JP7375347B2 - Epoxy compounds, compositions, cured products and laminates - Google Patents

Description

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

Automobiles and airplanes are becoming increasingly lighter due to _CO2 reduction and fuel efficiency improvements, and along with this, weight reductions are progressing by reducing the number of spot welds and combining fiber-reinforced resin with metal. There is a strong demand for higher performance agents. In particular, when thermally adhering aluminum, which has a large difference in thermal expansion, and fiber-reinforced resin, warping and waving due to interfacial stress due to expansion and contraction are seen as a problem, and adhesives that alleviate stress are needed.
In addition, as advanced electronic materials used for semiconductor encapsulation materials and insulating layers for multilayer printed circuit boards become ultra-thin, warping due to the difference in thermal expansion between silicon chips and metals has become a serious problem, causing stress. Mitigation capabilities are needed now more than ever.

On the other hand, epoxy resins are often used as adhesives because they have dimensional stability when cured, electrical insulation properties, and chemical resistance. However, when trying to maintain high adhesiveness, it becomes hard and brittle, so a high molecular weight epoxy compound ( For example, flexible epoxy compounds such as Patent Document 1) and high molecular weight epoxy compounds derived from hydroxy compounds having aliphatic hydrocarbon groups (Patent Document 2) have been disclosed. However, since the deformation mode of flexible epoxy compounds is plastic deformation, they cannot repeatedly follow the difference in expansion of the base material while maintaining the overall rigidity, which poses a problem in durability.
From the above, there is a need for an epoxy compound that provides a flexible cured product that has both a high elongation rate based on elastic deformation and high adhesiveness that can withstand the difference in thermal expansion of the base material.

Japanese Patent Application Publication No. 8-53533 Japanese Patent Application Publication No. 2006-335796

An object of the present invention is to provide an epoxy compound that provides a flexible cured product that has both a high elongation rate based on elastic deformation and high adhesiveness that can withstand differences in thermal expansion of base materials.
Another object of the present invention is to provide a laminate comprising a composition containing the epoxy compound, a cured product obtained by curing the composition, and a layer of the cured product and a base material.

As a result of extensive studies, the present inventors have found that by providing an epoxy compound A characterized by having a structure X represented by the following formula (1) and a glycidyl ether group or a 2-methylglycidyl ether group. It has been found that the above problem can be solved. That is, the present invention provides an epoxy compound A characterized by having a structure X represented by the following formula (1) and a glycidyl ether group or a 2-methylglycidyl ether group.

...(1)

(In formula (1), Ar represents a structure having an aromatic ring that is unsubstituted or has a substituent, n is an integer of 3 to 6, m is the average value of repetitions, and m is 0.5 to 10 And,
Y is a structure represented by formula (2-1) and/or formula (2-2) (however, each repeating unit present in the repeating unit may be the same or different)

...(2-1)

...(2-2)

(In formulas (2-1) and (2-2), p ₁ and p ₂ are each independently an integer of 4 to 16,
R ₃ to R ₆ each independently represent a hydrogen atom or an alkyl group having 1 or 2 carbon atoms,
R ₁ , R ₇ and R ₈ each independently represent a hydroxyl group, a glycidyl ether group and/or a 2-methylglycidyl ether group,
R ₂ , R ₉ and R ₁₀ each independently represent a hydrogen atom or a methyl group,
Ar represents a structure having an aromatic ring that is unsubstituted or has a substituent). ).

Epoxy compound A of the present invention can provide a flexible cured product that has both a high elongation rate based on elastic deformation and high adhesiveness that can withstand the difference in thermal expansion of the base material.

<Epoxy compound A>
The epoxy compound A of the present invention is characterized by having a structure X represented by the following formula (1) and a glycidyl ether group or a 2-methylglycidyl ether group.

...(1)

(In formula (1), Ar represents a structure having an aromatic ring that is unsubstituted or has a substituent, n is an integer of 3 to 6, m is the average value of repetitions, and m is 0.5 to 10 And,
Y is a structure represented by formula (2-1) and/or formula (2-2) (however, each repeating unit present in the repeating unit may be the same or different)

...(2-1)

...(2-2)

(In formulas (2-1) and (2-2), p ₁ and p ₂ are each independently an integer of 4 to 16,
R ₃ to R ₆ each independently represent a hydrogen atom or an alkyl group having 1 or 2 carbon atoms,
R ₁ , R ₇ and R ₈ each independently represent a hydroxyl group, a glycidyl ether group and/or a 2-methylglycidyl ether group,
R ₂ , R ₉ and R ₁₀ each independently represent a hydrogen atom or a methyl group,
Ar represents a structure having an aromatic ring that is unsubstituted or has a substituent). )

In the epoxy compound A having the above structure, it is preferable that the number of structures X is three or less because the resulting cured product has an appropriate crosslinking density and can have both flexibility and toughness and heat resistance. Preferably the number of structures X is two or less, particularly preferably one structure X.

In the epoxy compound A, Ar each independently represents a structure having an aromatic ring that is unsubstituted or has a substituent. The aromatic ring mentioned here includes, for example, 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 (5).

...(5)

(In formula (5), the aromatic ring may be substituted or unsubstituted, Ar in formula (1) and formula (3) is each independently an integer of n ₁ = 3 to 6, and the formula ( 2-2) and (Formula 4-2), Ar is n ₁ = 2, and * represents the bonding point.)

Further, in formula (1), a structure represented by the following formula (5-1) can also be mentioned as Ar.

...(5-1)

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

The aromatic ring that Ar has 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. Preferably, it is unsubstituted, or an alkyl group, a glycidyl ether group, or a 2-methylglycidyl ether group. The number of substituents per aromatic ring is preferably two or less, more preferably one or less, and particularly preferably unsubstituted.

As the structure of Ar, the following is particularly preferable.

As Ar in formula (1), the following structures are particularly preferable.

Ar in formula (2-2) preferably has the following structure.

As Ar in formula (2-2), the following structure is particularly preferable.

In the above formula (1), m is the average value of repetitions, and m is 0.5 to 10. The average value of this repetition can be obtained by measuring with GPC. From the viewpoint of achieving both flexibility, toughness and durability, m is preferably 0.6 to 5.0.

Furthermore, in the formulas (2-1) and (2-2), p ₁ and p ₂ are each independently an integer of 4 to 16. From the viewpoint of flexibility, toughness and durability, the number is preferably 6 to 15. Particularly preferably 6 to 12.

Furthermore, in the formulas (2-1) and (2-2), R ₃ to R ₆ each independently represent a hydrogen atom or an alkyl group having 1 or 2 carbon atoms,
R ₁ , R ₇ and R ₈ each independently represent a hydroxyl group, a glycidyl ether group and/or a 2-methylglycidyl ether group,
R ₂ , R ₉ and R ₁₀ each independently represent a hydrogen atom or a methyl group.
R ₃ to R ₆ are preferably hydrogen atoms.
R ₁ , R ₇ and R ₈ are preferably hydroxyl groups.
R ₂ , R ₉ and R ₁₀ are preferably hydrogen atoms.

A preferred structure of the epoxy compound A of the present invention includes a structure represented by the following formula (3).

