Epoxy resin curing agent, compound, epoxy resin composition, and epoxy resin cured product

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]

[0001] The present invention relates to a compound, an epoxy resin composition, and a cured epoxy resin product. [Background technology]

[0002] Epoxy resin forms a highly cross-linked network polymer through a cross-linking reaction with a curing agent, resulting in a hardened product (cured epoxy resin). Cured epoxy resins have excellent heat resistance, mechanical strength, adhesiveness, and electrical insulation properties, and are used in a variety of fields, including electrical and electronic materials, adhesives, paints, and building and civil engineering materials.

[0003] On the other hand, a common problem with epoxy resin cured materials is their low long-term reliability. In addition, the network structure of epoxy resin cured materials is formed by covalent bonds, so they are insoluble and infusible, making them difficult to reshape by heating or solvent treatment, and they are poorly recyclable and reusable, which poses problems in terms of reducing waste and putting a strain on the environment. In addition, if the microcracks that occur in epoxy resin cured materials could be repaired, it would be expected that the brittleness of thermosetting resin cured materials could be improved, but the infusibility of the network structure makes it difficult to repair them by heating.

[0004] To address these problems, a cured epoxy resin is known that is prepared using a diamine having a site where furan and maleimide are bonded by the Diels-Alder reaction as a curing agent (Non-Patent Document 1). When the cured epoxy resin is heated, the crosslinked structure is decrosslinked by a retro-Diels-Alder reaction, and when the temperature is lowered, it is recrosslinked by the Diels-Alder reaction. This reversible decrosslinking-recrosslinking gives the network structure thermoreversibility, making it possible to reshape or repair by heating. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] X.Kuang, G.Liu, X.Dong, X.Liu, J.Xu, D.Wang, J.Polym.Sci., Part A: Polym.Chem,. 53, 2094(2015). Summary of the Invention [Problem to be solved by the invention]

[0006] However, the Diels-Alder reaction product of furan and maleimide undergoes a retro-Diels-Alder reaction at around 120°C, causing the epoxy resin cured material to decrosslink at temperatures above 120°C. Therefore, the epoxy resin cured material produced by the Diels-Alder reaction of furan and maleimide is not suitable for applications at temperatures above 120°C. In addition, research has been actively conducted into the use of reversible bonds such as dynamic covalent bonds and supramolecular bonds to impart repairability and remoldability to epoxy resin cured materials, but generally issues such as thermal decomposition remain.

[0007] 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. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by providing a compound having a predetermined structure, an epoxy resin composition, and an epoxy resin cured product.

[0009] In one aspect, the present invention is a compound having one Diels-Alder reaction unit, which is composed of an anthracene structure and a maleimide structure, in the molecule, and the Diels-Alder reaction unit has at least one amino group.

[0010] In one embodiment, the compounds of the present invention are curing agents for epoxy resins.

[0011] In one embodiment, the compound of the present invention is represented by the following formula (1) or (1'). [ka] [ka] (In formulas (1) and (1′), R 1 ~R 11 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; R 1 ~R 11 At least one of is an amino group or a group having an amino group as a substituent.

[0012] In another embodiment of the compound of the present invention, the anthracene structure has an amino group or a phenolic hydroxyl group.

[0013] In yet another embodiment of the compound of the present invention, the maleimide structure has an amino group or a phenolic hydroxyl group.

[0014] In yet another embodiment, the compound of the present invention is represented by the following formula (2) or (2'). [ka] [ka]

[0015] In yet another embodiment, the compound of the present invention is represented by the following formula (3) or (3'). [ka] [ka]

[0016] In another aspect, the present invention is an epoxy resin composition comprising the compound of the present invention and an epoxy resin.

[0017] 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 10,000 g / eq. [ka] In formula (4), each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, X is a structural unit represented by the following formula (4-1), and Y is a structural unit represented by the following formula (4-2), [ka] [In formulas (4-1) and (4-2), each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, R 1 , R 2 each independently represents 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 , R 8 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group, n 1 is an integer between 4 and 16, and n 2 is the average number of repeating units and is between 2 and 30. R 11 , R 12 each independently represents a glycidyl ether group or a 2-methylglycidyl ether group; R 13 , R 14each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 15 , R 16 is a hydrogen atom or a methyl group, m 1 , m 2 , p 1 , p 2 , q is the average value of the iterations, m 1 , m 2 are each independently 0 to 25, and m 1 +m 2 ≧1, p 1 , p 2 are each independently 0 to 5, q is 0.5 to 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 the total number of the structural units X and Y present in one molecule is m 1 , m 2 It indicates that.)

[0018] In another embodiment of the epoxy resin composition of the present invention, the epoxy resin is represented by the following formula (5). [ka] (In formula (5), p 1 , p 2 , q, m 1 and n 1 is the average of the replicates, each independently, p 1 is 0 to 5, p 2 is 0~5, q is 0.5~5, m 1 is 0 to 25, n 1 is 2 to 30.)

[0019] In yet another aspect, the present invention relates to an epoxy resin cured product obtained by curing the epoxy resin composition of the present invention. Effect of the Invention

[0020] According to the present invention, it is possible to provide an epoxy resin cured product having good heat resistance, repairability and remoldability. [Brief description of the drawings]

[0021] [Figure 1] 1 is a 1H-NMR spectrum of the endo isomer of the compound obtained in Example 1 (DA compound described later). [Diagram 2] 1 is a graph showing the results of dynamic viscoelasticity measurement (DMA) of the epoxy resin cured material according to Example 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Next, the embodiments for carrying out the present invention will be described in detail. It should be understood that the present invention is not limited to the following embodiments, and that appropriate changes and improvements in the design may be made based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention.

[0023] (Compounds of the 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 compound of the present invention is also referred to as a "DA compound".

[0024] 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 certain temperature, resulting in dissociation (decrosslinking). At this time, if the temperature at which the retro Diels-Alder reaction occurs (dissociation temperature) is low, the crosslinking occurs in a high temperature range, and the crosslinking density of the cured product decreases, resulting in a decrease in mechanical strength. In contrast, the DA compound of the present invention has one Diels-Alder reaction unit consisting of an anthracene structure and a maleimide structure, which have high thermal stability, in the molecule, so that the dissociation temperature is as high as 250°C or higher, and the crosslinked structure is maintained without dissociation at least at about 200°C, resulting in excellent thermal stability. Therefore, by using the DA compound of the present invention as a curing agent for epoxy resin, it is possible to suppress the decrease in crosslinking density of the cured product (epoxy resin cured product) cured by the reaction of the curing agent with the epoxy resin, and to maintain good mechanical strength. It is also believed that by applying mechanical energy such as scratches or external force to the epoxy resin cured product produced by the DA compound of the present invention, the CC bond of the Diels-Alder reaction unit is broken, and anthracene and maleimide are generated on the broken surface. The CC bond of the Diels-Alder reaction unit has a lower bond energy than a normal covalent bond and is easily broken. In the Diels-Alder reaction of anthracene and maleimide, the equilibrium shifts toward the bond at temperatures below 200°C, so an adduct (Diels-Alder reaction unit) is formed again, which is believed to enable repair of scratches and remolding.

[0025] In the DA compound of the present invention, the Diels-Alder reaction unit has at least one amino group. This amino group may be primary or secondary, but if the Diels-Alder reaction unit has at least one primary amino group, the amino group can react with two epoxy groups, so that the crosslink density of the cured product is improved compared to, for example, a hydroxyl group that reacts only with one epoxy group, and a cured product with excellent toughness and adhesiveness can be produced. As a result, the elastic modulus and glass transition temperature of the epoxy resin cured product are improved, which is preferable. In addition, amino groups are generally more reactive than hydroxyl groups, etc., and have improved curability, and the epoxy resin can be cured even under milder curing conditions.

