JPH1081731A - Epoxy resin production method, epoxy resin composition and semiconductor encapsulant - Google Patents

Abstract

(57) [Summary] A polyphenol is obtained by reacting a crude dicyclopentadiene having a purity of dicyclopentadiene of 87% by weight or more with phenols, and then reacting this with epihalohydrin to obtain an epoxy resin. [Effect] It has excellent fluidity, heat resistance, and water resistance, and particularly has excellent solder crack resistance as a semiconductor sealing material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is 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. Epoxy resin composition that is extremely useful for insulating materials, fiber reinforced composite materials, coating materials, molding materials, adhesive materials, etc., and in addition to their properties, has excellent solder crack resistance during surface mounting, and furthermore, has high moisture resistance reliability Also relates to an excellent semiconductor sealing material.

[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] Particularly, in semiconductor encapsulant applications,
In recent years, the mounting method is rapidly shifting from the conventional pin insertion method to the surface mounting method, and a semiconductor sealing material having excellent solder crack resistance is required. Further, 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 have come to be used. Also, 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. In addition, computers are being used under increasingly severe conditions such as being mounted around an engine of a car, and therefore, excellent heat resistance is required. Therefore, to respond to these,
Demands for solder crack resistance, low melt viscosity, high-speed curable materials, and high heat resistance have been greatly increased.

Conventionally, ortho-cresol novolak type epoxy resins (hereinafter referred to as “EC
N)) is widely used, but the resin has excellent heat resistance, but has a defect that it is inferior in fluidity and solder crack resistance.

A sealing material using a dicyclopentadiene type epoxy resin is known as a high performance semiconductor sealing material. For example, Japanese Patent Application Laid-Open No. Sho 62-70413 discloses a sealing material.
When the content of the aliphatic cyclic hydrocarbon compound containing two double bonds is 70% by weight or more and less than 100% by weight, specifically, the content of dicyclopentadiene is 83% by weight. An epoxy resin composition using an epoxy resin which is a reaction product of a polyphenol and epihalohydrin obtained by reacting a certain non-single compound component with a phenol is disclosed.

[0006]

However, the above-mentioned Japanese Patent Application Laid-Open No. 62-7 / 1987.
The epoxy resin composition disclosed in Japanese Patent No. 0413 is improved in fluidity and further improved in water resistance, so that solder crack resistance can be improved to some extent, but heat resistance is significantly reduced and solder crack resistance is also reduced. The level currently required was not reached.

[0007] The problem to be solved by the present invention is that it has both excellent water resistance and heat resistance, and furthermore, in addition to these performances, the fluidity is also improved, so that an unprecedented solder crack resistance is exhibited. An object of the present invention is to provide an epoxy resin composition, particularly a semiconductor encapsulating material. Another object of the present invention is to provide a production method for obtaining an epoxy resin exhibiting these properties.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies and as a result, have found that the content of an aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule is not less than 87% by weight. By using a composition containing an epoxy resin as a main component obtained by reacting a hydrocarbon compound component with a phenol and then reacting the phenol with an epihalohydrin, it has been found that the above problems can be solved, and the present invention has been completed. Reached.

That is, the present invention provides two double bonds in one molecule.
Polyphenols (a) obtained by reacting an aliphatic cyclic hydrocarbon compound component containing at least 87% by weight of an aliphatic cyclic hydrocarbon compound contained therein with a phenol (a
1), and then reacting this with epihalohydrin (a2). An epoxy resin composition comprising an epoxy resin (A) and a curing agent (B) as essential components, Epoxy resin (A)
However, polyphenols (a1) obtained by reacting an organic compound component containing 87% by weight or more of an aliphatic cyclic hydrocarbon compound (C) containing two double bonds in one molecule with a phenol and a phenol Resin composition characterized in that it is a reaction product of epoxy resin and epihalohydrin (a2), and an epoxy resin composition containing epoxy resin (A), curing agent (B) and inorganic filler (E) as essential components In things
The epoxy resin (A) reacts an aliphatic cyclic hydrocarbon compound component containing 87% by weight or more of an aliphatic cyclic hydrocarbon compound (C) containing two double bonds in one molecule with a phenol. Polyphenols (a1) obtained by
And an epihalohydrin (a2).

