JPH10265466A - Phenolic epoxy resin and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject resin useful as an IC sealant material by a short time reaction in the absence of a solvent in a simple apparatus by using an imidazole-based compound as a catalyst and simultaneously introducing raw materials. SOLUTION: The objective compound is represented by the formula [R<1> to R<4> are each H, a 1-6C hydrocarbon or a (substituted) 6-10C aromatic; R<5> and R<6> are each H a 1-6C hydrocarbon, a (substituted) 6-10C aromatic, etc.]. The objective compound is obtained by reacting (B) 1 eq. polyfunctional phenol, especially bisphenol, etc., or a hydrocarbon or an aromatic derivative thereof with an epihalohydrin, especially epichlorohydrin, etc., in the presence of a catalyst of (A) 0.01-0.5 eq. imidazole-based compound, especially imidazole, etc., under a normal pressure and under heating and refluxing at a reaction temperature of 90-120 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenolic epoxy resin which can provide a group of phenolic epoxy resins, and more particularly to a phenolic epoxy resin suitable for use in electronic chemicals and materials, and a method for producing the same.

[0002]

2. Description of the Related Art Phenolic epoxy resins are one of the main components of semiconductor sealant materials. Of these, bisphenol epoxy resins have a relatively low viscosity, so that their fluidity can be increased only in the manufacturing process. In addition, the generation of the bubbles can be further reduced. Therefore, it is widely used as a thin sealant material for semiconductors.

[0003] Further, since trisphenol-based and tetrakisphenol-based epoxy resins have relatively high glass transition temperatures, their heat resistance can be effectively reduced by adding them to a sealant material or a substrate. Can be enhanced.

In addition, derivatives obtained by introducing a hydrocarbon or an aromatic group into the benzene ring of a phenolic epoxy resin include:
It has the effect of reducing the hygroscopicity after sealing and reducing cracking. Therefore, the viscosity is low,
Synthesizing a phenolic epoxy resin having heat resistance and low hygroscopicity is a major direction in the development of semiconductor electronic materials.

Meanwhile, US Pat. No. 5,028,686 discloses a method of simultaneously adding high-purity epoxy resins as a method for producing the same, and the method for improving the prior art includes simultaneous or continuous addition of (1). A) mixtures of epihalohydrins, epoxy compounds and solvents and (2)
A mixture of an alkali metal or alkaline earth metal hydroxide or manganese hydroxide and water, or an organic solvent is added to a mixture of epihalohydrin and a solvent, and at least one equivalent or more of an alkali metal or phenol group per equivalent is added. Alkaline earth metal hydroxides encompass stoichiometric substitution reactions used in the reaction.

Further, US Pat. No. 4,954,603 describes a flame-retardant epoxy resin composition having heat resistance, in which an epoxy compound having three functional groups and a halogenated bisphenol are used as catalysts. The halogen-containing epoxy resin obtained by acting below is included.

EP-A-579301 discloses a process for producing an epoxy resin containing a bisphenol structure, which comprises converting an alkali metal oxide to phenol in the presence of a solvent consisting of dialcohol monoether and water. 0.8 to 2.0 moles of 4,4'-
The synthesis method to be added to the mixture of bisphenol and epihalohydrin is included.

The epoxy resin used for the encapsulating semiconductor described in European Patent No. 396203 is obtained by reacting tetrakisphenol, epihalohydrin and an aqueous solution of sodium hydroxide in the presence of water and isopropanol.

The above-mentioned prior arts relate to methods for producing bisphenol, trisphenol and tetrakisphenol-based epoxy resins, respectively. In each case, bisphenol, trisphenol or tetrakisphenol is used as a raw material and an alcohol solvent (for example, Isopropanol, ethylene glycol, etc.)
This is a synthesis method in which a strong alkaline aqueous solution such as sodium hydroxide is added to react with epichlorohydrin to obtain an epoxy resin. The reaction involves at least 1 mol of sodium hydroxide per 1 mol of phenol groups. Is a stoichiometric substitution reaction used.

[0010]

In the above-mentioned conventional method for producing an epoxy resin, heat is radiated when a strong alkali is added as a raw material supply. In addition, since the reaction is a heterogeneous reaction containing water, alcohols, and organic compounds such as epichlorohydrin and phenol, the reaction must be performed under reduced pressure azeotropy. In addition, after the reaction is completed, water and alcohols, which are difficult to remove by distillation, are distilled, so that a complicated reaction facility is required, the operation is cumbersome, and much time must be spent. At present, no satisfactory synthesis method is known, so it is easy to imagine that it is desirable to develop a new method for synthesizing a phenolic epoxy resin that can shorten the reaction time with a simple production process.

