JP2887214B2 - Naphthol compound, its production method, epoxy compound, composition and cured product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound useful for encapsulating a highly reliable semiconductor, a method for producing the same, a composition and a cured product.

[0002]

2. Description of the Related Art Epoxy resins are widely used in the field of electric and electronic parts due to their excellent electrical properties, heat resistance, adhesiveness and the like.

However, in recent years, particularly with the development of the electric and electronic fields, further improvements in various properties such as heat resistance, moisture resistance and adhesion have been demanded. In order to improve these properties, epoxy resins have been used. And many compositions have been proposed. For example, a naphthol novolak resin has been proposed as a method for improving these properties (Japanese Patent Publication No. 62-20206). This resin is intended to improve physical properties such as heat resistance and moisture resistance of the cured product by introducing a naphthol skeleton, and in fact, it gives excellent properties in these points, but on the other hand, it is molded with high viscosity It is not yet satisfactory because of problems such as poor workability and poor adhesion.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a compound which is excellent in fluidity at the time of melting and which exhibits excellent heat resistance, moisture resistance and adhesion in a cured product, and which is useful as a highly reliable semiconductor encapsulation. The present invention provides a production method, a composition, and a cured product thereof.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on a method for imparting and improving the above-mentioned properties, and as a result, completed the present invention. That is, the present invention provides the following equation (1):

[0006]

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(Wherein R ₁ ′ is a hydrogen atom or a C ₁ -C 1)
4 represents an alkyl group, and R ₁ , R ₂ , R ₃ , and R ₄ each represent a halogen atom, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group. Is also good. ) A naphthol compound represented by
(2) Equation (2)

[0008]

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(Wherein R ₁ , R ₂ , R ₃ , and R ₄ each represent a halogen atom, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group.
It may be different. Phenols represented by the formula (3)

[0010]

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(Wherein R ₁ ′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and is subjected to a dehydration condensation reaction with a naphthol in the presence of an acid catalyst. A method for producing a naphthol compound represented by the above formula (1),

[0012]

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(Wherein R ₁ ′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and a naphthol monomethylol compound represented by the formula (5):

[0014]

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(Wherein R ₁ , R ₂ , R ₃ , and R ₄ each represent a halogen atom, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group.
It may be different. A method for producing a naphthol compound represented by the above formula (1), wherein the phenol represented by the formula (1) is subjected to a dehydration condensation reaction in the presence of an acid catalyst.
(4) Equation (6)

[0016]

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(Wherein, R ₁ ′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁ , R ₂ , R ₃ , and R ₄ each represent a halogen atom, a hydrogen atom, and a 1 to ₄ carbon atom. 4 represents an alkyl group or an aryl group, which may be the same or different.)

(5) A composition containing the epoxy compound represented by the above formula (6), a curing agent and, if necessary, a curing accelerator, and (6) a cured product of the composition of the above (5).

The naphthol compound of the formula (1) can be obtained by the above method (2) or (3). Examples of the phenol monomethylol compound of the formula (2) include 2-
Methylol-4,6-dimethylphenol, 4-methylol-2,6-dimethylphenol, 4-methylol-
2,3,6-trimethylphenol, 2-methylol-
4-methyl-6-t-butylphenol, and the like.

The naphthols of the formula (3) include 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methyl-1-naphthol and the like. As the naphthol monomethylol compound of the formula (4), 1-
Monomethylols such as naphthol, 2-naphthol, 2-methyl-1-naphthol and 4-methyl-1-naphthol are exemplified.

The phenols of the formula (5) include phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,6-xylenol,
3,5-xylenol, 2,3,6-trimethylphenol, 2,3,5-trimethylphenol, 2-t-butylphenol, 2,4-dichlorophenol, o-chlorophenol, p-bromophenol, o-ethyl Phenol, p-ethylphenol, o-phenylphenol, p-phenylphenol, 4-chloro-3,5-
Monofunctional, difunctional, and trifunctional phenols such as xylenol.

