JPH10324733A - Epoxy resin composition, method for producing epoxy resin, and semiconductor encapsulant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To exhibit excellent solder cracking resistance as a semiconductor encapsulating material and to have remarkably excellent curability, having excellent fluidity, capable of highly filling an inorganic filler, and being unprecedented as a semiconductor encapsulating material. Excellent and improves the productivity of molded products such as semiconductors. A glycidyl etherification mixture of a polyaddition reaction product of dicyclopentadiene and phenol,
The mixture contains an epoxy resin (A) having a binuclear content of 80% by weight or more and a curing agent (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel material having excellent balance of fluidity, curability, heat resistance, water resistance and moisture resistance of a cured product, especially at the time of molding, molding material, casting material, laminated component material, and the like. Epoxy resin manufacturing method, epoxy resin composition, which is extremely useful for electrical insulation materials, fiber reinforced composite materials, coating materials, adhesive materials, etc. The present invention relates to a semiconductor encapsulant having excellent solder crack resistance and excellent moisture resistance reliability.

[0002]

2. Description of the Related Art Epoxy resins are generally cured with various curing agents to give cured products having excellent mechanical properties, water resistance, chemical resistance, heat resistance, and electrical properties. It is used in a wide range of fields, such as paints, laminates, molding materials, and casting materials.

[0003] In particular, in the application of semiconductor encapsulation materials, further improvement in heat cycle resistance has been demanded in recent years due to higher integration. Furthermore, semiconductor packages tend to be thinner in order to cope with higher packaging densities, and TSOP-type packages having a thickness of 1 mm or less are also being used. Materials having cracking properties are required.

Further, in order to improve the productivity of semiconductors, the molding cycle tends to be shortened, and a semiconductor encapsulating material having high curability is required. Conventionally, ortho-cresol novolak type epoxy resin (hereinafter referred to as “ECN”) has been widely used for semiconductor encapsulant applications. Although the resin has excellent heat resistance, it has excellent fluidity and solder crack resistance. It had a defect of inferiority. On the other hand, as an epoxy resin having excellent fluidity, a biphenyl type epoxy resin which is a crystalline epoxy resin is also used, but the resin has a low degree of curability and heat resistance although solder crack resistance is improved to some extent. However, the above requirements are not sufficiently satisfied.

A sealing material using a dicyclopentadiene type epoxy resin as a high-performance semiconductor sealing material is disclosed in, for example, JP-A-61-293219 and JP-A-61-16.
No. 8618, U.S. Pat. No. 4,701,481, and the like.

[0006]

The epoxy resins described in these publications have low moisture absorption and high heat resistance, but have a high melt viscosity and a high filling rate of inorganic filler. Not possible, so solder crack resistance,
There was a limit to the effect of improving the moisture resistance reliability, and it was not possible to satisfy the performance required at present, and the melt viscosity was high and the curability was poor, so that it was not possible to sufficiently cope with the shortening of the molding cycle. .

The problem to be solved by the present invention is to provide a semiconductor encapsulant which has excellent fluidity without deteriorating its performance such as low moisture absorption and high heat resistance and can be filled with an inorganic filler at a high level. A method for producing an epoxy resin, an epoxy resin composition, and a semiconductor encapsulant, which exhibit unprecedented excellent solder cracking resistance, are extremely excellent in curability, and can significantly improve the productivity of molded products such as semiconductors. To provide.

[0008]

As a result of intensive studies, the present inventors have found that the glycidyl of a polyaddition product of an unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule with a phenol. It has been found that the above problems can be solved by using an epoxy resin which is an etherified mixture and has a binuclear content of 80% by weight or more in the mixture as a main component, and has completed the present invention. Was.

That is, the present invention provides two double bonds in one molecule.
A glycidyl etherified mixture of a polyaddition product of an unsaturated aliphatic cyclic hydrocarbon compound and a phenol containing 80% by weight of a binuclear substance in the mixture.
An epoxy resin composition comprising the above-described epoxy resin (A) and a curing agent (B) as essential components, and unsaturated aliphatic cyclic carbonization containing two double bonds in one molecule. A polyaddition product of a hydrogen compound and a phenol, wherein the binuclear content of the polyaddition product is 95
A method for producing an epoxy resin, which comprises reacting a polyhydric phenol mixture (a) having a content of not less than% by weight with epihalohydrin (b), and an unsaturated resin containing two double bonds in one molecule. An epoxy resin (A), which is a glycidyl etherified mixture of a polyaddition reaction product of an aliphatic cyclic hydrocarbon compound and a phenol, and which has a binuclear content of 80% by weight or more; (B) and a semiconductor encapsulating material comprising an inorganic filler (C) as an essential component.