...(3)
(In formula (3), Ar represents a structure having an aromatic ring that is unsubstituted or has a substituent, n is an integer of 3 to 6, m is the average value of repetitions, and m is 0.5 to 10 And,
Y is a structure represented by formula (2-1) and/or formula (2-2),
Q is each independently a hydroxyl group or a structure represented by formula (4-1) or formula (4-2) (however, each repeating unit present in the repeating unit is the same) It doesn't matter if they are different)

...(4-1)

...(4-2)

(In formula (4-1) and formula (4-2), R ₁₁ and R ₁₂ represent a hydrogen atom or a methyl group,
R ₁₃ represents a hydroxyl group, a glycidyl ether group and/or a 2-methylglycidyl ether group,
R ₁₄ represents a hydrogen atom or a methyl group,
Ar represents a structure having an aromatic ring that is unsubstituted or has a substituent). )

In the above formula (3), m is the average value of repetitions, and m is 0.5 to 10. The average value of this repetition can be obtained by measuring with gel permeation chromatography. From the viewpoint of achieving both flexibility, toughness and durability, m is preferably 0.6 to 5.0.

Moreover, the following structure is mentioned as a more preferable structure of the epoxy compound A of this invention.

Among the above structural formulas, it is preferable to use those represented by the following from the viewpoint of curability and heat resistance.

Among the above-mentioned structural formulas, it is most preferable to use those represented by the following in view of the excellent balance of physical properties of the resulting cured product.

On the other hand, the structure exemplified below can also be included within a range that does not deteriorate the performance.

<Method for producing epoxy compound A>
Although the method for producing the epoxy compound A of the present invention is not particularly limited, for example, the diglycidyl ether (a1) of an aliphatic dihydroxy compound and the aromatic hydroxy compound (a2) are An epoxy compound C obtained by reacting (a1) in a range of 1.01 to 3.0 moles with respect to 1 mole of phenolic hydroxyl group of the hydroxy compound (a2) is obtained, and an aromatic hydroxy compound ( It is preferable to use a method in which the hydroxy compound B obtained by reacting with a3) is further reacted with an epihalohydrin (a4) from the viewpoint of easy raw material acquisition and reaction.

<Epoxy compound C>
Epoxy compound C obtained by reacting the diglycidyl ether (a1) of an aliphatic dihydroxy compound with an aromatic hydroxy compound (a2) is obtained, and this is further reacted with an aromatic hydroxy compound (a3) to obtain an epoxy compound C. When epoxy compound A is obtained by further reacting hydroxy compound B with epihalohydrin (a4), as epoxy compound C, (a1) is added per mole of phenolic hydroxyl group of aromatic hydroxy compound (a2). It can be obtained by reacting in a range of 1.01 to 3.0 moles.
Although the epoxy compound C contains unreacted diglycidyl ether (a1) of an aliphatic dihydroxy compound, it may be used as it is in the present invention, or the diglycidyl ether (a1) of an aliphatic dihydroxy compound It may be removed and used.
The unreacted diglycidyl ether (a1) of the aliphatic dihydroxy compound can be removed by various methods. Examples include column chromatography separation methods that utilize differences in polarity, and distillation fractionation methods that utilize differences in boiling points. Among these, the distillation-fractionation method is preferred as a simple method, and vacuum distillation-fractionation under high vacuum is particularly preferred in order to suppress thermal alteration. The balance between toughness and flexibility of the cured product is such that the unreacted diglycidyl ether (a1) of the aliphatic dihydroxy compound in the resulting hydroxy compound B is in the range of 0.1 to 30% by mass. This is preferable because it provides good results.

The diglycidyl ether (a1) of the aliphatic dihydroxy compound is not particularly limited, and includes, for example, 1,11-undecanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and 1,9-nonane. Diol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, 1,14-tetradecanediol diglycidyl ether, 1,15-pentadecanediol diglycidyl ether, 1,16-hexadecanediol diglycidyl ether Glycidyl 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 during glycidyl etherification of hydroxy compounds, and may contain organic chlorine such as 1-chloromethyl-2-glycidyl ether (chloromethyl form) represented by the structure below. It's okay. These diglycidyl ethers may be used alone or in combination of two or more.

...Chloromethyl form

Among these, compounds with a structure in which a glycidyl group is connected to both ends of an alkylene chain having 4 to 16 carbon atoms via an ether group are preferred because of the excellent balance between flexibility and heat resistance of the resulting 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) is not particularly limited as long as it has three or more phenolic hydroxyl groups; for example, pyrogallol, 1,2,4-trihydroxybenzene, 1,3,5 - Trihydroxybenzenes such as trihydroxybenzene, triphenylmethane type phenols such as 4,4',4"-trihydroxytriphenylmethane, trihydroxynaphthalenes such as 1,3,6-trihydroxynaphthalene, dihydroxy 1,1'-methylene bis(2,7-naphthalenediol), 1,1'-binaphthalene-2,2',7,7'-tetraol, 1,1'-oxybis-2, which is a coupling reaction of naphthalenes. Tetrafunctional phenols such as (2,7-naphthalenediol), (1,1'-biphenyl)-2,4,4'-triol, (1,1'-biphenyl)-3,4',5-triol , (1,1'-biphenyl)-3,3',5,5'-tetraol and other biphenols, phenol novolac, cresol novolak and other novolac resins, polyadducts of phenol and dicyclopentadiene, and phenol. alicyclic structure-containing phenols such as polyadducts of and terpene compounds, naphthylene ethers obtained from the dehydration condensation reaction of dihydroxynaphthalene, and condensation reaction products of phenol and phenylene dimethyl chloride or biphenylene dimethyl chloride. Examples include so-called Zylock type phenolic resins, which may be used alone or in combination of two or more.Furthermore, the aromatic nucleus of each of the above compounds is substituted with a methyl group, t-butyl group, or a halogen atom as a substituent. Difunctional phenol compounds with a structure such as the above are also included.In addition, the above-mentioned alicyclic structure-containing phenols and the above-mentioned Zylock type phenol resin contain not only trifunctional or higher functional components but also bifunctional or lower functional components. However, in the present invention, it may be used as it is, or it may be used after undergoing a purification process using a column or the like to remove only components having less than two functionalities.

Among these, trihydroxybenzenes are the most preferred because they have an 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'-methylenebis(2,7-naphthalenediol) are preferable.In addition, when moisture resistance of the cured product is important, it is preferable to use phenols containing an alicyclic structure.

The reaction ratio between the diglycidyl ether (a1) of the aliphatic dihydroxy compound and the aromatic hydroxy compound (a2) is such that the aromatic hydroxy compound ( It is preferable to react 1.01 to 3.0 moles of (a1) with respect to 1 mole of the phenolic hydroxyl group of a2), from the viewpoint of achieving a well-balanced combination of flexibility and heat resistance of the resulting cured product. More preferably, the amount of (a1) is 1.1 to 2.0 mol per 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound (a2).

The reaction between the diglycidyl ether (a1) of the aliphatic dihydroxy compound and the aromatic hydroxy compound (a2) is preferably carried out in the presence of a catalyst. Various catalysts can be used as the catalyst, including alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide; alkali metals such as sodium carbonate and potassium carbonate; Carbonates, phosphorus compounds such as triphenylphosphine, DMP-30, DMAP, chlorides such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium, bromide, iodide, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium , chlorides such as benzyltributylphosphonium, quaternary ammonium salts such as bromide and iodide, triethylamine, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undecene, 1,4-diazabicyclo[2. 2.2] Tertiary amines such as octane, imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole, and the like. Two or more types of these catalysts may be used in combination. Among these, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred because the reaction proceeds quickly and they are highly effective in reducing the amount of impurities. The amount of these catalysts used is not particularly limited, but it is preferably used in an amount of 0.0001 to 0.01 mol per 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound (a2). The form of these catalysts is not particularly limited either, and they 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) can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of organic solvents 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 organic solvent used is usually 50 to 300% by weight, preferably 100 to 250% by weight based on the total weight of the raw materials charged. These organic solvents can be used alone or in combination. In order to carry out the reaction quickly, it is preferable to use no solvent, and on the other hand, it is preferable to use dimethyl sulfoxide in terms of reducing impurities in the final product.

