CN115605526A

CN115605526A - Novel epoxy resin and epoxy resin composition

Info

Publication number: CN115605526A
Application number: CN202180035314.3A
Authority: CN
Inventors: 中村宽子
Original assignee: Daicel Corp
Current assignee: Daicel Corp
Priority date: 2020-05-15
Filing date: 2021-05-14
Publication date: 2023-01-13
Also published as: JP2021178942A; WO2021230336A1

Abstract

The purpose of the present disclosure is to provide a novel epoxy resin and an epoxy resin composition thereof, which can provide a cured product having excellent heat resistance and mechanical properties, and which can be used as an electronic material or various composite materials. The present disclosure provides an epoxy resin represented by the following formula (1). [ in formula (1), ring A represents an aromatic hydrocarbon ring. R ¹ Represents a cyano group, a halogen atom or an alkyl group. R ² Represents a hydrocarbon group, an alkoxy group or the like. j represents an integer of 0 to 4. k represents 0 or an integer of 1 or more. R is ³ Represents a group represented by the following formula (1-1)][ formula (1-1) wherein R ⁴ Represents a carbon atom number of 2 to 4An alkyl group. R ⁵ Represents an alkylene group having 3 to 6 carbon atoms. R ⁶ Represents any one of the groups represented by the following formulae (1 a) to (1 c), R in formula (1-1) ⁶ At least one of them is a group represented by the formula (1 a). x represents an integer of 1 to 5. y represents an integer of 0 to 5. z represents an integer of 1 to 50]。

Description

Novel epoxy resin and epoxy resin composition

Technical Field

The present disclosure relates to a novel epoxy resin and an epoxy resin composition containing the same. More specifically, the present invention relates to a novel epoxy resin capable of providing a cured product excellent in heat resistance and mechanical properties, and an epoxy resin composition containing the epoxy resin. The present application claims priority from Japanese patent application No. 2020-086059, filed on Japan at 15/5/2020, the contents of which are incorporated herein by reference.

Background

Epoxy resins are generally used as electronic materials such as adhesives, paints, laminated plates, and molded articles, and various composite materials because they form cured products excellent in various properties such as heat resistance, mechanical properties, and electrical properties.

As such an epoxy resin, a 1, 2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol (trimethylolpropane) [ for example, a product name "EHPE3150" (manufactured by Daicel corporation) or the like ] is used as various composite materials such as a sealing agent for an optical semiconductor, an electronic material such as a substrate, a curing agent for a powder coating material or the like, a sizing agent for glass fibers, and the like, in order to provide a cured product having high reactivity and excellent heat resistance, weather resistance, electrical properties, and the like (for example, patent documents 1 and 2).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. Sho 60-161973

Patent document 2: japanese laid-open patent publication No. 2014-156591

Disclosure of Invention

Problems to be solved by the invention

An object of the present invention is to provide a novel epoxy resin which can provide a cured product having excellent heat resistance and mechanical properties and which can be used as an electronic material or various composite materials.

Another object of the disclosed invention is to provide an epoxy resin composition containing the novel epoxy resin, which can provide a cured product having excellent heat resistance and mechanical properties and is useful as an electronic material or various composite materials.

Technical scheme

The inventors of the present disclosure have conducted intensive studies to solve the above problems, and as a result, have found that an epoxy resin obtained by adding 1, 2-epoxy-4- (2-oxirane) cyclohexane to a specific initiator can provide a cured product excellent in heat resistance and mechanical properties, and is useful as an electronic material and various composite materials.

Namely, the disclosed invention provides an epoxy resin represented by the following formula (1).

[ chemical formula 1]

[ in the formula (1), the rings A are the same or different and each represents an aromatic hydrocarbon ring. R ¹ Identical or different, represents a cyano group, a halogen atom or an alkyl group. R is ² The same or different, represents a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, an alkoxycarbonyl group, a hydroxyl group, a halogen atom, a nitro group, a cyano group or a substituted amino group. j, which may be the same or different, represents an integer of 0 to 4. k is the same or different and represents 0 or an integer of 1 or more. R is ³ The same or different, represent a group represented by the following formula (1-1)]

[ chemical formula 2]

[ formula (1-1) wherein R ⁴ Represents an alkylene group having 2 to 4 carbon atoms. R is ⁵ Represents an alkylene group having 3 to 6 carbon atoms. R ⁶ Represents any one of the groups represented by the following formulae (1 a) to (1 c), R in formula (1-1) ⁶ At least one of them is a group represented by the formula (1 a). x represents an integer of 0 to 5. y represents an integer of 0 to 5. z represents an integer of 1 to 50. When x is an integer of 2 or more, a plurality of R ⁴ Optionally the same or different.When y is an integer of 2 or more, a plurality of R ⁵ Optionally the same or different. When z is an integer of 2 or more, a plurality of R ⁶ Optionally the same or different]

[ chemical formula 3]

[ chemical formula 4]

-CH＝CH ₂ (1b)

[ chemical formula 5]

[ in the formula (1 c), R ⁷ Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group]。

In the epoxy resin, ring a may be a benzene ring.

In the epoxy resin, x may be 1.

In the epoxy resin, y may be 0.

Further, the disclosed invention provides an epoxy resin composition containing the epoxy resin.

The epoxy resin composition may further contain a curing agent and a curing accelerator.

The epoxy resin composition may further contain a curing catalyst.

The epoxy resin composition may further contain an epoxy compound other than the epoxy resin represented by the formula (1).

In the epoxy resin composition, the epoxy compound may be an alicyclic epoxy compound.

In the epoxy resin composition, the alicyclic epoxy compound may be a compound having an epoxycyclohexyl group.

In the epoxy resin composition, the alicyclic epoxy compound may be a compound represented by the following formula (I).

[ chemical formula 6]

[ in the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms) ].

The epoxy resin composition may be a composite resin composition.

The invention of the present disclosure also provides a cured product of the epoxy resin composition.

The invention disclosed herein also provides an electronic product comprising the cured product.

Effects of the invention

Since the epoxy resin of the present disclosure has the above-described structure, a cured product having excellent heat resistance and mechanical properties can be formed by curing the epoxy resin composition containing the epoxy resin. Therefore, the epoxy resin of the present disclosure is extremely useful as an electronic material, various composite materials.

Drawings

FIG. 1 is a drawing showing an epoxy resin obtained in example 1 ¹ H-NMR spectrum.

Detailed Description

< epoxy resin >

The epoxy resin (hereinafter, sometimes referred to as "epoxy resin (a)") of the present disclosure is represented by the following formula (1).

[ chemical formula 7]

In the formula (1), the rings A may be the same or different and each represent an aromatic hydrocarbon ring. The aromatic hydrocarbon ring represented by ring a includes a benzene ring or a condensed polycyclic aromatic hydrocarbon ring. Examples of the condensed polycyclic aromatic hydrocarbon compound include: fused bicyclic hydrocarbon rings (e.g., indene, naphthalene, etc. C _8-20 Fused bicyclic hydrocarbon ring, preferably C _10-16 Fused bicyclic hydrocarbon rings), fused tricyclic hydrocarbon rings (e.g., anthracycline, phenanthrene ring, etc.), fused two-to tetracyclic hydrocarbon rings, and the like. Preferred aromatic hydrocarbon rings include: benzene ring, naphthalene ring, anthracene ring, etc., preferably benzene ring and naphthalene ring, more preferably benzene ring. The two rings a substituted at the 9-position of fluorene may be different rings or the same ring.

When ring a is a fused polycyclic aromatic hydrocarbon ring, the position of ring a substituted at the 9-position of fluorene is not particularly limited, and for example, naphthyl substituted at the 9-position of fluorene may be 1-naphthyl, 2-naphthyl, etc., and 2-naphthyl is particularly preferable.

In the formula (1), R ¹ Identical or different, represents a cyano group, a halogen atom or an alkyl group, preferably an alkyl group. Examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, etc. Examples of the alkyl group include: c such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like _1-6 Alkyl (preferably C) _1-4 Alkyl, especially methyl), and the like. R is substituted on two benzene rings constituting fluorene (or fluorene skeleton) ¹ Optionally the same or different. Furthermore, R ¹ The bonding position (substitution position) of the benzene ring constituting the fluorene is not particularly limited.

In the formula (1), j is the same or different and represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 or 1, and further preferably 0. When j is an integer of 2 or more, a plurality of R in formula (1) ¹ Optionally the same or different. Further, in the two benzene rings constituting the fluorene, j is optionally the same or different.

In the formula (1), R ² The same or different, represents a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, an alkoxycarbonyl group, a hydroxyl group, a halogen atom, a nitro group, a cyano group or a substituted amino group. R is substituted on two rings A ² Optionally the same or different. Furthermore, R ² The bonding position (substitution position) to the ring A is not particularly limitedAnd (4) limiting.

