JP2023069539A - Compound, epoxy resin composition and cured epoxy resin - Google Patents

Abstract

To provide a cured epoxy resin that is excellent in all of heat resistance, repairability and re-moldability.SOLUTION: A compound comprises one Diels-Alder reaction unit composed of an anthracene structure and a maleimide structure in each molecule, with the Diels-Alder reaction unit comprising at least one amino group.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to compounds, epoxy resin compositions and cured epoxy resins.

The epoxy resin forms a network polymer with a high degree of cross-linking through a cross-linking reaction with a curing agent, and becomes a cured product (cured epoxy resin product). Epoxy resin cured products are excellent in heat resistance, mechanical strength, adhesiveness, electrical insulation, etc., and are used in various fields such as electrical and electronic materials, adhesives, paints, construction and civil engineering materials.

On the other hand, low long-term reliability is a universal problem that epoxy resin cured products have. In addition, since the network structure of the cured epoxy resin is formed by covalent bonds, it is insoluble and infusible, making it difficult to re-mold by heating or solvent treatment. It can be said that there is a problem in terms of the burden on the environment. In addition, if it is possible to repair the minute cracks that occur in the cured epoxy resin, it is expected that the brittleness, which is a drawback of the cured thermosetting resin, can be improved. Have difficulty.

In order to solve such problems, there is known an epoxy resin cured product prepared by using a diamine having a site where furan and maleimide are bonded by Diels-Alder reaction as a curing agent (Non-Patent Document 1). When the epoxy resin cured product is heated, the crosslinked structure is de-crosslinked by retro-Diels-Alder reaction, and when the temperature is lowered, it is re-crosslinked by Diels-Alder reaction. This reversible de-crosslinking/re-crosslinking imparts thermoreversibility to the network structure, making it possible to reshape or repair by heating.

X.Kuang, G.Liu, X.Dong, X.Liu, J.Xu, D.Wang, J.Polym.Sci., Part A: Polym.Chem,. 53, 2094(2015).

However, since the Diels-Alder reaction product of furan and maleimide undergoes a retro-Diels-Alder reaction at around 120°C, the epoxy resin cured product is decrosslinked at 120°C or higher. Therefore, the epoxy resin cured product produced by the Diels-Alder reaction of furan and maleimide is not suitable for applications at 120°C or higher. In addition to this, research using reversible bonds such as dynamic covalent bonds and supramolecular bonds has been actively conducted to impart repairability and re-moldability to epoxy resin cured products, but in general, thermal decomposition Issues such as gender remain.

In view of the above problems, an object of the present invention is to provide an epoxy resin cured product having good heat resistance, repairability and remoldability.

As a result of extensive studies, the inventors of the present invention have found that the above problems can be solved by providing a compound having a predetermined structure, an epoxy resin composition, and a cured epoxy resin.

One aspect of the present invention is a compound having one Diels-Alder reaction unit consisting of an anthracene structure and a maleimide structure in the molecule, and the Diels-Alder reaction unit having at least one amino group.

The compounds of the invention are, in one embodiment, curing agents for epoxy resins.

（式（１）及び（１’）中、Ｒ¹～Ｒ¹¹は、それぞれ、互いに独立して水素原子、ハロゲン原子、ヒドロキシ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、ニトロ基、アミノ基、アミド基、カルボキシ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、シアノ基、アルキル基、シクロアルキル基、アラルキル基またはアリール基であり、Ｒ¹～Ｒ¹¹の少なくとも１つはアミノ基であるか、アミノ基を置換基として有している基である。） In one embodiment, the compound of the present invention is represented by the following formula (1) or (1').

(In formulas (1) and (1′), R ¹ to R ¹¹ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, and an amino group. , an amido group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, and at least one of R ¹ to R ¹¹ is an amino group , is a group having an amino group as a substituent.)

In another embodiment of the compound of the present invention, the anthracene structure has an amino group or a phenolic hydroxyl group.

In still another embodiment of the compound of the present invention, the maleimide structure has an amino group or a phenolic hydroxyl group.

In still another embodiment, the compound of the present invention is represented by the following formula (2) or (2').

In still another embodiment, the compound of the present invention is represented by the following formula (3) or (3').

Another aspect of the present invention is an epoxy resin composition comprising the compound of the present invention and an epoxy resin.

（式（４）中、Ａｒはそれぞれ独立して、無置換または置換基を有する芳香環を有する構造であり、
Ｘは下記式（４－１）で表される構造単位であり、Ｙは下記式（４－２）で表される構造単位であり、

［式（４－１）、（４－２）中、Ａｒはそれぞれ独立して、無置換または置換基を有する芳香環を有する構造であり、
Ｒ¹、Ｒ²はそれぞれ独立して水素原子、メチル基またはエチル基であり、
Ｒ’は炭素原子数２～１２の２価の炭化水素基であり、
Ｒ³、Ｒ⁴、Ｒ⁷、Ｒ⁸はそれぞれ独立して水酸基、グリシジルエーテル基または２－メチルグリシジルエーテル基であり、
Ｒ⁵、Ｒ⁶、Ｒ⁹、Ｒ¹⁰はそれぞれ独立して水素原子またはメチル基であり、
ｎ₁は４～１６の整数であり、ｎ₂は繰り返し単位の平均値で２～３０である。］
Ｒ¹¹、Ｒ¹²はそれぞれ独立して、グリシジルエーテル基または２－メチルグリシジルエーテル基であり、
Ｒ¹³、Ｒ¹⁴はそれぞれ独立して水酸基、グリシジルエーテル基または２－メチルグリシジルエーテル基であり、
Ｒ¹⁵、Ｒ¹⁶は水素原子又はメチル基であり、
ｍ₁、ｍ₂、ｐ₁、ｐ₂、ｑは繰り返しの平均値であり、
ｍ₁、ｍ₂は、それぞれ独立して０～２５であり、且つ、ｍ₁＋ｍ₂≧１であり、
ｐ₁、ｐ₂はそれぞれ独立して０～５であり、
ｑは０．５～５である。
ただし、前記式（４－１）で表される構造単位Ｘと前記式（４－２）で表される構造単位Ｙとの結合は、ランダムであってもブロックであってもよく、１分子中に存在する各構造単位Ｘ、Ｙの数の総数がそれぞれｍ₁、ｍ₂であることを示す。） In one embodiment of the epoxy resin composition of the present invention, the epoxy resin is represented by the following formula (4) and has an epoxy equivalent of 500 to 10000 g/eq.

(In formula (4), each Ar is independently a structure having an unsubstituted or substituted aromatic ring,
X is a structural unit represented by the following formula (4-1), Y is a structural unit represented by the following formula (4-2),

[In formulas (4-1) and (4-2), each Ar is independently a structure having an unsubstituted or substituted aromatic ring,
R ¹ and R ² are each independently a hydrogen atom, a methyl group or an ethyl group,
R' is a divalent hydrocarbon group having 2 to 12 carbon atoms,
R ³ , R ⁴ , R ⁷ and R ⁸ are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,
R ⁵ , R ⁶ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group;
n ₁ is an integer of 4 to 16, and n ₂ is an average repeating unit of 2 to 30; ]
R ¹¹ and R ¹² are each independently a glycidyl ether group or a 2-methylglycidyl ether group,
R ¹³ and R ¹⁴ are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,
R ¹⁵ and R ¹⁶ are a hydrogen atom or a methyl group;
m ₁ , m ₂ , p ₁ , p ₂ , q are average values of repetitions,
m ₁ and m ₂ are each independently 0 to 25, and m ₁ +m ₂ ≧1,
p ₁ and p ₂ are each independently 0 to 5,
q is 0.5-5.
However, the bond between the structural unit X represented by the formula (4-1) and the structural unit Y represented by the formula (4-2) may be random or block, and one molecule The total number of structural units X and Y present therein is m ₁ and m ₂ , respectively. )

（式（５）中、ｐ₁、ｐ₂、ｑ、ｍ₁及びｎ₁は繰り返しの平均値であり、それぞれ独立して、ｐ₁は０～５、ｐ₂は０～５、ｑは０．５～５、ｍ₁は０～２５、ｎ₁は２～３０である。） In another embodiment of the epoxy resin composition of the present invention, the epoxy resin is represented by the following formula (5).

(In formula (5), p ₁ , p ₂ , q, m ₁ and n ₁ are the average values of repetitions, and independently p ₁ is 0 to 5, p ₂ is 0 to 5, q is 0 .5 to 5, m ₁ is 0 to 25, and n ₁ is 2 to 30.)

Another aspect of the present invention is an epoxy resin cured product obtained by curing the epoxy resin composition of the present invention.

