Epoxy compound and method for producing the same and application

Abstract

To provide an epoxy compound having high solvent solubility.SOLUTION: There is provided a new epoxy compound represented by the following formula (1) (wherein, R1 and R2 each independently represents a substituent, n1 and n2 each independently represents an integer of 0 or more, ring Z1 and ring Z2 each independently represents an arene ring, A1 and A2 each independently represents an alkylene group, m1 and m2 each independently represents an integer of 0 or more, R3 and R4 each independently represents a hydrogen atom or a substituent, R5 represents a substituent, k represents an integer of 0 to 4, Ar represents a condensed polycyclic arene ring, R6 represents a substituent and s represents an integer of 0 or more.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to an epoxy compound having a specific fluorene skeleton, and a production method and use thereof. [Background technology]

[0002] Generally, epoxy resins are cured with various curing agents to form cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc. Therefore, epoxy resins are used in a wide range of fields such as adhesives, paints, laminates, molding materials, and casting materials. Bisphenol A type epoxy resins are known as the epoxy resins most widely used industrially.

[0003] However, with the rapid technological innovation in recent years, further improvement of the above properties is required. For example, epoxy resins used as electronic materials such as semiconductor sealants are required to have various high-performance properties such as high refractive index, high heat resistance, and low viscosity. In response to this, epoxy compounds having a fluorene skeleton (9,9-bisphenylfluorene skeleton) have been proposed as epoxy resins with high refractive index and high heat resistance.

[0004] Japanese Patent Laid-Open Publication No. 2005-162785 (Patent Document 1) discloses epoxy compounds having a fluorene skeleton, such as 9,9-bis(4-glycidyloxyphenyl)fluorene (bisphenol fluorene diglycidyl ether, BPFG), which are compounds having a fluorene skeleton that can be added to a thermoplastic resin to simply and efficiently impart excellent functions such as a high refractive index to the thermoplastic resin and mold it. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2005-162785 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, epoxy resins having a fluorene skeleton such as BPFG have low solubility in solvents and are not easy to handle.

[0007] Therefore, an object of the present disclosure is to provide an epoxy compound having high solvent solubility and a method for producing the same. [Means for solving the problem]

[0008] Means of the Invention The present inventors conducted extensive research to achieve the above object and discovered that a novel epoxy compound having a specific fluorene skeleton has high solvent solubility, thereby completing the present disclosure.

[0009] That is, the epoxy compound according to embodiment [1] of the present disclosure is represented by the following formula (1).

[0010] [ka]

[0011] (In the formula, R 1 and R 2 each independently represents a substituent; n1 and n2 each independently represent an integer of 0 or more; Ring Z 1 and Z 2 each independently represents an arene ring, A 1 and A 2 each independently represents an alkylene group; m1 and m2 each independently represent an integer of 0 or more; R 3 and R 4 each independently represents a hydrogen atom or a substituent, R 5 represents a substituent, k represents an integer of 0 to 4, Ar represents a fused polycyclic arene ring; R 6 represents a substituent, and s represents an integer of 0 or more.

[0012] The embodiment [2] of the present disclosure is an embodiment in which Ar in formula (1) of the embodiment [1] above represents a naphthalene ring.

[0013] The embodiment [3] of the present disclosure relates to the above embodiment [1] or [2], wherein in formula (1), ring Z 1 and Z 2 are independently a monocyclic arene ring, a fused polycyclic arene ring, or a ring-assembly arene ring.

[0014] The embodiment [4] of the present disclosure relates to a compound represented by formula (1) of any one of the embodiments [1] to [3] above, wherein the ring Z 1 and Z 2 are independently a benzene ring or a biphenyl ring.

[0015] The embodiment [5] of the present disclosure is an embodiment in which m1 and m2 are 0 in formula (1) of any one of the above embodiments [1] to [4].

[0016] The embodiment [6] of the present disclosure relates to a compound represented by the formula (1) of any one of the embodiments [1] to [5] above, wherein R 3 and R 4 each independently represents a hydrogen atom or an alkyl group; and n1, n2, k and s each represent 0.

[0017] The present disclosure also includes, as an embodiment [7], a method for producing an epoxy compound of any one of the embodiments [1] to [6] above, by reacting a compound represented by the following formula (2) with a compound represented by the following formula (3) and a compound represented by the following formula (4).

[0018] [ka]

[0019] (In the formula, R 1 and R 2 each independently represents a substituent; n1 and n2 each independently represent an integer of 0 or more; Ring Z1 and Z 2 each independently represents an arene ring, A 1 and A 2 each independently represents an alkylene group; m1 and m2 each independently represent an integer of 0 or more; R 5 represents a substituent, k represents an integer of 0 to 4, Ar represents a fused polycyclic arene ring; R 6 represents a substituent, and s represents an integer of 0 or more.

[0020] [ka]

[0021] (In the formula, R 3 and R 4 each independently represents a hydrogen atom or a substituent, X 1 and X 2 each independently represents a halogen atom)

[0022] The present disclosure also includes, as an embodiment [8], a liquid composition containing the epoxy compound according to any one of the embodiments [1] to [6] above and a solvent.

[0023] The embodiment [9] of the present disclosure is the embodiment [8], wherein the epoxy compound is represented by the formula (1) in which the ring Z 1 and Z 2 is an epoxy compound having a naphthalene ring, and the solvent is an aromatic hydrocarbon.

[0024] The present disclosure also includes, as an embodiment

[10] , a curable composition containing the epoxy compound according to any one of the embodiments [1] to [6] above.

[0025] The present disclosure also includes, as an embodiment

[11] , a cured product of the curable composition of the embodiment

[10] .

[0026] The present disclosure also includes, as an embodiment

[12] , a molded article formed from the cured product of the embodiment

[11] .

[0027] In the present specification and claims, the number of carbon atoms of a substituent is represented by C 1 , C 6 , C 10 For example, an alkyl group with one carbon atom is represented as "C 1 Alkyl groups with 6 to 10 carbon atoms are indicated as "C 6-10 Aryl group”.

[0028] Furthermore, in this specification and claims, when a numerical range is indicated using "X to Y," the numerical range is intended to include both ends, X and Y. Effect of the Invention

[0029] The present disclosure can provide an epoxy compound having high solvent solubility. [Brief description of the drawings]

[0030] [Figure 1] FIG. 1 is a 1H-NMR spectrum of BNBFG obtained in Example 1. [Diagram 2] FIG. 2 is a 1H-NMR spectrum of BOPPBFG obtained in Example 2. [Diagram 3] FIG. 3 is a 1H-NMR spectrum of BPBFG obtained in Example 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] [Epoxy compounds] The epoxy compound of the present disclosure is represented by formula (1).

[0032] In the formula (1), ring Z 1 and Z 2 In the present specification and claims, the term "independently" means that the two components are independent components, and the ring Z1 and Z 2 In this case, the ring Z 1 and Ring Z 2 This means that the arene rings do not necessarily have to be the same as each other, but may be different arene rings.

[0033] In the present disclosure, the novel epoxy compound has a specific fluorene skeleton, so that the solvent solubility can be improved even if the epoxy compound has a fluorene skeleton. In addition, the refractive index and heat resistance can be improved, and the thermosetting property is also excellent, probably because the epoxy compound has a specific fluorene skeleton.

[0034] In the formula (1), Z 1 and Z 2 Examples of the arene ring (aromatic hydrocarbon ring) represented by the formula (1) include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, etc. Examples of the polycyclic arene ring include a condensed polycyclic arene ring (condensed polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (ring-assembled polycyclic aromatic hydrocarbon ring), etc.

[0035] The fused polycyclic arene ring includes, for example, fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. The fused bicyclic arene ring includes, for example, fused bicyclic C rings such as naphthalene ring and indene ring. 10-16 Examples of the fused tricyclic arene ring include fused tricyclic C arene rings such as anthracene ring and phenanthrene ring. 14-20 A preferred fused polycyclic arene ring is a fused polycyclic C ring such as a naphthalene ring. 10-14 It is an arene ring.

[0036] Examples of the ring-assembled arene ring include C phenyl ring, phenylnaphthalene ring, binaphthyl ring, etc. 12-20 Biarene ring; o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, etc. 18-30 Preferred ring-assembly arene rings include C 12-18 This is a biarene ring.

