JP2001270930A - Polynuclear epoxy compound and thermosetting resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polynuclear epoxy compound which has well balanced heat resistance and toughness, and is excellent in adhesiveness, water resistance, chemical resistance, etc., and a thermosetting resin composition containing the same. SOLUTION: This polynuclear epoxy compound is represented by formula (1) (wherein X and Y are different aromatic rings provided X is an aromatic residue of at least one kind of difunctional aromatic epoxy compound selected from among biphenon, bixylenol, bixphenol, and naphthalene-type diglycidyl ethers and Y is an aromatic residue of at least one kind of dihydric aromatic alcohol selected from among dihydroxynaphthalene and its derivatives, biphenol and its derivatives, bixylenol and its derivatives, bisphenol and its derivatives, and hydroquinone and its derivatives; each M is indepndently grycidyl, methylglycidyl, or H; and n is an integer of 1-20).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel linear polynuclear epoxy compound containing regularly different kinds of aromatic rings, and more particularly to a cured product having excellent heat resistance and electrical insulation. The present invention relates to a novel polynuclear epoxy compound having high hardness and toughness, and further having excellent water resistance and chemical resistance. Further, the present invention relates to a thermosetting resin composition containing the polynuclear epoxy compound.

[0002]

2. Description of the Related Art Epoxy resins typified by bisphenol A type epoxy resins have excellent adhesiveness, heat resistance, chemical resistance, and electrical insulation properties. It is used for applications such as materials, paints and sealants. With respect to this epoxy resin, recently, with the development of the electric industry and the semiconductor industry, for example, improvements in properties such as heat resistance, toughness, water resistance, and chemical resistance are required, and various new epoxy resins are required to satisfy such properties. Compounds have been proposed.

For example, polynuclear epoxy resins such as cresol novolak type epoxy resin and phenol novolak type epoxy resin have been proposed as epoxy compounds having excellent heat resistance. However, although these epoxy resins are excellent in heat resistance, they have a drawback that cracks due to thermal shock are liable to occur due to large shrinkage upon curing, low elongation, and lack of toughness.

On the other hand, as a method capable of solving the above-mentioned disadvantages, a method of blending a rubber component with an epoxy resin (Japanese Patent Application Laid-Open No. 63-199218) and a method of blending two kinds of epoxy resins (Japanese Patent No. 2783116). Gazette), and a copolymerized epoxy resin of a biphenyl skeleton and a bisphenol skeleton (Japanese Patent No. 2789325). However, even in these methods, it has been impossible to provide an epoxy compound which can satisfy both heat resistance and toughness.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has, in addition to well-balanced heat resistance and toughness, adhesion to a substrate, water resistance, and chemical resistance. It is an object of the present invention to provide a polynuclear epoxy compound having excellent electrical insulation properties and good moldability and a thermosetting resin composition containing the same.

[0006]

According to the present invention, there is provided a polynuclear epoxy compound represented by the following general formula (1).

Embedded image (Wherein X and Y represent different aromatic rings, and X is at least one member selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthalene-type diglycidyl ether) Represents an aromatic ring residue of an aromatic epoxy compound having two glycidyl groups in one molecule, Y represents dihydroxynaphthalene and its derivative, biphenol and its derivative, bixylenol and its derivative, bisphenol and its derivative, and hydroquinone And at least one member selected from the group consisting of
M represents a glycidyl group, a methylglycidyl group or a hydrogen atom, independently of each other, and n represents an integer of 1 to 20; Represents )

The above-mentioned polynuclear epoxy compound can be produced by various methods. In particular, a polynuclear epoxy compound obtained by reacting an alcoholic hydroxyl group of an epoxy compound represented by the following general formula (2) with epihalohydrin is preferable. It can be easily manufactured.

Embedded image (In the formula, X, Y, and n have the same meaning as described above.)

According to a more specific preferred embodiment of the present invention, the epoxy compound represented by the following general formula (3) is represented by the following general formula (4) obtained by reacting an alcoholic hydroxyl group with epihalohydrin. A polynuclear epoxy compound is provided.

Embedded image (Wherein, R ¹ , R ² , R ³ , and R ⁴ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
M independently represents a glycidyl group, a methylglycidyl group or a hydrogen atom, and n represents an integer of 1 to 20. )

According to another more preferred embodiment of the present invention, there is provided a compound represented by the following general formula (6) obtained by reacting an alcoholic hydroxyl group of an epoxy compound represented by the following general formula (5) with epihalohydrin. Provided are the polynuclear epoxy compounds represented.

