JP2000072838A - Naphthol resin, epoxy resin, epoxy resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin useful as an insulating material for electric and electronic parts, a composite material for laminated sheets or the like, an adhesive, a coating material or the like, capable of manifesting excellent heat and moisture resistances by reacting a monomethylol derivative of a β-naph thol with phenylphenols in the presence of an acidic catalyst. SOLUTION: (A) One mol of a monomethylol derivative of a β-naphthol represented by formula I (R1 is H, a halogen or the like) (e.g. 1-methylol-2- naphthol) is reacted and condensed with (B) preferably 0.5-1.0 mol of phenylphenols represented by formula II [R2 and R3 are each H, a halogen or the like; (k) is 1 or 2; (m) is 1-5] (e.g. 2-phenylphenol) in the presence of an acidic catalyst (e.g. p-toluenesulfonic acid) preferably at 30-130 deg.C for 1-20 h to afford the objective resin. The resultant resin preferably contains a compound represented by formula III [(n) is 0-8]. The acidic catalyst used is used in an amount of preferably 0.1-20 pts.wt. based on 100 pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating material for electric and electronic parts such as a high-reliability semiconductor encapsulation, and various kinds of materials such as a laminate (printed wiring board) and CFRP (carbon fiber reinforced plastic). The present invention relates to a naphthol resin and an epoxy resin useful for a composite material, an adhesive, a paint, and the like, an epoxy resin composition containing the same, and a cured product thereof.

[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

However, in recent years, particularly in the electric and electronic fields, with the development thereof, various properties such as high purity, heat resistance, moisture resistance, adhesion, low viscosity for high filling of filler, and low dielectric property have been developed. Further improvement is required. As structural materials, lightweight and excellent in mechanical properties are required for aerospace materials, leisure and sports equipment applications, and the like.
Many proposals have been made on phenolic resins (epoxy resin curing agents), epoxy resins, and epoxy resin compositions containing them to meet these requirements, but they have not been satisfactory yet.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to an electric / electrical product which exhibits excellent heat resistance and moisture resistance (water resistance) in the cured product.
Naphthol resin, epoxy resin, epoxy useful for insulating materials for electronic components (high-reliability semiconductor encapsulation materials, etc.), laminated boards (printed wiring boards, etc.), composite materials including CFRP, adhesives, paints, etc. An object is to provide a resin composition and a cured product thereof.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on naphthol resins and epoxy resins having the above-mentioned characteristics, and have completed the present invention. That is, the present invention
(1) a naphthol resin obtained by reacting a β-naphthol monomethylol compound with a phenylphenol in the presence of an acid catalyst; (2) the above-mentioned (1) containing a compound represented by the general formula (1) Naphthol resin described,

[0006]

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(In the formula (1), R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an allyl group. K is an integer of 1 or 2;
m represents an integer of 1 to 5, and n represents an integer of 0 to 8, respectively. (3) an epoxy resin (a) obtained by glycidyl etherifying a phenolic hydroxyl group of the naphthol resin according to the above (1) or (2), (4) an epoxy resin (b),
An epoxy resin composition containing the naphthol resin (c) described in (1) or (2) above, and (5) an epoxy resin (a) described above in (3) above, containing a curing agent (d). An epoxy resin composition, (6) an epoxy resin composition containing the epoxy resin (a) described in (3) above, or the naphthol resin (c) described in (1) or (2) above, (7)
Any one of the above (4) to (6) containing a curing accelerator
(8) The epoxy resin composition according to (8) above,
(7) a cured product obtained by curing the epoxy resin composition according to any one of (7), (9) reacting a β-naphthol monomethylol compound with a phenylphenol in the presence of an acid catalyst, The present invention relates to a method for producing a naphthol resin, which comprises adding an acid catalyst to the system as required, then raising the temperature of the reaction system to 30 to 130 ° C., and further performing a post-reaction.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The naphthol resin of the present invention has β-
A product obtained by reacting naphthols with a formaldehyde generating source material can be reacted with phenylphenols in the presence of an acid catalyst. In the above, β-naphthols include β-naphthol, alkyl (methyl,
An alkyl group having 1 to 10 carbon atoms such as ethyl, propyl and butyl) -substituted β-naphthol, halogen (chlorine, bromine, iodine and the like) -substituted β-naphthol, allyl-substituted β-naphthol and the like, preferably β-naphthol. .