[0037] In the present specification and claims, a "ring assembly arene ring" refers to two or more ring systems (arene ring systems) directly linked by single bonds or double bonds, and the number of bonds directly linking the rings is one less than the number of ring systems; for example, as described above, a phenylnaphthalene ring, a binaphthyl ring, and the like are classified as ring assembly arene rings even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as a naphthalene ring (non-ring assembly arene ring).

[0038] Ring Z 1 and Z 2 may be either a monocyclic arene ring or a polycyclic arene ring, but from the viewpoint of easiness in improving the solvent solubility, a monocyclic arene ring or a ring assembly arene ring is preferred, and a ring assembly arene ring is particularly preferred. 1 and Z 2 As for C 6-14 arene rings, and more preferably C rings such as benzene rings, naphthalene rings, and biphenyl rings. 6-12 Ring Z is an arene ring, more preferably a benzene ring or a biphenyl ring, and most preferably a biphenyl ring. 1 and Ring Z 2 may be different, but are preferably the same.

[0039] In the fused ring in which a benzene ring and a fused polycyclic arene ring Ar are fused via a five-membered ring, the ring Z bonded to the five-membered ring 1 and Z 2 The substitution position of is not particularly limited, but for example, 1 and Z 2 When the ring Z is a naphthalene ring, it may be at either the 1-position or the 2-position, but the 2-position is preferred. 1 and Z 2 When is a biphenyl ring, it may be at any of the 2-, 3- and 4-positions, but the 3-position is preferred.

[0040] In this specification and claims, the fused ring skeleton in which the benzene ring and the fused polycyclic arene ring Ar are fused via a 5-membered ring in the formula (1) may be referred to as an "Ar-containing fused ring skeleton."

[0041] In the formula (1), A 1 and A 2 each independently represents an alkylene group.

[0042] A 1 and A 2 Examples of the alkylene group represented by the formula (I) include an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, a tetramethylene group, and the like. 2-6 These alkylene groups can be used alone or in combination of two or more. 2-4 Alkylene groups are preferred, and C groups such as ethylene and propylene groups are preferred. 2-3 An alkylene group is more preferred, and an ethylene group is most preferred. 1 and an alkylene group A 2 may be different, but are usually the same.

[0043] In the formula (1), m1 and m2 are each an oxyalkylene group. 1 Group and OA 2 The number of repeating groups is indicated, and each independently indicates an integer of 0 or more.

[0044] The repeat numbers m1 and m2 are each 0 or more and can be selected, for example, from the range of integers from 0 to 15, preferably 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 3, 0 to 1, and most preferably 0. The repeat numbers m1 and m2 may be the same or different from each other; when m1 and m2 are integers of 2 or more, two or more alkylene groups A 1 and A 2 The types may be the same or different.

[0045] In this specification and claims, the "repetition number (number of moles added)" may be an average value (arithmetic mean value, additive mean value) or an average number of moles added, and preferred embodiments are the same as the preferred ranges (range of integers) described above.

[0046] In the formula (1), R 3 and R 4 each independently represents a hydrogen atom or a substituent.

[0047] R 3 and R 4 Examples of the substituent represented by the formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. 1-6 Alkyl groups and the like are included. Group R 3 and R 4 As the group R, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable. 3 and group R 4 may be different, but are preferably the same.

[0048] Base (OA 1 ) m1 or group (OA 2 ) m2 The substitution position of the terminal epoxy group (epoxy-containing group) containing the ring Z 1 and Z 2 can be substituted at an appropriate position of ring Z. 1 and Z 2 When is a benzene ring, it is often substituted at the 3- or 4-position of the corresponding phenyl group, with the 4-position being preferred.

[0049] The substitution position of the epoxy-containing group is the ring Z 1 and Z 2is a naphthalene ring, it is often substituted at any one of the 5- to 8-positions of the corresponding naphthyl group. For example, the 1- or 2-position of the naphthalene ring is substituted with respect to the 5-membered ring interposed between the benzene ring and the Ar ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and with respect to this substitution position, a relationship of 1,5-positions, 2,6-positions, etc. is preferred, and a relationship of 2,6-positions is particularly preferred.

[0050] Further, the substitution position of the epoxy-containing group is 1 and Z 2 is a biphenyl ring, the biphenyl ring is often bonded to the 5-membered ring interposed between the benzene ring and the Ar ring at the 3- or 4-position (particularly bonded to the 3-position) and an epoxy-containing group is substituted at the 6- or 4'-position of the biphenyl ring, and it is preferred that the biphenyl ring is bonded to the 5-membered ring at the 3-position and an epoxy-containing group is substituted at the 6-position of the biphenyl ring.

[0051] In the formula (1), R 1 and R 2 each independently represents a substituent.

[0052] base R 1 and R 2 Examples of the substituent represented by the formula (I) include a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, and a substituted amino group.

[0053] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0054] Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0055] The alkyl group includes linear or branched alkyl groups, and C groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and t-butyl groups. 1-10 Alkyl groups, preferably C 1-6 Alkyl groups, more preferably C 1-4 Examples of such groups include alkyl groups.

[0056] Cycloalkyl groups include cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are included.

[0057] The aryl group is a C aryl group such as a phenyl group, a biphenylyl group, or a naphthyl group. 6-12 Aryl groups; mono- or tri-C such as methylphenyl (or tolyl), dimethylphenyl (or xylyl) groups 1-4 Examples include alkyl-phenyl groups.

[0058] Aralkyl groups include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples of such groups include alkyl groups.

[0059] The alkoxy group is a C group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, or a t-butoxy group. 1-10 Examples of the alkyl group include alkoxy groups.

[0060] Acyl groups include C such as acetyl groups. 1-6 Examples include alkyl-carbonyl groups.

[0061] The substituted amino group is a mono- or di-C group such as a monomethylamino group or a dimethylamino group. 1-4 Alkylamino groups; mono- or bis(C 1-4 alkyl-carbonyl)amino groups and the like.

[0062] Typical group R 1 and R 2 Examples of the R group include an alkyl group, an alkoxy group, an acyl group, a nitro group, and a cyano group. 1 and R 2 is an alkyl group, specifically, a C group such as a methyl group. 1-6 Alkyl groups; alkoxy groups, specifically, methoxy groups, etc. 1-4An alkoxy group is particularly preferred; 1-4 The group R is an alkyl group. 1 is the group R 2 may be different, but are preferably the same.

[0063] In the formula (1), n1 and n2 each represent a group R 1 and R 2 Each represents an integer of 0 or more.

[0064] The numbers of substitutions, n1 and n2, are, for example, integers of 0 to 3, preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. When n1 and n2 are each an integer of 2 or more, two or more groups R 1 and R 2 The types may be the same or different.

[0065] The fused polycyclic arene ring represented by Ar is ring Z 1 and Z 2 The preferred fused polycyclic arene rings Ar include the fused bicyclic C 10-16 Arene ring, fused tricyclic C 14-20 Among the condensed polycyclic arene rings, the condensed bicyclic C 10-14 An arene ring is more preferred, and a naphthalene ring is even more preferred.

[0066] In the Ar-containing fused ring skeleton, when the fused polycyclic arene ring Ar is a naphthalene ring, the fused ring formed by condensing the naphthalene ring with the benzene ring via a 5-membered ring forms a benzofluorene skeleton. In the benzofluorene skeleton, the position of the benzene ring fused to the fluorene skeleton may be any of the 1,2-position, 2,3-position, and 3,4-position of the fluorene ring. That is, the structure of the benzofluorene skeleton may be any of the following structures: a benzofluorene skeleton (benzo[a]fluorene with benzene condensed at the 1,2-position) represented by the following formula (a), a benzofluorene skeleton (benzo[b]fluorene with benzene condensed at the 2,3-position) represented by the following formula (b), and a benzofluorene skeleton (benzo[c]fluorene with benzene condensed at the 3,4-position) represented by the following formula (c).

[0067] [ka]

[0068] Among these benzofluorene skeletons, the benzo[b]fluorene skeleton represented by the above formula (b) is preferred since it can effectively improve the solvent solubility of the epoxy compound.

[0069] The chemical formula with position numbers indicating the substitution positions of the 2,3-benzofluorene ring (11H-benzo[b]fluorene) is shown below.

[0070] [ka]

[0071] R 5 Examples of the substituent represented by the formula (I) include a cyano group, a halogen atom, and a hydrocarbon group. Examples of the halogen atom include R 1 and R 2 The halogen atoms exemplified as the halogen atoms of R 1 and R 2 Among the above substituents, an alkyl group is preferred, and1-6 Alkyl groups are more preferred, and C 1-4 Alkyl groups are particularly preferred.

