Compounds, resins, polycarbonate resins and optical molded bodies

Abstract

This invention relates to compounds, resins, polycarbonate resins, and optically molded articles. A compound represented by general formula (1). In general formula (1), Ar1 and Ar2 independently represent groups selected from the following: wherein R1 to R6 represent hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms; A1 to A5 and B1 to B5 represent hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms; at least one of A1 to A5 is a -Y1-Ar3 group; at least one of B1 to B5 is a -Y2-Ar4 group; Y1 and Y2 represent single bonds or linking groups; Ar3 and Ar4 represent aromatic groups; X1 to X4 are -O-, -S-, -NR'-, or -C(Me)2-; Z1 to Z4 represent hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms; R' represents hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms; and o and p represent integers from 1 to 4.

Description

[0001] This application is a divisional application of the original Chinese patent application filed on July 27, 2021, with application number 202180006939.7 and entitled "Compounds, Resins, Polycarbonate Resins and Optical Molded Articles". Technical Field

[0002] This invention relates to compounds, resins obtained from the compounds and polycarbonate resins, and optically molded articles comprising the resins and polycarbonate resins. Background Technology

[0003] Optical lenses, used in the optical systems of various cameras such as camcorders, film cameras, and video cameras, are made of optical glass or optical resin. Optical glass possesses excellent heat resistance, transparency, dimensional stability, and chemical resistance, and is available in various refractive indices and Abbe numbers. However, it suffers from problems such as high material cost, poor processability, and low productivity.

[0004] On the other hand, optical lenses formed from optical resins have the advantage of being mass-producible through injection molding. For example, camera lenses use polycarbonate resins. However, in recent years, with the trend towards thinner and smaller products, there has been a demand for resins with high refractive indices. Generally speaking, if the optical material has a high refractive index, it is possible to achieve a lens element with the same refractive index using a surface with less curvature, thus reducing the amount of aberration generated by that surface. As a result, it is possible to reduce the number of lens elements, lower the lens's eccentricity sensitivity, or make the lens thinner and lighter.

[0005] As for technologies related to optical resins, examples include those described in Patent Documents 1 and 2.

[0006] Patent document 1 (Japanese Patent Application Publication No. 2005-241962) describes an optical lens made of polycarbonate resin having a fluorene structure.

[0007] Patent document 2 (Japanese Patent Application Publication No. 2005-187661) describes a method for easily increasing the refractive index by blending (mixing, adding) a sulfur-containing compound into a polyester containing fluorene.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2005-241962

[0011] Patent Document 2: Japanese Patent Application Publication No. 2005-187661 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] However, the polycarbonate resin described in Patent Document 1 has a low refractive index, which is not satisfactory enough.

[0014] Furthermore, as described in Patent Document 2, if a sulfur-containing compound is blended into a polyester containing fluorene, although the refractive index increases, the thermal stability decreases due to the addition of a low molecular weight component, and the transparency decreases when the two blended components have poor compatibility.

[0015] The present invention is made in view of the above circumstances, and provides a resin and polycarbonate resin capable of realizing optically molded articles with high refractive index and excellent transparency.

[0016] Methods for solving problems

[0017] The inventors conducted extensive research to provide a polycarbonate resin capable of producing optically molded articles with high refractive index and excellent transparency. As a result, they discovered that a resin obtained by polymerizing the compound shown in formula (1) below can produce optically molded articles with high refractive index and excellent transparency, thus completing this invention.

[0018] According to the present invention, compounds represented by the following general formula (1), resins obtained from the compounds, polycarbonate resins derived from the compounds, and optically molded articles can be provided.

[0019] [1] A compound represented by general formula (1).

[0020] [Chemistry 1]

[0021]

[0022] (In general formula (1), Ar1 and Ar2 independently represent groups selected from the following,

[0023] [Chemistry 2]

[0024]

[0025] R1 to R6 represent hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms; A1 to A5 and B1 to B5 represent hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms; at least one of A1 to A5 is a -Y1-Ar3 group; at least one of B1 to B5 is a -Y2-Ar4 group; Y1 and Y2 represent single bonds or linking groups; Ar3 and Ar4 represent aromatic groups; X1 to X4 are -O-, -S-, -NR'-, or -C(Me)2-; Z1 to Z4 represent hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms; R' represents hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms; o and p represent integers from 1 to 4.

[0026] [2] According to the compound described in [1] above, o and p in the above general formula (1) are 2.

[0027] [3] According to the compounds described in [1] or [2] above, Ar1 and Ar2 in the above general formula (1) independently represent groups selected from the following:

[0028] [Chemistry 3]

[0029]

[0030] R1 to R6 represent hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms, while o and p represent integers from 1 to 4.

[0031] [4] A resin is formed by polymerizing the compound of general formula (1) shown in any one of [1] to [3] above.

[0032] [5] A polycarbonate resin derived from the compound of general formula (1) shown in any one of [1] to [3] above.

[0033] [6] An optical molding body comprising the resin described in [4] or [5] above.

[0034] [7] The optical molded body described in [6] above is an optical lens.

[0035] [8] The optical molded body described in [6] above is an optical film.

[0036] The effects of the invention

[0037] According to the present invention, it is possible to provide resins and polycarbonate resins that can achieve optically molded articles with high refractive index and excellent transparency. Detailed Implementation

[0038] The embodiments of the present invention will now be described. Furthermore, unless otherwise specified, the "~" between numbers in the text indicates "above" to "below".

[0039] [Compound]

[0040] The compounds involved in this embodiment will be described. The compounds involved in this embodiment are those represented by general formula (1).

[0041] [Chemistry 4]

[0042]

[0043] In general formula (1), Ar1 and Ar2 independently represent groups selected from the following:

[0044] [Chemistry 5]

[0045]

[0046] R1 to R6 represent hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms.

[0047] A1~A5 and B1~B5 represent hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms, and at least one of A1~A5 is a -Y1-Ar3 group.

[0048] At least one of B1 to B5 is of the -Y2-Ar4 base.

[0049] Y1 and Y2 represent single bonds or linking groups, Ar3 and Ar4 represent aromatic groups, and X1 to X4 are -O-, -S-, -NR'-, or -C(Me)2-.

[0050] Z1 to Z4 represent hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms.

[0051] R' represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group containing heteroatoms.

[0052] o and p represent integers from 1 to 4.

[0053] In general formula (1), R1 to R6 are preferably each independently selected from hydrogen atoms and alkyl groups having 1 to 3 carbon atoms or aryl groups having 6 to 20 carbon atoms, more preferably each independently selected from hydrogen atoms, methyl, phenyl, biphenyl, naphthyl, and even more preferably hydrogen atoms.

[0054] In general formula (1), o and p are integers from 1 to 4, preferably 1 or 2, and more preferably 2. By making o and p within the above range, the polycarbonate resin obtained from the compound of general formula (1) has excellent heat resistance.

[0055] In one embodiment, Ar1 and Ar2 in the above general formula (1) independently represent groups selected from the following:

[0056] [Chemistry 6]

[0057]

[0058] R1 to R6 represent hydrogen atoms, hydrocarbon groups, or hydrocarbon groups containing heteroatoms, while o and p represent integers from 1 to 4.

[0059] As preferred methods for Ar1 and Ar2 in general formula (1), the following methods can be cited.

[0060] [Chemistry 7]

[0061]

[0062] [Chemistry 8]

[0063]

[0064] [Chemistry 9]

[0065]

