Fluorene compound and method for producing the same

Abstract

To provide a fluorene compound which exhibits a high refractive index and is used as a raw material monomer of an optical material.SOLUTION: The fluorene compound is represented by the following formula (1) (Y1a and Y1b each represent formula -Z1-(R1)m1; k1a and k1b each represent an integer of 0-4, provided that at least one of them represents 1 or more; R2a and R2b each represent a substituent; m2a and m2b each represent an integer of 0-4; k1a+m2a and k1b+m2b are each 4 or less; and Y2a and Y2b each represent formula -Z2(R3)m3-O-(A1O)n1-H (Z1 represents an arene ring; R1 represents a substituent; m1, m3 and n1 each represent an integer of 0 or more; Z2 represents a polycyclic arene ring; R3 represents a substituent; and A1 represents an alkylene 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 Art

[0002] A compound having a fluorene skeleton has excellent optical properties due to its chemical structure and is used as a resin material (optical material) for forming optical members.

[0003] Patent Document 1 discloses a thermoplastic resin containing a repeating unit represented by the following formula (1) as an optical material for forming optical members such as lenses.

[0004]

Chemical Formula

[0005] (In the formula, ring Z represents an aromatic hydrocarbon ring, R 1 and R 2 represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, Ar 1 and Ar 2 represent an aromatic group having 6 to 10 carbon atoms which may contain a substituent, L 1 and L 2 represent a divalent linking group, j and k represent integers of 0 or more, 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]

Chemical Formula

[0007] (In the formula, X represents a divalent linking group.)

[0008] Patent Document 1 describes a diol component represented by the following formula (a) as a raw material monomer for forming the above thermoplastic resin.

[0009] [Chemical formula]

[0010] (wherein, ring 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 those in the above formula (1), respectively).

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0012] Patent Document 1 describes that it is more preferable that ring Z is a benzene ring (or a 1,4-phenylene group). Also, among the numerous diol components represented by the above formula (a) exemplified, the diol components represented by formulas (a1) to (a24) in which ring Z is a benzene ring are also described as preferable.

[0013] Furthermore, in the examples of Patent Document 1, as the diol component represented by the formula (a), 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)fluorene (BPDN1) are used to prepare various polycarbonate resins and the like, and it is described that they are effective for increasing the refractive index and heat resistance.

[0014] However, even with these polycarbonate resins, the refractive index and heat resistance may not be sufficient depending on the application, and further improvement is required.

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

Means for Solving the Problems

[0016] As a result of intensive studies to achieve the above problems, the present inventors have found that a fluorene compound having a specific chemical structure exhibits a high refractive index, and completed the present invention.

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

[0018]

Chemical formula

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

[0020] [Chemical formula]

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

[0022] [Chemical formula]

[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.)

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

[0025] Further, in the formula (1), Y 1a and Y 1b Z in the formula (Y1) representing 1 may be a polycyclic arene ring such as a condensed polycyclic arene ring, and in particular, a condensed polycyclic C 10-14 arene ring such as a naphthalene ring. The fluorene compound may be at least one selected from a monomer for melt polymerization or solution polymerization and a resin additive for modifying a resin.

[0026] The present invention further includes a composition (liquid composition or solution) containing the fluorene compound and a solvent.

[0027] The present invention also includes a method for producing the fluorene compound including the reaction step described in the following (i) or (ii).

[0028] (i) A step of subjecting a compound represented by the following formula (2) to a coupling reaction with a compound represented by the following formula (3a) and a compound represented by the formula (3b)

[0029]

Chemical formula

[0030] [In the formula, X 1a and X 2a and X 1b and X 2b each independently represents a pair of reactive groups capable of forming a carbon-carbon bond by a coupling reaction, and Y 1a and Y 1b , k1a and k1b, R 2a and R 2b , m2a and m2b, and Y 2a and Y 2b are the same as those in the formula (1)].

[0031] (ii) A step of reacting a compound represented by the following formula (6) with a compound represented by the following formula (5a) and a compound represented by formula (5b)

[0032]

Chemical formula

[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 are the same as those in the formula (1).

[0034] The production method may further include a purification step (crystallization step or reprecipitation step) of precipitating (crystallizing or precipitating) the fluorene compound obtained in the reaction step from at least one solvent (crystallization solvent or reprecipitation solvent) selected from solvents such as (a) solvents containing aromatic hydrocarbons and aliphatic hydrocarbons, and (b) solvents containing ketones.

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

[0036]

Chemical formula

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

[0038]

Chemical formula

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

[0040] The present invention includes a method for producing a compound represented by the formula (1E) by reacting a compound represented by the formula (1) with an epihalohydrin component. The present invention also includes a curable composition containing the compound represented by the formula (1E), a cured product obtained by curing this curable composition, and an optical member containing this cured product.

[0041] In the present invention, as a secondary object, the following problems may be solved.

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

[0043] Still another object of the present invention is to provide a fluorene compound having high solubility (or compatibility) even when containing many benzene rings (aromatic rings) in its chemical structure, a method for producing the same, and a composition containing the compound.

[0044] Another object of the present invention is to provide a fluorene compound having a low melting temperature (melting temperature) even when containing many benzene rings (aromatic rings) in its chemical structure, a method for producing the same, and a composition containing the compound.

[0045] Also, in this specification and the claims, the number of carbon atoms of a substituent is C1, C6, C 10It may be represented by etc. For example, an alkyl group having 1 carbon atom is represented by "C1 alkyl", and an aryl group having 6 to 10 carbon atoms is represented by "C 6-10 aryl".

Advantages of the Invention

[0046] Since the fluorene compound of the present invention has a specific chemical structure, it exhibits a high refractive index. Further, the fluorene compound exhibits high heat resistance (or thermal decomposition resistance). Furthermore, although the fluorene compound contains many benzene rings (aromatic rings) in its chemical structure, it unexpectedly exhibits high solubility (or compatibility), so that it is possible to achieve both high solubility and high refractive index and high heat resistance. Therefore, the fluorene compound can easily or efficiently prepare a uniform composition with other reaction components such as solvents and curing agents. In addition, the fluorene compound shows a lower melting temperature (melting start or end temperature) contrary to expectations and can be easily melted, so that it can be effectively used not only as a monomer for melt polymerization but also can be easily or efficiently mixed into a resin by melt kneading or the like and can be effectively used as a resin modifier.

Modes for Carrying Out the Invention

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

[0048] Examples of the condensed polycyclic arene ring include condensed bicyclic to tetracyclic arene rings such as condensed bicyclic arene rings and condensed tricyclic arene rings. Examples of the condensed bicyclic arene ring include condensed bicyclic C such as naphthalene ring and indene ring10-16 Examples include an arene ring. Examples of the fused tricyclic arene ring include fused tricyclic C such as an anthracene ring and a phenanthrene ring 14-20 Examples include an arene ring. A preferred fused polycyclic arene ring is a fused polycyclic C such as a naphthalene ring 10-14 arene ring.

[0049] Examples of the ring assembly arene ring include biarene rings such as a biphenyl ring, a phenylnaphthalene ring, and a binaphthyl ring; and terarenene rings such as a terphenyl ring. A preferred ring assembly arene ring is a C such as a biphenyl ring 12-18 biarene ring.

[0050] In the present specification and claims, the "ring assembly arene ring" means that two or more ring systems (arene ring systems) are directly connected by a single bond or a double bond, and the number of bonds connecting the rings is one less than the number of ring systems. For example, as described above, a phenylnaphthalene ring, a binaphthyl ring, etc. are classified as ring assembly arene rings even if they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as a naphthalene ring (non-ring assembly arene ring).

[0051] Preferred ring Z 1 includes C 6-14 arene rings, more preferably C arene rings such as a benzene ring, a naphthalene ring, and a biphenyl ring 6-12 arene rings, still more preferably C arene rings such as a benzene ring and a naphthalene ring 6-10 arene rings, particularly a naphthalene ring. Note that when Z 1 is a polycyclic arene ring, particularly a fused polycyclic arene ring such as a naphthalene ring, it is not only easy to effectively improve the refractive index and heat resistance, but may also exhibit a low melting temperature and even high solubility (compatibility), which is preferable.

[0052] Also, in the monovalent groups Y 1a and Y 1b the ring Z 1It may be substituted at any position of the 1st to 4th positions or the 5th to 8th positions of the fluorene skeleton, and examples include the 2nd, 3rd, and / or 7th positions. Y 1a and Y 1b When the substitution numbers k1a and k1b of and are 1, preferable substitution positions (or bonding positions) are positions that are symmetric about the paper surface in the above formula (1), such as the 1,8-position, 2,7-position, 3,6-position, 4,5-position, etc., and particularly the 2,7-position is preferable.

[0053] In addition, the bonding position on the fluorene skeleton for ring Z 1 When ring Z 1 is a naphthalene ring, it may be either the 1st or 2nd position of the naphthalene ring, and the 2nd position of the naphthalene ring is preferable.

[0054] R 1 The substituent (non-reactive substituent or non-polymerizable substituent) represented by includes, for example, a halogen atom, a hydrocarbon group (or group [-R h ), group [-OR h (wherein R h represents the hydrocarbon group), group [-SR h (wherein R h represents the hydrocarbon group), an acyl group, a nitro group, a cyano group, a mono- or di-substituted amino group, etc.

[0055] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0056] The hydrocarbon group represented by the above R h includes, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, etc.

[0057] Examples of the alkyl group include linear or branched C 1-10 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, etc., and preferably linear or branched C 1-6An alkyl group, more preferably a linear or branched C 1-4 alkyl group.

[0058] Examples of the cycloalkyl group include C 5-10 cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group.

[0059] Examples of the aryl group include C 6-12 aryl groups such as a phenyl group, an alkylphenyl group, a biphenylyl group, and a naphthyl group. Examples of the alkylphenyl group include mono- to tri-C 1-4 alkyl-phenyl groups such as a methylphenyl group (or tolyl group) and a dimethylphenyl group (or xylyl group).

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

[0061] Examples of the group [-OR h include an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, etc., and specifically, groups corresponding to the examples of the hydrocarbon group R h . Examples of the alkoxy group include linear or branched C 1-10 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. Examples of the cycloalkyloxy group include C 5-10 cycloalkyloxy groups such as a cyclohexyloxy group. Examples of the aryloxy group include C 6-10 aryloxy groups such as a phenoxy group. Examples of the aralkyloxy group include C 6-10 aryl-C 1-4 alkyloxy groups such as a benzyloxy group.

[0062] Examples of the group [-SR hExamples thereof include an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, etc. Specifically, the hydrocarbon group R h includes groups corresponding to the examples given above. Examples of the alkylthio group include C 1-10 alkylthio groups such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, a t-butylthio group. Examples of the cycloalkylthio group include C 5-10 cycloalkylthio groups such as a cyclohexylthio group. Examples of the arylthio group include C 6-10 arylthio groups such as a thiophenoxy group (phenylthio group). Examples of the aralkylthio group include C 6-10 aryl-C 1-4 alkylthio groups such as a benzylthio group.

[0063] Examples of the acyl group include C 1-6 alkyl-carbonyl groups such as an acetyl group.

[0064] Examples of the mono- or di-substituted amino group include a dialkylamino group, a bis(alkylcarbonyl)amino group, etc. Examples of the dialkylamino group include diC 1-4 alkylamino groups such as a dimethylamino group. Examples of the bis(alkylcarbonyl)amino group include bis(C 1-4 alkyl-carbonyl)amino groups such as a diacetylamino group.

[0065] Among these groups R 1 , typical groups include a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, a substituted amino group, etc. When m1 is 1 or more, preferred groups R 1 include an alkyl group and an alkoxy group. Specifically, they include linear or branched C 1-6 alkyl groups such as a methyl group, and linear or branched C 1-4 alkoxy groups such as a methoxy group. Among them, linear or branched C 1-4An alkyl group is preferred. Note that when the group R 1 is an aryl group, the group R 1 may form the above ring-set arene ring together with the ring Z 1 .

[0066] The substitution number m1 may be selected according to the type of the ring Z 1 and can be selected, for example, from integers of about 0 to 7. The preferred range is, step by step, integers of 0 to 6, integers of 0 to 5, integers of 0 to 4, integers of 0 to 3, integers of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0067] Note that when the substitution number m1 is 2 or more, the types of two or more groups R 1 substituting on the ring Z 1 may be the same as or different from each other. Also, the substitution position of the group R 1 is not particularly limited and may be selected according to the type of the ring Z 1 .

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

[0069] The substitution numbers k1a and k1b of the monovalent groups Y 1a , Y 1b are, for example, integers of about 0 to 3, 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. Among k1a and k1b, at least one is an integer of 1 or more, preferably both are integers of 1 or more, and even more preferably both are 1.

