JP2021095515A - Epoxy compound, composition, cured product and laminate - Google Patents

Abstract

To provide an epoxy compound that gives a flexible cured product that has a high elongation percentage based on elastic deformation, and high adhesion sufficient to withstand a thermal expansion difference of a base material, and creep resistance sufficient to prevent the creep phenomenon; and provide a composition comprising the epoxy compound, a cured product obtained by curing the composition, and a laminate having the cured product layer and a base material.SOLUTION: An epoxy compound A has a specific aromatic ring structure, and a glycidyl ether group or 2-methyl glycidyl ether group, the epoxy compound represented by the formula shown below.SELECTED DRAWING: None

Description

The present invention relates to an epoxy compound having a specific structure, a composition having the epoxy compound, and a cured product obtained by curing the composition. It also relates to a laminate having the cured product layer.

The weight of automobiles and airplanes has been further reduced due to CO ₂ reduction and fuel efficiency improvement, and along with this, the number of spot welds has been reduced and the weight has been reduced by using fiber reinforced plastic and metal together. There is a strong demand for higher performance agents. In particular, in the heat adhesion between aluminum and a fiber reinforced plastic having a large difference in thermal expansion, the occurrence of warpage and waviness due to interfacial stress due to expansion and contraction is regarded as a problem, and an adhesive for alleviating the stress is required.
In addition, in structural materials, especially members that require high safety such as automobiles and airplanes, not only stress relaxation for momentary expansion and contraction, but also creep phenomenon in which strain increases under constant stress at high temperature. Response is required.

On the other hand, epoxy resins are often used as adhesives because they have dimensional stability during curing, electrical insulation, and chemical resistance. However, since it becomes hard and brittle when trying to maintain high adhesiveness, a high molecular weight epoxy compound obtained by reacting a liquid bisphenol A type epoxy resin with an aliphatic dicarboxylic acid such as dimer acid or sebacic acid as a molecular chain extender ( For example, flexible epoxy compounds such as (see Patent Document 1) and high molecular weight epoxy compounds derived from hydroxy compounds having an aliphatic hydrocarbon group (see Patent Document 2) are disclosed. However, since the deformation mode of the flexible epoxy compound is plastic deformation, it is not possible to repeatedly follow the expansion difference of the base material while maintaining the overall rigidity, and there is a problem in durability.
Based on the above, an epoxy compound that imparts a flexible cured product that has a high coefficient of elongation premised on elastic deformation, high adhesiveness that can withstand the difference in thermal expansion of the base material, and creep resistance that can suppress the creep phenomenon. It has been demanded.

Japanese Unexamined Patent Publication No. 8-53533 Japanese Unexamined Patent Publication No. 2006-335996

An object of the present invention is to provide a flexible cured product having a high elongation rate premised on elastic deformation, a high adhesiveness capable of withstanding a difference in thermal expansion of a base material, and a creep resistance capable of suppressing a creep phenomenon. The purpose is to provide an epoxy compound.
Another object of the present invention is to provide a composition containing the epoxy compound, a cured product obtained by curing the composition, and a laminate having the cured product layer and a base material.

As a result of diligent studies, the present inventors have found that the above problems can be solved by providing the epoxy compound A represented by the following formula (1).
That is, the present invention provides an epoxy compound A represented by the following formula (1).

・・・（１）

... (1)

(In formula (1), Ar represents a structure having an aromatic ring having an unsubstituted or substituent, respectively.
R _{1, R 2} and _R 1 ', _{R 2'} represents a hydrogen atom or an alkyl group having a carbon number of 1 or 2 independently,
R _{3 to} R ₈ represent a hydroxyl group, a glycidyl ether group and / or a 2-methyl glycidyl ether group, and _{at least one of R 3 to} R ₈ is a glycidyl ether group or a 2-methyl glycidyl ether group.
R _{9 to} R ₁₂ represent a hydrogen atom or a methyl group.
n is an integer of 4 to 16 independently,
m is an average value of repetitions of 0.5 to 10 and
l is the average value of repetitions of 0.5 to 10 and
Ar'is a structure represented by the following equation (2).

・・・（２）

... (2)

(In the formula (2), Y independently represents a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyl group having 1 to 8 carbon atoms, and X is a single bond, an −O− group, −. CH = CH-group, -CH = C (CH ₃ ) -group, -CH = C (CN) -group, -C≡C- group, -CH = N- group, -CH = CH-CO- group, -N = N- group, -COO- group, -CONH- group or -CO- group, q ₁ and q ₂ are independent integers from 0 to 4, and p ₁ is an integer from 1 to 3. Represent)
(However, each repeating unit existing in the repeating unit may be the same or different). )

The epoxy compound A of the present invention is a flexible cured product having a high elongation rate premised on elastic deformation, high adhesiveness capable of withstanding the difference in thermal expansion of the base material, and creep resistance capable of suppressing the creep phenomenon. Can be provided.

<Epoxy compound A>
The epoxy compound A of the present invention provides the epoxy compound A represented by the following formula (1).

・・・（１）

... (1)

(In formula (1), Ar represents a structure having an aromatic ring having an unsubstituted or substituent, respectively.
R _{1, R 2} and _R 1 ', _{R 2'} represents a hydrogen atom or an alkyl group having a carbon number of 1 or 2 independently,
R _{3 to} R ₈ represent a hydroxyl group, a glycidyl ether group and / or a 2-methyl glycidyl ether group, and _{at least one of R 3 to} R ₈ is a glycidyl ether group or a 2-methyl glycidyl ether group.
R _{9 to} R ₁₂ represent a hydrogen atom or a methyl group.
n is an integer of 4 to 16 independently,
m is an average value of repetitions of 0.5 to 10 and
l is the average value of repetitions of 0.5 to 10 and
Ar'is a structure represented by the following equation (2).

・・・（２）

... (2)

(In the formula (2), Y independently represents a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyl group having 1 to 8 carbon atoms, and X is a single bond, an −O− group, −. CH = CH-group, -CH = C (CH ₃ ) -group, -CH = C (CN) -group, -C≡C- group, -CH = N- group, -CH = CH-CO- group, -N = N- group, -COO- group, -CONH- group or -CO- group, q ₁ and q ₂ are independent integers from 0 to 4, and p ₁ is an integer from 1 to 3. Represent)
(However, each repeating unit existing in the repeating unit may be the same or different). )

The epoxy compound A having the above structure is characterized by having a long-chain alkyl moiety and an oriented Ar'portion. By having a long-chain alkyl moiety, the epoxy compound A of the present invention has flexibility and can follow the difference in thermal expansion of the base material. Further, since the Ar'part having orientation is provided in the middle part of the molecule, the creep resistance is improved.

In the epoxy compound A, Ar independently represents a structure having an aromatic ring having no substituent or a substituent. Examples of the aromatic ring here include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Ar, which is a structure having these aromatic rings, preferably represents a structure represented by the following formula (3).

・・・（３）

... (3)

(In the formula (3), the aromatic ring may be substituted or unsubstituted, and * represents a bonding point.)

The structure represented by the formula (3) is a non-oriented structure. In the epoxy compound A of the present invention, when Ar has a non-oriented structure, the epoxy compound A exhibits amorphousness even if it has an oriented Ar'in the molecule. As a result, since the epoxy compound A of the present invention has high fluidity, it can be suitably used in fields where fluidity is required, such as adhesives.

Further, in the formula (1), a structure represented by the following formula (3-1) is also mentioned as Ar.

・・・（３−１）

... (3-1)

(In the formula, the aromatic ring may be substituted or unsubstituted, n ₂ = 1 to 4, and * represents a bonding point.)

The aromatic ring contained in Ar may be substituted or unsubstituted, and when Ar has a substituent, the substituent preferably includes an alkyl group, a halogen atom, a glycidyl ether group, a 2-methylglycidyl ether group and the like. It is preferably unsubstituted, or an alkyl group and a glycidyl ether group, or a 2-methylglycidyl ether group. The number of substituents is preferably 2 or less per aromatic ring, more preferably 1 or less, and particularly preferably unsubstituted.

The following Ar structure is particularly preferable.

Particularly preferable structures of Ar having a substituent include the following structures.