[0026] 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, which is determined by the positional relationship between the functional group on the nitrogen atom of the maleimide structure and the functional group on the aromatic ring of the anthracene structure. An endo isomer is one in which the functional group on the nitrogen atom of the maleimide structure and the functional group on the aromatic ring of the anthracene structure are on the same side (close positions), and an exo isomer is one in which they are on the opposite sides (distant positions). [ka] [ka] (In formulas (1) and (1′), R 1 ~R 11 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; R 1 ~R 11 At least one of is an amino group or a group having an amino group as a substituent.

[0027] R in formula (1) and (1′) 1~R 11 Regarding ~R, the alkoxy group, aralkyloxy group, aryloxy group, carboxy group, alkyloxycarbonyl group, aryloxycarbonyl group, alkyl group, cycloalkyl group, aralkyl group, and aryl group include those in which various substituents are further bonded to the carbon atoms they have. For example, ~R in formulas (1) and (1’) 1 ~R 11 Regarding ~R, the aryl group includes an aminoaryl group in which an amino group is further bonded to the carbon atom thereof. Further, for example, ~R in formulas (1) and (1’) 1 ~R 11 When at least one of ~R is “a group having an amino group as a substituent”, examples of the group include an aminoaryl group (an aryl group having an amino group as a substituent).

[0028] In the D-A compound of the present invention, the anthracene structure may have an amino group or a phenolic hydroxyl group. Further, in the D-A compound of the present invention, the maleimide structure may have an amino group or a phenolic hydroxyl group. When the anthracene structure or the maleimide structure has a phenolic hydroxyl group, in addition to the effect that the above-mentioned Diels-Alder reaction unit has at least one amino group, since the phenolic hydroxyl group coexists with the amino group, the curability of the cured epoxy resin to be produced can be adjusted, the pot life can be prolonged, the storage stability can be improved, and further, the moisture resistance reliability of the cured epoxy resin can be improved. In the D-A compound of the present invention, it is preferable that both the anthracene structure and the maleimide structure have an amino group or a phenolic hydroxyl group, and one of them is at least an amino group.

[0029] The D-A 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 isomeric relationship with each other, the compound of formula (2) is an exo isomer, and the compound of formula (2’) is an endo isomer.

Chemical formula

Chemical formula

[0030] 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') are isomers, with the compound of formula (3) being an exo isomer and the compound of formula (3') being an endo isomer. [ka] [ka]

[0031] 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') are isomers, with the compound of formula (10) being an exo isomer and the compound of formula (10') being an endo isomer. [ka] [ka]

[0032] (Method of producing the compound of the present invention) The DA compound of the present invention is a compound having one Diels-Alder reaction unit in the molecule, which is an addition reaction moiety formed from an anthracene structure and a maleimide structure by Diels-Alder reaction, and the Diels-Alder reaction unit has at least one amino group. The 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 at temperatures higher than the temperature at which the addition reaction proceeds, the addition reaction site dissociates, returning the original conjugated diene and parent diene, resulting in a reverse reaction, the retro Diels-Alder reaction. The DA compound of the present invention is a compound having 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, and even after the Diels-Alder reaction, at least one functional group derived from each structure remains in the Diels-Alder reaction unit, at least one of which is an amino group. If each structural part does not have a functional group that reacts with an epoxy resin, the crosslink density of the resulting cured product will decrease, and not only will the heat resistance, mechanical properties, and adhesive strength deteriorate, but the structural parts dissociated by the retro Diels-Alder reaction will become free, making it difficult for the Diels-Alder reaction units to recombine after dissociation. On the other hand, if each structural part has a functional group that reacts with an epoxy group, each structural part will be fixed to a certain extent in the cured product, and each structural part will be close to each other, so that they can be easily recombined. By using this compound in an epoxy resin composition, it is possible to impart repairability and remoldability to the cured product.

[0033] The compound having an anthracene structure used in the method for producing a DA compound of the present invention can be any of the compounds listed in the following formula (11). Among these, hydroxyanthracenes and aminoanthracenes are preferred in terms of reactivity with epoxy groups, and monohydroxyanthracene and monoaminoanthracene are particularly preferred in terms of the balance between reactivity, cured product properties, and repairability and remolding properties. [ka]

[0034] The structures of the compounds listed in the above formula (11) each independently include a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group as a substituent. In the structures of the compounds listed in the above formula (11), the alkoxy group, the aralkyloxy group, the aryloxy group, the carboxy group, the alkyloxycarbonyl group, the aryloxycarbonyl group, the alkyl group, the cycloalkyl group, the aralkyl group, and the aryl group also include those having various substituents bonded to the carbon atom they have. For example, the aryl group includes an aminoaryl group having an amino group bonded to the carbon atom.

[0035] The compound having a maleimide structure used in the method for producing a DA compound of the present invention can include any of the compounds listed in the following formula (12). Among these, hydroxyphenylmaleimides and aminophenylmaleimides are preferred in terms of reactivity with epoxy groups, and monohydroxyphenylmaleimide and monoaminophenylmaleimide are particularly preferred in terms of the balance between reactivity and cured product properties, as well as repairability and remolding properties. Among the monoaminophenylmaleimides, paraaminophenylmaleimide is particularly preferred in terms of heat resistance. [ka]

[0036] The structures of the compounds listed in the above formula (12) each independently include a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group as a substituent. In the structures of the compounds listed in the above formula (12), the alkoxy group, the aralkyloxy group, the aryloxy group, the carboxy group, the alkyloxycarbonyl group, the aryloxycarbonyl group, the alkyl group, the cycloalkyl group, the aralkyl group, and the aryl group each include a carbon atom to which various substituents are further bonded. For example, the aryl group includes an aminoaryl group in which an amino group is further bonded to the carbon atom.

[0037] The DA compound of the present invention can be synthesized by combining a compound having the above anthracene structure and a compound having the above maleimide structure, at least one of which has at least one amino group, and carrying out a Diels-Alder reaction to add the conjugated diene structure to the parent diene structure. The Diels-Alder reaction may be carried out by a known method. For example, the conjugated diene compound and the parent diene compound are mixed in equimolar amounts, or in some cases one component is mixed in excess, and the mixture is melted by heating or dissolved in a solvent, and stirred at room temperature to 200°C for 1 to 24 hours. The product can be obtained by filtration or solvent distillation without purification, or by a commonly used isolation and purification method such as recrystallization, reprecipitation, and chromatography.

[0038] (Epoxy resin composition) The epoxy resin composition of the present invention contains the DA compound of the present invention and an epoxy resin. As the epoxy resin contained in the epoxy resin composition of the present invention, a generally known epoxy resin can be used. The epoxy resin contained in the epoxy resin composition of the present invention is not limited in any way, and examples thereof include liquid epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, and tetramethylbiphenyl type epoxy resin, brominated epoxy resins such as brominated phenol novolac type epoxy resin, solid bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenyl methacrylate type epoxy resin, and the like. Examples of epoxy resins include benzene-type epoxy resins, tetraphenylethane-type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, phenol aralkyl-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, naphthol novolac-type epoxy resins, naphthol aralkyl-type epoxy resins, naphthol-phenol co-condensed novolac-type epoxy resins, naphthol-cresol co-condensed novolac-type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type epoxy resins, biphenyl-modified novolac-type epoxy resins, etc., which may be used alone or in combination of two or more kinds, and are preferably selected and used according to the intended use, physical properties of the cured product, etc. Among these, from the viewpoint of general industrial availability, it is preferable to use bisphenol-type epoxy resins, novolac-type epoxy resins, etc.

