Fluorene compound and resin using same

Abstract

To provide a fluorene compound that can resist being colored even under a high temperature environment, and a resin made from the fluorene compound.SOLUTION: A fluorene compound has a 9,9-bis(hydroxy C2-4 alkoxy-naphthyl) structure, in which the content of a compound of formula (2) is 0.5% or less in HPLC area ratio, the content of a compound of formula (3) is 0.3% or less in HPLC area ratio, and the content of residual sulfur is 10 mass ppm or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound having a 9,9-bispolycyclic arylfluorene skeleton and a resin using the same. [Background technology]

[0002] In the field of optical materials, compounds having a 9,9-bisarylfluorene skeleton and resins using this compound as a raw material (or polymerization component) have attracted attention because of their excellent optical properties such as a high refractive index, a low Abbe number, a low birefringence, and high transparency, as well as their heat resistance. In recent years, the properties required for optical components have tended to become more sophisticated, and Patent Documents 1 to 5, etc., describe compounds in which the aryl group substituted at the 9,9-position of the fluorene skeleton is a polycyclic aryl group. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-155253 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-68624 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-69643 [Patent Document 4] Japanese Patent Application Publication No. 2017-179323 [Patent Document 5] Japanese Patent Application Laid-Open No. 2018-168124 Summary of the Invention [Problem to be solved by the invention]

[0004] The compounds having a 9,9-bisarylfluorene skeleton described in Patent Documents 1 to 5 have relatively high optical properties and heat resistance. On the other hand, for use as optical components, it is also extremely important that they are resistant to coloration.

[0005] Therefore, an object of the present invention is to provide a fluorene compound that can suppress coloration even in a high-temperature environment, and a resin made from this fluorene compound as a raw material.

[0006] Another object of the present invention is to provide a method for suppressing the coloration of a fluorene compound.

[0007] A further object of the present invention is to provide a method for improving the heat resistance of a resin made from a fluorene compound.

[0008] Another object of the present invention is to provide a method for suppressing the discoloration of a resin made from a fluorene compound. [Means for solving the problem]

[0009] As a result of intensive research to achieve the above object, the inventors have found that coloration can be effectively suppressed even in high temperature environments by adjusting the content of specific impurities that may be mixed into a compound having a 9,9-bispolycyclic arylfluorene skeleton during the manufacturing process, etc., to a predetermined range, and have completed the present invention.

[0010] That is, the fluorene compound of the present invention is a compound represented by the following formula (1), in which the content of the compound represented by the following formula (2) is 0.5% or less in terms of area percentage by HPLC, the content of the compound represented by the following formula (3) is 0.3% or less in terms of area percentage by HPLC, and the residual sulfur is 10 mass ppm or less.

[0011] [ka]

[0012] (In the formula, Z 1a and Z 1b each independently represents a polycyclic arene ring, R 1 represents a substituent, n1 represents an integer of 0 to 8, R 2a and R 2beach independently represents a substituent; n2a and n2b each independently represent an integer of 0 or more; A 1a and A 1b each independently represents a linear or branched alkylene group).

[0013] [ka]

[0014] (In the formula, R 3 represents a substituent, and n3 represents an integer of 0 to 8).

[0015] [ka]

[0016] (In the formula, Z 2 indicates an arene ring, R 4 represents a substituent, n4 represents an integer of 0 or more, A 2 represents a straight-chain or branched-chain alkylene group).

[0017] In the formula (1), Z 1a and Z 1b may be a naphthalene ring or a biphenyl ring. The content of the compound represented by formula (2) may be about 0.2% or less, the content of the compound represented by formula (3) may be about 0.05% or less, and the residual sulfur may be about 1.5 ppm by mass or less.

[0018] The fluorene compound represented by the formula (1) may have a content of a compound represented by the following formula (4) of 0.01 to 10% in terms of area percentage by HPLC.

[0019] [ka]

[0020] (In the formula, Z 3aand Z 3b each independently represents an arene ring, R 5 represents a substituent, n5 represents an integer of 0 to 8, R 6a and R 6b each independently represents a substituent, n6a and n6b each independently represent an integer of 0 or more, A 3a and A 3b each independently represents a linear or branched alkylene group, and m3a and m3b each independently represent an integer of 0 or more. 3a and Z 3b are polycyclic arene rings, m3a and m3b cannot be 1 at the same time).

[0021] The fluorene compound represented by the formula (1) may have a content of a compound in which one of m3a and m3b in the formula (4) is 0 and the other is 1 of 0.01 to 1% in terms of area percentage by HPLC.

[0022] The fluorene compound represented by the formula (1) may have a content of a compound in which one of m3a and m3b in the formula (4) is 1 and the other is 2 of 0.01 to 5% in terms of area percentage by HPLC.

[0023] The fluorene compound represented by the formula (1) may have a content of a compound represented by the following formula (11) of 0.1 to 10% in terms of area percentage by HPLC.

[0024] [ka]

[0025] (In the formula, Z 8a and Z 8b each independently represents an arene ring, R 17 represents a substituent, n17 represents an integer of 0 to 8, R 18a and R 18beach independently represents a substituent, n18a and n18b each independently represent an integer of 0 or more, A 8a ~A 8d each independently represents a linear or branched alkylene group, m8a and m8b each independently represent an integer of 0 or more, and m8c and m8d each independently represent an integer of 0 to 2, provided that m8c and m8d are not simultaneously 0.

[0026] The present invention encompasses a resin containing (using as a raw material) the fluorene compound represented by formula (1). The resin may be a thermoplastic resin containing an ester bond in the main chain. Alternatively, the resin may be a thermoplastic resin containing a carbonate ester bond in the main chain.

[0027] The present invention also encompasses a method for suppressing coloration of the compound represented by formula (1) in a molten state by adjusting the content of the compound represented by formula (2) to 0.5% or less in terms of area percentage by HPLC, the content of the compound represented by formula (3) to 0.3% or less in terms of area percentage by HPLC, and residual sulfur to 10 ppm by mass or less.

[0028] Furthermore, the present invention also encompasses a method for improving the glass transition temperature of the resulting resin by using the compound represented by formula (1) as a resin raw material, and a method for reducing the b* (color difference b* value) of the resulting resin.

[0029] In this specification and claims, the term "diol unit" refers to a structural unit derived from a diol component, i.e., a unit (or divalent group) obtained by removing hydrogen atoms from two hydroxyl groups of the corresponding diol, and the term "diol component" (including compounds exemplified as diol components) may be used synonymously with the corresponding "diol unit."

[0030] Similarly, the term "dicarboxylic acid unit" refers to a structural unit derived from a dicarboxylic acid component, i.e., a unit (or divalent group) obtained by removing OH (hydroxyl group) from two carboxyl groups of the corresponding dicarboxylic acid. The term "dicarboxylic acid component" is used to mean not only dicarboxylic acid but also derivatives that can be used as polymerization components, such as ester-forming derivatives. Examples of the ester-forming derivatives include dicarboxylic acid esters, dicarboxylic acid halides, and dicarboxylic acid anhydrides. Examples of the dicarboxylic acid esters include C alkyl esters of dicarboxylic acid components, particularly lower alkyl esters, such as methyl esters, ethyl esters, and t-butyl esters. 1-4 Examples of the dicarboxylic acid halide include dicarboxylic acid chloride and dicarboxylic acid bromide. The ester-forming derivative may be a monoester (half ester) or a diester. In addition, the term "dicarboxylic acid component" (including compounds exemplified as dicarboxylic acid components) may be used synonymously with the corresponding "dicarboxylic acid unit" in some cases.

[0031] In this specification and claims, the number of carbon atoms in a substituent is represented by C1, C6, C 10 For example, an alkyl group with 1 carbon atom is represented as "C1 alkyl," and an aryl group with 6 to 10 carbon atoms is represented as "C 6-10 It is indicated as "aryl".

[0032] In this specification and claims, unless otherwise specified, the term "fluorene compound" refers to a compound represented by the above formula (1).

[0033] Additionally, in this specification and claims, "HPLC" means high performance or high performance liquid chromatography. [Effects of the Invention]

[0034] The fluorene compound (or a composition containing a fluorene compound and an impurity) of the present invention can suppress or reduce coloring (or discoloration) even in a high-temperature environment. Therefore, the fluorene compound has excellent heat resistance. Furthermore, when a resin is prepared using this fluorene compound, coloring (or discoloration) of the resulting resin can be suppressed or reduced. Furthermore, the heat resistance of the resulting resin can be improved. DETAILED DESCRIPTION OF THE INVENTION

[0035] [Fluorene compound represented by formula (1)] The fluorene compound of the present invention is represented by the following formula (1).

[0036] [ka]

[0037] (In the formula, Z 1a and Z 1b each independently represents a polycyclic arene ring, R 1 represents a substituent, n1 represents an integer of 0 to 8, R 2a and R 2b each independently represents a substituent; n2a and n2b each independently represent an integer of 0 or more; A 1a and A 1b each independently represents a linear or branched alkylene group).

[0038] In the formula (1), ring Z 1a and Z 1b Examples of the polycyclic arene ring (polycyclic aromatic hydrocarbon ring) represented by the formula (I) include a fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring) and a ring-assembled arene ring (ring-assembled aromatic hydrocarbon ring).

[0039] Examples of the fused polycyclic arene ring include fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. Examples of the fused bicyclic arene ring include fused bicyclic C rings such as naphthalene rings and indene rings. 10-16 Examples of the fused tricyclic arene ring include an anthracene ring and a phenanthrene ring.

[0040] Preferred fused polycyclic arene rings include fused polycyclic C rings such as naphthalene rings and anthracene rings. 10-16 arene rings, more preferably fused polycyclic C 10-14 Examples include arene rings, and particularly, naphthalene rings are preferred.

[0041] Examples of the ring-assembled arene ring include biarene rings and terarene rings. Examples of the biarene ring include biphenyl rings, binaphthyl rings, phenylnaphthalene rings, and other biarene rings. 6-12 Examples of the phenylnaphthalene ring include a 1-phenylnaphthalene ring and a 2-phenylnaphthalene ring. Examples of the terarene ring include a terphenylene ring. 6-12 arene rings.

[0042] Preferred ring-assembled arene rings include biC 6-10 Examples include an arene ring, and a biphenyl ring is particularly preferred.

[0043] Ring Z 1a and Z 1b The types of rings Z may be the same or different, and are usually the same. 1a and Z 1b Among them, C such as naphthalene ring and biphenyl ring 10-14 An arene ring is preferred, and a naphthalene ring is particularly preferred. Ring Z 1a and Z 1b When the ring is a fused polycyclic arene ring such as a naphthalene ring, impurities such as sulfur components can be more effectively reduced.

[0044] In addition, the ring Z bonded to the 9-position of the fluorene ring 1a and Z 1b The substitution position of ring Z is not particularly limited. 1a and Z 1b When ring Z is a naphthalene ring, it may be at either the 1-position or the 2-position, preferably the 2-position. 1a and Z 1b When is a biphenyl ring, it may be at any one of the 2-, 3- and 4-positions, preferably the 3-position.

[0045] R 1 Examples of the substituent represented by the formula include a hydrocarbon group, a cyano group, and a halogen atom.

[0046] Examples of the hydrocarbon group include an alkyl group and an aryl group. Examples of the alkyl group include a linear or branched C alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. 1-6 Examples of the aryl group include C phenyl groups and the like. 6-10 Examples include an aryl group.

[0047] Examples of halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms.

[0048] These groups R 1 Among these, alkyl groups, cyano groups, and halogen atoms are preferred, and among these, alkyl groups, particularly linear or branched C groups such as methyl groups are preferred. 1-4 Alkyl groups are preferred.

[0049] base R 1 The number of substitutions n1 is, for example, an integer of about 0 to 6, and preferred ranges are, in the following stepwise order, integers of 0 to 4, integers of 0 to 3, integers of 0 to 2, and more preferably 0 or 1, and particularly 0. The number of substitutions in the two different benzene rings constituting the fluorene ring may be the same or different. In addition, the number of substitutions of the groups R substituted on the different benzene rings may be the same or different. 1The types of groups R may be different from each other, but are usually the same in many cases. When n1 is 2 or more, the number of groups R substituted on the fluorene ring is two or more. 1 The types of groups R may be the same or different. 1 The substitution position of is not particularly limited, and may be, for example, the 2- to 7-position of the fluorene ring, such as the 2-, 3- and / or 7-position.

[0050] base R 2a and R 2b Examples of the substituent represented by the formula (I) include a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, a mercapto group, an acyl group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, a nitro group, a cyano group, an amino group, a substituted amino group, and groups in which these substituents are bonded to each other.

[0051] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0052] Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0053] Examples of the alkyl group include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. 1-10 Preferred alkyl groups include linear or branched C 1-6 alkyl group, more preferably a linear or branched C 1-4 It is an alkyl group.

[0054] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Examples include a cycloalkyl group.

[0055] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12 Examples of the alkylphenyl group include a methylphenyl group (tolyl group) and a dimethylphenyl group (xylyl group).

[0056] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples include alkyl groups.

[0057] Examples of the alkoxy group include linear or branched C alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, s-butoxy, and t-butoxy groups. 1-10 Examples include an alkoxy group.

[0058] Examples of the cycloalkyloxy group include C 11 groups such as a cyclohexyloxy group. 5-10 Examples thereof include a cycloalkyloxy group.

[0059] Examples of the aryloxy group include C aryloxy groups such as phenoxy groups. 6-10 Examples thereof include an aryloxy group.

[0060] Examples of the aralkyloxy group include C aryloxy groups such as benzyloxy groups. 6-10 Aryl-C 1-4 Examples thereof include an alkyloxy group.

[0061] Examples of the alkylthio group include a C alkylthio group such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, and a t-butylthio group. 1-10 Examples include an alkylthio group.

[0062] Examples of the cycloalkylthio group include a C cyclohexylthio group. 5-10 Examples include a cycloalkylthio group.

[0063] Examples of the arylthio group include C thiophenoxy groups. 6-10 Examples include an arylthio group.

[0064] Examples of the aralkylthio group include C aryl groups such as benzylthio groups. 6-10 Aryl-C 1-4 Examples include an alkylthio group.

[0065] Examples of the acyl group include C acetyl groups. 1-6 Examples include an acyl group.

[0066] Examples of the alkoxycarbonyl group include C alkoxycarbonyl groups such as methoxycarbonyl groups. 1-6 Examples include an alkoxy-carbonyl group.

[0067] Examples of the substituted amino group include a dialkylamino group and a bis(alkylcarbonyl)amino group. Examples of the dialkylamino group include a di-C group such as a dimethylamino group. 1-4 Examples of the bis(alkylcarbonyl)amino group include bis(C 1-4 alkyl-carbonyl)amino groups.

[0068] Examples of groups in which these substituents are bonded to each other include C alkoxyaryl groups, specifically methoxyphenyl groups. 1-6 Alkoxy C 6-10 Aryl groups; alkoxycarbonylaryl groups, specifically, C such as methoxycarbonylphenyl groups 1-6 Alkoxy-carbonyl C 6-10 Examples include an aryl group.

[0069] These groups R 2a and R 2b Among these, representative examples include a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, and a substituted amino group. When the number of substitutions n2a and n2b is 1 or more, preferred groups R 2a and R2b Examples of the alkyl group include an alkyl group, an aryl group, and an alkoxy group. The alkyl group may be a straight or branched C 1-6 The alkyl group is preferred, and the aryl group is preferably a C aryl group such as a phenyl group. 6-12 An aryl group is preferred, and the alkoxy group is a straight-chain or branched C 1-4 Among them, an alkyl group and an aryl group are preferred, and a linear or branched C alkyl group such as a methyl group is more preferred. 1-4 C such as alkyl group and phenyl group 6-10 An aryl group is preferred, and a methyl group or a phenyl group is more preferred, with a methyl group being particularly preferred.

[0070] base R 2a and R 2b The substitution numbers n2a and n2b of the ring Z 1a and Z 1b The number of rings can be appropriately selected depending on the type of ring, and may be, for example, an integer of about 0 to 8, preferably an integer of 0 to 6, an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, and among these, 0 or 1, particularly 0. 1a and Z 1b In the formula, the group R 2a and R 2b The types of n2a and n2b and the number of substitutions n2a and n2b may be the same or different from each other. 1a and Z 1b Two or more groups R 2a and R 2b The types of groups R may be the same or different. 2a and R 2b The substitution position of ring Z is not particularly limited. 1a and Z 1b and a hydroxyalkoxy group [-OA 1a -OH] and [-OA 1b —OH] and at a position other than the bonding position to the 9-position of the fluorene ring.

[0071] Base A 1a and A1b Examples of the linear or branched alkylene group represented by the formula (I) include linear or branched C alkylene groups such as ethylene, propylene (1,2-propanediyl), trimethylene, 1,2-butanediyl, and tetramethylene. 2-6 Examples of the alkylene group include alkylene groups. 1a and A 1b As for the linear or branched chain C 2-4 Alkylene groups, more preferably linear or branched C groups such as ethylene groups and propylene groups 2-3 The alkylene group, in particular the ethylene group. 1a and A 1b The types may be different from each other, but are usually the same.

[0072] Hydroxyalkoxy group [-OA 1a -OH] and [-OA 1b -OH] is substituted at the ring Z 1a and Z 1b The position of the ring Z is not particularly limited as long as it is other than the bonding position of the ring Z to the 9-position of the fluorene ring. 1a and Z 1b When the ring Z is a naphthalene ring, it is usually substituted at the 1st or 2nd position of the naphthalene ring relative to the 9th position of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and in many cases it is substituted at any of the 5th to 8th positions relative to this substitution position, and preferably the hydroxyalkoxy group is substituted at the 1,5-position or 2,6-position, and particularly preferably at the 2,6-position. 1a and Z 1bWhen the fluorene ring is a biphenyl ring, the hydroxyalkoxy group may be substituted at any of the 2- to 6-positions or the 2'- to 6'-positions of the biphenyl ring, but for example, the 3- or 4-position of the biphenyl ring may be bonded to the 9-position of the fluorene ring. When the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene ring, the hydroxyalkoxy group may be substituted at any of the 2-, 4-, 5-, 6-, 2'-, 3'-, or 4'-positions of the biphenyl ring, preferably at either the 6- or 4'-position, and particularly preferably at the 6-position. When the 4-position of the biphenyl ring is bonded to the 9-position of the fluorene ring, the hydroxyalkoxy group may be substituted at any of the 2-, 3-, 2'-, 3'-, or 4'-positions of the biphenyl ring, preferably at either the 2- or 4'-position, and particularly preferably at the 2-position.

[0073] Representative examples of the fluorene compound represented by the formula (1) include compounds having a structure symmetrical with respect to the 9-position of the fluorene ring in the formula (1) (when written as a chemical formula on paper, they are linearly symmetrical with respect to a vertical line passing through the 9-position of the fluorene ring), i.e., Z 1a and Z 1b , R 2a and R 2b , n2a and n2b, and A 1a and A 1b are identical to each other including the relationship of the substitution positions, and in the two benzene rings that form the fluorene ring, there is a group R 1 and compounds having the same type, number of substitutions, and substitution positions. More specifically, 9,9-bis(hydroxyalkoxy-fused polycyclic aryl)fluorenes and 9,9-bis(hydroxyalkoxy-ring-assembled polycyclic aryl)fluorenes are included.

[0074] Examples of the 9,9-bis(hydroxyalkoxy-fused polycyclic aryl)fluorenes include 9,9-bis(hydroxy C) such as 9,9-bis(hydroxyalkoxynaphthyl)fluorene. 2-6 Alkoxy-C 10-14Specific examples include 9,9-bis(hydroxy C)s such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (also known as BNEF), 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene, and 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene. 2-6 Alkoxy-naphthyl)fluorene and the like.

[0075] Examples of the 9,9-bis(hydroxyalkoxy ring-assembled polycyclic aryl)fluorenes include 9,9-bis(hydroxy C) such as 9,9-bis(aryl-hydroxyalkoxyphenyl)fluorene. 2-6 Alkoxy-C 12-20 Specifically, 9,9-bis(C fluorenes) such as 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (also known as BOPPEF) and 9,9-bis[4-(2-hydroxypropoxy)-3-phenylphenyl]fluorene are included. 6-10 Aryl-Hydroxy C 2-6 alkoxyphenyl)fluorene and the like.

[0076] Among these fluorene compounds, 9,9-bis(hydroxy C) 2-4 9,9-bis(C alkoxy-naphthyl)fluorenes, such as BOPPEF 6-10 Aryl-Hydroxy C 2-4 Among them, 9,9-bis(hydroxyalkoxy fused polycyclic aryl)fluorenes are preferred because they have excellent heat resistance and are easily made to have a high refractive index, and 9,9-bis(hydroxy C 2-3 Alkoxy-naphthyl)fluorenes are particularly preferred.

[0077] The fluorene compound represented by the formula (1) may contain two or more kinds in combination, but usually it is often a single compound.

[0078] The HPLC purity (unit: area %) of the fluorene compound represented by formula (1) can be selected from a range of 90% or more, particularly 95% or more, for example 97% or more, and preferred ranges are 97.5% or more, 98% or more, 98.3% or more, 98.5% or more, and 99% or more in the following stepwise order. If the purity is too low, coloration may not be effectively suppressed, and when used as a resin raw material, coloration of the resulting resin may not be suppressed, or it may be difficult to adjust the resin composition to the desired ratio. In this specification and claims, purity can be measured by the method described in the Examples below.

[0079] [Impurities] In the present invention, discoloration, particularly discoloration under high temperature conditions, is suppressed by adjusting the content of specific impurity components in the compound represented by formula (1) to a predetermined range. The impurity components may be components that are mixed in or produced as by-products during the production process of the compound represented by formula (1), or may be components that are intentionally added to the purified compound represented by formula (1). The content of impurity components is usually adjusted by the production method or purification of the compound represented by formula (1). Representative impurity components include compounds represented by formula (2) (fluorenones), compounds represented by formula (3) (aryloxy alcohols), sulfur components (sulfur-containing components), etc.

[0080] (Compound represented by formula (2) (first impurity component))

[0081] [ka]

[0082] (In the formula, R 3 represents a substituent, and n3 represents an integer of 0 to 8).

[0083] In the formula (2), the group R 3 As examples of the group R 1 The same applies to the substituents exemplified above, including preferred embodiments.

[0084] base R 3 The number of substitutions n3 is, for example, the same as the range exemplified for n1 in the formula (1), including preferred embodiments. When n3 is 2 or more, two or more groups R 3 The types of groups R may be the same or different. In addition, in the two benzene rings that form the fluorene ring (fluorenone ring), the groups R 3 The types and numbers of substitutions may be the same or different.

[0085] Representative compounds represented by the formula (2) include 9-fluorenone, etc. The compounds represented by the formula (2) may be contained alone or in combination of two or more kinds.