Examples of the hydrocarbon group include: alkyl (e.g., C such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, etc.) _1-20 Alkyl, preferably C _1-8 Alkyl, more preferably C _1-6 Alkyl, etc.); cycloalkyl (C such as cyclopentyl and cyclohexyl) _5-10 Cycloalkyl, preferably C _5-8 Cycloalkyl, further preferably C _5-6 Cycloalkyl, etc.); aryl [ e.g., phenyl, alkylphenyl (e.g., methylphenyl (or tolyl, 2-methylphenyl, 3-methylphenyl, etc.), dimethylphenyl (xylyl), etc.), C such as naphthyl _6-10 Aryl, preferably C _6-8 Aryl, especially phenyl and the like](ii) a Aralkyl (C such as benzyl, phenethyl, etc.) _6-10 aryl-C _1-4 Alkyl, etc.), and the like.

Examples of the alkoxy group include: c such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, t-butoxy, etc _1-20 Alkoxy, preferably C _1-8 Alkoxy, more preferably C _1-6 Alkoxy, and the like. As the cycloalkoxy group, there may be mentioned cyclohexyloxy C _5-10 Cycloalkoxy, etc.), and the like. Examples of the aryloxy group include C such as phenoxy _6-10 Aryloxy groups, and the like. Examples of the aralkyloxy group include a benzyloxy group and the like having C as the substituent _6-10 aryl-C _1-4 An alkyloxy group, and the like. Examples of the alkylthio group include: methylthio, ethylthio, propylthio, n-butylthio, t-butylthio and the like C _1-20 Alkylthio, preferably C _1-8 Alkylthio, more preferably C _1-6 Alkylthio groups, and the like. Examples of the cycloalkylthio group include C such as cyclohexylthio group _5-10 Cycloalkylthio groups, and the like. Examples of the arylthio group include C such as phenylthio group _6-10 Arylthio groups, and the like. Examples of the aralkylthio group include a benzylthio group and the like _6-10 aryl-C _1-4 Alkylthio groups, and the like. Examples of the acyl group include C such as acetyl group _1-6 Acyl groups, and the like. Examples of the alkoxycarbonyl group include C such as methoxycarbonyl _1-4 Alkoxy-carbonyl, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Examples of the substituted amino group include N, N-di-C such as N, N-dimethylamino _1-6 Alkylamino groups, and the like.

As R ² Preferred are a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a halogen atom, a nitro group, a cyano group, and a substituted amino group, and more preferred is a hydrocarbon group [ e.g., an alkyl group (e.g., C) _1-6 Alkyl radical)]Alkoxy (C) _1-4 Alkoxy group, etc.), a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), etc.

In the formula (1), k is the same or different and represents an integer of 0 or 1 or more, preferably an integer of 0 to 8, more preferably an integer of 0 to 6, further preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and further preferably 0. When k is an integer of 2 or more, a plurality of R in formula (1) ² Optionally the same or different. Further, k is optionally the same or different in the two rings a.

In the formula (1), R ³ The same or different groups represent a group represented by the following formula (1-1). In two rings A, R ³ Optionally the same or different.

[ chemical formula 8]

In the above formula (1-1), R ⁴ Examples of the alkylene group having 2 to 4 carbon atoms include: ethylene, propylene, trimethylene, butylene, tetramethylene, and the like, and ethylene and propylene are preferred from the viewpoint of ease of production. x represents an integer of 0 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and further preferably 1. When x is an integer of 2 or more, a plurality of R in the formula (1-1) ⁴ Optionally the same or different.

In the above formula (1-1), R ⁵ Examples of the alkylene group having 3 to 6 carbon atoms include: trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, etc., and tetramethylene group and pentamethylene group are preferable from the viewpoint of ease of production. y represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, and still more preferably 0. When y is an integer of 2 or more, a plurality of the compounds represented by the formula (1-1)R ⁵ Optionally the same or different.

In the formula (1-1), z represents an integer of 1 to 50. The sum (total) of z in formula (1) is an integer of 3 to 100.

In the formula (1-1), R ⁶ The substituent on the cyclohexane ring represented by the formula (I) represents any one of the groups represented by the following formulae (1 a) to (1 c). R on the above cyclohexane ring ⁶ The bonding position of (b) is not particularly limited, and is usually a carbon atom at the 4-position or 5-position when the positions of two carbon atoms of the cyclohexane ring bonded to the oxygen atom are 1-position or 2-position. Further, in the case where the epoxy resin (a) of the present disclosure has a plurality of cyclohexane rings, R in each cyclohexane ring ⁶ Optionally the same or different.

[ chemical formula 9]

[ chemical formula 10]

-CH＝CH ₂ (1b)

[ chemical formula 11]

R in the formula (1-1) ⁶ At least one of them is a group (epoxy group) represented by formula (1 a). That is, the epoxy resin (a) of the present disclosure has at least one epoxy group in the molecule. When z is an integer of 2 or more, a plurality of R in the formula (1-1) ⁶ Optionally the same or different. Further, the epoxy resin (a) of the present disclosure has two or more R ⁶ In the case of (1), a plurality of R ⁶ Optionally the same or different.

In the formula (1 c), R ⁷ Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group. Examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, butyl, isopropylA linear or branched alkyl group having 1 to 20 carbon atoms such as a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, etc. Examples of the alkylcarbonyl group include: and alkylcarbonyl such as methylcarbonyl (acetyl), ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, and tert-butylcarbonyl. Examples of the arylcarbonyl group include a benzoyl group and a naphthoyl group.

Examples of the substituent that the alkyl group, the alkylcarbonyl group, and the arylcarbonyl group may have include: a substituent having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms), and the like. Examples of the substituent include: a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.; a hydroxyl group; alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy (preferably C) _1-6 Alkoxy, more preferably C _1-4 Alkoxy groups); an alkenyloxy group such as an allyloxy group (preferably C) _2-6 Alkenyloxy, more preferably C _2-4 Alkenyloxy); phenoxy, tolyloxy, naphthyloxy and the like optionally having C on the aromatic ring _1-4 Alkyl radical, C _2-4 Alkenyl group, halogen atom, C _1-4 Aryloxy group as a substituent such as alkoxy group (preferably C) _6-14 Aryloxy groups); aralkyloxy (preferably C) such as benzyloxy and phenethyloxy _7-18 Aralkyloxy); acyloxy groups such as acetoxy, propionyloxy, (meth) acryloyloxy, benzoyloxy and the like (preferably C _1-12 Acyloxy groups); a mercapto group; alkylthio (preferably C) such as methylthio or ethylthio _1-6 Alkylthio, more preferably C _1-4 Alkylthio); an alkenylthio group (preferably C) such as allylthio group _2-6 Alkenylthio, more preferably C _2-4 An alkenylthio group); optionally having C on the aromatic ring, e.g. phenylthio, tolylthio, naphthylthio _1-4 Alkyl radical, C _2-4 Alkenyl group, halogen atom, C _1-4 Arylthio (preferably C) as a substituent such as alkoxy _6-14 Arylthio groups); aralkylthio group (preferably C) such as benzylthio group, phenethylthio group and the like _7-18 Aralkylthio); a carboxyl group; alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl and the like (preferably C) _1-6 Alkoxy-carbonyl); aryloxycarbonyl groups such as phenoxycarbonyl, tolyloxycarbonyl and naphthyloxycarbonyl (preferably C) _6-14 Aryloxy-carbonyl); aralkoxycarbonyl group (preferably C) such as benzyloxycarbonyl _7-18 Aralkoxy-carbonyl); an amino group; mono-or dialkylamino (preferably mono-or di-C) such as methylamino, ethylamino, dimethylamino, diethylamino, etc _1-6 Alkylamino); acylamino group (preferably C) such as acetylamino, propionylamino, benzoylamino and the like _1-11 Acylamino groups); an oxetanyl group such as an ethyloxetanyl group; acyl groups such as acetyl, propionyl, and benzoyl; an oxo group; two or more of these groups are optionally substituted by C _1-6 And a group in which alkylene groups are bonded.

The group (epoxy group) represented by formula (1 a) is opposite to R in the epoxy resin (A) of the present disclosure ⁶ The proportion of the total amount (100 mol%) of (a) is not particularly limited, but is preferably 40 mol% or more (for example, 40 mol% to 100 mol%), more preferably 60 mol% or more, and still more preferably 80 mol% or more. If the above proportion is less than 40 mol%, the heat resistance, mechanical properties, and the like of the cured product may become insufficient. The above ratio can be determined, for example, by ¹ H-NMR spectrum measurement, ethylene oxide oxygen concentration measurement, and the like.

As one embodiment of the epoxy resin (a) of the present disclosure, an epoxy resin in which ring a is a benzene ring, x is 1, and y is 0 is preferable.

