JPH07258240A - Glycidyl ether compound and epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as e.g. a modifier for various resins such as epoxy resins as sealers, capable of improving such resins' moldability, heat resistance, moisture resistance, adhesivity and flexibility, by reaction between a specific monoallyl naphthol compound and an epihalohydrin. CONSTITUTION:This compound is obtained by reaction between a compound of the formula (R is H or OH) such as 2-allyl-1,6-dihydroxynaphthalene and an epihalohydrin. Specifically, this compound can be obtained, for example, by the following processes: a naphthol compound is dissolved in a solvent such as toluene; an aqueous solution of a base such as NaOH is then added to the resultant solvent solution followed by homogenization; subsequently, an allyl halide such as allyl chloride is dripped into the homogeneous liquid system to effect reaction, and the resultant reaction product is subjected to Claisen rearrangement reaction at 100-170 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a glycidyl ether compound based on a novel monoallylnaphthol compound, an epoxy resin composition containing the compound, and an epoxy resin composition further containing a curing agent.

[0002]

2. Description of the Related Art Conventionally, a method of encapsulating a semiconductor element with an epoxy resin composition has been widely adopted in order to protect the semiconductor element from the external environment. The composition is usually composed of an epoxy resin, a curing agent, a curing accelerator, a filler, and other additives. As the epoxy resin, a resin obtained by epoxidizing a novolak resin obtained by the reaction of phenols and formaldehyde, particularly an orthocresol novolac epoxy resin is widely used, and a phenol-formaldehyde novolac resin is used as a curing agent. .

However, the recent trend toward higher density and higher integration in semiconductor devices requires the encapsulant to be further improved in various properties such as heat resistance, moisture resistance and adhesion.

Particularly, in the case of mounting the semiconductor element by the surface mounting method, the package of the semiconductor element is 200
It is placed in an oven at a high temperature of about 260 ° C. and exposed to severe temperature conditions. Therefore, even if the above-mentioned epoxy resin composition is used, there is still a problem that cracks occur in the package of the semiconductor device, and the demand for high heat resistance, low water absorption and high adhesion to the cured product is becoming stronger. .

To meet these requirements, a resin obtained by epoxidizing a novolak resin obtained by reacting naphthol with an aldehyde has been proposed. This resin is intended to improve physical properties such as heat resistance and moisture resistance of a cured product by introducing a naphthol skeleton. In fact, these properties give excellent properties, but on the other hand, it has a high viscosity. It has not been put into practical use due to problems such as poor molding workability and poor adhesion.

On the other hand, no glycidyl ether compound based on a monoallylnaphthol compound is known,
Moreover, there is no example in which these are used as a diluent for an epoxy resin, particularly a resin obtained by epoxidizing an aldehyde condensate of naphthols, and an epoxy resin composition containing them or an epoxy resin composition further containing a curing agent is not known.

The object of the present invention is to be useful as a diluent, modifier or modifier of epoxy resin, which lowers the melting point and melt viscosity of the epoxy resin to impart excellent workability, and
To provide a novel monoallylnaphthol compound-based glycidyl ether compound which has a high glass transition temperature, heat resistance, moisture resistance, adhesion and flexibility and can give a cured product without cracks is there.

Another object of the present invention is to provide a novel epoxy resin composition having a high glass transition temperature, excellent heat resistance, moisture resistance, adhesiveness and flexibility, and capable of preventing cracks from occurring in the package. Is provided.

[0009]

The glycidyl ether compound of the present invention is obtained by reacting a monoallylnaphthol compound represented by the following general formula with epihalohydrin.

[0010]

[Chemical 2]

The glycidyl ether compound based on the monoallylnaphthol compound of the present invention is useful as a modifier for an epoxy resin. The epoxidized aldehyde condensate of naphthols, which has been proposed as a high-performance epoxy resin, has a problem of high viscosity and poor molding workability, but this epoxy resin is based on the monoallylnaphthol compound of the present invention. By blending the glycidyl ether compound described above, the melting point and melt viscosity are remarkably reduced, and excellent workability can be obtained. Moreover, the epoxy resin composition containing a glycidyl ether compound based on the monoallylnaphthol compound of the present invention, the crosslink density is increased by the reaction of the allyl group, the cured product shows a high glass transition temperature, heat resistance, Excellent in moisture resistance, adhesion and flexibility.

