JPH11181049A - Modified epoxy resin, epoxy resin composition and its hardened product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject epoxy resin that can reduce the melt viscosity, increase the softening point with the operability, storability (resistance to blocking) improved, and is useful as an insulating material for electric and electronic parts by glycidylating a specific bisphenol and polyhydric phenol. SOLUTION: A mixture of (A) a bisphenol represented by formula (R is H, a halogen, a 1-8C hydrocarbon group or the like) melting at a temperature of >=200 deg.C and a polyhydric phenol other than the component A (preferably an alkylphenol novolak) is subjected to glycidylation reaction. In a preferred embodiment, the weight ratio of the component A to the component (B) (A/B) is 0.05-20 and the all carbon atoms of the compound of formula I form the sp<2> hybrid orbitals, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to insulating materials for electric and electronic parts including sealing semiconductors, and various composite materials including laminated boards (printed wiring boards) and CFRP (carbon fiber reinforced plastic). The present invention relates to a modified epoxy resin, an epoxy resin composition, and a cured product thereof useful for an adhesive, a paint and the like.

[0002]

2. Description of the Related Art Epoxy resins are used in the fields of electric and electronic parts, structural materials, adhesives, paints, etc. due to workability and excellent electrical properties, heat resistance, adhesiveness, moisture resistance (water resistance), etc. of the cured product. Widely used in

[0003]

However, in recent years, in the field of electric and electronic devices, with rapid development, heat resistance, moisture resistance, adhesion, low viscosity for high filling of fillers, etc. Further improvement of various characteristics is required. On the other hand, it is desired to be solid at room temperature in order to improve workability. In addition, structural materials include aerospace materials,
In addition to being lightweight and having excellent mechanical properties for leisure and sports equipment applications, low viscosity resins are also required to improve workability. Many proposals have been made for epoxy resin compositions to meet these requirements, but they have not been satisfactory yet.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on epoxy resins having the above-mentioned characteristics, and have completed the present invention. That is, according to the present invention, the formula (1)

[0005]

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(In the formula (1), each R independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms. X represents a hydrocarbon group having 1 to 14 carbon atoms and 1 to 4 carbon atoms. 14
A halogenated hydrocarbon group, -N = CY-, -CY = N-
ZN = CY- or -N = CY-Z-CY = N- (wherein, Y independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms. Z is a direct bond, 1 carbon atom. ~ 24 hydrocarbon groups,
A halogenated hydrocarbon group having 1 to 24 carbon atoms, 1 to 2 carbon atoms
4 alkoxy-substituted aromatic hydrocarbon group, —C ₆ (R)
_{4 -S-C 6 (R)} 4 -, - C 6 (R) 4 -SO-C 6
(R) ₄ —, —C ₆ (R) ₄ —SO ₂ — (wherein R has the same meaning as described above). )) Is 2
A modified epoxy resin obtained by glycidylating a mixture of a bisphenol compound at a temperature of 00 ° C. or higher and a polyhydric phenol compound other than (b) and (a), and (2) a weight mixing ratio of (a) and (b) / (a) / The modified epoxy resin according to the above (1), wherein (b) is 0.05 or more and 20 or less, (3) (a)
The modified epoxy resin according to the above (1), wherein a weight mixing ratio (a) / (b) of the modified epoxy resin and the (b) is 0.05 or more and 1 or less;
(4) The above (1), (2) obtained using a compound of the formula (1) in which all carbon atoms form sp2 hybrid orbitals.
And the modified epoxy resin according to any one of (3),
(5) The modified epoxy resin according to any one of (1), (2), (3) and (4), having a softening point of 70 ° C. or higher and 130 ° C. or lower, (6) a melt viscosity of 2 The modified epoxy resin according to any one of (1), (2), (3), (4) and (5), wherein the component (b) is an alkylphenol novolak. (1) The modified epoxy resin according to any one of (2), (3), (4), (5) and (6), (8) any one of the above (1) to (7) An epoxy resin composition containing the modified epoxy resin according to the above item, (9) the epoxy resin composition according to the above (8), which is prepared for semiconductor encapsulation,
(10) A cured product obtained by curing the epoxy resin composition according to (8) or (9).

