JPH04366117A - New resin, production thereof, resin composition, and cured article - Google Patents

Abstract

PURPOSE:To provide a naphthol resin which exhibits an excellent melt flowability, gives a cured article excellent in heat resistance, moisture resistance, and adhesive properties, and is useful for semiconductor sealing with a high reliability by selecting a specific naphthol resin. CONSTITUTION:A naphthol resin of formula I (wherein R1 and R2 are each H, halogen, 1-4C alkyl, or aryl; and X is H or -CH2OH) which is prepd. by condensing methylolated 2-naphthol of formula II with a 1-naphthol compd. of formula III in the presence of an acid catalyst (e.g. p-toluenesulfonic acid) and, if necessary, reacting the resulting condensate with HCHO in the presence of an alkali metal hydroxide (e.g. NaOH).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to naphthol resins, epoxy resins, resin compositions, and cured products thereof useful for highly reliable semiconductor encapsulation.

0002

BACKGROUND OF THE INVENTION Epoxy resins are widely used in the fields of electrical and electronic parts due to their cured products having excellent electrical properties, heat resistance, adhesive properties, etc.

However, in recent years, especially with the development of the electrical and electronic fields, there has been an increase in purification, improvements in heat resistance, moisture resistance, adhesion, etc. of cured products, and the addition of fillers (fillers, etc.) into molded materials. There is a need for further improvements in various properties, such as lower viscosity for higher density filling and improved molding workability, and although many proposals have been made for epoxy resins and their compositions, they are still insufficient. No, no.

0004

[Problems to be Solved by the Invention] The present invention provides a resin useful for highly reliable semiconductor encapsulation, which exhibits excellent fluidity when melted and exhibits excellent heat resistance, moisture resistance, and adhesion in its cured product. The present invention provides a manufacturing method, a resin composition, and a cured product thereof.

[0005]

[Means for Solving the Problems] The present inventors have completed the present invention as a result of extensive research into methods for imparting or improving the above characteristics. That is, the present invention solves the problem of formula (1) (1)
)

[0006]

[C6]

(In the formula, R1 and R2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and X represents a hydrogen atom or -CH2 OH
shows. ) naphthol resin, (2) formula (2)

[0008]

[C7]

2-naphthol methylol compound represented by and formula (3)

0010

[Chemical formula 8]

(In the formula, R1 and R2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group.) A method for producing a naphthol resin of the above formula (1), (3) a method for producing a naphthol resin of the above formula (1), which is characterized by carrying out a dehydration condensation reaction in the presence of an alkali metal hydroxide, and further reacting with formaldehyde if necessary in the presence of an alkali metal hydroxide.

0012

[Chemical formula 9]

(In the formula, R1 and R2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and Y represents a hydrogen atom or a formula (5)

[Chemical 1
0]

The group shown below is shown below. ), (4) an epoxy resin composition containing an epoxy resin, a curing agent and, if necessary, a curing accelerator; Or (B) an epoxy resin composition containing the naphthol resin of the above formula (1) as a curing agent, (5) the above (
The present invention relates to the cured product of the epoxy resin composition of 4).

[0015] The naphthol resin of formula (1) has the above-mentioned (2)
According to the production method, the 2-naphthol methylol compound represented by formula (2) and the 1-naphthol compound represented by formula (3) are subjected to a dehydration condensation reaction in the presence of an acid catalyst, and if necessary, further can be obtained by reacting with formaldehyde in the presence of an alkali metal hydroxide.

The 2-naphthol methylol compound of formula (2) is a known compound, and can be synthesized, for example, by reacting 2-naphthol with formaldehyde in the presence of an alkali metal hydroxide.

The 1-naphthols represented by formula (3) include 1-naphthol, 2-methyl-1-naphthol, and 4-naphthol.
-Methyl-1-naphthol, etc., and the amount of 1-naphthol used is preferably 0.9 to 20 times, particularly preferably 1 to 2 times by mole, per mole of the 2-naphthol methylol compound. .