The present inventors have made intensive studies to solve the above problems, and as a result, as a method for producing a phenolic epoxy resin, a raw material such as phenol, imidazole and epihalohydrin was simultaneously introduced using an imidazole compound as a catalyst. However, they have found that they can be synthesized by a short reaction in a simple facility in the absence of a solvent, and have completed the present invention.

A first object of the present invention is to provide a group of phenolic epoxy resins for use as IC sealant materials, printed circuit board additives and electronic adhesives.

Another object of the present invention is to provide a method for producing the phenolic epoxy resin. That is, by using an imidazole-based compound as a catalyst and simultaneously introducing and reacting phenol, imidazole and epihalohydrin in the absence of a solvent, it is industrially advantageous that the reaction time can be shortened with simple equipment. It is characterized by a simple synthesis method.

[0014]

Means for Solving the Problems The phenolic epoxy resin of the present invention is represented by the following general formula (I).

[0015]

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Wherein R ¹ , R ² , R ³ and R ⁴ may be the same or different and each independently represents a hydrogen atom, C _1-6
It represents a hydrocarbon group, an aromatic group of C _{6 to 10} substituted by an aromatic group or a hydrocarbon group of C _{1 to 6} of C _{6 to 10;} R ⁵
And R ⁶ may be the same or different and are each independently substituted by a hydrogen atom, a C _1-6 hydrocarbon group, a C _6-10 aromatic group, or a C _1-6 hydrocarbon group. Done C
_{6 to 10} aromatic groups,

[0017]

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[0018] (wherein, R ⁷ is an aromatic hydrogen atom, a hydrocarbon group of C _{1 to 6,} C _{6 to 10} substituted by an aromatic group or a hydrocarbon group of C _{1 to 6} of C _{6 to 10} Represents a group), or

[0019]

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(Wherein R ⁸ and R ⁹ may be the same or different and each independently represents a hydrogen atom, a C _1-6 hydrocarbon group, a C _6-10 aromatic group or a C _1-6 Represents an aromatic group substituted by a hydrocarbon group); n represents 0 or 1. In the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different, and specific examples include a hydrogen atom, a C _1-6 alkyl group, and a C _3-6 A cyclic alkyl group, C
_2-6 alkenyl group, an alkynyl group of C _2-6, a phenyl group, a naphthyl group or an alkyl group of C _{1 to 6,} cyclic alkyl C _{3 to 6,} alkenyl or C ₂ of C _{2-6, ~ 6}
And a phenyl or naphthyl group substituted by an alkynyl group. Furthermore, hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-
A butyl group, an isobutyl group, a tertiary butyl group, an amyl group, a hexyl group, a phenyl group, a benzyl group, a phenylethyl group and the like are preferably used, and a hydrogen atom, a methyl group, a tert-butyl group and a phenyl group are particularly preferred. Used for

In the general formula (I), R ⁵ and R ⁶ may be the same or different, and specific examples include a hydrogen atom, a C _1-6 alkyl group and a C _3-6 cyclic alkyl group. , C
_2-6 alkenyl group, an alkynyl group of C _2-6, a phenyl group, a naphthyl group or an alkyl group of C _{1 to 6,} cyclic alkyl C _{3 to 6,} alkenyl or C ₂ of C _{2-6, ~ 6}
And a phenyl or naphthyl group substituted by a substituent such as an alkynyl group. Among them, specifically, hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tertiary butyl group, n-amyl group, isoamyl group, neopentyl group, A hexyl group, a phenyl group, a benzyl group, a phenylethyl group and the like are more preferably used, and particularly, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group and an isopropyl group are most preferably used.

In the general formula (I), R ⁵ and R ⁶ are specifically:

[0023]

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(Wherein R ⁷ is specifically a hydrogen atom, C
_1-6 alkyl group, cyclic alkyl group of C _{3 to 6,} an alkenyl group of C _{2 to 6,} an alkynyl group of C _{2 to 6,} a phenyl group, a naphthyl group or an alkyl group of C _1-6,, C _{3 And} a phenyl group or a naphthyl group substituted by a substituent such as a cyclic alkyl group of _{6 to 6,} an alkenyl group of C _{2 to 6} or an alkynyl group of C _{2 to 6} . Among them, especially methyl group, ethyl group, n-propyl group, isopropyl group,
N-butyl, isobutyl, tertiary butyl, amyl, hexyl and phenyl are preferably used. ).