According to the present invention, it is possible to provide an epoxy resin cured product having good heat resistance, repairability and remoldability.

1 is a ¹ H-NMR spectrum of the endo form of the compound obtained in Example 1 (DA compound described later). 10 is a graph showing the results of dynamic viscoelasticity measurement (DMA) of the epoxy resin cured product according to Example 3. FIG.

Next, the mode for carrying out the present invention will be described in detail. It is understood that the present invention is not limited to the following embodiments, and that design changes, improvements, etc., can be made as appropriate based on the ordinary knowledge of those skilled in the art without departing from the scope of the present invention. should.

(Compound of the present invention)
The compound of the present invention has one Diels-Alder reaction unit consisting of an anthracene structure and a maleimide structure in the molecule, and the Diels-Alder reaction unit has at least one amino group. Hereinafter, the compounds of the present invention are also referred to as "DA compounds".

In the Diels-Alder reaction, a conjugated diene and a parent diene undergo an addition reaction to form a six-membered ring. Since the Diels-Alder reaction is an equilibrium reaction, a retro-Diels-Alder reaction occurs at a predetermined temperature to cause dissociation (breaking of bridges). At this time, if the temperature at which the retro-Diels-Alder reaction occurs (dissociation temperature) is low, cross-linking will occur in a high temperature range, and the cross-linking density of the cured product will decrease, resulting in a decrease in mechanical strength. On the other hand, the DA compound of the present invention has one Diels-Alder reaction unit consisting of an anthracene structure and a maleimide structure with high thermal stability in the molecule, so the dissociation temperature is as high as 250 ° C. or higher, At least at about 200° C., it does not dissociate and maintains a crosslinked structure, and has excellent thermal stability. Therefore, by using the DA compound of the present invention as a curing agent for an epoxy resin, the reduction in the crosslink density of the cured product (epoxy resin cured product) cured by the reaction between the curing agent and the epoxy resin is suppressed. and maintain good mechanical strength. In addition, by applying mechanical energy such as damage or external force to the epoxy resin cured product produced by the DA compound of the present invention, the C—C bond of the Diels-Alder reaction unit is cleaved, and anthracene and maleimide are formed on the cleaved surface. generated. The C--C bond of the Diels-Alder reaction unit has lower bond energy than ordinary covalent bonds and is easily broken. In the Diels-Alder reaction of anthracene and maleimide, the equilibrium shifts in the direction of bonding at 200° C. or less, so it is thought that an adduct (Diels-Alder reaction unit) is formed again, and damage can be repaired or remolded.

The DA compounds of the present invention have at least one amino group in the Diels-Alder reaction unit. This amino group may be primary or secondary, but when the Diels-Alder reaction unit has at least one primary amino group, the amino group can react with two epoxy groups, so that, for example, one epoxy The crosslink density of the cured product is improved with respect to hydroxyl groups and the like that react only with groups, and a cured product having excellent toughness and adhesiveness can be produced. As a result, the elastic modulus and glass transition temperature of the cured epoxy resin are improved, which is preferable. In addition, amino groups generally have higher reactivity than hydroxyl groups and the like, improve curability, and enable curing of epoxy resins even under moderate curing conditions.

（式（１）及び（１’）中、Ｒ¹～Ｒ¹¹は、それぞれ、互いに独立して水素原子、ハロゲン原子、ヒドロキシ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、ニトロ基、アミノ基、アミド基、カルボキシ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、シアノ基、アルキル基、シクロアルキル基、アラルキル基またはアリール基であり、Ｒ¹～Ｒ¹¹の少なくとも１つはアミノ基であるか、アミノ基を置換基として有している基である。） The DA compound of the present invention may be represented by the following formula (1) or (1'). The compound of formula (1) and the compound of formula (1′) have an endo-exo isomer relationship with each other, and they are a functional group on the nitrogen atom of the maleimide structure and an anthracene structure. is determined by the positional relationship with the functional group on the aromatic ring. The functional group on the nitrogen atom of the maleimide structure and the functional group on the aromatic ring of the anthracene structure on the same side (close position) are endo isomers, and those on the opposite side (separate position) are exo isomers. Is an isomer.

(In formulas (1) and (1′), R ¹ to R ¹¹ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, and an amino group. , an amido group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, and at least one of R ¹ to R ¹¹ is an amino group , is a group having an amino group as a substituent.)

R ¹ to R ¹¹ in formulas (1) and (1′) are alkoxy group, aralkyloxy group, aryloxy group, carboxy group, alkyloxycarbonyl group, aryloxycarbonyl group, alkyl group, cycloalkyl group and aralkyl group. and aryl groups also include those in which various substituents are bonded to their carbon atoms. For example, for R ¹ -R ¹¹ in formulas (1) and (1′), aryl groups include aminoaryl groups having an additional amino group attached to the carbon atom. Further, for example, when at least one of R ¹ to R ¹¹ in formulas (1) and (1′) is “a group having an amino group as a substituent”, an example of the group is an aminoaryl group (amino aryl group having a group as a substituent).

In the DA compound of the present invention, the anthracene structure may have an amino group or a phenolic hydroxyl group. Further, in the DA compound of the present invention, the maleimide structure may have an amino group or a phenolic hydroxyl group. When the anthracene structure or maleimide structure has a phenolic hydroxyl group, in addition to the effect that the aforementioned Diels-Alder reaction unit has at least one amino group, the phenolic hydroxyl group coexists with the amino group. The curability of the product can be adjusted, the pot life is extended, the storage stability is improved, and the humidity resistance reliability of the epoxy resin cured product is improved. The DA compound of the present invention has an amino group or a phenolic hydroxyl group in both the anthracene structure and the maleimide structure, and preferably at least one of them is an amino group.

The DA compound of the present invention may be represented by the following formula (2) or (2'). The compound of formula (2) and the compound of formula (2') have an isomer relationship with each other, the compound of formula (2) is the exo isomer, and the compound of formula (2') is It is the endo isomer.

The DA compound of the present invention may be represented by the following formula (3) or (3'). The compound of formula (3) and the compound of formula (3′) have an isomer relationship with each other, the compound of formula (3) is the exo isomer, and the compound of formula (3′) is It is the endo isomer.

The DA compound of the present invention may be represented by the following formula (10) or (10'). The compound of formula (10) and the compound of formula (10′) have an isomer relationship with each other, the compound of formula (10) is the exo isomer, and the compound of formula (10′) is It is the endo isomer.

(Method for producing the compound of the present invention)
The DA compound of the present invention has one Diels-Alder reaction unit in the molecule, which is an addition reaction site formed by a Diels-Alder reaction from an anthracene structure and a maleimide structure, and the Diels-Alder reaction unit has at least one amino group. is a compound having
The so-called Diels-Alder reaction, in which a conjugated diene such as an anthracene structure and a parent diene such as a maleimide structure undergo an addition reaction to form a six-membered ring, is an equilibrium reaction. It is widely known that the retro-Diels-Alder reaction, which is a reverse reaction in which the moiety dissociates and returns to the original conjugated diene and the parent diene, proceeds.
The DA compound of the present invention has an anthracene structure having at least one functional group reactive with an epoxy group, and a maleimide structure having at least one functional group reactive with an epoxy group. It is a compound in which at least one functional group derived from each structure remains in the Diels-Alder reaction unit after the Diels-Alder reaction, at least one of which is an amino group.
If each structural part does not have a functional group that reacts with the epoxy resin, the crosslink density of the resulting cured product will decrease, resulting in poor heat resistance, mechanical properties, and adhesive strength. Therefore, the structural part that has been dissociated is released, and it becomes difficult for the Diels-Alder reaction unit to recombine after dissociation. On the other hand, when each structural part has a functional group that reacts with an epoxy group, each structural part is fixed to some extent in the cured product, so that each structural part exists in close proximity and can easily recombine. can do. By using this compound in the epoxy resin composition, it is possible to impart repairability and remoldability to the cured product.

Examples of the compound having an anthracene structure used in the method for producing a DA compound of the present invention include any of the compounds listed in formula (11) below. Among these, hydroxyanthracenes and aminoanthracenes are preferred in terms of reactivity with epoxy groups, and monohydroxyanthracenes and monoaminoanthracenes are particularly preferred in terms of the balance between reactivity, physical properties of the cured product, and repairability and remolding properties. preferable.

The structures of the compounds listed in the above formula (11) are, independently of each other, a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, Including those having an aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group or aryl group as a substituent. Further, in the structures of the compounds listed in the above formula (11), an alkoxy group, an aralkyloxy group, an aryloxy group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkyl group, a cycloalkyl group, an aralkyl group and Aryl groups also include those having various substituents attached to their carbon atoms. For example, the aryl group includes an aminoaryl group having an additional amino group attached to the carbon atom.