The epoxy resin composition of the present invention comprises a glycidyl ether compound based on the monoallylnaphthol compound represented by the above general formula, and an epoxidized product of the glycidyl ether compound and an aldehyde condensate of naphthols.

The present invention further provides an epoxy resin composition containing the epoxy resin composition and a curing agent (hereinafter referred to as "curing agent-containing epoxy resin composition").

The curing agent-containing epoxy resin composition of the present invention containing a glycidyl ether compound based on a monoallylnaphthol compound preferably contains a curing accelerator, and in that case, it is particularly effective as a semiconductor encapsulating composition. Is.

In the present specification, the term "epoxy resin" is used to include not only a resinous epoxy compound but also a low molecular weight epoxy compound unless otherwise specified.

The glycidyl ether compound of the first invention will be described. In order to obtain a monoallylnaphthol compound as a raw material (that is, a base) of the glycidyl ether compound of the present invention with high purity and high yield, it is preferable to produce it by the following two methods, and either method may be used.

(Method A) A naphthol, a base, and water, if necessary, and an organic solvent, if necessary, are mixed homogeneously to form a phenolate, and the allyl halide is added dropwise to the solution system over a long period of time to carry out the allylation reaction. And then heating at high temperature to cause Claisen rearrangement.

(Method B) A method in which naphthols and allyl halide and, if necessary, an organic solvent are added and uniformly mixed, and an allylation is carried out by dropping an aqueous solution of a base into the solution system, followed by heating to cause Claisen rearrangement. .

The naphthols to be allylated are α-naphthol, β-naphthol or dihydroxynaphthalene. As dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene,
1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,
4-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-
Examples thereof include dihydroxynaphthalene.

As the allyl halide to be used, allyl chloride and allyl bromide are usually used, but allyl chloride is preferred mainly for economical reasons.

As the base, sodium hydroxide,
Water-soluble bases such as alkali metal hydroxides such as potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal alcoholates of aliphatic alcohols such as sodium methoxide and sodium ethoxide; In particular, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferable in terms of reactivity and economy.

The amounts of the allyl halide and the base used in these methods are in the range of 1.0 to 2.0 mol, and 1.0 to 1.5 mol per 1 mol of the naphthols. preferable. The allyl halide is preferably used in an equimolar amount or more than the base. The amount of allyl halide and base used is 1.
If it is less than 0 mol, the reactivity becomes poor.

These reactions are preferably carried out in the presence of an organic solvent, and examples of the organic solvent include toluene, xylene, ethyl acetate, methyl ethyl ketone,
Examples include methyl isobutyl ketone.

The allylation reaction of Method A will be described in detail.
The naphthols are dissolved in a solvent, and a predetermined amount of a base or an aqueous solution of a base is added to the solution to homogenize it. Then, with stirring, the temperature of this reaction system is 20 to 100 ° C., preferably 5
The temperature is raised to 0 to 99 ° C., the allyl halide is heated for 1 hour or more,
Preferably, the reaction is carried out while dropping for 2 hours or more.
After completion of dropping, the mixture is further stirred for 1 to 4 hours if necessary. When water is used, the produced allyl ether is insoluble in water, so that the reaction solution becomes suspended and becomes non-uniform as the reaction progresses. Therefore, the reaction solution should be 100-1000 rpm.
It is preferable to stir at. After completion of the allylation reaction, the inorganic salt or the aqueous layer is removed, and the organic layer is washed several times with an appropriate amount of distilled water. Then, the solvent is distilled off from the organic layer to obtain an allyl ether compound-containing product. Then, this reaction product is subjected to a rearrangement reaction in the absence of a solvent or in the presence of a solvent. This rearrangement reaction is 1 to 12 at a temperature of 100 to 170 ° C.
The time is preferably 120 to 150 ° C. and 2 to 6 hours. In this way, almost 100% of the monoallylnaphthol compound is obtained.

