Novel epoxy resin and epoxy resin composition

Abstract

The purpose of the present disclosure is to provide a novel epoxy resin and epoxy resin composition thereof that can provide a cured product having excellent heat resistance and mechanical properties and can be used as electronic materials and 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. 2 represents a hydrocarbon group, an alkoxy group, etc. j represents an integer of 0 to 4. k represents an integer of 0 or more than 1. 3 represents a group represented by the following formula (1-1)] [In the formula (1-1), R 4 represents an alkylene group having 2 to 4 carbon atoms. 5 represents an alkylene group having 3 to 6 carbon atoms. 6 represents any one of the groups represented by the following formulae (1a) to (1c), wherein R in the formula (1-1) 6 At least one of the groups is a group represented by formula (1a). 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

Technical Field

[0001] The present disclosure relates to a novel epoxy resin and an epoxy resin composition containing the epoxy resin. In more detail, it relates to a novel epoxy resin capable of providing a cured product having excellent heat resistance and mechanical properties, and an epoxy resin composition containing the epoxy resin. This application claims priority to Japanese Patent Application No. 2020-086059 filed in Japan on May 15, 2020, and its contents are hereby incorporated by reference. Background Art

[0002] Epoxy resins generally form cured products with excellent properties such as heat resistance, mechanical properties, and electrical properties, and are therefore widely used as adhesives, coatings, laminates, electronic materials such as molded products, and various composite materials.

[0003] As such epoxy resins, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol (trimethylolpropane) [e.g., trade name "EHPE3150" (manufactured by Daicel Corporation)] are used as various composite materials such as sealants for optical semiconductors, electronic materials such as substrates, curing agents for powder coatings, sizing agents for glass fibers, etc. in order to provide cured products having high reactivity and excellent heat resistance, weather resistance, and electrical properties (e.g., Patent Documents 1 and 2).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 60-161973

[0007] Patent Document 2: Japanese Patent Application Publication No. 2014-156591 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] An object of the present invention is to provide a novel epoxy resin that can provide a cured product having excellent heat resistance and mechanical properties and is useful as an electronic material or various composite materials.

[0010] Another object of the present 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.

[0011] Technical Solution

[0012] The inventors of the present disclosure have conducted intensive studies to solve the above-mentioned problems, and as a result, have discovered the following fact, thereby completing the invention of the present disclosure: an epoxy resin to which 1,2-epoxy-4-(2-oxiranyl)cyclohexane is added to a specific initiator can provide a cured product having excellent heat resistance and mechanical properties, and is useful as an electronic material or various composite materials.

[0013] That is, the present invention provides an epoxy resin represented by the following formula (1).

[0014] [Chemical formula 1]

[0015]

[0016] [In formula (1), ring A is the same or different and represents an aromatic hydrocarbon ring. 1 are the same or different and represent a cyano group, a halogen atom or an alkyl group. 2 are the same or different and represent a hydrocarbon group, an alkoxy group, a cycloalkyloxy 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 are the same or different and represent an integer of 0 or more than 1. R 3 are the same or different and represent a group represented by the following formula (1-1)]

[0017] [Chemical formula 2]

[0018]

[0019] [In formula (1-1), R 4 represents an alkylene group having 2 to 4 carbon atoms. 5 represents an alkylene group having 3 to 6 carbon atoms. 6 represents any one of the groups represented by the following formulae (1a) to (1c), wherein R in the formula (1-1) 6 At least one of the R is a group represented by formula (1a). 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 When y is an integer greater than 2, a plurality of R 5 When z is an integer greater than 2, multiple R 6 optionally the same or different]

[0020] [Chemical formula 3]

[0021]

[0022] [Chemical formula 4]

[0023] -CH=CH2 (1b)

[0024] [Chemical formula 5]

[0025]

[0026] [In formula (1c), 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].

[0027] In the epoxy resin, ring A may be a benzene ring.

[0028] In the epoxy resin, x may be 1.

[0029] In the epoxy resin, y may be 0.

[0030] Furthermore, the presently disclosed invention provides an epoxy resin composition containing the epoxy resin.

[0031] Alternatively, the epoxy resin composition may further contain a curing agent and a curing accelerator.

[0032] The epoxy resin composition may further contain a curing catalyst.

[0033] The epoxy resin composition may further contain an epoxy compound other than the epoxy resin represented by the formula (1).

[0034] In the epoxy resin composition, the epoxy compound may be an alicyclic epoxy compound.

[0035] In the epoxy resin composition, the alicyclic epoxy compound may be a compound having an epoxycyclohexyl group.

[0036] In the epoxy resin composition, the alicyclic epoxy compound may be a compound represented by the following formula (I).

[0037] [Chemical formula 6]

[0038]

[0039] [In formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms)].

[0040] Alternatively, the epoxy resin composition may be a composite resin composition.

[0041] Furthermore, the present invention provides a cured product of the epoxy resin composition.

[0042] Furthermore, the present invention provides an electronic product including the cured product.

[0043] Effects of the Invention

[0044] Since the epoxy resin disclosed herein has the above-mentioned structure, a cured product having excellent heat resistance and mechanical properties can be formed by curing an epoxy resin composition containing the epoxy resin. Therefore, the epoxy resin disclosed herein is extremely useful as an electronic material or various composite materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 is the epoxy resin obtained in Example 1 1 H-NMR spectrum. DETAILED DESCRIPTION

[0046] <Epoxy resin>

[0047] The epoxy resin of the present disclosure (hereinafter, sometimes referred to as “epoxy resin (A)”) is represented by the following formula (1).

[0048] [Chemical formula 7]

[0049]

[0050] In formula (1), ring A is the same or different and represents 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 ring include: a condensed bicyclic hydrocarbon ring (for example, an indene ring, a naphthalene ring, etc.); 8-20 A fused bicyclic hydrocarbon ring, preferably C 10-16 The preferred aromatic hydrocarbon rings include benzene ring, naphthalene ring, anthracene ring, etc., preferably benzene ring and naphthalene ring, and more preferably benzene ring. It should be noted that the two rings A substituted at the 9-position of fluorene may be different rings or the same ring.

[0051] It should be noted that, when ring A is a condensed polycyclic aromatic hydrocarbon ring, the substitution position of ring A substituted at the 9-position of fluorene is not particularly limited. For example, the naphthyl substituted at the 9-position of fluorene can be 1-naphthyl, 2-naphthyl, etc., and 2-naphthyl is particularly preferred.

[0052] In formula (1), R 1 The same or different groups represent cyano, halogen or alkyl groups, preferably alkyl groups. Examples of halogen atoms include fluorine, chlorine and bromine atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl groups. 1-6 Alkyl (preferably C 1-4It should be noted that the R substituted on the two benzene rings constituting fluorene (or fluorene skeleton) 1 are optionally the same or different. In addition, R 1 The bonding position (substitution position) of the benzene ring constituting fluorene is not particularly limited.

[0053] In 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 even more preferably 0. It should be noted that when j is an integer of 2 or more, the plurality of R in formula (1) 1 In addition, in the two benzene rings constituting fluorene, j are optionally the same or different.

[0054] In formula (1), R 2 are the same or different and represent a hydrocarbon group, an alkoxy group, a cycloalkyloxy 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. 2 are optionally the same or different. In addition, R 2 The bonding position (substitution position) of Ring A is not particularly limited.

[0055] Examples of the hydrocarbon group include alkyl groups (e.g., 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 (cyclopentyl, cyclohexyl, etc. C 5-10 Cycloalkyl, preferably C 5-8 Cycloalkyl, more preferably C 5-6 cycloalkyl, etc.); aryl [e.g., phenyl, alkylphenyl (methylphenyl (or tolyl, 2-methylphenyl, 3-methylphenyl, etc.), dimethylphenyl (xylyl) etc.), naphthyl, etc. C 6-10 Aryl, preferably C 6-8 Aryl, especially phenyl, etc.]; Aralkyl (benzyl, phenethyl, etc. C 6-10 Aryl-C 1-4 Alkyl, etc.)

