JP2017186453A - Epoxy compound, epoxy compound-containing composition, and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy compound excellent in toughness, an epoxy compound-containing composition, and a cured product.SOLUTION: There are provided: an epoxy compound which is a reaction product of a bifunctional epoxy compound (A), a bifunctional phenolic compound (B), and a tri- or higher functional epoxy compound (C1) and/or a tri- or higher functional phenolic compound (C2) and has an epoxy equivalent of more than 800 g/eq and 200,000 g/eq or less; an epoxy compound-containing composition containing the epoxy compound and a curing agent; and a cured product of the epoxy compound-containing composition.SELECTED DRAWING: None

Description

  The present invention relates to an epoxy compound having excellent toughness. The present invention also relates to an epoxy compound-containing composition and a cured product obtained by using the epoxy compound.

  Epoxy compounds are widely used in the fields of paints, civil engineering, adhesion, electrical materials and the like because they are excellent in heat resistance, adhesion, chemical resistance, water resistance, mechanical strength, electrical properties, and the like. In recent years, various studies have been made to improve the toughness of epoxy resins, but conventional linear epoxy resins have insufficient toughness. Patent Document 1 describes an epoxy compound having a branched structure, but has a low epoxy equivalent and insufficient toughness.

JP 2014-24907 A

  The present invention has been made in view of the above problems of the prior art. That is, the subject of this invention is providing the epoxy compound excellent in toughness, an epoxy compound containing composition, and hardened | cured material.

  As a result of diligent studies to solve the above problems, the present inventors obtained a reaction between a bifunctional epoxy compound, a bifunctional phenolic compound, a trifunctional or higher functional epoxy compound and / or a trifunctional or higher functional phenolic compound. Thus, the inventors have found that an epoxy compound having an epoxy equivalent of more than 800 g / equivalent and not more than 200,000 g / equivalent can solve the above problems, and has completed the invention. That is, the gist of the present invention resides in the following [1] to [6].

[1] A reaction product of a bifunctional epoxy compound (A), a bifunctional phenolic compound (B), a trifunctional or higher functional epoxy compound (C1) and / or a trifunctional or higher functional phenolic compound (C2). An epoxy compound having an epoxy equivalent of more than 800 g / equivalent and not more than 200,000 g / equivalent.
[2] Trifunctional or higher occupying the total weight of the bifunctional epoxy compound (A), the bifunctional phenolic compound (B), the trifunctional or higher functional epoxy compound (C1) and / or the trifunctional or higher functional phenolic compound (C2) The epoxy compound according to [1], wherein the weight ratio of the epoxy compound (C1) and / or the trifunctional or higher functional phenol compound (C2) is 30% or less.
[3] An epoxy compound-containing composition comprising the epoxy compound according to [1] or [2] and a curing agent.
[4] The epoxy compound-containing composition according to [3], including 0.1 to 1000 parts by weight of a curing agent with respect to 100 parts by weight of the epoxy compound.
[5] The curing agent is composed of polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, mercaptan compounds, cationic polymerization initiators, and organic phosphines. The epoxy compound-containing composition according to [3] or [4], which is at least one selected from the group.
[6] A cured product obtained by curing the epoxy compound-containing composition according to any one of [3] to [5].

According to the present invention, an epoxy compound excellent in toughness and an epoxy compound-containing composition are provided.
Due to these features, the epoxy compound, the epoxy compound-containing composition and the cured product of the present invention can be applied in the fields of electrical / electronic materials, FRP (fiber reinforced resin), adhesives, paints, and the like. is there.

  Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following descriptions, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In this specification, when a value or physical property value is put before and after using “to”, the value before and after that is used.

[Epoxy compound]
The epoxy compound of the present invention is obtained by reacting a bifunctional epoxy compound (A), a bifunctional phenolic compound (B), a trifunctional or higher functional epoxy compound (C1) and / or a trifunctional or higher functional phenolic compound (C2). It is a compound obtained.

  The epoxy compound of this invention has the effect that it is excellent in toughness. This is because the epoxy compound of the present invention has a branched structure in the molecule, so that entanglement between molecules occurs, and stress applied from the outside is dispersed throughout, making it difficult to break down. Conceivable. Moreover, since the epoxy compound of this invention has a large epoxy equivalent compared with the conventional branched epoxy compound, it is thought that toughness is further improved.

[Bifunctional epoxy compound (A)]
The bifunctional epoxy compound (A) used in the present invention is a compound having two epoxy groups in the molecule.

  Examples of the bifunctional epoxy compound (A) used in the present invention include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol Z diglycidyl ether, bisphenol S diglycidyl ether, and bisphenol AD diglycidyl ether. Bisphenol acetophenone diglycidyl ether, bisphenol trimethylcyclohexane diglycidyl ether, bisphenol fluorenediglycidyl ether, tetramethyl bisphenol A diglycidyl ether, tetramethyl bisphenol F diglycidyl ether, tetra-t-butyl bisphenol A diglycidyl ether, tetramethyl bisphenol Bisphenols such as S-diglycidyl ether Glycidyl ethers; biphenol diglycidyl ethers such as biphenol diglycidyl ether, tetramethylbiphenol diglycidyl ether, dimethylbiphenol diglycidyl ether, tetra-t-butylbiphenol diglycidyl ether; hydroquinone diglycidyl ether, dihydroanthracene diglycidyl ether Benzenediol diglycidyl ethers such as methyl hydroquinone diglycidyl ether, dibutyl hydroquinone diglycidyl ether, resorcin diglycidyl ether, methyl resorcin diglycidyl ether; dihydroanthrahydroquinone diglycidyl ether, dihydroxydiphenyl ether diglycidyl ether, thiodiphenol di Glycidyl ether, dihydro Aromatic diglycidyl ethers such as sinaphthalene diglycidyl ether; diglycidyl selected from the bisphenol diglycidyl ethers, biphenol diglycidyl ethers, benzenediol diglycidyl ethers and aromatic diglycidyl ethers Epoxy compounds in which hydrogen is added to the aromatic ring of ethers; various types such as adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, biphenyldicarboxylic acid, dimer acid, etc. Epoxy resins produced from carboxylic acids of the above and epihalohydrins; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene Lenglycol diglycidyl ether, 1,4-butanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, 1,5-pentanediol diglycidyl ether, polypentamethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl Ether, polyhexamethylene glycol diglycidyl ether, 1,7-heptanediol diglycidyl ether, polyheptamethylene glycol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2, (Poly) alkylene glycol diglycidyl ethers consisting only of a chain structure such as 2-dimethyl-1,3-propanediol diglycidyl ether; 1,4-cyclohex Alkylene glycol diglycidyl ethers having a cyclic structure such as Nji methanol diglycidyl ether.

