JPH07242727A - Epoxy resin and epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyfunctional epoxy resin for semiconductor sealing which is excellent in sealing efficiency by reacting a specific allylnaphthol copolycondensate with an epihalohydrin. CONSTITUTION:An allylnaphthol copolycondensate having a weight-average mol.wt. of 300-2,000 and represented by formula I is reacted with an epihalohydrin. In the formula, A is an allylnaphthol compound (a) represented by formula II; B is a phenol derivative (b) represented by formula III; D is a naphthol represented by formula IV; E is at least either of the compound (a) and the phenol derivative (b), provided that the proportion of A is 10-0mol% based on the sum of A, B, D, and E (R<1>, R<2>, and R<3> each is H, an alkyl, hydroxy, or allyl, and R<4> is H or methyl); R<5> is an aldehyde residue; and k, l, m, and n each is a number of 0-10; provided that when k=l=0, then at least either of E's contains an allyl group; when k=m=0, then at least either of E's is a phenol residue; and when k=l=m=n=0, then one of E's is an allylnaphthol residue and the other is a phenol residue.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin based on a specific allylnaphthol cocondensate and having excellent workability, and an epoxy resin composition containing this epoxy resin and a curing agent.

[0002]

2. Description of the Related Art Conventionally, a method of encapsulating with a epoxy resin composition has been widely adopted in order to protect a 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. . Also, as a high-performance epoxy resin, an epoxy resin based on a novolac resin obtained by reacting α-naphthol with formalin water using an acid catalyst is introduced, but the performance such as heat resistance and moisture resistance is satisfactory. However, it has not been put to practical use because of its high melting point and melt viscosity and poor workability in molding and the like.

[0003]

The object of the present invention is to have excellent workability due to its low melting point and melt viscosity, and to have a high glass transition temperature, heat resistance and humidity resistance after curing with a curing agent.
It is an object of the present invention to provide a polyfunctional epoxy resin based on a specific allylnaphthol cocondensate which gives a cured product capable of preventing the package from cracking.

Another object of the present invention is to provide an epoxy resin composition which has a high glass transition temperature, is excellent in heat resistance and moisture resistance, and is useful as a semiconductor encapsulating material capable of preventing cracks from being generated in a package. It is in.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that allylnaphthols (10 to 50 mol%, converted to aldehyde exclusion) are added to polyhydroxy compounds which are the base of epoxy resin. ), A methyl group-substituted phenol and an aldehyde are co-condensed to obtain an allylnaphthol cocondensate having a weight average molecular weight of 300 to 2000, which is obtained by reacting this specific cocondensate with epihalohydrin. It was found that the obtained epoxy resin has a low melting point and a low melt viscosity, whereby it has excellent workability, exhibits a high glass transition temperature after curing, and has excellent heat resistance and moisture resistance, and completed the present invention.

That is, the following general formula (I) or (II)
To provide a polyfunctional epoxy resin obtained by reacting an allylnaphthol cocondensate having a weight average molecular weight of 300 to 2000 with epihalohydrin.

[0007]

[Chemical 3]

[0008]

[Chemical 4]

The present invention further provides an epoxy resin composition containing an epoxy resin based on the above allylnaphthol cocondensate and a curing agent.

The epoxy resin composition of the present invention containing an epoxy resin based on an allylnaphthol cocondensate preferably contains a curing accelerator, in which case it is particularly effective as a semiconductor encapsulating composition.

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.

(Requirements Constituting Means) The essential requirements for obtaining the high performance epoxy resin of the present invention are the above-mentioned general formula (I).
Or allylnaphthols represented by (II) (10 to 5
A compound having a weight average molecular weight of 300 to 2000, which has a molecular structure in which 0 mol% (excluding aldehyde) and a methyl group-substituted phenol and an aldehyde are co-condensed is used as the base of the epoxy resin.

The allyl group of allylnaphthols is present in the naphthalene nucleus in an amount of 1 to 2 but is preferably 1 in order to accelerate the condensation reaction.