The reaction temperature when carrying out the above reaction is usually 50 to 180°C, and the reaction time is usually 1 to 10 hours. From the viewpoint of reducing impurities in the final product, the reaction temperature is preferably 100 to 160°C. Furthermore, if the resulting compound is highly colored, an antioxidant or a reducing agent may be added to suppress it. Antioxidants are not particularly limited, but examples include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. I can do it. The reducing agent is not particularly limited, but includes, for example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfite, hydrosulfite, or salts thereof.

After the completion of the reaction, neutralization or washing with water may be carried out until the pH value of the reaction mixture becomes 3 to 7, preferably 5 to 7. Neutralization treatment and water washing treatment may be carried out according to conventional methods. For example, when a basic catalyst is used, an acidic substance such as hydrochloric acid, monobasic sodium 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 and heating to concentrate the product to obtain a compound.

Preferred structures of epoxy compound C include the following structures.

<Hydroxy compound B>
Epoxy compound C obtained by reacting the diglycidyl ether (a1) of an aliphatic dihydroxy compound with an aromatic hydroxy compound (a2) is obtained, and this is further reacted with an aromatic hydroxy compound (a3) to obtain an epoxy compound C. When the hydroxy compound B is further reacted with an epihalohydrin (a4) to obtain the epoxy compound A, the epoxy compound B is prepared by combining the epoxy compound C and the aromatic hydroxy compound (a3) with an aromatic hydroxy compound ( It can be obtained by reacting 1.01 to 3.0 moles of (a3) with respect to 1 mole of the phenolic hydroxyl group of a2).

Although the hydroxy compound B contains an unreacted aromatic hydroxy compound (a3), it may be used as is in the present invention, or may be used after removing the aromatic hydroxy compound (a3).

The unreacted aromatic hydroxy compound (a3) can be removed according to various methods. Examples include a column chromatography separation method that utilizes differences in polarity, a distillation fractionation method that utilizes differences in boiling point, and an aqueous alkaline extraction method that utilizes differences in solubility in alkaline water. Among these, the aqueous alkaline extraction method is preferred in terms of efficiency because it does not involve thermal alteration, and the organic solvent used to dissolve the target product at this time can be any organic solvent that does not mix with water, such as toluene or methyl isobutyl ketone. However, from the viewpoint of solubility with the target substance, methyl isobutyl ketone is preferred. The abundance ratio of the unreacted aromatic hydroxy compound (a3) in the obtained hydroxy compound B is 0.1 to 60% by mass, so that the cured product has a good balance between toughness and flexibility. Preferable from this point of view.

The aromatic hydroxy compound (a3) is not particularly limited, and includes, for example, hydroquinone, resorcinol, dihydroxybenzenes such as 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'-methylene bis(2, 7-naphthalene diol), 1,1'-binaphthalene-2,2',7,7'-tetraol, 1,1'-oxybis(2,7-naphthalene diol), -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, 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'diol, 4'-methyl-(1,1'-biphenyl)-3, Biphenols such as 4' diol, phenols containing alicyclic structures such as polyadducts of phenol and dicyclopentadiene, and polyadducts of phenol and terpene compounds, bis(2-hydroxy-1-naphthyl) Examples include methane, naphthols such as bis(2-hydroxy-1-naphthyl)propane, and so-called Zylock-type phenolic resins, which are condensation reaction products of phenol and phenylene dimethyl chloride or biphenylene dimethyl chloride. The above may be used in combination. Furthermore, bifunctional phenol compounds having a structure in which the aromatic nucleus of each of the above compounds is substituted with a methyl group, t-butyl group, or a halogen atom as a substituent may also be mentioned. In addition, in the alicyclic structure-containing phenols and the Zylock type phenol resin, not only bifunctional components but also trifunctional or higher functional components may be present at the same time, but they may be used as they are in the present invention, and Only the bifunctional components may be extracted and used after a purification process using a column or the like.

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- Bis(4-hydroxyphenyl)propane is preferred. In addition, when curability and heat resistance of the cured product are important, dihydroxynaphthalenes are preferable, and 2,7-dihydroxynaphthalene is particularly preferable since it imparts remarkable fast curing properties. Furthermore, when moisture resistance of the cured product is important, it is preferable to use phenols containing an alicyclic structure.

In order to use the obtained compound as a curing agent for epoxy resin, the reaction ratio of the epoxy compound C and the aromatic hydroxy compound (a3) is set to 1 mole of phenolic hydroxyl group of the aromatic hydroxy compound (a2). Therefore, it is essential to react with (a3) in a range of 1.01 to 3.0 mol, and from the viewpoint of achieving a well-balanced combination of flexibility and heat resistance of the resulting cured product, aromatic hydroxy compound (a2) It is preferable that (a3) be used in an amount of 1.1 to 2.0 mol per 1 mol of phenolic hydroxyl groups.

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 as the catalyst, including alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide; alkali metals such as sodium carbonate and potassium carbonate; Carbonates, phosphorus compounds such as triphenylphosphine, DMP-30, DMAP, chlorides such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium, bromide, iodide, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium , chlorides such as benzyltributylphosphonium, quaternary ammonium salts such as bromide and iodide, triethylamine, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undecene, 1,4-diazabicyclo[2. 2.2] Tertiary amines such as octane, imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole, and the like. Two or more types of these catalysts may be used in combination. Among these, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred because the reaction proceeds quickly and they are highly effective in reducing the amount of impurities. The amount of these catalysts used is not particularly limited, but it is preferably used in an amount of 0.0001 to 0.01 mol per 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound (a3). The form of these catalysts is not particularly limited either, and they 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 without a solvent or in the presence of an organic solvent. Examples of organic solvents 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 organic solvent used is usually 50 to 300% by weight, preferably 100 to 250% by weight based on the total weight of the raw materials charged. These organic solvents can be used alone or in combination. In order to carry out the reaction quickly, it is preferable to use no solvent, and on the other hand, it is preferable to use dimethyl sulfoxide in terms of reducing impurities in the final product.

The reaction temperature when carrying out the above reaction is usually 50 to 180°C, and the reaction time is usually 1 to 10 hours. From the viewpoint of reducing impurities in the final product, the reaction temperature is preferably 100 to 160°C. Furthermore, if the resulting compound is highly colored, an antioxidant or a reducing agent may be added to suppress it. Antioxidants are not particularly limited, but examples include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. I can do it. The reducing agent is not particularly limited, but includes, for example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfite, hydrosulfite, or salts thereof.

After the completion of the reaction, neutralization or washing with water may be carried out until the pH value of the reaction mixture becomes 3 to 7, preferably 5 to 7. Neutralization treatment and water washing treatment may be carried out according to conventional methods. For example, when a basic catalyst is used, an acidic substance such as hydrochloric acid, monobasic sodium 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 and heating to concentrate the product to obtain a compound.

