JPH0586167A - Production of epoxy resin, and epoxy resin composition - Google Patents

Abstract

PURPOSE:To produce an epoxy resin excellent in heat resistance, flexibility, and water resistance by reacting a specific polyepoxy resin, a bisphenol epoxy resin, and a bisphenol. CONSTITUTION:A polyepoxy resin having naphthalene rings (A), a bisphenol epoxy resin (B), and a bisphenol (C) are reacted. The polyepoxy resin having an epoxy equivalent of 130-400 is pref. to improve heat resistance. The wt. ratio of A/B is pref. 5/95-80/20, still pref. 10/90-60/40, to obtain excellent heat resistance, water resistance, and toughness; that of (A+B)/C, pref. 100/10-100/100, still pref. 100/20-100/70, to obtain excellent toughness.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel epoxy resin composition, and more specifically, it has excellent heat resistance and water resistance in laminated boards (printed wiring boards), and further has excellent mechanical strength and toughness. The present invention relates to an epoxy resin composition as an electric insulating material that has well-balanced properties.

[0002]

2. Description of the Related Art Conventionally, in order to improve heat resistance as an epoxy resin for laminates of printed wiring boards, for example, for so-called G-10 which does not require flame retardancy, a bisphenol A type epoxy resin and a polyfunctional resin are used. Mixture with other novolac type epoxy resin, and FR- which requires flame retardancy
For No. 4, tetrabromobisphenol A or a mixture of a brominated epoxy resin and a novolac type epoxy resin prepared to have a bromine content of 15% to 30% by co-condensation of tetrabromobisphenol A and bisphenol A is often used. It is used.

However, the epoxy resin used in combination with the novolac type epoxy resin has a tendency that its cured product is hard and brittle and its flexibility is lowered, and it is generally disadvantageous in terms of cost. .

As a technique for solving this problem, in JP-A-63-48323 and JP-A-63-48324, a bifunctional epoxy resin and various novolac type epoxy resins are grafted. Epoxy resins having different structures are disclosed.

[0005]

However, the technique of using an epoxy resin having a structure in which these conventional bifunctional epoxy resins and various novolac type epoxy resins are grafted is not suitable for the above-mentioned heat resistance and flexibility. Although the problem of heat resistance has been solved to some extent, there is a problem that the water resistance is poor, and the heat resistance is still insufficient.

In particular, in laminated plate applications, sufficient heat resistance, including solder resistance after moisture resistance, and adhesiveness between the base material and the copper foil, which is a performance contradictory to heat resistance, cannot be obtained, which is a big problem. It was.

The problems to be solved by the present invention are excellent in all of heat resistance, flexibility and water resistance, and particularly in laminated plate applications, heat resistance including solder resistance after moisture resistance,
It is intended to provide a method for producing an epoxy resin having excellent adhesion to a base material / copper foil, and an epoxy resin composition.

[0008]

The inventors of the present invention have made extensive studies in view of the above situation, and found that a polyfunctional epoxy resin having a naphthalene skeleton and a bisphenol epoxy resin were grafted via bisphenols. The inventors have found that an epoxy resin solves the above problems and completed the present invention.

That is, according to the present invention, a polyfunctional epoxy resin (A) having a naphthalene skeleton, a bisphenol epoxy resin (B), and a bisphenol (C) are reacted as essential components to produce an epoxy resin. A method, and an epoxy resin composition containing an epoxy resin and a curing agent, wherein a polyfunctional epoxy resin (A) having a naphthalene skeleton, a bisphenol epoxy resin (B), and a bisphenol (C) are used as epoxy resins. The present invention relates to an epoxy resin composition characterized by using an epoxy resin obtained by reacting as an essential component.