Embedded image (Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ⁹ and R ¹⁰ are the same or different ,
Represents a hydrogen atom, a methyl group or a halogenated methyl group,
M independently represents a glycidyl group, a methylglycidyl group or a hydrogen atom, and n represents an integer of 1 to 20. )

In a preferred embodiment, in the epoxy compounds represented by the general formulas (3), (4), (5) and (6), R ^{1 to} R ⁴ are all hydrogen atoms or R ¹ to R ⁴ R ⁴ is all methyl groups, R ^{5 to} R ⁸ are all hydrogen atoms, R ⁹ and R ¹⁰ are all methyl groups,
When the divalent naphthalene ring residue is 1,5-, 1,6-, 2,6
Or a 2,7-substituted product. In a particularly preferred embodiment, all of R ^{1 to} R ⁴ are methyl groups, and the divalent naphthalene ring residue is 1,5-, 1,6- or 2,6-
Is a substitution.

Further, according to the present invention, there is provided a thermosetting resin composition comprising the polynuclear epoxy compound as described above and a curing agent as essential components.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that a linear epoxy compound containing different aromatic rings represented by X and Y regularly and repeatedly, In particular, a polynuclear epoxy compound obtained by reacting an epihalohydrin with an alcoholic hydroxyl group in an alternating copolymerization type linear epoxy compound in which a biphenyl skeleton and a naphthalene skeleton having a high softening point, or a bisphenol skeleton and a naphthalene skeleton are alternately copolymerized, To provide a cured product having both excellent heat resistance and toughness,
The present invention has been completed. That is, the polynuclear epoxy compound of the present invention, as represented by the general formula (1), contains a different type of aromatic ring regularly and repeatedly, so that a cured product having high mechanical strength can be obtained, and a linear structure and By making it a polynuclear epoxy compound by further reacting with epihalohydrin, a cured product with high heat resistance can be obtained, and excellent adhesion to the substrate, water resistance, chemical resistance, electrical insulation, moldability, etc. A cured product is obtained. In addition, the epoxidation yield by epihalohydrin decreases with an increase in the number average molecular weight of the epoxy compound represented by the general formula (2). By adjusting the amount, alcoholic hydroxyl groups can be epoxidized at a desired ratio.

Hereinafter, the polynuclear epoxy compound of the present invention will be described in detail. First, the epoxy compound represented by the general formula (2) or (3) or (5) will be described. The epoxy compound represented by the general formula (2) includes an aromatic epoxy compound having two glycidyl groups in one molecule (hereinafter, referred to as a bifunctional aromatic epoxy compound) and two phenolic compounds in one molecule. It is easily produced by a method in which an aromatic alcohol having a hydroxyl group (hereinafter, referred to as a bifunctional aromatic alcohol) is used as a raw material and alternately polymerized in a solvent or without a solvent using a known etherification catalyst as described below. be able to.

The bifunctional aromatic epoxy compounds include biphenol-type diglycidyl ethers having an aromatic ring represented by the following formulas (A) to (D), bixylenol-type diglycidyl ethers, bisphenol-type diglycidyl ethers, and the like. At least one bifunctional aromatic epoxy compound selected from the group consisting of naphthalene-type diglycidyl ethers is preferably used. By using such a bifunctional aromatic epoxy compound as one of the monomer components in an alternating copolymer with a bifunctional aromatic alcohol, an epoxy compound having excellent strength, heat resistance, and electrical insulation properties of a cured product can be obtained. can get.

Embedded image (Wherein, R ¹ , R ² , R ³ , and R ⁴ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
R ⁵ , R ⁶ , R ⁷ , R ⁸ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ⁹ and R ¹⁰ are the same or different, a hydrogen atom,
Represents a methyl group or a methyl halide group. )

The biphenol type, the bixylenol type,
As the bisphenol-type or naphthalene-type diglycidyl ether, for example, a biphenol compound, a bixylenol compound, a bisphenol compound or a compound produced from the reaction of dihydroxynaphthalene with epihalohydrin can be used. Commercially available epoxy compounds can also be used. Examples of the biphenol-type diglycidyl ether include “Epicoat YL-6056” (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). Resin Co., Ltd. product name "Epicoat YX-4
000 "and bisphenol A type epoxy compounds such as" Araldite @ 260 "and" Araldite @ 6071 "(trade names) manufactured by Asahi Kasei Epoxy Co., Ltd., and Dainippon Ink & Chemicals, Inc. Bisphenol F type epoxy compounds such as "Epiclon 830S" or Bisphenol S type epoxy compounds such as "Epiclon EXA1514" manufactured by Dainippon Ink and Chemicals, Inc. Dainippon Ink is a naphthalene type diglycidyl ether. "Epiclon HP-4032 (D)" (trade name) manufactured by Chemical Industry Co., Ltd.
And the like, and these can be used alone or in combination of two or more.

