JP2000038430A - Naphthol resin, epoxy resin, epoxy resin composition and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin capable of providing its cured product excellent in heat and moisture resistances (water resistance) by reacting a reactional product of β-naphthols with a formaldehyde-generating source substance with α-naphthols in the presence of an acidic catalyst. SOLUTION: This naphthol resin is obtained by reacting a product (e.g. a monomethylol derivative of β-naphthols, specifically 1-methylol-2-naphthol) prepared by reacting β-naphthols (e.g. β-naphthol) with a formaldehyde- generating source substance (e.g. paraformaldehyde) with α-naphthols in the presence of an acidic catalyst (usually at 5-180 deg.C for 0.5-30 h) and preferably contains 5-50 wt.% of a compound represented by formula I (R1 and R2 are each H, a halogen, a 1-10C alkyl or allyl) and a compound represented by formula II [(n) is 0-8]. Furthermore the contents of the contained compound represented by formula II are 5-40 wt.% of the compound represented by formula II in which (n) is O, >=25 wt.% of the compound represented by formula II in which (n) is 1 and <50 wt.% of the compound represented by formula II in which (n) is >=2.

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 product obtained by reacting a β-naphthol with a formaldehyde generating substance with an α-naphthol in the presence of an acid catalyst; A naphthol resin obtained by reacting a naphthol monomethylol compound with an α-naphthol in the presence of an acid catalyst, wherein the naphthol resin contains a compound represented by the general formula (1) or (2).

[0006]

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(In the formula (1), R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an allyl group.)

[0008]

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(In the formula (2), n represents an integer of 0 to 8.)
R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an allyl group. (3) The naphthol resin according to the above (2), wherein the content of the component represented by the formula (1) is 5 to 50% by weight, and (4) the content of the component wherein n in the formula (2) is 0. The naphthol resin according to the above (2) or (3), wherein n is 1 in the formula (2) is 25% by weight or more. (4) The naphthol resin according to any one of (2) to (5), wherein (6) the content of the component in which n is 2 or more in the formula (2) is less than 50% by weight. The naphthol resin according to claim 1, (7) an epoxy resin (a) obtained by glycidyl etherifying a phenolic hydroxyl group of the naphthol resin according to any one of (1) to (6), and (8) an epoxy resin. (B) The naphthol resin according to any one of the above (1) to (6) An epoxy resin composition containing (c), (9) an epoxy resin composition containing the epoxy resin (a) described in (7) above, and a curing agent (d), (1)
0) The epoxy resin (a) according to the above (7), the above (1)
The naphthol resin (c) according to any one of (1) to (6).
(11) The epoxy resin composition according to any one of the above (8) to (10), which contains a curing accelerator, (12) the above (8) to ( 1
(1) a cured product obtained by curing the epoxy resin composition according to any one of (1), (13) reacting a β-naphthol monomethylol compound with an α-naphthol 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.

[0010]

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

[0011] 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 is represented by the following formula (3):

[0013]

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(In the formula (3), R ₁ has the same meaning as in the formula (1).) Monomethylols of β-naphthols, preferably 1-methylol-2-naphthol, Equation (4)

[0015]

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(In the formula (4), R ₂ has the same meaning as in the formula (1).) The naphthol resin of the present invention is condensed in the presence of an acidic catalyst. Obtainable. The reaction temperature is usually 5 to 180 ° C,
Preferably it is 30-130 degreeC. The reaction time is usually 0.1.
It is 5 to 30 hours, preferably 1 to 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 the α-naphthols that can be used include α-naphthol and alkyl (alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl and butyl).
-Naphthol, halogen (chlorine, bromine, iodine, etc.)-Substituted α-naphthol, allyl-substituted α-naphthol, and the like, with α-naphthol being preferred. These α-naphthols can be used alone or in combination of two or more. In the above reaction, the amount of the compound of the formula (4) to be used is generally 0.4 to 1.1 mol, preferably 0.5 to 1.0 mol, per 1 mol of the compound of the formula (3).