[0056] Examples of the alkoxy group include methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, tert-butoxy and the like. 1-20 Alkoxy, preferably C 1-8 Alkoxy, more preferably C 1-6 Examples of the cycloalkoxy group include cyclohexyloxy and C 5-10 Examples of the aryloxy group include C 6-10Examples of the aralkyloxy group include C 6-10 Aryl-C 1-4 Examples of the alkylthio group include methylthio, ethylthio, propylthio, n-butylthio, tert-butylthio, and the like. 1-20 Alkylthio, preferably C 1-8 Alkylthio, more preferably C 1-6 Examples of the cycloalkylthio group include cyclohexylthio and the like. 5-10 Examples of the arylthio group include phenylthio and the like. 6-10 Examples of the aralkylthio group include C 6-10 Aryl-C 1-4 Examples of the acyl group include C 2-hydroxy-2-yl group, ... 1-6 Examples of the alkoxycarbonyl group include C 1-4 Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Examples of the substituted amino group include N,N-dimethylamino and other N,N-diC 1-6 Alkylamino, etc.

[0057] As R 2 , preferably a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an acyl group, a halogen atom, a nitro group, a cyano group, a substituted amino group, more preferably a hydrocarbon group [e.g., an alkyl group (e.g., C 1-6 Alkyl)], alkoxy (C 1-4 alkoxy group, etc.), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), etc.

[0058] In 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, further preferably 0. It should be noted that when k is an integer of 2 or more, the plurality of R in formula (1) 2 In addition, in the two rings A, k is optionally the same or different.

[0059] In formula (1), R 3 are the same or different and represent a group represented by the following formula (1-1). 3 Optionally the same or different.

[0060] [Chemical formula 8]

[0061]

[0062] In the above formula (1-1), R 4represents an alkylene group having 2 to 4 carbon atoms, for example, ethylene, propylene, trimethylene, butylene, tetramethylene, etc., and ethylene and propylene are preferred from the perspective 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 even more preferably 1. It should be noted that when x is an integer of 2 or more, the plurality of R in formula (1-1) 4 Optionally the same or different.

[0063] In the above formula (1-1), R 5 represents an alkylene group having 3 to 6 carbon atoms, for example, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc., and tetramethylene and pentamethylene are preferred 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 further preferably 0. When y is an integer of 2 or more, the plurality of R in formula (1-1) 5 Optionally the same or different.

[0064] In the formula (1-1), z represents an integer of 1 to 50. The sum (total) of z in the formula (1) is an integer of 3 to 100.

[0065] In formula (1-1), R 6 is a substituent on the cyclohexane ring shown in the formula, and represents any one of the groups represented by the following formulae (1a) to (1c). 6 The bonding position of is not particularly limited, but is usually the carbon atom at the 4th or 5th position when the positions of the two carbon atoms of the cyclohexane ring bonded to the oxygen atom are set to the 1st or 2nd position. In addition, when the epoxy resin (A) of the present disclosure has a plurality of cyclohexane rings, R in each cyclohexane ring is 6 The bonding positions of are optionally the same or different.

[0066] [Chemical formula 9]

[0067]

[0068] [Chemical formula 10]

[0069] -CH=CH2 (1b)

[0070] [Chemical formula 11]

[0071]

[0072] R in formula (1-1) 6 At least one of the R is a group (epoxy group) represented by formula (1a). That is, the epoxy resin (A) disclosed in the present invention has at least one epoxy group in the molecule. It should be noted that when z is an integer greater than 2, the multiple R in formula (1-1)6 Optionally the same or different. In addition, the epoxy resin (A) of the present disclosure has two or more R 6 In the case of 6 Optionally the same or different.

[0073] In formula (1c), 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 a linear or branched alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and a 2-ethylhexyl group. Examples of the alkylcarbonyl group include an alkylcarbonyl group such as a methylcarbonyl (acetyl group), an ethylcarbonyl group, a n-propylcarbonyl group, an isopropylcarbonyl group, a n-butylcarbonyl group, an isobutylcarbonyl group, a sec-butylcarbonyl group, and a tert-butylcarbonyl group. Examples of the arylcarbonyl group include a benzoyl group and a naphthoyl group.

[0074] Examples of the substituents that the alkyl group, alkylcarbonyl group, and arylcarbonyl group may have include substituents having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms). Examples of the substituents include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; hydroxyl groups; alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups, and isobutoxy groups (preferably C 1-6 Alkoxy, more preferably C 1-4 Alkoxy); allyloxy and other alkenyloxy (preferably C 2-6 Alkenyloxy, more preferably C 2-4 phenyloxy, tolyloxy, naphthoxy and the like may have C 1-4 Alkyl, C 2-4 Alkenyl, halogen atom, C 1-4 Alkoxy and other substituted aryloxy (preferably C 6-14 aryloxy); benzyloxy, phenethoxy and other aralkyloxy (preferably C 7-18 arylalkyloxy); acetoxy, propionyloxy, (meth)acryloyloxy, benzoyloxy and other acyloxy groups (preferably C 1-12 acyloxy); mercapto; alkylthio such as methylthio and ethylthio (preferably C 1-6 Alkylthio, more preferably C 1-4 alkylthio); allylthio and other alkenylthio (preferably C 2-6 Alkenylthio, more preferably C 2-4 phenylthio, tolylthio, naphthylthio, etc. may have C 1-4 Alkyl, C 2-4 Alkenyl, halogen atom, C 1-4Arylthio (preferably C 6-14 arylthio); arylalkylthio such as benzylthio, phenethylthio (preferably C 7-18 arylalkylthio); carboxyl; alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl (preferably C 1-6 phenyloxycarbonyl, tolyloxycarbonyl, naphthoxycarbonyl and other aryloxycarbonyl (preferably C 6-14 Aryloxy-carbonyl); Aralkyloxycarbonyl such as benzyloxycarbonyl (preferably C 7-18 Aralkyloxy-carbonyl); amino; mono- or di-alkylamino such as methylamino, ethylamino, dimethylamino, diethylamino (preferably mono- or di-C 1-6 alkylamino); acetylamino, propionylamino, benzylamino and other acylamino groups (preferably C 1-11 ethyloxetaneoxy and other oxetane-containing groups; acetyl, propionyl, benzoyl and other acyl groups; oxo groups; two or more of these groups may be optionally C 1-6 A group formed by an alkylene bond, etc.

[0075] The group (epoxy group) represented by formula (1a) is relative to R in the epoxy resin (A) of the present disclosure. 6 The ratio of the total amount (100 mol%) is not particularly limited, but is preferably 40 mol% or more (e.g., 40 mol% to 100 mol%), more preferably 60 mol% or more, and further preferably 80 mol% or more. If the above ratio is less than 40 mol%, the heat resistance and mechanical properties of the cured product may become insufficient. It should be noted that the above ratio can be, for example, 1 The calculation can be performed by measuring the H-NMR spectrum and the oxygen concentration of ethylene oxide.

[0076] 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 preferred.

[0077] The epoxy resin (A) disclosed in the present invention is not particularly limited and is produced by the following method: using a hydroxyl-containing fluorene compound represented by the following formula (2) as an initiator (i.e., using the hydroxyl group (active hydrogen) of the compound as the starting point), 1,2-epoxy-4-vinylcyclohexane (3-vinyl-7-oxabicyclo[4.1.0]heptane) is subjected to ring-opening polymerization (cationic polymerization), and then epoxidized using an oxidizing agent.

[0078] [Chemical formula 12]

[0079]

[0080] In the above formula (2), R 3aare the same or different and represent a group represented by the following formula (2-1). 3a In the above formula (2), ring A, R 1 , R 2 The definitions, examples, and preferred embodiments of rings A, R, and k are the same as those of rings A, R, and k in the above formula (1). 1 , R 2 , j and k are the same.

[0081] [Chemical formula 13]

[0082]

[0083] In the above formula (2-1), R 4 , R 5 The definitions, examples, and preferred embodiments of x and y are the same as those of R in the above formula (1-1). 4 , R 5 , x, and y are the same.

[0084] The hydroxyl-containing fluorene compound represented by formula (2) can be prepared by a known method. 3a As a starting material, for example, according to the method described in Japanese Patent Application Laid-Open No. 2009-155256, ethylene oxide, propylene oxide and the like are reacted with C 2-4 The hydroxyl-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 alkylene oxide. 1-4 The ring-opening polymerization of alkylene oxides may use different types of alkylene oxides, or different types of alkylene oxides may be polymerized in stages. For example, by ring-opening polymerization of ethylene oxide followed by ring-opening polymerization of propylene oxide, it is possible to produce a propylene oxide having x being an integer greater than 2 and having a plurality of R 4 Different hydroxyl-containing fluorene compounds represented by formula (2).