In the general formula (I), R ⁵ and R ⁶ are specifically:

[0026]

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(Wherein R ⁸ and R ⁹ may be the same or different, and specifically include a hydrogen atom, a C _1-6 alkyl group,
A C _3-6 cyclic alkyl group, a C _2-6 alkenyl group,
_2-6 alkynyl group, phenyl group, naphthyl group, or _C1-6 alkyl group, _C3-6 cyclic alkyl group, _C2-6
And a phenyl or naphthyl group substituted by a substituent such as an alkenyl group or a C _2-6 alkynyl group. Of these, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl, phenyl and benzyl groups are more preferably used. Is done. ).

In the general formula (I), more preferred examples of R ⁵ and R ⁶ include a hydrogen atom, a methyl group, an ethyl group, n
-Propyl group, isopropyl group,

[0029]

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And the like.

The process for producing the phenolic epoxy resin represented by the general formula (I) of the present invention is carried out by reacting a polyhydric phenol compound or a hydrocarbon or aromatic derivative thereof with epihalohydrin in the presence of an imidazole compound. .

The polyhydric phenol compound used in the present invention includes bisphenol, trisphenol and tetrakisphenol. In the production process, an imidazole compound used as a catalyst is added to a solution of polyhydric phenol or a hydrocarbon or aromatic derivative thereof and epihalohydrin at normal pressure,
The mixture is heated and refluxed in a homogeneous system to obtain an epoxy resin containing a polyhydric phenol group or a hydrocarbon or aromatic derivative thereof. Among them, the bisphenol-based epoxy resin includes a bonded structure such as a para-position, a para-position (P, P'-) bond, an ortho-position, and an ortho-position (O, O'-) bond.

The polyhydric phenol compounds used in the production method of the present invention, for example, bisphenol, trisphenol, tetrakisphenol and hydrocarbon or aromatic derivatives thereof (shown in the following general formula (II)) are:
It can be synthesized by an oxidative coupling reaction or an acidic condensation reaction.

[0034]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as in the above formula (I).) In the production method of the present invention, an imidazole compound is used as a catalyst. Although there is no particular limitation, specifically, it is efficient to use imidazole, 2-methylimidazole, 2-ethylimidazole, 2-n-propylimidazole, 2-isopropylimidazole, 2-phenylimidazole, and the like. It is. It is preferable to use 0.01 to 0.5 equivalent of the imidazole compound per equivalent of the phenol group. In particular, it is most preferable to use 0.01 to 0.2 equivalent.

The epihalohydrin used in the production method of the present invention includes epichlorohydrin and epibromohydrin, and it is particularly preferable to use epichlorohydrin. The use amount thereof is preferably 1 to 20 equivalents of epihalohydrin per 1 equivalent of phenol group, and most preferably 1 to 5 equivalents.

The phenolic epoxy resin of the present invention is prepared by a homogeneous reaction in which a polyhydric phenol compound or its hydrocarbon or aromatic derivative and epihalohydrin are refluxed under normal pressure in the presence of an imidazole compound. The reaction temperature is usually 90 to 120 ° C., and the reaction time is not particularly limited. However, it is generally preferable to carry out the reaction for 1 to 4 hours, depending on the substituent.

The product obtained by the above reaction is further combined with an organic solvent (for example, methyl ethyl ketone, methyl-2-pentanone, toluene or a mixture thereof) in an amount of 3 to 5 times the volume thereof and the product. The same volume of 1N aqueous sodium hydroxide solution is added, and
Reflux for 4 hours and continue the reaction. Thereafter, a crude product is obtained through operations such as extraction, drying, and concentration. The crude product is further recrystallized with an organic solvent such as methyl ethyl ketone, methyl-2-pentanone, toluene or ethyl alcohol, or purified by a chromatography method. Yield 85
It is as efficient as ~ 95%.

The phenolic epoxy resin of the present invention comprises
It is useful as a sealant material for C, a substrate additive for printed circuit boards, and a component of an electronic adhesive. To prepare these materials, the phenolic epoxy resin of the present invention may be used in place of the conventionally used epoxy resin.

[0040]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 4,4'-bis (glycidyloxy) -3,3 ', 5
Synthesis of 5'-tetramethylbiphenyl A 500 ml round bottom two-necked flask equipped with a mechanical stirrer and a condenser was equipped with 4,3 g of 3,3 ', 5,5'-tetramethyl-4,4'-bisphenol (0.20 g).
Mol), 0.68 g (0.01 mol) of imidazole and 185.2 g (2.0 mol) of epichlorohydrin, and the mixture is heated to 115 ° C. and refluxed for 2 hours to continue the reaction (the starting material by chromatography). 3,3 ', 5,5'-tetramethyl-4,4'-bisphenol was completely reacted and disappeared). Return to room temperature and remove excess epichlorohydrin on a rotary evaporator.