The bifunctional aromatic alcohol used in the present invention is characterized by its structure. It may have an aromatic ring in order to enhance heat resistance, and may have a symmetric or rigid structure. it can. Such compounds include, for example, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene,
Dihydroxynaphthalene derivatives such as 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,8-dihydroxynaphthalene; biphenol derivatives such as bixylenol and biphenol; bisphenol A, bisphenol F, bisphenol S, and alkyl-substituted bisphenol. Examples thereof include bisphenol derivatives, hydroquinone derivatives such as hydroquinone, methylhydroquinone, and trimethylhydroquinone. These can be used alone or in combination of two or more.

Among the epoxy compounds represented by the general formula (2), an epoxy compound represented by the general formula (3) or (5) is particularly preferable. The epoxy compound represented by the general formula (3) or (5) includes a biphenyl type and / or a bixylenol type epoxy compound or a bisphenol type epoxy compound, and 1,5-,
At least one of 1,6-, 2,6-, 2,7-substituted products, etc.
The compound can be easily produced by a method of alternately polymerizing in a solvent or without a solvent using an etherification catalyst using a kind of dihydroxynaphthalene as a raw material. As dihydroxynaphthalene, 1,5-, 1,6- having a high softening point
Or 2,6-substituted, especially symmetrical 1,5- and 2,6
-It is preferred to use a substituent.

Examples of the catalyst used for synthesizing the epoxy compounds represented by the above general formulas (2), (3) and (5) include phosphines and alkali metal compounds in which a glycidyl group and a phenolic hydroxyl group react quantitatively. And amines are preferably used alone or in combination. Other catalysts are not preferred because they cause gelation. Examples of the phosphines include trialkyl or triaryl phosphines such as tributyl phosphine and triphenyl phosphine, and salts of these with an acid compound. Examples of the alkali metal compound include hydroxides, halides, alcoholates, and amides of alkali metals such as sodium, lithium, and potassium, and these can be used alone or in combination of two or more. Examples of the amines include aliphatic or aromatic primary, secondary, tertiary, and quaternary amines, and these can be used alone or in combination of two or more. Specific examples of amines include triethanolamine, N, N-dimethylpiperazine, triethylamine, tri-n-propylamine, hexamethylenetetramine, pyridine, tetramethylammonium bromide and the like.

These catalysts are used in an amount of 0.001 to 1 part by mass, preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total amount of the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol.
It is preferably used in the range of 01 to 1 part by mass. The reason for this is that if the amount of the catalyst used is less than 0.001 part by mass, the reaction takes a long time and is not economical, while if it exceeds 1 part by mass, the reaction is conversely difficult due to the rapid reaction. is there. The reaction between the bifunctional aromatic epoxy compound and the bifunctional aromatic alcohol is preferably carried out in the presence of the catalyst in an inert gas stream or air at a temperature in the range of 130 to 180 ° C.

Next, the above-mentioned general formula (1) or (4)
The polynuclear epoxy compound of the present invention represented by (6) will be described. The polynuclear epoxy compound of the present invention represented by the general formula (1) or (4) or (6) may be prepared in a known solvent as described below or in the absence of a solvent in the presence of an alkali metal hydroxide. It can be produced by reacting an alcoholic hydroxyl group in the epoxy compound of the general formula (2) or (3) or (5) with epihalohydrin.

As the epihalohydrin, for example, epichlorohydrin, epibromohydrin, epiiodohydrin, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepiiohydrin and the like are used. In the polynuclear epoxy compound of the present invention represented by the general formulas (1), (4), and (6), the amount of epihalohydrin used is determined by the general formula (2) or (3),
0.1 equivalent to 1 equivalent of the alcoholic hydroxyl group in (5).
What is necessary is just to use 1 time equivalent or more. However, use of an amount exceeding 15 equivalents to 1 equivalent of the hydroxyl group is not preferable because the volumetric efficiency is deteriorated.

As the solvent, known solvents such as aprotic polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide and N, N-dimethylacetamide, and aromatic hydrocarbons such as toluene and xylene are used. Among these, among these aprotic polar solvents,
Particularly, dimethyl sulfoxide is preferred. The amount of the solvent used is preferably 5 to 300% by mass based on the epoxy compound represented by the general formula (2) or (3) or (5). The reason for this is that if it is less than 5% by mass, the reaction between the alcoholic hydroxyl group and the epihalohydrin becomes slow, while
If the content exceeds 00% by mass, the volumetric efficiency becomes poor.

As the alkali metal hydroxide, caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, and caustic soda is particularly preferable. The amount of the alkali metal hydroxide to be used is 0.1 to 1 equivalent of the alcoholic hydroxyl group to be epoxidized in the epoxy compound represented by the general formula (2) or (3) or (5).
It is preferable to use 5 to 2 equivalents.

The reaction temperature between the alcoholic hydroxyl group and the epihalohydrin in the epoxy compound represented by the general formula (2) or (3) or (5) is 20 ° C. or higher, preferably 30 ° C. or higher and 100 ° C. or lower. preferable. The reason for this is that if the reaction temperature is lower than 20 ° C., the reaction rate becomes slow and the time required for the reaction becomes longer, while if the reaction temperature exceeds 100 ° C., many side reactions occur, which is not preferable.