[0085] Moreover, as needed, according to conventional methods, a lactone compound such as δ-valerolactone and ε-caprolactone can be ring-opening added / polymerized to a hydroxyl-containing fluorene compound represented by formula (2) in which y in formula (2-1) is 0, thereby producing a hydroxyl-containing fluorene compound represented by formula (2) in which y in formula (2-1) is 1 to 5.

[0086] As the hydroxyl-containing fluorene compound represented by formula (2), a commercially available product may be used. As a commercially available product of the hydroxyl-containing fluorene compound represented by formula (2), 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene [trade name "BPEF", manufactured by Osaka Gas Chemicals (Co., Ltd.)], 9,9-bis(4-hydroxyphenyl)fluorene [trade name "BPF", manufactured by Osaka Gas Chemicals (Co., Ltd.)], 9,9-bis(4-hydroxy-3-methylphenyl)fluorene [trade name "BCF", manufactured by Osaka Gas Chemicals (Co., Ltd.)], etc. may be used.

[0087] In particular, from the viewpoint of mold release properties during molding, the epoxy resin (A) is preferably an epoxy resin produced by the following method: in the presence of a fluorine-containing cationic polymerization catalyst, a hydroxyl-containing fluorene compound represented by formula (2) is used as an initiator to ring-opening polymerize 1,2-epoxy-4-vinylcyclohexane, and then epoxidize it using an oxidizing agent.

[0088] The above-mentioned 1,2-epoxy-4-vinylcyclohexane can be produced by a known or customary method without particular limitation, and can be obtained, for example, by partially epoxidizing 4-vinylcyclohexene obtained by dimerization reaction of butadiene using an oxidizing agent such as peracetic acid. In addition, as 1,2-epoxy-4-vinylcyclohexane, a commercially available product (for example, trade name "CELLOXIDE2000" (manufactured by Daicel Corporation)) can also be used.

[0089] The amount of the above-mentioned 1,2-epoxy-4-vinylcyclohexane used can be appropriately selected according to the desired degree of polymerization of 1,2-epoxy-4-vinylcyclohexane in the epoxy resin (A) (z in formula (1-1)), for example, it can be appropriately selected from the range of 1 equivalent to 20 equivalents, preferably 2 equivalents to 15 equivalents, and more preferably 3 equivalents to 10 equivalents relative to the hydroxyl group of the hydroxyl-containing fluorene compound represented by formula (2).

[0090] As the above-mentioned fluorine-containing cationic polymerization catalyst, Bronsted acid and Lewis acid having fluorine atoms can be listed, but are not particularly limited. For example, boron trifluoride, boron trifluoride etherate (e.g., diethyl ether complex of boron trifluoride, etc.) can be listed. The amount of the fluorine-containing cationic polymerization catalyst 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) relative to 100 parts by weight of 1,2-epoxy-4-vinylcyclohexane.

[0091] The temperature (reaction temperature) for ring-opening polymerization of 1,2-epoxy-4-vinylcyclohexane is not particularly limited, but is preferably -70°C to 200°C, more preferably -30°C to 100°C. The reaction time can be appropriately adjusted depending on the conversion rate of 1,2-epoxy-4-vinylcyclohexane and the like.

[0092] The ring-opening polymerization of 1,2-epoxy-4-vinylcyclohexane can 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, and methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether; aliphatic hydrocarbons such as hexane and heptane; esters such as ethyl acetate, etc. can be used. It should be noted that the solvent can be used alone or in combination of two or more.

[0093] By ring-opening polymerization of 1,2-epoxy-4-vinylcyclohexane using the hydroxyl-containing fluorene compound represented by the above formula (2) as an initiator, a compound represented by the following formula (3) (resin having a vinyl group) is generated. The compound can be directly subjected to the next reaction (epoxidation) or the next reaction can be subjected to the next reaction after purification. The purification method is not particularly limited, for example, it can be a known or customary method such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof.

[0094] [Chemical formula 14]

[0095]

[0096] In the above formula (3), R 3b are the same or different and represent a group represented by the following formula (3-1). 3b In the above formula (3), ring A, R 1 , R 2 The definitions, examples, and preferred embodiments of rings A, R, and k are the same as those of rings A, R, and k in the above formula (1). 1 , R 2 , j and k are the same.

[0097] [Chemical formula 15]

[0098]

[0099] In the above formula (3-1), R 4 , R 5 The definitions, examples, and preferred embodiments of x, y, and z are the same as those of R in the above formula (1-1). 4 , R 5 , x, y, and z are the same.

[0100] More specifically, the ring-opening polymerization can be carried out according to the method described in Japanese Patent Application Laid-Open No. 60-161973, for example.

[0101] Next, the vinyl group of the compound represented by the formula (3) is epoxidized with an oxidizing agent, thereby obtaining the epoxy resin (A) (epoxy resin represented by the formula (1)).

[0102] As the above-mentioned oxidant, known or commonly used oxidants such as hydrogen peroxide and organic peracids can be used without particular limitation. For example, as organic peracids, performic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid, etc. can be listed. Among them, peracetic acid can be obtained cheaply in industry and has high stability, so it is preferred. It should be noted that the oxidant can be used alone or in combination of two or more.

[0103] When the compound represented by formula (3) is reacted (epoxidation) with an organic peracid, a known or commonly used catalyst may be used. Examples of the catalyst include bases such as sodium carbonate and acids such as sulfuric acid.

[0104] The above reaction (epoxidation) can be carried out by determining whether or not to use a solvent, or by adjusting the reaction temperature, depending on the apparatus used and the physical properties of the raw materials.

[0105] The temperature (reaction temperature) at which the above reaction is carried out can be appropriately determined according to the reactivity of the oxidant used, and is not particularly limited. For example, when peracetic acid is used as the oxidant, it is preferably 0° C. to 70° C. When the reaction temperature is lower than 0° C., the reaction may proceed too slowly, while when the reaction temperature exceeds 70° C., peracetic acid may be easily decomposed.

[0106] In the above reaction, a solvent may be used for the purpose of reducing the viscosity of the raw material, stabilizing the raw material by diluting the oxidant, etc. When peracetic acid is used as the oxidant, 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, etc. may be used as the solvent.

[0107] The amount of the oxidant used in the above reaction relative to the vinyl group of the compound represented by formula (3) (charging molar ratio) is not particularly limited. For example, when peracetic acid is used as the oxidant, it is preferably used in an amount of 1 to 1.5 times the molar amount relative to the vinyl group.

[0108] Through the above reaction, part or all of the vinyl groups of the compound represented by formula (3) are epoxidized and converted into the groups (epoxy groups) represented by formula (1a), thereby generating the epoxy resin (epoxy resin (A)) represented by formula (1). It should be noted that the group represented by formula (1c) in formula (1) is generated, for example, by the following method: the organic acid (such as acetic acid) generated by the reaction of the vinyl group of the compound represented by formula (3) with an organic peracid, the water, alcohol, etc. present in the system react with the group represented by formula (1a) (side reaction), etc. It should be noted that the ratio (ratio) of the groups represented by formula (1a) to formula (1c) in formula (1) can be appropriately adjusted, for example, according to the type of oxidant, the amount of oxidant used (molar ratio of oxidant to vinyl group), reaction conditions, etc.

[0109] The epoxy resin (A) obtained by the above reaction can be purified by a known or customary method such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography or a combination of these separation methods.

[0110] The epoxy resin (A) may be composed of one epoxy resin represented by the formula (1), or may be composed of two or more epoxy resins represented by the formula (1).

[0111] The weight average molecular weight of epoxy resin (A) in terms of standard styrene is not particularly limited, but is preferably 300 to 100,000, and more preferably 1,000 to 10,000. If 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, if the weight average molecular weight exceeds 100,000, the viscosity may be increased and the fluidity during molding may be reduced. It should be noted that the weight average molecular weight may be measured, for example, by gel permeation chromatography (GPC).

[0112] The epoxy equivalent of the epoxy resin (A) is not particularly limited, but is preferably 50 to 1000, more preferably 100 to 500. If 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 be insufficient. It should be noted that the epoxy equivalent can be measured, for example, in accordance with JIS K7236:2001.