The epoxy resin (a) of the present disclosure is not particularly limited, and is produced by the following method: 1, 2-epoxy-4-vinylcyclohexane (3-vinyl-7-oxabicyclo [4.1.0] heptane) is ring-opening polymerized (cationic polymerized) using a hydroxyl group-containing fluorene compound represented by the following formula (2) as an initiator (i.e., using the hydroxyl group (active hydrogen) of the compound as a starting point), and then epoxidized with an oxidizing agent.

[ chemical formula 12]

In the above formula (2), R ^3a Are identical to each otherOr different, represents a group represented by the following formula (2-1). In two rings A, R ^3a Optionally the same or different. In the above formula (2), the rings A and R ¹ 、R ² The definitions, illustrations and preferred embodiments of j and k are given in connection with rings A and R in formula (1) ¹ 、R ² J and k are the same.

[ chemical formula 13]

In the above formula (2-1), R ⁴ 、R ⁵ The definitions, illustrations, and preferred embodiments of x and y are given above for R in formula (1-1) ⁴ 、R ⁵ X and y are the same.

The hydroxyl group-containing fluorene compound represented by formula (2) can be produced by a known method. For example, with R in the above formula (2) ^3a As a starting material, a compound which is a hydrogen atom or the like is prepared by, for example, reacting C such as ethylene oxide or propylene oxide according to the method described in Japanese patent laid-open publication No. 2009-155256 _2-4 The hydroxyl group-containing fluorene compound represented by formula (2) wherein x is an integer of 1 to 5 and y is 0 in formula (2-1) can be produced by ring-opening addition/polymerization of an alkylene oxide. C _1-4 The ring-opening polymerization of alkylene oxide may use alkylene oxides of different kinds, or may be conducted stepwise. For example, by ring-opening polymerizing ethylene oxide followed by ring-opening polymerizing propylene oxide, a plurality of R's, where x is an integer of 2 or more, can be produced ⁴ A different hydroxyl group-containing fluorene compound represented by formula (2).

Further, a lactone compound such as delta-valerolactone or epsilon-caprolactone can be produced by opening cycloaddition/polymerization of a lactone compound such as delta-valerolactone or epsilon-caprolactone to the hydroxyl group-containing fluorene compound represented by the formula (2) wherein y in the formula (2-1) is 0, as required, by a conventional method, thereby producing the hydroxyl group-containing fluorene compound represented by the formula (2) wherein y in the formula (2-1) is 1 to 5.

As the hydroxyl group-containing fluorene compound represented by formula (2), commercially available products can also be used. As a commercially available product of the hydroxyl group-containing fluorene compound represented by formula (2), 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene [ trade name "BPEF", manufactured by osaka Gas Chemicals, inc.), 9-bis (4-hydroxyphenyl) fluorene [ trade name "BPF", manufactured by osaka Gas Chemicals, inc.), 9-bis (4-hydroxy-3-methylphenyl) fluorene [ trade name "BCF", manufactured by osaka Gas Chemicals, etc. ] can be used.

In particular, from the viewpoint of mold releasability at the time of molding, the epoxy resin (a) is preferably an epoxy resin produced by the following method: 1, 2-epoxy-4-vinylcyclohexane is ring-opened polymerized using a hydroxyl group-containing fluorene compound represented by formula (2) as an initiator in the presence of a fluorine atom-containing cationic polymerization catalyst, and then epoxidized with an oxidizing agent.

The 1, 2-epoxy-4-vinylcyclohexane can be produced by a known or customary method, and is not particularly limited, and can be obtained, for example, by the following method: 4-vinylcyclohexene obtained by dimerization of butadiene is partially epoxidized using an oxidizing agent such as peracetic acid. Further, as the 1, 2-epoxy-4-vinylcyclohexane, a commercially available product (for example, trade name "CELLOXIDE2000" ((manufactured by Daicel Co., ltd.)) can also be used.

The amount of the 1, 2-epoxy-4-vinylcyclohexane used may be appropriately selected depending on the desired degree of polymerization of the 1, 2-epoxy-4-vinylcyclohexane in the epoxy resin (a) (z in the formula (1-1)), and for example, may be appropriately selected from the range of 1 to 20 equivalents, preferably 2 to 15 equivalents, and more preferably 3 to 10 equivalents, with respect to the hydroxyl group of the hydroxyl group-containing fluorene compound represented by the formula (2).

Examples of the fluorine atom-containing cationic polymerization catalyst include a bronsted acid having a fluorine atom, a lewis acid, and the like, and are not particularly limited, and examples thereof include boron trifluoride, and boron trifluoride etherate (etherate) (e.g., diethyl ether complex of boron trifluoride, and the like). The amount of the fluorine atom-containing cationic polymerization catalyst to be used is not particularly limited, and can be appropriately selected from the range of 0.01 to 10 parts by weight (more preferably 0.1 to 5 parts by weight) per 100 parts by weight of 1, 2-epoxy-4-vinylcyclohexane.

The temperature (reaction temperature) at the time of ring-opening polymerization of 1, 2-epoxy-4-vinylcyclohexane is not particularly limited, but is preferably-70 ℃ to 200 ℃, more preferably-30 ℃ to 100 ℃. The reaction time can be appropriately adjusted depending on the conversion of 1, 2-epoxy-4-vinylcyclohexane, and the like.

The ring-opening polymerization of 1, 2-epoxy-4-vinylcyclohexane may also be carried out in a solvent. As the solvent, a solvent having active hydrogen cannot be used. That is, as the solvent, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether; aliphatic hydrocarbons such as hexane and heptane; and esters such as ethyl acetate. One solvent may be used alone, or two or more solvents may be used in combination.

The compound represented by the following formula (3) (resin having a vinyl group) is produced by ring-opening polymerization of 1, 2-epoxy-4-vinylcyclohexane using the hydroxyl group-containing fluorene compound represented by the above formula (2) as an initiator. This compound may be directly subjected to the subsequent reaction (epoxidation), or may be subjected to the subsequent reaction after purification. The purification method is not particularly limited, and may be a known or conventional method such as a separation method including filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a separation method combining these methods.

[ chemical formula 14]

In the above formula (3), R ^3b The same or different groups represent a group represented by the following formula (3-1). In two rings A, R ^3b Optionally the same or different. In the above formula (3), the rings A and R ¹ 、R ² The definitions, illustrations, and preferred embodiments of j and k are the same as those of rings A and R in formula (1) ¹ 、R ² J and k are the same.

[ chemical formula 15]

In the above formula (3-1), R ⁴ 、R ⁵ Definitions, illustrations, preferred embodiments of x, y and z are defined in the above formula (1-1) for R ⁴ 、R ⁵ X, y and z are the same.

More specifically, the ring-opening polymerization can be carried out, for example, according to the method described in Japanese patent application laid-open No. 60-161973.

Next, the vinyl group of the compound represented by formula (3) is epoxidized with an oxidizing agent, whereby an epoxy resin (a) (an epoxy resin represented by formula (1)) can be obtained.

The oxidizing agent may be any known or customary oxidizing agent such as hydrogen peroxide and an organic peracid, and is not particularly limited, and examples of the organic peracid include performic acid, peracetic acid, perbenzoic acid, and trifluoroperacetic acid. Among these, peracetic acid is industrially available at low cost and has high stability, and thus is preferable. One oxidizing agent may be used alone, or two or more oxidizing agents may be used in combination.

When the compound represented by the formula (3) is reacted (epoxidized) with an organic peracid, a known or conventional catalyst may be used. Examples of the catalyst include an alkali such as sodium carbonate and an acid such as sulfuric acid.

The reaction (epoxidation) may be carried out by determining the presence or absence of the solvent used or by adjusting the reaction temperature depending on the apparatus used and the physical properties of the raw materials.

The temperature (reaction temperature) at which the above reaction is carried out may be appropriately determined depending on the reactivity of the oxidizing agent used, and is not particularly limited, and for example, when peracetic acid is used as the oxidizing agent, it is preferably 0 to 70 ℃. When the reaction temperature is lower than 0 ℃, the reaction may progress too slowly, while when the reaction temperature exceeds 70 ℃, the decomposition of peracetic acid may be easily caused.

In the above reaction, a solvent may be used for the purpose of lowering the viscosity of the raw material, stabilizing the raw material by dilution of the oxidizing agent, and the like. When peracetic acid is used as the oxidizing agent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether; esters such as ethyl acetate; ketones such as acetone, methyl isobutyl ketone, and methyl ethyl ketone.

The amount of the oxidizing agent used in the reaction (molar ratio of the oxidizing agent to the vinyl group contained in the compound represented by formula (3)) is not particularly limited, and for example, when peracetic acid is used as the oxidizing agent, the amount of the oxidizing agent is preferably 1 to 1.5 times the amount of the oxidizing agent to the vinyl group.