[0039] 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 10,000 g / eq may be used. [ka] In formula (4), each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, X is a structural unit represented by the following formula (4-1), and Y is a structural unit represented by the following formula (4-2), [ka] [In formulas (4-1) and (4-2), each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, R 1 , R 2 each independently represents 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 , R 8 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group, n 1 is an integer between 4 and 16, and n 2 is the average number of repeating units and is between 2 and 30. R 11 , R 12 each independently represents a glycidyl ether group or a 2-methylglycidyl ether group; R 13 , R 14 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 15 , R 16 is a hydrogen atom or a methyl group, m 1 , m 2 , p 1 , p 2 , q is the average value of the iterations, m 1 , m 2 are each independently 0 to 25, and m1 +m 2 ≧1, p 1 , p 2 are each independently 0 to 5, q is 0.5 to 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 the total number of the structural units X and Y present in one molecule is m 1 , m 2 It indicates that.)

[0040] The epoxy resin contained in the epoxy resin composition of the present invention may be an epoxy resin represented by the following formula (5). By using such an epoxy resin, the repairability and remoldability of the cured epoxy resin are improved, and a good balance between flexibility and toughness is achieved. [ka] (In formula (5), p 1 , p 2 , q, m 1 and n 1 is the average of the replicates, each independently, p 1 is 0 to 5, p 2 is 0~5, q is 0.5~5, m 1 is 0 to 25, n 1 is 2 to 30.)

[0041] 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. [ka] (In formula (7), n is an average value of the repetition and is from 0 to 100. Among these, n is preferably an average value of the repetition from 0 to 1 in terms of improving the fluidity of the composition.)

[0042] The epoxy resin composition of the present invention contains the D-A compound of the present invention as a curing agent for the epoxy resin, but may further contain another curing agent (a co-usable curing agent). The co-usable curing agent is not particularly limited as long as it reacts with the epoxy resin to produce a cured product. Examples thereof include amine compounds, acid anhydride compounds, amide compounds, phenolic compounds, carboxylic acid compounds, and the like.

[0043] Examples of the amine compounds include aliphatic polyamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, polypropylene glycol diamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, etc., aromatic polyamines such as metaxylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, phenylenediamine, etc., alicyclic polyamines such as 1,3-bis(aminomethyl)cyclohexane, isophoronediamine, norbornanediamine, etc., and dicyandiamide.

[0044] Examples of the acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride polypropylene glycol, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.

[0045] Examples of the 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, tetraphenylol ethane 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. Also, as latent catalysts, imidazole, BF 3-amine complexes, guanidine derivatives, etc.

[0046] Examples of the amide-based compound include aliphatic polyamides synthesized from polycarboxylic acids and polyamines, aromatic polyamides having aromatic rings introduced therein, aliphatic polyamide adducts obtained by adding an epoxy compound to a polyamide, and aromatic polyamide adducts.

[0047] Examples of the carboxylic acid compound include carboxylic acid polymers such as carboxylic acid-terminated polyesters, polyacrylic acid, and maleic acid-modified polypropylene glycol, and active ester resins.

[0048] The above-mentioned 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 coating materials, it is preferable to use the amine compounds, carboxylic acid compounds, and / or acid anhydride compounds. In applications such as adhesives and flexible wiring boards, amine compounds, particularly dicyandiamide, are preferred from the viewpoints of workability, curability, and long-term stability. In applications such as semiconductor encapsulation materials, solid phenol compounds are preferred from the viewpoint of heat resistance of the cured product.

[0049] The amounts of all the curing agents in the epoxy resin composition of the present invention, i.e., the DA compound of the present invention (including the above-mentioned curing agent which can be used in combination, when such a curing agent is used) and the epoxy resin to be blended are not particularly limited, but in terms of good mechanical properties of the obtained cured product, an amount such that the amount of active groups in all the curing agents is 0.7 to 1.5 equivalents per equivalent of the epoxy groups in the total amount of epoxy resin is preferred.

[0050] 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 based on the total mass of the epoxy resin and the DA compound of the present invention. According to this configuration, both the repairability and remolding property of the epoxy resin cured product obtained by subjecting the epoxy resin composition to a heat treatment are further improved. The concentration of the DA compound of the present invention described above is more preferably 0.10 to 3.00 mmol / g, and even more preferably 0.15 to 2.00 mmol / g. In addition, when the epoxy resin composition of the present invention contains the above-mentioned concomitant curing agent, 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 based on the total mass of the epoxy resin, the DA compound of the present invention, and the concomitant curing agent, and more preferably 0.10 to 3.00 mmol / g, and even more preferably 0.15 to 2.00 mmol / g. The concentration of the DA compound of the present invention can be appropriately selected based on the glass transition temperature defined by the tan δ peak top of a dynamic viscoelasticity measuring device (DMA) of the cured product obtained from the desired epoxy resin composition. For example, when the glass transition temperature is used as a guideline, if the glass transition temperature of the cured product is near room temperature, sufficient repairability and reshapeability functions are likely to be expressed even at the low concentration side of the preferred range. On the other hand, if the glass transition temperature of the target cured product is above 100°C as a guideline, the functions are likely to be expressed at the high concentration side of the preferred range. However, in the temperature range above the glass transition temperature measured by DMA, molecular mobility is generally high, and sufficient repairability and reshapeability functions are likely to be expressed even at a low concentration of the DA compound, so that the effect of expressing the repairability and reshapeability functions can be adjusted, for example, by adjusting the aging temperature for repair or the heating temperature for reshaping as appropriate. 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.

[0051] The epoxy resin composition of the present invention may further contain a filler, a fibrous substrate, a dispersion medium, a resin other than the above-mentioned various compounds, etc. Each of the contained substances will be specifically described below.

[0052] <Filler> The epoxy resin composition of the present invention may further contain a filler. Examples of the filler include inorganic fillers and organic fillers. Examples of the inorganic filler include inorganic fine particles.

[0053] Examples of inorganic fine particles having excellent heat resistance include alumina, magnesia, titania, zirconia, and silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine amorphous silica). Examples of inorganic fine particles having excellent thermal conductivity include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, and diamond. Examples of inorganic fine particles having excellent electrical conductivity include metal fillers and / or metal-coated fillers using simple metals or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, and stainless steel). Examples of inorganic fine particles having excellent barrier properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, and smectite, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, and magnesium hydroxide. Examples of materials with high refractive index include barium titanate, zirconia oxide, and titanium oxide. Examples of materials that exhibit photocatalytic properties include photocatalytic metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, terium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, and lead, composites of the above metals, and oxides thereof. Examples of materials with excellent wear resistance include metals such as silica, alumina, zirconia, and magnesium oxide, and composites and oxides thereof. Examples of materials with excellent electrical conductivity include metals such as silver and copper, tin oxide, and indium oxide. Examples of materials with excellent insulating properties include silica. Examples of materials with excellent ultraviolet shielding properties include titanium oxide and zinc oxide.

[0054] These inorganic fine particles may be selected according to the intended use, and may be used alone or in combination of two or more kinds. In addition, the inorganic fine particles have various properties other than those exemplified, so that they may be selected according to the intended use.

