JP2003165823A - Epoxy resin, method for producing the same and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin suitable for a semiconductor sealant, having a low melt viscosity and a high glass transition point. <P>SOLUTION: This epoxy resin is obtained by glycidylating a phenol-based polymer derived from a phenol, formaldehyde and a salicylaldehyde and having phenol novolak polymerization units and triphenol methane polymerization units, and a composition comprising the epoxy resin and a phenolic resin-based curing agent is provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a molding material, a varnish,
New epoxy resin useful for various binders, laminates, adhesives, encapsulants, reinforced plastics materials, powder coatings, etc.
The present invention relates to a method for producing the same and a composition with a phenol resin-based curing agent or a cured product thereof. In particular, low melt viscosity, useful as a binder for structural members that require a high glass transition temperature and a base resin for epoxy resin-based semiconductor encapsulants,
The present invention relates to an epoxy resin having a high glass transition temperature.

[0002]

2. Description of the Related Art Epoxy resins are widely used in various fields because they have excellent electric insulation, adhesiveness, heat resistance, chemical resistance, mechanical properties and the like. In recent years, along with the reduction in size and weight of products using this as a constituent material, the advent of an epoxy resin having a low viscosity and a high glass transition temperature has been desired. For example, a phenol novolac type epoxy resin has a low viscosity, but has a relatively low glass transition temperature. On the other hand, triphenol methane type epoxy resin (Japanese Patent Application Laid-Open No. 57-1414)
No. 19) is known as a resin having a high glass transition temperature, but has a high viscosity.

[0003]

The conventional epoxy resins have a problem in that they have both a low viscosity and a high glass transition temperature, as in the above examples. Therefore, an object of the present invention is to provide a novel epoxy resin having a low melt viscosity and a high glass transition temperature. Another object of the present invention is to provide a method for efficiently producing such an epoxy resin. Still another object of the present invention is to provide a composition containing such an epoxy resin and a phenol resin-based curing agent, and a cured product thereof.

[0004]

That is, according to the present invention, there is provided an epoxy resin represented by the following general formula (1) and having a melt viscosity at 150 ° C. of 10 to 300 mPa · s.

[0005]

[Chemical 3] (In the formula, G is a glycidyl group, R ¹ , R ² , R ³ and R ⁴
Are each hydrogen or an alkyl group, p, q, r and s are each 1-2, and m / n is 0.7-1.5).

According to the present invention, there is also provided a method for producing an epoxy resin of the above general formula (1), which comprises reacting a phenolic polymer represented by the following general formula (2) with epihalohydrin. It

[0007]

[Chemical 4] (In the formula, R ¹ , R ² , R ³ and R ⁴ are each hydrogen or an alkyl group, p, q, r and s are each 1 to 2, m /
n is 0.7 to 1.5)

The present invention also provides an epoxy resin composition comprising an epoxy resin represented by the above formula (1) and a phenol resin type curing agent, and a cured product thereof. According to the present invention, there is also provided a semiconductor device in which a semiconductor element is sealed with an epoxy resin composition containing an epoxy resin represented by the above formula (1) and a phenolic resin-based curing agent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As shown in formula (1), the epoxy resin of the present invention has n polymer units of a glycidylated triphenolmethane type resin and m polymer units of a glycidylated phenol novolac resin. It is a co-polymer type epoxy resin that has a number. R ¹ , R ² , R ³ and R ⁴ in the formula (1) are each hydrogen or an alkyl group, for example, an alkyl group such as methyl, ethyl, isopropyl, n-butyl, isobutyl and t-butyl, p,
q, r and s are each 1 to 2, but the most preferable ones are those in which R ¹ , R ² , R ³ and R ⁴ are all hydrogen, that is, those represented by the following formula (3).

[0010]

[Chemical 5]

The epoxy resins of the formulas (1) and (3) are
A melt viscosity at 150 ° C. of 10 to 300 mPa · s,
It is preferably in the range of 10 to 100 mPa · s and has an epoxy equivalent of 145 to 180 g / eq, particularly 155-1.
Those in the range of 65 g / eq are preferable. As a polymer having such a melt viscosity and an epoxy equivalent, the degree of polymerization n and m of each polymerized unit is usually a mixture of 0 to 10 and the average degree of polymerization is 0.6 to 2 for both n and m. ．
0, preferably 0.8 to 1.4 is used. When the average degree of polymerization is high and the melt viscosity is higher than the above range, the fluidity is lowered. Further, a polymer having a lower degree of polymerization and a lower melt viscosity than this is not preferable because it has a low glass transition temperature.