[0072] In the formula (1), k is a substituent R 5 indicates the number of substitutions.

[0073] Substituent R 5 When the number of substitutions k is 2 or more, two or more groups R 5 may be different, but are preferably the same. 5 When the Ar-containing fused ring skeleton is a benzo[b]fluorene skeleton, the bonding position (substitution position) of may be any of the 1-4 positions of the 2,3-benzofluorene ring, but the 2-position is preferred.

[0074] The number of substitutions k may be an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and most preferably 0.

[0075] R 6 Examples of the substituent represented by the formula (I) include a cyano group, a halogen atom, and a hydrocarbon group. Examples of the halogen atom include R 1 and R 2 The halogen atoms exemplified as the halogen atoms of R 1 and R 2 Among the above substituents, an alkyl group is preferred, and 1-6 Alkyl groups are more preferred, and C 1-4 Alkyl groups are particularly preferred.

[0076] In the formula (1), s is a substituent R 6 indicates the number of substitutions.

[0077] Substituent R 6 When the number of substitutions s is 2 or more, two or more groups R 6 The types of the substituents R may be different, but are preferably the same. 6When the Ar-containing fused ring skeleton forms a 2,3-benzofluorene ring, the bonding position (substitution position) of may be any of positions 5 to 10 of the 2,3-benzofluorene ring.

[0078] The number of substitutions s may be an integer of 0 or more, for example, an integer of 0 to 6, preferably an integer of 0 to 3, further preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 0.

[0079] A preferred embodiment of the epoxy compound of the present disclosure may be an epoxy compound in which Ar in formula (1) is a naphthalene ring, for example, an epoxy compound represented by the following formula (1b).

[0080] [ka]

[0081] (In the formula, R 1 , R 2 , n1, n2, Z 1 , Z 2 , A 1 , A 2 , m1, m2, R 3 , R 4 , R 5 ,k,R 6 , s is the same as in formula (1) above)

[0082] Among the epoxy compounds represented by the formula (1b), preferred epoxy compounds are those in which the ring Z in the formula (1b) is 1 and Z 2 Epoxy compounds in which ring Z is a benzene ring 1 and Z 2 Epoxy compounds in which ring Z is a naphthalene ring, 1 and Z 2 is a biphenyl ring.

[0083] Ring Z 1 and Z 2The epoxy compound in which m1 and m2 are benzene rings may be an epoxy compound in which m1 and m2 are 0, for example, bis(glycidyloxyphenyl)-benzofluorenes such as 11,11-bis(4-glycidyloxyphenyl)-benzo[b]fluorene, 11,11-bis(4-glycidyloxy-3-methylphenyl)-benzo[b]fluorene, and 11,11-bis(4-glycidyloxy-3,5-dimethyl-phenyl)-benzo[b]fluorene (particularly, 11,11-bis(glycidyloxyphenyl)-benzo[b]fluorenes).

[0084] Ring Z 1 and Z 2 The epoxy compound in which m1 and m2 are naphthalene rings may be an epoxy compound in which m1 and m2 are 0, for example, bis(glycidyloxynaphthyl)-benzofluorenes such as 11,11-bis(6-glycidyloxy-2-naphthyl)-benzo[b]fluorene and 11,11-bis(5-glycidyloxy-1-naphthyl)-benzo[b]fluorene (particularly, 11,11-bis(glycidyloxynaphthyl)-benzo[b]fluorenes).

[0085] Ring Z 1 and Z 2 The epoxy compound in which m1 and m2 are biphenyl rings may be an epoxy compound in which m1 and m2 are 0, for example, bis(glycidyloxybiphenyl)-benzofluorenes such as 11,11-bis(4-glycidyloxy-3-phenylphenyl)-benzo[b]fluorene and 11,11-bis[4-(4-glycidyloxyphenyl)phenyl]-benzo[b]fluorene (particularly, 11,11-bis(glycidyloxybiphenyl)-benzo[b]fluorenes).

[0086] [Method of manufacturing epoxy compounds] The epoxy compound represented by the formula (1) is not particularly limited, but can be produced by reacting a compound represented by the formula (2) with a compound represented by the formula (3) and a compound represented by the formula (4).

[0087] In the formula (2), R 1 , R 2 , n1, n2, ring Z 1 , ring Z 2 , A 1 , A 2 , m1, m2, R 5 , k, Ar, R 6 , s is the same as in formula (1) above.

[0088] Examples of the compound represented by the formula (2) include bis(4-hydroxyphenyl)-benzofluorene, for example, bis(hydroxyphenyl)-benzofluorenes such as 11,11-bis(4-hydroxyphenyl)-benzo[b]fluorene (particularly, 11,11-bis(hydroxyphenyl)-benzo[b]fluorenes), bis(hydroxynaphthyl)-benzofluorenes such as 11,11-bis(6-hydroxy-2-naphthyl)-benzo[b]fluorene (particularly, 11,11-bis(hydroxynaphthyl)-benzo[b]fluorenes), and bis(hydroxybiphenyl)-benzofluorenes such as 11,11-bis(4-hydroxy-3-phenylphenyl)-benzo[b]fluorene (particularly, 11,11-bis(hydroxybiphenyl)-benzo[b]fluorenes).

[0089] (Method for producing the compound represented by the above formula (2)) The compound represented by the formula (2) can be produced by a conventional method, for example, by reacting a compound represented by the following formula (2a) with a compound represented by the following formula (2b) and a compound represented by the following formula (2c).

[0090] [ka]

[0091] (In the formula, R 5 , k, Ar, R 6 , s is the same as in formula (1) above)

[0092] [ka]

[0093] (In the formula, R 1 , R 2 , n1, n2, Z 1 , Z 2 , A 1 , A 2 , m1, m2 are the same as in formula (1) above)

[0094] The compound represented by the formula (2a) includes 11-benzo[b]fluorenone.

[0095] The purity of the compound represented by the formula (2a) (fluorenones) used in the reaction is not particularly limited, but may usually be 95% by mass or more, and preferably 99% by mass or more.

[0096] Examples of the compounds represented by the formulas (2b) and (2c) include phenols such as phenol; phenylphenols such as o-phenylphenol; and naphthols such as β-naphthol.

[0097] The purity of the compounds represented by the formulas (2b) and (2c) is not particularly limited, but may usually be 95% by mass or more, preferably 97% by mass or more, and more preferably 99% by mass or more.

[0098] The total amount of the compounds represented by the formulas (2b) and (2c) is, for example, 2 to 10 mol, preferably 2 to 8 mol, further preferably 2 to 5 mol, more preferably 2.5 to 4 mol, and most preferably 2.5 to 3.5 mol, relative to 1 mol of the compound represented by the formula (2a).

[0099] The reaction may be carried out in the presence of a catalyst. As the catalyst, an acid catalyst can usually be used. The acid catalyst may be an inorganic acid or an organic acid. The acid catalyst may be a solid acid such as a cation exchange resin.

[0100] Examples of inorganic acids include sulfuric acid, hydrogen chloride, hydrochloric acid, and phosphoric acid. Examples of sulfuric acid include dilute sulfuric acid having a concentration of about 30 to 90% by mass, concentrated sulfuric acid having a concentration of 90% by mass or more, and fuming sulfuric acid. Any sulfuric acid that can be converted to sulfuric acid in the reaction system may be used, and may be a sulfuric acid precursor such as sulfur trioxide. Hydrochloric acid may be an aqueous solution of hydrogen chloride having a concentration of about 5 to 36% by mass, preferably about 20 to 36% by mass.

[0101] The organic acid may be a sulfonic acid, which may be an alkane sulfonic acid, such as methane sulfonic acid.

[0102] The acid catalyst may be used alone or in combination of two or more. Among these, inorganic acids are preferred, and sulfuric acid such as concentrated sulfuric acid is particularly preferred.

[0103] The proportion of the acid catalyst may be 0.05 mol or more relative to 1 mol of the compound represented by the formula (2a), and is, for example, 0.05 to 10 mol, preferably 0.1 to 5 mol, further preferably 0.2 to 4 mol, and further preferably 0.3 to 3 mol.

[0104] In addition to the acid catalyst, a thiol may be used as a co-catalyst. Examples of the thiol include conventional thiols that function as co-catalysts, such as mercaptocarboxylic acid, thiocarboxylic acid, alkyl mercaptan, alkyl mercaptan, and aralkyl mercaptan.