  Of these, bisphenol diglycidyl ethers and biphenol diglycidyl ethers are preferred.

  The bifunctional epoxy compound (A) mentioned above can be used alone or in combination of two or more. A preferred combination is a combination selected from bisphenol diglycidyl ethers and biphenol diglycidyl ethers.

[Bifunctional phenolic compound (B)]
The bifunctional phenol compound (B) used in the present invention is a compound having two hydroxyl groups bonded to an aromatic ring in the molecule.

  Examples of the bifunctional phenol compound (B) used in the present invention include bisphenol A, bisphenol F, bisphenol E, bisphenol Z, bisphenol S, bisphenol AD, bisphenol acetophenone, bisphenol trimethylcyclohexane, bisphenol fluorene, tetramethyl bisphenol A, tetra Bisphenols such as methyl bisphenol F, tetra-t-butyl bisphenol A, tetramethyl bisphenol S, 4,4 ′-(3,3,5-trimethyl-1,1-cyclohexanediyl) bis (phenol); biphenol, tetra Biphenols such as methylbiphenol, dimethylbiphenol, tetra-t-butylbiphenol; hydroquinone, methylhydroquinone, dibutylhydroxyl Benzenediols such as benzene, resorcin, and methylresorcin (herein, “benzenediols” are compounds having one benzene ring, in which two hydroxyl groups are directly bonded to the benzene ring. Dihydroanthrahydroquinones; dihydroxydiphenyl ethers such as dihydroxydiphenyl ether; thiodiphenols such as thiodiphenol; dihydroxynaphthalenes such as dihydroxynaphthalene; dihydroxystilbenes such as dihydroxystilbene.

Of these, bisphenols and biphenols are preferred.
The bifunctional phenol compound (B) mentioned above can be used alone or in combination of two or more. A preferred combination is a combination selected from bisphenols and biphenols.

[Trifunctional or higher functional epoxy compound (C1)]
The trifunctional or higher functional epoxy compound (C1) used in the present invention is a compound having three or more epoxy groups in the molecule.

  Examples of the trifunctional or higher functional epoxy compound used in the present invention include the following. In the following examples, “......... type epoxy resin” refers to a hydroxyl group substituted with a glycidyl ether group. That is, for example, "4,4 ', 4" -trihydroxytriphenylmethane type epoxy resin "is obtained by replacing the hydroxyl group of" 4,4', 4 "-trihydroxytriphenylmethane" with glycidyl ether. Sure.

  α, α-bis (4-hydroxyphenyl) -4- (4-hydroxy-α, α-dimethylbenzyl) -ethylbenzene type epoxy resin, 4,4 ′, 4 ″ -trihydroxytriphenylmethane type epoxy resin, 4 , 4 ′, 4 ″ -Ethyridinetris (2-methylphenol) type epoxy resin, 4,4 ′-(2-hydroxybenzylidene) bis (2,3,6-trimethylphenol) type epoxy resin, 2,3, 4-trihydroxydiphenylmethane type epoxy resin, 2,4,6-tris (4-hydroxyphenyl) -1,3,5-triazine type epoxy resin, 1,3,5-tris (4-hydroxyphenyl) benzene type epoxy Resin, 1,1,1-tris (4-hydroxyphenyl) ethane type epoxy resin, 4,4 ′-[1- [4- [1- (4-hydro Ci-3,5-dimethylphenyl) -1-methylethyl] phenyl] ethylidene] bis (2-methylphenol) type epoxy resin, 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4- Trifunctional epoxy resins such as methylphenol type epoxy resin; 2,2′-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol type epoxy resin, 4- [bis (4-hydroxy-3 -Methylphenyl) methyl] benzene-1,2-diol type epoxy resin, 1,1,2,2-tetrakis (p-hydroxyphenyl) ethane type epoxy resin, α, α, α ′, α ″ -tetrakis (4 Tetrafunctional epoxy resins such as -hydroxyphenyl) -p-xylene type epoxy resin; 2,4,6-tris [(4-hydroxyphenyl) methyl] Pentafunctional epoxy resins such as 1,3-benzenediol type epoxy resins; epoxy compounds produced from various amine compounds such as diaminodiphenylmethane, aminophenol, xylenediamine, and epihalohydrin; produced from aliphatic polyols and epihalohydrin Epoxy compounds; phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolak type epoxy resins, naphthol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, phenol modified xylene type epoxy resins, Polyvalents obtained by condensation reactions of these various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal. Phenol resins, polyfunctional epoxy resins of epoxy resin or the like using a co-condensed resin various phenolic compounds of such like of the heavy oil or pitch such phenols with formaldehydes, and the like.