Examples of the compound having a maleimide structure used in the method for producing a DA compound of the present invention include any of the compounds listed in formula (12) below.
Among these, hydroxyphenylmaleimides and aminophenylmaleimides are preferred in terms of reactivity with epoxy groups. is particularly preferred. Among monoaminophenylmaleimides, para-aminophenylmaleimide is particularly preferred from the viewpoint of heat resistance.

The structures of the compounds listed in the above formula (12) are, independently of each other, a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, Including those having an aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group or aryl group as a substituent. Further, in the structures of the compounds listed in the above formula (12), an alkoxy group, an aralkyloxy group, an aryloxy group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkyl group, a cycloalkyl group, an aralkyl group and Aryl groups also include those having various substituents attached to their carbon atoms. For example, the aryl group includes an aminoaryl group having an additional amino group attached to the carbon atom.

The DA compound of the present invention is obtained by combining the compound having the anthracene structure and the compound having the maleimide structure, at least one of which has at least one amino group, and subjecting the compound to Diels-Alder reaction. It can be synthesized by subjecting the conjugated diene structure and the parent diene structure to an addition reaction. A known method may be used for the Diels-Alder reaction. For example, equimolar amounts of a conjugated diene compound and a diene parent compound, optionally with an excess amount of one component, are heated and melted or dissolved in a solvent, stirred at a temperature of room temperature to 200° C. for 1 to 24 hours, and purified as such. It can be obtained by filtering or distilling off the solvent, or by commonly used isolation and purification methods such as recrystallization, reprecipitation and chromatography.

(Epoxy resin composition)
The epoxy resin composition of the present invention comprises the DA compound of the present invention and an epoxy resin. Generally known epoxy resins can be used as the epoxy resin contained in the epoxy resin composition of the present invention. The epoxy resin contained in the epoxy resin composition of the present invention is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, and resorcinol. Liquid epoxy resins such as type epoxy resins, hydroquinone type epoxy resins, catechol type epoxy resins, dihydroxynaphthalene type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, brominated epoxy resins such as brominated phenol novolac type epoxy resins , solid bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak 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, naphthylene ether type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon Examples include formaldehyde resin-modified phenolic resin type epoxy resins and biphenyl-modified novolac type epoxy resins. They may be used alone or in combination of two or more. It is preferable to use Of these, bisphenol type epoxy resins, novolak type epoxy resins, and the like are preferably used from the viewpoint of general industrial availability.

（式（４）中、Ａｒはそれぞれ独立して、無置換または置換基を有する芳香環を有する構造であり、
Ｘは下記式（４－１）で表される構造単位であり、Ｙは下記式（４－２）で表される構造単位であり、

［式（４－１）、（４－２）中、Ａｒはそれぞれ独立して、無置換または置換基を有する芳香環を有する構造であり、
Ｒ¹、Ｒ²はそれぞれ独立して水素原子、メチル基またはエチル基であり、
Ｒ’は炭素原子数２～１２の２価の炭化水素基であり、
Ｒ³、Ｒ⁴、Ｒ⁷、Ｒ⁸はそれぞれ独立して水酸基、グリシジルエーテル基または２－メチルグリシジルエーテル基であり、
Ｒ⁵、Ｒ⁶、Ｒ⁹、Ｒ¹⁰はそれぞれ独立して水素原子またはメチル基であり、
ｎ₁は４～１６の整数であり、ｎ₂は繰り返し単位の平均値で２～３０である。］
Ｒ¹¹、Ｒ¹²はそれぞれ独立して、グリシジルエーテル基または２－メチルグリシジルエーテル基であり、
Ｒ¹³、Ｒ¹⁴はそれぞれ独立して水酸基、グリシジルエーテル基または２－メチルグリシジルエーテル基であり、
Ｒ¹⁵、Ｒ¹⁶は水素原子又はメチル基であり、
ｍ₁、ｍ₂、ｐ₁、ｐ₂、ｑは繰り返しの平均値であり、
ｍ₁、ｍ₂は、それぞれ独立して０～２５であり、且つ、ｍ₁＋ｍ₂≧１であり、
ｐ₁、ｐ₂はそれぞれ独立して０～５であり、
ｑは０．５～５である。
ただし、前記式（４－１）で表される構造単位Ｘと前記式（４－２）で表される構造単位Ｙとの結合は、ランダムであってもブロックであってもよく、１分子中に存在する各構造単位Ｘ、Ｙの数の総数がそれぞれｍ₁、ｍ₂であることを示す。） As the epoxy resin contained in the epoxy resin composition of the present invention, an epoxy resin represented by the following formula (4) and having an epoxy equivalent of 500 to 10000 g/eq may be used.

(In formula (4), each Ar is independently a structure having an unsubstituted or substituted aromatic ring,
X is a structural unit represented by the following formula (4-1), Y is a structural unit represented by the following formula (4-2),

[In formulas (4-1) and (4-2), each Ar is independently a structure having an unsubstituted or substituted aromatic ring,
R ¹ and R ² are each independently a hydrogen atom, a methyl group or an ethyl group,
R' is a divalent hydrocarbon group having 2 to 12 carbon atoms,
R ³ , R ⁴ , R ⁷ and R ⁸ are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,
R ⁵ , R ⁶ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group;
n ₁ is an integer of 4 to 16, and n ₂ is an average repeating unit of 2 to 30; ]
R ¹¹ and R ¹² are each independently a glycidyl ether group or a 2-methylglycidyl ether group,
R ¹³ and R ¹⁴ are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,
R ¹⁵ and R ¹⁶ are a hydrogen atom or a methyl group;
m ₁ , m ₂ , p ₁ , p ₂ , q are average values of repetitions,
m ₁ and m ₂ are each independently 0 to 25, and m ₁ +m ₂ ≧1,
p ₁ and p ₂ are each independently 0 to 5,
q is 0.5-5.
However, the bond between the structural unit X represented by the formula (4-1) and the structural unit Y represented by the formula (4-2) may be random or block, and one molecule The total number of structural units X and Y present therein is m ₁ and m ₂ , respectively. )

（式（５）中、ｐ₁、ｐ₂、ｑ、ｍ₁及びｎ₁は繰り返しの平均値であり、それぞれ独立して、ｐ₁は０～５、ｐ₂は０～５、ｑは０．５～５、ｍ₁は０～２５、ｎ₁は２～３０である。） As an epoxy resin contained in the epoxy resin composition of the present invention, an epoxy resin represented by the following formula (5) may be used. By using such an epoxy resin, the repairability and remoldability of the epoxy resin cured product are improved, and the balance between flexibility and toughness is improved.

(In formula (5), p ₁ , p ₂ , q, m ₁ and n ₁ are the average values of repetitions, and independently p ₁ is 0 to 5, p ₂ is 0 to 5, q is 0 .5 to 5, m ₁ is 0 to 25, and n ₁ is 2 to 30.)

（式（７）中、ｎは繰り返しの平均値であり、０～１００である。これらの中でも組成物の流動性が良好になる点から、ｎは繰り返しの平均値として０～１が好ましい。） As the epoxy resin contained in the epoxy resin composition of the present invention, an epoxy resin (DGEBA) represented by the following formula (7) may be used.

(In formula (7), n is the average value of repetitions and ranges from 0 to 100. Among these, the average value of n is preferably 0 to 1 as the average value of repetitions from the viewpoint of improving the fluidity of the composition. )

The epoxy resin composition of the present invention contains the DA compound of the present invention as a curing agent for the epoxy resin, and may further contain another curing agent (curing agent that can be used in combination). The curing agent that can be used in combination is not particularly limited as long as it reacts with the epoxy resin to produce a cured product. acid-based compounds and the like.

Examples of the amine compounds include aliphatic polyamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, polypropyleneglycoldiamine, diethylenetriamine, triethylenetetramine, and pentaethylenehexamine; metaxylylenediamine; diaminodiphenylmethane; Aromatic polyamines such as diaminodiphenylsulfone and phenylenediamine; alicyclic polyamines such as 1,3-bis(aminomethyl)cyclohexane, isophoronediamine and norbornanediamine; and dicyandiamide.

Examples of the acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, polypropylene glycol maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methyl nadic anhydride. , hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like.

Examples of the phenol-based compound include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylolmethane resin, tetraphenyl Roll ethane resin, naphthol 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. Also, the latent catalysts include imidazole, BF ₃ -amine complexes, guanidine derivatives and the like.

