Biphenanthrene dicarboxylic acid compound

Abstract

The present invention addresses the problem of providing a novel dicarboxylic acid compound having excellent thermal stability in addition to an excellent refractive index. The problem is solved by providing a biphenanthrene dicarboxylic acid compound represented by general formula (1). (In the formula, each R1 independently represents a hydrogen atom, a methyl group or an ethyl group.)

Description

Biphenanthrene dicarboxylic acid compounds

[0001] The present invention relates to a biphenanthrene dicarboxylic acid compound.

[0002] Dicarboxylic acid compounds are used as raw materials for polyamides, raw materials for allyl ester compounds, and additives such as plasticizers and curing agents, and dicarboxylic acid compounds using bisphenol compounds as raw materials are also known (Patent Documents 1 and 2, etc.). In recent years, in the fields of application of such materials, demands for improved performance in various areas have become increasingly stringent, and further improvements in heat resistance, water resistance, electrical properties, and optical properties such as refractive index are particularly required, and new compounds that exhibit such performance are in demand. As dicarboxylic acid compounds with improved refractive index, biphenanthrene dicarboxylic acid compounds or alkali metal salts thereof, which are derived from biphenanthrols as raw materials, are known (Patent Document 3).

[0003] JP-A-62-292819 JP-A-05-170702 International Publication No. 2023 / 176687

[0004] 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthryl (hereinafter sometimes referred to as "compound α") described in the examples of Patent Document 3 is a compound with a high refractive index. However, when the present inventors investigated its physical properties, they found that its 1% thermal weight loss temperature and hue stability upon heating were not sufficiently high, as shown in the comparative examples described below. When used as a raw material for curable resins or polycondensation resins, the low thermal stability of dicarboxylic acid compounds not only leads to contamination of equipment due to volatilization upon heating and fluctuations in the raw material composition when producing resins, but also deteriorates the hue of the resulting resin. The present invention aims to provide a novel dicarboxylic acid compound that has excellent refractive index and thermal stability.

[0005] As a result of intensive investigations to solve the above-mentioned problems, the present inventors have found that a biphenanthrene dicarboxylic acid compound in which the alkylene chain length connecting the phenanthrene ring and the carboxylic acid group is of a specific length can solve the above-mentioned problems, and further that a thermoplastic resin having excellent optical properties such as refractive index and Abbe number and also excellent heat resistance can be obtained, thereby completing the present invention.

[0006] The present invention is as follows: 1. A biphenanthrene dicarboxylic acid compound represented by general formula (1). (In the formula, R １ each independently represents a hydrogen atom, a methyl group, or an ethyl group.) 2. The compound according to 1., wherein the biphenanthrene dicarboxylic acid compound represented by the general formula (1) is a compound represented by the chemical formula (1-1), (1-2), or (1-3). 3. A method for producing the compound according to 1., comprising reacting 10,10'-dihydroxy-9,9'-biphenanthryl with a halogenated butyric acid represented by general formula (2) in at least one solvent selected from N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, and sulfolane. (In the formula, R １has the same definition as in general formula (1), and Z represents a halogen atom. 4. A crystal of the compound according to 1., wherein the biphenanthrene dicarboxylic acid compound represented by general formula (1) is 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl. 5. The crystal according to 4., which exhibits an endothermic peak with an onset temperature in the range of 130 to 140°C in differential scanning calorimetry. 6. The crystal according to 4., which has diffraction peaks at diffraction angles 2θ of 6.7±0.2°, 10.5±0.2°, and 18.5±0.2° in a powder X-ray diffraction peak pattern using Cu-Kα radiation. 7. The crystal according to 4., which has a purity of 95.0% or more as determined by high performance liquid chromatography. 8. The crystal according to 4., wherein the hue measured in a 10% by weight solution of the crystal in tetrahydrofuran is APHA 250 or less. 9. A method for producing the crystal according to 4., which comprises precipitating the crystal from a solution containing 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl and a ketone solvent having 3 to 9 carbon atoms. 10. A crystal of the compound according to 1., in which the biphenanthrene dicarboxylic acid compound represented by general formula (1) is 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl. 11. The crystal according to 10., which exhibits an endothermic peak with an onset temperature in the range of 150 to 160°C in differential scanning calorimetry. 12. The crystal according to 10., which has diffraction peaks at diffraction angles 2θ of 6.4±0.2°, 20.0±0.2°, and 22.9±0.2° in a powder X-ray diffraction peak pattern using Cu-Kα radiation. 13. The crystal according to 10., which has a purity of 95.0% or more as determined by high performance liquid chromatography. 14. The crystal according to 10., wherein the hue measured in a 10 wt% tetrahydrofuran solution of the crystal is APHA 250 or less. 15. A method for producing the crystal according to 10., which comprises precipitating the crystal from a solution containing 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl and a ketone solvent having 3 to 9 carbon atoms.

[0007] The biphenanthrene dicarboxylic acid compound of the present invention has a high refractive index due to the biphenanthrene skeleton. Furthermore, due to the specific alkylene chain length structure, it has excellent thermal stability and a reduced melting point. Therefore, materials obtained using this compound as a raw material not only have an excellent refractive index, but also have excellent thermal stability and a reduced melting point, which facilitate melting of raw materials and suppress problems such as volatilization and discoloration of raw materials when carrying out polymerization or curing reactions at high temperatures, for example, 200°C or higher. Furthermore, it is possible to provide a thermoplastic resin that has excellent optical properties such as refractive index and Abbe number, and also has excellent heat resistance. The biphenanthrene dicarboxylic acid compound of the present invention is useful as a raw material for materials such as polyamide materials, curable materials, polyester carbonate resins, and polyester resins, as well as additives such as plasticizers and curing agents, and as a raw material for various other chemical products. The method for producing a biphenanthrene dicarboxylic acid compound of the present invention is extremely useful because it can produce such biphenanthrene dicarboxylic acid compounds in extremely high yields.

[0008] FIG. 1 shows a powder X-ray diffraction (PXRD) measurement chart of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl (compound represented by chemical formula (1-3)) obtained in Example 1. The vertical axis indicates the intensity range of 0 to 40,000 (cps), and the horizontal axis indicates 2θ range of 5 to 50 (°). FIG. 2 shows a differential scanning calorimetry (DSC) analysis chart of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl (compound represented by chemical formula (1-3)) obtained in Example 1. FIG. 3 shows a powder X-ray diffraction (PXRD) measurement chart of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl (compound represented by chemical formula (1-2)) obtained in Example 2. The vertical axis represents the intensity range of 0 to 30,000 (cps), and the horizontal axis represents 2θ range of 5 to 50 (°). This figure shows a differential scanning calorimetry (DSC) chart of 10,10′-bis(methoxycarbonylpropoxy)-9,9′-biphenanthryl (compound represented by chemical formula (1-2)) obtained in Example 2. This figure shows a PXRD measurement chart of 10,10′-bis(methoxycarbonylmethoxy)-9,9′-biphenanthryl (compound (β)) obtained in Comparative Example 2. This figure shows a differential scanning calorimetry (DSC) chart of 10,10′-bis(methoxycarbonylmethoxy)-9,9′-biphenanthryl (compound (β)) obtained in Comparative Example 2.

[0009] <Biphenanthrenedicarboxylic acid compound of the present invention> The biphenanthrenedicarboxylic acid compound of the present invention is represented by general formula (1). (In the formula, R １ each independently represents a hydrogen atom, a methyl group, or an ethyl group. １ are each independently a hydrogen atom, a methyl group, or an ethyl group, with a methyl group or an ethyl group being preferred, and a methyl group being particularly preferred. The biphenanthrene dicarboxylic acid compound of the present invention represented by general formula (1) is specifically a compound represented by any one of (1-1) to (1-3). Among these, (1-2) or (1-3) is preferred, with (1-2) being particularly preferred.

[0010] <Method for Producing the Compound of the Present Invention> There are no particular limitations on the starting materials or production method used in the production of the biphenanthrene dicarboxylic acid compound represented by general formula (1) in the present invention. Examples of methods for producing the biphenanthrene dicarboxylic acid compound represented by general formula (1) in the present invention include a method in which 10,10'-dihydroxy-9,9'-biphenanthryl is reacted with a halogenated butyric acid represented by general formula (2) to obtain the compound represented by general formula (1) through an etherification reaction. It is presumed that the target biphenanthrene dicarboxylic acid compound represented by general formula (1) is produced by etherifying one molecule of a halogenated butyric acid represented by general formula (2) with 10,10'-dihydroxy-9,9'-biphenanthryl to produce a mono-etherified product as an intermediate, and then etherifying this mono-etherified product with another molecule of a halogenated butyric acid represented by general formula (2). Furthermore, among the biphenanthrene dicarboxylic acid compounds represented by general formula (1), the compound represented by chemical formula (1-1) can be obtained by alkaline hydrolysis or neutralization of a biphenanthrene dicarboxylic acid compound represented by general formula (1) represented by chemical formula (1-2) or (1-3) with an alkali metal hydroxide to obtain a compound represented by the following chemical formula (1-1′), i.e., an alkali metal salt of the compound represented by chemical formula (1-1), and then further protonating it using an acid. (In the formula, R １ has the same definition as in general formula (1), Z has the same definition as in general formula (2), M represents an alkali metal atom, and MOH means an alkali metal hydroxide.

[0011] The reaction formula for an etherification reaction in which a compound represented by chemical formula (1-2) is obtained as a biphenanthrene dicarboxylic acid compound represented by general formula (1) using 9,9'-biphenanthrene-10,10'-diol and methyl chlorobutyrate as a halogenated butyric acid represented by general formula (2) is shown below. The reaction formula for obtaining the potassium salt of the compound represented by the chemical formula (1-1) from the compound represented by the chemical formula (1-2) using potassium hydroxide as the alkali metal hydroxide is shown below. The resulting potassium salt is reacted with an acid to obtain the compound represented by chemical formula (1-1), as shown in the reaction formula below.

[0012] <Raw Material 1: 10,10'-Dihydroxy-9,9'-biphenanthryl> 10,10'-Dihydroxy-9,9'-biphenanthryl used in the production of the biphenanthrene dicarboxylic acid compound of the present invention represented by general formula (1) can be produced by, for example, the method described in JP-A-60-181043 or Journal of American Chemical Society, 2008, Vol. 130, p. 6840.

[0013] <Raw Material 2: Halogenated Butyric Acids> Examples of halogenated butyric acids represented by general formula (2) to be reacted with 10,10'-dihydroxy-9,9'-biphenanthryl include chlorobutyric acid, methyl chlorobutyrate, ethyl chlorobutyrate, bromobutyric acid, methyl bromobutyrate, and ethyl bromobutyrate. Among these, methyl chlorobutyrate, ethyl chlorobutyrate, methyl bromobutyrate, and ethyl bromobutyrate are preferred, with methyl chlorobutyrate and ethyl chlorobutyrate being more preferred, and methyl chlorobutyrate being particularly preferred. The molar ratio of halogenated butyric acids to biphenanthrols is not particularly limited as long as it is equal to or greater than the theoretical value (2.0), but is typically in the range of 2.0 to 20.0 times by molar amount, preferably 2.0 to 10.0 times by molar amount, and more preferably 2.0 to 6.0 times by molar amount.