Preferred structures of hydroxy compound B include the following structures.

<Glycidyl etherification reaction>
In the method for producing epoxy compound A of the present invention, there are no particular limitations on the method of the glycidyl etherification reaction of hydroxy compound B. Examples 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 the reaction is easy.

As a method using epihalohydrin (a4), for example, 0.3 to 20 mol of epihalohydrin (a4) is added to 1 mol of phenolic hydroxyl group of hydroxy compound B obtained above, and to this mixture, A method of reacting 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 to 1 mol of the phenolic hydroxyl group of the hydroxy compound B is a method. Can be mentioned. The amount of epihalohydrin (a4) to be added is such that the larger the excess amount of epihalohydrin (a4), the closer the resulting epoxy compound will be to the theoretical structure, and the more The production of hydroxyl groups can be suppressed. From this point of view, the range of 2.5 to 20 equivalents is particularly preferable. This basic catalyst may be used as a solid or as an aqueous solution. When an aqueous solution is used, it is added continuously, and water and epihalohydrins (a4 ) may be distilled off, water may be removed by further liquid separation, and the epihalohydrin (a4) may be continuously returned to the reaction mixture.

In addition, when performing industrial production, all of the charged epihalohydrins (a4) are used new in the first batch of epoxy compound production, but from the next batch onward, epihalohydrins (a4) recovered from the crude reaction product are used. It is preferable to use a new epihalohydrin (a4) in an amount corresponding to the amount consumed in the reaction and the amount that disappears due to the amount consumed in the reaction. At this time, the epihalohydrin (a4) used is not particularly limited, and examples include epichlorohydrin and epibromohydrin. Among them, epichlorohydrin is preferred because it is easily available.

Further, the basic catalyst is not particularly limited, but examples include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferred from the viewpoint of excellent catalytic activity for epoxy resin synthesis reactions, such as sodium hydroxide, potassium hydroxide, and the like. When used, these alkali metal hydroxides may be used in the form of an aqueous solution of about 10 to 55% by mass, or 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 organic solvents are not particularly limited, but include, 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 include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more to adjust polarity.

After washing the reaction products of the glycidylation reaction with water, unreacted epihalohydrins (a4) and the organic solvent used in combination are distilled off by distillation under heating and reduced pressure. Furthermore, in order to obtain an epoxy compound with even less hydrolyzable halogen, the obtained epoxy compound is dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. 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 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 based on the epoxy resin used. After the reaction is completed, a highly purified epoxy compound can be obtained by removing the generated salt by filtration, washing with water, etc., and then distilling off a solvent such as toluene or methyl isobutyl ketone under heating and reduced pressure.

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

The composition may contain substances other than epoxy compound A. For example, it is preferable to contain a curing agent that can react with an epoxy compound.

The curing agent is not particularly limited as long as it can react with the epoxy compound, but examples include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, carboxylic acid compounds, and the above-mentioned curing agents. Examples include hydroxy compound B.

For example, amine compounds include aliphatic polyamines such as ethylenediamine, propylene diamine, butylene diamine, hexamethylene diamine, polypropylene glycol diamine, diethylene triamine, triethylene tetramine, and pentaethylene hexamine, metaxylylene diamine, diaminodiphenylmethane, and phenylene diamine. Examples include aromatic polyamines such as 1,3-bis(aminomethyl)cyclohexane, alicyclic polyamines such as isophoronediamine, norbornanediamine, and dicyandiamide.

Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, polypropylene glycol maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, and hexahydroanhydride. Examples include phthalic acid and methylhexahydrophthalic anhydride.

Phenolic compounds include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin. , naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin, aminotriazine-modified phenol resin, and modified products thereof. Further, examples of latent catalysts include imidazole, BF3-amine complexes, guanidine derivatives, and the like.

Examples of amide compounds include aliphatic polyamide synthesized from polycarboxylic acid and polyamine, aromatic polyamide with an aromatic ring introduced therein, aliphatic polyamide adduct obtained by adding an epoxy compound to polyamide, and aromatic polyamide. Examples include adduct.

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 using these curing agents, only one type of curing agent may be used, or two or more types may be mixed. In addition, in applications such as underfill materials and general paint applications, it is preferable to use the above-mentioned amine compounds, carboxylic acid compounds, and/or acid anhydride compounds. Furthermore, in applications such as adhesives and flexible wiring boards, amine compounds, particularly dicyandiamide, are preferred from the viewpoint of workability, curability, and long-term stability. Furthermore, in applications for semiconductor encapsulation materials, solid type phenolic compounds are preferred from the viewpoint of heat resistance of the cured product.

<Other epoxy compounds>
In addition to the epoxy compound A, the composition of the present invention may contain other epoxy compounds as long as the effects of the present invention are not impaired. At this time, the proportion of 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.

Epoxy compounds that can be used in combination are not limited in any way, and include, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, resorcinol epoxy resin, and hydroquinone epoxy resin. , liquid epoxy resins such as catechol type epoxy resins, dihydroxynaphthalene type epoxy resins, biphenyl type epoxy resins, and tetramethylbiphenyl type epoxy resins, brominated epoxy resins such as brominated phenol novolak type epoxy resins, solid bisphenol A type epoxy resins, 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, naphthi Renether type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol cocondensed novolac type epoxy resin, naphthol-cresol cocondensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin , biphenyl-modified novolac type epoxy resins, etc., and they may be used alone or in combination of two or more types, and it is preferable to use various selections depending on the intended use, physical properties of the cured product, etc.

The amounts of the epoxy compound and curing agent in the composition of the present invention are not particularly limited, but from the viewpoint of good mechanical properties of the resulting cured product, an epoxy compound containing epoxy compound A may be used. The amount of active groups in the curing agent is preferably 0.7 to 1.5 equivalents relative to the total 1 equivalent of 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 accelerator can be used, and examples thereof include urea compounds, phosphorus compounds, tertiary amines, imidazole, 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 preferred because of their excellent workability and low-temperature curability. When used as a semiconductor encapsulation material, triphenylphosphine is used as a phosphorus compound, and 1,8-diazabicyclo-[ 5.4.0]-undecene is preferred.

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

Examples of inorganic fine particles with excellent heat resistance include alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous powder) Examples of materials with excellent thermal conductivity include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond, etc.; materials with excellent conductivity include single metals or alloys ( For example, metal fillers and/or metal-coated fillers using iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.; Examples of materials with excellent barrier properties include mica, clay, kaolin, 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; materials with a high refractive index Examples include barium titanate, zirconia oxide, titanium oxide, etc.; those exhibiting photocatalytic properties include titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, terium, nickel, iron, cobalt, Photocatalytic metals such as silver, molybdenum, strontium, chromium, barium, and lead, composites of the above metals, and their oxides; those with excellent wear resistance include metals such as silica, alumina, zirconia, and magnesium oxide; Compounds and oxides of these materials; those with excellent conductivity include metals such as silver and copper, tin oxide, indium oxide, etc.; those with excellent insulation properties include silica; those with excellent ultraviolet shielding properties include: Titanium oxide, zinc oxide, etc.
These inorganic fine particles may be appropriately selected depending on the intended use, and may be used alone or in combination. Moreover, since the above-mentioned inorganic fine particles have various properties other than those listed in the examples, they may be selected depending on the application at the appropriate time.