The monomethylols of the formulas (2) and (4) are known compounds and can be obtained by reacting phenols or naphthols with formaldehyde in the presence of an alkali metal hydroxide. The phenol monomethylol and the naphthol monomethylol may be used as they are or crystallized and isolated, and further purified if necessary, and used as a raw material for the following dehydration condensation reaction of the above (2) or (3). Can be done.

The amount of the above-mentioned phenol monomethylol or naphthol monomethylol used for the naphthol or phenol to be subjected to a dehydration-condensation reaction is preferably 0.8 to 4 times, especially 0.8 to 4 times the amount of the monomethylol. Preferably it is 1-2 mole times.

The acid catalyst used in the dehydration condensation reaction includes protonic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, boron trifluoride, boron trifluoride ether complex, zinc chloride, aluminum chloride and the like. The Lewis acid,
Acetic acid, oxalic acid and the like can be mentioned. Of these, hydrochloric acid, p-toluenesulfonic acid, oxalic acid and the like are preferably used, and the amount of the acid catalyst used is preferably 0.001 to 0.1 mol times based on the raw material phenol methylol or naphthol monomethylol. You can choose between.

The dehydration-condensation reaction in the presence of the acid catalyst is usually carried out at a temperature of 10 to 120 ° C., and the reaction time is usually 1 to 120 ° C.
You can select within a range of 20 hours. This reaction is preferably carried out in the presence of an appropriate solvent such as water, methanol, toluene, methyl isobutyl ketone and the like. The preferred amount of the solvent used is 0.5 to 30 times the weight of the monomethylol compound of the above (2) or (4).

Further, the obtained condensation reaction liquid is repeatedly washed with water in the presence of an excess of a solvent such as toluene or methyl isobutyl ketone until the inside of the system becomes neutral. By removing the raw materials, a naphthol compound represented by the formula (1) is obtained.

Next, the epoxy compound of the formula (6) of the present invention is obtained by reacting an epihalohydrin with a naphthol compound synthesized by the above-mentioned method. Industrially, epichlorohydrin is preferred. This reaction can be carried out according to a conventionally known method for obtaining a polyglycidyl ether from a novolak-type phenol resin and epihalohydrin.

For example, a solid of an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like is added to a mixture of the naphthol compound of the formula (1) and an excess of epichlorohydrin, or, preferably, from 20 ° C. to 120 ° C.
The reaction is carried out at a temperature between At this time, the alkali metal hydroxide may be used in the form of an aqueous solution.In this case, the alkali metal hydroxide is continuously added, and water and epichlorohydrin are continuously removed from the reaction system under reduced pressure or normal pressure. A method may be employed in which the water is removed by distilling and separating water, and epichlorohydrin is continuously returned to the reaction system.

In the above method, the amount of epichlorohydrin used is usually 1 to 20 mol, preferably 2 to 10 mol, per equivalent of the hydroxyl group of the naphthol compound of the formula (1). The amount of the alkali metal hydroxide to be used is generally 0.8 to 1.5 mol, preferably 0.9 to 1.1 mol, per equivalent of the hydroxyl group of the naphthol compound. Further, in order to make the reaction proceed smoothly, it is preferable to add an aprotic polar solvent such as dimethyl sulfone and dimethyl sulfoxide (hereinafter referred to as DMSO) in addition to alcohols such as methanol and ethanol. This reaction is usually carried out for 1 to 20 hours.

Further, a mixture of a naphthol compound of the formula (1) and an excess epihalohydrin is added to tetramethylammonium chloride, tetramethylammonium bromide,
A quaternary ammonium salt such as trimethylbenzylammonium chloride is used as a catalyst, preferably at 50 ° C.
A solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the halohydrin ether obtained by reacting at ~ 150 ° C.
Glycidyl ethers (epoxy compounds of formula (6)) can also be obtained by reacting at a temperature between 120 ° C. and ring closing the halohydrin ether. In this case, the amount of the quaternary ammonium salt to be used is preferably 0.001 to 0.2 mol, more preferably 0.005 to 0.1 mol, per 1 equivalent of the hydroxyl group of the naphthol compound.

