Method for producing thermoplastic resin, thermoplastic resin obtained by said production method, and optical lens containing said resin

Abstract

According to the present invention, it is possible to provide a method for producing a thermoplastic resin having a structural unit (A) represented by formula (a), the method comprising a step of reacting a dicarboxylic acid diester crystal represented by formula (a) satisfying at least either (i) or (ii) with a diol compound, (i) the highest melting endothermic temperature measured by differential scanning calorimetry is 177-181 DEG C, and (ii) the powder has peaks at diffraction angles 2 [theta] = 7.6 + / -0.2 DEG, 8.7 + / -0.2 DEG, 18.0 + / -0.2 DEG, 19.2 + / -0.2 DEG, 19.7 + / -0.2 DEG, and 21.9 + / -0.2 DEG in a powder X-ray diffraction pattern measured by Cu-K [alpha] rays, said powder having peaks at diffraction angles 2 [theta] = 7.6 + / -0.2 DEG, 8.7 + / -0.2 DEG, 18.0 + / -0.2 DEG, 19.2 + / -0.2 DEG, 19.7 + / -0.2 DEG, and 21.9 + / -0.2 DEG. In formula (A), * represents a bonding part. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a method for producing a thermoplastic resin, a thermoplastic resin obtained by the production method, and an optical lens containing the resin. Background Art

[0002] Optical glass or optical resin has long been used as the material for optical lenses used in the optical systems of various cameras, including still cameras, film cameras, and video cameras. While optical glass offers excellent properties such as heat resistance, transparency, dimensional stability, and chemical resistance, it suffers from issues such as high material costs, poor moldability, and low productivity.

[0003] On the other hand, optical lenses made of optical resins have the advantage of being mass-produced by injection molding. As high-refractive-index materials for camera lenses, polycarbonate, polyester carbonate, polyester resin, etc. have been conventionally used.

[0004] When optical resins are used as optical lenses, in addition to optical properties such as refractive index and Abbe number, they are also required to have heat resistance, transparency, low water absorption, chemical resistance, low birefringence, and resistance to heat and humidity. In recent years, there has been a particular demand for optical lenses with high refractive index and high heat resistance, leading to the development of various resins (Patent Documents 1 to 5).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2018-2893

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2018-2894

[0009] Patent Document 3: Japanese Patent Application Laid-Open No. 2018-2895

[0010] Patent Document 4: Japanese Patent Application Laid-Open No. 2018-59074

[0011] Patent Document 5: WO2017 / 078073 Summary of the Invention

[0012] Problems to be solved by the invention

[0013] An object of the present invention is to provide a method for producing a thermoplastic resin having excellent reactivity and an excellent color tone.

[0014] Technical solutions to problems

[0015] The present inventors have conducted intensive studies to solve the above problems and have found that a thermoplastic resin having excellent reactivity and color tone can be obtained by using crystals of a dicarboxylic acid diester having a specific structure as a raw material, thereby completing the present invention.

[0016] That is, the present invention includes the following embodiments.

[0017] <1> A method for producing a thermoplastic resin, wherein the thermoplastic resin has a structural unit (A) represented by the following formula:

[0018] The production method includes the step of reacting a dicarboxylic acid diester crystal represented by the following formula (a) that satisfies at least one of the following (i) and (ii) with a diol compound.

[0019] (i) The maximum melting endotherm temperature measured by differential scanning calorimetry is 177-181°C,

[0020] (ii) having peaks at diffraction angles 2θ = 7.6 ± 0.2°, 8.7 ± 0.2°, 18.0 ± 0.2°, 19.2 ± 0.2°, 19.7 ± 0.2°, and 21.9 ± 0.2° in a powder X-ray diffraction pattern measured using Cu-Kα radiation,

[0021]

[0022] In formula (A), "*" represents a bonding portion,

[0023]

[0024] <2> The production method according to <1> above, wherein the crystals of the dicarboxylic acid diester satisfy both of the following (i) and (ii),

[0025] (i) The maximum melting endotherm temperature measured by differential scanning calorimetry is 177-181°C,

[0026] (ii) In a powder X-ray diffraction pattern measured using Cu-Kα radiation, the compound has peaks at diffraction angles 2θ = 7.6±0.2°, 8.7±0.2°, 18.0±0.2°, 19.2±0.2°, 19.7±0.2°, and 21.9±0.2°.

[0027] <3> The production method according to <1> or <2> above, wherein the thermoplastic resin is a polyester resin or a polyester carbonate resin.

[0028] <4> The production method according to any one of <1> to <3> above, wherein the thermoplastic resin contains a structural unit (B) derived from a monomer represented by the following general formula (b) and / or a structural unit (C) derived from a monomer represented by the following general formula (c).

[0029]

[0030] In the general formula (b), R a and R b Each of the following is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy 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 cycloalkoxy 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 may have a substituent and containing one or more heteroatoms selected from O, N and S, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R h ,

[0031] 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 may have a substituent and contains one or more heteroatoms selected from O, N and S,

[0032] X represents a single bond or a fluorenyl group which may have a substituent,

[0033] A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, m and n each independently represent an integer of 0 to 6,

[0034] a and b each independently represent an integer from 0 to 10;

[0035]

[0036] In the general formula (c), R c and R d Each of the following is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy 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 cycloalkoxy 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,

[0037] Y1 is a single bond, a fluorenyl group which may have a substituent, or any of the groups represented by the following structural formulae (1) to (7),

[0038]

[0039] In formulas (1) to (7), 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 represents R 61 With R 62 or R 71 With R 72 a carbon ring or heterocyclic ring having 1 to 20 carbon atoms, which is bonded to each other and may have a substituent,

[0040] r and s each independently represent an integer from 0 to 5000;

[0041] 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,

[0042] a and b each independently represent an integer of 0 to 10.

[0043] <5> The production method according to any one of <1> to <4> above, wherein a catalyst containing an alkali metal or an alkaline earth metal is used.

[0044] <6> The production method according to any one of <1> to <5> above, wherein the catalyst is contained in an amount of 0.1 to 10 ppm based on the thermoplastic resin.

[0045] <7> The production method according to any one of <1> to <6> above, wherein the thermoplastic resin has a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 to 100,000.

[0046] <8> The production method according to any one of <1> to <7> above, wherein the thermoplastic resin has a YI of 0.1 to 14.

[0047] <9> A thermoplastic resin comprising a structural unit (A) derived from a crystal of a dicarboxylic acid diester represented by the following formula (a) satisfying at least one of the following (i) and (ii),

[0048]

[0049] (i) The maximum melting endotherm temperature measured by differential scanning calorimetry is 177-181°C,

[0050] (ii) In a powder X-ray diffraction pattern measured using Cu-Kα radiation, the compound has peaks at diffraction angles 2θ = 7.6±0.2°, 8.7±0.2°, 18.0±0.2°, 19.2±0.2°, 19.7±0.2°, and 21.9±0.2°.

[0051] <10> The thermoplastic resin according to <9> above, wherein the crystals of the dicarboxylic acid diester satisfy both of the following (i) and (ii),

[0052] (i) The maximum melting endotherm temperature measured by differential scanning calorimetry is 177-181°C,

[0053] (ii) In a powder X-ray diffraction pattern measured using Cu-Kα radiation, the compound has peaks at diffraction angles 2θ = 7.6±0.2°, 8.7±0.2°, 18.0±0.2°, 19.2±0.2°, 19.7±0.2°, and 21.9±0.2°.

[0054] <11> The thermoplastic resin according to <9> or <10>, wherein the thermoplastic resin is a polyester resin or a polyester carbonate resin.

[0055] <12> An optical element comprising the thermoplastic resin according to any one of <9> to <11> above.

[0056] <13> An optical lens comprising the thermoplastic resin according to any one of <9> to <11> above.

[0057] <14> An optical film comprising the thermoplastic resin according to any one of <9> to <11> above.

[0058] Effects of the Invention

[0059] According to the present invention, a method for producing a thermoplastic resin having excellent reactivity and an excellent color tone can be provided.

[0060] In particular, when the crystals of the dicarboxylic acid diester represented by formula (a) are crystals having a maximum melting endotherm temperature of 177 to 181°C in <1> or crystals having the powder X-ray diffraction pattern described in <1>, the bulk density of the dicarboxylic acid diester, one of the raw materials for the thermoplastic resin, is increased, thereby facilitating handling during addition to the reactor. Furthermore, the polymerization activity is enhanced, allowing for a reduction in the amount of catalyst added, resulting in a resin having an excellent color tone. DETAILED DESCRIPTION

[0061] Hereinafter, the present invention will be described in detail with reference to synthesis examples and examples. However, the present invention is not limited to the synthesis examples and examples, and any method can be modified within the scope not significantly exceeding the scope of the present invention.

[0062] <Thermoplastic resin and its production method>

[0063] One embodiment of the present invention is a method for producing a thermoplastic resin having a structural unit (A) represented by the following formula, comprising reacting a crystal of a dicarboxylic acid diester represented by the following formula (a) that satisfies at least one of the following (i) and (ii) with a diol compound.