In the epoxy compound A represented by the formula (1), the repeating unit n is an integer of 4 to 16, preferably 6 to 12. When n is 4 or more, the adhesive force is improved and the deformation mode of the cured product is elastic deformation. Further, when n is 16 or less, a decrease in the crosslink density can be suppressed.

In the epoxy compound A represented by the formula (1), m and l are the average values of repetition, m is 0.5 to 10, and l represents 0.5 to 10.
The average value of these repetitions can be obtained by measuring with GPC. The m and l are preferably 0.6 to 5.0, respectively, from the viewpoint of having both flexibility and toughness and durability.

In the epoxy compound A represented by the formula (1), R ₁ , R ₂ and R ₁ ′, R ₂ ′ independently represent a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and R _{3 to} R respectively. ₈ represents a hydroxyl group or a glycidyl ether group or a 2-methylglycidyl ether group, and _{at least one of R 3 to} R ₈ is a glycidyl ether group or a 2-methyl glycidyl ether group, and R _{9 to} R ₁₂ are. Represents a hydroxyl group or a methyl group.

Preferred structures of the epoxy compound A represented by the formula (1) include the following structures.

In each of the above structural formulas, G is a glycidyl group, R ₁₃ is a hydrogen atom and / or a methyl group, n is an integer of 4 to 16, and m is a repeating average value of 0.5 to 10. L represents an average value of repetitions of 0.5 to 10.

Among the above structural formulas, it is most preferable to use those represented by the structural formulas (A-1), (A-4) and (A-5) from the viewpoint of excellent balance of physical properties of the obtained cured product. ..

<Manufacturing method of epoxy compound A>
The method for producing the epoxy compound A of the present invention is not particularly limited. For example, it can be manufactured by the following manufacturing method.
1) Diglycidyl ether (a1), which is an aliphatic dihydroxy compound, is reacted with an aromatic hydroxy compound (a2) having Ar', which has an oriented aromatic ring structure, to obtain an epoxy compound C.
2) The hydroxy compound B obtained by reacting the epoxy compound C with the aromatic hydroxy compound (a3) having Ar having an aromatic ring structure is obtained.
3) Hydroxy compound B is glycidyl etherified to obtain epoxy compound A.

<Epoxy compound C>
In the first step, the epoxy compound C obtained by reacting the aliphatic dihydroxy compound diglycidyl ether (a1) with the aromatic hydroxy compound (a2) having an oriented aromatic ring structure Ar'. To get. As the epoxy compound C, 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound (a2) is reacted with diglycidyl ether (a1) of the aliphatic dihydroxy compound in the range of 1.01 to 3.0 mol. Is preferable.
The obtained reaction product of epoxy compound C contains unreacted aliphatic dihydroxy compound diglycidyl ether (a1), but it may be used as it is in the present invention, or the aliphatic dihydroxy compound dihydroxy compound. Diglycidyl ether (a1) may be removed before use.
The method for removing the unreacted aliphatic dihydroxy compound diglycidyl ether (a1) can be carried out according to various methods. For example, a column chromatography separation method utilizing a difference in polarity, a distillation fractional distillation method utilizing a difference in boiling point, and the like can be mentioned. Of these, the distillation fractional distillation method is preferable as a simple method, and the vacuum distillation fractionation under high vacuum is particularly preferable in order to suppress thermal alteration. The abundance of diglycidyl ether (a1) of the unreacted aliphatic dihydroxy compound in the obtained hydroxy compound B is 0.1 to 30% by mass, which is the toughness and flexibility of the cured product. It is preferable from the viewpoint that the balance of the above is good.

The diglycidyl ether (a1) of the aliphatic dihydroxy compound is not particularly limited, and is, for example, 1,11-undecanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,9-nonane. Diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, 1,14-tetradecanediol diglycidyl ether, 1,15-pentadecanediol diglycidyl ether, 1,16-hexadecanediol di Diglycidyl ether, 2-methyl-1,11-undecanediol diglycidyl ether, 3-methyl-1,11-undecanediol diglycidyl ether, 2,6,10-trimethyl-1,11-undecanediol diglycidyl ether, etc. Can be mentioned. These may contain organic chlorine impurities generated in the glycidyl etherification of hydroxy compounds, and contain organic chlorine such as 1-chloromethyl-2-glycidyl ether (chloromethyl form) represented by the following structure. You may. These diglycidyl ethers may be used alone or in combination of two or more.

・・・クロロメチル体

・ ・ ・ Chloromethyl form

Among these, the compound has a structure in which glycidyl groups are linked to both ends of an alkylene chain having 4 to 16 carbon atoms via an ether group from the viewpoint of excellent balance between flexibility and heat resistance of the obtained cured product. Preferably, 1,6-hexanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, 1,14-tetradecanediol diglycidyl ether, Most preferably, 1,16-hexadecanediol diglycidyl ether is used.

The aromatic hydroxy compound (a2) having Ar', which is the aromatic ring structure having the orientation, is not particularly limited as long as it has the aromatic ring and exhibits the orientation. For example, the aromatic hydroxy compound (a2) is not particularly limited. 2,2'-biphenol, 4,4'-biphenol, (1,1'-biphenyl) -3,4-diol, 3,3'-dimethyl- (1,1'-biphenyl) -4,4'- Diol, 3-methyl- (1,1'-biphenyl) -4,4'-diol, 3,3', 5,5'-tetramethylbiphenyl-2,2'-diol, 3,3', 5, 5'-Tetramethylbiphenyl-4,4'-diol, 5-methyl- (1,1'-biphenyl) -3,4'diol, 3'-methyl- (1,1'-biphenyl) -3,4 Biphenols such as'diols, 4'-methyl- (1,1'-biphenyl) -3,4'diols, bis (4-hydroxyphenyl) methanones, bisphenols such as 4,4'-oxydiphenols, 4 , 4'-(ethylene-1,2-diyl) diphenol, 4-hydroxy-N- (4-hydroxyphenyl) benzamide and the like, and may be used alone or in combination of two or more.

Among these, trihydroxybenzenes are most preferable from the viewpoint of excellent balance between flexibility and toughness when made into a cured product, and when heat resistance is important, 4,4', 4 "-trihydroxytriphenyl" Methane and 1,1'-methylenebisu (2,7-naphthalenediol) are preferable. Further, when the moisture resistance of the cured product is important, it is preferable to use phenols containing an alicyclic structure.

The reaction ratio of the aliphatic dihydroxy compound diglycidyl ether (a1) to the aromatic hydroxy compound (a2) is such that the aromatic hydroxy compound (a1) maintains the final fluidity of the epoxy compound A. It is preferable to react (a1) with 1 mol of the phenolic hydroxyl group of a2) in the range of 1.01 to 3.0 mol, and the flexibility and heat resistance of the obtained cured product are well-balanced. It is more preferable that the amount of (a1) is 1.05 to 2.0 mol with respect to 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound (a2).

The reaction of the aliphatic dihydroxy compound diglycidyl ether (a1) with the aromatic hydroxy compound (a2) having the orientation is preferably carried out in the presence of a catalyst. Various catalysts can be used, for example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide, and alkali metals such as sodium carbonate and potassium carbonate. Phosphorus compounds such as carbonates and triphenylphosphine, chlorides such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium, bromide, iodide, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium , Chloride such as benzyltributylphosphonium, quaternary ammonium salt such as bromide and iodide, triethylamine, N, N-dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] undecene, 1,4-diazabicyclo [2. 2.2] Examples thereof include tertiary amines such as octane, and imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole. These may be used in combination with two or more kinds of catalysts. Of these, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferable because the reaction proceeds rapidly and the effect of reducing the amount of impurities is high. The amount of these catalysts used is not particularly limited, but it is preferable to use 0.0001 to 0.01 mol with respect to 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound (a2). The form of these catalysts is not particularly limited, and may be used in the form of an aqueous solution or in the form of a solid.