[0055] For example, when silica is used as inorganic fine particles, known silica fine particles such as powdered silica and colloidal silica can be used without any particular limitation. Commercially available powdered silica fine particles include, for example, Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., E220A and E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., and SG flake manufactured by Nippon Sheet Glass Co., Ltd. In addition, commercially available colloidal silica includes, for example, methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, and ST-OL manufactured by Nissan Chemical Industries, Ltd.

[0056] 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. Commercially available powdered silica modified with a compound having a (meth)acryloyl group includes Aerosil RM50, R711, etc. manufactured by Nippon Aerosil Co., Ltd., and commercially available colloidal silica modified with a compound having a (meth)acryloyl group includes MIBK-SD, etc. manufactured by Nissan Chemical Industries, Ltd.

[0057] The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous, or amorphous shapes can be used. The primary particle diameter is preferably in the range of 5 to 200 nm. If the diameter is 5 nm or more, the inorganic fine particles are sufficiently dispersed in the dispersion, and if the diameter is 200 nm or less, the cured product tends to maintain sufficient strength.

[0058] As the titanium oxide fine particles, not only extender pigments but also ultraviolet light responsive photocatalysts can be used, for example, anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, etc. can be used. Furthermore, particles designed to respond to visible light by doping different elements 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, phosphorus, etc., and cationic elements such as chromium, iron, cobalt, manganese, etc. are preferably used. In addition, as the form, powder, sol dispersed in an organic solvent or water, or slurry can be used. As commercially available powdered titanium oxide fine particles, for example, Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd., ATM-100 manufactured by Teika Co., Ltd., etc. can be used. In addition, as commercially available slurry-like titanium oxide fine particles, for example, TKD-701 manufactured by Teika Co., Ltd., etc. can be used.

[0059] <Fiber matrix> The epoxy resin composition of the present invention may further contain a fibrous substrate. The fibrous substrate is not particularly limited, but is preferably one used in fiber-reinforced resins, such as inorganic fibers and organic fibers.

[0060] Examples of inorganic fibers include inorganic fibers such as carbon fibers, glass fibers, boron fibers, alumina fibers, and silicon carbide fibers, as well as carbon fibers, activated carbon fibers, graphite fibers, glass fibers, tungsten carbide fibers, silicon carbide fibers (silicon carbide fibers), 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.

[0061] Examples of organic fibers include synthetic fibers made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate; natural fibers such as cellulose, pulp, cotton, wool, and silk; and regenerated fibers such as protein, polypeptide, and alginic acid.

[0062] Among these, carbon fiber and glass fiber are preferred because they have a wide range of industrial applications. Of these, only one type may be used, or a plurality of types may be used simultaneously.

[0063] The fibrous substrate may be an assembly of fibers, with continuous or discontinuous fibers, in the form of a woven or nonwoven fabric, in the form of a fiber bundle in which the fibers are aligned in one direction, or in the form of a sheet in which fiber bundles are arranged, or in the form of a three-dimensional shape in which a thickness is imparted to an assembly of fibers.

[0064] <Dispersion medium> The epoxy resin composition of the present invention may contain 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 examples of the dispersion medium include various organic solvents and liquid organic polymers.

[0065] 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; 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 of these, acetone and methyl ethyl ketone are preferred in terms of the solubility of constituent materials such as epoxy resins and curing agents, and volatility during coating and solvent recovery.

[0066] The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples thereof include acrylic polymers (Floren WK-20: Kyoeisha), amine salts of special modified phosphate esters (HIPLAAD ED-251: Kusumoto Chemicals), and modified acrylic block copolymers (DISPERBYK2000: BYK-Chemie).

[0067] <Resin> The epoxy resin composition of the present invention may contain a resin other than the various compounds described 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, a thermosetting resin or a thermoplastic resin may be used.

[0068] A thermosetting resin is a resin that has the property of becoming substantially insoluble and infusible when cured by means of heat, radiation, catalyst, etc. Specific examples include 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, thermosetting polyimide resin, benzoxazine resin, aniline resin, cyanate ester resin, styrene-maleic anhydride (SMA) resin, maleimide resin, etc. These thermosetting resins can be used alone or in combination of two or more.

[0069] Thermoplastic resin refers to 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 resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyetheretherketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndiotactic polystyrene resin, and cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.

[0070] (Method of producing epoxy resin composition) The epoxy resin composition of the present invention dissolves the aforementioned D-A compound and epoxy resin of the present invention, and further, if necessary, the aforementioned curable agent, filler, fibrous substrate, dispersion medium, and resin other than the aforementioned various compounds in a dispersion medium such as the aforementioned organic solvent. After dissolution, the solvent is distilled off, and the epoxy resin composition can be obtained by drying under reduced pressure using a vacuum oven or the like. Further, the epoxy resin composition of the present invention may be in a state where the aforementioned constituent materials are uniformly mixed. At this time, it is preferable to mix them uniformly using a mixer or the like. The blending ratio of each constituent material can be appropriately adjusted according to the properties such as the mechanical strength, heat resistance, reparability, and remoldability of the desired cured epoxy resin. In the production of the epoxy resin composition, as the mixing order of the specific constituent materials, first, an organic solvent such as acetone or methyl ethyl ketone is added to the epoxy resin and stirred, then the D-A compound of the present invention is added as a curing agent, and it is stirred again to make it uniform, and by concentration and drying under reduced pressure, an epoxy resin composition in which the constituent materials are more uniformly mixed can be obtained.

[0071] (Cured epoxy resin) The cured epoxy resin of the present invention has one Diels-Alder reaction unit composed of an anthracene structure and a maleimide structure in the molecule, and the epoxy resin is cured by the D-A compound of the present invention in which the Diels-Alder reaction unit has at least one amino group. Further, as the epoxy resin, a generally known epoxy resin as described as the epoxy resin contained in the epoxy resin composition of the present invention can be used.

[0072] Since the epoxy resin cured product of the present invention is cured by 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 maintain good mechanical strength. In addition, it is considered that the CC bond of the Diels-Alder reaction unit is cut by applying mechanical energy such as scratching or external force to the epoxy resin cured product of the present invention, and anthracene and maleimide are generated on the cut surface, but since the equilibrium of the Diels-Alder reaction of anthracene and maleimide shifts toward the bond at temperatures below 200°C, an adduct (Diels-Alder reaction unit) is formed again, which is considered to enable repair of scratches and remolding.

[0073] The following formula (8) shows a schematic diagram showing the Diels-Alder reaction (DA reaction: crosslinking reaction) and the retro Diels-Alder reaction (rDA reaction: reversible crosslinking / decrosslinking reaction) of the epoxy resin cured product obtained by curing the epoxy resin with the DA compound of the present invention. Formula (8) specifically shows the epoxy resin cured product obtained by curing the epoxy resin (DGEBA) represented by the above formula (7) with the compound represented by the above formula (2) as the DA compound of the present invention. 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 amino group of each of the anthracene structure and the maleimide structure in the Diels-Alder reaction unit of the compound represented by formula (2) are bonded to generate a three-dimensional network structure. In addition, by applying mechanical energy such as a scratch or an external force, the CC bond of the Diels-Alder reaction unit is cut, and the anthracene structure and the maleimide structure are separated and decrosslinked. Even if the crosslinking is decomposed, the Diels-Alder reaction occurs again when heated at a certain temperature, and the three-dimensional network structure is restored, making it possible to repair damage and reshape the material. It is also preferable to utilize phase separation and place the reversible bonds in the cured material in the low modulus phase to promote reversible crosslinking / decompassing reactivity. [ka]

[0074] (Method for producing cured epoxy resin) Next, the method for producing a cured epoxy resin of the present invention will be described in detail. The cured epoxy resin of the present invention can be produced by heating the epoxy resin composition of the present invention and curing the epoxy resin contained in the epoxy resin composition with the D-A compound of the present invention. Specifically, the epoxy resin composition of the present invention is cast into a silicone casting plate or the like, and after degassing if necessary, heat curing is performed to obtain a cured epoxy resin obtained by curing the epoxy resin. The step of casting into the above-mentioned silicone casting plate or the like can be performed, for example, by sandwiching the epoxy resin composition with an aluminum mirror plate or the like using a silicone tube as a spacer.