In the epoxy resins of the formulas (1) and (3), the ratio m / n of the average degree of polymerization of each polymerized unit is 0.
It is 7 to 1.5, preferably 0.9 to 1.4. m / n
If the value is larger than the above value, the glass transition temperature becomes low and the curing rate becomes slow. On the other hand, when m / n is smaller than the above value, the melt viscosity increases and the fluidity deteriorates.

The epoxy resin of the formula (1) and the formula (3) has a structure containing polymerized units of a glycidylated triphenolmethane type resin and a glycidylated phenol novolak resin in a specific ratio. Yes,
As a result, the polymer has a low melt viscosity, a high glass transition temperature, and excellent curability, which is suitable as an epoxy resin.

In the above-mentioned glycidylated phenol novolac polymer unit, the benzene ring has a methylene group and a glycidyl ether group for bonding to adjacent glycidyl phenol novolac polymer units. In the epoxy resin of the present invention, the position of methylene group substitution with respect to the glycidyl ether group is 1.5 or more, preferably 2.0 to 4.0, more preferably 2.5 to 3.5 in terms of p / o ratio. Some are preferred. Ie p
When the / o ratio is within the above range, the curing time is short,
In particular, the addition rate at the initial stage of the reaction is high, which is industrially advantageous.

The methylene group substitution position for the glycidyl ether group can be measured by ¹ H-NMR spectroscopy of the epoxy resin, and the methylene group substitution position for the hydroxyl group of the starting phenolic polymer before glycidylation can be determined by ¹ H-. It can be known by measuring by the NMR spectrum method.

The epoxy resin of the present invention is obtained by reacting the phenolic polymer represented by the general formula (2) with an epihalohydrin such as epichlorohydrin or epibromhydrin, preferably in the presence of a hydrogen halide scavenger. It can be easily obtained. In this reaction, as the phenolic polymer of formula (2),
The ratio m / n of the average degree of polymerization is 0.7 to 1.5, preferably 0.9 to 1.4, and the melt viscosity at 150 ° C. is 50 to 3
00 mPa · s, preferably 50 to 200 mPa · s,
m and n are each in the range of 0 to 10, and the average degree of polymerization is 0.6 to 2.0, preferably 0.8 to 1.4.
What is used. Further, the substitution position of the methylene group with respect to the hydroxyl group is 1.5 or more in p / o ratio, preferably 2.0 to
It is preferably 4.0, more preferably 2.5 to 3.5.

In the above reaction, 1.3 equivalents of epihalohydrin are added per equivalent of hydroxyl group of the phenolic polymer.
It is preferable to carry out the reaction at a ratio of about 20 equivalents, particularly 2.0 to 10 equivalents under the condition of excess epihalohydrin. If the amount of epihalohydrin used is too small, the reaction between the glycidyl ether group and the phenolic hydroxyl group increases the molecular weight, which increases the viscosity, which is not preferable. Further, even if epichlorohydrin is used in the above range or more, there is no remarkable effect, and it is economically unfavorable in view of the amount of epichlorohydrin used and the pot efficiency.

It is industrially advantageous to use an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide as the hydrogen halide scavenger in the above reaction. These can be added to the reaction system in a solid state or as an aqueous solution of about 40 to 50%. The suitable addition amount of the hydrogen halide scavenger is 0.8 to 1.5 equivalents, preferably 0.1 to 1 equivalent to the hydroxyl group of the phenolic polymer.
It is 9 to 1.1 equivalents.

The reaction of the above-mentioned phenolic polymer with epihalohydrin can also be carried out without the use of hydrogen halide scavengers,
It is also possible to volatilize and remove hydrogen halide generated by the reaction from the reaction system.