Examples of the amide-based compound include aliphatic polyamide synthesized from polycarboxylic acid and polyamine, aromatic polyamide obtained by introducing an aromatic ring into this, aliphatic polyamide adduct obtained by adding an epoxy compound to polyamide, aromatic family polyamide adducts, and the like.

Examples of the carboxylic acid-based compound include carboxylic acid-terminated polyesters, polyacrylic acid, carboxylic acid polymers such as maleic acid-modified polypropylene glycol, and active ester resins.

The curing agents that can be used in combination may be used alone or in combination of two or more. In applications such as underfill materials and general paint applications, it is preferable to use the amine-based compound, carboxylic acid-based compound, and/or acid anhydride-based compound. Amine-based compounds, particularly dicyandiamide, are preferred for use as adhesives and flexible wiring boards in terms of workability, curability, and long-term stability. Further, in semiconductor encapsulation applications, a solid type phenolic compound is preferable from the viewpoint of heat resistance of the cured product.

All curing agents in the epoxy resin composition of the present invention, that is, the DA compound of the present invention (including the curing agent that can be used in combination when using the above-mentioned curing agent that can be used in combination), and the amount of the epoxy resin Although it is not particularly limited, from the viewpoint that the mechanical properties of the resulting cured product are good, the activity An amount that results in 0.7 to 1.5 equivalents of the group is preferred.

The concentration of the DA compound of the present invention in the epoxy resin composition of the present invention is preferably 0.10 mmol/g or more with respect to the total mass of the epoxy resin and the DA compound of the present invention. According to such a configuration, both the repairability and remoldability of the epoxy resin cured product obtained by subjecting the epoxy resin composition to the heat treatment are further improved. More preferably, the concentration of the aforementioned DA compound of the present invention is between 0.10 and 3.00 mmol/g, even more preferably between 0.15 and 2.00 mmol/g. Further, when the epoxy resin composition of the present invention contains the curing agent that can be used in combination, the concentration of the DA compound of the present invention in the epoxy resin composition of the present invention is the same as that of the epoxy resin and the DA of the present invention. It is preferably 0.10 mmol/g or more, more preferably 0.10 to 3.00 mmol/g, more preferably 0.15 to 2.0 mmol/g, based on the total mass of the compound and the curing agent that can be used in combination. 00 mmol/g is even more preferred. The concentration of the DA compound of the present invention is appropriately selected depending on the glass transition temperature defined by the tan δ peak top of a dynamic viscoelasticity analyzer (DMA) of the cured product obtained from the desired epoxy resin composition. can do. For example, when the glass transition temperature is used as a guideline, if the glass transition temperature of the cured product is around room temperature, sufficient repairability and remoldability functions are likely to be exhibited even at the low concentration side of the preferable range. On the other hand, if the glass transition temperature of the desired cured product exceeds 100° C. as a guideline, the function is likely to be exhibited at the high concentration side of the preferred range. However, in the temperature region exceeding the glass transition temperature measured by DMA, molecular mobility is generally high, and sufficient repairability and remolding functions are likely to be expressed even at low concentrations of the DA compound. For example, it is also possible to adjust the effect of expression of the repairability and remolding functions by appropriately adjusting the aging temperature for restoration and the heating temperature for remolding. Thus, the relationship between the glass transition temperature of the cured product and the concentration of the DA compound of the present invention is not limited to these.

The epoxy resin composition of the present invention may further contain fillers, fibrous matrices, dispersion media, resins other than the various compounds described above, and the like. Hereinafter, each content will be specifically described in detail.

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

Examples of inorganic fine particles that have excellent heat resistance include alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc.). is mentioned. Boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond and the like are listed as materials having excellent heat conductivity. Also, as those having excellent conductivity, metal fillers and/or metal-coated fillers using single metals or alloys (for example, iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.) are used. mentioned. In addition, as materials with excellent barrier properties, minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate, sepiolite, xonolite, aluminum borate, calcium carbonate, titanium oxide, Barium sulfate, zinc oxide, magnesium hydroxide and the like can be mentioned. Materials having a high refractive index include barium titanate, zirconia oxide, and titanium oxide. In addition, titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, terium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, etc., which exhibit photocatalytic properties. Examples include photocatalytic metals, composites of the above metals, and oxides thereof. Materials having excellent wear resistance include metals such as silica, alumina, zirconia, and magnesium oxide, and composites and oxides thereof. In addition, metals such as silver and copper, tin oxide, indium oxide, and the like are listed as materials having excellent conductivity. Moreover, silica etc. are mentioned as what is excellent in insulation. Titanium oxide, zinc oxide and the like are listed as those having excellent ultraviolet shielding properties.

These inorganic fine particles may be appropriately selected depending on the application, and may be used alone or in combination of multiple types. In addition, since the inorganic fine particles have various properties other than the properties listed as examples, they may be appropriately selected according to the intended use.

For example, when silica is used as the inorganic fine particles, known silica fine particles such as powdered silica and colloidal silica can be used without any particular limitation. Examples of commercially available powdery silica fine particles include Aerosil 50 and 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 Silica Industry Co., Ltd. , E220, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet 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 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. mentioned. Commercially available powdery silica modified with a compound having a (meth)acryloyl group includes Aerosil RM50 and R711 manufactured by Nippon Aerosil Co., Ltd. Commercially available colloidal silica modified with a compound having a (meth)acryloyl group includes: Examples include MIBK-SD manufactured by Nissan Chemical Industries, Ltd., and the like.

The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous, or amorphous particles can be used. Also, the primary particle size is preferably in the range of 5 to 200 nm. When the diameter is 5 nm or more, the inorganic fine particles are sufficiently dispersed in the dispersion, and when the diameter is 200 nm or less, it becomes easy to maintain sufficient strength of the cured product.

As 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, and brookite-type titanium oxide. Furthermore, particles designed to respond to visible light by doping a different element into the crystal structure of titanium oxide can also be used. Anion elements such as nitrogen, sulfur, carbon, fluorine, and phosphorus, and cationic elements such as chromium, iron, cobalt, and manganese are preferably used as elements to be doped in titanium oxide. Moreover, as a form, a powder, a sol dispersed in an organic solvent or water, or a slurry can be used. Examples of commercially available powdery titanium oxide fine particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd., and ATM-100 manufactured by Tayca Corporation. Further, commercially available slurry-like titanium oxide fine particles include, for example, TKD-701 manufactured by Tayca Corporation.

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

Examples of inorganic fibers include inorganic fibers such as carbon fiber, glass fiber, boron fiber, alumina fiber, silicon carbide fiber, carbon fiber, activated carbon fiber, graphite fiber, glass fiber, tungsten carbide fiber, 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, proteins, polypeptides, and regenerated fibers such as alginic acid.

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

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

<Dispersion medium>
The epoxy resin composition of the present invention may use a dispersion medium for the purpose of adjusting the solid content mass 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. , toluene, xylene and other aromatics, carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether and other alcohols, which can be used alone or in combination. is preferable from the viewpoints of solubility of constituent materials such as epoxy resins and curing agents, volatility during coating, and solvent recovery.

The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction. acrylic block copolymers (DISPERBYK2000: BYK-Chemie);

<Resin>
In addition, the epoxy resin composition of the present invention may contain resins 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 it does not impair the effects of the present invention. For example, thermosetting resins and thermoplastic resins can be used.

Thermosetting resins are resins that have the property of being able to become substantially insoluble and infusible when cured by means of heat, radiation, catalysts, or the like. Specific examples include urea resins, melamine resins, benzoguanamine resins, alkyd resins, unsaturated polyester resins, vinyl ester resins, diallyl terephthalate resins, silicone resins, urethane resins, furan resins, ketone resins, xylene resins, and thermosetting polyimides. resins, benzoxazine resins, aniline resins, cyanate ester resins, styrene/maleic anhydride (SMA) resins, maleimide resins, and the like. These thermosetting resins can be used singly or in combination of two or more.

A 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, 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 Resins, polysulfone resins, polyphenylene sulfide resins, polyetherimide resins, polyethersulfone resins, polyarylate resins, thermoplastic polyimide resins, polyamideimide resins, polyetheretherketone resins, polyketone resins, liquid crystal polyester resins, fluororesins, synth otakutic polystyrene resins, cyclic polyolefin resins, and the like. These thermoplastic resins can be used singly or in combination of two or more.