[0070] Note that when k1a and k1b are each 1 or more, among the two benzene rings forming the fluorene skeleton, the groups Y 1a and Y1b The types may be different from each other, and preferably the same. Further, when k1a and k1b are 2 or more, among the two benzene rings forming the fluorene skeleton, two or more groups Y substituted on the same benzene ring 1a , Y 1b may be the same as or different from each other.

[0071] R 2a , R 2b The substituents (non-reactive substituents or non-polymerizable substituents) represented by are substituents other than the groups Y 1a , Y 1b and may be any substituents other than these. Typical groups include hydrocarbon groups such as alkyl groups (excluding aryl groups), halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, and cyano groups. Examples of the alkyl group include linear or branched C 1-6 alkyl groups such as methyl group, ethyl group, and t-butyl group. When the substitution numbers m2a and m2b are 1 or more, preferred R 2a , R 2b are linear or branched C 1-4 alkyl groups such as methyl group.

[0072] R 2a and R 2b The substitution numbers m2a and m2b are, for example, integers of about 0 to 3, preferably integers 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 m2a and m2b are each 1 or more, among the two benzene rings forming the fluorene skeleton, R 2a and R 2b substituted on different benzene rings may be different from each other, and preferably the same. Further, when m2a and m2b are 2 or more, among the two benzene rings forming the fluorene skeleton, two or more R 2a , R 2b substituted on the same benzene ring may be the same as or different from each other. Note that R 2a and R 2bThe substitution position is not particularly limited, and it may be substituted at a position other than the substitution positions of the group Y 1a , Y 1b . As long as it is substituted at a position other than the substitution positions of

[0073] The total values k1a + m2a and k1b + m2b of the number of substitutions in the two benzene rings forming the fluorene skeleton are, for example, integers from 0 to 4, preferably integers from 1 to 3, more preferably 1 or 2, and even more preferably 1. The total values k1a + m2a and k1b + m2b may be different from each other, but are preferably the same.

[0074] The monovalent group (or hydroxyl group-containing group) Y bonded to the 9,9-positions of the fluorene skeleton 2a and Y 2b The Z in the above formula (Y2) representing 2 Examples of the polycyclic arene ring represented by include condensed polycyclic arene rings, ring-assembled arene rings, etc. Examples of the condensed polycyclic arene ring and the ring-assembled arene ring include the same condensed polycyclic arene rings, ring-assembled arene rings, etc. as those including the preferred embodiments of Z 1 in the above formula (Y1).

[0075] Preferred ring Z 2 includes C 10-14 arene rings, more preferably C 10-12 arene rings such as naphthalene rings and biphenyl rings, and even more preferably naphthalene rings.

[0076] In addition, the bonding position of the ring Z 2 to the 9-position of the fluorene skeleton may be either the 1-position or the 2-position of the naphthalene ring when the ring Z 2 is a naphthalene ring, and the 2-position of the naphthalene ring is preferred. When the ring Z 2 is a biphenyl ring, the 3-position of the biphenyl ring is preferred.

[0077] R 3 Examples of the substituent (non-reactive substituent or non-polymerizable substituent) represented by include R 1 in the above formula (Y1).Examples thereof include the same groups as described above. When the substitution number m3 is 1 or more, preferred substituents R 3 include a halogen atom; a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group; an alkoxy group; an acyl group; a nitro group; a cyano group; a substituted amino group, etc. More preferably, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group are included. Even more preferably, a linear or branched C such as a methyl group 1-6 alkyl group, a C such as a cyclohexyl group 5-8 cycloalkyl group, a C such as a phenyl group 6-14 aryl group, a linear or branched C such as a methoxy group 1-4 alkoxy group are included. Among these, an alkyl group and an aryl group are preferred, and particularly a linear or branched C such as a methyl group 1-4 alkyl group, a C such as a phenyl group 6-10 aryl group is preferred. When the group R 3 is an aryl group, the group R 3 may form the above-mentioned ring assembly arenarene ring together with the ring Z 2 .

[0078] The substitution number m3 of the group R 3 may be 0 or an integer of 1 or more, and can be appropriately selected according to the type of the ring Z 2 . For example, it may be an integer of about 0 to 6. As a preferred range, step by step, it is an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, and 0 or 1 is even more preferred, and particularly 0 is preferred. When m3 is 2 or more, the types of two or more groups R 3 may be the same as or different from each other. Particularly when m3 is 1, the ring Z 2 may be a naphthalene ring or a biphenyl ring, and the group R 3 may be a methyl group. Also, the substitution position of the group R 3 is not particularly limited, and it may be substituted at a position other than the bonding position with the ring Z 2 , the group [-O-(A 1 O) n1 -H] and the 9-position of the fluorene ring. In the ring Z 2 , the group [-O-(A 1 O)n1 -H] is often substituted at the ortho position (the carbon atom adjacent to the bonding position of the group [-O-(A 1 O) n1 -H]).

[0079] The alkylene group A 1 Examples thereof include linear or branched C such as an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, and a tetramethylene group 2-6 alkylene groups. When the repetition number n1 is 1 or more, it is preferably a linear or branched C 2-4 alkylene group, more preferably a linear or branched C such as an ethylene group or a propylene group 2-3 alkylene group, and particularly preferably an ethylene group.

[0080] The repetition number (added mole number) n1 of the oxyalkylene group (-A 1 O-) may be 0 or 1 or more, and can be selected from, for example, the range of an integer of about 0 to 15. Preferred ranges are, stepwise, 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, 0 to 1. Also, from the viewpoint of improving polymerization reactivity etc., the repetition number n1 may be 1 or more, and can be selected from, for example, the range of an integer of about 1 to 15. Preferred ranges are, stepwise, 1 to 10, 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 "repetition number (added mole number)" may be an average value (arithmetic average value, additive average value) or an average added mole number, and the preferred embodiments are the same as the above preferred ranges (the above integer ranges). If the repetition number n1 is too large, the refractive index and heat resistance may decrease.

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

[0082] The group [-O-(A 1 O) n1 -H] of the ring Z2 The substitution position for 2 when ring Z is a naphthalene ring, may be substituted at any position of the 5th to 8th positions of the naphthyl group bonded to the 9th position of the fluorene ring. For example, the 1st or 2nd position of the naphthalene ring is substituted with respect to the 9th position of the fluorene ring (substituted in the relationship of 1-naphthyl or 2-naphthyl), and the relationships such as 1,5-position and 2,6-position are preferable with respect to this substitution position. In particular, substitution in the 2,6-position relationship is preferable. Also, ring Z 2 when is a ring assembly arene ring, may be substituted on the arene ring bonded to the 9th position of fluorene or the arene ring adjacent to this arene ring, and it is preferable to substitute on the arene ring bonded to the 9th position of fluorene. For example, when ring Z 2 is a biphenyl ring, the 3rd position of the biphenyl ring (3-biphenylyl group) is bonded to the 9th position of fluorene, and it is preferable that the group [-O-(A 1 O) n1 -H] is substituted at the 6th position of this biphenyl ring (3-biphenylyl group).

[0083] Typical groups of the monovalent group (or hydroxyl group-containing group) Y represented by the formula (Y2) 2a and Y 2b include a hydroxy polycyclic aryl group where n1 is 0, a hydroxy(poly)alkoxy polycyclic aryl group where n1 is 1 or more, and the like. In the present specification and claims, "(poly)alkoxy" is used in the meaning of including both an alkoxy group and a polyalkoxy group.

[0084] Examples of the hydroxy polycyclic aryl group include a hydroxy condensed polycyclic aryl group, a hydroxy ring assembly aryl group, and the like.

[0085] Examples of the hydroxy condensed polycyclic aryl group include a hydroxy C 10-14 condensed polycyclic aryl group such as a hydroxynaphthyl group. Specific examples of the hydroxynaphthyl group include a 6-hydroxy-2-naphthyl group, a 5-hydroxy-1-naphthyl group, and the like, and a 6-hydroxy-2-naphthyl group is preferable.

[0086] Examples of the hydroxy polycyclic aryl group include hydroxy C such as a hydroxybiphenylyl group (or phenyl-hydroxyphenyl group). 12-16 Examples of the polycyclic aryl group include a 6-hydroxy-3-biphenylyl group (or 4-hydroxy-3-phenylphenyl group) as a specific hydroxybiphenylyl group.

[0087] Examples of the hydroxy (poly) alkoxy polycyclic aryl group include a hydroxy (poly) alkoxy fused polycyclic aryl group and a hydroxy (poly) alkoxy polycyclic aryl group.

[0088] Examples of the hydroxy (poly) alkoxy fused polycyclic aryl group include hydroxy (poly) alkoxy C such as a hydroxy (poly) alkoxy naphthyl group. 10-14 Examples of the polycyclic aryl group include a 6-(2-hydroxyethoxy)-2-naphthyl group, a 6-(2-hydroxypropoxy)-2-naphthyl group, and a 6-(2-(2-hydroxyethoxy)ethoxy)-2-naphthyl group as specific hydroxy (poly) alkoxy naphthyl groups. 6-(mono to deca) C 2-4 Examples of the alkoxy-2-naphthyl group include 5-(2-hydroxyethoxy)-1-naphthyl group and other 5-(mono to deca) C 2-4 Examples of the alkoxy-1-naphthyl group include 6-(2-hydroxyethoxy)-2-naphthyl group and other 6-(mono to hexa) C 2-3 The 6-(mono to hexa) alkoxy-2-naphthyl group such as the 6-(2-hydroxyethoxy)-2-naphthyl group is preferred.

[0089] Examples of the hydroxy (poly) alkoxy polycyclic aryl group include hydroxy (poly) alkoxy C such as a hydroxy (poly) alkoxy biphenylyl group [or phenyl-hydroxy (poly) alkoxy phenyl group]. 12-16Examples include a cyclic aryl group, etc. Specific examples of the hydroxy(poly)alkoxybiphenylyl group include a 6-(2-hydroxyethoxy)-3-biphenylyl group [or a 4-(2-hydroxyethoxy)-3-phenylphenyl group], a 6-(2-hydroxypropoxy)-3-biphenylyl group, etc., and 6-hydroxy(mono to deca)C 2-4 Examples include a 6-hydroxy(mono to deca)C alkoxy-3-biphenylyl group, etc.

[0090] Among these monovalent groups (or hydroxyl group-containing groups) Y 2a and Y 2b Among them, a hydroxycondensed polycyclic aryl group and a hydroxy(poly)alkoxycondensed polycyclic aryl group in which Z 2 is a condensed polycyclic arene ring are preferred; a hydroxynaphthyl group and a hydroxy(poly)alkoxynaphthyl group in which Z 2 is a naphthalene ring are more preferred; a 6-hydroxy-2-naphthyl group, a 6-hydroxy(mono to deca)C 2-4 alkoxy-2-naphthyl group is even more preferred; among them, a 6-hydroxy(mono to hexa)C 2-3 alkoxy-2-naphthyl group such as a 6-hydroxy-2-naphthyl group and a 6-(2-hydroxyethoxy)-2-naphthyl group is preferred; particularly, a 6-hydroxy-2-naphthyl group is preferred.

[0091] Y 2a and Y 2b may be the same as or different from each other. When the types of Y 2a and Y 2b are different from each other, Z 2a and Y 2b in Y 2 R 3 m3, A 1 may have the same types and substitution positions respectively, and only the repeating number n1 may be different. Preferably, the types of Y 2a and Y 2b are the same.

[0092] Typical fluorene compounds represented by the above formula (1) include those in which k1a and k1b are 1 and Y1a and Y 1b ring Z in 1 is the same, and Y 2a and Y 2b ring Z in 2 include compounds where they are the same. Examples of such fluorene compounds include, 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 is a naphthalene ring or a biphenyl ring, preferably a naphthalene ring. In such a fluorene compound, m1, m2a, m2b and m3 may be 0, and n1 may be 0 or 1 or more. Among such fluorene compounds, compounds where Z 1 is a naphthalene ring and Z 2 is a naphthalene ring are preferred.

[0093] Said Z 1 is a naphthalene ring, and Z 2 is a naphthalene ring (that is, k1a and k1b are 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). Examples of such compounds include 9,9-bis(hydroxynaphthyl)-dinaphthylfluorene, 9,9-bis[hydroxy(poly)alkoxynaphthyl]-dinaphthylfluorene, etc.

[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)fluorene, 9,9-bis(5-hydroxy-1-naphthyl)-2,7-di(1-naphthyl)fluorene, and other 9,9-bis(hydroxynaphthyl)-2,7-dinaphthylfluorenes.