The epoxy resin (A) used in the present invention comprises 1
An aliphatic cyclic hydrocarbon compound component having a content of an aliphatic cyclic hydrocarbon compound having two double bonds in a molecule of 87% by weight or more, and a polyphenol (a1) obtained by reacting a phenol with a polyphenol (a1) The reaction product with epihalohydrin (a2) can be easily obtained by the production method of the present invention described in detail below. Hereinafter, the epoxy resin (A) will be described in detail based on the production method of the present invention.

That is, the production method of the present invention comprises an aliphatic cyclic hydrocarbon compound component containing 87% by weight or more of an aliphatic cyclic hydrocarbon compound having two double bonds in one molecule; A polyphenol (a1) obtained by reacting the same with an epihalohydrin (a2).

The double bond in one molecule used here is two.
The aliphatic cyclic hydrocarbon compound to be contained is not particularly limited as long as it is an aliphatic cyclic hydrocarbon compound having two or more unsaturated double bonds in one molecule, and examples thereof include dicyclopentadiene and tetrahydrogen. Inden, 4-
Vinylcyclohexene, 5-vinylnorbon-2-ene, α-pinene, β-pinene, limonene and the like. Among these, dicyclopentadiene is preferred from the viewpoint of the property balance, particularly the heat resistance and the hygroscopicity.

An aliphatic cyclic hydrocarbon compound represented by dicyclopentadiene, which contains two double bonds in one molecule, is contained in a petroleum fraction. Other aliphatic or aromatic dienes may be contained as impurities. In the present invention, by using an organic compound component having a purity of 87% by weight or more of an aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule, fluidity, water resistance and heat resistance of the cured product are obtained. In all cases, the solder cracking resistance can be remarkably improved as a semiconductor sealing material.

Next, the phenol to be reacted with the organic compound component is not particularly limited, but
Phenols and substituted phenols to which an alkyl group, an alkenyl group, an allyl group, an aryl group, an aralkyl group, a halogen group, or the like are bonded are exemplified. To be specific, cresol, xylenol, ethylphenol,
Isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol,
Bromophenol (each containing o, m, p-isomer),
Bisphenol A, naphthol, dihydroxynaphthalene and the like can be mentioned. Also, a mixture of these may be used. Among these, phenol and cresol are particularly preferred from the viewpoint of excellent fluidity and curability.

The reaction between these organic compounds and phenols is not particularly limited in their production conditions.
Fat having two double bonds in one molecule from the viewpoint that the melt viscosity of the finally obtained epoxy resin (A) can be reduced and the fluidity is excellent, and the epoxy group concentration is high and the curability is good. It is preferable to use 4 moles or more of phenols per 1 mole of the aromatic cyclic hydrocarbon compound. Among them, phenols / unsaturated alicyclic compounds = 2.5 / 1 to 15/1
When the synthesis is performed within the range of (molar ratio), a preferable intermediate for obtaining the desired epoxy resin is obtained.

Here, the reaction is described in more detail by adding a polyaddition catalyst to phenols in a molten or solution state,
After appropriately lowering the organic compound component, the mixture is heated and stirred to allow the polyaddition reaction to proceed. Thereafter, unreacted phenols are recovered by distillation to obtain a polyaddition reaction product. Here, as the polyaddition catalyst,
Examples include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as p-toluenesulfonic acid, and Lewis acids such as AlCl ₃ and BF ₃ .

In the production method of the present invention, the desired epoxy resin (A) is obtained by further reacting the polyphenols (a1) thus obtained with epihalohydrin (a2). This reaction may be performed according to a known method, for example, the following reaction.

First, epihalohydrin (a2) is added and dissolved in 2 to 15 equivalents, preferably 3 to 10 equivalents, of the polyphenols (a1) with respect to the hydroxyl group of the polyphenols (a1). 0.8 to 1.2 equivalents of 10 to 50% N based on hydroxyl groups in the polyaddition reaction product.
Aqueous aOH is applied at a temperature of 50-80 ° C. for 3-5 hours. After the lowering, the stirring is continued at that temperature for about 0.5 to 2 hours. 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 the epihalohydrin (a2) used here, epichlorohydrin is most common, but epiiodohydrin, epibromhydrin, β-methylepichlorohydrin and the like can also be used.

