Fluorene compound and method for producing the same

Abstract

To provide a fluorene compound exhibiting a high refractive index.SOLUTION: A fluorene compound of the present invention is represented by a formula (1E). [In the formula, Y1a and Y1b each represent a group of a specific structure having an arene ring; k1a and k1b each represent an integer of 0 to 4, at least one of which is 1 or more; R2a and R2b each represent a substituent; m2a and m2b each represent an integer of 0 to 4; k1a+m2a and k1b+m2b each represent 4 or less; and Y3a and Y3b each represent a group of a specific structure having a glycidyl group].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound having a fluorene skeleton and a method for producing the same. [Background technology]

[0002] Compounds with a fluorene skeleton have excellent optical properties due to their chemical structure. It is used as a resin material (optical material) for forming optical components.

[0003] Patent Document 1 discloses an optical material for forming an optical member such as a lens, which is represented by the following formula (1): Thermoplastic resins containing repeating units are disclosed.

[0004] [ka]

[0005] (wherein ring Z represents an aromatic hydrocarbon ring, and R 1 and R 2 is a hydrogen atom, a halogen atom, or an aromatic represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and Ar 1 and Ar 2 represents an aromatic group having 6 to 10 carbon atoms which may contain a substituent, and L 1 and L 2 teeth represents a divalent linking group, j and k represent integers of 0 or more, and m and n represent 0 or 1. and W is at least one selected from the group represented by the following formula (2) or (3):

[0006] [ka]

[0007] (wherein X represents a divalent linking group).

[0008] Patent Document 1 discloses that a raw material monomer for forming the thermoplastic resin is a compound represented by the following formula (a ) is described.

[0009] [ka]

[0010] (In the formula, rings Z, R 1 and R 2 , Ar 1 and Ar 2 , L 1 and L 2 , j and k, m and n are the same as in the above formula (1). [Prior art documents] [Patent documents]

[0011] [Patent Document 1] International Publication No. 2019 / 044214 Summary of the Invention [Problem to be solved by the invention]

[0012] Patent Document 1 describes that ring Z is more preferably a benzene ring (or a 1,4-phenylene group). Furthermore, it is described that many of the diamines represented by the formula (a) are preferable. Among the diol components, diols represented by formulas (a1) to (a24) in which ring Z is a benzene ring The ingredients are also described as being preferred.

[0013] Furthermore, in the examples of Patent Document 1, the diol component represented by the formula (a) is 9, 9-bis[4-(2-hydroxyethoxy)phenyl]-2,7-diphenylfluorene (BPDP2), 9,9-bis[4-(2-hydroxyethoxy)phenyl]-3,6- Diphenylfluorene (BPDP3), 9,9-bis[4-(2-hydroxyethoxy) phenyl]-4,5-diphenylfluorene (BPDP4), 9,9-bis[4-(2- hydroxyethoxy)phenyl]-2,7-di(2-naphthyl)fluorene (BPDN2 ), 9,9-bis[4-(2-hydroxyethoxy)phenyl]-2,7-di(1-naphthyl) Various polycarbonate resins have been prepared using methyl fluorene (BPDN1). It is described that this is effective in increasing the refractive index and heat resistance.

[0014] However, even these polycarbonate resins may not have sufficient refractive index or heat resistance depending on the application. However, this is not always the case, and further improvement is required.

[0015] Therefore, an object of the present invention is to provide a fluorene compound having a high refractive index and a method for producing the same. and a composition containing said compound. [Means for solving the problem]

[0016] As a result of extensive research to achieve the above object, the present inventors have discovered a novel compound having a specific chemical structure. The inventors have found that fluorene compounds exhibit a high refractive index, and have completed the present invention.

[0017] That is, the fluorene compound of the present invention is represented by the following formula (1).

[0018] [ka]

[0019] [In the formula, Y 1a and Y 1b are each independently represented by the following formula (Y1):

[0020] [ka]

[0021] (In the formula, Z 1 indicates an arene ring, R 1 represents a substituent, and m1 represents an integer of 0 or 1 or more. k1a and k1b each independently represent an integer of 0 to 4. , at least one of k1a and k1b is 1 or more; R 2a and R 2b each independently represents a substituent, m2a and m2b each represent a each independently represents an integer from 0 to 4, k1a+m2a and k1b+m2b are each independently 4 or less; Y 2a and Y 2b are each independently represented by the following formula (Y2)

[0022] [ka]

[0023] (In the formula, Z 2 represents a polycyclic arene ring, R 3 represents a substituent, m3 represents an integer of 0 or 1 or more, A 1 represents a linear or branched alkylene group, and n1 represents an integer of 0 or 1 or more. .) represents a monovalent group represented by the formula:

[0024] In the formula (1), Y 1a and Y 1b Z in formula (Y1) represents 1 is a benzene ring, It may be a naphthalene ring or a biphenyl ring, and k1a and k1b are integers of about 0 to 2. It can be a number, Y 2a and Y 2b Z in formula (Y2) represents 2 is a naphthalene ring or The fluorene compound represented by the formula (1) may be a crystalline biphenyl ring. It may be in the form of

[0025] In addition, in the formula (1), Y 1a and Y 1b Z in formula (Y1) represents 1 is condensed poly Polycyclic arene rings such as cyclic arene rings, especially fused polycyclic C1 rings such as naphthalene rings. 0-14 The fluorene compound may be an arene ring. and a resin additive for modifying the resin. It may be one type.

[0026] The present invention relates to a composition (liquid composition or solvent) containing the fluorene compound and a solvent. Includes liquid).

[0027] The present invention also provides a method for producing the fluorene compound, which comprises the reaction step (i) or (ii) described below: It includes the method of manufacturing an item.

[0028] (i) A compound represented by the following formula (2), a compound represented by the following formula (3a), and a compound represented by the following formula ( 3b) and a compound represented by the formula (I)

[0029] [ka]

[0030] [where, X 1a and X 2a and X 1b and X 2b are independently represents a pair of reactive groups capable of forming a carbon-carbon bond by a ring reaction, and Y 1a and Y 1 b , k1a and k1b, R 2a and R 2b , m2a and m2b, and Y 2a oh Yobi Y 2b is the same as the above formula (1)].

[0031] (ii) A compound represented by the following formula (6), a compound represented by the following formula (5a), and a compound represented by the following formula ( 5b) and a compound represented by the formula (I).

[0032] [ka]

[0033] [In the formula, Y 1a and Y 1b , k1a and k1b, R 2a and R 2b , m2a and m2b, and Y 2a and Y 2b is the same as the above formula (1)].

[0034] The production method includes dissolving the fluorene compound obtained in the reaction step in a solvent, for example, ( a) solvents containing aromatic and aliphatic hydrocarbons, and (b) solvents containing ketones Precipitation (crystallization) from at least one solvent (crystallization solvent or reprecipitation solvent) selected from the solvents The present invention may further comprise a purification step (crystallization step or reprecipitation step) of crystallizing the product.

[0035] The present invention includes a fluorene compound represented by the following formula (1E):

[0036] [ka]

[0037] [In the formula, Y 3a and Y 3b are each independently represented by the following formula (Y3):

[0038] [ka]

[0039] (In the formula, R 4 represents a hydrogen atom or a methyl group, Z 2 , R 3 , m3, A 1 and n1 are the same as those in formula (Y2). represents a monovalent group represented by Y 1a and Y 1b is the same as the formula (Y1), k1a and k1b, R 2a and R 2b , m2a and m2b, k1a+m2a and and k1b+m2b are each independently the same as in formula (1).

[0040] The present invention relates to a compound represented by the formula (1) which is reacted with an epihalohydrin component to produce the above compound. The present invention also encompasses a method for producing a compound represented by formula (1E). a curable composition containing a compound represented by formula (E), a cured product obtained by curing the curable composition, and The present invention also includes optical components containing the cured product.

[0041] The present invention may also solve the following problems as a secondary object.

[0042] That is, another object of the present invention is to provide a fluorenated fluorene compound having high heat resistance (or heat decomposition resistance). The present invention also provides a compound, a method for producing the compound, and a composition containing the compound.

[0043] Yet another object of the present invention is to provide a compound having many benzene rings (aromatic rings) in its chemical structure. Fluorene compounds having high solubility (or compatibility), and methods for producing the same, and The present invention provides a composition comprising the compound.

[0044] Another object of the present invention is to provide a method for producing a compound having a low molecular weight even if the compound contains many benzene rings (aromatic rings) in its chemical structure. Fluorene compound having a melting temperature (melting temperature), its production method, and said compound The present invention provides a composition comprising:

[0045] In addition, in the present specification and claims, the number of carbon atoms of a substituent is not limited to C1, C6, C 10 For example, an alkyl group with one carbon atom is represented as "C1 alkyl." However, aryl groups with 6 to 10 carbon atoms are 6-10 It is indicated as "aryl". [Effects of the Invention]

[0046] The fluorene compound of the present invention has a specific chemical structure and therefore exhibits a high refractive index. The fluorene compound exhibits high heat resistance (or thermal decomposition resistance). Although oleic compounds contain many benzene rings (aromatic rings) in their chemical structure, In addition, it exhibits high solubility (or compatibility), so it has both high solubility, a high refractive index, and high heat resistance. Therefore, the fluorene compound can be easily dissolved in other reactants such as a solvent and a curing agent. It is also possible to easily and efficiently prepare a uniform composition with the reaction components. Contrary to expectations, fluorene compounds exhibit low melting temperatures (temperatures at which melting begins or ends) and are easily It can be effectively used as a monomer for melt polymerization. It can be easily and efficiently mixed into resins by melt-kneading, and is also useful as a resin modifier. It can be used effectively. DETAILED DESCRIPTION OF THE INVENTION

[0047] [Fluorene compound (or diol compound) represented by formula (1)] In the formula (1), the monovalent group Y 1a and Y 1b Z in the formula (Y1) represents 1 in Examples of the arene ring (aromatic hydrocarbon ring) include monocyclic arenes such as benzene rings. Examples of the polycyclic arene ring include fused polycyclic arene rings. Arene ring (fused polycyclic aromatic hydrocarbon ring), ring-assembled arene ring (ring-assembled polycyclic aromatic hydrocarbon) Examples include hydrogen chloride rings.

[0048] Examples of the fused polycyclic arene ring include a fused bicyclic arene ring and a fused tricyclic arene ring. Examples of the fused bicyclic arene ring include fused bicyclic to tetracyclic arene rings such as is a fused bicyclic C ring such as a naphthalene ring or an indene ring. 10-16 Arene rings, etc. Examples of the fused tricyclic arene ring include an anthracene ring and a phenanthrene ring. Fused tricyclic rings such as C 14-20 Preferred fused polycyclic arenes include arene rings. The cyclohexane ring is a condensed polycyclic C ring such as a naphthalene ring. 10-14 It is an arene ring.

[0049] Examples of the ring-assembled arene ring include a biphenyl ring, a phenylnaphthalene ring, and a binaphthalene ring. and terarene rings such as terphenyl rings. The new ring-assembly arene ring is a C 12-18 It is a biarene ring.

[0050] In the present specification and claims, the term "ring assembly arene ring" refers to two or more ring-assembled arene rings. The ring systems (arene ring systems) are directly connected by single or double bonds, and the bonds that directly connect the rings are The number of ring systems is one less than the number of ring systems, for example, phenylnaphthalene, as described above. Even if the fused polycyclic arene ring, binaphthyl ring, etc. have a fused polycyclic arene ring skeleton, they are not considered to be ring-assembled arene rings. are clearly classified as "condensed polycyclic arene rings" such as naphthalene rings (non-cyclic aggregate arene rings). clearly distinguished.

[0051] Preferred Ring Z 1 As for C 6-14 arene rings, and more preferably benzene C ring, naphthalene ring, biphenyl ring, etc. 6-12 arene rings, more preferably benzene rings C such as phenyl ring and naphthalene ring 6-10 arene rings, especially naphthalene rings. 1 When the compound is a polycyclic arene ring, especially a fused polycyclic arene ring such as a naphthalene ring, the refractive index and Not only can it effectively improve heat resistance, but it also has a low melting temperature and high solubility (compatibility). This is sometimes preferable.

[0052] Also, the monovalent group Y 1a and Y 1b Ring Z in 1 are the fluorene skeletons 1 to The substitution may occur at any of the 4th, 5th, 6th, 7th, 8th, 9th, 10th, 11th, 12th, 13th, 14th, 15th, 16th, 17th, 18th, 19th, 20th, 21st, 22nd, 23rd, and / or 7th positions. Y 1a and Y 1b When the substitution numbers k1a and k1b are 1, Preferred substitution positions (or bonding positions) are 1,8-position, 2,7-position, 3,6-position, 4 , 5-positions, etc., are symmetrical positions on the paper in the formula (1), and in particular, the 2,7-positions preferable.

[0053] In addition, the ring Z relative to the fluorene skeleton 1 The bond position above is ring Z 1 When is a naphthalene ring, In this case, it may be either the 1st or 2nd position of the naphthalene ring, and it is preferably the 2nd position of the naphthalene ring. It is preferable that:

[0054] R 1 Examples of the substituent (non-reactive substituent or non-polymerizable substituent) represented by the formula: a halogen atom, a hydrocarbon group (or a group [-R h ]), the group [-OR h ](where R h The carbon (representing a hydrogen hydride group), the group [-SR h ](where R h represents the hydrocarbon group), an acyl group, Examples include a nitro group, a cyano group, and a mono- or di-substituted amino group.

[0055] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples include:

[0056] R h Examples of the hydrocarbon group represented by the formula include an alkyl group, a cycloalkyl group, an alkyl ... Examples include an aryl group and an aralkyl group.

[0057] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n -butyl, isobutyl, s-butyl, t-butyl, and other linear or branched C 1-10 alkyl groups, preferably straight-chain or branched-chain C 1-6 alkyl groups, More preferably, linear or branched C 1-4It is an alkyl group.

[0058] Examples of the cycloalkyl group include C5 alkyl groups such as cyclopentyl and cyclohexyl groups. -10 Cycloalkyl groups are exemplified.

[0059] Examples of the aryl group include a phenyl group, an alkylphenyl group, a biphenylyl group, and a naphthalene group. C such as butyl group 6-12 Examples of alkylphenyl groups include aryl groups. For example, methylphenyl group (or tolyl group), dimethylphenyl group (or xylyl group), etc. Which thing or bird C 1-4 Examples include alkyl-phenyl groups.

[0060] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl -C 1-4 Examples of suitable alkyl groups include:

[0061] The group [-OR h Examples of the alkyl group include an alkoxy group, a cycloalkyloxy group, an aryl group, and an aryl group. Specifically, the hydrocarbon group R h of Examples of the alkoxy group include methoxy and ethoxy groups. linear or tert-butoxy groups such as propoxy, n-butoxy, isobutoxy, and t-butoxy groups is branched chain C 1-10 Examples of the cycloalkyloxy group include: For example, C such as cyclohexyloxy group 5-10 Examples include cycloalkyloxy groups. Examples of the aryloxy group include C aryloxy groups such as phenoxy groups. 6-10 The aryloxy group Examples of the aralkyloxy group include C aryloxy groups such as benzyloxy groups.6-10 Aryl-C 1-4 Examples thereof include alkyloxy groups.