[0095] Examples of 9,9-bis[hydroxy(poly)alkoxynaphthyl]-dinaphthylfluorene include 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-hydroxyethoxy)-1-naphthyl]-2,7-di(1-naphthyl)fluorene, and other 9,9-bis[hydroxy(mono to deca)C 2-4 alkoxy-naphthyl]-2,7-dinaphthylfluorenes.

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

[0097] The fluorene compound represented by the formula (1) has a high refractive index. The refractive index of the fluorene compound may be, for example, about 1.75 to 1.85 at a temperature of 25 °C and a wavelength of 589 nm. The preferable ranges are, step by step, 1.76 to 1.82, 1.77 to 1.81, and 1.78 to 1.80.

[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. The preferable ranges are, step by step, 400 to 480 °C, 420 to 470 °C, 430 to 460 °C, and 440 to 450 °C.

[0099] Despite the high 5% mass loss temperature, the fluorene compound represented by the formula (1) surprisingly has a low melting temperature. The melting start temperature may be, for example, about 100 to 250 °C. Preferably, it is, step by step, 120 to 230 °C, 150 to 210 °C, 160 to 200 °C, and 170 to 190 °C. Also, the melting end temperature may be, for example, about 130 to 280 °C. Preferably, it is, step by step, 150 to 260 °C, 180 to 250 °C, 200 to 240 °C, and 210 to 230 °C. Therefore, it can also be used as a monomer component for melt polymerization or as a resin additive (resin modifier) by mixing it with a resin through melt kneading or the like.

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

[0101] In addition, the fluorene compound represented by the formula (1) is also excellent in solubility (compatibility), and can easily or efficiently form a uniform composition together with organic compounds such as solvents and / or resins. Further, even when the fluorene compound represented by the formula (1) is dissolved (compatible) at a high concentration in the composition, it is difficult to precipitate after dissolution (compatibility), and furthermore, even when placed in a low-temperature environment after dissolution (compatibility), it is difficult to precipitate, and can stably maintain the dissolved (compatible) state, and is also excellent in storage stability (solution stability or low-temperature stability).

[0102] Examples of the solvent for forming a composition with the fluorene compound represented by the formula (1) include hydrocarbons, specifically, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, etc.; alcohols such as methanol, ethanol, n-propanol, benzyl alcohol, etc.; ethers, specifically, dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, aromatic ethers such as anisole, etc.; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc.; ketones, specifically, chain ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), etc., cyclic ketones such as cyclohexanone, etc.; esters, acetic acid esters such as ethyl acetate, lactate esters such as methyl lactate, ethyl lactate, butyl lactate, etc., lactones such as γ-butyrolactone, etc.; ether esters, specifically, alkylene glycol monoalkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), etc., alkoxycarboxylic acid esters such as ethyl 3-ethoxypropionate, etc.; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.; sulfoxides such as dimethyl sulfoxide, etc. may also be used.

[0103] These solvents can be used alone or in combination of two or more. Among these solvents, they may be ether esters, preferably alkylene glycol monoalkyl ether acetates, such as C 2-4 Alkylene glycol mono C 1-4 Alkyl ether-acetates are preferred.

[0104] When forming a composition (liquid composition or solution) containing the fluorene compound represented by the formula (1) and a solvent, the proportion of the fluorene compound is, for example, 1 to 80% by mass, preferably 10 to 70% by mass, more preferably 20 to 60% by mass, particularly 30 to 50% by mass, based on the whole composition.

[0105] The composition may further be a reaction solution (reaction mixture) containing other reaction components, catalysts, etc., for example, a reaction solution for solution polymerization using the fluorene compound represented by the formula (1) as a monomer.

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

[0107] [Chemical formula]

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

[0109] (Preparation of the compound represented by formula (2) in the first reaction step formula) The compound represented by the formula (2) can be prepared by reacting the compound represented by the formula (4) with the compound represented by the formula (5a) and the compound represented by the formula (5b). For example, it may be prepared according to the methods described in JP-A-2011-68624, JP-A-2020-75904, etc.

[0110] In the formula (4), X 1a and X 1b Examples of the reactive groups and the like described in the section of the coupling reaction (reaction of the compound represented by the formula (2) with the compound represented by the formula (3a) and the compound represented by the formula (3b)) described below can be mentioned.

[0111] Examples of the compound represented by the formula (4) include dihalo-9-fluorenones such as 2,7-dibromo-9-fluorenone. The compound represented by the formula (4) may be used alone or in combination of two or more, but it is preferably used alone. Preferred compounds represented by the formula (4) are 2,7-dihalo-9-fluorenones such as 2,7-dibromo-9-fluorenone.

[0112] The compound represented by the formula (5a) and the compound represented by the formula (5b) are hydroxy polycyclic arenes (compounds corresponding to n1 = 0) or hydroxy(poly)alkoxy polycyclic arenes (compounds corresponding to n1 ≧ 1) corresponding to the monovalent group (hydroxyl group-containing group) Y 2a and Y 2b and preferred embodiments are also the above Y 2a and Y 2bThe same applies correspondingly. Specific hydroxy polycyclic arenes include naphthols such as 1-naphthol and 2-naphthol, hydroxybiphenyls such as 2-hydroxybiphenyl, etc. Specific hydroxy(poly)alkoxy polycyclic arenes include hydroxy(mono to deca)C 2-4 alkoxy-naphthalene, hydroxy(mono to deca)C 2-4 alkoxy-biphenyl, etc. The compounds represented by the above formula (5a) and the compounds represented by the formula (5b) may be used alone or in combination of two or more, but it is preferable to use them alone. In addition, the compounds represented by the formula (5a) and the compounds represented by the formula (5b) are preferably the same compound. Among the compounds represented by the above formula (5a) and the compounds represented by the formula (5b), naphthols such as 2-naphthol, hydroxy(mono to hexa)C 2-3 alkoxy-naphthalene is preferable.

[0113] The ratio of the compound represented by the formula (4) to the total amount of the compound represented by the formula (5a) and the compound represented by the formula (5b) may be, for example, about 1 / 2 to 1 / 10 for the former / latter (molar ratio), and the preferable ranges are, step by step, 1 / 2.2 to 1 / 5, 1 / 2.5 to 1 / 4, 1 / 2.7 to 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, etc. Examples of the inorganic acids include sulfuric acid, hydrogen chloride, phosphoric acid, etc. The inorganic acid may be in the form of an aqueous solution, for example, hydrochloric acid, etc. Examples of the organic acids include sulfonic acids, and examples of the sulfonic acids include (halo)alkanesulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, etc., arenesulfonic acids such as p-toluenesulfonic acid, etc. Examples of the solid acids include inorganic solid acids, specifically, metal oxides, composite metal oxides, metal sulfides, metal sulfates, metal compounds such as polyacids, non-metal sulfates, clay minerals, zeolites, kaolin, etc.; organic solid acids, specifically, cation exchange resins such as strongly acidic cation exchange resins, weakly acidic cation exchange resins, etc. Examples of the strongly acidic cation exchange resins include ion exchange resins having a sulfonic acid group such as Nafion manufactured by DuPont, etc. Examples of the weakly acidic cation exchange resins include ion exchange resins having a carboxylic acid group such as (meth)acrylic acid-divinylbenzene copolymer, etc.

[0115] These acid catalysts can be used alone or in combination of two or more. Preferred acid catalysts are inorganic acids such as sulfuric acid and cation exchange resins, and sulfuric acid, particularly concentrated sulfuric acid, is preferred in that it also acts as a dehydrating agent for the water generated during the progress of the reaction.

[0116] The sulfuric acid includes, for example, dilute sulfuric acid having a concentration of about 30 to 90% by mass, concentrated sulfuric acid having a concentration of 90% by mass or more, fuming sulfuric acid, etc. If it can be converted to sulfuric acid in the reaction system, sulfur trioxide may be used as a sulfuric acid precursor. The sulfuric acid may be selected from the range of about 80 to 99% by mass in terms of H2SO4 conversion, and the preferred ranges are, in order, concentrated sulfuric acid of 90 to 99% by mass, 93 to 99% by mass, 96 to 99% by mass, more preferably concentrated sulfuric acid of 97 to 98.5% by mass, and particularly preferably concentrated sulfuric acid of 98% by mass.

[0117] The proportion of the acid catalyst can be selected from, for example, the range of about 10 to 1000 parts by mass with respect to 100 parts by mass of the compound represented by the above formula (4). The preferable ranges are, step by step, 100 to 700 parts by mass, 300 to 500 parts by mass, and 350 to 450 parts by mass. If the proportion of the acid catalyst is too small, there is a possibility that the reaction cannot proceed efficiently.

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

[0119] Examples of the mercaptocarboxylic acids include 3-mercaptoalkanoic acids such as 3-mercaptopropionic acid (or β-mercaptopropionic acid), 2-mercaptoalkanoic acids, mercaptosuccinic acid, mercaptobenzoic acid, etc. Examples of the 2-mercaptoalkanoic acids include thioglycolic acid (mercaptoacetic acid or mercaptoethanoic acid), thiolactic acid (or α-mercaptopropionic acid), 2-mercaptobutyric acid (or 2-mercapto-n-butyric acid), 2-mercaptoisobutyric acid (or 2-mercapto-isobutyric acid), etc. of 2-mercapto C 2-6 alkanoic acids and the like.

[0120] Examples of the aminoalkanethiols include amino C such as 2-aminoethanethiol (or cysteamine), 2-aminopropanethiol, 3-aminopropanethiol, 2-aminobutanethiol, 3-aminobutanethiol, 4-aminobutanethiol, 6-aminohexanethiol, 8-aminooctanethiol, 11-aminoundecanethiol, 16-aminohexadecanethiol, etc. 2-20 alkanethiols and the like.

[0121] Examples of the thiocarboxylic acids include thioacetic acid, thiosuccinic acid, etc.

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

[0123] Examples of aralkyl mercaptans include benzyl mercaptan.

[0124] Typical salts of these include, for example, inorganic acid salts such as hydrochloride and sulfate; organic acid salts such as acetate; alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt; tetraalkylammonium salts such as ammonium salt and tetramethylammonium salt; or double salts thereof. Alkali metal salts such as sodium salt are preferred. Specific compounds include, for example, sodium methyl mercaptan and sodium ethyl mercaptan.

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

[0126] The proportion of thiols may be selected, for example, from the range of 0.1 part by mass or more, specifically about 1 to 50 parts by mass, based on 100 parts by mass of the compound represented by the formula (4). Preferred ranges are, stepwise, 2 to 20 parts by mass, 3 to 10 parts by mass, and 4 to 6 parts by mass. Also, the proportion of thiols can be selected from the range of, for example, about 0.01 to 0.5 mol, based on 1 mol of the compound represented by the formula (4). Preferred ranges are, stepwise, 0.05 to 0.4 mol, 0.1 to 0.3 mol, and 0.15 to 0.2 mol. Incidentally, the proportion of thiols can be selected from the range of, for example, about 0.001 to 50 parts by mass, based on 100 parts by mass of the acid catalyst. Preferred ranges are, stepwise, 0.005 to 10 parts by mass, 0.01 to 1 part by mass, and 0.01 to 0.1 part by mass. If the proportion of thiols is too small, the reaction may not proceed efficiently. If it is too large, the thiols may remain as impurities such as sulfur components.

[0127] The reaction may be carried out in a solvent. Examples of the solvent include ethers, specifically, chain ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc., cyclic ethers such as tetrahydrofuran (THF), 1,4-dioxane, etc.; ketones, specifically, chain ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., cyclic ketones such as cyclohexanone, etc.; esters, specifically, chain esters such as methyl acetate, ethyl acetate, butyl acetate, etc., cyclic esters (lactones) such as γ-butyrolactone, γ-valerolactone, γ-caprolactone (or γ-hexanolactone), etc.; carbonates, specifically, chain carbonates such as dimethyl carbonate (or methyl carbonate), diethyl carbonate (or ethyl carbonate), etc., cyclic carbonates such as ethylene carbonate (or ethylene carbonate), propylene carbonate (or propylene carbonate), etc.; amides, specifically, chain amides such as N,N-dimethylformamide (DMF), N,N-diethylformamide, N,N-dimethylacetamide (DMAc), etc., cyclic amides such as N-methyl-2-pyrrolidone (NMP), etc.; ureas, specifically, chain ureas such as tetramethylurea, tetraethylurea, etc., cyclic ureas such as 1,3-dimethyl-2-imidazolidinone (DMI or N,N'-dimethylethyleneurea), N,N'-dimethyl-N,N'-trimethyleneurea (or N,N'-propyleneurea), etc.; nitriles, specifically, hydrocarbon cyanides such as acetonitrile, propiononitrile, benzonitrile, etc.; nitrated hydrocarbons such as nitromethane, nitroethane, nitropropane, nitrobenzene, etc.; phosphoramides such as hexamethylphosphoramide; sulfones, specifically, chain sulfones such as ethyl methyl sulfone, etc., cyclic sulfones such as sulfolane, etc.; sulfoxides such as dimethyl sulfoxide (DMSO); hydrocarbons, specifically, aliphatic hydrocarbons such as hexane, heptane, octane, decane, etc., alicyclic hydrocarbons such as cyclohexane, etc., aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, etc.Halogenated hydrocarbons, specifically, haloalkanes such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, halobenzenes such as chlorobenzene, dichlorobenzene, etc. can be mentioned.;

[0128] These solvents can be used alone or in combination of two or more. Among these solvents, it is preferable to contain at least one selected from ethers, sulfones and ureas. In particular, a cyclic compound having at least a cyclic structure in the molecule (an aprotic polar solvent having a cyclic structure), among which, it is preferable to contain at least one selected from cyclic ethers such as 1,4-dioxane, cyclic sulfones such as sulfolane, and cyclic ureas such as DMI.