  Of these, trifunctional epoxy resins are preferred.

  The above trifunctional or higher functional epoxy compounds (C1) can be used alone or in combination of two or more. A preferred combination is a combination of trifunctional epoxy resins and polyfunctional epoxy resins having four or more functional groups.

[Trifunctional or higher functional phenolic compound (C2)]
The trifunctional or higher functional phenol compound (C2) used in the present invention is a compound having three or more hydroxyl groups bonded to an aromatic ring in the molecule.

  Examples of the trifunctional or higher functional phenol compound (C2) used in the present invention include α, α-bis (4-hydroxyphenyl) -4- (4-hydroxy-α, α-dimethylbenzyl) -ethylbenzene, 4,4. ', 4 "-trihydroxytriphenylmethane, 4,4', 4" -ethylidinetris (2-methylphenol), 4,4 '-(2-hydroxybenzylidene) bis (2,3,6-trimethylphenol) ), 2,3,4-trihydroxydiphenylmethane, 2,4,6-tris (4-hydroxyphenyl) -1,3,5-triazine, 1,3,5-tris (4-hydroxyphenyl) benzene, 1 , 1,1-tris (4-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [1- (4-hydroxy-3,5-dimethylphenyl) -1-methyl Trifunctional phenolic compounds such as til] phenyl] ethylidene] bis (2-methylphenol), 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenol; 2,2′- Methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol, 4- [bis (4-hydroxy-3-methylphenyl) methyl] benzene-1,2-diol, 1,1,2,2 Tetrafunctional phenolic compounds such as tetrakis (p-hydroxyphenyl) ethane, α, α, α ′, α ″ -tetrakis (4-hydroxyphenyl) -p-xylene; 2,4,6-tris [(4 -Hydroxyphenyl) methyl] -1,3-benzenediol and other pentafunctional phenolic compounds, phenol novolak resins, cresol novolak resins, Bisphenol-based novolak resins such as phenol A novolac resin; various phenol resins such as naphthol novolak resin, phenol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, phenol biphenylene resin, phenol-modified xylene resin, and various of these Polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, etc., co-condensation resin of heavy oil or pitches with phenols and formaldehyde, etc. Examples include polyfunctional phenolic compounds.

  Of these, trifunctional phenolic compounds are preferred.

  The above-described trifunctional or higher functional phenolic compounds (C2) can be used alone or in combination of two or more. A preferred combination is a combination of a trifunctional phenolic compound and a polyfunctional phenolic compound having 4 or more functional groups.

[Bifunctional epoxy compound (A), bifunctional phenolic compound (B), trifunctional or higher functional epoxy compound (C1), trifunctional or higher functional phenolic compound (C2)]
Mixing ratio of bifunctional epoxy compound (A), bifunctional phenolic compound (B), trifunctional or higher epoxy compound (C1), trifunctional or higher functional phenolic compound (C2) used in the production of the epoxy compound of the present invention Is preferably a compounding ratio at which the theoretical epoxy equivalent is 800 g / equivalent or more, more preferably a compounding ratio at 900 g / equivalent or more, and preferably a compounding ratio at 1,000 g / equivalent or more. It is particularly preferable in terms of ensuring a high toughness.

  In addition, the bifunctional epoxy compound (A), bifunctional phenolic compound (B), trifunctional or higher functional epoxy compound (C1), trifunctional or higher functional phenolic compound (C2) used for the production of the epoxy compound of the present invention. The blending ratio is preferably a blending ratio at which the theoretical epoxy equivalent is 200,000 g / equivalent or less, more preferably a blending ratio at which 150,000 g / equivalent or less is used, and a blending that is 100,000 g / equivalent or less. The ratio is particularly preferable from the viewpoint of ensuring compatibility with other materials.

Here, the theoretical epoxy equivalent refers to all the bifunctional epoxy compounds (A), bifunctional phenolic compounds (B), trifunctional or higher functional epoxy compounds (C1), and trifunctional or higher functional phenolic compounds (C2). It means the epoxy equivalent of the reaction product when the epoxy group and the phenolic hydroxyl group are reacted at 1: 1.
In the present invention, “epoxy equivalent” is defined as “mass of an epoxy compound containing one equivalent of an epoxy group” and can be measured according to JIS K7236.

[Content of trifunctional or higher component]
The bifunctional epoxy compound (A), the bifunctional phenolic compound (B), the trifunctional or higher functional epoxy compound (C1) and / or the trifunctional or higher functional phenolic compound (C2) used in the production of the epoxy compound of the present invention. Weight ratio of trifunctional or higher functional epoxy compound (C1) and / or trifunctional or higher functional phenolic compound (C2) in the total weight (hereinafter referred to as “(C) component in components (A) to (C)”) Is preferably 30% or less. When the proportion of the component (C) in the components (A) to (C) is 30% by weight or less, an epoxy compound having excellent toughness can be obtained. The proportion of the component (C) in the components (A) to (C) is more preferably 15% by weight or less, particularly preferably 8% by weight or less. However, if the proportion of the component (C) in the components (A) to (C) is too small, a branched structure or a crosslinked structure cannot be introduced into the resulting epoxy compound, and the desired toughness cannot be obtained. Therefore, the proportion of the component (C) in the components (A) to (C) is preferably 0.01% by weight or more, particularly 0.05% by weight or more, and particularly preferably 0.1% by weight or more.

[Method for producing epoxy compound]
The epoxy compound of the present invention comprises the aforementioned bifunctional epoxy compound (A), bifunctional phenolic compound (B), trifunctional or higher functional epoxy compound (C1) and / or trifunctional or higher functional phenolic compound (C2). It is produced by reacting at a suitable blending ratio as described above.