The weight average molecular weight of the allylnaphthol cocondensate is 300 to 2000. When it is less than 300, the number of OH groups in the molecule is too small and the number of epoxy groups becomes small, resulting in insufficient curing during curing, and when it exceeds 2000, the melting point and viscosity of the epoxy resin of the present invention become high and workability is improved. Inferior.

In addition, the methyl group-substituted phenols of 80
Co-condensates obtained by replacing mol% or less, preferably 70 mol% or less with at least one of α-naphthol and β-naphthol are also useful because of low viscosity.

Further, in this allylnaphthol cocondensation product, in the cocondensation product having a molecular structure in which allylnaphthols, methyl group-substituted phenols and aldehydes are cocondensed, allylnaphthol molecular units 10 to 10 are contained in one molecule. It contains 50 mol% and methyl group-substituted phenols (including α-naphthol and / or β-naphthol optionally added) in a molecular unit content of 50 to 90 mol% (excluding aldehyde molecular unit exclusion). If the molar ratio of allylnaphthols is smaller than this, the effect of lowering viscosity and flexibility is not imparted, and if it is larger, the cocondensation reaction does not proceed smoothly,
Moreover, since the amount of allyl groups in the cocondensate is too large, the glass transition temperature is lowered and the heat resistance is deteriorated, which is not preferable.

Further, since the allylnaphthol cocondensation product has an allyl group introduced therein, a steric hindrance effect is produced in the molecule to cause a decrease in viscosity, and the use of methyl group-substituted phenols makes it difficult to produce a high molecular weight. The viscosity becomes low. By both of these effects, a cocondensate having a low viscosity can be obtained.

Such an allylnaphthol cocondensation product is
Any compound having a molecular structure in which allylnaphthols, methyl group-substituted phenols (including α-naphthol and / or β-naphthol as necessary) and aldehydes are co-condensed may be used, and for example, they are produced by the following two methods. be able to.

(Method A) The naphthols are allylated in advance to synthesize allylnaphthols, and methyl group-substituted phenols (including α-naphthol and / or β-naphthol if necessary) and aldehydes are added, and if necessary, A method in which an acid or base is added to carry out a dehydration reaction in the same manner as in the usual synthesis of novolak.

(Method B) Naphthols and methyl group-substituted phenols in advance (α-naphthol and / or β if necessary)
-Including naphthol) and an aldehyde, and then reacting with an allyl halide, a base, and optionally water or an organic solvent to react them, and introducing an allyl group into the condensate.

In the case of Method A, as the naphthol to be allylated, one having one or more allyl groups introduced into the molecule and one or more positions to which aldehydes can be added can be used. For example, α-naphthol or Examples thereof include dihydroxynaphthalene and α-naphthol and dihydroxynaphthalene partially substituted with an alkyl group, and α-naphthol is particularly preferable.

To allylate naphthols, (1)
A method in which naphthols and a base are added to water to form a phenolate, and then an allyl halide is added to react with it, impurities are washed with water, and then Claisen rearrangement is carried out by heating, (2) In the method of (1) above, halogenation is performed. A method of adding allyl dropwise over a long period of time, (3) a method of adding naphthols and allyl halide and, if necessary, an organic solvent and adding an aqueous base solution to the reaction to wash the impurities, and then performing Claisen rearrangement. Any method may be used.

The methyl group-substituted phenols may be phenols in which the hydrogen atom of the benzene ring is substituted with a methyl group, and for example, o-cresol, m-cresol, p-cresol, xylenol and the like are preferable.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde,
Aliphatic aldehydes such as propylaldehyde, butyraldehyde and glyoxal, aromatic aldehydes such as benzaldehyde, p-hydroxybenzaldehyde, salicylaldehyde and terephthalaldehyde can be used,
Of these, paraformaldehyde, aromatic benzaldehyde, p-hydroxybenzaldehyde, salicylaldehyde, and terephthalaldehyde are preferable. One of these aldehydes may be used for the reaction, or two or more of them may be used in combination for the reaction.