The epoxy resin (A) used in the present invention comprises:
A glycidyl etherification mixture of a polyaddition product of an unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule and a phenol, and
The core content is 80% by weight or more. Where 2
The nucleus is a glycidyl ether compound having two aromatic hydrocarbon nuclei linked by an aliphatic cyclic hydrocarbon group, and examples thereof include the following structures.

[0011]

Embedded image

(In the general formula 1, X is an aliphatic hydrocarbon group, R
₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ each independently represent a halogen atom or an alkyl group having 1 to 10 hydrocarbons. ) The content of this binuclear substance is a value represented by a weight ratio analyzed by gel permeation chromatography (GPC).

According to the present invention, the dinuclear compound is contained in the epoxy resin (A) in an amount of 80% by weight or more so that the dicyclopentadiene-type epoxy resin can be melted while having high heat resistance and high water resistance. Although it has succeeded in reducing the viscosity, it is characterized in that the curability can be significantly improved at the same time. In general, thermosetting resins tend to decrease in curability with improvement in fluidity. However, the epoxy resin (A) of the present invention has a unique property that fluidity is extremely excellent and curability is also extremely excellent. Is expressed. The content of the binuclear body in the epoxy resin (A) is particularly preferably in the range of 80 to 95% by weight from the viewpoint that the effect of improving the fluidity and the curability becomes more remarkable.

The glycidyl ether compound constituting the epoxy resin (A) is a glycidyl ether of a polyaddition product of an unsaturated aliphatic cyclic hydrocarbon compound having two double bonds in one molecule and a phenol. Here, the phenols include phenols and substituted phenols in which one or more of an alkyl group, an alkenyl group, an allyl group, an aryl group, an aralkyl group or a halogen group is substituted. Specific examples include cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, naphthol, dihydroxynaphthalene, and the like. Although illustrated, it is not limited to these.
Also, a mixture of these may be used. Of these, phenol is particularly preferred because of its excellent fluidity and curability.

The unsaturated alicyclic hydrocarbon compound is not particularly limited as long as it is an unsaturated alicyclic hydrocarbon compound having two or more unsaturated double bonds in one molecule. Then, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorbon-2-ene, α-pinene, β-pinene, limonene and the like can be mentioned. Among these, dicyclopentadiene is preferred from the viewpoint of the property balance, particularly the heat resistance and the hygroscopicity. Further, since dicyclopentadiene is contained in the petroleum fraction, industrial aliphatic dicyclopentadiene may contain other aliphatic or aromatic dienes as impurities, but heat resistance, curability, In consideration of moldability and the like, it is desirable that the product be a product having a purity of 90% by weight or more of dicyclopentadiene.

As described above, the epoxy resin (A) has remarkably excellent fluidity. Specifically, the epoxy resin (A) preferably has a melt viscosity at 150 ° C. of 0.3 poise or less. The epoxy equivalent of the epoxy resin (A) is not particularly limited, but is preferably in the range of 220 to 260 g / eq from the viewpoint of improving heat resistance and water resistance. Further, it is preferable that the total chlorine concentration in the epoxy resin (A) is 800 ppm or less, particularly from the viewpoint of electric characteristics and solder crack resistance in semiconductor encapsulating materials.

That is, the epoxy resin (A) used in the present invention
Is a glycidyl etherified mixture of a polyaddition reaction product of phenol and dicyclopentadiene, the binuclear content of the mixture is in the range of 80 to 95% by weight, and the melt viscosity at 150 ° C. 0.3 poise or less, epoxy equivalent is 220-260 g / eq, and total chlorine concentration is 80
Epoxy resins within the range of 0 ppm or less are most preferable because they exhibit more excellent performance.

The method for producing such an epoxy resin (A) is not particularly limited, but can be easily obtained by the method for producing an epoxy resin of the present invention.

That is, a polyaddition product of an unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule with a phenol, and a binuclear compound in the polyaddition product The epoxy resin (A) can be easily obtained by reacting a polyhydric phenol mixture (a) having a content of 95% by weight or more with epihalohydrin (b).