The reaction between the alcoholic hydroxyl group and the epihalohydrin in the epoxy compound represented by the general formula (2) or (3) or (5) is carried out by a quaternary basic salt compound such as dimethyl sulfoxide or a quaternary ammonium salt. It can also be carried out by adjusting the amount of the alkali metal hydroxide in the coexistence of 1,3-dimethyl-2-imidazoline and the alkali metal hydroxide. At that time, alcohols such as methanol and ethanol, toluene,
Aromatic hydrocarbons such as xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, and cyclic ether compounds such as tetrahydrofuran may be used in combination.

Specific examples of quaternary basic salt compounds that can be used include, for example, tetramethylammonium chloride,
Tetrabutylammonium bromide, trimethylbenzylammonium halide, tetramethylammonium bicarbonate, tetramethylammonium benzoate, tetramethylammonium hydroxide,
Examples include tetraethylammonium hydroxide, tetramethylphosphonium hydroxide and the like. However, the above catalysts can be used alone or in combination of two or more. The amount used is determined by the general formula (2)
Or the range of 0.001-2 equivalent is preferable with respect to 1 equivalent of the hydroxyl group of the epoxy compound represented by (3) and (5). More preferably, it is in the range of 0.05 to 0.2 equivalent. When the amount is less than 0.001 equivalent, the effect is hardly exhibited, and the glycidyl ether group of the epoxy compound used as a raw material reacts with the hydroxyl group of the epoxy compound to increase the molecular weight, which is not preferable. On the other hand, even if an amount exceeding 2 equivalents is added, no further improvement in the effect is seen.

The polynuclear epoxy compound of the present invention thus obtained has a number average molecular weight of 400 to 5000, preferably 500 to 3000, more preferably 500 to 20.
00. The epoxy compound has a number average molecular weight of 40
If it is less than 0, the toughness of the obtained cured product is not sufficient. The epoxidation ratio can be appropriately selected according to the purpose (depending on desired physical properties), but is preferably 10 to 100%.
Is suitable, preferably 30 to 90%, more preferably 40 to 80%.

The polynuclear epoxy compound of the present invention is used alone or in combination with another epoxy resin, and is cured by adding a curing agent and, if necessary, a curing accelerator, as in the case of a normal epoxy resin. be able to. As other epoxy resins, bisphenol A type epoxy resin,
Brominated bisphenol A epoxy resin, novolak epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, glycidylamine epoxy resin, hydantoin epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane epoxy Resin, bixylenol type or biphenol type epoxy resin or a mixture thereof, bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, heterocyclic epoxy resin such as triglycidyl isocyanurate,
Diglycidyl phthalate resin, tetraglycidyl xylenoylethane resin, naphthalene group-containing epoxy resin, epoxy resin having a dicyclopentadiene skeleton, glycidyl methacrylate copolymer epoxy resin, copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, etc. Conventionally known various epoxy resins can be used alone or in combination of two or more.

Examples of the curing agent used include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. Specific examples include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, and pyromethylene anhydride. Melitic acid,
Maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolak, and modified products thereof, imidazole, BF ₃ -amine complex, guanidine Derivatives and the like. These curing agents may be used alone or in combination of two or more. Examples of the curing accelerator include imidazoles, tertiary amines, phenols, and metal compounds.

As described above, the epoxy resin composition of the present invention containing the polynuclear epoxy compound, the curing agent, and, if necessary, the curing accelerator, can be easily prepared under the same conditions as conventionally known methods. It can be a cured product of the composition. For example, the polynuclear epoxy compound of the present invention,
A curing agent, a filler and other additives are mixed, and if necessary, kneaded sufficiently using an extruder, a kneader, a roll, or the like to obtain an epoxy resin composition, and the epoxy resin composition is obtained. After being melted, the cured product can be obtained by molding using a casting or transfer molding machine, and further heating to 80 to 200 ° C. Also,
A prepreg obtained by dissolving an epoxy resin composition in a solvent, impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper, and drying by heating is subjected to hot press molding to obtain a cured product. You can also get In addition, in the said epoxy resin composition, various compounding agents, such as an inorganic filler or an organic filler, can be added as needed.

Further, the epoxy resin composition containing the polynuclear epoxy compound of the present invention, the curing agent, and, if necessary, the curing accelerator, etc., can be dissolved in a solvent to adjust the viscosity to a level suitable for the coating method. Examples of such a solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol,
Butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether,
Glycol ethers such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetates such as acetate; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. Is mentioned. These organic solvents can be used alone or as a mixture of two or more.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to the following Examples. In the following, "parts" are all parts by mass unless otherwise specified.