Further, the amount of aldehyde used is such that allylnaphthols as raw materials and methyl group-substituted phenols are added as necessary so that the composition of the high-nucleus body does not become too large.
It is preferably 0.30 to 0.85 mol with respect to 1 mol of the total amount of -naphthol and / or β-naphthol. When the amount of the aldehyde used is less than 0.30 mol, the molecular weight of the cocondensate becomes small, and thus the heat resistance of the cured product of the epoxy resin decreases. On the other hand, when it exceeds 0.85 mol, the content of the high-nuclear substance increases, the epoxy resin has a high melting point and a high melt viscosity, the workability deteriorates, and a problem occurs in moldability. From this point, 0.50 to 0.75 mol is particularly preferable.

The molar ratio of allylnaphthols and methyl group-substituted phenols (including α-naphthol and / or β-naphthol optionally added) used in the condensation reaction is in the range of 10:90 to 50:50. When the molar ratio of allylnaphthols used is smaller than this, the effect of lowering viscosity and flexibility is not imparted, and when it is large, the cocondensation reaction does not proceed smoothly, and moreover allyl groups in the cocondensate are large. Since it is too high, the glass transition temperature is lowered and the heat resistance is deteriorated, which is not preferable.

The cocondensation reaction for obtaining the allylnaphthol cocondensate used in the present invention is carried out only by heating to a high temperature in order to facilitate the control of the number of naphthalene nuclei. In this case, the reaction temperature is preferably 60 to 180 ° C, and particularly preferably 80 to 160 ° C. The reaction is usually completed in about 1 to 10 hours. If necessary, a catalyst such as acid or base may be used.

Although the reaction can be carried out without a solvent, it is preferable to use a solvent having a boiling point of 80 ° C. or higher and a low solubility in water, such as toluene, xylene or methyl isobutyl ketone.

After completion of the reaction, impurities may be removed by washing with water or the solvent and unreacted materials may be removed under reduced pressure, if necessary.

In the case of Method B, naphthols, methyl group-substituted phenols (including α-naphthol and / or β-naphthol optionally added) and the above-mentioned aldehydes are used in advance by the above-mentioned condensation method or the like. After synthesizing the condensate, the above allylation method (1), (2), (3)
When the allylation is performed using, for example, a cocondensate having the desired molecular structure is obtained.

The analysis and identification of this cocondensate was carried out by gel permeation chromatography (GPC method), infrared absorption spectrum (IR) and nuclear magnetic resonance spectrum (NMR). The measurement conditions of GPC and NMR are shown below.

(GPC analysis) Solvent: Tetrahydrofuran Flow rate: 0.8 ml / min Column: G4000H and 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 co-condensate was confirmed as belonging to the following.

[0034]

[Chemical 5]

The polyfunctional epoxy resin based on the allylnaphthol cocondensation product of the present invention can be obtained by reacting the above allylnaphthol cocondensation product with epihalohydrin. Two methods are available.

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

2) A two-step method in which an allylnaphthol cocondensate and an excess 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,
Examples thereof include β-methylepiodohydrin, and epichlorohydrin is preferable.

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. The alkali hydroxide is 0.8 to 1.5 molar equivalent, preferably 0.9 to 1 equivalent, per hydroxyl group of the allylnaphthol cocondensate.
Use 1.1 molar equivalents.

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 hydroxyl groups of the allylnaphthol cocondensate, and excess epihalohydrin can be recovered and reused after the reaction.

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

These first-stage and second-stage reactions may be carried out in the absence of solvent or in the presence of an inert solvent such as methyl isobutyl ketone, cyclohexane or toluene. After completion of the reaction, these are purified by washing with water or solvent, or evaporated and degassed to obtain the polyfunctional epoxy resin of the present invention.