Here, two double bonds are used in one molecule.
Any of the unsaturated aliphatic cyclic hydrocarbon compounds and phenols contained herein can be used.

The binuclear compound is a phenol compound having two aromatic hydrocarbon nuclei linked by an aliphatic cyclic hydrocarbon group, and examples thereof include the following structures.

[0022]

Embedded image

(In the general formula 2, X is an aliphatic hydrocarbon group, R
₂ and R ₃ each independently represent a halogen atom or an alkyl group having 1 to 10 hydrocarbons. In addition, the content of the binuclear body is a value represented by a weight ratio analyzed by gel permeation chromatography (GPC) as in the case of the glycidyl ether compound.

In order to obtain the polyhydric phenol mixture (a) having a binuclear content of 95% by weight or more, the production method is not particularly limited. A method of increasing the molar ratio of phenols / unsaturated aliphatic cyclic hydrocarbon compound in the polyaddition reaction between the aromatic cyclic hydrocarbon compound and phenol, and (2) the polyhydric phenol compound obtained by the conventional production method. Although a method of molecular distillation is mentioned, in order to efficiently increase the binuclear content in the polyhydric phenol compound to 95% by weight or more, (2)
Is preferred. That is, as the production method of the present invention, an unsaturated aliphatic cyclic hydrocarbon compound and a phenol are subjected to a polyaddition reaction, and the obtained polyhydric phenol compound is subjected to molecular distillation to obtain a binuclear substance content of 95% by weight or more. A method is preferred in which a certain polyhydric phenol mixture (a) is obtained, and then this is reacted with epihalohydrin (b).

The preferred method will be described in more detail. The polyhydric phenol mixture (a) is obtained by mixing an unsaturated aliphatic cyclic hydrocarbon compound and a phenol with the former / latter = 1 / (5 or more).
At a molar ratio of 1. At this time, as the polyaddition catalyst, an inorganic acid such as hydrochloric acid or sulfuric acid, an organic acid such as paratoluenesulfonic acid, or a Lewis acid such as AlCl3 or BF3 is used. The target polyhydric phenol mixture (a) can be obtained by subjecting the polyhydric phenol compound having a high molecular weight obtained by the polyaddition reaction to molecular distillation. As a method of molecular distillation, a low-molecular-weight region may be selectively separated using a thin-film evaporator or the like under a high-temperature and reduced-pressure condition of 250 ° C. or more / 0.5 Torr or less.

Next, the desired epoxy resin (A) can be obtained by reacting the thus obtained polyaddition reaction product with epihalohydrin. This reaction may be carried out according to a known method. For example, the following method can be mentioned.

That is, first, the polyhydric phenol compound (a)
2 to 15 equivalents, preferably 3 to 10 equivalents of epihalohydrin are added to and dissolved from the point of being excellent in the effect of lowering the melt viscosity, and then 0.1 to 10 equivalents to the hydroxyl groups in the polyaddition reaction product. 8 to 1.2 equivalents of 10 to 50% N
Aqueous aOH is applied at a temperature of 50-80 ° C. for 3-5 hours. After lowering, stirring is continued at that temperature for about 0.5 to 2 hours, and after standing, the lower saline solution is discarded. Next, the excess epihalohydrin is recovered by distillation to obtain a crude resin. To this, an organic solvent such as toluene or MIBK is added, and the desired resin can be obtained through a water washing-dehydration-filtration-desolvation step. In addition, a solvent such as dioxane or DMSO may be used in the reaction for the purpose of reducing the amount of impurity chlorine.

As epihalohydrin (b) used here, epichlorohydrin is the most common, but in addition, epiiodohydrin, epibromhydrin, β-methylepichlorohydrin and the like can also be used.

The epoxy resin thus obtained is an epoxy resin (A) which is a main component of the epoxy resin composition of the present invention.
However, it can also be used as a raw material resin in a two-stage reaction for obtaining a polymer type epoxy resin.