Synthesis Example 1 169 parts of 1,5-dihydroxynaphthalene and an epoxy equivalent of 194 g / eq. Were placed in a flask equipped with a gas inlet tube, a stirrer, a cooling tube and a thermometer. 1,3 parts of 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyldiglycidyl ether were charged under nitrogen atmosphere.
The solution was dissolved at 120 ° C. with stirring. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was lowered to 15%.
The temperature was raised to 0 ° C, and the temperature was maintained at 150 ° C while maintaining the temperature at about 9 ° C.
0 minutes, epoxy equivalent 402g / eq. The epoxy compound (1) was obtained. Next, the temperature in the flask was set to 7
After cooling to 0 ° C. or lower, 1922 parts of epichlorohydrin,
1690 parts of dimethyl sulfoxide was added, and the mixture was stirred at 70 ° C.
The temperature was raised to and maintained. Thereafter, 114 parts of 96% sodium hydroxide was added in portions over 90 minutes. After the addition, the reaction was further performed for 3 hours. After the completion of the reaction, most of the excess epichlorohydrin and dimethyl sulfoxide were removed at 120 ° C., 5
Distillation was performed under reduced pressure of 0 mmHg, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone and washed with water. Thereafter, methyl isobutyl ketone was distilled and recovered from the oil layer, and an epoxy equivalent of 304 g / eq.
The polynuclear epoxy compound (a-1) was obtained. When the obtained polynuclear epoxy compound (a-1) is calculated from the epoxy equivalent, 0.79 of the 1.76 alcoholic hydroxyl groups in the general formula (3) are epoxidized.
Therefore, the epoxidation rate of the alcoholic hydroxyl group is 45%.

Synthesis Example 2 232 parts of 1,5-dihydroxynaphthalene and an epoxy equivalent of 194 g / eq. Were added to a flask equipped with a gas inlet tube, a stirrer, a cooling tube and a thermometer. 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyldiglycidyl ether 1067 parts, and charged under a nitrogen atmosphere,
The solution was dissolved at 120 ° C. with stirring. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was lowered to 15%.
The temperature was raised to 0 ° C, and the temperature was maintained at 150 ° C while maintaining the temperature at about 9 ° C.
0 minute, epoxy equivalent 544 g / eq. The epoxy compound (2) was obtained. Next, the temperature in the flask was set to 7
After cooling to 0 ° C. or less, 1839 parts of epichlorohydrin,
1690 parts of dimethyl sulfoxide was added, and the mixture was stirred at 70 ° C.
The temperature was raised to and maintained. Thereafter, 159 parts of 96% sodium hydroxide were added in portions over 90 minutes. After the addition, the reaction was further performed for 3 hours. After the completion of the reaction, most of the excess epichlorohydrin and dimethyl sulfoxide were removed at 120 ° C., 5
Distillation was performed under reduced pressure of 0 mmHg, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone and washed with water. Thereafter, methyl isobutyl ketone was distilled and recovered from the oil layer, and an epoxy equivalent of 376 g / eq.
The polynuclear epoxy compound (a-2) was obtained. When the obtained polynuclear epoxy compound (a-2) is calculated from the epoxy equivalent, about 1.05 out of 2.28 alcoholic hydroxyl groups in the general formula (3) are epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 46
%. The infrared absorption spectrum (measured using a Fourier transform infrared spectrophotometer FT-IR) of the polynuclear epoxy compound (a-2) obtained in this synthesis example and its magnetic resonance spectrum (solvent CDCl ₃ , reference material TMS) (Tetramethylsilane)) are shown in FIGS. 1 and 2, respectively.

Synthesis Example 3 274 parts of 1,5-dihydroxynaphthalene and an epoxy equivalent of 194 g / eq. Were added to a flask equipped with a gas inlet tube, a stirrer, a cooling tube and a thermometer. 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyldiglycidyl ether (1025 parts) was charged under a nitrogen atmosphere.
The solution was dissolved at 120 ° C. with stirring. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was lowered to 15%.
The temperature was raised to 0 ° C, and the temperature was maintained at 150 ° C while maintaining the temperature at about 9 ° C.
0 minute, epoxy equivalent 723 g / eq. The epoxy compound (3) was obtained. Next, the temperature in the flask was set to 7
After cooling to 0 ° C. or less, 1779 parts of epichlorohydrin,
1690 parts of dimethyl sulfoxide was added, and the mixture was stirred at 70 ° C.
The temperature was raised to and maintained. Thereafter, 192 parts of 96% sodium hydroxide were added in portions over 90 minutes. After the addition, the reaction was further performed for 3 hours. After the completion of the reaction, most of the excess epichlorohydrin and dimethyl sulfoxide were removed at 120 ° C., 5
Distillation was performed under reduced pressure of 0 mmHg, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone and washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer, and an epoxy equivalent of 458 g / eq.
The polynuclear epoxy compound (a-3) was obtained. When the obtained polynuclear epoxy compound (a-3) is calculated from the epoxy equivalent, about 1.32 of the 2.93 alcoholic hydroxyl groups in the general formula (3) are epoxidized. Therefore, the epoxidation ratio of the alcoholic hydroxyl group is 45.
%.

