obtain test pieces in the same manner as in Examples 6 to 11. The mechanical properties of the test piece were measured according to JIS-K6911. A molding material was obtained and tested in the same manner as in Example 12 except that the compounding ratios shown in Table 1 were used. The results are shown in Table 1.

Comparative Example 2 Example 6 was repeated, except that the epoxy resin was replaced with an epoxidized product of dicyclopentadiene-modified phenol "Epiclon EXA-7200 (Dainippon Ink and Chemicals, Inc.)".
Test pieces were obtained in the same manner as described above. The test piece is JIS
Mechanical properties were measured according to K6911. A molding material was obtained and tested in the same manner as in Example 12 except that the compounding ratios shown in Table 1 were used. The results are shown in Table 1.

[0051]

[Table 1] Tg ； TMA method Flexural modulus ； JIS-K-6911 Water absorption ； 85 ℃ ・ 85% RH 72Hr

Example 11 76 g of the epoxy resin (A) produced in Example 1, phenol novolac resin, "Phenolite TD-213"
1 "(manufactured by Dainippon Ink and Chemicals Co., Ltd.), fused silica powder" FUUSELEX RD-8 "(trade name; manufactured by Tatsumori Co., Ltd.) 353 g, and the additives shown in Table 2 were added as a nider Was melt-kneaded at 85 ° C. for 10 minutes, cooled, and then pulverized to obtain a semiconductor sealing material.

The obtained semiconductor encapsulating material was tableted, and the test element was molded with the tableting molding material using a low pressure transfer molding machine at 175 ° C. and 70 kg / c.
After sealing under conditions of m ² and 120 seconds, post-curing was performed under conditions of 180 ° C. and 5 hours. Using the obtained cured product, a 6 × 6 mm chip is sealed in a 52p package for a solder crack test, and 3 × for a solder moisture resistance test.
A 6 mm chip was sealed in a 16 pSOP package.
The sealed test element was subjected to the following solder crack test and solder moisture resistance test. The results are shown in Table 2.

Solder crack test: The sealed test element was subjected to an environment of 85 ° C. and 85% RH for 48 hours and 72 hours.
After processing, after immersing in a solder bath at 280 ° C. for 10 seconds, external cracks were observed with a microscope.

Solder moisture resistance average life (hr); Sealed test element was treated for 48 hours and 72 hours in an environment of 85 ° C. and 85% RH, then immersed in a solder bath at 280 ° C. for 10 seconds, and then pressure cooker test was conducted. (125 ° C, 100%
RH) was performed to measure the time until 50% of the circuit's oven failure occurred.

Examples 12 to 15 Semiconductor encapsulating materials were obtained in the same manner as in Example 11 except that the formulations shown in Table 1 were followed, and each tablet was subjected to a test.
The test results are shown in Table 2.

Comparative Example 3 An epoxy resin was used as ECN, “EPICLON N-665”.
Table 2 instead of "Made by Dainippon Ink and Chemicals, Inc."
A molding material was obtained and tested in the same manner as in Example 12 except that the compounding ratio shown in was used. The results are shown in Table 2.

Comparative Example 4 Example 12 was repeated except that the epoxy resin was replaced only with the epoxidized product of dicyclopentadiene-modified phenol "Epiclon EXA-7200 (Dainippon Ink and Chemicals, Inc.)" and the compounding ratios shown in Table 2 were used. A molding material was obtained and tested in the same manner. The results are shown in Table 2.

[0059]

[Table 2] Tg ； TMA method Flexural modulus ； JIS-K-6911 Water absorption ； 85 ℃ ・ 85% RH 72Hr

[0060]

INDUSTRIAL APPLICABILITY According to the present invention, there are provided an epoxy resin having excellent properties in both heat resistance and moisture resistance, and an epoxy resin composition having excellent heat resistance and moisture resistance when being a cured product. Can be provided. The epoxy resin composition of the present invention can be used not only as a sealing material but also as a laminated board for a printed wiring board, a powder coating material, a casting material and the like.

Since the semiconductor encapsulating material of the present invention is excellent in mechanical characteristics, electrical characteristics, heat resistance and moisture resistance, it can be applied to encapsulation, coating and insulation of electronic parts or electric parts. . In particular, the semiconductor encapsulating material of the present invention is excellent in solder heat resistance when it is cured into a semiconductor package, and the semiconductor package during soldering of the lead wire is resistant to a sudden temperature change. However, it has an excellent performance that no cracks are generated in the resin molded portion and the interface between the lead wire resins is not deteriorated.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication location H01L 23/31 (72) Inventor Hitoshi Yuasa 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Nippon Petroleum Oil Co., Ltd. Company Central Research Institute

Claims (8)

[Claims] 1. An epoxy resin characterized by reacting an unsaturated cyclic hydrocarbon compound with a condensed polycyclic aromatic compound containing a hydroxyl group under an acid catalyst, and then reacting the resulting reaction product with epihalohydrin. Manufacturing method. 2. The method according to claim 1, wherein the unsaturated cyclic hydrocarbon compound has a cyclohexane ring or a cyclohexene ring. 3. The unsaturated cyclic hydrocarbon compound is 4-vinylcyclohexene, 5-vinylnorborna-2-ene,
3a, 4,7,7a-tetrahydroindene, dicyclopentadiene, α-pinene, β-pinene and limonene, and the hydroxyl group-containing condensed polycyclic aromatic compound is α The process according to claim 2, which is selected from the group consisting of -naphthol, β-naphthol, 1,1-bis (hydroxynaphthyl) methane and dihydroxynaphthalene. 4. An epoxy resin, which is a reaction product of a polyphenol having a structure in which a cycloaliphatic hydrocarbon group is bonded to a condensed polycyclic compound containing a hydroxyl group as a knot group, and epihalohydrin, a curing agent, and a curing accelerator. An epoxy resin composition, which comprises an agent as an essential component. 5. The composition according to claim 4, wherein the cyclic aliphatic hydrocarbon group has a cyclohexane ring in its skeleton. 6. The cycloaliphatic hydrocarbon group is 4-vinylcyclohexene, 5-vinylnorborna-2-ene, 3
The composition according to claim 5, which is a divalent hydrocarbon group derived from a, 4,7,7a-tetrahydroindene, dicyclopentadiene, α-pinene, β-pinene or limonene. 7. The condensed polycyclic compound containing a hydroxyl group is selected from the group consisting of α-naphthol, β-naphthol, 1,1-bis (hydroxynaphthyl) methane and dihydroxynaphthalene. Composition. 8. A semiconductor encapsulating material, characterized in that an inorganic filler is further added to the epoxy resin composition according to any one of claims 4 to 7.