The formaldehyde generating substance is a substance that generates formaldehyde under basic conditions.
Examples include paraformaldehyde, trioxane, tetraoxane and the like. The reaction between the β-naphthols and the formaldehyde-generating substance is usually carried out by adding 0.9 to 1.3 mol (as formaldehyde) of the formaldehyde-generating substance under basic conditions to 5 to 4 mols per mol of the β-naphthols.
Perform at 0 ° C. for 5 minutes to 5 hours. The reaction is usually performed in the presence of a basic catalyst. Specific examples of the basic catalyst that can be used include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like, with sodium hydroxide being preferred. The amount of the basic catalyst to be used is generally 0.02 to 1.5 equivalents per 1 mol of β-naphthols. The reaction can also be carried out in a solvent such as toluene, xylene or methyl isobutyl ketone. In this case, the amount of the solvent used is usually 30 to 300% by weight based on the total weight of the charged raw materials. After the completion of the reaction, using an acidic substance such as hydrochloric acid or sulfuric acid as a neutralizing agent,
For example, the separation and extraction operation with an aqueous solution containing a neutralizing agent is repeated until the pH of the washing solution of the reaction mixture becomes 4 to 7, preferably 5 to 7, and the solvent and the like are distilled off as necessary. Product can be obtained.

The reaction product (hereinafter referred to as naphthol methylol) of the thus obtained β-naphthols with a formaldehyde generating substance has the following formula (2)

[0011]

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(In the formula (2), R ₁ has the same meaning as in the formula (1).) Β-naphthols monomethylol, preferably 1-methylol-2-naphthol, Equation (3)

[0013]

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(Wherein R ₂ , R ₃ , k and m have the same meanings as in formula (1)) in the formula (3) in the presence of an acidic catalyst,
The naphthol resin of the present invention can be obtained. The reaction temperature is usually 5 to 180 ° C, preferably 30 to 130 ° C. The reaction time is usually 0.5 to 30 hours, preferably 1 to 30 hours.
20 hours. In addition, it is preferable to remove the water generated during the reaction to the outside of the reaction system using a fractionating tube or the like, in order to quickly perform the reaction.

Specific examples of phenylphenols that can be used include 2-phenylphenol, 3-phenylphenol, 4-phenylphenol and alkyl (alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl and butyl). Phenylphenol, halogen (chlorine, bromine,
Iodine and the like) substituted phenylphenol, allyl-substituted phenylphenol and the like, and 2-phenylphenol or 4-phenylphenol is preferable. These phenylphenols can be used alone or in combination of two or more. In the above reaction, the amount of the phenylphenol used is usually 0.4 to 1.1 mol, preferably 0.5 to 1.0 mol per mol of the naphthol methylol compound.
Is a mole.

When the compound of the formula (2), which is a preferred embodiment of the present invention, is used, a dimer of β-naphthols by-produced during the reaction (where n in the formula (1) is 0)
If the compound is present in a large amount in the naphthol resin, problems such as deterioration of heat resistance of the cured product may occur. Therefore, after the condensation reaction is completed, an acid catalyst is further added if necessary. Is preferably raised to a temperature of 30 to 130 ° C. to further carry out a post-reaction. It is estimated that rearrangement of the dimer of β-naphthols (dissociation of the dimer of β-naphthols and reaction with phenylphenols) occurs in the post-reaction.

In the above reaction, an acid catalyst is used. Various acid catalysts can be used, but hydrochloric acid, sulfuric acid, p-
Toluenesulfonic acid, organic or inorganic acids such as oxalic acid, boron trifluoride, anhydrous aluminum chloride, Lewis acids such as zinc chloride are preferred, especially p-toluenesulfonic acid,
Sulfuric acid and hydrochloric acid are preferred. The use amount of these acid catalysts is not particularly limited, but the naphthol methylol derivative 10
It is usually 0.05 to 50 parts by weight, preferably 0.1 to 20 parts by weight, based on 0 parts by weight.