[0064] (i) The maximum melting endotherm temperature measured by differential scanning calorimetry is 177-181°C,

[0065] (ii) In a powder X-ray diffraction pattern measured using Cu-Kα radiation, the compound has peaks at diffraction angles 2θ = 7.6±0.2°, 8.7±0.2°, 18.0±0.2°, 19.2±0.2°, 19.7±0.2°, and 21.9±0.2°.

[0066]

[0067] (In formula (A), "*" represents a bonding portion.)

[0068]

[0069] The inventors of the present invention have discovered that crystals of the dicarboxylic acid diester (phenyl ester) represented by formula (a) above have greater reactivity than their methyl esters or carboxylic acids, allowing polymerization reactions to proceed even with a small amount of catalyst. Furthermore, they have discovered that the resulting thermoplastic resin exhibits an excellent hue, likely due to the high thermal stability of the phenyl ester itself.

[0070] The crystals of the dicarboxylic acid diester represented by the above formula (a) can be produced by a specific production method described below, and have a melting point (maximum temperature of the melting endotherm measured by differential scanning calorimetry) of 177 to 181° C. Furthermore, in a powder X-ray diffraction pattern measured using Cu-Kα radiation, the crystals have characteristic peaks at diffraction angles 2θ = 7.6±0.2°, 8.7±0.2°, 18.0±0.2°, 19.2±0.2°, 19.7±0.2°, and 21.9±0.2°, and preferably also have peaks at diffraction angles 2θ = 14.1±0.2°, 16.1±0.2°, 22.8±0.2°, and 25.0±0.2°.

[0071] The crystals of the dicarboxylic acid diester represented by formula (a) may satisfy at least the following conditions: a maximum melting endotherm temperature of 177 to 181°C as measured by differential scanning calorimetry; and a powder X-ray diffraction pattern measured using Cu-Kα radiation having at least one peak at diffraction angles 2θ = 7.6 ± 0.2°, 8.7 ± 0.2°, 18.0 ± 0.2°, 19.2 ± 0.2°, 19.7 ± 0.2°, and 21.9 ± 0.2°. Preferably, both conditions are satisfied.

[0072] Hereinafter, the method for producing the crystal of the dicarboxylic acid diester represented by the above formula (a) will be described in detail.

[0073] [Crystal of Dicarboxylic Acid Diester Represented by Formula (a)]

[0074] The crystals of the dicarboxylic acid diester represented by the above formula (a) can be produced by the following production method, which sequentially comprises: a step of reacting a compound represented by the following general formula (2) with diphenyl carbonate or phenyl acetate in the presence of an organic titanium compound (reaction step); and a step of precipitating crystals of the dicarboxylic acid diester represented by the above formula (a) using at least one organic compound selected from aromatic hydrocarbons, alcohols, ethers and esters as a crystallization solvent (crystallization step).

[0075] The reaction steps are described in detail below.

[0076]

[0077] (Where R 1a 、R 1b Each independently represents an alkyl group having 1 to 6 carbon atoms which may have a branch.

[0078] R in the above general formula (2) 1a 、R 1b The alkyl group having 1 to 6 carbon atoms may be linear or branched, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0079] The compound represented by the general formula (2) may be a product purified by conventional methods (e.g., the crystals described in Japanese Patent Application Laid-Open No. 2021-017406), or an unpurified product (e.g., the compound represented by the general formula (2) contained in the reaction mixture obtained by the reaction of 1,1'-binaphthol with a haloacetic acid ester) may be used. In particular, since the dicarboxylic acid diester represented by the formula (a) has low solubility in general organic solvents such as aromatic hydrocarbons, even if the unpurified compound represented by the general formula (2) is used as a raw material, impurities contained in the previous step can be easily removed by crystallization after the reaction.

[0080] Examples of the organic titanium compound include alkoxytitanium catalysts. Examples of the alkoxytitanium catalyst include tetramethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-tert-butyl titanate, tetra-2-ethylhexyl titanate, tetraoctyl titanate, tetraphenyl titanate, tetrabenzyl titanate, and tetra(xylene) titanate. These organic titanium compounds may be used alone or in combination of two or more.

[0081] The amount of the organic titanium compound used is, for example, 0.025 to 0.10 mol per 1 mol of the compound represented by the above general formula (2).

[0082] The amount of diphenyl carbonate and phenyl acetate used is, for example, 4 to 25 mol per 1 mol of the compound represented by the above general formula (2).

[0083] The reaction of the compound represented by the general formula (2) with diphenyl carbonate or phenyl acetate can be carried out using diphenyl carbonate or phenyl acetate as a solvent, or can be carried out in the presence of other organic solvents other than diphenyl carbonate and phenyl acetate. Examples of other organic solvents include aromatic hydrocarbons. Examples of aromatic hydrocarbons include toluene, xylene, mesitylene, etc. When other organic solvents are used, their usage amount is, for example, 0.05 to 5.0 parts by weight relative to 1 part by weight of the compound represented by the general formula (2). These other organic solvents can be used alone or in combination of two or more.

[0084] The reaction of the compound represented by the general formula (2) with diphenyl carbonate or phenyl acetate can be carried out, for example, at 130 to 170°C. Alternatively, the reaction can be carried out under normal pressure or reduced pressure while removing by-products, as needed. When the reaction is carried out under reduced pressure, the internal pressure is, for example, 0.67 to 6.7 kPa.

[0085] After the reaction step, the resulting reaction mixture is subjected to a crystallization step to obtain crystals of the dicarboxylic acid diester represented by formula (a). It should be noted that the reaction mixture obtained after the reaction step may be subjected to subsequent treatments such as neutralization, water washing, and concentration, as needed, before being subjected to the crystallization step. The crystallization step is described in detail below.

[0086] The solvent (crystallization solvent) used in the crystallization step is at least one organic compound selected from aromatic hydrocarbons, alcohols, ethers and esters. As aromatic hydrocarbons, toluene, xylene, mesitylene, etc. can be listed. As alcohols, for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, etc. can be listed, which may have branched carbon atoms of 1 to 6. As ethers, for example, diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, etc. can be listed. As esters, ethyl acetate, propyl acetate, butyl acetate, etc. can be listed. Among these crystallization solvents, aromatic hydrocarbons are preferred. These crystallization solvents can be used alone or in combination of two or more. Since the solvent can be more easily recovered when used alone, it is preferably used alone from the perspective of reducing environmental load and cost.

[0087] The amount of the crystallization solvent used is, for example, 1 to 10 parts by weight relative to 1 part by weight of the dicarboxylic acid diester represented by the above formula (a). The amount of the dicarboxylic acid diester represented by the above formula (a) contained in the reaction mixture can be measured, for example, by an absolute calibration curve method using liquid chromatography, an internal standard method, or the like.

[0088] As a method for crystallizing the dicarboxylic acid diester represented by the above formula (a), for example, there can be mentioned a method in which the dicarboxylic acid diester represented by the above formula (a) is dissolved in a crystallization solvent, the resulting solution is cooled, crystals are precipitated, and the precipitated crystals are separated by filtration. The temperature at which the dicarboxylic acid diester represented by the above formula (a) is dissolved in the crystallization solvent is, for example, below the boiling point of the solvent used to 115°C. The temperature at which the resulting solution is cooled and crystals are precipitated is, for example, 80 to 100°C. It should be noted that seed crystals can be used for crystallization, but since the dicarboxylic acid diester represented by the above formula (a) can be crystallized without using seed crystals, it is not necessary to go through the above-mentioned complicated steps for crystallization, as in the case of 2,2'-bis(ethoxycarbonylmethoxy)-1,1'-binaphthyl, and crystallization can be easily performed.

[0089] Thereafter, further cooling may be performed as needed. The cooling rate at this time is, for example, 0.1 to 20°C / min, and the cooling end temperature is, for example, 0 to 25°C. The crystals can then be extracted by conventional methods such as filtration and centrifugation. Although the extracted crystals usually contain a solvent, the solvent can be removed by drying. Drying can be performed, for example, by heating under normal pressure or reduced pressure. The temperature during heating is, for example, 70 to 90°C.

[0090] The thus obtained crystals of the dicarboxylic acid diester represented by the above formula (a) may be further purified by recrystallization, distillation, adsorption, column chromatography, or the like.

[0091] [Other dicarboxylic acids or ester-forming derivatives thereof]

[0092] When the method for producing a thermoplastic resin of the present invention is a method for producing a polyester carbonate resin, other dicarboxylic acids or ester-forming derivatives thereof other than the crystals of the dicarboxylic acid diester represented by the above formula (a) may be used in combination in a range of 30 mol% or less. The dicarboxylic acids or ester-forming derivatives thereof used in the step of obtaining the intermediate product can be dicarboxylic acids or ester-forming derivatives thereof commonly used in the art for producing intermediate products.