[0062] The group [—SR h Examples of the alkylthio group include an alkylthio group, a cycloalkylthio group, an aryl group, and an alkylthio group. Specifically, the hydrocarbon group R h Example of Examples of the alkylthio group include a methylthio group, an ethylthio group, and the like. C groups such as propylthio, n-butylthio, and t-butylthio. 1-10 Alkyl Examples of the cycloalkylthio group include a cyclohexylthio group. Which C 5-10 Examples of the arylthio group include: C such as thiophenoxy group (phenylthio group) 6-10 An example of such a group is an arylthio group. Examples of the arylalkylthio group include C arylalkylthio groups such as benzylthio groups. 6-10 Aryl-C 1-4 Examples include alkylthio groups.

[0063] Acyl groups include C groups such as acetyl groups. 1-6 alkyl-carbonyl groups do.

[0064] Examples of the mono- or di-substituted amino group include a dialkylamino group, a bis(alkylamino group), and a methylamino group. Examples of the dialkylamino group include dimethylamino groups. DiC such as amino group 1-4 Examples include alkylamino groups. Bis(alkylcarbonyl) The amino group may be, for example, a bis(C 1-4 Alkyl-Carbo and (amino) groups.

[0065] These groups R 1 Representative groups include hydrocarbon groups, alkoxy groups, acyl groups, Examples of the m1 include a nitro group, a cyano group, and a substituted amino group. When m1 is 1 or more, it is preferably R 1 Examples of the alkyl group and the alkoxy group include a straight chain group such as a methyl group. C-shaped or branched chain 1-6 Linear or branched C such as alkyl group or methoxy group 1-4 Alkoxy groups are exemplified, among which straight or branched alkyl groups, particularly methyl groups, are preferred. Chain C 1-4 An alkyl group is preferred. 1 is an aryl group, the group R 1 is Z 1 may form the ring assembly arene ring together with

[0066] The number of substitutions m1 is the number of substitutions m1 in the ring Z 1 For example, it may be selected from integers from 0 to 7. The preferable ranges are as follows: integers of 0 to 6, integers of 0 to 5, integers of 0 to 4, an integer, an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0 is.

[0067] When the number of substitutions m1 is 2 or more, the ring Z 1 Two or more groups R 1 The types of They may be the same or different. 1 The substitution position of ring Z is not particularly limited. 1 The selection may be made depending on the type of

[0068] Representative monovalent groups Y represented by the formula (Y1) 1a , Y 1b Examples include phenyl groups, 1 naphthyl groups such as 1-naphthyl and 2-naphthyl groups, and biphenylyl groups. A 2-naphthyl group is particularly preferred, and a 2-naphthyl group is particularly preferred. I wish.

[0069] Monovalent group Y 1a , Y 1b The substitution numbers k1a and k1b are integers ranging from 0 to 3, for example. It is preferably 0 to 2, more preferably 1 or 2, and even more preferably 1. k1a and k1b may be different from each other, but are preferably the same. At least one of them is an integer of 1 or more, and preferably both of them are integers of 1 or more, More preferably, both are 1.

[0070] When k1a and k1b are each 1 or more, the two groups forming the fluorene skeleton are Of the two benzene rings, groups Y substituted on different benzene rings 1a and Y 1b The types of They may be different from each other, but are preferably the same. In this case, the same benzene ring is substituted with one of the two benzene rings that form the fluorene skeleton. Two or more groups Y 1a , Y 1b The types may be the same or different from each other.

[0071] R 2a , R 2b The substituent represented by the formula (non-reactive substituent or non-polymerizable substituent) is Y 1a , Y 1b Any substituent other than the above may be used. Representative groups include alkyl groups and other carbonyl groups. Hydrogen groups (excluding aryl groups), halogens such as fluorine atoms, chlorine atoms, and bromine atoms Examples of alkyl groups include methyl, ethyl, and t-butyl groups. Linear or branched chain C 1-6 Alkyl groups, etc. When m2b is 1 or more, preferred R 2a , R 2b As examples, straight chain or or branched chain C 1-4 It is an alkyl group.

[0072] R 2a and R 2b The substitution numbers m2a and m2b are, for example, integers of about 0 to 3. and is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. m2a and m2b may be different from each other, but are preferably the same. When 2a and m2b are each 1 or more, the two benzene rings forming the fluorene skeleton are R substituted on different benzene rings among the benzene rings 2a and R 2b The types are different from each other In addition, when m2a and m2b are 2 or more, Of the two benzene rings that form the olefin skeleton, two or more R groups are substituted on the same benzene ring. 2a , R 2b The types of R may be the same or different. 2a oh Yobi R 2b The substitution position of the group Y 1a , Y 1b Replace at a position other than the replacement position of That's fine.

[0073] The sum of the number of substitutions on the two benzene rings that form the fluorene skeleton, k1a + m2a , k1b+m2b are, for example, integers of 0 to 4, preferably integers of 1 to 3, more preferably Preferably, it is 1 or 2, and more preferably 1. The sums k1a + m2a and k1b + m2 Although b may be different from each other, it is preferable that they are the same.

[0074] A monovalent group (or hydroxyl group-containing group) Y bonded to the 9,9-position of the fluorene skeleton 2 a and Y 2b Z in the formula (Y2) 2 As the polycyclic arene ring represented by Condensed polycyclic arene rings, ring-assembled arene rings, etc. As the arene ring, Z in the above formula (Y1) 1 and similar contractions, including preferred embodiments. Examples include conjugated polycyclic arene rings and ring-assembled arene rings.

[0075] Preferred Ring Z 2 As for C 10-14 arene rings, and more preferably naphtha C such as phenyl ring and biphenyl ring 10-12 arene rings, more preferably naphthalene rings be.

[0076] In addition, the ring Z at the 9th position of the fluorene skeleton 2 The bond position above is ring Z 2 is the naphthalene ring When present, it may be at either the 1st or 2nd position of the naphthalene ring, and the 2nd position of the naphthalene ring and ring Z is preferably 2 is a biphenyl ring, the 3-position of the biphenyl ring is preferable.

[0077] R 3 The substituent represented by the formula (a non-reactive substituent or a non-polymerizable substituent) is a substituent represented by the formula ( R in Y1) 1 When the number of substitutions m3 is 1 or more, preferred Substituent R 3 Examples of the alkyl group include a halogen atom, an alkyl group, a cycloalkyl group, an aryl ... hydrocarbon groups such as alkyl groups; alkoxy groups; acyl groups; nitro groups; cyano groups; substituted amino groups More preferred are alkyl groups, cycloalkyl groups, aryl groups, and aryl groups. A linear or branched C group such as a methyl group is preferred. 1-6 a C such as alkyl group, cyclohexyl group 5-8 C such as cycloalkyl group and phenyl group 6- 14 Linear or branched C such as aryl group, methoxy group 1-4 Examples of the alkoxy group include Among these, alkyl groups and aryl groups are preferred, and straight-chain groups such as methyl groups are particularly preferred. C-shaped or branched chain 1-4 C such as alkyl group and phenyl group 6-10 Aryl groups are preferred. In addition, the group R 3 is an aryl group, the group R 3 is the ring Z 2 and the ring assembly array A cyclic ring may be formed.

[0078] base R 3 The number of substitutions m3 in the ring Z can be an integer of 0 or 1 or more. 2 Suitable for different types of It can be selected as appropriate, and may be, for example, an integer of about 0 to 6. The preferred range is as follows: In descending order, it is an integer of 0 to 4, an integer of 0 to 3, or an integer of 0 to 2, with 0 or 1 being more preferred. In particular, 0 is preferred. When m3 is 2 or more, two or more groups R 3 The types of They may be the same or different. In particular, when m3 is 1, ring Z 2 is a naphthalene ring or Biphenyl ring, group R 3 may be a methyl group.3 The substitution position of Ring Z 2 and the group [-O-(A 1 O) n1 -H] and the bonding position with the 9-position of the fluorene ring It is sufficient to substitute at a position other than the ring Z. 2 In the formula, the group [-O-(A 1 O) n1 -H] Ortho position (group [-O-(A 1 O) n1 -H] to the carbon atom adjacent to the bond position Often replaced.

[0079] Alkylene Group A 1 Examples of the alkyl group include an ethylene group, a propylene group (1,2-propanediol), and the like. linear or aryl groups such as trimethylene, 1,2-butanediyl, and tetramethylene groups or branched chain C 2-6 Alkylene groups are examples, and when the repeat number n1 is 1 or more , preferably linear or branched C 2-4 Alkylene groups, more preferably ethylene groups , linear or branched C such as propylene group 2-3 Alkylene groups, especially ethylene The group is preferred.

[0080] Oxyalkylene group (-A 1 The number of repeating units (number of moles added) n1 is 0 or 1 or more. It is sufficient that the value is above 15, and can be selected from the range of integers, for example, 0 to 15. , and then in stages: 0~10, 0~8, 0~6, 0~4, 0~2, 0~1. The number of repetitions n1 may be 1 or more, for example, 1, in order to improve the polymerization reactivity. The range can be selected from an integer of about 1 to 15, and the preferred range is 1 to 10 in the following order: , 1 to 8, 1 to 6, 1 to 4, 1 to 3, 1 to 2, and particularly preferably 1. In the present specification and claims, the "number of repetitions (number of moles added)" is an average value (calculated The preferred embodiment may be the above-mentioned preferred embodiment. If the number of repetitions n1 is too large, the refractive index and There is a risk of reduced heat resistance.

[0081] When n1 is 2 or more, two or more oxyalkylene groups (-A 1 O-) types are They may be different from each other, but are preferably the same.

[0082] The group [-O-(A 1 O) n1 -H] ring Z 2 The substitution position for ring Z 2 is a naphthalene ring In this case, the naphthyl group bonded to the 9-position of the fluorene ring is at any one of the 5- to 8-positions. For example, the 9-position of the fluorene ring may be substituted with the 1- or 2-position of the naphthalene ring. (substituted in the relationship of 1-naphthyl or 2-naphthyl), and 1,5 The relationship of -position, 2,6-position, etc. is preferred, and the relationship of 2,6-position is particularly preferred. Also, ring Z 2 is a ring-assembled arene ring, the arene ring bonded to the 9-position of the fluorene Alternatively, it may be substituted on an arene ring adjacent to this arene ring, and bonded to the 9-position of the fluorene. It is preferable to substitute the ring Z of the arene ring. 2 If is a biphenyl ring, The 3-position of the phenyl ring (3-biphenylyl group) is bonded to the 9-position of the fluorene, and this biphenyl ring ( 3-biphenylyl group) at the 6-position of the group [-O-(A 1 O) n1-H] is preferred as a substitute. .

[0083] The monovalent group (or hydroxyl group-containing group) Y represented by the formula (Y2) 2a and Y 2 b Representative groups include hydroxypolycyclic aryl groups where n1 is 0, and groups where n1 is 1 or more. Examples of the hydroxy(poly)alkoxy polycyclic aryl group include the hydroxy(poly)alkoxy polycyclic aryl group. In the claims, "(poly)alkoxy" refers to an alkoxy group, a polyalkoxy group, The term "alkoxy" is used to mean both alkoxy and alkoxy groups.

[0084] Examples of the hydroxy polycyclic aryl group include a hydroxy fused polycyclic aryl group. , hydroxy ring-assembled aryl groups, and the like.

[0085] Examples of the hydroxy-fused polycyclic aryl group include hydroxy groups such as hydroxy naphthyl groups. Roxy C 10-14 condensed polycyclic aryl groups, and specific examples include hydroxynaphthyl Examples of the group include 6-hydroxy-2-naphthyl and 5-hydroxy-1-naphthyl groups. Of these, 6-hydroxy-2-naphthyl is preferred.

[0086] Examples of the hydroxy ring-assembled aryl group include a hydroxybiphenylyl group (or a hydroxybiphenylyl group). Hydroxyphenyl (phenyl-hydroxyphenyl group) 12-16 Ring assembly aryl groups, etc. Specific examples of the hydroxybiphenylyl group include 6-hydroxy-3-biphenylyl. Examples include an alkyl group (or a 4-hydroxy-3-phenylphenyl group).

[0087] Examples of the hydroxy(poly)alkoxy polycyclic aryl group include hydroxy( Poly)alkoxy-fused polycyclic aryl group, hydroxy(poly)alkoxy ring-assembled aryl Examples include the group.

[0088] Examples of the hydroxy(poly)alkoxy fused polycyclic aryl group include hydroxy( Hydroxy(poly)alkoxy C such as poly)alkoxynaphthyl group 10-14 fused polycyclic rings Specific examples of the hydroxy(poly)alkoxynaphthyl group include aryl groups of the formula: is a 6-(2-hydroxyethoxy)-2-naphthyl group, a 6-(2-hydroxypropoxy) 6-(2-(2-hydroxyethoxy)ethoxy)-2-naphthyl group, 6-(2-(2-hydroxyethoxy)ethoxy)-2-naphthyl group 6-(mono- or deca-)C groups such as aryl groups 2-4 Alkoxy-2-naphthyl group; 5-(2-hydroxy 5-(mono- or deca)C such as hydroxyethoxy-1-naphthyl group 2-4 Alkoxy -1-naphthyl group, and 6-(2-hydroxyethoxy)-2-naphthyl group. Any 6-(mono or hexa)C 2-3 Alkoxy-2-naphthyl groups are preferred.

[0089] Examples of the hydroxy(poly)alkoxy ring-assembled aryl group include hydroxy(poly)alkoxy ring-assembled aryl groups. ) alkoxybiphenylyl group [or phenyl-hydroxy(poly)alkoxyphenyl Hydroxy(poly)alkoxy C such as group] 12-16 Ring assembly aryl groups are examples. Specific examples of the hydroxy(poly)alkoxybiphenylyl group include 6-(2-hydroxy 4-(2-hydroxyethoxy)-3-biphenylyl group [or 4-(2-hydroxyethoxy)-3-phenyl 6-(2-hydroxypropoxy)-3-biphenylyl group], and the like. Hydroxy (mono or deca) C 2-4Alkoxy-3-biphenylyl group do.

[0090] These monovalent groups (or hydroxyl group-containing groups) Y 2a and Y 2b Among them, Z 2 but Hydroxy-fused polycyclic aryl groups, hydroxy(poly)aryls, which are fused polycyclic arene rings A koxy-fused polycyclic aryl group is preferred; Z 2 is a naphthalene ring, hydroxynaphthyl A hydroxy(poly)alkoxynaphthyl group is more preferred; 6-hydroxy-2-naphthyl Butyl group, 6-hydroxy (mono or deca) C 2-4 The alkoxy-2-naphthyl group Among these, 6-hydroxy-2-naphthyl group, 6-(2-hydroxyethoxy) 6-Hydroxy (mono or hexa) C, such as 2-naphthyl 2-3 Alkoxy- The 2-naphthyl group is preferred; the 6-hydroxy-2-naphthyl group is particularly preferred.

[0091] Y 2a and Y 2b The types of Y may be the same or different from each other. 2a and Y 2b If the types of Y are different from each other, 2a and Y 2b Z in 2 , R 3 , m3, A 1 of The types and substitution positions of these may be the same, and only the number of repetitions n1 may differ. Preferably, Y 2a and Y 2b The types are the same.