For example, when using silica as the inorganic fine particles, there is no particular limitation, and known fine silica particles such as powdered silica and colloidal silica can be used. Examples of commercially available powdered silica fine particles include Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., and E220A manufactured by Nippon Silica Kogyo Co., Ltd. , E220, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., and SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.
In addition, commercially available colloidal silica includes, for example, methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, Examples 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 may be surface-treated with a reactive silane coupling agent having a hydrophobic group, or modified with a compound having a (meth)acryloyl group. can give. Examples of commercially available powdered silica modified with a compound having a (meth)acryloyl group include Aerosil RM50 and R711 manufactured by Nippon Aerosil Co., Ltd.; commercially available colloidal silica modified with a compound having a (meth)acryloyl group include: Examples include MIBK-SD manufactured by Nissan Chemical Industries, Ltd.

The shape of the silica fine particles is not particularly limited, and may be spherical, hollow, porous, rod-like, plate-like, fibrous, or irregularly shaped. Further, the primary particle diameter is preferably in the range of 5 to 200 nm. If the diameter is less than 5 nm, the inorganic fine particles in the dispersion will not be sufficiently dispersed, and if the diameter exceeds 200 nm, the cured product may not maintain sufficient strength.

As the titanium oxide fine particles, not only extender pigments but also ultraviolet light-responsive photocatalysts can be used, such as anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, and the like. Furthermore, particles designed 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 into titanium oxide, anion elements such as nitrogen, sulfur, carbon, fluorine, and phosphorus, and cation elements such as chromium, iron, cobalt, and manganese are suitably used. Moreover, as for the form, a powder, a sol or a slurry dispersed in 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 Teika Co., Ltd. Furthermore, examples of commercially available slurry-like titanium oxide fine particles include TKD-701 manufactured by Teika Corporation.

<Fibrous matrix>
The composition of the invention may further contain a fibrous matrix. The fibrous substrate of the present invention is not particularly limited, but those used for fiber-reinforced resins are preferred, and examples thereof include inorganic fibers and organic fibers.

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

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

Among them, carbon fibers and glass fibers are preferred because they have a wide range of industrial applications. Among these, only one type may be used, or a plurality of types may be used simultaneously.

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

<Dispersion medium>
A dispersion medium may be used in the composition of the present invention for the purpose of adjusting the solid content and viscosity of the composition. The dispersion medium may be any liquid medium that does not impair the effects of the present invention, and includes various organic solvents, liquid organic polymers, and the like.

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. , aromatics such as toluene and xylene, and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether.These can be used alone or in combination, but among them, methyl ethyl ketone is It is preferable from the viewpoint of volatility during processing and solvent recovery.

The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, such as carboxyl group-containing polymer modified products (Floren G-900, NC-500: Kyoei-sha), acrylic polymers (Floren WK-20: Kyoei-sha). , a special modified phosphoric acid ester amine salt (HIPLAAD ED-251: Kusumoto Kasei), a modified acrylic block copolymer (DISPERBYK2000; BYK Chemie), and the like.

<Resin>
Furthermore, the composition of the present invention may contain resins other than the various compounds of the present invention mentioned above. As the resin, any known and commonly used resin may be blended as long as it does not impair the effects of the present invention, and for example, thermosetting resins and thermoplastic resins can be used.

A thermosetting resin is a resin that has the property of becoming substantially insoluble and infusible when cured by means such as heating, radiation, or a catalyst. Specific examples include phenolic 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, thermal Examples 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.

Thermoplastic resin refers to resin that can be melt-molded by heating. Specific examples include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, 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, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyether ether ketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndication Examples include tactic polystyrene resin and cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.

<Other formulations>
The compositions of the present invention may also contain other ingredients. For example, catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, Examples include antioxidants, flame retardants, plasticizers, and reactive diluents.

<Cured product>
In the composition of the present invention, by applying a reaction product of diglycidyl ether of an aliphatic dihydroxy compound and an aromatic hydroxy compound, it becomes possible to obtain a cured product that is more flexible and tough than ever before. For example, a high molecular weight epoxy compound obtained by reacting the liquid bisphenol A type epoxy resin described above with an aliphatic dicarboxylic acid such as dimer acid or sebacic acid as a molecular chain extender gives a cured product with a flexible structure, but ester The effect is not sufficient due to aggregation of the 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 the cured product obtained by curing the epoxy compound A of the present invention is 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, a cured product having both flexibility and toughness can be provided. Furthermore, since the trifunctional aromatic hydroxy compound binds the centers of the soft segments, it is possible to achieve both a high elastic modulus and an excellent elongation rate, which are usually contradictory, and therefore a flexible adhesive layer with excellent creep resistance can be provided.

In particular, in the case of the epoxy compound A of the present invention, the part that functions as a hard segment and the part that functions as a soft segment combine to impart flexibility to the epoxy compound structure and exhibit excellent moisture resistance. I can do it. Furthermore, in the present invention, the glycidyloxy group is directly bonded to the aromatic nucleus, so that the toughness of the cured epoxy product is extremely excellent. That is, for example, a general-purpose epoxy resin has a structure in which a diol compound obtained by modifying a low-volume liquid bisphenol A type epoxy resin with ethylene oxide or propylene oxide is converted into a glycidyl ether, although the epoxy resin skeleton itself becomes flexible. , the activity of the epoxy group itself is poor, and sufficient crosslinking to develop toughness during curing cannot be obtained. However, the epoxy compound A of the present invention has a glycidyloxy group directly bonding to the aromatic nucleus, thereby forming an epoxy compound. Because the activity of the group increases, even though the resin itself is flexible, it forms appropriate crosslinks during the curing reaction and exhibits excellent toughness. Furthermore, since the hard segment is adjacent to the epoxy group serving as a crosslinking point, the physical strength at the crosslinking point is increased and toughness is improved.

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

When using a curing catalyst, 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; Titanate esters such as isopropyl titanate and tetrabutyl titanate; 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-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 various basic nitrogen atoms; various quaternary ammonium salts such as tetramethylammonium salt, tetrabutylammonium salt, dilauryldimethylammonium salt, etc. and quaternary ammonium salts having chloride, bromide, carboxylate or hydroxide as a counter anion; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetylacetonate, tin octylate or tin stearate. Tin carboxylates, such as; benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, t-butyl perbenzoate Organic peroxides such as, for example, can be used. The catalysts may be used alone or in combination of two or more.

Moreover, 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. As the active energy ray, visible light, ultraviolet rays, X-rays, electron beams, etc. can be used.

Examples of the photocationic polymerization initiator include aryl-sulfonium salts, aryl-iodonium salts, etc. Specifically, arylsulfonium hexafluorophosphate, arylsulfonium hexafluoroantimonate, arylsulfonium tetrakis(pentafluoro)borate , dialkylphenaxylsulfonium hexafluorophosphate, etc. can be used. The photocationic polymerization initiators may be used alone or in combination of two or more.

<Laminated body>
The cured product of the present invention can be made into a laminate by laminating it with a base material.
The base material for the laminate may be an inorganic material such as metal or glass, or an organic material such as plastic or wood, depending on the application, and the shape of the laminate may be a flat plate, sheet, or three-dimensional structure. It does not matter if it has a three-dimensional shape. It may have any shape depending on the purpose, such as having curvature on the entire surface or in part. Furthermore, 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 adhesion to metals and/or metal oxides, it can be used particularly well as a primer for metals. Examples of metals include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and composite materials of these metals, and examples of metal oxides include single oxides and materials of these metals. Or a composite oxide can be mentioned. In particular, it has excellent adhesion to iron, copper, and aluminum, so it can be used well as an adhesive for iron, copper, and aluminum.