The resulting reaction product was mixed with 200 ml of 4-methyl-2-pentanone and a 1N aqueous solution of sodium hydroxide 5
Add 0 ml, heat to 90 ° C. with vigorous stirring and continue the reaction for 2 hours under reflux. After the temperature is returned to room temperature, the mixture is extracted, separated into an organic layer and an aqueous layer, and the aqueous layer is further extracted using 4-methyl-2-pentanone (160 ml × 2). The organic layer was collected, dried over anhydrous sodium sulfate, filtered, and concentrated using a rotary concentrator to obtain a crude product.

The crude product was further recrystallized from 4-methyl-2-pentanone and filtered to obtain 60.4 g of a white solid. Yield 85%.

Mp. = 99.55 to 101.5 ° C ¹ H-NMR (CDCl ₃ , 200 MHz) δ: 2.32
(12H, s), 2.72 (2H, dd, J = 4.9,
2.7 Hz), 2.88 (2H, dd, J = 4.9,
4.4 Hz), 3.37 (2H, dddd, J = 5.
8, 4.4, 3.3, 2.7 Hz), 3.42 (2H,
dd, J = 11.0, 5.9 Hz), 4.06 (2H,
dd, J = 11.0, 3.3 Hz), 7.15 (4H,
s) ¹³ C-NMR (CDCl ₃ , 100 MHz) δ: 15.
8 (q), 51.3 (t), 51.7 (d), 73.2
(T), 128.2 (s), 130.9 (2C, d),
136.6 (2C, d), 154.8 (s)

Example 2 Synthesis of 4,4'-bis (glycidyloxy) biphenyl Using 4,4'-bisphenol as a polyhydric phenol, methyl ethyl ketone was used instead of 4-methyl-2-pentanone for separation and purification. Toluene mixture (3 /
Except for the extraction in 1), the synthesis was performed in the same manner as in Example 1, and recrystallized from methyl ethyl ketone to obtain a white solid. 95% yield.

Mp. = 144-146 ° C ¹ H-NMR (CDCl ₃ , 200 MHz) δ: 2.75
(2H, dd, J = 4.9, 2.6 Hz), 2.90
(2H, dd, J = 4.9, 4.3 Hz), 3.36
(2H, dddd, J = 5.6, 4.3, 3.0, 2.
6 Hz), 3.97 (2H, dd, J = 11.1,5.
6 Hz), 4.24 (2H, dd, J = 11.1,3.
0 Hz), 6.96 (4H, dd, J = 8.7, 2.0
Hz), 7.44 (4H, dd, J = 8.7, 2.0H)
z)

Example 3 Synthesis of 2,2'-bis (glycidyloxy) biphenyl Using 2,2'-bisphenol as a polyhydric phenol, toluene was used instead of 4-methyl-2-pentanone for separation and purification. The synthesis was carried out in the same manner as in Example 1 except that the extraction was carried out, and the resulting crude product was purified by silica gel chromatography to obtain a colorless liquid. Yield 92%.

Oil ¹ H-NMR (CDCl ₃ , 200 MHz) δ: 2.54
(2H, dd, J = 5.1, 2.5 Hz) 2.70
(2H, dd, J = 5.1, 4.0 Hz), 3.16
(2H, dddd, J = 5.5, 4.0, 2.9, 2.
5 Hz), 3.93 (2H, dd, J = 11.2, 5.
5 Hz), 4.17 (2H, dd, J = 11.2, 2.
9 Hz), 6.95 (2H, dd, J = 8.1, <1.
0 Hz), 7.03 (2H, dd, J = 7.3, 1.0
Hz), 7.24 (4H, m) ¹³ C-NMR (CDCl ₃ , 100 MHz) δ: 44.
3 (t), 50.2 (d), 68.9 (t), 112.
6 (d), 121.0 (d), 128.3 (s), 12
8.5 (d), 131.4 (d), 155.9 (s)

Examples 4 to 7 The same procedures as those of Example 1 were carried out except that the following bisphenol was used as the starting polyhydric phenol, and the mixture was subjected to separation and purification using a toluene mixture instead of 4-methyl-2-pentanone. Examples 4 to 7 were synthesized in the same manner as described above, and further reconstituted from toluene to obtain a white solid or oil. Yield 85-90%.

