Thermoplastic resin and optical lens including same

Abstract

The present invention can provide a thermoplastic resin including a structural unit (A) derived from a monomer represented by formula (1). (In formula (1), each R1 independently indicates a hydrogen atom, a methyl group, or an ethyl group.)　A preferred embodiment of the present invention is said thermoplastic resin, wherein said monomer represented by general formula (1) is a compound represented by chemical formula (1-1), (1-2), or (1-3).

Description

Thermoplastic resin and optical lens containing same

[0001] The present invention relates to a thermoplastic resin and an optical lens containing the same. More particularly, the present invention relates to a polyester carbonate resin or polyester resin and an optical lens containing the same.

[0002] Optical glass or optical resin is used as a material for optical lenses used in the optical systems of various cameras, such as cameras with integrated film, video cameras, etc. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., but has problems such as high material costs, poor moldability, and low productivity.

[0003] On the other hand, optical lenses made of optical resins have the advantage that they can be mass-produced by injection molding, and polycarbonate, polyester carbonate, polyester resin, etc. are used as high refractive index materials for camera lenses.

[0004] When an optical resin is used as an optical lens, in addition to optical properties such as refractive index and Abbe number, it is required to have heat resistance, transparency, low water absorption, chemical resistance, low birefringence, moist heat resistance, etc. In particular, in recent years, there has been a demand for optical lenses with high refractive index and high heat resistance, and various resins have been developed (Patent Documents 1 to 5).

[0005] JP 2018-2893 A JP 2018-2894 A JP 2018-2895 A JP 2018-59074 A WO2017 / 078073

[0006] An object of the present invention is to provide a thermoplastic resin that has excellent optical properties such as refractive index and Abbe number, and also has excellent heat resistance, and an optical lens using the same.

[0007] As a result of extensive research aimed at solving the problems of the past, the present inventors have found that a thermoplastic resin having excellent optical properties such as refractive index and Abbe number, as well as excellent heat resistance, can be obtained by using a monomer having a specific structure derived from a dicarboxylic acid compound using biphenanthrols as a raw material, and have thus completed the present invention.

[0008] That is, the present invention includes the following aspects: <1> A thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following formula (1). (In the formula, R １ each independently represents a hydrogen atom, a methyl group, or an ethyl group.) <2> The thermoplastic resin according to <1> above, wherein the monomer represented by general formula (1) is a compound represented by chemical formula (1-1), (1-2), or (1-3). <3> The thermoplastic resin according to <2> above, wherein the monomer represented by the general formula (1) is a compound represented by the chemical formula (1-2). <4> The thermoplastic resin according to the above item <1>, wherein the thermoplastic resin is a polyester carbonate resin or a polyester resin. <5> The thermoplastic resin according to the above item <1>, wherein the thermoplastic resin contains a structural unit (B) derived from a monomer represented by the following general formula (6) and / or a structural unit (C) derived from a monomer represented by the following general formula (7): (In general formula (6), R ａ and R ｂ each independently represents a hydrogen atom, 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 is selected from the group consisting of ｈrepresents 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; X represents a single bond or an optionally substituted fluorene group; A and B each independently represent an optionally substituted alkylene group having 1 to 5 carbon atoms; m and n each independently represent an integer of 0 to 6; and a and b each independently represent an integer of 0 to 10. (In general formula (7), R ｃ and R ｄ are each independently selected from the group consisting of a hydrogen atom, 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; １ represents a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following formulae (8) to (14): (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 ７２represent a carbon ring or hetero ring having 1 to 20 carbon atoms, which may have a substituent, formed by bonding together, and r and s each independently represent an integer of 0 to 5,000. A and B each independently represent an alkylene group having 1 to 5 carbon atoms, which may have a substituent, p and q each independently represent an integer of 0 to 4, and a and b each independently represent an integer of 0 to 10. <6> The thermoplastic resin according to <5> above, wherein in general formula (6) and general formula (7), A and B each independently represent an alkylene group having 2 or 3 carbon atoms. <7> The thermoplastic resin according to <5> above, wherein the thermoplastic resin contains at least a structural unit derived from any one of BPEF, BNE, BNEF, and DPBHBNA. <8> The thermoplastic resin according to <1> above, wherein the thermoplastic resin 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; and t represents an integer of 0 or 1. <9> R in the general formula (5) ３ and R ４ each independently represents a methyl group, a phenyl group, or a naphthyl group, and L in the general formula (5) １ each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent. <10> The thermoplastic resin according to <8> above, wherein the monomer represented by general formula (5) has a structure represented by the following formula (5'): <11> The thermoplastic resin according to <1> above, further comprising a structural unit derived from at least one monomer selected from the following group of monomers: (In the above formula, R １１ and R ２２each 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.) <12> The thermoplastic resin according to <1> above, wherein the weight average molecular weight (Mw) of the thermoplastic resin in terms of polystyrene is 10,000 to 100,000. <13> The thermoplastic resin according to <1> above, wherein the refractive index (nD) of the thermoplastic resin is 1.600 to 1.800. <14> The thermoplastic resin according to <1> above, wherein the Abbe number (ν) of the thermoplastic resin is 15.0 to 23.0. <15> The thermoplastic resin according to <1> above, wherein the glass transition temperature of the thermoplastic resin is 140 to 200°C. <16> The thermoplastic resin according to <1> above, wherein the longest absorption wavelength of the thermoplastic resin is 420 nm or less. <17> An optical lens comprising the thermoplastic resin according to <1> above.