When the compound of the formula (3), which is a preferred embodiment of the present invention, is used, a dimer of β-naphthols by-produced during the above reaction (wherein n in the formula (2) 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 presumed that rearrangement of the dimer of β-naphthols (dissociation of the dimer of β-naphthols and reaction with α-naphthols) occurs in the post-reaction.

In the above condensation reaction, an acid catalyst is used.
Various acid catalysts can be used, but hydrochloric acid, sulfuric acid,
Organic or inorganic acids such as p-toluenesulfonic acid and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride are preferable, and p-toluenesulfonic acid, sulfuric acid and hydrochloric acid are particularly preferable. The use amount of these acid catalysts is not particularly limited, but is usually 0.05 to 50 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the naphthol methylol body.

The above condensation reaction can be carried out in the absence of 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 treatment, the unreacted naphthol methylol and the solvent are distilled off under reduced pressure heating to concentrate the product, whereby the naphthol resin of the present invention can be obtained. In the naphthol resin of the present invention thus obtained, a skeleton in which β-naphthol and α-naphthol are condensed (the skeleton of formula (1) called β / α) and a skeleton in which β-naphthols are condensed (β / β, The weight ratio of the skeleton of the formula (2) is usually β / α: β / β = 5: 3 to 2: 3. Since the rearrangement of the dimer of β-naphthols occurs in the post-reaction as described above, this ratio may vary depending on the post-reaction temperature and time.

In the naphthol resin of the present invention thus obtained, the content of the component represented by the formula (1) is preferably from 5 to 50% by weight, particularly preferably from 10 to 40% by weight. The content of the component in which n in formula (2) is 0 is preferably 5 to 40% by weight, and particularly preferably 10 to 35% by weight. When the compound of the formula (1) or the component of the formula (2) wherein n is 0 out of these ranges, the epoxy resin of the present invention obtained by glycidyl etherification of a phenolic hydroxyl group in a naphthol resin; Alternatively, the heat resistance of the cured product of the epoxy resin composition containing the naphthol resin of the present invention may be lowered, or the naphthol resin may not be able to be filled with a high filler due to a high viscosity.

The content of the component where n in the formula (2) is 1 in the naphthol resin is preferably at least 25% by weight, particularly preferably 30 to 90% by weight. When the resin of the formula (2) is contained outside this range, the heat resistance of the cured product of the epoxy resin composition containing the naphthol resin of the present invention is reduced, or the filler is highly filled due to the increased viscosity of the naphthol resin. May not be possible.

In the formula (2), the component where n is 2 or more is preferably less than 50% by weight, particularly preferably 4% by weight.
5 to 0.1% by weight. When the compound of the formula (2) is contained outside of these ranges, the viscosity of the naphthol resin may be increased, and it may be difficult to increase the filling of the filler.

The epoxy resin described in the above item (7) can be obtained by reacting the naphthol resin of the present invention thus obtained with epihalohydrin. 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 the weight of epichlorohydrin.
-200%, preferably 10-100%. The addition of alcohols with methanol and ethanol other than the above solvents facilitates the reaction. Also,
Toluene, xylene and the like can also be used. Here, the amount of hydrolyzable halogen can be measured, for example, 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 olimethylbenzylammonium chloride is used as a catalyst in a mixture of the naphthol resin of the present invention and an excess of epihalohydrin at 50-150 ° 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, the by-produced salts are removed by filtration, washing with water, etc., and the solvent such as toluene and methyl isobutyl ketone 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 (8) or (10), 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 may be 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, particularly preferably 4% by weight.
0% 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, phenol compounds and the like. 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, bisphenols, biphenols, phenols (phenol, alkyl-substituted phenol, naphthol,
Examples include, but are not limited to, polycondensates of alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes and modified products thereof, imidazole, BF ₃ -amine complex, guanidine derivative, and the like. These may be used alone,
Two or more types may be used.