[0129] The proportion of the solvent may be selected from the range of, for example, about 100 to 10,000 parts by mass with respect to 100 parts by mass of the compound represented by the above formula (4). The preferable ranges are, step by step, 300 to 2,000 parts by mass, 400 to 1,500 parts by mass, and 500 to 1,000 parts by mass. If the proportion of the solvent is too large, the concentration of the raw material may be too low and the reactivity may decrease. If the proportion of the solvent is too small, the viscosity may be too high and the reactivity may decrease.

[0130] The reaction temperature can be selected from the range of, for example, about 0 to 200 °C. The preferable ranges are, step by step, 10 to 100 °C, 20 to 80 °C, and 30 to 60 °C. Also, the reaction time can be selected from the range of, for example, about 30 minutes to 48 hours. The preferable ranges are, step by step, 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 rare gas, and may be carried out at normal pressure or under pressure. Also, the reaction may be carried out while dehydrating.

[0132] After the reaction is completed, the reaction mixture (reaction solution or reaction mixture solution) may be separated (or purified) by conventional methods, for example, filtration, concentration, extraction, neutralization, washing, drying, crystallization, column chromatography, or means combining these methods.

[0133] (Preparation of the compound represented by formula (1) in the first reaction step formula) The fluorene compound (diol compound) represented by the formula (1) can be prepared by subjecting the compound represented by the formula (2) and the compounds represented by the formula (3a) and the formula (3b) to a coupling reaction (or cross-coupling reaction).

[0134] Examples of the coupling reaction include conventional coupling reactions, such as palladium-catalyzed (or palladium(0)-catalyzed) coupling reactions like the Suzuki-Miyaura coupling reaction, the Negishi-Kosugi-Stille coupling reaction, the Hiyama coupling reaction, etc., and nickel-catalyzed (or nickel(0)-catalyzed) coupling reactions like the Kumada-Tamao-Corriu coupling reaction. Among these coupling reactions, the Suzuki-Miyaura coupling reaction is preferred.

[0135] In the formula (2) (or formula (4)), X 1a and X 1b each independently represent 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 reactive group X 1b and together with X 1a and X 1b and X 2a and X 2b each represent a reactive group capable of forming a carbon-carbon bond by a coupling reaction. The reactive groups X 1a and X1b Examples include a halogen atom or a fluorinated alkanesulfonyloxy group. Examples of the halogen atom include an iodine atom, a bromine atom, and a chlorine atom. Examples of the fluorinated alkanesulfonyloxy group include a fluorinated C 1-4 alkanesulfonyloxy group such as a trifluoromethanesulfonyloxy group (or group [-OTf]). These one reactive groups may be used alone or in combination of two or more. Among these one reactive groups, a halogen atom is preferable, an iodine atom and a bromine atom are more preferable, and a bromine atom is even more preferable.

[0136] Said one reactive group X in the Suzuki-Miyaura coupling reaction 1a and X 1b and the other reactive group X capable of coupling with X 2a and X 2b Examples include a boronic acid group (dihydroxyboryl group or group [-B(OH)2]), a boronic acid ester group, etc. Examples of the boronic acid ester group include a dialkoxyboronyl group such as a dimethoxyboronyl group, a diisopropoxyboronyl group, and a dibutoxyboronyl group; a pinacolato boronyl group (or group [-Bpin]), a cyclic boronic acid ester group such as a 1,3,2-dioxaborinan-2-yl group and a 5,5-dimethyl-1,3,2-dioxaborinan-2-yl group. These other reactive groups may be used alone or in combination of two or more. Among the other reactive groups, the group [-B(OH)2] is preferable.

[0137] Note that the groups X 1a and X 1b and the groups X 2a and X 2b may be any reactive groups as long as they are a pair of reactive groups capable of coupling with each other. The groups X 1a and X 1b may be the other reactive groups such as a boronic acid group, and the groups X 2a and X 2b may be the one reactive group such as a halogen atom, but the groups X 1a and X 1bis the one reactive group such as a halogen atom, and group X 2a and X 2b is preferably the other reactive group such as a boronic acid group.

[0138] Examples of the compound represented by the formula (2) include compounds corresponding to the preferred embodiments of the fluorene compound represented by the formula (1), such as 9,9-bis(6-hydroxy-2-naphthyl)-2,7-dibromofluorene and other 9,9-bis(hydroxynaphthyl)-dihalofluorene; 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-dibromofluorene and other 9,9-bis[hydroxy(poly)alkoxy-naphthyl]-dihalofluorene.

[0139] Examples of the compound represented by the formula (3a) and the compound represented by the formula (3b) include compounds corresponding to the preferred embodiments of the fluorene compound represented by the formula (1), such as phenylboronic acid, 1-naphthylboronic acid, 2-naphthylboronic acid, etc., and 2-naphthylboronic acid is preferred. The compound represented by the formula (3a) and the compound represented by the formula (3b) are preferably the same compound. Commercially available products etc. can be used as the compound represented by the formula (3a) and the compound represented by the formula (3b).

[0140] The ratio of the compound represented by the formula (2) to the total amount of the compound represented by the formula (3a) and the compound represented by the formula (3b) may be, for example, the former / latter (molar ratio) = about 1 / 2 to 1 / 10, and the preferred ranges may be, step by step, 1 / 2.1 to 1 / 5, 1 / 2.2 to 1 / 3, 1 / 2.3 to 1 / 2.5, and more preferably 1 / 2.1 to 1 / 2.3 in terms of more efficient preparation.

[0141] The coupling reaction may be carried out in the presence of a catalyst. When synthesizing by the Suzuki-Miyaura coupling reaction, it may be reacted in the presence of a palladium catalyst, and examples of the palladium catalyst include conventional coupling catalysts such as palladium(0) catalysts and palladium(II) catalysts.

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

[0143] Examples of the palladium(II) catalyst include palladium(II)-phosphine complexes such as [1,2-bis(diphenylphosphino)ethane]palladium(II) dichloride [or PdCl2(dppe)], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride [or PdCl2(dppp)], [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride [or PdCl2(dppf)], bis(triphenylphosphine)palladium(II) dichloride [or PdCl2(PPh3)2], bis(tri-o-tolylphosphine)palladium(II) dichloride [or PdCl2(P(o-tolyl)3)2], and the like. When using a palladium(II) catalyst, for example, it is reduced to a zero-valent complex by a reducing compound in the reaction system such as phosphine, amine, or organometallic reagent, and the reaction starts.

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

[0145] These catalysts can be used alone or in combination of two or more. Among these catalysts, palladium(0)-phosphine complexes such as Pd(PPh3)4, catalyst precursors such as palladium(II) acetate, and palladium(II) acetate is particularly preferred in terms of excellent operability (stability in air). The proportion of the catalyst may be, for example, about 0.0001 to 0.1 mol in terms of metal per 1 mol of the compound represented by the above formula (2), preferably 0.01 to 0.07 mol, more preferably 0.04 to 0.06 mol, and particularly preferably in the following steps in terms of more efficient preparation, 0.0001 to 0.001 mol, 0.0003 to 0.0007 mol, and when using a catalyst precursor such as palladium(II) acetate, it 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. Examples of the base include metal carbonates or bicarbonates, metal hydroxides, metal fluorides, metal phosphates, metal organic acid salts, metal alkoxides, and the like.

[0147] Examples of the metal carbonate or bicarbonate include alkali metal carbonates or bicarbonates such as sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, and thallium(I) carbonate.

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

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

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

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

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

[0153] These bases can be used alone or in combination of two or more. Preferred bases are metal carbonates such as potassium carbonate. The proportion of the base may be, for example, about 0.1 to 50 moles, preferably stepwise as follows, 0.5 to 5 moles, 1 to 3 moles, 1.5 to 2.5 moles, and more preferably stepwise as follows, 5 to 10 moles, 6 to 8 moles, 6.5 to 7.5 moles, with respect to 1 mole of the compound represented by the formula (2).

[0154] The coupling reaction may be carried out in the presence or absence of a phase transfer catalyst. Examples of the phase transfer catalyst include tetraalkylammonium halides such as tetrabutylammonium bromide (TBAB) and trioctylmethylammonium 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 solvent inert to the reaction. Examples of the solvent include water; alcohols such as methanol and ethanol; ethers such as cyclic ethers and chain ethers; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK); esters such as ethyl acetate; nitriles such as acetonitrile and benzonitrile; amides such as N,N-dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide; and hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

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

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

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

[0159] The coupling reaction may be carried out under an inert gas atmosphere, for example, under an atmosphere of nitrogen gas; noble gases such as helium and argon. The reaction temperature is, for example, 50 to 200 °C, preferably 60 to 100 °C, more preferably 70 to 90 °C, particularly 75 to 83 °C. The reaction time may be, for example, about 0.5 to 24 hours, preferably about 10 to 20 hours, and more preferably about 0.5 to 8 hours, 0.5 to 1.5 hours in terms of more efficient preparation.

[0160] After completion of the reaction, if necessary, the reaction mixture may be separated and purified by conventional separation and purification methods, for example, neutralization, washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption, and methods combining these.

[0161] In addition, the fluorene compound represented by the formula (1) may be prepared according to a method different from the above method, for example, according to the following reaction process formula (the second reaction process formula).

[0162]

Chem.

[0163] (wherein Y 1a and Y 1b , k1a and k1b, R 2a and R 2b , m2a and m2b, and Y 2a and Y 2b are the same as those in the said formula (1) including the preferred embodiments, X 1a and X 2a and also X 1b and X 2b are the same as those in the said first reaction step formula including the preferred embodiments).

[0164] In the second reaction step formula, the step of reacting the compound represented by the said formula (5a) and the compound represented by the formula (5b) to introduce the groups Y 2a and Y 2b , and the step of reacting the compound represented by the said formula (3a) and the compound represented by the formula (3b) to introduce the groups Y 1a and Y 1b are in the reverse order compared with those in the said first reaction step formula. Therefore, the preparation of the compound represented by the said formula (6) in the second reaction step formula can be carried out by using the compound represented by the said formula (4) in place of the compound represented by the said formula (2) (or by replacing the said formula (2) with the said formula (4)) in the description of the item of (the preparation of the compound represented by the formula (1) in the first reaction step formula). Similarly, for the preparation of the compound represented by the said formula (1) in the second reaction step formula, it can be carried out by using the compound represented by the said formula (6) in place of the compound represented by the said formula (4) (or by replacing the said formula (4) with the said formula (6)) in the description of the item of (the preparation of the compound represented by the formula (2) in the first reaction step formula).

[0165] As described above, the method for producing the fluorene compound (diol compound) represented by the formula (1) may include either (i) a step of subjecting the compound represented by the formula (2) to a coupling reaction with the compound represented by the following formula (3a) and the compound represented by the formula (3b); or (ii) a step of reacting the compound represented by the formula (6) with the compound represented by the following formula (5a) and the compound represented by the formula (5b). The compounds represented by the formulas (2) and (6), which are reaction intermediates, may be prepared using the methods described above or other conventional methods.

[0166] (Purification step) The fluorene compound (diol compound) represented by the formula (1) may be purified by the conventional separation and purification methods described above. However, due to the influence of the reaction conditions, it may not be possible to separate and purify it sufficiently or efficiently, and it is difficult to prepare it with relatively high purity and high yield. However, when the fluorene compound obtained in the reaction step is precipitated (crystallized or recrystallized or reprecipitated) from at least one solvent selected from a solvent such as the solvent exemplified as a solvent for forming a composition (liquid composition or solution) with the fluorene compound represented by the formula (1), preferably (a) a solvent containing at least aromatic hydrocarbons and aliphatic hydrocarbons (reprecipitation solvent), and (b) a solvent containing at least ketones (crystallization solvent), it seems to be easier to prepare the fluorene compound with high purity and efficiency compared to other separation and purification methods such as column chromatography.