<Catalyst (D)>
A catalyst (D) may be used in the reaction step for producing the epoxy compound of the present invention. The catalyst (D) is not particularly limited as long as it is usually used as an advanced catalyst.

  Examples of the catalyst (D) include alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like.

  Specific examples of the alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide; alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride; sodium Examples thereof include alkali metal alkoxides such as methoxide and sodium ethoxide; alkali metal hydrides such as alkali metal phenoxide, sodium hydride and lithium hydride; alkali metal salts of organic acids such as sodium acetate and sodium stearate.

  Specific examples of the organic phosphorus compound include triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri-2,4-xylylphosphine, tri-2,5- Xylylphosphine, tri-3,5-xylylphosphine, tris (p-tert-butylphenyl) phosphine, tris (p-methoxyphenyl) phosphine, tris (p-tert-butoxyphenyl) phosphine, tri (pn) -Octylphenyl) phosphine, tri (pn-nonylphenyl) phosphine, triallylphosphine, tributylphosphine, trimethylphosphine, tribenzylphosphine, triisobutylphosphine, tri-tert-butylphosphine, tri-n-octylphosphine, tri Cyclohex Ruphosphine, tri-n-propylphosphine, di-t-butylmethylphosphine, tri-n-butylphosphine, cyclohexyldi-tert-butylphosphine, diethylphenylphosphine, di-n-butylphenylphosphine, di-tert-butyl Phenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, isopropyldiphenylphosphine, cyclohexyldiphenylphosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, Trimethylbenzylphosphonium chloride, Limethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, triphenyl Examples thereof include phenylbenzylphosphonium bromide.

  Specific examples of the tertiary amines include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine and the like.

  Specific examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, Tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride Id, and phenyl trimethylammonium chloride and the like.

  Specific examples of cyclic amines include 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5-nonene.

  Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.

  The catalyst (D) mentioned above may be used alone or in combination of two or more.

  When using the catalyst (D), the amount used is usually 10,000 ppm by weight or less, for example, 10 to 5000 ppm by weight, based on the total amount used of the bifunctional epoxy compound (A) and the trifunctional or higher functional epoxy compound (C1). It is preferable to do.

<Reaction solvent (E)>
In the reaction step for producing the epoxy compound of the present invention, a reaction solvent (E) may be used. The reaction solvent (E) may be any solvent as long as it dissolves the raw material, but is usually an organic solvent.

  Examples of the organic solvent include aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, and the like. Specific examples of the aromatic solvent include benzene, toluene, xylene and the like. Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, and acetylacetone. Specific examples of the amide solvent include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like. Specific examples of the glycol ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. Examples include mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate and the like.

The reaction solvent (E) mentioned above may be used alone or in combination of two or more.
When a highly viscous product is produced during the reaction, the reaction can be continued by further adding a reaction solvent (E).

[Reaction conditions]
The reaction between the bifunctional epoxy compound (A), the bifunctional phenolic compound (B), the trifunctional or higher functional epoxy compound (C1) and / or the trifunctional or higher functional phenolic compound (C2) is performed under normal pressure, pressure, It can be performed under any conditions of reduced pressure.

  Moreover, reaction temperature is 80-240 degreeC normally, Preferably it is 100-220 degreeC, More preferably, it is 120 degreeC-200. It is preferable that the reaction temperature is equal to or higher than the above lower limit because the reaction can easily proceed. Moreover, side reaction is hard to advance that reaction temperature is below the said upper limit, and it is preferable from a viewpoint of obtaining a highly purified epoxy compound.

  Although it does not specifically limit as reaction time, Usually, it is 0.5 to 24 hours, Preferably it is 1 to 22 hours, More preferably, it is 1.5 to 20 hours. When the reaction time is not more than the above upper limit, it is preferable from the viewpoint of improving production efficiency, and when the reaction time is not less than the above lower limit, it is preferable from the viewpoint that unreacted components can be reduced.

<Diluted solvent (F)>
The epoxy compound of the present invention may be mixed with a diluting solvent (F) after completion of the reaction to adjust the solid content concentration. As the diluting solvent (F), any solvent can be used as long as it usually dissolves an epoxy compound, but it is usually an organic solvent. Specific examples of the organic solvent can be the same as those mentioned as the reaction solvent (E).

  In the present invention, the terms “solvent” and “solvent” are used as the “solvent” when used in the reaction of the epoxy compound, and as the “solvent” as used after the completion of the reaction. Alternatively, different types may be used.

[Epoxy equivalent]
The epoxy equivalent of the epoxy compound of the present invention needs to exceed 800 g / equivalent. Thereby, toughness can be made favorable. The epoxy equivalent of the epoxy compound of this invention becomes like this. Preferably it is 820 g / equivalent or more, More preferably, it is 900 g / equivalent or more, More preferably, it is 1,000 g / equivalent or more. Thereby, the toughness can be further improved.
The upper limit of the epoxy equivalent of the epoxy compound of the present invention is not particularly limited, but is 200,000 g / equivalent, preferably 150,000 g / equivalent from the viewpoint of compatibility with other materials. More preferably, it is 1,000 g / equivalent.

[Weight average molecular weight (Mw)]
The weight average molecular weight (Mw) of the epoxy compound of the present invention is preferably 6,000 or more, more preferably 7,000 or more, and particularly preferably 8,000 or more from the viewpoint of improving toughness. The weight average molecular weight (Mw) of the epoxy compound of the present invention is preferably 200,000 or less, more preferably 150,000 or less, and 100,000 or less being compatible with other materials. From the viewpoint of

  In addition, the weight average molecular weight of an epoxy compound can be measured by the gel permeation chromatography method (GPC method). An example of a more detailed method will be described in the examples described later.