[0009] According to the present invention, it is possible to provide a thermoplastic resin that is excellent in optical properties such as refractive index and Abbe number, and also excellent in heat resistance, and an optical lens containing the same.

[0010] FIG. 1 shows a powder X-ray diffraction (PXRD) measurement chart of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl (compound represented by chemical formula (1-2)) obtained in Synthesis Example 1. The vertical axis indicates the intensity range of 0 to 30,000 (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(methoxycarbonylpropoxy)-9,9'-biphenanthryl (compound represented by chemical formula (1-2)) obtained in Synthesis 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 (1-3)) obtained in Synthesis 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 (°). Fig. 1 shows a differential scanning calorimetry (DSC) chart of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl (compound represented by chemical formula (1-3)) obtained in Synthesis Example 2.

[0011] Hereinafter, the present invention will be described in detail by way of examples and synthesis examples. However, the present invention is not limited to the synthesis examples and examples exemplified, and can be carried out by any method as long as it does not significantly deviate from the content of the present invention.

[0012] <Thermoplastic Resin> One embodiment of the present invention is a thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following general formula (1): The biphenanthrene dicarboxylic acid compound used in the present invention is represented by the following general formula (1). In the formula, R １ R in general formula (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. Specific examples of the biphenanthrene dicarboxylic acid compound represented by general formula (1) include compounds represented by formulas (1-1) to (1-3). Among these, formulas (1-2) and (1-3) are preferred, with formula (1-2) being particularly preferred.

[0013] <Method for Producing a Compound Represented by General Formula (1)> There are no particular limitations on the starting materials and production method used in the production of the biphenanthrene dicarboxylic acid compound represented by general formula (1). Examples of methods for producing a biphenanthrene dicarboxylic acid compound represented by general formula (1) include a method of obtaining a compound represented by general formula (1) by an etherification reaction in which 10,10'-dihydroxy-9,9'-biphenanthryl is reacted with a halogenated butyric acid represented by general formula (2). 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 represents a halogen atom, M represents an alkali metal atom, and MOH represents an alkali metal hydroxide.

[0014] The reaction formula of the 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.

[0015] <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 represented by general formula (1) can be produced by a method described, for example, in JP-A-60-181043 or Journal of American Chemical Society, 2008, 130, 6840.

[0016] <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.

[0017] <Reaction Conditions for the Etherification Reaction> 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 to be charged 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 cations generated from the base relative to the 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 to be 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 amount of biphenanthrols.

[0018] 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.