Further, the reaction between the diglycidyl ether (a1) of the aliphatic dihydroxy compound and the aromatic hydroxy compound (a2) having the orientation can be carried out in the absence of a solvent or in the presence of an organic solvent. it can. Examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propyl alcohol, butyl alcohol and the like. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the charged raw materials. These organic solvents can be used alone or in admixture of several types. Solvent-free is preferable for rapid reaction, while dimethyl sulfoxide is preferable from the viewpoint of reducing impurities in the final product.

When the reaction is carried out, the reaction temperature is usually 50 to 180 ° C., and the reaction time is usually 1 to 10 hours. The reaction temperature is preferably 100 to 160 ° C. from the viewpoint of reducing impurities in the final product. Further, when the coloration of the obtained compound is large, an antioxidant or a reducing agent may be added in order to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite ester compounds containing a trivalent phosphorus atom. Can be done. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfite, hydrosulfite, and salts thereof.

After completion of the reaction, neutralization or washing with water can be carried out until the pH value of the reaction mixture reaches 3 to 7, preferably 5 to 7. Neutralization treatment and washing treatment may be performed according to a conventional method. For example, when a basic catalyst is used, an acidic substance such as hydrochloric acid, monosodium hydrogen phosphate, p-toluenesulfonic acid, or oxalic acid can be used as a neutralizing agent. After neutralization or washing with water, if necessary, the solvent is distilled off under reduced pressure heating to concentrate the product, and the compound can be obtained.

Preferred structures of the epoxy compound C include the following structures.

<Hydroxy compound B>
In the second step, the epoxy compound C is reacted with an aromatic hydroxy compound (a3) having Ar having an aromatic ring structure to obtain a hydroxy compound B.
Although the hydroxy compound B contains an unreacted aromatic hydroxy compound (a3), it may be used as it is in the present invention, or the aromatic hydroxy compound (a3) may be removed and used.

As a method for removing the unreacted aromatic hydroxy compound (a3), various methods can be followed. For example, a column chromatography separation method utilizing a difference in polarity, a distillation fractional distillation method utilizing a difference in boiling point, an alkaline water-soluble extraction method utilizing a difference in solubility in alkaline water, and the like can be mentioned. Of these, the alkaline water-soluble extraction method is preferable in terms of efficiency because it does not involve thermal alteration. At this time, the organic solvent used to dissolve the target product can be used as long as it is not mixed with water, such as toluene or methyl isobutyl ketone. However, methyl isobutyl ketone is preferable from the viewpoint of solubility in the target product. When the abundance of the unreacted aromatic hydroxy compound (a3) in the obtained hydroxy compound B is 0.1 to 60 by mass, the balance between the toughness and the flexibility of the cured product is good. It is preferable from the point of view.

The aromatic hydroxy compound (a3) having Ar having an aromatic ring structure is not particularly limited, and for example, dihydroxybenzenes such as hydroquinone, resorcin, and catechol, pyrogallol, 1,2,4-tri Trihydroxybenzenes such as hydroxybenzene and 1,3,5-trihydroxybenzene, triphenylmethane-type phenols such as 4,4', 4 "-trihydroxytriphenylmethane, 1,6-dihydroxynaphthalene, 2, Dihydroxynaphthalene such as 7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene, and dihydroxynaphthalene were coupled to each other. , 1'-methylenebisu (2,7-naphthalenediol), 1,1'-binaphthalene-2,2', 7,7'-tetraol, 1,1'-oxybisu (2,7-naphthalenediol), etc. Tetrafunctional phenols, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis ( 4-Hydroxyphenyl) cyclohexane, and 1,1-bis (4-hydroxyphenyl) -1-phenylethane, and bis (4-hydroxyphenyl) sulfal, bis (4-hydroxyphenyl) methanone, 4,4'-oxy Biphenols such as diphenol, 2,2'-biphenol, 4,4'-biphenol, (1,1'-biphenyl) -3,4-diol, 3,3'-dimethyl- (1,1'-biphenyl) ) -4,4'-diol, 3-methyl- (1,1'-biphenyl) -4,4'-diol, 3,3', 5,5'-tetramethylbiphenyl-2,2'-diol, 3,3', 5,5'-tetramethylbiphenyl-4,4'-diol, 5-methyl- (1,1'-biphenyl) -3,4'diol, 3'-methyl- (1,1' Biphenols such as −biphenyl) -3,4'diol, 4'-methyl- (1,1'-biphenyl) -3,4'diol, polyadditives of phenol and dicyclopentadiene, and phenol and terpene. Alicyclic structure-containing phenols such as heavy adducts with compounds, naphthols such as bis (2-hydroxy-1-naphthyl) methane, and bis (2-hydroxy-1-naphthyl) propane. Examples thereof include so-called zylock-type phenol resins, which are condensation reaction products of phenol and phenylenedimethyl chloride or biphenylene methyl chloride, and may be used alone or in combination of two or more. Further, a bifunctional phenol compound having a structure in which a methyl group, a t-butyl group, or a halogen atom is substituted as a substituent on the aromatic nucleus of each of the above compounds can also be mentioned. In the alicyclic structure-containing phenols and the Zyroc-type phenol resin, not only bifunctional components but also components having trifunctionality or higher may be present at the same time, but they may be used as they are in the present invention. Only the bifunctional component may be taken out and used through a purification step of a column or the like.

Of these, Ar has a non-oriented structure.
The non-oriented Ar preferably has the following structure.

Specific examples of the aromatic hydroxy compound (a3) having these structures as Ar include dihydroxybenzenes such as hydroquinone, resorcin, and catechol, pyrogallol, 1,2,4-trihydroxybenzene, 1,3,5. Trihydroxybenzenes such as -trihydroxybenzene, triphenylmethane-type phenols such as 4,4', 4 "-trihydroxytriphenylmethane, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4 1,1'-Methylenebisu (2,1'-methylenebisu) obtained by coupling dihydroxynaphthalene such as −dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene, and dihydroxynaphthalene. 7-naphthalenediol), 1,1'-binaphthalene-2,2', 7,7'-tetraol, 1,1'-oxybisu (2,7-naphthalenediol) and other tetrafunctional phenols, bis (4) -Hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, and Bisphenols such as 1,1-bis (4-hydroxyphenyl) -1-phenylethane and bis (4-hydroxyphenyl) sulfone, heavy adducts of phenol and dicyclopentadiene, and phenol and terpene compounds. Examples include alicyclic structure-containing phenols such as heavy adducts, naphthols such as bis (2-hydroxy-1-naphthyl) methane, and bis (2-hydroxy-1-naphthyl) propane, and two types alone. The above may be used in combination. Further, a bifunctional phenol compound having a structure in which a methyl group, a t-butyl group or a halogen atom is substituted as a substituent on the aromatic nucleus of each of the above compounds can be mentioned. The alicyclic structure-containing phenols may contain not only bifunctional components but also components having trifunctionality or higher at the same time, but may be used as they are in the present invention, or may be used as they are in the present invention, or may be used as they are, or may be used as they are through a purification step such as a column. Only the functional component may be taken out and used.

Among these, bisphenols are preferable because they have an excellent balance between flexibility and toughness when made into a cured product, and bis (4-hydroxyphenyl) methane, 2,2- because of their remarkable toughness-imparting performance. Bis (4-hydroxyphenyl) propane is preferred. Further, when the curability and heat resistance of the cured product are emphasized, dihydroxynaphthalene is preferable, and 2,7-dihydroxynaphthalene is particularly preferable because the fast-curing property is remarkably imparted. When the moisture resistance of the cured product is important, it is preferable to use phenols containing an alicyclic structure.

The reaction ratio of the epoxy compound C to the aromatic hydroxy compound (a3) was determined with respect to 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound (a2) in order to use the obtained compound as a curing agent for the epoxy resin. Therefore, it is preferable to react (a3) in the range of 1.01 to 3.0 mol, and from the viewpoint of balancing the flexibility and heat resistance of the obtained cured product in a well-balanced manner, 1 mol of the epoxy group of the epoxy compound C is used. On the other hand, it is more preferable that (a3) is 1.05 to 2.0 mol.