The reaction temperature in the reaction of the phenolic polymer and epihalohydrin is preferably in the range of 50 to 150 ° C., and the reaction time is generally 1 to 20 hours. This epoxidation reaction, even without solvent, dimethyl sulfoxide,
It can also be carried out in the presence of a suitable solvent such as dimethylformamide or methyl ethyl ketone. This reaction also proceeds without a catalyst, but if desired, it can be carried out using a suitable catalyst such as a phase transfer catalyst.

After completion of the epoxidation reaction, the excess epihalohydrin is distilled off, and then the excess hydrogen halide scavenger remaining in the reaction product and the salt produced by this capture are treated with water or another solvent. When the reaction product is removed by washing or the like, the desired epoxy resin is obtained.
It is considered that this epoxy resin contains the compound represented by the general formula (1) as a main product, but it may contain a small amount of a high molecular weight by-product depending on the reaction conditions. Even in this case, it can be directly used as a raw material for curing without performing a separation operation.

The phenol-based polymer represented by the formula (2) used as a raw material has the following formula (4) when phenol is used as phenols and salicylaldehyde is used as salicylaldehydes. It can be produced by condensing phenol, salicylaldehyde and formaldehyde in the presence of an acid catalyst.

[0023]

[Chemical 6]

The condensation reaction can be carried out in a single stage by simultaneously adding salicylaldehyde and formaldehyde as shown in formula (4). In this case, phenol is added to 3. mol of salicylaldehyde and formaldehyde in a total amount of 3. It is used in an amount of 0 mol or more, preferably 3.3 to 10.0 mol, and the reaction temperature is lowered to preferentially react the phenol and formaldehyde to form a low molecular weight phenol novolac resin. It is necessary to adopt a method of reacting the phenol novolac resin, salicylaldehyde and phenol by raising the temperature or increasing the amount of the catalyst. The reaction temperature is not particularly limited, but it is preferably set in the range of about 60 to 100 ° C. Particularly, in order to obtain a phenolic polymer having a p / o ratio of 2.0 or more at the methylene substitution position, the reaction is preferably carried out at 70 ° C. or lower. When the amount of phenol used is less than 3.0 mol per mol of salicylaldehyde and formaldehyde, it is difficult to obtain a phenolic polymer having a low molecular weight and a low melt viscosity when the above reaction conditions are deviated. .

The phenolic polymer is also a two-step reaction in which phenol and formaldehyde are condensed in the presence of an acid catalyst to form a phenol novolac resin in advance, salicylaldehyde is added, and condensation is performed in the presence of an acid catalyst. You can also do it. In such a two-step reaction,
Phenol can be newly added in the second reaction. Also in this case, it is important to use an excess amount of phenol as in the case of the one-step reaction. For example, in the reaction of the first step, 2.5 mol or more, preferably 3.3 to 10.0, of phenols relative to 1 mol of formaldehyde.
The amount of salicylaldehyde and phenol added in the second-stage reaction is 3 mol of the total amount of the salicylaldehyde and formaldehyde charged in the first-second reaction, and the total amount of phenol added in the first-second reaction is 3 mol. It is important to use in an amount of 0.0 mol or more, preferably 3.3 to 10.0 mol. Also in this case, in order to obtain a phenolic polymer having a p / o ratio of the methylene substitution position of 2.0 or more, the reaction is preferably performed at 70 ° C. or less. When the reaction is carried out in such a two-step reaction, the degree of polymerization of each polymerization unit of the triphenolmethane type resin and the phenol novolac resin, that is, the distribution of n and m is narrowed, the control of the molecular weight is facilitated, and the weight of the desired melt viscosity is reduced. Easy to combine.

In the production of the phenolic polymer, the melt viscosity at 150 ° C. and the desired viscosity can be controlled by controlling the amounts of the raw materials phenols, salicylaldehydes and formaldehyde used and setting the reaction conditions as described above. A polymer having a polymerization degree ratio m / n of polymerized units can be obtained. The amount of the acid catalyst used in the one-step reaction and the two-step reaction varies depending on the kind, but is about 0.1 to 2.0% by weight in the case of oxalic acid and 0.02 to 2.0% in the case of hydrochloric acid. %, Or 0.002-0.01% by weight in the case of trifluoromethanesulfonic acid
It is good to use it to some extent. Especially when performing a two-step reaction,
When reacting the salicylaldehydes in the second stage with the phenols and the phenol novolac resin, it is preferable to use hydrochloric acid or trifluoromethanesulfonic acid.