The above condensation reaction can be carried out without a solvent or in the presence of a solvent. Specific examples of the case where a solvent is used include toluene, xylene, methyl isobutyl ketone, and water, and these may be used alone or in combination of two or more. The amount of the solvent to be used is generally 50 to 300% by weight, preferably 100 to 250% by weight, based on the total weight of the charged raw materials.

After completion of the reaction, the pH of the water washing solution of the reaction product
Is preferably 3 to 7, preferably 5 to 7. When performing a water washing treatment, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogen phosphate, diethylene triamine, triethylene The treatment may be performed using various basic substances such as organic amines such as ethylenetetramine, aniline, and phenylenediamine as neutralizing agents. In the case of a water washing treatment, it may be carried out according to a conventional method. For example, water in which the neutralizing agent is dissolved is added to the reaction mixture, and the liquid separation extraction operation is repeated.

After the water washing (neutralization) treatment, the unreacted naphthol methylol and the solvent are distilled off under reduced pressure heating, and the product is concentrated to obtain the naphthol resin of the present invention. Of the naphthol resins of the present invention thus obtained, those obtained by reacting the compound of the formula (2) with the compound of the formula (3) are represented by the above formula (1).

The epoxy resin described in the above item (3) can be obtained by reacting epihalohydrin with the naphthol resin of the present invention thus obtained. The epihalohydrin used in this reaction includes epichlorohydrin, epibromhydrin, epiiodohydrin and the like, but epichlorohydrin, which is easily available industrially and is inexpensive, is preferable. This reaction can be performed according to a conventionally known method.

For example, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a mixture of the naphthol resin of the present invention and epichlorohydrin, or at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while the solid is added. Let react. 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 mixture 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 during the reaction and mixing.

In the above method, the amount of epichlorohydrin used is usually 0.5 to 20 mol, preferably 0.7 to 10 mol, per equivalent of the hydroxyl group of the naphthol resin of the present invention. The amount of the alkali metal hydroxide to be used is generally 0.5 to 1. 1 equivalent to 1 equivalent of the hydroxyl group in the naphthol resin of the present invention.
It is 5 mol, preferably 0.7 to 1.2 mol. By adding an aprotic solvent such as dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, and 1,3-dimethyl-2-imidazolidinone, an epoxy resin having a low hydrolyzable halogen content defined below is obtained. Is suitable for electronic material sealing applications.

The amount of the aprotic polar solvent used is 5 to 200%, preferably 10%, based on the weight of epichlorohydrin.
１００100%. The addition of alcohols with methanol and ethanol other than the above solvents facilitates the reaction. Further, toluene, xylene and the like can also be used. Here, the amount of hydrolyzable halogen is
For example, it can be measured by placing the epoxy resin in dioxane and titrating with a KOH / ethanol solution while refluxing for several tens minutes.

A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is used as a catalyst in a mixture of the naphthol resin of the present invention and an excess of epihalohydrin 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 naphthol resin of the present invention, and the reaction is performed again at 20 to 120 ° C. for 1 to 10 hours. Then, the epoxy resin of the present invention can be obtained by ring closure of the halohydrin ether. In this case, the amount of the quaternary ammonium salt used is usually 0.001 to 0.2 mol, preferably 0.05 to 1 equivalent of the hydroxyl group of the naphthol resin of the present invention.
０．１0.1 mol.

Usually, these reaction products are washed with water, or without heating, under heating and reduced pressure to remove excess epihalohydrin, and then dissolved again in a solvent such as toluene or methyl isobutyl ketone. The reaction is carried out again by adding an aqueous solution of an alkali metal hydroxide. In this case, the amount of the alkali metal hydroxide to be used is usually 0.01 to 1 equivalent of the hydroxyl group of the naphthol resin of the present invention.
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 completion of the reaction, by-produced salts are removed by filtration, washing with water, etc., and the solvent such as toluene, methyl isobutyl ketone or the like is distilled off under reduced pressure under heating to obtain the epoxy of the present invention having a small amount of hydrolyzable halogen. A resin can be obtained.