[0075] In the method for producing a cured epoxy resin of the present invention, a known curing accelerator can be used. The curing accelerator is not particularly limited, and examples thereof include urea compounds, phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, quaternary ammonium salts, tin carboxylates, organic peroxides, and the like. When used for adhesive applications, urea compounds, particularly 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), etc. are preferable from the viewpoints of excellent workability and low-temperature curability. When used as an electronic material such as a semiconductor encapsulation material, a printed circuit board, or a build-up board, triphenylphosphine is used for phosphorus compounds, dimethylaminopyridine, imidazoles, 1,8-diazabicyclo-[5.4.0]-undecene (DBU), benzyldimethylamine, etc. are preferable for tertiary amines from the viewpoints of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc.

[0076] The structure of the obtained cured epoxy resin can be confirmed by infrared absorption (IR) spectrometry using Fourier transform infrared spectroscopy (FT-IR), elemental analysis, X-ray scattering method, etc.

[0077] (Uses of epoxy resin composition and cured epoxy resin) The epoxy resin composition of the present invention and the cured epoxy resin product produced from the epoxy resin composition are excellent in both heat resistance and repairability, and also have remoldability, and are useful for the following applications.

[0078] <Laminate> The epoxy resin cured product of the present invention can be laminated with a substrate to form a laminate. The substrate of the laminate may be an inorganic material such as metal or glass, or an organic material such as plastic or wood, and may be used as appropriate depending on the application. The substrate may be in the form of a laminate, a flat plate, a sheet, or a three-dimensional structure, or may be three-dimensional. The substrate may have any shape according to the purpose, such as a shape having a curvature on the entire surface or a part thereof. There is no restriction on the hardness, thickness, etc. of the substrate. A multilayer laminate may be formed by laminating a first substrate, a layer made of the cured product of the epoxy resin composition of the present invention, and a second substrate in this order. The epoxy resin composition of the present embodiment has excellent adhesiveness, and therefore can be suitably used as an adhesive for bonding a first substrate and a second substrate. The epoxy resin cured product of the present invention may be used as a substrate, and the cured product of the present invention may be further laminated.

[0079] The epoxy resin composition of the present invention has particularly high adhesion to metals and / or metal oxides, and can be particularly well used 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. Examples of metal oxides include single oxides and / or composite oxides of these metals. Since the epoxy resin composition of the present invention has particularly high adhesion to iron, copper, and aluminum, it can be particularly well used as an adhesive for iron, copper, and aluminum.

[0080] In addition, the epoxy resin cured product of the present invention can be suitably used for bonding different materials because it can relieve stress. For example, even in a laminate in which the substrate is a metal and / or metal oxide and the second substrate is a different material such as a plastic layer, the adhesive strength is maintained due to the stress relaxation ability of the epoxy resin cured product of the present invention.

[0081] In the laminate obtained by laminating the epoxy resin cured product of the present invention and the substrate, the layer containing the cured product may be formed by direct coating or molding on the substrate, or an already molded product may be laminated. When directly coating, the coating method is not particularly limited, and examples thereof include spraying, spin coating, dip coating, roll coating, blade coating, doctor roll, doctor blade, curtain coating, slit coating, screen printing, and inkjet. When directly molding, examples include in-mold molding, insert molding, vacuum molding, extrusion lamination molding, and press molding. When laminating a molded composition, 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. In addition, the epoxy resin cured product of the present invention may be laminated by coating a precursor that can be a substrate and curing it, or the precursor that can be a substrate or the epoxy resin composition of the present invention may be adhered in an uncured or semi-cured state and then cured. The precursor that can be a substrate is not particularly limited, and examples thereof include various curable resin compositions.

[0082] <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 used to bond different materials such as between metal and nonmetal, the adhesive can maintain high adhesion without being affected by changes in temperature environment, and peeling is unlikely to occur. In addition to structural member applications, the adhesive can also be used as an adhesive for general office use, medical use, carbon fiber, storage battery cells, modules, and cases, and can be used as an adhesive for bonding optical components, an adhesive for bonding optical disks, an adhesive for mounting printed wiring boards, a die bonding adhesive, an adhesive for semiconductors such as underfill, an underfill for reinforcing BGA, an anisotropic conductive film, an anisotropic conductive paste, and other mounting adhesives.

[0083] <Fiber reinforced resin> When the epoxy resin composition of the present invention has a fibrous substrate, and the fibrous substrate is a reinforcing fiber, the epoxy resin composition containing the fibrous substrate 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, and includes methods of combining the fibrous substrate and the composition by methods such as kneading, coating, impregnation, injection, and pressure bonding, and can be appropriately selected depending on the form of the fiber and the use of the fiber-reinforced resin.

[0084] There is no particular limitation on the method of molding the fiber-reinforced resin. If a plate-shaped product is to be manufactured, an extrusion molding method is generally used, but it can also be manufactured by a flat press. In addition, extrusion molding, blow molding, compression molding, vacuum molding, injection molding, etc. can be used. If a film-shaped product is to be manufactured, in addition to the melt extrusion method, a solution casting method can be used. When a melt molding method is used, examples of the method include inflation film molding, cast molding, extrusion lamination molding, calendar molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, and coating molding. In addition, in the case of a resin that is cured by active energy rays, a cured product can be manufactured using various curing methods using active energy rays. In particular, when a thermosetting resin is used as the main component of the matrix resin, examples of the molding method include a molding method in which the molding material is made into a prepreg and pressurized and heated by a press or autoclave, and other examples of the molding method include RTM (Resin Transfer Molding) molding, VaRTM (Vacuum assist Resin Transfer Molding) molding, lamination molding, and hand layup molding.

[0085] <Other molding materials> The epoxy resin composition of the present invention, when used in cured epoxy resin products, has good heat resistance and repairability, and is also remoldable, and can therefore be used as molding materials for large cases, motor housings, casting materials for the inside of cases, gears, pulleys, etc. These may be cured products of the resin alone, or cured products reinforced with fibers such as glass chips.

[0086] <Prepreg> The fiber reinforced resin can form a state called 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, then laminate other layers and then perform final curing, since this allows the formation of a laminate in which each layer is in close contact with each other. 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 resin content in the prepreg to be 20 to 60 mass%.

[0087] <Heat-resistant materials and electronic materials> The epoxy resin composition of the present invention is suitable for use as a heat-resistant material and an electronic material, since the epoxy resin cured product using the composition has good heat resistance and repairability, and has remoldability. In particular, the composition can be suitably used for semiconductor encapsulation materials, circuit boards, build-up films, build-up boards, adhesives, and resist materials. The composition 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 and electronic components thus obtained can be suitably used for various applications, including, but not limited to, industrial machine parts, general machine parts, automobile, railway, and vehicle parts, space and aviation-related parts, electronic and electrical parts, building materials, containers and packaging parts, daily necessities, sports and leisure goods, and housing parts for wind power generation.