The workability of the polyfunctional epoxy resin of the present invention is related to its melting point and melt viscosity, and a lower one is required. These depend on the melting point and melt viscosity of the base allylnaphthol co-condensate, and if these are kept as low as possible, an epoxy resin with good workability can be obtained. When the base allylnaphthol cocondensate is made into an epoxy resin, the melting point is lowered by 5 to 30 ° C and the viscosity is lowered to about 1/5 to 4/5. Therefore, the melting point is 30 to 100 ° C and the viscosity at 150 ° C is 5 to 200 cp. An epoxy resin having excellent workability can be obtained.

The second invention provides an epoxy resin composition containing a curing agent and an epoxy resin based on the allylnaphthol cocondensation product. This composition preferably further contains a curing accelerator, and in this case, it is particularly useful as a resin composition for semiconductor encapsulation.

The polyfunctional epoxy resin of the present invention may be used alone, or 70% by weight or less, preferably 50% by weight.
The following general epoxy resins such as ortho-cresol resin epoxy resin, bisphenol epoxy resin,
It can also be used in combination with a phenol resin epoxy resin.

Next, the curing agent used in the present invention has two or more, preferably three or more phenolic hydroxyl groups in the molecule. Specifically, phenol and substituted phenols such as o-cresol, p-cresol, t-
Examples include butylphenol, cumylphenol, phenylphenol and formaldehyde reacted with an acid or 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 epoxy resin composition of the present invention is not particularly limited and can be carried out by a conventional method. The conditions for encapsulating a semiconductor using the resin composition of the present invention are not particularly limited, and are usually 175 ° C. and a molding pressure of 100 kg.
/ Cm ² , conditions such as molding for 3 minutes and post-curing at 180 ° C. for 6 hours are adopted.

[0058]

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 (Allylnaphthol Cocondensate 1) 144 g (1 mol) of α-naphthol and 10% of sodium hydroxide were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet.
Aqueous solution 440g and methyl isobutyl ketone 144g
Was charged, and the mixture was heated to 80 ° C. with stirring to homogenize it to obtain a phenolate. Allyl chloride 84.
2 g (1.1 mol) was added dropwise using a dropping funnel over 3 hours, and after completion of the dropping, the mixture was further stirred for 1 hour to react.
After the reaction was completed, the reaction mixture was separated and washed with water, and the solvent was completely distilled off under reduced pressure. Then, the obtained reaction product is transferred to a reaction vessel,
Allylnaphthol (OH group equivalent: 185) was obtained by heating at 140 ° C. and stirring for 2 hours for reaction.

61 g of the above-mentioned allylnaphthol was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet.
(0.33 mol), 72 g (0.66 mol) of o-cresol and 19.5 g of paraformaldehyde (total of allylnaphthol and o-cresol: paraformaldehyde = 1: 0.65 (molar ratio, formaldehyde conversion)).
Was charged, heated to 140 ° C., and stirred for 3 hours under a nitrogen stream to react. Next, the mixture was heated to 200 ° C. and the unreacted material and water were removed under reduced pressure to obtain an allylnaphthol cocondensate represented by the following formula. The melting point of this compound is 51 ° C., 150
The melt viscosity at ° C was as low as 30 centipoise (hereinafter referred to as CP), and the work performance was excellent. (In the following Examples and Comparative Examples, all viscosity measurements were also made at 150 ° C.) Weight average molecular weight (measured by GPC method,
The same applies hereinafter) was 440 and the OH group equivalent was 145.

[0061]

[Chemical 6]

(Epoxy resin 1) The total amount of the co-condensate, 460 g of epichlorohydrin and 3 g of tetrabutylammonium bromide were charged and reacted under heating and reflux for 3 hours, and excess epichlorohydrin was removed under reduced pressure. The same amount of toluene as the contents was added, the mixture was cooled to 60 ° C., 41 g of sodium hydroxide was added with a water removing device, and the produced water was subjected to a ring-closing reaction while continuously removing the 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 epoxy resin had an epoxy equivalent of 230, a melting point of 46 ° C., and a viscosity of 10 CP and was low in workability.