Usually, these first-stage reactants are washed with water or after removing excess epihalohydrin under heating and reduced pressure without washing with water, and then dissolved again in a solvent such as toluene, methyl isobutyl ketone, and the like. A second stage reaction is performed by adding an aqueous solution of an alkali metal hydroxide such as potassium. In this case, the amount of the alkali metal hydroxide to be used is preferably 0.01 to 0.2 mol, more preferably 0.0 to 1 mol of the hydroxyl group of the naphthol compound of the formula (1) used.
5 to 0.1 mol. The reaction temperature is preferably 50-1.
The reaction is performed at 20 ° C., and the reaction time is usually 0.5 to 2 hours.

After the completion of the reaction, salts produced as by-products are removed by filtration, washing with water, and the like, and the solvent such as toluene, methyl isobutyl ketone or the like is distilled off under reduced pressure under heating to obtain a compound of the formula (6) of the present invention having a small hydrolyzable halogen. An epoxy compound can be obtained.

Hereinafter, the composition of the present invention will be described.
As the curing agent, various ones can be used and are not particularly limited. For example, phenolic curing agents such as phenol novolak and cresol novolac, polyamine curing agents such as aliphatic polyamine, aromatic polyamine and polyamide polyamine, and trifluoride Examples thereof include Lewis acids such as boron or salts thereof, acid anhydride-based curing agents such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, and curing agents such as dicyandiamide. Further, the naphthol compound of the above formula (1) may be used as a curing agent.

The composition of the present invention may contain other epoxy compounds in addition to the epoxy compound of the formula (6).
Other epoxy compounds include novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin,
An alicyclic epoxy resin, a biphenol-type epoxy resin and the like can be mentioned.

The curing agent is the epoxy group 1 of the epoxy compound.
It is preferable to use 0.5 to 1.5 equivalents to the equivalents,
It is particularly preferable to use 0.6 to 1.2 equivalents.

Examples of the curing accelerator include imidal compounds such as 2-methylimidazole and 2-ethylimidazole, and third curing agents such as 2- (dimethylaminomethyl) phenol.
Examples thereof include an amine compound and a triphenylphosphine compound, and various known curing agent accelerators can be used, and are not particularly limited. When a curing accelerator is used, the amount is 0.01 to 100 parts by weight of the epoxy compound.
The range is preferably from 15 to 15 parts by weight, and particularly preferably from 0.1 to 10 parts by weight.

The composition of the present invention may further contain known additives, if necessary.
Examples thereof include inorganic fillers such as silica, alumina, talc, and glass fibers, surface treatment agents for fillers such as silane coupling agents, release agents, and pigments.

The composition of the present invention is obtained by uniformly mixing the components, and is usually prepared at a temperature of 130 to 170 ° C. for 3 hours.
Precured in the range of 0 to 300 seconds, and 150 to 20 seconds
By post-curing at a temperature of 0 ° C. for 2 to 8 hours, a sufficient curing reaction proceeds, and the cured product of the present invention is obtained. Further, the components of the composition can be uniformly dispersed or dissolved in a solvent or the like, and the solvent can be removed and cured.

The cured product thus obtained has heat resistance and moisture resistance, and the naphthol compound and epoxy compound of the present invention are excellent in fluidity at the time of melting. Therefore, the compounds and compositions of the present invention can be used in a wide range of fields where heat resistance and moisture resistance are required. Specifically, it is useful as a compounding component of all electric and electronic materials such as an insulating material, a laminate, and a sealing material. Further, it can be used in the fields of molding materials, coating materials, composite materials and the like.

[0040]

The present invention will be specifically described below with reference to examples. The softening point in the examples is a value according to JIS K2425 (ring and ball method), a hydroxyl equivalent and an epoxy equivalent are g / eq.
Is shown. Further, the present invention is not limited to these examples.