[0066] Examples of compounds represented by the general formula (1) above include, for example, 9,9-bis(1'-hydroxymethyl)-2,7-dinaphth-2”-yl-9H-fluorene, 9,9-bis(1'-hydroxymethyl)-2,7-dinaphth-1”-yl-9H-fluorene, 9,9-bis(1'-hydroxymethyl)-3,6-dinaphth-2”-yl-9H-fluorene, 9,9-bis(1'-hydroxymethyl)-3,6-dinaphth-1”-yl-9H-fluorene, 9,9-bis(1'-hydroxymethyl)-2,7-di-p-biphenyl-9H-fluorene, 9,9-bis(1'-hydroxymethyl)-2,7-di-m-biphenyl-9H-fluorene, 9,9-bis(1'-hydroxymethyl)-2,7-bis(3”,5”-diphenylphenyl)-9H-fluorene, 9 9,9-bis(1'-hydroxymethyl)-2,7-bis[dibenzo[b,d]furan-4”-yl]-9H-fluorene, 9,9-bis(1'-hydroxymethyl)-2,7-bis[dibenzo[b,d]thiophen-4”-yl]-9H-fluorene, 9,9-bis(1'-hydroxymethyl)-2,7-bis(4”-phenoxyphenyl)-9H-fluorene, 9,9-bis(1'-hydroxymethyl)-2,7-bis(4”-phenylnaphthyl-1”-yl)-9H-fluorene, 9,9-bis(1'-hydroxymethyl)-2,7-bis[4-(naphthyl-2-yl)phenyl]-9H-fluorene, 9,9-bis(1'-hydroxymethyl)-2,7-bis[3-naphthyl-2-yl]phenyl]-9H-fluorene, 9,9-bis(2'-hydroxyethyl) 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-1"-yl-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-3,6-dinaphth-2"-yl-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-3,6-dinaphth-1"-yl-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-3,6-dinaphth-1"-yl-9H-naphthal ... 9,9-bis(2'-hydroxyethyl)-2,7-di-p-phenyl-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-di-m-phenyl-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-di-o-phenyl-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-bis(3',5'-diphenylphenyl)-9H-fluorene, 9,9-bis( 2'-hydroxyethyl)-2,7-bis[dibenzo[b,d]furan-4”-yl]-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-bis[dibenzo[b,d]thiophen-4”-yl]-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-bis(4”-phenoxyphenyl)-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-bis(3”,5”-diphenoxyphenyl)-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-bis(4”-phenylnaphthyl-1”-yl)-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-bis[4-(naphthyl-2-yl)phenyl]-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-bis[4-(naphthyl-2-yl)phenyl]-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-Bis[3-(naphthyl-2-yl)phenyl]-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-bis[3-(naphthyl-1-yl)phenyl]-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-bis[4-(naphthyl-1-yl)phenyl]-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-diphenoxy-9”-yl-9H-fluorene, 9,9-bis(2'-hydroxyethyl)-2,7-bis[9”,9”-dimethyl-9”-fluorene-2”-yl]-9H-fluorene, 9,9-bis(3'-hydroxypropyl)-2,7-dinaphthyl-2”-yl-9H-fluorene, 9,9-bis(3'-hydroxypropyl)-2,7-dinaphthyl-1”-yl 9H-fluorene, 9,9-bis(3'-hydroxypropyl)-3,6-dinaphth-2”-yl-9H-fluorene, 9,9-bis(3'-hydroxypropyl)-3,6-dinaphth-1”-yl-9H-naphthalene, 9,9-bis(4'-hydroxybutyl)-2,7-dinaphth-2”-yl-9H-fluorene, 9,9-bis(4'-hydroxybutyl)-2,7-dinaphth-1”-yl-9H-fluorene, 9,9-bis(4'-hydroxybutyl)-3,6-dinaphth-2”-yl-9H-fluorene, 9,9-bis(4'-hydroxybutyl)-3,6-dinaphth-1”-yl-9H-naphthalene, 9,9-bis(4'-hydroxybutyl)-3,6-bis[4-(naphth-2-yl)phenyl]-9H-fluorene, etc.

[0067] Among these, 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-2”-yl-9H-fluorene and 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-1”-yl-9H-fluorene are preferred. They can be used alone or in combination of two or more.

[0068] [Method for manufacturing the compound represented by general formula (1)]

[0069] The compound represented by general formula (1) in this embodiment can be synthesized through the following steps (i) and (ii).

[0070] Step (i): By placing dihalo-9H-fluorene such as 2,7-dibromo-9H-fluorene or 3,6-dibromo-9H-fluorene in a solvent (e.g., tetrahydrofuran, 1,4-dibromo-9H-fluorene) In alkanes, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, the hydrogen at the 9-position of dihalo-9H-fluorene is removed by treatment with an alkali (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, n-butyllithium), and then a hydroxyalkyl group having a leaving group (e.g., halogens such as chlorine, bromine, iodine, p-toluenesulfonyloxy, methylsulfonyloxy, trifluoromethylsulfonyloxy, etc.) is brought into action to produce 9,9-bis(hydroxyalkyl)-2,7-dibromo-9H-fluorene or 9,9-bis(hydroxyalkyl)-3,6-9H-fluorene, etc.

[0071] Step (ii): In a solvent (e.g., toluene and water, tetrahydrofuran and water, dimethyl sulfoxide and water), in the presence of a base (e.g., sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium phosphate, potassium phosphate) and a palladium-based catalyst such as tetra(triphenylphosphine)palladium, naphthylboronic acid is acted on 9,9-bis(hydroxyalkyl)-2,7-dibromo-9H-fluorene or 9,9-bis(hydroxyalkyl)-3,6-9H-fluorene, etc., obtained in step (i), according to the so-called Suzuki-Miyaura coupling conditions, to produce the target compound of general formula (1).

[0072] Here, the reaction in step (i) can be carried out at any temperature between -78°C and the boiling point of the solvent. Furthermore, the reaction conditions can be those of a conventional alkylation reaction. The hydroxyl group of the hydroxyalkyl group having the leaving group can be protected with any protecting group (e.g., ester groups such as acetyl, ether groups such as tetrahydropyranyl, carbonate groups such as tert-butoxycarbonyl), and finally deprotection is performed.

[0073] The reaction in step (ii) can be carried out at any temperature from room temperature to the boiling point of the solvent. The reaction conditions can be the same as those commonly used in the so-called Suzuki-Miyaura coupling.

[0074] [Resin]

[0075] One aspect of the present invention is a resin formed by polymerizing a compound of general formula (1).

[0076] Here, examples of resins obtained by polymerizing the compound shown in general formula (1) include polyester resin, polyurethane resin, polycarbonate resin, polyether resin, etc.

[0077] Polyester resins can be obtained by reacting compounds of general formula (1) with aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid) or aliphatic dicarboxylic acids (e.g., oxalic acid, malonic acid, succinic acid).

[0078] Polyurethane resins can be obtained by reacting a compound of general formula (1) with an aromatic diisocyanate (e.g., toluene diisocyanate, phenyl diisocyanate) or an aliphatic diisocyanate (e.g., pentamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate).

[0079] As will be described later, polycarbonate resins can be obtained by reacting the compound of general formula (1) with carbonate precursors such as diesters.

[0080] Polyether resins can be obtained by reacting a compound of general formula (1) with an aliphatic dihalogen compound (e.g., dibromoethane, dibromopropane) in the presence of a base.

[0081] In these resins, reactants other than those represented by general formula (1) of this application can be used alone or in combination. Furthermore, it is also possible to polymerize the resin with dihydroxy compounds other than those represented by general formula (1) of this application.

[0082] When using dihydroxy compounds other than those shown in general formula (1) of this application, the proportion of the compound shown in general formula (1) is preferably 5 mol% or more and 99 mol% or less, more preferably 10 mol% or more and 99 mol% or less, and even more preferably 15 mol% or more and 99 mol% or less, relative to the total of the compound shown in general formula (1) of this application and the dihydroxy compounds other than those shown in general formula (1).

[0083] Here, examples of dihydroxy compounds other than those shown in general formula (1) include, for example, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-ethylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-n-propylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-n-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-sec-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-sec-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-sec-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-n ... [4,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-2-phenylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-(3-methylphenyl)phenyl]fluorene, bis[4-(2'-hydroxyethoxy)phenyl]sulfide, bis[4-(2'-hydroxyethoxy)-3-methylphenyl]sulfide, bis[4-(2'-hydroxyethoxy)phenyl]sulfone, bis[4-(2'-hydroxyethoxy)-3-methylphenyl]sulfone, bis[4-(2'-hydroxyethoxy)phenyl]sulfide Sulfones, bis[4-(2'-hydroxyethoxy)phenyl]sulfoxide, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 4,4-dihydroxyphenyl-1,1-m-diisopropylbenzene, and other bis(4-hydroxyaryl)alkanes; 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2,2,2-tetrahydro-3,3,3,3-tetramethyl-1,1-spirobis[1Hinden]-6,6-diol and other bis(hydroxyaryl)cycloalkanes; bis(4-hydroxyphenyl) ethers, bis(4-hydroxy-3,5-dichlorophenyl) ethers and other dihydroxyaryl ethers; 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene;Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 2,2-dimethyl-1,3-propanediol, 1,10-decanediol, diethylene glycol, tetraethylene glycol, norbornenediol, decahydronaphthalenediol, tricyclic [5.2.1.0; 2.6 Decanediethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-diethanol, spirodiol, etc.

[0084] [Polycarbonate resin]

[0085] The polycarbonate resin involved in this embodiment can be manufactured using the compound shown in general formula (1) of this embodiment. The polycarbonate resin of this embodiment has structural units derived from the compound shown in general formula (1p). Such a polycarbonate resin can realize optical molded articles with high refractive index and excellent transparency. As a result, it can be suitably used as a material for optical lenses.

[0086] [Chemistry 10]

[0087]

[0088] In equation (1p), the meanings of Ar1 and Ar2, R1 and R2, and o and p are the same as in equation (1). The same applies to the preferred method.

[0089] The polycarbonate resin involved in this embodiment has a preferred weight-average molecular weight (Mw) of 1.5 × 10⁻⁶ for polystyrene. 3 Above 2.0×10 5 Hereinafter, 2.0 × 10 is preferred. 3 Above 1.2×10 5 the following.

[0090] If Mw is above the lower limit mentioned above, the resulting molded article can be further suppressed from becoming brittle, which is therefore preferred. If Mw is below the upper limit mentioned above, the melt viscosity becomes more moderate, thus making it easier to remove the manufactured resin, further improving its fluidity, and facilitating injection molding in a molten state, which is also preferred.

[0091] The refractive index (nD) of the polycarbonate resin involved in this embodiment at 23°C and a wavelength of 633nm is preferably 1.70 or more and 1.85 or less, more preferably 1.70 or more and 1.82 or less, even more preferably 1.71 or more and 1.81 or less, and particularly preferably 1.72 or more and 1.81 or less.