By the above reaction, a part or all of the vinyl groups of the compound represented by formula (3) are epoxidized and converted into a group (epoxy group) represented by formula (1 a), thereby producing an epoxy resin (a)) represented by formula (1). The group represented by formula (1 c) in formula (1) is produced, for example, by the following method: an organic acid (for example, acetic acid) generated by the reaction of the vinyl group of the compound represented by the formula (3) and the organic peracid, water, an alcohol, and the like present in the system, and the group represented by the formula (1 a) react (side reaction), and the like. The ratio of the groups represented by the formulae (1 a) to (1 c) in the formula (1) can be appropriately adjusted depending on, for example, the type of the oxidizing agent, the amount of the oxidizing agent used (the molar ratio of the oxidizing agent to the vinyl group), and the reaction conditions.

The epoxy resin (a) obtained by the above reaction can be purified by a known or conventional method such as a separation method such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a separation method combining these separation methods.

The epoxy resin (a) may be composed of one of the epoxy resins represented by the formula (1), or may be composed of two or more of the epoxy resins represented by the formula (1).

The weight average molecular weight of the epoxy resin (a) in terms of standard styrene is not particularly limited, but is preferably 300 to 100000, and more preferably 1000 to 10000. When the weight average molecular weight is less than 300, the mechanical properties and heat resistance of the cured product may be insufficient. On the other hand, when the weight average molecular weight exceeds 100000, the viscosity may be increased and the fluidity at the time of molding may be lowered. The weight average molecular weight can be measured by, for example, a Gel Permeation Chromatography (GPC) method.

The epoxy equivalent of the epoxy resin (a) is not particularly limited, but is preferably 50 to 1000, and more preferably 100 to 500. When the epoxy equivalent is less than 50, the cured product may be brittle. On the other hand, if the epoxy equivalent exceeds 1000, the mechanical properties of the cured product may become insufficient. The epoxy equivalent may be determined, for example, according to JIS K7236:2001, respectively.

The epoxy resin (a) is not particularly limited, and may contain a fluorine atom. For example, when the ring-opening polymerization is carried out in the presence of a cationic polymerization catalyst containing a fluorine atom, the obtained epoxy resin (a) tends to contain a fluorine atom. The content of the fluorine atom in the epoxy resin (A) is not particularly limited, but is preferably 100ppm to 30000ppm, more preferably 2000ppm to 15000ppm. If the fluorine atom content is less than 100ppm, the releasability of the cured product may be insufficient. On the other hand, if the fluorine atom content exceeds 30000ppm, peeling may easily occur at the interface with a metal, another resin, or the like. The content of fluorine atoms can be measured, for example, by combustion ion chromatography. Examples of the form in which fluorine atoms are contained in the epoxy resin (a) include: the form of the epoxy resin containing a constituent element, the form of the epoxy resin containing a constituent element of a component (impurity or the like) different from the epoxy resin, and the like are not particularly limited, and may be, for example, a form in which at least one of hydrogen atoms bonded to carbon atoms in the epoxy resin represented by the formula (1) is substituted. The presence of a C-F bond in the epoxy resin of formula (1) is, for example, by ¹ H-NMR spectroscopy, etc.

< epoxy resin composition >

The epoxy resin composition of the present disclosure is a curable resin composition containing an epoxy resin (a) as an essential component, and the epoxy resin (a) is an epoxy resin represented by the above formula (1). The epoxy resin composition of the present disclosure may contain other components as necessary in addition to the above essential components. In the epoxy resin composition of the present disclosure, one kind of the epoxy resin (a) may be used alone, or two or more kinds may be used in combination.

The content (blending amount) of the epoxy resin (a) in the epoxy resin composition of the present disclosure is not particularly limited, and is preferably 2 to 90 wt%, more preferably 4 to 80 wt%, and still more preferably 6 to 70 wt% with respect to the total amount (100 wt%) of the epoxy resin composition. If the content of the epoxy resin (a) is less than 2% by weight, the heat resistance and mechanical properties of the cured product may be insufficient. On the other hand, if the content of the epoxy resin (a) exceeds 90% by weight, the viscosity may become too high and the workability may be deteriorated.

The proportion of the epoxy resin (a) to the total amount (100 wt%) of the epoxy compound (epoxy resin) contained in the epoxy resin composition of the present disclosure is not particularly limited, but is preferably 2 wt% or more (for example, 2 wt% to 100 wt%), more preferably 4 wt% or more, and further preferably 6 wt% or more. When the proportion of the epoxy resin (a) is less than 2% by weight, the heat resistance and mechanical properties (strength, elongation, etc.) of the cured product tend to be insufficient.

[ other epoxy Compounds ]

The epoxy resin composition of the present disclosure may contain an epoxy compound (sometimes referred to as "other epoxy compound") other than the epoxy resin (a) within a range not impairing the effect of the invention of the present disclosure. The other epoxy compounds include known or customary epoxy compounds, and are not particularly limited, and examples thereof include: aromatic glycidyl ether epoxy compounds [ e.g., bisphenol a-type epoxy compounds, bisphenol F-type epoxy compounds, biphenol-type epoxy compounds, phenol novolac-type epoxy compounds, cresol novolac-type epoxy compounds, bisphenol a-cresol novolac-type epoxy compounds, naphthalene-type epoxy compounds, epoxy compounds derived from trisphenol methane, etc. ]; aliphatic epoxy compounds such as aliphatic glycidyl ether-based epoxy compounds [ for example, aliphatic polyglycidyl ethers and the like ]; examples of the epoxy resin (a) include (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms constituting an alicyclic group (aliphatic hydrocarbon ring) and an oxygen atom, (ii) a compound in which an epoxy group is directly bonded to an alicyclic group by a single bond (excluding the epoxy resin (a)), and (iii) an alicyclic epoxy compound such as a hydrogenated aromatic glycidyl ether epoxy compound. The other epoxy compounds may be used alone or in combination of two or more.

The compound having the alicyclic epoxy group (i) may be arbitrarily selected from known or conventional compounds and used. Among them, the alicyclic epoxy group is preferably an epoxycyclohexyl group. That is, as the compound having an alicyclic epoxy group (I), a compound having an epoxycyclohexyl group is preferable from the viewpoint of transparency and heat resistance of the cured product, and a compound represented by the following formula (I) (alicyclic epoxy compound) is particularly preferable.

[ chemical formula 16]

In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the above-mentioned linking group include: a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, a group formed by connecting a plurality of these groups, and the like.

Examples of the compound of formula (I) in which X is a single bond include 3,4,3',4' -diepoxybicyclohexane and the like.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include: methylene, methyl methylene, dimethyl methylene, ethylene, propylene, trimethylene and the like. Examples of the divalent alicyclic hydrocarbon group include: divalent cycloalkylene groups (including cycloalkylidene groups) such as 1, 2-cyclopentylene group, 1, 3-cyclopentylene group, cyclopentylidene group, 1, 2-cyclohexylene group, 1, 3-cyclohexylene group, 1, 4-cyclohexylene group and cyclohexylidene group, and the like.

The linking group X is particularly preferably a linking group containing an oxygen atom, and specifically, includes: -CO-, -O-CO-O-, -COO-, -O-, -CONH-; a plurality of these groups being linked to each other; and a group in which one or more of these groups are bonded to one or more of divalent hydrocarbon groups. Examples of the divalent hydrocarbon group include those exemplified above.

Representative examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulae (I-1) to (I-10). In the following formulae (I-5) and (I-7), l and m each represent an integer of 1 to 30. R in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, and examples thereof include: a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. Among them, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group is preferable. N1 to n6 in the following formulae (I-9) and (I-10) are each an integer of 1 to 30.

[ chemical formula 17]

[ chemical formula 18]

Examples of (II) the compound in which an epoxy group is directly and singly bonded to an alicyclic ring include compounds represented by the following formula (II). Specific examples of the above-mentioned compounds include 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexanecarboxylate represented by the above-mentioned formula (I-1), trade name "CELLOXIDE 2021P" ((manufactured by Daicel, ltd.), and the like.

[ chemical formula 19]

In formula (II), R' represents a p-valent organic group. p represents an integer of 1 to 20. q represents an integer of 1 to 50, and is represented by the formula (II)The sum (total) of q in (b) is an integer of 3 to 100. R' is the same as R in the above formula (1-1) ⁶ Similarly, the compound represents any of the groups represented by the above formulae (1 a) to (1 c). Wherein at least one of R' in the formula (II) is a group represented by the formula (1 a). In the case where p is 2 or more, q in the group within each () (within parentheses) is optionally the same or different. Specific examples of the above-mentioned compound include 1, 2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol (trimethylolpropane) and the product name "EHPE3150" (manufactured by Daicel, ltd.).