Hereinafter, the epoxy resin composition of the present invention will be described. In the epoxy resin composition according to the above (4) or (6), the naphthol resin of the present invention acts as a curing agent for the epoxy resin. In this case, the naphthol resin of the present invention is used alone or in combination with another curing agent. Can be. When used in combination, the proportion of the naphthol resin of the present invention in the total curing agent is preferably at least 30% by weight, more preferably at least 40% by weight.
% By weight or more is preferred.

Other curing agents that can be used in combination with the naphthol resin of the present invention include, for example, amine compounds, acid anhydride compounds, amide compounds and phenol compounds. 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 trimellit anhydride. Acid, pyromellitic anhydride,
Maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenol A, bisphenol S, bisphenol F, fluorene bisphenol, terpene diphenol, 4, 4′-biphenol, 2,2′-biphenol, hydroquinone, resorcinol, naphthalene diol, tris- (4-hydroxyphenyl) methane, 1,
1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-
Polycondensates with hydroxybenzaldehyde, dicyclopentadiene, etc. and modified products thereof, imidazole, BF
Examples include, but are not limited to, ₃ -amine complexes and guanidine derivatives. These may be used alone or in combination of two or more.

In the epoxy resin composition described in the above (5) or (6), the 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 epoxy resin of the present invention in the total epoxy resin is preferably at least 30% by weight, more preferably at least 40% by weight.
% By weight or more is preferred.

Other epoxy resins that can be used in combination with the epoxy resin of the present invention include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol,
2,2′-biphenol, hydroquinone, resorcinol, naphthalene diol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde,
Benzaldehyde, p-hydroxybenzaldehyde,
Polycondensates with dicyclopentadiene and the like and modified products thereof, glycidyl ether compounds derived from halogenated bisphenols such as tetrabromobisphenol A,
Examples include, but are not limited to, solid or liquid epoxy resins such as alicyclic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins. These may be used alone or in combination of two or more.

In the epoxy resin composition described in the above item (4), when the naphthol resin of the present invention is used as a curing agent, the other epoxy resin or the epoxy resin of the present invention can be used as the epoxy resin.

In the epoxy resin composition described in the above item (5), when the epoxy resin of the present invention is used as the epoxy resin, the above-mentioned other curing agent or the naphthol resin of the present invention can be used as a curing agent. .

The amount of the curing agent used in the epoxy resin composition of the present invention is preferably 0.5 to 1.5 equivalents, and particularly preferably 0.6 to 1.2 equivalents, per equivalent of the epoxy group of the epoxy resin. . When less than 0.5 equivalent, or more than 1.5 equivalent to 1 equivalent of epoxy group,
In any case, curing may be incomplete and good cured physical properties may not be obtained.

When using the above cured product, a curing accelerator may be used in combination. Examples of the curing accelerator that can be used include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, and 2-ethyl-4.
Imidazoles such as -methylimidazole, tertiary amines such as 2- (dimethylaminomethyl) phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo (5,4,0) undecene-7, triphenylphosphine Organic phosphines such as diphenylphosphine and tributylphosphine, metal compounds such as tin octylate, tetra-substituted phosphonium / tetra-substituted borates such as tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, and 2-ethyl-. Tetraphenylboron salts such as 4-methylimidazole / tetraphenylborate and N-methylmorpholine / tetraphenylborate. When the curing accelerator is used, the amount is 0.01 to 15 parts by weight per 100 parts by weight of the epoxy resin.
Parts by weight are used as needed.

Further, the epoxy resin composition of the present invention includes:
If necessary, filler, silane coupling material, release agent,
Various compounding agents such as pigments can be added. As the filler, crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite,
Examples include, but are not limited to, powders of steatite, spinel, titania, talc and the like, and spherical beads of these. These may be used alone or in combination of two or more. These fillers are preferably used in a proportion occupying 50 to 90% by weight in the epoxy resin composition from the viewpoint of heat resistance, moisture resistance, mechanical properties and the like of the cured product of the epoxy resin composition.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the components. 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, the epoxy resin of the present invention, a curing agent, and, if necessary, additives such as a curing accelerator and a filler are mixed as necessary using an extruder, a kneader, a roll, or the like, until the mixture is uniformly mixed, and the mixture is cured. The epoxy resin composition of the present invention is obtained, and after the epoxy resin composition is melted, molded using a casting or transfer molding machine or the like, and further heated at 80 to 200 ° C. for 2 to 10 hours. You can get things.