After condensing phenols, formaldehyde and salicylaldehydes in the presence of an acid catalyst, the unreacted phenols and acid catalyst are removed,
A phenolic polymer represented by the formula (2) can be obtained. The phenols are generally removed by heating under reduced pressure or while blowing an inert gas to distill the phenols out of the system. There are methods such as washing with water to remove the acid catalyst, but when using a volatile acid, the method of removing the acid catalyst by distillation together with phenols shortens the reaction process and improves pot efficiency. It is preferable in that respect.

Examples of phenols include phenol,
Cresol, ethylphenol, propylphenol,
Butylphenol, hexylphenol, nonylphenol, xylenol, butylmethylphenol and the like can be used, but phenol is particularly preferable.

As salicylaldehydes, in addition to salicylaldehyde, alkyl-substituted salicylaldehyde and the like can be used, but salicylaldehyde is particularly preferably used. It is also possible to use together with p-hydroxybenzaldehyde.

Further, as formaldehyde, 37%
Formaldehyde aqueous solution, and paraformaldehyde,
A polymer such as trioxane which decomposes in the presence of an acid to formaldehyde can be used.

The acid catalyst is not particularly limited, and known ones such as hydrochloric acid, oxalic acid, trifluoromethanesulfonic acid, sulfuric acid, phosphoric acid and paratoluenesulfonic acid can be used alone or in combination of two or more kinds. Hydrochloric acid, oxalic acid or trifluoromethanesulfonic acid are particularly preferred. These catalysts have high catalytic activity, and the catalyst can be removed together with unreacted phenol, salicylaldehyde, and formaldehyde by a reduced pressure treatment after the completion of the reaction, so that a washing step such as washing with water is not necessary.

For the details of the method for producing these phenolic polymers, see Japanese Patent Application No. 2001-26767 and Japanese Patent Application No. 20.
No. 01-55793.

The epoxy resin according to the present invention can be used as a molding material, various binders, coating materials, laminated materials and the like by using together with various curing agents. In particular, when used in combination with a phenol resin-based curing agent, an epoxy resin composition having a low melt viscosity, a high glass transition temperature and good curing characteristics can be obtained, which is suitable as a semiconductor encapsulating material.

As the curing agent for the epoxy resin of the present invention,
There is no particular limitation, and known ones can be used. Phenolic resin-based curing agents such as phenol novolac resin, cresol novolac resin and Japanese Patent Publication No. 47-1378.
No. 2, JP-B-47-15111, JP-A-6-1842.
58, JP-A-6-136082, JP-A-7-258.
Phenol aralkyl resins, phenol biphenyl aralkyl resins, phenol naphthyl aralkyl resins, naphthol aralkyl resins, triphenol methane type novolac resins, etc. disclosed in Japanese Patent No. 364, Patent No. 3122834 and the like, amine-based curing agents, for example, aliphatic diamines such as ethylenediamine Systems, alicyclic systems such as bisaminomethylcyclohexane, aromatic amines such as metaxylenediamine and diaminodiphenylmethane, and acid anhydride curing agents such as phthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydro. Mention may be made of latent hardeners such as phthalic anhydride, such as benzylsulfonium salts, hydrazinium salts. In particular, it is preferable to use a phenol resin type curing agent for semiconductor encapsulation.

The epoxy resin of the present invention can be used in combination with other epoxy resins when curing with the above-mentioned phenol resin type curing agent. Examples of such other epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, phenylbiphenylaralkyl type epoxy resin, phenol, naphthol. Epoxidized aralkyl resin by xylylene bond such as, dicyclopentadiene type epoxy resin, glycidyl ether type epoxy resin such as dihydroxynaphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, halogenated epoxy resin, etc. One or two or more of epoxy resins having two or more epoxy groups can be mentioned therein.