[Epoxy compound-containing composition]
The epoxy compound-containing composition of the present invention contains at least the above-described epoxy compound of the present invention and a curing agent. Moreover, the epoxy compound containing composition of this invention can mix | blend suitably another epoxy compound, a hardening accelerator, another component, etc. as needed.

[Curing agent]
The curing agent used in the epoxy compound-containing composition of the present invention is a substance that contributes to a crosslinking reaction and / or chain length extension reaction between epoxy groups of the epoxy compound. In the present invention, even if what is usually called a “curing accelerator” is a substance that contributes to a crosslinking reaction and / or chain extension reaction between epoxy groups of an epoxy compound, it is regarded as a curing agent. To do.

The content of the curing agent in the epoxy compound-containing composition of the present invention is preferably 0.1 to 1000 parts by weight, more preferably 100 parts by weight or less, with respect to 100 parts by weight of the epoxy compound of the present invention. The amount is preferably 80 parts by weight or less, and particularly preferably 60 parts by weight or less.
Moreover, in the epoxy compound containing composition of this invention, when other epoxy compounds mentioned later other than the epoxy compound of this invention are contained, content of a hardening | curing agent is with respect to 100 weight part of all the epoxy compound components as solid content. It is preferably 0.1 to 1000 parts by weight, more preferably 100 parts by weight or less, still more preferably 80 parts by weight or less, and particularly preferably 60 parts by weight or less.
More preferable amounts of the curing agent are as described below depending on the type of the curing agent.

  In the present invention, the “solid content” means a component excluding a solvent, and includes not only a solid epoxy compound but also a semi-solid or viscous liquid material. Further, the “total epoxy compound component” means the total of the epoxy compound of the present invention and other epoxy compounds described later.

  In the epoxy compound-containing composition of the present invention, polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, cationic polymerization initiators, and organic phosphines are used as curing agents. Preferably, at least one of the group consisting of:

  Examples of polyfunctional phenols include bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, tetrabromobisphenol A, bisphenols, 4,4′-biphenol, 3,3 ′, 5, Biphenols such as 5′-tetramethyl-4,4′-biphenol; catechol, resorcin, hydroquinone, dihydroxynaphthalene; and hydrogen atoms bonded to the aromatic ring of these compounds are halogen groups, alkyl groups, aryl groups, ethers And those substituted with a non-interfering substituent such as an organic substituent containing a hetero element such as a group, an ester group, sulfur, phosphorus or silicon.

  Furthermore, novolaks and resoles which are polycondensates of monofunctional phenols such as phenols, phenols, cresols, alkylphenols, and aldehydes can be used.

  Examples of polyisocyanate compounds include tolylene diisocyanate, methylcyclohexane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, trimethylhexamethylene diisocyanate, And polyisocyanate compounds such as lysine triisocyanate. Furthermore, the polyisocyanate compound obtained by the reaction of these polyisocyanate compounds with a compound having at least two active hydrogen atoms such as amino group, hydroxyl group, carboxyl group and water, or 3 to 5 amount of the above polyisocyanate compound The body etc. can be mentioned.

  Examples of amine compounds include aliphatic primary, secondary, tertiary amines, aromatic primary, secondary, tertiary amines, cyclic amines, guanidines, urea derivatives, and the like. Ethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, metaxylenediamine, dicyandiamide, 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5-nonene, dimethyl Examples include urea and guanylurea.

  Examples of the acid anhydride compound include phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and a condensate of maleic anhydride and an unsaturated compound.

  Examples of imidazole compounds include 1-isobutyl-2-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole and the like. It is done. The imidazole compound also functions as a curing accelerator described later, but in the present invention, it is classified as a curing agent.

  Examples of amide compounds include dicyandiamide and its derivatives, polyamide resins, and the like.

Cationic polymerization initiators generate cations by heat or active energy ray irradiation, and include aromatic onium salts. Specifically, anion components such as SbF ₆ ⁻ , BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , CF ₃ SO ₃ ²⁻ , B (C ₆ F ₅ ) ₄ ^{− and the} like, iodine, sulfur, nitrogen, phosphorus and the like And a compound comprising an aromatic cation component containing the above atoms. In particular, diaryl iodonium salts and triaryl sulfonium salts are preferred.

  Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like, and phosphonium salts include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, Examples include tetrabutylphosphonium / tetrabutylborate, and examples of the tetraphenylboron salt include 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, and the like.

When polyfunctional phenols, amine compounds, and acid anhydride compounds are used as the curing agent, the functional groups in the curing agent with respect to all epoxy groups in the epoxy compound-containing composition (hydroxy groups of polyfunctional phenols, amine compounds) It is preferable to use it so that it may become the range of 0.8-1.5 in the equivalent ratio of the amino group of this, or the acid anhydride group of an acid anhydride type compound. When using a polyisocyanate compound, the number of isocyanate groups in the polyisocyanate compound relative to the number of hydroxyl groups in the epoxy compound-containing composition may be used in an equivalent ratio of 1: 0.01 to 1: 1.5. preferable. When using an imidazole-type compound, it is preferable to use in the range of 0.5-10 weight part with respect to 100 weight part of all the epoxy compound components as solid content in an epoxy compound containing composition. When using an amide type compound, it is preferable to use it in the range of 0.1-20 weight% with respect to the total amount of all the epoxy compound components and amide type compounds as solid content in an epoxy compound containing composition. When using a cationic polymerization initiator, it is preferable to use in 0.01-15 weight part with respect to 100 weight part of all the epoxy compound components as solid content in an epoxy compound containing composition. When using organic phosphines, it is preferably used in the range of 0.1 to 20% by weight based on the total amount of all epoxy compound components and organic phosphines as a solid content in the epoxy compound-containing composition.
In addition to the curing agents listed above, for example, mercaptan compounds, organic acid dihydrazides, boron halide amine complexes, and the like can be used as the curing agent in the epoxy compound-containing composition of the present invention.