Example 4 2,2'-bis [(4-glycidyloxy-3,5-dimethyl) phenyl] propane: Starting polyhydric phenol: 2,2'-bis (3,5-dimethyl-4) -Hydroxyphenyl) propane Oil ¹ H-NMR (CDCl ₃ , 200 MHz) δ: 1.56
(6H, s), 2.15 (12H, s), 2.69 (2
H, dd, J = 4.9, 2.6 Hz), 2.85 (2
H, dd, J = 4.9, 4.2 Hz), 3.33 (2
H, dddd, J = 5.9, 4.2, 3.3, 2.6H
z), 3.71 (2H, dd, J = 11.0, 5.9H
z), 4.00 (2H, dd, J = 11.0, 3.3H
z), 6.80 (4H, s)

Example 5 1,1'-bis [(4-glycidyloxy-3-phenyl) phenyl] propane: Starting polyhydric phenol: 1,1'-bis (3-phenyl-)
4-Hydroxyphenyl) propane Oil ¹ H-NMR (CDCl ₃ , 400 MHz) δ: 0.92
(3H, t, J = 7.2 Hz), 2.06 (2H, d
q, J = 7.7, 7.2 Hz), 2.64 (2H, d
d, J = 4.9, 2.6 Hz), 2.78 (2H, d
d, J = 4.9, 4.4 Hz), 3.22 (2H, dd)
dd, J = 5.1, 4.4, 3.0, 2.6 Hz),
3.76 (1H, t, J = 7.7 Hz), 3.93 (2
H, dd, J = 11.1, 5.1 Hz), 4.15 (2
H, dd, J = 11.1, 3.0 Hz), 6.89 (2
H, d, J = 8.4, Hz), 7.15 (2H, dd,
J = 8.4, 2.2 Hz), 7.21 (2H, d, J =
2.2 Hz), 7.30 (2H, tt, J = 7.3,
2.0 Hz), 7.39 (4H, t, J = 7.3H)
z), 7.52 (4H, dd, J = 7.3, 2.0H
z)

Example 6 1,1'-bis [(4-glycidyloxy-3-phenyl) phenyl] butane: Starting polyhydric phenol: 1,1'-bis (3-phenyl-)
4-Hydroxyphenyl) butane Oil ¹ H-NMR (CDCl ₃ , 200 MHz) δ: 0.91
(3H, t, J = 7.2 Hz), 1.27 (2H, t
q, J = 9.1, 7.2 Hz), 1.99 (2H, t
d, J = 9.1, 4.8 Hz), 2.63 (2H, d
d, J = 4.9, 2.5 Hz), 2.76 (2H, d
d, J = 4.9, 4.4 Hz), 3.21 (2H, dd)
dd, J = 5.0, 4.4, 3.0, 2.5 Hz),
3.68 (1H, t, J = 4.8 Hz), 3.93 (2
H, dd, J = 11.1, 5.0 Hz), 4.14 (2
H, dd, J = 11.1, 3.0 Hz), 6.87 (2
H, d, J = 8.3 Hz), 7.14 (2H, dd, J)
= 8.3, 2.1 Hz), 7.20 (2H, d, J =
2.1Hz), 7.35 (6H, m), 7.51 (4
(H, dd, J = 7.1, 1.7 Hz)

Example 7 1,1'-bis [(4-glycidyloxy-3-phenyl) phenyl] -2-methylpropane Starting polyhydric phenol: 1,1'-bis (3-phenyl-
4-hydroxyphenyl) -2-methylpropane mp. = 131 to 134 ° C ¹ H-NMR (CDCl ₃ , 200 MHz) δ: 0.83
(6H, d, J = 6.5 Hz), 2.37 (1H, ds
ept, J = 11.0, 6.5 Hz), 2.57 (2
H, dd, J = 4.9, 2.7 Hz), 2.71 (2
H, dd, J = 4.9, 4.4 Hz), 3.15 (2
H, dddd, J = 5.0, 4.4, 3.0, 2.7H
z), 3.21 (1H, d, J = 11.0 Hz);
86 (2H, dd, J = 11.1, 5.0 Hz);
07 (2H, dd, J = 11.1, 3.0 Hz);
81 (2H, d, J = 8.2 Hz), 7.12 (2H,
dd, J = 8.2, 2.0 Hz), 7.20 (2H,
d, J = 2.0 Hz), 7.30 (6H, m), 7.4
5 (4H, dd, J = 6.9, 1.7 Hz)

Example 8 2,2'-bis (glycidyloxy) -3,3 ', 5
Synthesis of 5'-tetra-tert-butylbiphenyl Except for using 3,3 ', 5,5'-tetra-tert-butyl-2,2'-bisphenol as a polyhydric phenol and recrystallizing ethanol in separation and purification, All were synthesized according to Example 1 to obtain a white solid. Yield 85%.