[0019] The reaction pressure is not limited and may be normal pressure, reduced pressure, or pressurized pressure. Normal 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 from 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 from the reaction system, thereby accelerating the reaction and shortening the reaction time compared to a reaction under normal 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.

[0020] 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.

[0021] When producing the biphenanthrene dicarboxylic acid compound used in 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 used in 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.

[0022] 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.

[0023] <Crystals of 10,10′-bis(ethoxycarbonylpropoxy)-9,9′-biphenanthryl> Among the biphenanthrene dicarboxylic acid compounds used in the present invention, crystals of 10,10′-bis(ethoxycarbonylpropoxy)-9,9′-biphenanthryl, which is a compound represented by chemical formula (1-3), can be handled as a crystalline solid and is therefore very useful because it has excellent handleability. The crystal of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl, which is the compound represented by chemical formula (1-3) used in the present invention, 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 crystals of 10,10'-bis(ethoxycarbonylpropoxy)-9,9'-biphenanthryl, which is the compound represented by chemical formula (1-3) used in the present invention, preferably have any of the following embodiments (i) to (iii): (i) in differential scanning calorimetry, they exhibit 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, they have 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, they exhibit an endothermic peak having an onset temperature in the range of 150 to 160°C, and they also have 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. 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 in 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 analysis method for powder X-ray diffraction analysis. 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 93.0% or more, and even more preferably 96.0% or more.

[0024] <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 according to 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 an 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.

[0025] 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 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 (1-3), the type of organic solvent, and the solubility depending on the type of poor solvent used. However, it 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.

[0026] 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.

[0027] 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.

[0028] <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 represented by chemical formula (1-2) used in the present invention, 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 crystals of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl, which is the compound represented by chemical formula (1-2) used in the present invention, preferably have any of the following embodiments (i) to (iii): (i) in differential scanning calorimetry, they exhibit 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, they have 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, they exhibit an endothermic peak having an onset temperature in the range of 130 to 140°C, and they also have 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. 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, and 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 an analysis method for ordinary powder X-ray diffraction analysis. 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 90.0% or more, more preferably 93.0% or more, and even more preferably 96.0% or more.

[0029] <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 according to 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 an 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.

[0030] 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, it 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.

[0031] 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.

[0032] 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 to be used as seed crystals, and the crystals used in the present invention that were initially precipitated without seed crystals can also be used as seed crystals.

[0033] 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.

[0034] The thermoplastic resin in one embodiment of the present invention 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.

[0035] In a thermoplastic resin according to one embodiment of the present invention, 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), a thermoplastic resin according to one embodiment of the present invention can contain structural units 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.

[0036] Furthermore, the thermoplastic resin according to one embodiment of the present invention preferably contains a structural unit (B) derived from a monomer represented by the following general formula (6). In general formula (6), R ａ and 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.

[0037] 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.

[0038] Specific examples of the structural unit (B) include those derived from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE), DPBHBNA, and the like.

[0039] Furthermore, the thermoplastic resin according to one embodiment of the present invention 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.

[0040] 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.

[0041] 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.

[0042] 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) include those derived from BPEF or BNEF.

[0043] The thermoplastic resin according to one embodiment of the present invention essentially contains the structural unit (A), but may also be a polymer containing the structural unit (B) but not the structural unit (C), a polymer containing the structural unit (C) but not 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 the structural unit (B) include those having structural units represented by 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 represented by 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.

[0044] Furthermore, the thermoplastic resin according to one embodiment of the present invention 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.

[0045] 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.

[0046] Furthermore, the monomer represented by the general formula (5) preferably has a structure represented by the following formula (5').

[0047] 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.

[0048] <Method for Producing Polyester Carbonate Resin> A preferred embodiment of the polyester carbonate resin of the present invention 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 polycondensation catalyst, such as a basic compound catalyst, a transesterification catalyst, or a mixed catalyst consisting of both.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] In the method for producing a polyester carbonate resin of the present invention, 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.

[0056] 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.

[0057] It is desirable that the polyester carbonate resin of the present invention have as little foreign matter content as possible, and therefore 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.