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.
A prepreg obtained by impregnating a substrate such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper or the like and drying by heating may be subjected to hot press molding to obtain a cured product.

The amount of the diluting solvent used at this time is usually 10 to 70% by weight, preferably 15 to 65% by weight, based on the total weight of the epoxy resin composition of the present invention and the diluting solvent.

[0040]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In addition, the unit of the epoxy equivalent and the hydroxyl equivalent in Examples is g /
eq.

Production Example 1 282 parts by weight of β-naphthol were dissolved in 600 parts by weight of methyl isobutyl ketone (hereinafter, MIBK), and 53 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added. 67 parts by weight of paraformaldehyde (93%) was added to this solution,
The reaction was performed at 0 ° C. for 3 hours. After completion of the reaction, about 42 parts by weight of 35% hydrochloric acid was added for neutralization to obtain a reaction solution containing a compound in which R ₁ is a hydrogen atom in the formula (2). This reaction solution
Contains 1-methylol-2-naphthol as a main component.

Example 1 2-Phenylphenol 1 was added to the reaction solution obtained in Production Example 1.
After adding 70 parts by weight, 2 parts by weight of p-toluenesulfonic acid was added, and the reaction was carried out at 30 ° C. for 2 hours and at 70 ° C. for 10 hours. Thereafter, the reaction solution was washed with water until the water washing solution became neutral, and MIBK in the oil layer was distilled off under heating and reduced pressure. As a result, 459 parts by weight of the naphthol resin of the present invention was obtained. The softening point of the obtained naphthol resin (P1) is 121.
° C and a hydroxyl equivalent were 161. In addition, this resin is G
As a result of analysis by PC (gel permeation chromatography), the following formula (4) was obtained.

[0043]

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In the above, the content of the component in which n is 1 is 35
% By weight. The analysis conditions are as follows.

GPC device: Hitachi, Ltd. (Column: GPC KF-803 (1 pc.) + GPC K
F-802.5 (1) + GPC KF-802 (1) (Showa Denko) Solvent: tetrahydrofuran 1 ml / min Detection: UV (254 nm)

Example 2 To 161 parts by weight of the naphthol resin (P1) obtained in Example 1 were added 370 parts by weight of epichlorohydrin and 93 parts by weight of dimethyl sulfoxide, and the mixture was heated. 42% by weight (purity: 99%) was added over 100 minutes. Thereafter, the reaction was further performed at 50 ° C. for 2 hours and at 70 ° C. for 1 hour. Subsequently, after repeatedly washing with water until the water washing solution of the reaction solution became neutral, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 391 parts by weight of MIBK was added to the residue and dissolved. Further, the MIBK solution was heated to 70 ° C., 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added, and the mixture was allowed to react for 1 hour. Thereafter, the water washing was repeated until the reaction solution became neutral. Then, MIBK was distilled off from the oil layer under heating and reduced pressure to obtain 204 parts by weight of the epoxy resin (E1) of the present invention. The obtained epoxy resin (E1) had an epoxy equivalent of 223 and a softening point of 97 ° C. The epoxy resin (E1) of the present invention thus obtained is obtained by glycidyl etherification of the phenolic hydroxyl group of the naphthol resin (P1).

Example 3 Using the epoxy resin (E1) obtained in Example 2, a curing agent (phenol novolak resin (PN-8, manufactured by Nippon Kayaku Co., Ltd.)
0, ICI viscosity at 150 ° C. 1.5 ps, softening point 8
6 ° C., hydroxyl equivalent 106), 1 hydroxyl equivalent, 1 part by weight of a curing accelerator (triphenylphosphine) per 100 parts by weight of epoxy resin, transfer molding to prepare a resin molded body, 160 ° C. for 2 hours And one more
Cured at 80 ° C. for 8 hours.