Example 1 (1) Synthesis of Monomethylol Phenol In a flask equipped with a thermometer, a cooling tube, a dropping funnel and a stirrer, 122 parts by weight of 2,4-xylenol (1 mol) were added.
A 40 wt% -sodium hydroxide aqueous solution (50 parts by weight) was charged and the inside of the system was heated to 40 ° C. Next, 34 parts by weight (1.05 mol) of granular paraformaldehyde (92% pure content) was added and reacted at 50 ° C. for 4 hours. After completion of the reaction, the temperature in the system is 10 ° C.
Then, 63 parts by weight of acetic acid (99% pure) was added dropwise while paying attention to heat generation, and neutralized. Subsequently, after adding 500 parts by weight of methyl isobutyl ketone, washing with water was repeated to remove excess formaldehyde to obtain a reaction solution containing 2-methylol-4,6-dimethylphenol.

(2) Synthesis of naphthol compound 288 parts by weight (2 mol) of 1-naphthol was charged into this reaction solution to make the system a homogeneous phase. Further, after adding 2 parts by weight of paratoluenesulfonic acid, the mixture was reacted at 30 ° C. for 2 hours, and then reacted at 50 ° C. for 1 hour. After the completion of the reaction, the reaction mixture was transferred to a separating funnel, and repeatedly washed with water to return to neutral.
Thereafter, methyl isobutyl ketone and 1-naphthol were removed from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 256 parts by weight of a naphthol compound (A).
I at 150 ° C. of the obtained naphthol compound (A)
The CI viscosity was 0.2 ps, the softening point was 60 ° C., and the hydroxyl equivalent was 140.

Further, using the naphthol compound (A) as a solvent and tetrahydrofuran (hereinafter referred to as THF),
When analyzed by the analyzer, the molecular weight distribution curve shown in FIG. 1 was obtained.

GPC device: Liquid sending pump: L-6000 (manufactured by Hitachi, Ltd.) Column: GPC KF-803 (one) + GPC KF-802.5 (two) + GPC KF-802 (one) (Showa Denko ) Column temperature: 40 ° C Solvent: THF 1 ml / min Detector: RI ERC-7510 (manufactured by Elma Optics) Data processing: CR-4A (manufactured by Shimadzu Corporation)

The retention time of the main peak of the naphthol compound (A) analyzed under the above analysis conditions was determined from the calibration curve using standard polystyrene, based on the molecular weight of a binuclear having one naphthol ring and one benzene ring. The main peak component considered to be a binuclear body was fractionated and analyzed by mass spectrum (FAB-MS). As a result, M ⁺ 278 was obtained. I confirmed my body.

[0046]

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(3) Synthesis of Epoxy Compound Next, the naphthol compound (A) thus obtained is obtained.
To 140 parts by weight, 555 parts by weight (6 mol) of epichlorohydrin and 140 parts by weight of DMSO were added and dissolved. The mixture was heated to 50 ° C., and flaked sodium hydroxide (99% pure) was added.
Parts by weight (1.04 mol) were added over a period of 100 minutes, and then the mixture was further reacted at 60 ° C. for 2 hours and at 70 ° C. for 1 hour. Then, after washing was repeatedly returned to neutrality, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure using a rotary evaporator, and 500 parts by weight of methyl isobutyl ketone was added to the residue and dissolved.

Further, the methyl isobutyl ketone solution was heated to 70 ° C., and 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added. After reacting for 1 hour, washing with water was repeated to make the solution neutral. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain an epoxy compound (B) 1
86 parts by weight were obtained. 1 of the obtained epoxy compound (B)
The ICI viscosity at 50 ° C. was 0.1 ps and the epoxy equivalent was 202.

The epoxy compound (B) was analyzed by liquid chromatography (GPC, under the same analysis conditions as for the naphthol compound) to obtain a molecular weight distribution curve shown in FIG. The main peak component considered to be a binucleate was fractionated and analyzed by mass spectrum (FAB-MS) to obtain M ⁺ 390, indicating that it was a binucleate represented by the following formula (8). It was confirmed.