  These curing agents may be used alone or in combination of two or more.

[Other epoxy compounds]
In the epoxy compound-containing composition of the present invention, an epoxy compound other than the epoxy compound of the present invention (sometimes referred to as “other epoxy compound” in the present specification) can be used.

  Examples of other epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin. , Glycidyl ether type epoxy resins such as tetrabromobisphenol A type epoxy resins, other polyfunctional phenol type epoxy resins, epoxy resins obtained by hydrogenating aromatic rings of the above aromatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxies Examples thereof include epoxy compounds such as resins, linear aliphatic epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. The other epoxy compounds mentioned above may be used alone or in combination of two or more.

  When the epoxy compound-containing composition of the present invention contains the epoxy compound of the present invention and another epoxy compound, the ratio of the other epoxy compounds in the total epoxy compound component as a solid content in the epoxy compound-containing composition is The amount is preferably 1% by weight or more, more preferably 5% by weight or more, and preferably 99% by weight or less, more preferably 95% by weight or less. When the ratio of the other epoxy compound is not less than the above lower limit value, the effect of improving physical properties by blending the other epoxy compound can be sufficiently obtained. On the other hand, the toughness improvement effect by the epoxy compound of this invention can be acquired because the ratio of another epoxy compound is below the said upper limit.

[solvent]
The epoxy compound-containing composition of the present invention may be diluted by blending a solvent in order to appropriately adjust the viscosity of the epoxy compound-containing composition during handling such as coating film formation. In the epoxy compound-containing composition of the present invention, the solvent is used to ensure the handleability and workability in the molding of the epoxy compound-containing composition, and the amount used is not particularly limited. As described above, in the present invention, the term “solvent” and the term “solvent” are distinguished from each other depending on the form of use, but the same or different ones may be used independently.

  As a solvent which the epoxy compound of this invention can contain, the 1 type (s) or 2 or more types of the organic solvent illustrated as reaction solvent (E) used for manufacture of the epoxy compound of this invention can be used.

[Other ingredients]
The epoxy compound-containing composition of the present invention may contain other components in addition to the components listed above. Examples of other components include a curing accelerator (except for those corresponding to the curing agent), a coupling agent, a flame retardant, an antioxidant, a light stabilizer, a plasticizer, a reactive diluent, a pigment, An inorganic filler, an organic filler, etc. are mentioned. The other components listed above can be used in appropriate combination depending on the desired physical properties of the epoxy compound-containing composition.

[Cured product]
A cured product can be obtained by curing the epoxy compound-containing composition of the present invention. The term “curing” as used herein means that the epoxy compound is intentionally cured by heat and / or light or the like, and the degree of curing may be controlled by desired physical properties and applications.

  The curing method of the epoxy compound-containing composition when making the cured product obtained by curing the epoxy compound-containing composition of the present invention varies depending on the blending component and blending amount in the epoxy compound-containing composition, and the shape of the blend. Usually, the heating conditions are 50 to 200 ° C. for 5 seconds to 180 minutes. This heating is performed by a two-stage process of primary heating at 50 to 160 ° C. for 5 seconds to 30 minutes and secondary heating at 90 to 200 ° C. that is 40 to 120 ° C. higher than the primary heating temperature for 1 to 150 minutes. However, it is preferable in terms of reducing poor curing.

  When producing the cured product as a semi-cured product, the curing reaction of the epoxy compound-containing composition may be advanced to such an extent that the shape can be maintained by heating or the like. When the epoxy compound-containing composition contains a solvent, most of the solvent is removed by techniques such as heating, reduced pressure, and air drying, but 5% by weight or less of the solvent may be left in the semi-cured product. .

[Use]
The epoxy compound of the present invention is excellent in toughness. From this, the epoxy compound of this invention and the epoxy compound containing composition which mix | blended it can be used suitably in field | areas, such as a coating material, an electrical / electronic material, an adhesive agent, and fiber reinforced resin (FRP).

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by the following example. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

[Raw materials]
The raw materials, catalysts, solvents and solvents used in the following examples and comparative examples are as follows.

[Bifunctional epoxy compound (A)]
A-1: bisphenol A diglycidyl ether (Mitsubishi Chemical Corporation jER (registered trademark) 828US, epoxy equivalent: 186 g / equivalent)
A-2: Tetramethylbiphenol diglycidyl ether (JER (registered trademark) YX4000, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / equivalent)

[Bifunctional phenolic compound (B)]
B-1: Bisphenol A (phenolic hydroxyl group equivalent: 114 g / equivalent)
B-2: 4,4 ′-(3,3,5-trimethyl-1,1-cyclohexanediyl) bis (phenol) (phenolic hydroxyl group equivalent: 155 g / equivalent)

[Trifunctional or higher functional epoxy compound (C1)]
C1-1: Phenol-modified xylene-type epoxy resin (Mitsubishi Chemical Corporation jER (registered trademark) YX7700, epoxy equivalent: 270 g / equivalent)

[Trifunctional or higher functional phenolic compound (C2)]
C2-1: α, α-bis (4-hydroxyphenyl) -4- (4-hydroxy-α, α-dimethylbenzyl) -ethylbenzene (TP-TG manufactured by Honshu Chemical Industry Co., Ltd., phenolic hydroxyl group equivalent: 142 g / equivalent )
C2-2: 4,4 ′, 4 ″ -Ethyridinetris (2-methylphenol) (TrisOC-HAP manufactured by Honshu Chemical Industry Co., Ltd., phenolic hydroxyl group equivalent: 116 g / equivalent)

[Catalyst (D)]
D-1: Tetramethylammonium hydroxide 27% aqueous solution (Nippon Specialty Chemicals)
D-2: Tri-p-tolylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Reaction solvent (E)]
E-1: Toluene E-2: Cyclohexanone

[Diluted solvent (F)]
F-1: Methyl ethyl ketone

〔Evaluation method〕
Evaluation methods in the following Examples and Comparative Examples are as follows.