(Method for producing epoxy resin composition)
The epoxy resin composition of the present invention comprises the above-mentioned DA compound and epoxy resin of the present invention, and if necessary, the above-mentioned curing agent, filler, fibrous substrate, dispersion medium, and other compounds other than the above-mentioned various compounds. The resin is dissolved in a dispersion medium such as the organic solvent described above. After dissolution, the solvent is distilled off, and the epoxy resin composition can be obtained by drying under reduced pressure in a vacuum oven or the like. Further, the epoxy resin composition of the present invention may be in the state of uniformly mixing the constituent materials described above. At this time, it is preferable to mix uniformly with a mixer or the like. The mixing ratio of each constituent material can be appropriately adjusted according to the desired properties of the cured epoxy resin, such as mechanical strength, heat resistance, repairability, and remoldability. In addition, in the preparation of the epoxy resin composition, as a specific mixing order of the constituent materials, first, an organic solvent such as acetone or methyl ethyl ketone is added to the epoxy resin and stirred, and then the DA compound of the present invention is added as a curing agent. The mixture is stirred again to make it uniform, concentrated, and dried under reduced pressure to obtain an epoxy resin composition in which the constituent materials are more uniformly mixed.

(Epoxy resin cured product)
The epoxy resin cured product of the present invention has one Diels-Alder reaction unit consisting of an anthracene structure and a maleimide structure in the molecule, and the Diels-Alder reaction unit has at least one amino group. Hardened epoxy resin. As the epoxy resin, generally known epoxy resins such as those described as the epoxy resin contained in the epoxy resin composition of the present invention can be used.

Since the epoxy resin cured product of the present invention is cured with the DA compound of the present invention, which has excellent thermal stability, as described above, it is possible to suppress the decrease in crosslink density even in a high temperature environment, and it has good mechanical properties. strength can be maintained. In addition, it is thought that by applying mechanical energy such as scratches or external force to the epoxy resin cured product of the present invention, the C—C bond of the Diels-Alder reaction unit is cleaved and anthracene and maleimide are generated on the cleaved surface. In the Diels-Alder reaction of maleimide, the equilibrium shifts in the bonding direction at 200° C. or less, so it is thought that an adduct (Diels-Alder reaction unit) is formed again, and damage repair and remolding become possible.

In the following formula (8), the Diels-Alder reaction (DA reaction: cross-linking reaction) and the retro-Diels-Alder reaction (rD- A schematic diagram showing Reaction A: reversible cross-linking/de-cross-linking reaction) is shown. Specifically, in the formula (8), as the DA compound of the present invention, an epoxy obtained by curing the epoxy resin (DGEBA) represented by the above formula (7) with the compound represented by the above formula (2) It shows about resin hardened material. In the example of formula (8), when an epoxy resin composition containing the compound represented by formula (2) and an epoxy resin is heat-treated, the epoxy group of the epoxy resin and the Diels-Alder compound represented by formula (2) The amino groups of the anthracene structure and the maleimide structure in the reaction unit are combined to form a three-dimensional network structure. Further, by applying mechanical energy such as damage or external force, the C—C bond of the Diels-Alder reaction unit is cleaved, and the anthracene structure and the maleimide structure are separated and cross-linked. Even if the material has been cross-linked, heating it at a predetermined temperature causes the Diels-Alder reaction to occur again, restoring the three-dimensional network structure, making it possible to repair damage and reshape the material. In addition, it is preferable to promote reversible crosslinking/decrosslinking reactivity by utilizing phase separation and arranging reversible bonds in the cured product in the low elastic modulus phase.

(Method for producing cured epoxy resin)
Next, the method for producing the epoxy resin cured product of the present invention will be described in detail. The epoxy resin cured product of the present invention can be produced by heating the epoxy resin composition of the present invention to cure the epoxy resin contained in the epoxy resin composition with the DA compound of the present invention. Specifically, an epoxy resin obtained by casting the epoxy resin composition of the present invention on a silicone casting plate or the like, degassing if necessary, and then curing the epoxy resin by heating. A cured product is obtained. The step of casting on the aforementioned silicone casting plate or the like can be carried out, for example, by sandwiching the epoxy resin composition between aluminum mirror plates or the like using a silicon tube as a spacer.

A known curing accelerator can be used in the method for producing the epoxy resin cured product of the present invention. The curing accelerator is not particularly limited, but for example, urea compound, phosphorus compound, tertiary amine, imidazole, organic acid metal salt, Lewis acid, amine complex salt, quaternary ammonium salts, tin carboxylate, organic peroxide things, etc. When used as an adhesive, urea compounds, particularly 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), are preferred from the viewpoint of excellent workability and low-temperature curability. When used as a semiconductor encapsulating material or as an electronic material for printed circuit boards and build-up boards, triphenylphosphine, triphenylphosphine, Preferred tertiary amines are dimethylaminopyridine, imidazoles, 1,8-diazabicyclo-[5.4.0]-undecene (DBU), and benzyldimethylamine.

The structure of the obtained cured epoxy resin can be confirmed by infrared absorption (IR) spectroscopy using Fourier transform infrared spectroscopy (FT-IR), elemental analysis, X-ray scattering, and the like.

(Use of epoxy resin composition and cured epoxy resin)
INDUSTRIAL APPLICABILITY The epoxy resin composition of the present invention and the epoxy resin cured product produced from the epoxy resin composition are excellent in both heat resistance and repairability, and have remoldability, and are useful for the following applications. .

<Laminate>
The epoxy resin cured product of the present invention can be laminated with a substrate to form a laminate. As the base material of the laminate, an inorganic material such as metal or glass, or an organic material such as plastic or wood may be used as appropriate depending on the application. It may have an original structure or may be three-dimensional. It may have any shape according to the purpose, such as one having a curvature on the entire surface or a part thereof. Moreover, there are no restrictions on the hardness, thickness, etc. of the base material. Moreover, it is good also as a multilayer laminated body which laminates|stacks in order of a 1st base material, the layer which consists of a hardened|cured material of the epoxy resin composition of this invention, and a 2nd base material. Since the epoxy resin composition of the present embodiment has excellent adhesiveness, it can be suitably used as an adhesive for bonding the first base material and the second base material. Further, the epoxy resin cured product of the present invention may be used as a base material, and the cured product of the present invention may be laminated thereon.

Since the epoxy resin 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. Metals 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 / Or a composite oxide is mentioned. In particular, since it has excellent adhesion to iron, copper and aluminum, it can be used favorably as an adhesive for iron, copper and aluminum.

In addition, since the epoxy resin cured product of the present invention can relax stress, it can be suitably used particularly for bonding different materials. For example, even if the base material is a metal and/or metal oxide and the second base material is a laminate of different materials such as a plastic layer, the stress relaxation ability of the epoxy resin cured product of the present invention allows adhesion. power is maintained.

In the laminate obtained by laminating the epoxy resin cured product of the present invention and the base material, the layer containing the cured product may be formed by direct coating or molding on the base material, or by laminating an already molded product. I don't mind. In the case of direct coating, the coating method is not particularly limited, and includes a spray method, spin coating method, dipping method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, A screen printing method, an inkjet method, and the like can be mentioned. Direct molding includes in-mold molding, insert molding, vacuum molding, extrusion lamination molding, press molding, and the like. When the molded composition is laminated, an uncured or semi-cured composition layer may be laminated and then cured, or a layer containing a cured product obtained by completely curing the composition may be laminated on the substrate. may Alternatively, the epoxy resin 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 epoxy resin composition of the present invention is not yet present. It may be cured after bonding in a cured or semi-cured state. Precursors that can serve as base materials are not particularly limited, and various curable resin compositions and the like can be mentioned.

<Adhesive>
The epoxy resin cured product of the present invention can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft and the space industry. Even when the adhesive is used to bond dissimilar materials such as between metals and non-metals, the adhesive can maintain high adhesiveness without being affected by changes in the temperature environment, and peeling or the like is unlikely to occur. In addition to structural members, the adhesive can also be used for general office, medical, carbon fiber, storage battery cells, modules, and cases. mounting adhesives, printed wiring board mounting adhesives, die bonding adhesives, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films, and mounting adhesives such as anisotropic conductive pastes can be used as an agent.

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

A method for molding the fiber-reinforced resin is not particularly limited. If a plate-like product is to be manufactured, extrusion molding is generally used, but flat pressing is also possible. In addition, it is possible to use an extrusion molding method, a blow molding method, a compression molding method, a vacuum molding method, an injection molding method, and the like. If a film-like product is to be produced, a solution casting method can be used in addition to the melt extrusion method. When using a melt molding method, inflation film molding, cast molding, extrusion lamination molding, calender molding, and sheet molding can be used. , fiber molding, blow molding, injection molding, rotational molding, coating molding, and the like. Moreover, in the case of a resin that is cured by an active energy ray, a cured product can be produced using various curing methods using an active energy ray. In particular, when a thermosetting resin is used as the main component of the matrix resin, there is a molding method in which the molding material is prepregized and pressurized and heated by a press or an autoclave. VaRTM (Vacuum Assist Resin Transfer Molding) molding, lamination molding, hand lay-up molding and the like can be mentioned.