[0050]

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Example 2 (1) Phenol Monomethylol Body 122 parts by weight (1 mol) of 2,6-xylenol were placed in a flask equipped with a thermometer, a cooling tube, a dropping funnel, and a stirrer.
220 wt% of 20 wt% -sodium hydroxide aqueous solution (1.1 wt.
Mol) was heated to 50 ° C. and reacted for 30 minutes. Next, after cooling the inside of the system to 20 ° C, 39 parts by weight (1.2 mol) of particulate paraformaldehyde (92% pure content) was added and reacted at 20 ° C for 5 hours. After the reaction is completed,
C. and neutralized by dropping 66 parts by weight of acetic acid (99% pure) while paying attention to heat generation. Subsequently, after adding 500 parts by weight of methyl isobutyl ketone, washing with water was repeated to remove excess formaldehyde, and 4-methylol-2,6-
A reaction solution containing dimethylphenol was obtained.

(2) Synthesis of naphthol compound 288 parts by weight (2 mol) of 1-naphthol was charged into this reaction solution, and the system was made a homogeneous phase. Further, 2 parts by weight of p-toluenesulfonic acid was added, the temperature was raised to 20 ° C, and the reaction was performed for 2 hours, and then the reaction was performed at 40 ° C for 2 hours. After the reaction,
The reaction mixture was transferred to a separating funnel and washed repeatedly with water to return to neutral. Thereafter, 1-naphthol and the solvent were removed from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 250 parts by weight of a brown, solid naphthol compound (C) at room temperature. The obtained naphthol compound (C) had an ICI viscosity at 150 ° C. of 0.2 ps, a softening point of 64.5 ° C. and a hydroxyl equivalent of 141.

The naphthol compound (C) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1), and a molecular weight distribution curve shown in FIG. 3 was obtained.
Further, binuclear and seems main peak component preparative Shi Mass spectrum (FAB-MS) was analyzed by M ⁺ 2
78 was confirmed to be a binuclear represented by the following formula (9).

[0054]

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(3) Synthesis of Epoxy Compound Next, the naphthol compound (C) thus obtained is obtained.
An epoxidation reaction was carried out in the same manner as in Example 1 except that 141 parts by weight was used, to obtain 183 parts by weight of an epoxy compound (D). The obtained epoxy compound (D) had an ICI viscosity at 150 ° C. of 0.2 ps and an epoxy equivalent of 198.

The epoxy compound (D) was analyzed by liquid chromatography (GPC, under the same analysis conditions as in Example 1) to obtain a molecular weight distribution curve shown in FIG. Further, the main peak component considered to be a binuclear body was fractionated and analyzed by mass spectrum (FAB-MS). As a result, M ⁺ 390 was obtained. It was confirmed.

[0057]

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Example 3 (1) Synthesis of Monomethylol Phenol In a flask equipped with a thermometer, a cooling tube, a dropping funnel and a stirrer, 272 parts by weight of 2,3,6-trimethylphenol (2 mol), 20 wt% -440 parts by weight (2.2 mol) of an aqueous sodium hydroxide solution was charged and the inside of the system was heated to 40 ° C to make the inside of the system a uniform phase. Next, the inside of the system was cooled to 20 ° C, and 68 parts by weight (2.1 mol) of granular paraformaldehyde (92% pure content) was added, followed by reaction at 20 ° C for 5 hours. After the reaction,
The system was cooled to 5 ° C., and 210 parts by weight of a 38 wt% hydrochloric acid aqueous solution was neutralized dropwise while paying attention to heat generation, and further filtered to obtain white crystals of 4-methylol-2,3,6-trimethylphenol.

(2) Synthesis of naphthol compound 193 parts by weight of crystals of 4-methylol-2,3,6-trimethylphenol (86% by weight of pure content) were added with 288 parts by weight of 1-naphthol (2 mol) and methyl isobutyl ketone. 500 parts by weight were charged into the system to form a uniform phase, and the temperature was set to 20 ° C. Next, 3 parts by weight of a 38 wt% hydrochloric acid aqueous solution was added, and the mixture was reacted for 2 hours, and further reacted at 40 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was transferred to a separating funnel, and repeatedly washed with water to return to neutral. Thereafter, 1-naphthol and the solvent were removed from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 275 parts by weight of a brown and solid naphthol compound (E) at room temperature. The obtained naphthol compound (E) had an ICI viscosity at 150 ° C. of 0.4 ps, a softening point of 83 ° C. and a hydroxyl equivalent of 147.