Upon curing the epoxy resin, it is desirable to use a curing accelerator together. As such a curing accelerator, a known curing accelerator for curing an epoxy resin with a phenol resin-based curing agent can be used. For example, a tertiary amine, a quaternary ammonium salt, an imidazole and its tetraphenylboron salt, An organic phosphine compound and its boron salt, a quaternary phosphonium salt, etc. can be mentioned. More specifically, triethylamine, triethylenediamine, benzyldimethylamine, 2,4
6-tris (dimethylaminomethyl) phenol, 1,
Tertiary amines such as 8-diazabicyclo (5,4,0) undecene-7, 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4- Imidazoles such as methylimidazole, organic phosphine compounds such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetranaphthoic acid borate, etc. Can be mentioned. Among them, organic phosphine compounds and quaternary phosphonium quaternary borate salts are preferable from the viewpoint of low water absorption and reliability.

If necessary, an inorganic filler, a coupling agent, a release agent, a colorant, a flame retardant, a flame retardant aid, a low stress agent, etc. are added to the epoxy resin composition of the present invention or previously added. It can be used by reacting. Also, other curing agents can be used in combination. Especially when used for semiconductor encapsulation, the addition of an inorganic filler is essential. Examples of such inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, gypsum, calcium carbonate,
Magnesite, clay, talc, mica, magnesia,
Barium sulfate and the like can be mentioned, but amorphous silica and crystalline silica are particularly preferable. Further, in order to increase the compounding amount of the filler while maintaining excellent moldability, it is preferable to use a spherical filler having a wide particle size distribution that enables fine packing.

Examples of the coupling agent include vinylsilane-based, aminosilane-based, epoxysilane-based, and other silane-based coupling agents and titanium-based coupling agents, and examples of the release agent include carnauba wax, paraffin wax, and the like.
Stearic acid, montanic acid, a carboxyl group-containing polyolefin wax and the like, and examples of the colorant include carbon black and the like. Examples of flame retardants include halogenated epoxy resins, halogen compounds, phosphorus compounds and the like, and flame retardant aids such as antimony trioxide. Examples of the stress reducing agent include silicone rubber, modified nitrile rubber, modified butadiene rubber,
Examples include modified silicone oil.

Considering heat resistance and mechanical properties, the epoxy resin of the present invention and the phenolic resin type curing agent are mixed at an equivalent ratio of 0.5 of the hydroxyl group of the phenolic resin type curing agent / the epoxy group of the epoxy resin. ~ 1.5, especially 0.8 ~
It is preferably in the range of 1.2. When another epoxy resin is used in combination, it is preferable to use it so that the equivalent ratio of the hydroxyl group of the phenol resin type curing agent to the epoxy group of the whole epoxy resin is in the above range. The curing accelerator is preferably used in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin in consideration of the curing characteristics and various physical properties. Further, in the epoxy resin composition for semiconductor encapsulation, although slightly different depending on the type of the inorganic filler, considering solder heat resistance, moldability (melt viscosity, fluidity), low stress, low water absorption, etc., 60% of the total composition of the inorganic filler
It is preferable to mix it in such a proportion that it occupies ˜93% by weight.

As a general method for preparing the epoxy resin composition as a molding material, the respective raw materials in a predetermined ratio are thoroughly mixed with, for example, a mixer, and then subjected to a kneading treatment with a hot roll or a kneader, followed by cooling. After solidification, a method of pulverizing to an appropriate size can be mentioned. Using the molding material thus obtained, a semiconductor device can be obtained by sealing a semiconductor element by, for example, low-pressure transfer molding. Curing of the epoxy resin composition can be performed, for example, in a temperature range of 100 to 250 ° C.

[0041]

EXAMPLES The present invention will be specifically described with reference to the following examples. The physical property measuring methods in Reference Examples and Examples are
It is as follows. (1) 150 ° C. Melt Viscosity The melt viscosity of the starting phenolic polymer and the epoxy resin at 150 ° C. was measured using an ICI melt viscometer.

(2) Polymerization Degree Ratio m / n The reaction rate of formaldehyde and salicylaldehydes in the production of the raw material phenolic polymer was determined, and the methylene bond / methine bond (m) in the polymer was determined from the charged amount and the reaction rate.
The ratio of / n) was determined. The formaldehyde reaction rate is
The formaldehyde remaining after the reaction was measured and determined by the hydroxylamine hydrochloride method. The reaction rate of salicylaldehydes was determined by measuring the salicylaldehydes remaining after the reaction by gas chromatography.