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The modified epoxy resin of the present invention comprises a bisphenol compound represented by the formula (1) (component (a), hereinafter simply referred to as (a)) and a polyhydric phenol compound other than the above bisphenol ( It can be obtained by a glycidylation reaction in which a mixture of the component (b) (hereinafter simply referred to as (b)) (hereinafter simply referred to as a phenol mixture) and epihalohydrins are reacted.

Specific examples of the compound of the formula (1) that can be used include dihydroxyterphenyl, dihydroxyquarterphenyl, dihydroxystilbene, 2,2-bis (4'-hydroxyphenyladamantanone, 4,4 '
-[(2,3,5,6-tetramethyl) -1,4-phenylenebismethylene] bisphenol, 4-hydroxy-N- (4-hydroxybenzylidene) aniline, HO
_{-C 6 H 4 -N = CH-} C 6 H 4 -CH = N-C 6 H 4
_{-OHHO-C 6 H 4 -CH =} N-C 6 H 4 -N = CH
_{-C 6 H 4 -OHHO-C 6} H 4 -CH = N-N = CH
_{-C 6 H 4 -OHHO-C 6} H 4 -C (CH 3) = N-
N = C (CH ₃ ) —C ₆ H ₄ —OH and the like, but are not limited thereto. Further, two or more kinds may be used in combination. In addition, among the above bisphenols, when a bisphenol in which all carbon atoms form an sp2 hybrid orbital is used, a modified epoxy resin finally obtained has a low viscosity and a high softening point (or component (a)). Alternatively, the softening point equivalent to that of the glycidylated product of the component (b) alone can be simultaneously performed, which is preferable.

Specific examples of (b) that can be used include bisphenol A, bisphenol F, 1,1-bis- (4-
(Hydroxyphenyl) -cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, terpene diphenol, phenol / formaldehyde polycondensate, phenol / dicyclopentadiene polymer, phenol Polyphenols / xylylene glycol polycondensates, phenols / biphenyl dimethanols polycondensates, phenols / hydroxybenzaldehydes polycondensates, alkylphenol novolaks obtained by condensing formaldehyde with phenols having an alkyl group, and the like. It is not limited. Examples of the phenol in each polycondensate include phenol, cresol, xylenol, tert-butyl-cresol, naphthol, and the like, but are not limited thereto. Further, two or more kinds may be used in combination.

The mixing ratio of (a) and (b) is not particularly limited, but preferably the weight mixing ratio (a) / (b) is 0.0
It is 5 or more and 20 or less, more preferably 0.05 or more and 1 or less.

Specific examples of epihalohydrins used in the glycidylation reaction for obtaining the modified epoxy resin of the present invention include epichlorohydrin, β-methylepichlorohydrin, epibromohydrin, β-methylepibromohydrin, epiiodohydrin Hydrin, β-ethyl epichlorohydrin and the like can be mentioned, but epichlorohydrin, which is easily available industrially and is inexpensive, is preferable. This glycidylation reaction itself can be performed according to a conventionally known method.

For example, a solid of alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like is added to the above-mentioned mixture of phenol mixture and epihalohydrin in a lump or gradually, usually at 20 to 120 ° C. for 0.5 to 10 minutes.
Let react for hours. At this time, an aqueous solution of the alkali metal hydroxide may be used. In such a case, the alkali metal hydroxide is continuously added, and water and epihalohydrin are continuously added to the reaction mixture under reduced pressure or normal pressure. May be distilled off, the resulting distillate is separated, water is removed, and epihalohydrins are continuously returned to the reaction mixture.