The naphthol compound (E) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1) to obtain a molecular weight distribution curve shown in FIG.
Further, binuclear and seems main peak component preparative Shi Mass spectrum (FAB-MS) was analyzed by M ⁺ 2
By obtaining 92, it was confirmed to be a binuclear represented by the following formula (11).

[0061]

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(3) Synthesis of Epoxy Compound Next, the naphthol compound (E) thus obtained
An epoxidation reaction was carried out in the same manner as in Example 1 except that 147 parts by weight was used, to obtain 189 parts by weight of an epoxy compound (F). The obtained epoxy compound (F) had an ICI viscosity at 150 ° C. of 0.3 ps and an epoxy equivalent of 210.

The epoxy compound (F) was analyzed by liquid chromatography (GPC, under the same analysis conditions as in Example 1) to obtain a molecular weight distribution curve shown in FIG. Further, the main peak component considered to be a binuclear body was fractionated and analyzed by mass spectrum (FAB-MS). As a result, M ⁺ 404 was obtained, so that it was a binuclear body represented by the following formula (12). It was confirmed.

[0064]

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Example 4 (1) Synthesis of Monomethylols of Naphthols In a flask equipped with a thermometer, a cooling tube, a dropping funnel and a stirrer, 144 parts by weight (1 mol) of 2-naphthol, 15 wt.
% -293 parts by weight of sodium hydroxide aqueous solution (1.1 mol)
After charging, the system was heated to 40 ° C. to cause a reaction. Next, the inside of the system was cooled to 5 ° C., and 49 parts by weight (1.5 mol) of granular paraformaldehyde (92% pure content) was added, followed by reaction at 5 ° C. for 2 hours. After the completion of the reaction, 66 parts by weight of acetic acid (99% pure) was neutralized by dropping while paying attention to heat generation. After addition of 600 parts by weight of methyl isobutyl ketone, washing with water was repeated at 25 ° C. to remove unreacted formaldehyde.
A reaction solution containing methylol-2-naphthol was obtained.

(2) Synthesis of naphthol compound 244 parts by weight (2 mol) of 2,6-xylenol was charged into this reaction solution to make the inside of the system a homogeneous phase. Further, after adding 2 parts by weight of paratoluenesulfonic acid, the mixture was reacted at 30 ° C. for 1 hour, and then reacted at 70 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was transferred to a separating funnel, and repeatedly washed with water to return to neutral. Thereafter, 2,6-xylenol was removed from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 262 parts by weight of a light brown, crystalline naphthol compound (G) at room temperature. The melting point of the obtained naphthol compound (G) is 163.
° C and the hydroxyl equivalent was 139.

The naphthol compound (G) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1) to obtain a molecular weight distribution curve shown in FIG.
When the main peak component considered to be a binucleate was collected and analyzed by mass spectrum (FAB-MS), it was found that M ⁺
By obtaining 278, 2 represented by the following equation (13) is obtained.
It was confirmed to be a nucleus.

[0068]

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(3) Synthesis of Epoxy Compound Next, the naphthol compound (G) thus obtained is obtained.
An epoxidation reaction was carried out in the same manner as in Example 1 except for using 140 parts by weight, to obtain 176 parts by weight of an epoxy compound (H). The obtained epoxy compound (H) had an ICI viscosity at 150 ° C. of 0.2 Ps and an epoxy equivalent of 195.

The epoxy compound (H) was subjected to liquid chromatography (GPC, analysis conditions were the same as in Example 1) to obtain a molecular weight distribution curve shown in FIG. In addition, the main peak component considered to be a binuclear body is fractionated and mass spectrum (F
(AB-MS), M ⁺ 390 was obtained, and it was confirmed that it was a binuclear body represented by the following formula (14).