Example 2 (Allylnaphthol co-condensate 2) 61 g (0.33 mol) of allylnaphthol, the same as that synthesized in the previous stage of Example 1, 72 g (0.66 mol) of o-cresol, 71 g of benzaldehyde (allyl) Total of naphthol and o-cresol: benzaldehyde = 1: 0.66 (molar ratio))
A cocondensate was produced in the same manner as in Example 1 except that and 0.2 g of hydrochloric acid were charged. The obtained allylnaphthol cocondensate (shown by the following formula) has a melting point of 61 ° C. and a viscosity of 14
It was as low as 0 CP and had excellent workability. The weight average molecular weight was 560 and the OH group equivalent was 184.

[0064]

[Chemical 7]

(Epoxy resin 2) An epoxy resin was produced in the same manner as in Example 1 using the entire amount of the condensate obtained in the above 2. The obtained epoxy resin has an epoxy equivalent of 280 and a melting point of 55.
It had a low workability of 30 ° C. and a viscosity of 30 CP.

Example 3 (Allylnaphthol Cocondensate 3) 61 g (0.33 mol) of allylnaphthol, 72 g (0.66 mol) of o-cresol, and p-hydroxybenzaldehyde, which were the same as those synthesized in the previous step of Example 1. 81.3 g (total of allylnaphthol and o-cresol: p-hydroxybenzaldehyde = 1: 0.66 (molar ratio)), 0.3 g of toluenesulfonic acid and 80 g of xylene were used in the same manner as in Example 1. A cocondensate was produced. After the reaction, xylene was removed under reduced pressure with heating. The obtained allylnaphthol cocondensate (shown by the following formula) has a melting point of 78 ° C. and a viscosity of 8
It was as low as 0 CP and had excellent workability. The weight average molecular weight was 650 and the OH group equivalent was 132.

[0067]

[Chemical 8]

(Epoxy resin 3) An epoxy resin was produced in the same manner as in Example 1 using the whole amount of the condensate obtained in the above 3. The obtained epoxy resin has an epoxy equivalent of 210 and a melting point of 6
It had a low workability of 5 ° C and a viscosity of 20 CP, and was excellent in workability.

Example 4 (Allylnaphthol Cocondensation Product 4) Allylnaphthol 7
3.2 g (0.4 mol), o-cresol 64.8 g
A cocondensate was produced in the same manner as in Example 3 except that (0.6 mol) and 34 g of terephthalaldehyde were used instead of p-hydroxybenzaldehyde. The melting point of the obtained allylnaphthol cocondensate (shown by the following formula) is 8:
It had a low workability of 2 ° C and a viscosity of 80 CP.
The weight average molecular weight was 700 and the OH group equivalent was 177.

[0070]

[Chemical 9]

(Epoxy Resin 4) An epoxy resin was produced in the same manner as in Example 1 using the entire amount of the condensate obtained in 4 above. The obtained epoxy resin has an epoxy equivalent of 270 and a melting point of 7
The workability was excellent with a low temperature of 1 ° C and a viscosity of 20 CP.

Example 5 (Allylnaphthol Cocondensate 5) A cocondensate was produced in the same manner as in Example 1 except that p-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) has a melting point of 52 ° C. and a viscosity of 2
It was as low as 0 CP and had excellent workability. The weight average molecular weight was 450 and the OH group equivalent was 144.

[0073]

[Chemical 10]

(Epoxy resin 5) An epoxy resin was produced in the same manner as in Example 1 using the entire amount of the condensate obtained in 5 above. The obtained epoxy resin has an epoxy equivalent of 230 and a melting point of 4
It had a low workability of 3 ° C and a viscosity of 10 CP.

Example 6 (Allylnaphthol Cocondensation Product 6) A cocondensation product was produced in the same manner as in Example 2 except that p-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) has a melting point of 58 ° C. and a viscosity of 8
It was as low as 0 CP and had excellent workability. The weight average molecular weight was 550 and the OH group equivalent was 182.