[0014] <Reaction Conditions for the Etherification Reaction, etc.> The reaction is preferably carried out in the presence of a base. Examples of the base to be used include triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. Of these, sodium carbonate and potassium carbonate are preferred. The molar ratio of the base charged, in terms of cations generated from the base used, is typically 1.6 to 8.0 times, preferably 1.7 to 6.0 times, and more preferably 1.8 to 4.0 times, the molar amount of 10,10'-dihydroxy-9,9'-biphenanthryl. A catalyst may also be used, and examples thereof include alkali metal bromide salts such as sodium bromide and potassium bromide, alkali metal iodide salts such as sodium iodide and potassium iodide, ammonium bromide, and ammonium iodide. The amount of the catalyst used is typically 0.1 to 100% by weight, preferably 0.1 to 20% by weight, and more preferably 0.1 to 10% by weight, relative to the biphenanthrols.

[0015] The reaction temperature is usually in the range of 25 to 180° C., preferably in the range of 60 to 160° C., more preferably in the range of 70 to 140° C., and particularly preferably in the range of 80 to 130° C. A high reaction temperature reduces the yield, while a low reaction temperature slows the reaction rate, which is undesirable.

[0016] The reaction pressure is not limited and may be atmospheric pressure, reduced pressure, or pressurized. Atmospheric pressure or reduced pressure is preferred. In a pressurized reaction, the reaction can be carried out under a pressurized condition, for example, by circulating a gas inert to the reaction, such as nitrogen. This allows carbon dioxide gas generated from the carbonate or bicarbonate used in the reaction to be discharged to the outside of the reaction system, thereby accelerating the reaction. From the viewpoint of shortening the reaction time, reduced pressure is more preferred. By carrying out the reaction under reduced pressure, carbon dioxide gas generated from the carbonate or bicarbonate used in the reaction can be discharged to the outside of the reaction system, thereby accelerating the reaction and shortening the reaction time compared to a reaction under atmospheric pressure. Furthermore, by carrying out the reaction under reduced pressure and distilling the solvent out of the reaction system, the production of by-products can be suppressed. Specifically, the reaction pressure is preferably in the range of 5 kPa to 80 kPa, more preferably in the range of 10 kPa to 70 kPa, and even more preferably in the range of 30 kPa to 60 kPa. The reaction pressure can be reduced by a pressure reducing device, and when the reaction pressure is maintained within the above range, the pressure reducing device may be operated intermittently or continuously, but it is more preferable to operate it continuously.

[0017] A reaction solvent is preferably used during the reaction for reasons such as improving operability and reaction rate during industrial production, and an aprotic polar solvent having a high boiling point and a high dielectric constant is preferably used in order to carry out the reaction with good reaction selectivity and reaction rate. Specific examples of such solvents include amide solvents such as N-methylpyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide, sulfoxide solvents such as dimethyl sulfoxide, and sulfone solvents such as sulfolane. At least one solvent selected from these solvents is preferred, and at least one solvent selected from N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, and sulfolane is more preferred, and at least one solvent selected from N-methylpyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide is even more preferred, with N-methylpyrrolidone being particularly preferred. The amount of the solvent used is not particularly limited as long as it does not interfere with the reaction, but it is usually preferably used in an amount in the range of 1.0 to 7.0 times by weight, more preferably 1.0 to 4.0 times by weight, and even more preferably 1.0 to 3.0 times by weight, relative to the amount of the biphenanthrols.

[0018] In producing the biphenanthrene dicarboxylic acid compound of the present invention, the water content of the reaction solution in the etherification reaction is preferably in the range of 0.01% by weight or more and 2.0% by weight or less relative to the biphenanthrols. By setting the water content in the reaction solution within this range, the biphenanthrene dicarboxylic acid compound of the present invention can be produced with a good reaction yield. The upper limit of this water content is more preferably 1.5% by weight or less, even more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less. Methods for setting the water content of the reaction solution within this range include, for example, using pre-dehydrated raw materials or solvents, and removing water by distillation before the etherification reaction.

[0019] In the present invention, when the biphenanthrene dicarboxylic acid compound represented by general formula (1) is an ester compound, after completion of the etherification reaction, it can be purified and isolated by conventional post-treatment procedures such as neutralization, water washing, crystallization, filtration, distillation, and separation by column chromatography. To further increase the purity, conventional purification procedures such as distillation, recrystallization, and column chromatography may be performed. After the etherification reaction, it is preferable to neutralize the reaction product mixture, dissolve the biphenanthrene dicarboxylic acid compound represented by general formula (1) in a water-separable organic solvent in which it dissolves, wash with water to remove water-soluble impurities such as salts, and then perform a crystallization procedure.

[0020] <Crystals of 10,10′-bis(ethoxycarbonylpropoxy)-9,9′-biphenanthryl> Among the biphenanthrene dicarboxylic acid compounds of the present invention, crystals of 10,10′-bis(ethoxycarbonylpropoxy)-9,9′-biphenanthryl, which is the compound represented by chemical formula (1-3), can be handled as a crystalline solid and are therefore very useful because they have excellent handleability. The crystal of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl, which is the compound of the present invention represented by chemical formula (1-3), preferably exhibits an endothermic peak having an onset temperature in the range of 150 to 160°C in differential scanning calorimetry, or has diffraction peaks at diffraction angles 2θ of 6.4±0.2°, 20.0±0.2°, and 22.9±0.2° in a powder X-ray diffraction peak pattern using Cu-Kα radiation, and is a crystal having either one or both of the characteristics of "an endothermic peak at the onset temperature" and "the powder X-ray diffraction peak pattern". That is, the crystal of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl, which is the compound represented by chemical formula (1-3) of the present invention, preferably has any of the following embodiments (i) to (iii): (i) in differential scanning calorimetry, it exhibits an endothermic peak having an onset temperature in the range of 150 to 160°C; (ii) in a powder X-ray diffraction peak pattern using Cu-Kα radiation, it has diffraction peaks at diffraction angles 2θ of 6.4±0.2°, 20.0±0.2°, and 22.9±0.2°; and (iii) in differential scanning calorimetry, it exhibits an endothermic peak having an onset temperature in the range of 150 to 160°C, and in a powder X-ray diffraction peak pattern using Cu-Kα radiation, it has diffraction peaks at diffraction angles 2θ of 6.4±0.2°, 20.0±0.2°, and 22.9±0.2°. Among these, embodiment (iii) is more preferable. In differential scanning calorimetry, the crystal preferably exhibits an endothermic peak with an onset temperature in the range of 150 to 160°C, more preferably in the range of 152 to 158°C, and particularly preferably in the range of 153 to 156°C. The onset temperature of the endothermic peak in differential scanning calorimetry (DSC) is sometimes referred to as the melting point.In the powder X-ray diffraction peak pattern using Cu-Kα radiation of the present invention, in addition to the above peaks, it is more preferable that the diffraction angle 2θ further includes diffraction peaks at 9.4±0.2°, 19.2±0.2°, and 24.5±0.2°. The peaks in the powder X-ray diffraction using Cu-Kα radiation preferably have a relative intensity of 5 or more, more preferably 10 or more, based on the most intense peak. However, the relative intensity may vary depending on the measurement device and conditions, or in the case of a mixture with other crystals. Therefore, the crystalline phase can be identified based on a typical powder X-ray diffraction analysis method. The purity of the crystal of the compound represented by chemical formula (1-3) is preferably such that the ratio of the peak area of ​​Compound A to the peak areas of all components detected at a wavelength of 280 nm in high performance liquid chromatography (HPLC) analysis is 90.0% or more, more preferably 95.0% or more, even more preferably 97.0% or more, and particularly preferably 99.0% or more. The method for HPLC analysis of the purity of the crystals of the present invention is a method in accordance with the HPLC analysis in the analytical methods of the Examples described below.

[0021] <Method for Producing Crystals of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl> A method for producing crystals of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl, which is the compound represented by chemical formula (1-3), is to precipitate crystals from a solution containing 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl and a ketone solvent having 3 to 9 carbon atoms. There are no particular restrictions on the 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl used, but as described above, a product that has been subjected to post-treatment in accordance with a conventional method after completion of the etherification reaction can be used. Specific examples of ketone solvents having 3 to 9 carbon atoms include chain ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl isoamyl ketone, and cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, and isophorone. Among these, chain ketone solvents having 3 to 9 carbon atoms are preferred, chain ketone solvents having 3 to 6 carbon atoms are more preferred, and acetone or methyl isobutyl ketone is particularly preferred. The amount of the organic solvent used can be adjusted appropriately in consideration of the solubility depending on the type of organic solvent used, but is in the range of 0.5 to 10.0 times by weight, more preferably 1.0 to 8.0 times by weight, even more preferably 1.0 to 6.0 times by weight, and particularly preferably 1.5 to 4.0 times by weight relative to the amount of the compound represented by chemical formula (1-3). The temperature at which the compound represented by chemical formula (1-3) is dissolved in the organic solvent to form a solution can be adjusted appropriately in consideration of the type of organic solvent used, but is in the range of 40 to 90°C.

[0022] The procedure for precipitating crystals in this crystallization method can include mixing a poor solvent in which the compound represented by chemical formula (1-3) has low solubility, cooling the solution, or removing the solvent from the solution by distillation or the like. Among these, the procedure for mixing a poor solvent or the procedure for cooling the solution is preferred. Examples of poor solvents used when precipitating crystals by mixing a poor solvent include water, alcohol solvents having 1 to 4 carbon atoms, and aliphatic hydrocarbon solvents having 5 to 8 carbon atoms. The poor solvent to be mixed is at least one selected from these, and it is preferable to select one from these. Specific examples of alcohol solvents having 1 to 4 carbon atoms include methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol. Alcohol solvents having 1 to 3 carbon atoms are preferred, alcohol solvents having 1 or 2 carbon atoms are more preferred, and methanol is particularly preferred. Specific examples of aliphatic hydrocarbon solvents having 5 to 8 carbon atoms include chain aliphatic hydrocarbon solvents having 5 to 8 carbon atoms, such as pentane, hexane, heptane, octane, and isooctane, and cyclic aliphatic hydrocarbon solvents having 5 to 8 carbon atoms, such as cyclopentane, cyclohexane, and cycloheptane. Among these, chain aliphatic hydrocarbon solvents having 5 to 8 carbon atoms are preferred, chain aliphatic hydrocarbon solvents having 6 to 8 carbon atoms are more preferred, chain aliphatic hydrocarbon solvents having 7 carbon atoms are even more preferred, and normal heptane is particularly preferred. The amount of the poor solvent used can be adjusted appropriately in consideration of the amount of solution of the compound represented by chemical formula (1-3), the type of organic solvent, and the solubility depending on the type of poor solvent used. However, the amount is in the range of 0.5 to 10.0 times by weight, more preferably 1.0 to 8.0 times by weight, even more preferably 1.0 to 6.0 times by weight, and particularly preferably 1.5 to 4.0 times by weight relative to the amount of the compound represented by chemical formula (1-3). The temperature at which the poor solvent is mixed to precipitate the crystals of the compound represented by the chemical formula (1-3) is not particularly limited, but is in the range of 20 to 85°C.

[0023] When crystals are precipitated by cooling a solution of the compound represented by chemical formula (1-3), the poor solvent used in the case of precipitating crystals by mixing the poor solvent may be mixed with the solution of the compound represented by chemical formula (1-3) before cooling the solution. The temperature at which the solution of the compound represented by chemical formula (1-3) is cooled to precipitate crystals is not particularly limited, and is in the range of 10 to 80°C, as long as the temperature is lowered from the temperature at which the compound is dissolved to form a solution.