[0167] (a) In a solvent containing at least aromatic hydrocarbons and aliphatic hydrocarbons, examples of the aromatic hydrocarbons that are good solvents include benzene, toluene, xylene, etc., and toluene is preferred. Examples of the aliphatic hydrocarbons that are poor solvents include C 5-12 alkanes such as hexane, heptane, decane, etc., and C 6-8 alkanes such as heptane are preferred.

[0168] The ratio of the aromatic hydrocarbons such as toluene and the aliphatic hydrocarbons such as heptane may be selected, for example, from the range of about former / latter (volume ratio) = 10 / 90 to 90 / 10, and the preferred ranges are, step by step, 10 / 90 to 90 / 10, 20 / 80 to 70 / 30, 30 / 70 to 50 / 50. The volume ratio may be the volume ratio at 20 to 25 °C and 1 atm.

[0169] The ratio of the total amount of the aromatic hydrocarbons and the aliphatic hydrocarbons is, for example, 50% by mass or more, preferably, step by step, 70% by mass or more, 90% by mass or more, and more preferably substantially 100% by mass, based on the entire solvent containing the aromatic hydrocarbons and the aliphatic hydrocarbons.

[0170] Also, in the crystallization solvent (b) containing at least ketones, examples of the ketones include C 3-6 such as acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK). The ratio of the ketones is, for example, 50% by mass or more, preferably, step by step, 70% by mass or more, 90% by mass or more, and more preferably substantially 100% by mass, based on the entire crystallization solvent containing the ketones.

[0171] When purified using the solvent (a), an amorphous (non-crystalline) substance is obtained, and it seems that crystals are obtained with the solvent (b). Among the solvents (a) and (b), the crystallization solvent (b) is preferred from the viewpoint of being easy to reduce coloring while maintaining high purity and yield. In particular, it is preferable to crystallize from a crystallization solvent containing C 5-6 ketones such as MIBK.

[0172] In the purification process, particularly the crystallization process, for example, the solution may be adjusted to a concentration of 10 to 60% by mass, preferably 20 to 50% by mass, more preferably 30 to 50% by mass. Further, crystallization may be carried out while stirring and / or cooling the temperature. For example, while stirring at about 100 to 500 rpm, preferably about 200 to 300 rpm, the temperature may be decreased from, for example, about 40 to 100 °C, preferably about 50 to 70 °C, to a precipitation temperature of, for example, about 30 to 60 °C, preferably about 40 to 50 °C for crystallization. Further, crystallization may be carried out by allowing the solution to stand still while cooling the temperature without stirring, for example, by cooling to room temperature of about 20 to 30 °C.

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

[0174] Further, the yield of the fluorene compound represented by the formula (1) obtained may be, for example, 40% or more, and preferably in the following stepwise manner: 50% or more, 60% or more, 70% or more, and more preferably 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), in which the group Y bonded to the 9,9-positions of the fluorene skeleton 2a and Y 2b [Hydroxyl group-containing group represented by the formula (Y2)] is replaced by the group Y 3a and Y 3b and has an epoxy group-containing group

[0176] The epoxy group-containing group Y represented by the formula (Y3) 3a and Y 3b in which R 4is preferably a hydrogen atom. Further, in the formula (Y3), R 3 , m3, A 1 and n1 are the same as those in the formula (Y2) including their preferred embodiments, respectively.

[0177] Therefore, typical epoxy group-containing groups Y 3a and Y 3b correspond to the hydroxyl group-containing groups Y 2a and Y 2b exemplified in the item of the formula (1), and examples include groups in which the hydroxyl group is replaced with a glycidyloxy group or a β-methylglycidyloxy group. Preferred epoxy group-containing groups Y 3a and Y 3b are also the same as the hydroxyl group-containing groups Y 2a and Y 2b respectively. Among them, 6-glycidyloxy(mono to hexa)C 2-3 alkoxy-2-naphthyl groups such as 6-glycidyloxy-2-naphthyl group and 6-(2-glycidyloxyethoxy)-2-naphthyl group are preferred; particularly, 6-glycidyloxy-2-naphthyl group is preferred. Note that the types of the epoxy group-containing groups Y 3a and Y 3b may be the same as or different from each other, and the same is preferred.

[0178] Further, in the formula (1E), Y 1a and Y 1b , k1a and k1b, R 2a and R 2b , m2a and m2b, and k1a + m2a and k1b + m2b are the same as those in the formula (1) and (Y1) including their preferred embodiments, respectively. Note that when the ring Z 1a and Y 1b in Y 1 is a condensed polycyclic arene ring such as a naphthalene ring in particular, not only can the refractive index and heat resistance be effectively improved easily, but also surprisingly, a low melting start temperature and high solubility (compatibility) can be exhibited, which is preferred.

[0179] Therefore, for the typical epoxy compound represented by the aforementioned formula (1E), corresponding to the typical diol compound represented by the aforementioned formula (1), compounds in which two hydroxyl groups are replaced with glycidyloxy groups or β-methylglycidyloxy groups can be mentioned. The same applies to the preferred epoxy compound represented by the formula (1E), corresponding to the preferred embodiments of the diol compound represented by the formula (1). Among them, 9,9-bis(glycidyloxynaphthyl)-2,7-dinaphthylfluorene such as 9,9-bis(6-glycidyloxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene; 9,9-bis[6-(2-(glycidyloxy)ethoxy)-2-naphthyl]-2,7-di(2-naphthyl)fluorene such as 9,9-bis[glycidyloxy(mono to deca)C 2-4 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 epoxy compound may be, for example, about 1.67 to 1.8, specifically about 1.67 to 1.77 at a temperature of 25 °C and a wavelength of 589 nm. The preferred range may be, step by step, 1.69 to 1.75, 1.7 to 1.74, 1.71 to 1.73; more preferably, step by step, 1.72 to 1.79, 1.73 to 1.78, 1.74 to 1.775, 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. The preferred range may be, step by step, 350 to 450 °C, 370 to 430 °C, 380 to 420 °C.

[0182] The epoxy compound represented by the formula (1E) shows an unexpectedly low melting (fusion) temperature despite having a high 5% mass loss temperature. The melting (fusion) start temperature may be, for example, about 100 to 250 °C, preferably, in the following steps, 120 to 200 °C, 130 to 180 °C, 140 to 160 °C. Therefore, it is also possible to easily or efficiently prepare a uniform curable composition by melt-kneading with other components described later.

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

[0184] Also, the epoxy equivalent of the epoxy compound (or epoxy resin) may be selected from, for example, the range of about 300 to 1500 g / eq, preferably 350 to 1000 g / eq, more preferably 400 to 500 g / eq; particularly preferably, 350 to 480 g / eq, especially 370 to 450 g / eq. In the present specification and claims, the epoxy equivalent of the epoxy compound can be measured by the method described in the examples below in accordance with JIS K 7236:2001.

[0185] Note that the epoxy compound (or the curable composition described later) may be a mixture containing not only the compound (monomer) represented by the formula (1E) but also its multimers, for example, dimers, trimers, tetramers, etc., up to decamers. The multimers may be included alone or in combination of two or more.

[0186] In this specification and the claims, unless otherwise specified, the "multimer" of the epoxy compound means an epoxy compound having two or more structures (skeletons) derived from the starting compound [the diol compound represented by the formula (1)] in its chemical structure, and the structures derived from two or more of these diol compounds are bonded (linked) via a linking group derived from an epihalohydrin component described later, such as a 2-hydroxypropane-1,3-diyl group. Such a multimer may inevitably be mixed or mixed as an impurity during the production process of the compound (monomer) represented by the formula (1E) described later, and if necessary, a multimer prepared by a conventional method such as a one-step method (tuffy method or direct method) or a two-step method (Advanced method, melting method or indirect method) may be intentionally added to the monomer.

[0187] The proportion of the multimer may be, for example, about 0 to 50 mol%, specifically about 0 to 20 mol%, preferably 0 to 10 mol%, and more preferably 0 to 5 mol% based on the total number of moles of the monomer and the multimer. The proportion may be, for example, 0.1 to 8 mol%, preferably 0.2 to 3 mol%.

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

[0189] [Production method of fluorene compound (epoxy compound) represented by formula (1E)] The production method of the epoxy compound represented by the formula (1E) is not particularly limited, and for example, it may be prepared by reacting the diol compound represented by the formula (1) with an epihalohydrin component.

[0190] Examples of the epihalohydrin component (epihalohydrins) include epihalohydrin, β-methylepihalohydrin, etc. Examples of epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, etc. Examples of β-methylepihalohydrin include β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepiiodohydrin, etc. These epihalohydrin components can be used alone or in combination of two or more. Among these epihalohydrin components, epihalohydrins such as epichlorohydrin and β-methylepichlorohydrin are preferred, and epichlorohydrin is more preferred.

[0191] The proportion of the epihalohydrin component may be, for example, 2 moles or more per mole of the diol compound represented by the formula (1), but is an excessive amount with respect to the diol compound, for example, 5 to 100 moles, preferably 10 to 50 moles, more preferably 15 to 30 moles.

[0192] In addition, if necessary, the reaction may be carried out in the presence of a catalyst or in the absence of a catalyst. Examples of the catalyst include quaternary ammonium salts, specifically, tetraalkylammonium halides such as tetramethylammonium chloride and tetramethylammonium bromide, benzyltrialkylammonium halides such as benzyltrimethylammonium chloride; 1-20 trialkylamine boranes such as trimethylamine borane, crown ethers, phosphonium salts, pyridinium salts, etc. The catalyst may be used alone or in combination of two or more. 1-4 benzyltrialkylammonium halides, etc.; 1-4 When using a catalyst, its proportion is not particularly limited, but is, for example, 0.001 to 1 mole, preferably 0.01 to 0.2 mole, more preferably 0.05 to 0.1 mole per mole of the diol compound represented by the formula (1).

[0193]

[0194] ​In addition, in order to trap hydrogen halide generated by the reaction, the reaction may be carried out in the presence of a base. Examples of the base include inorganic bases such as metal hydroxides, metal carbonates or hydrogen carbonates; organic bases such as amines. Examples of the metal hydroxide include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide. Examples of the metal carbonate or hydrogen carbonate include alkali metal or alkaline earth metal salts such as sodium carbonate and sodium hydrogen carbonate. Examples of the amines include trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, and heterocyclic tertiary amines such as pyridine. The base may be used alone or in combination of two or more. Among these bases, strong bases (strong alkalis) are preferred, and metal hydroxides such as sodium hydroxide are more preferred.

[0195] The proportion of the base is not particularly limited. For example, it is 0.01 to 20 moles, preferably in the following steps, 0.05 to 10 moles, 1 to 5 moles, and 2 to 4 moles, relative to 1 mole of the hydroxyl group of the compound represented by the formula (1).

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

[0197] The reaction may be carried out in air or in an inert atmosphere such as nitrogen gas or noble gas, and may be carried out with stirring. Also, the reaction may be carried out under normal pressure, under pressure or under reduced pressure.

[0198] The reaction temperature and reaction time may be appropriately selected according to the type of raw materials etc. The reaction temperature is, for example, 30 to 150 °C, preferably in the following stages, 50 to 140 °C, 100 to 130 °C, and may be carried out while refluxing (at the reflux temperature); more preferably 30 to 50 °C. Also, the reaction time is, for example, 30 minutes to 48 hours, preferably 2 to 6 hours.

[0199] After completion of the reaction, if necessary, the reaction mixture may be separated and purified by conventional separation and purification methods, for example, washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption, methods combining these etc.

[0200] [Curable Composition] The curable composition only needs to contain at least the epoxy compound represented by the formula (1E), and may be a thermosetting or photocurable composition, etc. Further, if necessary, it may or may not contain other components such as other epoxy compounds (epoxy resins), curing agents, curing accelerators, photopolymerization initiators, reactive diluents, solvents, and additives, which are different from the epoxy compound. The epoxy compound represented by the formula (1E) is particularly Y 1a and Y 1b in the ring Z 1 is a polycyclic arene ring such as a condensed polycyclic arene ring. Despite having many benzene ring skeletons in the chemical structure, it surprisingly has excellent solubility (compatibility). Therefore, even if it contains the other components, a uniform curable composition and cured product can be easily or efficiently prepared.