[0113] The epoxy resin (A) is not particularly limited and may contain fluorine atoms. For example, when the above-mentioned ring-opening polymerization is carried out in the presence of a fluorine-containing cationic polymerization catalyst, there is a tendency for the obtained epoxy resin (A) to contain fluorine atoms. The content of fluorine atoms in the epoxy resin (A) is not particularly limited, and is preferably 100ppm to 30000ppm, and more preferably 2000ppm to 15000ppm. If the content of fluorine atoms is less than 100ppm, the demolding property of the cured product sometimes becomes insufficient. On the other hand, if the content of fluorine atoms exceeds 30000ppm, peeling at the interface with metals, other resins, etc. sometimes occurs easily. It should be noted that the content of fluorine atoms can be measured, for example, by combustion ion chromatography. It should be noted that the fluorine atoms contained in the epoxy resin (A) may be contained as a constituent element of the epoxy resin, or as a constituent element of a component different from the epoxy resin (impurities, etc.), but are not particularly limited. For example, the fluorine atoms may be contained in a form of substitution with at least one of the hydrogen atoms bonded to the carbon atoms in the epoxy resin represented by formula (1). The presence of the CF bond in the epoxy resin represented by formula (1) is, for example, 1 The results were confirmed by H-NMR spectroscopy measurement and the like.

[0114] <Epoxy resin composition>

[0115] The epoxy resin composition disclosed herein 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). In addition to the above essential components, the epoxy resin composition disclosed herein may also contain other components as needed. In addition, in the epoxy resin composition disclosed herein, the epoxy resin (A) may be used alone or in combination of two or more.

[0116] The content (compounding 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% by weight, more preferably 4% to 80% by weight, and further preferably 6% to 70% by weight, relative to the total amount (100% by weight) 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 become 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 decrease.

[0117] The ratio of the epoxy resin (A) to the total amount (100% by weight) of the epoxy compound (epoxy resin) contained in the epoxy resin composition of the present disclosure is not particularly limited, but is preferably 2% by weight or more (e.g., 2% by weight to 100% by weight), more preferably 4% by weight or more, and further preferably 6% by weight or more. If the ratio 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.

[0118] [Other epoxy compounds]

[0119] The epoxy resin composition of the present disclosure may contain epoxy compounds other than the epoxy resin (A) (sometimes referred to as “other epoxy compounds”) within a range that does not impair the inventive effects of the present disclosure. Examples of the other epoxy compounds include known or commonly used epoxy compounds without particular limitation, and include aromatic epoxy compounds such as aromatic glycidyl ether epoxy compounds [e.g., bisphenol A epoxy compounds, bisphenol F epoxy compounds, biphenol epoxy compounds, phenol novolac epoxy compounds, cresol novolac epoxy compounds, cresol novolac epoxy compounds of bisphenol A, naphthalene epoxy compounds, and epoxy compounds obtained from trisphenol methane]; aliphatic epoxy compounds such as aliphatic glycidyl ether epoxy compounds [e.g., aliphatic polyglycidyl ethers]; (i) compounds having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring (aliphatic hydrocarbon ring); (ii) compounds in which an epoxy group is directly bonded to an alicyclic ring by a single bond (excluding the epoxy resin (A)); and (iii) alicyclic epoxy compounds such as hydrogenated aromatic glycidyl ether epoxy compounds. In addition, other epoxy compounds may be used alone or in combination of two or more.

[0120] As the compound having the above-mentioned (i) alicyclic epoxy group, it can be arbitrarily selected from known or commonly used compounds and used. Among them, as the above-mentioned alicyclic epoxy group, it is preferably an epoxy cyclohexyl group. That is, as the compound having the above-mentioned (i) alicyclic epoxy group, from the viewpoint of transparency and heat resistance of the cured product, a compound having an epoxy cyclohexyl group is preferred, and a compound represented by the following formula (I) (alicyclic epoxy compound) is particularly preferred.

[0121] [Chemical formula 16]

[0122]

[0123] In formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group formed by connecting a plurality of these groups.

[0124] Examples of the compound wherein X in the formula (I) is a single bond include 3,4,3',4'-diepoxybicyclohexane and the like.

[0125] Examples of the divalent hydrocarbon group include linear or branched alkylene groups and divalent alicyclic hydrocarbon groups having 1 to 18 carbon atoms. Examples of the linear or branched alkylene groups having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene. Examples of the divalent alicyclic hydrocarbon group include divalent cycloalkylene groups (including cycloalkylidene groups) such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene.

[0126] As the above-mentioned linking group X, a linking group containing an oxygen atom is particularly preferred, and specifically, -CO-, -O-CO-O-, -COO-, -O-, -CONH-; a group formed by connecting a plurality of these groups; a group formed by connecting one or more of these groups to one or more of divalent hydrocarbon groups, etc. As the divalent hydrocarbon group, the groups exemplified above can be listed.

[0127] Representative examples of the alicyclic epoxy compounds represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-10). It should be noted that l and m in the following formulas (I-5) and (I-7) represent integers of 1 to 30, respectively. R in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, and examples thereof include linear or branched alkylene groups such as methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, pentylene, hexylene, heptylene, and octylene. Among them, linear or branched alkylene groups having 1 to 3 carbon atoms such as methylene, ethylene, propylene, and isopropylene are preferred. n1 to n6 in the following formulas (I-9) and (I-10) represent integers of 1 to 30, respectively.

[0128] [Chemical formula 17]

[0129]

[0130] [Chemical formula 18]

[0131]

[0132] As (ii) a compound having an epoxy group directly bonded to an alicyclic ring by a single bond, for example, a compound represented by the following formula (II) can be cited. As the above compound, specifically, 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexylcarboxylate represented by the above formula (I-1), trade name "CELLOXIDE 2021P" (manufactured by Daicel Co., Ltd.) can be cited.

[0133] [Chemical formula 19]

[0134]

[0135] 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 the sum (total) of q in formula (II) is an integer of 3 to 100. R" and R in formula (1-1) above 6 The same represents any one of the groups represented by the above formulas (1a) to (1c). Among them, at least one of the R"s in formula (II) is a group represented by formula (1a). When p is greater than 2, q in each group in () (in parentheses) is optionally the same or different. As the above-mentioned compound, specifically, 1,2-epoxy-4-(2-ethylene oxide) cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (trimethylolpropane), trade name "EHPE3150" (manufactured by Daicel Co., Ltd.), etc. can be listed.

[0136] Examples of the (iii) hydrogenated glycidyl ether epoxy compounds include compounds obtained by hydrogenating bisphenol A epoxy compounds such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane (hydrogenated bisphenol A epoxy compounds); bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane, Compounds obtained by hydrogenating bisphenol F type epoxy compounds such as bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane and bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane (hydrogenated bisphenol F type epoxy compounds); hydrogenated biphenol type epoxy compounds; hydrogenated phenol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds of bisphenol A; hydrogenated naphthalene type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from trisphenol methane, etc.

[0137] The content (compounding amount) of other epoxy compounds in the epoxy resin composition of the present disclosure is not particularly limited, and relative to the total amount (100 weight %) of the epoxy compounds (epoxy resins) contained in the epoxy resin composition, it is preferably less than 70 weight % (for example, 0 weight % or more, less than 70 weight %), and more preferably less than 60 weight %. If the content of other epoxy compounds is more than 70 weight %, the heat resistance and mechanical properties of the cured product sometimes become insufficient. On the other hand, the content (compounding amount) of other epoxy compounds is not particularly limited, and relative to the total amount (100 weight %) of the epoxy compounds (epoxy resins) contained in the epoxy resin composition, it is preferably more than 10 weight %, and more preferably more than 20 weight %. If the content of other epoxy compounds is less than 10 weight %, sometimes the viscosity becomes too high and the operability is reduced.

[0138] [Curing agent]

[0139] The epoxy resin composition disclosed herein may also contain a curing agent (hereinafter sometimes referred to as curing agent (B)) in addition to the epoxy resin (A). The curing agent (B) is a compound that reacts with a compound having an epoxy group such as the epoxy resin (A) to cure the epoxy resin composition. As the curing agent (B), a curing agent known or commonly used as a curing agent for epoxy resins can be used, without particular limitation, for example, an anhydride curing agent, an amine curing agent, an imidazole curing agent, a polythiol curing agent, etc. It should be noted that the curing agent (B) can be used alone or in combination of two or more. Among them, as the curing agent (B), an anhydride curing agent is preferred.