[0024] When precipitating the crystals, seed crystals may not be used, but it is preferable to use seed crystals. There are no limitations on the crystals used as seed crystals, and the crystals of the present invention that have been initially precipitated without seed crystals can also be used as seed crystals.

[0025] <Crystals of 10,10′-bis(methoxycarbonylpropoxy)-9,9′-biphenanthryl> Among the biphenanthrene dicarboxylic acid compounds of the present invention, crystals of 10,10′-bis(methoxycarbonylpropoxy)-9,9′-biphenanthryl, which is the compound represented by chemical formula (1-2), can be handled as a crystalline solid and has excellent handleability, making them very useful. The crystal of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl, which is the compound of the present invention represented by chemical formula (1-2), preferably exhibits an endothermic peak having an onset temperature in the range of 130 to 140°C in differential scanning calorimetry, or has diffraction peaks at diffraction angles 2θ of 6.7±0.2°, 10.5±0.2°, and 18.5±0.2° in a powder X-ray diffraction peak pattern using Cu-Kα radiation, and is a crystal having either one or both of the characteristics of "an endothermic peak at the onset temperature" and "the powder X-ray diffraction peak pattern". That is, the crystal of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl, which is the compound represented by chemical formula (1-2) of the present invention, preferably has any one of the following embodiments (i) to (iii): (i) in differential scanning calorimetry, it exhibits an endothermic peak having an onset temperature in the range of 130 to 140°C; (ii) in a powder X-ray diffraction peak pattern using Cu-Kα radiation, it has diffraction peaks at diffraction angles 2θ of 6.7±0.2°, 10.5±0.2°, and 18.5±0.2°; and (iii) in differential scanning calorimetry, it exhibits an endothermic peak having an onset temperature in the range of 130 to 140°C, and in a powder X-ray diffraction peak pattern using Cu-Kα radiation, it has diffraction peaks at diffraction angles 2θ of 6.7±0.2°, 10.5±0.2°, and 18.5±0.2°. Among these, embodiment (iii) is more preferred. In differential scanning calorimetry, the crystals preferably exhibit an endothermic peak with an onset temperature in the range of 130 to 140°C, more preferably in the range of 132 to 138°C, and particularly preferably in the range of 133 to 136°C. The onset temperature of the endothermic peak in differential scanning calorimetry (DSC) is sometimes referred to as the melting point.The peaks in powder X-ray diffraction using Cu-Kα radiation preferably have a relative intensity of 5 or more, more preferably 10 or more, based on the most intense peak. However, the relative intensity may vary depending on the measurement device and conditions, or in the case of a mixture with other crystals. Therefore, the crystalline phase can be identified based on a typical powder X-ray diffraction analysis method. The purity of the crystals of the compound represented by chemical formula (1-2) is preferably such that the ratio of the peak area of ​​Compound A to the peak areas of all components detected at a wavelength of 280 nm in high performance liquid chromatography (HPLC) analysis is preferably 90.0% or more, more preferably 95.0% or more, even more preferably 97.0% or more, and particularly preferably 99.0% or more. The method for HPLC analysis of the purity of the crystals of the present invention is a method in accordance with the HPLC analysis in the analytical method of the Examples described below.

[0026] <Method for Producing Crystals of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl> A method for producing crystals of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl, which is the compound represented by chemical formula (1-2), is to precipitate crystals from a solution containing 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl and a ketone solvent having 3 to 9 carbon atoms. There are no particular restrictions on the 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl used, but as described above, a product that has been subjected to post-treatment in accordance with a conventional method after completion of the etherification reaction can be used. Specific examples of ketone solvents having 3 to 9 carbon atoms include chain ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl isoamyl ketone, and cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, and isophorone. Among these, chain ketone solvents having 3 to 9 carbon atoms are preferred, chain ketone solvents having 3 to 6 carbon atoms are more preferred, and acetone or methyl isobutyl ketone is particularly preferred. The amount of the organic solvent used can be adjusted appropriately in consideration of the solubility depending on the type of organic solvent used, but is in the range of 0.5 to 10.0 times by weight, more preferably 1.0 to 8.0 times by weight, even more preferably 1.0 to 6.0 times by weight, and particularly preferably 1.5 to 4.0 times by weight relative to the amount of the compound represented by chemical formula (1-2). The temperature at which the compound represented by chemical formula (1-2) is dissolved in the organic solvent to form a solution can be adjusted appropriately in consideration of the type of organic solvent used, but is in the range of 40 to 90°C.

[0027] The procedure for precipitating crystals in this crystallization method can include mixing a poor solvent in which the compound represented by chemical formula (1-2) has low solubility, cooling the solution, or removing the solvent from the solution by distillation or the like. Among these, the procedure for mixing a poor solvent or the procedure for cooling the solution is preferred. Examples of poor solvents used when precipitating crystals by mixing a poor solvent include water, alcohol solvents having 1 to 4 carbon atoms, and aliphatic hydrocarbon solvents having 5 to 8 carbon atoms. The poor solvent to be mixed is at least one selected from these, and it is preferable to select one from among these. Specific examples of alcohol solvents having 1 to 4 carbon atoms include methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol. Alcohol solvents having 1 to 3 carbon atoms are preferred, alcohol solvents having 1 or 2 carbon atoms are more preferred, and methanol is particularly preferred. Specific examples of aliphatic hydrocarbon solvents having 5 to 8 carbon atoms include chain aliphatic hydrocarbon solvents having 5 to 8 carbon atoms, such as pentane, hexane, heptane, octane, and isooctane, and cyclic aliphatic hydrocarbon solvents having 5 to 8 carbon atoms, such as cyclopentane, cyclohexane, and cycloheptane. Among these, chain aliphatic hydrocarbon solvents having 5 to 8 carbon atoms are preferred, chain aliphatic hydrocarbon solvents having 6 to 8 carbon atoms are more preferred, chain aliphatic hydrocarbon solvents having 7 carbon atoms are even more preferred, and normal heptane is particularly preferred. The amount of the poor solvent used can be adjusted appropriately in consideration of the amount of solution of the compound represented by chemical formula (1-2), the type of organic solvent, and the solubility depending on the type of poor solvent used. However, the amount is in the range of 0.5 to 10.0 times by weight, more preferably 1.0 to 8.0 times by weight, even more preferably 1.0 to 6.0 times by weight, and particularly preferably 1.5 to 4.0 times by weight relative to the amount of the compound represented by chemical formula (1-2). The temperature at which the poor solvent is mixed to precipitate the crystals of the compound represented by the chemical formula (1-2) is not particularly limited, but is in the range of 20 to 85°C.

[0028] When crystals are precipitated by cooling a solution of the compound represented by chemical formula (1-2), the poor solvent used in the case of precipitating crystals by mixing the poor solvent may be mixed with the solution of the compound represented by chemical formula (1-2) before cooling the solution. The temperature at which the solution of the compound represented by chemical formula (1-2) is cooled to precipitate crystals is not particularly limited, and is in the range of 10 to 80°C, as long as the temperature is lowered from the temperature at which the compound is dissolved to form a solution.

[0029] When precipitating the crystals, seed crystals may not be used, but it is preferable to use seed crystals. There are no limitations on the crystals used as seed crystals, and the crystals of the present invention that have been initially precipitated without seed crystals can also be used as seed crystals.

[0030] Each step, such as reaction, alkaline hydrolysis, neutralization, washing with water, crystallization, filtration, distillation, separation by column chromatography, drying, packaging, melting, and cooling, is preferably carried out in an inert gas atmosphere such as nitrogen or argon, or in an atmosphere with an oxygen content lower than that of air, in order to suppress oxidation, deterioration, coloration, and the like due to the influence of oxygen.

[0031] <Thermoplastic Resin> The biphenanthrene dicarboxylic acid compound of the present invention can give a thermoplastic resin containing the structural unit (A) derived from the monomer represented by general formula (1).

[0032] The thermoplastic resin is not particularly limited and may be a polyester resin, a polyester carbonate resin, an epoxy resin, a polyurethane resin, a polyacrylic acid ester resin, a polymethacrylic acid ester resin, or the like, but is preferably a polyester carbonate resin or a polyester resin.

[0033] In the thermoplastic resin, the proportion of the structural unit (A) represented by the general formula (1) in all structural units is not particularly limited, but is preferably 1 to 80 mol %, more preferably 1 to 60 mol %, and particularly preferably 5 to 50 mol % of all structural units. In other words, in addition to the structural unit (A) represented by the general formula (1), the thermoplastic resin of one embodiment of the present invention can contain a structural unit derived from an aliphatic dihydroxy compound or a structural unit derived from an aromatic dihydroxy compound, which are generally used as structural units in polycarbonate resins and polyester carbonate resins. Specific examples of aliphatic dihydroxy compounds include various compounds, particularly ethylene glycol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 1,3-adamantanedimethanol, 2,2-bis(4-hydroxycyclohexyl)-propane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 2-(5-ethyl-5-hydroxymethyl-1,3-dioxan-2-yl)-2-methylpropan-1-ol, isosorbide, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. Examples of aromatic dihydroxy compounds include various compounds, particularly 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bisphenoxyethanolfluorene, and the like.

[0034] The thermoplastic resin preferably contains a structural unit (B) derived from a monomer represented by the following general formula (6). In general formula (6), R ａand R ｂ each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ R ｈ represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent. ａ and R ｂ is preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, more preferably a hydrogen atom, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferably a hydrogen atom, or an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0035] In general formula (6), X represents a single bond or a fluorene group which may have a substituent. X is preferably a single bond or a fluorene group which may have a substituent and has a total of 12 to 20 carbon atoms. In general formula (6), A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 2 or 3 carbon atoms. In general formula (6), m and n each independently represent an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably 0 or 1. In general formula (6), a and b each independently represent an integer of 0 to 10, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0036] Specific examples of the structural unit (B) include those derived from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE), DPBHBNA, and the like.

[0037] The thermoplastic resin preferably contains a structural unit (C) derived from a monomer represented by the following general formula (7). In general formula (7), R ｃ and R ｄ are each independently selected from the group consisting of a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent. ｃ and R ｄ is preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, more preferably a hydrogen atom, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferably a hydrogen atom, or an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0038] In the general formula (7), Y １ represents a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following formulas (8) to (14), and is preferably a single bond or the structural formula represented by the following formula (8): In formulas (8) to (14), R ６１ , R ６２ , R ７１ and R ７２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R ６１ and R ６２ , or R ７１ and R ７２are bonded to each other to form a carbon ring or hetero ring having 1 to 20 carbon atoms, which may have a substituent. In formulas (8) to (14), r and s each independently represent an integer of 0 to 5,000.

[0039] In the general formula (7), A and B each independently represent an alkylene group having 1 to 5 carbon atoms, which may have a substituent, and preferably an alkylene group having 2 or 3 carbon atoms. In the general formula (7), p and q each independently represent an integer of 0 to 4, and preferably 0 or 1. In the general formula (7), a and b each independently represent an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 0 to 2, for example, 0 or 1.