[0105] Examples of the mercaptocarboxylic acid include mercaptoacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, mercaptosuccinic acid, and mercaptobenzoic acid.

[0106] Examples of the thiocarboxylic acid include thioacetic acid and thiooxalic acid.

[0107] Alkyl mercaptans include C mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, and dodecyl mercaptan (1-dodecanethiol). 1-16 Alkyl mercaptans and the like.

[0108] Examples of the aralkyl mercaptan include benzyl mercaptan.

[0109] The thiols may be in the form of a salt, such as an alkali metal salt, for example, a sodium salt.

[0110] These thiols can be used alone or in combination of two or more. 2-6 Carboxylic acid, dodecyl mercaptan, etc. 4-18 Alkyl mercaptans are preferred.

[0111] The proportion of the thiols is preferably 0.001 to 1 mol, more preferably 0.003 to 0.5 mol, further preferably 0.005 to 0.1 mol, and even more preferably 0.01 to 0.05 mol, relative to 1 mol of the compound represented by the formula (2a).

[0112] The reaction (liquid phase reaction) may be carried out in the presence of a solvent inert to the reaction. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; aromatic ethers such as anisole; dialkyl ethers such as diethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; and halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride. These solvents can be used alone or in combination of two or more. Among these, aromatic hydrocarbons such as toluene and cyclic ethers such as dioxane are preferred.

[0113] The proportion of the solvent is, for example, 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 40 to 200 parts by mass, relative to 100 parts by mass of the compound represented by the formula (2a).

[0114] The reaction temperature is not particularly limited, but is, for example, 20 to 200° C., preferably 30 to 100° C., more preferably 40 to 80° C., and more preferably 45 to 70° C. The reaction time can be adjusted depending on the type of raw material, the reaction temperature, the concentration in the solvent, and the like, and is, for example, 30 minutes to 48 hours, preferably 1 to 24 hours, and more preferably 1 to 10 hours.

[0115] The reaction may be carried out with stirring, in air or in an inert atmosphere such as nitrogen or a rare gas, under normal pressure or under pressure, and may be carried out while dehydrating.

[0116] The target product (the compound represented by the formula (2)) may be purified from the reaction mixture after completion of the reaction by a conventional purification method (extraction, crystallization, etc.). In addition, in view of the tendency to easily produce the epoxy compound represented by the formula (1), a method of reacting the compound represented by the formula (2) with the compound represented by the formula (3) and the compound represented by the formula (4) without purifying the compound represented by the formula (2) is preferred, and in view of the tendency to easily produce the epoxy compound represented by the formula (1) with high purity and good yield, a method of purifying the compound represented by the formula (2) and then reacting it with the compound represented by the formula (3) and the compound represented by the formula (4) is preferred.

[0117] (Method for producing the epoxy compound represented by the above formula (1)) In the formulas (3) and (4), X 1 and X 2 Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. These halogen atoms can be used alone or in combination of two or more. Among these, a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred.

[0118] The compounds represented by the formulas (3) and (4) include epihalohydrins (halomethyloxiranes) such as epichlorohydrin (chloromethyloxirane) and epibromohydrin (bromomethyloxirane); 1-halomethyl-2-methyloxirane such as 1-chloromethyl-2-methyloxirane, etc. These compounds can be used alone or in combination of two or more. Among these, epihalohydrins such as epichlorohydrin are preferred.

[0119] The total amount of the compounds represented by the formulas (3) and (4) is, for example, 2 to 30 mol, preferably 2.5 to 25 mol, further preferably 3 to 20 mol, more preferably 4 to 15 mol, and most preferably 5 to 10 mol, relative to 1 mol of the compound represented by the formula (2).

[0120] The reaction may be carried out in the presence of a catalyst. The catalyst may be a base (base catalyst). The base catalyst may be an inorganic base or an organic base.

[0121] Examples of inorganic bases include metal carbonates, metal carboxylates, metal hydroxides, and ammonia. Examples of metal carbonates include alkali metal or alkaline earth metal carbonates such as sodium carbonate, and alkali metal or alkaline earth metal hydrogen carbonates such as sodium hydrogen carbonate. Examples of metal carboxylates include alkali metal or alkaline earth metal acetates such as sodium acetate and calcium acetate. Examples of metal hydroxides include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide.

[0122] The organic base includes amines, basic ion exchange resins, etc. The amines may be tertiary amines such as trialkylamines, benzylalkylamines, aromatic tertiary amines, and heterocyclic tertiary amines. The trialkylamines include triethylamine, triisopropylamine, and tributylamine. The benzylalkylamines include benzyldimethylamine, etc. The aromatic tertiary amines include N,N-dimethylaniline, etc. The heterocyclic tertiary amines include pyridine, etc. The basic ion exchange resins include strongly basic anion exchange resins having quaternary ammonium bases, etc.

[0123] These catalysts can be used alone or in combination of two or more. Among these, inorganic bases are preferred, and alkali metal hydroxides such as sodium hydroxide are preferred.

[0124] The proportion of the catalyst is, for example, 0.01 to 10 mol, preferably 0.1 to 8 mol, further preferably 0.5 to 5 mol, more preferably 1 to 3 mol, and most preferably 1.2 to 2 mol, relative to 1 mol of the compound represented by the formula (2).

[0125] The reaction may be carried out without a solvent or in a solvent inert to the reaction. Examples of such solvents include aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; dialkyl ethers such as diethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; aromatic ethers such as anisole; dialkyl ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK); cyclic ketones such as cyclohexanone; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide (DMSO); and sulfones such as dimethyl sulfone, diphenyl sulfone, and sulfolane.

[0126] These solvents can be used alone or in combination of two or more. Among these, ketones such as methyl isobutyl ketone, and sulfoxides such as DMSO are preferred.

[0127] The proportion of the solvent is, for example, 50 to 1000 parts by mass, preferably 100 to 500 parts by mass, more preferably 150 to 400 parts by mass, and even more preferably 180 to 350 parts by mass, relative to 100 parts by mass of the compound represented by the formula (2).

[0128] The reaction temperature and reaction time can be appropriately selected depending on the type of raw material used. The reaction temperature is, for example, 30 to 120° C., preferably 35 to 100° C., and more preferably 40 to 80° C. The reaction time is, for example, 30 minutes to 48 hours, preferably 1 to 36 hours, and more preferably 2 to 24 hours.

[0129] The reaction may be carried out under reflux or while removing by-products. The reaction may be carried out with stirring, in air or in an inert atmosphere such as nitrogen or a rare gas, or under normal pressure, elevated pressure, or reduced pressure.

[0130] The produced epoxy compound represented by the formula (1) may be separated and purified by a conventional method, for example, a separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination of these separation means.

[0131] The LC purity of the obtained epoxy compound may be 90 area % or more, and is from 90 to 99.9 area %, preferably from 95 to 99.8 area %, and more preferably from 96 to 99.5 area %.

[0132] In the present specification and claims, the LC purity of the epoxy compound can be measured by HPLC, and more specifically, by the method described in the examples below.

[0133] The obtained epoxy compound may contain a polymer (dimer, trimer, etc.) of the epoxy compound represented by the formula (1) as long as the properties of the product are not impaired. The proportion of the polymer is, for example, 0 to 20 parts by mass, preferably 0 to 10 parts by mass, further preferably 0 to 8 parts by mass, more preferably 0 to 5 parts by mass, and most preferably 0 to 3 parts by mass, and may be, for example, 0.1 to 3 parts by mass, relative to 100 parts by mass of the epoxy compound represented by the formula (1).

[0134] [Characteristics and uses of the epoxy compound represented by the above formula (1)] The epoxy compound of the present disclosure (the epoxy compound represented by the formula (1)) has a bulky structure in which an arene ring is further condensed to a bisarylfluorene skeleton, and has properties specific to the fluorene skeleton, such as high heat resistance, high refractive index, etc. Moreover, despite having such a bulky skeleton, it has excellent solvent solubility.

[0135] The refractive index of the epoxy compound of the present disclosure can be selected, for example, from the range of about 1.6 to 1.7 at a temperature of 25° C. and a wavelength of 589 nm, and is preferably 1.62 to 1.69, 1.63 to 1.69, 1.64 to 1.69, and more preferably 1.645 to 1.69 in the following stepwise manner.