The reaction between the epoxy compound C and the aromatic hydroxy compound (a3) is preferably carried out in the presence of a catalyst. Various catalysts can be used, for example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide, and alkali metals such as sodium carbonate and potassium carbonate. Phosphorus compounds such as carbonates and triphenylphosphine, chlorides such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium, bromide, iodide, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium , Chloride such as benzyltributylphosphonium, quaternary ammonium salt such as bromide and iodide, triethylamine, N, N-dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] undecene, 1,4-diazabicyclo [2. 2.2] Examples thereof include tertiary amines such as octane, and imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole. These may be used in combination with two or more kinds of catalysts. Of these, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferable because the reaction proceeds rapidly and the effect of reducing the amount of impurities is high. The amount of these catalysts used is not particularly limited, but it is preferable to use 0.0001 to 0.01 mol with respect to 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound (a3). The form of these catalysts is not particularly limited, and may be used in the form of an aqueous solution or in the form of a solid.

Further, the reaction between the epoxy compound C and the aromatic hydroxy compound (a3) can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propyl alcohol, butyl alcohol and the like. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the charged raw materials. These organic solvents can be used alone or in admixture of several types. Solvent-free is preferable for rapid reaction, while dimethyl sulfoxide is preferable from the viewpoint of reducing impurities in the final product.

When the reaction is carried out, the reaction temperature is usually 50 to 180 ° C., and the reaction time is usually 1 to 10 hours. The reaction temperature is preferably 100 to 160 ° C. from the viewpoint of reducing impurities in the final product. Further, when the coloration of the obtained compound is large, an antioxidant or a reducing agent may be added in order to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite ester compounds containing a trivalent phosphorus atom. Can be done. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfite, hydrosulfite, and salts thereof.

After completion of the reaction, neutralization or washing with water can be carried out until the pH value of the reaction mixture reaches 3 to 7, preferably 5 to 7. Neutralization treatment and washing treatment may be performed according to a conventional method. For example, when a basic catalyst is used, an acidic substance such as hydrochloric acid, monosodium hydrogen phosphate, p-toluenesulfonic acid, or oxalic acid can be used as a neutralizing agent. After neutralization or washing with water, if necessary, the solvent is distilled off under reduced pressure heating to concentrate the product, and the compound can be obtained.

Preferred structures of hydroxy compound B include the following structures.

<Glysidyl etherification reaction>
In step 3, 3) hydroxy compound B is glycidyl etherified to obtain epoxy compound A.
In the method for producing the epoxy compound A of the present invention, the method for the glycidyl etherification reaction of the hydroxy compound B is not particularly limited, and a method of reacting a phenolic hydroxyl group with epihalohydrins or an olefinization of a phenolic hydroxyl group to form an olefin. Examples thereof include a method of oxidizing a carbon-carbon double bond with an oxidizing agent. Among these, it is preferable to use a method using epihalohydrins because it is easy to obtain raw materials and react.

As a method using epihalohydrins (a4), for example, 0.3 to 20 mol of epihalohydrins (a4) is added to 1 mol of the phenolic hydroxyl group of the hydroxy compound B obtained above, and the mixture is added to the mixture. A method of reacting 1 mol of the phenolic hydroxyl group of hydroxy compound B at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding 0.9 to 2.0 mol of a basic catalyst all at once or gradually is mentioned. Be done. As for the amount of the epihalohydrins (a4) added, the larger the excess amount of the epihalohydrins (a4), the closer the obtained epoxy compound is to the theoretical structure, and the reaction between the unreacted phenolic hydroxyl group and the epoxy group occurs. The formation of secondary hydroxyl groups can be suppressed. From this point of view, it is preferably in the range of 2.5 to 20 equivalents. This basic catalyst may be solid or an aqueous solution thereof may be used. When an aqueous solution is used, water and epihalohydrins (a4) are continuously added from the reaction mixture under reduced pressure or under normal pressure. ) Is distilled off, and the solution is further separated to remove water, and the epihalohydrins (a4) may be continuously returned to the reaction mixture.

In the case of industrial production, all of the charged epihalohydrins (a4) are used in the first batch of epoxy compound production, but from the next batch onward, the epihalohydrins (a4) recovered from the crude reaction product are used. And new epihalohydrins (a4) corresponding to the amount consumed in the reaction and the amount disappeared in the reaction are preferably used in combination. At this time, the epichlorohydrins (a4) used are not particularly limited, and examples thereof include epichlorohydrin and epibromohydrin. Of these, epichlorohydrin is preferable because it is easily available.

The basic catalyst is also not particularly limited, and examples thereof include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity in the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. At the time of use, these alkali metal hydroxides may be used in the form of an aqueous solution of about 10 to 55% by mass, or may be used in the form of a solid.

Further, by using an organic solvent in combination, the reaction rate in the synthesis of the epoxy compound can be increased. Such an organic solvent is not particularly limited, but for example, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol and tertiary butanol, and methyl. Examples thereof include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotonic polar solvents such as acetonitrile, dimethylsulfoxide and dimethylformamide. Each of these organic solvents may be used alone, or two or more kinds may be used in combination as appropriate to adjust the polarity.

After washing the reaction products of these glycidylation reactions with water, the unreacted epihalohydrins (a4) and the organic solvent used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy compound having less hydrolyzable halogen, the obtained epoxy compound is dissolved again in an organic solvent such as toluene, methyl isobutyl ketone and methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide and potassium hydroxide is used. Further reaction can be carried out by adding an aqueous solution of the substance. At this time, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether may be present for the purpose of improving the reaction rate.
When a phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by mass with respect to the epoxy resin used. After completion of the reaction, the produced salt is removed by filtration, washing with water, or the like, and further, a solvent such as toluene or methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain a high-purity epoxy compound.

<Composition>
The composition of the present invention contains the epoxy compound A of the present invention.

The composition may contain a composition other than the epoxy compound A. For example, it is preferable to contain a curing agent capable of reacting with an epoxy compound.

The curing agent is not particularly limited as long as it can react with the epoxy compound, and for example, an amine compound, an acid anhydride compound, an amide compound, a phenol compound, a carboxylic acid compound, or the above-mentioned curing agent. Hydroxyl compound B and the like can be mentioned.

For example, amine-based compounds include aliphatic polyamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, polypropylene glycoldiamine, diethylenetriamine, triethylenetetramine, and pentaethylenehexamine, and metaxylylene diamine, diaminodiphenylmethane, and phenylenediamine. Aromatic polyamines such as 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, alicyclic polyamines such as norbornandiamine, and dicyandiamide can be mentioned.

Examples of the acid anhydride-based compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, polypropylene glycol maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, and hexahydroanhydride. Examples thereof include phthalic acid and methylhexahydrophthalic anhydride.

Examples of phenol-based compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylolmethane resin, and tetraphenylol ethane resin. , Naftol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin, aminotriazine-modified phenol resin, modified products thereof and the like. Further, examples of the latent catalyst include imidazole, a BF3-amine complex, and a guanidine derivative.

Examples of the amide compound include an aliphatic polyamide synthesized from polycarboxylic acid and polyamine, an aromatic polyamide having an aromatic ring introduced therein, an aliphatic polyamide adduct obtained by adding an epoxy compound to the polyamide, and an aromatic polyamide. Adduct and the like can be mentioned.

Examples of the carboxylic acid compound include carboxylic acid polymers such as carboxylic acid-terminated polyester, polyacrylic acid, and maleic acid-modified polypropylene glycol.

When these curing agents are used, only one type of curing agent may be used, or two or more types may be mixed. It is preferable to use the amine-based compound, the carboxylic acid-based compound, or the acid anhydride-based compound in applications such as underfill materials and general coating materials. Further, in adhesives and flexible wiring board applications, amine compounds, particularly dicyandiamide, are preferable from the viewpoint of workability, curability, and long-term stability. Further, in the use of semiconductor encapsulant materials, solid type phenolic compounds are preferable from the viewpoint of heat resistance of cured products.

<Other epoxy compounds>
In the composition of the present invention, in addition to the epoxy compound A, other epoxy compounds may be used in combination as long as the effects of the present invention are not impaired. At this time, the proportion of the epoxy compound A used in the composition of the present invention is preferably 30% by mass or more, particularly preferably 40% by mass or more, based on the total epoxy compounds.