Mp. = 185-186 ° C ¹ H-NMR (CDCl ₃ , 200 MHz) δ: 1.33
(18H, s), 1.43 (18H, s), 2.19
(2H, dd, J = 4.9, 2.7 Hz), 2.63
(2H, dd, J = 4.9, 4.4 Hz), 3.00
(2H, dddd, J = 5.5, 4.4, 3.3, 2 ..
7 Hz), 3.57 (2H, dd, J = 11.0,5.
6 Hz), 3.68 (2H, dd, J = 11.0, 3.
3 Hz), 7.14 (2H, d, J = 2.4 Hz),
7.38 (2H, d, J = 2.4 Hz) MS (m / e): 522 (M ⁺ ), 466 (bas)
e), 451, 337, 225, 57, 41, 29

Examples 9 to 11 During the synthesis, the following polyhydric phenols were used as the starting polyhydric phenols, the amount of imidazole and epichlorohydrin used was increased to 1.5 times, and during the extraction process, The amount of sodium hydroxide aqueous solution was increased to 1.5 times, and after extraction, 4-methyl-2-pentanone was concentrated to obtain a white semi-solid substance. Was synthesized. Yield 85-90%.

Example 9 Tris (4-glycidyloxyphenyl) methane: Starting polyhydric phenol: Tris (4-hydroxyphenyl) methane Oil ¹ H-NMR (CDCl ₃ , 200 MHz) δ: 2.72
(3H, dd, J = 4.9, 2.7 Hz) 2.87
(3H, dd, J = 4.9, 4.2 Hz) 3.31
(3H, dddd, J = 5.5, 4.2, 3.1, 2.
7 Hz), 3.92 (3H, dd, J = 11.0, 5.
5 Hz), 4.16 (3H, dd, J = 11.0,3.
1Hz), 5.37 (1H, s), 6.81 (6H, d
d, J = 8.6, 2.5 Hz), 6.97 (6H, d
d, J = 8.6, 2.5 Hz)

Example 10 Bis [(4-glycidyloxy-3-phenyl) phenyl]-(4-glycidyloxyphenyl) methane: Starting polyhydric phenol: bis (3-phenyl-4-hydroxyphenyl)-( 4-Hydroxyphenyl) methane Oil ¹ H-NMR (CDCl ₃ , 200 MHz) δ: 2.58
(2H, dd, J = 4.9, 2.7 Hz), 2.66
(1H, dd, J = 4.9, 2.6 Hz), 2.71
(2H, dd, J = 4.9, 4.0 Hz), 2.81
(1H, dd, J = 4.9, 4.2 Hz), 3.16
(2H, dddd, J = 5.0, 4.0, 3.0, 2.
7 Hz), 3.25 (1H, dddd, J = 5.5,
4.2, 3.0, 2.6 Hz), 3.86 (1H, d
d, J = 11.1, 5.5 Hz), 3.87 (2H, d
d, J = 11.1, 5.0 Hz), 4.10 (3H, d
d, J = 11.1, 3.0 Hz), 5.39 (1H,
s), 6.76 (2H, d, J = 8.9 Hz), 6.8
1 (2H, d, J = 8.4 Hz), 6.94 (2H, d
d, J = 8.4, 2.2 Hz), 6.99 (2H, d,
J = 8.9 Hz), 7.05 (2H, d, J = 2.2H)
z), 7.25 (6H, m), 7.41 (4H, dd,
J = 6.9, 2.0 Hz) MS (m / e): 612 (M ⁺ , base), 539;
536, 463, 387, 298, 273, 197, 3
1

Example 11 1- [α-methyl-α- (4-glycidyloxyphenyl) ethyl] -4- [α, α-bis (4-glycidyloxy-phenyl) ethyl] benzene: Starting polyvalent Phenol: 1- [α-methyl-α- (4-glycidyloxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene: softening point = 63 ° C. ¹ H-NMR (CDCl ₃ , 200 MHz) δ: 1.57
(6H, s), 2.02 (3H, s), 2.67 (3
H, dd, J = 4.9, 2.5 Hz), 2.82 (3
H, dd, J = 4.9, 4.4 Hz), 3.26 (3
H, dddd, J = 5.4, 4.4, 3.3, 2.5H
z), 3.87 (3H, dd, J = 11.0, 5.4H
z), 4.11 (3H, dd, J = 11.0, 3.3H
z), 6.72 (4H, d, J = 8.8 Hz), 6.7
5 (2H, d, J = 8.6 Hz), 6.86 (2H, d, J = 8.6 Hz)
d, J = 8.8 Hz), 6.91 (4H, d, J = 8.
8 Hz), 7.01 (2H, d, J = 8.6 Hz),
7.08 (2H, d, J = 8.8 Hz)

Examples 12 to 13 During the synthesis, the following polyhydric phenols were used as starting polyhydric phenols, the use of imidazole and epichlorohydrin was increased by a factor of two, and sodium hydroxide was added during the extraction process. The synthesis was carried out in the same manner as in Example 1 except that the amount of the aqueous solution used was also doubled. After extracting and concentrating the reaction product, recrystallization was performed with 4-methyl-2-pentanone to obtain a white solid. Yield 85-87%.