Examples of the hydrogenated glycidyl ether epoxy compound (iii) include: compounds obtained by hydrogenating bisphenol a type epoxy compounds (hydrogenated bisphenol a type epoxy compounds) such as 2, 2-bis [4- (2, 3-epoxypropoxy) cyclohexyl ] propane, 2-bis [3, 5-dimethyl-4- (2, 3-epoxypropoxy) cyclohexyl ] propane and the like; compounds obtained by hydrogenating bisphenol F type epoxy compounds (hydrogenated bisphenol F type epoxy compounds) such as bis [ o, o- (2, 3-epoxypropoxy) cyclohexyl ] methane, bis [ o, p- (2, 3-epoxypropoxy) cyclohexyl ] methane, bis [ p, p- (2, 3-epoxypropoxy) cyclohexyl ] methane, bis [3, 5-dimethyl-4- (2, 3-epoxypropoxy) cyclohexyl ] methane and the like; hydrogenated biphenyldiol type epoxy compounds; epoxy compounds of the hydrogenated phenol novolak type; hydrogenated cresol novolak type epoxy compounds; hydrogenated cresol novolak type epoxy compounds of bisphenol a; hydrogenated naphthalene type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from trisphenol methane, and the like.

The content (blending amount) of the other epoxy compound in the epoxy resin composition of the present disclosure is not particularly limited, and is preferably less than 70% by weight (for example, 0% by weight or more and less than 70% by weight), and more preferably less than 60% by weight, based on the total amount (100% by weight) of the epoxy compound (epoxy resin) contained in the epoxy resin composition. When the content of the other epoxy compound is 70% by weight or more, the heat resistance and mechanical properties of the cured product may be insufficient. On the other hand, the content (blending amount) of the other epoxy compound is not particularly limited, and is preferably 10% by weight or more, and more preferably 20% by weight or more, relative to the total amount (100% by weight) of the epoxy compound (epoxy resin) contained in the epoxy resin composition. If the content of the other epoxy compound is less than 10% by weight, the viscosity may be too high and the workability may be deteriorated.

[ curing agent ]

The epoxy resin composition of the present disclosure may contain a curing agent (hereinafter, sometimes referred to as a curing agent (B)) in addition to the epoxy resin (a). The curing agent (B) is a compound having an action of curing the epoxy resin composition by reacting with a compound having an epoxy group such as the epoxy resin (a). As the curing agent (B), any of the curing agents known or used for epoxy resins can be used, and there are no particular limitations thereon, and examples thereof include: acid anhydride curing agents, amine curing agents, imidazole curing agents, polythiol curing agents, and the like. The curing agent (B) may be used alone or in combination of two or more. Among them, the curing agent (B) is preferably an acid anhydride curing agent.

Examples of the acid anhydride-based curing agent include: acid anhydrides which are liquid at 25 ℃ such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, and methylendomethylenetetrahydrophthalic anhydride; and acid anhydrides which are solid at 25 ℃ such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic anhydride. The acid anhydride curing agent may be used alone or in combination of two or more.

As the curing agent (B), a commercially available one can be used. Examples of commercially available products of the acid anhydride-based curing agent include: trade names "RIKACID MH-700", "RIKACID MH-700F" and "RIKACID HH" (manufactured by Nissian Sukkiso chemical Co., ltd.); and "HN-5500" (manufactured by Hitachi chemical industries, ltd.).

The content (blending amount) of the curing agent (B) in the epoxy resin composition of the present disclosure is not particularly limited, and is preferably 50 to 200 parts by weight, and more preferably 70 to 150 parts by weight, based on 100 parts by weight of the total amount of the compound having an epoxy group contained in the epoxy resin composition. More specifically, the curing agent (B) is preferably used in a proportion of 0.5 to 1.5 equivalents relative to 1 equivalent of epoxy group in all the compounds having epoxy groups contained in the epoxy resin composition of the present disclosure. If the content of the curing agent (B) is less than 50 parts by weight, the progress of curing may be insufficient, the toughness of the cured product may be insufficient, or the yellowing resistance of the cured product may be reduced. On the other hand, if the content of the curing agent (B) exceeds 200 parts by weight, curing becomes insufficient similarly, and the cured product may be colored and the hue may be easily deteriorated.

[ curing accelerators ]

The epoxy resin composition of the present disclosure may further include a curing accelerator (hereinafter, sometimes referred to as a curing accelerator (C)). The curing accelerator (C) is a compound having a function of accelerating a curing speed when a compound having an epoxy group such as the epoxy resin (a) is cured by the curing agent (B). As the curing accelerator (C), a known or customary curing accelerator can be used, and examples thereof include: 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) or a salt thereof (e.g., phenolate, octanoate, p-toluenesulfonate, formate, tetraphenylborate); 1, 5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (e.g., phenolate, octoate, p-toluenesulfonate, formate, tetraphenylborate); tertiary amines such as benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine, and the like; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphines such as phosphoric acid ester and triphenylphosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate; organic metal salts such as zinc octylate and tin octylate; metal chelates, and the like. The curing accelerator may be used singly or in combination of two or more.

Further, as the curing accelerator, for example, trade names of "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U-CAT 18X" and "12XD" (products of development) (manufactured by San-Apro corporation, supra); trade names "TPP-K" and "TPP-MK" (manufactured by Beixing chemical industry Co., ltd.); commercially available products such as "PX-4ET" (manufactured by Nippon chemical industry Co., ltd.).

The content (blending amount) of the curing accelerator (C) in the epoxy resin composition of the present disclosure is not particularly limited, and is preferably 0.1 to 8 parts by weight, and more preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the total amount of the compounds having epoxy groups contained in the epoxy resin composition. If the content of the curing accelerator (C) is less than 0.1 part by weight, curing may become insufficient. On the other hand, if the content of the curing accelerator (C) exceeds 8 parts by weight, the storage stability may be deteriorated, and the cured product may be colored and the hue may be easily deteriorated.

[ curing catalyst ]

The epoxy resin composition of the present disclosure may contain a curing catalyst (hereinafter, sometimes referred to as a curing catalyst (D)) instead of the curing agent (B). Similarly to the case of using the curing agent (B), the curing reaction of the compound having an epoxy group such as the epoxy resin (a) can be progressed by using the curing catalyst (D), and a cured product can be obtained. The curing catalyst (D) is not particularly limited, and for example, a cationic catalyst (cationic polymerization initiator) which generates cationic species by ultraviolet irradiation or heat treatment and can initiate polymerization can be used.

Examples of the cationic catalyst that generates cationic species by ultraviolet irradiation include: hexafluoroantimonate, pentafluoro hydroxy antimonate, hexafluorophosphate, hexafluoroarsenate, and the like. These cationic catalysts may be used alone or in combination of two or more. As the above cationic catalyst, commercially available products such as the trade name "UVACURE1590" (manufactured by DAICEL-CYTEC, inc.), the trade name "CD-1010", "CD-1011", "CD-1012" (manufactured by Sartomer, USA), the trade name "Irgacure 264" (manufactured by Chiba Japan, inc.), and the trade name "CIT-1682" (manufactured by Nippon Caoda, inc.) can be preferably used.

Examples of the cationic catalyst that generates cationic species by heat treatment include: aryl diazonium salts, aryl iodonium salts, aryl sulfonium salts, allene-ion complexes, and the like. These cationic catalysts may be used alone or in combination of two or more. As the above cationic catalyst, commercially available products such as the trade names "PP-33", "CP-66", "CP-77" (manufactured by ADEKA, co., ltd.), the trade name "FC-509" (manufactured by 3M), the trade name "UVE1014" (manufactured by G.E.), the trade name "SAN-AID SI-60L", "SAN-AID SI-80L", "SAN-AID SI-100L", "SAN-AID SI-110L", "SAN-AID SI-150L" (manufactured by shin-Kagaku, co., ltd.), and the trade name "CG-24-61" (manufactured by Chiba Japan, co., ltd.) can be preferably used. The cationic catalyst may be a compound of a metal such as aluminum or titanium and a chelate compound of acetoacetic acid or a diketone and a silanol such as triphenyl silanol, a compound of a metal such as aluminum or titanium and a chelate compound of acetoacetic acid or a diketone and a phenol such as bisphenol S, or the like.

The amount (content) of the curing catalyst (D) is not particularly limited, and is preferably 0.01 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, even more preferably 0.05 to 10 parts by weight, and particularly preferably 0.1 to 10 parts by weight, based on the total amount (100 parts by weight) of the compound having an epoxy group contained in the epoxy resin composition. By using the curing catalyst (D) in the above range, a cured product excellent in heat resistance and light resistance can be obtained.