(3) p of the methylene group substitution position for the hydroxy group in the raw material phenol novolac resin polymerized unit
/ O position ratio: determined by using ¹ H-NMR spectroscopy.

(4) A glass transition temperature epoxy resin composition was molded using a transfer molding machine at 175 ° C. for 120 seconds and then post-cured at 180 ° C. for 6 hours. Was cut out and the glass transition temperature was measured by the TMA method (heating rate 5 ° C./min).

[Reference Example 1] Based on Example 1 of Japanese Patent Application No. 2001-55793, a phenolic polymer as a raw material of the epoxy resin of the present invention was prepared. That is, 94 g (1 mol) of phenol, 19.5 g of 37% formalin aqueous solution
(0.24 mol of formaldehyde) and 0.57 g of oxalic acid dihydrate were reacted at 65 ° C. for 4 hours to give a phenol novolac resin having a p / o position ratio of methylene group substitution position to hydroxy group of 1.2. Got

Thereafter, 106.2 g of phenol was further added.
(1.13 mol), salicylaldehyde 29.3 g
(0.24 mol), 7.1 g of 35% hydrochloric acid aqueous solution was additionally charged, reacted at 65 ° C. for 4 hours, and the obtained condensation liquid was further heat-treated under reduced pressure to obtain unreacted phenol,
By removing water, oxalic acid and HCl out of the system, 9
9.2 g of phenolic polymer was obtained. The properties of the obtained phenolic polymer were as follows. Hydroxyl equivalent: 100 g / eq 150 ° C. melt viscosity: 190 mPa · s m / n: 1.0 (value obtained from the reaction rate of aldehydes) p / o ratio: 2.5

[Example 1] In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a condenser with a separating tube, 100 g of the phenolic polymer obtained in Reference Example 1 and 574 g of epichlorohydrin (of the phenolic polymer) were added. (Equivalent to 6.2 equivalents of hydroxyl group) and 200 g of dimethyl sulfoxide as a solvent were charged, and the mixture was stirred at 115 to 120.
After the temperature was raised to 0 ° C., 165 g of 49% sodium hydroxide aqueous solution was continuously added dropwise at the same temperature over 2 hours. During this time, while keeping the temperature at 115 to 120 ° C., the mixture of distilled epichlorohydrin and water is cooled and concentrated to separate the liquid, and the epichlorohydrin layer is allowed to react while returning to the reaction system to carry out the epoxidation reaction (glycidyl of hydroxyl group). Etherification).

After completion of the reaction, excess epichlorohydrin was removed by distillation under reduced pressure, the residue (epoxidation product containing by-product salt and dimethylsulfoxide) was dissolved in methyl isobutyl ketone, and the resulting solution was washed with water. The by-product salt and dimethyl sulfoxide were removed. Thereafter, methyl isobutyl ketone was distilled off from the organic layer to obtain 144 g of a target epoxy resin. The epoxy equivalent of this epoxy resin was 160 g / eq, and the ICI melt viscosity at 150 ° C. was 60 mPa · s, which was approximately the same as the m / n of the phenolic polymer represented by the general formula (2).

[Reference Example 2] 94 g (1 mol) of phenol, 14.6 g of a 37% formalin aqueous solution (0.18 mol in terms of formaldehyde) and 1.1 g of oxalic acid dihydrate were used and reacted at 40 ° C. for 5 hours. After that, 17.4 g of phenol (0.19 mol) and salicylaldehyde 1
6.9 g (0.14 mol), 35% hydrochloric acid aqueous solution 8.2 g
Was additionally charged, the mixture was reacted at 40 ° C. for 8 hours, and the same post-treatment as in Reference Example 1 was performed to obtain 65.0 g of a phenol-based polymer. The properties of the obtained phenolic polymer were as follows. Hydroxyl equivalent: 101 g / eq 150 ° C. melt viscosity: 180 mPa · s m / n: 1.3 (value obtained from the reaction rate of aldehydes) p / o ratio: 3.0

[Embodiment 2] Reference Example 1 in Embodiment 1
Epoxidation reaction was carried out in the same manner as in Example 1 except that 100 g of the phenolic polymer obtained in Reference Example 2 was used instead of using the phenolic polymer used in Example 2, and an epoxy equivalent of 162 g / eq. 142 g of an epoxy resin having an ICI melt viscosity of 50 mPa · s at 150 ° C. was obtained.
This epoxy equivalent was approximately the same as that of m / n of the phenolic polymer represented by the general formula (2).