[0201] (Other epoxy compounds) Examples of other epoxy compounds (epoxy resins) different from the formula (1E) include glycidyl ether type epoxy resins, specifically, bi- or bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, biphenol type, novolak type epoxy resins such as phenol novolak type, cresol novolak type, phenol aralkyl type epoxy resins, triphenol alkane type epoxy resins, tetrakisphenol type epoxy resins such as tetrakis (glycidyloxyphenyl) ethane, condensed ring aromatic hydrocarbon modified epoxy resins such as 1,6-bis (glycidyloxy) naphthalene, other epoxy resins having a 9,9-bisarylfluorene skeleton such as 9,9-bis (glycidyloxyaryl) fluorenes, 9,9-bis [glycidyloxy (poly) alkoxyaryl] fluorenes, etc.; glycidyl ester type epoxy resins such as diglycidyl esters of aromatic dicarboxylic acids (or their hydrogenated products); glycidylamine type epoxy resins such as tetraglycidyl diaminodiphenylmethane, tetraglycidyl bisaminomethylcyclohexane, triglycidyl aminophenol; cycloaliphatic type epoxy resins such as bis (3,4-epoxycyclohexylmethyl) adipate, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate; stilbene type epoxy resins; heterocyclic type epoxy resins such as isocyanurate type epoxy resins, hydantoin type epoxy resins, epoxy resins containing xanthene units; bromine-containing epoxy resins such as tetrabromobisphenol A type epoxy resins, etc.

[0202] These other epoxy resins may be monomers or multimers such as dimers and trimers. These other epoxy resins may be used alone or in combination of two or more. Preferred other epoxy resins are bi- or bisphenol type epoxy resins such as bisphenol A type epoxy resin.

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

[0204] (Hardening agent, hardening accelerator, photopolymerization initiator) The curable composition may or may not contain at least one selected from a hardening agent, a hardening accelerator, and a photopolymerization initiator. Examples of the hardening agent include amine-based hardening agents, polyaminoamide-based hardening agents, acid anhydride-based hardening agents, phenolic resin-based hardening agents, and the like.

[0205] The amine-based hardening agent may particularly be a primary amine, and examples thereof include chain aliphatic amines, specifically, chain aliphatic polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine; cycloaliphatic amines, specifically, monocyclic, bridged cyclic, or spirocyclic aliphatic polyamines such as m-xylenediamine, isophoronediamine, bis(4-amino-3-methylcyclohexyl)methane, norbornanediamine, and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; araliphatic polyamines such as xylylenediamine; and aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, and 4,4'-diaminodiphenylsulfone.

[0206] Examples of the polyaminoamide-based hardening agent include condensates of polyethylene polyamines such as ethylenediamine, diethylenetriamine, and triethylenehexamine, dimer acid, and, if necessary, fatty acids.

[0207] Examples of the acid anhydride-based curing agents include aliphatic acid anhydrides such as dodecenyl succinic anhydride and polyadipic anhydride; alicyclic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhimic anhydride, and methylcyclohexene dicarboxylic anhydride; and aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic anhydride.

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

[0209] These curing agents can be used alone or in combination of two or more. Among these curing agents, phenol resin-based curing agents are preferred, and novolak resins such as phenol novolak resin are more preferred.

[0210] The proportion of the curing agent is, for example, 0.1 to 500 parts by mass, preferably 1 to 300 parts by mass, and more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin component (compound having an epoxy group) in the curable composition. Further, the proportion of the functional group (or active hydrogen) of the curing agent is, for example, 0.1 to 4 equivalents, preferably 0.3 to 2 equivalents, and 0.5 to 1.5 equivalents in stages with respect to 1 equivalent of the epoxy group of the epoxy resin component.

[0211] Examples of the curing accelerator include amines such as tertiary amines, imidazoles and their derivatives; alkali metal or alkaline earth metal alkoxides; phosphines, specifically triarylphosphines such as triphenylphosphine; amide compounds such as dimer acid polyamide; Lewis acid complex compounds such as boron trifluoride-ethylamine complex; sulfur compounds such as polysulfide and mercaptan compounds (thiol compounds); boron compounds such as phenyldichloroborane; and condensable organometallic compounds such as organic titanium compounds and organic aluminum compounds. Regarding the amines, examples of the tertiary amines include triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]-7-undecene, etc.; examples of the imidazoles include mono- or dialkylimidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, and arylimidazoles such as 2-phenylimidazole; and examples of the derivatives include salts such as phenol salts, phenol novolak salts, carbonates, and formates. These curing accelerators may be used alone or in combination of two or more. Among these curing accelerators, phosphines are preferred, and triarylphosphines such as triphenylphosphine are more preferred.

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

[0213] The curable composition may be, for example, a photocurable composition containing a photopolymerization initiator such as a cationic polymerization initiator, a photoacid generator, etc. Examples of the photopolymerization initiator include onium salts of Bronsted acids such as aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, etc.

[0214] Examples of the aromatic diazonium salts include benzenediazonium salts such as benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, etc.

[0215] Examples of the aromatic sulfonium salts include triphenylsulfonium salts such as triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, etc., and 4,4'-bis(diphenylsulfonio)diphenyl sulfide salts such as 4,4'-bis(diphenylsulfonio)diphenyl sulfide bishexafluorophosphate, etc.

[0216] Examples of the aromatic iodonium salts include diphenyliodonium salts such as diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, etc., and di(4-nonylphenyl)iodonium salts such as di(4-nonylphenyl)iodonium hexafluorophosphate, etc.

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

[0218] (Reactive diluent) As the reactive diluent, a monofunctional or polyfunctional epoxy compound having a low viscosity, for example, a viscosity at 25 °C of about 200 mPa·s or less, preferably 30 mPa·s or less, may be used. Examples of the monofunctional epoxy compound include alkyl glycidyl ethers such as 2-ethylhexyl glycidyl ether, alkenyl glycidyl ethers such as allyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether and p-t-butylphenyl glycidyl ether, and glycidyl ethers such as glycidyl ethers of alkylene oxide adducts corresponding to these compounds; alkene oxides such as octylene oxide, styrene oxide, and 4-vinylcyclohexene monooxide, and the like.

[0219] Examples of the polyfunctional epoxy compound include diglycidyl ether, polyol polyglycidyl ether, diglycidylaniline, cycloalkene oxide, and the like. Examples of the polyol polyglycidyl ether include (poly)alkanediol diglycidyl ethers such as butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; cyclohexanedimethanol diglycidyl ether; trimethylolpropane di- to triglycidyl ether; glycerin di- to triglycidyl ether, and the like. Examples of the cycloalkene oxide include vinylcyclohexene dioxide and methylated vinylcyclohexene dioxide, and the like.

[0220] These reactive diluents may be used alone or in combination of two or more. The proportion of the reactive diluent is, for example, 1 to 1000 parts by mass, preferably 5 to 500 parts by mass, more preferably 10 to 200 parts by mass, based on 100 parts by mass of the total amount of the epoxy resin component (compound having an epoxy group) in the curing agent composition.

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

[0222] These solvents may be used alone or in combination of two or more. These solvents can also be used alone or in combination of two or more. Among these solvents, alkylene glycol monoalkyl ether acetates are preferred, such as C 2-4 Alkylene glycol mono C 1-4 alkyl ether-acetates are preferred. The proportion of the solvent may be selected, for example, from the range of 0 to 500 parts by mass, preferably in the following steps, 10 to 400 parts by mass, 20 to 300 parts by mass, 30 to 200 parts by mass, based on 100 parts by mass of the total amount of the epoxy resin component (compound having an epoxy group) in the curing agent composition. Also, when the solvent is included, the solid content concentration of the curable composition is not particularly limited and may be adjusted so that the curable composition exhibits a desired fluidity, and may be, for example, about 0.1 to 70% by mass.

[0223] (Additive) Examples of the additive include conventional additives such as colorants such as dyes and pigments, stabilizers, fillers, conductive agents, antistatic agents, flame retardants, flame retardant aids, flexibilizers, plasticizers, surfactants, dispersants, compatibilizers, flow regulators, leveling agents, defoamers, surface modifiers, antibacterial agents, and preservatives. Examples of the stabilizer include heat stabilizers, antioxidants, and ultraviolet absorbers. Examples of the filler include silica, talc, mica, etc. Examples of the flame retardant include phosphorus-based flame retardants, halogen-based flame retardants, and inorganic-based flame retardants. These additives may be used alone or in combination of two or more. The total proportion of these additives may be, for example, 10% by mass or less, preferably 0 to 3% by mass, based on the total solid content; for example, about 0.01 to 5% by mass, preferably 0.1 to 1% by mass.

[0224] The curable composition may be prepared by a method of mixing and dispersing the epoxy compound represented by the above formula (1E) and, if necessary, other components as described above using a mixer or a stirrer. Examples of the mixer or stirrer include a ball mill, a tumble mixer, a ribbon blender, a Henschel mixer, a mixing roll, a kneader, a Banbury mixer, and the like. The temperature during mixing (kneading) or stirring may be, for example, about 50 to 250°C, 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). The curing treatment can be carried out by using a curing catalyst, heating, light irradiation (active energy ray irradiation), etc., and these may be combined.

[0226] When the curing treatment is carried out by heating, the heating temperature may be, for example, 50 to 250°C, preferably 70 to 220°C, 80 to 200°C, 90 to 170°C stepwise, more preferably 150 to 200°C, particularly 170 to 180°C. The curing treatment may be carried out stepwise. For example, after heat treatment at a relatively low temperature, specifically about 50 to 130°C, preferably 70 to 120°C, heat treatment may be carried out at a relatively high temperature, specifically about 140 to 350°C, preferably 150 to 300°C. Such a curing treatment may be carried out during and / or after molding (or pre-molding) of the curable composition according to the shape of the cured product. For example, if necessary, the curable composition can be heated and melted, poured into a predetermined mold, heated and cured to obtain a molded body having a desired shape. The molding method and curing conditions are not particularly limited. For example, when molding using a predetermined mold, a molding method by heating and pressing or a low-temperature molding method called cold press may be used. Also, the curable composition may be applied to an adhesion site and cured, or the substrate may be coated with the curable composition and cured, for example, by light irradiation described below.

[0227] When performing a curing treatment by light irradiation, the wavelength of the light may be appropriately selected according to the type of the acid generator or the like, and may be ultraviolet light, visible light, or the like. The irradiation light amount (exposure amount) of the light can be selected according to the thickness of the curable composition (coating film) or the like. For example, it may be about 10 to 10,000 mJ / cm 2 and may be preferably about 100 to 5,000 mJ / cm 2 and more preferably about 500 to 3,000 mJ / cm 2 . As the light source, for example, laser light such as a high-pressure mercury lamp, a deuterium lamp, a halogen lamp, a metal halide lamp, a xenon lamp, an LED laser, or the like can be used. In order to accelerate the curing of the curable composition, not only light irradiation but also the heat treatment may be performed.

[0228] The shape of the cured product is not particularly limited and may be any of a one-dimensional shape (such as a rod shape), a two-dimensional shape (such as a sheet shape, a film shape, a plate shape), and a three-dimensional shape [for example, a block shape, a rod shape, a hollow shape (a tubular shape or a tube shape), etc.]. Since such a cured product contains the compound represented by the formula (1E), it 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, preferably, step by step, 400 to 450 °C, 410 to 430 °C. Further, the glass transition temperature Tg (TMA) measured by a thermomechanical analysis measuring device (TMA) of the cured product may be, for example, about 150 to 300 °C, preferably, step by step, 200 to 250 °C, 200 to 220 °C. Further, the glass transition temperature Tg (DMA) measured by a dynamic viscoelasticity measuring device (DMA) of the cured product may be, for example, about 150 to 300 °C, preferably, step by step, 200 to 250 °C, 210 to 230 °C.

[0230] Note that the 5% mass loss temperature, Tg (TMA), and Tg (DMA) of the cured product can be measured according to the methods described in the following examples.

Examples

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

[0232] [Evaluation Method] (HPLC) Using "LC-2010A HT" manufactured by Shimadzu Corporation as an HPLC (high performance or high speed liquid chromatograph) device and "ODS-80TM" manufactured by Tosoh Corporation as a column, the sample was dissolved in acetonitrile for measurement, and the HPLC purity [area%] was calculated.

[0233] ( 1 1H-NMR) The sample was dissolved in a heavy solvent (CDCl3) containing tetramethylsilane as an internal standard substance, and using a nuclear magnetic resonance apparatus ("AVANCE III HD" manufactured by BRUKER), 1 a 1H-NMR spectrum was measured.