[0136] The 5% weight loss temperature of the epoxy compound of the present disclosure is, for example, 250 to 450°C, preferably 300 to 420°C, further preferably 320 to 400°C, further preferably 350 to 390°C, and most preferably 360 to 385°C.

[0137] The epoxy equivalent of the epoxy compound of the present disclosure is, for example, 200 to 1000 g / eq, preferably 230 to 500 g / eq, and more preferably 250 to 350 g / eq.

[0138] In this specification and claims, the refractive index, 5% weight loss temperature and epoxy equivalent of the epoxy compound can be measured by the method described in the examples below.

[0139] [Liquid composition] Since the epoxy compound of the present disclosure has excellent solvent solubility, it is preferable to prepare it as a liquid composition in combination with a solvent.

[0140] Examples of the solvent include hydrocarbons, halogenated hydrocarbons, alcohols, ethers, glycol ethers, glycol ether acetates, ketones, carboxylic acids, esters, carbonates, amides, ureas, nitriles, nitrated hydrocarbons, phosphoramides, sulfones, and sulfoxides.

[0141] Examples of the hydrocarbons include aliphatic hydrocarbons such as hexane and dodecane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene.

[0142] Examples of halogenated hydrocarbons include dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, and dichlorobenzene.

[0143] Alcohols include C12, C22, C32, C42, C52, C62, C72, C82, C92, C102, C12 ... 1-6 Alcohol, etc.

[0144] Examples of the ethers include chain ethers and cyclic ethers. Examples of the chain ethers include di-C ethers such as diethyl ether, diisopropyl ether, and dibutyl ether. 1-6 Examples of the cyclic ethers include 5- to 7-membered ring ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran, 4-methyltetrahydropyran, 1,4-dioxane, 1,3-dioxane, 4-methyl-1,3-dioxane, 1,3-dioxolane, and 2-methyl-1,3-dioxolane.

[0145] Examples of glycol ethers include (poly)alkylene glycol monoalkyl ethers, (poly)alkylene glycol dialkyl ethers, etc. Examples of (poly)alkylene glycol monoalkyl ethers include cellosolves such as methyl cellosolve (ethylene glycol monomethyl ether) and ethyl cellosolve, carbitols such as methyl carbitol and ethyl carbitol, (mono- to hexa)C alkyl ethers such as triethylene glycol monomethyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether. 2-4 Alkylene glycol mono C 1-6 Examples of the (poly)alkylene glycol dialkyl ether include (mono- to hexa)C alkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. 2-4 Alkylene glycol di-C 1-6 Alkyl ethers and the like.

[0146] Examples of glycol ether acetates include cellosolve acetates such as methyl cellosolve acetate, carbitol acetates such as methyl carbitol acetate, (poly)C acetates such as propylene glycol monomethyl ether acetate (PGMEA) and dipropylene glycol monobutyl ether acetate, 2-4 Alkylene glycol mono C 1-4 Alkyl ether acetates and the like.

[0147] Examples of the ketones include chain ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); and cyclic ketones such as cyclohexanone.

[0148] Examples of the carboxylic acids include acetic acid and propionic acid.

[0149] Examples of the esters include chain esters and cyclic esters. Examples of the chain esters include acetates such as methyl acetate, ethyl acetate, and butyl acetate, and lactates such as methyl lactate. Examples of the cyclic esters (or lactones) include 5- to 7-membered ring lactones that may have a substituent, such as γ-butyrolactone, γ-valerolactone, and γ-caprolactone (or γ-hexanolactone).

[0150] Examples of carbonates include linear carbonates and cyclic carbonates. Examples of linear carbonates include di-C carbonates such as dimethyl carbonate (or dimethyl carbonate), ethyl methyl carbonate, and diethyl carbonate (or diethyl carbonate). 1-6 Examples of the cyclic carbonates include 5- to 7-membered cyclic carbonates such as ethylene carbonate (or ethylene carbonate) and propylene carbonate (or propylene carbonate).

[0151] Examples of the amides include linear amides and cyclic amides (or lactams). Examples of the linear amides include N,N-diC amides such as N,N-dimethylformamide (DMF), N,N-diethylformamide, and N,N-dimethylacetamide (DMAc). 1-6 Alkyl-C 1-6 Examples of the cyclic amides include 5- to 7-membered ring lactams such as N-methyl-2-pyrrolidone.

[0152] Examples of ureas (or ureas) include chain ureas and cyclic ureas. Examples of chain ureas include tetra-C ureas such as tetramethylurea, tetraethylurea, and tetraisopropylurea. 1-6Examples of cyclic ureas include N,N'-diC alkyl ureas such as 1,3-dimethyl-2-imidazolidinone (DMI or N,N'-dimethylethyleneurea) and N,N'-dimethyl-N,N'-trimethyleneurea (or N,N'-propyleneurea). 1-6 Examples thereof include alkyl-N,N'-di- or tetramethylene urea.

[0153] Nitriles include, for example, cyanides such as acetonitrile and propionitrile. 1-6 Examples of the cyanide include alkanes, cyanides such as benzonitrile, and the like.

[0154] Examples of sulfones include chain sulfones and cyclic sulfones. Examples of chain sulfones include di-C sulfones such as ethyl methyl sulfone and isopropyl ethyl sulfone. 1-6 Examples of the cyclic sulfones include tri- to hexamethylene sulfones such as sulfolane (or tetramethylene sulfone or tetrahydrothiophene-1,1-dioxide), 3-methylsulfolane, and 2,4-dimethylsulfolane.

[0155] Examples of sulfoxides include di-C sulfoxides such as dimethyl sulfoxide (DMSO). 1-6 Alkyl sulfoxides and the like.

[0156] These solvents can be used alone or in combination of two or more. Among these solvents, hydrocarbons, ketones, glycol ethers, and glycol ether acetates are preferred from the viewpoint of excellent solubility of the epoxy compound of the present disclosure, and aromatic hydrocarbons, chain ketones, cyclic ketones, cellosolves, C 2-4 Alkylene glycol mono C 1-4 Alkyl ether acetates are preferred.

[0157] The epoxy compound of the present disclosure is represented by the formula (1), 1 and Z 2In the case where R is an epoxy compound having a condensed polycyclic arene ring such as a naphthalene ring, the solvent of the liquid composition is preferably an aromatic hydrocarbon. In the case of this epoxy compound, when the solvent is an aromatic hydrocarbon, the effect of improving the solvent solubility is excellent.

[0158] The proportion of the solvent is, for example, 10 to 10,000 parts by mass relative to 100 parts by mass of the epoxy compound represented by the formula (1), and when the solvent is an aromatic hydrocarbon, it may be, for example, 30 to 5,000 parts by mass.

[0159] [Curable composition] The epoxy compound of the present disclosure can be used as a curable composition. The curable composition of the present disclosure may further contain a curing agent in addition to the epoxy compound represented by formula (1). The liquid composition further containing a curing agent can also be used as a curable resin composition.

[0160] Examples of the curing agent include an amine-based curing agent, a polyaminoamide-based curing agent, an acid anhydride-based curing agent, and a phenol resin-based curing agent.

[0161] The amine-based curing agent may be a primary amine. Examples of the primary amine include chain aliphatic polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine; monocyclic aliphatic polyamines such as menthenediamine, isophoronediamine, bis(4-amino-3-methylcyclohexyl)methane, and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; crosslinked cyclic polyamines such as norbornanediamine; aromatic aliphatic polyamines such as xylylenediamine; and aromatic amines such as metaphenylenediamine and diaminodiphenylmethane.

[0162] Examples of the acid anhydride curing agent include aliphatic acid anhydrides such as dodecenyl succinic anhydride and polyadipic anhydride; alicyclic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhimic anhydride and methylcyclohexene dicarboxylic anhydride; and aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride and benzophenone tetracarboxylic anhydride.

[0163] Examples of the phenol resin-based hardener include novolac resins such as phenol novolac resin and cresol novolac resin.

[0164] These curing agents can be used alone or in combination of two or more. Among these, amine-based curing agents are widely used.

[0165] The ratio of the curing agent is 0.1 to 600 parts by mass, preferably 1 to 500 parts by mass, and more preferably 10 to 400 parts by mass, relative to 100 parts by mass of the epoxy compound represented by the formula (1). The ratio of the curing agent may be adjusted so that the functional group of the curing agent is 0 to 4.0 equivalents, preferably 0 to 2.0 equivalents, and more preferably 0 to 1.5 equivalents (e.g., 0.5 to 1.5 equivalents) relative to 1 equivalent of the epoxy group of the epoxy compound.