The polyfunctional epoxy resin (A) used in the present invention has two or more glycidyl groups in one molecule and has a naphthalene skeleton in its molecular structure, and is not particularly limited. It's not something, for example, 1,
3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene,
Diglycidyloxynaphthalene such as 1,7-diglycidyloxynaphthalene, 2,3-diglycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, 1- (2,7-
Diglycidyloxy-1-naphthyl) -1- (2-glycidyloxy-1-naphthyl) methane, 1- (2,7-
Diglycidyloxy-1-naphthyl) -1- (2-glycidyloxy-1-naphthyl) ethane, 1- (2,7-
Diglycidyloxy-1-naphthyl) -1- (2-glycidyloxy-1-naphthyl) butane, 1- (2,7-
Diglycidyloxy-1-naphthyl) -1- (2-glycidyloxy-1-naphthyl) -1-phenylmethane,
1- (2,7-diglycidyloxy-1-naphthyl)-
1- (2-glycidyloxy-1-naphthyl), 1-
(2,7-Diglycidyloxy-1-naphthyl) -1-
(2-glycidyloxy-1-naphthyl) -1-hydroxyphenylmethane, 1- (2,7-diglycidyloxy-1-naphthyl) -1- (2-glycidyloxy-1
-Naphthyl) -1-chloromethane, 1- (2,7-diglycidyloxy-1-naphthyl) -1- (2-glycidyloxy-1-naphthyl) -1-bromomethane, and other dinaphthalene-based trifunctional epoxies Resin, 1,1-bis (2,
7-diglycidyloxy-1-naphthyl) methane, 1,
1-bis (2,7-diglycidyloxy-1-naphthyl) ethane, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) propane, 1,1-bis (2,7-
Diglycidyloxy-1-naphthyl) -1-phenylmethane, 1,1-bis (2,7-diglycidyloxy-1)
-Naphthyl) -1-hydroxyphenylmethane, 1,1
-Bis (2,7-diglycidyloxy-1-naphthyl)
Dinaphthalene-based tetrafunctional epoxy resins such as -1-chloromethane and 1,1-bis (2,7-diglycidyloxy-1-naphthyl) -1-bromomethane, JP-A-61-69
826 and JP-A-2-189326,
1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,
Reaction of dihydroxynaphthalene such as 2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene with aldehydes such as formaldehyde, p-hydroxybenzaldehyde, salicylaldehyde, and vanillin with epihalohydrin. Epoxy resin obtained by
Phenol, cresol, butylphenol, octylphenol, nonylphenol, tertiary butylphenol, resorcin, methylresorcin, biphenol, dimethylbiphenol, bisphenol A, bisphenol F, bisphenol S, dihydroxyphenyl ether, 1,6-dihydroxynaphthalene, 2,7-
Α-on the benzene ring of phenolic compounds such as dihydroxynaphthalene and 1,2,10-anthracentriol
Examples of the naphthol or the epoxy resin include a novolak compound having a structure in which a β-naphthol skeleton is bonded through a methylene bond and having at least three hydroxyl groups in one molecule, which are reacted with epihalohydrin. May be used alone or in combination of two or more.

The epoxy equivalent of the polyfunctional epoxy resin having a naphthalene skeleton used in the present invention is usually 100.
However, those of 130 to 400 can be preferably used in order to improve heat resistance.
The above-mentioned dinaphthalene-based trifunctional epoxy resin, dinaphthalene-based tetrafunctional epoxy resin, novolak-type epoxy resin obtained by reacting dihydroxynaphthalene with aldehydes, α-naphthol or β-in the benzene ring of the phenolic compound. A novolac type epoxy resin obtained by reacting a novolac compound having a structure in which a naphthol skeleton is bonded via a methylene bond and having at least three hydroxyl groups in one molecule with epihalohydrin is mentioned.

When a novolac type epoxy resin is used as the polyfunctional epoxy resin having a naphthalene skeleton, it is preferable that at least 10% by weight or more of the compound has a naphthalene skeleton. It is particularly preferable that 30 to 80% by weight has a naphthalene skeleton.

The polyfunctional epoxy resin used in the present invention is
Those having 2 to 10 functional groups in the molecule can be preferably used, but among them, those having 3 or 4 functional groups are preferable from the viewpoint of significantly improving heat resistance.

As such a polyfunctional epoxy resin,
Particularly preferred are 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane and 1-
(2,7-Diglycidyloxy-1-naphthyl) -1-
Examples thereof include (2-glycidyloxy-1-naphthyl) alkane, and specifically, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) methane and 1,1-bis (2,7-). Diglycidyloxy-1-naphthyl) ethane, 1,1-bis (2,7-diglycidyloxy-1-
Naphthyl) propane, 1- (2,7-diglycidyloxy-1-naphthyl) -1- (2-glycidyloxy-1)
-Naphthyl) methane, 1- (2,7-diglycidyloxy-1-naphthyl) -1- (2-glycidyloxy-1
-Naphthyl) ethane, 1- (2,7-diglycidyloxy-1-naphthyl) -1- (2-glycidyloxy-1
-Naphthyl) propane.