The epoxy resin (A) thus obtained
Is not particularly limited in its structure. As described above, the aliphatic cyclic hydrocarbon compound having two double bonds in one molecule used as a raw material may have a purity of 87% by weight or more. And the aliphatic cyclic hydrocarbon compound is dicyclopentadiene, the binuclear content is in the range of 40 to 75% by weight, and the melt viscosity at 150 ° C is 3. Epoxy resins having 0 poise or less and an epoxy equivalent in the range of 220 to 280 g / eq have more excellent performance. The epoxy resin (A) that satisfies these conditions has a lower molecular weight and more excellent fluidity, but also has a higher concentration of the epoxy group as a functional group, so that it can have both excellent curability and heat resistance. .

Further, a phenol is reacted with an organic compound component in which the content of an aliphatic cyclic hydrocarbon compound having two double bonds in one molecule is at least 90% by weight and less than 98% by weight. Polyphenols obtained (a1)
And an epihalohydrin (a2), wherein the aliphatic cyclic hydrocarbon compound is dicyclopentadiene, and the content of the binuclear substance is 45 to 70% by weight.
And the melt viscosity at 150 ° C. is 0.1-1.
0 poise range and an epoxy equivalent of 230 to 2
An epoxy resin in the range of 65 g / eq has extremely excellent performance in terms of curability and heat resistance.

Further, the epoxy resin of the present invention will be described in detail. An epoxy resin satisfying such conditions has a lower molecular weight and lower melt viscosity than the above-mentioned ECN.
Therefore, even if the blending amount of the inorganic filler is increased in order to reduce the moisture absorption coefficient and the coefficient of linear expansion, it has excellent fluidity during molding. Therefore, the solder crack resistance during surface mounting is particularly excellent.

On the other hand, the epoxy resin described in Examples of the above-mentioned Japanese Patent Application Laid-Open No. 62-70413 has a dicyclopentadiene content of 83% by weight. Excellent in dielectric properties. That is, by increasing the concentration of dicyclopentadiene, while maintaining good water resistance, excellent curability,
Heat resistance and dielectric properties can be imparted.

The term "binuclear" as used herein refers to a diglycidyl ether product of a bisphenol compound having an alicyclic compound as a bonding group in a reaction product of an unsaturated alicyclic compound and a phenol. This content is a value represented by a weight ratio analyzed by gel permeation chromatography (GPC).

Next, as the curing agent (B) used in the present invention, all compounds commonly used as curing agents for epoxy resins can be used, and are not particularly limited. Novolak resin, orthocresol novolak resin, bisphenol A novolak resin, bisphenol F novolak resin, phenol-dicyclopentadiene polyaddition resin, dihydroxynaphthalene novolak resin, polyphenols having a xylidene group as a bonding group, phenol-aralkyl Resins, naphthol resins Aliphatic amines such as diethylenetriamine and triethylenetetramine, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone, polyamide resins and modified products thereof Maleic anhydride, phthalic anhydride,
Acid anhydride curing agents such as hexahydrophthalic anhydride, pyromellitic anhydride, dicyandiamide, imidazole,
Latent curing agents such as BF3 -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 amount of the curing agent used is not particularly limited as long as it can cure the epoxy resin, and is preferably, but not limited to, the number of epoxy groups contained in one molecule of the epoxy resin to be used and the curing agent. This is the amount at which the number of active hydrogens in the vicinity becomes equivalent.

When each of the above compounds is used as a curing agent, a curing accelerator can be appropriately used.

As the curing accelerator, any of those known and used can be used. Examples thereof include phosphorus compounds, tertiary amines, imidazoles, metal salts of organic acids, Lewis acids, and amine complex salts. Not only one kind but also two or more kinds can be used in combination.