[0140] Examples of the acid anhydride curing agent include: acid anhydrides that are liquid at 25° C., such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, and methylendomethylenetetrahydrophthalic anhydride; and acid anhydrides that are solid at 25° C., such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic anhydride. It should be noted that the acid anhydride curing agent may be used alone or in combination of two or more.

[0141] As the curing agent (B), commercial products may be used. For example, commercial products of the acid anhydride curing agent include: trade names "RIKACID MH-700", "RIKACID MH-700F", "RIKACID HH" (all manufactured by Shin Nippon Chemical Co., Ltd.); trade name "HN-5500" (manufactured by Hitachi Chemical Co., Ltd.), etc.

[0142] The content (compounding 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, relative to 100 parts by weight of the total amount of the compounds having epoxy groups contained in the epoxy resin composition. More specifically, the curing agent (B) is preferably used in a ratio of 0.5 to 1.5 equivalents relative to 1 equivalent of epoxy groups 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 curing becomes insufficient, and sometimes the toughness of the cured product is insufficient, or the yellowing resistance of the cured product is reduced. On the other hand, if the content of the curing agent (B) exceeds 200 parts by weight, the curing becomes insufficient in the same manner, and sometimes the cured product is colored and the hue is easily deteriorated.

[0143] [Curing accelerator]

[0144] 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 the curing speed when a compound having an epoxy group such as an epoxy resin (A) is cured by a curing agent (B). As the above-mentioned curing accelerator (C), a known or commonly used curing accelerator can be used, for example, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or a salt thereof (for example, phenolate, octanoate, p-toluenesulfonate, formate, tetraphenylborate); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or a salt thereof (for example, phenolate, octanoate, p-toluenesulfonate, formate, tetraphenylborate); tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and N,N-dimethylcyclohexylamine; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphines such as phosphate esters and triphenylphosphine; phosphonium compounds such as tetraphenylphosphonium tetra(p-tolyl)borate; organic metal salts such as zinc octanoate and tin octanoate; metal chelates, etc. In addition, the curing accelerator may be used alone or in combination of two or more.

[0145] In addition, as a curing accelerator, for example, commercial products such as those with the trade names "U-CAT SA 506", "U-CAT SA102", "U-CAT 5003", "U-CAT 18X", "12XD" (development products) (all manufactured by San-Apro Co., Ltd.); those with the trade names "TPP-K", "TPP-MK" (all manufactured by Hokko Chemical Industry Co., Ltd.); and those with the trade name "PX-4ET" (manufactured by Nippon Chemical Industry Co., Ltd.) can also be used.

[0146] The content (compounding amount) of the curing accelerator (C) in the epoxy resin composition disclosed herein is not particularly limited, and is preferably 0.1 to 8 parts by weight, more preferably 0.3 to 5 parts by weight, relative to 100 parts by weight of the total amount of the compound having an epoxy group contained in the epoxy resin composition. If the content of the curing accelerator (C) is less than 0.1 parts by weight, curing sometimes becomes insufficient. On the other hand, if the content of the curing accelerator (C) exceeds 8 parts by weight, sometimes the storage property deteriorates, the cured product is colored, and the hue is easily deteriorated.

[0147] [Curing catalyst]

[0148] The epoxy resin composition of the present disclosure may also include a curing catalyst (hereinafter, sometimes referred to as a curing catalyst (D)) instead of the above-mentioned curing agent (B). As in the case where the curing agent (B) is used, by using the curing catalyst (D), the curing reaction of the compound having an epoxy group such as the epoxy resin (A) can be carried out to obtain a cured product. The above-mentioned curing catalyst (D) is not particularly limited, and for example, a cationic catalyst (cationic polymerization initiator) that can generate cationic species by ultraviolet irradiation or heat treatment and can initiate polymerization can be used.

[0149] As the cationic catalyst that produces cationic species by ultraviolet irradiation, for example, hexafluoroantimonate, pentafluorohydroxy antimonate, hexafluorophosphate, hexafluoroarsenate, etc. can be listed. These cationic catalysts can be used alone or in combination of two or more. As the above-mentioned cationic catalyst, for example, commercial products such as trade name "UVACURE1590" (DAICEL-CYTEC (strain) system), trade name "CD-1010", "CD-1011", "CD-1012" (above, U.S. Sartomer system), trade name "Irgacure 264" (Chiba Japan (strain) system), trade name "CIT-1682" (Japan Soda (strain) system) can also be preferably used.

[0150] As a cationic catalyst that generates cationic species by heat treatment, for example, aryl diazonium salts, aryl iodonium salts, aryl sulfonium salts, allene-ion complexes, etc. can be listed. These cationic catalysts can be used alone or in combination of two or more. As the above-mentioned cationic catalyst, for example, commercial products such as trade names "PP-33", "CP-66", "CP-77" (above, (strain) ADEKA system), trade name "FC-509" (3M system), trade name "UVE1014" (GE system), trade name "SAN-AID SI-60L", "SAN-AID SI-80L", "SAN-AID SI-100L", "SAN-AID SI-110L", "SAN-AID SI-150L" (above, Sanshin Chemical Industry (Strain) system), trade name "CG-24-61" (Chiba Japan (Strain) system) can be preferably used. As the above-mentioned cationic catalyst, a chelate compound of a metal such as aluminum, titanium, acetoacetate or diketone and a silanol compound such as triphenylsilanol, or a chelate compound of a metal such as aluminum, titanium, acetoacetate or diketone and a phenol compound such as bisphenol S can be further used.

[0151] The amount (content) of the curing catalyst (D) used is not particularly limited, but is preferably 0.01 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, further preferably 0.05 to 10 parts by weight, and particularly preferably 0.1 to 10 parts by weight, relative to 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) within the above range, a cured product having excellent heat resistance and light resistance can be obtained.

[0152] [additive]

[0153] The epoxy resin composition disclosed herein may contain various additives in addition to the above-mentioned components within the scope of not damaging the inventive effects of the present disclosure. As the above-mentioned additives, for example, when containing compounds having hydroxyl groups such as ethylene glycol, diethylene glycol, propylene glycol, glycerol, etc., the reaction can be slowly carried out. In addition, within the scope of not damaging viscosity and transparency, defoamers, leveling agents, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, surfactants, inorganic fillers such as silicon dioxide and aluminum oxide, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, fluorescent bodies (for example, inorganic fluorescent particles such as fluorescent particles of YAG system, silicate fluorescent particles, etc.), release agents and other conventional additives may also be used. As the amount of these additives used, it is about 5% by weight or less relative to the total amount of the epoxy resin composition.

[0154] The epoxy resin composition disclosed in the present invention is not particularly limited, and can be prepared by mixing and kneading the above-mentioned components in a state where they are heated as required. The above-mentioned kneading method is not particularly limited, and for example, a known or commonly used kneading method such as a dissolver, a homogenizer, a mixer, a kneader, a roller, a bead mill, a rotation and revolution stirring device, etc. can be used.

[0155] From the perspective of operability and processability, the epoxy resin composition of the present disclosure is preferably in a liquid state at room temperature (25°C), and the viscosity (25°C) is preferably 100,000 mPa·s or less (e.g., 200 mPa·s to 100,000 mPa·s), and more preferably 50,000 mPa·s or less (e.g., 200 mPa·s to 50,000 mPa·s). In addition, the glass transition temperature is preferably 120°C to 200°C, and more preferably 130°C to 180°C.

[0156] It should be noted that the above viscosity can be measured by the measurement method described in the Examples.

[0157] In addition, by further heating the epoxy resin composition of the present disclosure to react part of the compound having an epoxy group in the epoxy resin composition, a B-staged epoxy resin composition (epoxy resin composition in a B-stage state) can also be obtained.