In the above method, the amount of the epihalohydrin used is usually 0.5 to 10 mol, preferably 1.0 to 6.0 mol, per equivalent of the hydroxyl group of the phenol mixture. The amount of the alkali metal hydroxide to be used is generally 0.5 to 1.5 mol, preferably 0.7 to 1.2 mol, per 1 equivalent of the hydroxyl group in the phenol mixture. Also, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide,
By adding an aprotic polar solvent such as 1,3-dimethyl-2-imidazolidinone, a modified epoxy resin having a low hydrolyzable halogen concentration defined below is obtained,
This modified epoxy resin is suitable for use in sealing electronic materials. The amount of the aprotic polar solvent used is usually 5 to 200% by weight, preferably 10 to 10% by weight based on the epihalohydrin.
0% by weight. In addition to the above-mentioned solvents, the reaction is facilitated by addition of alcohols such as methanol and ethanol, and cyclic ethers such as 1,4-dioxane. It is higher than the case, but lower than when these solvents are not used. Further, toluene, xylene and the like can be used. Here, the concentration of the hydrolyzable halogen can be measured, for example, by placing the modified epoxy resin in a dioxane and 1N-KOH / ethanol solution, refluxing for several tens minutes, and then titrating with a silver nitrate solution.

A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is used as a catalyst in a mixture of a phenol mixture and an excess of epihalohydrins, usually at 50 to 150 ° C.
The reaction is performed for 10 hours, and a solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the resulting halohydrin ether of the phenol mixture,
The modified epoxy resin of the present invention can also be obtained by reacting at 20 to 120 ° C. for 1 to 10 hours to close the ring of the halohydrin ether. In this case, the amount of the quaternary ammonium salt used is usually 0.1 to 1 equivalent of the hydroxyl group of the phenol mixture.
It is 001 to 0.2 mol, preferably 0.05 to 0.1 mol. The amount of the alkali metal hydroxide to be used is usually 0.8 to 1.5 mol per 1 equivalent of the hydroxyl group of the phenol mixture,
Preferably it is 0.9 to 1.1 mol.

[0015] Usually, these reaction products are washed with water or without water, and the excess epihalohydrins,
After removing the solvent and the like, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, and methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added thereto. The modified epoxy resin of the present invention having a low concentration can be obtained. In this case, the amount of the alkali metal hydroxide used is usually from 0.01 to 1 equivalent of the hydroxyl group of the phenol mixture.
It is 0.2 mole, preferably 0.05-0.1 mole.
The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5.
~ 2 hours. After the reaction is completed, salts formed as by-products are removed by filtration, washing with water, etc., and the modified epoxy resin of the present invention having a low hydrolyzable halogen concentration is obtained by distilling off solvents such as toluene, methyl isobutyl ketone and methyl ethyl ketone under reduced pressure under heating. Obtainable. The modified epoxy resin of the present invention thus obtained comprises a component (a) and a component (b)
Contains a trace amount of a component bonded by a group represented by —CH ₂ CZ (OH) CH ₂ — (wherein Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). For this reason, the familiarity of each epoxy resin component is better than that of a mixture of (a) and (b) glycidyl compounds alone, and when blended with the epoxy resin composition of the present invention described later, When the adhesiveness is improved and the condition of the above item (4) is satisfied, the storage stability (blocking resistance) of the epoxy resin composition is improved. The modified epoxy resin of the present invention preferably has a softening point of 130 ° C.
° C or higher. If the softening point is less than 70 ° C., the storage stability is poor, and if it exceeds 130 ° C., the workability is reduced when kneading the epoxy resin composition using a kneader or the like, or kneading unevenness of the epoxy resin composition occurs. Or

Hereinafter, the epoxy resin composition of the present invention will be described. In the epoxy resin composition of the present invention, the modified epoxy resin of the present invention can be used alone or in combination with another epoxy resin. When used in combination, the proportion of the modified epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.

Specific examples of other epoxy resins that can be used in combination with the modified epoxy resin of the present invention include bisphenols,
Phenols (phenol, alkyl-substituted phenol,
Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes, polymers of phenols with various diene compounds, polycondensates of phenols with aromatic dimethylols, biphenols, alcohols Glycidyl ether-based epoxy resins, alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, etc., obtained by glycidylation of glycidyl groups and the like are not limited thereto. These may be used alone or in combination of two or more.