[0088] Below, we will explain some representative products by giving examples. 1. Semiconductor encapsulation materials 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 an inorganic filler are melt-mixed sufficiently until homogeneous using an extruder, kneader, roll, etc. as necessary. In this case, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulation material for power transistors and power ICs, it is preferable to use highly filled crystalline silica, alumina, silicon nitride, etc., which have a higher thermal conductivity than fused silica, or fused silica, crystalline silica, alumina, silicon nitride, etc. The filling rate is preferably in the range of 30 to 95 mass% per 100 parts by mass of the epoxy resin composition, and among them, in order to improve flame retardancy, moisture resistance, and solder crack resistance and to reduce the linear expansion coefficient, it is more preferable to use 70 parts by mass or more, and even more preferable to use 80 parts by mass or more.

[0089] 2. Semiconductor Devices The semiconductor package molding for obtaining a semiconductor device from the epoxy resin composition of the present invention can be carried out by molding the semiconductor encapsulating material using a casting machine, a transfer molding machine, an injection molding machine or the like, and then heating the molded product at 50 to 250°C for 2 to 10 hours.

[0090] 3. Printed wiring board A method for obtaining a printed wiring board from the epoxy resin composition of the present invention includes laminating the above prepregs by a conventional method, overlaying copper foil as appropriate, and subjecting them to heat-pressure bonding at 170 to 300°C under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0091] 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, the above composition, which is appropriately blended with rubber, filler, etc., is applied to a circuit board on which a circuit is formed by using a spray coating method, a curtain coating method, etc., and then cured (step 1). Then, if necessary, a predetermined through-hole portion or the like is drilled, treated with a roughening agent, and the surface is washed with hot water to form unevenness, and a metal such as copper is plated (step 2). These operations are repeated as desired, and a resin insulating layer and a conductor layer of a predetermined circuit pattern are alternately built up to form the build-up (step 3). Note that the drilling of the through-hole portion is performed after the formation of the outermost resin insulating layer. In addition, the build-up board of the present invention can also be produced by forming a roughened surface by heating and pressing the resin-attached copper foil, which is obtained by semi-curing the resin composition on the copper foil, on a wiring board on which a circuit is formed, at 170 to 300 ° C., thereby omitting the steps of forming a roughened surface and plating.

[0092] 5. Build-up film A build-up film can be obtained from the epoxy resin composition of the present invention by applying the above-mentioned epoxy resin composition to the surface of a support film, which is a substrate, and then drying the organic solvent by heating or blowing hot air thereon to form a layer of the epoxy resin composition.

[0093] The organic solvent used here preferably includes, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc., carbitols such as cellosolve, butyl carbitol, etc., aromatic hydrocarbons such as toluene, xylene, etc., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is preferable to use the organic solvent in a proportion such that the nonvolatile content is 30 to 60 mass%.

[0094] The thickness of the epoxy resin composition layer formed is usually equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm. The epoxy resin composition layer may be protected with a protective film described below. By protecting the resin composition layer with a protective film, it is possible to prevent the adhesion of dirt and the like to the surface of the resin composition layer and prevent scratches.

[0095] Examples of the support film and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be subjected to a mud treatment, a corona treatment, and / or a release treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0096] The support film is peeled off after laminating it onto 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 heat cured, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is usually subjected to a release treatment in advance.

[0097] A multi-layer printed circuit board can be manufactured using the build-up film obtained as described above. For example, when the epoxy resin composition layer is protected by a protective film, the film is peeled off, and then the epoxy resin composition layer 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 lamination method. The lamination method may be a batch method or a continuous method using a roll. If necessary, the build-up film and the circuit board may be heated (preheated) before lamination. The lamination conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140°C and a pressure bonding pressure of 1 to 11 kgf / cm. 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and lamination is preferably performed under reduced air pressure of 20 mmHg (26.7 hPa) or less.

[0098] 6.Conductive paste A method for obtaining a conductive paste from the epoxy resin composition of the present invention includes, for example, 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

[0099] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these.

[0100] <Example 1> -Synthesis of DA compounds- The DA compounds were synthesized according to the schemes shown in the following formulae (9-1) to (9-3). The specific procedures are described in detail below. [ka]

[0101] According to the scheme shown in the above formula (9-1), N-(4-aminophenyl) maleimide (APM) was prepared. 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 while stirring, 4.85 g (49.5 mmol) of maleic anhydride dissolved in 36 mL of THF was added dropwise at room temperature over 1 hour. After the addition was completed, stirring (r.t. / 12 h) was carried out, and the precipitate formed was collected by suction filtration and dried under reduced pressure (r.t. / 12 h) 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. After purging the system with argon, 36 mL of N,N-dimethylformamide (DMF) and 9.60 mL (68.9 mmol) of triethylamine (NEt 3 ) were added, and the mixture was stirred and dissolved at room temperature. The flask was cooled in ice, 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. The resulting solution was poured into 257 mL of pure water (0 °C), and then the pH was adjusted to 4.5 - 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 a 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 the temperature was raised to 95 °C. Then, 3.88 g (47.3 mmol) of sodium acetate (AcONa) was added and stirring (95 °C / 2 h) was carried out. After the stirring was completed, the pale yellow solid precipitated by standing at room temperature for 12 h was stirred (r.t. / 10 min) after adding 800 mL of pure water, and then recovered by suction filtration and washing with a saturated aqueous sodium hydrogen carbonate solution and pure water. The obtained solid was dissolved in dichloromethane, washed with pure water and saturated brine, and then dried over sodium sulfate, filtered, the solvent was distilled off, and dried under reduced pressure (r.t. / 12 h) to obtain 10.2 g of Boc-APM (pale yellow solid). Subsequently, dichloromethane (CH2 Cl 2 ) was added to 56 mL of trifluoroacetic acid (CF 3 After adding 68.5 g (0.601 mol) of toluene (COOH) to the mixture, the mixture was stirred (rt / 2 h). After the reaction was completed, the solvent was distilled off, and the residue was dissolved in pure water and extracted three times with dichloromethane / saturated aqueous sodium hydrogen carbonate solution. The organic layer obtained was washed with pure water and saturated saline, and then dried over sodium sulfate, filtered, the solvent was distilled off, and dried under reduced pressure (rt / 12 h) to obtain a crude product of APM (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). The yield was 52% over four steps.

[0102] 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-neck flask and stirred (rt / 30 min). Next, the temperature was raised to 100 ° C using an oil bath, and 10.6 g (0.162 mol) of Zn (powder) was added and stirred for 30 minutes. Furthermore, 10.6 g (0.162 mol) of Zn (powder) was added and refluxed for 24 hours at an oil bath temperature of 115 ° C. After cooling to room temperature, the solid phase was collected by suction filtration, washed with pure water, and then dried under reduced pressure (60 ° C / ovn.). Acetone was added to the obtained solid, and the acetone insoluble portion was removed by suction filtration, and the soluble portion was collected. After acetone was distilled off under reduced pressure, the residue was dried under reduced pressure (rt / 1 h). The resulting solid was purified by recrystallization (solvent: toluene) to obtain 9.63 g of AA (green solid) (yield: 55%).