[0092] Other resins can be blended into the polycarbonate resin according to this embodiment for use in the manufacture of molded articles. Examples of other resins include polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, and polybutylene terephthalate.

[0093] Furthermore, antioxidants, release agents, ultraviolet absorbers, flow modifiers, crystal nucleating agents, reinforcing agents, dyes, antistatic agents, antibacterial agents, etc., can be added to the polycarbonate resin involved in this embodiment.

[0094] In addition to injection molding, other molding methods include compression molding, casting, rolling, extrusion molding, stretching, etc., but are not limited to these.

[0095] When using the polycarbonate resin described in this embodiment for injection molding, a glass transition temperature (Tg) of 80°C to 190°C is preferred, more preferably 85°C to 180°C, and even more preferably 90°C to 170°C. If Tg is above the lower limit, the operating temperature range becomes wider, which is therefore preferable. Furthermore, if Tg is below the upper limit, the resin's melting temperature becomes lower, and resin decomposition and coloring become less likely to occur, which is also preferable. Additionally, if Tg is below the upper limit, even with a general-purpose mold temperature controller, the difference between the mold temperature and the resin's glass transition temperature can be reduced. Therefore, it is easy to use in applications requiring strict surface precision, which is also preferable.

[0096] In the optical molded articles obtained using the polycarbonate resin according to this embodiment, the total light transmittance measured according to JIS K-7361-1 (1997) is preferably 82% or more, more preferably 85% or more, and is not inferior to that of bisphenol A type polycarbonate resins, etc.

[0097] [Manufacturing method of polycarbonate resin]

[0098] The polycarbonate resin described in the embodiments can be manufactured using the compound shown in the above general formula (1) as a raw material. Specifically, it can be manufactured by reacting the compound shown in general formula (1) and carbonate precursors such as diesters in the presence of an alkaline compound catalyst or an ester exchange catalyst or a mixed catalyst containing both, or without a catalyst, via melt polycondensation.

[0099] Examples of dicarbonate esters used in the manufacture of the polycarbonate resin according to this embodiment include diphenyl carbonate, di-p-toluene carbonate, di-m-toluene carbonate, di-o-toluene carbonate, bis(p-chlorophenyl) carbonate, bis(m-chlorophenyl) carbonate, bis(o-chlorophenyl) carbonate, m-cresol carbonate, dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, and dicyclohexyl carbonate. Among these, diphenyl carbonate is preferred. Diphenyl carbonate is preferably used at a ratio of 0.97 to 1.20 moles relative to 1 mole of the compound represented by general formula (1), more preferably at a ratio of 0.98 to 1.10 moles.

[0100] Examples of alkaline compound catalysts used in the manufacture of the polycarbonate resin according to this embodiment include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds. Preferably, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, or alkoxides, or quaternary ammonium hydroxides and their salts, amines, etc., of alkali metal and alkaline earth metal compounds are used; these compounds can be used alone or in combination.

[0101] Examples of alkali metal compounds include, for example, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, or alkoxides of alkali metals. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylborate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salts of bisphenol A (sodium, dipotassium, dicesium, or dilithium salts), and sodium, potassium, cesium, or lithium salts of phenol, etc.

[0102] Examples of alkaline earth metal compounds include, for example, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, or alkoxides of alkaline earth metal compounds. Specifically, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, and magnesium phenyl phosphate.

[0103] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides and their salts, amines, etc. Specifically, quaternary ammonium hydroxides containing alkyl, aryl, or other groups, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine; secondary amines such as diethylamine and dibutylamine; primary amines such as n-propylamine and n-butylamine; imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; or bases or basic salts such as ammonia, tetramethylborohydride, tetra-n-butylborohydride, tetra-n-butyltetraphenylborate, and tetraphenyltetraphenylborate.

[0104] Salts of zinc, tin, zirconium, lead, etc., are preferred as transesterification catalysts and can be used alone or in combination. Specifically, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyldimethoxytin, zirconium acetylacetonate, zirconium oxoacetate, tetrabutoxyzirconium, lead(II) acetate, lead(IV) acetate, etc., can be used as transesterification catalysts.

[0105] Relative to a total of 1 mole of the compound represented by general formula (1), in 10 -9 ~10 -3 The molar ratio of these catalysts is preferably 10:10. -7 ~10 -4 The ratio of moles is used.

[0106] Melt polycondensation is a method that uses the above-mentioned raw materials and catalysts to carry out melt polycondensation under heating, atmospheric pressure or reduced pressure, while removing by-products through transesterification.

[0107] The melt polycondensation method involved in this embodiment aims to melt the compound shown in the above general formula (1) and the diester in a reaction vessel, and then react them while the by-product monohydroxy compound is retained.

[0108] To retain the byproducts, the reaction apparatus can be sealed, or the pressure can be controlled by reducing or increasing the pressure. The reaction time for this step is preferably 20 to 240 minutes, more preferably 40 to 180 minutes, and particularly preferably 60 to 150 minutes. If the byproduct monohydroxy compounds are immediately removed by distillation after generation, the final polycarbonate resin will contain a low content of high molecular weight compounds. However, if the byproduct monohydroxy compounds are retained in the reaction vessel for a certain period, a polycarbonate resin with a high content of high molecular weight compounds can be obtained.

[0109] Generally, melt polycondensation reactions are carried out in multiple stages or more. Specifically, the first stage reaction is preferably carried out at a temperature of 120–260°C, more preferably 180–240°C, under normal or pressurized conditions for 0.1–5 hours, more preferably 0.5–3 hours. Next, the reaction temperature is preferably increased while the pressure of the reaction system is increased to carry out the reaction of the compound represented by general formula (1) with the diester, and finally the polycondensation reaction is carried out at a pressure of 200–350°C and a pressure of 133 Pa (1 mmHg) or less for 0.05–2 hours.

[0110] Melt polycondensation can be carried out continuously or intermittently.

[0111] The reaction apparatus used can be a vertical type equipped with anchor-type stirring blades, Maxblend stirring blades, ribbon-type stirring blades, etc., or a horizontal type equipped with paddle blades, grid blades, spectacle blades, etc., or an extruder type equipped with a screw. Furthermore, it is also possible to use a reaction apparatus that appropriately combines these reaction components, taking into account the viscosity of the polymer.

[0112] For the polycarbonate resin involved in this embodiment, in order to maintain thermal stability and hydrolytic stability after the polycondensation reaction, the catalyst can be removed or deactivated. Generally, it is feasible to implement a method for deactivating the catalyst by adding a known acidic substance. Specifically, as acidic substances, esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonates such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphite esters such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, di-n-octyl phosphite, and mono-n-octyl phosphite; phosphate esters such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, di-n-butyl phosphate, di-n-octyl phosphate, and mono-n-octyl phosphate; phosphonic acids such as diphenylphosphonic acid, di-n-octylphosphonic acid, and di-n-butylphosphonic acid; phosphonic esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboronic acid; and tetra-n-butyl dodecylbenzenesulfonate. Aromatic sulfonates such as salts; organohalides such as stearoyl chloride, benzoyl chloride, and p-toluenesulfonyl chloride; alkyl sulfuric acid such as dimethyl sulfuric acid; organohalides such as benzyl chloride, etc. These deactivators are preferably used at 0.01 to 50 moles relative to the catalyst amount, more preferably 0.3 to 20 moles. If the amount is less than 0.01 moles relative to the catalyst amount, the deactivation effect is insufficient and is therefore not preferred. Furthermore, if the amount is more than 50 moles relative to the catalyst amount, the heat resistance of the resin decreases, and the molded article becomes easily colored, which is also not preferred.

[0113] After catalyst deactivation, a step can be set up to remove low-boiling-point compounds from the polymer by volatilization at a pressure of 13–133 Pa (0.1–1 mmHg) and a temperature of 200–350 °C. In this step, a horizontal device or a thin-film evaporator equipped with stirring blades that have excellent surface renewal capabilities, such as paddle blades, grid blades, or spectacle blades, can be appropriately used.

[0114] In this embodiment, the polycarbonate resin is intended to have a minimal amount of foreign matter, and filtration of the molten raw material and catalyst solution can be appropriately implemented. The mesh size of the filter is preferably 5 μm or less, more preferably 1 μm or less. Furthermore, filtration of the generated resin using a polymer filter can be appropriately implemented. The mesh size of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. In addition, the process of collecting resin particles is preferably performed in a low-dust environment, more preferably with a cleanliness level of 1000 or less.

[0115] [Optical Shaped Body]

[0116] The optical molding body according to this embodiment includes the polycarbonate resin according to this embodiment, and the optical molding body can be manufactured using the polycarbonate resin according to this embodiment.

[0117] For example, it can be formed by any method such as injection molding, compression molding, injection compression molding, extrusion molding, solution casting, etc.

[0118] The polycarbonate resin described in this embodiment has excellent moldability and heat resistance, making it particularly advantageous for use in optical lenses that require injection molding. During molding, the polycarbonate resin described in this embodiment can be mixed with other polycarbonate resins, polyester resins, or other resins.