[0040] Specific examples of the structural unit (C) include BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene), 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene (BNEF), bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol P-CDE (4,4'-cyclododecylidenebisphenol). bisphenol), bisphenol P-HTG (4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol), bisphenol P-MIBK (4,4'-(1,3-dimethylbutylidene)bisphenol), bisphenol P-3MZ (4-[1-(4-hydroxyphenyl)-3-methylcyclohexyl]phenol), bisphenol OC-FL (9,9-bis(4-hydroxy-3-methylphenyl)fluorene), bisphenol Z, BP-2EO (2,2'-[[1,1'-biphenyl]-4,4'-diylbis(oxy)bisethanol]), S-BOC (4,4'-(1-methylethylidene)bis(2-methylphenol)), TrisP-HAP (4,4',4''-ethylidenetrisphenol), and the like. Among these, preferred examples of the structural unit (C) are those derived from BPEF or BNEF.

[0041] The thermoplastic resin essentially contains the structural unit (A), but may also be a polymer containing the structural unit (B) but not containing the structural unit (C), a polymer containing the structural unit (C) but not containing the structural unit (B), a copolymer containing the structural unit (B) and the structural unit (C), a mixture of a polymer containing the structural unit (B) and a polymer containing the structural unit (C), or a combination thereof. Examples of polymers containing the structural unit (C) but not containing the structural unit (B) include those having structural units of the following formulas (I-1) to (I-3), and examples of copolymers having the structural unit (B) and the structural unit (C) include those having structural units of the following formulas (II-1) to (II-4). In formula (I-1), m and n each represent an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1. The number of repeating units in formula (I-3) is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1. As the polymer having multiple types of structural units, both a block copolymer in which the values ​​of m and n are large, for example, 100 or more, and a random copolymer can be used, but a random copolymer is preferred, and more preferably a random copolymer in which the values ​​of m and n are 1 is used. In formulas (II-1) to (II-4), m and n each independently represent an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1. Furthermore, as the polymer having multiple types of structural units, both block copolymers in which the values ​​of m and n (or m, n, and l) are large, for example, 100 or greater, and random copolymers can be used, although random copolymers are preferred, and more preferably random copolymers in which the values ​​of m and n (or m, n, and l) are 1 are used. In the copolymer, the molar ratio of structural unit (B) to structural unit (C) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, even more preferably 15:85 to 85:15, and particularly preferably 30:70 to 70:30. Furthermore, in the mixture, the mass ratio of the polymer having the structural unit (B) to the polymer having the structural unit (C) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, even more preferably 15:85 to 85:15, and particularly preferably 30:70 to 70:30.

[0042] The thermoplastic resin preferably contains a structural unit (D) derived from a monomer represented by the following general formula (5). In general formula (5), L １ each independently represents a divalent linking group; R ３ and R ４ j each independently represents a halogen atom or a substituent having 1 to 20 carbon atoms which may contain an aromatic group; ３ and j ４ each independently represents an integer of 0 to 4; t represents an integer of 0 or 1.

[0043] R in the general formula (5) ３ and R ４ It is preferable that each independently represents a methyl group, a phenyl group, or a naphthyl group. １ Preferably, each independently represents an alkylene group having 1 to 5 carbon atoms which may have a substituent.

[0044] Furthermore, the monomer represented by the general formula (5) preferably has a structure represented by the following formula (5').

[0045] The thermoplastic resin according to one embodiment of the present invention preferably further contains a structural unit derived from at least one monomer selected from the following group of monomers: In the above formula, R １１ and R ２２ each independently represents a hydrogen atom, a methyl group, or an ethyl group; R ３ and R ４ R each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms. ｍ１ and R ｍ２ each independently represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group.

[0046] <Method for producing polyester carbonate resin> A polyester carbonate resin, which is a preferred embodiment of the thermoplastic resin, can be produced by melt polycondensation using the dicarboxylic acid or carboxylic acid diester constituting the structural unit (A), a diol compound, and a carbonate diester as raw materials. Examples of the diol compound include the aliphatic dihydroxy compounds and aromatic dihydroxy compounds described above, but preferred examples include the monomer represented by general formula (6) and / or the monomer represented by general formula (7). This reaction can be produced in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst consisting of both, as a polycondensation catalyst.

[0047] Examples of carbonate diesters include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Among these, diphenyl carbonate is particularly preferred from the standpoint of reactivity and purity. The amount of carbonate diester added can be determined by assuming that equimolar amounts of the diol component and the dicarboxylic acid component react, with the remainder reacting with the carbonate diester. The carbonate diester is preferably used in a ratio of 0.60 to 1.50 moles per mole of the difference between the diol component and the dicarboxylic acid component, more preferably 0.80 to 1.40 moles, even more preferably 1.00 to 1.30 moles, even more preferably 1.00 to 1.25 moles, and particularly preferably 1.00 to 1.20 moles. Adjusting this molar ratio allows for control of the molecular weight of the polyester carbonate resin.

[0048] Examples of basic compound catalysts include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds. Examples of alkali metal compounds used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. From the viewpoints of catalytic effect, price, distribution volume, and influence on the color of the resin, sodium carbonate and sodium bicarbonate are preferred. Examples of alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds. Examples of nitrogen-containing compounds include quaternary ammonium hydroxides and their salts, amines, and the like.

[0049] As the transesterification catalyst, zinc, tin, zirconium, and lead salts are preferably used, and these may be used alone or in combination, or may be used in combination with the above-mentioned alkali metal compounds or alkaline earth metal compounds.

[0050] Specific examples of the transesterification catalyst include tris(2,4-pentanedionato)aluminum(III), diethyl (4-methylbenzyl)phosphonate, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead(II) acetate, lead(IV) acetate, zirconium acetate, and titanium tetrabutoxide. Of these, zinc acetate, zirconium acetate, tris(2,4-pentanedionato)aluminum(III), and diethyl (4-methylbenzyl)phosphonate are preferred, and tris(2,4-pentanedionato)aluminum(III) and diethyl (4-methylbenzyl)phosphonate are more preferred.

[0051] These catalysts are used so that the metal component in the catalyst is preferably 0.001 ppm to 1000 ppm, more preferably 0.01 ppm to 100 ppm, and particularly preferably 0.1 ppm to 100 ppm, relative to the amount of resin theoretically produced.

[0052] The melt polycondensation method uses the above-mentioned raw materials and catalyst, and performs melt polycondensation under heating at normal or reduced pressure while removing by-products through a transesterification reaction. Specifically, the reaction is carried out at a temperature of 120 to 260°C, preferably 180 to 260°C, for 0.1 to 5 hours, preferably 0.5 to 3 hours. The reaction temperature is then increased while increasing the degree of vacuum in the reaction system to allow the diol compound and the carbonate diester to react, and finally the polycondensation reaction is carried out at a temperature of 200 to 350°C under a reduced pressure of 1 mmHg or less for 0.05 to 2 hours. This reaction may be carried out continuously or batchwise. The reaction apparatus used in the above reaction may be a vertical type equipped with an anchor-type impeller, Maxblend impeller, helical ribbon impeller, etc.; a horizontal type equipped with a paddle impeller, lattice impeller, spectacle impeller, etc.; or an extruder type equipped with a screw. It is preferable to use an appropriate combination of these types of reaction apparatus taking into account the viscosity of the polymer.

[0053] In the method for producing the polyester carbonate resin, the catalyst may be removed or deactivated after the polymerization reaction to maintain thermal stability and hydrolytic stability. Generally, a method of deactivating the catalyst by adding a known acidic substance is preferably carried out. Specific examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate, phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid, phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite, and esters such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, and dioctyl phosphate. Suitable deactivators include phosphate esters such as octyl phosphate and monooctyl phosphate, phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid, phosphonic acid esters such as diethyl phenylphosphonate, phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane, boric acids such as boric acid and phenylboric acid, aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate, organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonyl chloride, alkyl sulfates such as dimethyl sulfate, and organic halides such as benzyl chloride. From the viewpoints of deactivation effect, resin hue, and stability, aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate are preferred. These deactivators are used in an amount of 0.01 to 50 times, preferably 0.3 to 20 times, the molar amount of the catalyst. Less than 0.01 times the molar amount of the catalyst results in insufficient deactivation effect, which is undesirable. On the other hand, if the amount is more than 50 times by mole the amount of the catalyst, the heat resistance decreases and the molded article tends to be discolored, which is undesirable.

[0054] After catalyst deactivation, a step of removing low-boiling compounds in the polymer by volatilization at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350°C may be provided. For this purpose, a horizontal apparatus equipped with stirring blades with excellent surface renewal ability, such as paddle blades, lattice blades, or spectacle blades, or a thin-film evaporator is preferably used.

[0055] It is desirable that the polyester carbonate resin contain as little foreign matter as possible, and filtration of the molten raw material and the catalyst solution is preferably carried out. The mesh of the filter is preferably 5 μm or less, more preferably 1 μm or less. Furthermore, filtration of the produced resin through a polymer filter is preferably carried out. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Furthermore, the process of collecting resin pellets must naturally be carried out in a low-dust environment, preferably class 1000 or less, more preferably class 100 or less.

[0056] <Method for producing polyester resin> A preferred embodiment of the thermoplastic resin can be produced by a conventionally known polyester production method using a dicarboxylic acid or carboxylic acid diester constituting the structural unit (A) and a diol compound. Examples include melt polymerization methods such as transesterification and direct esterification, and solution polymerization. Examples of the diol compound include the aliphatic dihydroxy compounds and aromatic dihydroxy compounds described above, and preferred examples include the monomer represented by the general formula (6) and / or the monomer represented by the general formula (7).

[0057] When producing the polyester resin, transesterification catalysts, esterification catalysts, polycondensation catalysts, etc., which are typically used in the production of polyester resins, can be used. These catalysts are not particularly limited, but examples include compounds of metals such as zinc, lead, cerium, cadmium, manganese, cobalt, lithium, sodium, potassium, calcium, nickel, magnesium, vanadium, aluminum, titanium, antimony, germanium, and tin (e.g., fatty acid salts, carbonates, phosphates, hydroxides, chlorides, oxides, and alkoxides), and metallic magnesium. These catalysts can be used alone or in combination of two or more. Among the catalysts listed above, compounds of manganese, cobalt, zinc, titanium, calcium, antimony, germanium, and tin are preferred, and compounds of manganese, titanium, antimony, germanium, and tin are more preferred. The amount of these catalysts used is not particularly limited, but the amount of metal components relative to the raw materials for the polyester resin is preferably 1 to 1,000 ppm, more preferably 3 to 750 ppm, and even more preferably 5 to 500 ppm.

[0058] The reaction temperature in the polymerization reaction depends on the type of catalyst, the amount used, etc., but is usually selected in the range of 150° C. to 300° C., and in consideration of the reaction rate and coloration of the resin, it is preferably 180° C. to 280° C. The pressure in the reaction chamber is preferably adjusted from atmospheric pressure to 1 kPa or less, and more preferably 0.5 kPa or less.

[0059] When carrying out the polymerization reaction, a phosphorus compound may be added if desired. Examples of phosphorus compounds include, but are not limited to, phosphoric acid, phosphorous acid, phosphoric acid esters, and phosphite esters. Examples of phosphate esters include, but are not limited to, methyl phosphate, ethyl phosphate, butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, diphenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, and triphenyl phosphate. Examples of phosphites include, but are not limited to, methyl phosphite, ethyl phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and triphenyl phosphite. These compounds may be used alone or in combination. The concentration of phosphorus atoms in the polyester resin of the present invention is preferably 1 to 500 ppm, more preferably 5 to 400 ppm, and even more preferably 10 to 200 ppm.