[0234] (Refractive Index nD) The refractive index was measured at a temperature of 25 °C and a wavelength of 589 nm (D line) using a refractometer ("RX-7000i" manufactured by Atago Co., Ltd.). The refractive index was calculated by dissolving the sample in dimethyl sulfoxide and preparing solutions with concentrations of 5.0 mass%, 10.0 mass% and 30.0 mass% (only 5.0 mass%, 10.0 mass% and 14.7 mass% of DPBNFG obtained in Example 4), and measuring the refractive indices of the obtained solutions and a solution with a concentration of 0 mass% (dimethyl sulfoxide only). The refractive index was obtained by extrapolating the concentration to 100 mass% in a calibration curve (approximate straight line) created.

[0235] (Melting or Fusion Temperature) Using a melting point measuring device ("Melting Point M-565" manufactured by BUCHI), the measurement was carried out under the following conditions, and the melting (fusion) start temperature and the melting (fusion) end temperature were read. The average values of the melting (fusion) start temperature and the melting (fusion) end temperature measured three times were calculated respectively.

[0236] Measurement start temperature: 100 °C Temperature rising rate: 10 °C / min Melting start detection condition: 15% (The temperature at which the change rate of the transmittance of the sample is 15% or more was defined as the melting start temperature). Measurement mode: Local method mode Number of measurements: n = 3

[0237] (Temperature at 5% mass loss) Using a thermogravimetric-differential thermal analyzer (TG-DTA) ("TG / DTA6200" manufactured by SII NanoTechnology Inc.), the temperature at which the mass of the sample decreased by 5% was measured under a nitrogen atmosphere at a heating rate of 10 °C / min.

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

[0239] Test dimensions: Approximately 10 mm × 5 mm × 3 mm Heating rate: 5 °C / min Measurement temperature range: Room temperature to 300 °C Measurement mode: Compression (load 49 mN) Atmosphere: In a nitrogen gas stream (100 mL / min) Number of measurements: n = 1

[0240] Also, the glass transition temperature Tg (DMA, tan δ) of the cured product was measured under the following conditions using a dynamic viscoelasticity (DMA) measuring device ("Rheogel-E4000" manufactured by UBM Corporation) in accordance with JIS K 7244.

[0241] Heating rate: 4 °C / min Frequency: 1 Hz Atmosphere: In an air stream Measurement mode: Bending Number of measurements: n = 1

[0242] (Solubility) For 200 mg of the sample, each of the solvents described below was added so as to have a concentration of 30% by mass or 50% by mass, and the solubility of the sample in each solvent was confirmed when stirred at room temperature (25°C). When it did not dissolve at room temperature (25°C), it was gradually heated up to 50°C or 80°C, and the solubility was confirmed according to the following evaluation criteria.

[0243] ○(25°C): Dissolved at 25°C ○(50°C): Did not dissolve at 25°C and dissolved when heated to 50°C ○(80°C): Did not dissolve at 50°C and dissolved when heated to 80°C ×: Did not dissolve even when heated up to 80°C

[0244] (Storage stability) A solution obtained by completely dissolving the sample in propylene glycol monomethyl ether acetate (PGMEA) at a concentration of 30% by mass was stored at 5°C, and the solution state after 24 hours was observed to confirm the storage stability (solution stability or low-temperature stability) according to the following evaluation criteria.

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

[0246] (Epoxy equivalent) In accordance with JIS K 7236:2001, titration was performed with a perchloric acid solution (acetic acid type) using an automatic titrator (GT-100 manufactured by Mitsubishi Chemical Corporation).

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

[0248] [Chemical formula]

[0249] 12.5 g (0.037 mol) of 2,7-dibromo-9-fluorenone, 16.0 g (0.11 mol) of 2-naphthol, 90 mL of 1,4-dioxane, 0.5 mL (5.8 mmol) of 3-mercaptopropionic acid, and 26 mL of 98% by mass concentrated sulfuric acid were charged into a reaction vessel, stirred under a nitrogen atmosphere, and reacted at 60 °C for 24 hours. After cooling to room temperature, the solvent was removed by heating under reduced pressure, and then 300 mL of dichloromethane and 300 mL of ion-exchanged water were added for liquid-liquid extraction. After adjusting the pH to 7 with an aqueous sodium hydrogen carbonate solution, 300 mL of ion-exchanged water was added for washing again. This operation of washing with ion-exchanged water was repeated three times, and then dichloromethane was removed by heating under reduced pressure to obtain yellow crude crystals. The obtained yellow crude crystals were purified by column chromatography (silica gel carrier, developing solvent: dichloromethane) and dried under reduced pressure to obtain 6.01 g of DBrBNF (light brown solid, yield 24%, HPLC purity 95.2%). The 1 The results of 1H-NMR of the obtained DBrBNF are shown below.

[0250] 1 1H-NMR (CDCl3, 300 MHz): δ (ppm) 5.2 (s, 2H), 7.0 - 7.1 (m, 4H), 7.3 (d, 2H), 7.5 (m, 12H).

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

[0252] [Chemical formula]

[0253] 0.78 g (1.3 mmol) of DBrBNF, 0.54 g (3.1 mmol) of 2-naphthylboronic acid, 10 mL of toluene, and 2.6 mL (2.6 mmol) of 1 M aqueous potassium carbonate solution were charged into a reactor. Under a nitrogen stream, 75 mg (0.065 mmol) of tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)4] was added, and the mixture was heated to reflux at an internal temperature of 85 °C for 15 hours to effect the reaction. 50 mL of ion-exchanged water and 75 mL of dichloromethane were added to the reaction solution, and after stirring, liquid separation extraction was performed. After repeating the water washing operation with this ion-exchanged water three times, the organic layer was concentrated to obtain a light brown crude product. The obtained light brown crude product was purified by column chromatography [silica gel carrier, developing solvent: dichloromethane / ethyl acetate (volume ratio) = 100 / 1], and then dried under reduced pressure to obtain 351 mg of DNBNF (pale yellow solid, yield 49.9%, HPLC purity 97.4%). The refractive index nD of the obtained DNBNF was 1.79, and the 5% mass loss temperature was 443 °C, 1 The results of 1H-NMR are shown below.

[0254] 1 1H-NMR (CDCl3, 300 MHz): 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 21.3 g (0.035 mol) of DBrBNF, 13.2 g (0.077 mol) of 2-naphthylboronic acid, 130 mL of toluene, and 30 mL (0.245 mol) of 8.1 M aqueous potassium carbonate solution were charged into a reactor and dissolved at 70 - 80 °C under a nitrogen stream. Further, 20.2 mg (0.018 mmol) of tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)4] was added and reacted at an internal temperature of 80 °C for 1 hour. 30 mL of ion-exchanged water was added to the reaction solution, stirred, and then subjected to liquid separation extraction. This washing operation with ion-exchanged water was repeated 3 times, and then the organic layer was diluted 2-fold with toluene, 350 ml of heptane was added dropwise, and pale red-orange crude crystals were obtained. After drying under reduced pressure, 20.5 g of DNBNF (pale red-orange solid, yield 83.3%, HPLC purity 88.6%) was obtained. The refractive index nD, 5% mass loss temperature of the obtained DNBNF, 1 The results of 1H-NMR were the same as in Example 1A. Also, the melting start temperature was 176.4 °C and the melting end temperature was 224.1 °C. In addition, in X-ray diffraction (XRD), a halo peak was observed, and it was confirmed to be amorphous.

[0256] [Example 1C] Synthesis of DNBNF 21.3 g (0.035 mol) of DBrBNF, 13.8 g (0.081 mol) of 2-naphthylboronic acid, 36.7 mg (0.140 mmol) of triphenylphosphine, 80 mL of methyl isobutyl ketone (MIBK), and 60 mL (0.245 mol) of 4 M aqueous potassium carbonate solution were charged into a reactor and dissolved at 70 °C under a nitrogen stream. Further, 7.9 mg (0.035 mmol) of palladium acetate was added, and the reaction was carried out at an internal temperature of 75 °C for 7 hours. The water in the reaction solution was discharged, 30 mL of ion-exchanged water was added, and then it was neutralized with 10 mass% hydrochloric acid. Thereafter, the washing operation with ion-exchanged water was repeated three times. The reaction solution was concentrated to adjust the concentration to about 40 - 45 mass%, and crystallization was carried out by cooling from 60 °C to room temperature while stirring at 250 rpm to lower the temperature. Note that precipitation started at about 45 °C. After drying under reduced pressure, 18.7 g of DNBNF (white solid, yield 76.0%, HPLC purity 99.0%) was obtained. Compared with the DNBNF obtained in Examples 1A and 1B, the coloring was greatly reduced, and the yield and purity were also high. Note that the refractive index nD, 5% mass loss temperature of the obtained DNBNF, 1 The results of 1H-NMR were the same as those in Example 1A. Also, the melting start temperature was 188.5 °C and the melting end temperature was 218.8 °C. Note that in X-ray diffraction (XRD), a predetermined diffraction pattern was observed instead of a halo peak, and it was confirmed that it was a crystal, different from Example 1B.

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

[0258]

Chemical formula

[0259] 21.3 g (0.035 mol) of DBrBNF, 9.9 g (0.081 mol) of phenylboronic acid, 36.7 mg (0.140 mmol) of triphenylphosphine, 80 mL of MIBK, and 60 mL (0.245 mol) of 4M aqueous potassium carbonate solution were charged into a reactor and dissolved at 70 °C under a nitrogen stream. Further, 7.9 mg (0.035 mmol) of palladium acetate was added, and the reaction was carried out at an internal temperature of 75 °C for 5 hours. The water in the reaction solution was discharged, 30 mL of ion-exchanged water was added, and the pH was adjusted to 7 with 10 mass% hydrochloric acid. Thereafter, the washing operation with ion-exchanged water was repeated three times. The reaction solution was concentrated to remove MIBK, and 21 g (0.230 mmol) of toluene was added. By dropping the toluene solution into 21 g (0.210 mmol) of heptane, 17.7 g of DPBNF (pale yellow solid, yield 84.0%, HPLC purity 87.9%) was obtained. The refractive index nD of the obtained DPBNF was 1.75, the 5% mass loss temperature was 360 °C, 1 The results of 1H-NMR are shown below. Also, the melting start temperature was 180.7 °C and the melting end temperature was 227.4 °C.

[0260] 1 1H-NMR (CDCl3, 300 MHz): δ (ppm) 5.49 (s, 2H), 7.0 (m, 4H), 7.2 - 8.0 (m, 24H)

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

[0262] [Comparative Example 2] The refractive index nD of 9,9-bis(4-hydroxyphenyl)fluorene (“BPF” manufactured by Osaka Gas Chemical Co., Ltd., melting point 223 - 224 °C) was 1.68, and the 5% mass loss temperature was 301 °C.

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

[0264] [Comparative Example 4] The refractive index nD of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (manufactured by Osaka Gas Chemical Co., Ltd., "BPEF", melting point 161 - 163 °C) was 1.65, and the 5% mass loss temperature was 342 °C.

[0265] Table 1 below shows the physical properties (refractive index, 5% mass loss temperature, melting temperature) of the fluorene compounds obtained in the examples and comparative examples (the numerical values in parentheses of the melting temperature in Table 1 indicate the melting points of commercially available products).

[0266]

Table 1

[0267] As is clear from the results in Table 1, the examples show a very high refractive index compared to the comparative examples. Also, in Example 2 (DPBNF) where a benzene ring was introduced at the 2,7-positions of the fluorene skeleton of Comparative Example 1 (BNF), a decrease in the 5% mass loss temperature was observed, while in Example 1 (DNBNF) where a naphthalene ring was introduced, the 5% mass loss temperature was greatly improved, showing better heat resistance. Note that Example 1 (DNBNF) and Example 2 (DPBNF) show a high 5% mass loss temperature, but unexpectedly, the melting start temperature is low. In particular, in Example 1 (DNBNF), despite introducing a naphthalene ring with more benzene ring skeletons than in Example 2 (DPBNF), the melting end temperature is also low, indicating that it can be easily melted.

[0268] Table 2 below shows the evaluation results of the solubility when the fluorene compounds obtained in Example 1C, Example 2, and Comparative Example 1 were dissolved in each solvent at a concentration of 30% by mass. In the table, PGMEA represents propylene glycol monomethyl ether acetate, PGME represents propylene glycol monomethyl ether, n-PrOH represents n-propanol, NMP represents N-methyl-2-pyrrolidone, DMF represents N,N-dimethylformamide, and DMSO represents dimethyl sulfoxide (the same applies hereinafter). [Table 2]

[0269] As is clear from the results in Table 2, since Example 1 (DNBNF) and Example 2 (DPBNF) contain many benzene ring skeletons, it was expected that the solubility would decrease significantly. However, unexpectedly, they showed high solubility. In particular, Example 1 (DNBNF) was soluble in all the measured solvent species.