The epoxy compound that can be used in combination is not limited in any way. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin. , Catecol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, liquid epoxy resin such as tetramethylbiphenyl type epoxy resin, brominated epoxy resin such as brominated phenol novolac type epoxy resin, solid bisphenol A type epoxy resin, Phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, phenylene ether type epoxy resin, naphthic Lene ether type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin , Biphenyl-modified novolak type epoxy resin and the like, and may be used alone or in combination of two or more, and it is preferable to select and use variously depending on the intended use and the physical properties of the cured product.

The blending amount of the epoxy compound and the curing agent in the composition of the present invention is not particularly limited, but the epoxy compound containing the epoxy compound A is excellent in terms of the mechanical properties of the obtained cured product and the like. The amount of the active group in the curing agent is preferably 0.7 to 1.5 equivalents with respect to the total 1 equivalent of the epoxy groups in the total amount.

<Curing accelerator>
For example, the composition of the present invention may contain a curing accelerator. Various types of curing accelerators can be used, and examples thereof include urea compounds, phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. When used as an adhesive, urea compounds, particularly 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), are preferable from the viewpoint of excellent workability and low-temperature curability. When used as a semiconductor encapsulant material, it is excellent in curability, heat resistance, electrical properties, moisture resistance reliability, etc., so it is triphenylphosphine for phosphorus compounds and 1,8-diazabicyclo-[for tertiary amines. 5.4.0] -Undesen is preferred.

<Filler>
The composition of the present invention may further contain a filler. Examples of the filler include an inorganic filler and an organic filler. Examples of the inorganic filler include inorganic fine particles.

Examples of the inorganic fine particles include alumina, magnesia, titania, zirconia, and silica (quartz, fumed silica, precipitated silica, silicic anhydride, molten silica, crystalline silica, and ultrafine powder amorphous. Silica, etc.), etc .; Boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond, etc.; For example, metal fillers and / or metal-coated fillers using iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc .; Minerals such as talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; Barium titanate, zirconia oxide, titanium oxide, etc .; Titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, terium, nickel, iron, cobalt, etc. Photocatalyst metals such as silver, molybdenum, strontium, chromium, barium, and lead, composites of the metals, oxides thereof, etc .; Such composites and oxides; metals such as silver and copper, tin oxide, indium oxide, etc. as having excellent conductivity; silica, etc. as having excellent insulating properties; Titanium oxide, zinc oxide, etc.
These inorganic fine particles may be selected in a timely manner depending on the intended use, and may be used alone or in combination of two or more. Further, since the inorganic fine particles have various properties other than the properties mentioned in the examples, they may be selected according to the timely application.

For example, when silica is used as the inorganic fine particles, there is no particular limitation, and known silica fine particles such as powdered silica and colloidal silica can be used. Commercially available powdered silica fine particles include, for example, Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., and E220A manufactured by Nippon Silysia Chemical Ltd. , E220, SYLYSIA470 manufactured by Fuji Silysia Chemical Ltd., SG flakes manufactured by Nippon Plate Glass Co., Ltd., and the like.
Examples of commercially available colloidal silica include methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, and the like. Examples thereof include ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like.

Surface-modified silica fine particles may be used. For example, the silica fine particles are surface-treated with a reactive silane coupling agent having a hydrophobic group, or modified with a compound having a (meth) acryloyl group. can give. Commercially available powdered silica modified with a compound having a (meth) acryloyl group includes Aerosil RM50, R711 manufactured by Nippon Aerosil Co., Ltd., and commercially available colloidal silica modified with a compound having a (meth) acryloyl group. MIBK-SD manufactured by Nissan Chemical Industry Co., Ltd. and the like can be mentioned.

The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or indefinite shapes can be used. The primary particle size is preferably in the range of 5 to 200 nm. If it is less than 5 nm, the dispersion of the inorganic fine particles in the dispersion becomes insufficient, and if the diameter exceeds 200 nm, the sufficient strength of the cured product may not be maintained.

As the titanium oxide fine particles, not only extender pigments but also ultraviolet light-responsive photocatalysts can be used, and for example, anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide and the like can be used. Further, particles designed to be made to respond to visible light by doping a different element into the crystal structure of titanium oxide can also be used. As the element to be doped in titanium oxide, anionic elements such as nitrogen, sulfur, carbon, fluorine and phosphorus, and cationic elements such as chromium, iron, cobalt and manganese are preferably used. Further, as a form, a sol or slurry dispersed in a powder, an organic solvent or water can be used. Examples of commercially available powdered titanium oxide fine particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd. and ATM-100 manufactured by TAYCA Corporation. Examples of commercially available slurry-like titanium oxide fine particles include TAYCA Corporation TKD-701.

<Fibrous substrate>
The composition of the present invention may further contain a fibrous substrate. The fibrous substrate of the present invention is not particularly limited, but those used for fiber reinforced resins are preferable, and inorganic fibers and organic fibers can be mentioned.

Inorganic fibers include carbon fibers, glass fibers, boron fibers, alumina fibers, silicon carbide fibers, and other inorganic fibers, as well as carbon fibers, activated carbon fibers, graphite fibers, glass fibers, tungsten carbide fibers, and silicon carbide fibers (silicon carbide fibers). ), Ceramic fibers, alumina fibers, natural fibers, mineral fibers such as genbuiwa, boron fibers, boron nitride fibers, boron carbide fibers, metal fibers and the like. Examples of the metal fiber include aluminum fiber, copper fiber, brass fiber, stainless fiber, and steel fiber.

Organic fibers include synthetic fibers made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate, cellulose, pulp, and the like. Examples include natural fibers such as cotton, wool and silk, and regenerated fibers such as proteins, polypeptides and alginic acid.

Among them, carbon fiber and glass fiber are preferable because they have a wide range of industrial applicability. Of these, only one type may be used, or a plurality of types may be used at the same time.

The fibrous substrate of the present invention may be an aggregate of fibers, may be continuous or discontinuous, and may be woven or non-woven. Further, a fiber bundle in which fibers are arranged in one direction may be used, or a sheet in which the fiber bundles are arranged may be used. Further, the aggregate of fibers may have a three-dimensional shape having a thickness.

<Dispersion medium>
In the composition of the present invention, a dispersion medium may be used for the purpose of adjusting the solid content and viscosity of the composition. The dispersion medium may be a liquid medium that does not impair the effects of the present invention, and examples thereof include various organic solvents and liquid organic polymers.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), cyclic ethers such as tetrahydrofuran (THF) and dioxolane, and esters such as methyl acetate, ethyl acetate and butyl acetate. , Aromatic substances such as toluene and xylene, and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanone and propylene glycol monomethyl ether. These can be used alone or in combination, and among them, methyl ethyl ketone is applied. It is preferable from the viewpoint of volatileness during construction and solvent recovery.

The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and is, for example, a carboxyl group-containing polymer modified product (Floren G-900, NC-500: Kyoeisha), an acrylic polymer (Floren WK-20: Kyoeisha). , Amine salt of special modified phosphoric acid ester (HIPLAAD ED-251: Kusumoto Kasei), modified acrylic block copolymer (DISPERBYK2000; Big Chemie) and the like.

<Resin>
Further, the composition of the present invention may have a resin other than the above-mentioned various compounds of the present invention. As the resin, a known and commonly used resin may be blended as long as the effect of the present invention is not impaired, and for example, a thermosetting resin or a thermoplastic resin can be used.

A thermosetting resin is a resin having a property of being substantially insoluble and insoluble when cured by means such as heating or radiation or a catalyst. Specific examples thereof include phenol resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, silicone resin, urethane resin, furan resin, ketone resin, xylene resin, and heat. Examples thereof include curable polyimide resin, benzoxazine resin, active ester resin, aniline resin, cyanate ester resin, styrene / maleic anhydride (SMA) resin, and maleimide resin. These thermosetting resins can be used alone or in combination of two or more.

The thermoplastic resin is a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethylmethacrylate resin, acrylic resin, and polyvinyl chloride resin. Polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate Resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyether sulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyether ether ketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, Shinji Examples thereof include otakutic polystyrene resin and cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.