[0158] <Cured product>

[0159] By curing the epoxy resin composition (or epoxy resin composition in B-stage state) of the present disclosure by heating, a cured product (referred to as "cured product of the present disclosure") having excellent 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°C to 200°C, more preferably 100°C to 190°C, and further preferably 100°C to 180°C. In addition, the heating time (curing time) during curing is not particularly limited, but is preferably 30 minutes to 600 minutes, more preferably 45 minutes to 540 minutes, and further preferably 60 minutes to 480 minutes. When the curing temperature and curing time are lower than the lower limit of the above range, the curing will become insufficient, and conversely, when the curing temperature and curing time are higher than the upper limit of the above range, the decomposition of the resin component sometimes occurs, so both are not preferred. The curing conditions depend on various conditions and can be appropriately adjusted by shortening the curing time when the curing temperature is high and extending the curing time when the curing temperature is low. The heat curing treatment may be performed in one step, but in order to prevent cracking during curing due to heat generation during curing, the treatment may be performed while increasing the temperature in stages.

[0160] The curing degree of the cured product of the present disclosure is preferably 90% or more, more preferably 95% or more, and further preferably 97% or more. When the curing degree of the cured product of the present disclosure is less than 90%, heat resistance and mechanical properties may become insufficient.

[0161] The degree of curing of the cured product of the present disclosure can be calculated by measuring the heat release of the epoxy resin composition of the present disclosure and the heat release of the cured product of the present disclosure by DSC, and by using the following formula.

[0162] Curing degree (%) = [1-(heat release of cured product / heat release of epoxy resin composition)] × 100

[0163] More specifically, the degree of cure can be measured by the measurement method described in Examples.

[0164] The glass transition temperature (Tg) of the cured product disclosed herein (e.g., a cured product having a degree of cure of 90% or more) is preferably 100°C or more (e.g., 100°C to 250°C), and more preferably 140°C or more (e.g., 140°C to 250°C). If the glass transition temperature is lower than 100°C, the heat resistance of the cured product may sometimes become insufficient depending on the usage scenario. The glass transition temperature of the cured product can be measured by various thermal analyses (DSC (differential scanning calorimeter), TMA (thermomechanical analysis device), etc.), dynamic viscoelasticity measurement, etc., and more specifically, can be measured by the measurement method described in the examples.

[0165] The linear expansion coefficient (α1) of the cured product disclosed in the present invention (for example, a cured product with a degree of cure of 90% or more) below the glass transition temperature is preferably 40ppm / °C to 100ppm / °C, and more preferably 70ppm / °C to 95ppm / °C. In addition, the linear expansion coefficient (α2) of the cured product disclosed in the present invention (for example, a cured product with a degree of cure of 90% or more) above the glass transition temperature is preferably 90ppm / °C to 170ppm / °C, and more preferably 90ppm / °C to 160ppm / °C. It should be noted that the linear expansion coefficients α1 and α2 of the cured product can be measured by TMA, etc., and more specifically, can be measured by the measurement method described in the examples.

[0166] The temperature (T d5 ) is not particularly limited, but is preferably 330°C or higher (e.g., 330°C to 450°C), more preferably 340°C or higher, and further preferably 350°C or higher. By setting the temperature for 5% weight loss to 330°C or higher, the heat resistance of the cured product tends to be further improved.

[0167] The flexural strength of the cured product of the present disclosure (eg, a cured product having a degree of cure of 90% or more) is not particularly limited, but is preferably 40 MPa or more (eg, 40 MPa to 200 MPa), and more preferably 70 MPa or more (eg, 70 MPa to 200 MPa).

[0168] The flexural modulus of the cured product of the present disclosure (eg, a cured product having a degree of cure of 90% or more) is not particularly limited, but is preferably 1500 MPa or more (eg, 1500 MPa to 2000 MPa), and more preferably 1800 MPa or more.

[0169] The bending elongation of the cured product of the present disclosure (eg, a cured product having a degree of cure of 90% or more) is not particularly limited, but is preferably 2.0% or more (eg, 2.0% to 20%), and more preferably 2.5% or more (eg, 2.5% to 20%).

[0170] The flexural strength, flexural modulus and flexural elongation of the cured product can be measured, for example, in accordance with JIS K6911 (for example, under the condition of a bending speed of 2 mm / min), and more specifically, can be measured according to the measurement method described in the Examples.

[0171] The epoxy resin composition of the present disclosure can be cured to form a cured product (cured product of the present disclosure) having excellent heat resistance and mechanical properties, and thus can be suitably used as electronic materials and various composite materials.

[0172] That is, the epoxy resin composition of the present disclosure and its cured product (cured product of the present disclosure) are useful as, for example, insulating materials between layers of electronic components, solder resists for printed substrates, resist materials for cover layers, semiconductor sealing materials, color filters, printing inks, sealants (semiconductor sealants, etc.), coatings, coating agents, adhesives, and all other electrical / electronic materials. In addition, it can also be used in molding materials, adhesives, coatings, electrical insulating materials, laminates, coatings, inks, coatings, sealants, resists, composite materials, substrates, sheets, films, optical elements, optical lenses, optical components, light shaping, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and other fields.

[0173] Furthermore, various composite materials prepared by blending various inorganic fillers, organic fillers, reinforcing fibers, and the like into the epoxy resin composition of the present disclosure can also be used as the above-mentioned electric / electronic materials and the like.

[0174] Examples of inorganic fillers include calcium carbonate, magnesium carbonate, clay, kaolin, calcium phosphate, hydroxyapatite, mica, talc, silicon dioxide, 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, etc. Examples of organic fillers include granular materials of various polymers such as cross-linked polymethyl methacrylate, etc. These can be used alone or in combination of two or more.

[0175] Examples of the reinforcing fibers include carbon fibers, glass fibers, aramid fibers, boron fibers, graphite fibers, silicon carbide fibers, high-strength polyethylene fibers, tungsten carbide fibers, polyparaphenylenebenzobisoxazole fibers (PBO fibers), etc. These may be used alone or in combination of two or more.

[0176] The various solutions disclosed in this specification may be combined with any other features disclosed in this specification.

[0177] Example

[0178] Hereinafter, the invention of the present disclosure will be described in more detail based on the embodiments, but each configuration and their combination in each embodiment is an example, and the addition, omission, substitution and other changes of the configuration can be appropriately made within the scope of the main purpose of the invention of the present disclosure. The present disclosure is not limited by the embodiments, but only by the claims. It should be noted that the unit of the amount of each component of the epoxy resin composition in Table 1 is part by weight.

[0179] The product 1 The H-NMR spectrum was measured using JNM-ECZ400S (manufactured by JEOL Ltd.) using deuterated chloroform as solvent and measuring conditions at 20°C.

[0180] 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, measurement conditions: 40°C, flow rate: 0.350 mL / min, molecular weight: standard polystyrene conversion.

[0181] Comparative Example 1

[0182] [Production of epoxy resin using trimethylolpropane as initiator]

[0183] At room temperature and in a nitrogen atmosphere, 50.0 g (0.373 mol) of trimethylolpropane [manufactured by Tokyo Chemical Industry Co., Ltd.], 694.2 g (5.59 mol) of 1,2-epoxy-4-vinylcyclohexane [manufactured by Daicel Co., Ltd.], and 282.3 g of ethyl acetate were added to a 2 L glass reactor and stirred. The temperature was then raised to 50°C to dissolve the trimethylolpropane. After dissolution, 88.1 g (net amount: 13.2 g) of an ethyl acetate solution (15%) of boron trifluoride diethyl ether complex [manufactured by Stella-Chemifa Co., Ltd.] was added dropwise over 4 hours. After the addition, the mixture was stirred for 1 hour. After the reaction was completed, the temperature was lowered to 45°C, and 387 g of ethyl acetate and 558 g of water were added for washing. After washing, the organic layer was separated.

[0184] 250 g of the separated organic layer (solid content concentration 51.31%) was heated to 60°C, and 277.6 g (1.06 mol) of ethyl acetate solution (29%) of peracetic acid was added dropwise under a nitrogen atmosphere over 2 hours. After the addition, the mixture was stirred for 5 hours. After the reaction was completed, the temperature was lowered to 45°C and washed with water. The separated organic layer was ethyl acetate removed by an evaporator to obtain 140 g of the target product (EHPE3150). The softening point measured by the ring and ball method based on JIS K2207 was 76°C.