The allylation reaction of Method B will be described in detail.
Naphthols are dissolved in a solvent, and a predetermined amount of allyl halide is added to the solution to homogenize it. Then, while stirring, the temperature of the reaction system is 20 to 100 ° C, preferably 40 to 90 ° C.
The temperature is raised to 1, and an aqueous solution of an alkali metal hydroxide is added dropwise over 1 to 10 hours, preferably 2 to 6 hours to react.
After completion of dropping, the mixture is further stirred for 1 to 4 hours if necessary. When water is used, the reaction system is 100 to 100 as in Method A.
It is better to stir at 0 rpm. After completion of the allylation reaction,
As in Method A, washing and purification are performed and the Claisen rearrangement reaction is performed. By this method, almost 100% of the monoallylnaphthol compound can be obtained.

The analysis and identification of the monoallylnaphthol compound was carried out by gel permeation chromatography (GPC method), infrared absorption spectrum (IR) and nuclear magnetic resonance spectrum (NMR). Below G
The measurement conditions of PC and NMR are shown.

(GPC analysis) Solvent: Tetrahydrofuran Flow rate: 0.8 ml / min Column: G4000H, G3000 manufactured by Tosoh Corporation
H and G2000H (series) with exclusion limit molecular weights of 400,000, 60,000 and 10,000, respectively.
Is. Carrier: Styrene / divinylbenzene copolymer

(NMR) The NMR spectrum of the monoallylnaphthol compound was confirmed as belonging to the following.

[0029]

[Chemical 3]

The glycidyl ether compound of the present invention can be obtained by reacting the above-mentioned monoallylnaphthol compound with epihalohydrin, and for the usual reaction, the following two typical methods can be used.

1) A one-step method in which a monoallylnaphthol compound and an excess of epihalohydrin are simultaneously subjected to an addition reaction and a ring-closing reaction to form an epoxy ring in the presence of an alkali metal hydroxide.

2) A two-step method in which a monoallylnaphthol compound and an excess of epihalohydrin are subjected to an addition reaction in the presence of a basic catalyst, and then an alkali metal hydroxide is added to carry out a ring-closing reaction.

Epihalohydrin in this reaction is
Epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, β-methylepibromohydrin,
β-methyl epiiodohydrin and the like can be mentioned, but epichlorohydrin is preferred from the economical point of view.

As the alkali metal hydroxide in this reaction, caustic soda and caustic potash are used,
These remain solid or aqueous solutions, preferably 40-50%
It is added to the reaction system as an aqueous solution.

As the basic catalyst in the above reaction, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, triethylmethylammonium chloride, trimethylbenzyl. Quaternary ammonium salts such as ammonium chloride and triethylbenzylammonium chloride are used.

In the above one-step method, 50 to 150
The reaction is carried out at a temperature of 80 ° C, preferably 80 to 120 ° C. 0.8 to 1 per equivalent of hydroxyl group of monoallylnaphthol compound
1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents are used.

In the above two-step method, the reaction in the first step is carried out at a temperature of 60 to 150 ° C, preferably 100 to 140 ° C. The amount of epihalohydrin used is 1.3 to 20 molar equivalents, preferably 2 to 10 molar equivalents, relative to 1 equivalent of the hydroxyl group of the monoallylnaphthol compound, and excess epihalohydrin can be recovered and reused after the reaction.

The basic catalyst is used in an amount of 0.002 to 3.0 mol% based on the hydroxyl group of the monoallylnaphthol compound.
Used in proportion. The latter reaction is carried out at 50 to 150 ° C, preferably 60 to 120 ° C. The alkali metal hydroxide is usually 1 to 1.1 with respect to the produced halohydrin.
Used in molar amounts.