Synthesis Example 4 169 parts of 2,6-dihydroxynaphthalene and an epoxy equivalent of 194 g / eq. Were added to a flask equipped with a gas inlet tube, a stirrer, a cooling tube and a thermometer. 1,3 parts of 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyldiglycidyl ether were charged under nitrogen atmosphere.
The solution was dissolved at 120 ° C. with stirring. Thereafter, 0.65 parts of triphenylphosphine was added, and the temperature in the flask was lowered to 15%.
The temperature was raised to 0 ° C, and the temperature was maintained at 150 ° C while maintaining the temperature at about 9 ° C.
0 minutes, epoxy equivalent 371 g / eq. The epoxy compound (4) was obtained. Next, the temperature in the flask was set to 7
After cooling to 0 ° C. or less, 1952 parts of epichlorohydrin,
1690 parts of dimethyl sulfoxide was added, and the mixture was stirred at 70 ° C.
The temperature was raised to and maintained. Thereafter, 231 parts of 96% sodium hydroxide were added in portions over 90 minutes. After the addition, the reaction was further performed for 3 hours. After the completion of the reaction, most of the excess epichlorohydrin and dimethyl sulfoxide were removed at 120 ° C., 5
Distillation was performed under reduced pressure of 0 mmHg, and the reaction product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone and washed with water. Thereafter, methyl isobutyl ketone was recovered by distillation from the oil layer, and an epoxy equivalent of 267 g / eq.
The polynuclear epoxy compound (a-4) was obtained. When the obtained polynuclear epoxy compound (a-4) is calculated from the epoxy equivalent, about 0.99 of the 1.65 alcoholic hydroxyl groups in the general formula (3) are epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is 60
%.

Synthesis Example 5 An epoxy equivalent of 309 g / e was prepared in the same manner as in Synthesis Example 4 except that the amount of 96% sodium hydroxide used was changed to 58 parts.
q. The polynuclear epoxy compound (a-5) was obtained. In the obtained polynuclear epoxy compound (a-5), when calculated from the epoxy equivalent, about 0.50 of the 1.65 alcoholic hydroxyl groups in the general formula (3) were epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is 30.
%.

Synthesis Example 6 A reaction vessel equipped with a gas inlet pipe, a stirrer, a cooling pipe and a thermometer was charged with a hydroxyl equivalent of 80 g / eq. 224.2 parts of 1,5-dihydroxynaphthalene and an epoxy equivalent of 189 g / eq. Manufactured by Japan Epoxy Resin Co., Ltd. Bisphenol A type epoxy compound (trade name “Epicoat 828”)
1075.8 parts were charged, and stirred under a nitrogen atmosphere.
Dissolved at 10 ° C. Thereafter, 0.65 part of triphenylphosphine was added, the temperature in the reaction vessel was raised to 150 ° C., and the reaction was carried out for about 90 minutes while maintaining the temperature at 150 ° C. to obtain an epoxy equivalent of 452 g / eq. The epoxy compound (6) was obtained. Next, the temperature in the reaction vessel was cooled to 40 ° C., and 1920 parts of epichlorohydrin and 16 parts of toluene were added.
After adding and dissolving 90 parts, 70 parts of tetramethylammonium bromide was added, and the mixture was heated to 60 ° C. and kept under stirring. Thereafter, a 48% aqueous sodium hydroxide solution 36
4 parts were continuously dropped over 60 minutes. After dropping, 6 more
Allowed to react for hours. After completion of the reaction, most of the excess unreacted epichlorohydrin and toluene were recovered by distillation under reduced pressure,
The reaction product containing the by-product salt and toluene was dissolved in methyl isobutyl ketone and washed with water. After separating the organic solvent layer and the aqueous layer, methyl isobutyl ketone was distilled off from the organic solvent layer by distillation under reduced pressure, and an epoxy equivalent of 277 g / eq. The polynuclear epoxy compound (a-6) was obtained. The obtained polynuclear epoxy compound (a-6) was calculated from the epoxy equivalent,
The alcoholic hydroxyl group 1.98 in the general formula (5)
About 1.59 of them are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is about 80%.