In the laminate of the present invention, the cured material layer may be formed by direct coating or molding on the base material, or may be formed by laminating already molded layers. In the case of direct coating, there are no particular limitations on the coating method, including 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, Examples include screen printing method, inkjet method, and the like. In the case of direct molding, examples include in-mold molding, insert molding, vacuum molding, extrusion lamination molding, press molding, and the like.
When laminating molded compositions, uncured or semi-cured composition layers may be laminated and then cured, or a completely cured composition layer may be laminated on the base material. good.
Furthermore, the cured product of the present invention may be laminated by coating and curing a precursor that can serve as a base material, and the precursor that can serve as a base material or the composition of the present invention may be uncured or semi-cured. It may be hardened after adhering in this state. There are no particular limitations on the precursor that can serve as the base material, and examples include various curable resin compositions.

<Fiber reinforced resin>
When the composition of the present invention has a fibrous matrix and the fibrous matrix is a reinforcing fiber, the composition containing the fibrous matrix can be used as a fiber reinforced resin.
The method of incorporating the fibrous matrix into the composition is not particularly limited as long as it does not impair the effects of the present invention. Examples include a method of compositing, which can be appropriately selected depending on the form of the fiber and the use of the fiber-reinforced resin.

There are no particular limitations on the method for molding the fiber-reinforced resin of the present invention. If a plate-shaped product is to be manufactured, extrusion molding is generally used, but flat pressing is also possible. In addition, extrusion molding, blow molding, compression molding, vacuum molding, injection molding, and the like can be used. In addition, if a film-shaped product is to be manufactured, a solution casting method can be used in addition to the melt extrusion method.When using the melt molding method, blown film molding, cast molding, extrusion lamination molding, calendar molding, and sheet molding can be used. , fiber molding, blow molding, injection molding, rotational molding, coating molding, etc. Further, in the case of a resin that is cured by active energy rays, a cured product can be produced using various curing methods using active energy rays. In particular, when a thermosetting resin is the main component of the matrix resin, there is a molding method in which the molding material is made into a prepreg and heated under pressure using a press or an autoclave.In addition, RTM (Resin Transfer Molding) molding, Examples include VaRTM (Vaccum assist Resin Transfer Molding) molding, lamination molding, hand lay-up molding, and the like.

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

<Heat-resistant materials and electronic materials>
The composition of the present invention can be suitably used for heat-resistant members because its cured product has a high glass transition temperature and excellent heat decomposition resistance. Moreover, since it has excellent adhesion to a base material, it can be particularly suitably used for electronic components. In particular, it can be suitably used for semiconductor sealing materials, circuit boards, build-up films, build-up substrates, adhesives, and resist materials. Further, it can be suitably used as a matrix resin of fiber reinforced resin, and is particularly suitable as a highly heat resistant prepreg. The heat-resistant components and electronic components thus obtained can be suitably used for various purposes, such as industrial mechanical parts, general mechanical parts, automobile/railway/vehicle parts, space/aviation related parts, electronic/electrical parts, etc. Examples include, but are not limited to, building materials, containers/packaging members, household goods, sports/leisure goods, wind power generation casing members, etc.

Below, representative products will be explained using examples.

1. Semiconductor Encapsulation Material As a method for obtaining a semiconductor encapsulant material from the composition of the present invention, the composition and compounding agents such as a curing accelerator and an inorganic filler may be mixed in an extruder, a kneader, Examples include a method of sufficiently melting and mixing using a roll or the like until the mixture becomes uniform. At that time, fused silica is usually used as the inorganic filler, but when used as a highly thermally conductive semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, nitride, etc., which have higher thermal conductivity than fused silica, It is preferable to use highly filled silicon or the like, or use fused silica, crystalline silica, alumina, silicon nitride, or the like. The filling rate is preferably 30 to 95% by mass of the inorganic filler per 100 parts by mass of the curable resin composition. In order to reduce the amount, the amount is more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more.

2. Semiconductor device For molding a semiconductor package to obtain a semiconductor device from the curable resin composition of the present invention, the semiconductor encapsulating material is molded using a casting, transfer molding machine, injection molding machine, etc., and then heated at 50 to 250°C. A method of heating for 2 to 10 hours is mentioned.

3. Printed circuit board A method for obtaining a printed circuit board from the composition of the present invention is to laminate the prepregs described above by a conventional method, overlay copper foil as appropriate, and then under a pressure of 1 to 10 MPa at 170 to 300°C for 10 minutes to A method of heat-pressing for 3 hours may be mentioned.

4. Buildup Substrate A method for obtaining a buildup substrate from the composition of the present invention includes, for example, the following steps. First, the above-mentioned composition containing rubber, filler, etc. as appropriate is applied to a circuit board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then cured (step 1). After that, after drilling a predetermined through-hole section as necessary, the surface is treated with a roughening agent, and the surface is washed with hot water to form unevenness, and the process of plating metal such as copper (process 2). A step (step 3) of repeatedly repeating such operations as desired to alternately build up and form a resin insulating layer and a conductor layer of a predetermined circuit pattern. Note that the through-hole portions are formed after the outermost resin insulating layer is formed. In addition, the build-up board of the present invention can be produced by heat-pressing a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil at 170 to 300°C onto a wiring board on which a circuit has been formed. It is also possible to fabricate a build-up board by omitting the steps of forming a chemical surface and plating.

5. Build-up film A method for obtaining a build-up film from the composition of the present invention is to apply the above-mentioned composition onto the surface of the support film (Y) as a base material, and then apply an organic solvent by heating or blowing hot air. It can be manufactured by drying to form the layer (X) of the composition.

Examples of the organic solvent used here include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, butyl carbitol, and the like. It is preferable to use carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is also preferable to use them in a proportion such that the nonvolatile content is 30 to 60% by mass. preferable.

The thickness of the formed layer (X) is usually greater than or equal to the thickness of the conductor layer. Since the thickness of a conductor layer included in a circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably in the range of 10 to 100 μm. In addition, the layer (X) of the said composition in this invention may be protected with the protective film mentioned 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 from scratching it.

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

The support film (Y) described above is peeled off after being laminated onto the circuit board or after forming an insulating layer by heating and curing. If the support film (Y) is peeled off after the curable resin composition layer constituting the build-up film is cured by heating, it is possible to prevent dust and the like from adhering during the curing process. When peeling is performed after curing, the support film is usually subjected to a release treatment in advance.

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, after peeling off these layers, the layer (X) is 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 lamination method may be a batch method or a continuous method using rolls. Moreover, if necessary, the build-up film and the circuit board may be heated (preheated) before lamination. As for lamination conditions, it is preferable that the pressure bonding temperature (laminate temperature) be 70 to 140°C, and the pressure bonding pressure be 1 to 11 kgf/cm2 (9.8 x 104 to 107.9 x 104 N/m2). It is preferable to laminate under reduced air pressure of 20 mmHg (26.7 hPa) or less.

6. Conductive Paste A method for obtaining a conductive paste from the composition of the present invention includes, for example, a method of dispersing conductive particles in the composition. The above-mentioned conductive paste can be made into 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 explained with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified.