The epoxy resin composition 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,
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 colorant, a flame retardant, a release agent, and a coupling agent can be appropriately blended. Further, 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 or kneaded. The epoxy resin composition of the present invention thus obtained can be obtained by melt-kneading, etc., pulverizing after injection or cooling.
Its use is not particularly limited, and examples thereof include a semiconductor encapsulating material and a varnish for electric laminates because of its excellent solvent solubility in epoxy resin. Further, an oligomer type epoxy resin obtained by modifying the epoxy resin of the present invention with a brominated polyhydric phenol may be used for a laminate. Furthermore, a system in which a polyfunctional epoxy resin is blended or modified to impart heat resistance can also be used.

In order to obtain a polymer type epoxy resin, it is also possible to use the resin as a raw material resin for a two-stage reaction. Among these applications, semiconductor encapsulant applications are extremely useful, in particular, due to their advantages such as remarkably excellent solder crack resistance.

Hereinafter, the semiconductor encapsulating material of the present invention will be described in detail. The semiconductor encapsulating material of the present invention is an epoxy resin composition comprising an epoxy resin (A), a curing agent (B) and an inorganic filler (C) as essential components.
But polyphenols (a1) obtained by reacting an organic compound component containing 87% by weight or more of an aliphatic cyclic hydrocarbon compound having two double bonds in one molecule with phenols, and epihalohydrin (A2).

Here, the epoxy resin (A) is the epoxy resin obtained by the above-mentioned production method of the present invention, and the epoxy resin (A) used in the epoxy resin composition of the present invention.
Can be used.

As the curing agent (B), any of the curing agents (B) in the epoxy resin composition described above can be used.

Next, the inorganic filler (E) used in the present invention
Is not only to increase the mechanical strength and hardness of the cured product,
It is an essential component for achieving low water absorption and low coefficient of linear expansion and improving solder crack resistance.

The blending amount of the inorganic filler (C) is not particularly limited, but when it is in the range of 70 to 95% by weight in the composition, the characteristics thereof are particularly remarkable. It is preferable because the solder cracking resistance is very excellent in mass use. Also noteworthy here,
In the present invention, even if 80% by weight or more of the inorganic filler is added, fluidity and moldability are not impaired 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.

Further, in addition to the components of the epoxy resin composition described above, 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 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, 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 colorant, a flame retardant, a release agent, and a coupling agent can be appropriately blended. Further, 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 or kneaded. The mixture can be obtained by melt-kneading, etc., pulverizing after cooling and tableting.

The semiconductor encapsulating material of the present invention described in detail above
All required characteristics such as fluidity, curability, moldability, heat resistance after sealing and curing, water resistance, and solder crack resistance when mounting on a printed circuit board when sealing semiconductors. Is pleased.

[0042]

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 determined by dissolving 0.2 g of a sample in 20 ml of n-butanol, adding 1 g of metallic sodium, and heat-treating the solution at 120 ° C. for 2 hours by potentiometric titration using silver nitrate. It was measured. The melt viscosity was measured under the condition of 50 Hz.
ipment LTD. "ICI CONE &PLA"
TE VISCOMETER ". The content of the binuclear component is determined by "Gel Permeation Chromatography (GPC)" (manufactured by Tosoh Corporation)
1.0 ml / min, pressure = 92 Kg / cm2, column = G
4,3,2,2HXL, detector = RI 32 × 10−6
RIUFS). The softening point is "Softening point measuring device" manufactured by Meifou Seisakusho Co., Ltd. (Heating device: HU-MK, detector ASP
-M2) Measured.

Production 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 BF _3.
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 52 hours, 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.

In a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dean-Stark trap, and a condenser, 338 g of the resin and epichlorohydrin 740 were placed.
Add g and dissolve. It was heated to 55 ° C. and 163 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. Then, 600 g of MIBK and 200 g of water were added to the obtained crude resin solution.
And inorganic salts were removed by washing with water. 5% in this solution
100 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 is desolvated at 150 ° C. to remove the desired epoxy resin (I) 408
g was obtained. This resin was a black solid, had a melt viscosity of 0.4 poise at 150 ° C., a binuclear component content of 57% by weight, and an epoxy equivalent of 252 g / eq.