[0119] Furthermore, various additives can be used to impart various properties without compromising the purpose of this embodiment. Examples of additives include antioxidants, processing stabilizers, release agents, ultraviolet absorbers, bluing agents, polymer metal deactivators, flame retardants, lubricants, antistatic agents, heat shielding agents, fluorescent dyes (including fluorescent whitening agents), pigments, light scattering agents, reinforcing fillers, surfactants, antibacterial agents, plasticizers, solubilizers, other resins, elastomers, etc.

[0120] Examples of antioxidants include, for instance, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. Butyl-4-hydroxybenzyl)benzene, N,N-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane, etc.

[0121] The antioxidant content in polycarbonate resin is preferably 0.001 to 0.3 parts by weight relative to 100 parts by weight of polycarbonate resin.

[0122] Examples of processing stabilizers include phosphorus-based processing heat stabilizers and sulfur-based processing heat stabilizers.

[0123] Examples of phosphorus-based heat stabilizers include, for example, phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and their esters. Specifically, examples include triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, tri-n-decyl phosphite, tri-n-octyl phosphite, tri-n-octadecyl phosphite, di-n-decyl monophenyl phosphite, di-n-octyl monophenyl phosphite, diisopropyl monophenyl phosphite, mono-n-butyl diphenyl phosphite, mono-decyl diphenyl phosphite, mono-n-octyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylene bis(4,6-di-tert-butylphenyl) octyl phosphite, bis(n-nonylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, and bis( 2,4-Di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tri-n-butyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenylmono-o-biphenyl phosphate, di-n-butyl phosphate, di-n-octyl phosphate, diisopropyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, tetra(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphonate, tetra(2,4-di-tert-butylphenyl)-4,3'-biphenyl diphosphonate, tetra(2,4-di-tert-butylphenyl)-3,3'-biphenyl diphosphonate, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenyl phosphonate, and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenyl phosphonate, etc.

[0124] The content of phosphorus-based processing heat stabilizer in polycarbonate resin is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of polycarbonate resin.

[0125] Examples of sulfur-based heat stabilizers include pentaerythritol tetrakis(3-lauryl thiopropionate), pentaerythritol tetrakis(3-myristyl thiopropionate), pentaerythritol tetrakis(3-stearyl thiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearate-3,3'-thiodipropionate.

[0126] The content of sulfur-based processing heat stabilizer in polycarbonate resin is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of polycarbonate resin.

[0127] As a release agent, it is preferable that 90% or more by mass is a release agent formed from an ester of an alcohol and a fatty acid. Specifically, examples of esters of alcohols and fatty acids include esters of monohydric alcohols and fatty acids, and partial or complete esters of polyhydric alcohols and fatty acids. Among the aforementioned esters of monohydric alcohols and fatty acids, esters of monohydric alcohols with 1 to 20 carbon atoms and saturated fatty acids with 10 to 30 carbon atoms are preferred. Furthermore, among the aforementioned partial or complete esters of polyhydric alcohols and fatty acids, partial or complete esters of polyhydric alcohols with 1 to 25 carbon atoms and saturated fatty acids with 10 to 30 carbon atoms are preferred.

[0128] Examples of esters of monohydric alcohols and saturated fatty acids include stearyl stearate, palmityl palmitate, n-butyl stearate, methyl laurate, and isopropyl palmitate. Examples of partial or full esters of polyhydric alcohols and saturated fatty acids include monoglycerides of stearate, diglycerides of stearate, triglycerides of stearate, monosorbitol stearate, behenicol monoglyceride, decanoic acid monoglyceride, laurate monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetranonanoate, propylene glycol monostearate, biphenyl biphenyl ester, sorbitol monostearate, 2-ethylhexyl stearate, and dipentaerythritol hexastearate, as well as full or partial esters of dipentaerythritol.

[0129] The content of these release agents is preferably in the range of 0.005 to 2.0 parts by weight relative to 100 parts by weight of polycarbonate resin, more preferably in the range of 0.01 to 0.6 parts by weight, and even more preferably in the range of 0.02 to 0.5 parts by weight.

[0130] The preferred UV absorber is at least one UV absorber selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic imino ester UV absorbers, and cyanoacrylate UV absorbers. The UV absorbers listed below can be used alone or in combination of two or more.

[0131] Examples of benzotriazole-based ultraviolet absorbers include, for instance, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazole-2-yl)phenol], 2-(2-hydroxy-3, 5-Di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-n-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzotriazole) (e.g., azinon-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidemethyl)-5-methylphenyl]benzotriazole, etc.

[0132] Examples of benzophenone-based ultraviolet absorbers include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonyloxybenzophenone, and 2-hydroxy-4-methoxy-5-sulfonyloxytrihydratebenzophenone. 2,2'-Dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfonyl benzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc.

[0133] Examples of triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(n-hexyl)oxy]-phenol and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(n-octyl)oxy]-phenol.

[0134] Examples of cyclic imino ester-based ultraviolet absorbers include, for example, 2,2'-bis(3,1-benzo[]]. 2,2'-p-phenylenebis(3,1-benzo[a]one), 2,2'-p-phenylenebis(3,1-benzo[a]one) 4-azine-one), 2,2'-m-phenylenebis(3,1-benzo[] 2,2'-(4,4'-diphenylene)bis(3,1-benzo[a]one), 2,2'-(4,4'-diphenylene)bis(3,1-benzo[a]one) 2,2'-(2,6-naphthyl)bis(3,1-benzo[] 2,2'-(1,5-naphthyl)bis(3,1-benzo[] 2,2'-(2-methyl-p-phenylene)bis(3,1-benzo[a]one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzo[a]one) 2,2'-(2-nitro-p-phenylene)bis(3,1-benzo[] (azin-4-one) and 2,2'-(2-chloro-p-phenylene)bis(3,1-benzo[] (e.g., azinon-4-one).

[0135] Examples of cyanoacrylate-based ultraviolet absorbers include, for example, 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0136] The content of the ultraviolet absorber relative to 100 parts by weight of polycarbonate resin is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and even more preferably 0.05 to 0.8 parts by weight. Within this range of proportions, sufficient weather resistance can be imparted to the polycarbonate resin depending on the application.

[0137] Examples of blueing agents include Bayer's Macrolex Violet B and Macrolex Blue RR, and Clariant's Polysynthren Blue RLS.

[0138] Bluing agents are effective in removing the yellow tint from polycarbonate resins. Especially in the case of weather-resistant polycarbonate resins, the presence of a certain amount of UV absorber can cause molded polycarbonate resin products to tend to have a yellow tint due to the "effect and color of the UV absorber." Bluing agents are particularly effective in imparting a natural transparency to sheets and lenses.

[0139] The amount of bluing agent added relative to the polycarbonate resin is preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm.

[0140] The polycarbonate resin involved in this embodiment exhibits a high refractive index and excellent heat resistance, and also possesses flowability suitable for molding. Furthermore, due to its low birefringence and low susceptibility to optical strain, it can be advantageously used, in addition to optical lenses, as a structural or functional material for optical components such as transparent conductive substrates used in liquid crystal displays, organic EL displays, and solar cells, as well as optical discs, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic mirrors, and displays.

[0141] Depending on the requirements, an anti-reflective layer or a hard coating can be applied to the surface of the optically shaped object. The anti-reflective layer can be a single layer or multiple layers, and can be organic or inorganic, but is preferably inorganic. Specifically, examples include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride.

[0142] (Optical lens)

[0143] Optical lenses made from the polycarbonate resin described in this embodiment have a high refractive index and excellent heat resistance, making them extremely useful in fields such as telescopes, binoculars, and television projectors where expensive high-refractive-index glass lenses were previously used. Preferably, they are used in the form of aspherical lenses as needed. Aspherical lenses can achieve substantially zero spherical aberration with a single lens, eliminating the need for a combination of multiple spherical lenses to remove spherical aberration, thus enabling weight reduction and lower production costs. Therefore, aspherical lenses are useful in optical lenses, especially as camera lenses.

[0144] The optical lens involved in this embodiment can be formed by any method, such as injection molding, compression molding, or injection compression molding. This embodiment provides a simpler way to obtain a high-refractive-index, low-birefractive-index aspherical lens that is technically difficult to manufacture in the case of glass lenses.

[0145] (Optical film)

[0146] The optical film made using the polycarbonate resin described in this embodiment has excellent transparency and heat resistance, and is therefore suitable for use in films for liquid crystal substrates, optical memory cards, etc.

[0147] The embodiments of the present invention have been described above, but they are merely examples of the present invention, and various configurations other than those described above may also be employed.

[0148] Example

[0149] Hereinafter, this embodiment will be described in detail with reference to embodiments and comparative examples. However, this embodiment is not limited to the descriptions in these embodiments.

[0150] 1. Measurement and evaluation methods

[0151] In the following examples and comparative examples, the determination and evaluation of each physical property were carried out by the following methods.

[0152] 1) Weight-average molecular weight (Mw) of polystyrene: Using gel permeation chromatography (GPC: Waters 1515, 2414, and 2489), with chloroform as the eluent, a standard curve was prepared using standard polystyrene with known molecular weights (molecular weight distribution = 1). Based on this standard curve, Mw was calculated from the retention time of GPC.