[0093] Examples of the dicarboxylic acid include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid; monocyclic aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, 9,9-bis(carboxymethyl)fluorene, 9,9-bis(2-carboxyethyl)fluorene, 9,9-bis(1-carboxyethyl)fluorene, and 9,9-bis(1-carboxypropyl)fluorene. Polycyclic aromatic dicarboxylic acids such as 9,9-bis(2-carboxypropyl)fluorene, 9,9-bis(2-carboxy-1-methylethyl)fluorene, 9,9-bis(2-carboxy-1-methylpropyl)fluorene, 9,9-bis(2-carboxybutyl)fluorene, 9,9-bis(2-carboxy-1-methylbutyl)fluorene, 9,9-bis(5-carboxypentyl)fluorene, and 9,9-bis(carboxycyclohexyl)fluorene; biphenyl dicarboxylic acids such as 2,2'-biphenyl dicarboxylic acid; and alicyclic dibasic acids such as 1,4-cyclohexane dicarboxylic acid and 2,6-naphthalene dicarboxylic acid, preferably isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, and 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl. These dicarboxylic acids may be used alone or in combination of two or more. Furthermore, as ester-forming derivatives, acid chlorides of the above-mentioned carboxylic acids and esters such as methyl ester, ethyl ester, and phenyl ester can also be used.

[0094] As the dicarboxylic acid, for example, a compound represented by the following general formula (C) is preferably used.

[0095]

[0096] In the above formula, R 1 and R 2 R each independently represents a hydrocarbon group having 1 to 10 carbon atoms and optionally containing an aromatic group, and n and m each independently represent an integer greater than 0. 3 ~R 10 Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may contain an aromatic group.

[0097] Representative specific examples of the dicarboxylic acid represented by the general formula (C) or its ester-forming derivative are shown below, but the present invention is not limited thereto.

[0098] Examples thereof include 2,2'-dicarboxy-1,1'-binaphthyl, 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, 2,2'-bis(2-carboxyethoxy)-1,1'-binaphthyl, 2,2'-bis(3-carboxypropoxy)-1,1'-binaphthyl, 2,2'-dimethoxycarbonyl-1,1'-binaphthyl, 2,2'-bis(methoxycarbonylmethoxy)-1,1'-binaphthyl, 2,2'-bis(2-methoxycarbonylethoxy)-1,1'-binaphthyl, 2,2'-bis(3-methoxycarbonylpropoxy)-1,1'-binaphthyl, 2,2'-diethoxycarbonyl-1,1'-binaphthyl, 2,2'-bis(ethoxycarbonylmethoxy)-1,1'-binaphthyl, Naphthalene, 2,2'-bis(2-ethoxycarbonylethoxy)-1,1'-binaphthyl, 2,2'-bis(3-ethoxycarbonylpropoxy)-1,1'-binaphthyl, 2,2'-diphenoxycarbonyl-1,1'-binaphthyl, 2,2'-bis(2-phenoxycarbonylethoxy)-1,1'-binaphthyl, 2,2'-bis(3-phenoxycarbonylpropoxy)-1,1'-binaphthyl, 2,2'-di-tert-butoxycarbonyl-1,1'-binaphthyl, 2,2'-bis(tert-butoxycarbonylmethoxy)-1,1'-binaphthyl, 2,2'-bis(2-tert-butoxycarbonylethoxy)-1,1'-binaphthyl, 2,2'-bis(3-tert-butoxycarbonylpropoxy)-1,1'-binaphthyl, etc. Among them, R in the general formula (C) is preferably 1 and R 2 is methylene, o and p are 1, R 3 ~R 10 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl or its ester-forming derivatives containing a hydrogen atom.

[0099] Another embodiment of the present invention is a thermoplastic resin comprising structural units (A) derived from crystals of a dicarboxylic acid diester represented by the following formula (a) having a maximum melting endothermic temperature of 177 to 181°C as measured by differential scanning calorimetry.

[0100]

[0101] The melting point of the crystal of the dicarboxylic acid diester represented by the above formula (a) (maximum temperature of the melting endotherm measured by differential scanning calorimetry) is 177 to 181°C. In addition, in a powder X-ray diffraction pattern measured using Cu-Kα radiation, peaks are present at diffraction angles 2θ = 7.6±0.2°, 8.7±0.2°, 18.0±0.2°, 19.2±0.2°, 19.7±0.2°, and 21.9±0.2°, and preferably peaks are also present at diffraction angles 2θ = 14.1±0.2°, 16.1±0.2°, 22.8±0.2°, and 25.0±0.2°.

[0102] The thermoplastic resin in one embodiment of the present invention is not particularly limited and is preferably a polyester carbonate resin or a polyester resin, and is not particularly limited to polyester resins, polycarbonate resins, polyester carbonate resins, epoxy resins, polyurethane resins, polyacrylate resins, polymethacrylate resins, and the like.

[0103] In the thermoplastic resin according to one embodiment of the present invention, the proportion of the structural unit (A) represented by the above formula 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.

[0104] That is, the thermoplastic resin according to one embodiment of the present invention may contain, in addition to the structural unit (A) represented by the above formula, structural units derived from aliphatic dihydroxy compounds and structural units derived from aromatic dihydroxy compounds, which are generally used as structural units of polycarbonate resins, polyester carbonate resins, etc.

[0105] Specifically, examples of the aliphatic dihydroxy compound include various compounds, particularly 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, 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-methyl-1-propanol, isosorbide, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0106] Examples of the aromatic dihydroxy compound 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'-dihydroxybiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, and bisphenoxyethanolfluorene.

[0107] Furthermore, the thermoplastic resin according to one embodiment of the present invention preferably includes a structural unit (B) derived from a monomer represented by the following general formula (b).

[0108]

[0109] In the general formula (b), R a and R b each independently selected from a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy 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 cycloalkoxy 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 may have a substituent and containing one or more heteroatoms selected from O, N and S, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R h . R h It 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 heteroatoms selected from O, N and S and may have a substituent.

[0110] R a and R b Preferred are a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 6 to 20 carbon atoms which may have a substituent and contains one or more heterocyclic atoms selected from O, N, and S. More preferred are a hydrogen atom and an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferred are a hydrogen atom and an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0111] In general formula (b), X represents a single bond or a fluorenyl group which may have a substituent. X is preferably a single bond or a fluorenyl group which may have a substituent having a total of 12 to 20 carbon atoms.

[0112] In the general formula (b), A and B are each independently 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.

[0113] In the general formula (b), m and n are each independently an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably 0 or 1.

[0114] In the general formula (b), a and b are each independently an integer of 0 to 10, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0115] Specific examples of the structural unit (B) include structural units derived from 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthyl (BNE), DPBHBNA, and the like.

[0116]

[0117] Furthermore, the thermoplastic resin according to one embodiment of the present invention preferably has a structural unit (C) derived from a monomer represented by the following general formula (c).

[0118]

[0119] In the general formula (c), R c and R d Each is independently selected from a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy 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 cycloalkoxy 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.

[0120] R c and R d Preferred are a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 6 to 20 carbon atoms which may have a substituent and contains one or more heterocyclic atoms selected from O, N, and S. More preferred are a hydrogen atom and an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferred are a hydrogen atom and an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0121] In general formula (c), Y1 is a single bond, a fluorenyl group which may have a substituent, or any of the structural formulae represented by the following formulae (1) to (7), preferably a single bond or a structural formula represented by the following formula (1).

[0122]

[0123] In formulas (1) to (7), R 61 、R 62 、R 71 and R 72Each 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 represents R 61 With R 62 or R 71 With R 72 a carbon ring or heterocyclic ring having 1 to 20 carbon atoms, which is bonded to each other and may have a substituent,

[0124] In formulae (1) to (7), r and s are each independently an integer of 0 to 5000.

[0125] In the general formula (c), A and B are each independently 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 (c), p and q are each independently an integer of 0 to 4, and preferably 0 or 1. In the general formula (c), a and b are each independently an integer of 0 to 10, and preferably an integer of 0 to 5, and more preferably an integer of 0 to 2, for example, 0 or 1.

[0126] Specific examples of the structural unit (C) include bisphenols derived from 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)naphth-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, bisphenol P-AP (4,4'-(1-phenylethylidene) bisphenol), bisphenol P-CDE (4,4'-cyclododecylene bisphenol), bisphenol P-HTG (4,4'-(3,3,5-trimethylcyclohexylene) bisphenol), bisphenol P-MIBK (4,4'-(1,3-dimethylbutylene) bisphenol), bisphenol PEO-FL (bisphenoxyethanol fluorene), bisphenol P-3MZ (4-[1-(4-hydroxyphenyl)-3-methyl Bisphenol Z, BP-2EO (2,2'-[[1,1'-biphenyl]-4,4'-diylbis(oxy)diethanol), S-BOC (4,4'-(1-methylethylidene)bis(2-methylphenol)), TrisP-HAP (4,4',4"-ethylenetriphenol), 1,1-bis(4-hydroxyphenyl)-1-phenylenediol), The structural unit (C) may be a structural unit derived from 1,3-bis(1-methyl-1-phenylethyl)benzene (BPM), 1,1-bis(4-hydroxyphenyl)cyclododecane (BPAP), 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (BCFL), bis(4-hydroxyphenyl)diphenylmethane (BPBP), or the like. Among these, preferred structural units include those derived from BPEF, BNEF, or BCFL.