[0185] Example 1

[0186] [Production of epoxy resin using 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (Bisphenoxyethanolfluorene) as an initiator]

[0187] At room temperature and in a nitrogen atmosphere, 30.0 g (0.068 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene [manufactured by Osaka Gas Chemicals Co., Ltd.], 127.4 g (1.026 mol) of 1,2-epoxy-4-vinylcyclohexane [manufactured by Daicel Co., Ltd.], and 59.7 g of ethyl acetate were added to a 2 L glass reactor and stirred. The temperature was then raised to 50°C to dissolve the 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene. After dissolution, 16.2 g (net amount: 2.43 g) of an ethyl acetate solution (15%) of a boron trifluoride diethyl ether complex [manufactured by Stella-Chemifa Co., Ltd.] was added dropwise over 1 hour. After the addition, the mixture was stirred for 1 hour. After the reaction was completed, the temperature was lowered to 45°C, and 84.0 g of ethyl acetate and 118.1 g of water were added for washing. After washing, the organic layer was separated.

[0188] The separated organic layer (294.1 g) was heated to 60 °C, and a solution of peracetic acid in ethyl acetate (28%, 333.7 g, 1.23 mol) was added dropwise over 2 hours under a nitrogen atmosphere. After the addition, the mixture was stirred for 5 hours. After the reaction was completed, the temperature was lowered to 45 °C and washed with water. The separated organic layer was evaporated to remove ethyl acetate, and 170 g of the target product (epoxy resin (1)) was obtained. The softening point measured by the ring and ball method based on JIS K2207 was 82 °C.

[0189] The obtained epoxy resin (1) 1 The 1H-NMR spectrum is shown in Figure 1 . Peaks attributed to the fluorene skeleton and phenyl group were observed at chemical shifts (δ) of 7.8 ppm (16H) to 6.7 ppm (16H), and peaks attributed to epoxy groups were observed at chemical shifts (δ) of 2.7 ppm (2H) and 2.5 ppm (1H).

[0190] The weight-average molecular weight in terms of standard styrene conversion measured by GPC for epoxy resin (1) was 1256.

[0191] Example 2, Comparative Examples 2 and 3

[0192] According to the composition in Table 1, each epoxy resin and curing catalyst were mixed and added, and using a planetary mixer (trade name "THINKY MIXER (Awatori Rentaro) AR-250", manufactured by THINKY CORPORATION), they were uniformly blended and defoamed to obtain an epoxy resin composition.

[0193] The epoxy resin composition obtained above was cast into a molding machine and heated under the curing conditions shown in Table 1 to cure it, thereby producing a cured product.

[0194] [Evaluation]

[0195] The following evaluations were carried out on the epoxy resin compositions and cured products obtained in Example 2, Comparative Examples 2 and 3.

[0196] [Viscosity]

[0197] Using an E-type viscometer (model "VISCOMETER TV-22", manufactured by Toki Sangyo Co., Ltd.), the viscosity (mPa·s) at 25 °C of the epoxy resin compositions obtained in Example 2, Comparative Examples 2 and 3 was measured. The results are shown in Table 1.

[0198] [Degree of curing]

[0199] The degree of curing (%) was measured using the epoxy resin compositions and cured products obtained in Example 2, Comparative Examples 2 and 3. The results are shown in Table 1.

[0200] The degree of cure (%) was calculated by comparing the heat release before curing and the residual heat after curing when measured at a temperature increase rate of 5°C / min using a differential scanning calorimeter (DSC6200, manufactured by Hitachi Hightech Science Corporation).

[0201] [Heat resistance (TMA)]

[0202] The glass transition temperature (Tg(TMA)) of the cured products obtained in Example 2 and Comparative Examples 2 and 3 was determined by using a TMA measuring apparatus ("TMA / SS100" manufactured by SII Nanotechnology Co., Ltd.) in accordance with JIS K7197. After measuring the thermal expansion coefficient in the measuring temperature range of 30°C to 300°C at a heating rate of 5°C / min in a nitrogen atmosphere, tangent lines were drawn to the curves before and after the glass transition point, and the glass transition temperature was determined from the intersection of these tangent lines. The results are shown in Table 1.

[0203] Furthermore, the linear expansion coefficients of the cured products obtained in Example 2 and Comparative Examples 2 and 3 were determined by setting the slope of the straight line on the lower temperature side than the glass transition temperature determined above as α1 and setting the slope of the straight line on the higher temperature side than the glass transition temperature as α2. The results are shown in Table 1.

[0204] [Heat resistance (Tg-DTA)]

[0205] The thermal decomposition temperature (temperature at which the weight is reduced by 5%) of the cured products obtained in Example 2 and Comparative Examples 2 and 3 was measured using a differential thermal gravimetric measurement apparatus (TG / DTA) [manufactured by Seiko Instruments Co., Ltd.]. d5 The measurement was performed by heating the sample from 25° C. to 400° C. at a heating rate of 10° C. / min under a nitrogen flow. The results are shown in Table 1.

[0206] [Bending properties]

[0207] The cured products (thickness 4 mm×width 10 mm×length 80 mm) obtained in Example 2, Comparative Examples 2 and 3 were used as samples, and a three-point bending test was performed using a TENSILON universal testing machine (manufactured by Orientec) under the conditions of edge span: 67 mm and bending speed 2 mm / min to measure the bending strength, bending modulus and bending elongation of the cured products. The results are shown in Table 1.

[0208] [Table 1]

[0209]

[0210] In Example 2, compared with Comparative Example 2 in which epoxy resin (1) is not added and Comparative Example 3 in which 45 parts by weight of EHPE3150 is added instead of epoxy resin (1), an increase in the glass transition temperature (Tg) is observed. In addition, the flexural modulus is not reduced, and the flexural strength and flexural elongation (especially flexural elongation) are greatly improved.

[0211] As described above, it is understood that the epoxy resin composition including the epoxy resin of the present disclosure provides a cured product that exhibits superior heat resistance and / or mechanical properties than the epoxy resin composition of the comparative example including EHPE3150.

[0212] It should be noted that the components in Table 1 are as follows.

[0213] [Epoxides]

[0214] CELLOXIDE 2021P: Trade name: “CELLOXIDE 2021P” (3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexylcarboxylate, manufactured by Daicel Corporation).

[0215] EHPE3150: the epoxy resin produced in Comparative Example 1.

[0216] Epoxy resin (1): the epoxy resin produced in Example 1.

[0217] [Curing catalyst]

[0218] SI-100L: Trade name “SAN-AID SI-100L” (manufactured by Sanshin Chemical Industry Co., Ltd.).

[0219] Hereinafter, modifications of the present disclosure described above will be described.

[0220] [1] An epoxy resin, wherein the epoxy resin is an epoxy resin represented by the following formula (1).

[0221] [Chemical formula 20]

[0222]

[0223] [In formula (1), ring A is the same or different and represents an aromatic hydrocarbon ring. 1 are the same or different and represent a cyano group, a halogen atom or an alkyl group. 2 are the same or different and represent a hydrocarbon group, an alkoxy group, a cycloalkyloxy 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 are the same or different and represent an integer of 0 or more than 1. R 3 are the same or different and represent a group represented by the following formula (1-1)]

[0224] [Chemical formula 21]

[0225]

[0226] [In formula (1-1), R 4 represents an alkylene group having 2 to 4 carbon atoms. 5 represents an alkylene group having 3 to 6 carbon atoms. 6 represents any one of the groups represented by the following formulae (1a) to (1c), wherein R in the formula (1-1) 6 At least one of the R is a group represented by formula (1a). 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 When y is an integer greater than 2, a plurality of R 5 When z is an integer greater than 2, multiple R 6 optionally the same or different]

[0227] [Chemical formula 22]

[0228]

[0229] [Chemical formula 23]

[0230] -CH=CH2 (1b)

[0231] [Chemical formula 24]

[0232]

[0233] [In formula (1c), 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].

[0234] [2] The epoxy resin according to [1], wherein ring A is a benzene ring.

[0235] [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).

[0236] [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).

[0237] [5] The epoxy resin according to any one of [1] to [4], wherein the group represented by formula (1a) is 6The ratio of the total amount (100 mol %) is 40 mol % or more (preferably 60 mol % or more, more preferably 80 mol % or more).

[0238] [6] The epoxy resin according to [1], wherein ring A is a benzene ring, x is 1, and y is 0.

[0239] [7] The epoxy resin according to any one of [1] to [6], wherein the weight average molecular weight calculated as standard styrene is 300 to 100,000 (preferably 1,000 to 10,000).