Acid catalysts used in the dehydration condensation reaction include protonic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and para-toluenesulfonic acid; Lewis acids such as boron trifluoride, boron trifluoride ether complex, zinc chloride, and aluminum chloride; Others, acetic acid,
Oxalic acid etc. can be used. Among these, hydrochloric acid,
Oxalic acid, para-toluenesulfonic acid, etc. are preferably used, and the amount of these acid catalysts used is preferably 0.01 to 0.2 times the mole of the 2-naphthol methylol compound.

This 2-naphthol methylol compound and 1-
The dehydration condensation reaction with naphthols in the presence of an acid catalyst is usually carried out at 10 to 100°C, preferably 20 to 60°C.
It will be held in Furthermore, the reaction time can usually be selected within the range of 1 to 10 hours. Further, this reaction is preferably carried out in the presence of a suitable solvent such as water, methanol, methyl isobutyl ketone, toluene, and the like. The amount of the solvent used is not particularly limited, but it is usually used in an amount of 1 to 30 times the weight of the 2-naphthol methylol compound.

Furthermore, the dehydration condensation reaction solution contains excess toluene,
In the presence of a solvent such as methyl isobutyl ketone, the system is repeatedly washed with water until the system becomes neutral, and after separating and draining the water, the solvent and unreacted substances are removed under heating and reduced pressure. X=H) is obtained.

A naphthol resin in which X is -CH2OH in formula (1) can be obtained by reacting a naphthol resin in which X=H in formula (1) with formaldehyde in the presence of an alkali metal hydroxide. It will be done.

In this reaction, the amount of alkali metal hydroxide (eg, sodium hydroxide, potassium hydroxide) used is preferably 0 per equivalent of hydroxyl group of the naphthol resin where X=H in formula (1). .2 to 3 mol, particularly preferably 0.4 to 1.2 mol, and an aqueous solution (usually 5 mol) of the alkali metal hydroxide is added before the reaction with formaldehyde.
~50% by weight aqueous solution), and in formula (1), X=
It is preferable that part or all of the hydroxyl groups of the naphthol resin (H) be made into an alkali metal salt to form a homogeneous phase in the system. This reaction to form the alkali metal salt is usually carried out at a temperature of 20 to 80°C, preferably 40 to 60°C.

Next, formaldehyde is preferably added in an amount of 0.8 to 2.0 mol, particularly preferably 1 to 1.2 mol, per 1 mol of naphthol resin in which part or all of the alkali metal salt is used. - carry out the conversion reaction.

As the formaldehyde used in this reaction, formalin in the form of an aqueous solution, paraformaldehyde in the form of powder or granules, etc. can be used. Also, this reaction starts with water,
In addition to alcohols such as methanol and ethanol, solvents such as toluene can be used alone or in combination, but water is preferably used, and the temperature is preferably 0 to 60°C, particularly preferably 0 to 60°C. The reaction is carried out at a temperature of 30°C. Although the amount of solvent such as water to be used is not particularly limited, it is preferable that the formula (1
), 50 to 500% by weight is used based on the total weight of the naphthol resin with X=H and its alkali metal salt.

[0025]Also, the reaction time depends on the reaction temperature, but the reaction time is 0.
5 to 5 hours is appropriate. After this reaction, neutralization is carried out with an acid. This neutralization with an acid is preferably carried out at 0 to 30 DEG C. in the same manner as the methylolation reaction, taking care to avoid heat generation.

In this way, in equation (1), X is -
A solution is obtained containing naphthol resin which is CH2OH.

The epoxy resin of formula (4) can be obtained by reacting the naphthol resin of formula (1) with epihalohydrin. Epihalohydrin used in this reaction includes epichlorohydrin, epibromohydrin, etc., and epichlorohydrin is preferred because it is industrially easily available and inexpensive. This reaction can be carried out in accordance with a conventionally known method for obtaining polyglycidyl ether from a novolac type phenol resin and epihalohydrin.