[0071]

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Test Examples 1-4, Comparative Example The epoxy compound (B) obtained in the above Examples 1-4,
(D), (F) and (H) were used, and a bisphenol A type epoxy compound (Z) having an epoxy equivalent of 189 was used as a comparative example, and a curing agent (phenol novolak) was added to 150 parts by weight of these epoxy compounds. Resin (manufactured by Nippon Kayaku Co., Ltd.) PN-80, ICI viscosity at 150 ° C. 1.5 ps, softening point 86 ° C., OH equivalent 106) and curing accelerator (triphenylphosphine) in the amounts shown in Table 1 The mixture was blended, a resin molded body was prepared by transfer molding, and further cured under the curing conditions shown in Table 1. Table 1 shows the results obtained by measuring the heat distortion temperature and the water absorption of the cured product thus obtained.

Table 1 Test Example 1 2 3 4 Comparative Example Epoxy compound (B) (D) (F) (H) (Z) Curing agent wt part 80 80 75 82 84 Curing accelerator wt part 1.5 1.5 1.5 1.5 1.5 Curing Conditions 160 ° C × 2 hours + 180 ° C × 8 hours Heat deformation temperature * 1 ° C 127 131 139 142 125 Water absorption * 2 wt% 0.9 1.1 0.9 1.1 1.4

* 1 According to JIS K7207 * 2 Water absorption (wt%) of a 3 mm thick, 50 mm diameter disk (cured product) after 24 hours in boiling water

[0075]

The epoxy compound of the present invention can provide excellent heat resistance and moisture resistance in a cured product thereof and has excellent fluidity at the time of melting. High-density packing of inorganic fillers (fillers) and the like becomes possible. Further, according to the production method of the present invention, binuclears containing naphthols can be easily obtained in high yield.

[Brief description of the drawings]

FIG. 1 is a molecular weight distribution curve of a naphthol compound (A) obtained in Example 1.

FIG. 2 is a molecular weight distribution curve of an epoxy compound (B) obtained in Example 1.

FIG. 3 is a molecular weight distribution curve of a naphthol compound (C) obtained in Example 2.

FIG. 4 is a molecular weight distribution curve of an epoxy compound (D) obtained in Example 2.

FIG. 5 is a molecular weight distribution curve of a naphthol compound (E) obtained in Example 3.

FIG. 6 is a molecular weight distribution curve of the epoxy compound (F) obtained in Example 3.

FIG. 7 is a molecular weight distribution curve of the naphthol compound (G) obtained in Example 4.

FIG. 8 is a molecular weight distribution curve of the epoxy compound (H) obtained in Example 4.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI H01L 23/31 (56) References JP-A-3-50223 (JP, A) JP-A-4-279627 (JP, A) ( 58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 39/12 C07D 303/28 C08G 8/00 C08G 59/00 C08G 61/12 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] (1) Formula (1) (Wherein, R ₁ ′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁ , R ₂ , R ₃ , and R ₄ each represent a halogen atom, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, Or an aryl group, which may be the same or different.) (2) Formula (2) (Wherein, R ₁ , R ₂ , R ₃ , and R ₄ each represent a halogen atom, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and may be the same or different. ) And a phenolic monomethylol derivative represented by the formula (3): (Wherein R ₁ ′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The naphthols are subjected to a dehydration condensation reaction in the presence of an acid catalyst. 1
A method for producing the naphthol compound according to the above. (3) Formula (4) (Wherein R ₁ ′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) and a naphthol monomethylol compound represented by the formula (5): (Wherein, R ₁ , R ₂ , R ₃ , and R ₄ each represent a halogen atom, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and may be the same or different. ) In the presence of an acid catalyst
The method for producing a naphthol compound according to claim 1, wherein a dehydration condensation reaction is carried out. 4. A compound of the formula (6) (Wherein, R ₁ ′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁ , R ₂ , R ₃ , and R ₄ each represent a halogen atom, a hydrogen atom, and an alkyl group having 1 to 4 carbon atoms. Or an aryl group, which may be the same or different.) 5. A composition comprising the epoxy compound according to claim 4, a curing agent and, if necessary, a curing accelerator. 6. A cured product of the composition according to claim 5.