[ additives ]

The epoxy resin composition of the present disclosure may contain various additives in addition to the above components within a range not impairing the effects of the invention of the present disclosure. When the additive contains a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin, the reaction can be allowed to proceed slowly. In addition, conventional additives such as antifoaming agents, leveling agents, silane coupling agents such as γ -glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, surfactants, inorganic fillers such as silica and alumina, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion absorbers, pigments, phosphors (for example, inorganic phosphor fine particles such as YAG phosphor fine particles and silicate phosphor fine particles), and release agents may be used within a range not impairing the viscosity and transparency. The amount of these additives used is about 5% by weight or less based on the total amount of the epoxy resin composition.

The epoxy resin composition of the present disclosure is not particularly limited, and can be prepared by blending and kneading the above-mentioned respective components in a heated state as necessary. The method of the above-mentioned kneading is not particularly limited, and known or conventional kneading methods such as various mixers such as dissolvers and homogenizers, kneaders, rolls, bead mills, and autorotation stirring apparatuses can be used.

From the viewpoint of handling and processability, the epoxy resin composition of the present disclosure is preferably in a liquid state at room temperature (25 ℃) and has a viscosity (25 ℃) of preferably 100000mPa · s or less (e.g., 200mPa · s to 100000mPa · s), more preferably 50000mPa · s or less (e.g., 200mPa · s to 50000mPa · s). The glass transition temperature is preferably 120 to 200 ℃ and more preferably 130 to 180 ℃.

The viscosity can be measured by the measurement method described in examples.

Further, by heating the epoxy resin composition of the present disclosure to react a part of the compound having an epoxy group in the epoxy resin composition, a B-staged epoxy resin composition (B-staged epoxy resin composition) can be obtained.

< cured product >

By curing the epoxy resin composition of the present disclosure (or the epoxy resin composition in a B-stage state) by heating, a cured product (sometimes referred to as "cured product of the present disclosure") excellent in heat resistance and mechanical properties (particularly, strength and elongation) can be obtained. The heating temperature (curing temperature) during curing is not particularly limited, but is preferably 45 to 200 ℃, more preferably 100 to 190 ℃, and still more preferably 100 to 180 ℃. The time for heating at the time of curing (curing time) is not particularly limited, but is preferably 30 minutes to 600 minutes, more preferably 45 minutes to 540 minutes, and still more preferably 60 minutes to 480 minutes. If the curing temperature and curing time are lower than the lower limit of the above range, curing may be insufficient, whereas if the curing temperature and curing time are higher than the upper limit of the above range, decomposition of the resin component may occur, which is not preferable. The curing conditions depend on various conditions, and can be adjusted as appropriate by shortening the curing time when the curing temperature is high, or by lengthening the curing time when the curing temperature is low. The heat curing treatment may be performed in one stage, but may be performed while raising the temperature in stages in order to prevent cracking during curing due to heat generation during curing.

The degree of cure of the cured product of the present disclosure is, for example, preferably 90% or more, more preferably 95% or more, and still more preferably 97% or more. When the degree of cure of the cured product of the present disclosure is less than 90%, heat resistance and mechanical properties may be insufficient.

The curing degree of the cured product of the present disclosure can be calculated by measuring the heat release amount of the epoxy resin composition of the present disclosure and the heat release amount of the cured product of the present disclosure by DSC according to the following equations.

Degree of cure (%) = [1- (heat release of cured product/heat release of epoxy resin composition) ] × 100

More specifically, the degree of curing can be measured by the measurement method described in examples.

The glass transition temperature (Tg) of the cured product of the present disclosure (e.g., a cured product having a degree of cure of 90% or more) is preferably 100 ℃ or more (e.g., 100 to 250 ℃), and more preferably 140 ℃ or more (e.g., 140 to 250 ℃). When the glass transition temperature is less than 100 ℃, the heat resistance of the cured product may be insufficient depending on the use. The glass transition temperature of the cured product can be measured by various thermal analyses (DSC (differential scanning calorimeter), TMA (thermal mechanical analyzer), and the like), dynamic viscoelasticity measurement, and the like, and more specifically, can be measured by the measurement methods described in examples.

The linear expansion coefficient (α 1) of the cured product of the present disclosure (for example, a cured product having a degree of curing of 90% or more) at a glass transition temperature or lower is preferably 40ppm/° c to 100ppm/° c, and more preferably 70ppm/° c to 95ppm/° c. In addition, the linear expansion coefficient (α 2) of the cured product of the present disclosure (for example, a cured product having a degree of curing of 90% or more) at a glass transition temperature or higher is preferably 90 ppm/degree C to 170 ppm/degree C, and more preferably 90 ppm/degree C to 160 ppm/degree C. The linear expansion coefficients α 1 and α 2 of the cured product can be measured by TMA or the like, more specifically, by the measurement methods described in examples.

Temperature (T) for 5% weight reduction of cured product of the present disclosure (e.g., cured product having a degree of cure of 90% or more) _d5 ) Not particularly limited, it is preferably 330 ℃ or higher (for example, 330 ℃ to 450 ℃), more preferably 340 ℃ or higher, and still more preferably 350 ℃ or higher. When the temperature at which the weight is reduced by 5% is 330 ℃ or more, the heat resistance of the cured product tends to be further improved.

The flexural strength of the cured product of the present disclosure (for example, a cured product having a degree of curing of 90% or more) is not particularly limited, but is preferably 40MPa or more (for example, 40MPa to 200 MPa), and more preferably 70MPa or more (for example, 70MPa to 200 MPa).

The flexural modulus of the cured product of the present disclosure (for example, a cured product having a degree of curing of 90% or more) is not particularly limited, but is preferably 1500MPa or more (for example, 1500MPa to 2000 MPa), and more preferably 1800MPa or more.

The bending elongation of the cured product of the present disclosure (for example, a cured product having a degree of curing of 90% or more) is not particularly limited, but is preferably 2.0% or more (for example, 2.0% to 20%), and more preferably 2.5% or more (for example, 2.5% to 20%).

The flexural strength, flexural modulus and flexural elongation of the cured product can be measured, for example, according to JIS K6911 (for example, under the condition of a bending speed of 2 mm/min), more specifically, according to the measurement methods described in examples.

By curing the epoxy resin composition of the present disclosure, a cured product (cured product of the present disclosure) having excellent heat resistance and mechanical properties can be formed, and thus the epoxy resin composition can be suitably used as an electronic material and various composite materials.

That is, the epoxy resin composition of the present disclosure and the cured product thereof (cured product of the present disclosure) are useful as, for example, insulating materials between layers of electronic components, solder resists for printed boards, resist materials for coverlays and the like, semiconductor sealing materials, color filters, printing inks, sealants (semiconductor sealants and the like), paints, coating agents, adhesives and all electrical/electronic materials. Further, the resin composition can be used in the fields of molding materials, adhesives, paints, electrical insulating materials, laminates, coatings, inks, paints, sealants, resists, composite materials, substrates, sheets, films, optical elements, optical lenses, optical members, optical moldings, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and the like.

In addition, various composite materials in which various inorganic fillers, organic fillers, reinforcing fibers, and the like are blended in the epoxy resin composition of the present disclosure may be used as the electric/electronic materials and the like.

Examples of the inorganic filler include: calcium carbonate, magnesium carbonate, clay, kaolin, calcium phosphate, hydroxyapatite, mica, talc, silica, quartz powder, glass powder, diatomaceous earth, nepheline syenite, cristobalite, wollastonite, aluminum hydroxide, iron oxide, zinc oxide, titanium oxide, aluminum oxide, calcium sulfate, barium sulfate, dolomite, silicon carbide, silicon nitride, boron nitride, metal powder, graphite, carbon black, silver hydroxyapatite, silver zeolite, and the like. Examples of the organic filler include: and granules of various polymers such as crosslinked polymethyl methacrylate. These may be used singly or in combination of two or more.

Examples of the reinforcing fiber include: carbon fibers, glass fibers, aramid fibers, boron fibers, graphite fibers, silicon carbide fibers, high-strength polyethylene fibers, tungsten carbide fibers, polyparaphenylene benzobisoxazole fibers (PBO fibers), and the like. These may be used alone or in combination of two or more.

The various aspects disclosed in this specification may be combined with any other features disclosed in this specification.

Examples

The invention of the present disclosure will be described in more detail below with reference to examples, but the respective configurations and combinations thereof in the respective embodiments are merely examples, and additions, omissions, substitutions, and other modifications of the configurations can be appropriately made within the scope not departing from the gist of the invention of the present disclosure. The present disclosure is not to be limited by the embodiments, but only by the claims. The unit of the amount of each component of the epoxy resin composition in table 1 is part by weight.

Of the product ¹ H-NMR spectra were measured by JNM-ECZ400S (manufactured by Nippon electronics Co., ltd.), solvent: deuterated chloroform and measurement conditions: at 20 ℃.