[0060] In addition, during the production of the polyester resin, various stabilizers such as an etherification inhibitor, a heat stabilizer, a light stabilizer, and a polymerization adjuster may be used.

[0061] <Physical Properties of Thermoplastic Resin> (1) Refractive Index (nD) One of the characteristics of the thermoplastic resin is that it has a high refractive index, and the refractive index is preferably 1.600 to 1.750, more preferably 1.665 to 1.750, and particularly preferably 1.665 to 1.720. The refractive index can be measured by the method described in the examples below.

[0062] (2) Abbe number (ν) The Abbe number of the thermoplastic resin is preferably 15.0 to 23.0, more preferably 15.0 to 20.4, and particularly preferably 16.0 to 20.0. The Abbe number can be measured by the method described in the examples below.

[0063] (3) Glass Transition Temperature (Tg) One of the characteristics of the thermoplastic resin is high heat resistance, and the glass transition temperature (Tg) is preferably 140 to 180°C, more preferably 147 to 180°C, and particularly preferably 148 to 175°C. The glass transition temperature (Tg) is also preferably 140 to 160°C, and more preferably 148 to 158°C. The glass transition temperature can be measured by the method described in the examples below.

[0064] (4) Weight Average Molecular Weight (Mw) in Polystyrene Equivalent The weight average molecular weight (Mw) of the thermoplastic resin in polystyrene equivalent is preferably 10,000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 10,000 to 60,000.

[0065] (5) Longest Absorption Wavelength The longest absorption wavelength of the thermoplastic resin is preferably 420 nm or less, more preferably 350 to 420 nm, even more preferably 360 to 410 nm, and particularly preferably 370 to 400 nm. Resins with a longest absorption wavelength of 420 nm or less have a reduced color tone, mainly yellow, red to orange, and are useful when used as optical lenses. The longest absorption wavelength can be measured by the method described in the examples below.

[0066] <Thermoplastic Resin Composition> The thermoplastic resin described above can be a thermoplastic resin composition containing an additive. The thermoplastic resin composition can be used in combination with a resin other than the thermoplastic resin containing the structural unit (A) described above, as long as the desired effect is not impaired. Examples of such resins include, but are not limited to, at least one resin selected from the group consisting of polycarbonate resins, polyester resins, polyester carbonate resins, (meth)acrylic resins, polyamide resins, polystyrene resins, cycloolefin resins, acrylonitrile-butadiene-styrene copolymer resins, vinyl chloride resins, polyphenylene ether resins, polysulfone resins, polyacetal resins, and methyl methacrylate-styrene copolymer resins. Various known resins can be used, and one type can be added alone or two or more types can be added in combination to the thermoplastic resin composition.

[0067] [Antioxidant] The thermoplastic resin composition preferably contains an antioxidant as the additive. The antioxidant preferably contains at least one of a phenolic antioxidant and a phosphite-based antioxidant. Examples of phenolic antioxidants include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine e-2,4,6(1H,3H,5H)-trione, 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol, ocladecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentane, methyl ... Examples of the hydroxybenzoate include pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxospiro[5.5]undecane, and pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and preferably pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].Phosphite antioxidants include 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxy-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite, Examples of the antioxidant include tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra-C12-15-alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and preferably 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. As the antioxidant, any one of the above may be used alone, or a mixture of two or more may be used.

[0068] The antioxidant content in the thermoplastic resin composition is preferably 1 ppm by weight to 3,000 ppm by weight based on the total weight of the resin composition, more preferably 50 ppm by weight to 2,500 ppm by weight, even more preferably 100 ppm by weight to 2,000 ppm by weight, particularly preferably 150 ppm by weight to 1,500 ppm by weight, and even more preferably 200 ppm by weight to 1,200 ppm by weight.

[0069] [Release Agent] The thermoplastic resin composition preferably contains a release agent as the additive. Examples of the release agent include ester compounds, such as glycerin fatty acid esters such as mono- and diglycerides of glycerin fatty acid, glycol fatty acid esters such as propylene glycol fatty acid esters and sorbitan fatty acid esters, higher alcohol fatty acid esters, and full esters or mono-fatty acid esters of aliphatic polyhydric alcohols and aliphatic carboxylic acids. When an ester of aliphatic polyhydric alcohols and aliphatic carboxylic acids is used as the release agent, either a monoester or a full ester can be used, but other than a full ester, such as a monoester, may also be used. Specific examples of the release agent include the following.That is, sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan tribehenate, sorbitan stearate, sorbitan tristearate, and sorbitan caprylate; propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate, and propylene glycol monopalmitate; higher alcohol fatty acid esters such as stearyl stearate; glycerin monohydroxystearates such as glycerin monostearate and glycerin mono-12-hydroxystearate, glycerin monooleate, glycerin monobehenate, glycerin monocaprylate, glycerin monocaprate, and glycerin Examples of the monoglyceride include monoglycerides such as monolaurate, and mono-diglycerides such as glycerin monodistearate, glycerin monodistearate, glycerin monodibehenate, and glycerin monodiolate; acetylated monoglycerides of glycerin fatty acid ester such as glycerin diacetomonolaurate; organic acid monoglycerides of glycerin fatty acid ester such as citric acid fatty acid monoglyceride, succinic acid fatty acid monoglyceride, and diacetyltartaric acid fatty acid monoglyceride; and polyglycerin fatty acid esters such as diglycerin stearate, diglycerin laurate, diglycerin oleate, diglycerin monostearate, diglycerin monolaurate, diglycerin monomyristate, diglycerin monooleate, tetraglycerin stearate, decaglycerin laurate, decaglycerin oleate, and polyglycerin polyricinoleate.

[0070] The thermoplastic resin composition preferably contains 1 ppm by weight to 5,000 ppm by weight of the release agent based on the total weight of the resin composition, more preferably 50 ppm by weight to 4,000 ppm by weight, even more preferably 100 ppm by weight to 3,500 ppm by weight, particularly preferably 500 ppm by weight to 3,000 ppm by weight, and even more preferably 1,000 ppm by weight to 2,500 ppm by weight.

[0071] [Other Additives] In addition to the antioxidant and mold release agent described above, other additives may be added to the thermoplastic resin composition. For example, additives that may be contained in the thermoplastic resin composition include compounding agents, catalyst deactivators, heat stabilizers, plasticizers, fillers, UV absorbers, rust inhibitors, dispersants, antifoaming agents, leveling agents, flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents, and clarifying agents. The content of other additives other than the antioxidant and mold release agent in the thermoplastic resin composition is preferably 10 ppm by weight to 5.0% by weight, more preferably 100 ppm by weight to 2.0% by weight, and even more preferably 1000 ppm by weight to 1.0% by weight, but is not limited thereto. The above-mentioned additives may adversely affect transmittance, so it is preferable not to add them in excess; for example, the total amount added is within the above-mentioned range.

[0072] <Optical Members> Thermoplastic resins or thermoplastic resin compositions (hereinafter simply referred to as "resin compositions") can be suitably used for optical members. Optical members containing the resin compositions can be provided. Optical members include, but are not limited to, optical disks, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, hard coat films, and the like. The resin compositions can be molded by a casting method with high flow, and are therefore particularly suitable for producing thin optical members. The optical member produced using the resin composition may be an optical lens. The optical member produced using the resin composition may be an optical film.

[0073] When an optical component containing the resin composition is produced by injection molding, molding is preferably performed under conditions of a cylinder temperature of 260 to 350°C and a mold temperature of 90 to 170°C. More preferably, molding is performed under conditions of a cylinder temperature of 270 to 320°C and a mold temperature of 100 to 160°C. If the cylinder temperature is higher than 350°C, the resin composition will decompose and discolor, and if it is lower than 260°C, the melt viscosity will be high, making molding difficult. Furthermore, if the mold temperature is higher than 170°C, it will be difficult to remove a molded piece made of the resin composition from the mold. On the other hand, if the mold temperature is lower than 90°C, the resin will harden too quickly in the mold during molding, making it difficult to control the shape of the molded piece and making it difficult to sufficiently transfer the shape applied to the mold.

[0074] <Optical Lens> The resin composition can be suitably used for optical lenses. Optical lenses produced using the resin composition have a high refractive index and excellent heat resistance, and are therefore extremely useful in fields where expensive high-refractive-index glass lenses have traditionally been used, such as telescopes, binoculars, and television projectors. For example, in smartphone lenses, a lens molded from a thermoplastic resin containing the structural unit (A) and a lens molded from a resin containing a structural unit of any of formulas (II-1) to (II-4), or a resin containing a structural unit derived from a monomer of any of the following formulas, can be stacked to form a lens unit. (In the above formula, R １１ and R ２２ each independently represents a hydrogen atom, a methyl group, or an ethyl group; R ３ and R ４ R each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms. ｍ１ and R ｍ２ each independently represents a hydrogen atom, a methyl group, an ethyl group, or a phenyl group.

[0075] Optical lenses are preferably implemented in the form of aspherical lenses as necessary. Aspherical lenses can substantially eliminate spherical aberration with a single lens, eliminating the need to combine multiple spherical lenses to eliminate spherical aberration, thereby enabling weight reduction and reduced molding costs. Therefore, aspherical lenses are particularly useful as camera lenses, among other optical lenses.

[0076] Furthermore, because the optical lens has high molding fluidity, it is particularly useful as a material for optical lenses that are thin, small, and have complex shapes. Specifically, the lens size preferably has a central thickness of 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and even more preferably 0.1 to 2.0 mm. The diameter is preferably 1.0 to 20.0 mm, more preferably 1.0 to 10.0 mm, and even more preferably 3.0 to 10.0 mm. Furthermore, the lens preferably has a meniscus shape, with one side convex and the other concave. The optical lens can be molded by any method, such as mold molding, cutting, polishing, laser machining, electrical discharge machining, or etching. Among these, mold molding is more preferable in terms of manufacturing costs.

[0077] <Optical Film> The resin composition can be suitably used for optical films. In particular, optical films produced using the polyester carbonate resin or polyester resin have excellent transparency and heat resistance, and are therefore suitable for use as films for liquid crystal substrates, optical memory cards, etc. In order to prevent foreign matter from being mixed into the optical film as much as possible, the molding environment must also be a low-dust environment, preferably class 6 or less, and more preferably class 5 or less.

[0078] The present invention will be explained in more detail below with reference to the following examples. <Analytical Method> 1. Purity Analysis (Analytical Values ​​are Area Percentages) Measuring Apparatus: High-Performance Liquid Chromatography Analyzer Prominence UFLC (Shimadzu Corporation) Pump: LC-20AD Column Oven: CTO-20A Detector: SPD-20A Column: HALO-C18 (Inner Diameter 3 mm, Length 75 mm) Oven Temperature: 50°C Flow Rate: 0.7 mL / min Sample Injection Volume: 5 μL Detection Wavelength: 280 nm Mobile Phase: (A) 0.1% by volume aqueous phosphoric acid solution, (B) acetonitrile Gradient Conditions: (B) Volume % (Time from Start of Analysis) 40% (0 min) → 100% (17 min) → 100% (20 min)

[0079] 2. NMR analysis Measurement device: Fourier transform nuclear magnetic resonance AVANCE III HD 400 (manufactured by BRUKER) A measurement sample was dissolved in deuterated dimethyl sulfoxide, １ H-NMR, １３ The C-NMR spectrum was measured.