Example 12 1,1 ', 2,2'-tetrakis (4-glycidyloxyphenyl) ethane: Starting polyhydric phenol: 1,1', 2,2'-tetrakis (4-glycidyloxyphenyl) ) Ethane mp. = 169-172 ° C ¹ H-NMR (CDCl ₃ , 200 MHz) δ: 2.67
(4H, dd, J = 4.9, 2.6 Hz), 2.83
(4H, dd, J = 4.9, 4.4 Hz), 3.25
(4H, dddd, J = 5.6, 4.4, 3.3, 2 ..
6 Hz), 3.81 (4H, dd, J = 11.0,5.
6 Hz), 4.06 (4H, dd, J = 11.0,3.
3Hz), 4.52 (2H, s), 6.64 (8H,
d, J = 8.5 Hz), 6.95 (8H, d, J = 8.
5 Hz) MS (m / e): 622 (M ⁺ ), 473, 347, 3
11 (base), 255, 136, 107, 57

Example 13 1,1 ', 2,2'-tetrakis [(4-glycidyloxy-3-phenyl) phenyl] ethane: Starting polyhydric phenol: 1,1', 2,2'-tetrakis (3-phenyl-4-hydroxyphenyl) ethane Oil ¹ H-NMR (CDCl ₃ , 200 MHz) δ: 2.67
(4H, dd, J = 4.9, 2.5 Hz), 2.82
(4H, dd, J = 4.9, 4.4 Hz), 3.24
(4H, dddd, J = 5.5, 4.4, 3.3, 2.
5 Hz), 3.85 (4H, dd, J = 11.1,5.
5 Hz), 4.08 (4H, dd, J = 11.1,3.
3Hz), 4.53 (2H, s), 6.80 (4H,
d, J = 8.2 Hz), 7.10 (4H, dd, J =
8.2, 2.1 Hz), 7.20 (4H, d, J = 2.
1 Hz), 7.31 (12H, m), 7.44 (8H,
dd, J = 7.0, 1.8 Hz)

The above-described specific examples for carrying out the present invention are merely intended for explanation of the present invention, and it is conceivable that other improvements and modifications can be made by the disclosure of the present invention. The specific examples selected and described above are the best applied examples and illustrative examples for carrying out the present invention, and for those skilled in the art, those skilled in the art may use the specific examples and other special applications. The present invention can be more effectively applied by making use of the above-mentioned variations. If legitimacy and balance in law are considered from a fair standpoint, such improvements and modifications are naturally included in the present invention.

[0064]

The phenolic epoxy resin of the present invention has low viscosity, excellent heat resistance, and low hygroscopicity, and is therefore widely used as a semiconductor sealant material, a substrate additive for printed circuit boards, and an electronic adhesive. You. In addition, the method for producing a phenolic epoxy resin according to the present invention is a method in which all the raw materials are simultaneously supplied, and the reaction is carried out in a homogeneous system while refluxing under normal pressure. In comparison, the process can be simplified and the reaction time can be reduced with a simple reaction facility, the yield is good, and the industrial value is extremely high and useful.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 23/31

Claims (25)