The weight average molecular weight (Mw) of the product was measured by Gel Permeation Chromatography (GPC) using HLC-8420GPC (manufactured by Tosoh corporation), solvent: THF, assay conditions: 40 ℃ and flow rate: 0.350mL/min, molecular weight: under the condition of conversion to standard styrene.

Comparative example 1

[ production of epoxy resin Using trimethylolpropane as initiator ]

50.0g (0.373 mol) of trimethylolpropane (manufactured by Tokyo Kasei Co., ltd.) and 694.2g (5.59 mol) of 1, 2-epoxy-4-vinylcyclohexane (manufactured by Daicel Co., ltd.) and 282.3g of ethyl acetate were charged into a 2L glass reactor at room temperature under a nitrogen atmosphere and stirred. The temperature was then raised to 50 ℃ to dissolve the trimethylolpropane. After the dissolution, 88.1g (net amount: 13.2 g) of an ethyl acetate solution (15%) of boron trifluoride diethyl ether complex [ Stella-Chemifa (Ltd.)) was added dropwise thereto over 4 hours. After the dropwise addition, the mixture was stirred for 1 hour, and after the completion of the reaction, the temperature was lowered to 45 ℃ and 387g of ethyl acetate and 558g of water were added to wash with water. After washing with water, the organic layer was separated.

250g of the separated organic layer (solid content concentration: 51.31%) was heated to 60 ℃ and 277.6g (1.06 mol) of an ethyl acetate solution (29%) of peracetic acid was added dropwise over 2 hours under a nitrogen atmosphere. After the dropwise addition, the mixture was stirred for 5 hours, and after the reaction was completed, the temperature was lowered to 45 ℃ to carry out water washing. The resulting organic layer was separated, and ethyl acetate was removed by an evaporator to obtain 140g of an aimed product (EHPE 3150). The softening point measured by the ring and ball method according to JIS K2207 was 76 ℃.

Example 1

[ production of epoxy resin Using 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (Bisphenoxythane) as initiator ]

30.0g (0.068 mol) of 9,9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene [ Osaka Gas Chemicals (Ltd.) ] and 127.4g (1.026 mol) of 1, 2-epoxy-4-vinylcyclohexane [ (Daicel Co., ltd.) ] and 59.7g of ethyl acetate were charged into a 2L glass reactor at room temperature under a nitrogen atmosphere and stirred. The temperature was then raised to 50 ℃ to dissolve the 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene. After the dissolution, 16.2g (net amount: 2.43 g) of an ethyl acetate solution (15%) of boron trifluoride diethyl ether complex [ Stella-Chemifa (Ltd.) ] was added dropwise over 1 hour. After the dropwise addition, the mixture was stirred for 1 hour, and after the completion of the reaction, the temperature was lowered to 45 ℃ and 84.0g of ethyl acetate and 118.1g of water were added to wash with water. After washing with water, the organic layer was separated.

294.1g of the separated organic layer was heated to 60 ℃ and 333.7g (1.23 mol) of an ethyl acetate solution (28%) of peracetic acid was added dropwise over 2 hours under a nitrogen atmosphere. After the dropwise addition, the mixture was stirred for 5 hours, and after the completion of the reaction, the temperature was lowered to 45 ℃ to carry out water washing. The resulting organic layer was separated, and ethyl acetate was removed by an evaporator to obtain 170g of the objective compound (epoxy resin (1)). The softening point of the alloy was 82 ℃ as measured by the ring and ball method according to JIS K2207.

Preparation of the resulting epoxy resin (1) ¹ The H-NMR spectrum is shown in FIG. 1. Peaks ascribed to a fluorene skeleton and a phenyl group were observed at chemical shifts (. Delta.) of 7.8ppm (16H) to 6.7ppm (16H), and peaks ascribed to an epoxy group were observed at chemical shifts (. Delta.) of 2.7ppm (2H) and 2.5ppm (1H).

The weight average molecular weight of the epoxy resin (1) in terms of standard styrene, as measured by GPC, was 1256.

Example 2, comparative examples 2 and 3

According to the composition of table 1, each epoxy resin and a curing catalyst were mixed and added, and uniformly blended using a rotation revolution type stirring apparatus (trade name "THINKY MIXER (12354124313192\1242667676tailang) AR-250".

The epoxy resin composition obtained in the above was cast into a molding machine and heated under the curing conditions shown in table 1 to be cured, thereby producing a cured product.

[ evaluation ]

The epoxy resin compositions and cured products obtained in example 2 and comparative examples 2 and 3 were evaluated as follows.

[ viscosity ]

The viscosities (mPas) at 25 ℃ of the epoxy resin compositions obtained in example 2 and comparative examples 2 and 3 were measured with an E-type VISCOMETER (model "VISCOMETER TV-22", manufactured by Toyobo industries, ltd.). The results are shown in Table 1.

[ degree of curing ]

The degree of cure (%) was measured using the epoxy resin compositions and cured products obtained in example 2 and comparative examples 2 and 3. The results are shown in Table 1.

The degree of cure (%) was calculated by comparing the heat release before curing and the residual heat after curing, measured at a temperature rise rate of 5 ℃/min using a differential scanning calorimeter (DSC 6200, hitachi-rightech Science, inc.).

[ Heat resistance (TMA) ]

The glass transition temperatures (Tg (TMA)) of the cured products obtained in example 2 and comparative examples 2 and 3 were measured by a TMA measuring apparatus ("TMA/SS 100", manufactured by SII Nanotechnology, inc.) under a nitrogen atmosphere at a temperature rise rate of 5 ℃/min using a method according to JIS K7197, and then tangent lines were drawn to the curves before and after the glass transition point to determine the glass transition temperatures from the intersection points of the tangent lines. The results are shown in Table 1.

The linear expansion coefficients of the cured products obtained in example 2 and comparative examples 2 and 3 were determined, with the slope of the line on the lower temperature side of the glass transition temperature determined above being α 1 and the slope of the line on the higher temperature side of the glass transition temperature being α 2. The results are shown in Table 1.

[ Heat resistance (Tg-DTA) ]

Using a differential thermal gravimetric synchronous measurement apparatus (TG/DTA) [ product of Seiko Instruments (Ltd.)]The thermal decomposition temperature (T) decreased by 5% by weight) of the cured products obtained in example 2 and comparative examples 2 and 3 was measured _d5 )). The measurement was carried out under nitrogenThe temperature was raised from 25 ℃ to 400 ℃ at a temperature raising rate of 10 ℃/min under flowing. The results are shown in Table 1.

[ bending Property ]

The cured products (thickness: 4 mm. Times. Width: 10 mm. Times. Length: 80 mm) obtained in example 2 and comparative examples 2 and 3 were sampled using a TENSILON Universal tester (manufactured by Orientec corporation) at a side span (edge span): a three-point bending test was carried out under conditions of 67mm and a bending speed of 2 mm/min, whereby the flexural strength, flexural modulus and flexural elongation of the cured product were measured. The results are shown in Table 1.

[ Table 1]

In example 2, compared with comparative example 2 in which the epoxy resin (1) was not blended and comparative example 3 in which 45 parts by weight of EHPE3150 was blended instead of the epoxy resin (1), an increase in glass transition temperature (Tg) was observed, and further, the flexural strength and flexural elongation (particularly, flexural elongation) were greatly improved without lowering the flexural modulus.

As described above, it was found that the epoxy resin composition including the epoxy resin of the present disclosure provides a cured product exhibiting superior heat resistance and/or mechanical properties than the epoxy resin composition of the comparative example including EHPE 3150.

The components in table 1 are as follows.

[ epoxy Compound ]

Celloxin 2021P: the trade name is "CELLOXIDE 2021P" (3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexanecarboxylate, manufactured by Daicel).

EHPE3150: the epoxy resin produced in comparative example 1.

Epoxy resin (1): the epoxy resin produced in example 1.

[ curing catalyst ]

SI-100L: the trade name is "SAN-AID SI-100L" (manufactured by Sanxin chemical industries, ltd.).

Hereinafter, the modifications of the present disclosure explained above will be attached.

[1] An epoxy resin represented by the following formula (1).