[0058] <Method for producing polyester resin> A preferred embodiment of the polyester resin of the present invention can be produced by a conventionally known method for producing polyesters 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).

[0059] When producing the polyester resin of the present invention, 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.

[0060] 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.

[0061] 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.

[0062] In addition, during the production of the polyester resin of the present invention, various stabilizers such as an etherification inhibitor, a heat stabilizer, a light stabilizer, and a polymerization adjuster may be used.

[0063] <Physical Properties of Thermoplastic Resin> (1) Refractive Index (nD) In ​​one embodiment of the present invention, 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. In the present invention, the refractive index can be measured by the method described in the examples below.

[0064] (2) Abbe number (ν) In one embodiment of the present invention, 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. In the present invention, the Abbe number can be measured by the method described in the examples below.

[0065] (3) Glass Transition Temperature (Tg) In one embodiment of the present invention, 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.

[0066] (4) Weight Average Molecular Weight (Mw) in Polystyrene Equivalents In one embodiment of the present invention, the weight average molecular weight of the thermoplastic resin in polystyrene equivalents is preferably 10,000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 10,000 to 60,000.

[0067] (5) Longest Absorption Wavelength In one embodiment of the present invention, 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.

[0068] <Thermoplastic Resin Composition> Another embodiment of the present invention is a thermoplastic resin composition containing the above-described thermoplastic resin and an additive. The thermoplastic resin composition of this embodiment can be used in combination with a resin other than the thermoplastic resin of the present invention containing the above-described structural unit (A), as long as the desired effects of this embodiment are 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, polyestercarbonate 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.

[0069] [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.

[0070] 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.

[0071] [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 monoglycerides 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 esters such as glycerin diacetomonolaurate; organic acid monoglycerides of glycerin fatty acid esters 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.

[0072] 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.

[0073] [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.

[0074] <Optical Members> The thermoplastic resin or thermoplastic resin composition of the present invention (hereinafter simply referred to as "resin composition") can be suitably used for optical members. In one embodiment of the present invention, an optical member comprising the resin composition of the present invention is provided. In one embodiment of the present invention, 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 composition of the present invention can be molded by a casting method with high flowability, and is therefore particularly suitable for producing thin optical members. In a preferred embodiment of the present invention, the optical member produced using the resin composition of the present invention may be an optical lens. In another preferred embodiment of the present invention, the optical member produced using the resin composition of the present invention may be an optical film.

[0075] When an optical element containing the resin composition of the present invention 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 of the molded piece.

[0076] <Optical Lens> In one embodiment of the present invention, the resin composition can be suitably used for optical lenses. Optical lenses produced using the resin composition of the present invention 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 resin containing any one of the structural units of formulas (II-1) to (II-4), or (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.) A lens molded from a resin containing a structural unit derived from any one of the monomers of the above formulas can be superimposed on the resin to be used as a lens unit.

[0077] The optical lens of the present invention is preferably implemented as an aspherical lens, if necessary. Since an aspherical lens can substantially eliminate spherical aberration with a single lens, it is not necessary to eliminate spherical aberration by combining multiple spherical lenses, which allows for weight reduction and reduced molding costs. Therefore, aspherical lenses are particularly useful as camera lenses, among other optical lenses.

[0078] Furthermore, because the optical lens of the present invention 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 of the present invention can be molded by any method, such as mold molding, cutting, polishing, laser processing, electrical discharge machining, or etching. Among these, mold molding is more preferred in terms of production costs.

[0079] <Optical Film> In one embodiment of the present invention, the resin composition can be suitably used for optical films. In particular, optical films produced using the polyester carbonate resin or polyester resin of the present invention 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 minimize the inclusion of foreign matter in the optical film, the molding environment must naturally be a low-dust environment, preferably class 6 or less, and more preferably class 5 or less.

[0080] Examples of the present invention will be described below together with comparative examples to illustrate the details of the invention, but the present invention is not limited to these examples. The physical properties of the obtained monomers and resins were measured using the following methods and devices.