<Other molding materials>
The epoxy resin composition of the present invention is excellent in both heat resistance and repairability, and remoldability. It can be used for casting materials, molding materials such as gears and pulleys. These may be a cured product of resin alone or a cured product reinforced with fibers such as glass chips.

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

<Heat resistant materials and electronic materials>
The epoxy resin composition of the present invention has good heat resistance and good repairability, and remoldability in the epoxy resin cured product using it, and can be used as a heat-resistant material and an electronic material. be. In particular, it can be suitably used for semiconductor encapsulants, circuit boards, build-up films, build-up substrates, adhesives, and resist materials. It can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a highly heat-resistant prepreg. The heat-resistant members and electronic members obtained in this way can be suitably used for various applications, for example, industrial machine parts, general machine parts, automobile/railroad/vehicle parts, aerospace-related parts, electronic/electrical parts, Building materials, containers/packaging members, daily necessities, sports/leisure goods, housing members for wind power generation, etc., but not limited to these.

Representative products will be described below with examples.
1. Semiconductor Encapsulation Material As a method for obtaining a semiconductor encapsulation material from the epoxy resin composition of the present invention, the composition, a curing accelerator, and compounding agents such as inorganic fillers are optionally extruded, kneaded, A method of sufficiently melting and mixing using a roll or the like until the mixture becomes uniform can be used. At that time, fused silica is usually used as the inorganic filler, but when it is used as a high thermal conductive semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, and nitride, which have higher thermal conductivity than fused silica, are used. High filling of silicon or the like, or fused silica, crystalline silica, alumina, silicon nitride, or the like may be used. The filling rate of the inorganic filler is preferably in the range of 30 to 95% by mass per 100 parts by mass of the epoxy resin composition. 70 parts by mass or more is more preferable, and 80 parts by mass or more is even more preferable in order to reduce the amount.

2. Semiconductor device For molding a semiconductor package to obtain a semiconductor device from the epoxy resin composition of the present invention, the above semiconductor sealing material is cast, or molded using a transfer molding machine, an injection molding machine, etc. A method of heating for 2 to 10 hours may be mentioned.

3. Printed Wiring Board As a method for obtaining a printed wiring board from the epoxy resin composition of the present invention, the above prepregs are laminated by a conventional method, appropriately overlaid with copper foil, and heated at 170 to 300° C. for 10 minutes under a pressure of 1 to 10 MPa. A method of thermocompression bonding for minutes to 3 hours may be mentioned.

4. Build-up board The method for obtaining a build-up board from the epoxy resin composition of the present invention includes, for example, the following steps. First, a step of applying the above-mentioned composition properly containing rubber, filler, etc. to a circuit board having a circuit formed thereon by using a spray coating method, a curtain coating method, or the like, and then curing (step 1). After that, after drilling a predetermined through hole portion etc. as necessary, it is treated with a roughening agent, the surface is washed with hot water to form unevenness, and a step of plating a metal such as copper (step 2). Step 3 of alternately building up and forming resin insulating layers and conductor layers having a predetermined circuit pattern by repeating such operations as desired (step 3). The through-hole portion is formed after the outermost resin insulation layer is formed. In addition, the build-up board of the present invention is obtained by heat-pressing a resin-coated copper foil obtained by semi-curing the resin composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 300 ° C. It is also possible to produce a build-up board by omitting the steps of forming a hardened surface and plating.

5. Build-up Film As a method for obtaining a build-up film from the epoxy resin composition of the present invention, the epoxy resin composition is applied to the surface of a support film which is a substrate, and then heated or blown with hot air to form an organic solvent. can be produced by drying to form a layer of the epoxy resin 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 and butyl carbitol. Carbitols, toluene, aromatic hydrocarbons such as xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and the nonvolatile content is 30 to 60% by mass. preferable.

The thickness of the layer of the epoxy resin composition to be formed is usually set to be 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. In addition, the layer of the epoxy resin composition may be protected with a protective film to be described later. By protecting the surface of the resin composition layer with a protective film, it is possible to prevent the surface of the resin composition layer from being dusted or scratched.

The support film and protective film described above are polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; Paper patterns and metal foils such as copper foils and aluminum foils can be used. The support film and protective film may be subjected to release treatment in addition to mud treatment and corona treatment. Although the thickness of the support film is not particularly limited, it is usually 10 to 150 μm, preferably 25 to 50 μm. Also, the thickness of the protective film is preferably 1 to 40 μm.

The support film 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 is peeled off after the curable resin composition layer constituting the build-up film is cured by heating, it is possible to prevent the adhesion of dust and the like during the curing process. When peeling after curing, the support film is normally subjected to a release treatment in advance.

A multilayer printed circuit board can be produced using the build-up film obtained as described above. For example, if the epoxy resin composition layer is protected by a protective film, after removing these, the epoxy resin composition layer is applied to one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by vacuum lamination. Laminate with The method of lamination may be a batch type or a continuous roll type. If necessary, the build-up film and the circuit board may be heated (preheated) before lamination. The conditions for lamination are preferably a pressure bonding temperature (laminating temperature) of 70 to 140° C. and a pressure bonding pressure of 1 to 11 kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ). It is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less.

6. Conductive Paste A method of obtaining a conductive paste from the epoxy resin composition of the present invention includes, for example, a method of dispersing conductive particles in the composition. 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.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these.

<Example 1>
-Synthesis of DA compound-
A DA compound was synthesized based on the schemes shown in formulas (9-1) to (9-3) below. Specific procedures are described in detail below.

N-(4-aminophenyl)maleimide (APM) was prepared according to the scheme shown in formula (9-1) above. That is, 5.35 g (49.5 mmol) of p-phenylenediamine and 97 mL of tetrahydrofuran (THF) were added to a 300 mL eggplant flask, and 4.85 g (49.5 mmol) of maleic anhydride dissolved in 36 mL of THF was stirred at room temperature. was added dropwise over 1 hour. After completion of dropping, stirring (r.t./12h) was performed, and the precipitate formed by suction filtration was collected and dried under reduced pressure (r.t./12h) to obtain 9.49 g of APMA (yellow solid).
Subsequently, 9.47 g (45.9 mmol) of APMA was added to a 200 mL two-necked flask, and after the system was replaced with argon, 36 mL of N,N-dimethylformamide (DMF) and 9.60 mL (68 mL) of triethylamine (NEt ₃ ) were added. .9 mmol) was added and dissolved by stirring at room temperature. The flask was ice-cooled, 10.6 mL (46.0 mmol) of di-tert-butyl dicarbonate (Boc ₂ O) was added, and the mixture was stirred for 15 minutes and then stirred at room temperature for 17 hours. After pouring the resulting solution into 257 mL of pure water (0° C.), the pH was adjusted to 4.5 to 5.5 with dilute hydrochloric acid to form a precipitate. This precipitate was collected by suction filtration and dried under reduced pressure (70° C./12 h) to obtain 13.5 g of pale yellow solid.
13.2 g of this pale yellow solid was added to a 1000 mL eggplant flask together with 133 mL of acetic anhydride (Ac ₂ O) and heated to 95° C., then 3.88 g (47.3 mmol) of sodium acetate (AcONa) was added and stirred. (95°C/2h) was performed. After stirring for 12 h at room temperature after stirring, the precipitated pale yellow solid was added with 800 mL of pure water and stirred (r.t./10 min), followed by suction filtration, saturated sodium bicarbonate aqueous solution and pure water. It was recovered by washing with The resulting solid is dissolved in dichloromethane, washed with pure water and saturated brine, dried with sodium sulfate, filtered, evaporated and dried under reduced pressure (r.t./12h) to obtain Boc-APM. 10.2 g of (pale yellow solid) was obtained.
Subsequently, 56 mL of dichloromethane (CH ₂ Cl ₂ ) was added to a ₅₀₀ mL eggplant flask containing 10.1 g (35.0 mmol) of Boc-APM, and 68.5 g (0 .601 mol) was added followed by stirring (r.t./2h). After completion of the reaction, the solvent was distilled off, the residue was dissolved in pure water, and an extraction operation with dichloromethane/saturated sodium bicarbonate aqueous solution was performed three times. After washing the obtained organic layer with pure water and saturated saline, drying with sodium sulfate, filtration, solvent distillation and drying under reduced pressure (r.t./12 h) gave a crude APM product ( 5.84 g). This crude product was purified by silica gel column chromatography (developing solvent: chloroform/ethyl acetate=20/1) to obtain 4.66 g of APM (red solid). Yield was 52% over four steps.