[0086] The compound represented by the formula (2) is usually left as an unreacted component of the raw material when preparing the compound represented by the formula (1), and therefore, the group R 3 and n3 is a group R 1 and n1 are often compounds corresponding to

[0087] The content of the compound represented by formula (2) is, for example, about 0.5% or less in terms of HPLC area percentage, and preferred ranges are the following stepwise ranges: 0.4% or less, 0.3% or less, 0.2% or less, 0.15% or less, 0.1% or less, 0.05% or less, and 0.03% or less, more preferably 0.02% or less, particularly 0.01% or less. If the content of the compound represented by formula (2) is too high, the resin may be easily discolored, and when used as a resin raw material, the resulting resin may also be easily discolored, and the heat resistance of the resin, such as the glass transition temperature, may be reduced. In this specification and claims, the "HPLC area percentage" can be measured by the method described in the Examples below.

[0088] (Compound represented by formula (3) (second impurity component))

[0089] [ka]

[0090] (In the formula, Z 2 indicates an arene ring, R 4 represents a substituent, n4 represents an integer of 0 or more, A 2 represents a straight-chain or branched-chain alkylene group).

[0091] In the formula (3), ring Z 2 may be, for example, a monocyclic arene ring such as a benzene ring, or a polycyclic arene ring. 1a and Z 1b The preferred embodiments of the arene ring Z are the same as those of the arene ring Z exemplified above. 2 C such as benzene ring, naphthalene ring, biphenyl ring 6-14 arene rings, and more preferably C 6-12 Arene rings, especially benzene rings and naphthalene rings 6-10 An arene ring is preferred, and a naphthalene ring is particularly preferred.

[0092] R 4 The substituent represented by the formula (1) can be, for example, the group R 2a and R 2b The number of substitutions n4 is the same as the ranges exemplified for n2a and n2b in the section on formula (1), including preferred embodiments. When n4 is 2 or more, two or more groups R 4 The types of groups R may be the same or different. 4 The substitution position of is not particularly limited.

[0093] A 2 The alkylene group represented by the formula (1) is, for example, the group A 1a and A 1b The preferred embodiments are the same as those of the groups exemplified as the group [-OA 2 The substitution position of —OH] is not particularly limited.

[0094] Representative compounds represented by the formula (3) include phenoxy C compounds such as 2-phenoxyethanol. 2-6 Alcohols; naphthoxy C such as 2-(2-naphthoxy)ethanol, 2-(1-naphthoxy)ethanol 2-6 Alcohols; Biphenylyloxy C such as 2-(o-phenylphenyloxy)ethanol 2-6 Alcohol, etc.

[0095] The compound represented by the formula (3) may be contained alone or in combination of two or more kinds. Among these compounds represented by the formula (3), phenoxy C 2-4 Alcohol; Naphthoxy C 2-4 Alcohols; o-phenylphenyloxy C such as 2-(o-phenylphenyloxy)ethanol 2-4 Alcohols are preferred, more preferably phenoxy C such as 2-phenoxyethanol. 2-3 Alcohols; 2-naphthoxy C such as 2-(2-naphthoxy)ethanol 2-3 It's alcohol.

[0096] The compound represented by the formula (3) may remain as an unreacted component of the raw material when preparing the compound represented by the formula (1). 2 is Z in the formula (1). 1a and Z 1b To, R 4 is R in the formula (1). 2a and R 2b n4 is n2a and n2b in the formula (1), A 2 is A in the formula (1). 1a and A 1b and the like.

[0097] The content of the compound represented by formula (3) is, for example, about 3% or less in terms of area ratio by HPLC. Preferred ranges are the following stepwise ranges: 2% or less, 1% or less, 0.5% or less, 0.3% or less, 0.2% or less, 0.15% or less, 0.1% or less, 0.05% or less, and 0.03% or less, more preferably 0.02% or less, particularly 0.01% or less. If the content of the compound represented by formula (3) is too high, it may be prone to discoloration. Furthermore, when used as a resin raw material, the resulting resin may also be prone to discoloration. The compound may also function as a polymerization terminator, preventing the molecular weight of the resin from being sufficiently improved. Furthermore, when the compound represented by formula (1) is in powder form, its fluidity may be reduced, making it difficult to handle. On the other hand, if the content is too low, the compound represented by formula (1) in powder form may be prone to scattering, making it difficult to handle.

[0098] (Sulfur component (third impurity component)) The sulfur component is not particularly limited as long as it contains at least a sulfur atom in its chemical structure. In general, in the production of the compound represented by formula (1), an acid containing a sulfur atom, such as sulfuric acid, is often used as an acid catalyst, and thiols are often used as co-catalysts, as will be described later. Therefore, the sulfur component is contained in the compound represented by formula (1) as a result of the residue of these components or by-products generated by the side reaction of these components.

[0099] The content of sulfur components (residual sulfur or total sulfur content) is, for example, about 100 ppm by mass or less in terms of sulfur atoms relative to the total amount of the compound represented by formula (1) and its impurities. Preferred ranges are as follows: 50 ppm by mass or less, 20 ppm by mass or less, 10 ppm by mass or less, 8 ppm by mass or less, 5 ppm by mass or less, 4 ppm by mass or less, 3 ppm by mass or less, and 2 ppm by mass or less. More preferably, the content is 1.8 ppm by mass or less, and even more preferably, 1.6 ppm by mass or less, particularly, 1.5 ppm by mass or less, and particularly, 1.4 ppm by mass or less. If the residual sulfur content is too high, the resin may be easily discolored. Furthermore, the resin obtained when used as a resin raw material may also be easily discolored, and the heat resistance of the resin, such as the glass transition temperature, may be reduced. Furthermore, side reactions during polymerization may occur, the polymerization rate may decrease, the amount of polymerization catalyst required may increase, and the reaction vessel may become corroded. On the other hand, in the present invention, the residual sulfur is adjusted to a small range, thereby effectively suppressing coloration and improving heat resistance. In particular, when used as a raw material for polyester resins such as polycarbonate resins, the sulfur component content is 1.8 mass ppm or less, preferably 1.7 mass ppm or less, more preferably 1.6 mass ppm or less, even more preferably 1.5 mass ppm or less, and particularly preferably 1.4 mass ppm or less, calculated as sulfur atoms, from the viewpoint of further improving heat resistance. Reducing the sulfur component content to such a range appears to enable even greater improvement in heat resistance, even if a relatively large amount of impurities that may reduce heat resistance, such as the first impurity component represented by the aforementioned formula (2), is contained. In this specification and claims, residual sulfur can be measured by the method described in the Examples below.

[0100] (Other impurities) The compound represented by formula (1) may or may not contain other impurity components different from the first to third impurity components. The other impurity components may be impurities that may be mixed in during the production and / or purification process of the compound represented by formula (1), or may be impurities that are intentionally added in trace amounts. Representative other impurity components (a) to (j) will be described below.

[0101] (a) A compound represented by formula (4) The compound represented by the following formula (4) contains a compound represented by the formula (1) having a hydroxyalkoxy group [—OA 1a -OH] and [-OA 1b -OH] is replaced with a hydroxyl group or two or more alkylene oxide (alkylene carbonate or haloalkanol) adducts (or multi-adducts) thereof; in the 9,9-bisarylfluorene skeleton, a compound in which (ring Z) is attached to the 9-position of the fluorene ring 3a and Z 3b These include compounds in which monocyclic arene rings such as benzene rings are bonded.

[0102] [ka]

[0103] (In the formula, Z 3a and Z 3b each independently represents an arene ring, R 5 represents a substituent, n5 represents an integer of 0 to 8, R 6a and R 6b each independently represents a substituent, n6a and n6b each independently represent an integer of 0 or more, A 3a and A 3b each independently represents a linear or branched alkylene group, and m3a and m3b each independently represent an integer of 0 or more. 3a and Z 3b are polycyclic arene rings, m3a and m3b cannot be 1 at the same time).

[0104] In the formula (4), Z 3a and Z 3b is a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, etc., and examples of the polycyclic arene ring include Z 1a and Z 1bThe preferred embodiments are the same as those of the rings exemplified as Z. 3a and Z 3b Examples include C rings such as benzene ring, naphthalene ring, and biphenyl ring. 6-14 arene rings, and more preferably C 6-12 Arene rings, especially benzene rings and naphthalene rings 6-10 An arene ring is preferred, and a naphthalene ring is particularly preferred. 3a and Z 3b The types may be different from each other, but are usually the same.

[0105] R 5 The substituent represented by the formula (1) and the number of substitutions n5 are 1 and n1 are the same as n1, including preferred embodiments. 5 Preferred embodiments such as the type and substitution position of R in the formula (1) are also 1 and similarly for n1.

[0106] R 6a and R 6b The substituents represented by the formula (1) and the numbers of substitutions n6a and n6b are 2a and R 2b and n2a and n2b, including preferred embodiments. 6a , R 6b Preferred embodiments such as the type and substitution position of R in the formula (1) are also 2a and R 2b and similarly for n2a and n2b.

[0107] A 3a and A 3b The alkylene group represented by the formula (1) is 1a and A 1b The same applies to the above, including preferred embodiments.

[0108] The repeat numbers m3a and m3b are each, for example, 0 to 10, and preferred ranges are 0 to 6, 0 to 4, and 0 to 3, more preferably 0 to 2, and particularly preferably 0 to 1. m3a and m3b may be the same as each other, but are often different. When the repeat numbers m3a and m3b are 2 or more, 2 or more A 3a and A 3b The types may be different from each other, but are usually the same.

[0109] Group [-(OA 3a ) m3a -OH] and [-(OA 3b ) m3b -OH] substitution position is Z 3a and Z 3b When Z is a benzene ring, it is located at the 2nd to 4th positions, preferably the 3rd or 4th position, and more preferably the 4th position, relative to the phenyl group substituted at the 9th position of the fluorene ring. 3a and Z 3b is a naphthalene ring or a biphenyl ring, the hydroxyalkoxy group [—OA 1a -OH] and [-OA 1b -OH]Z 1a and Z 1b The same applies to the respective substitution positions, including preferred embodiments.

[0110] Representative compounds represented by the formula (4) include: (i) Z 3a and Z 3b is an arene ring such as a benzene ring, a naphthalene ring, or a biphenyl ring, and m3a and m3b are 0 (9,9-bis(hydroxyaryl)fluorenes or alkylene oxide-free compounds); (ii) Z 3a and Z 3b is an arene ring such as a benzene ring, a naphthalene ring or a biphenyl ring, and one of m3a and m3b is 0 and the other is 1 (alkylene oxide-1 adduct); (iii) Z 3a and Z 3bis an arene ring such as a benzene ring, a naphthalene ring or a biphenyl ring, and one of m3a and m3b is 1 and the other is 2 (alkylene oxide 3 adduct); (iv) Z 3a and Z 3b is a benzene ring, and m3a and m3b are 1 (9,9-bis(hydroxyalkoxyphenyl)fluorenes).

[0111] Specific examples of the 9,9-bis(hydroxyaryl)fluorenes of (i) include 9,9-bis(hydroxyphenyl)fluorenes such as 9,9-bis(4-hydroxyphenyl)fluorene; 9,9-bis(alkyl-hydroxyphenyl)fluorenes such as 9,9-bis(mono- or di-C) such as 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene and 9,9-bis(3,5-dimethyl-4-hydroxyphenyl)fluorene; 1-6 9,9-bis(aryl-hydroxyphenyl)fluorenes, such as 9,9-bis(C 3-phenyl-4-hydroxyphenyl)fluorene; 6-10 aryl-hydroxyphenyl)fluorene; 9,9-bis(hydroxynaphthyl)fluorenes such as 9,9-bis(6-hydroxy-2-naphthyl)fluorene and 9,9-bis(5-hydroxy-1-naphthyl)fluorene; and the like.

[0112] Specific examples of the alkylene oxide monoadduct (ii) include the following compounds.

[0113] [ka]

[0114] Specific examples of the alkylene oxide triadduct (iii) include the following compounds: can be done.

[0115] [ka]

[0116] Specific examples of the 9,9-bis(hydroxyalkoxyphenyl)fluorenes of (iv) include 9,9-bis(hydroxy C) such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, and 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene. 2-6 Alkoxyphenyl)fluorene or 9,9-bis(mono or di C 1-6 Alkyl-Hydroxy C 2-6 alkoxyphenyl)fluorene and the like.

[0117] These compounds may be contained alone or in combination of two or more. 3a and Z 3b In the production of the compound represented by formula (1), when an alkylene oxide (alkylene carbonate or haloalkanol) is added to 9,9-bis(hydroxypolycyclic aryl)fluorenes obtained by reacting fluorenones with polycyclic phenols, compounds in which R is a polycyclic arene ring such as a naphthalene ring or a biphenyl ring often remain as unreacted components or by-products.

[0118] The content of the compound represented by formula (4) is, for example, about 10% or less, as measured by HPLC, and can be selected from the range of 0.1 to 10%, preferably in the following stepwise order: 7.5% or less, 5% or less, 3% or less, 1% or less, 0.3% or less, 0.1% or less, 0.05% or less, more preferably 0.01% or less, particularly 0.005% or less, and particularly substantially 0% or below the detection limit. If the content of the compound represented by formula (4) is too high, especially if there is too much of a compound having a phenolic hydroxyl group as in (i) and (ii), coloration may not be effectively suppressed due to susceptibility to oxidation, etc., and there is a risk of deactivating the polymerization catalyst when used as a resin raw material, and the moldability (or melt fluidity) of the resulting resin may be reduced. Furthermore, if there is too much of an adduct to which multiple alkylene oxides have been added, as in (iii), there is a risk of the heat resistance, water resistance, and / or impact strength of the resin being reduced. Furthermore, if there is too much of Z 3a and Z 3b If the amount of the compound having a benzene ring is too large, the heat resistance and refractive index of the resin may decrease. However, if the alkylene oxide triadduct (iii) is contained, the moldability (melt fluidity) and / or tensile strength of the resin may be improved.

[0119] On the other hand, even if the alkylene oxide tri-adduct (iii) is contained, the properties are not significantly deteriorated as long as the content of the compound represented by formula (4) is 5% or less, for example, 0.1 to 5%, preferably 0.2 to 4%, more preferably 0.3 to 3%, and even more preferably 0.5 to 2%, in terms of HPLC area percentage. In particular, by combining the alkylene oxide mono-adduct (ii) with the compound represented by formula (4), the heat resistance may be improved.

[0120] That is, when the alkylene oxide mono-adduct (ii) is contained in a predetermined proportion, heat resistance may be improved while suppressing coloration in the resin. Therefore, the content of the alkylene oxide mono-adduct (ii) may be, for example, about 0.01 to 2%, particularly about 0.01 to 1%, in terms of area percentage by HPLC, and preferably the following stepwise values: 0.05 to 2%, 0.1 to 2%, 0.2 to 1.5%, 0.3 to 1%, 0.4 to 0.9%, 0.45 to 0.85%, 0.5 to 0.8%, and 0.6 to 0.75%. When the alkylene oxide mono-adduct (ii) is contained in such a proportion, heat resistance may be effectively improved while suppressing coloration in polyester resins, preferably polycarbonate resins and polyester-polycarbonate copolymers, and more preferably polycarbonate resins. In particular, when the content of the compound represented by formula (2) (first impurity component) and the sulfur component (third impurity component) is low, the heat resistance can be further improved by including the alkylene oxide monoadduct (ii) in a predetermined proportion.

[0121] The content of the alkylene oxide triadduct (iii) may be, for example, about 0.01 to 5% in terms of area percentage by HPLC, and preferred ranges are 0.05 to 5%, 0.1 to 5%, 0.5 to 4.5%, 1 to 4%, 1.1 to 3%, 1.2 to 2%, and 1.3 to 1.5%, in the following stepwise order.

[0122] (b) Polymers containing multiple 9,9-bisarylfluorene structures The compound represented by formula (1) may or may not contain a polymer containing multiple 9,9-bisarylfluorene skeletons. A polymer containing multiple 9,9-bisarylfluorene skeletons has a chemical structure in which one arene ring is bonded to the 9-position of at least two fluorene rings, and is typically a compound represented by formula (5) below.

[0123] [ka]

[0124] (In the formula, Z 4a ~Z 4d each independently represents an arene ring, R 7a ~R 7c each independently represents a substituent, n7a to n7c each independently represents an integer of 0 to 8, R 8a ~R 8d each independently represents a substituent, n8a to n8d each independently represents an integer of 0 or more, A 4a ~A 4d each independently represents a linear or branched alkylene group, m4a to m4d each independently represent an integer of 0 or more, where k is an integer greater than or equal to 0).

[0125] In the formula (5), Z 4a ~Z 4d As the arene ring, Z in the formula (4) 3a and Z 3b The same applies to the preferred embodiments. 4a ~Z 4d The types may be different from each other, but are usually the same.

[0126] R 7a ~R 7c and n7a to n7c are R in the formula (1). 1 and n1 are the same as n1, including preferred embodiments. 7a ~R 7c Preferred embodiments such as the type and substitution position of R in the formula (1) are also 1 and n1. 7a ~R 7c and n7a to n7c may be the same or different from each other.

[0127] R 8a ~R 8d and n8a to n8d are R in the formula (1). 2a and R 2b and n2a and n2b, including preferred embodiments.8a ~R 8d Preferred embodiments such as the type and substitution position of R in the formula (1) are also 2a and R 2b The same applies to n2a and n2b. 8a ~R 8d and n8a to n8d may be the same or different from each other.

[0128] A 4a ~A 4d is A in the formula (3). 3a and A 3b The same applies to the above, including preferred embodiments. 4a ~A 4d The preferred embodiments of the type and substitution position of A in the formula (3) are also 3a and A 3b The same applies to m4a to m4d. Examples of m4a to m4d include the same ranges as m3a and m3b in the formula (3), and are preferably 1. Note that, unlike m3a and m3b, all of m4a to m4d may be 1. Also, A 4a ~A 4d and m4a to m4d may be the same as or different from each other.

[0129] The number of repetitions k may be, for example, about 0 to 10, and the preferred ranges are 0 to 8, 0 to 5, 0 to 3, and 0 to 2, stepwise, and more preferably 0 or 1. When k is 2 or more, Z 4c , R 7b , n7b, R 8c , n8c, A 4c and m4c may be the same as or different from each other.

[0130] Representative compounds represented by formula (5) include Z 4a ~Z 4d is a benzene ring, a naphthalene ring, or a biphenyl ring, and A 4a ~A 4d is linear or branched C 2-4alkylene group, m4a to m4d are integers of 0 to 2, and k is 0 or 1. Preferred compounds include compounds in which Z 4a ~Z 4d is a naphthalene ring, and A 4a ~A 4d is linear or branched C 2-3 The compound is an alkylene group, m4a to m4d are 1, and k is 0 or 1.

[0131] The content of the multimer containing multiple 9,9-bisarylfluorene structures may be, for example, about 0.02 to 4% in terms of area percentage by HPLC, with preferred ranges being 0.02 to 3%, 0.02 to 2%, 0.02 to 1%, 0.02 to 0.8%, and 0.02 to 0.6% in the following stepwise order. The presence of such a multimer can suppress coloration in the resin, improve moldability (melt fluidity), and evenly or stably increase resin strength. Furthermore, when the compound represented by formula (1) is powdery, the powder's fluidity or handleability may be improved. If the proportion of the multimer is too high, gelation may occur during polymerization.

[0132] (c) A compound represented by formula (6) The compound represented by the formula (1) may or may not contain a compound represented by the following formula (6).

[0133] [ka]

[0134] (In the formula, Z 5a ~Z 5c each independently represents an arene ring, R 9 represents a substituent, n9 represents an integer of 0 to 8, R 10a ~R 10c each independently represents a substituent, n10a to n10c each independently represents an integer of 0 or more, A 5a ~A 5ceach independently represents a linear or branched alkylene group, and m5a to m5c each independently represent an integer of 0 or more).

[0135] In the formula (6), Z 5a ~Z 5c is Z in the above formula (4). 3a and Z 3b The same applies to the preferred embodiments. 5a ~Z 5c The types may be different from each other, but are usually the same.

[0136] R 9 The substituents and the number of substitutions n9 are R 1 and n1 are the same as n1, including preferred embodiments. 9 Preferred embodiments such as the type and substitution position of R in the formula (1) are also 1 and similarly for n1.

[0137] Substituent R 10a ~R 10c The numbers of substitutions n10a to n10c are R 2a and R 2b and n2a and n2b, including preferred embodiments. 10a , R 10b The preferred embodiments of the type and substitution position of R in the formula (1) are as follows: 2a and R 2b and n2a and n2b. When n10c is 2 or more, 2 or more R 10c The types of R may be the same or different. 10c The substitution position of R is not particularly limited. 10a ~R 10c and n10a to n10c may be the same as or different from each other.

[0138] Alkylene Group A 5a ~A 5c As for A in the formula (4), 3a and A3b The same applies to m5a to m5c, including preferred embodiments. Examples of m5a to m5c include the same ranges as m3a and m3b in the formula (4), and the range is preferably 1. Note that, unlike m3a and m3b, all of m5a to m5c may be 1. In addition, when A is 2 or more, 5a and A 5b The type of Z substituted through the oxygen atom 5a and Z 5b A preferred embodiment of the substitution position for A in the formula (4) is 3a and A 3b If m5c is 2 or more, then A is 2 or more. 5c The types of A may be the same or different. 5c is substituted through an oxygen atom 5c The substitution position of A is not particularly limited. 5a ~A 5c and m5a to m5c may be the same as or different from each other.

[0139] Representative compounds represented by formula (6) include Z 5a ~Z 5c is a benzene ring, a naphthalene ring, or a biphenyl ring, and A 5a ~A 5c is linear or branched C 2-4 An alkylene group, and m5a to m5c are integers of 1 to 2. Preferred compounds include compounds in which Z 5a ~Z 5c is a naphthalene ring, and A 5a ~A 5c is linear or branched C 2-3 The compound is an alkylene group, and m5a to m5c are each 1.

[0140] The content of the compound represented by formula (6) may be, for example, about 0.02 to 4% in terms of area percentage by HPLC, and preferred ranges are 0.05 to 3%, 0.08 to 2%, 0.1 to 1%, 0.15 to 1%, 0.2 to 1%, 0.25 to 0.8%, and 0.3 to 0.4% in the following stepwise manner. The inclusion of the compound represented by formula (6) may improve the moldability (melt fluidity) and / or tensile strength of the resin. If the proportion of the compound represented by formula (6) is too high, it may act as a polymerization terminator, preventing the molecular weight of the resin from being sufficiently increased.

[0141] (d) Compounds having a 9,9-bis(alkylthio)fluorene skeleton The compound represented by formula (1) may or may not contain a compound having a 9,9-bis(alkylthio)fluorene skeleton. Examples of compounds having a 9,9-bis(alkylthio)fluorene skeleton include compounds represented by formula (7) below. The compound represented by formula (7) may be, for example, a by-product generated in the preparation of the compound represented by formula (1) during a reaction between a raw material fluorenone and a thiol such as β-mercaptopropionic acid, which is often used as a co-catalyst, particularly during a reaction in which an excessive amount of thiol is added.