[0081] <Analysis of Monomer> 1) NMR Analysis Measurement apparatus: Fourier transform nuclear magnetic resonance AVANCE III HD 400 (manufactured by BRUKER) A measurement sample was dissolved in deuterated dimethyl sulfoxide, １ The H-NMR spectrum was measured.

[0082] 2) Melting Point 3 mg of the crystals obtained in the Synthesis Example 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 with aluminum oxide as a control. 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

[0083] 3) Refractive index Measuring device: Refractometer (RA-500, manufactured by Kyoto Electronics Manufacturing Co., Ltd.) Tetrahydrofuran solutions of the measurement sample (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 used as the refractive index of the measurement sample.

[0084] 4) Powder X-ray diffractometry (PXRD) 0.1 g of the compound obtained in Synthesis Example 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

[0085] <Analysis of Resin> 5) Weight-average molecular weight (Mw) The weight-average molecular weight of the obtained resin 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 Columns: 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

[0086] 6) Glass transition temperature (Tg): Measured according to JIS K7121-1987 using a differential scanning calorimeter with a temperature increase program of 10°C / min. Differential scanning calorimeter: TA Instruments DSC2500

[0087] 7) Refractive index (nD) Based on JIS B 7071-2: 2018, a polyester resin was molded to obtain a V-block, which was used as a test piece. The refractive index was measured at 23°C using a refractometer (Shimadzu Corporation KPR-3000).

[0088] 8) Abbe number (ν) Using the same test piece (V-block) as used in the refractive index measurement, the refractive index was measured at wavelengths of 486 nm, 589 nm, and 656 nm at 23°C 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

[0089] 9) Low Molecular Weight Compound Ratio The content of low molecular weight compounds represents the area ratio of compounds having a Mw value of less than 1,000 in GPC analysis. Therefore, the content of low molecular weight compounds was determined according to the following formula. GPC analysis is performed as described above to determine the molecular weight of compounds having Mw values ​​less than 1,000.

[0090] 10) Longest absorption wavelength The longest absorption wavelength of the resins obtained in the examples and comparative examples was evaluated using a spectroscopic haze meter. Measuring device: Hitachi High-Tech Science U-2910 Sample concentration: 0.25 mg / mL dichloromethane solution (cell length: 10 mm) Analysis method: The longest wave number at the absorption edge was read.

[0091] Synthesis Example 1: 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. The temperature inside the flask was then maintained at 90°C while stirring. 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 １３C-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] 　１ H-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 as measured by high performance liquid chromatography was 99.5%, and the hue of a 10% THF solution obtained by the above analytical method was APHA20. The PXRD measurement chart of the obtained solid biphenanthrene dicarboxylic acid compound is shown in Figure 1. The peak pattern revealed that the solid of the target compound obtained 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 are shown in Table 1, with peaks having a relative integrated intensity of 5 or more being selected. The melting point of the obtained biphenanthrene dicarboxylic acid compound crystals was measured by the above analytical method and found to be 134° C. The differential scanning calorimetry chart is shown in FIG.

[0092] Synthesis Example 2: 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 are shown in Table 2. Peaks with a relative integrated intensity of 5 or more are selected. 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 1 As raw materials, 149.0553 g (0.2541 mol) of 10,10′-bis(methoxycarbonylpropoxy)-9,9′-biphenanthryl (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 －３ mol) 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 3.

[0094] Examples 2 and 3 Polyester resins were obtained in the same manner as in Example 1, except that the raw materials used were those shown in Table 3. Table 3 shows the composition and physical properties of the obtained resins.

[0095] (Example 4) As raw materials, 846.08 g (1.442 mol) of 10,10'-bis(methoxycarbonylpropoxy)-9,9'-biphenanthryl (abbreviation: BIPOL-DMB) represented by the structural formula above, 333.26 g (0.601 mol) of 2,2'-bis(phenoxycarbonylmethoxy)-1,1'-binaphthyl (abbreviation: BINOL-DP) represented by the structural formula below, 150.00 g (0.401 mol) of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (abbreviation: BNE) represented by the structural formula below, 863.11 g (1.602 mol) of 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene (abbreviation: BNEF) represented by the structural formula above, 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 3.