[0103] Next, the DA compound was synthesized according to the scheme shown in the above formula (9-3). 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-neck flask, and the inside of the system was replaced with Ar, and then 214 mL of chlorobenzene (degassed by Ar bubbling) was added. Then, after refluxing for 21 h, the mixture was cooled to room temperature, and a solid was precipitated by adding hexane. Next, the solid was collected by suction filtration and dried under reduced pressure (70 °C / 4 h), to obtain a mixture of 14.3 g of endo-APM-AA and exo-APM-AA. Then, separation was performed by silica gel column chromatography (developing solvent: dichloromethane / ethyl acetate = 1 / 1 (v / v)), and the exo isomer (Rf value: 0.40) and endo isomer (Rf value: 0.28) were separated. After the developing solvent was distilled off, each product was dried under reduced pressure (60°C / 12h) to obtain 5.53g (yield 38%) of exo-APM-AA and 6.52g (yield 44%) of endo-APM-AA as pale orange solids. 1 The H-NMR spectrum is shown in Figure 1. According to Figure 1, peaks derived from the bond formed between APM-AA by the Diels-Alder reaction were observed at 3.29 ppm and 4.74 ppm, confirming the formation of the target compound (endo-APM-AA).

[0104] <Example 2> -Preparation of epoxy resin cured material- The endo or exo isomer of the DA compound obtained in Example 1 and the epoxy resin represented by the above formula (7) (DGEBA, epoxy equivalent (EEW): 190 g / eq) were added to a flask, and the NH of the endo isomer and the exo isomer and the epoxy group of DGEBA were dissolved in acetone so that the equivalent ratio was 1:1. The solvent was then distilled off and the mixture was dried under reduced pressure (rt / 4 h) in a vacuum oven to obtain an epoxy resin composition. The epoxy resin composition was melted at 140°C, cast into a silicone casting plate, and degassed (140°C / 15 min) and heat cured (140°C for 1 h + 180°C for 2 h + 200°C for 2 h + 220°C for 2 h) to produce an epoxy resin cured product of the endo isomer and DGEBA (endo-APM-AA / DGEBA) and an epoxy resin cured product of the exo isomer and DGEBA (exo-APM-AA / DGEBA).

[0105] <Example 3> -Evaluation of the cured product- Dynamic Mechanical Analysis (DMA) The glass transition temperature (Tg) of the epoxy resin cured product was measured by dynamic viscoelasticity measurement (DMA measurement) using DMS6100 manufactured by SII Nano Technology Co., Ltd. The measurement was performed at a heating rate of 5°C / min and a frequency of 1.0 Hz. The results of dynamic viscoelasticity measurement (DMA) of the obtained epoxy resin cured product are shown in Figure 2. The Tg of the epoxy resin cured product of the endo isomer and DGEBA (endo-APM-AA / DGEBA) was 210°C, and the Tg of the epoxy resin cured product of the exo isomer and DGEBA (exo-APM-AA / DGEBA) was 209°C. Both had a Tg of more than 200°C, and were found to have excellent physical heat resistance. In addition, when the thermal weight loss analysis of each epoxy resin cured product was performed, all of the epoxy resin cured products had a 5% weight loss temperature (Tds) of more than 370°C, and were found to have excellent chemical heat resistance.

[0106] Tensile Test Tensile tests were carried out under the following conditions for the epoxy resin cured material of the endo isomer and DGEBA (endo-APM-AA / DGEBA) and the epoxy resin cured material of the exo isomer and DGEBA (exo-APM-AA / DGEBA). The epoxy resin cured product of the endo isomer and DGEBA, and the epoxy resin cured product of the exo isomer and DGEBA were cut into a size of 1 mm in thickness, 10 mm in length, and 46 mm in length, respectively, to prepare test pieces. The test pieces were subjected to a tensile test at a measurement environment of 23°C and a test speed of 1.0 mm / min using a Shimadzu AG-X 10kN universal testing machine. The breaking stress and tensile elongation of the tensile test were evaluated as they were (initial). Next, for the test pieces of the epoxy resin cured product of the endo isomer and DGEBA, the center of the test piece was cut with a razor, the cut surfaces were butted together, and aged for 12 hours at Tg+10°C (=220°C) for a similar tensile test and evaluation was performed (after repair (220°C / 12h)). In addition, the breaking stress and tensile elongation after repair were also evaluated in the same manner for the test pieces that were cut with a razor in the center, the cut surfaces were butted together, and aged for 24 hours at Tg+10°C (=220°C) for a similar evaluation (after repair (220°C / 24h)). In addition, for the test pieces of the epoxy resin cured material of the exo body and DGEBA, the center of the test piece was cut with a razor, the cut surfaces were butted together, and aged for 12 hours at Tg+10℃ (=219℃) and Tg+20℃ (=229℃). The tensile test was also performed and evaluated in the same way (after repair (219℃ / 12h, 229℃ / 12h)). In addition, the breaking stress and tensile elongation after repair were also evaluated in the same way for the test pieces that were cut with a razor in the center, the cut surfaces were butted together, and aged for 24 hours at Tg+10℃ (=219℃) and Tg+20℃ (=229℃) (after repair (219℃ / 24h, 229℃ / 24h)). The repair rate (%) was calculated for the obtained breaking stress and tensile elongation percentage based on the formula (value after repair / initial value)×100%.

[0107] <Comparative Example 1> A flask was charged with 4,4'-diaminodiphenylsulfone (DDS) as a curing agent and an epoxy resin represented by the above formula (7) (DGEBA, epoxy equivalent (EEW): 190 g / eq), and the NH of the DDS and the epoxy group of the DGEBA were dissolved in acetone so that the equivalent ratio was 1:1. The solvent was then distilled off and the mixture was dried under reduced pressure (rt / 4 h) in a vacuum oven to obtain a resin mixture. The resin mixture was melted at 120°C and cast into a silicone casting plate, and degassed (120°C / 15 min) and heat cured (120°C for 1 h + 180°C for 2 h + 200°C for 3 h + 220°C for 3 h + 240°C for 1 h) to obtain a cured epoxy resin. The cured epoxy resin was subjected to a tensile test in the same manner as in Example 3. Note that in Example 3, the aging temperature for repair was 220°C, but in Comparative Example 1, it was performed at Tg+10°C=234°C. The evaluation results are shown in Table 1.

[0108] [Table 1]

[0109] It can be seen from Table 1 that the epoxy resin cured material of Example 3 is superior to Comparative Example 1 in both the breaking stress and the repair rate of the tensile elongation.

[0110] [Synthesis Example 1] -Synthesis of PTMG-type (BPA) hydroxy compounds- In a flask equipped with a thermometer and a stirrer, 445 g (0.5 mol) of polytetramethylene glycol diglycidyl ether (Nagase ChemteX "Denacol EX-991L": epoxy equivalent 445 g / eq) and 228 g (1.0 mol) of bisphenol A (hydroxyl equivalent 114 g / eq) were added, and the mixture was heated to 140°C over 30 minutes, after which 3.4 g of a 4% aqueous sodium hydroxide solution was added. The mixture was then heated to 150°C over 30 minutes, and further reacted at 150°C for 16 hours. Thereafter, 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 was found to be m 1=1, n 1 A peak of M+=1380 was obtained, which corresponds to the theoretical structure of =11, confirming that the product contained the target PTMG (polytetramethylene ether glycol) type (BPA: bisphenol A) hydroxy compound. The hydroxyl equivalent of this hydroxy compound (Ph-6) calculated from GPC was 526 g / eq, and n 1 The average value of 10.6,m 1 The mean value was 0.73.