Production Example 2 The purity of a mixture mainly containing crude dicyclopentadiene was determined to be 92.9% by weight of dicyclopentadiene, 1.1% by weight of methyldicyclopentadiene, 1.8% by weight of propenylnorbornene, Nilnorbornene 0.1
388 g of an epoxy resin (II) was obtained in the same manner as in Production Example 1 except that the amount was changed to 1.7% by weight, and the compound having no double bond was 1.7% by weight. This resin is a black solid, 1
Melt viscosity at 50 ° C. 0.3 poise, binucleate component content 5
7% by weight, epoxy equivalent was 244 g / eq.

Production Example 3 367 g of epoxy resin (III) was obtained in the same manner as in Production Example 1 except that the amount of phenol was changed to 790 g. This resin is a black solid, the melt viscosity at 150 ° C. is 2.9 poise,
Binucleate content 49% by weight, epoxy equivalent 258g
/ Eq.

Production Comparative Example 1 The purity of a mixture mainly containing crude dicyclopentadiene was determined to be 83.1% by weight of dicyclopentadiene, 0.2% by weight of methyldicyclopentadiene, 5.2% by weight of propenylnorbornene, 329 g of an epoxy resin (IV) was obtained in the same manner as in Production Example 1, except that 3.9% by weight of penylnorbornene and 7.6% by weight of a compound having no double bond were used. This resin is a black solid, 15
Melt viscosity at 0 ° C. 1.1 poise, binuclear component content 52
% By weight, epoxy equivalent was 265 g / eq.

Examples 1-3 and Comparative Examples 1-2 The mixtures prepared according to the formulations shown in Table 1 were kneaded with a hot roll at 100 ° C. for 8 minutes to obtain epoxy resin compositions. 1200 to 1400 kg
/ Cm ² at a pressure of 80 kg / cm ² using a transfer molding machine.
The package was sealed under the conditions of cm ² , a mold temperature of 175 ° C., and a molding time of 100 seconds, and a 20 mm-thick 20-pin flat package was prepared as a test piece for evaluation. Then at 175 ° C 8
Post-curing was performed for an hour. The curability index at that time is 1
The spiral flow value was measured at 175 ° C./70 kg / cm ² for 120 seconds using a test mold as a gel time at 75 ° C. and as an index of fluidity. Using the test piece for evaluation thus obtained, 85 ° C./85% RH, 30
The moisture absorption rate under 0 hour condition, glass transition temperature by DMA, and 20 test pieces were left in an atmosphere of 85 ° C. and 85% RH for 168 hours to perform a 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.

N-665 is an ortho-cresol novolak type epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc.)
Trade name: EPICLON N-665, softening point 68 ° C,
Epoxy equivalent 208 g / eq, melt viscosity at 150 ° C. 3.0 poise), 153 is a tetrabromobisphenol A type epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc., trade name: E)
PICLON 153, softening point 70 ° C, epoxy equivalent 4
TD-2131 is a phenol novolak resin (trade name: Phenolite TD-2131, manufactured by Dainippon Ink and Chemicals, softening point 80 ° C., hydroxyl equivalent 104)
g / eq). As the silica powder, spherical silica having an average particle size of 25 μm was used.

[0051]

[Table 1]

[0052]

According to the present invention, the water resistance and the heat resistance are remarkably improved, and the fluidity is also improved.

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Claims (21)