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=50.00-2000.00
Rate of change: 25.6mA/min
Final current value: 40mA
Cathode voltage: -10kV

<Gel permeation chromatograph>
GPC: “HLC-8320GPC” manufactured by Tosoh Corporation
Column: Tosoh Corporation "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL"
Detector: RI (suggestion refractometer)
Measurement conditions: 40℃
Mobile phase: Tetrahydrofuran Flow rate: 1ml/min
Standard: "PStQuick A", "PStQuick B", "PStQuick E", "PStQuick F" manufactured by Tosoh Corporation

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

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

Synthesis Example 1 Synthesis of epoxy compound C-1

In a flask equipped with a thermometer and a stirrer, 630 parts by mass (1.5 molar equivalent) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Gosei Co., Ltd.: epoxy equivalent 210 g/eq) and 1,3,5- 42 parts by mass (0.33 molar equivalent) of trihydroxybenzene (hydroxyl equivalent: 42 g/eq) was charged, the temperature was raised to 140°C over 30 minutes, and then 3.4 parts by mass of a 4% aqueous sodium hydroxide solution was charged. . Thereafter, the temperature was raised to 150°C over 30 minutes, and the reaction was further carried out at 150°C for 3 hours. Thereafter, a neutralizing amount of sodium phosphate was added to obtain 660 parts by mass of reactant C-1 containing epoxy compound C-1.

Synthesis Example 2 Synthesis of epoxy compound C-2

1,3,5-trihydroxybenzene (0.33 molar equivalent) in Synthesis Example 1 was added to 97 parts by mass (0. The reaction was carried out in the same manner as in Synthesis Example 1, except that the amount was changed to (33 molar equivalent), and 720 parts by mass of reactant C-2 containing epoxy compound C-2 was obtained.

Synthesis Example 3 Synthesis of hydroxy compound B-1

360 parts by mass of reactant C-1 and 342 parts by mass (1.5 molar equivalent) of bisphenol A (hydroxyl equivalent: 114 g/eq) were placed in a flask equipped with a thermometer and a stirrer, and the mixture was heated to 140°C for 30 minutes. After raising the temperature, 1.7 parts by mass of a 4% aqueous sodium hydroxide solution was charged. Thereafter, the temperature was raised to 150°C over 30 minutes, and the reaction was further carried out at 150°C for 3 hours. Thereafter, a neutralizing amount of sodium phosphate was added to obtain 680 parts by mass of reactant B-1. Reactant B-1 was identified as the diglycidyl ether of 1,3,5-trihydroxybenzene and 1,12-dodecanediol, which is the target product, because a peak of M+ = 1754 was confirmed in FD-MS spectrum analysis. It was confirmed that there was a hydroxy compound B-1, which was obtained by reacting 1.0 mol: 3.0 mol: 3.0 mol with bisphenol A.

Synthesis Example 4 Synthesis of hydroxy compound B-2

The reaction was carried out in the same manner as in Synthesis Example 3, except that 360 parts by mass of reactant C-1 was changed to 410 parts by mass of reactant C-2, and 730 parts by mass of reactant B-2 was obtained. Reactant B-2 was confirmed to have a peak of M+=1920 in FD-MS spectrum analysis, so it was found that the target products triphenylolmethane, diglycidyl ether of 1,12-dodecanediol, and bisphenol A were 1 It was confirmed that hydroxy compound B-2 reacted in a ratio of .0 mol: 3.0 mol: 3.0 mol.

Synthesis Example 5 Synthesis of hydroxy compound B-3

The reaction was carried out in the same manner as in Synthesis Example 3, except that 342 parts by mass (1.5 molar equivalent) of bisphenol A in Synthesis Example 3 was changed to 240 parts by mass (1.5 molar equivalent) of 2,7-dihydroxynaphthalene. 830 parts by mass of Product B-3 was obtained. 730g of hydroxy compound B-3 was obtained. Reactant B-3 is a diglycidyl ether of 1,3,5-trihydroxybenzene and 1,12-dodecanediol, which is the target product, because a peak of M+ = 1549 was confirmed in FD-MS spectrum analysis. It was confirmed that there was a hydroxy compound B-3 in which 2,7-dihydroxynaphthalene was reacted with 1.0 mol: 3.0 mol: 3.0 mol.

Synthesis Example 6 Synthesis of hydroxy compound B-4

In a flask equipped with a thermometer and a stirrer, 210 parts by mass (0.5 molar equivalent) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Gosei Co., Ltd.: epoxy equivalent 210 g/eq) and bisphenol A (hydroxyl equivalent 114 g) were added. /eq) 228 parts by mass (1.0 molar equivalent) was charged, the temperature was raised to 140° C. over 30 minutes, and then 1.0 parts by mass of a 4% aqueous sodium hydroxide solution was charged. Thereafter, the temperature was raised to 150°C over 30 minutes, and the reaction was further carried out at 150°C for 3 hours. Thereafter, a neutralizing amount of sodium phosphate was added to obtain 430 parts by mass of Reactant B-4. Regarding reaction product B-4, a peak of M+=771 was confirmed in FD-MS spectrum analysis, so it was confirmed that the target compound hydroxy compound B-4 existed.

Synthesis Example 7 Synthesis of hydroxy compound B-5

The reaction was carried out in the same manner as in Synthesis Example 6, except that 228 parts by mass (1.0 molar equivalent) of bisphenol A was changed to 126 parts by mass (1.0 molar equivalent) of pyrogallol, and reactant B-5 was converted to 330 parts by mass (1.0 molar equivalent). Part by mass obtained. Regarding reaction product B-5, a peak of M+=567 was confirmed in FD-MS spectrum analysis, so it was confirmed that the target compound hydroxy compound B-5 existed.

Example 1 Synthesis and evaluation of epoxy compound A-1

(Synthesis of epoxy compound A-1)
In a flask equipped with a thermometer, dropping funnel, cooling tube, and stirrer, while purging with nitrogen gas, 680 parts by mass of hydroxy compound B-1 obtained in Synthesis Example 3 and 1110 parts by mass of epichlorohydrin (12.0 molar equivalents) were added. ) and 280 parts by mass of n-butanol were charged and dissolved. After raising the temperature to 65° C., the pressure was reduced to an azeotropic pressure, and 122 parts by mass (1.5 molar equivalent) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hour under the same conditions. During this time, the distillate distilled out by azeotropy was separated using a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while the oil layer was returned to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 1000 parts by mass of methyl isobutyl ketone and 100 parts by mass of n-butanol were added and dissolved in the resulting reaction product. Further, 20 parts by mass of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80° C. for 2 hours, followed by washing with water until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropy, and after passing through precision filtration, the solvent was distilled off under reduced pressure to obtain 730 parts by mass of reactant A-1. In the obtained reaction product A-1, a peak of M+=1921 was confirmed by FD-MS spectrum analysis, so it was confirmed that the target product, epoxy compound A-1, existed.

(Production and evaluation of resin compositions and cured products)
The reactant A-1, curing agent, and curing accelerator were uniformly mixed in a mixer ("Awatori Rentaro ARV-200" manufactured by Thinky Co., Ltd.) according to Table 1, and an epoxy resin composition was prepared. I got it. This epoxy resin composition was sandwiched between aluminum mirror plates ("JIS H 4000 A1050P" manufactured by Engineering Test Service Co., Ltd.) using a silicone tube as a spacer, and heated and cured at 170°C for 30 minutes to form a resin with a thickness of 0.8 mm. A cured product was obtained.