[Claims] 1. A phenolic epoxy resin represented by the following general formula (I). Embedded image [Wherein, R ¹ , R ² , R ³ and R ⁴ may be the same or different and each independently represents a hydrogen atom, a C _1-6 hydrocarbon group, a C _6-10 aromatic group or a C _6-10 aromatic group. A C _6-10 aromatic group substituted by a substituent of a hydrocarbon group of _1-6 ; R ⁵ and R ⁶ may be the same or different, and each independently represents a hydrogen atom, C _1-6 A hydrocarbon group, a C _6-10 aromatic group,
C _6-10 substituted by a substituent of a C _1-6 hydrocarbon group
An aromatic group of the formula (Wherein R ⁷ is a hydrogen atom, a hydrocarbon group, an aromatic group of C _{6 to 10} substituted by a substituent an aromatic group or a hydrocarbon group of C _{1 to 6} of C _{6 to 10} of the C _{1 to 6} Represents) or (Wherein R ⁸ and R ⁹ may be the same or different and each independently represents a hydrogen atom, a C _1-6 hydrocarbon group, a C _6-10
Represents an aromatic group or a C _6-10 aromatic group substituted by a substituent of a C _1-6 hydrocarbon group); n is 0 or 1
Is shown. ] 2. The aforementioned R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a C _1-6 alkyl group, a C _3-6 cyclic alkyl group, or a C _2-6 alkenyl group. A C _2-6 alkynyl group, a phenyl group, a naphthyl group, or a C _1-6 alkyl group, a C _3-6 cyclic alkyl group, a C _2-6 alkenyl group or a C _2-6 alkynyl group. The epoxy resin according to claim 1, which is a phenyl group or a naphthyl group substituted with a substituent. Wherein the R ^1, R ^2, R ³ and R ⁴ are each independently a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, tert-butyl radical, n
The epoxy resin according to claim 2, which is an amyl group, a neopentyl group, an isoamyl group, a hexyl group, a phenyl group or a naphthyl group. 4. R ⁵ and R ⁶ each independently represent a hydrogen atom, a C _1-6 alkyl group, a C _3-6 cyclic alkyl group,
_2-6 alkenyl group, an alkynyl group of C _2-6, a phenyl group, a naphthyl group or an alkyl group of C _{1 to 6,} cyclic alkyl C _{3 to 6,} alkenyl or C ₂ of C _{2-6, ~ 6}
The epoxy resin according to claim 1, which is a phenyl group or a naphthyl group substituted by a substituent of the alkynyl group. 5. R ⁵ and R ⁶ each independently represent a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
The epoxy resin according to claim 4, which is a butyl group, an isobutyl group, a tert-butyl group, an amyl group or a hexyl group. 6. The above-mentioned R ⁷ is a hydrogen atom, a C _1-6 alkyl group, a C _3-6 cyclic alkyl group, a C _2-6 alkenyl group,
A C _2-6 alkynyl group, a phenyl group, a naphthyl group, or a C _1-6 alkyl group, a C _3-6 cyclic alkyl group,
_2-6 alkenyl or claim 1 wherein the epoxy resin is a phenyl group or a naphthyl group substituted by a substituent of the alkynyl group of C _2-6. 7. The epoxy resin according to claim 1, wherein said R ⁷ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an amyl group or a hexyl group. . 8. The aforementioned R ⁸ and R ⁹ each independently represent a hydrogen atom, a C _1-6 alkyl group, a C _3-6 cyclic alkyl group,
_2-6 alkenyl group, an alkynyl group of C _2-6, a phenyl group, a naphthyl group or an alkyl group of C _{1 to 6,} cyclic alkyl C _{3 to 6,} alkenyl or C ₂ of C _{2-6, ~ 6}
The epoxy resin according to claim 1, which is a phenyl group or a naphthyl group substituted by a substituent of the alkynyl group. 9. The aforementioned R ⁸ and R ⁹ are each independently a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
The epoxy resin according to claim 8, which is a butyl group, an isobutyl group, a tert-butyl group, an n-amyl group, an isoamyl group, a neopenticyl group, a phenyl group, a phenylmethyl group or a naphthyl group. 10. The epoxy resin according to claim 1, wherein the bisphenol group has a p, p'-bond or an o, o'-bond. 11. The formula: embedded image The epoxy resin according to claim 1, wherein the epoxy resin is selected from the group consisting of compounds represented by the formula: 12. A method for producing a phenolic epoxy resin, comprising reacting a polyhydric phenol compound or a hydrocarbon or aromatic derivative thereof with epihalohydrin in the presence of an imidazole compound as a catalyst. 13. The method according to claim 12, wherein the phenolic epoxy resin is an epoxy resin represented by the general formula (I) according to claim 1. 14. The method according to claim 12, wherein the polyhydric phenol compound contains bisphenol, trisphenol or tetrakisphenol. 15. The method according to claim 12, wherein the epihalohydrin is epichlorohydrin or epibromohydrin. 16. The method according to claim 1, wherein 1 to 20 equivalents of epihalohydrin is used per equivalent of the polyhydric phenol compound.
2. The production method according to 2. 17. The method according to claim 16, wherein 1 to 5 equivalents of epihalohydrin is used per equivalent of the polyhydric phenol compound.
Production method as described. 18. The method according to claim 12, wherein the imidazole compound is selected from the group consisting of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-n-propylimidazole, 2-isopropylimidazole and 2-phenylimidazole. Manufacturing method. 19. The method according to claim 12, wherein the imidazole compound is used in an amount of 0.01 to 0.5 equivalent per equivalent of the polyhydric phenol compound. 20. The method according to claim 19, wherein the imidazole compound is used in an amount of 0.01 to 0.2 equivalent per equivalent of the polyhydric phenol compound. 21. The process according to claim 12, wherein the reaction is carried out by heating and refluxing under a normal pressure under a homogeneous reaction. 22. The method according to claim 21, wherein the reaction temperature is 90 to 120 ° C. 23. I containing the epoxy resin according to claim 1.
Sealant material for C. 24. A substrate additive for a printed circuit board, comprising the epoxy resin according to claim 1. 25. An electronic adhesive comprising the epoxy resin according to claim 1.