Next, 2-aminoanthracene (AA) was prepared according to the scheme shown in formula (9-2) above. That is, 20.0 g (89.6 mmol) of 2-aminoanthraquinone, 16.9 g (0.258 mol) of Zn (powder), and 50 mL of 10% sodium hydroxide aqueous solution were added to a 1000 mL three-necked flask and stirred (r. t./30 min) was performed. Subsequently, after heating to 100° C. using an oil bath, 10.6 g (0.162 mol) of Zn (powder) was added and stirred for 30 minutes. Further, 10.6 g (0.162 mol) of Zn (powder) was added and refluxed at an oil bath temperature of 115° C. for 24 hours. After cooling to room temperature, the solid phase was collected by suction filtration, washed with pure water, and dried under reduced pressure (60° C./ovn.). After adding acetone to the obtained solid, the acetone-insoluble portion was removed by suction filtration, and the soluble portion was recovered. After acetone was distilled off under reduced pressure, drying under reduced pressure (r.t./1h) was performed, and the resulting solid was purified by recrystallization (solvent: toluene) to obtain 9.63 g of AA (green solid) (yield 55%).

Next, a DA compound was synthesized according to the scheme shown in formula (9-3) above. That is, 7.10 g (36.7 mmol) of AA and 7.61 g (40.4 mmol, 1.1 eq) of APM were added to a 500 mL three-necked flask, the system was replaced with Ar, and then 214 mL of chlorobenzene (degassed by Ar bubbling) was added. added. Subsequently, after refluxing for 21 hours, the mixture was cooled to room temperature, and hexane was added to precipitate a solid. Next, the solid was collected by suction filtration and dried under reduced pressure (70° C./4h) to obtain 14.3 g of a mixture of endo-APM-AA and exo-APM-AA. Subsequently, when separation was performed by silica gel column chromatography (developing solvent: dichloromethane/ethyl acetate = 1/1 (v/v)), exo form (Rf value: 0.40) and endo form (Rf value: 0.40) were obtained. 28) was isolated. After distilling off the developing solvent for each, drying under reduced pressure (60° C./12 h) gave 5.53 g (yield 38%) of exo-APM-AA and 6.5 g of endo-APM-AA as pale orange solids. 52 g (yield 44%) was obtained. FIG. 1 shows the ¹ H-NMR spectrum of the endo form obtained at this time. According to FIG. 1, peaks derived from the bond formed between APM-AA by the Diels-Alder reaction are observed at 3.29 ppm and 4.74 ppm, and the target compound (endo-APM-AA) is produced. confirmed.

<Example 2>
-Preparation of cured epoxy resin-
In a flask, the endo or exo form of the DA compound obtained in Example 1 and the epoxy resin represented by the above formula (7) (DGEBA, epoxy equivalent weight (EEW): 190 g / eq) were added, After dissolving in acetone such that the equivalent ratio of the NH of the endo form and the exo form and the epoxy group of DGEBA is 1:1, the solvent is distilled off and dried under reduced pressure in a vacuum oven (r.t./ 4h) to obtain an epoxy resin composition. The epoxy resin composition is melted at 140°C, cast on a silicone casting plate, degassed (140°C/15 minutes) and heat-cured (140°C for 1h + 180°C for 2h + 200°C for 2h + 220°C for 2h). Thus, a cured epoxy resin product of the endo form and DGEBA (endo-APM-AA/DGEBA) and a cured epoxy resin product of the exo form and DGEBA (exo-APM-AA/DGEBA) were prepared.

<Example 3>
-Evaluation of cured product-
・Dynamic viscoelasticity measurement (DMA)
The glass transition temperature (Tg) of the cured epoxy resin was measured by performing dynamic viscoelasticity measurement (DMA measurement) using DMS6100 manufactured by SII Nanotechnology. The measurement was performed at a heating rate of 5° C./min and a frequency of 1.0 Hz. FIG. 2 shows the results of dynamic viscoelasticity measurement (DMA) of the obtained cured epoxy resin. The epoxy resin cured product (endo-APM-AA/DGEBA) of the endo form and DGEBA has a Tg of 210°C, and the epoxy resin cured product of the exo form and DGEBA (exo-APM-AA/DGEBA) has a Tg of 209. °C. All of them have a Tg exceeding 200° C. and are found to be excellent in physical heat resistance. In addition, when the thermal weight loss analysis of each epoxy resin cured product was performed, all epoxy resin cured products had a 5% weight loss temperature (Tds) exceeding 370 ° C., and were excellent in chemical heat resistance. It turns out that

・ Tensile test Each tensile test of the epoxy resin cured product of the endo body and DGEBA (endo-APM-AA/DGEBA) and the epoxy resin cured product of the exo body and DGEBA (exo-APM-AA/DGEBA) was performed under the following conditions.
The epoxy resin cured product of the endo form and DGEBA and the epoxy resin cured product of the exo form and DGEBA were each cut into a size of 1 mm in thickness, 10 mm in length and 46 mm in length, and used as a test piece. Using an AG-X 10 kN universal testing machine manufactured by Shimadzu Corporation, a tensile test was performed on the test piece at a measurement environment of 23° C. and a test speed of 1.0 mm/min.
The test piece was directly evaluated for the breaking stress and tensile elongation in the tensile test (initial stage).
Next, a test piece of the epoxy resin cured product of endo body and DGEBA was cut at the center of the test piece with a razor, the cut surfaces were brought together, and aged at Tg + 10 ° C. (= 220 ° C.) for 12 hours. was similarly subjected to a tensile test and evaluated (after restoration (220°C/12h)). In addition, the breaking stress and tensile elongation after restoration were evaluated in the same manner by cutting the center of the test piece with a razor blade, putting the cut surfaces together, and aging at Tg + 10 ° C. (= 220 ° C.) for 24 hours. (after restoration (220°C/24h)).
In addition, for the test piece of the epoxy resin cured product of the exo body and DGEBA, after cutting the center of the test piece with a razor, the cut surfaces were put together, and Tg + 10 ° C. (= 219 ° C.) and Tg + 20 ° C. (= 229 ° C.) Tensile tests were similarly performed on those that had been aged for 12 hours, and evaluations were made (after restoration (219°C/12h, 229°C/12h)). In addition, the breaking stress and tensile elongation after restoration were measured by cutting the center of the test piece with a razor blade and then mating the cut surfaces together and aging at Tg + 10°C (= 219°C) and Tg + 20°C (= 229°C) for 24 hours. The same evaluation was made for those that were performed (after restoration (219°C/24h, 229°C/24h)).
Regarding the obtained breaking stress and tensile elongation rate, the repair rate (%) was calculated based on the formula (numerical value after restoration/initial numerical value)×100%.

<Comparative Example 1>
4,4′-Diaminodiphenylsulfone (DDS) as a curing agent and an epoxy resin (DGEBA, epoxy equivalent weight (EEW): 190 g/eq) represented by the above formula (7) were added to a flask, and the DDS was added. After dissolving NH and the epoxy group of DGEBA in acetone so that the equivalent ratio is 1:1, the solvent is distilled off and the resin mixture is dried under reduced pressure in a vacuum oven (r.t./4h). got The resin mixture is melted at 120° C. and cast on a silicone casting plate, deaerated (120° C./15 minutes) and heat cured (1 h at 120° C. + 2 h at 180° C. + 3 h at 200° C. + 3 h at 220° C. + 1 h at 240° C.). An epoxy resin cured product was obtained by carrying out. A tensile test was carried out in the same manner as in Example 3 for the epoxy resin cured product. In Example 3, the aging temperature for restoration was set to 220°C, but in Comparative Example 1, it was set to Tg + 10°C = 234°C.
Table 1 shows the evaluation results.

According to Table 1, it can be seen that the epoxy resin cured product according to Example 3 is superior to Comparative Example 1 in both breaking stress and tensile elongation repair rates.

[Synthesis Example 1]
-Synthesis of PTMG-type (BPA) hydroxy compounds-
A flask equipped with a thermometer and a stirrer was charged with 445 g (0.5 mol) of diglycidyl ether of polytetramethylene glycol ("Denacol EX-991L" manufactured by Nagase ChemteX: epoxy equivalent 445 g/eq) and bisphenol A (hydroxyl equivalent 228 g (1.0 mol) of 114 g/eq) was added, and after the temperature was raised to 140° C. for 30 minutes, 3.4 g of a 4% aqueous sodium hydroxide solution was added. After that, the temperature was raised to 150° C. over 30 minutes, and the reaction was continued at 150° C. for 16 hours. After that, a neutralizing amount of sodium phosphate was added to obtain 673 g of a hydroxy compound represented by the following formula (6). The hydroxy compound had a peak of M+=1380 corresponding to the theoretical structure of m ₁ =1, n ₁ =11 in the following formula (6) in the mass spectrum. methylene ether glycol) type (BPA: bisphenol A) was confirmed to contain a hydroxy compound. The hydroxyl equivalent weight of this hydroxy compound (Ph-6) calculated from GPC was 526 g/eq, the average value of n ₁ was 10.6, and the average value of m ₁ was 0.73.