<Other formulations>
The composition of the present invention may have other formulations. For example, catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow modifiers, coupling agents, dyes, leveling agents, rheology control agents, UV absorbers, etc. Examples include antioxidants, flame retardants, plasticizers, reactive diluents and the like.

<Cured product>
In the composition of the present invention, by applying a reaction product of the aliphatic dihydroxy compound diglycidyl ether and the aromatic hydroxy compound, it is possible to obtain an unprecedentedly flexible and tough cured product. For example, a high-molecular-weight epoxy compound obtained by reacting the above-mentioned liquid bisphenol A type epoxy resin with an aliphatic dicarboxylic acid such as dimer acid or sebacic acid as a molecular chain extender gives a cured product having a flexible structure, but an ester. The effect is not sufficient due to the aggregation of groups.

On the other hand, in the present invention, the skeleton generated from the aliphatic compound functions as a so-called soft segment that imparts flexibility, so that the cured product obtained by curing the epoxy compound A of the present invention becomes extremely flexible. .. On the other hand, since the skeleton generated from the aromatic hydroxy compound functions as a so-called hard segment that imparts rigidity to the epoxy compound A of the present invention, it is possible to provide a cured product having both flexibility and toughness. Furthermore, since the oriented skeleton generated from the aromatic hydroxy compound having orientation agglomerates the soft segments, it is possible to provide a flexible adhesive layer having excellent creep resistance because it is possible to achieve both a high elastic modulus and an excellent elongation, which are usually contradictory to each other. ..

In particular, in the case of the epoxy compound A of the present invention, the portion that functions as a hard segment and the portion that functions as a soft segment are bonded to impart flexibility to the epoxy compound structure and exhibit excellent moisture resistance. Can be done. Further, in the present invention, the toughness of the cured epoxy product becomes extremely excellent by directly bonding the glycidyloxy group to the aromatic nucleus. That is, for example, a general-purpose epoxy resin having a structure in which a low-volume type liquid bisphenol A type epoxy resin is modified with ethylene oxide or a propylene oxide and a diol compound obtained by converting it into a glycidyl ether is a flexible epoxy resin skeleton itself. , The activity of the epoxy group itself was inferior, and sufficient cross-linking was not obtained to develop toughness at the time of curing. However, the epoxy compound A of the present invention is an epoxy due to the direct bonding of the glycidyloxy group to the aromatic nucleus. Since the activity of the group is high, although the resin itself is flexible, it forms an appropriate crosslink during the curing reaction and exhibits excellent toughness. Further, since the hard segment is adjacent to the epoxy group serving as the cross-linking point, the physical strength at the cross-linking point is increased and the toughness is improved.

When the composition of the present invention is cured, it may be cured at room temperature or by heating. When curing, a known and commonly used curing catalyst may be used.
When thermosetting is performed, it may be cured by one heating or may be cured through a multi-step heating step.

When a curing catalyst is used, for example, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate and acetic acid; inorganic bases such as sodium hydroxide or potassium hydroxide; tetra. Titanium esters such as isopropyl titanate and tetrabutyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonen-5 (DBN) , 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 2-ethyl-4-methyl-imidazole, 1-methylimidazole, N , N-Dimethyl-4-aminopyridine (DMAP) and other compounds containing basic nitrogen atoms; various quaternary ammonium salts such as tetramethylammonium salt, tetrabutylammonium salt and dilauryldimethylammonium salt. There are quaternary ammonium salts having chloride, bromide, carboxylate or hydrooxide as counter anions; dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diacetylacetonate, tin octylate or tin stearate. Tin carboxylate ,; benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, t-butyl perbenzoate, etc. Organic peroxides such as, etc. can be used. The catalyst may be used alone or in combination of two or more.

The composition of the present invention can also be cured with active energy rays. In that case, a photocationic polymerization initiator may be used as the polymerization initiator. Visible light, ultraviolet rays, X-rays, electron beams and the like can be used as the active energy rays.

Examples of the photocationic polymerization initiator include aryl-sulfonium salts, aryl-iodonium salts, and the like. Specific examples thereof include aryl sulfonium hexafluorophosphate, aryl sulfonium hexafluoroantimonate, and aryl sulfonium tetrakis (pentafluoro) borate. , Dialkylphenaxylsulfonium hexafluorophosphate and the like can be used. The photocationic polymerization initiator may be used alone or in combination of two or more.

<Laminated body>
The cured product of the present invention can be laminated with a base material to form a laminated body.
The base material of the laminate may be an inorganic material such as metal or glass, an organic material such as plastic or wood, etc., depending on the application, and the laminate may be shaped like a flat plate, a sheet, or a three-dimensional structure. It does not matter whether it is held or has a three-dimensional shape. It may have any shape depending on the purpose, such as one having a curvature on the entire surface or a part thereof. Further, there are no restrictions on the hardness, thickness, etc. of the base material. Further, the cured product of the present invention may be used as a base material, and the cured product of the present invention may be further laminated.

Since the composition of the present invention has particularly high adhesiveness to metals and / or metal oxides, it can be used particularly well as a primer for metals. Examples of the metal include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and composite materials thereof, and metal oxides include single oxides of these metals and single oxides of these metals. Alternatively, a composite oxide may be mentioned. In particular, it has excellent adhesive strength to iron, copper, and aluminum, so it can be used satisfactorily as an adhesive for iron, copper, and aluminum.

In the laminated body of the present invention, the cured product layer may be formed by directly coating or molding on the base material, or the already molded product may be laminated. In the case of direct coating, the coating method is not particularly limited, and the spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, etc. Examples include a screen printing method and an inkjet method. In the case of direct molding, in-mold molding, insert molding, vacuum forming, extrusion laminating molding, press molding and the like can be mentioned.
When laminating the molded composition, the uncured or semi-cured composition layer may be laminated and then cured, or the cured composition layer in which the composition is completely cured may be laminated on the substrate. Good.
Further, the cured product of the present invention may be laminated by coating and curing a precursor that can be a base material, and the precursor that can be a base material or the composition of the present invention is uncured or semi-cured. It may be cured after adhering in the state of. The precursor that can be used as a base material is not particularly limited, and examples thereof include various curable resin compositions.

<Fiber reinforced plastic>
When the composition of the present invention has a fibrous substrate and the fibrous substrate is a reinforcing fiber, the composition containing the fibrous substrate can be used as a fiber-reinforced resin.
The method for incorporating the fibrous substrate into the composition is not particularly limited as long as the effects of the present invention are not impaired, and the fibrous substrate and the composition are kneaded, coated, impregnated, injected, pressure-bonded, etc. A method of compounding by a method is mentioned, and it can be selected in a timely manner depending on the form of the fiber and the use of the fiber reinforced resin.

The method for molding the fiber-reinforced resin of the present invention is not particularly limited. If a plate-shaped product is to be manufactured, an extrusion molding method is common, but a flat press can also be used. In addition, an extrusion molding method, a blow molding method, a compression molding method, a vacuum forming method, an injection molding method and the like can be used. In addition to the melt extrusion method, a solution cast method can be used to manufacture film-like products. When the melt molding method is used, inflation film molding, cast molding, extrusion lamination molding, calendar molding, and sheet molding can be used. , Fiber molding, blow molding, injection molding, rotary molding, coating molding and the like. Further, in the case of a resin that is cured by an active energy ray, a cured product can be produced by using various curing methods using the active energy ray. In particular, when a thermosetting resin is used as the main component of the matrix resin, a molding method in which the molding material is made into a prepreg and pressurized and heated by a press or an autoclave can be mentioned. In addition, RTM (Resin Transfer Molding) molding, Examples include VaRTM (Vaccum assist Resin Transfer Molding) molding, laminated molding, hand lay-up molding and the like.

<Prepreg>
The fiber-reinforced resin of the present invention can form a state called an uncured or semi-cured prepreg. After the product is distributed in the state of prepreg, the final curing may be performed to form a cured product. When forming a laminate, it is preferable to form a prepreg, then laminate other layers, and then perform final curing to form a laminate in which each layer is in close contact with each other.
The mass ratio of the composition to the fibrous substrate used at this time is not particularly limited, but it is usually preferable to prepare the resin content in the prepreg to be 20 to 60% by mass.