For example, by adding a solid alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to a mixture of the naphthol resin of formula (1) and excess epichlorohydrin,
Alternatively, the reaction is carried out at a temperature between 20<0>C and 120<0>C while being added. At this time, an aqueous solution of the alkali metal hydroxide may be used. In that case, the alkali metal hydroxide is continuously added and water and epichlorohydrin are continuously added from the reaction system under reduced pressure or normal pressure. A method may also be used in which the water is removed by distillation, followed by liquid separation, and the epichlorohydrin is continuously returned to the reaction system.

In the above method, the amount of epichlorohydrin used is usually 1 to 2 per equivalent of hydroxyl group (phenolic hydroxyl group and alcoholic hydroxyl group) in the naphthol resin.
0 mol, preferably 2 to 10 mol. The amount of alkali metal hydroxide used is usually 0.8 to 1.5 mol, preferably 0.9 to 1.1 mol per equivalent of hydroxyl group (phenolic hydroxyl group and alcoholic hydroxyl group) in the naphthol resin. It is in the molar range. Furthermore, in order to make the reaction proceed smoothly, it is preferable to add an alcohol such as methanol or ethanol or an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide (hereinafter referred to as DMSO).
This reaction is usually carried out for 1 to 20 hours.

[0030]Also, a mixture of naphthol resin and excess epihalohydrin is reacted at 50°C to 150°C using a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride as a catalyst,
A solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the obtained halohydrin ether and reacted again at a temperature between 20 and 120°C to ring-close the halohydrin ether to form glycidyl ether. You can also get In this case, the amount of quaternary ammonium salt used is 0.001 to 1 equivalent of hydroxyl group (phenolic hydroxyl group and alcoholic hydroxyl group) of the naphthol resin.
0.2 mol, preferably in the range of 0.005 to 0.1 mol.

[0031] Usually, these reactants are washed with water or
After removing excess epihalohydrin under heating and reduced pressure without washing with water, it is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out the reaction again. . In this case, the amount of alkali metal hydroxide used is 0.01 to 0.2 mol, preferably 0.05 to 0.2 mol, per equivalent of hydroxyl group (phenolic hydroxyl group and alcoholic hydroxyl group) of the naphthol resin used. It is 0.1 mole. The reaction temperature is usually 5
It is carried out between 0 and 120°C, and the reaction time is usually 0.5 to 2
It's time.

After the completion of the reaction, by-produced salts are removed by filtration, washing with water, etc., and solvents such as toluene and methyl isobutyl ketone are distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention with less hydrolyzable halogen. be able to.

In addition, when a solution containing a naphthol resin in which X in the above formula (1) is -CH2OH is used as a raw material, an epihalohydrin such as epichlorohydrin is added to the solution containing the naphthol resin, and the solution is washed with water. After this, an epoxy resin is obtained by dehydrating by azeotropy under reduced pressure and further performing an epoxidation reaction in the same manner as above.

The epoxy resin composition of the present invention will be explained below. When using the epoxy resin of formula (4) in the epoxy resin composition of the present invention, the epoxy resin of the present invention can be used alone or in combination with other epoxy resins. When used together, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.

Other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, alicyclic epoxy resins, and biphenyl type epoxy resins. Examples include epoxy resins, but the use of novolac type epoxy resins is particularly advantageous in terms of heat resistance. Specific examples thereof include, but are not limited to, cresol novolac type epoxy resins, phenol novolac type epoxy resins, brominated phenol novolac type epoxy resins, and the like. These may be used alone or in combination of two or more.

When the naphthol resin of formula (1) is used in the epoxy resin composition of the present invention, the naphthol resin of the present invention can be used alone or in combination with other epoxy resin curing agents. When used together, the proportion of the naphthol resin of the present invention in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.

Other epoxy resin curing agents that can be used in combination with the naphthol resin of the present invention include, for example, polyamine curing agents such as aliphatic polyamines, aromatic polyamines, and polyamide polyamines, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. Examples include, but are not limited to, curing agents such as acid anhydride curing agents such as acids, phenol curing agents such as phenol novolak and cresol novolak, Lewis acids such as boron trifluoride or their salts, and dicyandiamides. It's not something you can do. These may be used alone or in combination of two or more.