<Tensile test>
The cured resin was punched out into a dumbbell shape (JIS K 7161-2-1BA) using 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). .

<Tensile shear test>
The resin composition was applied to one of two cold-rolled steel plates (SPCC-SB manufactured by TP Giken Co., Ltd., 1.0 mm x 25 mm x 100 mm), and glass beads (Potters Ballotini Co., Ltd.) were applied as spacers. "J-80" manufactured by the company) was added, and another sheet of SPCC-SB was bonded (adhesion area: 25 mm x 12.5 mm). This was heated and cured at 170° C. for 1 hour to obtain a test piece. Adhesion was evaluated by performing a tensile shear test using the test piece. The test was conducted according to JIS K 6850, and the maximum point stress was compared.

Example 2 Synthesis and evaluation of epoxy compound A-2

Example 1 was the same as Example 1 except that 680 parts by mass of hydroxy compound B-1 obtained in Synthesis Example 3 was replaced with 730 parts by mass of hydroxy compound B-2 obtained in Synthesis Example 4. The reaction was carried out in the same manner to obtain 780 parts by mass of reactant A-2. In the obtained reaction product A-2, a peak of M+=2087 was confirmed in FD-MS spectrum analysis, so it was confirmed that the target product, epoxy compound A-2, existed. The obtained reaction product was evaluated in the same manner as in Example 1.

Example 3 Synthesis of epoxy compound A-3

Example 1 was the same as Example 1 except that 680 parts by mass of hydroxy compound B-1 obtained in Synthesis Example 3 was replaced with 830 parts by mass of hydroxy compound B-3 obtained in Synthesis Example 5. The reaction was carried out in the same manner to obtain 870 parts by mass of Reactant A-3. In the obtained reaction product A-3, a peak of M+=1717 was confirmed in FD-MS spectrum analysis, so it was confirmed that the target product, epoxy compound A-3, existed. The obtained reaction product was evaluated in the same manner as in Example 1.

Comparative Example 1 Synthesis of epoxy compound A-4

In Example 1, 680 parts by mass of hydroxy compound B-1 obtained in Synthesis Example 3 was replaced with 330 parts by mass of hydroxy compound B-4 obtained in Synthesis Example 6. The reaction was carried out in the same manner to obtain 350 parts by mass of Reactant A-4. In the obtained reaction product A-4, a peak of M+=883 was confirmed in FD-MS spectrum analysis, so it was confirmed that the target product, epoxy compound A-4, existed. The obtained reaction product was evaluated in the same manner as in Example 1.

Comparative Example 2 Synthesis of epoxy compound A-5

In Example 1, 680 parts by mass of hydroxy compound B-1 obtained in Synthesis Example 3 was replaced with 121 parts by mass of hydroxy compound B-5 obtained in Synthesis Example 7. The reaction was carried out in the same manner to obtain 160 parts by mass of Reactant A-5. In the obtained reaction product A-5, a peak of M+=790 was confirmed in FD-MS spectrum analysis, so it was confirmed that the target product, epoxy compound A-5, existed. 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)

Epoxy compound A of the present invention can provide a flexible cured product that has both a high elongation rate based on elastic deformation and high adhesiveness that can withstand the difference in thermal expansion of the base material. In particular, it can be suitably used for adhesives for structural materials, advanced electronic materials such as semiconductor sealing materials and insulating layers for multilayer printed circuit boards.

Claims (12)

A composition containing a structure X represented by formula (1) and an epoxy compound A having a glycidyl ether group or a 2-methylglycidyl ether group,
A composition, wherein the epoxy compound A is one or more selected from the group consisting of the following formulas (A-1), (A-2) and (A-3).
...(1)
(In formula (1), Ar represents a structure having an aromatic ring that is unsubstituted or has a substituent, n = 3 , m is the average value of repetitions, m is 1 ,
Y is a structure represented by formula (2-1) and/or formula (2-2) (however, each repeating unit present in the repeating unit may be the same or different)
...(2-1)
...(2-2)
(In formula (2-1) and formula (2-2), p ₁ and p ₂ are each independently 12 ,
R ₃ to R ₆ each independently represent a hydrogen atom or an alkyl group having 1 or 2 carbon atoms,
R ₁ , R ₇ and R ₈ each independently represent a hydroxyl group, a glycidyl ether group and/or a 2-methylglycidyl ether group,
R ₂ , R ₉ and R ₁₀ each independently represent a hydrogen atom or a methyl group,
Ar represents a structure having an aromatic ring that is unsubstituted or has a substituent). )
...(A-1)
...(A-2)
...(A-3) The composition according to claim 1 , further comprising a curing agent. The composition according to claim 2 , wherein the curing agent is at least one selected from amine compounds, phenol compounds, carboxylic acid compounds, and/or acid anhydride compounds. The composition according to claim 1 or 2 , further comprising a filler. A cured product obtained by curing the composition according to any one of claims 1 to 4 . A laminate comprising a base material and the cured material layer according to claim 5 . The laminate according to claim 6 , wherein the base material is a metal or a metal oxide. A laminate formed by laminating a base material, the cured product layer according to claim 5 , and a second base material in this order, wherein the base material is a metal or a metal oxide, and the second base material is a plastic layer. The laminate according to claim 6 or 7 . An electronic component comprising the laminate according to any one of claims 6 to 8 . An adhesive for metals or metal oxides, comprising a structure X represented by formula (1) and an epoxy compound A having a glycidyl ether group or a 2-methylglycidyl ether group,
An adhesive for metals or metal oxides, characterized in that the epoxy compound A is one or more selected from the group consisting of the following formulas (A-1), (A-2) and (A-3). .
...(1)
(In formula (1), Ar represents a structure having an aromatic ring that is unsubstituted or has a substituent, n = 3, m is the average value of repetitions, m is 1,
Y is a structure represented by formula (2-1) and or formula (2-2)
(However, each repeating unit that exists in a repeating unit may be the same or different.)
...(2-1)
...(2-2)
(In formula (2-1) and formula (2-2), p ₁ and p ₂ are each independently 12,
R ₃ to R ₆ each independently represent a hydrogen atom or an alkyl group having 1 or 2 carbon atoms,
R ₁ , R ₇ and R ₈ each independently represent a hydroxyl group, a glycidyl ether group and/or a 2-methylglycidyl ether group,
R ₂ , R ₉ and R ₁₀ each independently represent a hydrogen atom or a methyl group,
Ar represents a structure having an aromatic ring that is unsubstituted or has a substituent). )
...(A-1)
...(A-2)
...(A-3) a step of reacting diglycidyl ether (a1) of an aliphatic dihydroxy compound with an aromatic hydroxy compound (a2) to obtain an epoxy compound C;
A step of reacting epoxy compound C and aromatic hydroxy compound (a3) to obtain hydroxy compound B;
A step of reacting the hydroxy compound B with an epihalohydrin (a4) to obtain the epoxy compound A,
A method for producing the composition according to claim 1 . a step of reacting diglycidyl ether (a1) of an aliphatic dihydroxy compound with an aromatic hydroxy compound (a2) to obtain an epoxy compound C;
A step of reacting epoxy compound C and aromatic hydroxy compound (a3) to obtain hydroxy compound B;
A step of reacting the hydroxy compound B with an epihalohydrin (a4) to obtain the epoxy compound A,
The method for producing an adhesive for metal or metal oxide according to claim 10 .