[0142] [ka]

[0143] (In the formula, R 11 represents a substituent, n11 represents an integer of 0 to 8, R 12a and R 12b each independently represents a monovalent to trivalent hydrocarbon group, X 1a and X 1b each independently represents a heteroatom-containing group, and p1a and p1b each independently represent an integer of 0 to 2).

[0144] In the formula (7), R 11The substituents represented by the formula (1) and the number of substitutions n11 are 1 and n1 are the same as n1, including preferred embodiments. 11 Preferred embodiments such as the type and substitution position of R in the formula (1) are also 1 and similarly for n1.

[0145] R 12a and R 12b The monovalent hydrocarbon group represented by the formula (1) is 2a and R 2b Examples of the hydrocarbon groups include those exemplified as R and hydrocarbon groups that are combinations of these. 12a and R 12b Examples of the divalent or trivalent hydrocarbon group represented by the formula (I) include groups obtained by removing a hydrogen atom from the above monovalent hydrocarbon group according to the valence.

[0146] Preferred R 12a and R 12b is a divalent hydrocarbon group, and is more preferably a linear or branched alkylene group. As the linear or branched alkylene group, A in the formula (1) is 1a and A 1b The same applies to the alkylene groups exemplified above, including preferred embodiments.

[0147] X 1a and X 1b In the heteroatom-containing group represented by the formula (I), examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom, and preferably a nitrogen atom or an oxygen atom, and more preferably an oxygen atom. The number of heteroatoms contained is not particularly limited, and is usually 1 to 3, and preferably 1 to 2.

[0148] Representative heteroatom-containing groups include amino groups; mono- or di-substituted amino groups such as dialkylamino groups and diacylamino groups; hydroxyl groups; carboxyl groups; and alkoxycarbonyl groups such as methoxycarbonyl groups. 1a and X 1bis an amino group or a carboxyl group, and more preferably a carboxyl group. 1a and X 1b The types may be different from each other, but are usually the same.

[0149] The substitution numbers p1a and p1b are R 12a and R 12b may be selected depending on the valence of, for example, 0 to 1, preferably 1. When p1a and p1b are 2, the two X 1a , X 1b The types may be the same or different from each other.

[0150] Representative compounds represented by formula (7) include 9,9-bis(carboxyalkylthio)fluorenes, such as 9,9-bis(carboxymethylthio)fluorene and 9,9-bis(2-carboxyethylthio)fluorene. 1-6 9,9-bis(amino alkylthio)fluorenes, such as 9,9-bis(amino C alkylthio)fluorene; 1-6 alkylthio)fluorenes; 9,9-bis(alkylthio)fluorenes, for example, 9,9-bis(C such as 9,9-bis(ethylthio)fluorene; 1-12 alkylthio)fluorene.

[0151] The compound represented by the formula (7) may be contained alone or in combination of two or more kinds. Among the compounds represented by the formula (7), 9,9-bis(carboxyalkylthio)fluorene, especially 9,9-bis(carboxyC) such as 9,9-bis(2-carboxyethylthio)fluorene, is preferred. 1-4 It is often an alkylthio)fluorene.

[0152] The content of the compound represented by formula (7) may be, for example, about 0.5% or less in terms of area ratio by HPLC, and preferred ranges are 0.3% or less, 0.1% or less, 0.05% or less, 0.03% or less, and 0.01% or less in the following stepwise manner. If the proportion of the compound represented by formula (7) is too high, it may cause coloration, and when used as a resin raw material, polymerization may be difficult to proceed, or the heat resistance of the resin may be reduced.

[0153] (e) Compound represented by formula (8) The compound represented by formula (1) may or may not contain a compound represented by formula (8): The compound represented by formula (8) may be, for example, a by-product produced in the reaction of a raw material phenol or aryloxy alcohol with a thiol that is often used as a co-catalyst in the preparation of the compound represented by formula (1).

[0154] [ka]

[0155] (In the formula, Z 6 indicates an arene ring, A 6 represents a linear or branched alkylene group, m6 represents an integer of 0 or more, R 13 represents a substituent, n13 represents an integer of 0 or more, R 14 represents a monovalent to trivalent hydrocarbon group, X 2 represents a heteroatom-containing group, and p2 represents an integer of 0 to 2).

[0156] In the formula (8), Z 6 Examples of the group include Z in the formula (4). 3a and Z 3b The same applies to the above, including preferred embodiments.

[0157] A 6 Examples of the compound include A in the formula (4). 3a and A3b The repeating number m6 is the same as m3a and m3b in the formula (4), including preferred embodiments. 6 ) m6 The substitution position of —OH] is not particularly limited.

[0158] Substituent R 13 and the number of substitutions n13 is R in the formula (1). 2a and R 2b and n2a and n2b, including preferred embodiments. When n13 is 2 or more, two or more R 13 The types may be the same or different from each other.

[0159] R 14 is R in the formula (7). 12a and R 12b The same applies to the above, including preferred embodiments.

[0160] Heteroatom-containing group X 2 is X in the formula (7). 1a and X 1b The same applies to the above, including preferred embodiments. The number of substitutions p2 is usually 0 to 1 in many cases, and may be 0 or 1. The group [—SR 14 -(X 2 ) p2 The substitution position of ] is not particularly limited.

[0161] Representative compounds represented by the formula (8) include Z 6 is a benzene ring, a naphthalene ring, or a biphenyl ring, and A 6 is linear or branched chain C 2-6 is an alkylene group, m6 is an integer of 0 to 2, and R 14 C 1-20 Alkyl group or linear or branched C 2-6 is an alkylene group, and X 2 is a carboxyl group or an amino group, and p2 is 0 or 1. Preferred compounds represented by the formula (8) include compounds in which Z 6 is a naphthalene ring, and A 6is linear or branched chain C 2-4 an alkylene group, m6 is 0 or 1, and R 14 C 1-16 Alkyl group or linear or branched C 2-4 is an alkylene group, and X 2 is a carboxyl group or an amino group, and p2 is 0 or 1.

[0162] The content of the compound represented by formula (8) may be, for example, about 0.1 mass ppb to 1 mass%, and preferred ranges are 0.5 mass ppb to 5000 mass ppm, 1 mass ppb to 3000 mass ppm, and 10 mass ppb to 1000 mass ppm, in the following stepwise order. When the compound represented by formula (8) is contained, coloration in a high-temperature environment may be suppressed. If the proportion of the compound represented by formula (8) is too high, it may be difficult to adjust the desired resin composition ratio, and coloration may not be suppressed.

[0163] (f) A compound represented by formula (9) The compound represented by formula (1) may or may not contain a compound represented by formula (9): The compound represented by formula (9) may be, for example, a by-product generated in a side reaction of thiols that are often used as co-catalysts in the preparation of the compound represented by formula (1).

[0164] [ka]

[0165] (In the formula, R 15a and R 15b each independently represents a monovalent to trivalent hydrocarbon group, X 3a and X 3b each independently represents a heteroatom-containing group, and p3a and p3b each independently represent an integer of 0 to 2).

[0166] In the formula (9), R 15a and R 15bAs the R in the formula (7), 12a and R 12b The same applies to the preferred embodiments. 15a and R 15b The types may be different from each other, but are usually the same.

[0167] X 3a and X 3b As the X in the formula (7), 1a and X 1b The same applies to the above, including preferred embodiments. The number of substitutions p3a and p3b is usually 0 to 1, and may be either 0 or 1. X 3a and X 3b The types of p3a and p3b may be the same or different. When p3a and p3b are 2, the two X 3a , X 3b The types may be the same or different from each other.

[0168] Representative compounds represented by the formula (9) include R 15a and R 15b C 1-20 Alkyl group or linear or branched C 2-6 is an alkylene group, and X 3a and X 3b is a carboxyl group or an amino group, and p3a and p3b are 0 or 1. Preferred compounds represented by the formula (9) include compounds in which R 15a and R 15b C 1-16 Alkyl group or linear or branched C 2-4 is an alkylene group, and X 3a and X 3b is a carboxyl group or an amino group, and p3a and p3b are 0 or 1.

[0169] The content of the compound represented by formula (9) may be, for example, about 0.1 mass ppb to 1 mass%, and preferred ranges are 0.5 mass ppb to 5000 mass ppm, 1 mass ppb to 3000 mass ppm, and 10 mass ppb to 1000 mass ppm, in the following stepwise order. The inclusion of the compound represented by formula (9) may prevent discoloration in high-temperature environments. If the proportion of the compound represented by formula (9) is too high, it may be difficult to adjust the resin composition ratio to the desired level, and discoloration may not be prevented.

[0170] (g) A compound represented by formula (10) or a salt thereof The compound represented by formula (1) may or may not contain a compound represented by formula (10) below or a salt thereof. The compound represented by formula (10) or a salt thereof may be, for example, a by-product generated in a side reaction between a raw material phenol or aryloxy alcohol and an acid catalyst such as sulfuric acid in the preparation of the compound represented by formula (1).

[0171] [ka]

[0172] (In the formula, Z 7 indicates an arene ring, A 7 represents a linear or branched alkylene group, m7 represents an integer of 0 or more, R 16 represents a substituent, and n16 represents an integer of 0 or more).

[0173] In the formula (10), Z 7 Examples of the group include Z in the formula (4). 3a and Z 3b The same applies to the above, including preferred embodiments.

[0174] A 7 Examples of the compound include A in the formula (4). 3a and A 3bThe repeating number m6 is the same as m3a and m3b in the formula (4), including preferred embodiments. 7 ) m7 The substitution position of —OH] is not particularly limited.

[0175] Substituent R 16 and the number of substitutions n16 is R in the formula (1). 2a and R 2b and n2a and n2b, including preferred embodiments. When n16 is 2 or more, two or more R 16 The types may be the same or different from each other.

[0176] In the formula (10), the substitution position of the sulfo group (or sulfonic acid group) [—SO 3 H] is not particularly limited.

[0177] Examples of salts of the compound represented by formula (10) include alkali metal salts such as lithium salt, sodium salt, and potassium salt, and ammonium salt. Of these, sodium salt or potassium salt is usually used, and sodium salt is preferred. The compound represented by formula (10) is preferably in the form of a salt.

[0178] Representative compounds represented by the formula (10) include Z 7 is a benzene ring, a naphthalene ring, or a biphenyl ring, and A 7 is linear or branched C 2-6 Examples of the preferred compound represented by the formula (10) include compounds in which m7 is an alkylene group and m7 is an integer of 0 to 2, and salts thereof such as alkali metal salts. 7 is a naphthalene ring, and A 7 is linear or branched C 2-4 The compound is an alkylene group, and m7 is an integer of 0 or 1, or a sodium salt or potassium salt thereof.

[0179] The content of the compound represented by formula (10) or its salt may be, for example, about 0.1 ppb to 1% by mass, and preferred ranges are, in the following stepwise order: 1 ppb to 1000 ppm by mass, 5 ppb to 100 ppm by mass, 8 ppb to 80 ppm by mass, and 10 ppb to 50 ppm by mass. The inclusion of the compound represented by formula (10) or its salt may enable efficient resin polymerization and suppression of resin discoloration. If the proportion of the compound represented by formula (10) or its salt is too high, it may be difficult to adjust the desired resin composition ratio, and discoloration may not be suppressed.

[0180] (h) A compound represented by formula (11) The compound represented by the formula (1) may or may not contain a compound represented by the following formula (11).

[0181] [ka] (In the formula, Z 8a and Z 8b each independently represents an arene ring, R 17 represents a substituent, n17 represents an integer of 0 to 8, R 18a and R 18b each independently represents a substituent, n18a and n18b each independently represent an integer of 0 or more, A 8a ~A 8d each independently represents a linear or branched alkylene group, m8a and m8b each independently represent an integer of 0 or more, and m8c and m8d each independently represent an integer of 0 to 2, provided that m8c and m8d are not both 0.

[0182] In the formula (11), Z 8a and Z 8b is Z in the above formula (4). 3a and Z 3b The same applies to the preferred embodiments. 8a and Z 8bThe types may be different from each other, but are usually the same.

[0183] R 17 The substituents and the number of substitutions n17 are R 1 and n1 are the same as n1, including preferred embodiments. 17 Preferred embodiments such as the type and substitution position of R in the formula (1) are also 1 and similarly for n1.

[0184] Substituent R 18a and R 18b and the number of substitutions n18a and n18b is R 2a and R 2b and n2a and n2b, including preferred embodiments. 18a , R 18b The preferred embodiments of the type and substitution position of R in the formula (1) are as follows: 2a and R 2b and similarly for n2a and n2b.

[0185] Alkylene Group A 8a ~A 8d As for A in the formula (4), 3a and A 3b The same applies to the above, including preferred embodiments.

[0186] Examples of m8a and m8b include the same ranges as m3a and m3b in the formula (4), and are preferably 1. Note that, unlike m3a and m3b, both m8a and m8b may be 1. In addition, A of 2 or more 8a and A 8b The type of Z substituted through the oxygen atom 8a and Z 8b A preferred embodiment of the substitution position for A in the formula (4) is 3a and A 3b The same applies to

[0187] Group(―A8c -OH) and group (-A 8d The number of substitutions of —OH), m8c and m8d, is 0 to 2, and preferably 0 or 1. m8c and m8d may be the same or different. The total of m8c and m8d is, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. A 8c and A 8d The types may be different from each other, but are usually the same.

[0188] Group(―A 8c -OH) and group (-A 8d The substitution position of —OH) is ring Z 8a and ring Z 8b When the ring Z is a benzene ring, it is located at the 2nd to 4th positions, preferably the 3rd or 4th position, and more preferably the 3rd position relative to the phenyl group substituted at the 9th position of the fluorene ring. 8a and ring Z 8b When the group (—A) is a naphthalene ring, the 1st or 2nd position of the naphthalene ring is usually substituted with respect to the 9th position of the fluorene ring (substitution in the form of 1-naphthyl or 2-naphthyl), and the 5th to 8th positions of the fluorene ring are often substituted. 8c -OH) and group (-A 8d It is preferred that —OH) is substituted at the 1,6-position or the 2,7-position, particularly at the 2,7-position. 8a and ring Z 8b When is a biphenyl ring, the group (-A 8c -OH) and group (-A 8d —OH) may be substituted at any of the 2- to 6-positions and the 2′ to 6′-positions of the biphenyl ring.

[0189] Representative compounds represented by formula (11) include Z 8a and Z 8b is a benzene ring, a naphthalene ring, or a biphenyl ring, and A 8a ~A 8d is linear or branched C 2-4alkylene group, m8a and m8b are integers of 1 to 2, m8c and m8d are 0 or 1, and m8c and m8d are not simultaneously 0. 8a and Z 8b is a naphthalene ring, and A 8a ~A 8c is linear or branched C 2-3 It is an alkylene group, and compounds in which m8a and m8b are 1, m8c is 1, and m8d is 0.

[0190] The content of the compound represented by formula (11) is, for example, about 10% or less in terms of area percentage by HPLC, preferably 7.5% or less, 5% or less, 4% or less, 3% or less, 1% or less, 0.5% or less, 0.1% or less, more preferably 0.01% or less, particularly 0.005% or less, and particularly substantially 0% or below the detection limit. In particular, if the content of the compound represented by formula (11) is 3.5% or less, deterioration in heat resistance, water resistance, impact strength, and refractive index of the resin can be suppressed, resulting in a resin raw material with an excellent balance of various properties. If the content of the compound represented by formula (11) is too high, gelation may occur during polymerization.

[0191] Furthermore, when the compound represented by the formula (11) is contained in a predetermined ratio, the molecular weight of the resin can be improved. In particular, when the compound represented by the formula (11) is contained in a predetermined ratio, the molecular weight of the resin can be improved. 8a and Z 8b is a naphthalene ring, and A 8a ~A 8c is linear or branched C 2-3When a compound in which m8a and m8b are 1, m8c is 1, and m8d is 0 is contained in a predetermined proportion, the molecular weight of the polyester resin can be increased, and in particular, the molecular weight of the polyester resin can be significantly increased. The content of the compound represented by the formula (11) is, for example, 0.1 to 10% in terms of area percentage by HPLC, and preferred ranges are 0.5 to 7%, 1 to 6%, 1.2 to 5.5%, 1.5 to 5%, 2 to 4.5%, 2.5 to 4%, and 3 to 3.5% in the following stepwise manner ... terms of area percentage by HPLC. 8a and Z 8b is a naphthalene ring, and A 8a ~A 8c is linear or branched C 2-3 It may also be the content of a compound in which m8a and m8b are 1, m8c is 1, and m8d is 0, which is an alkylene group.

[0192] (i) Organic solvent The compound represented by formula (1) may or may not contain an organic solvent that may be mixed in during the manufacturing process, such as preparation or purification. The organic solvent may be a conventional organic solvent that is in a liquid state at 25°C and 1 atmosphere, and examples thereof include hydrocarbons, halogenated hydrocarbons, alcohols, ethers, glycol ethers, glycol ether acetates, ketones, carboxylic acids, esters, carbonates, amides, ureas, nitriles, nitrated hydrocarbons, phosphoramides, sulfones, and sulfoxides.

[0193] Examples of hydrocarbons include aliphatic hydrocarbons such as hexane and dodecane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene.

[0194] Examples of halogenated hydrocarbons include dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, and dichlorobenzene.

[0195] Alcohols include C ethanol, propanol, isopropanol, n-butanol, isobutanol, s-butanol, and t-butanol. 1-6 Alcohol, etc.

[0196] Examples of the ethers include chain ethers and cyclic ethers. Examples of the chain ethers include di-C ethers such as diethyl ether, diisopropyl ether, and dibutyl ether. 1-6 Examples of cyclic ethers include 5- to 7-membered ring ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran, 4-methyltetrahydropyran, 1,4-dioxane, 1,3-dioxane, 4-methyl-1,3-dioxane, 1,3-dioxolane, and 2-methyl-1,3-dioxolane.

[0197] Examples of glycol ethers include (poly)alkylene glycol monoalkyl ethers, (poly)alkylene glycol dialkyl ethers, etc. Examples of (poly)alkylene glycol monoalkyl ethers include cellosolves such as methyl cellosolve and ethyl cellosolve, carbitols such as methyl carbitol and ethyl carbitol, and (mono- to hexa)C alkyl ethers such as triethylene glycol monomethyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether. 2-4 Alkylene glycol mono C 1-6 Examples of the (poly)alkylene glycol dialkyl ether include (mono to hexa)C alkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. 2-4 Alkylene glycol di C 1-6Alkyl ethers and the like.

[0198] Examples of glycol ether acetates include cellosolve acetates such as methyl cellosolve acetate, carbitol acetates such as methyl carbitol acetate, and (poly)C such as propylene glycol monomethyl ether acetate (PGMEA) and dipropylene glycol monobutyl ether acetate. 2-4 Alkylene glycol mono C 1-4 Alkyl ether acetates and the like.

[0199] Examples of ketones include chain ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); and cyclic ketones such as cyclohexanone. Examples of carboxylic acids include acetic acid and propionic acid.

[0200] Examples of esters include chain esters and cyclic esters. Examples of chain esters include acetate esters such as methyl acetate, ethyl acetate, and butyl acetate, and lactate esters such as methyl lactate. Examples of cyclic esters (or lactones) include 5- to 7-membered ring lactones that may have a substituent, such as γ-butyrolactone, γ-valerolactone, and γ-caprolactone (or γ-hexanolactone).

[0201] Examples of carbonates include chain carbonates and cyclic carbonates. Examples of chain carbonates include di-C carbonates such as dimethyl carbonate (or dimethyl carbonate), ethyl methyl carbonate, and diethyl carbonate (or diethyl carbonate). 1-6 Examples of the cyclic carbonates include 5- to 7-membered cyclic carbonates such as ethylene carbonate (or ethylene carbonate) and propylene carbonate (or propylene carbonate).

[0202] Examples of amides include linear amides and cyclic amides (or lactams). Examples of linear amides include N,N-diC amides such as N,N-dimethylformamide (DMF), N,N-diethylformamide, and N,N-dimethylacetamide (DMAc). 1-6 Alkyl-C 1-6 Examples of the cyclic amides include 5- to 7-membered ring lactams such as N-methyl-2-pyrrolidone.

[0203] Examples of ureas (or ureas) include chain ureas, cyclic ureas, etc. Examples of chain ureas include tetra C ureas such as tetramethylurea, tetraethylurea, and tetraisopropylurea. 1-6 Examples of cyclic ureas include N,N'-diC alkyl ureas such as 1,3-dimethyl-2-imidazolidinone (DMI or N,N'-dimethylethyleneurea) and N,N'-dimethyl-N,N'-trimethyleneurea (or N,N'-propyleneurea). 1-6 Examples include alkyl-N,N'-di- or tetramethylene urea.

[0204] Nitriles include, for example, cyanides such as acetonitrile and propionitrile. 1-6 Examples include alkanes, cyanated arenes such as benzonitrile, etc.

[0205] Examples of nitrated hydrocarbons include nitro C such as nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane. 1-6 Examples include alkanes and nitroarenes such as nitrobenzene.

[0206] Examples of phosphoramides include hexaC phosphoramides such as hexamethylphosphoramide. 1-6 Alkyl phosphoramides and the like.

[0207] Examples of sulfones include chain sulfones and cyclic sulfones. Examples of chain sulfones include di-C sulfones such as ethyl methyl sulfone and isopropyl ethyl sulfone. 1-6 Examples of cyclic sulfones include tri- to hexamethylene sulfones such as sulfolane (or tetramethylene sulfone or tetrahydrothiophene-1,1-dioxide), 3-methyl sulfolane, and 2,4-dimethyl sulfolane.

[0208] Examples of sulfoxides include di-C such as dimethyl sulfoxide (DMSO). 1-6 Alkyl sulfoxides and the like.

[0209] These solvents may be contained alone or in combination of two or more thereof. Among these solvents, aromatic hydrocarbons such as toluene, alcohols such as methanol, and ketones such as MEK and MIBK are usually used, and among these, alcohols such as methanol are often used.

[0210] The content of the organic solvent is, for example, about 0.2% or less in terms of area ratio by HPLC, and preferred ranges are 0.1% or less, 0.05% or less, 0.03% or less, more preferably 0.02% or less, and particularly 0.01% or less. The content of the organic solvent may be, for example, about 3500 ppm by mass to 4800 ppm by mass, preferably 3700 ppm by mass to 4600 ppm by mass, and more preferably 3900 ppm by mass to 4400 ppm by mass. If the proportion of the organic solvent is too high, when used as a resin raw material, coloration may not be suppressed or it may be difficult to adjust the resin composition to the desired ratio. Furthermore, when the compound represented by formula (1) is in powder form, the flowability or handleability may be reduced. When the compound represented by formula (1) is in powder form, containing a predetermined proportion of the organic solvent may easily suppress scattering and improve the flowability or handleability.