[Claims] 1. A polyphenol (a1) obtained by reacting an organic compound component containing 87% by weight or more of an aliphatic cyclic hydrocarbon compound having two double bonds in one molecule with a phenol. ), And then reacting this with epihalohydrin (a2). 2. The method according to claim 1, wherein the content of the aliphatic cyclic hydrocarbon compound component is 90 to 98% by weight of the aliphatic cyclic hydrocarbon compound having two double bonds in one molecule. 3. The reaction ratio between an organic compound component and a phenol is such that phenol is added to one mole of an aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule contained in the organic component. The production method according to claim 1 or 2, wherein the ratio of the compounds is 4 mol or more. 4. The production method according to claim 1, wherein the aliphatic cyclic hydrocarbon compound having two double bonds in one molecule is dicyclopentadiene, and the phenol is phenol. 5. The reaction ratio between the polyphenols (a1) and epihalohydrin (a2) is 2 to 15 equivalents to the hydroxyl groups of the polyphenols (a1).
5. The production method according to any one of items 4 to 4. 6. An epoxy resin composition comprising an epoxy resin (A) and a curing agent (B) as essential components, wherein the epoxy resin (A) is an aliphatic cyclic resin containing two double bonds in one molecule. Epoxy resin composition characterized in that it is a reaction product of polyphenols (a1) obtained by reacting an organic compound component having a hydrogen compound content of 87% by weight or more with phenols and epihalohydrin (a2). Stuff. 7. The epoxy resin (A) reacts an organic compound component containing 90 to 98% by weight of an aliphatic cyclic hydrocarbon compound having two double bonds in one molecule with a phenol. Polyphenols (a1) obtained by
7. The composition according to claim 6, which is a reaction product between the compound and epihalohydrin (a2). 8. An aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule is dicyclopentadiene,
8. The composition according to claim 6, wherein the phenol is phenol. 9. The epoxy resin (A) having a binuclear content of 40 to 75% by weight.
A composition as described. 10. The composition according to claim 6, wherein the epoxy resin (A) has a melt viscosity at 150 ° C. of 3.0 poise or less. 11. The epoxy resin (A) having an epoxy equivalent in the range of 220 to 280 g / eq.
0. The composition according to any one of 0. 12. The epoxy resin (A) reacts an organic compound component containing 90 to 98% by weight of an aliphatic cyclic hydrocarbon compound having two double bonds in one molecule with a phenol. Polyphenols (a1) obtained by
And a reaction product with epihalohydrin (a2), the aliphatic cyclic hydrocarbon compound is dicyclopentadiene, and the content of binuclear substance is in the range of 45 to 70% by weight, and melting at 150 ° C. The viscosity is in the range of 0.1 to 1.0 poise and the epoxy equivalent is 230 to 265 g / e
The composition according to any one of claims 6 to 11, which is in the range of q. 13. An epoxy resin composition comprising an epoxy resin (A), a curing agent (B) and an inorganic filler (C) as essential components, wherein the epoxy resin (A) has two double bonds in one molecule. A polyphenol (a1) and an epihalohydrin (a2) obtained by reacting an organic compound component containing at least 87% by weight of an aliphatic cyclic hydrocarbon compound contained therein with a phenol. Characteristic semiconductor sealing material. 14. An epoxy resin (A) comprising an organic compound component containing 90 to 98% by weight of an aliphatic cyclic hydrocarbon compound having two double bonds in one molecule, and a phenol. Polyphenols obtained by the reaction (a
14. The semiconductor encapsulant according to claim 13, which is a reaction product of 1) and epihalohydrin (a2). 15. The aliphatic cyclic hydrocarbon compound having two double bonds in one molecule is dicyclopentadiene, and the phenol is phenol.
5. The semiconductor sealing material according to 4. 16. The semiconductor encapsulating material according to claim 13, wherein the content of the binuclear body of the epoxy resin (A) is in the range of 40 to 75% by weight. 17. The melt viscosity at 150 ° C. of the epoxy resin (A) is 3.0 poise or less.
7. The semiconductor sealing material according to any one of 6. 18. The epoxy resin (A) having an epoxy equivalent in the range of 220 to 280 g / eq.
18. The semiconductor encapsulation material according to any one of the above items 17. 19. An epoxy resin (A) wherein the content of the aliphatic cyclic hydrocarbon compound having two double bonds in one molecule is 90 to 98% by weight; A reaction product of a polyphenol (a1) obtained by reacting a phenol with an epihalohydrin (a2), wherein the aliphatic cyclic hydrocarbon compound is dicyclopentadiene, and the content of the binuclear compound is 45 to 45; 70% by weight, and the melt viscosity at 150 ° C. is 0.1 to
1.0 poise range and an epoxy equivalent of 230
20 to 265 g / eq.
The semiconductor sealing material according to any one of the above. 20. The semiconductor encapsulating material according to claim 13, wherein the inorganic filler is silica, and the content thereof is 70 to 95% by weight. 21. The semiconductor sealing material according to claim 20, wherein the silica contains spherical silica having an average particle size of 10 to 50 μm.