In the epoxy resin composition of the present invention, the amount of curing agent used is preferably 0.5 to 1.5 equivalents, particularly 0.6 to 1.2 equivalents per equivalent of epoxy groups in the epoxy resin.
Equivalent amounts are preferred.

A curing accelerator is used as necessary, and 2-
Various known curing accelerators can be used, including imidazole compounds such as methylimidazole and 2-ethylimidazole, tertiary amine compounds such as 2-(dimethylaminomethyl)phenol, and triphenylphosphine compounds, and are not particularly limited. It's not a thing. When using a curing accelerator, the amount used is 0.01 parts by weight per 100 parts by weight of the epoxy resin.
A range of 15 parts by weight is preferred, and a range of 0.1 to 10 parts by weight is particularly preferred.

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

The epoxy resin composition of the present invention is obtained by uniformly mixing each component, and usually has a molecular weight of 130 to 170
Precure at a temperature of 30 to 300 seconds, and further,
By post-curing at a temperature of 150 to 200°C for 2 to 8 hours, a sufficient curing reaction proceeds, and the cured product of the present invention can be obtained. Alternatively, the components of the epoxy resin composition can be uniformly dispersed or dissolved in a solvent, and the composition can be cured after removing the solvent.

[0042] The cured product thus obtained has excellent performance in that it maintains heat resistance and also has moisture resistance. Moreover, the effect is increased by using the resin of the present invention for both the epoxy resin component and the curing agent component. Therefore, the naphthol resin and epoxy resin of the present invention can be used as an epoxy resin or as a curing agent in a wide range of fields where heat resistance and moisture resistance are required. Specifically, it is useful as a compounding component of all electrical and electronic materials such as insulating materials, laminates, and sealing materials. In addition to molding materials and composite materials, it can also be used in fields such as paint materials.

Furthermore, since the naphthol resin and epoxy resin of the present invention have a low melt viscosity, they enable high-density filling with fillers and the like, and furthermore, they can be used in conventional methods such as transfer molding. can also be used and has good workability.

[0044]

[Examples] The present invention will be specifically explained below using examples. In addition, the softening point in the examples is a value according to JIS K2425 (ring and ball method), and the hydroxyl equivalent and epoxy equivalent are g
/eq is shown. The amount of hydrolyzable chlorine is the amount (ppm) of chlorine produced (titrated) when decomposed with 1N-KOH-ethanol in dioxane under reflux for 30 minutes. Note that the present invention is not limited to these examples.

Example 1 (1) Synthesis of 2-naphthol methylol compound In a flask equipped with a thermometer, condenser, dropping funnel, and stirrer, 2-naphthol methylol compound was added.
288 parts by weight (2 mol) of naphthol and 400 parts by weight (2 mol) of a 20 wt % aqueous sodium hydroxide solution were charged, and the inside of the system was heated to 40°C and reacted for 1 hour. Then 5 inside the system
Cool to ℃ and add granular paraformaldehyde (92% purity)6
8 parts by weight (2.1 mol) was added and reacted at 5° C. for 4 hours. After the reaction was completed, 126 parts by weight of acetic acid (purity 99%) was added dropwise to neutralize the mixture while being careful not to generate heat. Next, 1000 parts by weight of methyl isobutyl ketone was added and water washing was repeated to remove excess formaldehyde to obtain a solution (reaction mixture) containing the 2-naphthol methylol compound represented by formula (2).

(2) Synthesis of naphthol resin 576 parts by weight (4 moles) of 1-naphthol was added to the reaction mixture to form a homogeneous phase in the system. Furthermore, para-toluenesulfonic acid 5
After adding parts by weight, the mixture was reacted at 30°C for 2 hours, and then at 50°C for 1 hour. After the reaction was completed, the reaction mixture was transferred to a separatory funnel and washed with water repeatedly to return it to neutrality. Thereafter, methyl isobutyl ketone and 1-naphthol were removed from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 570 parts by weight of naphthol resin (A). The resulting naphthol resin (A) had an ICI viscosity of 1.7 ps at 150°C, a softening point of 82°C, and a hydroxyl equivalent of 151.