[0211] The content of aromatic hydrocarbons, particularly toluene, is, for example, about 0.2% or less in terms of area percentage by HPLC, with preferred ranges being 0.1% or less, 0.05% or less, 0.03% or less, more preferably 0.02% or less, and particularly 0.01% or less. The content of aromatic hydrocarbons, particularly toluene, is, for example, 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.3% by mass or less. If the content of aromatic hydrocarbons, such as toluene, is too high, when the compound represented by formula (1) is in powder form, the flowability or handleability may be reduced, and when used as a resin raw material, coloration may not be suppressed or it may be difficult to adjust the desired resin composition ratio.

[0212] (j) water The compound represented by formula (1) may or may not contain water (or moisture). The moisture content is, for example, 1% by mass or less, preferably 0.8% by mass or less, and more preferably 0.5% by mass or less. The moisture content may be, for example, about 6,000 ppm by mass to 12,000 ppm by mass, preferably 7,000 ppm by mass to 11,900 ppm by mass, and more preferably 8,000 ppm by mass to 11,800 ppm by mass. If the moisture content is too high, when used as a resin raw material, coloration may not be suppressed, the polymerization catalyst may be deactivated, or it may be difficult to adjust the desired resin composition ratio. Furthermore, when the compound represented by formula (1) is a powder, the flowability or handleability may be reduced. When the compound represented by formula (1) contains moisture at a predetermined ratio, coloration in the resin may be suppressed, and when the compound represented by formula (1) is a powder, scattering may be easily suppressed, thereby improving the flowability or handleability.

[0213] (Characteristics of fluorene compounds) The fluorene compound of the present invention has a content of specific impurity components adjusted to a predetermined range, and therefore coloration (or discoloration), particularly coloration under high temperature environments, can be effectively suppressed or reduced.

[0214] Therefore, the hue APHA of the fluorene compound when kept in a molten state at 280°C for 2 hours is, for example, 500 or less, and preferred ranges are 450 or less, 400 or less, 350 or less, more preferably 300 or less, and particularly preferably 270 or less, in the following stepwise order.

[0215] The hue YI of the fluorene compound when kept in a molten state at 280°C for 2 hours is, for example, 100 or less, and preferred ranges are, in the following order, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, and 50 or less, more preferably 48 or less, particularly 45 or less.

[0216] The heating residue of the fluorene compound at 180° C. is, for example, 97% or more, preferably 98% or more, more preferably 99% or more, and particularly preferably 99.5% or more. If the heating residue is too low, it may be difficult to adjust the desired resin composition ratio when used as a resin raw material.

[0217] The bulk density of the fluorene compound is, for example, 0.4 to 0.8 mg / mL, and preferably 0.5 to 0.75 mg / mL.

[0218] The melting point of the fluorene compound may be, for example, about 130 to 230°C. 1a and Z 1b is a ring-assembled arene ring such as a biphenyl ring, the temperature is 135 to 165°C, preferably 140 to 160°C, and more preferably 145 to 155°C, and Z 1a and Z 1b When is a fused polycyclic arene ring such as a naphthalene ring, the melting point may be, for example, about 200 to 230° C., and preferred ranges are the following stepwise: 210 to 225° C., 215 to 223° C., 216 to 222° C., 216.5 to 221° C., 217 to 220.5° C., and 217.5 to 220° C. If the impurity content is too high, the melting point may decrease.

[0219] In this specification and claims, the color APHA, color YI, heating residue, bulk density and melting point can be measured by the methods described in the examples below.

[0220] (Method of producing fluorene compound) The method for producing the fluorene compound represented by the formula (1) is not particularly limited, and the compound can be prepared by a conventional method. 1a , Z 1b and an alkylene group A 1a and A 1b and polycyclic aryloxy alcohols corresponding to the substituent R 1 and a 9-fluorenone corresponding to the substitution number n1 in the presence of a catalyst such as an acid, a co-catalyst such as a thiol, a solvent, etc. (first method); 1a and Z 1b The 9,9-bis(hydroxypolycyclic aryl)fluorenes obtained by using polycyclic phenols corresponding to the polycyclic arene ring of 1a and A 1b and a method (method 2) in which an alkylene oxide (alkylene carbonate or haloalkanol) corresponding to the formula (11) is added in the presence of a catalyst such as 1-methylimidazole. The first method is preferred because it is less likely to contain by-products such as alkylene oxide non-adducts, mono-adducts, and tri-adducts (such as the aforementioned other impurity component (a)). The second method is preferred because it allows the compound represented by formula (11) to be easily incorporated at a predetermined ratio.

[0221] In the first method, the polycyclic aryloxy alcohols include compounds corresponding to the fluorene compound represented by formula (1) including preferred embodiments thereof, and more preferably C aryloxy alcohols such as 2-(2-naphthoxy)ethanol and 2-(o-phenylphenoxy)ethanol. 10-14 Polycyclic Aryloxy C 2-4 Alcohols are preferred, and C 10-14Fused Polycyclic Aryloxy C 2-4 Alcohols, particularly naphthoxy C such as 2-(2-naphthoxy)ethanol 2-3 Alcohol is preferred.

[0222] Examples of the 9-fluorenones include compounds corresponding to the fluorene compound represented by formula (1) above, including preferred embodiments thereof, and among these, 9-fluorenone is preferred.

[0223] The ratio of the polycyclic aryloxy alcohols to the 9-fluorenones used in the reaction is, for example, the former / latter (molar ratio) = 1 / 2 to 1 / 10, and preferred ranges are 1 / 2.5 to 1 / 5, 1 / 3 to 1 / 4.5, and 1 / 3.5 to 1 / 4 in the following stepwise manner. If the ratio of either the polycyclic aryloxy alcohols or the 9-fluorenones is too high, the impurity content may increase.

[0224] Examples of the acid catalyst used in the reaction include inorganic acids, organic acids, and solid acids.

[0225] Examples of inorganic acids include sulfuric acid, hydrogen chloride, phosphoric acid, etc. The inorganic acid may be in the form of an aqueous solution, such as hydrochloric acid, and the concentration of the hydrochloric acid is, for example, 5 to 36% by mass, preferably 20 to 36% by mass.

[0226] Examples of organic acids include sulfonic acids, such as (halo)alkanesulfonic acids (e.g., methanesulfonic acid, trifluoromethanesulfonic acid), and arenesulfonic acids (e.g., p-toluenesulfonic acid).

[0227] Examples of solid acids include inorganic solid acids and organic solid acids. Examples of inorganic solid acids include metal compounds such as metal oxides, composite metal oxides, metal sulfides, metal sulfates, and polyacids, as well as non-metal sulfates, clay minerals, zeolites, and kaolin. Examples of organic solid acids include cation exchange resins such as strong acid cation exchange resins and weak acid cation exchange resins. Examples of strong acid cation exchange resins include ion exchange resins having sulfonic acid groups, such as Nafion manufactured by DuPont. Examples of weak acid cation exchange resins include ion exchange resins having carboxylic acid groups, such as (meth)acrylic acid-divinylbenzene copolymers.

[0228] 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 because it also acts as a dehydrating agent for water produced as the reaction proceeds.

[0229] Examples of sulfuric acid include dilute sulfuric acid with a concentration of about 30 to 90% by mass, concentrated sulfuric acid with a concentration of 90% by mass or more, fuming sulfuric acid, etc. Sulfur trioxide may also be used as a sulfuric acid precursor as long as it can be converted to sulfuric acid in the reaction system. Typically, the sulfuric acid may be selected from a range of about 80 to 99% by mass in terms of H2SO4. Preferred ranges are 90 to 99% by mass, 93 to 99% by mass, and 96 to 99% by mass of concentrated sulfuric acid, with 97 to 98.5% by mass being more preferred, and 98% by mass being particularly preferred.

[0230] The proportion of the acid catalyst can be selected from the range of, for example, about 10 to 1,000 parts by mass relative to 100 parts by mass of the 9-fluorenones, with preferred ranges being 50 to 800 parts by mass, 100 to 600 parts by mass, 150 to 500 parts by mass, and 200 to 450 parts by mass, more preferably 250 to 400 parts by mass, and particularly preferably 270 to 360 parts by mass. If the proportion of the acid catalyst is too low, the reaction may not proceed efficiently (or the reaction rate may decrease significantly).

[0231] As the thiol as a promoter, the first thiol such as 2-mercaptoalkanoic acid, aminoalkanethiol, and salts thereof is preferred from the viewpoint of being able to effectively reduce residual sulfur (content of the third impurity component) and also to reduce coloration due to heat melting.

[0232] Examples of 2-mercaptoalkanoic acids include 2-mercapto C alkanoic acids such as thioglycolic acid (mercaptoacetic acid or mercaptoethanoic acid), thiolactic acid (or α-mercaptopropionic acid), 2-mercaptobutyric acid (or 2-mercapto-n-butanoic acid), and 2-mercaptoisobutyric acid (or 2-mercaptoisobutanoic acid). 2-6 Preferred 2-mercaptoalkanoic acids include 2-mercapto C 2-4 Alkanoic acids, especially 2-mercapto C such as thioglycolic acid and thiolactic acid 2-3 Alkanoic acids are preferred.

[0233] Examples of aminoalkanethiols include amino C thiols such as 2-aminoethanethiol (or cysteamine), 2-aminopropanethiol, 3-aminopropanethiol, 2-aminobutanethiol, 3-aminobutanethiol, 4-aminobutanethiol, 6-aminohexanethiol, 8-aminooctanethiol, 11-aminoundecanethiol, and 16-aminohexadecanethiol. 2-20 Preferred aminoalkanethiols include amino C 2-16 It is an alkanethiol.

[0234] Representative salts 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; and double salts thereof.

[0235] These first thiols can be used alone or in combination of two or more. Among these first thiols, from the viewpoint of being able to significantly reduce residual sulfur (total sulfur content) and improve yield, it is preferable to include at least aminoalkanethiol or its salt, and more preferably, to include amino C in the following stepwise manner: 2-12 Alkanethiol, Amino C 2-8 Alkanethiol, Amino C 2-6 Alkanethiol, Amino C 2-4 Alkanethiol, more preferably amino C 2-3 Alkanethiols are preferred, with cysteamine being particularly preferred.

[0236] The thiols may optionally contain other thiols (also simply referred to as second thiols) different from the first thiols. Examples of the second thiols include thiocarboxylic acids, mercaptocarboxylic acids (excluding 2-mercaptoalkanoic acids), alkyl mercaptans, aralkyl mercaptans, and salts thereof.

[0237] Examples of thiocarboxylic acids include thioacetic acid and thiooxalic acid.

[0238] Examples of mercaptocarboxylic acids (excluding 2-mercaptoalkanoic acids) include β-mercaptopropionic acid, mercaptosuccinic acid, and mercaptobenzoic acid.

[0239] Examples of alkyl mercaptans include C mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, and dodecyl mercaptan. 1-16 Preferred alkyl mercaptans include C 1-4 It is an alkyl mercaptan.

[0240] Examples of aralkyl mercaptans include benzyl mercaptan.

[0241] Examples of these salts include the above-mentioned alkali metal salts, typically sodium salts, and specific compounds include sodium methyl mercaptan and sodium ethyl mercaptan.

[0242] These second thiols can be used alone or in combination of two or more. If second thiols, in particular mercaptocarboxylic acids such as β-mercaptopropionic acid (excluding 2-mercaptoalkanoic acids), are contained, the content of impurities may increase, so it is preferable that they are substantially free of them.

[0243] The proportion of the first thiols can be selected from a range of, for example, 10% by mass or more (e.g., 10 to 100% by mass) relative to the total thiols. Preferred ranges are, in the following stepwise order, 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, and more preferably 90% by mass or more. Of these, 95% by mass or more is preferred, and 100% by mass (an embodiment in which the thiols essentially contain only the first thiols) is particularly preferred. If the proportion of the first thiols is too low, the total sulfur content and coloration after heat melting may not be effectively reduced. Note that when the thiols contain second thiols, the proportion of the first thiols can be selected from a range of, for example, 60 to 99.9% by mass relative to the total thiols, and is preferably 80 to 99% by mass, and more preferably 90 to 98% by mass.

[0244] The proportion of thiols may be selected from the range of, for example, 0.1 parts by mass or more, specifically, about 1 to 50 parts by mass, relative to 100 parts by mass of the 9-fluorenones. Preferred ranges are 2 to 30 parts by mass, 3 to 20 parts by mass, 4 to 15 parts by mass, 5 to 10 parts by mass, and more preferably 6 to 9 parts by mass, with 6.5 to 8 parts by mass being preferred, and 7 to 7.5 parts by mass being particularly preferred.

[0245] The proportion of thiols relative to 100 parts by mass of the acid catalyst can be selected, for example, from 0.01 parts by mass or more, specifically from a range of about 0.1 to 50 parts by mass, and preferred ranges are 0.5 to 30 parts by mass, 1 to 20 parts by mass, 1.5 to 10 parts by mass, 2 to 5 parts by mass, 2.3 to 4 parts by mass, 2.4 to 3.5 parts by mass, and 2.5 to 3 parts by mass, in the following stepwise manner.

[0246] If the proportion of thiols is too low, the reaction may not proceed efficiently, and there is also a risk of coloration due to impurities such as unreacted components. If the proportion of thiols is too high, there is a risk of the thiols remaining as impurities such as sulfur components. However, by using the first thiols, impurities such as sulfur components can be effectively reduced, and coloration of the fluorene compound represented by formula (1) when melted can also be effectively suppressed.

[0247] Examples of reaction solvents include hydrocarbons and halogenated hydrocarbons (also referred to as first solvents).

[0248] Examples of hydrocarbons include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. Examples of aliphatic hydrocarbons include linear or branched C 4 hydrocarbons such as hexane, heptane, octane, and decane. 5-12 Examples of alicyclic hydrocarbons include C 5-10 Examples of aromatic hydrocarbons include mono- and tri-C hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. 1-6 Examples include alkyl-benzenes.

[0249] Examples of halogenated hydrocarbons include halo-C such as methylene chloride, chloroform, carbon tetrachloride, and 1,2-dichloroethane. 1-6 Alkanes, etc.; halobenzenes such as chlorobenzene and dichlorobenzene.

[0250] These first solvents may be used alone or in combination of two or more. Among these first solvents, aromatic hydrocarbons are preferred, and mono- to tri-C 1-4 Alkyl-benzenes, among others, mono- or di-C such as toluene, xylene, ethylbenzene 1-2 Alkyl-benzenes are preferred, especially toluene.

[0251] The reaction solvent may or may not contain an aprotic polar solvent (also referred to as a second solvent) in addition to the first solvent. If the second solvent is contained, the reaction proceeds efficiently even at a low reaction temperature, and the production of by-products can be effectively suppressed, impurities such as sulfur components can be reduced, and coloration of the fluorene compound represented by the formula (1) due to heat melting can also be effectively suppressed in some cases.

[0252] Examples of aprotic polar solvents include ethers, ketones, esters, carbonates, amides, ureas, nitriles, nitrated hydrocarbons, phosphoramides, sulfones, and sulfoxides.

[0253] Examples of the ethers include chain ethers, cyclic ethers, and anisole.

[0254] Examples of the chain ethers include di-C ethers such as diethyl ether, diisopropyl ether, and dibutyl ether. 1-6 Alkyl ethers; (mono to hexa) C such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether 2-4 Alkylene glycol di C 1-6 Alkyl ethers and the like.

[0255] Examples of cyclic ethers include tetrahydrofurans, such as tetrahydrofuran (THF) and 2-methyltetrahydrofuran, which may have a substituent; tetrahydropyrans, such as tetrahydropyran and 4-methyltetrahydropyran, which may have a substituent; dioxanes, such as 1,4-dioxane, 1,3-dioxane, and 4-methyl-1,3-dioxane, which may have a substituent; and dioxolanes, such as 1,3-dioxolane and 2-methyl-1,3-dioxolane, which may have a substituent. Examples of the substituent include hydrocarbon groups such as alkyl groups. When substituted, preferred substituents are C groups such as methyl and ethyl groups. 1-6 alkyl group, more preferably C 1-4 The number of the substituents is not particularly limited, and is usually about 0 to 3, preferably 0 to 2, more preferably 0 or 1, and particularly 0.

[0256] Examples of ketones include chain ketones and cyclic ketones. Examples of chain ketones include di-C ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. 1-6 Examples of cyclic ketones include C alkyl ketones such as cyclohexanone. 5-10 Cycloalkanones and the like.

[0257] Examples of the esters include chain esters, cyclic esters (or lactones), etc. Examples of the chain esters include C esters such as methyl acetate, ethyl acetate, and butyl acetate. 2-6 Alkanoic acid C 1-6 Examples of lactones include 5- to 7-membered lactones which may have a substituent, such as γ-butyrolactone, γ-valerolactone, and γ-caprolactone (or γ-hexanolactone). The substituents and the number of substitutions are the same as those exemplified for the cyclic ethers, including preferred embodiments.

[0258] Examples of carbonates include chain carbonates and cyclic carbonates. Examples of chain carbonates include di-C carbonates such as dimethyl carbonate (or dimethyl carbonate), ethyl methyl carbonate, and diethyl carbonate (or diethyl carbonate). 1-6 Examples of cyclic carbonates include di- and tetramethylene carbonates which may have a substituent, such as ethylene carbonate (or ethylene carbonate) and propylene carbonate (or propylene carbonate). The substituents and the number of substitutions are the same as those exemplified for the cyclic ethers, including preferred embodiments.

[0259] Examples of the amides include linear amides, cyclic amides (or lactams), etc. Examples of the linear amides include N,N-diC amides such as N,N-dimethylformamide (DMF), N,N-diethylformamide, and N,N-dimethylacetamide (DMAc). 1-6 Alkyl-C 1-6 Examples of the cyclic amides include alkanoic acid amides. Examples of the cyclic amides include lactams which may have a substituent, such as N-methyl-2-pyrrolidone (NMP), preferably 5- to 7-membered lactams which may have a substituent. The substituents and the number of substitutions are the same as those exemplified for the cyclic ethers, including preferred embodiments.

[0260] Examples of ureas (or ureas) include chain ureas, cyclic ureas, etc. Examples of chain ureas include tetra C ureas such as tetramethylurea, tetraethylurea, and tetraisopropylurea. 1-6 Examples of cyclic ureas include N,N'-diC alkyl ureas such as 1,3-dimethyl-2-imidazolidinone (DMI or N,N'-dimethylethyleneurea) and N,N'-dimethyl-N,N'-trimethyleneurea (or N,N'-propyleneurea). 1-6Examples of the cyclic ureas include alkyl-N,N'-di- and tetramethylene urea. These cyclic ureas may have a substituent, and the substituents and the number of substitutions are the same as those exemplified for the cyclic ethers, including preferred embodiments thereof.

[0261] Examples of nitriles include cyanide hydrocarbons, specifically cyanide C such as acetonitrile and propiononitrile. 1-6 Examples include alkanes, cyanated arenes such as benzonitrile, etc.

[0262] Examples of nitrated hydrocarbons include nitro C such as nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane. 1-6 Examples include alkanes and nitroarenes such as nitrobenzene.

[0263] Examples of phosphoramides include hexaC phosphoramides such as hexamethylphosphoramide. 1-6 Alkyl phosphoramides and the like.

[0264] Examples of sulfones include chain sulfones and cyclic sulfones. Examples of chain sulfones include di-C sulfones such as ethyl methyl sulfone and isopropyl ethyl sulfone. 1-6 Examples of cyclic sulfones include tri- to hexamethylene sulfones which may have a substituent, such as sulfolane (or tetramethylene sulfone or tetrahydrothiophene-1,1-dioxide), 3-methyl sulfolane, and 2,4-dimethyl sulfolane. The substituents and the number of substitutions are the same as those exemplified for the cyclic ethers, including preferred embodiments. Preferred cyclic sulfones include C 1-6 Examples include tetra- or pentamethylene sulfones which may have an alkyl group.

[0265] Examples of sulfoxides include di-C such as dimethyl sulfoxide (DMSO).1-6 Alkyl sulfoxides and the like.

[0266] These aprotic polar solvents (second solvents) can be used alone or in combination of two or more. Preferred aprotic polar solvents include ethers, sulfones, sulfoxides, ureas, and amides, more preferably ethers, sulfones, ureas, and amides, and even more preferably contain a cyclic compound (aprotic polar solvent having a cyclic structure) having at least a cyclic structure in the molecule, and among these, cyclic ethers, cyclic sulfones, cyclic ureas, and cyclic amides are preferred.

[0267] Examples of the cyclic ethers include C 1-4 Examples thereof include tetrahydrofurans or dioxanes which may have an alkyl group, and among these, C 1-3 Dioxanes which may have an alkyl group are preferred, and in particular, C 1-2 1,4-dioxanes which may have an alkyl group are preferred, and 1,4-dioxane is most preferred.

[0268] Examples of the cyclic sulfones include C 1-4 tetra- to pentamethylene sulfones which may have an alkyl group; C 1-3 Sulfolanes which may have an alkyl group are more preferred, and C 1-2 Sulfolanes which may have an alkyl group are more preferred, and sulfolane is most preferred.

[0269] Examples of the cyclic ureas include C ureas such as DMI and N,N'-dimethyl-N,N'-trimethylene urea. 1-4 N,N'-diC optionally having an alkyl group 1-6 Alkyl-N,N'-di- or trimethylene ureas are included, and C 1-3 N,N'-diC optionally having an alkyl group 1-4 Alkyl-ethylene ureas are more preferred, C 1-2N,N'-diC optionally having an alkyl group 1-3 Alkyl-ethylene ureas are more preferred, with DMI being most preferred.

[0270] Examples of the cyclic amides include C 1-4 5- to 7-membered lactams which may have an alkyl group, and C 1-3 A 5- to 6-membered lactam optionally having an alkyl group is more preferred, and C 1-2 A 5-membered lactam which may have an alkyl group is more preferred, and NMP is most preferred.

[0271] The total ratio of the first solvent and the aprotic polar solvent (second solvent) to the total solvent can be selected, for example, from a range of about 10% by mass or more (i.e., 10 to 100% by mass), with preferred ranges being 30% by mass or more, 50% by mass or more, 70% by mass or more, 90% by mass or more, and even more preferably 95% by mass or more, and particularly 100% by mass, i.e., a ratio consisting essentially of the first and / or second solvents. When a solvent other than the first and second solvents (also referred to as a third solvent) is included, the total ratio of the first solvent and the second solvent can be selected, for example, from a range of about 60 to 99% by mass, and preferably 80 to 95% by mass.

[0272] When the solvent contains both a first solvent and an aprotic polar solvent (second solvent), the mass ratio thereof (former / latter) can be selected, for example, from a range of about 50 / 50 to 99.9 / 0.1, with preferred ranges being the following stepwise: 70 / 30 to 99 / 1, 80 / 20 to 98 / 2, 82 / 18 to 97 / 3, 85 / 15 to 96 / 4, 87 / 13 to 95 / 5, 88 / 12 to 93 / 7, and 89 / 11 to 91 / 9. If the proportion of the aprotic polar solvent is too high, reactivity (reaction rate or reaction rate) may decrease, while if it is too low, viscosity may not be reduced and reactivity may decrease.