[0166] The curable composition of the present disclosure may further contain a curing accelerator. Examples of the curing accelerator include amines such as tertiary amines and imidazoles; alkali metal or alkaline earth metal alkoxides; phosphines; amide compounds such as dimer acid polyamide; Lewis acid complex compounds such as boron trifluoride-ethylamine complex; sulfur compounds such as polysulfides and mercaptan compounds (thiol compounds); boron compounds such as phenyldichloroborane; and condensable organometallic compounds such as organotitanium compounds and organoaluminum compounds. These curing accelerators can be used alone or in combination of two or more.

[0167] Among these curing accelerators, tertiary amines and imidazoles are widely used. Tertiary amines include triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]undecene-1, and the like. Imidazoles include alkylimidazoles such as 2-methylimidazole; arylimidazoles such as 2-phenylimidazole, and the like, and their derivatives. Derivatives include salts such as phenol salts, phenol novolac salts, carbonates, and formates.

[0168] The ratio of the curing accelerator is, for example, 0 to 30 parts by mass, preferably 0 to 20 parts by mass, and more preferably 0 to 10 parts by mass, and may be, for example, 0.01 to 30 parts by mass, relative to 100 parts by mass of the epoxy compound represented by the formula (1).

[0169] The curable composition of the present disclosure may further contain a second epoxy compound (another epoxy resin) other than the epoxy compound represented by the formula (1). Examples of the second epoxy resin include a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, and another epoxy resin having a fluorene skeleton.

[0170] Examples of the glycidyl ether type epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins; phenol novolac type epoxy resins; cresol novolac type epoxy resins; dicyclopentadiene modified phenol (or cresol) novolac type epoxy resins; biphenyl type epoxy resins; triphenol alkane type epoxy resins such as triphenol methane type epoxy resins; phenol aralkyl type epoxy resins; heterocyclic type epoxy resins such as epoxy resins containing xanthene units; stilbene type epoxy resins; and condensed ring aromatic hydrocarbon modified epoxy resins (naphthalene ring-containing epoxy resins such as 1,6-bis(glycidyloxy)naphthalene, bis(2,7-bis(glycidyloxy)naphthalene)alkane, etc.).

[0171] Examples of the glycidyl ester type epoxy resin include glycidyl esters of polyvalent carboxylic acids such as diglycidyl ester of phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid.

[0172] Examples of the glycidylamine type epoxy resin include tetraglycidylaminodiphenylmethane and triglycidylaminophenol.

[0173] Other epoxy resins having a fluorene skeleton include 9,9-bis(glycidyloxyphenyl)fluorenes, 9,9-bis[(2-glycidyloxy(poly)ethoxy)phenyl]fluorenes, and the like.

[0174] The ratio of the other epoxy resins may be 100 parts by mass or less, preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and may be, for example, 0.1 to 100 parts by mass, relative to 100 parts by mass of the epoxy compound represented by the formula (1).

[0175] The curable composition of the present disclosure may further contain a solvent. The solvent, including preferred embodiments, may be selected from the solvents exemplified as the liquid composition. The ratio of the solvent may be 500 parts by mass or less, for example, 0 to 400 parts by mass, preferably 0 to 300 parts by mass, more preferably 0 to 200 parts by mass, and may be, for example, 10 to 500 parts by mass, relative to 100 parts by mass of the epoxy compound represented by formula (1).

[0176] The curable composition of the present disclosure may contain conventional additives, such as reactive diluents, colorants, heat stabilizers, antioxidants, UV absorbers, fillers, antistatic agents, flame retardants, and flame retardant assistants. These additives may be used alone or in combination of two or more. The total proportion of these additives may be 50 parts by mass or less, for example, 0 to 40 parts by mass, preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, and may be, for example, 0.1 to 50 parts by mass, relative to 100 parts by mass of the epoxy compound represented by formula (1).

[0177] The molded article of the present disclosure is formed from a cured product of the curable composition. The shape of the molded article is not particularly limited, and may be a one-dimensional shape such as a line, fiber (or fiber), or thread, a two-dimensional shape such as a film, sheet, or plate, or a three-dimensional shape such as a rod or hollow (tube). The molded article is obtained by applying thermal energy or active energy (or active energy rays) to the curable composition to cure it and generate a cured product. EXAMPLES

[0178] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. Details of the abbreviations of the raw materials used in the examples and the evaluation methods in the examples are as follows.

[0179] [Raw material abbreviation] BPBF: 11,11-bis(4-hydroxyphenyl)benzo[b]fluorene BPBFG: 11,11-bis(4-glycidyloxyphenyl)benzo[b]fluorene BNBF: 11,11-bis(6-hydroxy-2-naphthyl)benzo[b]fluorene BNBFG: 11,11-bis(6-glycidyloxy-2-naphthyl)benzo[b]fluorene BOPPBF: 11,11-bis(4-hydroxy-3-phenylphenyl)benzo[b]fluorene BOPPBFG: 11,11-bis(4-glycidyloxy-3-phenylphenyl)benzo[b]fluorene BPFG: 9,9-bis(4-glycidyloxyphenyl)fluorene BNFG: 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene BOPPFG: 9,9-bis(4-glycidyloxy-3-phenylphenyl)fluorene

[0180] [ 1 H-NMR] Deuterated solvent (CDCl) containing tetramethylsilane as an internal standard 3 The sample was dissolved in 1000 ml of ... 1 H-NMR spectrum was measured.

[0181] [LC purity] The sample was dissolved in acetonitrile and the purity [area %] was calculated using a HPLC (high performance or high performance liquid chromatograph) device made by Shimadzu Corporation, a MS unit made by LCMS-2020, and a column made by Phenomenex, Kinetex C-18.

[0182] [Solvent solubility] The samples were adjusted to a concentration of 50 mass % in various solvents (cyclohexanone, PGMEA, MIBK, toluene, methyl cellosolve), and the solvent solubility was evaluated according to the following criteria.

[0183] ◎: When the sample is placed in the solvent and stirred at 25℃ at 350 rpm, it dissolves within 6 hours. ○: When the sample is placed in a solvent and stirred at 50℃ and 350 rpm, it dissolves within 6 hours. ×: The sample is placed in the solvent and stirred at 50°C at 350 rpm for 6 hours, but does not dissolve.

[0184] [Refractive index nD] The refractive index of the epoxy compound was measured at a temperature of 25° C. and a wavelength of 589 nm (D line) using a refractometer (RX-7000i manufactured by Atago Co., Ltd.).

[0185] [5% weight loss temperature] Using a thermogravimetry-differential thermal analyzer (TG-DTA) ("TG / DTA6200" manufactured by SII NanoTechnology, Inc.), the sample was heated in a nitrogen atmosphere from 30°C at a heating rate of 10°C / min, and the temperature at which the sample lost 5% by weight was measured.

[0186] [Melt Viscosity] Using an AMETEK BROOKFIELD "CAP 2000+ VISCOMETER," measurements were taken three times at 150°C and 200°C in accordance with JIS K 5600-2-3, and the average value was calculated.

[0187] [Epoxy equivalent] The solution was titrated with perchloric acid (acetic acid) using an automatic titrator (GT-100, manufactured by Mitsubishi Chemical Corporation).

[0188] Example 1 (Synthesis of BNBF)

[0189] [ka]

[0190] BNBF was synthesized according to the above reaction formula. In detail, 23g (0.1mol) of 11-benzo[b]fluorenone, 43.3g (0.3mol) of β-naphthol, 0.5g (5mmol) of β-mercaptopropionic acid, and 35.2g of 1,4-dioxane were placed in a separable flask, stirred and dissolved at 60°C, and 29.4g (0.3mol, 3eq) of 98% by mass sulfuric acid was dropped into the obtained solution and stirred for 4 hours. After confirming that the conversion rate of the raw materials was 98% or more, 40g of MIBK and 40g of ion-exchanged water were added to remove the aqueous phase, and 40g of ion-exchanged water was added to the organic phase for washing, and this washing operation was repeated five times until the pH was about 4. The obtained organic phase was concentrated under reduced pressure to remove the solvent, and then 150g of methanol was added, cooled from 60°C to room temperature, and then further cooled to 5°C and aged for 12 hours. After aging, the mixture was filtered to obtain 40.00 g of BNBF (reddish brown solid, 80% yield, LC purity 99%).