When this naphthol resin (A) was analyzed using the following GPC analyzer using tetrahydrofuran (hereinafter referred to as THF) as a solvent, the molecular weight distribution curve shown in FIG. 1 was obtained.

Liquid pump: L-6000 (manufactured by Hitachi) Column: GPC KF-803 (1 piece) +
GPC KF-802.5 (2 pieces)
+GPC KF-802 (1 piece) (
(manufactured by Showa Denko) Column temperature: 40°C Solvent: THF 1ml/min Detector: RI
(Manufactured by Elma Optical) Data processing: CR-4A (Manufactured by Shimadzu Corporation)

0
[049] The retention time of the main peak of the above naphthol resin (A) analyzed under these analysis conditions corresponds to the molecular weight of a dinuclear substance having two naphthol rings, as determined from the calibration curve using standard polystyrene. The main peak component, which is thought to be a dinuclear body, was separated and subjected to mass spectrum (FAB).
-MS), M+ 300 was obtained, confirming that it was a dinuclear body represented by the following formula (6).

[0050]

[Chemical formula 11]

Example 2 Synthesis of epoxy resin Naphthol resin (A) 15 obtained in Example 1 (2)
555 parts by weight (6 moles) of epichlorohydrin per part by weight
, 140 parts by weight of DMSO was added and dissolved, heated to 40°C, 42 parts by weight (1.04 mol) of flaky sodium hydroxide (99% pure) was added over 100 minutes, and then further heated at 50°C for 2 hours. The reaction was carried out at 70° C. for 1 hour.
Next, after returning to neutrality by repeated washing with water, 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 and dissolved in the residue.

Further, this methyl isobutyl ketone solution was heated to 70° C., 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added, and after reacting for 1 hour, the solution was made neutral by repeated washing with water. Next, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain epoxy resin (B) 19
0 parts by weight were obtained. 150 of the obtained epoxy resin (B)
ICI viscosity at °C is 0.9 ps, softening point is 70.5
°C, epoxy equivalent is 212, hydrolyzable chlorine amount is 250
It was ppm.

This epoxy resin (B) was analyzed by liquid chromatography (GPC, the analysis conditions were the same as those for the naphthol resin) to obtain the molecular weight distribution curve shown in FIG. 2. In addition, when the main peak component that is thought to be a dinuclear substance was fractionated and analyzed by mass spectrometry (FAB-MS), M+ 412 was obtained, so the main peak component was 2 expressed by the following formula (7). It was confirmed that it was a nuclear body.

[0054]

[Chemical formula 12]

Example 3 (1) Synthesis of methylolated naphthol resin 151 parts by weight of the naphthol resin (A) obtained in (2) of Example 1 was placed in a flask equipped with a thermometer, cooling tube, dropping funnel, and stirrer. (1 hydroxyl group equivalent), 200 parts by weight (1 mol) of a 20 wt % aqueous sodium hydroxide solution was added, the inside of the system was heated to 50° C., and the reaction was carried out for 1 hour. Next, the inside of the system was cooled to 5°C, and 18 parts by weight (0
．． 55 mol) was added and reacted at 5°C for 4 hours. After the reaction was completed, 63 parts by weight of acetic acid (99% pure) was added dropwise to neutralize the mixture while being careful not to generate heat. Then, epichlorohydrin 60
After adding 0 parts by weight, excess formaldehyde was removed by repeated washing with water, and then water was distilled off from the oil layer by azeotropic dehydration under reduced pressure using a rotary evaporator.

(2) Synthesis of epoxy resin Next, the methylolated naphthol resin [formula (1)
), R1=H, R2=H, X=-CH2O
After adding 350 parts by weight of epichlorohydrin and 210 parts by weight of DMSO to an epichlorohydrin solution containing H],
Heat to 40℃ and add flaky sodium hydroxide (purity 9
9%) was added over 100 minutes, and then the reaction was further carried out at 50°C for 2 hours and at 60°C for 1 hour. Next, after repeatedly washing with water to return it to neutrality,
Excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure using a rotary evaporator, and the residue was
Parts by weight of methyl isobutyl ketone were added and dissolved.