[ chemical formula 20]

[ in the formula (1), the rings A may be the same or different and each represent an aromatic hydrocarbon ring. R ¹ Identical or different, represents a cyano group, a halogen atom or an alkyl group. R ² The same or different, represents a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, an alkoxycarbonyl group, a hydroxyl group, a halogen atom, a nitro group, a cyano group or a substituted amino group. j, which may be the same or different, represents an integer of 0 to 4. k is the same or different and represents 0 or an integer of 1 or more. R ³ The same or different represent a group represented by the following formula (1-1)]

[ chemical formula 21]

[ formula (1-1) wherein R ⁴ Represents an alkylene group having 2 to 4 carbon atoms. R ⁵ Represents an alkylene group having 3 to 6 carbon atoms. R ⁶ Represents any one of the groups represented by the following formulae (1 a) to (1 c), R in formula (1-1) ⁶ At least one of them is a group represented by the formula (1 a). x represents an integer of 0 to 5. y represents an integer of 0 to 5. z represents an integer of 1 to 50. When x is an integer of 2 or more, a plurality of R ⁴ Optionally the same or different. When y is an integer of 2 or more, a plurality of R ⁵ Optionally the same or different. When z is an integer of 2 or more, a plurality of R ⁶ Optionally the same or different]

[ chemical formula 22]

[ chemical formula 23]

-CH＝CH ₂ (1b)

[ chemical formula 24]

[2] The epoxy resin according to [1], wherein the ring A is a benzene ring.

[3] The epoxy resin according to [1] or [2], wherein x is an integer of 1 to 3 (preferably 1 or 2, more preferably 1).

[4] The epoxy resin according to any one of [1] to [3], wherein y is an integer of 0 to 3 (preferably 0 or 1, more preferably 0).

[5]According to [1]～[4]The epoxy resin according to any one of the above, wherein the group represented by the formula (1 a) is represented by R ⁶ The proportion of (b) is 40 mol% or more (preferably 60 mol% or more, and more preferably 80 mol% or more) to the total amount (100 mol%).

[6] The epoxy resin according to [1], wherein ring A is a benzene ring, x is 1, and y is 0.

[7] The epoxy resin according to any one of [1] to [6], wherein the weight average molecular weight in terms of standard styrene is 300 to 100000 (preferably 1000 to 10000).

[8] The epoxy resin according to any one of [1] to [7], wherein the epoxy equivalent is 50 to 1000 (preferably 100 to 500).

[9] An epoxy resin composition comprising the epoxy resin according to any one of [1] to [8 ].

[10] The epoxy resin composition according to [9], wherein the content (blending amount) of the epoxy resin is 2 to 90 wt% (preferably 4 to 80 wt%, more preferably 6 to 70 wt%) with respect to the total amount (100 wt%) of the epoxy resin composition.

[11] The epoxy resin composition according to [9] or [10], wherein the proportion of the epoxy resin relative to the total amount (100 wt%) of epoxy compounds contained in the epoxy resin composition is 2 wt% or more (preferably 4 wt% or more, more preferably 6 wt% or more).

[12] The epoxy resin composition according to any one of [9] to [11], further comprising a curing agent and a curing accelerator.

[13] The epoxy resin composition according to any one of [9] to [11], further comprising a curing catalyst.

[14] The epoxy resin composition according to any one of [9] to [13], further comprising an epoxy compound other than the epoxy resin represented by the formula (1).

[15] The epoxy resin composition according to [14], wherein the epoxy compound is an alicyclic epoxy compound.

[16] The epoxy resin composition according to [15], wherein the alicyclic epoxy compound is a compound having an epoxycyclohexyl group.

[17] The epoxy resin composition according to [15] or [16], wherein the alicyclic epoxy compound is a compound represented by the following formula (I).

[ chemical formula 25]

[18] The epoxy resin composition according to any one of [14] to [17], wherein a content (blending amount) of the epoxy compound other than the epoxy resin represented by the formula (1) is less than 70% by weight (preferably less than 60% by weight) relative to a total amount (100% by weight) of the epoxy compounds contained in the epoxy resin composition.

[19] The epoxy resin composition according to any one of [14] to [18], wherein the content (blending amount) of the epoxy compound other than the epoxy resin represented by the formula (1) is 10% by weight or more (preferably 20% by weight or more) relative to the total amount (100% by weight) of the epoxy compounds contained in the epoxy resin composition.

[20] The epoxy resin composition according to any one of [9] to [19], wherein the epoxy resin composition is a composite resin composition.

[21] A cured product of the epoxy resin composition according to any one of [9] to [20 ].

[22] The cured product according to item [21], wherein the degree of curing is 90% or more (preferably 95% or more, more preferably 97% or more).

[23] The cured product according to [21] or [22], wherein the glass transition temperature (Tg) is 100 ℃ or higher (e.g., 100 ℃ to 250 ℃) (preferably 140 ℃ or higher (e.g., 140 ℃ to 250 ℃).

[24] The cured product according to any one of [21] to [23], wherein the coefficient of linear expansion (. Alpha.1) at a temperature of not more than the glass transition temperature is from 40 ppm/DEG C to 100 ppm/DEG C (preferably from 70 ppm/DEG C to 95 ppm/DEG C).

[25] The cured product according to any one of [21] to [24], wherein the linear expansion coefficient (. Alpha.2) at a temperature not lower than the glass transition temperature is from 90 ppm/DEG C to 170 ppm/DEG C (preferably from 90 ppm/DEG C to 160 ppm/DEG C).

[26]According to [21]]～[25]The cured product of any one of the above, wherein the temperature (T) is decreased by 5% by weight _d5 ) Is 330 ℃ or higher (e.g., 330 ℃ to 450 ℃) (preferably 340 ℃ or higher, more preferably 350 ℃ or higher).

[27] The cured product according to any one of [21] to [26], wherein the flexural strength is 40MPa or more (e.g., 40MPa to 200 MPa) (preferably 70MPa or more (e.g., 70MPa to 200 MPa)).

[28] The cured product according to any one of [21] to [27], wherein the flexural modulus is 1500MPa or more (for example, 1500MPa to 2000 MPa) (preferably 1800MPa or more).

[29] The cured product according to any one of [21] to [28], wherein the flexural elongation is 2.0% or more (e.g., 2.0% to 20%) (preferably 2.5% or more (e.g., 2.5% to 20%)).

[30] An electronic product comprising the cured product according to any one of [21] to [29 ].

Industrial applicability of the invention

The epoxy resin of the present disclosure is extremely useful as an electronic material, various composite materials.

Claims

1. An epoxy resin represented by the following formula (1),

[ chemical formula 1]

In the formula (1), the rings A are the same or different and represent an aromatic hydrocarbon ring, R ¹ Identical or different, represents a cyano group, a halogen atom or an alkyl group, R ² The same or different alkyl groups represent a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, an alkoxycarbonyl group, a hydroxyl group, a halogen atom, a nitro group, a cyano group or a substituted amino group, j are the same or different and represent an integer of 0 to 4, k is the same or different and represents an integer of 0 or 1 or more, R is a linear or branched chain ³ The same or different, represent a group represented by the following formula (1-1),

[ chemical formula 2]

In the formula (1-1), R ⁴ Represents an alkylene group having 2 to 4 carbon atoms, R ⁵ Represents an alkylene group having 3 to 6 carbon atoms, R ⁶ Represents any one of the groups represented by the following formulae (1 a) to (1 c), R in formula (1-1) ⁶ At least one of them is a group represented by the formula (1 a), x represents an integer of 0 to 5, y represents an integer of 0 to 5, z represents an integer of 1 to 50, and when x is an integer of 2 or more, a plurality of R' s ⁴ Optionally phase (c)When y is an integer of 2 or more, a plurality of R's may be the same or different ⁵ Optionally the same or different, in the case where z is an integer of 2 or more, a plurality of R ⁶ Optionally the same or different, and optionally,

[ chemical formula 3]

[ chemical formula 4]

-CH＝CH ₂ (1b)

[ chemical formula 5]

In the formula (1 c), R ⁷ Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group.

2. The epoxy resin according to claim 1,

ring A is a benzene ring.

3. The epoxy resin according to claim 1 or 2, wherein,

x is 1.

4. The epoxy resin according to any one of claims 1 to 3, wherein,

y is 0.

5. An epoxy resin composition comprising the epoxy resin according to any one of claims 1 to 4.

6. The epoxy resin composition according to claim 5, wherein,

also contains a curing agent and a curing accelerator.

7. The epoxy resin composition according to claim 5, wherein,

also contains a curing catalyst.

8. The epoxy resin composition according to any one of claims 5 to 7, wherein,

and an epoxy compound other than the epoxy resin represented by the formula (1).

9. The epoxy resin composition according to claim 8, wherein,

the epoxy compound is an alicyclic epoxy compound.

10. The epoxy resin composition according to claim 9, wherein,

the alicyclic epoxy compound is a compound having an epoxycyclohexyl group.

11. The epoxy resin composition according to claim 9 or 10, wherein,

the alicyclic epoxy compound is a compound shown in the following formula (I),

[ chemical formula 6]

In the formula (I), X represents a single bond or a linking group, and the linking group is a divalent group having one or more atoms.

12. The epoxy resin composition according to any one of claims 5 to 11, wherein,

the epoxy resin composition is a composite resin composition.

13. A cured product of the epoxy resin composition according to any one of claims 5 to 12.

14. An electronic product comprising the cured product according to claim 13.