[0092] Representative fluorene compounds represented by the formula (1) include those in which k1a and k1b are 1 and Y1a and Y 1b Ring Z in 1 are identical, and Y 2a and Y 2b in Ring Z 2 Examples of such fluorene compounds include compounds in which the groups are the same. For example, Y 1a and Y 1b Ring Z in 1 is a benzene ring, a naphthalene ring or a biphenyl ring, preferably a naphthalene ring, and Y 2a and Y 2b Ring Z in 2 Naphthalene Examples of the ring include a phenyl ring or a biphenyl ring, and preferably a naphthalene ring. In such a fluorene compound, m1, m2a, m2b and m3 are 0; n1 may be 0 or 1 or more. Among such fluorene compounds, , Z 1 is a naphthalene ring, and Z 2 is a naphthalene ring.

[0093] Said Z 1 is a naphthalene ring, and Z 2 is a naphthalene ring (i.e., k1a and k1b is 1, and Y 1a and Y 1b Ring Z in 1 is a naphthalene ring, and Y 2a and Y 2b Ring Z in 2 is a naphthalene ring), for example, 9, 9-bis(hydroxynaphthyl)-dinaphthylfluorene, 9,9-bis[hydroxy( poly)alkoxynaphthyl]-dinaphthylfluorene and the like.

[0094] Examples of 9,9-bis(hydroxynaphthyl)-dinaphthylfluorene include 9, 9-bis(6-hydroxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(1-naphthyl)fluorene 9,9-bis(5-hydroxy-1-naphthyl)-2,7-di(2-naphthyl)fluorenone Olene, 9,9-bis(5-hydroxy-1-naphthyl)-2,7-di(1-naphthyl) Fluorene, such as 9,9-bis(hydroxynaphthyl)-2,7-dinaphthylfluorene Examples include:

[0095] 9,9-bis[hydroxy(poly)alkoxynaphthyl]-dinaphthylfluorene For example, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2, 7-Di(2-naphthyl)fluorene, 9,9-bis[6-(2-hydroxypropoxy) -2-naphthyl]-2,7-di(2-naphthyl)fluorene, 9,9-bis[6-(2- (2-hydroxyethoxy)ethoxy)-2-naphthyl]-2,7-di(2-naphthyl) Fluorene, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7 -di(1-naphthyl)fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1 -naphthyl]-2,7-di(2-naphthyl)fluorene, 9,9-bis[5-(2-hydroxy 9, such as [(1-naphthyl)-2,7-di(1-naphthyl)fluorene]- 9-bis[hydroxy(mono or deca)C 2-4 Alkoxy-naphthyl]-2,7-di naphthylfluorene and the like.

[0096] Among these fluorene compounds, 9,9-bis(6-hydroxy-2-naphthyl)- 2,7-di(2-naphthyl)fluorene, 9,9-bis[6-(2-hydroxyethoxy) )-2-naphthyl]-2,7-di(2-naphthyl)fluorene is preferred, and 9,9-bis (6-hydroxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene is more preferred. I wish.

[0097] The fluorene compound represented by the formula (1) has a high refractive index. The refractive index of the compound is, for example, 1.75 to 1.85 at a temperature of 25°C and a wavelength of 589 nm. The preferred ranges are as follows: 1.76 to 1.82, 1. 77~1.81, 1.78~1.8.

[0098] In addition, the fluorene compound represented by the formula (1) has high heat resistance. The 5% mass loss temperature of the fluorene compound may be, for example, about 350 to 500°C, and preferably The preferred ranges are as follows, in stages: 400 to 480°C, 420 to 470°C, 430 to 4 60℃, 440-450℃.

[0099] Although the fluorene compound represented by the formula (1) exhibits a high 5% mass loss temperature, It has a surprisingly low melting temperature (melting temperature), and the melting onset temperature is, for example, 100 to The temperature may be about 250°C, and preferably the temperature is set to 120 to 230°C, 150 to 2 The melting end temperature is, for example, 10°C, 160 to 200°C, or 170 to 190°C. The temperature may be about 130 to 280°C, and preferably the temperature is set to 150 to 260°C, 1 80 to 250°C, 200 to 240°C, 210 to 230°C. It is used as a monomer component for resins, or as a resin additive (resin modifier) ​​when mixed with resins by melt kneading. It can also be used.

[0100] In the present specification and claims, the fluorenated compound represented by the formula (1) The refractive index, 5% mass loss temperature, and melting temperature of the compound are shown in the examples below. It can be measured by the method described.

[0101] In addition, the fluorene compound represented by the formula (1) has excellent solubility (compatibility). and / or organic compounds such as solvents and / or resins to easily or efficiently form a uniform composition. The composition can also be formed by adding a fluorene compound represented by the formula (1). Even if a substance is dissolved (miscible) at a high concentration, it is difficult for it to precipitate after dissolution (miscibility), and even after dissolution (miscibility), It is difficult to precipitate even in a low-temperature environment, and can maintain a stable dissolved (compatible) state, making it storage stable. It also has excellent properties (solution stability or low temperature stability).

[0102] The solvent for forming a composition with the fluorene compound represented by formula (1) is For example, hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, benzene Aromatic hydrocarbons such as benzene and toluene; methanol, ethanol, n-propanol alcohols such as benzyl alcohol and benzyl alcohol; ethers, specifically diethyl ether dialkyl ethers such as tetrahydrofuran and 1,4-dioxane; aromatic ethers such as ethylene glycol monomethyl ether, anisole, etc. ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether PGME, ethylene glycol dimethyl ether, diethylene glycol monomethyl glycol ethers such as diethylene glycol monoethyl ether; Tonnes, specifically acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone Chain ketones such as methyl ketone (MIBK), cyclic ketones such as cyclohexanone; esters such as ethyl acetate, lactates such as methyl lactate, ethyl lactate, and butyl lactate Acid esters, lactones such as γ-butyrolactone; ether esters, specifically Contains methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol alkylene glycol monoalkyl ether acetate (PGMEA) ether acetates, alkoxycarboxylic acids such as ethyl 3-ethoxypropionate Esters, etc.; N,N-dimethylformamide, N,N-dimethylacetamide, N- Amides such as methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide Any of these is acceptable.

[0103] These solvents can be used alone or in combination of two or more. The solvent may be an ether ester, alkylene glycol monoalkyl ester, or Terephthalates are preferred, and C such as PGMEA 2-4 Alkylene glycol mono C1 -4 Alkyl ether-acetates are preferred.

[0104] A composition (liquid composition or solvent) containing the fluorene compound represented by the formula (1) and a solvent When forming a liquid, the ratio of the fluorene compound to the entire composition is, for example, 1 to 80% by mass, preferably 10 to 70% by mass, more preferably 20 to 60% by mass, particularly preferably 3 The content is 0 to 50% by mass.

[0105] The composition may be further used as a reaction solution (reaction mixture) containing other reaction components, a catalyst, etc. For example, the fluorene compound represented by the formula (1) may be solution polymerized as a monomer. It may also be used as a reaction solution for the purpose of

[0106] [Method for producing a fluorene compound (diol compound) represented by formula (1)] (Reaction step) The fluorene compound represented by the formula (1) can be prepared, for example, by the following reaction scheme (first reaction step): It may also be prepared according to the following procedure.

[0107] [ka]

[0108] (In the formula, X 1a and X 2a and X 1b and X 2b are independently A pair of reactive groups capable of forming a carbon-carbon bond (or direct bond) through a ring reaction. , Y 1a and Y 1b , k1a and k1b, R 2a and R 2b , m2a and m2b , and Y 2a and Y 2b is the same as the above formula (1), including preferred embodiments.

[0109] (Preparation of the compound represented by formula (2) in the first reaction scheme) The compound represented by the formula (2) is a compound represented by the formula (4) and a compound represented by the formula (5a) and a compound represented by formula (5b), for example For example, the methods described in JP 2011-68624 A and JP 2020-75904 A It may be prepared according to the method.

[0110] In the formula (4), X 1a and X 1b As for the coupling reaction (formula (2), a compound represented by formula (3a) and a compound represented by formula (3b) Examples of the reactive groups include those described in the section on the reaction with the compound.

[0111] The compound represented by the formula (4) is, for example, 2,7-dibromo-9-fluorenone. The compound represented by the formula (4) is a dihalo-9-fluorenone. They may be used alone or in combination of two or more, but are preferably used alone. A preferred compound represented by formula (4) is a 2,7-dibromo-9-fluorenone. ,7-dihalo-9-fluorenone.

[0112] The compound represented by the formula (5a) and the compound represented by the formula (5b) are (hydroxyl group-containing group) Y 2a and Y 2b Hydroxypolycyclic arenes corresponding to ( Compounds corresponding to n1=0) or hydroxy(poly)alkoxy polycyclic arenes (n 1≧1), and a preferred embodiment is also a compound corresponding to the above Y 2a and Y 2b In response to the same Specific examples of hydroxy polycyclic arenes include 1-naphthol, 2-naphthol, naphthols such as 2-hydroxybiphenyl, and hydroxybiphenyls such as 2-hydroxybiphenyl. Specific examples of hydroxy(poly)alkoxy polycyclic arenes include 1-(2- 2-(2-hydroxyethoxy)naphthalene, 2-( 2-hydroxypropoxy)naphthalene, 2-[2-(2-hydroxyethoxy)ethoxy Hydroxy (mono or deca) C such as naphthalene 2-4 Alkoxy-naphthalenes, Hydroxy (mono or deca) C such as 2-(2-hydroxyethoxy)biphenyl 2- 4 alkoxy-biphenyl, etc. These compounds represented by the formula (5a) The compound represented by formula (5b) may be used alone or in combination of two or more kinds. However, it is preferable to use the compound represented by the formula (5a) alone. It is preferable that the compounds represented by the formula (5a) and (b) are the same compound. Among the compounds represented by formula (5b) and the compounds represented by formula (5b), naphthols such as 2-naphthol are , hydroxy(mono to hexa)C such as 2-(2-hydroxyethoxy)naphthalene 2-3 Alkoxy-naphthalenes are preferred.

[0113] The compound represented by the formula (4), the compound represented by the formula (5a), and the compound represented by the formula (5b) The ratio of the total amount of the compound represented by the formula (1) to the total amount of the compound represented by the formula (1) is, for example, the former / latter (molar ratio) = 1 / 2 to 1 / 1. The preferred range is 1 / 2.2 to 1 / 5, ... / 2.5~1 / 4, 1 / 2.7~1 / 3.3.

[0114] The reaction may be carried out in the presence of an acid catalyst. Examples of the acid catalyst include inorganic acids, organic acids, solid acids, and the like. Examples of inorganic acids include sulfuric acid, hydrogen chloride, and phosphoric acid. The inorganic acid may be in the form of an aqueous solution, such as hydrochloric acid. Examples of sulfonic acids include methanesulfonic acid, trimethylsilyl sulfonic acid, and the like. (Halo)alkanesulfonic acids such as fluoromethanesulfonic acid, p-toluenesulfonic acid Examples of solid acids include inorganic solid acids, Specifically, metal oxides, composite metal oxides, metal sulfides, metal sulfates, polyacids, etc. compounds, non-metallic sulfates, clay minerals, zeolites, kaolin, etc.; organic solid acids, specifically, Examples include cation exchange resins such as strong acid cation exchange resins and weak acid cation exchange resins. Examples of strongly acidic cation exchange resins include sulfone cation exchange resins such as Nafion manufactured by DuPont. Examples of weakly acidic cation exchange resins include ion exchange resins with acid groups. For example, an ionic surfactant having a carboxylic acid group such as (meth)acrylic acid-divinylbenzene copolymer Examples include ion exchange resins.

[0115] These acid catalysts can be used alone or in combination of two or more. The acid catalyst is an inorganic acid such as sulfuric acid or a cation exchange resin, and it is used to convert the water produced by the reaction into Sulfuric acid, particularly concentrated sulfuric acid, is preferred because it also acts as a dehydrating agent for the above-mentioned compounds.

[0116] The sulfuric acid may be, for example, a dilute sulfuric acid having a concentration of about 30 to 90% by mass, or a concentrated sulfuric acid having a concentration of 90% by mass or more. Sulfuric acid, fuming sulfuric acid, etc. are included, and if they can be converted into sulfuric acid in the reaction system, they can be used as sulfuric acid precursors. Sulfur trioxide may be used. Sulfuric acid should have a concentration of 80-99% in terms of H2SO4. The content may be selected from the range of about % by mass, and the preferred range is 90 to 90% by mass in the following order: 9 mass%, 93 to 99 mass%, 96 to 99 mass% concentrated sulfuric acid, and more preferably 97 Concentrated sulfuric acid of 98% by mass or less is preferred, and concentrated sulfuric acid of 98% by mass is particularly preferred.

[0117] The ratio of the acid catalyst is, for example, 10 The range can be selected from the range of about 10 to 1000 parts by mass, and the preferred range is as follows: The proportion of the acid catalyst is 0 to 700 parts by mass, 300 to 500 parts by mass, or 350 to 450 parts by mass. If the amount is too small, the reaction may not proceed efficiently.

[0118] The reaction may be carried out in the presence of thiols. Examples of thiols include mercaptoethanol, ... captocarboxylic acids, aminoalkanethiols, thiocarboxylic acids, alkyl mercaptans, aralkyl mercaptans and salts thereof.

[0119] Examples of mercaptocarboxylic acids include 3-mercaptopropionic acid (or β-mercaptopropionic acid). 3-mercaptoalkanoic acids, 2-mercaptoalkanoic acids, such as mercaptopropionic acid, Examples include mercaptosuccinic acid and mercaptobenzoic acid. 2-Mercaptoalkanoic acid Examples of suitable thioglycolic acids include thioglycolic acid (mercaptoacetic acid or mercaptoethanoic acid), lactic acid (or α-mercaptopropionic acid), 2-mercaptobutyric acid (or 2-mercapto 2-mercaptoisobutyric acid (or 2-mercaptoisobutanoic acid) ) and other 2-mercapto C 2-6 Alkanoic acids are included.

[0120] Examples of aminoalkanethiols include 2-aminoethanethiol (or cysteine). amine), 2-aminopropanethiol, 3-aminopropanethiol, 2-aminobutanethiol 3-aminobutanethiol, 4-aminobutanethiol, 6-aminohexanethiol 8-aminooctanethiol, 11-aminoundecanethiol, 16-amino Amino C such as aminohexadecanethiol 2-20 Alkanethiols and the like are included.

[0121] Examples of thiocarboxylic acids include thioacetic acid and thiooxalic acid.

[0122] Examples of alkyl mercaptans include methyl mercaptan, ethyl mercaptan, Propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, dodecyl C such as mercaptan 1-16 alkyl mercaptans, etc.

[0123] Examples of aralkyl mercaptans include benzyl mercaptan.

[0124] Representative salts of these compounds include inorganic acid salts such as hydrochlorides and sulfates; acetates; organic acid salts such as sodium salts and potassium salts; alkali metal salts such as calcium salts, magnesium salts alkaline earth metal salts such as neodymium salts; ammonium salts, tetramethylammonium salts, etc. tetraalkylammonium salts; or double salts thereof. Examples of the compound include alkali metal salts such as sodium salts. mercaptan sodium, ethyl mercaptan sodium, etc.

[0125] These thiols can be used alone or in combination of two or more. Among these thiols, 3-mercaptopropionic acid, thioglycolic acid, thiolactic acid, etc. Preferred are mercaptoalkanoic acids such as methyl mercaptoalkanoic acid, and aminoalkanethiols such as cysteamine.