[Synthesis Example 2]
-Synthesis of PTMG type (BPA) epoxy resin-
A flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer was charged with 200 g of the hydroxy compound represented by the formula (6) obtained by the above synthesis and 437 g (4.72 mol) of epichlorohydrin while purging with nitrogen gas. , and 118 g of n-butanol were added and dissolved. After raising the temperature to 65° C., the pressure was reduced to an azeotropic pressure, and 6.66 g (0.08 mol) of a 49% sodium hydroxide aqueous solution was added dropwise over 5 hours.
Next, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate fraction distilled azeotropically was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was removed by vacuum distillation. 150 g of methyl isobutyl ketone and 150 g of n-butanol were added to the obtained crude epoxy resin and dissolved.
Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80° C. for 2 hours, followed by washing with 50 g of water three times until the pH of the washing liquid became neutral.
Next, the inside of the system was dehydrated by azeotropy, and after passing through precision filtration, the solvent was distilled off under reduced pressure to obtain 190 g of the epoxy resin represented by the above formula (5). The epoxy equivalent of the obtained epoxy resin was 722 g/eq. The epoxy resin has a peak of M+=1492 corresponding to the theoretical structure of m ₁ =1, n ₁ =11, q=1, p ₁ =0, p ₂ =0 in the above formula (5) in the mass spectrum. From the results obtained, it was confirmed that the desired PTMG-type (BPA) epoxy resin was contained.

<Example 4>
-Synthesis of DA compound-
226 g (1 mol) of 2-aminoanthracene, 226 g (1.2 mol) of 4-hydroxyphenylmaleimide and 450 g of toluene were added to a flask equipped with a thermometer, a stirrer and a condenser, and reacted at 80° C. for 24 hours. . Then, it was cooled to room temperature, and the precipitate was collected by suction filtration and dried under reduced pressure to obtain a Diels-Alder reaction adduct (DA compound represented by the above formulas (3) and (3′)). . Yield was 415 g, 100% yield.

<Example 5>
-Preparation and evaluation of cured epoxy resin-
Epoxy resin, DA compound and curing accelerator (triphenylphosphine: TPP) were uniformly mixed in a mixer (Thinky Co., Ltd. "Awatori Mixer ARV-200") with a formulation according to Table 2. to obtain an epoxy resin composition. This epoxy resin composition was sandwiched between aluminum mirror plates (“JIS H 4000 A1050P” manufactured by Engineering Test Service Co., Ltd.) using a silicon tube as a spacer, and heat-cured at 160° C. for 3 hours to form a 0.7 mm thick film. An epoxy resin cured product was obtained.

<Comparative Example 2>
Dicyandiamide (DICY) was prepared as a curing agent for epoxy resin. Next, an epoxy resin, a curing agent and a curing accelerator (3-(3,4-dichlorophenyl)-1,1-dimethylurea: DCMU) are added to a blending machine (manufactured by Thinky Co., Ltd.) according to Table 2. The mixture was uniformly mixed with a Thread Mixer ARV-200") to obtain an epoxy resin composition. This epoxy resin composition was sandwiched between aluminum mirror plates (“JIS H 4000 A1050P” manufactured by Engineering Test Service Co., Ltd.) using silicon tubes as spacers, and heat-cured at 170° C. for 1 hour to form a 0.7 mm thick film. An epoxy resin cured product was obtained.

- Tensile test -
A dumbbell shape (JIS K 7161-2-1BA) was punched out from each of the epoxy resin cured products prepared in Example 2 and Comparative Example 2 using a punching blade, and this was used as a test piece. Using a tensile tester (“Autograph AG-IS” manufactured by Shimadzu Corporation), the breaking stress and tensile elongation at a measurement environment of 23 ° C. were evaluated according to JIS K 7162-2 (test speed: 2 mm / min). .
The breaking stress and tensile elongation in the tensile test were evaluated by aging the test piece at 150° C. for 24 hours (initial stage). Also, after cutting the center of the test piece with a razor, the cut surfaces were brought together and aged at 150° C. for 24 hours.
Regarding the obtained breaking stress and tensile elongation rate, the repair rate (%) was calculated based on the formula (numerical value after restoration/initial numerical value)×100%.
Table 2 shows the evaluation results.

According to Table 2, it can be seen that the epoxy resin cured product according to Example 5 is superior to Comparative Example 2 in both breaking stress and tensile elongation repair rate.

<Example 6, Comparative Example 3>
- Remolding test -
0.1 g of the epoxy resin cured product prepared in each of Example 5 and Comparative Example 2 was finely cut with scissors. A Teflon (registered trademark) plate having a thickness of 1.08 mm with a window of 5 mm×40 mm was placed on the aluminum plate, and the cut hardened material was placed therein. Further, an aluminum plate and a weight of 1 kg were placed thereon, and continuous heating was performed at 150° C. for 24 hours. The shape of the obtained cured product was visually observed. The evaluation results of the epoxy resin cured products prepared in Example 5 and Comparative Example 2 are shown in Example 6 and Comparative Example 3 below in order.
Example 6: The seams disappeared and the cured product was unified.
Comparative Example 3: Pieces of the cured product were stuck together, but fell apart when lightly touched.

Claims (11)

A compound having one Diels-Alder reaction unit consisting of an anthracene structure and a maleimide structure in the molecule, wherein the Diels-Alder reaction unit has at least one amino group. 2. The compound of claim 1, which is a curing agent for epoxy resins. 3. The compound according to claim 1 or 2, represented by the following formula (1) or (1').

(In formulas (1) and (1′), R ¹ to R ¹¹ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, and an amino group. , an amido group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, and at least one of R ¹ to R ¹¹ is an amino group , is a group having an amino group as a substituent.) The compound according to any one of claims 1 to 3, wherein the anthracene structure has an amino group or a phenolic hydroxyl group. The compound according to any one of claims 1 to 4, wherein the maleimide structure has an amino group or a phenolic hydroxyl group. 6. The compound according to claim 5, represented by the following formula (2) or (2').

6. The compound according to claim 5, represented by the following formula (3) or (3').

An epoxy resin composition comprising the compound according to any one of claims 1 to 7 and an epoxy resin. 9. The epoxy resin composition according to claim 8, wherein the epoxy resin is represented by the following formula (4) and has an epoxy equivalent of 500 to 10000 g/eq.

(In formula (4), each Ar is independently a structure having an unsubstituted or substituted aromatic ring,
X is a structural unit represented by the following formula (4-1), Y is a structural unit represented by the following formula (4-2),

[In formulas (4-1) and (4-2), each Ar is independently a structure having an unsubstituted or substituted aromatic ring,
R ¹ and R ² are each independently a hydrogen atom, a methyl group or an ethyl group,
R' is a divalent hydrocarbon group having 2 to 12 carbon atoms,
R ³ , R ⁴ , R ⁷ and R ⁸ are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,
R ⁵ , R ⁶ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group;
n ₁ is an integer of 4 to 16, and n ₂ is an average repeating unit of 2 to 30; ]
R ¹¹ and R ¹² are each independently a glycidyl ether group or a 2-methylglycidyl ether group,
R ¹³ and R ¹⁴ are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,
R ¹⁵ and R ¹⁶ are a hydrogen atom or a methyl group;
m ₁ , m ₂ , p ₁ , p ₂ , q are average values of repetitions,
m ₁ and m ₂ are each independently 0 to 25, and m ₁ +m ₂ ≧1,
p ₁ and p ₂ are each independently 0 to 5,
q is 0.5-5.
However, the bond between the structural unit X represented by the formula (4-1) and the structural unit Y represented by the formula (4-2) may be random or block, and one molecule The total number of structural units X and Y present therein is m ₁ and m ₂ , respectively. ) The epoxy resin composition according to claim 9, wherein the epoxy resin is represented by the following formula (5).

(In formula (5), p ₁ , p ₂ , q, m ₁ and n ₁ are the average values of repetitions, and independently p ₁ is 0 to 5, p ₂ is 0 to 5, q is 0 .5 to 5, m ₁ is 0 to 25, and n ₁ is 2 to 30.) A cured epoxy resin obtained by curing the epoxy resin composition according to any one of claims 8 to 10.

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