[0080] 3. Solution hue A tetrahydrofuran solution with a concentration of 10% by weight of the obtained biphenanthrene dicarboxylic acid compound was prepared, and the hue of the solution was measured using the following device to evaluate the hue of the obtained target product. Device: Colorimeter (ZE6000, manufactured by Nippon Denshoku Industries Co., Ltd.) Cell used: Glass test tube (diameter 24 mm)

[0081] 4. Measurement of Weight Loss Temperature The obtained measurement sample of biphenanthrene dicarboxylic acid compound was analyzed using the following apparatus and conditions to measure the thermal weight loss temperature. Apparatus: DTG-60A / Shimadzu Corporation Temperature: 30 to 400°C (heating rate 10°C / min.) Measurement atmosphere: open, nitrogen 50 mL / min. Sample weight: 8 to 12 mg Sample container material: aluminum

[0082] 5. Measurement of Melt Color The obtained biphenanthrene dicarboxylic acid compound was placed in a test tube, heated to 200°C or 230°C using a metal block (Hot Dry Bath HOTB624K, manufactured by AS ONE Corporation), and held for 30 minutes and 120 minutes, after which the hue (melt color) of the biphenanthrene dicarboxylic acid compound when molten was measured using the following apparatus: Measuring instrument: TZ 6000 manufactured by Nippon Denshoku Industries Co., Ltd. (standard calibration was performed with distilled water).

[0083] 6. Melting Point 3 mg of the obtained biphenanthrene dicarboxylic acid compound crystals were weighed into an aluminum pan and measured using a differential scanning calorimeter (DSC7020 manufactured by Hitachi High-Tech Science Corporation) under the following operating conditions, using aluminum oxide as a reference. The onset temperature of the endothermic peak in differential scanning calorimetry (DSC) was taken as the melting point. (Operating Conditions) Heating rate: 10°C / min. Measurement temperature range: 30 to 400°C. Measurement atmosphere: open, nitrogen 50 mL / min.

[0084] 7. Refractive Index Measuring Device: Refractometer (Kyoto Electronics Manufacturing Co., Ltd.: RA-500) Tetrahydrofuran solutions of the obtained biphenanthrene dicarboxylic acid compound (solutions with concentrations of 20%, 15%, and 10%) were prepared, and the refractive index was measured with the refractometer. From the obtained results, the relationship between concentration and refractive index was derived, and the value at a concentration of 100% was calculated by extrapolation, and this value was defined as the refractive index of the biphenanthrene dicarboxylic acid compound.

[0085] 8. Powder X-ray Diffraction Method (PXRD) 0.1 g of the obtained biphenanthrene dicarboxylic acid compound crystals was filled into the sample filling section of a glass test plate, and measurement was performed using the following apparatus and conditions. [Measurement apparatus] MiniFlex600-C / Rigaku Corporation [Measurement conditions] X-ray source: CuKα Tube voltage: 40 kV Tube current: 15 mA Scan axis: 2θ / θ Mode: Continuous Measurement range: 2θ = 5° to 90° Step: 0.03° Speed ​​measurement time: 1.0° / min Entrance slit: 0.25° Receiving slit: 13.00 mm

[0086] 9. Weight-average molecular weight (Mw) The weight-average molecular weight of the resins obtained in the Synthesis Examples and Comparative Synthesis Examples was measured by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene. The apparatus, column, and measurement conditions used were as follows: GPC apparatus: HLC-8420GPC, manufactured by Tosoh Corporation; Column: TSKgel SuperHM-M x 3, manufactured by Tosoh Corporation; TSKgel guard column SuperH-H x 1, manufactured by Tosoh Corporation; TSKgel SuperH-RC x 1, manufactured by Tosoh Corporation; Detector: RI detector; Standard polystyrene: Standard polystyrene kit PStQuick C, manufactured by Tosoh Corporation; Sample solution: 0.2% by mass tetrahydrofuran solution; Eluent: tetrahydrofuran; Eluent flow rate: 0.6 mL / min; Column temperature: 40°C.

[0087] 10. Glass Transition Temperature (Tg) The glass transition temperatures (Tg) of the resins obtained in the Synthesis Examples and Comparative Synthesis Examples were measured using a differential scanning calorimeter with a temperature increase program of 10°C / min in accordance with JIS K7121-1987. Differential scanning calorimeter: TA Instruments DSC2500

[0088] 11. Refractive index (nD) Based on JIS B 7071-2:2018, the polyester resins obtained in the synthesis examples and comparative synthesis examples were molded into V-shaped blocks to serve as test specimens. The refractive index was measured at 23°C using a refractometer (Shimadzu KPR-3000).

[0089] 12. Abbe number (ν) Using the same test piece (V-block) as used in the refractive index measurement, the refractive indexes at wavelengths of 486 nm, 589 nm, and 656 nm at 23°C were measured using a refractometer, and the Abbe number was calculated using the following formula: Refractometer: KPR-3000 manufactured by Shimadzu Corporation ν=(nD-1) / (nF-nC) nD: refractive index at wavelength 589 nm nC: refractive index at wavelength 656 nm nF: refractive index at wavelength 486 nm

[0090] 13. Low Molecular Weight Compound Ratio The content of low molecular weight compounds in the resins obtained in the Synthesis Examples and Comparative Synthesis Examples represents the area ratio of compounds with Mw values ​​of less than 1,000 in GPC analysis. Therefore, the content of low molecular weight compounds was determined according to the following calculation formula: [Calculation formula] Low molecular weight compound ratio (%) = (total area of ​​peaks for compounds with Mw values ​​of less than 1,000 in GPC analysis) ÷ (total area of ​​peaks for all compounds in GPC analysis) × 100 GPC analysis is performed as described above to measure the molecular weight of compounds with Mw values ​​of less than 1,000.

[0091] 14. Longest Absorption Wavelength The longest absorption wavelength of the resins obtained in the Synthesis Examples and Comparative Synthesis Examples was evaluated using a spectroscopic haze meter. Measuring instrument: Hitachi High-Tech Science U-2910 Sample concentration: 0.25 mg / mL dichloromethane solution (cell length: 10 mm) Analysis method: The longest wavenumber at the absorption edge was read.

[0092] Example 1 100.2 g (0.26 mol) of 9,9'-biphenanthrene-10,10'-diol, 151 g of N-methylpyrrolidone, 75.7 g of potassium carbonate, and 6.2 g of potassium iodide were charged into a four-neck flask and purged with nitrogen. The temperature was then raised to 90°C, and 97.5 g (0.65 mol) of ethyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature of the reaction solution at 90°C. Stirring was then performed while maintaining the temperature inside the flask at 90°C. The reaction was completed after 11 hours of stirring (hereinafter referred to as "post-stirring") following the completion of the dropwise addition. HPLC analysis of the reaction solution after the reaction showed that the reaction selectivity of the target compound, compound (1-3), was 99.8%. 75 g of water was then added, the mixture was cooled, and the mixture was stirred overnight at 25°C, after which the precipitated solid was filtered off. 206.8 g of the obtained solid and 927 g of methyl isobutyl ketone were placed in a four-neck flask, and after nitrogen substitution, the mixture was heated to dissolve. 207 g of water was then added, and the mixture was washed with water at 80°C, and the aqueous layer was extracted. This operation was repeated four times. 555 g of methyl isobutyl ketone and water were then distilled off. The liquid was then cooled and stirred overnight while maintaining the temperature at 25°C, and the precipitated solid was filtered off. The filtered solid was dried at 80°C under reduced pressure to obtain 145.9 g of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl (a compound represented by chemical formula (1-3)) (yield: 91.5%). The obtained compound was analyzed by liquid chromatography mass spectrometry and １ H-NMR and １３ C-NMR analysis revealed that the compound was 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl (compound represented by chemical formula (1-3)). Liquid chromatography mass spectrometry (mass spectrometry / electrospray ionization): mass 637.25 [M+Na] １H-NMR analysis (400 MHz, solvent: deuterated chloroform) δ (ppm): 8.81-8.83 (d, 2H), 8.75-8.76 (d, 2H), 8.30-8.32 (dd, 2H), 7.75-7.79 (dt, 2H), 7.69-7.73 (dt, 2H), 7.55-7 .59 (m, 2H), 7.32-7.33 (d, 4H), 3.88-3.94 (m, 2H), 3.80-3.87 (m, 4H), 3.5 1-3.57 (m, 2H), 1.86-1.94 (m, 2H), 1.56-1.72 (m, 6H), 1.05-1.09 (t, 6H). １３ C-NMR (400 MHz, solvent: deuterated chloroform) δ (ppm): 173.01, 151.74, 132.77, 131.81, 128.25, 128.13, 127.15, 126.92, 126.86, 126.83, 125.51, 123.44, 122.91, 122.65, 122.32, 72.43, 59.95, 30.28, 25.26, 12.06. The purity of the obtained biphenanthrene dicarboxylic acid compound represented by chemical formula (1-3) was 99.6% as measured by high performance liquid chromatography, and the hue of a 10% THF solution obtained by the above analytical method was APHA20. The PXRD measurement chart of the obtained biphenanthrene dicarboxylic acid compound represented by chemical formula (1-3) is shown in FIG. The peak pattern revealed that the solid biphenanthrene dicarboxylic acid compound represented by chemical formula (1-3) was crystalline. The diffraction angle 2θ (°) of the diffraction peaks that appeared, the relative integrated intensity based on the peak with the strongest integrated intensity, and the relative intensity based on the peak with the strongest intensity were selected, and peaks with a relative integrated intensity of 5 or more are shown in Table 1. The melting point of the obtained crystals of biphenanthrene dicarboxylic acid compound represented by chemical formula (1-3) was measured by the above analytical method and found to be 155° C. The differential scanning calorimetry chart is shown in FIG.