The epoxy resin composition of the present invention contains a curing agent in a preferred embodiment. As the curing agent, amine compounds, acid anhydride compounds, amide compounds, phenol compounds and the like can be used. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, and trianhydride. Mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenols (phenol, alkyl substitution Polycondensates of phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes, polymerization of phenols with various diene compounds , Polycondensates of phenols with aromatic dimethylol, biphenols and modified products thereof, imidazo -
BF ₃ -amine complex, guanidine derivative and the like. The amount of the curing agent used is preferably 0.5 to 1.5 equivalents to 1 equivalent of the epoxy group of the epoxy resin,
-1.2 equivalents is particularly preferred. If the amount is less than 0.5 equivalents or more than 1.5 equivalents with respect to 1 equivalent of the epoxy group, curing may be incomplete and good cured physical properties may not be obtained.

When the above curing agent is used, a curing accelerator may be used in combination. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol,
1,8-diaza-bicyclo (5,4,0) undecene-
Tertiary amines such as 7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The hardening accelerator is used in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the epoxy resin as required.

Further, the epoxy resin composition of the present invention may contain, if necessary, fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia,
Aluminum nitride, forsterite, steatite,
Powders such as spinel, mullite, titania, talc, etc., or various fillers such as inorganic fillers, silane coupling agents, mold release agents, pigments, etc., made of these spherical or crushed, and various thermosetting resins are added. can do. In particular, when an epoxy resin composition for semiconductor encapsulation is obtained, the above-mentioned inorganic filler is usually used in an amount of 80 to 92% by weight, preferably 83 to 90% by weight, more preferably 85 to 92% by weight in the epoxy resin composition. It is used in a proportion occupying 90% by weight.

The epoxy resin composition of the present invention is obtained by uniformly mixing the above-mentioned components in the above-mentioned ratio, and is preferably used for encapsulating a semiconductor. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin and a curing agent, and if necessary, a curing accelerator, an inorganic filler, a compounding agent, and various thermosetting resins are made uniform using an extruder, a kneader, a roll, or the like as necessary. The epoxy resin composition of the present invention is obtained by sufficiently mixing the epoxy resin composition and the epoxy resin composition by a melt casting method or a transfer method.
The cured product of the present invention can be obtained by molding by a molding method, an injection molding method, a compression molding method, or the like, and heating at 80 to 200 ° C. if necessary.

Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like, and glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. The prepreg obtained by impregnating the base material and drying by heating may be subjected to hot press molding to obtain the cured product of the present invention.

In this case, the proportion of the solvent to the total weight of the epoxy resin composition of the present invention and the solvent is usually 10%.
７０70% by weight, preferably 15-65% by weight.

[0024]

The present invention will be described in more detail with reference to the following examples. Note that the present invention is not limited to these examples. The epoxy equivalent, melt viscosity, and softening point were measured under the following conditions. In the examples, parts mean parts by weight. Epoxy equivalent Measured in accordance with JIS K-7236, unit is g
/ Eq. Melt viscosity Melt viscosity in cone plate method at 150 ° C Measurement machine: cone plate (ICI) high temperature viscometer (RESE)
ARCH EQUIPMENT (LONDON) LTD. : 3 (measurement range: 0 to 20 poise) Sample amount: 0.15 ± 0.01 g Softening point Measured by a method according to JIS K-7234