[0270] Table 3 below shows the evaluation results of the storage stability of the solutions (solutions prepared in the solubility test in Table 2) in which the fluorene compounds obtained in Example 1C, Example 2, and Comparative Example 1 were dissolved in PGMEA at a concentration of 30% by mass. [Table 3]

[0271] As is clear from the results in Table 3, in all the examples, they maintained a stable solution state without precipitation under high-concentration and low-temperature environments where precipitation was likely to occur.

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

[0273] [Chemical formula]

[0274] 105.43 g (0.15 mol) of DNBNF obtained in Example 1C, 303.6 g (3.3 mol) of chloromethyloxirane, and 83.2 g of dimethyl sulfoxide were added into a reactor, and heated and dissolved at 40 °C for 30 minutes under a nitrogen stream. Then, 13.2 g (0.33 mol) of flaky sodium hydroxide was added. Four hours after the addition of sodium hydroxide, while maintaining the temperature at 40 °C, heating and stirring were carried out, and as a result, disappearance of DNBNF as a raw material was confirmed by HPLC. Then, chloromethyloxirane was concentrated and removed with an evaporator. After adding 550 g of MIBK, a water washing operation with 200 mL of ion-exchanged water was repeated 5 times. The MIBK solution was adjusted to 20 mass% of solid content, and 107 g of DNBNFG (white solid, yield 88%, HPLC purity 95%) was obtained by dropping it over 1 hour with respect to 1635 g of isopropyl alcohol (IPA). The refractive index nD of the obtained DNBNFG was 1.76, the 5% mass loss temperature was 405 °C, showing a very high refractive index and heat resistance. The melting start temperature (starting temperature of melting) of the obtained DNBNFG was 149 °C, and the epoxy equivalent was 432.4 g / eq, 1 The results of 1H-NMR are shown below.

[0275] 1 1H-NMR (CDCl3, 300 MHz): 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 Into a 200 mL four-necked eggplant flask, 35.1 g (0.05 mol) of DNBNF obtained in Example 1B and 101 g (1.1 mol, 22 eq.) of epichlorohydrin were placed, and the inside of the container was replaced with nitrogen. 6.6 g (0.17 mol, 3.3 eq.) of sodium hydroxide (granules) was added, and the refluxed epichlorohydrin was returned to the system with a Dean-Stark while heating under reflux at 118 °C. After stirring for 3 hours, epichlorohydrin was concentrated and removed. After dissolving with 199 g (2.0 mol, 40 eq.) of methyl isobutyl ketone (MIBK), 117 g of distilled water and 2 g of celite were added, and the mixture was stirred at 70 °C. The celite was filtered, and after draining, the operation of washing the organic layer with 80 mL of distilled water was repeated 4 times. The organic layer was reprecipitated with 205 g of methanol, and the obtained solid was dried at 70 °C to obtain a pale yellow solid. Further, by purification with silica gel chromatography (dichloromethane / hexane = 6 / 4 (volume ratio)), 5.64 g of DNBNFG (pale 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 start temperature were the same as those in Example 3A. In addition, the 1 The results of 1H-NMR of DNBNFG are shown below.

[0277] 1 1H-NMR (CDCl3, 300 MHz): 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] Synthesis of 9,9-bis(6-glycidyloxy-2-naphthyl)-2,7-diphenylfluorene (hereinafter also referred to as DPBNFG)

Chemical formula

[0279] Instead of DNBNF, DPBNFG 93 g (light yellow solid, yield 87%, HPLC purity 87%) was obtained in the same manner as in Example 3A, except that 90.4 g (0.15 mol) of DPBNF was used. The refractive index nD of the obtained DPBNFG was 1.72, the 5% mass loss temperature was 380 °C, the melting start temperature was 195 °C, the epoxy equivalent was 384.4 g / eq, 1 The results of 1H-NMR are shown below.

[0280] 1 1H-NMR (CDCl3, 300 MHz): 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] The refractive index nD of 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene ("BNFG" manufactured by Osaka Gas Chemical Co., Ltd.) was 1.70, the 5% mass loss temperature was 391 °C, the melting start temperature was 113 °C, and the epoxy equivalent was 292.0 g / eq.

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

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

[0284]

Table 4

[0285] As is clear from the results in Table 4, the examples show a very high refractive index compared to the comparative examples. Also, in Example 4 (DPBNFG) where a benzene ring was introduced at the 2,7 positions of the fluorene skeleton of Comparative Example 5 (BNFG), a decrease in the 5% mass loss temperature was observed, while in Example 3 (DNBNFG) where a naphthalene ring was introduced, the 5% mass loss temperature was greatly improved and it has excellent heat resistance. The examples are excellent in heat resistance, but it was found that the melting start temperature is relatively low and they can be easily or efficiently mixed with other components such as curing agents. In particular, it was unexpected that Example 3 with a naphthalene ring introduced had a lower melting start temperature than Example 4 with a benzene ring introduced.

[0286] Table 5 below shows the evaluation results of the solubility when the fluorene compounds (epoxy resins) obtained in Example 3A and Examples 4 and Comparative Example 5 were dissolved in each solvent at a concentration of 30% by mass.

Table 5

[0287] As is clear from the results in Table 5, since Example 3A (DNBNFG) contains many benzene ring skeletons, it was expected that the solubility would greatly decrease, but it was soluble in all the measured solvent species and unexpectedly showed high solubility. In particular, it was unexpected that Example 3 with a naphthalene ring introduced had better solubility than Example 4 with a benzene ring introduced.

[0288] Note that Example 3A (DNBNFG) was dissolved in ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, DMF and DMSO at room temperature (25°C) even at a concentration of 50% by mass, and was dissolved in cyclohexanone, PGMEA, PGME, benzyl alcohol, 1,4-dioxane, methyl lactate, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, γ-butyrolactone, NMP and toluene by heating at 80°C or lower, respectively.

[0289] In contrast, in Example 4 (DPBNFG), it was only dissolved in NMP at room temperature (25 °C) at a concentration of 50 wt%.

[0290] <Preparation of curable composition and cured product> The epoxy resins of Example 3A and Comparative Examples 5 to 6 and a phenol novolak resin as a curing agent ("PSM-4261" manufactured by Gunei Chemical Industry Co., Ltd., hydroxyl equivalent 105 g / eq) were charged so as to have an equivalent ratio of 1:1, and kneaded at 190 °C using a two-roll mill. After cooling the recovered kneaded product to room temperature, TPP (triphenylphosphine, manufactured by Kanto Chemical Co., Inc.) as a catalyst was added in an amount of 1 part by mass with respect to 100 parts by mass of the total amount of the epoxy resin and the phenol novolak resin, and kneaded at 120 °C using a roll. The obtained kneaded product was press-molded at 175 °C for 30 minutes and then heated (post-cured) at 175 °C for 5 hours using an oven to obtain a cured product.

[0291] Table 6 below shows the physical properties of the fluorene compounds (epoxy resins) obtained in the examples and comparative examples and the cured products obtained using these epoxy resins.

[0292]

Table 6

[0293] As is clear from Table 6, in Example 3A, higher heat resistance was shown compared to Comparative Examples 5 to 6. In addition, DNBNFG used in Example 3A has many benzene ring skeletons in its chemical structure compared to Comparative Examples 5 to 6. Therefore, although a decrease in solubility (compatibility) was expected, unexpectedly, it showed good compatibility with the curing agent and the like, and a uniform curable composition and a cured product could be prepared.

Industrial applicability

[0294] The fluorene compound represented by the formula (1) of the present invention exhibits a high refractive index and excellent heat resistance. Therefore, it can be effectively used as a monomer component of thermoplastic resins such as resin raw materials, for example, polyester resins such as polyarylate resins, polycarbonate resins, polyether resins, polyether ketone resins, polyether ether ketone resins, etc., or as a raw material for curable resins such as (meth)acrylic resins, vinyl ester resins (or epoxy (meth)acrylate resins), vinyl ether resins, epoxy resins, etc. In particular, the fluorene compound represented by the formula (1) has a high 5% mass loss temperature and, unexpectedly, a low melting (fusion) temperature despite exhibiting high heat resistance. Furthermore, since it also has excellent solubility, it may be used as a monomer for melt polymerization or solution polymerization.

[0295] In addition, the fluorene compound represented by the formula (1) can be effectively used as additives (or resin additives) such as refractive index improvers, heat resistance improvers, curing agents, etc. Examples of the curing agent include curing agents for epoxy resins. The fluorene compound represented by the formula (1) not only has a low melting (fusion) temperature but also has excellent solubility (compatibility), so a uniform composition may be easily or efficiently prepared by melt kneading or the like.

[0296] A resin using the fluorene compound represented by the formula (1) of the present invention as a raw material or a composition containing fluorene as an additive can be suitably used for optical members (optical materials or transparent materials). Examples of the optical member include optical lenses such as reflow lenses, pickup lenses, and microlenses, optical films such as polarizing films, antireflection films, touch panel films, flexible substrate films, and display films, fuel cell membranes, optical fibers, optical waveguides, holograms, etc.

[0297] In addition, the epoxy resin represented by the formula (1E) and the curable composition (or its cured product) containing this epoxy resin are excellent in properties such as high refractive index and high heat resistance. Therefore, for example, insulating materials between layers of electronic components, solder resists for printed circuit boards, resist materials such as coverlays, inks such as color filters and printing inks, encapsulants such as electronic component or semiconductor encapsulants, paints, coating agents, adhesives, pressure-sensitive adhesives, underfills, antistatic agents, fillers, conductive members or conductive materials, laminated materials, heat-sensitive materials such as heat-sensitive paper materials, carbon materials, insulating materials, foams, pressure-sensitive materials, and all materials such as the optical materials (or transparent materials) are useful. The epoxy resin represented by the formula (1E) is unexpectedly not only relatively low in melting start temperature but also excellent in solubility (compatibility), so that a uniform curable composition can be easily or efficiently prepared even at a relatively low temperature.

Claims

1. The following formula (1) 【Chemical 1】 [In the formula, Y1a and Y1b are each independently the following formula (Y1) 【Chemical 2】 (In the formula, Z1 represents an arene ring,[[]] R1 represents a substituent, and m1 represents an integer of 0 or 1 or more.) represents a monovalent group, k1a and k1b each independently represent an integer of 0 to 4, and at least one of k1a and k1b is 1 or more,[[]] R2a and R2b each independently represent a substituent, and m2a and m2b each independently represent an integer of 0 to 4,[[]] k1a + m2a and k1b + m2b are each independently 4 or less,[[]] Y2a and Y2b are each independently the following formula (Y2) 【Chemical Formula 3】 (In the formula, Z2 represents a polycyclic arene ring,[[]] R3 represents a substituent, and m3 represents an integer of 0 or 1 or more,[[]] A1 represents a linear or branched alkylene group, and n1 represents an integer of 0 or 1 or more.) represents a monovalent group.] It is a method for producing a fluorene compound represented by the following formula (1), A method for producing a fluorene compound including the reaction step described in the following (i). (i) A step of subjecting a compound represented by the following formula (2) to a coupling reaction with a compound represented by the following formula (3a) and a compound represented by the formula (3b) [Chemical Formula 4] [wherein, X １ａ and X ２ａ as well as X １ｂ and X ２ｂ each independently represents a pair of reactive groups capable of forming a carbon-carbon bond by a coupling reaction, Y １ａ and Y １ｂ , k1a and k1b, R ２ａ and R ２ｂ , m2a and m2b, and Y ２ａ and Y ２ｂ are the same as in the formula (1).

2. Further including a purification step of precipitating the fluorene compound represented by the formula (1) obtained in the reaction step from a solvent, and the solvent is at least one solvent selected from (a) a solvent containing aromatic hydrocarbons and aliphatic hydrocarbons, and (b) a solvent containing ketones. The production method according to Claim 1.

3. In the formula (1), Z1 in the formula (Y1) representing Y1a and Y1b is a benzene ring, a naphthalene ring or a biphenyl ring, k1a and k1b are integers of 0 to 2, and Z2 in the formula (Y2) representing Y2a and Y2b is a naphthalene ring or a biphenyl ring. The production method according to Claim 1 or 2.

4. In the formula (1), Z1 in the formula (Y1) representing Y1a and Y1b is a condensed polycyclic arene ring. The production method according to any one of Claims 1 to 3.

5. The fluorene compound represented by the formula (1) is at least one selected from a monomer for melt polymerization or solution polymerization, and a resin additive for modifying a resin. The production method according to any one of Claims 1 to 4.

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