[0127]

[0128] The thermoplastic resin according to one embodiment of the present invention necessarily contains the structural unit (A), but may also be a polymer containing the structural unit (B) but not containing the structural unit (C), a polymer containing the structural unit (C) but not containing the structural unit (B), a copolymer containing the structural unit (B) and the structural unit (C), a mixture of a polymer containing the structural unit (B) and a polymer containing the structural unit (C), and combinations thereof. Examples of the polymer containing the structural unit (C) but not containing the structural unit (B) include polymers having structural units of the following formulae (I-1) to (I-3), and examples of the copolymer containing the structural unit (B) and the structural unit (C) include copolymers having structural units of the following formulae (II-1) to (II-4).

[0129]

[0130] (In formula (I-1), m and n are each an integer of 1 to 10, preferably an integer of 1 to 5, more preferably 1,

[0131] The number of repeating units in formula (I-2) and formula (I-3) is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1.

[0132] Furthermore, as the polymer having multiple structural units, either a block copolymer or a random copolymer having m and n values ​​as large as, for example, 100 or more can be used. A random copolymer is preferred, and a random copolymer having m and n values ​​of 1 is more preferred.

[0133]

[0134] (In formulae (II-1) to (II-4), m, n, and l are each independently an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1.)

[0135] In addition, as a polymer having multiple structural units, any of block copolymers and random copolymers in which the values ​​of m and n (or m, n and l) are as large as, for example, 100 or more can be used, preferably a random copolymer, and more preferably a random copolymer in which the values ​​of m and n (or m, n and l) are 1.

[0136] 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, further 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 structural unit (B) to the polymer having structural unit (C) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, further preferably 15:85 to 85:15, and particularly preferably 30:70 to 70:30.

[0137] The thermoplastic resin according to one embodiment of the present invention preferably further includes a structural unit derived from at least one monomer selected from the following monomer group.

[0138]

[0139] (In the above formula, R1 and R2 each independently represent a hydrogen atom, a methyl group, or an ethyl group, and R3 and R4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms.)

[0140] In addition, the thermoplastic resin according to one embodiment of the present invention preferably has a structural unit (D) derived from a monomer represented by the following general formula (16). In this case, the content of the structural unit (D) derived from the monomer represented by the general formula (16) is preferably 1 to 50 mol%, more preferably 1 to 30 mol% of all the structural units.

[0141]

[0142] In general formula (16),

[0143] L 1 Each independently represents a divalent linking group;

[0144] R 3 and R 4 Each independently represents a halogen atom or a substituent having 1 to 20 carbon atoms which may contain an aromatic group;

[0145] j3 and j4 each independently represent an integer from 0 to 4;

[0146] t represents an integer of 0 or 1.

[0147] In the above general formula (16), L 1 Each independently represents a divalent linking group. 1 An alkylene group having 1 to 12 carbon atoms which may have a substituent is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, an alkylene group having 2 or 3 carbon atoms is further preferred, and an ethylene group is particularly preferred. 1The substituents of the alkylene group include alkyl, cycloalkyl, aryl, alkoxy and combinations thereof. Specific examples of these groups include methyl, ethyl, n-propyl, isopropyl, phenyl, methoxy and ethoxy.

[0148] In the presence of R 3 and R 4 In the case of R 3 and R 4 Each independently represents a halogen atom or a substituent having 1 to 20 carbon atoms that may contain an aromatic group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and the like. Examples of the substituent having 1 to 20 carbon atoms that may contain an aromatic group include a methyl group, a phenyl group, a naphthyl group, a thienyl group, a benzothienyl group, and the like. Examples of the naphthyl group include 1-naphthyl and 2-naphthyl, and examples of the thienyl group include 2-thienyl and 3-thienyl. In addition, examples of the benzothienyl group include 2-benzo[b]thienyl and 3-benzo[b]thienyl. These groups may further have a substituent, and examples of such a substituent include the above-mentioned L 1 The substituents of the alkylene group include, but are not limited to, the groups described above.

[0149] j3 and j4 each independently represent an integer of 0 to 4. j3 and j4 are preferably integers of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0150] t represents an integer of 0 or 1, and is preferably 1.

[0151] The monomer represented by the general formula (16) preferably has a structure represented by the following formula (16').

[0152]

[0153] <Production Method of Polyester Carbonate Resin>

[0154] The polyester carbonate resin of a preferred embodiment of the present invention can be produced by a melt polycondensation method using the dicarboxylic acid diester crystals, a diol compound, and a carbonate diester constituting the structural unit (A) as raw materials. Examples of the diol compound include aliphatic dihydroxy compounds and aromatic dihydroxy compounds as described above, and preferably include the monomer represented by the general formula (b) and / or the monomer represented by the general formula (c). In this reaction, the resin can be produced in the presence of a basic compound catalyst, an ester exchange catalyst, or a mixed catalyst containing both as a polycondensation catalyst.

[0155] Examples of carbonic acid diesters include diphenyl carbonate, dibenzyl carbonate, bis(chlorophenyl) carbonate, meta-cresol carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Among these, diphenyl carbonate is particularly preferred from the perspective of reactivity and purity. Regarding the amount of carbonic acid diester added, the diol component and the dicarboxylic acid component can be reacted in equimolar amounts, with the remainder reacting with the carbonic acid diester, thereby determining the amount of addition. Relative to 1 mole of the difference between the diol component and the dicarboxylic acid component, the carbonic acid diester is preferably used in a ratio of 0.60 to 1.50 moles, more preferably 0.80 to 1.40 moles, further preferably 1.00 to 1.30 moles, even more preferably 1.00 to 1.25 moles, and particularly preferably 1.00 to 1.20. By adjusting this molar ratio, the molecular weight of the polyester carbonate resin can be controlled.

[0156] Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.

[0157] Examples of the alkali metal compound used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. Sodium bicarbonate and sodium carbonate are preferred from the viewpoints of catalytic effect, price, circulation, and effect on resin color.

[0158] Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds, and calcium acetate monohydrate and magnesium acetate tetrahydrate are preferred.

[0159] Examples of the nitrogen-containing compound include quaternary ammonium hydroxylates and salts thereof, and amines.

[0160] As the transesterification catalyst, salts of zinc, tin, zirconium, lead, etc. are preferably used, and these can be used alone or in combination. In addition, they can also be used in combination with the above-mentioned alkali metal compounds and alkaline earth metal compounds.

[0161] Specific examples of transesterification catalysts include tris(2,4-pentanedione)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. Among these, zinc acetate, zirconium acetate, tris(2,4-pentanedione)aluminum(III), and diethyl(4-methylbenzyl)phosphonate are preferred, and tris(2,4-pentanedione)aluminum(III) and diethyl(4-methylbenzyl)phosphonate are more preferred.

[0162] In one embodiment of the present invention, aluminum or a compound thereof may be used as a polymerization catalyst.

[0163] Even as a monomer, aluminum or its compound used as a polymerization catalyst has a certain degree of catalytic activity as a catalyst for polymerizing polyester carbonate by transesterification. Examples of such aluminum or its compound include metallic aluminum, aluminum salts, aluminum chelate compounds, organoaluminum compounds, and inorganic aluminum compounds.

[0164] Examples of aluminum salts include organic acid salts and inorganic acid salts of aluminum. Examples of organic acid salts of aluminum include aluminum carboxylates, specifically aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, and aluminum salicylate. Examples of inorganic acid salts of aluminum include aluminum chloride, aluminum hydroxide, basic aluminum chloride, aluminum carbonate, aluminum phosphate, and aluminum phosphonate.

[0165] Examples of the aluminum chelate compound include aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, and aluminum diisopropoxide ethylacetoacetate.

[0166] Examples of the organoaluminum compound include aluminum alkoxides such as trialkylaluminum, dialkylaluminum alkoxides, alkylaluminum dialkoxides, aluminum trialkoxides, and their hydrolyzates. Specific examples include aluminum alkoxides such as aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, and aluminum tert-butoxide; trimethylaluminum, triethylaluminum, and their hydrolyzates. Examples of the inorganic aluminum compound include aluminum oxide.

[0167] Aluminum carboxylates, inorganic acid salts, and chelate compounds are particularly preferred, and among these, aluminum acetate, aluminum chloride, aluminum hydroxide, basic aluminum chloride, and aluminum acetylacetonate are particularly preferred.

[0168] In one embodiment of the present invention, a phosphorus compound may be used as a polymerization catalyst.