[0153] 2) Refractive index (n633): Using a spin coater, an 8.5 wt% chloroform solution of resin was coated on a silicon wafer at 200 rpm for 20 seconds and 1000 rpm for 5 seconds. The wafer was then baked at 120°C for 5 minutes and at 200°C for 2 minutes to prepare the sample. Using a spectroscopic ellipsometry GES5E (SEMILAB), the optical measurement data for wavelengths of 200-1000 nm were fitted with the optical model shown below, thereby calculating the refractive index and thickness of the film.

[0154] (Optical model)

[0155] Layered structure: film / SiO2 (2nm thick) / Si substrate (500μm thick)

[0156] Dispersed membrane: Cauchy+Lorentz oscillator model

[0157] 3) Glass transition temperature (Tg): Measured by differential scanning calorimetry (DSC: Shimadzu DSC-60).

[0158] 1. Modulation of the compound shown in formula (1)

[0159] (Example 1)

[0160] Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-2”-yl-9H-fluorene

[0161] Step (i): Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-dibromo-9H-fluorene

[0162] In a 500 mL flask, 66.5 g (0.2 mol) of 2,7-dibromo-9H-fluorene, 56 g (0.998 mol) of potassium hydroxide (powder), 3.4 g (0.02 mol) of potassium iodide, and 150 mL of dimethyl sulfoxide were added and cooled to 10 °C with ice water. Then, 58.4 g (0.467 mol) of 2-bromoethanol was added dropwise over 45 minutes, and the mixture was stirred overnight at room temperature. The reaction mixture was then heated to 50 °C and stirred for 40 hours. The reaction mixture was drained into 2 L of distilled water, and the pH was adjusted to 6 using concentrated hydrochloric acid. The resulting solid was filtered and washed with 3 L of water. The solid was dissolved in 1 L of ethyl acetate, washed with 500 mL of distilled water, concentrated using an evaporator, and chloroform was added to obtain 34.8 g of colorless crystals of 9,9-bis(2'-hydroxyethyl)-2,7-dibromo-9H-fluorene.

[0163] Step (ii): Modulation of 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-2”-yl-9H-fluorene

[0164] In a 1-liter flask, 20.75 g (50 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-dibromo-9H-fluorene, 19.17 g (0.11 mol) of naphthalene-2-boronic acid, 15.3 g (0.11 mol) of potassium carbonate, 250 g of distilled water, and 400 g of dimethyl sulfoxide were added. 3.0 g of tetra(triphenylphosphine)palladium was added to the reaction mixture, and the mixture was heated to 100 °C and stirred for 5 hours. After cooling, the resulting solid was filtered, washed with 500 g of water, and dried under vacuum at 50 °C. After drying, the solid was resuspended and washed with chloroform to obtain 20.87 g of 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-2”-yl-9H-fluorene as colorless crystals. The melting point, determined by DSC, was 236 °C.

[0165] (Example 2)

[0166] Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-2”-yl-9H-fluorene

[0167] Step (i): Synthesis of 2-(2'-bromoethoxy)tetrahydropyran

[0168] In a 2-liter round-bottom flask equipped with a stirrer, thermometer, and dropping funnel, 150 g (1.20 mol) of 2-bromoethanol and 800 ml of dichloromethane were added and cooled with ice water. Then, when the internal temperature reached 5°C, 130 g (1.56 mol) of 3,4-dihydro-2H-pyran was added dropwise below 10°C. After the addition was complete, pyridine p-toluenesulfonic acid was added. 30 g (0.12 mol) of salt was added and stirred overnight at room temperature. Then, saturated water containing sodium bicarbonate was added, and the dichloromethane layer was washed with water. The resulting dichloromethane layer was concentrated by evaporation to obtain 255 g of 2-(2'-bromoethoxy)tetrahydropyran as a pale yellow oil.

[0169] Step (ii): Synthesis of 9,9-bis[2-(2'-tetrahydropyranoxy)ethyl]-2,7-dibromo-9H-fluorene

[0170] In a 2-liter round-bottom flask equipped with a stirrer, thermometer, and reflux tube, 255 g of 2-(2'-bromoethoxy)tetrahydropyran, 270 ml of toluene, and 164 g (0.506 mol) of 2,7-dibromo-9H-fluorene were added, followed by 270 ml of a 50% sodium hydroxide aqueous solution. Then, 8.5 g (26.2 mmol) of tetrabutylammonium bromide was added, and the mixture was heated to 100 °C and stirred for 11.5 hours. The reaction mixture was then cooled to room temperature, and the aqueous layer was separated. 700 ml of ethyl acetate and 700 ml of distilled water were added for washing. After further repeated washing, the layer formed by ethyl acetate and toluene was separated and concentrated using an evaporator. A small amount of 9,9-bis[2-(2'-tetrahydropyranoxy)ethyl]-2,7-dibromo-9H-fluorene seed crystals were added to the concentrated viscous liquid, followed by crystallization with methanol. The obtained crystals were filtered, washed with a small amount of methanol, and then recrystallized by heating with 500 ml of methanol to obtain 246 g of 9,9-bis[2-(2'-tetrahydropyranyl)ethoxy]-2,7-dibromo-9H-fluorene, which was the target and appeared as pale yellow crystals.

[0171] mp98.5℃

[0172] 1 H-NMR (CDCl3) δ1.30-1.53 ​​(m, 12H), 2.34-2.38 (t, 4H), 2.70-3.5 (m, 8H), 4.1 (t, 2H), 7.43-7.55 (m, 6H)

[0173] Step (iii): Synthesis of 9,9-bis[2-(2'-tetrahydropyranoxy)ethyl]-2,7-dinaphth-2”-yl-9H-fluorene

[0174] In a 1-liter round-bottom flask equipped with a stirrer, thermometer, and reflux tube, 72.55 g (125 mmol) of 9,9-bis[2-(2'-tetrahydropyranoxy)ethyl]-2,7-dibromo-9H-fluorene, 475 ml of toluene, 61 g (442 mmol) of potassium carbonate, 47.29 g (275 mmol) of 2-naphthenic acid, and 211 ml of distilled water were added. While stirring, 1.4 g of tetra(triphenylphosphine)palladium was added to the reaction mixture, and the temperature was raised to 80 °C. The mixture was heated and stirred at 80 °C for 12 hours, and then cooled to room temperature. After separating the aqueous layer, the toluene layer was washed with distilled water, and then concentrated by evaporation. 730 ml of methanol was added to the concentrated residue, and the resulting solid was filtered and washed with methanol. The sample was then purified by silica gel column chromatography (eluent: toluene-toluene / ethyl acetate = 9 / 1), followed by recrystallization with methyl cellosolve to obtain 121.01 g of the target substance. Yield: 72%, HPLC purity: 99.3%, mp: 148℃.

[0175] 1 H-NMR (CDCl3) δ1.20-1.70 (m, 12H), 2.55 (t, 4H), 2.8-3.5 (m, 8H), 4.16 (m, 2H), 7.40-7.65 (m, 4H), 7.70-8.05 (m, 14H), 8.1 (s, 2H)

[0176] Step (iv): Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-2”-yl-9H-fluorene

[0177] In a 1-liter round-bottom flask equipped with a stirrer, thermometer, and reflux tube, 60.00 g (88.9 mmol) of 9,9-bis[2-(2'-tetrahydropyranoxy)ethyl]-2,7-dinaphth-2”-yl-9H-fluorene, 600 ml of methyl cellosol, 25 ml of distilled water, and 7 ml of concentrated hydrochloric acid were added. The mixture was heated to 115 °C while stirring, and maintained at this temperature for 4 hours. Then, it was cooled to room temperature, 180 ml of water was added, and the resulting crystals were filtered. The crystals were washed with distilled water, dried under reduced pressure at 50 °C, and then resuspended and washed with hot methyl cellosol to obtain 38.73 g of the target substance. Yield: 85%, mp 249.5 °C.

[0178] 1 H-NMR (DMSO-d6) δ2.43 (t, 4H), 2.80 (t, 4H), 4.16 (t, 2H), 7.50-7.60 (m, 4H), 7.8-8.1 (m, 12H), 8.35 (s, 2H)

[0179] (Example 3)

[0180] Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-bis[dibenzo[b,d]furan-4”-yl]-9H-fluorene

[0181] In step (iii) of Example 2, 58.85 g (275 mmol) of dibenzo[b,d]furan-4-ylboronic acid was used instead of 47.29 g (275 mmol) of 2-naphthoboronic acid. Otherwise, following the procedure described in step (iii) of Example 2, 66.05 g of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[dibenzo[b,d]furan-4”-yl]-9H-fluorene was obtained. Yield: 70%, HPLC purity: 97.5%, mp: 176.7 °C.

[0182] 1 H-NMR (CDCl3) δ1.29-1.45 (10H, m), 1.58 (2H, m), 2.58 (4H, t), 2.98 (2H, q), 3.24 (2H, dt), 3.40 (2H, q), 3 .55(2H,dt),4.23(2H,s),7.39(2H,t),7.48(4H,q),7.64(2H,d),7.68-7.71(2H,m),7.90-8.03(10H,m)

[0183] In step (iv) of Example 2, instead of using 60.00 g (88.9 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-dinaphth-2”-yl-9H-fluorene, 600 ml of methyl cellosolve, 25 ml of distilled water, and 7 ml of concentrated hydrochloric acid, 60.00 g (79.4 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[dibenzo[b,d]furan-4”-yl]-9H-fluorene, 540 ml of methyl cellosolve, 22 ml of distilled water, and 6.2 ml of concentrated hydrochloric acid were used. Otherwise, following the procedure (iv) of Example 2, 41.03 g of the target substance was obtained. Yield: 88%, HPLC purity: 99.4%, mp: 247.4 °C.