[0240] [8] The epoxy resin according to any one of [1] to [7], wherein the epoxy equivalent is 50 to 1000 (preferably 100 to 500).

[0241] [9] An epoxy resin composition comprising the epoxy resin according to any one of [1] to [8].

[0242]

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

[0243]

[11] The epoxy resin composition according to [9] or

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

[0244]

[12] The epoxy resin composition according to any one of [9] to

[11] , further comprising a curing agent and a curing accelerator.

[0245]

[13] The epoxy resin composition according to any one of [9] to

[11] , further comprising a curing catalyst.

[0246]

[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).

[0247]

[15] The epoxy resin composition according to

[14] , wherein the epoxy compound is an alicyclic epoxy compound.

[0248]

[16] The epoxy resin composition according to

[15] , wherein the alicyclic epoxy compound is a compound having an epoxycyclohexyl group.

[0249]

[17] The epoxy resin composition according to

[15] or

[16] , wherein the alicyclic epoxy compound is a compound represented by the following formula (I).

[0250] [Chemical formula 25]

[0251]

[0252] [In formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms)].

[0253]

[18] An epoxy resin composition according to any one of

[14] to

[17] , wherein the content (compounding amount) of the epoxy compound other than the epoxy resin represented by the formula (1) is less than 70 wt % (preferably less than 60 wt %) relative to the total amount (100 wt %) of the epoxy compounds contained in the epoxy resin composition.

[0254]

[19] An epoxy resin composition according to any one of

[14] to

[18] , wherein the content (compounding amount) of the epoxy compound other than the epoxy resin represented by the formula (1) is 10 wt % or more (preferably 20 wt % or more) relative to the total amount (100 wt %) of the epoxy compounds contained in the epoxy resin composition.

[0255]

[20] The epoxy resin composition according to any one of [9] to

[19] , wherein the epoxy resin composition is a composite resin composition.

[0256]

[21] A cured product, which is a cured product of the epoxy resin composition according to any one of [9] to

[20] .

[0257]

[22] The cured product according to

[21] , wherein the degree of cure is 90% or more (preferably 95% or more, more preferably 97% or more).

[0258]

[23] The cured product according to

[21] or

[22] , wherein the glass transition temperature (Tg) is 100°C or higher (e.g., 100°C to 250°C) (preferably 140°C or higher (e.g., 140°C to 250°C)).

[0259]

[24] The cured product according to any one of

[21] to

[23] , wherein the linear expansion coefficient (α1) below the glass transition temperature is 40 ppm / °C to 100 ppm / °C (preferably 70 ppm / °C to 95 ppm / °C).

[0260]

[25] The cured product according to any one of

[21] to

[24] , wherein the linear expansion coefficient (α2) above the glass transition temperature is 90 ppm / °C to 170 ppm / °C (preferably 90 ppm / °C to 160 ppm / °C).

[0261]

[26] The cured product according to any one of

[21] to

[25] , wherein the temperature at which the weight is reduced by 5% (T d5 ) is 330°C or higher (for example, 330°C to 450°C) (preferably 340°C or higher, more preferably 350°C or higher).

[0262]

[27] The cured product according to any one of

[21] to

[26] , wherein the flexural strength is 40 MPa or more (e.g., 40 MPa to 200 MPa) (preferably 70 MPa or more (e.g., 70 MPa to 200 MPa)).

[0263]

[28] The cured product according to any one of

[21] to

[27] , wherein the flexural modulus is 1500 MPa or more (e.g., 1500 MPa to 2000 MPa) (preferably 1800 MPa or more).

[0264]

[29] The cured product according to any one of

[21] to

[28] , wherein the bending elongation is 2.0% or more (e.g., 2.0% to 20%) (preferably 2.5% or more (e.g., 2.5% to 20%)).

[0265]

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

[21] to

[29] .

[0266] Industrial Applicability

[0267] The epoxy resin disclosed in the present invention is extremely useful as electronic materials and various composite materials.

Claims

1. An epoxy resin composition comprising an epoxy resin (A) represented by the following formula (1), and an epoxy compound (A') other than the epoxy resin (A), wherein the content of the epoxy compound (A') is 10% by weight or more and less than 70% by weight relative to 100% by weight of the total amount of the epoxy resin (A) and the epoxy compound (A'), [Chemical formula 1] In formula (1), ring A is the same or different and represents an aromatic hydrocarbon ring, and R 1 are the same or different, representing a cyano group, a halogen atom or an alkyl group, R 2 are the same or different and represent a hydrocarbon group, an alkoxy group, a cycloalkyloxy 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 are the same or different and represent an integer of 0 or more; R 3 are the same or different and represent a group represented by the following formula (1-1), [Chemical formula 2] In 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 (1a) to (1c), wherein R in the formula (1-1) 6 At least one of them is a group represented by formula (1a), x represents an integer of 0 to 5, y represents an integer of 0 to 5, and z represents an integer of 1 to 50. When x is an integer of 2 or more, a plurality of R 4 are optionally the same or different, and when y is an integer greater than 2, a plurality of R 5 are optionally the same or different, and when z is an integer greater than 2, a plurality of R 6 optionally the same or different, [Chemical formula 3] [Chemical formula 4] -CH=CH2 (1b) [Chemical formula 5] In formula (1c), 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 composition according to claim 1, wherein Ring A is a benzene ring.

3. The epoxy resin composition according to claim 1 or 2, wherein x is an integer from 1 to 3.

4. The epoxy resin composition according to claim 1 or 2, wherein x is 1.

5. The epoxy resin composition according to claim 1 or 2, wherein y is an integer from 0 to 3.

6. The epoxy resin composition according to claim 1 or 2, wherein y is 0.

7. The epoxy resin composition according to claim 1 or 2, wherein The group represented by formula (1a) is relative to R 6 The ratio of the total amount, that is, 100 mol %, is 40 mol % or more.

8. The epoxy resin composition according to claim 1, wherein Ring A is a benzene ring, x is 1, and y is 0.

9. The epoxy resin composition according to claim 1 or 2, wherein The epoxy resin (A) has a weight average molecular weight of 300 to 100,000 in terms of standard polystyrene.

10. The epoxy resin composition according to claim 1 or 2, wherein The epoxy equivalent of the epoxy resin (A) is 50 to 1000.

11. The epoxy resin composition according to claim 1 or 2, wherein The content, ie, the amount of the epoxy resin (A) is 2 to 90% by weight relative to 100% by weight of the total amount of the epoxy resin composition.

12. The epoxy resin composition according to claim 1 or 2, wherein It also contains a curing agent and a curing accelerator.

13. The epoxy resin composition according to claim 1 or 2, wherein It also contains a curing catalyst.

14. The epoxy resin composition according to claim 1 or 2, wherein The epoxy compound (A') is an alicyclic epoxy compound.

15. The epoxy resin composition according to claim 14, wherein The alicyclic epoxy compound (A') is a compound having an epoxycyclohexyl group.

16. The epoxy resin composition according to claim 14, wherein The alicyclic epoxy compound (A') is a compound represented by the following formula (I): [Chemical formula 6] In formula (I), X represents a single bond or a linking group, and the linking group is a divalent group having one or more atoms.

17. The epoxy resin composition according to claim 1 or 2, wherein The epoxy resin composition is a composite resin composition. 18 . A cured product, which is a cured product of the epoxy resin composition according to claim 1 .

19. The cured product according to claim 18, wherein The curing degree is more than 90%.

20. The cured product according to claim 18 or 19, wherein The glass transition temperature Tg is 100°C or higher.

21. The cured product according to claim 18 or 19, wherein The linear expansion coefficient α1 below the glass transition temperature is 40 to 100 ppm / °C.

22. The cured product according to claim 18 or 19, wherein The linear expansion coefficient α2 above the glass transition temperature is 90 to 170 ppm / °C.

23. The cured product according to claim 18 or 19, wherein Temperature T at which 5% weight reduction occurs d5 It is above 330°C.

24. The cured product according to claim 18 or 19, wherein The bending strength is 40 MPa or more.

25. The cured product according to claim 18 or 19, wherein The flexural modulus is 1500 MPa or more.

26. The cured product according to claim 18 or 19, wherein The bending elongation is 2.0% or more. 27 . An electronic product comprising the cured product according to claim 18 .

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