[0169] Phosphorus compounds used as polymerization catalysts can enhance the catalytic activity of aluminum and its compounds in polyester carbonate polymerization reactions. While not being bound by theory, it is believed that this is because the phosphorus compound prevents the catalytic activity of aluminum and its compounds from being deactivated by the presence of alcohol or water in the reaction system.

[0170] Examples of such phosphorus compounds include phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphinous acid compounds, phosphinous acid compounds, and phosphine compounds. Among these, phosphonic acid compounds, phosphinic acid compounds, and phosphine oxide compounds are particularly preferred, with phosphonic acid compounds being particularly preferred.

[0171] Here, the phosphonic acid compound refers to a compound having the following structure.

[0172]

[0173] Examples of the phosphonic acid compounds include dimethyl methylphosphonate, diethyl methylphosphonate, dihexyl methylphosphonate, dioctyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dihexyl phenylphosphonate, dioctyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, dihexyl benzylphosphonate, dioctyl benzylphosphonate, diphenyl benzylphosphonate, dimethyl p-methylbenzylphosphonate, and p-methylbenzylphosphonate. 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dihexyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dimethyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dihexyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diphenyl ester, etc.

[0174] The phosphinic acid compound refers to a compound having the following structure.

[0175]

[0176] Examples of the phosphinic acid compound include diphenylphosphinic acid, methyl diphenylphosphinic acid, phenyl diphenylphosphinic acid, phenylphosphinic acid, methyl phenylphosphinic acid, and phenyl phenylphosphinic acid.

[0177] The phosphine oxide compound refers to a compound having the following structure.

[0178]

[0179] Examples of the phosphine oxide compound include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide.

[0180] The phosphonous acid compound refers to a compound having the following structure.

[0181]

[0182] Examples of the phosphite-based compound include dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, and diphenyl phosphite.

[0183] The phosphinic acid-based compound refers to a compound having the following structure.

[0184]

[0185] Examples of the phosphinic acid-based compound include hydroxyphosphine, methyl dibutylphosphinite, propyl diphenylphosphinite, methoxydiphenylphosphine, and ethoxydiphenylphosphine.

[0186] The phosphine-based compound refers to a compound having the following structure.

[0187]

[0188] Examples of the phosphine-based compound include trimethylphosphine, triethylphosphine, methyldibutylphosphine, and phenylisopropylphosphine.

[0189] Among the above-mentioned phosphorus compounds, phosphorus compounds having an aromatic ring are particularly preferred, and phosphonic acid compounds having an aromatic ring structure are particularly preferred.

[0190] The phosphorus compound may be a compound represented by the following general formulas (P7) to (P9).

[0191]

[0192] (In formulas (P7) to (P9), R o 、R r 、R s and R t R each independently represents a hydrogen atom, and a hydrocarbon group having 1 to 50 or 1 to 20 carbon atoms, which may contain a hydroxyl group, a halogen group, an alkoxy group, or an amino group, and may also have an alicyclic structure or an aromatic ring structure; p and R q Each independently represents hydrogen and a hydrocarbon group having 1 to 10 or 1 to 5 carbon atoms.

[0193] In the above formula, R o 、R r 、R s and / or R t It preferably has an aromatic ring, and particularly preferably has a benzyl group. p and R q It is preferably hydrogen or a 1-3 hydrocarbon group.

[0194] These catalysts are used so that the metal content in the catalyst is preferably 0.1 to 10 ppm, more preferably 0.1 to 7.0 ppm, further preferably 0.1 to 5.0 ppm, further preferably 0.1 to 3.0 ppm, particularly preferably 0.1 to 1.0 ppm, relative to the theoretical amount of resin produced.

[0195] In the melt polycondensation method, the above-mentioned raw materials and catalyst are used to carry out melt polycondensation under heating at normal pressure or reduced pressure while removing by-products by an ester exchange reaction.

[0196] Specifically, the reaction is carried out at a temperature of 120-260°C, preferably 180-260°C, for 0.1-5 hours, preferably 0.5-3 hours. Subsequently, the reaction temperature is increased while increasing the vacuum level of the reaction system to allow the diol compound and the carbonate diester to react. Finally, a polycondensation reaction is carried out at a temperature of 200-350°C under a reduced pressure of 1 mmHg or less for 0.05-2 hours. This reaction can be carried out continuously or batchwise. The reaction apparatus used for the above reaction can be a vertical type equipped with an anchor stirring blade, a maximum mixing stirring blade, a spiral ribbon stirring blade, etc., a horizontal type equipped with a paddle blade, a grid blade, a spectacled blade, etc., or an extruder equipped with a screw. In addition, a reaction apparatus combining these types of devices is preferably used in accordance with the viscosity of the polymer.

[0197] In the method for producing a polyester carbonate resin according to a preferred embodiment of the present invention, after the polymerization reaction is completed, the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolytic stability. Generally speaking, it is suitable to implement a method in which a known acidic substance is added to deactivate the catalyst. As these substances, specifically, it is suitable to use: 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, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, Phosphates such as monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonates 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 stearoyl chloride, benzoyl chloride, and p-toluenesulfonyl chloride; alkyl sulfates such as dimethyl sulfate; and organic halides such as benzyl chloride. Aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate are preferably used from the perspectives of deactivation effect, resin color tone, and stability. These deactivators are used in an amount of 0.01 to 50 times the molar amount of the catalyst, preferably 0.3 to 20 times the molar amount. An amount less than 0.01 times the molar amount of the catalyst is not preferred because the deactivation effect is insufficient. On the other hand, when the molar amount exceeds 50 times the amount of the catalyst used, heat resistance is reduced and the molded article is easily colored, which is not preferred.

[0198] After the catalyst is deactivated, a step can be set up to devolatilize low-boiling-point compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350°C. For this purpose, a horizontal device or a thin-film evaporator equipped with stirring blades with excellent surface renewal capabilities, such as paddle blades, grid blades, and spectacled blades, is suitable.

[0199] The polyester carbonate resin of a preferred embodiment of the present invention desirably has as low an impurity content as possible and is suitable for filtering molten raw materials and catalyst solutions. The filter mesh size is preferably 5 μm or less, more preferably 1 μm or less. Furthermore, the produced resin is suitable for filtering using a polymer filter. The polymer filter mesh size is preferably 100 μm or less, more preferably 30 μm or less. Furthermore, the resin pellet collection process must naturally be conducted in a low-dust environment, preferably 1000 class or less, more preferably 100 class or less.

[0200] <Production Method of Polyester Resin>

[0201] The polyester resin of a preferred embodiment of the present invention can be produced by conventionally known polyester production methods using crystals of the dicarboxylic acid diester constituting the structural unit (A) and a diol compound. Examples include melt polymerization methods such as transesterification and direct esterification, or solution polymerization methods. Examples of the diol compound include the aliphatic dihydroxy compounds and aromatic dihydroxy compounds described above, with monomers represented by the general formula (b) and / or the monomers represented by the general formula (c) being preferred.

[0202] In the production of the polyester resin of the preferred embodiment of the present invention, transesterification catalysts, esterification catalysts, polycondensation catalysts, etc. commonly used in the production of polyester resins can be used. These catalysts are not particularly limited, and examples thereof 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 (such as fatty acid salts, carbonates, phosphates, hydroxides, chlorides, oxides, alkoxides), and metallic magnesium. These catalysts can be used alone or in combination of two or more. As the catalyst, compounds of manganese, cobalt, zinc, titanium, calcium, antimony, germanium, and tin are more preferred, and compounds of manganese, titanium, antimony, germanium, and tin are more preferred. The amount of these catalysts used is not particularly limited, and the amount calculated as the metal component relative to the raw material of the polyester resin is preferably 1 to 1000 ppm, more preferably 3 to 750 ppm, and even more preferably 5 to 500 ppm.

[0203] The reaction temperature in the polymerization reaction depends on the type of catalyst, the amount used, and other factors, but is generally selected within the range of 150°C to 300°C. Taking into account the reaction rate and resin coloration, it is preferably 180°C to 280°C. The pressure within the reaction layer is preferably ultimately adjusted from atmospheric pressure to 1 kPa or less, more preferably 0.5 kPa or less.

[0204] During the polymerization reaction, a phosphorus compound may be added as needed. Examples of phosphorus compounds include, but are not limited to, phosphoric acid, phosphorous acid, phosphoric acid esters, and phosphite esters. Examples of phosphoric acid 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 phosphorus compounds may be used alone or in combination of two or more. 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.

[0205] Furthermore, in the production of the polyester resin of a preferred embodiment of the present invention, various stabilizers such as an anti-etherification agent, a heat stabilizer, and a light stabilizer, and a polymerization regulator may be used.

[0206] <Physical Properties of Thermoplastic Resins>

[0207] (1) Polystyrene equivalent weight average molecular weight (Mw)

[0208] In one embodiment of the present invention, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably 10,000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 10,000 to 60,000. Mw can be measured by the method described in the Examples below.