[0126] The ratio of thiols to 100 parts by mass of the compound represented by the formula (4) is, for example, 0 It may be selected from the range of 0.1 parts by mass or more, specifically, 1 to 50 parts by mass, and is preferable. The ranges are 2 to 20 parts by mass, 3 to 10 parts by mass, and 4 to 6 parts by mass in the following stepwise manner. The ratio of thiols to 1 mole of the compound represented by formula (4) is, for example, 0. The amount can be selected from the range of about 0.1 to 0.5 moles, and the preferred range is as follows: The thiol is 0.5 to 0.4 mol, 0.1 to 0.3 mol, or 0.15 to 0.2 mol. The ratio of the acid catalyst to the acid catalyst is, for example, in the range of about 0.001 to 50 parts by mass. The range can be selected from the following range, and the preferred range is 0.005 to 10 parts by mass, 0. If the proportion of thiols is too low, the reaction If the amount is too large, the reaction may not proceed efficiently, and if the amount is too large, the thiols may react with impurities such as sulfur components. There is a risk that it will remain as a

[0127] The reaction may be carried out in a solvent. Examples of the solvent include ethers, specifically, dienes. ethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether Chain ethers such as tetrahydrofuran (THF), 1,4-dioxane, etc. cyclic ethers such as acetone, methyl ethyl ketone, methyl ketone, Chain ketones such as isobutyl ketone, cyclic ketones such as cyclohexanone, etc.; esters, specifically, chain esters such as methyl acetate, ethyl acetate, and butyl acetate; γ- Butyrolactone, γ-valerolactone, γ-caprolactone (or γ-hexanolactone) cyclic esters (lactones) such as dimethyl carbonates; Carbonate (or dimethyl carbonate), diethyl carbonate (or diethyl carbonate), etc. Any chain carbonates, ethylene carbonate (or ethylene carbonate), propylene carbonate cyclic carbonates such as propylene carbonate; amides, specifically N,N-dimethylformamide (DMF), N,N-diethylformamide, N, Chain amides such as N-dimethylacetamide (DMAc), N-methyl-2-pyrrolide cyclic amides such as methyl methyl urea (MMP); ureas, specifically, tetramethyl urea ... Chain ureas such as ethyl urea, 1,3-dimethyl-2-imidazolidinone (DMI or N,N'-dimethylethyleneurea), N,N'-dimethyl-N,N'-trimethyleneurea (or N,N'-propylene urea) and other cyclic ureas; nitriles, specifically, Cyanide hydrocarbons such as acetonitrile, propiononitrile, benzonitrile; Nitro hydrocarbons such as tromethane, nitroethane, nitropropane, and nitrobenzene phosphoramides such as hexamethylphosphoramide; sulfones, specifically ethyl chain sulfones such as dimethyl sulfone, cyclic sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide (DMSO); hydrocarbons, specifically hexane; aliphatic hydrocarbons such as heptane, octane, and decane; alicyclic hydrocarbons such as cyclohexane; Hydrogen fluorides, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene Halogenated hydrocarbons, specifically methylene chloride, chloroform, carbon tetrachloride, 1, Haloalkanes such as 2-dichloroethane, haloalkanes such as chlorobenzene and dichlorobenzene Benzene, etc.

[0128] These solvents can be used alone or in combination of two or more. The solvent contains at least one selected from ethers, sulfones, and ureas. It is particularly preferable to use a cyclic compound having at least a cyclic structure in the molecule (a compound having a cyclic structure). aprotic polar solvents), especially cyclic ethers such as 1,4-dioxane, sulfur At least one selected from cyclic sulfones such as folane and cyclic ureas such as DMI It is preferred to include seeds.

[0129] The ratio of the solvent is, for example, 100 to 100 parts by mass of the compound represented by the formula (4). The amount may be selected from a range of about 10,000 parts by mass, and the preferred range is as follows: , 300 to 2000 parts by mass, 400 to 1500 parts by mass, 500 to 1000 parts by mass. If the solvent ratio is too high, the concentration of the raw material may be too low, resulting in reduced reactivity. If the proportion is too small, the viscosity may become too high, which may reduce the reactivity.

[0130] The reaction temperature can be selected from the range of, for example, about 0 to 200°C. Preferred ranges are as follows: The reaction temperature is 10 to 100°C, 20 to 80°C, and 30 to 60°C in descending order. For example, the range can be selected from about 30 minutes to 48 hours, and the preferred ranges are as follows: , 1 to 24 hours, 2 to 12 hours, and 4 to 8 hours.

[0131] The reaction may be carried out with stirring in air or in an inert atmosphere such as nitrogen gas or a rare gas. The reaction may be carried out in air, under normal pressure or under pressure. It is also possible.

[0132] After the reaction is complete, the reaction mixture (reaction solution or reaction mixture) can be purified by a conventional method, for example, Filtration, concentration, extraction, neutralization, washing, drying, crystallization, column chromatography, and combinations of these The compounds may be separated (or purified) by a combination of methods.

[0133] (Preparation of Compound Represented by Formula (1) in First Reaction Scheme) The fluorene compound (diol compound) represented by the formula (1) is The compound represented by formula (3a) and the compound represented by formula (3b) are It can be prepared by a coupling reaction (or cross-coupling reaction).

[0134] The coupling reaction may be a conventional coupling reaction, such as Suzuki-Miyaura coupling. Reaction, Migita-Kosugi-Stille coupling reaction, Negishi coupling reaction, Hinoki Palladium-catalyzed (or palladium(0)-catalyzed) coupling reactions, such as the Yama coupling reaction Nickel-catalyzed reactions such as the cyclohexane-coupling reaction, the Kumada-Tamao-Corriu coupling reaction, etc. Coupling reactions using a nickel (0) catalyst are also possible. Among these coupling reactions, the Suzuki-Miyaura coupling reaction is preferred.

[0135] In the formula (2) (or formula (4)), X 1a and X 1b are each independently represents a reactive group capable of forming a carbon-carbon bond (or a direct bond) by a coupling reaction; In the formulas (3a) and (3b), X 2a is the reactive group X 1a and X 2b is the above Reactive Group X 1b and each of which is capable of forming a carbon-carbon bond by a coupling reaction. Reactive group X is shown. 1a and X 1b and X 2a and X 2b is before The coupling reaction can be appropriately selected depending on the type of coupling reaction. In the synthesis, one reactive group, e.g., group X 1a and X 1b As for the halogen atoms, or a fluorinated alkanesulfonyloxy group. Examples of halogen atoms include Examples include iodine atoms, bromine atoms, and chlorine atoms. Examples of the oxy group include a trifluoromethanesulfonyloxy group (or a group [-OTf ]) and other fluorides 1-4 Alkanesulfonyloxy groups are also included. The reactive groups may be used alone or in combination of two or more. Among these, a halogen atom is preferred, an iodine atom or a bromine atom is more preferred, and a bromine atom is particularly preferred. Preferred.

[0136] One of the reactive groups X in the Suzuki-Miyaura coupling reaction 1a and X 1b and cup The other reactive group X that can be ringed 2a and X 2b Examples of suitable boronic acid groups include dihydroboronic acid groups. Examples include a boronic acid group or group [-B(OH)2], and a boronic acid ester group. Examples of the boronic acid ester group include a dimethoxyboryl group and a diisopropoxyboryl group. , dialkoxyboryl groups such as dibutoxyboryl groups; pinacolatoboryl groups (or groups [ -Bpin]), 1,3,2-dioxaborinan-2-yl group, 5,5-dimethyl-1, Examples include cyclic boronic acid ester groups such as 3,2-dioxaborinan-2-yl groups. These other reactive groups may be used alone or in combination of two or more. Of the groups, the group [-B(OH)2] is preferred.

[0137] In addition, the group X 1a and X 1b and group X 2a and X 2b Each of these is a couple Any reactive group may be used as long as it is a pair of reactive groups capable of undergoing a crosslinking reaction. 1a Oh and X 1b is the other reactive group such as a boronic acid group, and group X 2a and X 2b Haloge The reactive group X may be a fluorine atom or the like. 1a and X 1b is a halogen atom and the group X is a reactive group such as a 2a and X 2b is the other group such as a boronic acid group Preferably, the reactive group is

[0138] The compound represented by the formula (2) is preferably a fluorene compound represented by the formula (1). Preferred embodiments of the compounds include, for example, 9,9-bis(6-hydroxy-2-naphthyl) 9,9-bis(hydroxynaphthyl)-dihalofluorene, such as 2,7-dibromofluorene 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diol; 9,9-bis[hydroxy(poly)alkoxy-naphthyl]-diamines such as bromofluorene Halofluorenes and the like.

[0139] The compounds represented by the formula (3a) and the compounds represented by the formula (3b) include compounds represented by the formula Compounds corresponding to preferred embodiments of the fluorene compound represented by (1), for example, phenyl Boronic acid, 1-naphthylboronic acid, 2-naphthylboronic acid, etc. Boronic acid is preferred. The compound represented by the formula (3a) and the compound represented by the formula (3b) The compound represented by the formula (3a) and the compound represented by the formula (3) are preferably the same compound. The compound represented by b) can be a commercially available product.

[0140] The compound represented by the formula (2), the compound represented by the formula (3a), and the compound represented by the formula (3b) The ratio of the total amount of the compound represented by the formula (1) to the total amount of the compound represented by the formula (1) is, for example, the former / latter (molar ratio) = 1 / 2 to 1 / 1. The preferred range is 1 / 2.1 to 1 / 5, ... / 2.2 to 1 / 3, 1 / 2.3 to 1 / 2.5 are also acceptable, and the preparation can be more efficient. and more preferably 1 / 2.1 to 1 / 2.3.

[0141] The coupling reaction may be carried out in the presence of a catalyst. When the compound is synthesized by the above reaction, the reaction may be carried out in the presence of a palladium catalyst. , a conventional coupling catalyst, such as a palladium (0) catalyst, a palladium (II) catalyst, etc. Examples include:

[0142] Examples of the palladium (0) catalyst include tetrakis(triphenylphosphine)palladium. Pd(PPh3)4, bis(tri-t-butylphosphine)para Palladium(0) [or palladium(0)-phosphine, such as Pd(P(t-Bu)3)2] Examples include fluorine complexes.

[0143] Examples of palladium (II) catalysts include [1,2-bis(diphenylphosphino) ethane]palladium(II) dichloride [or PdCl2(dppe)], [1,3- Bis(diphenylphosphino)propane]palladium(II) dichloride [or PdC l2(dppp)], [1,1'-bis(diphenylphosphino)ferrocene]palladium Pd(II) dichloride [or PdCl2(dppf)], bis(triphenylphosphine palladium(II) dichloride [or PdCl2(PPh3)2], bis(tri- o-Tolylphosphine)palladium(II) dichloride [or PdCl2(P(ot olyl)3)2] and other palladium(II)-phosphine complexes. When a palladium (II) catalyst is used, for example, phosphines, amines, organometallic reagents, etc. The reaction begins when a reducing compound in the reaction system reduces it to a zero-valent complex.

[0144] The palladium catalyst is, for example, tris(dibenzylideneacetone)dipalladium. Palladium(0) chloroform complex [or Pd2(dba)3·CHCl3], palladium acetate (II) and a catalyst precursor, a phosphine such as triphenylphosphine, a carbene The catalyst precursor may be prepared in the reaction system by adding a ligand such as In this case, the molar ratio of the former to the latter may be, for example, about 1 / 4 to 1 / 10, and preferably is 1 / 4 to 1 / 5.

[0145] These catalysts can be used alone or in combination of two or more. Among the catalysts, palladium(0)-phosphine complexes such as Pd(PPh3)4, palladium acetate, Catalyst precursors such as ammonium (II) and acetic acid are particularly preferred due to their excellent operability (stability in air). The catalyst is preferably palladium(II) phosphate. The catalyst ratio is 1 mol of the compound represented by the formula (2) In terms of metal, the amount may be, for example, about 0.0001 to 0.1 moles relative to the may be 0.01 to 0.07 mol, more preferably 0.04 to 0.06 mol, In terms of more efficient preparation, it is particularly preferable to use the following stepwise method: 0.0001 to 0.001 molar ratio. palladium(II) acetate, etc., in the presence of a catalyst. When a precursor is used, the amount is particularly preferably 0.0005 to 0.0015 mol.

[0146] The Suzuki-Miyaura coupling reaction may be carried out in the presence of a base. , metal carbonates or bicarbonates, metal hydroxides, metal fluorides, metal phosphates, metal organics Examples of suitable metal alkoxides include metal salts and metal alkoxides.

[0147] Examples of metal carbonates or hydrogen carbonates include sodium carbonate, potassium carbonate, and carbonate Cesium, alkali metal carbonates or bicarbonates such as sodium bicarbonate, thalinium carbonate Examples include Mu (I).

[0148] Examples of metal hydroxides include sodium hydroxide, potassium hydroxide, and cesium hydroxide. Alkali metal hydroxides such as barium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, hydroxide Examples include thallium(I).

[0149] Examples of metal fluorides include alkali metals such as potassium fluoride and cesium fluoride. Fluoride and the like.

[0150] Examples of metal phosphates include alkali metal phosphates such as tripotassium phosphate. Examples include:

[0151] Examples of metal organic acid salts include alkali metal acetates such as potassium acetate. can be.

[0152] Examples of metal alkoxides include sodium methoxide, sodium ethoxide, Examples include alkali metal alkoxides such as potassium t-butoxide.

[0153] These bases can be used alone or in combination of two or more. The base is preferably a metal carbonate such as potassium carbonate. The ratio of the base is determined by the above formula (2). The amount of the compound represented by the formula (I) may be, for example, about 0.1 to 50 moles, and is preferably Alternatively, the amount may be 0.5 to 5 mol, 1 to 3 mol, or 1.5 to 2.5 mol in the following stepwise order. In terms of more efficient preparation, it is more preferable to use 5 to 10 moles, 6 to 8 moles, or the like in the following stepwise manner. The amount of HCl is 6.5 to 7.5 mol.

[0154] The coupling reaction may be carried out in the presence or absence of a phase transfer catalyst. Examples of the catalyst include tetrabutylammonium bromide (TBAB), trioctyl Examples include tetraalkylammonium halides such as methylammonium chloride. These phase transfer catalysts can be used alone or in combination of two or more. .

[0155] The coupling reaction may be carried out in the absence or presence of a reaction-inert solvent. Examples of the solvent include water; alcohols such as methanol and ethanol; cyclic ethers; Ethers such as chain ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as methyl benzoate (MIBK); esters such as ethyl acetate; acetonitrile, benzophenone Nitriles such as nitrile; N,N-dimethylformamide, dimethylacetamide, N amides such as 2-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide ;Aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and other hydrocarbons are included. can be.

[0156] Examples of cyclic ethers include dioxane and tetrahydrofuran. Examples of chain ethers include dialkyl ethers such as diethyl ether and diisopropyl ether. Examples of the glycol ethers include: For example, (poly)alkylene glycol monomers such as methyl cellosolve and methyl carbitol (Poly)alkylene glycol dialkyl ethers, dimethoxyethane, etc. ether, etc.

[0157] Examples of aliphatic hydrocarbons include hexane and dodecane. Examples of hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include Examples include toluene and xylene.

[0158] These solvents can be used alone or in combination of two or more. Among the solvents, a mixture of water and aromatic hydrocarbons such as toluene or ketones such as MIBK A solvent is preferred.