[0096] Examples 5 to 8 Polyester resins were obtained in the same manner as in Example 4, except that the raw materials used were those shown in Table 3. Table 3 shows the compositions and physical properties of the resins obtained.

[0097] Comparative Example 1 A polyester resin was obtained in the same manner as in Example 1, except that 141.9288 g (0.2541 mol) of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthryl (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 3.

[0098] Comparative Examples 2 to 4 Polyester resins were obtained in the same manner as in Comparative Example 1, except that the raw materials used were those shown in Table 3. Table 3 shows the compositions and physical properties of the resins obtained.

[0099] Comparative Example 5 A polyester resin was obtained in the same manner as in Example 4, except that the raw materials shown in Table 3 were used. Table 3 shows the composition and physical properties of the obtained resin.

[0100]

Claims

1. A thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following formula (1): (In the formula, R １ each independently represents a hydrogen atom, a methyl group, or an ethyl group.

2. The thermoplastic resin according to claim 1, wherein the monomer represented by the general formula (1) is a compound represented by the chemical formula (1-1), (1-2) or (1-3).

3. The thermoplastic resin according to claim 2, wherein the monomer represented by the general formula (1) is a compound represented by the chemical formula (1-2).

4. The thermoplastic resin according to claim 1, wherein the thermoplastic resin is a polyester carbonate resin or a polyester resin.

5. The thermoplastic resin according to claim 1, wherein the thermoplastic resin contains a structural unit (B) derived from a monomer represented by the following general formula (6) and / or a structural unit (C) derived from a monomer represented by the following general formula (7): (In general formula (6), R ａ and R ｂ each independently represents a hydrogen atom, 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 is selected from the group consisting of 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; X represents a single bond or an optionally substituted fluorene group; A and B each independently represent an optionally substituted alkylene group having 1 to 5 carbon atoms; m and n each independently represent an integer of 0 to 6; and a and b each independently represent an integer of 0 to 10. (In general formula (7), R ｃ and R ｄ are each independently selected from the group consisting of a hydrogen atom, 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; １ represents a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following formulae (8) to (14): (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 ７２ are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; r and s each independently represent an integer of 0 to 5,000; A and B each independently represent an alkylene group having 1 to 5 carbon atoms, which may have a substituent; p and q each independently represent an integer of 0 to 4; a and b each independently represent an integer of 0 to 10.

6. The thermoplastic resin according to claim 5, wherein in the general formula (6) and the general formula (7), A and B each independently represent an alkylene group having 2 or 3 carbon atoms.

7. The thermoplastic resin according to claim 5, wherein the thermoplastic resin contains at least a structural unit derived from any one of BPEF, BNE, BNEF, and DPBHBNA.

8. The thermoplastic resin according to claim 1, wherein the thermoplastic resin 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; and t represents an integer of 0 or 1.

9. R in the general formula (5) ３ and R ４ each independently represents a methyl group, a phenyl group, or a naphthyl group, and L in the general formula (5) １ and each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent.

10. The thermoplastic resin according to claim 8, wherein the monomer represented by general formula (5) has a structure represented by the following formula (5'):

11. The thermoplastic resin according to claim 1, wherein the thermoplastic resin 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.

12. The thermoplastic resin according to claim 1, wherein the weight average molecular weight (Mw) of the thermoplastic resin in terms of polystyrene is 10,000 to 100,000.

13. The thermoplastic resin according to claim 1, wherein the refractive index (nD) of the thermoplastic resin is 1.600 to 1.

800.

14. The thermoplastic resin according to claim 1, wherein the Abbe number (ν) of the thermoplastic resin is 15.0 to 23.

0.

15. The thermoplastic resin according to claim 1, wherein the glass transition temperature of the thermoplastic resin is 140 to 200°C.

16. The thermoplastic resin according to claim 1, wherein the longest absorption wavelength of said thermoplastic resin is 420 nm or less.

17. An optical lens comprising the thermoplastic resin of claim 1.

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