[0209] (2) YI value (yellowness)

[0210] In one embodiment of the present invention, the YI value of the thermoplastic resin is preferably 0.1 to 14, more preferably 0.1 to 10, further preferably 0.1 to 7, and particularly preferably 0.3 to 5. The YI value can be measured by the method described in the Examples below.

[0211] (3) Refractive index (nD)

[0212] In one embodiment of the present invention, one of its characteristics is that the thermoplastic resin has a high refractive index, which is preferably 1.600 to 1.700, more preferably 1.626 to 1.700, and even more preferably 1.630 to 1.650.

[0213] (4) Abbe number (ν)

[0214] In one embodiment of the present invention, the Abbe number of the thermoplastic resin is preferably 22.0 to 26.0, more preferably 23.0 to 26.0, and particularly preferably 23.0 to 24.7.

[0215] (5) Glass transition temperature (Tg)

[0216] In one embodiment of the present invention, one of its characteristics is that the thermoplastic resin has high heat resistance, and the glass transition temperature (Tg) is preferably 70 to 200°C, more preferably 100 to 200°C, further preferably 100 to 150°C, further preferably 125 to 150°C, further preferably 125 to 145°C, and particularly preferably 125 to 140°C.

[0217] (6) Photoelastic coefficient

[0218] In one embodiment of the present invention, one of its characteristics is that the thermoplastic resin has a low photoelastic coefficient, which is preferably 25 to 45, more preferably 25 to 38, and particularly preferably 30 to 38.

[0219] <Thermoplastic resin composition>

[0220] Another embodiment of the present invention is a thermoplastic resin composition comprising the above-mentioned thermoplastic resin and an additive. In the thermoplastic resin composition of this embodiment, a resin other than the thermoplastic resin of the present invention comprising the above-mentioned structural unit (A) can be used in combination within the range that does not impair the desired effect of this embodiment. Such resins are not particularly limited, and examples thereof include at least one resin selected from polycarbonate resins, polyester resins, polyester carbonate resins, (meth) acrylic resins, polyamide resins, polystyrene resins, cycloolefin resins, acrylonitrile-butadiene-styrene copolymer resins, vinyl chloride resins, polyphenylene ether resins, polysulfone resins, polyacetal resins, and methyl methacrylate-styrene copolymer resins. Various known products can be used for these resins, and one or more can be used alone or in combination and added to the thermoplastic resin composition.

[0221] [Antioxidants]

[0222] The thermoplastic resin composition preferably contains an antioxidant as the above-mentioned additive.

[0223] As the antioxidant, it is preferable to contain at least one of a phenolic antioxidant and a phosphite antioxidant.

[0224] 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-2,4,6-(1H,3H,5H)-trione, 4,4',4"-(1-methylpropyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylene-m-cresol, 3-(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, Examples of the present invention include octadecyl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 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-tetraoxaspiro[5.5]undecane, and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is preferred.

[0225] Examples of the phosphite antioxidant include 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-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, and 1,2'-di-tert-butyl- ... ester, tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-15)alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), 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.

[0226] As the antioxidant, any one of the above may be used alone, or a mixture of two or more may be used.

[0227] The thermoplastic resin composition preferably contains an antioxidant in an amount of 1 to 3000 ppm by weight based on the total weight of the resin composition. The antioxidant content in the thermoplastic resin composition is more preferably 50 to 2500 ppm by weight, even more preferably 100 to 2000 ppm by weight, particularly preferably 150 to 1500 ppm by weight, and even more preferably 200 to 1200 ppm by weight.

[0228] [Release agent]

[0229] The thermoplastic resin composition preferably contains a release agent as the above-mentioned additive.

[0230] Examples of the release agent include ester compounds, such as glycerol fatty acid esters such as monoglycerides and diglycerides of glycerol fatty acid, glycol fatty acid esters such as propylene glycol fatty acid ester and sorbitan fatty acid ester, higher alcohol fatty acid esters, and full or monoesters of aliphatic polyols and fatty carboxylic acids. When an ester of aliphatic polyols and fatty carboxylic acids is used as the release agent, either a monoester or a full ester may be used, and an ester other than a full ester such as a monoester may also be used.

[0231] Specific examples of the release agent include the following compounds.

[0232] That is, we can list:

[0233] Sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan tribehenate, sorbitan stearate, sorbitan tristearate, and sorbitan octanoate;

[0234] Propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate, and propylene glycol monopalmitate;

[0235] Higher alcohol fatty acid esters such as stearyl stearate;

[0236] Glycerol fatty acid esters, monoglycerides, including glycerol monohydroxystearate such as glycerol monostearate and glycerol mono-12-hydroxystearate, glycerol monooleate, glycerol monobehenate, glycerol monocaprylate, glycerol monocaprate, glycerol monolaurate and other glycerol monoesters, glycerol mono / distearate, glycerol mono / distearate, glycerol mono / dibehenate, glycerol mono / dioleate and other glycerol monoesters;

[0237] Glyceryl fatty acid esters such as glyceryl diacetyl monolaurate, acetylated monoglycerides;

[0238] Glycerol fatty acid ester organic acid monoglycerides such as citric acid fatty acid monoglyceride, succinic acid fatty acid monoglyceride, and diacetyltartaric acid fatty acid monoglyceride;

[0239] Polyglycerol fatty acid esters such as diglyceryl stearate, diglyceryl laurate, diglyceryl oleate, diglyceryl monostearate, diglyceryl monolaurate, diglyceryl monomyristate, diglyceryl monooleate, tetraglyceryl stearate, decaglyceryl laurate, decaglyceryl oleate, and polyglyceryl polyricinoleate.

[0240] The thermoplastic resin composition preferably contains a release agent in an amount of 1 to 5000 ppm by weight, based on the total weight of the resin composition. The content of the release agent in the thermoplastic resin composition is more preferably 50 to 4000 ppm by weight, further preferably 100 to 3500 ppm by weight, particularly preferably 500 to 13000 ppm by weight, and even more preferably 1000 to 2500 ppm by weight.

[0241] [Other additives]

[0242] In addition to the aforementioned antioxidants and release agents, other additives may be added to the thermoplastic resin composition. For example, additives that may be included in the thermoplastic resin composition include compounding agents, catalyst deactivators, heat stabilizers, plasticizers, fillers, UV absorbers, rust inhibitors, dispersants, defoamers, leveling agents, flame retardants, lubricants, dyes, pigments, blue light emitting agents, nucleating agents, and clarifiers.

[0243] The content of additives other than the antioxidant and the release agent in the thermoplastic resin composition is preferably 10 ppm to 5.0 wt%, more preferably 100 ppm to 2.0 wt%, and further preferably 1000 ppm to 1.0 wt%, but is not limited thereto.

[0244] The above-mentioned additives may adversely affect light transmittance, and therefore are preferably not added in excess. For example, the total amount added is within the above-mentioned range.

[0245] Optical components

[0246] The thermoplastic resin or thermoplastic resin composition of the present invention (hereinafter abbreviated as "resin composition") can be applied to optical elements. In one embodiment of the present invention, an optical element containing the resin composition of the present invention is provided. In one embodiment of the present invention, the optical element includes an optical disc, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, a lens, a prism, an optical film, a substrate, an optical filter, a hard coating, etc., but is not limited to these. Since the resin composition of the present invention has high fluidity and can be formed by a casting method, it is particularly suitable for the manufacture of thin optical elements. In a preferred embodiment of the present invention, the optical element manufactured using the resin composition of the present invention can be an optical lens. In another preferred embodiment of the present invention, the optical element manufactured using the resin composition of the present invention can be an optical film.

[0247] When an optical element containing the resin composition of the present invention is manufactured by injection molding, it is preferably molded under the conditions of a barrel temperature of 260 to 350°C and a mold temperature of 90 to 170°C. More preferably, it is molded under the conditions of a barrel temperature of 270 to 320°C and a mold temperature of 100 to 160°C. When the barrel temperature is higher than 350°C, the resin composition decomposes and colors, and when it is lower than 260°C, the melt viscosity increases, making it difficult to mold. In addition, when the mold temperature is higher than 170°C, the molded piece formed by the resin composition tends to become difficult to remove from the mold. On the other hand, when the mold temperature is lower than 90°C, the resin solidifies prematurely in the mold during molding, making it difficult to control the shape of the molded piece or to fully transfer the template attached to the mold.

[0248] <Optical lens>

[0249] In one embodiment of the present invention, the resin composition can be applied to an optical lens. Since the optical lens manufactured using the resin composition of the present invention has a high refractive index and good heat resistance, it can be used in fields such as telescopes, binoculars, and television projectors, which currently use expensive high-refractive-index glass lenses, and is extremely useful.

[0250] For example, in a smartphone lens, a lens molded from a thermoplastic resin containing the above-mentioned structural unit (A) can be superimposed with a lens molded from a resin containing any structural unit of formulae (II-1) to (II-4) or a resin containing a structural unit derived from any monomer in the following formulae to be used as a lens unit.