[Epoxy equivalent]
About the epoxy compound obtained in Examples 1-5 and Comparative Examples 1-3, the epoxy equivalent was measured based on JISK7236.

[Weight average molecular weight (Mw)]
About the epoxy compound obtained in Examples 1-5 and Comparative Examples 1-3, the weight average molecular weight was measured by gel permeation chromatography (GPC). The apparatus and measurement conditions used for GPC measurement are as follows.
Device: GPC
Model: HLC-8120GPC (manufactured by Tosoh)
Column: TSKGEL HM-H + H4000 + H4000 + H3000 + H2000 (manufactured by Tosoh Corporation)
Detector: UV-8020 (manufactured by Tosoh), 254 nm
Eluent: THF (0.5 mL / min, 40 ° C.)
Sample: 1% tetrahydrofuran solution (10μ injection)
Calibration curve: Standard polystyrene (manufactured by Tosoh)

[Toughness]
After apply | coating the epoxy compound obtained in Examples 1-5 and Comparative Examples 1-3 on a release film using an applicator, a solvent is removed by heating at 200 degreeC for 30 minutes, and thickness is 20-25 micrometers. Made a film. Elongation (%) until the film was broken when the obtained film was pulled at 5 mm / min by the following tensile tester was evaluated as an evaluation index of toughness.
Tensile testing machine: Instron Digital Universal Material Testing Machine Model 5582

[Production and evaluation of epoxy compounds]
Example 1
400 parts by weight of bisphenol A diglycidyl ether (A-1), 224 parts by weight of bisphenol A (B-1), α, α-bis (4-hydroxyphenyl) -4- (4-hydroxy-α, α-dimethylbenzyl ) -Ethylbenzene (C2-1) 6 parts by weight, tetramethylammonium hydroxide 27% aqueous solution (D-1) 1.48 parts by weight, toluene (E-1) 210 parts by weight are put in a pressure-resistant reaction vessel, and a nitrogen gas atmosphere A polymerization reaction was carried out at 135 ° C. for 6 hours to obtain the target epoxy compound. This was dissolved in 735 parts by weight of methyl ethyl ketone (F-1) (solid content: 40% by weight). About the obtained epoxy compound solution, an epoxy equivalent, a weight average molecular weight (Mw), and toughness were evaluated by the said method, and the result was shown in Table-1.

(Example 2)
400 parts by weight of bisphenol A diglycidyl ether (A-1), 222 parts by weight of bisphenol A (B-1), 5 parts by weight of 4,4 ′, 4 ″ -ethylidinetris (2-methylphenol) (C2-2) , 0.4 parts by weight of tri-p-tolylphosphine (D-2) and 157 parts by weight of toluene (E-1) were put in a pressure-resistant reaction vessel and subjected to a polymerization reaction at 170 ° C. for 6 hours in a nitrogen gas atmosphere. This was dissolved in 470 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight) The epoxy compound solution thus obtained was epoxy equivalent and weight average molecular weight (Mw). And the toughness was evaluated by the above methods, and the results are shown in Table-1.

(Example 3)
400 parts by weight of bisphenol A diglycidyl ether (A-1), 224 parts by weight of bisphenol A (B-1), 6 parts by weight of phenol-modified xylene-type epoxy resin (C1-1), 27% aqueous solution of tetramethylammonium hydroxide (D -1) 1.5 parts by weight and 210 parts by weight of cyclohexanone (E-2) were put in a pressure-resistant reaction vessel and subjected to a polymerization reaction at 135 ° C. for 6 hours in a nitrogen gas atmosphere to obtain a target epoxy compound. This was dissolved in 735 parts by weight of methyl ethyl ketone (F-1) (solid content: 40% by weight). About the obtained epoxy compound solution, an epoxy equivalent, a weight average molecular weight (Mw), and toughness were evaluated by the said method, and the result was shown in Table-1.

Example 4
200 parts by weight of bisphenol A diglycidyl ether (A-1), 49 parts by weight of bisphenol A (B-1), 20 parts by weight of 4,4 ′, 4 ″ -ethylidinetris (2-methylphenol) (C2-2) , 0.15 parts by weight of tri-p-tolylphosphine (D-2) and 34 parts by weight of toluene (E-1) were placed in a pressure-resistant reaction vessel and subjected to a polymerization reaction at 170 ° C. for 6 hours in a nitrogen gas atmosphere. The resulting epoxy compound was dissolved in 145 parts by weight of methyl ethyl ketone (F-1) (solid content 60% by weight), and the resulting epoxy compound solution was epoxy equivalent and weight average molecular weight (Mw). And the toughness was evaluated by the above methods, and the results are shown in Table-1.