In the epoxy resin composition according to the above (9) or (10), the epoxy resin of the present invention can be used alone or in combination with another epoxy resin. When used together, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably at least 30% by weight, particularly preferably at least 40% by weight.

Other epoxy resins which can be used in combination with the epoxy resin of the present invention include novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin. Epoxy resin, glycidylamine epoxy resin, solid or liquid epoxy resin such as glycidyl ester epoxy resin, and the like,
It is not limited to these. These may be used alone or in combination of two or more.

In the epoxy resin composition described in the above item (8), 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.

When the epoxy resin of the present invention is used as the epoxy resin in the epoxy resin composition described in the above item (9), the 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 from 0.5 to 1.5 equivalents, more preferably from 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 the above-mentioned cured product is used, a curing accelerator may be used in combination. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8-diazabicyclo (5, Tertiary amines such as (4,0) undecene-7; phosphines such as triphenylphosphine; and metal compounds such as tin octylate. When the curing accelerator is used, 0.01 to 15 parts by weight is used as needed based on 100 parts by weight of the epoxy resin.

Further, the epoxy resin composition of the present invention comprises
If necessary, fillers such as silica, alumina, and talc, and various compounding agents such as silane coupling agents, release agents, and pigments can be added. From the viewpoint of heat resistance, moisture resistance, mechanical properties and the like of the cured product of the epoxy resin composition, the filler is preferably used in a proportion occupying 60 to 90% by weight in 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, mesoisobutyl ketone and the like, and the base resin such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. A prepreg obtained by impregnating a material with heat and drying can 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.

[0044]

The present invention will be described in more detail with reference to the following examples. In addition, the unit of the epoxy equivalent and the hydroxyl equivalent in the examples is g / eq. Note that the present invention is not limited to these examples.

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 1-methylol-2-naphthol.

Example 1 After adding 144 parts by weight of α-naphthol to the reaction solution obtained in Production Example 1, 2 parts by weight of p-toluenesulfonic acid were added, and the reaction was carried out at 30 ° C. for 2 hours and at 40 ° C. for 1 hour. Was done. 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, 4
39 parts by weight of the naphthol resin (P1) of the present invention were obtained.
The obtained naphthol resin had a softening point of 103 ° C. and a hydroxyl equivalent of 151. Further, as a result of analyzing the resin by liquid chromatography, in the formula (1), R ₁ = R ₂
The content of the component represented by = H was 28% by weight, and the content of the component wherein R ₁ = R ₂ = H and n was 0 in the formula (2) was 19% by weight. Equation (2)
In the formula, R ₁ = R ₂ = H and the content of the component where n is 1 is 39% by weight, and in the formula (2), R ₁ = R ₂ =
The content of the component that was H and n was 2 or more was 9% by weight. The analysis conditions are as follows.

Liquid chromatograph: Shimadzu (Column: Inertsil ODS-2, manufactured by GL Sciences) Solvent: Acetonitrile / water = 70/30, 28
After a minute, a gradient is applied so that acetonitrile / water = 100/0. Detection: UV (254 nm)

Example 2 To 151 parts by weight of the naphthol resin (P1) obtained in Example 1, 370 parts by weight of epichlorohydrin and 93 parts by weight of dimethyl sulfoxide were added and dissolved. 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. Then, after washing was repeatedly returned to neutral, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 414 parts by weight of MIBK was added to the residue.
Was added 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. Then, water washing was repeated until the pH of the reaction mixture became neutral. Then, MIBK was distilled off from the oil layer under heating and reduced pressure to obtain 200 parts by weight of the epoxy resin (E1) of the present invention. The epoxy equivalent of the obtained epoxy resin (E1) was 234, and the softening point was 76 ° 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.