[0191] (Synthesis of BNBFG)

[0192] [ka]

[0193] BNBFG was synthesized according to the above reaction formula. In detail, 15.65g (31mmol) of BNBF, 25.15g (272mmol) of epichlorohydrin, 14.30g (14mmol) of MIBK, and 28.55g (37mmol) of DMSO were added to a reaction vessel under a nitrogen atmosphere and stirred to dissolve. 2.5g (60mmol) of sodium hydroxide (granules) was added and heated to reflux. After confirming the disappearance of the raw materials, 56.0g of MIBK was added, and 56.0g of distilled water was further added and stirred at 70°C. After removing insoluble matter by filtration, the mixture was concentrated, and the obtained concentrate was reprecipitated with 120mL of methanol. The crystals were filtered off, washed with methanol, and then dried to obtain 14.33g of BNBFG (light orange solid, 75% yield, 99% LC purity). The obtained epoxy compound 1 The results of the H-NMR spectrum are shown in FIG. 1 and below.

[0194] 1 H-NMR (300MHz, CDCl 3 ):δ2.79(2H, q), 2.92(2H, t), 3.37-3.43(2H, m), 4.03(2H, dd), 4.31(2H, dd), 7.09-7.1 3(4H, m), 7.30-7.59(11H, m), 7.65(2H, d), 7.76(1H, d), 7.90-7.99(3H, m), 8.25(1H, s)

[0195] Example 2 (Synthesis of BOPPBF)

[0196] [ka]

[0197] BOPPBF was synthesized according to the above reaction formula. In detail, 23g (0.1mol) of 11-benzo[b]fluorenone, 44.3g (0.26mol) of o-phenylphenol, 0.5g (5mmol) of β-mercaptopropionic acid, and 35.2g of 1,4-dioxane were placed in a separable flask, stirred and dissolved at 60°C, and 29.4g (0.3mol, 3eq) of 98% by mass sulfuric acid was dropped into the obtained solution and stirred for 4 hours. After confirming that the raw materials had disappeared, 40g of MIBK and 40g of ion-exchanged water were added to remove the aqueous phase, and 40g of ion-exchanged water was added to the organic phase for washing, and this washing operation was repeated five times until the pH was about 4. The obtained organic phase was concentrated under reduced pressure to remove the solvent, and then 150g of methanol was added, cooled from 60°C to room temperature, and then further cooled to 5°C and aged for 12 hours. After aging, the mixture was filtered to obtain 26.50 g of BOPPBF (reddish brown solid, yield 48%, LC purity 98%).

[0198] (Synthesis of BOPPBFG)

[0199] [ka]

[0200] BOPPBFG was synthesized according to the above reaction formula. In detail, 20.71g (37mmol) of BOPPBF, 30.17g (326mmol) of epichlorohydrin, 17.14g (17mmol) of MIBK, and 34.29g (44mmol) of DMSO were added to a reaction vessel under a nitrogen atmosphere and dissolved by stirring. 3.0g (70mmol) of sodium hydroxide (granules) was added and heated to reflux. After confirming the disappearance of the raw materials, 74.2g of MIBK was added, 74.2g of distilled water was added, and the mixture was stirred at 70°C. After removing insoluble matter by filtration, the mixture was concentrated, and the obtained concentrate was reprecipitated with 150mL of methanol. The crystals were filtered off, washed with methanol, and then dried to obtain 19.93g of BOPPBFG (white solid, 80% yield, 99% LC purity). The obtained epoxy compound 1 The results of the H-NMR spectrum are shown in FIG. 2 and below.

[0201] 1 H-NMR (300MHz, CDCl 3 ):δ2.63(2H, q), 2.77(2H, t), 3.19-3.25(2H, m), 3.92(2H, dd), 4.15(2H, dd), 6.80(2H, d ), 7.14(2H, dd), 7.27-7.49(17H, m), 7.78(1H, d), 7.84(1H, s), 7.91(2H, d), 8.18(1H, s)

[0202] Example 3 (Synthesis of BPBF)

[0203] [ka]

[0204] BPBF was synthesized according to the above reaction formula. In detail, 196g (0.85mol) of 11-benzo[b]fluorenone, 241g (2.56mol, 3.0eq), 1-dodecanethiol 1.0g (0.01mol, 0.006eq), and 98g of toluene were placed in a separable flask and stirred at 45°C. 43g (0.43mol, 0.5eq) of 98% by mass sulfuric acid was added dropwise to the obtained solution and stirred for 3 hours. After confirming the disappearance of the raw materials, 400g of toluene and 200g of ion-exchanged water were added to remove the aqueous phase, and 200g of ion-exchanged water was added to the organic phase for washing, and this operation was repeated five times until the pH was about 4. The obtained organic phase was concentrated under reduced pressure to remove the solvent, and then 1L of methanol was added, heated to 60°C and dissolved, and 660g of ion-exchanged water was heated to 60°C and stirred, and the previous methanol solution was added dropwise to the obtained solution to precipitate crystals. The crystallization solution was cooled from 60° C. to room temperature, then cooled to 5° C. and aged for 2 hours. After aging, the solution was filtered to obtain 348.0 g of BPBF (light yellowish white solid, yield 62%, LC purity 99%).

[0205] (Synthesis of BPBFG)

[0206] [ka]

[0207] BPBFG was synthesized according to the above reaction formula. In detail, 15.00g (37mmol) of BPBF, 30.17g (326mmol) of epichlorohydrin, 17.14g (17mmol) of MIBK, and 34.29g (44mmol) of DMSO were added to a reaction vessel under a nitrogen atmosphere and stirred to dissolve. 3.0g (70mmol) of sodium hydroxide (granules) was added and heated to reflux. After confirming the disappearance of the raw materials, 74.2g of MIBK was added, and 74.2g of distilled water was further added and stirred at 70°C. After removing insoluble matter by filtration, the mixture was concentrated, and the obtained concentrate was reprecipitated with 150mL of methanol. The crystals were filtered off, washed with methanol, and then dried to obtain 14.70g of BPBFG (light yellow solid, 77% yield, 99% LC purity). The obtained epoxy compound 1The results of the H-NMR spectrum are shown in FIG.

[0208] 1 H-NMR (300MHz, CDCl 3 ):δ2.71(2H, q), 2.87(2H, t), 3.28-3.33(2H, m), 3.90(2H, dd), 4.14(2H, dd), 6.7 8(4H, dt), 7.17(4H, dt), 7.28-7.48(5H, m), 7.76(2H, t), 7.91(2H, d), 8.18(1H, s)

[0209] Reference example 1 BNFG was obtained in accordance with the method described in Synthesis Example 1 in the Examples of JP 2012-102228 A.

[0210] Reference example 2 BOPPFG was obtained in accordance with the method described in Synthesis Example 4 in the Examples of JP2012-102228A.

[0211] Reference example 3 BPFG was obtained in accordance with the method described in Synthesis Example 2 in the Examples of JP 2012-102228 A.

[0212] The solvent solubility of the epoxy compounds obtained in Examples 1 to 3 and Reference Examples 1 to 3 was evaluated, and the results are shown in Table 1. The refractive index, 5% weight loss temperature, melt viscosity, and epoxy equivalent were evaluated, and the results are shown in Table 2.

[0213] [Table 1]

[0214] As is clear from the results in Table 1, the epoxy compounds of the Examples have superior solvent solubility compared to the Reference Examples, and in particular, the solvent solubility of the epoxy compounds of Examples 2 and 3 was significantly improved compared to the Reference Examples. Among them, the epoxy compound of Example 2 did not precipitate crystals even when stirred at 25°C at a stirring speed of 350 rpm for 20 hours or more, and had the best solvent solubility.

[0215] On the other hand, the epoxy compound of Example 1 had improved solubility in toluene compared to Reference Example 1. Furthermore, the epoxy compound of Reference Example 1 was evaluated as "○", and once completely dissolved at 50°C after 1 hour had elapsed since stirring, but crystals precipitated after 20 hours of continued stirring, possibly due to supersaturation (metastable region).

[0216] [Table 2]

[0217] As is clear from the results in Table 2, the epoxy compounds of the Examples exhibited high refractive index and heat resistance equivalent to those of the epoxy compounds of the Reference Examples. Note that the epoxy compounds of the Examples were thermally cured during the melt viscosity measurement, so the melt viscosity could not be measured. This fact indicates that the epoxy compounds of the Examples have excellent reactivity required for thermosetting resins.