Next, the curing agent (B) used as an essential component in the epoxy resin composition of the present invention includes:
All compounds commonly used as curing agents for epoxy resins can be used, and are not particularly limited. For example, phenol novolak resin, orthocresol novolak resin, bisphenol A novolak resin, bisphenol F novolak resin, phenol Class-
Dicyclopentadiene polyaddition type resin, dihydroxynaphthalene novolak resin, polyhydric phenols having a xylidene group as a binding group, phenol-aralkyl resins, naphthols resins diethylenetriamine, aliphatic amines such as triethylenetetramine, metaphenylenediamine,
Aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone, polyamide resins and their modified products, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, acid anhydride-based curing agents such as pyromellitic anhydride, dicyandiamide, Imidazole, BF3-
Latent curing agents such as amine complexes and guanidine derivatives. Above all, for semiconductor encapsulants, aromatic hydrocarbon-formaldehyde resins such as the above-mentioned phenol novolak resins have excellent curability, moldability and heat resistance, and phenol-aralkyl resins have curability, moldability and low water absorption. It is preferable because it is excellent.

The curing agent (B) may be used in any amount as long as it can cure the epoxy resin (A).
Although not particularly limited, the amount is preferably such that the number of epoxy groups contained in one molecule of the epoxy resin to be used and the number of active hydrogens in the curing agent are close to equivalents.

When each of the above compounds is used as the curing agent (B), a curing accelerator can be used as appropriate. As the curing accelerator, any known and commonly used curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. In addition, two or more kinds can be used in combination.

The epoxy resin composition of the present invention may use another epoxy resin in addition to the above-mentioned epoxy resin (A) which is an essential component. As the epoxy resin used at this time, any known and commonly used epoxy resin can be used, for example, bisphenol A diglycidyl ether type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin,
Examples include, but are not limited to, bisphenol A novolak epoxy resin, bisphenol F novolak epoxy resin, brominated phenol novolak epoxy resin, naphthol novolak epoxy resin, biphenyl type bifunctional epoxy resin, and the like.

If necessary, various known and commonly used additive components such as a coloring agent, a flame retardant, a release agent, and a coupling agent can be appropriately blended.

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 uniformly mixed by a mixer or the like, and then further heated. Alternatively, it can be obtained by melt-kneading with a kneader or the like, and pulverizing after injection or cooling.

The thus obtained epoxy resin composition of the present invention is not particularly limited in its use.
For example, semiconductor sealing materials and varnishes for use in electric laminates because of their excellent solvent solubility in epoxy resins. In addition, an oligomer type epoxy resin obtained by modifying the epoxy resin (A) of the present invention with a brominated polyhydric phenol can also be used for laminates. Further, a polyfunctional epoxy resin may be blended or modified to impart heat resistance before use.

Among these applications, semiconductor encapsulant applications are extremely useful because of their advantages such as remarkably excellent solder crack resistance. The semiconductor encapsulating material of the present invention will be described below in detail. In addition to the epoxy resin (A) and the curing agent (B) described above, the semiconductor encapsulating material further contains an inorganic filler (C) as an essential component.

The semiconductor encapsulating material of the present invention can be used for molding a semiconductor when encapsulating a semiconductor with fluidity, curability, moldability, heat resistance after encapsulation and curing, and also solder resistance when mounting on a printed circuit board. Satisfies all required characteristics such as cracking properties.

The inorganic filler (C) used in the present invention not only enhances the mechanical strength and hardness of the cured product, but also achieves a low water absorption and a low coefficient of linear expansion, and is essential for enhancing solder crack resistance. Component.

The blending amount of the inorganic filler (C) is not particularly limited. However, since the epoxy resin (A) has excellent fluidity, it can be filled at a higher level than ever before. , 80 to 95% by weight, from the viewpoint of solder crack resistance.

It should be noted that the addition of 85% by weight or more of the inorganic filler in the present invention does not impair the fluidity and moldability at all. .

The kind of the inorganic filler (C) is not particularly limited, but includes crushed silica, spherical silica, alumina, talc, clay, glass fiber and the like. Among them, crushed silica and spherical silica are generally used especially for semiconductor encapsulating materials, and among them, it is preferable to mix spherical silica from the viewpoint of excellent fluidity. In particular, when the average particle diameter is in the range of 10 to 50 μm, more excellent fluidity can be obtained.

In addition to the above-mentioned components of the epoxy resin composition, a tetrabromobisphenol A type epoxy resin,
Brominated epoxy resins such as brominated phenol novolak type epoxy resins, flame retardants such as antimony trioxide and hexabromobenzene, coloring agents such as carbon black and red iron oxide, release agents such as natural wax and synthetic wax, and silicone oil Various additives such as low-stress additives such as synthetic rubber and silicone rubber may be appropriately compounded.