Example 1 55 parts of o-cresol novolak (softening point: 90 ° C.), trans-4,4′-dihydroxy-3,3 ′, 5,5 ′
A reaction vessel was charged with 14 parts of tetramethylstilbene, 240 parts of epichlorohydrin (ECH, hereinafter the same), and 100 parts of dimethyl sulfoxide (DMSO, the same hereinafter), and after heating, stirring and dissolving, the reaction was carried out while maintaining the temperature at 45 ° C. While maintaining the inside of the system at 45 Torr, 54 parts of a 40% aqueous sodium hydroxide solution was continuously dropped over 4 hours. At this time, after cooling and separating the ECH and water distilled off by azeotropic distillation, the reaction was performed while returning only the organic layer, ECH, into the reaction system. After the completion of the aqueous sodium hydroxide solution, 45
The reaction was carried out at 70 ° C for 2 hours and at 70 ° C for 30 minutes. Subsequently, washing with water was repeated to remove by-product salts and dimethyl sulfoxide. After that, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 200 parts of methyl isobutyl ketone was added to the residue to dissolve the residue. The solution of methyl isobutyl ketone was heated to 70 ° C., 4 parts of a 30% aqueous sodium hydroxide solution was added, and the mixture was reacted for 1 hour. Then, the reaction solution was repeatedly washed with water until the washing solution became neutral. Subsequently, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain the modified epoxy resin (E1) 93 of the present invention.
Got a part. The resulting modified epoxy resin (E1) had an epoxy equivalent of 198, a softening point of 62 ° C., and a melt viscosity of 1.6 poise.

Example 2 In Example 1, o-cresol novolak was added to 58 parts of trans-4,4'-dihydroxy-3,3 ',
Trans-5,5'-tetramethylstilbene is converted to trans-4,
The same operation as in Example 1 was performed, except that 10 parts of 4'-dihydroxy-stilbene was used. As a result, 94 parts of the modified epoxy resin (E2) of the present invention was obtained. The resulting modified epoxy resin (E2) had an epoxy equivalent of 195, a softening point of 118 ° C., and a melt viscosity of 2.0 poise.

Example 3 In Example 1, o-cresol novolak was added to 48 parts of trans-4,4'-dihydroxy-3,3 ',
Trans-5,5'-tetramethylstilbene is converted to trans-4,
4'-dihydroxy-3,3'-tertbutyl-6,6
The same operation as in Example 1 was performed, except that 23 parts of 6′-dimethylstilbene was used. As a result, 97 parts of the modified epoxy resin (E3) of the present invention was obtained. The resulting modified epoxy resin (E3) has an epoxy equivalent of 212 and a softening point of 61.
C. and the melt viscosity was 0.9 poise.

Example 4 In Example 1, o-cresol novolak was added to 34 parts of trans-4,4'-dihydroxy-3,3 ',
The same operation as in Example 1 was performed, except that 5,5′-tetramethylstilbene was changed to 37 parts of 2,2-bis (4′-hydroxyphenyl) adamantane. as a result,
91 parts of the modified epoxy resin (E4) of the present invention was obtained. The resulting modified epoxy resin (E4) has an epoxy equivalent of 21.
0, the softening point was 101 ° C., and the melt viscosity was 1.5 poise.

Example 5 In Example 1, o-cresol novolak was added to 34 parts of trans-4,4'-dihydroxy-3,3 ',
5,5′-Tetramethylstilbene is converted to 4,4 ′-[1,
4-Phenylenebis (methylene)] The same operation as in Example 1 was carried out except that the amount was changed to 37 parts of bis (4-hydroxybenzene). As a result, the modified epoxy resin (E
5) 93 parts were obtained. Obtained modified epoxy resin (E5)
Has an epoxy equivalent of 215, a softening point of 98 ° C., and a melt viscosity of 1.3 poise.

Example 6 In Example 1, o-cresol novolak was added to 58 parts of trans-4,4'-dihydroxy-3,3 ',
5,5′-Tetramethylstilbene is represented by the following formula (2)

[0031]

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The same operation as in Example 1 was carried out, except that 11 parts of the compound represented by the following formula was used. As a result, 90 parts of the modified epoxy resin (E6) of the present invention was obtained. The resulting modified epoxy resin (E6) has an epoxy equivalent of 202 and a softening point of 1
At 20 ° C., the melt viscosity was 2.5 poise.

Example 7 In Example 1, o-cresol novolak was added to 58 parts of trans-4,4'-dihydroxy-3,3 ',
The same operation as in Example 1 was performed, except that 5,5'-tetramethylstilbene was changed to 11 parts of 4,4'-dihydroxyta-phenyl. As a result, 87 parts of the modified epoxy resin (E7) of the present invention was obtained. The resulting modified epoxy resin (E7) has an epoxy equivalent of 200, a softening point of 122 ° C.,
The melt viscosity was 1.9 poise.