[Examples 3 and 4, Comparative Examples 1 and 2] Epoxy resin (of Examples 1 and 2, epoxy resin A or epoxy resin B below), phenolic resin-based curing agent (phenolic resin below), melted Silica, triphenylphosphine, aminosilane coupling agent, and carnauba wax were blended in the proportions shown in Table 1 (numerical values in the table are parts by weight), mixed well, and then 3 minutes with a two-roll 85 ° C. ± 3 ° C. By kneading, cooling and pulverizing, a molding composition was obtained.
100 kg pressure of molding composition with transfer molding machine
After molding at 175 ° C. for 2 minutes at f / cm ² , post-curing was performed at 180 ° C. for 6 hours to obtain a test piece for glass transition temperature (Tg).

Epoxy resin A: In the general formula (1),
The epoxy equivalent of R ³ is hydrogen and n is 159 g /
eq phenol novolac resin epoxy resin B: in the general formula (1), R ¹ and R ² are hydrogen, and m is 0. Epoxy equivalent is 168 g / eq. Triphenol methane type epoxy resin Phenolic resin: Hydroxyl equivalent 106
g / eq phenol formaldehyde resin

[0053]

[Table 1] Numerical values of raw materials in the table are parts by weight

[0054]

The epoxy resin of the present invention has polymerized units of a glycidylated triphenolmethane type resin and a glycidylated phenol novolak type resin in the molecule, and the degree of polymerization and the degree of polymerization of both are specified. Since it is adjusted to the range, it has the properties of low melt viscosity and high glass transition temperature. As a result, it can be used as a semiconductor encapsulating material, a structural member material, etc., which requires high performance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 23/31 F term (reference) 4J002 CD032 CD052 CD061 CD102 CD132 CD172 DE076 DE146 DE236 DG046 DJ006 DJ016 DJ036 DJ046 DJ056 DL006 FD016 GQ05 4J036 AF05 AF06 AF07 DB15 DC02 DC41 FA01 FB07 JA01 JA05 JA07 4M109 AA01 BA01 CA21 EA04 EA06 EB03 EB12 EC20

Claims (11)

[Claims] 1. An epoxy resin represented by the following general formula (1), which has a melt viscosity at 150 ° C. of 10 to 300 mPa · s. [Chemical 1] (In the formula, G is a glycidyl group, R ¹ , R ² , R ³ and R ⁴
Are each hydrogen or an alkyl group, p, q, r and s are each 1-2, and m / n is 0.7-1.5). 2. The epoxy resin according to claim ¹ , wherein R ¹ , R ² , R ³ and R ⁴ are all hydrogen. 3. The average value of m and n is 0.6 to respectively.
The epoxy resin according to claim 1 or 2, which is 2.0. 4. The epoxy resin according to claim 1, wherein the p / o ratio of the methylene group substitution position to the glycidyl ether group in the glycidylated phenol novolac polymerized unit is 1.5 or more. 5. The method for producing an epoxy resin according to claim 1, which comprises reacting a phenolic polymer represented by the following general formula (2) with epihalohydrin. [Chemical 2] (In the formula, R ¹ , R ² , R ³ and R ⁴ are each hydrogen or an alkyl group, p, q, r and s are each 1 to 2, m /
n is 0.7 to 1.5) 6. An epoxy resin composition containing the epoxy resin according to claim 1 and a phenol resin curing agent. 7. The epoxy resin composition according to claim 6, which contains another epoxy resin. 8. The epoxy resin composition according to claim 6, which contains an inorganic filler. 9. The method according to claim 6, which is used for semiconductor encapsulation.
The epoxy resin composition described. 10. An epoxy resin composition obtained by curing the epoxy resin composition according to claim 7. 11. A semiconductor device obtained by encapsulating a semiconductor element using the epoxy resin composition according to claim 9.