Synthesis Example 7 A reaction vessel equipped with a gas inlet pipe, a stirrer, a cooling pipe and a thermometer was charged with a hydroxyl equivalent of 80 g / eq. 219.2 parts of 1,5-dihydroxynaphthalene and an epoxy equivalent of 192 g / eq. Manufactured by Japan Epoxy Resin Co., Ltd. Bixylenol epoxy compound (trade name “Epicoat YX400”)
0 "), and dissolved at 110 ° C. under stirring in a nitrogen atmosphere. Thereafter, 0.65 part of triphenylphosphine was added, and the temperature in the reaction vessel was increased to 150 ° C.
C., and while maintaining the temperature at 150.degree.
For 451 g / eq. Of epoxy equivalent. The epoxy compound (7) was obtained. Next, the temperature in the reaction vessel was set to 40
After cooling to ℃, 1899 parts of epichlorohydrin and 1690 parts of toluene were added and dissolved, 69 parts of tetramethylammonium bromide was added, and the temperature was raised to 60 ° C with stirring and maintained. Thereafter, 360 parts of a 48% aqueous sodium hydroxide solution was continuously dropped over 60 minutes. After the addition, the reaction was further performed for 6 hours. After completion of the reaction, the excess unreacted epichlorohydrin and most of toluene were recovered by distillation under reduced pressure, and the reaction product containing by-product salts and toluene was dissolved in methyl isobutyl ketone and washed with water. After separating the organic solvent layer and the aqueous layer, methyl isobutyl ketone was distilled off from the organic solvent layer by distillation under reduced pressure, and an epoxy equivalent of 278 g / eq.
The polynuclear epoxy compound (a-7) was obtained. When the obtained polynuclear epoxy compound (a-7) was calculated from the epoxy equivalent, about 1.56 of the 1.95 alcoholic hydroxyl groups in the general formula (3) were epoxidized. Therefore, the epoxidation rate of alcoholic hydroxyl groups is about 8
0%.

Examples 1 to 7 and Comparative Examples 1 to 4 In Examples 1 to 7, the polynuclear epoxy compounds (a-1) to (a-7) synthesized in Synthesis Examples 1 to 7 were used, respectively. In Examples 1 to 4, the epoxy compounds (1) to (4) obtained in Synthesis Examples 1 to 4 were used, respectively, and phenol resin (phenol novolak, hydroxyl equivalent 106 g / eq.) At the ratio shown in Table 1 was cured. Accelerator (2-
Phenyl-4,5-dihydroxymethylimidazole,
PDMI) and a solvent (carbitol acetate) were mixed and kneaded with a three-roll mill to obtain a thermosetting resin composition.

[0041]

[Table 1]

The compositions of the above Examples and Comparative Examples were heated to 80 ° C.
And then cured at 180 ° C for 1 hour, and measured the glass transition point, tensile strength, elongation, tensile elasticity, water absorption, electrical insulation, pencil hardness, adhesion, acid resistance And the alkali resistance was evaluated. Each physical property was evaluated by the following methods.

<Glass transition point>: The compositions of the above Examples and Comparative Examples were applied to a Teflon (registered trademark) plate which had been washed and dried in advance by a screen printing method, and was heated to 80 ° C. in a hot air circulation drying oven. For 40 minutes. After cooling this to room temperature, it was exposed under the condition of an exposure amount of 500 mJ / cm ² , and was cured at 180 ° C. for 60 minutes in a hot air circulation type drying furnace.
After cooling to room temperature, the cured coating film was peeled off from the Teflon plate to obtain an evaluation sample. The glass transition point of this evaluation sample was measured by the DMA method.

<Tensile strength (tensile breaking strength), elongation (tensile breaking elongation), tensile elastic modulus>: Determined in accordance with JIS K7127.

<Water absorption, pencil hardness>: JIS K54
00 was determined.

<Adhesion>: Determined visually according to JIS D0202. The criteria are as follows. ：: no peeling was observed at all △: slight peeling ×: completely peeled

<Electrical Insulation Property>: The compositions of the above Examples and Comparative Examples were applied to the entire surface of a comb-type electrode B coupon of IPC B-25 using a roll coater manufactured by Pilot Seiko Co., Ltd. For 30 minutes and at 180 ° C. for 1 hour to prepare an evaluation substrate. DC5
A bias voltage of 00 V was applied, and the insulation resistance was measured.

<Acid resistance test>: The same evaluation substrate as used for electrical insulation was immersed in a 10% by volume sulfuric acid aqueous solution at 20 ° C. for 30 minutes, taken out, and the state and adhesion of the coating film were comprehensively evaluated. did. The criteria are as follows. ：: no change observed Δ: slight change ×: swelling or swelling-off of coating film

<Alkali Resistance Test>: The test was evaluated in the same manner as the acid resistance test except that the 10% by volume aqueous sulfuric acid solution was changed to a 10% by volume aqueous sodium hydroxide solution.

Table 2 shows the obtained results.

[Table 2]

As is clear from the results shown in Table 2, the cured product obtained from the polynuclear epoxy compound of the present invention has a high glass transition point, excellent mechanical strength, water absorption, adhesion, and electrical insulation. It has excellent properties such as resistance, hardness and chemical resistance. On the other hand, the cured product obtained from the aromatic epoxy compound of the comparative example had a low glass transition point and was inferior in water absorption, hardness and the like.