As the bisphenol type epoxy resin (B) used in the present invention, for example, at least one compound selected from bisphenol A, bisphenol F and tetrabromobisphenol A and epihalohydrin in the same molecule can be used. Liquid or solid epoxy resin having two glycidyl ethers, or at least one selected from bisphenol A, bisphenol F, and tetrabromobisphenol A, which are used as bisphenols based on the epoxy resin thus obtained Is a resin having a bisphenol skeleton and having an epoxy equivalent of 150 to 1000, preferably 170 to 800. That.

The bisphenols (C) as the other component include, for example, bisphenol A, bisphenol F, tetrabromobisphenol A and the like, and at least one kind or several kinds may be used in combination.

As the method for obtaining the epoxy resin by reacting the polyfunctional epoxy resin (A) having a naphthalene skeleton, the bisphenol epoxy resin (B) and the bisphenol (C), the reaction conditions are particularly limited. Although not limited, for example, an alkali hydroxide such as sodium hydroxide, a tertiary amine such as toluethylamine and benzyldimethylamine, a quaternary ammonium salt such as tetramethylammonium chloride, an imidazole compound, A method of reacting at 110 to 180 ° C. using triphenylphosphine or the like as a catalyst can be mentioned. In the production method of the present invention, the ratio of use of each raw material component is (A) / (B) 5/95 to 80 /
20 and above all, the range of 10/90 to 60/40 is preferable from the viewpoint of excellent heat resistance, water resistance and toughness of the epoxy resin composition, and {(A) + (B)} / (C) is 100/10.
~ 100/100, especially 100/20 ~ 100/70
The range is preferable because the toughness is excellent.

The epoxy resin thus obtained usually has an epoxy equivalent of 100 to 2000, but among them, those having an epoxy equivalent of 200 to 1000 are excellent in storage stability when the epoxy resin composition is used for a laminate. Is preferred.

The use ratio of each of the above-mentioned raw material components is preferably set appropriately within the above-mentioned use range depending on the use and required characteristics of the composition of the present invention. For example, if heat resistance must be emphasized as much as possible, the type and ratio of the polyfunctional epoxy resin having a naphthalene skeleton should be increased, and (A) in order to increase the grafting ratio to this resin. However, it is also necessary to increase the amount of the (B) bisphenols used. Further, in obtaining the epoxy resin of the present invention for a laminated plate, as described above from the point where impregnability is important, the molecular weight of the (A) polyfunctional epoxy resin having the naphthalene skeleton cannot be increased so much. Therefore, the molecular weight of the (B) bisphenol type epoxy resin should be kept as low as possible, while the amount of the (C) bisphenol used should be raised to an appropriate level.

In addition to using the polyfunctional epoxy resin (A), the bisphenol type epoxy resin (B) and the bisphenols (C) as essential components, other polyfunctional epoxy resins may be used in combination. That is, the naphthalene skeleton in the produced epoxy resin is 1% by weight.
It can be used in the range of 0% or more.

The polyfunctional epoxy resin may be any polyfunctional epoxy resin, for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, glycidyl amine type epoxy resin. , Alicyclic epoxy resin, glycidyl ester type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, etc.
Although not particularly limited, the naphthalene skeleton in the epoxy resin obtained by the reaction is preferably 10% or more in terms of weight% from the viewpoint of water resistance.

As the curing agent for the epoxy resin constituting the epoxy resin composition of the present invention, any known and commonly used compound can be used, and examples thereof include the following. That is, aliphatic amines such as diethylenetriamine and triethylenetetramine; aromatic amines such as metaphenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; polyamide resins or their modified products; maleic anhydride, phthalic anhydride, anhydrous Hexahydrophthalic acid, pyromellitic dianhydride, methyltetrahydrophthalic anhydride, acid anhydrides such as methylhexahydrophthalic anhydride, phenol novolac resins, cresol novolac resins, phenol novolac resins such as BPA novolac resins, and dicyandiamide, imidazole , BF
Examples thereof include latent curing agents such as ₃ -amine chains and guanidine derivatives, but are not particularly limited.