The semiconductor encapsulating material of the present invention may use other epoxy resins in addition to the above-mentioned epoxy resin (A) which is an essential component. As the epoxy resin used at this time, any known and commonly used epoxy resin can be used, for example, bisphenol A diglycidyl ether type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, Examples include, but are not limited to, bisphenol F novolak epoxy resin, brominated phenol novolak epoxy resin, naphthol novolak epoxy resin, biphenyl type bifunctional epoxy resin, and the like. Of these, orthocresol novolak epoxy resin is particularly preferable from the viewpoint of excellent heat resistance, and biphenyl type bifunctional epoxy resin is preferable from the viewpoint of excellent fluidity.

If necessary, various known and commonly used additive components such as a coloring agent, a flame retardant, a release agent, and a coupling agent can be appropriately compounded. To prepare a semiconductor encapsulating material from the epoxy resin composition of the present invention, an epoxy resin (A), a curing agent (B), an inorganic filler (C), and if necessary, a curing accelerator and other additives. After thoroughly mixing the agent and the epoxy resin other than (A) with a mixer or the like, the mixture is further melt-kneaded with a hot roll or a kneader, cooled, pulverized, and tableted to obtain a mixture.

The semiconductor encapsulating material of the present invention uses the above-described ECN
In addition to having better solder crack resistance and heat cycle resistance than semiconductor encapsulation materials using, the melt viscosity is even lower than that of the conventional dicyclopentadiene type epoxy resin, so the fluidity is lower. It is possible to fill the same inorganic filler as that of the biphenyl type without damage. Moreover, since the moisture absorption rate is lower than that of the biphenyl type, the solder crack resistance is extremely excellent. It also has better curability and heat resistance than biphenyl type. Therefore, the epoxy resin of the present invention can be used as a semiconductor encapsulant with a high level of fluidity, curability, resistance to solder cracking, and resistance to heat cycling in a well-balanced manner.

[0047]

Next, the present invention will be described in detail with reference to Production Examples, Examples and Comparative Examples. In the examples, all parts are by weight unless otherwise specified.

The total chlorine content was 0.2 g of the epoxy resin obtained in each of Examples and Comparative Examples and 20 m of n-butanol.
and 1 g of metallic sodium is added.
The measurement was performed by potentiometric titration of the solution heat-treated at 2 ° C. for 2 hours using silver nitrate. The melt viscosity is 50 Hz
Under research equipmentL
TD. "ICI CONE & PLATE VIS
COMMETER ". Further, the content of the binuclear component is determined by “Gel Permeation Chromatography (GPC)” manufactured by Tosoh Corporation (measurement conditions: flow rate = 1.0 ml /
Min, pressure = 92 Kg / cm2, column = G4,3
2,2HXL, detector = RI 32 × 10-6 RIUF
It measured in S). The softening point is "Softening point measuring device" manufactured by Meifou Seisakusho Co., Ltd. (Heating device: HU-MK, detector ASP-M2)
It was measured.

Example 1 1222 g of phenol was placed in a 2-liter four-necked flask equipped with a stirrer, a thermometer and a condenser, and BF3.
17 g of the phenol complex was added and mixed well. Then a mixture 1 containing crude dicyclopentadiene as a main component
92 g was added over 4 hours while maintaining the temperature in the system at 110 to 120 ° C. The purity of the crude dicyclopentadiene was 95.2% by weight of dicyclopentadiene, 2.8% by weight of methyldicyclopentadiene, 0.1% by weight of propenyl norbornene, and 0.1% by weight of isophenyl norbornene.
1% by weight, other compound having no double bond 1.8
% By weight. Thereafter, the temperature in the system is maintained at 120 ° C.
After heating and stirring for an hour, 52 g of magnesium compound "KW-1000" (trade name; manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the obtained reaction product solution, and the mixture was stirred for 1 hour to deactivate the catalyst. The reaction solution was filtered. The resulting clear solution was heated to 230 ° C. while distilling and recovering unreacted phenol, and then 1 To
Hold for 4 hours under reduced pressure of rr. As a result, 368 g of a brown solid resin was obtained. The softening point of this resin was 91 ° C., and the hydroxyl equivalent was 169 g / eq.