[0273] The proportion of the solvent may be selected from the range of, for example, about 100 to 1000 parts by mass relative to 100 parts by mass of the 9-fluorenones, with preferred ranges being 150 to 800 parts by mass, 200 to 700 parts by mass, 250 to 680 parts by mass, 280 to 650 parts by mass, and 300 to 630 parts by mass in the following stepwise order. If the proportion of the solvent is too high, the concentration of the raw materials may be too low, resulting in a decrease in reactivity, whereas if the proportion of the solvent is too low, the viscosity may be too high, resulting in a decrease in reactivity.

[0274] In this specification and claims, when an acid catalyst such as sulfuric acid or hydrochloric acid contains water, the water contained as the acid catalyst is treated as the acid catalyst rather than as a solvent, and is not added to the proportion of the solvent.

[0275] The reaction temperature is not particularly limited, but can be selected from the range of about 0 to 200°C, with preferred ranges being 5 to 100°C, 10 to 80°C, 20 to 70°C, 30 to 60°C, 35 to 55°C, and 40 to 50°C, in the following stepwise order. The reaction time is also not particularly limited, and can be selected from the range of about 30 minutes to 48 hours, with preferred ranges being 1 to 24 hours, 3 to 12 hours, and 5 to 8 hours, in the following stepwise order.

[0276] The reaction may be carried out with stirring, in air or in an inert atmosphere such as nitrogen gas or a rare gas, under normal pressure, elevated pressure, or reduced pressure. The reaction may also be carried out while dehydrating.

[0277] The reaction mixture (reaction solution or reaction mixture) after completion of the reaction contains, in addition to the target product or reaction product, the fluorene compound represented by formula (1), unreacted polycyclic aryloxy alcohols, the 9-fluorenones, the compound represented by formula (4), an acid catalyst, thiols, a solvent, water, etc. As a method for separating (or purifying) the fluorene compound represented by formula (1) from such a reaction mixture, a conventional method, for example, a purification or separation means such as filtration, concentration, extraction, neutralization, washing, drying, crystallization, recrystallization, column chromatography, or a combination of these purification or separation means, can be used.

[0278] For example, the acid catalyst (and thiols) may be removed by a method such as adding an alkaline aqueous solution such as an aqueous sodium hydroxide solution to neutralize and washing, followed by crystallization to separate and purify the fluorene compound represented by formula (1).

[0279] Examples of solvents used in crystallization include aromatic hydrocarbons such as toluene, ethers such as 1,4-dioxane, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, and isopropanol, and water. These solvents can be used alone or in combination of two or more. Among these solvents, those containing ketones are preferred, and di-C are more preferred. 1-4 The solvent is preferably a chain ketone such as alkyl ketone, and particularly preferably acetone. Crystallization using a solvent containing ketones, particularly acetone, is preferred because it can further reduce the content of impurities and easily improve the purity of the fluorene compound represented by formula (1). Furthermore, the mixed solvent is preferably a mixed solvent containing aromatic hydrocarbons, ethers and / or ketones, and water.

[0280] The crystallization may be carried out by adding seed crystals, which are added at a temperature of, for example, 30 to 50°C, preferably 35 to 45°C.

[0281] The crystallization may be cooling crystallization, and the cooling rate is, for example, 1 to 20°C / hour, preferably 5 to 15°C / hour, and more preferably 8 to 12°C / hour. The temperature reached after cooling is, for example, -10 to 20°C, and preferably 0 to 10°C. Cooling may be carried out after adding seed crystals and precipitating crystals by aging (or leaving to stand) for, for example, 1 to 10 hours, preferably 2 to 5 hours. After cooling to the temperature reached, the mixture may be further aged (or left to stand) for, for example, 1 to 10 hours, preferably 2 to 5 hours, to precipitate crystals. Cooling crystallization may be repeated multiple times by appropriately changing the crystallization conditions.

[0282] The crystals obtained by crystallization may be further washed or rinsed with the solvent used for the crystallization. During washing, the crystals may be washed with a solvent cooled to a low temperature, or may be washed while heated. Among the solvents used for the crystallization, aromatic hydrocarbons such as toluene, or alcohols such as methanol and isopropanol are often used for washing. In particular, washing with an alcohol such as methanol while heating, for example, at 40°C or higher, preferably 50 to 70°C, and more preferably 55 to 65°C, is preferred because it may be easier to reduce residual sulfur.

[0283] Crystallization may be carried out once or multiple times, and is preferably carried out at least twice in order to effectively reduce the content of impurities. When crystallization is carried out multiple times, the types of solvents used for crystallization may be the same or different.

[0284] In addition, crystallization is usually performed to precipitate the target fluorene compound represented by the formula (1), but the purity of the fluorene compound may be improved by precipitating impurities that crystallize more easily than the fluorene compound. For example, the fluorene compound (and a mixture containing impurities) may be dissolved in a ketone such as acetone, and then impurity components such as the first impurity component represented by the formula (2) may be precipitated and separated for purification by a method such as aging (or leaving to stand), cooling, or removing the solvent under reduced pressure.

[0285] In the present invention, the fluorene compound obtained by the above method is purified to adjust the specific impurities to a predetermined ratio.

[0286] In the second method, the 9,9-bis(hydroxypolycyclic aryl)fluorenes include compounds corresponding to the fluorene compounds represented by the formula (1) above, including preferred embodiments thereof, and more preferably, 9,9-bis(hydroxy C) such as 9,9-bis(6-hydroxy-2-naphthyl)fluorene (also referred to as BNF) and 9,9-bis(5-hydroxy-1-naphthyl)fluorene. 10-149,9-bis(hydroxypolycyclic aryl)fluorenes may be commercially available products.

[0287] In addition, alkylene oxides include C alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide (1,2-epoxybutane). 2-6 Alkylene oxide, preferably C 2-4 Examples of alkylene carbonates include C alkylene carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate. 2-6 Alkylene carbonate, preferably C 2-4 Alkylene carbonates and the like are included. Haloalkanols include halo C such as chloroethanol. 2-6 Alkanols, preferably halo C 2-4 Examples of suitable fluorenes include alkanols. When an alkylene oxide (alkylene carbonate or haloalkanol) is reacted, a (poly)oxyalkylene unit can be introduced via the hydroxyl group of the 9,9-bis(hydroxypolycyclic aryl)fluorene. When an alkylene carbonate is used, the alkylene carbonate is added, followed by a decarboxylation reaction, thereby introducing an oxyalkylene unit (alkoxy unit).

[0288] The ratio of the 9,9-bis(hydroxypolycyclic aryl)fluorene to the alkylene oxide (alkylene carbonate or haloalkanol) used in the reaction is, for example, the former / latter (molar ratio) = 1 / 2 to 1 / 50, with preferred ranges being 1 / 2 to 1 / 40, 1 / 2 to 1 / 30, and 1 / 2 to 1 / 20, in the following stepwise order. When the compound represented by formula (11) is contained in a specific ratio to improve the molecular weight of the resin, the former / latter (molar ratio) = 1 / 2 to 1 / 15, preferably 1 / 3 to 1 / 13, further preferably 1 / 5 to 1 / 12, more preferably 1 / 6 to 1 / 10, and most preferably 1 / 7 to 1 / 9.

[0289] The reaction may be carried out in the absence of a catalyst, but is usually carried out in the presence of a catalyst. Examples of catalysts include base catalysts and acid catalysts, and a base catalyst is usually used. The base catalyst may be an inorganic base or an organic base. Examples of inorganic bases include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, alkali metal or alkaline earth metal carbonates such as sodium carbonate, and alkali metal or alkaline earth metal hydrogen carbonates such as sodium hydrogen carbonate. Examples of organic bases include trialkylamines such as triethylamine, aromatic tertiary amines such as N,N-dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole, and alkali metal or alkaline earth metal acetates such as sodium acetate and calcium acetate. These catalysts can be used alone or in combination. Among these, organic bases such as heterocyclic tertiary amines are preferred.

[0290] The proportion of the catalyst is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 8 parts by mass, further preferably 1 to 5 parts by mass, even more preferably 1.5 to 4 parts by mass, and most preferably 2 to 3 parts by mass, relative to 100 parts by mass of the 9,9-bis(hydroxypolycyclicaryl)fluorenes.

[0291] The reaction may be carried out in a solvent, such as ethers, hydrocarbons, halogenated hydrocarbons, and alcohols.

[0292] Examples of the ethers, hydrocarbons and halogenated hydrocarbons include the ethers, hydrocarbons and halogenated hydrocarbons exemplified as reaction solvents in the first method.

[0293] Alcohols include C, such as methanol, ethanol, and isopropanol. 1-4 Alcohols; (poly)C such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol 2-3 alkylene glycols and the like.

[0294] These solvents can be used alone or in combination. These solvents can be selected depending on the raw materials used. When alkylene oxide is used, the solvent may be an alcohol such as diethylene glycol.

[0295] The proportion of the solvent is, for example, 100 to 1000 parts by mass, preferably 200 to 800 parts by mass, and more preferably 300 to 500 parts by mass, relative to 100 parts by mass of the 9,9-bis(hydroxypolycyclicaryl)fluorenes. If the proportion of the solvent is too high, the concentration of the raw materials may be too low, resulting in a decrease in reactivity, while if the proportion of the solvent is too low, the viscosity may be too high, resulting in a decrease in reactivity.

[0296] The reaction temperature is not particularly limited, but can be selected from the range of about 0 to 200°C, with preferred ranges being 30 to 180°C, 50 to 150°C, 60 to 140°C, 70 to 130°C, 80 to 120°C, and 90 to 110°C, in the following stepwise order. The reaction time is also not particularly limited, and can be selected from the range of about 30 minutes to 48 hours, with preferred ranges being 1 to 24 hours, 2 to 12 hours, and 3 to 8 hours, in the following stepwise order.

[0297] The reaction may be carried out with stirring, in air or in an inert atmosphere such as nitrogen gas or a rare gas, under normal pressure, elevated pressure, or reduced pressure. The reaction may also be carried out while dehydrating. If necessary, the reaction may also be carried out while removing generated gases (such as carbon dioxide).

[0298] The reaction mixture (reaction solution or reaction mixture) after completion of the reaction contains, in addition to the target product or reaction product, the fluorene compound represented by formula (1), unreacted 9,9-bis(hydroxypolycyclic aryl)fluorenes, the compound represented by formula (4), the compound represented by formula (11), a catalyst, a solvent, water, etc. Methods for separating (or purifying) the fluorene compound represented by formula (1) from such a reaction mixture include the methods exemplified in the first method. Among these methods, cooling crystallization is preferred.

[0299] [Resins made from fluorene compounds] The present invention also encompasses resins that use, as raw materials or polymerization components, fluorene compounds with adjusted content of specific impurity components. Perhaps because the raw material fluorene compound is resistant to coloration even after undergoing chemical reactions such as polymerization, the resins exhibit significantly reduced coloration, making them useful for optical components, etc. Furthermore, the resins also have excellent heat resistance and can improve glass transition temperatures. The resins may be heat- or photo-curable resins such as glycidyl ether-type epoxy resins and polyfunctional (meth)acrylic resins such as di(meth)acrylate, but are typically thermoplastic resins.

[0300] Examples of thermoplastic resins include polyester resins, thermoplastic polyurethane resins, polyether resins, etc. Among these resins, polyester resins containing an ester bond in the main chain, such as polyester resins, polycarbonate resins, and polyester-polycarbonate copolymers, are preferred, and among these, polycarbonate resins and polyester-polycarbonate copolymers are preferred, with polycarbonate resins being more preferred, as they can further improve heat resistance while suppressing coloration.

[0301] In the present specification and claims, the term "ester bond" is used to include not only [-C(=O)-O-] but also a carbonate ester bond [-OC(=O)-O-].

[0302] (polyester resin) The polyester resin can be prepared by polymerizing a diol component containing at least a fluorene compound (first diol component) represented by the formula (1) with a dicarboxylic acid component. The fluorene compound represented by the formula (1) can be used alone or in combination of two or more.

[0303] The diol component may optionally contain a second diol component corresponding to a second diol unit represented by the following formula (12): The second diol component not only enhances polymerization reactivity and facilitates an increase in molecular weight, but also imparts flexibility or toughness to the resin, thereby significantly improving moldability and handleability in some cases.

[0304] [ka]

[0305] (In the formula, A 9 represents a linear or branched alkylene group, and m9 represents an integer of 1 or more).

[0306] In the formula (12), A 9 Examples of the alkylene group represented by the formula (I) include linear or branched C alkylene groups such as ethylene, propylene, trimethylene, 1,2-butanediyl, 1,3-butanediyl, tetramethylene, 1,5-pentanediyl, 1,6-hexanediyl, 1,8-octanediyl, and 1,10-decanediyl. 2-12 Examples of the alkylene group include alkylene groups. 9 As for the following, linear or branched chain C 2-10 Alkylene group, linear or branched C 2-8 Alkylene group, linear or branched C 2-6 Alkylene group, linear or branched C 2-4 alkylene groups, more preferably linear or branched C groups such as ethylene groups and propylene groups. 2-3 An alkylene group is preferred, with an ethylene group being particularly preferred.

[0307] The repeat number m9 can be selected, for example, from the range of about 1 to 10, and preferred ranges are 1 to 8, 1 to 6, 1 to 4, 1 to 3, and 1 to 2 in the following stepwise order, with 1 being particularly preferred. The repeat number m9 may be an average value (arithmetic mean value or additive mean value), and preferred embodiments are the same as the range of integers described above. When m9 is 2 or more, two or more oxyalkylene groups (-A9 The types of O-) may be different from each other, but are usually the same.

[0308] Examples of the second diol component include alkanediols (or alkylene glycols), polyalkanediols (or polyalkylene glycols), and the like.

[0309] As the alkylene glycol, for example, in the formula (11), m9 is 1, A 9 corresponding to the alkylene group exemplified above, specifically, linear or branched C alkylene compounds such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, tetramethylene glycol (or 1,4-butanediol), 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol. 2-12 alkylene glycol, etc., and a preferred embodiment is 9 The same applies to

[0310] The polyalkylene glycol is preferably a polyalkylene glycol in which m8 in the formula (12) is 2 or more, for example, about 2 to 10; 9 corresponding to the alkylene group exemplified above, specifically, di- or deca-linear or branched C alkylenes such as diethylene glycol, dipropylene glycol, and triethylene glycol. 2-12 alkylene glycols, and the like, preferably di- or hexa-straight or branched chain C 2-6 Alkylene glycol, more preferably di- or tetra-linear or branched C 2-4 Alkylene glycols are included.

[0311] These second diol units may be contained alone or in combination of two or more. A preferred second diol unit is an alkylene glycol, from the viewpoint of easily improving the refractive index and preventing a decrease in heat resistance, and more preferably a linear or branched C alkylene glycol. 2-6Alkylene glycol, more preferably linear or branched C alkylene glycol such as ethylene glycol, propylene glycol, 1,4-butanediol, etc. 2-4 Alkylene glycols, especially linear or branched C alkylene glycols such as ethylene glycol and propylene glycol 2-3 A structural unit derived from an alkylene glycol, particularly ethylene glycol, is preferred.

[0312] The diol component may or may not contain another diol component (third diol component) different from the first and second diol components, as required.

[0313] Examples of the third diol component include alicyclic diols, aromatic diols (excluding the first diol component), and alkylene oxide (alkylene carbonate or haloalkanol) adducts of these diol components.

[0314] Examples of alicyclic diols include cycloalkanediols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; and hydrogenated aromatic diols exemplified below, such as hydrogenated bisphenol A.

[0315] Examples of aromatic diols include dihydroxyarenes such as hydroquinone and resorcinol; aromatic aliphatic diols such as benzenedimethanol; bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, and bisphenol S; biphenols such as p,p'-biphenol; and those represented by the formula (1), wherein Z 1a and Z 1b and compounds having a 9,9-bisphenylfluorene skeleton, such as a compound in which the polycyclic arene ring is replaced with a benzene ring.

[0316] Examples of alkylene oxide (corresponding alkylene carbonate or haloalkanol) adducts of these diol components include C2-4 C alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, etc. 2-3 Examples thereof include alkylene oxide adducts, and the number of moles added is not particularly limited. Specific examples include adducts in which about 2 to 10 moles of ethylene oxide are added to 1 mole of a diol such as bisphenol A.

[0317] The diol component may contain these third diol components either alone or in combination of two or more.

[0318] In the polyester resin, the total proportion of the first diol units and the second diol units corresponding to the first diol component is, for example, 10 mol% or more, and preferred ranges are 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, 95 mol% or more, and more preferably substantially 100 mol% based on the total diol units.

[0319] The ratio of the first diol units to the second diol units (molar ratio) may be about 99 / 1 to 50 / 50, with preferred ranges being 90 / 10 to 55 / 45, 80 / 20 to 60 / 40, and 75 / 25 to 65 / 35, respectively. If the amount of the first diol units is too small, the coloration suppression effect may not be fully exhibited, the heat resistance and refractive index may be reduced, and birefringence may not be reduced. Conversely, if the amount is too large, the polymerization reactivity may be reduced and the flexibility may be reduced.

[0320] The dicarboxylic acid component is not particularly limited, and may or may not contain a first dicarboxylic acid component derived from a first dicarboxylic acid unit represented by the following formula (13a) or (13b): When the first dicarboxylic acid unit is contained, birefringence tends to be easily reduced while maintaining relatively high heat resistance and refractive index, and polymerization reactivity tends to be easily improved even if the polymer has a rigid fluorene skeleton.

[0321] [ka]

[0322] (In the formula, R 19 and R 20 each independently represents a substituent, n19 and n20 each independently represents an integer of 0 to 8, A 10a , A 10b and A 11 each independently represents a divalent hydrocarbon group which may have a substituent, and q represents an integer of 0 to 4.

[0323] In the formula (13a) or (13b), R 19 and R 20 and the number of substitutions n19 and n20 are R 1 and n1 are the same as n1, including preferred embodiments. 19 and R 20 Preferred embodiments such as the type and substitution position of R in the formula (1) are also 1 and similarly for n1.

[0324] A 10a , A 10b and A 11 Examples of the hydrocarbon group represented by the formula (I) include linear or branched alkylene groups, such as methylene, ethylene, trimethylene, propylene, 1,2-butanediyl, and 2-methylpropane-1,3-diyl groups. 1-8 Preferred alkylene groups include linear or branched C alkylene groups such as methylene, ethylene, trimethylene, propylene, and 2-methylpropane-1,3-diyl. 1-6 alkylene groups, and more preferably linear or branched C 1-4 It is an alkylene group.

[0325] The substituent that the hydrocarbon group may have is usually a substituent that is inactive in the polymerization reaction (non-polymerizable group), for example, an aryl group such as a phenyl group, or a cycloalkyl group such as a cyclohexyl group. 10a , A 10b and A 11 Examples of the alkyl group include a 1-phenylethylene group and a 1-phenylpropane-1,2-diyl group.

[0326] Base A 10a , A 10b is linear or branched chain C 2-4 Alkylene groups are preferred, and among these, linear or branched C alkylene groups such as ethylene and propylene groups are preferred. 2-3 The group A is preferably an alkylene group, particularly an ethylene group. 11 is a straight or branched chain C such as methylene group or ethylene group 1-3 It is preferably an alkylene group.

[0327] In the formula (13b), the number of repeating methylene groups, q, is, for example, an integer of about 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1.

[0328] Examples of the first dicarboxylic acid component corresponding to the structural unit represented by the formula (13a) include: 10a , A 10b is linear or branched C 2-6 Compounds with alkylene groups, such as 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene 2-6 alkyl)fluorenes and ester-forming derivatives thereof.

[0329] Examples of the first dicarboxylic acid component corresponding to the structural unit represented by the formula (13b) include 9-(dicarboxy C 2-8 q is 0 and A is an alkyl)fluorene and its ester-forming derivatives, specifically, 9-(1,2-dicarboxyethyl)fluorene, etc. 11is linear or branched C 1-6 a compound in which q is 1 and A is an alkylene group; such as 9-(2,3-dicarboxypropyl)fluorene; 11 is linear or branched C 1-6 Examples include compounds having an alkylene group.

[0330] These first dicarboxylic acid units may be contained alone or in combination of two or more. Among these first dicarboxylic acid units, it is preferable to contain at least a dicarboxylic acid unit represented by the formula (13a) in view of ease of reducing birefringence, and 9,9-bis(carboxy C 2-6 More preferred are structural units derived from 9,9-bis(carboxyalkyl)fluorenes such as 9,9-bis(carboxyC alkyl)fluorenes. 2-4 9,9-bis(carboxy C alkyl)fluorene, more preferably 9,9-bis(carboxy C alkyl)fluorene such as 9,9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene. 2-3 It is preferred that the compound contains a structural unit derived from 9,9-bis(2-carboxyethyl)fluorene, particularly 9,9-bis(2-carboxyethyl)fluorene.

[0331] The dicarboxylic acid component may or may not contain a dicarboxylic acid component (second dicarboxylic acid component) different from the first dicarboxylic acid component, as required.

[0332] Examples of the second dicarboxylic acid component include an aromatic dicarboxylic acid component (excluding the first dicarboxylic acid component), an alicyclic dicarboxylic acid component, and an aliphatic dicarboxylic acid component.

[0333] Examples of the aromatic dicarboxylic acid component include monocyclic aromatic dicarboxylic acids, polycyclic aromatic dicarboxylic acids, and ester-forming derivatives thereof. Examples of the monocyclic aromatic dicarboxylic acids include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid; alkyl benzene dicarboxylic acids, specifically, C alkyl benzene dicarboxylic acids such as 4-methylisophthalic acid; 1-4alkyl-benzenedicarboxylic acids and the like.

[0334] Examples of polycyclic aromatic dicarboxylic acids include condensed polycyclic aromatic dicarboxylic acids, specifically condensed polycyclic C dicarboxylic acids such as naphthalenedicarboxylic acid, anthracenedicarboxylic acid, and phenanthrenedicarboxylic acid. 10-24 Arene-dicarboxylic acids, preferably fused polycyclic C 10-14 C arene dicarboxylic acids, such as aryl arene dicarboxylic acids, specifically 2,2'-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, etc. 6-10 Aryl-C 6-10 arene-dicarboxylic acids, etc.; diarylalkanedicarboxylic acids, specifically, di-C such as 4,4'-diphenylmethanedicarboxylic acid 6-10 Aryl C 1-6 Alkane-dicarboxylic acids, etc.; diaryl ketone dicarboxylic acids, specifically, di(C) such as 4,4'-diphenyl ketone dicarboxylic acid 6-10 aryl) ketone-dicarboxylic acid and the like.

[0335] Examples of the naphthalenedicarboxylic acid include 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid is most common.