Examples 8 to 14 Using the modified epoxy resins (E1) to (E7) of the examples, a curing agent (phenol novolak resin (Nippon Kayaku Co., Ltd.) Made,
PN-80, ICI viscosity at 150 ° C. 1.5 poise, softening point 86 ° C., hydroxyl equivalent 106 g / eq), 1 hydroxyl equivalent, and a curing accelerator (triphenylphosphine) at 1 part per 100 parts of epoxy resin It was blended, and a resin molded body was prepared by transfer molding, and cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.

Table 1 shows the results of measuring the physical properties of the cured product thus obtained. The measurement of the physical properties was performed under the following conditions. Glass transition temperature (TMA): TM-7000 manufactured by Vacuum Riko Co., Ltd. Temperature rise rate 2 ° C./min. -Copper foil peel strength: Measured according to JIS C-6481 (peel strength). Izod impact test: Measured according to JIS K7710.

[0036]

Table 1 Table 1 8910 10 11 12 13 14 Epoxy resin E1 E2 E3 E4 E5 E6 E7 Glass transition temperature (° C) 147 149 146 146 151 141 149 150 Copper foil peel strength (Kg / cm) 2.5 2.3 2.6 2.6 2.8 2.6 2.2 Izod impact test value (Kg / mm ² ) 14 13 13 12 18 13 15

[0037]

The modified epoxy resin of the present invention has a low melt viscosity, and its softening point can be raised by using bisphenols composed of only those whose carbon atoms form sp2 orbitals. And workability and storage stability (blocking resistance) can be improved. Accordingly, the modified epoxy resin of the present invention can be used as an insulating material for electric and electronic parts (such as a highly reliable semiconductor encapsulating material) and various composite materials such as a laminated board (such as a printed wiring board) and CFRP, an adhesive, and a paint. It is extremely useful when used for

Claims (10)

[Claims] (A) Formula (1) (In Formula (1), R independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 8 carbon atoms. X represents a hydrocarbon group having 1 to 14 carbon atoms, and a halogen having 1 to 14 carbon atoms. Hydrocarbon group, -N = CY-, -CY = NZN = CY
-Or -N = CY-Z-CY = N- (wherein Y independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Z is a direct bond, a hydrocarbon group having 1 to 24 carbon atoms, Carbon number 1-24
Halogenated hydrocarbon group, an alkoxy group-substituted aromatic hydrocarbon radical having 1 to 24 carbon _{atoms, -C 6 (R) 4 -S} -C
_{6 (R) 4 -, -} C 6 (R) 4 -SO-C 6 (R) 4 -
Or —C ₆ (R) ₄ —SO ₂ —C ₆ (R) ₄ —
Represents the same meaning as described above. ). A modified epoxy resin obtained by glycidylating a mixture of a bisphenol compound having a melting point of 200 ° C. or higher and a polyhydric phenol compound other than (b) and (a). 2. A weight mixing ratio of (a) and (b) (a) /
The modified epoxy resin according to claim 1, wherein (b) is 0.05 or more and 20 or less. 3. A weight mixing ratio of (a) and (b) (a) /
The modified epoxy resin according to claim 1, wherein (b) is 0.05 or more and 1 or less. 4. The modified epoxy resin according to claim 1, wherein the modified epoxy resin is obtained by using the compound of (1) in which all carbon atoms form sp2 hybrid orbitals. 5. The modified epoxy resin according to claim 1, which has a softening point of 70 ° C. or higher and 130 ° C. or lower. 6. The method according to claim 1, wherein the melt viscosity is 2.0 or less.
6. The modified epoxy resin according to any one of 2, 3, 4, and 5. 7. The composition of claim 1, wherein component (b) is an alkylphenol novolak.
The modified epoxy resin as described in the item. 8. An epoxy resin composition containing the modified epoxy resin according to claim 1. 9. The epoxy resin composition according to claim 8, which is prepared for encapsulating a semiconductor. 10. A cured product obtained by curing the epoxy resin composition according to claim 8 or 9.