These first-stage and second-stage reactions may be carried out in the absence of a solvent or in the presence of an inert solvent such as methyl isobutyl ketone, cyclohexane or toluene. After completion of the reaction, these may be purified by washing with water or solvent, or may be evaporated and degassed. Thus, the glycidyl ether compound of the present invention is obtained.

A second invention is an epoxy resin composition containing the glycidyl ether compound based on the monoallyl naphthol and an epoxy resin based on an aldehyde condensate of naphthols.

Any aldehyde condensate of naphthols may be used, but especially α-naphthol aldehyde condensate, β-naphthol aldehyde condensate, α
-Naphthol / β-naphthol / aldehyde condensation product, naphthol / phenol / aldehyde condensation product, naphthol / alkylphenol / aldehyde condensation product, dihydroxynaphthalene / aldehyde condensation product, dihydroxynaphthalene / phenol / aldehyde condensation product, dihydroxynaphthalene / alkylphenol / aldehyde condensation product , A dihydroxynaphthalene / naphthol / aldehyde condensate, or a mixture thereof is useful. Also,
Aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, glyoxal, and aromatic aldehydes such as benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, and terephthalaldehyde are useful as the aldehyde.

The aldehyde condensate of this naphthol is
According to a conventional method, it can be easily obtained by adding an alkali catalyst or an acid catalyst to a raw material or a raw material dissolved in a solvent, if necessary, and stirring with heating.

The epoxy resin based on the aldehyde condensate of naphthols can be obtained by subjecting the aldehyde condensate of naphthols alone to the epoxidation reaction of the above 1) or 2). You may obtain the epoxy resin composition which is the 2nd invention by mix | blending with the aldehyde condensate of this naphthol, and making it epoxidize simultaneously. The blending ratio of the glycidyl ether compound and the epoxy resin based on the aldehyde condensate of this naphthol is 3/97 to 50/50, preferably 5/95 to 35/65 by weight.

The epoxy resin based on the aldehyde condensate of naphthols may be blended alone and used, and 70% by weight or less, preferably 50% by weight or less of a general epoxy resin such as orthocresol resin epoxy resin may be used. , Bisphenol epoxy resin, phenol resin epoxy resin can also be used instead.

The curing agent-containing epoxy resin composition of the third invention further comprises a curing agent in addition to the epoxy resin composition of the second invention, and the composition further comprises a curing accelerator. In this case, it is particularly useful as a resin composition for semiconductor encapsulation.

The curing agent used at this time has two or more, preferably three or more phenolic hydroxyl groups in the molecule. Specific examples include phenols and substituted phenols such as o-cresol, p-cresol, t-butylphenol, cumylphenol, phenylphenol and formaldehyde reacted with an acid or an alkali. Instead of formaldehyde, other aldehydes such as benzaldehyde, crotonaldehyde, salicylaldehyde, hydroxybenzaldehyde, glyoxal, and terephthalaldehyde can be used. A reaction product of resorcin and an aldehyde and polyvinylphenol can also be used as the curing agent of the present invention.

Further, polyhydroxynaphthalene compounds such as α-naphthol formalin condensate, α-naphthol aldehyde condensate, β-naphthol aldehyde condensate, α-naphthol / β-naphthol aldehyde co-condensate, naphthol / phenol aldehyde Cocondensate,
Naphthol-cresol aldehyde co-condensate, naphthol xylenol aldehyde co-condensate, naphthol-alkyl (C ₃ or more) phenol-aldehyde co-condensate, dihydroxynaphthalene aldehyde condensate, dihydroxynaphthalene-naphthol aldehyde co-condensate, dihydroxynaphthalene-phenol Aldehyde cocondensates, dihydroxynaphthalene / cresol / aldehyde cocondensates, dihydroxynaphthalene / xylenol / aldehyde cocondensates, dihydroxynaphthalenealkyl (C ₃ or more) phenol / aldehyde cocondensates, etc. are also useful as curing agents.