When using each of these cured products as a curing agent, it is often necessary to use a curing accelerator together. In such a case, a tertiary amine such as dimethylbenzylamine is required. Needless to say, known and commonly used compounds such as imidazoles and various metal compounds are applicable.

Thus, the epoxy resin composition of the present invention is
It is obtained by mixing the epoxy resin containing the epoxy resin as an essential component and the epoxy resin curing agent in a ratio of 1 to 70 parts by weight with respect to 100 parts by weight of the solid content of the resin component.

However, it should be noted that the compounding ratio varies within the above range depending on the kind of the curing agent component used. The composition of the present invention thus obtained can be further compounded with various additives such as a filler and a colorant, if necessary, and is also thermosetting such as an amino resin, an alkyd resin, or a phenol resin. A resin can also be used together.

[0026]

【Example】

Reference Example 1 (Synthesis Example of Polyfunctional Epoxy Resin Having Naphthalene Skeleton) 0.5 mol of 2,7-dihydroxynaphthalene 1 mol
polyfunctional resin obtained by reacting ol of formaldehyde with sodium hydroxide as a catalyst is epoxidized by a predetermined method, and has a naphthalene skeleton mainly composed of a tetrafunctional component having an epoxy equivalent of 159 and a softening point of 96 ° C. A resin was obtained.

Hereinafter, this epoxy resin is abbreviated as "NE-1". Reference Example 2 (Synthesis Example of Polyfunctional Epoxy Resin Having Naphthalene Skeleton) 2,7-Dihydroxynaphthalene was used instead of 2,
A polyfunctional epoxy resin having a naphthalene skeleton having an epoxy equivalent of 180 and a softening point of 80 ° C. was obtained by performing the same operation as in Synthesis Example 1 except that 0.5 mol of 7-dihydronaphthalene and 0.5 mol of β-naphthol were used. It was

Hereinafter, this epoxy resin is abbreviated as "NE-2". Reference Example 3 (Synthesis Example of Polyfunctional Epoxy Resin Having Naphthalene Skeleton) 1 mol of orthocresol and 2 mol of formalin are added to N
After synthesizing a compound dimethylolated with an aOH catalyst and washing with neutralized water, 2 mol of β-naphthol was further added, and oxalic acid was added as a condensation reaction catalyst to synthesize novalac resin as a raw material, which was epoxidized by a predetermined method to obtain an epoxy equivalent of 235. A polyfunctional epoxy resin having a naphthalene skeleton with a softening point of 85 ° C. was obtained.

Hereinafter, this is abbreviated as "NE-3". Example 1 Liquid type "EPICLON" having an epoxy equivalent of 190
850 "(bisphenol A type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.) and 15 parts of the multifunctional epoxy resin" NE-1 "having a naphthalene skeleton obtained in Synthesis Example 1 , 34 parts of tetrabromobisphenol A are added, and the mixture is heated to 120 ° C. and stirred, and further 2
By adding 0.01 mol of -methyl-imidazole
After reacting at 50 ° C. for 4 hours, a solid epoxy resin having an epoxy equivalent of 422 and a bromine content of 20% was obtained.

Hereinafter, this is abbreviated as resin (A-1). Example 2 The amount of "EPICLON 850" used was 51 parts and 56 parts.
Parts, and except that the amount of the polyfunctional epoxy resin (A-1) having a naphthalene skeleton was changed from 15 parts to 10 parts, the epoxy equivalent was 430 and the bromine content was the same as in Reference Example 1. To obtain a solid epoxy resin having a ratio of 20%.

Hereinafter, this is abbreviated as resin (A-2). Example 3 The epoxy equivalent was 475 and the bromine content was the same as in Reference Example 2 except that the polyfunctional epoxy resin having a naphthalene skeleton used was changed from "NE-1" to "NE-3". 20% solid epoxy resin was obtained.

Hereinafter, this is abbreviated as resin (A-3). Example 4 30 parts of "EPICLON 850" and "NE-1" 30
Tetrabromobisphenol A to a mixture consisting of
Was reacted in the same manner as in Example 1 except that 40 parts of was reacted to give an epoxy equivalent of 505 and a bromine content of 2
A solid epoxy resin of 3% was obtained.