Comparative Example 1 As a comparative example, an epoxy resin (o-cresol novolak type epoxy resin (EOCN-10 manufactured by Nippon Kayaku Co., Ltd.)
20-55, ICI viscosity 0.8 ps at 150 ° C.,
A curing agent (phenol novolak resin (manufactured by Nippon Kayaku Co., Ltd., PN-80, ICI viscosity at 150 ° C. 1.5 ps, softening point 86 ° C., hydroxyl equivalent) relative to 1 epoxy equivalent, softening point 54 ° C., epoxy equivalent 198) 106) was added in an amount of 1 hydroxyl group, a curing accelerator (triphenylphosphine) was added in an amount of 1 part by weight per 100 parts by weight of the epoxy resin, and a resin molded product was prepared by transfer molding.
Curing was carried out at 60 ° C. for 2 hours and further at 180 ° C. for 8 hours.

Table 1 shows the results of measuring the physical properties of the cured products obtained in Examples 3 to 5 and Comparative Example 1. 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 piece of 5 cm in diameter x 4 mm in water at 100 ° C for 24 hours.

[0054]

Table 1 Example 3 Example 4 Example 5 Comparative Example 1 Epoxy resin E1 EOCN- E1 EOCN- 1020-55 1020-55 Curing agent PN-80 P1 P1 PN-80 Glass transition temperature (° C.) 159 158 160 147 Water absorption (%) 1.0 1.0 0.9 1.2

As shown in Table 1, 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 has excellent moisture resistance.

[0056]

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.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CC03X CD02W CD05W CD06W CD13W EJ026 EL136 EN046 EN076 ER026 EU116 EU117 EU137 EV216 EW147 FD146 FD157 FD157 GQ00 4J033 CA01 CA02 CA03 CA22 CA29 CA34 CC01 CC03 CC08 CC09 CC14 HB04 AF05 DA01 FB08 JA01 JA05 JA07 JA08

Claims (13)

[Claims] 1. A naphthol resin obtained by reacting a product obtained by reacting a β-naphthol with a formaldehyde generating substance and an α-naphthol in the presence of an acid catalyst. 2. A β-naphthol monomethylol compound and α-naphthol
A naphthol resin obtained by reacting naphthols with naphthols in the presence of an acid catalyst, wherein the naphthol resin contains the compounds represented by the general formulas (1) and (2). Embedded image (In the formula (1), R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an allyl group.) (In the formula (2), n represents an integer of 0 to 8. R ₁ and R ₂
Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an allyl group, respectively. ) 3. The content of the component represented by the formula (1) is 5-5.
The naphthol resin according to claim 2, which is 0% by weight. 4. The naphthol resin according to claim 2, wherein the content of the component where n is 0 in the formula (2) is 5 to 40% by weight. 5. The naphthol resin according to claim 2, wherein the content of the component wherein n in the formula (2) is 1 is at least 25% by weight. 6. The naphthol resin according to claim 2, wherein the content of the component in which n is 2 or more in the formula (2) is less than 50% by weight. 7. An epoxy resin (a) obtained by glycidyl etherifying a phenolic hydroxyl group of the naphthol resin according to any one of claims 1 to 6. 8. An epoxy resin composition comprising an epoxy resin (b) and the naphthol resin (c) according to any one of claims 1 to 6. 9. An epoxy resin composition comprising the epoxy resin (a) according to claim 7 and a curing agent (d). 10. An epoxy resin composition comprising the epoxy resin (a) according to claim 7 and the naphthol resin (c) according to any one of claims 1 to 6. 11. The epoxy resin composition according to claim 8, further comprising a curing accelerator. 12. A cured product obtained by curing the epoxy resin composition according to any one of claims 8 to 11. 13. A β-naphthol monomethylol compound and α
-Reaction with naphthols in the presence of an acid catalyst, an acid catalyst is added to the reaction system if necessary,
A method for producing a naphthol resin, comprising raising the temperature to 0 to 130 ° C. and further performing a post-reaction.