[0052]

As described above, the epoxy compound of the present invention is a linear polynuclear epoxy compound containing regularly different kinds of aromatic rings, particularly a biphenyl skeleton and a naphthalene skeleton having a high softening point, or a bisphenol skeleton. Since it is a linear polynuclear epoxy compound of an alternating copolymerization type in which a naphthalene skeleton is alternately copolymerized, heat resistance and toughness can be balanced at a high level, and it has excellent adhesion to a substrate, A cured product excellent in chemical properties, electrical insulation properties, etc. can be obtained. Further, the composition containing the polynuclear epoxy compound of the present invention together with a curing agent is heat-curable, and since the cured product has excellent characteristics as described above, various resist agents, adhesives, casting agents , Laminates, paints,
It can be used advantageously for applications such as sealants.

[Brief description of the drawings]

FIG. 1 shows the polynuclear epoxy compound (a) obtained in Synthesis Example 2
2 is an infrared absorption spectrum of 2).

FIG. 2 shows the polynuclear epoxy compound (a-
It is a nuclear magnetic resonance spectrum of 2).

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tadahiro Sanyu No. 388, Ookura, Oaza, Arashiyama-cho, Hiki-gun, Saitama Prefecture Taiyo Ink Manufacturing Co., Ltd. Ban Tai Ink Manufacturing Co., Ltd. Arashiyama Office

Claims (9)

[Claims] 1. A polynuclear epoxy compound represented by the following general formula (1). Embedded image (Wherein X and Y represent different aromatic rings, and X is at least one member selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthalene-type diglycidyl ether) Represents an aromatic ring residue of an aromatic epoxy compound having two glycidyl groups in one molecule, Y represents dihydroxynaphthalene and its derivative, biphenol and its derivative, bixylenol and its derivative, bisphenol and its derivative, and hydroquinone And at least one member selected from the group consisting of
M represents a glycidyl group, a methylglycidyl group or a hydrogen atom, independently of each other, and n represents an integer of 1 to 20; Represents ) 2. The polynuclear epoxy compound according to claim 1, wherein the polynuclear epoxy compound is obtained by reacting an alcoholic hydroxyl group of an epoxy compound represented by the following general formula (2) with epihalohydrin. Embedded image (Wherein X and Y represent different aromatic rings, and X is at least one member selected from the group consisting of biphenol-type diglycidyl ether, bixylenol-type diglycidyl ether, bisphenol-type diglycidyl ether, and naphthalene-type diglycidyl ether) Represents an aromatic ring residue of an aromatic epoxy compound having two glycidyl groups in one molecule, Y represents dihydroxynaphthalene and its derivative, biphenol and its derivative, bixylenol and its derivative, bisphenol and its derivative, and hydroquinone And at least one member selected from the group consisting of
It represents an aromatic ring residue of an aromatic alcohol having two phenolic hydroxyl groups in one species molecule, and n represents an integer of 1 to 20. ) 3. A polynuclear epoxy compound represented by the following general formula (4) obtained by reacting an alcoholic hydroxyl group of an epoxy compound represented by the following general formula (3) with epihalohydrin. Embedded image (Wherein, R ¹ , R ² , R ³ , and R ⁴ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
M independently represents a glycidyl group, a methylglycidyl group or a hydrogen atom, and n represents an integer of 1 to 20. ) 4. In the general formulas (3) and (4),
Polynuclear epoxy compound according to claim 3, R ¹ to R ⁴ is wherein all hydrogen atoms. 5. In the general formulas (3) and (4),
Polynuclear epoxy compound according to claim 3, R ¹ to R ⁴ is characterized in that all are methyl groups. 6. A polynuclear epoxy compound represented by the following general formula (6) obtained by reacting an alcoholic hydroxyl group of an epoxy compound represented by the following general formula (5) with epihalohydrin. Embedded image (Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ⁹ and R ¹⁰ are the same or different ,
Represents a hydrogen atom, a methyl group or a halogenated methyl group,
M independently represents a glycidyl group, a methylglycidyl group or a hydrogen atom, and n represents an integer of 1 to 20. ) 7. In the general formulas (5) and (6),
R ⁵ to R ⁸ are all hydrogen atoms, polynuclear epoxy compound according to claim 6, wherein R ⁹ and R ¹⁰ are all methyl groups. 8. In the general formulas (3), (4), (5) and (6), the divalent naphthalene ring residue is 1,5-,
The polynuclear epoxy compound according to any one of claims 3 to 7, which is a 1,6-, 2,6- or 2,7-substituted product. 9. A thermosetting resin composition comprising the polynuclear epoxy compound according to any one of claims 1 to 8 and a curing agent as essential components.