<Heat-resistant materials and electronic materials>
The composition of the present invention can be suitably used for a heat-resistant member because the cured product has a high glass transition temperature and is excellent in heat-resistant decomposition. Further, since it has excellent adhesion to a base material, it can be particularly preferably used for an electronic member. In particular, it can be suitably used for semiconductor encapsulants, circuit boards, build-up films, build-up boards, etc., adhesives and resist materials. Further, it can be suitably used for a matrix resin of a fiber reinforced resin, and is particularly suitable as a prepreg having high heat resistance. The heat-resistant members and electronic members thus obtained can be suitably used for various purposes. For example, industrial machine parts, general machine parts, automobile / railroad / vehicle parts, space / aviation-related parts, electronic / electrical parts, etc. Building materials, container / packaging materials, daily necessities, sports / leisure products, wind power generation housing materials, etc. are included, but are not limited to these.

Hereinafter, typical products will be described with examples.

1. 1. Semiconductor encapsulation material As a method for obtaining a semiconductor encapsulation material from the composition of the present invention, the composition, a curing accelerator, and a compounding agent such as an inorganic filler are used as necessary in an extruder, a feeder, or the like. Examples thereof include a method of sufficiently melting and mixing until the mixture becomes uniform using a roll or the like. At that time, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, and silicon nitride having higher thermal conductivity than fused silica are used. It is preferable to use high-filling silicon or the like, or use molten silica, crystalline silica, alumina, silicon nitride, or the like. It is preferable to use an inorganic filler in the range of 30 to 95% by mass per 100 parts by mass of the curable resin composition, and among them, improvement of flame retardancy, moisture resistance and solder crack resistance, linear expansion coefficient. 70 parts by mass or more is more preferable, and 80 parts by mass or more is further preferable.

2. Semiconductor device For semiconductor package molding to obtain a semiconductor device from the curable resin composition of the present invention, the above semiconductor encapsulant material is cast or molded using a transfer molding machine, injection molding machine, or the like, and further 50 to 250 ° C. There is a method of heating for 2 to 10 hours.

3. 3. Printed circuit board As a method for obtaining a printed circuit board from the composition of the present invention, the above prepregs are laminated by a conventional method, copper foils are appropriately laminated, and a pressure of 1 to 10 MPa is applied at 170 to 300 ° C. for 10 minutes. A method of heat-bonding for 3 hours can be mentioned.

4. Build-up substrate A method for obtaining a build-up substrate from the composition of the present invention includes, for example, the following steps. First, a step (step 1) of applying the above composition, which is appropriately blended with rubber, a filler, and the like, to a circuit board on which a circuit is formed by using a spray coating method, a curtain coating method, or the like, and then curing the composition. After that, if necessary, a predetermined through-hole portion or the like is drilled, treated with a roughening agent, and the surface thereof is washed with hot water to form irregularities, and a metal such as copper is plated (process). 2). A step of alternately building up and forming a resin insulating layer and a conductor layer having a predetermined circuit pattern by sequentially repeating such an operation as desired (step 3). The through-hole portion is drilled after the outermost resin insulating layer is formed. Further, the build-up substrate of the present invention is roughened by heat-pressing a resin-containing copper foil obtained by semi-curing the resin composition on a copper foil onto a wiring substrate on which a circuit is formed at 170 to 300 ° C. It is also possible to produce a build-up substrate by omitting the steps of forming a chemical surface and plating.

5. Build-up film As a method of obtaining a build-up film from the composition of the present invention, the above composition is applied to the surface of the support film (Y) which is a base material, and an organic solvent is further applied by heating or blowing hot air. It can be produced by drying to form a layer (X) of the composition.

Examples of the organic solvent used here include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used, and the non-volatile content is 30 to 60% by mass. preferable.

The thickness of the layer (X) formed is usually equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm. The layer (X) of the composition in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches.

The support film and protective film described above include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and further release. Examples include metal foils such as paper patterns, copper foils, and aluminum foils. The support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the curable resin composition layer constituting the build-up film is heat-cured, it is possible to prevent the adhesion of dust and the like in the curing step. When peeling after curing, the support film is usually preliminarily subjected to a mold release treatment.

A multilayer printed circuit board can be manufactured using the build-up film obtained as described above. For example, when the layer (X) is protected by a protective film, the layer (X) is peeled off and then laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. If necessary, the build-up film and the circuit board may be preheated if necessary before laminating. As for the laminating conditions, the crimping temperature (lamination temperature) is preferably 70 to 140 ° C., and the crimping pressure is preferably 1 to 11 kgf / cm2 (9.8 × 104 to 107.9 × 104 N / m2). , It is preferable to laminate under a reduced air pressure of 20 mmHg (26.7 hPa) or less.

6. Conductive Paste As a method for obtaining a conductive paste from the composition of the present invention, for example, a method of dispersing conductive particles in the composition can be mentioned. The conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of conductive particles used.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified.

The FD-MS spectrum and GPC were measured under the following conditions.

<Mass spectrum>
FD-MS: "JMS-T100GC AccuTOF" manufactured by JEOL Ltd.
Measurement range: m / z = 50.00 to 2000.0
Rate of change: 25.6 mA / min
Final current value: 40mA
Cathode voltage: -10kV

<Gel Permeation Chromatograph>
GPC: "HLC-8320GPC" manufactured by Tosoh Corporation
Column: "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (Differential Refractometer)
Measurement conditions: 40 ° C
Mobile phase: tetrahydrofuran Flow rate: 1 ml / min
Standard: "PStQuick A""PStQuickB""PStQuickE""PStQuickF" manufactured by Tosoh Corporation

The epoxy equivalent of the synthesized epoxy compound was measured according to JIS K7236, and the epoxy equivalent (g / eq) was calculated.

Examples of the method for calculating the number of repeating units include GPC molecular weight measurement and calculation from various appropriate instrumental analysis conclusions such as FD-MS.

Synthesis Example 1 Synthesis of epoxy compound C-1 420 g (1.0 mol) of 1,12-dodecanediol diglycidyl ether (manufactured by Yokkaichi Chemical Co., Ltd .: epoxy equivalent 210 g / eq) in a flask equipped with a thermometer and a stirrer. And 4,4'-biphenol (hydroxyl equivalent 93 g / eq) 93 g (0.50 mol) were charged, and the temperature was raised to 140 ° C. for 30 minutes, and then 2.6 g of a 4% sodium hydroxide aqueous solution was charged. Then, it took 30 minutes to raise the temperature to 150 ° C., and further reacted at 150 ° C. for 3 hours. Then, a neutralized amount of sodium phosphate was added to obtain 513 g of epoxy compound C-1. The epoxy equivalent of the obtained epoxy compound C-1 was 513 g / eq.

Synthesis Example 2 Synthesis of hydroxy compound B-1 513 g (0.5 mol) of epoxy compound C-1 and bisphenol A (hydroxyl equivalent 114 g / eq) 228 g (1.0 mol) in a flask equipped with a thermometer and a stirrer. Was charged, and the temperature was raised to 140 ° C. for 30 minutes, and then 3.7 g of a 4% sodium hydroxide aqueous solution was charged. Then, it took 30 minutes to raise the temperature to 150 ° C., and further reacted at 150 ° C. for 3 hours. Then, a neutralized amount of sodium phosphate was added to obtain 740 g of hydroxy compound B-1. The peak of M + = 1272 was confirmed in the mass spectrum of this hydroxy compound B-1. The hydroxyl group equivalent of this hydroxy compound B-1 calculated from GPC was 544 g / eq.

Synthesis Example 3 Synthesis of Epoxy Compound C-2 93 g (0.5 mol) of 4,4'-biphenol (hydroxyl equivalent 93 g / eq) in Synthesis Example 1 was added to 114 g (0.5 mol) of bisphenol A (hydroxyl equivalent 114 g / eq). ), The reaction was carried out in the same manner as in Synthesis Example 1 to obtain 534 g of epoxy compound C-2. The epoxy equivalent of the obtained epoxy compound C-2 was 536 g / eq.