[0336] Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids, specifically, C 1,4-cyclohexane dicarboxylic acids. 5-10 Cycloalkane dicarboxylic acids, etc.; bridged cyclic cycloalkane dicarboxylic acids, specifically, di- or tricycloalkane dicarboxylic acids such as decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.; cycloalkene dicarboxylic acids, specifically, C such as cyclohexene dicarboxylic acid, etc. 5-10Examples thereof include cycloalkene-dicarboxylic acids; bridged cyclic cycloalkene dicarboxylic acids, specifically di- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid; and ester-forming derivatives thereof.

[0337] Examples of the aliphatic dicarboxylic acid component include alkanedicarboxylic acids, specifically, C carboxylic acids such as succinic acid, adipic acid, sebacic acid, and decanedicarboxylic acid. 2-12 Alkane dicarboxylic acids, etc.; unsaturated aliphatic dicarboxylic acids, specifically C such as maleic acid, fumaric acid, and itaconic acid 2-10 Alkene-dicarboxylic acids and their ester-forming derivatives are included.

[0338] These second dicarboxylic acid components may be used alone or in combination of two or more.

[0339] The proportion of the first dicarboxylic acid units relative to the total dicarboxylic acid units is, for example, 10 mol% or more, and preferred ranges are 30 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, 95 mol% or more, and more preferably substantially 100 mol%. If the proportion of the first dicarboxylic acid units is too small, the heat resistance and refractive index may decrease, and birefringence may increase.

[0340] The polyester resin does not necessarily contain any other structural units different from the diol unit and the dicarboxylic acid unit, but may contain such units as necessary.

[0341] Examples of other structural units include structural units derived from hydroxyalkanoic acids and corresponding lactones, polyfunctional polymerizable components having three or more carboxyl groups and / or hydroxyl groups, and carbonate bond-forming components.

[0342] Examples of the hydroxyalkanoic acids and corresponding lactones include hydroxyalkanoic acids such as lactic acid, 3-hydroxybutyric acid, and 6-hydroxyhexanoic acid; and lactones corresponding to hydroxyalkanoic acids such as ε-caprolactone.

[0343] Examples of the polyfunctional polymerization component include polyfunctional polymerization components having a total of three or more carboxyl groups and / or hydroxyl groups, such as trivalent or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid, and trivalent or higher polyhydric alcohols such as glycerin and pentaerythritol.

[0344] The carbonate ester-forming component may be any compound capable of forming a carbonate ester bond upon reaction with two diol components. In other words, the "structural unit derived from a carbonate ester bond-forming component" refers to a carbonyl group [-C(=O)-], which forms a carbonate ester bond together with the terminal oxygen atoms of the two diol units bonded adjacent to this carbonyl group. Representative carbonate ester bond-forming components include, for example, phosgenes such as phosgene and triphosgene, and carbonate diesters such as diphenyl carbonate. The polyester-polycarbonate copolymer can be formed by including a structural unit derived from such a carbonate ester bond-forming component.

[0345] The proportion of such other structural units relative to the total amount of structural units (total amount of diol units, dicarboxylic acid units, and other structural units) is, for example, 50 mol% or less, with preferred ranges being 40 mol% or less, 30 mol% or less, 20 mol% or less, 10 mol% or less, and 5 mol% or less, stepwise thereafter, and usually, other structural units are not substantially contained in many cases. The proportion may be about 0 to 10 mol%, for example, 0.01 to 1 mol%.

[0346] The method for producing the polyester resin is not particularly limited except that a diol component containing the first diol component is used as a polymerization component, and a conventional method can be used depending on the other polymerization components (copolymerization components). For example, the polyester resin can be produced by reacting a diol acid component corresponding to the diol unit described above with a dicarboxylic acid component corresponding to each dicarboxylic acid unit described above. Conventional methods include, for example, transesterification, melt polymerization such as direct polymerization, solution polymerization, and interfacial polymerization, with melt polymerization being preferred. The reaction may be carried out in the presence or absence of a solvent depending on the polymerization method.

[0347] The ratio (or charge ratio) of the dicarboxylic acid component to the diol component is usually, for example, 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9 (molar ratio), but this range is not necessarily required, and at least one component selected from each dicarboxylic acid component and each diol component may be used in excess of the intended introduction ratio. For example, a second diol component such as ethylene glycol that can be distilled from the reaction system may be used in excess of the ratio (or introduction ratio) introduced into the resin.

[0348] The reaction may be carried out in the presence of a catalyst. Conventional esterification catalysts, such as metal catalysts, can be used as the catalyst. Examples of metal catalysts include metal compounds containing alkali metals such as sodium; alkaline earth metals such as magnesium, calcium, and barium; transition metals such as titanium, manganese, and cobalt; metals in Group 12 of the periodic table such as zinc and cadmium; metals in Group 13 of the periodic table such as aluminum; metals in Group 14 of the periodic table such as germanium and lead; and metals in Group 15 of the periodic table such as antimony. Examples of metal compounds include alkoxides; organic acid salts such as acetates and propionates; inorganic acid salts such as borates and carbonates; oxides, and hydrates thereof. Representative metal compounds include germanium compounds such as germanium dioxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, and germanium-n-butoxide; antimony compounds such as antimony trioxide, antimony acetate, and antimony ethylene glycolate; titanium compounds such as tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate (titanium(IV) tetrabutoxide), titanium oxalate, and potassium titanium oxalate; manganese compounds such as manganese acetate tetrahydrate; and calcium compounds such as calcium acetate monohydrate.

[0349] These catalysts can be used alone or in combination of two or more. When using multiple catalysts, each catalyst can be added according to the progress of the reaction. Among these catalysts, manganese acetate tetrahydrate, calcium acetate monohydrate, germanium dioxide, titanium (IV) tetrabutoxide, etc. are preferred. The amount of catalyst used is, for example, 0.01 × 10 per mole of the dicarboxylic acid component. -4 ~100×10 -4 moles, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0350] The reaction may be carried out in the presence of a stabilizer such as a heat stabilizer or an antioxidant, if necessary. Heat stabilizers are commonly used, and examples of such stabilizers include phosphorus compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dibutyl phosphate (dibutyl phosphate or dibutyl phosphate), phosphorous acid, trimethyl phosphite, and triethyl phosphite. Among these, dibutyl phosphate is commonly used. The amount of heat stabilizer used is, for example, 0.01 × 10 per mole of the dicarboxylic acid component. -4 ~100×10 -4 moles, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0351] The reaction is usually carried out in an atmosphere of an inert gas, such as nitrogen gas, or a rare gas such as helium or argon. Alternatively, the reaction may be carried out under reduced pressure, for example, at a pressure of 1×10 2 ~1×10 4 The reaction can be carried out at a pressure of about Pa. Usually, the transesterification reaction is carried out in an inert gas atmosphere such as nitrogen gas, and the polycondensation reaction is carried out under reduced pressure. The reaction temperature can be selected depending on the polymerization method. For example, the reaction temperature in the melt polymerization method is 150 to 320°C, preferably 180 to 310°C, and more preferably 200 to 300°C.

[0352] The polyester resin thus obtained is suppressed in coloration and exhibits high heat resistance and refractive index.

[0353] The color difference b* of the polyester resin may be, for example, about 0 to 10, and the lower the better. Preferred ranges are 0.01 to 9, 0.1 to 8.5, 0.5 to 8, 1 to 7.5, 2 to 7, 3 to 6.5, and 4 to 6, in the following stepwise order.

[0354] The glass transition temperature Tg of the polyester resin may be, for example, in the range of about 100 to 250°C, and preferred ranges are 120 to 200°C, 130 to 180°C, 140 to 160°C, and more preferably 145 to 150°C, in the following stepwise order.

[0355] The refractive index of the polyester resin can be selected, for example, from the range of about 1.6 to 1.7 at a temperature of 20° C. and a wavelength of 589 nm, preferably in the following stepwise order: 1.62 to 1.69, 1.64 to 1.68, 1.65 to 1.67, and more preferably 1.66 to 1.665.

[0356] The weight-average molecular weight Mw of the polyester resin can be measured by gel permeation chromatography (GPC) or the like and can be selected from a range of, for example, about 10,000 to 1,000,000 in terms of polystyrene, with preferred ranges being the following stepwise ranges: 15,000 to 150,000, 20,000 to 100,000, 25,000 to 80,000, 30,000 to 60,000, 35,000 to 50,000, and 40,000 to 45,000. If the weight-average molecular weight Mw is too low, heat resistance and moldability (productivity) may be easily reduced.

[0357] In this specification and claims, the color difference b*, glass transition temperature Tg, refractive index nD, and weight average molecular weight Mw can be measured by the methods described in the examples below.

[0358] (Polycarbonate resin) The polycarbonate resin can be prepared by polymerizing a diol component containing at least the fluorene compound (first diol component) represented by the formula (1) with a carbonate bond-forming component. The fluorene compound represented by the formula (1) can be used alone or in combination of two or more.

[0359] The diol component may or may not contain another diol component different from the first diol component. Examples of the other diol component include the second diol component and the third diol component exemplified in the polyester resin section.

[0360] These other diol components can be used alone or in combination of two or more. Among these other diol components, aromatic diols and their alkylene oxide (alkylene carbonate or haloalkanol) adducts are preferred, and more preferred are bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, and bisphenol S; biphenols such as p,p'-biphenol; and compounds of the formula (1) where Z 1a and Z 1b Compounds having a 9,9-bisphenylfluorene skeleton, such as compounds in which the polycyclic arene ring is replaced by a benzene ring, and alkylene oxide adducts thereof. Among these, bisphenols and alkylene oxide adducts thereof are preferred, and bis(hydroxyaryl)alkanes and alkylene oxide adducts thereof are particularly preferred, and bis(hydroxyaryl)alkanes such as bisphenol A and bisphenol F are most preferred. 6-10 Aryl)C 1-4 Alkanes and their C 2-4 It is an alkylene oxide adduct.

[0361] In the polycarbonate resin, the ratio of the first diol units corresponding to the first diol component to the other diol units corresponding to the other diol components may be, for example, a former / latter (molar ratio) of about 90 / 10 to 10 / 90, with preferred ranges being 80 / 20 to 20 / 80, 70 / 30 to 30 / 70, 60 / 40 to 40 / 60, and more preferably 55 / 45 to 45 / 55. If the ratio of the first diol units is too low, the coloration suppression effect may not be fully exerted, the heat resistance and refractive index may be reduced, and birefringence may not be reduced.

[0362] The carbonate bond-forming component is the same as the phosgenes and carbonate diesters exemplified as components forming other structural units in the polyester resin section.

[0363] The polycarbonate resin can be produced by reacting (polymerizing or condensing) a diol component with a phosgene or a carbonate diester by a conventional method, such as the phosgene method (solvent method) or the transesterification method (melt method). The diol component needs to contain at least the first diol component for forming the structural unit represented by formula (1), and may further contain the other diol components as needed. Of these methods, the transesterification method is preferred because it does not require a solvent.

[0364] In the transesterification method, the proportion of the carbonic acid diester is, for example, 0.8 to 1.5 mol, and preferably 0.9 to 1.2 mol, per 1 mol of the diol component.

[0365] The transesterification reaction may be carried out in the presence of a catalyst, such as a nitrogen-containing compound or a metal compound, which are commonly used in transesterification reactions.

[0366] Examples of the nitrogen-containing compound include quaternary ammonium hydroxide and tertiary amine.

[0367] Examples of quaternary ammonium hydroxides include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; and trialkyl-aralkylammonium hydroxides such as trimethylbenzylammonium hydroxide.

[0368] Tertiary amines include trialkylamines such as trimethylamine and triethylamine; dialkyl-aralkylamines such as dimethylbenzylamine; and triarylamines such as triphenylamine.

[0369] Examples of metals contained in the metal compound include alkali metals such as sodium, alkaline earth metals such as magnesium, calcium, and barium, transition metals such as manganese, zinc, cadmium, lead, cobalt, and titanium, metals in Group 13 of the periodic table such as aluminum, metals in Group 14 of the periodic table such as germanium, and metals in Group 15 of the periodic table such as antimony. Examples of metal compounds include alkoxides of the above metals, organic acid salts such as acetates and propionates, inorganic acid salts such as borates and carbonates, oxides, and hydroxides.

[0370] These catalysts can be used alone or in combination of two or more. Among these catalysts, nitrogen-containing compounds such as quaternary ammonium hydroxides are preferred, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide are particularly preferred. The amount of catalyst used is, for example, 0.01 × 10 per mole of the diol component. -4 ~100×10 -4 moles, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0371] The reaction may be carried out in the presence of an additive such as a stabilizer, if necessary. Examples of the stabilizer include an antioxidant and a heat stabilizer.

[0372] The reaction can be carried out in an atmosphere of an inert gas, such as nitrogen gas, or a rare gas such as helium or argon. 2 ~1×10 4 The reaction can also be carried out under reduced pressure at around Pa. The reaction temperature can be selected depending on the polymerization method, and for example, the reaction temperature in the transesterification method is, for example, 150 to 320°C, preferably 200 to 310°C, and more preferably 250 to 300°C. In particular, when diphenyl carbonate is used as the carbonate diester, it is effective to carry out polycondensation while distilling off phenol at high temperature under reduced pressure.

[0373] The polycarbonate resin thus obtained is suppressed in coloration and exhibits high heat resistance and refractive index.

[0374] The color difference b* of the polycarbonate resin may be, for example, about 0 to 17, and the lower the better. Preferred ranges are 0.01 to 30, 0.1 to 25, 0.3 to 20, 0.5 to 18, 0.7 to 16, 1 to 15, 5 to 14.5, 10 to 14, 11 to 13.5, and 11.5 to 13, in the following stepwise order.

[0375] The glass transition temperature Tg of the polycarbonate resin may be, for example, in the range of about 100 to 250°C, and preferred ranges are 130 to 230°C, 150 to 200°C, 160 to 190°C, and 170 to 185°C, and more preferably 175 to 180°C.

[0376] The refractive index of the polycarbonate resin can be selected, for example, from the range of about 1.6 to 1.7 at a temperature of 20° C. and a wavelength of 589 nm, preferably in the following stepwise order: 1.63 to 1.68, 1.64 to 1.67, 1.645 to 1.66, and more preferably 1.65 to 1.655.

[0377] The weight-average molecular weight Mw of the polycarbonate resin can be measured by gel permeation chromatography (GPC) or the like and can be selected from a range of, for example, about 10,000 to 1,000,000 in terms of polystyrene, with preferred ranges being 15,000 to 150,000, 20,000 to 100,000, 25,000 to 80,000, 30,000 to 50,000, 32,000 to 40,000, and 34,000 to 39,000. If the weight-average molecular weight Mw is too low, heat resistance and moldability (productivity) may be easily reduced.

[0378] In this specification and claims, the color difference b*, glass transition temperature Tg, refractive index nD, and weight average molecular weight Mw can be measured by the methods described in the examples below.

[0379] (Molded body) Molded articles may be prepared using the resin of the present invention. Molded articles contain at least the resin and have excellent optical properties, such as a high refractive index, a low absolute value of birefringence, and a low Abbe number, as well as high heat resistance. Therefore, they can be used as optical components such as optical films (or optical sheets) and optical lenses. Such molded articles may contain conventional additives. Examples of additives include fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, mold release agents, antistatic agents, dispersants, flow control agents, leveling agents, antifoaming agents, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, and stress-reducing agents. Examples of stabilizers include antioxidants, ultraviolet absorbers, and heat stabilizers. Examples of stress-reducing agents include silicone oil, silicone rubber, various plastic powders, and various engineering plastic powders. These additives may be used alone or in combination.

[0380] The molded article can be produced by, for example, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, casting molding, or the like.

[0381] The shape of the molded body is not particularly limited, and examples thereof include one-dimensional structures such as linear, fibrous (or fiber-like) and thread-like structures, two-dimensional structures such as film-like, sheet-like and plate-like structures, and three-dimensional structures such as concave or convex lens-like, rod-like and hollow (tubular) structures.

[0382] In particular, the resin of the present invention is useful for forming optical films because of its excellent optical properties, and therefore the present invention also includes films (optical films or optical sheets) formed from the resin.

[0383] The average thickness of such a film can be selected from the range of about 1 to 1000 μm depending on the application, and is, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably 10 to 120 μm.

[0384] Such a film (optical film) can be produced by forming (or molding) the resin using a conventional film-forming method, such as a casting method (solvent casting method), a melt extrusion method, or a calendar method.

[0385] The film may be a stretched film. The film of the present invention can maintain low birefringence even when stretched. Such a stretched film may be either a uniaxially stretched film or a biaxially stretched film.

[0386] The stretching ratio in each direction in uniaxial or biaxial stretching is, for example, 1.1 to 10 times, preferably 1.2 to 6 times, and more preferably 1.5 to 3 times. In the case of biaxial stretching, equal stretching, for example, stretching of about 1.5 to 5 times in both the longitudinal and transverse directions, or unbalanced stretching, for example, stretching of about 1.1 to 4 times in the longitudinal direction and about 2 to 6 times in the transverse direction, may be used. In the case of uniaxial stretching, longitudinal stretching, for example, stretching of about 2.5 to 8 times in the longitudinal direction, or transverse stretching, for example, stretching of about 1.2 to 5 times in the transverse direction, may be used.

[0387] The average thickness of the stretched film is, for example, 1 to 150 μm, preferably 3 to 120 μm, and more preferably 5 to 100 μm.

[0388] Such a stretched film can be obtained by stretching a film (or an unstretched film) after film formation. The stretching method is not particularly limited, and in the case of uniaxial stretching, either a wet stretching method or a dry stretching method may be used, and in the case of biaxial stretching, either a tenter method (flat method) or a tube method may be used, although the tenter method, which has excellent uniformity in stretched thickness, is preferred.

[0389] The molded article may be joined or adhered to another substrate, and the type and material of the substrate are not particularly limited, and may be, for example, a one-dimensional, two-dimensional, or three-dimensional substrate formed from a resin material, a ceramic material, a metal material, etc. For example, when the molded article is in the form of a film, it may be combined with a two-dimensional substrate such as a film to form a laminate or a laminate film.

[0390] Representative examples of the two-dimensional substrate include ceramic substrates such as glass substrates, resin films, etc., and are usually transparent substrates. Examples of the resin forming the resin film include polyolefin resins such as chain olefin resins and cyclic olefin resins (or cycloolefin resins); (meth)acrylic resins; styrene resins; polyester resins such as polyalkylene arylate resins, polyarylate resins, and polycarbonate resins; polyamide resins, etc., and among these, the resin film may be used by being stuck to a resin film formed from a cycloolefin resin, a polyamide resin, etc. [Example]

[0391] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. Details of evaluation items and raw materials are shown below.

[0392] [Evaluation method] (HPLC) The HPLC (high performance or high performance liquid chromatograph) was performed using a Shimadzu Corporation "Nexera-i LC-2040C Plus" column and a Shimadzu GLC Corporation "Luna PFP (2)" column. The sample was dissolved in acetonitrile to a 2000-fold dilution, and acetonitrile and 0.1% by mass phosphoric acid aqueous solution were used as the eluent. The HPLC purity of the main component and the proportion [area %] of the specified minor component were measured. The detection limit of the measurement device was 0.01% by area.

[0393] (GC) The sample was dried under reduced pressure at 80°C overnight, then dissolved in tetrahydrofuran or dioxane, and the amount of residual solvent (area %) was measured using a gas chromatography GC system (Shimadzu Corporation "GC-2014", column: CBP-1, detector: FID) at a measurement temperature range of 40 to 290°C. The detection limit of the measuring system was 0.01 area %.

[0394] (residual sulfur) Residual sulfur (total sulfur content) was measured in terms of sulfur atoms using the oxidative decomposition-ultraviolet fluorescence method using a Mitsubishi Chemical Analytech "TS-2100H."

[0395] (Hue APHA) 20 g of the sample was placed in a test tube, heated to 280°C under a nitrogen atmosphere, and held for 2 hours (molten sample). The hue of the sample was measured using a color difference turbidity meter ("COH-400" manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K0071.

[0396] (Hue YI) Hue (YI) [or yellowness index (YI)] was measured by melting the sample at 280°C for 2 hours under a nitrogen gas flow using a color and turbidity simultaneous measuring instrument ("COH-400" manufactured by Nippon Denshoku Industries Co., Ltd.).

[0397] (heated residue) The heating residue (mass %) was measured at 180°C using a measuring device (Mettler-Toledo HX204 Halogen Moisture Analyzer).

[0398] (bulk density) The bulk density [mg / mL] was measured according to the bulk density measurement method of the Japanese Pharmacopoeia.

[0399] (Melting Point) Using a differential scanning calorimeter (Hitachi High-Tech Science Corporation, "EXSTAR6000 DSC6220 ASD-2"), measurements were performed under conditions of a nitrogen atmosphere, a measurement temperature of 40 to 300°C, and a temperature rise rate of 10°C / min.

[0400] (Refractive index nD) The refractive index of the resin sample was measured as follows. The sample was heat-pressed at 200 to 240°C to form a film with a thickness of 200 to 300 μm. This film was cut into strips measuring 20 to 30 mm in length and 10 mm in width to obtain test pieces. The refractive index nD of the obtained test pieces at 589 nm (D line) was measured using a multi-wavelength Abbe refractometer (Atago Co., Ltd., "DR-M4 (circulating constant temperature water bath 60-C3)") at a measurement temperature of 20°C and diiodomethane as the contact liquid.

[0401] (molecular weight) The sample was dissolved in tetrahydrofuran (THF), and the weight average molecular weight Mw in terms of polystyrene was determined using gel permeation chromatography ("HLC-8320GPC" manufactured by Tosoh Corporation).

[0402] (glass transition temperature Tg) Measurement was carried out using a differential scanning calorimeter ("EXSTAR6000 DSC6220 ASD-2" manufactured by Hitachi High-Tech Science Corporation) in a nitrogen gas atmosphere at a temperature increase rate of 10°C / min.

[0403] (color difference b*) Using a spectrophotometer (Konica Minolta, "SPECTROPHOTOMETER CM-3500"), the b* value of the Lab color difference system was measured at room temperature (20 to 30°C), under reflective conditions, with a measurement diameter of 30 mm.