[0159] The coupling reaction is carried out under an inert gas atmosphere, such as nitrogen gas, helium, or argon. The reaction may be carried out under any atmosphere such as a rare gas. The reaction temperature is, for example, 50 to 200°C, preferably The temperature is preferably 60 to 100°C, more preferably 70 to 90°C, and particularly preferably 75 to 83°C. The reaction time may be, for example, about 0.5 to 24 hours, and is preferably 10 to 20 hours. It may take 0.5 to 8 hours, and more preferably 0.5 to 8 hours, 0. 5 to 1.5 hours.

[0160] After the reaction is completed, the reaction mixture may be subjected to a conventional separation and purification method, for example, neutralization, washing, Extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography Separation and purification may be carried out by methods such as filtering, adsorption, or a combination of these.

[0161] The fluorene compound represented by the formula (1) can also be produced by a method different from the above method, for example, For example, it may be prepared according to the following reaction scheme (second reaction scheme).

[0162] [ka]

[0163] (In the formula, Y 1a and Y 1b , k1a and k1b, R 2a and R 2b , m2a and m2b, and Y 2a and Y 2b is the same as the formula (1) including preferred embodiments. , X 1a and X 2a and X 1b and X 2b The first reaction scheme and the preferred embodiment (The same applies to all terms, including the name, address, etc.).

[0164] In the second reaction scheme, a compound represented by the formula (5a) and a compound represented by the formula (5b) The compound is reacted to form the group Y 2a and Y 2b and introducing a compound represented by the formula (3a) and a compound of formula (3b) to form a group Y 1a and Y 1b Introduce The order of the steps is reversed from the first reaction scheme. The preparation of the compound represented by the formula (6) in the formula (1) can be carried out by the reaction of the compound represented by the formula (6) in the formula (2) In the description of the section "Preparation of the compound represented by formula (1)," Instead, a compound represented by the formula (4) is used (or the formula (2) is read as the formula (4)). In addition, the compound represented by the formula (1) in the second reaction scheme can be prepared by Similarly, the compound can be prepared by the above-mentioned method (the compound represented by formula (2) in the first reaction scheme). In the description of the section "Preparation of Compounds," the compound represented by the formula (4) is replaced with the compound represented by the formula (6) (or by replacing the formula (4) with the formula (6)) It can be manufactured.

[0165] As described above, the production of the fluorene compound (diol compound) represented by the formula (1) The method includes: (i) mixing a compound represented by the formula (2) with a compound represented by the following formula (3a): and a compound represented by formula (3b); or (ii) coupling the compound represented by formula ( 6), a compound represented by the following formula (5a) and a compound represented by the following formula (5b): The reaction intermediate may be a compound of the formula (2 The compounds represented by (6) and (7) can be prepared by the above-mentioned methods or other conventional methods. Good too.

[0166] (purification process) The fluorene compound (diol compound) represented by the formula (1) can be separated and purified by the conventional separation method described above. However, due to the influence of the reaction conditions, it is difficult to separate the product sufficiently or efficiently. However, it is sometimes impossible to isolate and purify the compound, and it is difficult to prepare it with a relatively high purity and high yield. The fluorene compound obtained in the reaction step is then dissolved in a solvent, for example, a solvent represented by the formula (1). As a solvent for forming a composition (liquid composition or solution) with the fluorene compound Solvents similar to those exemplified above, preferably (a) aromatic hydrocarbons and aliphatic hydrocarbons (b) a solvent containing at least ketones (crystallization solvent) Precipitation (crystallization or recrystallization or reprecipitation) from at least one solvent selected from the group consisting of The crystallization process, recrystallization process, or reprecipitation process is used to separate and refine the product. This allows for more efficient and highly purified separation compared to other separation and purification methods such as column chromatography. The fluorene compounds appear to be easy to prepare.

[0167] (a) Good solubility in solvents containing at least aromatic hydrocarbons and aliphatic hydrocarbons Examples of the aromatic hydrocarbons that serve as the solvent include benzene, toluene, and xylene. Examples of the aliphatic hydrocarbons that are poor solvents include: C such as hexane, heptane, and decane 5-12 Alkanes such as heptane C 6-8 Alkanes are preferred.

[0168] The ratio of the aromatic hydrocarbons such as toluene to the aliphatic hydrocarbons such as heptane In this case, for example, the former / latter (volume ratio) is selected from the range of about 10 / 90 to 90 / 10. The preferred ranges are as follows: 10 / 90 to 90 / 10, 20 / 80 to The volume ratio is 70 / 30, 30 / 70 to 50 / 50. It may also be a volume ratio under pressure.

[0169] The ratio of the total amount of aromatic hydrocarbons and aliphatic hydrocarbons is For example, 50% by mass or more, preferably in the following stepwise manner, based on the total amount of the solvent containing the aliphatic hydrocarbons. Preferably, the content is 70% by mass or more, 90% by mass or more, and more preferably substantially 100% by mass. be.

[0170] In addition, (b) the crystallization solvent containing at least ketones, the ketones include, for example, , acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), etc. 3- 6 ketones. The ratio of ketones to the total crystallization solvent containing ketones is For example, 50% by mass or more, preferably 70% by mass or more, 90% by mass or more in a stepwise manner. It is more preferably substantially 100% by mass.

[0171] When purified using solvent (a), an amorphous substance is obtained, while when purified using solvent (b), a crystal is obtained. Among solvents (a) and (b), the most suitable one is the one that can be used while maintaining high purity and yield. The crystallization solvent (b) is preferred from the viewpoint of easily reducing coloration, and in particular, C such as MIBK. 5-6 Ke It is preferable to carry out crystallization from a crystallization solvent containing toluene.

[0172] In the purification step, particularly in the crystallization step, for example, the solution is adjusted to a concentration of 10 to 60 mass %, preferably 20 The content may be adjusted to 50% by mass, more preferably 30% by mass to 50% by mass. Alternatively, crystallization may be performed while lowering the temperature, for example, at a speed of about 100 to 500 rpm, preferably 2 While stirring at about 00 to 300 rpm, the mixture is heated to, for example, 40 to 100°C, preferably 50 to 70°C. The temperature is lowered from about 30 to 60°C, preferably about 40 to 50°C, and crystallization is carried out at this temperature. Alternatively, the mixture may be left standing without stirring to lower the temperature, for example, to about 20 to 30°C. Alternatively, the temperature may be lowered to room temperature to cause crystallization.

[0173] The HPLC purity of the obtained fluorene compound represented by the formula (1) is, for example, 75% or more. It may be 80% or more, preferably 80% or more, more preferably 85% or more, and even more preferably is 90% or more, particularly 95% or more, and particularly 98% or more. In the claims, HPLC purity can be measured by the method described in the Examples below.

[0174] The yield of the obtained fluorene compound represented by the formula (1) is, for example, 40% or more. The preferred ranges are 50% or more, 60% or more, and 70% or more in the following order: More preferably, it is 80% or more.

[0175] [Fluorene compound (epoxy compound or epoxy resin) represented by formula (1E)] The fluorene compound represented by the formula (1E) is a compound represented by the formula (1). and a group Y bonded to the 9,9-position of the fluorene skeleton. 2a and Y 2b [Represented by the formula (Y2) a group Y in place of the hydroxyl group-containing group 3a and Y 3b [Represented by the formula (Y3) The epoxy compound (or epoxy resin) has an epoxy group-containing group.

[0176] The epoxy group-containing group Y represented by the formula (Y3) 3a and Y 3b In R 4 is hydrogen In addition, in the formula (Y3), R 3 , m3, A 1 and n1 are the same as those in the formula (Y2) above, including preferred embodiments thereof.

[0177] Therefore, a typical epoxy group-containing group Y 3a and Y 3b is exemplified in the above formula (1) The hydroxyl-containing group Y 2a and Y 2b Correspondingly, the hydroxyl group is converted to glycidyl Examples of the substituted alkyl group include a group substituted with an oxy group or a β-methylglycidyloxy group. Epoxy group-containing group Y 3a and Y 3b The hydroxyl group-containing group Y 2a and Y 2b Against The same applies to the corresponding groups, and among them, 6-glycidyloxy-2-naphthyl group, 6-(2-glycidyloxy) 6-glycidyloxy (mono- or hexyloxy) such as 6-glycidyloxyethoxy-2-naphthyl group Sa)C 2-3 Alkoxy-2-naphthyl groups are preferred; in particular 6-glycidyloxy-2- A naphthyl group is preferred. 3a and Y 3b The types are the same They may be one or different, and are preferably the same.

[0178] In addition, in the formula (1E), Y 1a and Y 1b , k1a and k1b, R 2a oh Yobi R2b , m2a and m2b, and k1a+m2a and k1b+m2b are The preferred embodiments are the same as those of the formulas (1) and (Y1). 1a and Y 1b Ring Z 1 However, in particular, when the ring is a fused polycyclic arene ring such as a naphthalene ring, the Not only is it easy to effectively improve refractive index and heat resistance, but it also has a surprisingly low melting point and high melting point. This is preferable because it can also exhibit compatibility.

[0179] Therefore, the epoxy compound represented by the representative formula (1E) is also The diol compound represented by the formula (1) is obtained by converting two hydroxyl groups into glycerol. Examples include compounds in which the glycidyloxy group or the β-methylglycidyloxy group is substituted. The preferred epoxy compound represented by the formula (1E) is also a compound represented by the formula (1). The same applies to the preferred embodiments of the diol compounds, among which 9,9-bis(6- 9, such as glycidyloxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene 9-Bis(glycidyloxynaphthyl)-2,7-dinaphthylfluorene;9,9-Bis [6-(2-(glycidyloxy)ethoxy)-2-naphthyl]-2,7-di(2-naphthyl) 9,9-bis[glycidyloxy(mono or deca)C 2-4 a alkoxy-naphthyl]-2,7-dinaphthylfluorene is preferred, and 9,9-bis(6- Hydroxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene is more preferred. .

[0180] The epoxy compound represented by the formula (1E) has a high refractive index. The refractive index of the compound is, for example, 1.67 to 1.8 at a temperature of 25°C and a wavelength of 589 nm. Specifically, it may be about 1.67 to 1.77, and the preferred range is as follows: , 1.69 to 1.75, 1.7 to 1.74, or 1.71 to 1.73; Preferably, the following stepwise: 1.72 to 1.79, 1.73 to 1.78, 1.74 to 1.7 75, 1.75 to 1.77.

[0181] In addition, the epoxy compound represented by the formula (1E) has high heat resistance. The 5% mass loss temperature of the epoxy compound may be, for example, about 300 to 500°C, and is preferably The recommended ranges are as follows: 350-450°C, 370-430°C, 380-420°C. It's 0℃.

[0182] Although the epoxy compound represented by the formula (1E) exhibits a high 5% mass loss temperature, , unexpectedly exhibits a low melting (melting) temperature, and the melting (melting) onset temperature is, for example, 100 to 25 0°C, and preferably in the following stepwise manner: 120 to 200°C, 130 to 180°C, Therefore, it can be easily melt-mixed with other components, which will be described later, by melt kneading or the like. Alternatively, a uniform curable composition can be efficiently prepared.

[0183] In the present specification and claims, the fluorene represented by the formula (1E) The refractive index, 5% mass loss temperature, and melting temperature of the compound were determined by the methods described in the Examples below. It can be measured.

[0184] The epoxy equivalent of the epoxy compound (or epoxy resin) is, for example, 300 to It may be selected from a range of about 1500 g / eq, preferably 350 to 1000 g / eq More preferably, it may be 400 to 500 g / eq; particularly preferably, it may be 350 to 500 g / eq. 480g / eq, and in particular 370 to 450g / eq. In the range of the required epoxy equivalent of the epoxy compound, JIS K 7236:20 It can be measured by the method described in the Examples below in accordance with Item 01.

[0185] The epoxy compound (or the curable composition described later) is a compound represented by the formula (1E). Not only the compounds (monomers) that are produced, but also their multimers, such as dimers, trimers, tetramers, etc. The multimer may be a mixture containing dimers to decamers. It may also be included.

[0186] In this specification and claims, unless otherwise specified, the epoxy compound The "polymer" is a structure ( This refers to an epoxy compound having two or more diols in its chemical structure. The structure derived from the compound may contain a linking group derived from an epihalohydrin component, such as a 2-hydroxy group, which will be described later. They are bonded (linked) via cyclopropane-1,3-diyl groups, etc. is inevitably generated during the production process of the compound (monomer) represented by the formula (1E) described below. It may be mixed in as an impurity, and if necessary, it may be used in a one-stage method (taffy method or direct method) or a two-stage method. The polymers prepared by conventional methods such as the advanced method, the melting method, or the indirect method are intentionally converted into monomers. It may also be added to.

[0187] The ratio of the polymer to the total number of moles of the monomer and polymer is, for example, 0 to 50 moles. % by mole, specifically 0 to 20 mol %, preferably 0 to 10 mol %, The ratio is more preferably 0 to 5 mol %. may be 0.2 to 3 mol %.

[0188] The HPLC purity of the fluorene compound (monomer) represented by the formula (1E) can be, for example, It may be about 75% or more, preferably 85% or more, and more preferably 90% or more. In the present specification and claims, the HPLC purity is determined by the method described below. It can be measured by the method described in the Examples.

[0189] [Method for producing a fluorene compound (epoxy compound) represented by formula (1E)] The method for producing the epoxy compound represented by the formula (1E) is not particularly limited, and for example, By reacting a diol compound represented by formula (1) with an epihalohydrin component, It may also be prepared.

[0190] The epihalohydrin components (epihalohydrins) include epihalohydrin, β-methyl Examples of epihalohydrins include epichlorohydrins, Examples include β-methylepihydrin, epibromohydrin, and epiiodohydrin. Halohydrins include β-methylepichlorohydrin and β-methylepibromohydrin , β-methyl epiiodohydrin, etc. These epihalohydrin components include: These epihalohydrin compounds can be used alone or in combination. Among these, epihalohydrins such as epichlorohydrin, β-methylepichlorohydrin is preferred, and epichlorohydrin is more preferred.

[0191] The ratio of the epihalohydrin component to 1 mole of the diol compound represented by the formula (1) is For example, 2 moles or more may be used, but an excess amount, for example, 5 to 10 moles, relative to the diol compound may be used. The amount is 100 mol, preferably 10 to 50 mol, and more preferably 15 to 30 mol.

[0192] If necessary, the reaction may be carried out in the presence or absence of a catalyst. The catalyst may be, for example, a quaternary ammonium salt, specifically, tetramethylammonium Tetra-C such as ammonium chloride and tetramethylammonium bromide 1-20 Alkyria Benzyltrimethylammonium chloride, such as ammonium halides and benzyltrimethylammonium chloride 1-4 Alkylammonium halides, etc.; Trimethylamine borane, etc. 1-4 Examples include alkylamine borane, crown ether, phosphonium salt, and pyridinium salt. The catalyst may be used alone or in combination of two or more kinds.

[0193] When a catalyst is used, the proportion thereof is not particularly limited, but the diol represented by the formula (1) For example, 0.001 to 1 mol, preferably 0.01 to 0.2 mol, relative to 1 mol of the compound More preferably, it is 0.05 to 0.1 moles.

[0194] In addition, in order to trap the hydrogen halide produced by the reaction, the reaction is carried out in the presence of a base. The base may be, for example, an inorganic salt such as a metal hydroxide, a metal carbonate or a hydrogen carbonate. Examples of the metal hydroxide include sodium hydroxide, Alkaline metal hydroxides such as potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide Metal hydroxides, etc. Metal carbonates or hydrogen carbonates include sodium carbonate. and alkali metal or alkaline earth metal carbonates such as sodium hydrogen carbonate. The amines include trialkylamines such as triethylamine, benzyldimethylamine, Examples include aromatic tertiary amines such as amines and heterocyclic tertiary amines such as pyridine. The bases may be used alone or in combination of two or more. Among these bases, strong bases ( A strong alkali is preferred, and a metal hydroxide such as sodium hydroxide is more preferred.