[0076]

[Chemical 11]

(Epoxy resin 6) An epoxy resin was produced in the same manner as in Example 1 using the entire amount of the condensate obtained in 6 above. The obtained epoxy resin has an epoxy equivalent of 270 and a melting point of 4
It had a low workability of 9 ° C and a viscosity of 20 CP.

Example 7 (Allylnaphthol Cocondensation Product 7) A cocondensation product was produced in the same manner as in Example 3 except that p-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) has a melting point of 82 ° C. and a viscosity of 6
It was as low as 0 CP and had excellent workability. The weight average molecular weight was 640 and the OH group equivalent was 130.

[0079]

[Chemical 12]

(Epoxy resin 7) An epoxy resin was produced in the same manner as in Example 1 using the whole amount of the condensate obtained in the above 7. The obtained epoxy resin has an epoxy equivalent of 220 and a melting point of 7
It had a low workability of 0 ° C and a viscosity of 20 CP.

Example 8 (Allylnaphthol Cocondensate 8) A cocondensate was produced in the same manner as in Example 4 except that p-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) has a melting point of 81 ° C. and a viscosity of 6
It was as low as 0 CP and had excellent workability. The weight average molecular weight was 710 and the OH group equivalent was 172.

[0082]

[Chemical 13]

(Epoxy resin 8) An epoxy resin was produced in the same manner as in Example 1 using the whole amount of the condensate obtained in the above 8. The obtained epoxy resin has an epoxy equivalent of 260 and a melting point of 7
It had a low workability of 5 ° C and a viscosity of 20 CP, and was excellent in workability.

Example 9 (Allylnaphthol Cocondensate 9) A cocondensate was produced in the same manner as in Example 1 except that m-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) has a melting point of 48 ° C. and a viscosity of 2
It was as low as 0 CP and had excellent workability. The weight average molecular weight was 440 and the OH group equivalent was 142.

[0085]

[Chemical 14]

(Epoxy Resin 9) An epoxy resin was produced in the same manner as in Example 1 using the whole amount of the condensate of 9 above. The obtained epoxy resin 9 had an epoxy equivalent of 230, a melting point of 41 ° C., and a viscosity of 10 CP and was low in workability.

Example 10 (Allylnaphthol Cocondensation Product 10) A cocondensation product was produced in the same manner as in Example 2 except that m-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point as low as 55 ° C. and a viscosity of 60 CP and was excellent in work performance. The weight average molecular weight was 530 and the OH group equivalent was 180.

[0088]

[Chemical 15]

(Epoxy Resin 10) An epoxy resin was produced in the same manner as in Example 1 using the total amount of the above condensate 10. The obtained epoxy resin 10 has an epoxy equivalent of 270.
The melting point was 46 ° C. and the viscosity was 20 CP, which was low and workability was excellent.

Example 11 (Allylnaphthol Cocondensation Product 11) A cocondensation product was produced in the same manner as in Example 3 except that m-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point as low as 76 ° C. and a viscosity of 50 CP and was excellent in workability. The weight average molecular weight was 630 and the OH group equivalent was 128.

[0091]

[Chemical 16]

(Epoxy Resin 11) An epoxy resin was produced in the same manner as in Example 1 using the total amount of the condensate obtained in 11 above. The obtained epoxy resin 11 has an epoxy equivalent of 220.
The melting point was 70 ° C. and the viscosity was 15 CP, which was low and the workability was excellent.

Example 12 (Allylnaphthol Cocondensation Product 12) A cocondensation product was produced in the same manner as in Example 4 except that m-cresol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point as low as 80 ° C. and a viscosity as low as 50 CP, and was excellent in workability. The weight average molecular weight was 700 and the OH group equivalent was 170.

[0094]

[Chemical 17]

(Epoxy Resin 12) An epoxy resin was produced in the same manner as in Example 1 using the total amount of the condensate of 12 above. The obtained epoxy resin 12 has an epoxy equivalent of 260.
The melting point was 71 ° C. and the viscosity was 15 CP, which was low and workability was excellent.