[0093] Example 2 80.4 g (0.21 mol) of 9,9'-biphenanthrene-10,10'-diol, 123 g of N-methylpyrrolidone, 60.5 g of potassium carbonate, and 4.0 g of potassium iodide were charged into a four-neck flask and purged with nitrogen. The temperature was then raised to 90°C, and 70.9 g (0.52 mol) of methyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature of the reaction solution at 90°C. Stirring was then performed while maintaining the temperature inside the flask at 90°C. The reaction was completed after 18 hours of post-stirring. HPLC analysis of the reaction solution after the reaction showed that the reaction selectivity of the target compound, compound (1-2), was 99.7%. 240 g of water was then added, the mixture was cooled, and the mixture was stirred overnight at 25°C, after which the precipitated solid was filtered off. 157.0 g of the obtained solid and 367 g of methyl isobutyl ketone were placed in a four-neck flask, and after nitrogen substitution, the mixture was heated to dissolve. 249 g of water was then added, and the mixture was washed with water at 80°C, and the aqueous layer was extracted. This operation was repeated four times. 141 g of methyl isobutyl ketone and water were then distilled off by distillation. The liquid was then cooled and stirred overnight while maintaining the temperature at 25°C, and the precipitated solid was filtered off. The filtered solid was dried at 80°C under reduced pressure to obtain 108.4 g of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl (a compound represented by chemical formula (1-2)) (yield: 90.7%). The obtained compound was analyzed by liquid chromatography mass spectrometry and １ H-NMR and １３ C-NMR analysis revealed that the compound was 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl (compound represented by chemical formula (1-2)). Liquid chromatography mass spectrometry (mass spectrometry / electrospray ionization): mass 609.23 [M+Na] １H-NMR analysis (400MHz, solvent: deuterated chloroform) δ (ppm): 8.81-8.83 (d, 2H), 8.75-8.77 (d, 2H), 8.29-8.31 (dd, 2H), 7.69-7.79 (dt, 2H), 7.69-7.73 (dt , 2H), 7.55-7.59 (m, 2H), 7.31-7.33 (d, 4H), 3.88-3.93 (m, 2H), 3.54-3.58 (m, 2H), 3.36 (s, 6H), 1.88-1.94 (m, 2H), 1.58-1.74 (m, 6H). １３ C-NMR (400 MHz, solvent: deuterated chloroform) δ (ppm): 173.42, 151.70, 132.75, 131.84, 128.22, 128.14, 127.16, 126.94, 126.88, 126.86, 125.54, 123.43, 122.93, 122.66, 122.32, 72.33, 51.21, 29.95, 25.25. The purity of the obtained biphenanthrene dicarboxylic acid compound represented by chemical formula (1-2) as measured by high performance liquid chromatography was 99.5%, and the hue of a 10% THF solution measured by the above analytical method was APHA20. A PXRD measurement chart of the solid of the obtained biphenanthrene dicarboxylic acid compound represented by chemical formula (1-2) is shown in FIG. The peak pattern revealed that the obtained solid biphenanthrene dicarboxylic acid compound represented by chemical formula (1-2) was a crystal. The diffraction angle 2θ (°) of the diffraction peaks that appeared, the relative integrated intensity based on the peak with the strongest integrated intensity, and the relative intensity based on the peak with the strongest intensity are shown in Table 2, with peaks with a relative integrated intensity of 5 or more selected. The melting point of the obtained crystals of biphenanthrene dicarboxylic acid compound represented by chemical formula (1-2) was measured by the above analytical method and found to be 134° C. The differential scanning calorimetry chart is shown in FIG.

[0094] Comparative Example 1 30.1 g (0.08 mol) of 9,9'-biphenanthrene-10,10'-diol, 75 g of methyl isobutyl ketone, 22.6 g of potassium carbonate, and 1.7 g of potassium iodide were charged into a four-neck flask and purged with nitrogen. The temperature was then raised to 100°C, and 29.2 g of methyl isobutyl ketone was distilled off under reduced pressure. 24.0 g (0.20 mol) of ethyl chloroacetate was then added dropwise over 1 hour while maintaining the temperature of the reaction solution at 90°C. Stirring was then performed while maintaining the temperature inside the flask at 90°C. The reaction was completed after 10 hours of post-stirring. 45 g of methyl isobutyl ketone and 120 g of water were then added while maintaining the temperature at 70°C. After washing with water at 80°C, the aqueous layer was removed. 30 g of water was then added, washing with water was performed at 80°C, and the aqueous layer was removed. Thereafter, normal heptane was added, and the mixture was cooled and stirred overnight at 25°C, after which the precipitated solid was filtered off. 42.6 g of the obtained solid and 184 g of methyl isobutyl ketone were charged into a four-necked flask, and after nitrogen substitution, the mixture was heated to dissolve. 100 g of water was then added, and the mixture was washed with water at 75°C, and the aqueous layer was removed. This operation was repeated once. 85 g of methyl isobutyl ketone and water were then distilled off by distillation. 106 g of normal heptane was then added, and the mixture was cooled and stirred overnight while maintaining the temperature at 25°C, after which the precipitated solid was filtered off. The filtered solid was dried under reduced pressure at 80°C, and 33.8 g of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthryl (compound (α)) was obtained (reaction yield: 77.7%). The purity of the obtained target product was 99.0% as measured by high performance liquid chromatography, and the color of a 10% THF solution obtained by the above analytical method was APHA 20. 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthryl (compound (α)) is a compound represented by chemical formula (α).

[0095] Comparative Example 2: 194.8 g (0.50 mol) of 9,9'-biphenanthrene-10,10'-diol, 145.7 g of potassium carbonate, and 10.18 g of potassium iodide were charged into a four-neck flask and subjected to nitrogen substitution. The temperature was then raised to 100°C, and 166.4 g of methyl isobutyl ketone was distilled off under reduced pressure. Then, 156.5 g (1.44 mol) of methyl chloroacetate was added dropwise over 1 hour while maintaining the temperature of the reaction solution at 90°C. The temperature inside the flask was then maintained at 90°C while stirring. The internal pressure was reduced to 45 kPa after 7 hours of post-stirring, and the reaction was completed after 9 hours of post-stirring. Then, 69.9 g of 75% phosphoric acid and 194.9 g of water were added while maintaining the temperature at 85°C, and the mixture was cooled and stirred at 25°C overnight, after which the precipitated solid was filtered off. 354.1 g of the obtained solid, 2729.5 g of methyl isobutyl ketone, and 389.4 g of water were charged into a four-neck flask, and after nitrogen substitution, the flask was heated to 85°C for dissolution. After dissolution, the mixture was washed with water and the aqueous layer was removed. This operation was repeated three times. Thereafter, distillation was performed to remove 2447.6 g of methyl isobutyl ketone and water. Thereafter, the liquid was cooled and stirred overnight while maintaining the temperature at 25°C, and the precipitated solid was filtered off. The filtered solid was dried at 75°C under reduced pressure to obtain 244.2 g of 10,10'-bis(methoxycarbonylmethoxy)-9,9'-biphenanthryl (compound β) (yield 91.5%). The obtained compound was analyzed by liquid chromatography mass spectrometry and １ H-NMR and １３ C-NMR analysis revealed that the compound was 10,10'-bis(methoxycarbonylmethoxy)-9,9'-biphenanthryl (compound (β)). 10,10'-bis(methoxycarbonylmethoxy)-9,9'-biphenanthryl (compound (β)) is a compound represented by chemical formula (β). Liquid chromatography mass spectrometry (mass spectrometry / electrospray ionization): mass 531.18 [M+H] １H-NMR analysis (400 MHz, solvent: deuterated chloroform) δ (ppm): 8.82-8.80 (d, 2H), 8.77-8.75 (d, 2H), 8.51-8.49 (dd, 2H), 7.80- 7.71 (m, 4H), 7.61-7.56 (td, 2H), 7.35-7.27 (m, 4H), 4.49-4.45 (d, 2H), 4.25-4.21 (d, 2H), 3.32 (s, 6H). １３ C-NMR (400 MHz, solvent: deuterated chloroform) δ (ppm): 169.20, 151.76, 132.41, 131.92, 128.44, 127.92, 127.64, 127.32, 127.21, 126.62, 126.07, 123.71, 122.79, 122.76, 121.69, 70.15, 51.59. The purity of the obtained compound (β) measured by high performance liquid chromatography was 99.7%, and the hue of a 10% THF solution obtained by the above analytical method was APHA10. The PXRD measurement chart of the obtained compound (β) is shown in Figure 5. The peak pattern revealed that the obtained solid of compound (β) was crystalline. The diffraction angles 2θ (°) of the diffraction peaks that appeared, the relative integrated intensities based on the peak with the strongest integrated intensity, and the relative intensities based on the peak with the strongest intensity were selected and shown in Table 3, with peaks having a relative integrated intensity of 10 or more. The melting point of the resulting crystals of compound (β) was measured by the above analytical method and found to be 187° C. The differential scanning calorimetry chart is shown in FIG.

[0096] <Evaluation of Refractive Index of Biphenanthrene Dicarboxylic Acid Compounds> The refractive indexes of the biphenanthrene dicarboxylic acid compounds obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were measured by the above-described analytical method. The results are shown in Table 4. These results reveal that the biphenanthrene dicarboxylic acid compounds of the present invention have refractive indices equivalent to those of compound (α) and compound (β).

[0097] <Melting Point of Crystals of Biphenanthrenedicarboxylic Acid Compound> The melting points of the crystals of the biphenanthrenedicarboxylic acid compounds obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were measured by the above-mentioned analytical method. The results are shown in Table 5. These results reveal that the biphenanthrenedicarboxylic acid compounds of the present invention have lower melting points than compound (α).

[0098] <Evaluation of Thermal Stability of Biphenanthrene Dicarboxylic Acid Compounds> The thermal weight loss temperatures and melting colors of the biphenanthrene dicarboxylic acid compounds obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were measured by the above-described analytical method. The results of the thermal weight loss temperature measurements are shown in Table 6, and the results of the melting colors are shown in Table 7. In Table 7, "APHA" means the Hazen color index, "G" means the Gardner color index, and the hue at "0 minutes" before heating is the solution hue measured by the above-described analytical method.

[0099] From the measurement results of the thermal weight loss temperature shown in Table 6 above, it was found that compounds (α) and (β), which are conventionally known compounds having a short alkylene chain length between the alkoxycarbonyl group and the ether group (1 carbon atom), begin to lose weight at a relatively low temperature, whereas compounds (1-3) and (1-2), which are compounds of the present invention having a long alkylene chain length (3 carbon atoms), begin to lose weight at a higher temperature, demonstrating that the compounds of the present invention have excellent thermal stability. In other words, it was revealed that the compounds of the present invention can be used to perform the reaction to obtain a resin at a higher temperature. Furthermore, from the measurement results of the melt hue after heating shown in Table 7 above, it was found that compounds (1-2) and (1-3), which are compounds of the present invention having a long alkylene chain length, have a weaker melt hue and show less change in hue after heating than compounds (α) and (β), which are conventionally known compounds having a short alkylene chain length. This also clarifies that the compounds of the present invention have excellent thermal stability. That is, it has become clear that coloration at high temperatures and at high temperatures for long periods of time is suppressed, and therefore a resin with a good hue can be obtained.

[0100] Comparative Example 3 25.1 g (0.06 mol) of 9,9'-biphenanthrene-10,10'-diol, 65 g of methyl isobutyl ketone, 18.9 g of potassium carbonate, and 1.3 g of potassium iodide were charged into a four-neck flask and purged with nitrogen. The mixture was then heated to 100°C, and 30 g of methyl isobutyl ketone was distilled off under reduced pressure. The mixture was cooled to 90°C, and 24.6 g (0.16 mol) of ethyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature of the reaction solution at 90°C. The mixture was then stirred for 28 hours while maintaining the temperature inside the flask at 90°C. HPLC analysis of the reaction solution after the reaction showed that the reaction selectivity of the target compound, compound (1-3), was 21.5%.

[0101] Comparative Example 4 25.0 g (0.06 mol) of 9,9'-biphenanthrene-10,10'-diol, 75 g of acetonitrile, 18.9 g of potassium carbonate, and 1.3 g of potassium iodide were charged into a four-neck flask and purged with nitrogen. The temperature was then raised to 75°C, and 24.4 g (0.16 mol) of ethyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature of the reaction solution at 75°C. The mixture was then stirred for 50 hours while maintaining the temperature inside the flask at 75°C. HPLC analysis of the reaction solution after the reaction showed that the reaction selectivity of the target compound, compound (1-3), was 26.7%.