[0195] The ratio of the base is not particularly limited. For example, For example, 0.01 to 20 moles per mole of silyl group, preferably 0.05 to 10 moles in the following stepwise manner. up to 10 mol, 1 to 5 mol, or 2 to 4 mol.

[0196] The reaction may be carried out in an inert solvent or without a solvent. As the solvent, an aprotic solvent can be used, for example, a hydrocarbon, specifically, hexane. aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as benzene and toluene; Halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; ethyl acetate, etc. esters; ethers, specifically dialkyl ethers such as diethyl ether cyclic ethers such as tetrahydrofuran; acetone, methyl ethyl ketone (ME Ketones such as methyl isobutyl ketone (MIBK); dimethylformamide (D MF), amides such as dimethylacetamide; sulfoxides such as dimethyl sulfoxide The solvents may be used alone or in combination of two or more. Among the solvents, ketones such as MEK and MIBK, amides, and sulfoxides are preferred in terms of reactivity. Preferred are amides such as DMF, and sulfoxides such as dimethyl sulfoxide. More preferable.

[0197] The reaction may be carried out in air or in an inert atmosphere such as nitrogen gas or a rare gas. The reaction may be carried out under normal pressure, elevated pressure, or reduced pressure.

[0198] The reaction temperature and reaction time may be appropriately selected depending on the type of raw material. For example, 30 to 150°C, preferably 50 to 140°C, 100 to 130°C in a stepwise manner. The reaction may be carried out under reflux (at reflux temperature); more preferably at 30 to 50°C. The reaction time is, for example, 30 minutes to 48 hours, preferably 2 to 6 hours.

[0199] After the reaction is completed, the reaction mixture may be subjected to a conventional separation and purification method, for example, washing, extraction, Filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography Alternatively, the product may be separated and purified by methods such as adsorption, or a combination of these.

[0200] [Curable composition] The curable composition contains at least an epoxy compound represented by the formula (1E). The composition may be a thermosetting or photocurable composition. Other epoxy compounds (epoxy resins) different from epoxy compounds, hardeners, curing accelerators, light It may contain other components such as polymerization initiators, reactive diluents, solvents, and additives. The epoxy compound represented by the formula (1E) is particularly preferably Y 1a and Y 1b Medium Ring Z1 When the compound is a polycyclic arene ring such as a fused polycyclic arene ring, many Despite having a benzene ring skeleton, it has surprisingly excellent solubility (compatibility), Even if other components are contained, a uniform curable composition and a cured product can be easily and efficiently prepared. can.

[0201] (Other epoxy compounds) Examples of epoxy compounds (epoxy resins) other than those represented by the formula (1E) include: Ricinyl ether type epoxy resin, specifically, bisphenol A type, bisphenol F type Bisphenols such as bisphenol A, bisphenol B, bisphenol S, and biphenol Novolac resins such as phenolic epoxy resins, phenolic novolac resins, and cresol novolac resins Rack-type epoxy resin, phenol aralkyl-type epoxy resin, triphenol alkane epoxy resins, tetrakis(glycidyloxyphenyl)ethane, etc. phenol-type epoxy resins, condensed ring aromatics such as 1,6-bis(glycidyloxy)naphthalene Aromatic hydrocarbon modified epoxy resins, 9,9-bis(glycidyloxyaryl)fluorenes , 9,9-bis[glycidyloxy(poly)alkoxyaryl]fluorenes, etc. Epoxy resins with a 9,9-bisarylfluorene skeleton; aromatic dicarboxylic acids Glycidyl ester type epoxy resins such as diglycidyl ester (or its hydrogenated derivatives) ;Tetraglycidyldiaminodiphenylmethane, tetraglycidylbisaminomethylcyclohexyl glycidylamine-type epoxy resins such as cyclohexane and triglycidylaminophenol; Bis(3,4-epoxycyclohexylmethyl) adipate, (3,4-epoxycyclo cycloaliphatic compounds such as hexyl)methyl-3,4-epoxycyclohexanecarboxylate type epoxy resin; stilbene type epoxy resin; isocyanurate type epoxy resin, hydan Heterocyclic epoxy resins such as tetrahydropyran-type epoxy resins and epoxy resins containing xanthene units ; Bromine-containing epoxy resins such as tetrabromobisphenol A type epoxy resins. can be.

[0202] These other epoxy resins may be monomers or polymers such as dimers and trimers. These other epoxy resins may be used alone or in combination of two or more. Other preferred epoxy resins include bisphenol A type epoxy resins and the like. It is a phenolic epoxy resin.

[0203] When other epoxy resins are contained, the epoxy resins (the epoxy resins represented by the formula (1E)) The ratio of the epoxy resin to the total epoxy resin in the curable composition is, for example, 50 to 99 mass %. %, preferably 60 to 98 mass %, and more preferably 70 to 95 mass %.

[0204] (hardener, hardening accelerator, photopolymerization initiator) The curable composition contains at least one selected from a curing agent, a curing accelerator, and a photopolymerization initiator. The curing agent may or may not contain a seed. Examples include curing agents, polyaminoamide-based curing agents, acid anhydride-based curing agents, and phenolic resin-based curing agents. can be done.

[0205] The amine-based curing agent may be, in particular, a primary amine, for example, a chain aliphatic amine. Specifically, ethylenediamine, hexamethylenediamine, diethylenetriamine, Linear aliphatic polyamines such as triethylenetetramine; cyclic aliphatic amines, specifically These include menthenediamine, isophoronediamine, bis(4-amino-3-methylcyclohexane) xyl)methane, norbornanediamine, 3,9-bis(3-aminopropyl)-2,4 ,8,10-tetraoxaspiro[5.5]undecane, and other monocyclic, bridged or symmetrical rings. Pyrocyclic aliphatic polyamines, etc.; aromatic aliphatic polyamines such as xylylenediamine; meta Phenylenediamine, diaminodiphenylmethane, 4,4'-diaminodiphenylsulfonyl Examples of suitable amines include aromatic amines such as methyl amines.

[0206] Examples of polyaminoamide curing agents include ethylenediamine and diethylenetriamine. Polyethylene polyamines such as ethylenediamine and triethylenehexamine, dimer acid, and optionally Depending on the case, condensation products with fatty acids and the like may also be mentioned.

[0207] Examples of acid anhydride curing agents include dodecenyl succinic anhydride and polyadipic anhydride. Aliphatic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride , Hexahydrophthalic Anhydride, Methyl Hexahydrophthalic Anhydride, Methyl Himic Anhydride cyclohexanedicarboxylic acid anhydride; phthalic anhydride; Trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, etc. Examples of suitable aromatic acid anhydrides include the following:

[0208] Examples of phenolic resin-based curing agents include phenol novolac resin and cresol novolac resin. Examples include novolak resins such as volak resins, and resol-type phenolic resins.

[0209] These curing agents can be used alone or in combination of two or more. Among these curing agents, phenolic resin curing agents are preferred, and phenolic novolac resins and the like are also preferred. Novolac resins are more preferred.

[0210] The ratio of the curing agent to the epoxy resin component (compound having an epoxy group) in the curable composition is For example, 0.1 to 500 parts by mass, preferably 1 to 300 parts by mass, relative to 100 parts by mass in total The amount is more preferably 10 to 150 parts by mass. The ratio of the epoxy group of the epoxy resin component is, for example, 0.1 to 4 equivalents, preferably Preferably, the amount is 0.3 to 2 equivalents and 0.5 to 1.5 equivalents in the following stepwise manner.

[0211] Examples of the curing accelerator include tertiary amines, imidazoles and their derivatives. amines; alkali metal or alkaline earth metal alkoxides; phosphines, in particular Examples of suitable phosphines include triarylphosphines such as triphenylphosphine; dimer acid polyamides; Amide compounds; Lewis acid complex compounds such as boron trifluoride-ethylamine complex; poly Sulfur compounds such as sulfides, mercaptan compounds (thiol compounds); phenyl dichloride Boron compounds such as borane; condensation of organotitanium compounds, organoaluminum compounds, etc. As for the amines, examples of the tertiary amines include thiazolinone, ... Triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol phenol, tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4 0]-7-undecene, and the imidazoles include 2-methylimidazoline. Mono- or dialkyl imidazoles such as 2-ethyl-4-methylimidazole, and aryl imidazoles such as 2-phenylimidazole. Examples of the salts include phenol salts, phenol novolac salts, carbonates, and formates. These curing accelerators may be used alone or in combination of two or more. Among the polymerization accelerators, phosphines are preferred, and triaryl phosphine such as triphenylphosphine is preferred. Phosphines are more preferred.

[0212] The proportion of the curing accelerator is determined based on the epoxy resin component (compound having an epoxy group) in the curable composition. For example, 0.01 to 30 parts by mass, preferably in the following stepwise manner, relative to 100 parts by mass of the total amount of , 0.05 to 20 parts by mass, 0.1 to 10 parts by mass, 0.1 to 5 parts by mass. The ratio of the accelerator is based on 100 parts by mass of the total amount of the epoxy resin component and the curing agent in the curable composition. For example, 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0 0.5 to 2 parts by mass.

[0213] The curable composition contains a photopolymerization initiator such as a cationic polymerization initiator or a photoacid generator. The photopolymerization initiator may be, for example, an aromatic diazonium salt. onium salts of Bronsted acids such as aromatic sulfonium salts and aromatic iodonium salts Examples include:

[0214] Examples of aromatic diazonium salts include benzenediazonium hexafluoroantimony. Benzenediazonium compounds such as benzodiazonium monate and benzenediazonium hexafluorophosphate Examples include the mussels.

[0215] Examples of aromatic sulfonium salts include triphenylsulfonium hexafluorophosphate. triphenylsulfonium sulphate, triphenylsulfonium hexafluoroantimonate, etc. Sulfonium compounds, 4,4'-bis(diphenylsulfonio)diphenylsulfide bis 4,4'-bis(diphenylsulfonio)diphenyl, such as hexafluorophosphate Sulfides and the like are included.

[0216] Examples of aromatic iodonium salts include diphenyliodonium tetrakis(penta ... fluorophenyl)borate, diphenyliodonium hexafluorophosphate, etc. Diphenyliodonium compounds, di(4-nonylphenyl)iodonium hexafluorophosphate Examples include di(4-nonylphenyl)iodonium sulfate.

[0217] These photopolymerization initiators can be used alone or in combination of two or more. The ratio of these photopolymerization initiators is determined based on the epoxy resin component (having an epoxy group) in the curing agent composition. 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the compound (compounds containing the compound) It may be about a few parts.

[0218] (reactive diluent) Reactive diluents with low viscosity, for example, a viscosity of about 200 mPa·s at 25°C Preferably, the epoxy compound is a monofunctional or polyfunctional epoxy compound having a viscosity of 30 mPa·s or less. Examples of monofunctional epoxy compounds include 2-ethylhexylglycidyl ether. alkyl glycidyl ethers such as glycidyl ether; alkenyl glycidyl ethers such as allyl glycidyl ether; phenyl glycidyl ether, phenyl glycidyl ether, pt-butylphenyl glycidyl aryl glycidyl ethers such as diglycidyl ethers; alkyl groups corresponding to these compounds; Glycidyl ethers such as glycidyl ethers of octylene oxide adducts; Alkene oxy such as cyclohexene, styrene oxide, and 4-vinylcyclohexene monoxide Examples include mosquitoes.

[0219] Examples of polyfunctional epoxy compounds include diglycidyl ether, polyol polyglycol, Examples include glycidyl ether, diglycidyl aniline, and cycloalkene oxide. The polyol polyglycidyl ether may be butanediol diglycidyl ether. , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol (Poly)alkanediol diglycidyl ethers such as diglycidyl ethers, cyclo Hexane dimethanol diglycidyl ether, trimethylolpropane diglycidyl or triglycidyl glycerin diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, etc. Alkene oxides include vinylcyclohexene dioxide, methylated vinylcyclohexene, Xene dioxide, etc.

[0220] These reactive diluents may be used alone or in combination of two or more. The ratio is based on the total amount of epoxy resin components (compounds having epoxy groups) in the hardener composition (100%). For example, 1 to 1000 parts by mass, preferably 5 to 500 parts by mass, more preferably The amount is preferably 10 to 200 parts by mass.

[0221] (solvent) The solvent may be, for example, a solvent containing the fluorene compound represented by the formula (1) and the composition (liquid composition). The solvent may be the same as the solvents exemplified as the solvent for forming the compound or solution.

[0222] These solvents may be used alone or in combination of two or more. These solvents can be used alone or in combination of two or more. Glycol monoalkyl ether acetates are preferred, and C 2-4 Alkylene glycol mono C 1-4 Alkyl ether acetates are preferred. The ratio is based on the total amount of epoxy resin components (compounds having epoxy groups) in the hardener composition (100%). The amount may be selected from the range of, for example, 0 to 500 parts by mass, and is preferably selected from the following ranges: The amount is stepwise 10 to 400 parts by mass, 20 to 300 parts by mass, and 30 to 200 parts by mass. When a solvent is contained, the solid content concentration of the curable composition is not particularly limited, and the curable composition can be cured as long as it has a desired flowability. The content may be adjusted to exhibit mobility, for example, about 0.1 to 70 mass %.

[0223] (additives) The additives include conventional additives such as colorants such as dyes and pigments, stabilizers, fillers, Conductive agents, antistatic agents, flame retardants, flame retardant assistants, flexibilizers, plasticizers, surfactants, dispersants, compatibility Examples include additives, flow control agents, leveling agents, antifoaming agents, surface modifiers, antibacterial agents, and preservatives. Examples of the stabilizer include a heat stabilizer, an antioxidant, and an ultraviolet absorber. Examples of the filler include silica, talc, and mica. Examples of the flame retardant include phosphorus. These additives can be used alone. These additives may be used singly or in combination of two or more. The total proportion of these additives is based on the total solid content. It may be, for example, 10% by mass or less, preferably 0 to 3% by mass, based on the total mass; for example, 0 It may be about 0.01 to 5% by mass, preferably 0.1 to 1% by mass.

[0224] The curable composition contains an epoxy compound represented by the formula (1E) and, if necessary, the above-mentioned It may also be prepared by mixing and dispersing the above-mentioned other ingredients in a mixer or agitator. Examples of the mixer or mixer include a ball mill, a tumble mixer, and a ribbon blender. , Henschel mixer, mixing roll, kneader, Banbury mixer, etc. The temperature during mixing (kneading) or stirring may be, for example, about 50 to 250°C. The temperature is preferably 100 to 200°C.

[0225] [Cured product] The cured product can be prepared by subjecting the curable composition to a curing reaction (curing treatment). This can be achieved by using a chemical catalyst, heating, or irradiating with light (active energy rays). These may be combined.