Example 13 (Allylnaphthol Cocondensation Product 13) A cocondensation product was prepared in the same manner as in Example 1 except that 81.3 g of 3,5-xylenol was used instead of o-cresol. The obtained allylnaphthol cocondensate (represented by the following formula) had a melting point of 42 ° C. and a viscosity of 10 CP, which was low and was excellent in workability. Weight average molecular weight is 470, OH group equivalent is 154
Met.

[0097]

[Chemical 18]

(Epoxy resin 13) An epoxy resin was produced in the same manner as in Example 1 using the whole amount of the condensate obtained in 13 above. The resulting epoxy resin 13 has an epoxy equivalent of 240
The melting point was 35 ° C. and the viscosity was 6 CP, which was low and the workability was excellent.

Example 14 (Allylnaphthol Cocondensation Product 14) A cocondensation product was produced in the same manner as in Example 2 except that 81.3 g of 3,5-xylenol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point as low as 48 ° C. and a viscosity as low as 30 CP and was excellent in workability. Weight average molecular weight is 590, OH group equivalent is 194
Met.

[0100]

[Chemical 19]

(Epoxy resin 14) An epoxy resin was produced in the same manner as in Example 1 using the whole amount of the condensate obtained in 14 above. The obtained epoxy resin 14 has an epoxy equivalent of 280.
The melting point was 41 ° C. and the viscosity was 10 CP, which was low and workability was excellent.

Example 15 (Allylnaphthol Cocondensate 15) A cocondensate was produced in the same manner as in Example 3 except that 81.3 g of 3,5-xylenol was used instead of o-cresol. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point of 68 ° C. and a viscosity of 50 CP, which was low, and was excellent in workability. Weight average molecular weight is 670, OH group equivalent is 141
Met.

[0103]

[Chemical 20]

(Epoxy resin 15) An epoxy resin was produced in the same manner as in Example 1 using the entire amount of the condensate of 15 above. The obtained epoxy resin 15 has an epoxy equivalent of 230
The melting point was 61 ° C. and the viscosity was 15 CP, which was low and the workability was excellent.

Example 16 (Allylnaphthol Cocondensate 16) A cocondensate was produced in the same manner as in Example 4 except that 61 g of 3,5-xylenol was used instead of o-cresol. The melting point of the obtained allylnaphthol cocondensate (shown by the following formula) is 7:
It had a low workability of 1 ° C. and a viscosity of 60 CP.
The weight average molecular weight was 720 and the OH group equivalent was 185.

[0106]

[Chemical 21]

(Epoxy resin 16) An epoxy resin was produced in the same manner as in Example 1 using the entire amount of the condensate obtained in 16 above. The obtained epoxy resin 16 has an epoxy equivalent of 280.
The melting point was 61 ° C. and the viscosity was 20 CP, which was low and workability was excellent.

Comparative Example 1 (Condensate 17) A condensate was obtained in the same manner as in Example 1, except that no allylnaphthol was used and the amount of α-naphthol was changed to 144 g (1.0 mol). Hydroxyl equivalent is 168, melting point is 135 ° C, melt viscosity at 150 ° C is 32.
It was as high as 00 CP, and the workability was poor because the fluidity was extremely poor.

(Epoxy resin 17) An epoxy resin was produced in the same manner as in Example 1 except that the entire amount of the condensate 17 was used. The obtained epoxy resin 17 has an epoxy equivalent of 250.
The melting point was 121 ° C. and the viscosity was 2400 CP, which was very poor and the workability was poor.

Comparative Example 2 (Condensate 18) Condensate 18 was prepared in the same manner as in Comparative Example 1 except that 0.5 g of paratoluenesulfonic acid was used as a catalyst and 60 g of formalin water (35%) was used instead of paraformaldehyde. Manufactured. The hydroxyl group equivalent was 172, the melting point was 135 ° C., the viscosity was as high as 3200 CP, and the fluidity was extremely poor, resulting in poor workability.