[0404] [Raw materials] (Reagents used in the preparation of BNEF) FLN: 9-Fluorenone, manufactured by Osaka Gas Chemicals Co., Ltd., 99.0% or more NEO: 2-(2-naphthoxy)ethanol, manufactured by Osaka Gas Chemicals Co., Ltd., 99.0% or more PHE: 2-phenoxyethanol, manufactured by Kanto Chemical Co., Ltd., 99.0% or more Concentrated sulfuric acid: 98% by mass, manufactured by Kanto Chemical Co., Ltd. β-mercaptopropionic acid: Tokyo Chemical Industry Co., Ltd., 98.0% or more Cysteamine: Tokyo Chemical Industry Co., Ltd., 95.0% or more Sulfolane: Tokyo Chemical Industry Co., Ltd., 99.0% or more BNF: 9,9-bis(6-hydroxy-2-naphthyl)fluorene, manufactured by Osaka Gas Chemicals Co., Ltd. Diethylene glycol: Kanto Chemical Co., Ltd., 99.0% or more 1-Methylimidazole: Wako Pure Chemical Industries, Ltd., 98.0% or more

[0405] (Resin raw material) EG: Ethylene glycol FDP-m: 9,9-bis(2-methoxycarbonylethyl)fluorene [or 9,9-bis(2-carboxyethyl)fluorene or dimethyl ester of fluorene-9,9-dipropionic acid], synthesized in the same manner as in Example 1 of JP-A-2005-89422, except that methyl acrylate [37.9 g (0.44 mol)] was used instead of t-butyl acrylate. BisA: Bisphenol A DPC: Diphenyl carbonate

[0406] Comparative Example 1 Preparation of BNEF (A) A 2-L separable flask was charged with 90.1 g (0.500 mol) of FLN, 470.2 g (2.500 mol) of NEO, 562.3 g of toluene, and 9.0 g (0.085 mol) of β-mercaptopropionic acid, and dissolved. After dissolution, 322.3 g of concentrated sulfuric acid was added dropwise at a temperature range of 40 to 45°C, and the mixture was stirred at 50°C for 4 hours. HPLC confirmed that the conversion of FLN was 99% or higher.

[0407] The resulting reaction mixture was pre-neutralized by adding 374.7 g of distilled water, 53.7 g of 48% by weight sodium hydroxide solution, and 280.9 g of dioxane. The mixture was then heated to 85-90°C and thoroughly stirred. The aqueous phase was removed, and the resulting organic phase was washed several times with distilled water. 249.8 g of distilled water, 7.4 g of concentrated sulfuric acid, and 107.3 g of 48% by weight sodium hydroxide solution were then added. The mixture was stirred at 100°C for 2 hours for strong alkali treatment. After removing the aqueous phase, 135.2 g of dioxane was added to the resulting organic phase, thoroughly washed with distilled water, 374.7 g of toluene was added, and cooling crystallization was carried out.

[0408] For cooling crystallization, seed crystals were added to the resulting solution (organic phase) at 40°C, and the solution was aged for 3 hours to precipitate crystals. The solution was then cooled to below 10°C at a rate of 10°C / hour. After the temperature reached below 10°C, the solution was aged for an additional 4 hours at a temperature range of 0 to 10°C, filtered, and rinsed with cold toluene adjusted to 0 to 10°C to obtain crude crystals. The resulting crude crystals were redissolved in 570.5 g of toluene, 285.5 g of dioxane, and 16.4 g of distilled water, and cooling crystallization was performed. For cooling crystallization, seed crystals were added to the resulting solution (organic phase) at 55°C, and the solution was aged for 3 hours at 55°C to precipitate crystals. The solution was then cooled to below 10°C at a rate of 10°C / hour. After the temperature reached 10°C or below, the mixture was aged for another 4 hours at a temperature ranging from 0 to 10°C, filtered, and rinsed with cold toluene adjusted to 0 to 10°C to obtain 168.7 g of the target product (9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF)) (yield: 63%, HPLC purity: 98.03%) (hereinafter, also referred to as BNEF(A)).

[0409] [Example 1] Preparation of BNEF(B) A 2-L separable flask was charged with 90.1 g (0.500 mol) of FLN, 376.5 g (2.000 mol) of NEO, 562.8 g of toluene, and 6.6 g (0.085 mol) of cysteamine, and dissolved. After dissolution, 322.6 g of concentrated sulfuric acid was added dropwise at a temperature range of 40 to 45°C, and the mixture was stirred at 45°C for 7 hours. HPLC confirmed that the conversion of FLN was 99% or higher.

[0410] To the resulting reaction solution, 375.7 g of distilled water and 281.2 g of dioxane were added, and the mixture was heated to 85°C and thoroughly stirred. The aqueous layer was removed. Subsequently, 107.5 g of 48% by mass aqueous sodium hydroxide, 187.4 g of dioxane, and 375.1 g of toluene were added, and the mixture was stirred at 95-100°C for 2 hours. After washing with water multiple times, 137.7 g of dioxane was added, and cooling crystallization was carried out. For cooling crystallization, seed crystals were added to the resulting solution (organic phase) at 45°C, and the mixture was aged at 45°C for 3 hours to precipitate crystals. The mixture was then cooled to below 10°C at a rate of 10°C / hour. After reaching below 10°C, the mixture was aged for an additional 4 hours at a temperature range of 0-10°C and filtered. The mixture was then rinsed with cold toluene adjusted to 0-10°C and filtered, and then rinsed with cold methanol adjusted to 0-10°C and filtered to obtain crude crystals. The resulting crude crystals were mixed with 649.0 g of methanol and stirred at 60 °C. The mixture was then cooled to room temperature (20-30 °C), filtered, and rinsed with methanol. The crude crystals were then dissolved in 787.0 g of acetone and aged at 30 °C. The precipitated FLN was removed by filtration. The filtrate was concentrated, and then 513.3 g of toluene, 157.4 g of dioxane, and 13.8 g of distilled water were added. Cooling crystallization was performed by adding seed crystals to the resulting solution (organic phase) at 50 °C and aging at 50 °C for 3 hours to precipitate crystals. The mixture was then cooled to below 10 °C at a rate of 10 °C / hour. After reaching below 10 °C, the mixture was aged for another 4 hours at a temperature range of 0-10 °C, filtered, and rinsed with toluene. The resulting crude crystals were then mixed with 792.0 g of methanol and stirred at 60 °C. The mixture was then cooled to room temperature (20 to 30°C), filtered, and rinsed with methanol to obtain 132.1 g of the target BNEF (yield 49%, HPLC purity 99.10%) (hereinafter simply referred to as BNEF(B)).

[0411] Comparative Example 2: Preparation of BNEF(C) A 2-L separable flask was charged with 90.1 g (0.500 mol) of FLN, 329.4 g (1.750 mol) of NEO, 281.4 g of toluene, and 6.6 g (0.085 mol) of cysteamine, and dissolved. After dissolution, 244.9 g of concentrated sulfuric acid was added dropwise at a temperature range of 40-50°C, followed by stirring at 50°C for 6 hours. 69.0 g of PHE was then added, and the mixture was stirred at 50°C for 3 hours. HPLC confirmed that the conversion of FLN was 99% or higher.

[0412] To the resulting reaction solution, 294.1 g of distilled water and 281.3 g of methyl ethyl ketone (MEK) were added, and the mixture was heated to 75°C and thoroughly stirred. The aqueous layer was removed. Subsequently, 230.4 g of 25% by mass aqueous sodium hydroxide solution and 230.4 g of distilled water were added, and the mixture was stirred at 75°C for 30 minutes. The aqueous layer was removed, and the mixture was washed multiple times with distilled water. Then, 11.9 g of distilled water was added, and cooling crystallization was carried out. For cooling crystallization, seed crystals were added to the resulting solution (organic phase) at 45°C, and the mixture was aged at 45°C for 3 hours to precipitate crystals. The mixture was then cooled to below 10°C at a rate of 10°C / hour. After the temperature reached below 10°C, the mixture was aged for another 4 hours at a temperature range of 0 to 10°C, filtered, rinsed with cold toluene adjusted to 0 to 10°C, and then further rinsed with cold methanol adjusted to 0 to 10°C and filtered to obtain crude crystals. To the obtained crude crystals, 623.5 g of methanol was added, and the mixture was stirred at 60°C and then cooled to room temperature (20-30°C). The mixture was then filtered and rinsed with methanol to obtain 152.3 g of the target BNEF (57% yield, 97.33% HPLC purity) (hereinafter simply referred to as BNEF(C)).

[0413] [Example 2] Preparation of BNEF(D) A 2-L separable flask was charged with 90.1 g (0.500 mol) of FLN, 329.4 g (1.750 mol) of NEO, 278.3 g of toluene, and 6.6 g (0.085 mol) of cysteamine, and dissolved. After dissolution, 245.0 g of concentrated sulfuric acid was added dropwise at a temperature range of 40-50°C, followed by stirring at 45-50°C for 6 hours. 69.2 g of PHE was then added, and the mixture was stirred at 45-50°C for 2 hours. HPLC confirmed that the conversion of FLN was 99% or higher.

[0414] 294.0 g of distilled water and 281.3 g of MEK were added to the resulting reaction solution, which was then heated to 75°C and thoroughly stirred. The aqueous layer was removed. 80.7 g of 48% by weight aqueous sodium hydroxide solution and 311.4 g of distilled water were then added, and the mixture was stirred at 75°C for 30 minutes. The aqueous layer was removed, and the mixture was washed multiple times with distilled water. 11.5 g of distilled water was then added, and cooling crystallization was carried out. For cooling crystallization, seed crystals were added to the resulting solution (organic phase) at 45°C, and the mixture was aged at 45°C for 3 hours to precipitate crystals. The mixture was then cooled to below 10°C at a rate of 10°C / hour. After reaching below 10°C, the mixture was aged for an additional 4 hours at a temperature range of 0 to 10°C and filtered. The mixture was then rinsed with cold toluene adjusted to 0 to 10°C and filtered, and then rinsed with cold methanol adjusted to 0 to 10°C and filtered to obtain crude crystals. To the obtained crude crystals, 737.5 g of methanol was added, stirred at 60 ° C, cooled to room temperature (20-30 ° C), and filtered to obtain crude crystals. 277.1 g of toluene, 83.1 g of acetone, 41.6 g of dioxane, and 10.0 g of distilled water were added to the obtained crude crystals, and redissolved at 70 ° C. After that, 41.6 g of dioxane was added and cooling crystallization was performed. For cooling crystallization, seed crystals were added to the obtained solution (organic phase) at 35 ° C., and the solution was aged at 35 ° C. for 3 hours to precipitate crystals, and then cooled to 10 ° C. or below at a rate of 10 ° C. / hour. After the temperature reached 10°C or below, the mixture was aged for another 4 hours at a temperature ranging from 0 to 10°C and then filtered. The mixture was then rinsed with cold toluene adjusted to 0 to 10°C and filtered, and then rinsed with cold methanol adjusted to 0 to 10°C and filtered to obtain 137.2 g of the desired BNEF (yield 51%, HPLC purity 99.24%) (hereinafter simply referred to as BNEF(D)).

[0415] [Example 3] Preparation of BNEF(E) A 2-L separable flask was charged with 90.1 g (0.500 mol) of FLN, 329.4 g (1.750 mol) of NEO, 280.8 g of toluene, and 6.6 g (0.085 mol) of cysteamine, and dissolved. After dissolution, 245.0 g of concentrated sulfuric acid was added dropwise at a temperature range of 40-50°C, followed by stirring at 40-50°C for 6 hours. 69.0 g of PHE was then added, and the mixture was stirred at 40-50°C for 3 hours. HPLC confirmed that the conversion of FLN was 99% or higher.

[0416] To the resulting reaction solution, 293.3 g of distilled water and 281.4 g of MEK were added, then the temperature was raised to 75°C and the mixture was thoroughly stirred, and the aqueous layer was removed. Subsequently, 80.5 g of 48% by mass aqueous sodium hydroxide solution and 312.1 g of distilled water were added, and the mixture was stirred at 75°C for 30 minutes, the aqueous layer was removed, and the mixture was washed multiple times with distilled water, followed by cooling crystallization. For cooling crystallization, seed crystals were added to the resulting solution (organic phase) at 45°C, and the mixture was aged at 45°C for 3 hours to precipitate crystals, followed by cooling to below 10°C at a rate of 10°C / hour. After reaching below 10°C, the mixture was aged for an additional 4 hours at a temperature range of 0 to 10°C, filtered, rinsed with cold toluene adjusted to 0 to 10°C, and then further rinsed with cold methanol adjusted to 0 to 10°C and filtered to obtain crude crystals. The resulting crude crystals were redissolved in 282.8 g of toluene and 283.0 g of MEK, 7.7 g of distilled water was added, and the mixture was concentrated. After 352.7 g of toluene was added, cooling crystallization was performed. For cooling crystallization, seed crystals were added to the resulting solution (organic phase) at 45 °C, and the mixture was aged at 45 °C for 3 hours to precipitate crystals. The mixture was then cooled to room temperature (20-30 °C) at a rate of 10 °C / hour and filtered. The mixture was then rinsed with cold toluene adjusted to 0-10 °C, and then further rinsed with cold methanol adjusted to 0-10 °C to obtain crude crystals. 500.4 g of methanol was added to the crude crystals, stirred at 60 °C, and cooled to room temperature (20-30 °C). The mixture was then filtered and rinsed with methanol to obtain 141.2 g of the desired BNEF (53% yield, 98.33% HPLC purity) (hereinafter simply referred to as BNEF(E)).

[0417] [Example 4] Preparation of BNEF(F) A 2-L separable flask was charged with 90.1 g (0.500 mol) of FLN, 282.4 g (1.500 mol) of NEO, 210.4 g of toluene, 6.6 g (0.085 mol) of cysteamine, and 15.0 g (0.125 mol) of sulfolane, and dissolved. After dissolution, 245.3 g of concentrated sulfuric acid was added dropwise at a temperature range of 25-40°C, followed by stirring at 40°C for 12 hours. Further addition of 69.1 g of PHE was followed by stirring at 40°C for 3 hours. The conversion of FLN was confirmed to be over 99% by HPLC.

[0418] To the resulting reaction solution, 294.3 g of distilled water, 56.2 g of toluene, and 281.3 g of MEK were added, and the mixture was heated to 75°C and thoroughly stirred. The aqueous layer was removed. Subsequently, 80.6 g of 48% by weight aqueous sodium hydroxide solution and 312.8 g of distilled water were added, and the mixture was stirred at 75°C for 30 minutes. The aqueous layer was removed, and the mixture was washed with distilled water several times, followed by cooling crystallization. For cooling crystallization, seed crystals were added to the resulting solution (organic phase) at 40°C, and the mixture was aged at 40°C for 3 hours to precipitate crystals. The mixture was then cooled to below 10°C at a rate of 10°C / hour. After the temperature reached below 10°C, the mixture was aged for another 4 hours at a temperature range of 0 to 10°C and filtered. The mixture was then rinsed with cold toluene adjusted to 0 to 10°C and filtered, and then rinsed with cold methanol adjusted to 0 to 10°C and filtered to obtain crude crystals. To the obtained crude crystals, 657.6 g of methanol was added, and the mixture was stirred at 60°C and then cooled to room temperature (20-30°C). The mixture was then filtered and rinsed with methanol to obtain 162.2 g of the target BNEF (yield 60%, HPLC purity 98.56%) (hereinafter simply referred to as BNEF(F)).

[0419] [Example 5] Preparation of BNEF(G) A 2-liter separable flask was charged with 90.0 g (0.2 mol) of BNF, 88.1 g (2.0 mol) of ethylene oxide gas, and 300 g (3.4 mol) of diethylene glycol as a solvent. 2 g of 1-methylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst, and the mixture was heated to 100°C and reacted for 5 hours.

[0420] After the reaction was completed, 1000 mL of isopropyl alcohol was added and cooling crystallization was performed. The mixture was cooled from 75°C to room temperature (20-30°C) at a rate of 10°C / hour. After crystallization, the mixture was aged at room temperature (20-30°C) for 3 hours to precipitate crystals, and then cooled to below 10°C at a rate of 10°C / hour. After reaching below 10°C, the mixture was aged for an additional 4 hours at a temperature range of 0-10°C. The mixture was filtered and rinsed with cold isopropyl alcohol adjusted to 0-10°C to obtain 80.7 g of the desired BNEF (75% yield, 93.76% HPLC purity) (hereinafter simply referred to as BNEF(G)).

[0421] Example 6 Preparation of BNEF(H) A 2-liter separable flask was charged with 90.0 g (0.2 mol) of BNF, 70.5 g (1.6 mol) of ethylene oxide gas, and 300 g (3.4 mol) of diethylene glycol as a solvent. 2 g of 1-methylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst, and the mixture was heated to 100°C and reacted for 5 hours.

[0422] After the reaction was completed, 1000 mL of isopropyl alcohol was added and cooling crystallization was performed. The mixture was cooled from 75°C to room temperature (20-30°C) at a rate of 10°C / hour. After crystallization, the mixture was aged at room temperature (20-30°C) for 3 hours to precipitate crystals, and then cooled to below 10°C at a rate of 10°C / hour. After reaching below 10°C, the mixture was aged for an additional 4 hours at a temperature range of 0-10°C. The mixture was filtered and rinsed with cold isopropyl alcohol adjusted to 0-10°C to obtain 74.6 g of the desired BNEF (yield 69.3%, HPLC purity 94.44%) (hereinafter simply referred to as BNEF(H)).

[0423] [Example 7] Preparation of BNEF (I) A 2-L separable flask was charged with 90.1 g (0.500 mol) of FLN, 282.4 g (1.500 mol) of NEO, 210.4 g of toluene, 6.6 g (0.085 mol) of cysteamine, and 21.0 g (0.18 mol) of sulfolane, and dissolved. After dissolution, 245.0 g of concentrated sulfuric acid was added dropwise at a temperature range of 25 to 40°C, followed by stirring at 40°C for 3 hours. 96.7 g of PHE was then added and stirred at 40°C for 4 hours. 24.5 g of concentrated sulfuric acid was added and stirred at 40°C for 5 hours. The conversion of FLN was confirmed to be over 99% by HPLC.

[0424] To the resulting reaction solution, 452.8 g of distilled water, 70.0 g of toluene, and 281.3 g of MEK were added, and the mixture was heated to 95°C and thoroughly stirred. The aqueous layer was removed. Subsequently, 89.8 g of 48% by weight aqueous sodium hydroxide solution and 204.8 g of distilled water were added, and the mixture was stirred at 75°C for 30 minutes. The aqueous layer was removed, and the mixture was washed with distilled water several times, followed by cooling crystallization. For cooling crystallization, seed crystals were added to the resulting solution (organic phase) at 50°C, and the mixture was aged at 40°C for 4 hours to precipitate crystals. The mixture was then cooled to below 10°C at a rate of 10°C / hour. After reaching below 10°C, the mixture was aged for another 4 hours at a temperature range of 0 to 10°C and filtered. The mixture was then rinsed with cold toluene adjusted to 0 to 10°C and filtered, and then rinsed with cold methanol adjusted to 0 to 10°C and filtered to obtain crude crystals. To the obtained crude crystals, 712.9 g of methanol was added, and the mixture was stirred at 60°C and then cooled to room temperature (20-30°C). The mixture was then filtered and rinsed with methanol to obtain 167.0 g of the target BNEF (yield 62%, HPLC purity 99.36%) (hereinafter simply referred to as BNEF(I)).

[0425] [Example 8] Preparation of BNEF(J) A 2-L separable flask was charged with 90.1 g (0.500 mol) of FLN, 282.4 g (1.500 mol) of NEO, 210.4 g of toluene, 6.6 g (0.085 mol) of cysteamine, and 21.0 g (0.18 mol) of sulfolane, and dissolved. After dissolution, 245.0 g of concentrated sulfuric acid was added dropwise at a temperature range of 25 to 40°C, followed by stirring at 40°C for 3 hours. 96.7 g of PHE was then added and stirred at 40°C for 4 hours. 24.5 g of concentrated sulfuric acid was added and stirred at 40°C for 5 hours. The conversion of FLN was confirmed to be over 99% by HPLC.

[0426] To the resulting reaction solution, 452.8 g of distilled water, 70.0 g of toluene, and 281.3 g of MEK were added, and the mixture was heated to 95°C and thoroughly stirred. The aqueous layer was removed. Subsequently, 89.8 g of 48% by weight aqueous sodium hydroxide solution and 204.8 g of distilled water were added, and the mixture was stirred at 75°C for 30 minutes. The aqueous layer was removed, and the mixture was washed with distilled water several times, followed by cooling crystallization. For cooling crystallization, seed crystals were added to the resulting solution (organic phase) at 50°C, and the mixture was aged at 40°C for 4 hours to precipitate crystals. The mixture was then cooled to below 10°C at a rate of 10°C / hour. After reaching below 10°C, the mixture was aged for another 4 hours at a temperature range of 0 to 10°C and filtered. The mixture was then rinsed with cold toluene adjusted to 0 to 10°C and filtered, and then rinsed with cold methanol adjusted to 0 to 10°C and filtered to obtain crude crystals. The resulting crude crystals were dissolved in 404.0 g of methyl ethyl ketone (hereinafter referred to as MEK) and 712.9 g of toluene at 80°C, followed by cooling crystallization. For cooling crystallization, seed crystals were added to the resulting solution (organic phase) at 50°C, and the solution was aged at 40°C for 4 hours to precipitate crystals. The solution was then cooled to below 10°C at a rate of 10°C / hour. After reaching below 10°C, the solution was aged for another 4 hours in the temperature range of 0 to 10°C, filtered, rinsed with cold toluene adjusted to 0 to 10°C, and then filtered. Finally, the solution was rinsed with cold methanol adjusted to 0 to 10°C to obtain 123.6 g of the desired BNEF (45.9% yield, 99.59% HPLC purity) (hereinafter referred to simply as BNEF(J)).