Hereinafter, this is abbreviated as resin (A-4). Example 5 45 parts of "EPICLON 850" and "NE-2" 30
A solid epoxy resin having an epoxy equivalent of 545 was obtained by the same operation as in Example 1 except that 25 parts of bisphenol A was reacted with the mixture consisting of 10 parts.

Hereinafter, this is abbreviated as resin (A-5). Example 6 44 parts of "EPICLON 850" and the multifunctional epoxy resin "NE- having the naphthalene skeleton obtained in Synthesis Example 1"
1 "10 parts and epoxy equivalent 213" EPI
CLON N673 "[Orthocresol novolac type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.] in a mixture of 10 parts and 26 parts of tetrabromobisphenol A
Part, and the mixture was heated to 120 ° C. and stirred, and then 2 methyl-
When 0.01 part of imidazole was added and reacted at 150 ° C. for 4 hours, a solid epoxy resin having an epoxy equivalent of 410 and a bromine content of 15% was obtained.

Hereinafter, this is abbreviated as resin (A-6). Example 7 The polyfunctional epoxy resin having a naphthalene skeleton used was changed from "NE-1" to "NE-2", and "EPICL" was used.
ON 850 "was used in an amount of 46 parts, and the epoxy equivalent was 424 in the same manner as in Example 1 except that 10 parts of a bifunctional epoxy resin" EPICLON HP-4032 "having a naphthalene skeleton with an epoxy equivalent of 149 was used. A solid epoxy resin having a bromine content of 20% was obtained.

Hereinafter, this is abbreviated as resin (A-7). Example 8 By the same operation as in Example 1 except that the polyfunctional epoxy resin having a naphthalene skeleton used was changed from "NE-1" to "NE-2", the epoxy equivalent was 446 and the bromine content was 20% solid epoxy resin was obtained.

Hereinafter, this is abbreviated as resin (A-8). Comparative Example 1 In Example 2, instead of “NE-1”, “EPIC” was used.
A solid epoxy resin having an epoxy equivalent of 465 and a bromine content of 20% was obtained by the same method except that "LON N673" was used.

Hereinafter, this is abbreviated as resin (A-9). Comparative Example 2 In Example 8, “EPIC” was used instead of “NE-2”.
A solid epoxy resin having an epoxy equivalent of 465 and a bromine content of 20% was obtained by the same method except that "LON N673" was used.

Hereinafter, this is abbreviated as resin (A-10). Examples 7 to 14 and Comparative Examples 3 to 4 Resins (A-1) to (A) shown in Tables 1 to 3 below.
-5), resin (A-6) and "EPICLON 153"
And the epoxy resin of each of Resin (A-6) to Resin (A-10) were dissolved in a methyl ethyl ketone solution.

When dicyandiamide is used as a curing agent, dicyandiamide is dissolved in methyl cellosolve in advance, this is mixed with the above methyl ethyl ketone solution, and a curing accelerator dimethylbenzylamine is further added. Methyl ethyl ketone was added so that the content (N.V.) was 55% to obtain a mixed solution.

The amounts of the curing agent and the curing accelerator used in this case are as shown in Tables 1 and 2, but the amount of the curing agent used is
The ratio is set to be 0.6 mol with respect to the epoxy equivalent in the epoxy resin.

On the other hand, when the BPA novolac resin is used as the curing agent, the BPA novolac resin is dissolved in methyl ethyl ketone in advance, and this is added to the methyl ethyl ketone solution containing the above epoxy resin, and further the curing accelerator dimethylbenzylamine is added. , Methyl ethyl ketone was added so that the nonvolatile content (N.V.) of the blended composition was 55% to obtain a mixed solution.

The amounts of the curing agent and the curing accelerator used in this case are as shown in Table 3, but the amount of the curing agent used is such that it is 1.0 equivalent to the epoxy equivalent in the epoxy resin. It is the one.

After that, using the respective mixed solutions, a face copper foil laminate was made as a trial according to the following conditions for producing the laminate,
Each physical property test was conducted. The results are shown in Tables 1 to 3.