[0111] [ka]

[0112] [Synthesis Example 2] -Synthesis of PTMG type (BPA) epoxy resin- In a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, 200 g of the hydroxy compound represented by formula (6) obtained by the above synthesis, 437 g (4.72 mol) of epichlorohydrin and 118 g of n-butanol were added and dissolved while purging with nitrogen gas. After heating to 65°C, the pressure was reduced to an azeotropic pressure, and 6.66 g (0.08 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Next, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropy was separated using a Dean-Stark trap, the water layer was removed, and the oil layer was returned to the reaction system while the reaction was continued. After that, the unreacted epichlorohydrin was distilled off 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 solution of sodium hydroxide was added to this solution, and the mixture was reacted at 80° C. for 2 hours, after which the mixture was washed three times with 50 g of water until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after microfiltration, 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 was found to have the m 1 =1, n1 =11, q=1, p 1 =0, p 2 Since a peak of M+=1492 corresponding to the theoretical structure of M+=0 was obtained, it was confirmed that the product contained the target PTMG type (BPA) epoxy resin.

[0113] <Example 4> -Synthesis of DA compounds- 226g (1 mol) of 2-aminoanthracene, 226g (1.2 mol) of 4-hydroxyphenylmaleimide, and 450g of toluene were added to a flask equipped with a thermometer, a stirrer, and a cooling tube, and reacted at 80°C for 24 hours. After that, the mixture 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')). The yield was 415g, which was 100%.

[0114] <Example 5> -Preparation and evaluation of cured epoxy resin- An epoxy resin composition was obtained by uniformly mixing the epoxy resin, DA compound, and curing accelerator (triphenylphosphine: TPP) according to the formulation in Table 2 in a mixer (Thinky Corporation's "Awatori Rentaro ARV-200") This epoxy resin composition was sandwiched between aluminum mirror plates (Engineering Test Service Corporation's "JIS H 4000 A1050P") using a silicon tube as a spacer, and heat curing was carried out at 160°C for 3 hours to obtain a 0.7 mm thick cured epoxy resin product.

[0115] <Comparative Example 2> Dicyandiamide (DICY) was prepared as a curing agent for epoxy resin. Next, epoxy resin, curing agent, and curing accelerator (3-(3,4-dichlorophenyl)-1,1-dimethylurea: DCMU) were mixed uniformly in a mixer (Thinky Corporation's "Awatori Rentaro ARV-200") according to the formulation in Table 2 to obtain an epoxy resin composition. This epoxy resin composition was sandwiched between aluminum mirror plates (Engineering Test Service Corporation's "JIS H 4000 A1050P") using a silicon tube as a spacer, and heat cured at 170°C for 1 hour to obtain a 0.7mm-thick cured epoxy resin.

[0116] -Tensile test- The epoxy resin cured products produced in Example 2 and Comparative Example 2 were punched into dumbbell shapes (JIS K 7161-2-1BA) using a punching blade to prepare test pieces. The breaking stress and tensile elongation were evaluated in a measurement environment of 23°C (test speed: 2 mm / min) using a tensile tester (Shimadzu Corporation, Autograph AG-IS) in accordance with JIS K 7162-2. The breaking stress and tensile elongation of the tensile test were evaluated after aging the test pieces at 150°C for 24 hours (initial state). In addition, the center of the test pieces was cut with a razor, the cut surfaces were butted together, and the test pieces were aged at 150°C for 24 hours. The tensile test was also performed in the same manner and evaluated (after repair). The repair rate (%) was calculated for the obtained breaking stress and tensile elongation percentage based on the formula (value after repair / initial value)×100%. The evaluation results are shown in Table 2.

[0117] [Table 2]

[0118] It can be seen from Table 2 that the epoxy resin cured material of Example 5 is superior to Comparative Example 2 in both the breaking stress and the repair rate of the tensile elongation.

[0119] <Example 6, Comparative Example 3> -Remolding test- 0.1 g of the epoxy resin cured products prepared in Example 5 and Comparative Example 2 were cut into small pieces with scissors. A 1.08 mm thick Teflon (registered trademark) plate with a 5 mm x 40 mm window was placed on an aluminum plate, and the cut cured products were placed in it. An aluminum plate and a 1 kg weight were placed on top of it, and the mixture was heated continuously at 150°C for 24 hours. The shape of the obtained cured products 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, respectively. Example 6: The seams disappeared and the cured product became integrated. Comparative Example 3: The pieces of the cured product stuck together, but fell apart when touched lightly.

Claims

1. An epoxy resin curing agent, which is a compound having one Diels-Alder reaction unit in its molecule, the Diels-Alder reaction unit consisting of an anthracene structure represented by any one of the following formulas (11) and a maleimide structure represented by any one of the following formulas (12), wherein the Diels-Alder reaction unit has at least one amino group. 【Chemistry 1】 【Chemistry 2】

2. A compound having one Diels-Alder reaction unit consisting of an anthracene structure and a maleimide structure in the molecule, the Diels-Alder reaction unit having at least one amino group, and represented by the following formula (2) or (2'). 【Chemistry 3】 【Chemistry 4】

3. A compound having one Diels-Alder reaction unit consisting of an anthracene structure and a maleimide structure in the molecule, the Diels-Alder reaction unit having at least one amino group, and represented by the following formula (3) or (3'). 【Chemistry 5】 【Chemistry 6】

4. An epoxy resin composition comprising the compound according to claim 2 or 3 and an epoxy resin.

5. An epoxy resin composition comprising: a compound having one Diels-Alder reaction unit in the molecule, the Diels-Alder reaction unit consisting of an anthracene structure represented by any one of the following formulas (11) and a maleimide structure represented by any one of the following formulas (12), the Diels-Alder reaction unit having at least one amino group; and an epoxy resin. 【Chemistry 7】 【Chemistry 8】

6. The epoxy resin composition according to claim 4 or 5, wherein the epoxy resin is represented by the following formula (4) and has an epoxy equivalent of 500 to 10,000 g / eq. 【Chemistry 9】 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), and Y is a structural unit represented by the following formula (4-2): 【Chemistry 10】 [In formulas (4-1) and (4-2), each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, R 1 , R 2 each independently represents 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 , R 8 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group, n 1 is an integer from 4 to 16, and n 2 is the average value of the repeating units and is from 2 to 30. R 11 , R 12 each independently represents a glycidyl ether group or a 2-methylglycidyl ether group; R 13 , R 14 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 15 , R 16 is a hydrogen atom or a methyl group, m 1 、 m 2 、 p 1 、 p 2 、 q is the average value of the repetition, m 1 , m 2 are each independently 0 to 25, and m 1 +m 2 ≧1, p 1 , p 2 each independently represents 0 to 5; q is 0.5 to 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 the total number of the structural units X and Y present in one molecule is m 1 , m 2 It indicates that.)

7. The epoxy resin composition according to claim 6, wherein the epoxy resin is represented by the following formula (5): 【Chemistry 11】 (In formula (5), p 1 , p 2 , q, m 1 and n 1 is the average value of the replicates, each 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, n 1 is between 2 and 30.)

8. An epoxy resin composition described in any one of claims 4 to 7, wherein the concentration of the compound in the epoxy resin composition is 0.10 mmol / g or more relative to the total mass of the epoxy resin and the compound.

9. A cured epoxy resin product obtained by curing the epoxy resin composition according to any one of claims 4 to 8.

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