[0184] 1 H-NMR(DMSO-d6)δ2.40(4H,t),2.98(4H,m),4.24(2H,t),7.46(2H,t),7.58(4H,dt),7.82(4H,dd),8.03-8.10(6H,m),8.22(4H,dd)

[0185] (Example 4)

[0186] Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-bis[4-(naphth-2-yl-)phenyl]-9H-fluorene

[0187] In step (iii) of Example 2, 68.22 g (275 mmol) of 4-(naphth-2-yl)phenylboronic acid was used instead of 47.29 g (275 mmol) of 2-naphtholic boric acid. Otherwise, following the procedure described in step (iii) of Example 2, 68.23 g of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[4-(naphth-2-yl-)phenyl]-9H-fluorene was obtained. Yield: 66%, HPLC purity: 99.2%, mp: 209.4 °C.

[0188] 1 H-NMR (CDCl3) δ1.26-1.61 (12H, m), 2.55 (4H, t), 2.86 (2H, q), 3.22-3.32 (4H, m), 3.51-3.56 (2H, m), 4.17 (2H, t ), 7.49-7.55(4H, m), 7.67(2H, d), 7.75(2H, d), 7.78-7.82(6H, m), 7.84-7.90(8H, m), 7.95(4H, t), 8.13(2H, s)

[0189] In step (iv) of Example 2, instead of using 60.00 g (88.9 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-dinaphth-2”-yl-9H-fluorene, 600 ml of methyl cellosolve, 25 ml of distilled water, and 7 ml of concentrated hydrochloric acid, 60.00 g of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[4-(naphth-2-yl-)phenyl]-9H-fluorene, 500 ml of methyl cellosolve, 20 ml of distilled water, and 6 ml of concentrated hydrochloric acid were used. Otherwise, following the procedure (iv) of Example 2, 41.10 g of the target substance was obtained. Yield: 86%, HPLC purity: 99.6%, mp3: 41.3 °C.

[0190] 1 H-NMR (DMSO-d6) δ2.41 (4H, t), 2.83 (4H, q), 4.20 (2H, t), 7.53-7.60 (4H, m), 7.83 (2H, d), 7.94-8.00 (16H, m), 8.06 (4H, d), 8.33 (2H, s)

[0191] (Example 5)

[0192] Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-bis[3-(naphth-2-yl-)phenyl]-9H-fluorene

[0193] In step (iii) of Example 2, 68.22 g (275 mmol) of 3-(naphth-2-yl)phenylboronic acid was used instead of 47.29 g (275 mmol) of 2-naphtholic boric acid. Otherwise, following the procedure described in step (iii) of Example 2, 70.30 g of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[3-(naphth-2-yl-)phenyl]-9H-fluorene was obtained. Yield: 68%, HPLC purity: 98.9%, mp: 171.6 °C.

[0194] 1 H-NMR (CDCl3) δ1.26-1.58 (12H, m), 2.54 (4H, t), 2.86 (2H, q), 3.22-3.30 (4H, m), 3.49-3.54 (2H, m), 4.16 (2H, t ), 7.51-7.61(6H, m), 7.66-7.74(8H, m), 7.81(2H, d), 7.84(2H, dd), 7.90(2H, d), 7.94-7.99(6H, m), 8.14(2H, s)

[0195] In step (iv) of Example 2, instead of using 60.00 g (88.9 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-dinaphth-2”-yl-9H-fluorene, 600 ml of methyl cellosolve, 25 ml of distilled water, and 7 ml of concentrated hydrochloric acid, 60.00 g (72.5 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[3-(naphth-2-yl-)phenyl]-9H-fluorene, 500 ml of methyl cellosolve, 20 ml of distilled water, and 5.7 g of concentrated hydrochloric acid were used. Otherwise, following the procedure (iv) of Example 2, 41.58 g of the target substance was obtained. The yield was 87%. Furthermore, the final product was purified by column chromatography (elution: The assay was performed using HPLC with a purity of 99.7% and an mp value of 143.1℃.

[0196] 1H-NMR (DMSO-d6) δ: 2.52 (4H, t), 3.17 (4H, q), 7.51-7.54 (4H, m), 7.60 (2H, t), 7.67-7.6 9(2H,m),7.74(2H,dd),7.76(2H,s),7.82-7.91(6H,m),7.94-7.99(6H,m),8.14(2H,s)

[0197] (Example 6)

[0198] Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-diphenanthrene-9”-yl-9H-fluorene

[0199] In step (iii) of Example 2, 61.06 g (275 mmol) of phenanthrene-9-ylboronic acid was used instead of 47.29 g (275 mmol) of 2-naphthoboronic acid. Otherwise, following the procedure described in step (iii) of Example 2, 73.62 g of 9,9-bis[2-(2'-tetrahydropyranoxy)ethyl]-2,7-diphenanthrene9”-yl-9H-fluorene was obtained. Yield 76%, HPLC purity 95.9%, viscous solid.

[0200] 1 H-NMR (CDCl3) δ1.36-1.64 (12H, m), 2.50 (4H, t), 2.99 (2H, q), 3.30-3.43 (4H, m), 3.58 (2H, dt), 4.29 (2H, s ), 7.57 (4H, d), 7.63-7.72 (8H, m), 7.77 (2H, s), 7.90 (2H, d), 7.93-7.95 (2H, m), 8.03 (2H, d), 8.79 (4H, dd)

[0201] In step (iv) of Example 2, instead of using 60.00 g (88.9 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-dinaphthyl-2”-yl-9H-fluorene, 600 ml of methyl cellosolve, 25 ml of distilled water, and 7 ml of concentrated hydrochloric acid, 70.00 g (90.3 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-diphenoxy-9”-yl-9H-fluorene, 610 ml of methyl cellosolve, 25 ml of distilled water, and 7 ml of concentrated hydrochloric acid were used. Otherwise, following the procedure (iv) of Example 2, 48.22 g of the target substance was obtained. The yield was 88%. Furthermore, the final product was purified by column chromatography (elution buffer: The assay was performed using HPLC with a purity of 99.3% and an mp value of 226.9℃.

[0202] 1 H-NMR (DMSO-d6) δ2.48 (4H, t), 3.31 (4H, q), 7.57-7.73 (12H, m), 7.77 (2H, s), 7.95 (6H, dd), 8.79 (4H, dd)

[0203] (Example 7)

[0204] Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-bis[dibenzo[b,d]thiophene-4”-yl]-9H-fluorene

[0205] In step (iii) of Example 2, 62.72 g (275 mmol) of dibenzo[b,d]thiophene-4-ylboronic acid was used instead of 47.29 g (275 mmol) of 2-naphthoboronic acid. Otherwise, following the procedure described in step (iii) of Example 2, 68.87 g of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[dibenzo[b,d]thiophene-4”-yl]-9H-fluorene was obtained. Yield 70%, HPLC purity 99.1%, viscous solid.

[0206] 1 H-NMR (CDCl3) δ1.28-1.43 (10H, m), 1.55 (2H, m), 2.56 (4H, t), 2.95 (2H, q), 3.22 (2H, dt), 3.37 (2H, q), 3 .52(2H,dt),4.20(2H,s),7.51(2H,t),7.68(4H,q),7.85(2H,d),7.82-7.89(2H,m),8.11-8.24(10H,m)

[0207] In step (iv) of Example 2, instead of using 60.00 g (88.9 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-dinaphthio-2”-yl-9H-fluorene, 600 ml of methyl cellosolve, 25 ml of distilled water, and 7 ml of concentrated hydrochloric acid, 60.00 g (76.4 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[dibenzo[b,d]thiophene-4”-yl]-9H-fluorene, 500 ml of methyl cellosolve, 20 ml of distilled water, and 6.0 ml of concentrated hydrochloric acid were used. Otherwise, following the procedure (iv) of Example 2, 40.10 g of the target substance was obtained. Yield: 85%, HPLC purity: 98.9%, mp: 223.6 °C.

[0208] 1H-NMR (DMSO-d6) δ2.38 (4H, t), 2.93 (4H, dt), 4.26 (2H, t), 7.57 (4H, dd), 7.69-7.7 1(4H,m),7.79(2H,d),7.97(2H,s),8.04(2H,dd),8.10(2H,d),8.43-8.47(4H,dd)

[0209] (Example 8)

[0210] Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-bis[4”-phenoxyphenyl]-9H-fluorene

[0211] In step (iii) of Example 2, 58.86 g (275 mmol) of 4-phenoxyphenylboronic acid was used instead of 47.29 g (275 mmol) of 2-naphthoboronic acid. Otherwise, following the procedure described in step (iii) of Example 2, 68.31 g of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[4-phenoxyphenyl]-9H-fluorene was obtained. Yield 72%, HPLC purity 98.8%, viscous solid.