[0226] When the curing treatment is carried out by heating, the heating temperature is, for example, 50 to 250°C, preferably The temperature may be 70 to 220°C, 80 to 200°C, or 90 to 170°C in the following stepwise manner. The temperature is more preferably 150 to 200°C, and particularly preferably 170 to 180°C. For example, the heating may be carried out at a relatively low temperature, specifically, at about 50 to 130°C, preferably 70 After heat treatment at 120°C, the mixture is heated at a relatively high temperature, specifically, at about 140 to 350°C, preferably Alternatively, heat treatment may be performed at 150 to 300°C. Such curing treatment may be performed depending on the shape of the cured product. If necessary, this may be done during and / or after molding (or pre-molding) of the curable composition. For example, if necessary, the curable composition is heated and melted, poured into a predetermined mold, and heated to harden. The molding method and curing conditions are not particularly limited. For example, when molding using a predetermined mold, molding methods using heat and pressure or cold pressing are used. Alternatively, a low-temperature molding method called "latheless" may be used. Alternatively, the curable composition may be coated on a substrate and cured, for example, by photopolymerization using the photopolymerization method described below. It may be cured by irradiation or the like.

[0227] When performing curing treatment by light irradiation, the wavelength of the light is selected appropriately depending on the type of acid generator, etc. The amount of light to be irradiated (exposure amount) may be, for example, ultraviolet light or visible light. The curing rate can be selected depending on the thickness of the curable composition (coating film), for example, 10 to 10,000 mJ / cm 2 The dose may be about 100 to 5000 mJ / cm. 2 , more preferably 5 00~3000mJ / cm 2 The light source may be, for example, a high-pressure mercury lamp or a deuterium lamp. lamps, halogen lamps, metal halide lamps, xenon lamps, LED lasers, etc. In order to promote the curing of the curable composition, not only light irradiation but also laser light can be used. The heat treatment may be carried out.

[0228] The shape of the cured product is not particularly limited, and may be one-dimensional (e.g., rod-like), two-dimensional (e.g., sheet-like), or the like. , film, plate, etc.), three-dimensional shape [for example, block, rod, hollow (tube or Such a cured product may be any of the following: Since the compound represented by the formula (I) is contained, the composition exhibits a high refractive index and high heat resistance.

[0229] The 5% mass loss temperature of the cured product may be, for example, about 350 to 500°C, and is preferably The temperature is 400 to 450°C and 410 to 430°C in the following stages. The glass transition temperature Tg(TMA) measured by a thermomechanical analyzer (TMA) is, for example, 150 to The temperature may be about 300°C, and preferably the temperature is set to 200 to 250°C, 200 to 2 The temperature was 20°C. The glass transition temperature of the cured product was measured using a dynamic viscoelasticity measuring device (DMA). The temperature Tg (DMA) may be, for example, about 150 to 300°C, and preferably The temperature ranges are 200-250°C and 210-230°C.

[0230] The 5% mass loss temperatures of the cured product, Tg(TMA) and Tg(DMA), are as follows: It can be measured according to the method described in the Examples. [Example]

[0231] The present invention will be described in more detail below based on examples, but the present invention will not be limited to these examples. However, the evaluation method is not limited to the above. Details of the evaluation method are shown below.

[0232] [Evaluation method] (HPLC) The HPLC (High Performance Liquid Chromatograph) equipment used was the "L" manufactured by Shimadzu Corporation. C-2010A HT" and Tosoh Corporation's "ODS-80TM" column. The sample was dissolved in acetonitrile and measured, and the HPLC purity [area %] was calculated.

[0233] ( 1 H-NMR) The sample was dissolved in a deuterated solvent (CDCl3) containing tetramethylsilane as an internal standard. Using a nuclear magnetic resonance spectrometer (BRUKER "AVANCE III HD"), 1 H -NMR spectrum was measured.

[0234] (Refractive index nD) The refractive index was measured using a refractometer (ATAGO Co., Ltd., "RX-7000i") at a temperature of 25°C. Measurement was performed at a wavelength of 589 nm (D line). The refractive index was calculated by using a sample in dimethyl sulfoxide. The resulting solution was dissolved in ethanol at concentrations of 5.0 mass %, 10.0 mass %, and 30.0 mass % (as obtained in Example 4). The solution of only DPBNFG at 5.0 mass%, 10.0 mass% and 14.7 mass% was Prepare and measure the refractive index of the resulting solution and the solution with a concentration of 0% by mass (dimethyl sulfoxide only). The concentration was calculated by extrapolating the calibration curve (approximate straight line) to 100% by mass.

[0235] (melting or melting temperature) Measured using a melting point measuring device (BUCHI "Melting Point M-565") under the following conditions: The melting (melting) start temperature and melting (melting) end temperature were read. The average values ​​of the melting start temperature and melting end temperature were calculated.

[0236] Measurement start temperature: 100℃ Heating rate: 10℃ / min Melting start detection condition: 15% (The point at which the change in the sample's transmittance reaches 15% or more is considered to be the start of melting. temperature) Measurement mode: Stationary mode Number of measurements: n=3

[0237] (5% mass reduction temperature) Thermogravimetry-Differential Thermal Analysis (TG-DTA) (SII Nanotechnology Co., Ltd.) ) "TG / DTA6200" under a nitrogen atmosphere at a temperature rise rate of 10°C / min. The temperature at which the mass of the sample decreased by 5% was measured.

[0238] (glass transition temperature Tg) The glass transition temperature Tg (TMA) of the cured product is measured by thermomechanical analysis in accordance with JIS K 7197. Measurement was performed using a TMA measuring device (Rigaku Corporation "TMA 8311") under the following conditions: did.

[0239] Test dimensions: approx. 10mm x 5mm x 3mm Heating rate: 5℃ / min Measurement temperature range: Room temperature to 300°C Measurement mode: Compression (load 49mN) Atmosphere: Nitrogen flow (100 mL / min) Number of measurements: n=1

[0240] In addition, the glass transition temperature Tg (DMA, tanδ) of the cured product is In accordance with this, a dynamic viscoelasticity (DMA) measuring device (Rheogel-E4 manufactured by UBM Co., Ltd.) was used. 000") was used and measurements were taken under the following conditions.

[0241] Heating rate: 4℃ / min Frequency: 1Hz Atmosphere: Air flow Measurement mode: bending Number of measurements: n=1

[0242] (Solubility) For 200 mg of sample, add each of the solvents described below to a concentration of 30 mass % or 50 mass %. The solubility of the sample in each solvent was confirmed when the sample was added to each solvent and stirred at room temperature (25°C). If it does not dissolve at room temperature (25°C), heat it stepwise to 50°C or 80°C. The solubility was confirmed according to the following evaluation criteria.

[0243] ○(25℃): Dissolved at 25℃ ○ (50℃): Not dissolved at 25℃, dissolved when heated to 50℃ ○ (80℃): Not dissolved at 50℃, dissolved when heated to 80℃ ×: Not dissolved even when heated to 80°C

[0244] (Storage stability) The sample was dissolved in propylene glycol monomethyl ether acetate (PGM The solution was completely dissolved in EA) and stored at 5°C. After 24 hours, the state of the solution was observed and the following results were obtained: The evaluation criteria were storage stability (solution stability or low-temperature stability).

[0245] ○: No precipitation of the sample was observed ×: Precipitation of the sample was confirmed

[0246] (epoxy equivalent) In accordance with JIS K 7236:2001, an automatic titrator (GT-10 manufactured by Mitsubishi Chemical Corporation) was used. 0) was titrated with perchloric acid solution (acetic acid).

[0247] [Synthesis Example 1] 9,9-bis(6-hydroxy-2-naphthyl)-2,7-dibromofluoro Synthesis of orene (hereinafter referred to as DBrBNF)

[0248] [ka]

[0249] In a reaction vessel, 12.5 g (0.037 mol) of 2,7-dibromo-9-fluorenone and 2 -Naphthol 16.0g (0.11mol), 1,4-dioxane 90mL, 3-mercaptoethanol Charge 0.5 mL (5.8 mmol) of butyropropionic acid and 26 mL of 98% by mass concentrated sulfuric acid. The mixture was stirred under a nitrogen atmosphere and reacted at 60°C for 24 hours. After cooling to room temperature, the mixture was heated and decompressed to dissolve the After removing the solvent, 300 mL of dichloromethane and 300 mL of ion-exchanged water were added for liquid separation and extraction. After adjusting the pH to 7 with sodium bicarbonate aqueous solution, 300 mL of ion-exchanged water was added. This washing procedure with ion-exchanged water was repeated three times, and then the mixture was heated and decompressed. Dichloromethane was removed to give yellow crude crystals. The obtained yellow crude crystals were subjected to column chromatography. - (silica gel carrier, developing solvent: dichloromethane) and dried under reduced pressure. 6.01 g of DBrBNF was obtained (slightly brown solid, yield 24%, HPLC purity 95.2%). The resulting DBrBNF 1 The results of H-NMR are shown below.

[0250] 1 H-NMR (CDCl3, 300MHz): δ(ppm)5.2(s, 2H), 7. 0-7.1(m,4H), 7.3(d,2H), 7.5(m,12H).

[0251] [Example 1A] 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(2-naphthyl) Synthesis of butyl)fluorene (hereinafter referred to as DNBNF)

[0252] [ka]

[0253] In the reactor, 0.78 g (1.3 mmol) of DBrBNF and 0.2 g (1.3 mmol) of 2-naphthylboronic acid were added. 54 g (3.1 mmol), 10 mL of toluene, and 2.6 mL of 1 M aqueous potassium carbonate solution L (2.6 mmol) was charged and tetrakis(triphenylphosphine) peroxide was added under a nitrogen stream. Add 75 mg (0.065 mmol) of radium (0) [or Pd(PPh3)4] The reaction was carried out by heating under reflux at an internal temperature of 85°C for 15 hours. After adding 75 mL of chloromethane and stirring, the mixture was subjected to separation and extraction. After repeating this procedure three times, the organic layer was concentrated to obtain a light brown crude product. Silica gel chromatography [developing solvent: dichloromethane / ethyl acetate (volume After purifying with a 2000 / 1000 ratio, 351 mg of DNBNF was obtained by drying under reduced pressure. A pale yellow solid was obtained, with a yield of 49.9% and an HPLC purity of 97.4%. The refractive index nD is 1.79, the 5% mass loss temperature is 443°C, 1 H-NMR results is shown below.

[0254] 1 H-NMR (CDCl3, 300MHz): δ(ppm)4.9(s,2H), 7. 0(d,2H), 7.1(s,2H), 7.4-7.7(m,14H), 7.8-8.1 (m,14H)

[0255] [Example 1B] Synthesis of DNBNF In a reactor, 21.3 g (0.035 mol) of DBrBNF and 1 g of 2-naphthylboronic acid were added. 3.2 g (0.077 mol), 130 mL of toluene, and 8.1 M aqueous potassium carbonate solution 30 mL (0.245 mol) of the solution was added and dissolved at 70 to 80°C under a nitrogen stream. Tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)] 4] 20.2 mg (0.018 mmol) was added, and the mixture was reacted at an internal temperature of 80°C for 1 hour. 30 mL of ion-exchanged water was added to the reaction mixture, which was then stirred and separated for extraction. After repeating this water washing procedure three times, the organic layer was diluted twice with toluene and 350 ml of heptane was added. After drying under reduced pressure, 20.5 g of DNBNF (a pale reddish orange solid, The yield was 83.3% and the HPLC purity was 88.6%. The refractive index of the obtained DNBNF was nD, 5% mass loss temperature; 1 The results of H-NMR were the same as those of Example 1A. The melting temperature was 176.4°C and the melting temperature was 224.1°C. In addition, a halo peak was observed in X-ray diffraction (XRD), indicating that it was an amorphous material. It was confirmed that:

[0256] [Example 1C] Synthesis of DNBNF In a reactor, 21.3 g (0.035 mol) of DBrBNF and 1 g of 2-naphthylboronic acid were added. 3.8g (0.081mol), triphenylphosphine 36.7mg (0.140mm ol), 80 mL of methyl isobutyl ketone (MIBK), and 4 M aqueous potassium carbonate solution 60 mL (0.245 mol) of acetic acid was added and dissolved at 70°C under a nitrogen stream. 7.9 mg (0.035 mmol) of palladium was added, and the mixture was allowed to react at an internal temperature of 75°C for 7 hours. The water in the reaction solution was drained, 30 mL of ion-exchanged water was added, and the mixture was neutralized with 10% by mass hydrochloric acid. After that, the reaction solution was washed with ion-exchanged water three times. The mixture was adjusted to 0 to 45% by mass, and the temperature was allowed to cool from 60°C to room temperature while stirring at 250 rpm. The crystallization occurred when the temperature was lowered. The precipitation started at about 45°C. After drying under reduced pressure, Obtained 18.7 g (white solid, yield 76.0%, HPLC purity 99.0%). Example 1A Compared with DNBNF obtained in 1B and 1C, the coloring was significantly reduced and the yield and purity were also high. The refractive index nD, 5% mass loss temperature, 1 H-NMR results The results were the same as in Example 1A. The melting start temperature was 188.5°C and the melting end temperature was The temperature was 218.8°C. In X-ray diffraction (XRD), the peaks were not halo peaks but regular peaks. A fold pattern was observed, and it was confirmed that the product was crystalline, unlike Example 1B.

[0257] [Example 2] 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenyl Synthesis of Luoren (hereinafter also referred to as DPBNF)

[0258] [ka]

[0259] In the reactor, 21.3 g (0.035 mol) of DBrBNF and 9.9 g of phenylboronic acid were added. g (0.081 mol), triphenylphosphine 36.7 mg (0.140 mmol) , 80 mL of MIBK, and 60 mL (0.245 mol) of 4 M potassium carbonate aqueous solution The mixture was dissolved at 70°C under a nitrogen stream. 5 mmol) was added and the mixture was allowed to react at an internal temperature of 75°C for 5 hours. After adding 30 mL of ion-exchange water, the pH was adjusted to 7 with 10% by mass hydrochloric acid. The reaction solution was concentrated to remove MIBK, and toluene was added. The toluene solution was diluted with 21 g (0.210 mmol) of heptane. 17.7 g of DPBNF (pale yellow solid, yield 84.0%, HP The refractive index nD of the obtained DPBNF was 1.75, and the LC purity was 87.9%. The mass loss temperature is 360°C. 1 The results of H-NMR are shown below. The melting temperature was 180.7°C and the melting end temperature was 227.4°C.

[0260] 1 H-NMR (CDCl3, 300MHz): δ(ppm)5.49(s,2H), 7 .0 (m, 4H), 7.2-8.0 (m, 24H)

[0261] [Comparative Example 1] 9,9-bis(6-hydroxy-2-naphthyl)fluorene (Osaka Gas Chemicals Co., Ltd.) The refractive index nD of the cellulose acylate copolymer (manufactured by cellulose acylate copolymer "BNF") is 1.74, the 5% mass loss temperature is 369°C, and the melting point is 1.74. The melting start temperature was 259°C and the melting end temperature was 263°C.

[0262] Comparative Example 2 9,9-bis(4-hydroxyphenyl)fluorene (Osaka Gas Chemicals Co., Ltd. "B The refractive index nD of PF (melting point 223-224°C) is 1.68, and the 5% mass loss temperature is 3 The temperature was 01℃.

[0263] Comparative Example 3 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (Osaka Gas Chemicals) The refractive index nD of "BCF" manufactured by Epson Corporation (melting point 218-219°C) is 1.68, and 5% by mass The reduction temperature was 313°C.

[0264] Comparative Example 4 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (Osaka Gas Chemical Co., Ltd.) The refractive index nD of "BPEF" manufactured by Cal Corporation (melting point 161-163°C) is 1.65, The % mass loss temperature was 342°C.