(Epoxy resin 18) An epoxy resin was produced in the same manner as in Example 1 except that the whole amount of the condensate 18 was used. The obtained epoxy resin 18 has an epoxy equivalent of 250.
The melting point was 119 ° C. and the viscosity was as high as 2600 CP, and the workability was poor because the fluidity was extremely poor.

Comparative Example 3 (Condensation Product 19) 122.6 g (0.
66 mol), and an allylnaphthol cocondensate was obtained in the same manner as in Example 1 except that 35.6 g (0.33 mol) of o-cresol was used. The resulting product contained 30.6 g of unreacted allylnaphthol and had an OH group equivalent of 17
It was 0.

(Epoxy resin 19) An epoxy resin was produced in the same manner as in Example 1 except that the whole amount of the condensate 19 was used. The obtained epoxy resin 19 has an epoxy equivalent of 260.
The melting point was 80 ° C. and the viscosity was 400 CP, and the workability was poor because the fluidity was extremely poor.

Examples 17 to 32 and Comparative Examples 4 to 5 The following epoxy resins, curing agents, curing accelerators, fillers, antimony trioxide, silane coupling agents, waxes and carbon blacks are shown in Tables 1 to 4. Was mixed in a proportion (parts by weight) shown in (1), 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 obtained in Examples 1 to 16 Epoxy resin obtained in Comparative Example 3 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) Curing agent: phenol novolac resin (hydroxyl group equivalent 106, melting point 80 ° C) Curing accelerator: triphenylphosphine Filler: spherical silica (BF100 of Mitsubishi Metals Co., Ltd.)

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.

When the epoxy resins of Comparative Examples 1 and 2 were used, the epoxy resin compositions had high viscosity and poor flowability and workability, and good test pieces could not be obtained. It was impossible.

[0118]

[Table 1]

[0119]

[Table 2]

[0120]

[Table 3]

[0121]

[Table 4]

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 Tables 5 to 8.

The bending strength (high temperature strength) at 200 ° C. of the obtained test piece, the glass transition temperature, the coefficient of thermal expansion,
The water absorption was examined after a humidification test at 85 ° C./85% RH for 500 hours. The results are shown in Tables 9-12.

[0124]

[Table 5]

[0125]

[Table 6]

[0126]

[Table 7]

[0127]

[Table 8]

[0128]

[Table 9]

[0129]

[Table 10]

[0130]

[Table 11]

[0131]

[Table 12]

[0132]

The epoxy resin based on the allylnaphthol cocondensation product of the present invention has a low melting point and melt viscosity and is excellent in workability. Further, when used in combination with a curing agent, the obtained epoxy resin cured product has a high glass transition temperature, heat resistance and moisture resistance. That is, the cured product of this epoxy resin composition has a high glass transition temperature, excellent heat resistance, high mechanical strength, low water absorption rate, and excellent moisture resistance, and very few cracks are generated during soldering. Therefore, the epoxy resin composition of the present invention is useful as a semiconductor encapsulating composition.

Claims (4)

[Claims] 1. A polyfunctional epoxy resin obtained by reacting an allylnaphthol cocondensate having a weight average molecular weight of 300 to 2000, which is represented by the following general formula (I), with epihalohydrin. [Chemical 1] 2. A polyfunctional epoxy resin obtained by reacting an allylnaphthol cocondensate having a weight average molecular weight of 300 to 2000, which is represented by the following general formula (II), with epihalohydrin. [Chemical 2] 3. An allylnaphthol cocondensation product having a weight average molecular weight of 300 to 2000, obtained by cocondensing allylnaphthols, methyl group-substituted phenols and aldehydes, wherein allyl is calculated by excluding aldehydes. A polyfunctional epoxy resin obtained by the reaction of an allylnaphthol cocondensate having a naphthol ratio of 10 to 50 mol% and epihalohydrin. 4. An epoxy resin composition containing the epoxy resin according to claim 1 and a curing agent.