[0212] 1 H-NMR (CDCl3) δ1.24-1.59 (12H, m), 2.48 (4H, t), 2.81 (2H, q), 3.20-3.27 (4H, m), 3.48-3.54 (2H , m), 4.14 (2H, t), 7.07-7.15 (10H, m), 7.37 (4H, dt), 7.55 (2H, d), 7.60-7.63 (6H, m), 7.74 (2H, d)

[0213] In step (iv) of Example 2, instead of using 60.00 g (88.9 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-dinaphth-2”-yl-9H-fluorene, 600 ml of methyl cellosolve, 25 ml of distilled water, and 7 ml of concentrated hydrochloric acid, 60.00 g (79.1 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[4”-phenoxyphenyl]-9H-fluorene, 530 ml of methyl cellosolve, 22 ml of distilled water, and 6.2 ml of concentrated hydrochloric acid were used. Otherwise, following the procedure (iv) of Example 2, 38.29 g of the target substance was obtained. Yield: 82%, HPLC purity: 99.7%, mp: 134.1 °C.

[0214] 1H-NMR(DMSO-d6)δ2.34(4H,t),2.76(4H,q),4.14(2H,t),7.07-7.20(10H,m),7.43(4H,t),7.67(2H,dd),7.81(6H,t),7.90(2H,d)

[0215] (Example 9)

[0216] Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-bis[4”-phenylnaphth-1”-yl]-9H-fluorene

[0217] In step (iii) of Example 2, 68.22 g (275 mmol) of 4-phenylnaphth-1-ylboronic acid was used instead of 47.29 g (275 mmol) of 2-naphtholic boric acid. Otherwise, following the procedure described in step (iii) of Example 2, 73.4 g of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[4”-phenylnaphth-1”-yl]-9H-fluorene was obtained. Yield: 71%, HPLC purity: 99.8%, mp: 230.3 °C.

[0218] 1 H-NMR (CDCl3) δ1.36-1.61 (12H, m), 2.50 (4H, t), 2.97 (2H, q), 3.30 (2H, dt), 3.38 (2H, q), 3.57 (2H, d t), 4.27 (2H, s), 7.45-7.58 (20H, m), 7.66 (2H, s), 7.89 (2H, d), 7.98-8.00 (2H, m), 8.05-8.10 (2H, m)

[0219] In step (iv) of Example 2, instead of using 60.00 g (88.9 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-dinaphth-2”-yl-9H-fluorene, 600 ml of methyl cellosolve, 25 ml of distilled water, and 7 ml of concentrated hydrochloric acid, 70.00 g (84.6 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[4”-phenylnaphth-1”-yl]-9H-fluorene, 570 ml of methyl cellosolve, 24 ml of distilled water, and 7.0 ml of concentrated hydrochloric acid were used. Otherwise, following the procedure (iv) of Example 2, 47.95 g of the target substance was obtained. Yield: 86%, HPLC purity: 99.0%, mp: 271.4 °C.

[0220] 1H-NMR(DMSO-d6)δ2.34(4H,t),2.95(4H,dt),4.24(2H,t),7.51-7.63(20H,m),7.72(2H,s),7.90-7.93(2H,m),7.99-8.01(2H,m),8.08(2H,d)

[0221] (Example 10)

[0222] Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-bis[9”,9”-dimethyl-9”H-fluorene-2”-yl]-9H-fluorene

[0223] In step (iii) of Example 2, 65.47 g (275 mmol) of 9,9-dimethyl-9H-fluorene-2-ylboronic acid was used instead of 47.29 g (275 mmol) of 2-naphthalenedoric acid. Otherwise, following the procedure described in step (iii) of Example 2, 76.67 g of 9,9-bis[2-(2'-tetrahydropyranoxy)ethyl]-2,7-bis[9”,9”-dimethyl-9”H-fluorene-2”-yl]-9H-fluorene was obtained. Yield 76%, HPLC purity 91.0%, viscous solid.

[0224] 1 H-NMR (CDCl3) δ1.25-1.50 (12H, m), 1.58 (12H, s), 2.56 (4H, t), 2.87 (2H, q), 3.23-3.32 (4H, m), 3.51-3.57 (2 H, m), 4.16 (2H, t), 7.32-7.39 (4H, m), 7.47 (2H, dd), 7.62-7.67 (4H, m), 7.69-7.72 (4H, m), 7.76-7.82 (6H, m)

[0225] In step (iv) of Example 2, instead of using 60.00 g (88.9 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-dinaphth-2”-yl-9H-fluorene, 600 ml of methyl cellosolve, 25 ml of distilled water, and 7 ml of concentrated hydrochloric acid, 70.00 g (89.7 mmol) of 9,9-bis[2-(2'-tetrahydropyranyloxy)ethyl]-2,7-bis[9”,9”-dimethyl-9”H-fluorene-2”-yl]-9H-fluorene, 590 ml of methyl cellosolve, 24 ml of distilled water, and 6.8 ml of concentrated hydrochloric acid were used. Otherwise, following the procedure (iv) of Example 2, 48.21 g of the target substance was obtained. Yield: 87%, HPLC purity: 96.9%, mp: 272.3 °C.

[0226] 1 H-NMR (DMSO-d6) δ1.55 (12H, s), 2.42 (4H, t), 2.79 (4H, m), 4.18 (2H, t), 7.3 3-7.40 (4H, m), 7.59 (2H, dd), 7.76-7.79 (4H, m), 7.88 (2H, d), 7.95 (8H, dd)

[0227] (Example 11)

[0228] Synthesis of 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-1”yl-9H-fluorene

[0229] In step (iii) of Example 2, 47.29 g (275 mmol) of 1-naphthoic acid was used instead of 47.29 g (275 mmol) of 2-naphthoic acid. Otherwise, following the procedure described in step (iii) of Example 2, 65.80 g of 9,9-bis[2-(2'-tetrahydropyranoxy)ethyl]-2,7-dinaphthyl-1”-yl-9H-fluorene was obtained. Yield 78%, HPLC purity 91.0%, viscous solid.

[0230] 1 H-NMR (CDCl3) δ1.14-1.46 (m, 12H), 2.47 (t, 4H), 2.9-3.6 (m, 8H), 4.2 (s, 2H), 7.5-8.1 (m, 20H)

[0231] In step (iv) of Example 2, instead of using 60.00 g (88.9 mmol) of 9,9-bis[2-(2'-tetrahydropyranoxy)ethyl]-2,7-dinaphth-2”-yl-9H-fluorene, 60.00 g (88.9 mmol) of 9,9-bis[2-(2'-tetrahydropyranoxy)ethyl]-2,7-dinaphth-1”-yl-9H-fluorene was used. Otherwise, following the procedure described in step (iv) of Example 2, 35.13 g of the target substance was obtained. Yield 78%, HPLC purity 95.4%, viscous solid.

[0232] 1 H-NMR(DMSO-d6)δ2.3(t, 4H), 2.9(t, 4H), 4.2(2,2H), 7.5-8.2(m, 20H)

[0233] (Comparative Synthesis Example 1)

[0234] In Example 1, 13.41 g (0.11 mol) of phenylboronic acid was used instead of 19.17 g (0.11 mol) of naphthalene-2-boronic acid. Otherwise, 19.9 g of 9,9-bis(2'-hydroxyethyl)-2,7-didiphenyl-9H-fluorene as colorless crystals was obtained according to the operation described in Example 1.

[0235] 2. Manufacturing of polycarbonate resin

[0236] (Example 12)

[0237] 20.26 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-2”-yl-9H-fluorene obtained from Example 1, 8.56 g (40 mmol) of diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"), and 15 μL (3 × 10⁻⁶) of 0.02 M sodium bicarbonate aqueous solution were prepared. -6 The polycarbonate resin (in molar form) was loaded into a reactor equipped with a distillation device and reacted at 240°C and 100 kPa for 1 hour. Then, the pressure was adjusted to 19 kPa, and the reaction was continued for 20 minutes, followed by 70 minutes at the same temperature and pressure. Next, the pressure was adjusted to 16 kPa, and the reaction was continued for 20 minutes. Further, the pressure was adjusted to 13 kPa, and the reaction was continued for 20 minutes. After 40 minutes, the pressure was adjusted to 130 Pa, and the reaction was continued at the same pressure for 30 minutes. When the predetermined torque was reached, the vacuum was released using nitrogen gas, and the polycarbonate resin was removed.

[0238] The obtained polycarbonate resin had a weight-average molecular weight (Mw) of 32,300 and a Tg of 135℃.

[0239] The refractive index (n633) of this polycarbonate resin is 1.7608.

[0240] (Comparative Example 2)

[0241] In Example 12, instead of using 20.26 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-2”-yl-9H-fluorene obtained in Example 1, 16.26 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-diphenyl-9H-fluorene was used. Otherwise, polycarbonate resin was obtained according to the procedures described in Example 12.

[0242] The obtained polycarbonate resin had a weight-average molecular weight (Mw) of 28,300 and a Tg of 112℃.

[0243] The refractive index (n633) of this polycarbonate resin is 1.6959.