Synthesis Example 4 Synthesis of hydroxy compound B-2 As in Synthesis Example 2, except that 513 g (0.5 mol) of epoxy compound C-1 in Synthesis Example 2 was changed to 534 g (0.5 mol) of epoxy compound C-2. The reaction was carried out in the same manner to obtain 760 g of hydroxy compound B-2. For this hydroxy compound B-2, a peak of M + = 1313 was confirmed in the mass spectrum. The hydroxyl group equivalent of this hydroxy compound B-2 calculated from GPC was 564 g / eq.

Synthesis example 5
Same as Synthesis Example 2 except that the epoxy compound C-1 in Synthesis Example 2 was changed to 210 g (0.5 mol) of 1,12-dodecanediol diglycidyl ether (manufactured by Yokkaichi Chemical Co., Ltd .: epoxy equivalent 210 g / eq). To obtain 430 g of hydroxy compound B-3. For the hydroxy compound B-3, a peak of M + = 771 was confirmed in the mass spectrum. The hydroxyl group equivalent of this hydroxy compound B-3 calculated from GPC was 330 g / eq.

Example 1
While performing nitrogen gas purging in a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, 544 g of the hydroxy compound B-1 obtained in Synthesis Example 2, 1110 g (12.0 mol) of epichlorohydrin, and n-butanol 280 g was charged and dissolved. After the temperature was raised to 65 ° C., the pressure was reduced to an azeotropic pressure, and 122 g (1.5 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Then, stirring was continued for 0.5 hours under the same conditions. During this period, the distillate distilled off by azeotrope was separated by a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Then, unreacted epichlorohydrin was distilled off by vacuum distillation. To the obtained crude epoxy compound, 1000 g of methyl isobutyl ketone and 100 g of n-butanol were added and dissolved. Further, 20 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water was repeated 3 times with 300 g of water until the pH of the washing liquid became neutral. Then, the inside of the system was dehydrated by azeotrope, and after undergoing microfiltration, the solvent was distilled off under reduced pressure to obtain 580 g of epoxy compound A-1. The epoxy equivalent of the obtained epoxy compound A-1 was 612 g / eq.

(Manufacturing and evaluation of resin composition and cured product)
Epoxy resin composition by uniformly mixing epoxy compound A-1, curing agent and curing accelerator with a mixer (“Awatori Rentaro ARV-200” manufactured by Shinky Co., Ltd.) according to the formulation according to Table 1. Got This epoxy resin composition is sandwiched between aluminum mirror plates ("JIS H 4000 A1050P" manufactured by Engineering Test Service Co., Ltd.) using a silicon tube as a spacer, and is thermoset at 170 ° C. for 30 minutes to obtain a resin having a thickness of 0.8 mm. A cured product was obtained.

<Tensile test>
The cured resin product was punched into a dumbbell shape (JIS K 7162-1BA) with a punching blade, and this was used as a test piece. This test piece was evaluated for tensile strength, elongation, and elastic modulus according to JIS K 7162-2 using a tensile tester (“Autograph AG-IS” manufactured by Shimadzu Corporation) (test speed: 2 mm / min). ..

<Tension shear test>
The resin composition is applied to one of two cold-rolled steel sheets (TPCC-SB manufactured by TP Giken Co., Ltd., 1.0 mm x 25 mm x 100 mm), and glass beads (Potters Barotini stock) are used as spacers. A company-made "J-80") was added, and another SPCC-SB was bonded (adhesion area: 25 mm x 12.5 mm). This was heat-cured at 170 ° C. for 1 hour to obtain a test piece. Adhesiveness was evaluated by performing a tensile shear test using the test piece. The test was performed according to JIS K 6850, and the maximum point stress was compared.
<Creep test>
The cured resin product was punched into a dumbbell shape (JIS K 7162-1BA) with a punching blade, and this was used as a test piece. A vertical load of 100 g was applied to one end of the test piece, a creep test was performed for 24 hours, and the strain rate was measured.

Comparative Example 1
The reaction was carried out in the same manner as in Example 1 except that 544 g of the hydroxy compound B-1 obtained in Synthesis Example 2 was changed to 564 g of the hydroxy compound B-2 obtained in Synthesis Example 4, and 601 g of the epoxy compound Ep-1 was obtained. Obtained. The epoxy equivalent of the obtained epoxy compound Ep-1 was 642 g / eq. The obtained reaction product was evaluated in the same manner as in Example 1.

Comparative Example 2
The reaction was carried out in the same manner as in Example 1 except that 680 g of the hydroxy compound B-1 obtained in Synthesis Example 2 was changed to 430 g of the hydroxy compound B-3 obtained in Synthesis Example 5, and 350 g of the epoxy compound Ep-2 was added. Obtained. The epoxy equivalent of the obtained epoxy compound Ep-2 was 425 g / eq. The obtained reaction product was evaluated in the same manner as in Example 1.

The materials used in the table are as follows.
DICY: dicyandiamide ("DICY7" manufactured by Mitsubishi Chemical Corporation)
DCMU: 3- (3,4-dichlorophenyl) -1,1-dimethylurea ("B-605-IM" manufactured by DIC Corporation)

The epoxy compound A of the present invention is a flexible cured product having a high elongation rate premised on elastic deformation, high adhesiveness capable of withstanding the difference in thermal expansion of the base material, and creep resistance capable of suppressing the creep phenomenon. Can be provided. In particular, it can be suitably used for adhesives for structural materials and advanced electronic materials such as semiconductor encapsulant materials and insulating layers for multilayer printed circuit boards.

Claims (14)

Epoxy compound A having the structure of the general formula (1).

... (1)
(In formula (1), Ar represents a structure having an aromatic ring having an unsubstituted or substituent, respectively.
R _{1, R 2} and _R 1 ', _{R 2'} represents a hydrogen atom or an alkyl group having a carbon number of 1 or 2 independently,
R _{3 to} R ₈ represent a hydroxyl group, a glycidyl ether group and / or a 2-methyl glycidyl ether group, and _{at least one of R 3 to} R ₈ is a glycidyl ether group or a 2-methyl glycidyl ether group.
R _{9 to} R ₁₂ represent a hydrogen atom or a methyl group.
n is an integer of 4 to 16 independently,
m is an average value of repetitions of 0.5 to 10 and
l is the average value of repetitions of 0.5 to 10 and
Ar'is a structure represented by the following equation (2).

... (2)
(In the formula (2), Y independently represents a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyl group having 1 to 8 carbon atoms, and X is a single bond, an −O− group, −. CH = CH-group, -CH = C (CH ₃ ) -group, -CH = C (CN) -group, -C≡C- group, -CH = N- group, -CH = CH-CO- group, -N = N- group, -COO- group, -CONH- group or -CO- group, q ₁ and q ₂ are independent integers from 0 to 4, and p ₁ is an integer from 1 to 3. Represent)
(However, each repeating unit existing in the repeating unit may be the same or different). ) The epoxy compound A according to claim 1 _{, wherein R 3} and R ₄ are glycidyl ether groups in the formula (1). The epoxy compound A according to claim 1 or 2, wherein in the formula (1), Ar has any structure represented by the following formula (3).

... (3)
(In the formula (3), the aromatic ring may be substituted or unsubstituted, and * represents a bonding point.) The epoxy compound A according to any one of claims 1 to 3, wherein Ar further has a glycidyl ether group and / or a 2-methylglycidyl ether group in the formula (1). A composition comprising the epoxy compound A according to any one of claims 1 to 4. The composition according to claim 5, further comprising a curing agent. The composition according to claim 6, wherein the curing agent is at least one selected from an amine compound, a phenol compound, a carboxylic acid compound, and an acid anhydride compound. The composition according to any one of claims 5 to 7, further comprising a filler. A cured product obtained by curing the composition according to any one of claims 5 to 8. A laminate having a base material and the cured product layer according to claim 9. The laminate according to claim 9, wherein the base material is a metal or a metal oxide. A laminate in which the base material, the cured product layer according to claim 9, and the second base material are laminated in this order, the base material is a metal or a metal oxide, and the second base material is a plastic layer. The laminate according to claim 10 or 11. An electronic member comprising the laminate according to any one of claims 9 to 12. An adhesive for a metal or a metal oxide, which contains the epoxy compound A according to any one of claims 1 to 4.