[0251]

[0252] (In the above formula, R1 and R2 each independently represent a hydrogen atom, a methyl group, or an ethyl group, and R3 and R4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms.)

[0253] The optical lens of the present invention can be implemented using an aspheric lens as needed. Because an aspheric lens can achieve virtually zero spherical aberration with a single lens, eliminating the need for combining multiple spherical lenses to eliminate spherical aberration can lead to lighter lenses and reduced manufacturing costs. Therefore, aspheric lenses are particularly useful as camera lenses among optical lenses.

[0254] Furthermore, due to the high molding fluidity of the optical lens of the present invention, it is particularly useful as a material for thin-walled, small, and complex-shaped optical lenses. Specifically, the lens dimensions are preferably 0.05 to 3.0 mm thick at the center, more preferably 0.05 to 2.0 mm, and even more preferably 0.1 to 2.0 mm. Furthermore, 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 shape is preferably a meniscus lens with one convex side and one concave side.

[0255] The optical lens of the present invention can be formed by any method such as die forming, cutting, grinding, laser processing, electrical discharge machining, etching, etc. Among them, die forming is more preferred from the viewpoint of production cost.

[0256] <Optical Film>

[0257] In one embodiment of the present invention, the resin composition can be used for optical films. In particular, optical films produced using the polycarbonate resin of the present invention have excellent transparency and heat resistance and are therefore suitable for films for liquid crystal substrates, optical memory cards, and the like.

[0258] In order to avoid impurities from mixing into the optical film as much as possible, the molding environment must naturally be a low-dust environment, preferably below level 6, and more preferably below level 5.

[0259] Example

[0260] Hereinafter, the present invention will be described in detail by showing examples and comparative examples of the present invention, but the present invention is not limited to these examples. The physical properties of the obtained resin were measured using the following methods and apparatus.

[0261] 1) Solution YI (yellowness)

[0262] The resulting resin was dissolved in dichloromethane to prepare a 2% by mass resin solution. This resin solution was filtered through a 1 μm filter, and the resulting filtrate was used as the measurement sample. This sample was injected into a cuvette with a 50 mm optical path length, and the YI of the solution was measured using a spectroscopic haze meter.

[0263] Measuring equipment: Nippon Denshoku Industries Co., Ltd. "SH 7000"

[0264] 2) Weight average molecular weight (Mw)

[0265] The weight-average molecular weight (Mw) 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 are shown below.

[0266] GPC device: HLC-8420GPC manufactured by Tosoh Corporation

[0267] Chromatographic column: TSKgel SuperHM-M manufactured by Tosoh Corporation

[0268] Detector: RI detector

[0269] Standard polystyrene: Tosoh Corporation standard polystyrene reagent kit PStQuick C

[0270] Sample solution: 0.2 mass% tetrahydrofuran solution

[0271] Eluent: tetrahydrofuran

[0272] Eluent flow rate: 0.6 mL / min

[0273] Column temperature: 40°C

[0274] <Synthesis example 1>

[0275] To a glass reactor equipped with a stirrer, a heating and cooling device, and a thermometer, 50 g (0.18 mol) of 1,1'-bin-2-naphthol, 150 g of acetonitrile, 55.5 g (0.40 mol) of potassium carbonate, and 5 g of potassium iodide were added. The internal temperature was raised to 80°C and stirred at this temperature for 1 hour. Next, 59.9 g (0.49 mol) of ethyl chloroacetate was added dropwise while maintaining the reaction mixture at 70-80°C. After stirring at this temperature for 24 hours, 125 g of ion-exchanged water was added dropwise to dissolve the inorganic salts, and the aqueous layer was separated. The resulting organic layer was then concentrated to remove water and some acetonitrile by distillation, and then 150 g of toluene was added and the organic layer was washed with water. Thereafter, the obtained organic layer was concentrated to distill off water and part of toluene to obtain 111.4 g of a toluene solution of 2,2'-bis(ethoxycarbonylmethoxy)-1,1'-binaphthyl (containing 25.1% by weight of toluene).

[0276] 187 g (0.87 mol) of diphenyl carbonate was added to the toluene solution at 25°C, and the internal temperature was raised to 80°C to dissolve the diphenyl carbonate. Next, 1.3 g (0.0046 mol) of tetraisopropyl orthotitanate was added, and after reducing the internal pressure to 1.3 kP, the internal temperature was raised to 150°C. At this temperature, the reaction was continued for 8 hours while distilling off toluene and by-products. Subsequently, when the internal temperature was cooled to 100°C, crystals had already precipitated. Therefore, 150 g of toluene was added, and the internal temperature was raised to 110°C to redissolve the precipitated crystals. Next, the internal temperature was cooled to 85°C, and crystals were precipitated without adding seed crystals. The internal temperature was then cooled to 5°C at a cooling rate of 10°C / hour. The precipitated crystals were then separated by filtration at the same temperature and dried under reduced pressure at 1.3 kPa for 11 hours while being heated in a water bath at 90°C to obtain 73.2 g of crystals of the compound represented by the following formula (1) (yield 76%).

[0277]

[0278] The HPLC purity of the obtained crystals of the compound represented by the above formula (1) (hereinafter sometimes referred to as "BINOL-DP") was measured by the following method and found to be 98.7%.

[0279] <HPLC measurement>

[0280] Device: Shimadzu LC-2030

[0281] Chromatographic column: XBridge Phenyl (3.5 μm, )

[0282] Column temperature: 40°C

[0283] Detection wavelength: UV 254nm

[0284] Mobile phase: Solution A = ultrapure water containing 0.1% formic acid, Solution B = acetonitrile containing 0.1% formic acid (it should be noted that the concentration of Solution B was changed as described below for analysis).

[0285] Concentration of solution B: 40% (maintained for 5 minutes) → 30 minutes → 70% (maintained for 10 minutes) → 5 minutes → 100% (10 minutes)

[0286] Mobile phase flow rate: 1.0 ml / min

[0287] Sample injection volume: 5 μL

[0288] The maximum melting endothermic temperature of the obtained crystals of the compound represented by the above formula (1) was measured by differential scanning calorimetry (DSC) by the following method and was found to be 179.1°C. Furthermore, the thermal decomposition temperature (Td5) of the obtained crystals of the compound represented by the above formula (1) was measured by a differential thermal balance by the following method and was found to be 330.4°C. Furthermore, the main X-ray diffraction peaks (diffraction peaks having a relative intensity exceeding 5%) of the obtained crystals of the compound represented by the above formula (1) obtained by powder X-ray diffraction by the following method are shown in Table 1 below.

[0289] Differential Scanning Calorimetry (DSC)

[0290] 5 mg of the crystals of the compound represented by the above formula (1) were precisely weighed in an aluminum pan and measured using a differential scanning calorimeter (DSC7020, manufactured by SIINano Technology Co., Ltd.) under the following operating conditions using alumina as a reference.

[0291] (Operating Conditions)

[0292] Heating rate: 10℃ / min,

[0293] Measuring range: 30~300℃,

[0294] Environment: open, nitrogen 40ml / min.

[0295] <Measurement of thermal decomposition temperature (Td5)>

[0296] Using a differential thermal balance ("Thermoplus EVO2" manufactured by Rigaku Corporation), 5 mg of the crystals were accurately weighed in an aluminum pan, leaving the other pan empty. After returning the weight to zero, the temperature was raised to 450°C at a rate of 10°C / min under a nitrogen atmosphere, and the thermal decomposition temperature was measured. The thermal decomposition temperature was defined as the temperature at which the weight decreased by 5%.

[0297] <Powder X-ray Diffraction>

[0298] 150 mg of the compound crystal represented by the above formula (1) was placed in the sample filling portion of a glass test plate, and the result was measured using a powder X-ray diffractometer (manufactured by Spectris: X'Pert PRO) under the following conditions.

[0299] X-ray source: CuKα,

[0300] Power: 1.8kW (45kV-40mA),

[0301] Measuring range: 2θ=5°~70°,

[0302] Scanning speed: 2θ = 2° / min,

[0303] Slit: DS = 1°, mask = 15 mm, RS = variable (0.1 mm ~).

[0304] [Table 1]

[0305]

[0306] Furthermore, the obtained crystals of the compound represented by the above formula (1) were subjected to NMR measurement and LC-MS measurement by the following methods. 1 H-NMR, 13 The C-NMR and LC-MS spectral values ​​are shown below each measurement method.

[0307] NMR measurement

[0308] Tetramethylsilane was used as an internal standard and deuterated chloroform (CDCl3) was used as a solvent. The spectrometer was used to record the results. 1 H-NMR and 13 C-NMR.

[0309] [ 1 H-NMR (CDCl3)]

[0310] δ(ppm)=4.78(4H,s), 6.92(4H,d), 7.17~7.22(6H,m), 7.29~7.34(6H,m), 7.44(2H,d), 7.88(2H,d), 7.99(2H,d).