(Conditions for producing laminated plate) Base material: WE-18K-106-RB84 [Nitto Boseki]
Glass cloth manufactured by Co., Ltd.] Number of plies: 8 Prepreg forming conditions: 160 ° C./3 minutes Copper foil: 35 μ Curing conditions: 170 ° C. for 1 hour Thickness after molding: 1.4 mm Resin content: 38% (moisture resistant solder 270) The solder resistance test was performed after the pressure cooker test was performed on the test piece under steam at 120 ° C.
Evaluation was performed by immersing in a solder bath at a temperature of 30 ° C. for 30 seconds.

The evaluation was carried out by visually observing the appearance of the test piece, especially the presence or absence of measling property. ◯: No abnormality at all Δ: Slight measling occurred ×: Mesling occurred (peel strength) The measurement was performed according to JIS K-6481.

(Delamination strength) It was measured in accordance with JIS K-6481.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3] * 1: Temperature rising speed 3 ° C / min * 2: Tetrabromobisphenol A type epoxy resin [manufactured by Dainippon Ink and Chemicals, Inc.] Epoxy resin 400, softening point 69 ° C, bromine content
48% * 3: BPA novolac resin [manufactured by Dainippon Ink and Chemicals, Inc.] Hydroxyl equivalent 118, Softening point 106 ° C

[0051]

According to the present invention, it is possible to provide an epoxy resin having excellent properties such as heat resistance, flexibility and water resistance. In particular, a laminated board using the epoxy resin composition of the present invention is extremely excellent in heat resistance including solder resistance after moisture resistance and adhesion to a base material / copper foil, and thus the epoxy resin composition of the present invention Is extremely useful for printed wiring board applications.

Claims (11)

[Claims] 1. A method for producing an epoxy resin, which comprises reacting a polyfunctional epoxy resin (A) having a naphthalene skeleton, a bisphenol type epoxy resin (B) and a bisphenol (C) as essential components. 2. The method according to claim 1, wherein the polyfunctional epoxy resin (A) having a naphthalene skeleton has an epoxy equivalent of 130 to 400. 3. The production method according to claim 2, wherein the polyfunctional epoxy resin (A) having a naphthalene skeleton is a trifunctional epoxy resin or a tetrafunctional epoxy resin. 4. The polyfunctional epoxy resin (A) having a naphthalene skeleton is 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane and / or 1- (2.
7-Diglycidyloxy-1-naphthyl) -1- (2-
The production method according to claim 3, which is glycidyloxy-1-naphthyl) alkane. 5. A polyfunctional epoxy resin (A) having a naphthalene skeleton / bisphenol epoxy resin (B) = 10/90 to 60/40 in a weight ratio of the respective components.
And the sum of the polyfunctional epoxy resin (A) having a naphthalene skeleton and the bisphenol epoxy resin (B) / bisphenol (C) = 100/20 to 100
/ 70, The manufacturing method of Claim 1, 2, 3 or 4. 6. An epoxy resin composition containing an epoxy resin and a curing agent, wherein a polyfunctional epoxy resin (A) having a naphthalene skeleton as an epoxy resin, a bisphenol type epoxy resin (B) and a bisphenol (C).
An epoxy resin composition comprising an epoxy resin obtained by reacting with as an essential component. 7. The composition according to claim 6, wherein the epoxy resin has a structure in which a polyfunctional epoxy resin (A) having a naphthalene skeleton and a bisphenol epoxy resin (B) are grafted via a bisphenol (C). Stuff. 8. The composition according to claim 6 or 7, wherein the polyfunctional epoxy resin (A) having a naphthalene skeleton has an epoxy equivalent of 130 to 400. 9. The composition according to claim 8, wherein the polyfunctional epoxy resin (A) having a naphthalene skeleton is a trifunctional epoxy resin or a tetrafunctional epoxy resin. 10. The polyfunctional epoxy resin (A) having a naphthalene skeleton is 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane and / or 1-
(2,7-Diglycidyloxy-1-naphthyl) -1-
The composition according to claim 9, which is (2-glycidyloxy-1-naphthyl) alkane. 11. The epoxy resin has a weight ratio of polyfunctional epoxy resin (A) / bisphenol epoxy resin (B) having a naphthalene skeleton = 10/90 to 60/40.
And obtained by reacting the polyfunctional epoxy resin (A) and the bisphenol epoxy resin (B) at a ratio of sum / bisphenol (C) = 100/20 to 100/70. Claims 6, 7, 8, 9 or 10
The composition as described.