350 g of this solid resin was added at 280 ° C./0.1
Under a condition of Torr, molecular distillation was performed by a thin film molecular still to obtain 185 g of a light brown solid resin. 2 in this solid resin
The core content was 98% by weight.

In a 2-liter four-necked flask equipped with a stirrer, a thermometer, a Dean-Stark trap, and a condenser, 150 g of this resin and 338 epichlorohydrin were added.
Add g and dissolve. It was heated to 55 ° C. and 76 g of 49% NaOH was added dropwise thereto under reduced pressure over 4 hours. At that time, the liquid azeotropically distilled was separated into water and epichlorohydrin using a Dean-Stark trap, and the reaction was performed while returning only epichlorohydrin into the reaction system. After stirring for 1 hour at the same temperature after the dropwise addition, the mixture was heated to 120 ° C., and unreacted epichlorohydrin was recovered by distillation. Next, 300 g of MIBK and 100 g of water were added to the obtained crude resin solution.
And inorganic salts were removed by washing with water. 5% in this solution
10 g of NaOH was added and the mixture was stirred at 85 ° C. for 3 hours. Thereafter, the mixture was allowed to stand and separated, the lower layer was removed, and washing with water was repeated twice. Then, after azeotropic dehydration and filtration, MIBK was reduced to 1
Remove the solvent at 50 ° C and obtain 179 g of the desired epoxy resin (I)
I got This resin was a brown semisolid, had a melt viscosity at 150 ° C. of 0.15 poise, a binuclear component content of 81% by weight, an epoxy equivalent of 242 g / eq, and a total chlorine content of 870 ppm.

Example 2 178 g of the desired epoxy resin (II) was obtained in the same manner as in Production Example 1, except that 150 g of dimethyl sulfoxide was added during the epoxidation reaction. This resin was a brown semi-solid, had a melt viscosity of 0.10 poise at 150 ° C., a binuclear component content of 85% by weight, an epoxy equivalent of 237 g / eq, and a total chlorine content of 620 ppm.

Comparative Example 1 The objective epoxy resin (III) 165 was prepared in the same manner as in Production Example 1 except that the starting phenol resin was not subjected to molecular distillation.
g was obtained. This resin was a brown solid, had a melt viscosity at 150 ° C. of 0.57 poise, a binuclear component content of 57% by weight, an epoxy equivalent of 259 g / eq, and a total chlorine content of 1190 ppm.

Examples 3 to 4 and Comparative Examples 2 to 4 Mixtures prepared according to the formulations shown in Table 1 were kneaded with a hot roll at 100 ° C. for 8 minutes to obtain an epoxy resin composition.

At this time, the gel time at 175 ° C. of the composition and the index of fluidity were measured using a test mold at 175 ° C.
The spiral flow value was measured under conditions of ° C./70 kg / cm 2 and 120 seconds.

Next, tablets obtained by pulverizing the obtained epoxy resin composition at a pressure of 1200 to 1400 Kg / cm 2 were used, and a plunger pressure of 80 kg / cm 2 and a mold temperature were obtained using a transfer molding machine. Sealing was performed under the conditions of 175 ° C. and a molding time of 100 seconds, and a 20-pin flat package having a thickness of 2 mm was prepared as a test piece for evaluation.

Thereafter, after preparing the test piece for evaluation, 8
Post-curing was performed for an hour. At that time, as an index of curability, the same test piece was used for 2 hours after the start of post-curing, 4 hours after the start, 8
The glass transition point at the elapse of time was measured by the DMA method, and the change in Tg was observed.

Using the test specimens thus obtained, the moisture absorption under a condition of 85 ° C./85% RH for 300 hours, and 20 test pieces were placed in an atmosphere of 85 ° C./85% RH. After leaving it for 168 hours and performing moisture absorption treatment,
The crack generation rate when immersed in a solder bath at 60 ° C. for 10 seconds was used as an index of the solder crack resistance.