Example 4 As an epoxy resin, EOCN-1020-55 (o-cresol novolak type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), ICI viscosity at 150 ° C. 0.8 ps, softening point 5
Using a naphthol resin (P1) obtained in Example 1 as a curing agent for 1 epoxy equivalent at 4 ° C. and an epoxy equivalent of 198), 1 hydroxyl equivalent was added, and a curing accelerator (triphenylphosphine) was added to the epoxy equivalent. One part by weight was added per 100 parts by weight of the resin, 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.

Example 5 The epoxy resin (E1) obtained in Example 2 was used, and the naphthol resin (P1) obtained in Example 1 was used as a curing agent for one epoxy equivalent of these epoxy resins. Compounding, and further 1 part by weight of a curing accelerator (triphenylphosphine) per 100 parts by weight of the epoxy resin,
A resin molded body is prepared by transfer molding, and 160
Curing was carried out at 2 hours at 180 ° C and further at 8 hours at 180 ° C.

Table 1 shows the results of measuring the physical properties of the cured product thus obtained. In addition, the measurement of the physical property value was performed by the following method. Glass transition temperature (TMA): TM-7000 manufactured by Vacuum Riko Co., Ltd. Temperature rising rate 2 ° C./min.・ Water absorption: Weight increase rate (%) after boiling a disc-shaped test specimen of 5 cm in diameter x 4 mm in water at 100 ° C for 24 hours.

[0051]

Table 1 Example 3 Example 4 Example 5 Epoxy resin E1 EOCN- E1 1020-55 Curing agent PN-80 P1 P1 Glass transition temperature (° C) 157 158 162 Water absorption (%) 1.0 0 0.9

From Table 1, it is clear that the cured product of the present invention has a high glass transition temperature and excellent heat resistance, and also has a low water absorption and therefore excellent moisture resistance.

[0053]

The epoxy resin composition of the present invention containing a naphthol resin and / or an epoxy resin has excellent heat resistance, moisture resistance (water resistance) and mechanical strength in the cured product, and is therefore suitable for electric and electronic parts. It is extremely useful when used for insulating materials (such as highly reliable semiconductor encapsulating materials) and laminates (such as printed wiring boards) and various composite materials such as CFRP, adhesives, and paints.

Continued on the front page F term (reference) 4J033 CA01 CA02 CA22 CA32 CA34 CC03 CC04 CC08 CC09 HB02 HB03 HB06 HB08 HB09 4J036 AC02 AC03 AC05 AD07 AD08 AD09 AD12 AF05 AF06 AF34 AF36 BA01 DB06 DB20 DB21 DB22 DC03 DC06 DC09 DC10 DC31 DC41 DC46 DD07 FA01 FA05 FB08 FB13 GA04 GA06 GA09 GA20 JA07 JA08

Claims (9)

[Claims] 1. A naphthol resin obtained by reacting a β-naphthol monomethylol compound with a phenylphenol in the presence of an acid catalyst. 2. The naphthol resin according to claim 1, which contains a compound represented by the general formula (1). Embedded image (In the formula (1), R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a halogen atom, an alkyl group or an allyl group having 1 to 10 carbon atoms. K is an integer of 1 or 2, and m is 1 to 2. 5
And n represents an integer of 0 to 8, respectively. ) 3. An epoxy resin (a) obtained by glycidyl etherification of a phenolic hydroxyl group of the naphthol resin according to claim 1 or 2. 4. An epoxy resin composition comprising the epoxy resin (b) and the naphthol resin (c) according to claim 1 or 2. 5. An epoxy resin composition comprising the epoxy resin (a) according to claim 3 and a curing agent (d). 6. An epoxy resin composition comprising the epoxy resin (a) according to claim 3 and the naphthol resin (c) according to claim 1 or 2. 7. The epoxy resin composition according to claim 4, which comprises a curing accelerator. 8. A cured product obtained by curing the epoxy resin composition according to any one of claims 4 to 7. 9. After reacting a β-naphthol monomethylol compound with phenylphenol in the presence of an acid catalyst, an acid catalyst is added to the reaction system if necessary, and then the temperature of the reaction system is raised to 30 to 130 ° C. A method for producing a naphthol resin, which comprises heating and further performing a post-reaction.