The mixing ratio of these curing agents is usually such that the equivalent ratio of the phenolic hydroxyl groups of the curing agent to the epoxy groups of the epoxy resin (epoxy group / phenolic hydroxyl group) is 1.
/0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 /
The range of 1.1 is selected from the viewpoint of heat resistance and moisture resistance.

The curing accelerator is a usual catalyst and is not particularly limited. Specific examples of the curing accelerator include, for example, triphenylphosphine, tris-2,6dimethoxyphenylphosphine, tri-p-tolylphosphine,
Phosphorus compounds such as triphenyl phosphite, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-
Imidazoles such as ethyl-4-methylimidazole, tertiary amines such as 2-dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzylmethylamine, 1,8-diazabicyclo (5,4,0)
Undecene-7,1,8-diazabicyclo (5,4,
0) Organic acid salts of undecene-7 and the like.

From the viewpoint of heat resistance and moisture resistance, it is preferable that the amount of the curing accelerator is 0.1 to 3.0% by weight in the composition of the present invention.

In the present invention, in addition to the above-mentioned components, various compounds may be blended as required. For example, it is a surface treatment agent for treating the surface of the filler or the filler, a flame retardant, a release agent, a coloring agent, and a flexibility imparting agent.

The filler is not particularly limited, and examples thereof include crystalline silica powder, fusible silica powder, quartz glass powder,
Examples thereof include talc, calcium silicate powder, zirconium silicate powder, alumina powder, and calcium carbonate powder, with silica-based powders being preferred.

The blending ratio of the filler is 6 with respect to the total composition.
0 to 90% by weight, preferably 70 to 85% by weight. If the compounding amount of the filler exceeds 90% by weight, the fluidity of the composition will be low and molding will be difficult. If it is less than 60% by weight, the thermal expansion tends to be large.

Examples of the surface treatment agent include known silane coupling agents, flame retardants such as antimony trioxide, antimony pentoxide, phosphates and bromides, and various release agents such as waxes. Carbon black or the like is used as the colorant, and silicone resin, butadiene-acrylonitrile rubber or the like is used as the flexibility-imparting agent. However, it is not limited to these.

The method for preparing the two epoxy resin compositions of the present invention is not particularly limited, and the conventional method can be used. Further, there is no particular limitation on the conditions for sealing a semiconductor using the curing agent-containing epoxy resin composition of the present invention, and usually,
Conditions such as 175 ° C., molding pressure 100 kg / cm ² , molding for 3 minutes and post-curing at 180 ° C. for 6 hours are adopted.

[0056]

The glycidyl ether compound based on the monoallylnaphthol compound of the present invention is useful as a thermosetting resin raw material, a modifier of various resins, a modifier, a diluent or a curing agent, an intermediate raw material for fine chemicals, and the like. In particular,
When used as a modifier for an epoxy resin based on an aldehyde condensate of naphthols, which has been investigated as a high-performance epoxy resin, the resulting resin composition has remarkably improved fluidity and excellent molding workability. Furthermore, the resulting cured product has heat resistance, moisture resistance, adhesion and flexibility,
Generation of cracks is prevented.

[0057]

EXAMPLES Hereinafter, the embodiments of the present invention will be specifically illustrated and described with reference to Examples. The invention is not limited to these examples.

Example 1 (Monoallylnaphthol Compound 1) β-naphthol 14 was placed in a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer.
4 g (1 mol), an aqueous solution of sodium hydroxide 48 g (1.2 mol) 240 g and methyl isobutyl ketone 2
00 g was charged, and the mixture was heated to 80 ° C. with stirring to homogenize it to form a phenolate. To this reaction solution, 91.8 g (1.2 mol) of allyl chloride was added dropwise using a dropping funnel over 3 hours, and after completion of the addition, the mixture was stirred for 1 hour to react. After the reaction was completed, the reaction solution separated into two layers was transferred to a separating funnel, the lower aqueous layer was separated and removed, and then the organic layer was separated into 50 layers.
It was washed 5 times with 0 ml of distilled water. Then, methyl isobutyl ketone was completely distilled off from this organic layer under reduced pressure.
The obtained reaction product was liquid. The reaction product is 0% by weight of unreacted naphthol and 1 of allyl ether compound.
It was a mixture of 2.0% by weight and 88.0% by weight of allylnaphthol.