In the table, N-665 is an orthocresol novolak type epoxy resin (trade name: EPICLON N-665, manufactured by Dainippon Ink and Chemicals, Inc., softening point: 68 ° C., epoxy equivalent: 208 g / eq, 150 ° C.) Melt viscosity: 3.0 poise), Biphenyl type epoxy resin (trade name: Epicoat YX-4 manufactured by Yuka Shell Epoxy Co., Ltd.)
000H, melting point 104 ° C, epoxy equivalent 195g / eq, 1
153 is a tetrabromobisphenol A type epoxy resin (trade name: EPICLON 153, trade name: EPICLON 153, softening point 70 ° C., epoxy equivalent 401 g / eq), TD is TD -2131
Indicates a phenol novolak resin (trade name: Phenolite TD-2131, softening point 80 ° C, hydroxyl equivalent 104 g / eq, manufactured by Dainippon Ink and Chemicals, Inc.). As the silica powder, spherical silica having an average particle size of 25 μm was used.

[0060]

[Table 1]

[0061]

According to the present invention, excellent fluidity can be obtained without deteriorating the performance such as low moisture absorption and high heat resistance, and the inorganic filler can be highly filled. A method for producing an epoxy resin, an epoxy resin composition, and a semiconductor, which, as a sealing material, exhibit unprecedented excellent solder crack resistance, are extremely excellent in curability, and can significantly improve the productivity of molded articles such as semiconductors. A sealing material can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 23/31

Claims (14)

[Claims] 1. A glycidyl etherified mixture of a polyaddition product of an unsaturated aliphatic cyclic hydrocarbon compound having two double bonds in one molecule and a phenol, and
An epoxy resin composition comprising, as essential components, an epoxy resin (A) having a binuclear content of 80% by weight or more in the mixture and a curing agent (B). 2. The composition according to claim 1, wherein the content of the binuclear substance in the epoxy resin (A) is in the range of 80 to 95% by weight. 3. The composition according to claim 1, wherein the epoxy resin (A) has a melt viscosity at 150 ° C. of 0.3 poise or less. 4. The epoxy equivalent of the epoxy resin (A) is:
4. The composition according to claim 1, wherein the composition ranges from 220 to 260 g / eq. 5. The total chlorine concentration in the epoxy resin (A) is 8
5. The epoxy resin composition according to claim 1, wherein the content is at most 00 ppm. 6. A polyaddition product between an unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule and a phenol, and a binuclear compound in the polyaddition product A method for producing an epoxy resin, comprising reacting a polyhydric phenol mixture (a) having a content of 95% by weight or more with epihalohydrin (b). 7. A polyhydric phenol mixture (a) is subjected to a polyaddition reaction between an unsaturated aliphatic cyclic hydrocarbon compound having two double bonds in one molecule and a phenol,
7. The production method according to claim 6, wherein the reaction product is purified by molecular distillation until the binuclear substance content becomes 95% by weight or more. 8. An unsaturated aliphatic cyclic hydrocarbon compound having two double bonds in one molecule and a phenol are mixed at a ratio of the former / the latter = 1 / (5 or more) on a weight basis. An addition reaction is carried out, and the obtained reaction product is subjected to molecular distillation to obtain a polyhydric phenol mixture (a) having a binuclear content of 95% by weight or more, and then this is mixed with epihalohydrin (b) by 8. The production method according to claim 6, wherein epihalohydrin (b) is reacted at a ratio of 2 to 15 equivalents to the hydroxyl group in a). 9. The unsaturated aliphatic cyclic hydrocarbon compound having two double bonds in one molecule is dicyclopentadiene, and the phenol is phenol. The manufacturing method as described. 10. A glycidyl etherified mixture of a polyaddition product of an unsaturated aliphatic cyclic hydrocarbon compound having two double bonds in one molecule and a phenol, and wherein the glycidyl etherified mixture is a glycidyl etherified mixture. A semiconductor encapsulating material comprising an epoxy resin (A) having a core content of 80% by weight or more, a curing agent (B), and an inorganic filler (C) as essential components. 11. The semiconductor encapsulating material according to claim 10, wherein the content of the binuclear body in the epoxy resin (A) is in the range of 80 to 95% by weight. 12. The semiconductor sealing material according to claim 10, wherein the epoxy resin (A) has a melt viscosity at 150 ° C. of 0.3 poise or less. 13. The epoxy resin (A) having an epoxy equivalent in the range of 220 to 260 g / eq.
Or a semiconductor sealing material according to 12. 14. The method according to claim 10, wherein the total chlorine concentration in the epoxy resin (A) is 800 ppm or less.
The semiconductor encapsulating material according to the above.