[0265] The physical properties (refractive index, 5% mass % ) of the fluorene compounds obtained in the examples and comparative examples are shown in Table 1 below. The melting point of the commercially available product is shown in Table 1. vinegar).

[0266] [Table 1]

[0267] As is clear from the results in Table 1, the examples showed much higher refractive indices than the comparative examples. In addition, benzene rings were introduced into the 2,7 positions of the fluorene skeleton of Comparative Example 1 (BNF). In Example 2 (DPBNF) containing naphthalene, a decrease in the 5% mass loss temperature was observed. In Example 1 (DNBNF) where a cyclic ring was introduced, the 5% mass loss temperature was significantly improved, and it became more heat resistant. In addition, Example 1 (DNBNF) and Example 2 (DPBNF) have high While exhibiting a 5% mass loss temperature, the melting onset temperature was surprisingly low, especially in Example 1 (DNBN In F), the naphthalene rings, which have more benzene ring skeletons than in Example 2 (DPBNF), are introduced. Nevertheless, the melting end temperature was low and it was found that it could be easily melted.

[0268] The following Table 2 shows the concentrations of the fluorene compounds obtained in Examples 1C, 2, and Comparative Example 1. The results of the evaluation of solubility when dissolved in each solvent at 30% by mass are shown below. Propylene glycol monomethyl ether acetate, PGME is propylene glycol monomethyl ether, n-PrOH is n-propanol, NMP is N-methyl-2-pyro DMF is N,N-dimethylformamide, and DMSO is dimethyl sulfoxide. Each of these is shown below (same below). [Table 2]

[0269] As is clear from the results in Table 2, Example 1 (DNBNF) and Example 2 (DPBNF) ) contains many benzene ring structures, it was expected that the solubility would be significantly reduced. In particular, in Example 1 (DNBNF), all the solvents tested were soluble in It was soluble in

[0270] The following Table 3 shows the concentrations of the fluorene compounds obtained in Examples 1C, 2, and Comparative Example 1. Storage stability of a solution dissolved in PGMEA at 30% by mass (solution prepared in the solubility test in Table 2) The results of the evaluation are shown below. [Table 3]

[0271] As is clear from the results in Table 3, in all Examples, the high concentration and low temperature environment in which precipitation is likely to occur In this case, the solution state was stably maintained without precipitation.

[0272] [Example 3A] 9,9-bis(6-glycidyloxy-2-naphthyl)-2,7-di( Synthesis of 2-naphthyl)fluorene (hereinafter referred to as DNBNFG)

[0273] [ka]

[0274] Into the reactor, 105.43 g (0.15 mol) of DNBNF obtained in Example 1C, 303.6g (3.3mol) of methyl oxirane, 83.2g of dimethyl sulfoxide The mixture was heated and dissolved at 40°C for 30 minutes under a nitrogen stream. 13.2g (0.33mol) of sodium was added. 4 hours after adding sodium hydroxide As a result of heating and stirring while maintaining the temperature at 40°C, the raw material DNBNF was found to be completely consumed by HPLC. After that, chloromethyloxirane was concentrated and removed using an evaporator, and MI After adding 550 g of BK, the mixture was washed five times with 200 mL of ion-exchanged water. Adjust the IBK solution to a solid content of 20% by mass and add 1635 g of isopropyl alcohol (IPA). The resulting mixture was added dropwise over 1 hour to give 107 g of DNBNFG (white solid, 88% yield). The refractive index nD of the obtained DNBNFG was 1.76, and the The mass loss temperature was 405°C, and the resulting D exhibited very high refractive index and heat resistance. The melting temperature of NBNFG is 149°C, and the epoxy equivalent is 432 0.4g / eq, 1 The results of H-NMR are shown below.

[0275] 1 H-NMR (CDCl3, 300MHz): δ(ppm)2.8(t,2H), 2. 9(t,2H), 3.4(m,2H), 4.0(dd,2H), 4.3(dd,2H), 7.1 (m, 4H), 7.4-7.9 (m, 28H)

[0276] [Example 3B] Synthesis of DNBNFG In a 200 mL four-necked recovery flask, 35.1 g (0 Add 101g (1.1mol, 22eq.) of epichlorohydrin and The atmosphere inside the vessel was replaced with nitrogen. Sodium hydroxide (granules) 6.6 g (0.17 mol, 3.3 eq .) was added, and the refluxed epichlorohydrin was added to the solution while heating to reflux at 118°C. After stirring for 3 hours, epichlorohydrin was concentrated and removed. Dissolve in 199g (2.0mol, 40eq.) of isobutyl ketone (MIBK), then add 100ml of distilled water. 17g of cellulose acetate and 2g of celite were added and stirred at 70°C. The celite was filtered off and the organic layer was The organic layer was washed with 80 mL of distilled water four times. The solid obtained was dried at 70°C to obtain a pale yellow solid. By purifying it by chromatography (dichloromethane / hexane = 6 / 4 (volume ratio)), 5.64 g of DNBNFG (slightly yellow solid, yield 16.1%, HPLC purity 94%) was obtained. The refractive index nD of the obtained DNBNFG, the 5% mass loss temperature and the melting onset temperature are the same as those in Example 1. The results were the same as those for 3A. 1 The results of H-NMR are shown below.

[0277] 1 H-NMR (CDCl3,300MHz): δ(ppm)2.8(t,2H), 2. 9(t,2H), 3.4(m,2H), 4.0(dd,2H), 4.4(dd,2H), 7.1(m,4H), 7.4-7.7(m,14H), 7.8-8.0(m,14H)

[0278] [Example 4] 9,9-bis(6-glycidyloxy-2-naphthyl)-2,7-diphenyl Synthesis of diphenylfluorene (hereinafter referred to as DPBNFG) [ka]

[0279] The same procedure was carried out except that 90.4 g (0.15 mol) of DPBNF was used instead of DNBNF. In the same manner as in Example 3A, 93 g of DPBNFG (pale yellow solid, yield 87%, HPLC The refractive index nD of the obtained DPBNFG was 1.72, and the mass was reduced by 5%. The initial temperature is 380°C, the melting point is 195°C, and the epoxy equivalent is 384.4g. / eq, 1 The results of H-NMR are shown below.

[0280] 1 H-NMR (CDCl3, 300MHz): δ(ppm)2.8(t,2H), 2. 9(t,2H), 3.4(m,2H), 4.0(dd,2H), 4.3(dd,2H), 7 .1(m,4H), 7.3-7.9(m,24H)

[0281] Comparative Example 5 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene (Osaka Gas Chemicals) The refractive index nD of the "BNFG" manufactured by Epson Corporation is 1.70, and the 5% mass loss temperature is 391°C. The melting initiation temperature was 113°C, and the epoxy equivalent was 292.0 g / eq.

[0282] Comparative Example 6 Refractive index nD of bisphenol A epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation) is 1.58, the 5% mass loss temperature is 380°C, and the epoxy equivalent is 187g / eq It was.

[0283] Table 4 below shows the physical properties of the fluorene compounds (epoxy resins) obtained in the examples and comparative examples. Shows.

[0284] [Table 4]

[0285] As is clear from the results in Table 4, the examples showed a much higher refractive index than the comparative examples. In Comparative Example 5 (BNFG), benzene rings are attached to the 2,7 positions of the fluorene skeleton. In Example 4 (DPBNFG), a 5% mass loss temperature decrease was observed, while naphtha In Example 3 (DNBNFG) where the talen ring was introduced, the 5% mass loss temperature was significantly improved, and the resistance While the examples have excellent heat resistance, the melting point is relatively low and the hardener In particular, it has been found that the naphthalene ring can be easily or efficiently mixed with other components such as The melting temperature of Example 3, in which a benzene ring was introduced, was lower than that of Example 4, in which a benzene ring was introduced. was unexpected.

[0286] The following Table 5 shows the fluorene compounds (epoxides) obtained in Examples 3A and 4 and Comparative Example 5. The results of the evaluation of solubility when a hydroxyl resin was dissolved in each solvent at a concentration of 30% by mass are shown. [Table 5]

[0287] As is clear from the results in Table 5, Example 3A (DNBNFG) has many benzene ring skeletons. However, the solubility was significantly reduced for all the solvents tested. It was soluble in water and showed unexpectedly high solubility. It was surprising that Example 3 had better solubility than Example 4, which had a benzene ring introduced.

[0288] In addition, in Example 3A (DNBNFG), even at a concentration of 50 mass %, ethyl acetate, acetone ton, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, DMF and D Dissolve each of the cyclohexanone, PGMEA, and P in MSO at room temperature (25°C). GME, benzyl alcohol, 1,4-dioxane, methyl lactate, ethyl lactate, butyl lactate ethyl 3-ethoxypropionate, γ-butyrolactone, NMP, and toluene Each was dissolved by heating to 80°C or less.

[0289] In contrast, Example 4 (DPBNFG) was dissolved in NMP at room temperature (25 It only dissolved at 20°C.

[0290] <Preparation of Curable Composition and Cured Product> The epoxy resins of Example 3A and Comparative Examples 5 and 6 and phenol novolak as a curing agent were Resin (Gun-ei Chemical Industry Co., Ltd. "PSM-4261", hydroxyl group equivalent 105g / eq) The mixture was charged at an equivalent ratio of 1:1 and kneaded at 190°C using a two-roll mill. After the kneaded mixture was cooled to room temperature, TPP (triphenylphosphine, Kanto Chemical Co., Ltd.) to 100 parts by weight of epoxy resin and phenol novolac resin. The resulting kneaded mixture was kneaded at 120°C using a roll. After press molding for 30 minutes, the mixture was heated in an oven at 175°C for 5 hours (post-cure). A cured product was obtained.

[0291] Table 6 below shows the fluorene compounds (epoxy resins) obtained in the examples and comparative examples, and The physical properties of the cured product obtained using this epoxy resin are shown below.

[0292] [Table 6]

[0293] As is clear from Table 6, Example 3A exhibits higher heat resistance than Comparative Examples 5 and 6. Furthermore, the DNBNFG used in Example 3A had a larger amount of hydroxybenzoates in the chemical structure than the comparative examples 5 and 6. Although it is expected that the solubility (compatibility) will decrease due to the large number of benzene rings in the structure, Surprisingly, it exhibits good compatibility with curing agents, making it possible to prepare uniform curable compositions and cured products. It was possible to make it. [Industrial Applicability]

[0294] The fluorene compound of the present invention represented by the formula (1) exhibits a high refractive index and excellent heat resistance. Therefore, resin raw materials, for example, polyester resins such as polyarylate resins, polycarbonates, Carbonate resin, polyether resin, polyether ketone resin, polyether ether Monomer components of thermoplastic resins such as polyetherketone resins, including ketone resins, and p) acrylic resin, vinyl ester resin (or epoxy (meth) acrylate resin), It can be effectively used as a raw material for curable resins such as vinyl ether resins and epoxy resins. In particular, the fluorene compound represented by the formula (1) has a high 5% mass loss temperature and high durability. Despite its thermal properties, it has a surprisingly low melting point. Furthermore, it has excellent solubility. Therefore, it may be used as a monomer for melt or solution polymerization.

[0295] The fluorene compound represented by the formula (1) can also be used as a refractive index improver, a heat resistance improver, a hardener, a It can be effectively used as an additive (or resin additive) for curing agents. For example, a curing agent for epoxy resin can be used. The compound not only has a low melting temperature but also has excellent solubility (compatibility), making it suitable for melt mixing. A homogeneous composition may be easily or efficiently prepared by kneading or the like.

[0296] The resin or fluorene compound of the present invention represented by the formula (1) is used as a raw material. The composition containing the compound as an additive can be suitably used for optical members (optical materials or transparent materials), etc. The optical members include, for example, reflow lenses, pickup lenses, and micro lenses. Optical lenses, polarizing films, anti-reflective films, touch panel films, flexible films Films for flexible substrates, optical films such as display films, membranes for fuel cells, Examples include fibers, optical waveguides, and holograms.

[0297] The epoxy resin represented by the formula (1E) and the curable composition containing this epoxy resin are also The composition (or its cured product) has excellent properties such as a high refractive index and high heat resistance, so it can be used in applications such as Resist such as insulating material between layers of electronic components, solder resist for printed circuit boards, and coverlay materials, color filters, printing inks, electronic components or semiconductor sealants, etc. sealants, paints, coatings, adhesives, pressure sensitive adhesives, underfills, antistatic agents, Fillers, conductive members or materials, laminate materials, heat-sensitive materials such as materials for thermal paper, carbon materials , insulating materials, foams, pressure-sensitive materials, optical materials (or transparent materials), and any other materials. The epoxy resin represented by the formula (1E) is surprisingly useful in melting (melting ) Not only is the starting temperature relatively low, but the solubility (compatibility) is also excellent, so it can be used at relatively low temperatures. It is also possible to easily and efficiently prepare a uniform curable composition.

Claims

1. The following formula (1E) 【Chemical 1】 [In the formula, Y １ａ and Y １ｂ are each independently represented by the following formula (Y1): 【Chemistry 2】 (In the formula, Z １ indicates an arene ring, R １ represents a substituent, and m1 represents an integer of 0 or 1 or more. k1a and k1b each independently represent an integer of 0 to 4, and at least one of k1a and k1b is 1 or greater; R ２ａ and R ２ｂ each independently represents a substituent; m2a and m2b each independently represent an integer of 0 to 4; k1a + m2a and k1b + m2b are each independently 4 or less; Y ３ａ and Y ３ｂ are each independently represented by the following formula (Y3): 【Chemistry 3】 (In the formula, Z ２ represents a polycyclic arene ring, R ３ represents a substituent, m3 represents 0 or an integer of 1 or more, A １ represents a linear or branched alkylene group, n1 represents 0 or an integer of 1 or more, R ４ represents a hydrogen atom or a methyl group.) represents a monovalent group represented by the following formula: A fluorene compound represented by the formula:

2. In the formula (1E), Y １ａ and Y １ｂ Z in formula (Y1) represents １ is a benzene ring, a naphthalene ring, or a biphenyl ring, k1a and k1b are integers of 0 to 2, and Y ３ａ and Y ３ｂ Z in formula (Y3) represents ２ 2. The fluorene compound according to claim 1, wherein is a naphthalene ring or a biphenyl ring.

3. In the formula (1E), Y １ａ and Y １ｂ Z in formula (Y1) represents １ 3. The fluorene compound according to claim 1, wherein is a fused polycyclic arene ring.

4. The following formula (1) 【Chemistry 4】 [In the formula, Y ２ａ and Y ２ｂ are each independently represented by the following formula (Y2): 【Chemistry 5】 (In the formula, Z ２ , R ３ , m3, A １ and n1 are the same as those in formula (Y3) of claim 1. represents a monovalent group represented by Y １ａ and Y １ｂ is the same as formula (Y1) in claim 1, k1a and k1b, R ２ａ and R ２ｂ , m2a and m2b, k1a + m2a and k1b + m2b are each independently the same as in formula (1E) of claim 1. A method for producing a compound represented by formula (1E) according to any one of claims 1 to 3, comprising reacting a fluorene compound represented by the following formula with an epihalohydrin component.

5. A curable composition comprising the compound represented by formula (1E) according to any one of claims 1 to 3.

6. A cured product obtained by curing the curable composition according to claim 5.

7. An optical component comprising the cured product according to claim 6.

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