[0427] [Comparative Example 3] Preparation of polyester resin A reactor was charged with BNEF(A) (64.1 g (0.119 mol)) and EG (22.1 g (0.357 mol)) as diol components, FDP-m (53.7 g (0.159 mol)) as a dicarboxylic acid component, and 858.8 mg of a 1.0 mass% ethylene glycol solution of manganese(II) acetate tetrahydrate (8.6 mg (0.04 mmol)), 4402.2 mg of a 0.9 mass% aqueous solution of germanium(IV) oxide (39.6 mg (0.28 mmol)), and 1243.7 mg of a 1.0 mass% aqueous solution of trimethyl phosphate (12.4 mg (0.09 mmol)) as catalysts for the transesterification reaction and polycondensation reaction. The mixture was gradually heated to 250°C under a nitrogen gas atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 275°C and the pressure was reduced to 330 Pa, and the polycondensation reaction was carried out while removing EG until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0428] [Example 9] Preparation of polyester resin A reactor was charged with the following diol components: BNEF(B) (69.9 g (0.130 mol)), EG (24.2 g (0.389 mol)), FDP-m (58.5 g (0.173 mol)), and the following catalysts for the transesterification and polycondensation reactions: manganese(II) acetate tetrahydrate (9.4 mg (0.04 mmol)) in a 1.0 mass% ethylene glycol solution (936.9 mg), germanium(IV) oxide (43.2 mg (0.42 mmol)) in a 0.9 mass% aqueous solution (4802.4 mg), and trimethyl phosphate (12.2 mg (0.10 mmol)) in a 1.0 mass% aqueous solution (1356.8 mg). The mixture was gradually heated to 250°C under a nitrogen gas atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 275°C and the pressure was reduced to 410 Pa, and the polycondensation reaction was carried out while removing EG until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0429] [Comparative Example 4] Preparation of polyester resin A reactor was charged with BNEF(C) (46.6 g (0.087 mol)) and EG (16.1 g (0.259 mol)) as diol components, FDP-m (39.0 g (0.115 mol)) as dicarboxylic acid component, and 624.6 mg of a 1.0 mass% ethylene glycol solution of manganese(II) acetate tetrahydrate (6.3 mg (0.03 mmol)), 3201.6 mg of a 0.9 mass% aqueous solution of germanium(IV) oxide (28.8 mg (0.28 mmol)), and 904.5 mg of a 1.0 mass% aqueous solution of trimethyl phosphate (9.1 mg (0.06 mmol)) as catalysts for the transesterification reaction and polycondensation reaction. The mixture was gradually heated to 250°C under a nitrogen gas atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 275°C and the pressure was reduced to 570 Pa, and the polycondensation reaction was carried out while removing EG until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0430] [Example 10] Preparation of polyester resin A reactor was charged with BNEF(D) (69.9 g (0.130 mol)) and EG (24.2 g (0.389 mol)) as diol components, FDP-m (58.5 g (0.173 mol)) as a dicarboxylic acid component, and 936.9 mg of a 1.0 mass% ethylene glycol solution of manganese(II) acetate tetrahydrate (9.4 mg (0.04 mmol)), 4802.4 mg of a 0.9 mass% aqueous solution of germanium(IV) oxide (43.2 mg (0.42 mmol)), and 1356.8 mg of a 1.0 mass% aqueous solution of trimethyl phosphate (12.2 mg (0.10 mmol)) as catalysts for the transesterification reaction and polycondensation reaction. The mixture was gradually heated to 250°C under a nitrogen gas atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 275°C and the pressure was reduced to 330 Pa, and the polycondensation reaction was carried out while removing EG until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0431] [Example 11] Preparation of polyester resin A reactor was charged with BNEF(E) (69.9 g (0.130 mol)) and EG (24.2 g (0.389 mol)) as diol components, FDP-m (58.5 g (0.173 mol)) as a dicarboxylic acid component, and 936.9 mg of a 1.0 mass% ethylene glycol solution of manganese(II) acetate tetrahydrate (9.4 mg (0.04 mmol)), 4802.4 mg of a 0.9 mass% aqueous solution of germanium(IV) oxide (43.2 mg (0.42 mmol)), and 1356.8 mg of a 1.0 mass% aqueous solution of trimethyl phosphate (12.2 mg (0.10 mmol)) as catalysts for the transesterification reaction and polycondensation reaction. The mixture was gradually heated to 250°C under a nitrogen gas atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 275°C and the pressure was reduced to 530 Pa, and the polycondensation reaction was carried out while removing EG until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0432] [Example 12] Preparation of polyester resin A reactor was charged with BNEF(F) (69.9 g (0.130 mol)) and EG (24.2 g (0.389 mol)) as diol components, FDP-m (58.5 g (0.173 mol)) as a dicarboxylic acid component, and 936.9 mg of a 1.0 mass% ethylene glycol solution of manganese(II) acetate tetrahydrate (9.4 mg (0.04 mmol)), 4802.4 mg of a 0.9 mass% aqueous solution of germanium(IV) oxide (43.2 mg (0.42 mmol)), and 1356.8 mg of a 1.0 mass% aqueous solution of trimethyl phosphate (12.2 mg (0.10 mmol)) as catalysts for the transesterification reaction and polycondensation reaction. The mixture was gradually heated to 250°C under a nitrogen gas atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 275°C and the pressure was reduced to 440 Pa, and the polycondensation reaction was carried out while removing EG until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0433] [Example 13] Preparation of polyester resin A reactor was charged with BNEF(G) (69.9 g (0.130 mol)) and EG (24.2 g (0.389 mol)) as diol components, FDP-m (58.5 g (0.173 mol)) as a dicarboxylic acid component, and 936.9 mg of a 1.0 mass% ethylene glycol solution of manganese(II) acetate tetrahydrate (9.4 mg (0.04 mmol)), 4802.4 mg of a 0.9 mass% aqueous solution of germanium(IV) oxide (43.2 mg (0.42 mmol)), and 1356.8 mg of a 1.0 mass% aqueous solution of trimethyl phosphate (12.2 mg (0.10 mmol)) as catalysts for the transesterification reaction and polycondensation reaction. The mixture was gradually heated to 250°C under a nitrogen gas atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 275°C and the pressure was reduced to 560 Pa, and the polycondensation reaction was carried out while removing EG until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0434] [Example 14] Preparation of polyester resin A reactor was charged with BNEF(H) (69.9 g (0.130 mol)) and EG (24.2 g (0.389 mol)) as diol components, FDP-m (58.5 g (0.173 mol)) as a dicarboxylic acid component, and 936.9 mg of a 1.0 mass% ethylene glycol solution of manganese(II) acetate tetrahydrate (9.4 mg (0.04 mmol)), 4802.4 mg of a 0.9 mass% aqueous solution of germanium(IV) oxide (43.2 mg (0.42 mmol)), and 1356.8 mg of a 1.0 mass% aqueous solution of trimethyl phosphate (12.2 mg (0.10 mmol)) as catalysts for the transesterification reaction and polycondensation reaction. The mixture was gradually heated to 250°C under a nitrogen gas atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 275°C and the pressure was reduced to 370 Pa, and the polycondensation reaction was carried out while removing EG until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0435] [Example 15] Preparation of polyester resin A reactor was charged with BNEF(I) (69.9 g (0.130 mol)) and EG (24.2 g (0.389 mol)) as diol components, FDP-m (58.5 g (0.173 mol)) as dicarboxylic acid component, and 936.9 mg of a 1.0 mass% ethylene glycol solution of manganese(II) acetate tetrahydrate (9.4 mg (0.04 mmol)), 4802.4 mg of a 0.9 mass% aqueous solution of germanium(IV) oxide (43.2 mg (0.42 mmol)), and 1356.8 mg of a 1.0 mass% aqueous solution of trimethyl phosphate (12.2 mg (0.10 mmol)) as catalysts for the transesterification reaction and polycondensation reaction. The mixture was gradually heated to 250°C under a nitrogen gas atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 275°C and the pressure was reduced to 280 Pa, and the polycondensation reaction was carried out while removing EG until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0436] [Example 16] Preparation of polyester resin A reactor was charged with BNEF(J) (69.9 g (0.130 mol)) and EG (24.2 g (0.389 mol)) as diol components, FDP-m (58.5 g (0.173 mol)) as a dicarboxylic acid component, and 936.9 mg of a 1.0 mass% ethylene glycol solution of manganese(II) acetate tetrahydrate (9.4 mg (0.04 mmol)), 4802.4 mg of a 0.9 mass% aqueous solution of germanium(IV) oxide (43.2 mg (0.42 mmol)), and 1356.8 mg of a 1.0 mass% aqueous solution of trimethyl phosphate (12.2 mg (0.10 mmol)) as catalysts for the transesterification reaction and polycondensation reaction. The mixture was gradually heated to 250°C under a nitrogen gas atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 275°C and the pressure was reduced to 310 Pa, and the polycondensation reaction was carried out while removing EG until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0437] [Comparative Example 5] Preparation of polycarbonate resin As diol components, BNEF(A) (60.4 g (112.1 mmol)) and BisA (25.6 g (112.1 mmol)), DPC (50.4 g (235.4 mmol)), and 65.8 mg of sodium bicarbonate (0.33 mg (3.9 μmol)) as a transesterification catalyst in the form of a 0.5 mass% aqueous solution were added, gradually heated to melt while stirring, and the temperature was raised to 250 ° C. After that, the temperature was gradually raised to 275 ° C. and 520 Pa, and phenol was removed while reducing the pressure. After reaching the predetermined stirring torque, the contents were removed from the reactor, and a polycarbonate resin was obtained.

[0438] [Example 17] Preparation of polycarbonate resin As diol components, BNEF(B) (67.1 g (124.5 mmol)) and BisA (28.4 g (124.5 mmol)), DPC (56.0 g (261.5 mmol)), and 51.2 mg of sodium bicarbonate (0.37 mg (4.3 μmol)) as a transesterification catalyst in the form of a 0.5% by mass aqueous solution were added, gradually heated to melt with stirring, and the temperature was raised to 250 ° C. After that, the temperature was gradually raised to 275 ° C. and 490 Pa, and phenol was removed while reducing the pressure. After reaching the predetermined stirring torque, the contents were removed from the reactor, and a polycarbonate resin was obtained.

[0439] [Comparative Example 6] Preparation of polycarbonate resin BNEF(C) (53.7 g (99.6 mmol)) and BisA (22.8 g (99.6 mmol)) as diol components, DPC (44.8 g (209.2 mmol)), and 58.5 mg of sodium bicarbonate (0.29 mg (3.5 μmol)) as a transesterification catalyst in the form of a 0.5 mass% aqueous solution were added, gradually heated to melt with stirring, and the temperature was raised to 250 ° C. After that, the temperature was gradually raised to 275 ° C. and 480 Pa, and phenol was removed while the pressure was reduced. After the predetermined stirring torque was reached, the contents were removed from the reactor, and a polycarbonate resin was obtained.

[0440] [Example 18] Preparation of polycarbonate resin As diol components, BNEF(D) (67.1 g (124.5 mmol)) and BisA (28.4 g (124.5 mmol)), DPC (56.0 g (261.5 mmol)), and 51.2 mg of sodium bicarbonate (0.37 mg (4.3 μmol)) as a 0.5 mass% aqueous solution as a transesterification catalyst were added, gradually heated to melt with stirring, and the temperature was raised to 250 ° C. After that, the temperature was gradually raised to 275 ° C. and 390 Pa, and phenol was removed while reducing the pressure. After reaching the predetermined stirring torque, the contents were removed from the reactor, and a polycarbonate resin was obtained.

[0441] [Example 19] Preparation of polycarbonate resin As diol components, BNEF(E) (67.1 g (124.5 mmol)) and BisA (28.4 g (124.5 mmol)), DPC (56.0 g (261.5 mmol)), and 51.2 mg of sodium bicarbonate (0.37 mg (4.3 μmol)) as a transesterification catalyst in the form of a 0.5% by mass aqueous solution were added, gradually heated to melt with stirring, and the temperature was raised to 250 ° C. After that, the temperature was gradually raised to 275 ° C. and 680 Pa, and phenol was removed while the pressure was reduced. After the predetermined stirring torque was reached, the contents were removed from the reactor, and a polycarbonate resin was obtained.

[0442] [Example 20] Preparation of polycarbonate resin As diol components, BNEF(F) (67.1 g (124.5 mmol)) and BisA (28.4 g (124.5 mmol)), DPC (56.0 g (261.5 mmol)), and 51.2 mg of sodium bicarbonate (0.37 mg (4.3 μmol)) as a 0.5 mass% aqueous solution as a transesterification catalyst were added, gradually heated to melt while stirring, and the temperature was raised to 250 ° C. After that, the temperature was gradually raised to 275 ° C. and 810 Pa, and phenol was removed while reducing the pressure. After reaching the predetermined stirring torque, the contents were removed from the reactor, and a polycarbonate resin was obtained.

[0443] [Example 21] Preparation of polycarbonate resin BNEF(H) (67.1 g (124.5 mmol)) and BisA (28.4 g (124.5 mmol)) as diol components, DPC (56.0 g (261.5 mmol)), and 51.2 mg of sodium bicarbonate (0.37 mg (4.3 μmol)) as a transesterification catalyst in the form of a 0.5 mass% aqueous solution were added, gradually heated to melt with stirring, and the temperature was raised to 250 ° C. After that, the temperature was gradually raised to 275 ° C. and 490 Pa, and phenol was removed while the pressure was reduced. After the predetermined stirring torque was reached, the contents were removed from the reactor, and a polycarbonate resin was obtained.

[0444] [Example 22] Preparation of polycarbonate resin As diol components, BNEF (I) (67.1 g (124.5 mmol)) and BisA (28.4 g (124.5 mmol)), DPC (56.0 g (261.5 mmol)), and 51.2 mg of sodium bicarbonate (0.37 mg (4.3 μmol)) as a 0.5 mass% aqueous solution as a transesterification catalyst were added, gradually heated to melt while stirring, and the temperature was raised to 250 ° C. After that, the temperature was gradually raised to 275 ° C. and 490 Pa, and phenol was removed while reducing the pressure. After reaching the predetermined stirring torque, the contents were removed from the reactor, and a polycarbonate resin was obtained.

[0445] [Example 23] Preparation of polycarbonate resin BNEF(J) (67.1 g (124.5 mmol)) and BisA (28.4 g (124.5 mmol)) as diol components, DPC (56.0 g (261.5 mmol)), and 51.2 mg of sodium bicarbonate (0.37 mg (4.3 μmol)) as a transesterification catalyst in the form of a 0.5% by mass aqueous solution were added, gradually heated to melt with stirring, and the temperature was raised to 250°C. After that, the temperature was gradually raised to 275°C and the pressure was reduced to 490 Pa, and phenol was removed while the pressure was reduced. After the predetermined stirring torque was reached, the contents were removed from the reactor, and a polycarbonate resin was obtained.

[0446] The evaluation results of the Examples and Comparative Examples are shown in Tables 1 to 4. In Table 1, "1EO isomer" refers to the compound represented by the formula (4) Z 3a and Z 3b is a naphthalene ring, n5 is 0, n6a and n6b are 0, A 3b is an ethylene group, m3a is 0, and m3b is 1, that is, an impurity component (a) represented by the following formula:

[0447] [ka]

[0448] The "3EO form" means 9-(6-hydroxy-2-naphthyl)-9-[6-(2-hydroxyethoxy)-2-naphthyl]fluorene represented by the formula (4):3a and Z 3b is a naphthalene ring, n5 is 0, n6a and n6b are 0, A 3a and A 3b is an ethylene group, m3a is 1, and m3b is 2, that is, an impurity component (a) represented by the following formula:

[0449] [ka]

[0450] and "trifunctional compound" means 9-[6-(2-hydroxyethoxy)-2-naphthyl]-9-[6-(2-(2-hydroxyethoxy)ethoxy)-2-naphthyl]fluorene represented by the formula (11); 8a and Z 8b is a naphthalene ring, n17 is 0, n18a and n18b are 0, A 8a ~A 8c is an ethylene group, m8a, m8b and m8c are 1, and m8d is 0, that is, an impurity component (h) represented by the following formula:

[0451] [ka]

[0452] "MIBK" means methyl isobutyl ketone; "MEK" means methyl ethyl ketone; "MeOH" means methanol; and "nd" indicates that the result was below the detection limit of the measuring device.

[0453] [Table 1]

[0454] [Table 2]

[0455] [Table 3]

[0456] [Table 4]

[0457] As is clear from Tables 1 to 4, in the Examples, discoloration during melting or after polymerization was suppressed and the glass transition temperature (Tg) of the resin was higher than in the Comparative Examples. In particular, in the Examples using BNEF(B), BNEF(D), BNEF(E), BNEF(I), and BNEF(J), which have relatively high purity and particularly low amounts of FLN, NEO, and residual sulfur, discoloration suppression and heat resistance of the resin were excellent.

[0458] Those skilled in the art would recognize that an improvement in Tg of 3°C or more indicates a significant difference in resin performance. In particular, Example 19, which used BNEF (E), showed a significant improvement in Tg. Impurities that affect Tg are presumably FLN and residual sulfur. However, the improvement of 3°C or more was surprising compared to Example 17, which used BNEF (B), which had a FLN content of approximately 1 / 11 and a similar amount of residual sulfur, and Example 18, which used BNEF (D), which had a similar amount of FLN and residual sulfur. While the reasons for this are unclear, the main factors are presumably the low FLN content and low residual sulfur, as well as the presence of a specific proportion of 1EO units (as seen in Examples 18 and 19 (Examples 2 and 3)) and the high proportion of BNEF-derived structural units relative to the overall resin (as seen in Examples 11 and 19).

[0459] Furthermore, in Examples 13 and 14, which used BNEFs (G) and (H) containing trifunctional units, the molecular weight of the polyester resin was improved, and a particularly remarkable effect was observed in Example 14, which used BNEF (H), which contained a high proportion of trifunctional units. Furthermore, in Example 21, which used BNEF (H), the molecular weight of the polycarbonate resin was also improved. [Industrial Applicability]

[0460] The fluorene compound of the present invention has excellent heat resistance and can suppress coloration, and therefore can be effectively used as a resin raw material or an additive (or resin additive) such as a heat resistance improver or a refractive index improver.

[0461] Furthermore, resins using the fluorene compound of the present invention as a raw material (or polymerization component) not only have high heat resistance and can suppress coloration, but also exhibit excellent optical properties such as a high refractive index, a low Abbe number, and a low birefringence, and therefore may be used in a variety of applications, such as coating agents or coating films, specifically, protective films for paints, inks, electronic devices, liquid crystal components, etc.; adhesives, pressure-sensitive adhesives; resin fillers; electric and electronic materials or electric and electronic components (electric and electronic devices), specifically, antistatic agents, carrier transport agents, light-emitting bodies, organic photoreceptors, thermosensitive recording materials, photochromic materials, hologram recording materials, charging trays, conductive sheets, optical disks, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, EMI shielding films, etc.; and mechanical materials or mechanical components (equipment), specifically, automotive materials or components, aerospace-related materials or components, sliding members, etc.

[0462] The resin of the present invention satisfies a good balance between excellent optical properties and high heat resistance, and can therefore be used particularly effectively as an optical member.

[0463] Representative optical members include optical films (optical sheets) such as films for liquid crystal displays and organic EL displays; optical lenses such as lenses for glasses and cameras; prisms, holograms, and optical fibers.

[0464] Examples of optical films include polarizing films, polarizing elements and polarizing plate protective films that constitute polarizing films, retardation films, alignment films (alignment films), viewing angle widening (compensation) films, diffuser plates (films), prism sheets, light guide plates, brightness enhancement films, near-infrared absorbing films, reflective films, anti-reflection (AR) films, reflection reducing (LR) films, anti-glare (AG) films, transparent conductive (ITO) films, anisotropic conductive films (ACF), electromagnetic shielding (EMI) films, films for electrode substrates, films for color filter substrates, barrier films, color filter layers, black matrix layers, and adhesive layers or release layers between optical films. These optical films can be effectively used as optical films for displays such as liquid crystal displays (LCDs), organic light-emitting diode displays (OLEDs), plasma displays (PDPs), field emission displays (FEDs), and electronic paper.Specific devices or apparatuses include televisions; personal computers (PCs) such as desktop PCs, notebook PCs, and tablet PCs; smartphones, mobile phones; car navigation systems; and devices or apparatuses equipped with flat panel displays (FPDs) such as touch panels.

[0465] Examples of optical lenses include eyeglass lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar concentrating lenses, objective lenses, and rod lens arrays. In particular, the resins of the present invention are suitable for use in lenses that require a low Abbe number, such as camera lenses. Typical examples of devices or apparatuses that incorporate such optical lenses include small or mobile devices with camera functions, such as smartphones, mobile phones, and digital cameras; and in-vehicle cameras, such as drive recorders and backup cameras (rear cameras). In particular, the resins of the present invention have high heat resistance and are therefore suitable for use in applications where high-temperature environments are anticipated, such as in-vehicle optical lenses.

Claims

1. The following formula (1) 【Chemical 1】 (In the formula, Z １ａ and Z １ｂ each independently represents a naphthalene ring, R １ represents a substituent, n1 represents an integer of 0 to 8, R ２ａ and R ２ｂ each independently represents a substituent; n2a and n2b each independently represent an integer of 0 or more; A １ａ and A １ｂ each independently represents a linear or branched alkylene group; The following formula (2) 【Chemistry 2】 (In the formula, R ３ represents a substituent, and n3 represents an integer of 0 to 8. The content of the compound represented by the formula (I) is 0.5% or less in terms of HPLC area ratio, The following formula (3) 【Chemistry 3】 (In the formula, Z ２ indicates an arene ring, R ４ represents a substituent, n4 represents an integer of 0 or more, A ２ represents a linear or branched alkylene group. The content of the compound represented by the formula (I) is 0.3% or less in terms of HPLC area percentage, The following formula (4) 【Chemistry 4】 (In the formula, Z ３ａ and Z ３ｂ each independently represents an arene ring, R ５ represents a substituent, n5 represents an integer of 0 to 8, R ６ａ and R ６ｂ each independently represents a substituent; n6a and n6b each independently represent an integer of 0 or more; A ３ａ and A ３ｂ each independently represents a linear or branched alkylene group, and m3a and m3b each independently represent an integer of 0 or more. ３ａ and Z ３ｂ are polycyclic arene rings, m3a and m3b cannot be 1 at the same time.) The content of the compound represented by the formula (I) is 0.01 to 10% in terms of HPLC area ratio, A compound having a residual sulfur content of 10 ppm by mass or less.

2. The content of the compound represented by the formula (2) is 0.2% or less, the content of the compound represented by the formula (3) is 0.05% or less, and residual sulfur is 1.5 mass ppm or less. The compound according to claim 1.

3. 3. The compound according to claim 1, wherein the content of a compound in which one of m3a and m3b is 0 and the other is 1 in formula (4) is 0.01 to 1% by area percentage in HPLC.

4. The compound according to any one of claims 1 to 3, wherein the content of a compound in which, in formula (4), one of m3a and m3b is 1 and the other is 2 is 0.01 to 5% in terms of HPLC area percentage.

5. The following formula (11) 【Chemistry 5】 (In the formula, Z ８ａ and Z ８ｂ each independently represents an arene ring, R １７ represents a substituent, n17 represents an integer of 0 to 8, R １８ａ and R １８ｂ each independently represents a substituent; n18a and n18b each independently represent an integer of 0 or more; A ８ａ ~A ８ｄ each independently represents a linear or branched alkylene group, m8a and m8b each independently represent an integer of 0 or more, and m8c and m8d each independently represent an integer of 0 to 2, provided that m8c and m8d are not simultaneously 0. The compound according to any one of claims 1 to 4, wherein the content of the compound represented by the formula (I) is 0.01 to 10% in terms of area percentage by HPLC.

6. A resin comprising the compound according to any one of claims 1 to 5 as a resin raw material.

7. The resin according to claim 6, which is a thermoplastic resin containing an ester bond in the main chain.

8. 8. The resin according to claim 6, which is a thermoplastic resin containing a carbonate bond in the main chain.

9. A method for suppressing coloration of the compound represented by formula (1) according to claim 1 in a molten state by adjusting the content of the compound represented by formula (2) according to claim 1 to 0.5% or less in terms of an area percentage by HPLC, the content of the compound represented by formula (3) according to claim 1 to 0.3% or less in terms of an area percentage by HPLC, the content of the compound represented by formula (4) according to claim 1 to 0.01 to 10% in terms of an area percentage by HPLC, and residual sulfur to 10 ppm by mass or less.

10. A method for improving the glass transition temperature of a resin obtained by using the compound according to any one of claims 1 to 5 as a resin raw material.

11. A method for reducing b* of a resin obtained by using the compound according to any one of claims 1 to 5 as a resin raw material.

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