(Example 5)
200 parts by weight of tetramethylbiphenol diglycidyl ether (A-2), 164 parts by weight of 4,4 ′-(3,3,5-trimethyl-1,1-cyclohexanediyl) bis (phenol) (B-2), α , Α-bis (4-hydroxyphenyl) -4- (4-hydroxy-α, α-dimethylbenzyl) -ethylbenzene (C2-1) 6 parts by weight, tetramethylammonium hydroxide 27% aqueous solution (D-1) 1 .48 parts by weight and 200 parts by weight of cyclohexanone (E-2) were put in a pressure-resistant reaction vessel, and a polymerization reaction was performed at 135 ° C. for 6 hours in a nitrogen gas atmosphere to obtain a target epoxy compound. This was dissolved in 487 parts by weight of methyl ethyl ketone (F-1) (solid content: 35% by weight). About the obtained epoxy compound solution, an epoxy equivalent, a weight average molecular weight (Mw), and toughness were evaluated by the said method, and the result was shown in Table-1.

(Comparative Example 1)
Bisphenol A diglycidyl ether (A-1) 400 parts by weight, bisphenol A (B-1) 230 parts by weight, tetramethylammonium hydroxide 27% aqueous solution (D-1) 1.48 parts by weight, toluene (E-1) 210 parts by weight were placed in a pressure resistant reactor and subjected to a polymerization reaction at 135 ° C. for 6 hours in a nitrogen gas atmosphere to obtain a target epoxy compound. This was dissolved in 735 parts by weight of methyl ethyl ketone (F-1) (solid content: 40% by weight). About the obtained epoxy compound solution, an epoxy equivalent, a weight average molecular weight (Mw), and toughness were evaluated by the said method, and the result was shown in Table-1.

(Comparative Example 2)
200 parts by weight of tetramethylbiphenol diglycidyl ether (A-2), 164 parts by weight of 4,4 ′-(3,3,5-trimethyl-1,1-cyclohexanediyl) bis (phenol) (B-2), water 1.48 parts by weight of a 27% aqueous solution of tetramethylammonium oxide (D-1) and 200 parts by weight of cyclohexanone (E-2) are placed in a pressure-resistant reaction vessel and subjected to a polymerization reaction at 135 ° C. for 6 hours in a nitrogen gas atmosphere. An epoxy compound was obtained. This was dissolved in 487 parts by weight of methyl ethyl ketone (F-1) (solid content: 35% by weight). About the obtained epoxy compound solution, an epoxy equivalent, a weight average molecular weight (Mw), and toughness were evaluated by the said method, and the result was shown in Table-1.

(Comparative Example 3)
200 parts by weight of bisphenol A diglycidyl ether (A-1), 100 parts by weight of bisphenol A (B-1), 100 parts by weight of phenol-modified xylene type epoxy resin (C1-1), 27% aqueous solution of tetramethylammonium hydroxide (D -1) 1.48 parts by weight and 44 parts by weight of toluene (E-1) were put in a pressure-resistant reaction vessel, and a polymerization reaction was performed at 135 ° C. for 6 hours in a nitrogen gas atmosphere to obtain a target epoxy compound. This was dissolved in 127 parts by weight of methyl ethyl ketone (F-1) (solid content: 70% by weight). About the obtained epoxy compound solution, an epoxy equivalent, a weight average molecular weight (Mw), and toughness were evaluated by the said method, and the result was shown in Table-1.

[Evaluation results]
As can be seen from Table 1, the bifunctional epoxy compound (A), the bifunctional phenolic compound (B), the trifunctional or higher functional epoxy compound (C1) and / or the trifunctional or higher functional phenolic compound (C2) is used as a catalyst. The epoxy compounds of Examples 1 to 5 obtained by reacting in the presence and having an epoxy equivalent of more than 800 g / equivalent and not more than 200,000 g / equivalent have good film elongation and excellent toughness. there were. On the other hand, Comparative Examples 1 and 2 not using a trifunctional or higher functional epoxy compound (C1) and / or a trifunctional or higher functional phenol compound (C2), a trifunctional or higher functional epoxy compound (C1) and / or a trifunctional or higher functional In Comparative Example 3 in which the epoxy equivalent was 800 g / equivalent or less even when the phenolic compound (C2) was used, the toughness was insufficient.

  The epoxy compound of the present invention has excellent toughness. Therefore, the epoxy compound of the present invention, the epoxy compound-containing composition containing the epoxy compound, and the cured product thereof are suitably used in the fields of paints, electrical / electronic materials, adhesives, fiber reinforced resins (FRP), and the like. be able to.

Claims (6)

  A reaction product of a bifunctional epoxy compound (A), a bifunctional phenolic compound (B), a trifunctional or higher functional epoxy compound (C1) and / or a trifunctional or higher functional phenolic compound (C2), An epoxy compound having an epoxy equivalent of more than 800 g / equivalent and 200,000 g / equivalent or less.   The trifunctional or higher functional epoxy compound (A), the bifunctional phenolic compound (B), the trifunctional or higher functional epoxy compound (C1) and / or the trifunctional or higher functional phenolic compound (C2) account for the total weight. The epoxy compound according to claim 1, wherein the weight ratio of (C1) and / or a trifunctional or higher functional phenol compound (C2) is 30% or less.   An epoxy compound-containing composition comprising the epoxy compound according to claim 1 or 2 and a curing agent.   The epoxy compound containing composition of Claim 3 containing 0.1-1000 weight part of hardening | curing agents with respect to 100 weight part of said epoxy compounds.   The curing agent is selected from the group consisting of polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, mercaptan compounds, cationic polymerization initiators, and organic phosphines. The epoxy compound-containing composition according to claim 3 or 4, which is at least one selected from the group consisting of:   Hardened | cured material formed by hardening | curing the epoxy compound containing composition of any one of Claims 3 thru | or 5.