[0311] [ 13 C-NMR (CDCl3)]

[0312] δ(ppm)=67.08,115.44,120.46,121.23,124.30,125.66,126.01,126.68,127.96,129.39,129.85,129.93,133.99,150.06,153.57,167.84.

[0313] LC-MS measurement

[0314] Device: Xevo G2Q-Tof manufactured by Waters

[0315] Chromatographic column: L-Column 2ODS (2μm, )

[0316] Column temperature: 40°C

[0317] Detection wavelength: UV 200~500nm

[0318] Mobile phase: Solution A = 10 mM ammonium acetate in methanol, Solution B = methanol (Note: The concentration of Solution B was varied as described below for analysis).

[0319] Concentration of solution B: 60% (maintained for 1 minute) → 7 minutes → 90% (maintained for 2 minutes)

[0320] Mobile phase flow rate: 0.35 ml / min

[0321] Detection method: Q-Tof

[0322] Ionization method: ESI (+) method

[0323] Ion source: voltage (+) 2.0 kV, temperature 120 ° C

[0324] Sampling cone: voltage 10V, gas flow 50L / h

[0325] Desolvation gas: temperature 400°C, gas flow rate 1000L / h

[0326] [LC-MS]

[0327] Mass spectrometry analysis value ([M+NH4] ﹢ ):572.20650

[0328] (Calculated molecular weight of the compound represented by the above formula (1) (ESI+; [C 36 H 26 O6+NH4] ﹢ ):572.20676).

[0329] (Example 1)

[0330] As raw materials, 167.63 g (0.302 mol) of BINOL-DP crystals synthesized in Synthesis Example 1, 128.73 g (0.239 mol) of BNEF represented by the following structural formula, 60.53 g (0.162 mol) of BNE, 21.50 g (0.100 mol) of DPC (diphenyl carbonate), and 0.7 mg (4.0 × 10 ﹣6mol), and under a nitrogen atmosphere of 101.3 kPa, the raw materials were dissolved while stirring at a heat medium temperature of 200°C for 10 minutes. Next, the heat medium temperature was raised to 220°C over 30 minutes, and the reaction was carried out at 101.3 kPa for 60 minutes. The pressure was then reduced from 101.3 kPa to 13.3 kPa over 90 minutes, maintained at 13.3 kPa for 30 minutes, and the generated phenol was removed from the reaction system. Then, while the heat medium temperature was raised to 250°C over 30 minutes, the pressure was reduced to below 0.1 kPa, and the generated phenol was removed from the reaction system. Then, the pressure was maintained below 0.1 kPa for 30 minutes to obtain a polyester carbonate resin. The physical properties of the obtained resin are shown in Table 2.

[0331]

[0332] (Examples 2 to 4)

[0333] A polyester carbonate resin was obtained in the same manner as in Example 1 except that the amount of the catalyst was changed to the amount shown in Table 2. The physical properties of the obtained resin are shown in Table 2.

[0334] (Examples 5 and 6)

[0335] A polyester carbonate resin was obtained in the same manner as in Example 1 except that the catalyst was replaced with the catalyst shown in Table 2. The physical properties of the obtained resin are shown in Table 2.

[0336] (Comparative Example 1)

[0337] A polyester carbonate resin was obtained in the same manner as in Example 1 except that the crystals of BINOL-DP (phenyl ester) were replaced with BINOL-DC (carboxylic acid) represented by the following structural formula.

[0338] The physical properties of the obtained resin are shown in Table 2.

[0339]

[0340] (Comparative Example 2)

[0341] A polyester carbonate resin was obtained in the same manner as in Example 1 except that the crystals of BINOL-DP (phenyl ester) were replaced with BINOL-DM (methyl ester) represented by the following structural formula. The physical properties of the obtained resin are shown in Table 2.

[0342]

[0343] (Comparative Example 3)

[0344] A polyester carbonate resin was obtained in the same manner as in Comparative Example 2, except that the amount of the catalyst was changed to the amount shown in Table 2. The physical properties of the obtained resin are shown in Table 2.

[0345] [Table 2]

[0346]

[0347] ※1DPC molar ratio = DPC moles / (glycol moles - carboxylic acid moles)

[0348] ※2 Theoretically obtainable resin amount = (weight of all raw materials) - (total weight of water and hydroxy alcohol theoretically removed by distillation)

Claims

1. A method for producing a thermoplastic resin, characterized in that: The thermoplastic resin has a structural unit (A) represented by the following formula: The production method includes the step of reacting a dicarboxylic acid diester crystal represented by the following formula (a) that satisfies at least one of the following (i) and (ii) with a diol compound. (i) The maximum melting endotherm temperature measured by differential scanning calorimetry is 177-181°C, (ii) having peaks at diffraction angles 2θ = 7.6 ± 0.2°, 8.7 ± 0.2°, 18.0 ± 0.2°, 19.2 ± 0.2°, 19.7 ± 0.2°, and 21.9 ± 0.2° in a powder X-ray diffraction pattern measured using Cu-Kα radiation, In formula (A), "*" represents a bonding portion, 2. The manufacturing method according to claim 1, wherein: The crystals of the dicarboxylic acid diester satisfy both of the following (i) and (ii), (i) The maximum melting endotherm temperature measured by differential scanning calorimetry is 177-181°C, (ii) In a powder X-ray diffraction pattern measured using Cu-Kα radiation, the compound has peaks at diffraction angles 2θ = 7.6±0.2°, 8.7±0.2°, 18.0±0.2°, 19.2±0.2°, 19.7±0.2°, and 21.9±0.2°.

3. The manufacturing method according to claim 1 or 2, wherein: The thermoplastic resin is polyester resin or polyester carbonate resin.

4. The manufacturing method according to any one of claims 1 to 3, wherein: The thermoplastic resin comprises a structural unit (B) derived from a monomer represented by the following general formula (b) and / or a structural unit (C) derived from a monomer represented by the following general formula (c), In the general formula (b), R a and R b Each of the following is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy 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 cycloalkoxy 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 may have a substituent and containing one or more heteroatoms selected from O, N and S, 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 may have a substituent and contains one or more heteroatoms selected from O, N and S, X represents a single bond or a fluorenyl group which may have a substituent, A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, m and n each independently represent an integer of 0 to 6, a and b each independently represent an integer from 0 to 10; In the general formula (c), R c and R d Each of the following is independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy 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 cycloalkoxy 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, Y1 is a single bond, a fluorenyl group which may have a substituent, or any of the groups represented by the following structural formulae (1) to (7), In formulas (1) to (7), 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 represents R 61 With R 62 or R 71 With R 72 a carbon ring or heterocyclic ring having 1 to 20 carbon atoms, which is bonded to each other and may have a substituent, r and s each independently represent an integer from 0 to 5000, 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.

5. The manufacturing method according to any one of claims 1 to 4, characterized in that: A catalyst containing an alkali metal or an alkaline earth metal is used.

6. The manufacturing method according to any one of claims 1 to 5, wherein: The catalyst is contained in an amount of 0.1 to 10 ppm relative to the thermoplastic resin.

7. The manufacturing method according to any one of claims 1 to 6, wherein: The thermoplastic resin has a polystyrene-equivalent weight average molecular weight Mw of 10,000 to 100,000.

8. The manufacturing method according to any one of claims 1 to 7, wherein: The YI of the thermoplastic resin is 0.1-14.

9. A thermoplastic resin, characterized in that: Containing a structural unit (A) derived from a crystal of a dicarboxylic acid diester represented by the following formula (a) that satisfies at least one of the following (i) and (ii), (i) The maximum melting endotherm temperature measured by differential scanning calorimetry is 177-181°C, (ii) In a powder X-ray diffraction pattern measured using Cu-Kα radiation, the compound has peaks at diffraction angles 2θ = 7.6±0.2°, 8.7±0.2°, 18.0±0.2°, 19.2±0.2°, 19.7±0.2°, and 21.9±0.2°.

10. The thermoplastic resin according to claim 9, wherein: The crystals of the dicarboxylic acid diester satisfy both of the following (i) and (ii), (i) The maximum melting endotherm temperature measured by differential scanning calorimetry is 177-181°C, (ii) In a powder X-ray diffraction pattern measured using Cu-Kα radiation, the compound has peaks at diffraction angles 2θ = 7.6±0.2°, 8.7±0.2°, 18.0±0.2°, 19.2±0.2°, 19.7±0.2°, and 21.9±0.2°.

11. The thermoplastic resin according to claim 9 or 10, wherein: The thermoplastic resin is polyester resin or polyester carbonate resin.

12. An optical element, characterized in that: Contains the thermoplastic resin according to any one of claims 9 to 11.

13. An optical lens, characterized in that: Contains the thermoplastic resin according to any one of claims 9 to 11.

14. An optical film, characterized in that: Contains the thermoplastic resin according to any one of claims 9 to 11.

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