Further, this methyl isobutyl ketone solution was heated to 70° C., 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added, and after reacting for 1 hour, the solution was made neutral by repeated washing with water. Next, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain epoxy resin (C) 19
0 parts by weight were obtained. 150 of the obtained epoxy resin (C)
ICI viscosity at °C is 1.2 ps, softening point is 64.0
°C, epoxy equivalent is 188, hydrolyzable chlorine amount is 420
It was ppm.

This epoxy resin (C) was analyzed by liquid chromatography (GPC, the analysis conditions were the same as those for the above-mentioned naphthol resin), and the molecular weight distribution curve shown in FIG. 3 was obtained. In addition, when the main peak component that is thought to be a dinuclear substance was fractionated and analyzed by mass spectrometry (FAB-MS), M+ 498 was obtained, so the main peak component was a dinuclear compound expressed by the following formula (8) I confirmed that it was the body.

[0059]

[Chemical formula 13]

Application Examples 1-3, Comparative Examples 1-2 Example 1
In addition, as Comparative Example 1, a bisphenol A type resin (hydroxyl equivalent: 116,
An epoxy resin (o-cresol novolak type epoxy resin, EOCN-102) was used for 100 parts by weight of these curing agents.
0 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 200, 150°C
(ICI viscosity 3.2 ps) and a curing accelerator (triphenylphosphine) were blended in the amounts shown in Table 1, a resin molded body was prepared by transfer molding, and cured under the curing conditions shown in Table 1.

Furthermore, the epoxy resins (B) and (C) obtained in Examples 2 to 3 were used, and as Comparative Example 2, bisphenol A type epoxy resins (epoxy equivalents 189, 15
A curing agent (phenol novolac 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 a curing accelerator (triphenylphosphine) in the amounts shown in Table 1, a resin molded body was prepared by transfer molding, and cured under the curing conditions shown in Table 1.

Table 1 shows the results of measuring the heat distortion temperature and water absorption of the cured product thus obtained. The measurement conditions for heat distortion temperature and water absorption rate are as follows.

Heat distortion temperature: Conditions specified in JIS K7207 Water absorption: Test piece (cured product) Diameter
50mm thickness 3mm
Weight increase after boiling the disk in water at 100℃ for 24 hours (weight%)

[0064]

[0065]

[Effects of the Invention] The naphthol resin and epoxy resin of the present invention not only provide excellent heat resistance and moisture resistance in their cured products, but also have excellent fluidity when melted.
Filler when used as a semiconductor encapsulant
This enables high-density packing such as Furthermore, according to the production method of the present invention, polyfunctional dinuclear bodies of naphthols can be easily obtained in high yield.

[Brief explanation of drawings]

[Figure 1] Molecular weight distribution curve of naphthol resin (A) obtained in Example 1

[Figure 2] Molecular weight distribution curve of epoxy resin (B) obtained in Example 2

[Figure 3] Molecular weight distribution curve of epoxy resin (C) obtained in Example 3

Claims (5)

[Claims] Claim 1: Formula (1) [Formula 1] (wherein R1 and R2 are each independently a hydrogen atom,
A halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and X represents a hydrogen atom or -CH2OH. ) naphthol resin. [Claim 2] A 2-naphthol methylol compound represented by formula (2) [Chemical formula 2] and a 2-naphthol methylol compound represented by formula (3) [
embedded image (wherein R1 and R2 are each independently a hydrogen atom,
It represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group. ) in the presence of an acid catalyst, and if necessary further reacted with formaldehyde in the presence of an alkali metal hydroxide. method for producing naphthol resin. Claim 3: Formula (4) [Image Omitted] (wherein R1 and R2 are each independently a hydrogen atom,
Y represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and Y represents a hydrogen atom or a group represented by formula (5). ) Epoxy resin. 4. An epoxy resin composition containing an epoxy resin, a curing agent, and optionally a curing accelerator, which contains the epoxy resin according to claim 3 as (A) the epoxy resin;
and/or (B) an epoxy resin composition comprising the naphthol resin according to claim 1 as a curing agent. 5. A cured product of the epoxy resin composition according to claim 4.