[0244] (Example 13)

[0245] 20.26 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-2”-yl-9H-fluorene obtained in Example 2, 8.56 g (40 mmol) of diphenyl carbonate, and 15 μL (3 × 10⁻⁶) of 0.02 M sodium bicarbonate aqueous solution were prepared. -6 The polycarbonate resin was loaded into a reactor equipped with a distillation device and reacted at 260°C and 100 kPa for 20 minutes, then at 270°C and 100 kPa for 30 minutes. The pressure was then adjusted to 22 kPa, and the reaction was continued for 20 minutes, followed by 60 minutes at the same temperature and pressure. Next, the pressure was adjusted to 16 kPa, and the reaction was continued for 20 minutes. Further adjustments were made to 13 kPa, and the reaction was continued for 20 minutes. After 40 minutes, the pressure was adjusted to 130 Pa, and the reaction was continued for 30 minutes at the same pressure. At the predetermined torque, the pressure was released using nitrogen, and the polycarbonate resin was removed.

[0246] The obtained polycarbonate resin is a crystalline polymer with a weight-average molecular weight (Mw) of 4250, a Tg of 115℃, and a Tm of 172℃ (heat: 1.87J / g).

[0247] The refractive index (n633) of this polycarbonate resin is 1.7708.

[0248] (Example 14)

[0249] 23.46 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-bis[dibenzo[b,d]furan-4”-yl]-9H-fluorene obtained from Example 3, 8.56 g (40 mmol) of DPC, and 15 μL (3 × 10⁻⁶) of 0.02 M sodium bicarbonate aqueous solution were prepared. -6 The polycarbonate resin was loaded into a reactor equipped with a distillation device and reacted at 240°C and 100 kPa for 1 hour. Then, the pressure was adjusted to 22 kPa and the reaction was continued for 20 minutes. The pressure was further adjusted to 13 kPa and the reaction was continued for 20 minutes. After 40 minutes, the pressure was adjusted to 130 Pa and the reaction was continued at the same pressure for 30 minutes. When the predetermined torque was reached, the pressure was released by nitrogen gas to remove the polycarbonate resin.

[0250] The obtained polycarbonate resin had a weight-average molecular weight (Mw) of 8430 and a Tg of 118℃.

[0251] The refractive index (n633) of this polycarbonate resin is 1.730.

[0252] (Example 15)

[0253] In Example 14, instead of using 23.46 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-bis[dibenzo[b,d]furan-4”-yl]-9H-fluorene obtained in Example 3, 26.35 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-bis[3-(naphthyl-2-yl-)phenyl]-9H-fluorene obtained in Example 5 was used, and otherwise, a polycarbonate resin was manufactured according to the operation described in Example 14.

[0254] The obtained polycarbonate resin had a weight-average molecular weight (Mw) of 5240 and a Tg of 105℃.

[0255] The refractive index (n633) of this polycarbonate resin is 1.735.

[0256] (Example 16)

[0257] In Example 14, instead of using 23.46 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-bis[dibenzo[b,d]furan-4”-yl]-9H-fluorene obtained in Example 3, 24.27 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-diphenanthrene-9”-yl-9H-fluorene obtained in Example 6 was used, and polycarbonate resin was manufactured according to the procedures described in Example 14.

[0258] The obtained polycarbonate resin had a weight-average molecular weight (Mw) of 5550 and a Tg of 126℃.

[0259] The refractive index (n633) of this polycarbonate resin is 1.718.

[0260] (Example 17)

[0261] In Example 14, instead of using 23.46 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-bis[dibenzo[b,d]furan-4”-yl]-9H-fluorene obtained in Example 3, 23.63 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-bis(4”-phenoxyphenyl)-9H-fluorene obtained in Example 8 was used, and otherwise polycarbonate resin was manufactured according to the operation described in Example 14.

[0262] The obtained polycarbonate resin had a weight-average molecular weight (Mw) of 4870 and a Tg of 67℃.

[0263] The refractive index (n633) of this polycarbonate resin is 1.715.

[0264] (Example 18)

[0265] In Example 14, instead of using 23.46 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-bis[dibenzo[b,d]furan-4”-yl]-9H-fluorene obtained in Example 3, 26.35 g (40 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-bis(4”-phenylnaphth-1”-yl)-9H-fluorene obtained in Example 9 was used, and polycarbonate resin was manufactured according to the operation described in Example 14.

[0266] The obtained polycarbonate resin is a crystalline polymer with a weight-average molecular weight (Mw) of 6170, a Tg of 122℃, and a Tm of 273℃ (heat: 8.82J / g).

[0267] The refractive index (n633) of this polycarbonate resin is 1.796.

[0268] (Example 19)

[0269] 4.04 g (8 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-2”yl-9H-fluorene, 10.52 g (24 mmol) of 9,9-bis[4'-(2”-hydroxyethoxy)phenyl]-9H-fluorene, 1.32 g (8 mmol) of bisphenol A, 8.57 g (40 mmol) of DPC, and 15 μL (3 × 10⁻⁶) of 0.02 M sodium bicarbonate aqueous solution obtained in Example 2 were added. -6 The polycarbonate resin was loaded into a reactor equipped with a distillation device and reacted at 240°C and 100 kPa for 1 hour. Then, the pressure was adjusted to 22 kPa and the reaction was continued for 20 minutes. The pressure was further adjusted to 13 kPa and the reaction was continued for 20 minutes. After 40 minutes, the pressure was adjusted to 130 Pa and the reaction was continued at the same pressure for 30 minutes. When the predetermined torque was reached, the pressure was released by nitrogen gas to remove the polycarbonate resin.

[0270] The obtained polycarbonate resin had a weight-average molecular weight (Mw) of 32,500 and a Tg of 139℃.

[0271] The refractive index (n633) of this polycarbonate resin is 1.713.

[0272] Furthermore, the total light transmittance of a 500 μm thick sheet of polycarbonate resin that was hot-pressed at 250°C was 82%.

[0273] (Example 20)

[0274] 4.00 g (6 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-bis[4-(naphth-2-yl-)phenyl]-9H-fluorene, 7.98 g (18 mmol) of 9,9-bis[4'-(2”-hydroxyethoxy)phenyl]-9H-fluorene, 1.39 g (6 mmol) of bisphenol A, 6.55 g (30 mmol) of DPC, and 10 μL (2 × 10⁻⁶) of 0.02 M sodium bicarbonate aqueous solution obtained in Example 4 were added. -6 The mol) was loaded into a reactor equipped with a distillation device and reacted at 270°C and 100 kPa for 1 hour. Then, the pressure was adjusted to 22 kPa and the reaction was continued for 20 minutes. The pressure was further adjusted to 13 kPa and the reaction was continued for 20 minutes. After 40 minutes, the pressure was adjusted to 130 Pa and the reaction was continued at the same pressure for 70 minutes. When the predetermined torque was reached, the pressure was released by nitrogen gas to remove the polycarbonate resin.

[0275] The obtained polycarbonate resin has a weight-average molecular weight (Mw) of 27,800 and a Tg of 157℃. The polycarbonate resin is colorless and transparent.

[0276] (Example 21)

[0277] A mixture comprising 3.0375 g (6 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-dinaphth-2”yl-9H-fluorene obtained in Example 2, 6.1380 g (14 mmol) of 9,9-bis[4'-(2”-hydroxyethoxy)phenyl]-9H-fluorene, 4.8850 g (8 mmol) of dimethyl 2,6-naphthalenedicarboxylate, and 3.7 μl of titanium tetraisopropoxide (as Ti, 50 ppm) was charged into a reactor equipped with a distillation apparatus and reacted at 280 °C and 100 kPa for 1 hour. Then, the pressure was adjusted to 20 kPa, and the reaction was continued for 20 minutes. The pressure was further adjusted to 13 kPa, and the reaction continued for 20 minutes. After 30 minutes, the pressure was adjusted to 130 Pa, and the reaction continued for 30 minutes at the same pressure. When the predetermined torque was reached, the vacuum was released by nitrogen, and the polyester resin was removed.

[0278] The obtained polyester resin had a weight-average molecular weight (Mw) of 6300 and a Tg of 118℃.

[0279] As can be understood from the above, the polycarbonate resin obtained from the compound represented by general formula (1) involved in this embodiment has a high refractive index.

[0280] This application claims priority based on Japanese Patent Application No. 2020-127221, filed on July 28, 2020, and incorporates all of its disclosures into this application.

Claims

1. A compound represented by general formula (1), In general formula (1), R1 and R2 are hydrogen atoms, and Ar1 and Ar2 independently represent groups selected from the following: R3 and R4 represent hydrogen atoms, X1 is -O-, Z1 and Z2 represent hydrogen atoms, and o and p represent integers from 1 to 4.

2. The compound according to claim 1, wherein o and p in the general formula (1) are 2.

3. The compound according to claim 1, wherein Ar1 and Ar2 in the general formula (1) independently represent groups selected from the group consisting of, R3 and R4 represent hydrogen atoms, and o and p represent integers from 1 to 4.

4. A polycarbonate resin derived from a compound of general formula (1) as described in claim 1 or 2.

5. An optically molded article comprising the polycarbonate resin of claim 4.

6. The optically shaped body according to claim 5, wherein it is an optical lens.

7. The optically shaped body according to claim 5, wherein it is an optical film.

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