[0218] Example 4 (Synthesis of BNBFG)

[0219] [ka]

[0220] BNBFG was synthesized according to the above reaction formula. That is, in the method for producing BNBFG described in Example 1, after the first reaction step (after the synthesis of BNBF), the crystals were not extracted by crystallization, but were reacted with epichlorohydrin, and then the crystals were extracted by crystallization to produce BNBFG.

[0221] Specifically, 23g (0.1mol) of 11-benzo[b]fluorenone, 43.3g (0.3mol) of β-naphthol, 0.5g (5mmol) of β-mercaptopropionic acid, and 35.2g of 1,4-dioxane were placed in a separable flask, stirred and dissolved at 60°C, and 29.4g (0.3mol, 3eq) of 98% by mass sulfuric acid was added dropwise to the resulting solution and stirred for 4 hours. After confirming that the conversion rate of the raw materials was 98% or more, 60g of MIBK and 60g of ion-exchanged water were added to remove the aqueous phase, 120g of 5% by mass aqueous sodium bicarbonate was added to the organic phase for water washing, and 120g of distilled water was added and stirred. 37.73g (408mmol) of epichlorohydrin and 28.55g (37mmol) of DMSO were added to the resulting organic phase and stirred. Sodium hydroxide (granules) 3.0g (72mmol) was added and heated to reflux. After confirming the disappearance of the raw materials, 56.0g of MIBK was added, followed by 56.0g of distilled water and stirring at 70℃. The mixture was then concentrated, and 300mL of methanol was added to the resulting concentrate for crystallization. The crystals were filtered off, washed with methanol, dissolved by adding MIBK, and 400mL of methanol was added again for crystallization. The crystals were filtered off, washed with methanol, and dried to obtain 35.78g of BNBFG (orange solid, 58% yield, 94% LC purity).

[0222] Example 5 (Synthesis of BOPPBFG)

[0223] [ka]

[0224] BOPPBFG was synthesized according to the above reaction formula. That is, in the method for producing BOPPBFG described in Example 2, after the first reaction stage (after synthesis of BOPPBF), the crystals were not extracted by crystallization, but were reacted with epichlorohydrin, and then the crystals were extracted by crystallization to produce BOPPBFG.

[0225] Specifically, 23g (0.1mol) of 11-benzo[b]fluorenone, 44.3g (0.26mol) of o-phenylphenol, 0.5g (5mmol) of β-mercaptopropionic acid, and 35.2g of 1,4-dioxane were placed in a separable flask, stirred and dissolved at 60°C, and 29.4g (0.3mol, 3eq) of 98% by mass sulfuric acid was added dropwise to the resulting solution and stirred for 4 hours. After confirming that the raw materials had disappeared, 60g of MIBK and 60g of ion-exchanged water were added to remove the aqueous phase, 120g of 5% by mass aqueous sodium bicarbonate solution was added to the organic phase for washing, and 120g of distilled water was added and stirred. 37.73g (408mmol) of epichlorohydrin and 28.55g (37mmol) of DMSO were added to the resulting organic phase and stirred. 3.0g (72mmol) of sodium hydroxide (granules) was added and heated to reflux. After confirming the disappearance of the raw materials, 56.0 g of MIBK was added, followed by 56.0 g of distilled water and stirring at 70°C. The mixture was then concentrated, and 300 mL of methanol was added to the resulting concentrate for crystallization. The crystals were filtered off, washed with methanol, dissolved by adding MIBK, and then crystallized by adding 400 mL of methanol again. The crystals were filtered off, washed with methanol, and dried to obtain 25.39 g of BOPPBFG (white solid, yield 38%, LC purity 94%).

[0226] Example 6 (Synthesis of BPBFG)

[0227] [ka]

[0228] BPBFG was synthesized according to the above reaction formula. That is, in the method for producing BPBFG described in Example 3, after the first reaction step (after synthesis of BPBF), the crystals were not extracted by crystallization, but were reacted with epichlorohydrin, and then the crystals were extracted by crystallization to produce BPBFG.

[0229] Specifically, 23g (0.1mol) of 11-benzo[b]fluorenone, 28.3g (0.30mol, 3.0eq), 0.12g (0.001mol, 0.006eq), and 11.5g of toluene were placed in a separable flask and stirred at 45°C. 5g (0.05mol, 0.5eq) of 98% by mass sulfuric acid was added dropwise to the resulting solution and stirred for 3 hours. After confirming the disappearance of the raw materials, 50g of toluene and 25g of ion-exchanged water were added to remove the aqueous phase, 120g of 5% by mass aqueous sodium bicarbonate was added to the organic phase for washing, and 120g of distilled water was added and stirred. 37.73g (408mmol) of epichlorohydrin and 28.55g (37mmol) of DMSO were added to the resulting organic phase and stirred. 3.0g (72mmol) of sodium hydroxide (granules) was added and heated to reflux. After confirming the disappearance of the raw materials, 56.0 g of MIBK was added, followed by 56.0 g of distilled water and stirring at 70°C. The mixture was then concentrated, and 300 mL of methanol was added to the resulting concentrate for crystallization. The crystals were filtered off, washed with methanol, dissolved by adding MIBK, and then crystallized by adding 400 mL of methanol again. The crystals were filtered off, washed with methanol, and dried to obtain 24.71 g of BPBFG (light yellow solid, 48% yield, 94% LC purity). [Industrial Applicability]

[0230] The epoxy compounds of the present disclosure can be suitably used for applications such as paints, wire coating materials, sealing materials and insulating materials for electronic devices, printed wiring boards, protective films, photoresists, printing plate materials, inks, adhesives, pressure sensitive adhesives, and optical thin films (such as high refractive index layers in anti-reflection films for liquid crystal displays and the like, and reflectors).

Claims

1. An epoxy compound represented by the following formula (1): 【Chemistry 1】 (In the formula, R １ and R ２ each independently represents a substituent; n1 and n2 each independently represent an integer of 0 or more; Ring Z １ and Z ２ each independently represents an arene ring, A １ and A ２ each independently represents an alkylene group; m1 and m2 each independently represent an integer of 0 or more; R ３ and R ４ each independently represents a hydrogen atom or a substituent, R ５ represents a substituent, k represents an integer of 0 to 4, Ar represents a fused polycyclic arene ring; R ６ represents a substituent, and s represents an integer of 0 or more.

2. The epoxy compound according to claim 1, wherein, in the formula (1), Ar represents a naphthalene ring.

3. In the formula (1), ring Z １ and Z ２ The epoxy compound according to claim 1 or 2, wherein each independently represents a monocyclic arene ring, a condensed polycyclic arene ring, or a ring-assembled arene ring.

4. In the formula (1), ring Z １ and Z ２ The epoxy compound according to claim 1 or 2, wherein each independently represents a benzene ring or a biphenyl ring.

5. The epoxy compound according to claim 1 or 2, wherein in the formula (1), m1 and m2 each represent 0.

6. In the formula (1), R ３ and R ４ 3. The epoxy compound according to claim 1 or 2, wherein independently represent a hydrogen atom or an alkyl group, and n1, n2, k and s represent 0.

7. A method for producing the epoxy compound according to claim 1 or 2, comprising reacting a compound represented by the following formula (2) with a compound represented by the following formula (3) and a compound represented by the following formula (4): 【Chemistry 2】 (In the formula, R １ and R ２ each independently represents a substituent; n1 and n2 each independently represent an integer of 0 or more; Ring Z １ and Z ２ each independently represents an arene ring, A １ and A ２ each independently represents an alkylene group; m1 and m2 each independently represent an integer of 0 or more; R ５ represents a substituent, k represents an integer of 0 to 4, Ar represents a fused polycyclic arene ring; R ６ represents a substituent, and s represents an integer of 0 or more. 【Chemistry 3】 (In the formula, R ３ and R ４ each independently represents a hydrogen atom or a substituent, X １ and X ２ each independently represents a halogen atom)

8. A liquid composition comprising the epoxy compound according to claim 1 or 2 and a solvent.

9. The epoxy compound is represented by the formula (1), １ and Z ２ 9. The liquid composition according to claim 8, wherein said epoxy compound has a naphthalene ring, and said solvent is an aromatic hydrocarbon.

10. A curable composition comprising the epoxy compound according to claim 1 or 2.

11. A cured product of the curable composition according to claim 10.

12. A molded article formed from the cured product according to claim 11.

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