Next, the reaction product was transferred to a reaction vessel,
The rearrangement reaction was performed by heating to 140 ° C. and stirring for 2 hours. As a result, a reddish brown liquid was obtained. This product was a compound (A-1) containing 0% by weight of unreacted naphthol, 0.5% by weight of allyl ether, and 99.5% by weight of monoallyl β-naphthol represented by the following formula. The infrared absorption spectrum of this compound is shown in FIG. The hydroxyl equivalent was 190.

[0060]

[Chemical 4]

(Glycidyl ether compound 1) The total amount of the above compound, 460 g of epichlorohydrin and 3 g of tetrabutylammonium bromide were charged and reacted under heating under reflux for 3 hours, and excess epichlorohydrin was removed under reduced pressure. Add the same amount of toluene as the contents, cool to 60 ° C,
With a water removal device, add 41 g of sodium hydroxide,
A ring-closing reaction was carried out while continuously removing the produced water at a reduced pressure of 100 to 150 mmHg. After washing with water to remove salts and unreacted alkali, toluene and water were removed under reduced pressure. The obtained compound (B-1) had an epoxy equivalent of 270.
It was a liquid product with extremely low viscosity.

Example 2 (Monoallyl naphthol compound 2) α-naphthol 14 was placed in a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer.
4 g (1 mol), 200 g of methyl isobutyl ketone, and 99.5 g (1.3 mol) of allyl chloride were charged, heated to 80 ° C. and uniformly dissolved, and then stirred with sodium hydroxide (1.3 mol). A 10% aqueous solution was added dropwise by a dropping funnel over 2 hours, and after completion of the dropping, the mixture was stirred for 1 hour to cause a reaction. After completion of the reaction, the reaction solution separated into two layers was transferred to a separating funnel, the lower aqueous layer was separated and removed, and the organic layer was washed 5 times with 500 ml of distilled water. Then, the methyl isobutyl ketone was completely distilled off under reduced pressure. The obtained reaction product was a reddish brown liquid. The reaction product is 0% by weight of unreacted naphthol and 1 of allyl ether compound.
It was a mixture of 0% by weight and 90% by weight of allylnaphthol.

Next, the reaction product was transferred to a reaction vessel,
The rearrangement reaction was performed by heating to 140 ° C. and stirring for 2 hours. As a result, a reddish brown liquid was obtained. This product was a compound (A-2) of monoallyl α-naphthol (purity 99%) represented by the following formula. The hydroxyl equivalent was 192.

[0064]

[Chemical 5]

(Glycidyl ether compound 2) Example 1
Glycidyl ether (B-2) was obtained in the same manner as in Glycidyl ether B-1. It was a liquid product having an epoxy equivalent of 280 and extremely low viscosity.

Example 3 (Monoallylnaphthol Compound 3) An allylnaphthol compound (A-3 was prepared in the same manner as in Example 1 except that 160 g (1 mol) of 1,6-dihydroxynaphthalene was used in place of β-naphthol. ) Was synthesized. The obtained final product was a yellowish brown liquid substance, which was monoallyl 1,6-dihydroxynaphthalene (purity 98.2%) represented by the following formula. The hydroxyl equivalent was 105.

[0067]

[Chemical 6]

(Glycidyl ether compound 3) A glycidyl ether (B-3) was obtained in the same manner as in Example 1 except that the total amount of the compound 3 was changed to 920 g of epichlorohydrin and 82 g of sodium hydroxide. The epoxy equivalent was a liquid product having a low viscosity of 190.