[0102] Comparative Example 5 29.9 g (0.08 mol) of 9,9'-biphenanthrene-10,10'-diol, 45 g of methyl isobutyl ketone, 22.7 g of potassium carbonate, and 1.7 g of potassium iodide were charged into a four-neck flask and purged with nitrogen. The temperature was then raised to 120°C, and 26.4 g (0.19 mol) of methyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature of the reaction solution at 120°C. The mixture was then stirred for 23 hours while maintaining the temperature inside the flask at 120°C. HPLC analysis of the reaction solution after the reaction showed that the reaction selectivity of the target compound (1-2) was 78.0%.

[0103] Comparative Example 6 28.4 g (0.07 mol) of 9,9'-biphenanthrene-10,10'-diol, 43 g of methanol, 21.3 g of potassium carbonate, and 1.4 g of potassium iodide were charged into a four-neck flask and purged with nitrogen. The temperature was then raised to 60°C, and 25.0 g (0.18 mol) of methyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature of the reaction solution at 60°C. The temperature inside the flask was then maintained at 65°C while stirring for 24 hours. HPLC analysis of the reaction solution after the reaction showed that the reaction selectivity of the target compound (1-2) was 17.4%.

[0104] Comparative Example 7 28.3 g (0.07 mol) of 9,9'-biphenanthrene-10,10'-diol, 84.9 g of acetone, 21.3 g of potassium carbonate, and 1.4 g of potassium iodide were charged into a four-neck flask and purged with nitrogen. The temperature was then raised to 60°C, and 25.0 g (0.18 mol) of methyl chlorobutyrate was added dropwise over 1 hour while maintaining the temperature of the reaction solution at 60°C. The mixture was then stirred for 20 hours while maintaining the temperature inside the flask at 60°C. HPLC analysis of the reaction solution after the reaction showed that the reaction selectivity of the target compound (1-2) was 9.1%.

[0105] In Comparative Example 3, the synthesis reaction of compound (1-3) was carried out for 28 hours at the same temperature, 90°C, using methyl isobutyl ketone, the reaction solvent used in the production of compound (α) in Comparative Example 1. The reaction selectivity was 21.5%, which was a low reaction selectivity for producing compound (1-3). Furthermore, in Comparative Example 4, the reaction was carried out for a longer period of 50 hours using acetonitrile instead of methyl isobutyl ketone, and the results were similar to those of Comparative Example 3. Meanwhile, in Example 1, when N-methylpyrrolidone was used as the reaction solvent, the reaction was completed in 11 hours, demonstrating that the target compound (1-3) can be produced with very high efficiency. In Comparative Example 5, the synthesis reaction of compound (1-2) was carried out for 23 hours at a higher temperature, 120°C, using methyl isobutyl ketone, the reaction solvent used in the production of compound (α) in Comparative Example 1. The reaction selectivity was 78.0%. This reaction selectivity was not sufficiently high for producing compound (1-2). In Comparative Examples 6 and 7, in which the reaction was carried out using methanol and acetone as the reaction solvent, the reaction selectivity for producing compound (1-2) was low even when the reaction was carried out for a long period of time. In Example 2, N-methylpyrrolidone was used as the reaction solvent in the same manner as in Example 1 to obtain compound (1-2). The reaction was completed in 18 hours, demonstrating that compound (1-2) can be produced with similarly high efficiency.

[0106] <Synthesis Example 1> As raw materials, 149.0553 g (0.2541 mol) of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl (compound represented by chemical formula (1-2)) (abbreviation: BIPOL-DMB) represented by the following structural formula, 109.4800 g (0.2033 mol) of 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene (abbreviation: BNEF), 22.0778 g (0.3557 mol) of ethylene glycol (EG), 0.0307 g (0.1251 × 10) of manganese (II) acetate tetrahydrate, and －３ mol), and 0.0302 g (0.1715 x 10 －３mol) was placed in a 500 mL reactor equipped with a stirrer and a distillation device, and the system was placed under nitrogen flow conditions. The reactor was placed in a mantle heater set to 100°C to initiate the transesterification reaction. Stirring was started 5 minutes after the start of the reaction, and the temperature was raised to 230°C at 120 minutes after the start of the reaction and maintained at that temperature for an additional 290 minutes. Then, 0.4349 g (0.4438 × 10) of phosphoric acid was added. －２ mol) and 0.9902 g (0.9466 x 10) of germanium dioxide －２ The polycondensation reaction was initiated by adding 1 mole of ethanol. The temperature was raised to 270°C over 90 minutes, and the pressure was reduced to 0 kPa. After maintaining this temperature for 120 minutes, nitrogen gas was introduced into the reaction system and the pressure was returned to 101.3 kPa to obtain a polyester resin. The refractive index of the obtained polyester resin was 1.695, the Abbe number was 17.3, the Tg was 153°C, the weight average molecular weight (Mw) in terms of polystyrene was 29,472, the low molecular weight content was 1.3%, and the longest absorption wavelength was 380 nm. Based on the composition ratio of the raw materials, the obtained polyester resin had a BIPOL-DMB-derived structural unit:BNEF-derived structural unit ratio of 50:40 (molar ratio). It is generally believed that polyester resins are polymerized by the reaction of equimolar amounts of a carboxylic acid ester and a dialcohol. Assuming that the excess EG was distilled out of the reaction system together with the ethanol distilled off by the transesterification reaction, the composition of the resulting resin was estimated to be BIPOL-DMB-derived structural units: BNEF-derived structural units: EG-derived structural units = 50:40:10 (molar ratio). The composition and physical properties of the resulting resin are shown in Table 8.

[0107] Synthesis Examples 2 and 3 Polyester resins were obtained in the same manner as in Synthesis Example 1, except that the raw materials shown in Table 8 were used. The compositions and physical properties of the obtained resins are shown in Table 8.

[0108] <Synthesis Example 4> As raw materials, 846.08 g (1.442 mol) of 10,10′-bis(methoxycarbonylpropoxy)-9,9′-biphenanthryl (compound represented by chemical formula (1-2)) (abbreviation: BIPOL-DMB) represented by the above structural formula, 333.26 g (0.601 mol) of 2,2′-bis(phenoxycarbonylmethoxy)-1,1′-binaphthyl (abbreviation: BINOL-DP) represented by the following structural formula, 150.00 g (0.401 mol) of 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene (abbreviation: BNE) represented by the following structural formula, 863.11 g (1.602 mol) of 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene (abbreviation: BNEF) represented by the above structural formula, and 5.0 × 10 －４ mol of aluminum acetylacetonate and 8.71 x 10 －４ A toluene solution of 100 moles of diethyl (4-methylbenzyl)phosphonate was placed in a 10-liter reactor equipped with a stirrer and a distillation device, and after nitrogen substitution, the mixture was heated to 205°C under a nitrogen atmosphere of 760 Torr and stirred. After confirming complete dissolution of the raw materials, the temperature was adjusted to 215°C and the vacuum level to 200 Torr over 30 minutes, and the mixture was maintained at 215°C and 200 Torr for 10 minutes to carry out a transesterification reaction. The temperature was then further increased to 225°C over 10 minutes. The pressure was then reduced to 180 Torr over 10 minutes. The temperature was then adjusted to 235°C over 10 minutes, and then adjusted to 150 Torr over 10 minutes. The pressure was then adjusted to 245°C and 120 Torr over 10 minutes. The pressure was then further reduced to 100 Torr over 10 minutes. The temperature was then adjusted to 255°C and 50 Torr over 10 minutes, and then to 1 Torr over another 10 minutes, and polymerization was carried out at 255°C and 1 Torr for 60 minutes. After completion of the reaction, nitrogen was introduced into the reactor to pressurize the reaction system, and the produced polyester resin was pelletized and extracted to obtain a resin. The physical properties of the obtained resin are shown in Table 8.

[0109] Synthesis Examples 5 to 8 Polyester resins were obtained in the same manner as in Synthesis Example 4, except that the raw materials shown in Table 8 were used. Table 8 shows the compositions and physical properties of the obtained resins.

[0110] Comparative Synthesis Example 1 A polyester resin was obtained in the same manner as in Synthesis Example 1, except that 141.9288 g (0.2541 mol) of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthryl (compound (α)) (abbreviation: BIPOL-DEC) represented by the following structural formula was used instead of BIPOL-DMB as a raw material. The composition and physical properties of the obtained resin are shown in Table 8.

[0111] Comparative Synthesis Examples 2 to 4 Polyester resins were obtained in the same manner as in Comparative Synthesis Example 1, except that the raw materials shown in Table 8 were used. Table 8 shows the compositions and physical properties of the obtained resins.

[0112] Comparative Synthesis Example 5 A polyester resin was obtained in the same manner as in Synthesis Example 4, except that the raw materials shown in Table 8 were used. Table 8 shows the composition and physical properties of the obtained resin.

[0113]

Claims

1. A biphenanthrene dicarboxylic acid compound represented by general formula (1). (In the formula, R １ each independently represents a hydrogen atom, a methyl group, or an ethyl group.

2. The compound according to claim 1, wherein the biphenanthrene dicarboxylic acid compound represented by the general formula (1) is a compound represented by the chemical formula (1-1), (1-2) or (1-3).

3. A method for producing the compound according to claim 1, which comprises reacting 10,10'-dihydroxy-9,9'-biphenanthryl with a halogenated butyric acid represented by general formula (2) in at least one solvent selected from N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, and sulfolane. (In the formula, R １ has the same definition as in general formula (1), and Z represents a halogen atom.

4. A crystal of the compound according to claim 1, wherein the biphenanthrene dicarboxylic acid compound represented by the general formula (1) is 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl.

5. The crystal according to claim 4, which exhibits an endothermic peak with an onset temperature in the range of 130 to 140°C in differential scanning calorimetry.

6. The crystal according to claim 4, which has diffraction peaks at diffraction angles 2θ of 6.7±0.2°, 10.5±0.2°, and 18.5±0.2° in a powder X-ray diffraction peak pattern using Cu-Kα radiation.

7. The crystal of claim 4, having a purity of 95.0% or more as determined by high performance liquid chromatography.

8. The crystal according to claim 4, wherein the color of the crystal measured in a 10% by weight solution of the crystal in tetrahydrofuran is APHA 250 or less.

9. A method for producing the crystals according to claim 4, wherein the crystals are precipitated from a solution containing 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl and a ketone solvent having 3 to 9 carbon atoms.

10. A crystalline compound according to claim 1, wherein the biphenanthrene dicarboxylic acid compound represented by the general formula (1) is 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl.

11. The crystal according to claim 10, which exhibits an endothermic peak with an onset temperature in the range of 150 to 160°C in differential scanning calorimetry.

12. The crystal according to claim 10, which has diffraction peaks at diffraction angles 2θ of 6.4±0.2°, 20.0±0.2°, and 22.9±0.2° in a powder X-ray diffraction peak pattern using Cu-Kα radiation.

13. The crystal of claim 10, having a purity of 95.0% or more as determined by high performance liquid chromatography.

14. The crystal according to claim 10, wherein the color of the crystal measured in a 10% by weight solution of the crystal in tetrahydrofuran is APHA 250 or less.

15. A method for producing the crystals according to claim 10, wherein the crystals are precipitated from a solution containing 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl and a ketone solvent having 3 to 9 carbon atoms.

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