Examples 4 to 10 Aldehyde condensate-based epoxy resins of naphthols shown in Table 1 were added to monoallyl β-naphthol-based glycidyl ether compound (B-1) or monoallyl α-.
Naphthol-based glycidyl ether compound (B-
2) or monoallyl 1,6-dihydroxynaphthalene-based glycidyl ether compound (B-3) was blended in the proportion (parts by weight) shown in Table 2 to prepare an epoxy resin composition.

[0070]

[Table 1]

[0071]

[Table 2]

The melt viscosity (150 ° C.) and melting point of the formulation are
It is shown in Table 3 in comparison with that of the epoxy resin (C-1 to C-6) based on the naphthol / aldehyde condensate before blending.

[0073]

[Table 3]

Examples 11 to 17 and Comparative Example 1 The following epoxy resin, curing agent, curing accelerator, filler, antimony trioxide, silane coupling agent, wax and carbon black were used in the proportions (weight) shown in Table 4. Parts), kneaded with a two-roll mill at a temperature of 70 to 110 ° C., then cooled and pulverized to prepare an epoxy resin composition for semiconductor encapsulation.

Epoxy resin: Epoxy resin composition obtained in Examples 4 to 10 o-cresol novolac type epoxy resin (epoxy equivalent 195, melting point 85 ° C) Brominated phenol novolac type epoxy resin (epoxy equivalent 280, melting point 83 ° C) ) Hardening agent: Phenol novolac resin (hydroxyl group equivalent 106, melting point 80 ° C) Curing accelerator: Triphenylphosphine Filler: Spherical silica (BF10 of Mitsubishi Metals Co., Ltd.)
0)

The composition obtained was treated at 175 ° C. and 100 kg.
/ Cm ² , molded under curing conditions of 3 minutes, then 180
A post-cure was performed under the conditions of ° C and 6 hours to prepare a molded test piece. This test piece is an 80-pin four-way flat package (80-pin QFP, size 20 x 14 x 2 mm)
And the die pad size is 8 × 8 mm.

The semiconductor device thus obtained was subjected to a TCT test of −50 ° C./5 minutes to 150 ° C./5 minutes to check the number of cracks. In addition, the test piece,
A crack resistance test was conducted by allowing the sample to stand in a constant temperature bath having a relative humidity of 85 ° C./85% RH to absorb moisture, and then immersing it in a solder melt at 260 ° C. for 10 seconds. The results are shown in Table 5.

The bending strength (high temperature strength) of the obtained test piece at 200 ° C., the glass transition temperature, the thermal expansion coefficient,
The water absorption was examined after a humidification test at 85 ° C./85% RH for 500 hours. The results are shown in Table 6.

[0079]

[Table 4]

[0080]

[Table 5]

[0081]

[Table 6]

[0082]

The glycidyl ether compound based on the monoallylnaphthol compound of the present invention can be effectively used as a modifier, modifier or diluent for various resins. In particular, when used as a modifier for an epoxy resin, the epoxy resin cured product has excellent heat resistance, moisture resistance, adhesion and flexibility as well as excellent molding workability, and cracks occur in the package during soldering. Hateful.

A cured product of the curing agent-containing epoxy resin composition of the present invention containing the glycidyl ether compound based on the monoallylnaphthol compound and a curing agent has a high glass transition temperature, excellent heat resistance, and mechanical strength. Also has a small water absorption rate, excellent moisture resistance, and extremely few cracks even during soldering. Therefore, it is useful as a composition for semiconductor encapsulation.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the monoallylnaphthol compound produced in Example 1.

Claims (3)

[Claims] 1. A glycidyl ether compound obtained by reacting a naphthol compound having one allyl group represented by the following general formula with epihalohydrin. [Chemical 1] 2. An epoxy resin composition comprising the glycidyl ether compound according to claim 1 and an epoxy resin obtained by the reaction of an aldehyde condensate of naphthols with epihalohydrin. 3. An epoxy resin composition comprising the epoxy resin composition according to claim 2 and a curing agent.