JP7790873B2 - Polyester resin or polyester carbonate resin, and optical member using said resin - Google Patents

Description

The present invention relates to a polyester resin or polyester carbonate resin that has a high refractive index, low birefringence, and an excellent balance between heat resistance and moldability, as well as excellent color and moist heat resistance.

Image capture modules are used in cameras, video cameras, camera-equipped mobile phones, videophones, and camera-equipped door phones. In recent years, there has been a particular demand for miniaturization of the optical systems used in these image capture modules. As optical systems become more compact, chromatic aberration in the optical system becomes a major problem. It is known that chromatic aberration can be corrected by combining an optical lens material with a high refractive index and a small Abbe number for high dispersion with an optical lens material with a low refractive index and a large Abbe number for low dispersion.

Glass, which has traditionally been used as a material for optical systems, is capable of achieving the various optical properties required and has excellent environmental resistance, but suffers from poor processability. In response to this, resins, which are cheaper than glass materials and have excellent processability, are being used for optical components. In particular, resins with fluorene or binaphthalene skeletons are used because of their high refractive index.

To achieve a high refractive index, materials with less oxygen in the condensed portions, such as polyester or polyester carbonate, are more effective than polycarbonate.

To give polyester resin or polyester carbonate resin a high refractive index, both the monomers used in the diol and carboxylic acid portions of the resin must be materials that are expected to have a high refractive index.

It has been reported that high refractive index resins can be obtained by using a substance with a binaphthalene skeleton as the dicarboxylic acid moiety that constitutes the high refractive index resin. In particular, polyester resins or polyester carbonate resins that use 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl or its ester as the dicarboxylic acid component are useful as resins with high refractive index, high heat resistance, and low birefringence.

For example, Patent Document 1 describes a polyester resin using 2,2'-bis(ethoxycarbonylmethoxy)-1,1'-binaphthyl and 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene. Patent Documents 2 to 4 describe resins with repeating units formed by the reaction of a specific diol with a carboxylic acid. While these resins have a high refractive index, they lack an adequate balance between birefringence, heat resistance, and moldability, leaving room for improvement.

To solve these problems, Patent Document 5 describes a resin containing a certain ratio of repeating units formed from the reaction product of a specific diol and 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl (BCMB) as a dicarboxylic acid, and repeating units formed from the reaction product of another specific diol and 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, resulting in a resin with desirable high refractive index, high heat resistance, and low birefringence. However, because dicarboxylic acid is used as a raw material, carboxylic acid remains at the resin's terminal. Terminal carboxylic acid has a negative effect on dry heat resistance and color.

JP 2017-171885 A Japanese Patent Application Laid-Open No. 2018-002895 Japanese Patent Application Laid-Open No. 2018-002894 JP 2018-002893 A International Publication No. 2019/176874

The object of the present invention is to provide a polyester resin or polyester carbonate resin that has a high refractive index, low birefringence, and an excellent balance between heat resistance and moldability, as well as excellent color and moist heat resistance.

As a result of extensive research to achieve this goal, the inventors discovered that polyester resins or polyester carbonate resins that have a fluorene skeleton and a binaphthyl skeleton to which specific aromatic groups have been introduced, and that further have an extremely low amount of terminal carboxylic acid, have a high refractive index and low birefringence, provide a high level of balance between heat resistance and moldability, and also exhibit excellent hue and moist heat resistance, leading to the present invention.

That is, the present invention is as follows.
1. A polyester resin or polyester carbonate resin containing repeating units represented by the following formulas (1) and (2), in which the ratio of the repeating units represented by the following formula (1) to the repeating units represented by the following formula (2) is 15:85 to 85:15, and the amount of terminal carboxylic acid is 0.8 equivalents/ton or less.

(In the formula, rings Z ¹ and Z ² each represent a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms; R ¹ , R ² , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ³ to R ⁶ and R ⁹ to R ¹⁶ each represent a hydrogen atom or an aliphatic or aromatic substituent; j, k, r and s each independently represent an integer of 0 or greater; and m, n, p and q each independently represent 1 or 2.)

(In the formula, R ⁷ , R ⁸ , R ¹⁷ and R ¹⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ⁹ to R ¹⁶ and R ¹⁹ to R ²⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; and r, s, t and u each independently represent an integer of 0 or greater.)

2. The polyester resin or polyester carbonate resin according to 1 above, wherein Z ¹ and Z ² in formula (1) are naphthalenediyl groups.
3. The polyester resin or polyester carbonate resin according to 1 above, wherein the formula (1) comprises a unit represented by the following formula (3):

(In the formula, R ¹ , R ² , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ³ to R ⁶ and R ⁹ to R ¹⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; j, k, r and s each independently represent an integer of 0 or greater; and m, n, p and q each independently represent 1 or 2.)

4. The polyester resin or polyester carbonate resin according to 3 above, wherein formula (3) is the following formula (4):

(In the formula, R ¹ , R ² , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group.)

5. The polyester resin or polyester carbonate resin according to 3 or 4 above, wherein R ¹ and R ² in formula (3) or (4) are ethylene groups, and R ⁷ and R ⁸ are methylene groups.
6. The polyester resin or polyester carbonate resin according to any one of items 1 to 5 above, wherein the repeating units represented by formula (1) account for 20 mol % or more of all repeating units.
7. The polyester resin or polyester carbonate resin according to any one of items 1 to 6 above, wherein R ⁹ to R ¹⁶ and R ¹⁹ to R ²⁶ in formula (2) are hydrogen atoms, and r, s, t, and u are 1.
8. The polyester resin or polyester carbonate resin according to any one of items 1 to 7 above, wherein R ⁷ and R ⁸ in formula (2) are methylene groups, and R ¹⁷ and R ¹⁸ are ethylene groups.
9. The polyester resin or polyester carbonate resin according to any one of items 1 to 8 above, wherein the repeating units represented by formula (2) account for 20 mol % or more of all repeating units.
10. The polyester resin or polyestercarbonate resin according to any one of items 1 to 9 above, wherein the ratio of the repeating unit represented by formula (1) to the repeating unit represented by formula (2) is 25:75 to 75:25.
11. The polyester resin or polyestercarbonate resin according to any one of items 1 to 10 above, which has a specific viscosity of 0.12 to 0.40 as measured on a solution dissolved in methylene chloride at 0.53% by mass.
12. The polyester resin or polyester carbonate resin according to any one of items 1 to 11 above, which has a refractive index of 1.675 to 1.695.
13. The polyester resin or polyester carbonate resin according to any one of 1 to 12 above, which has a glass transition temperature of 140 to 155°C.
14. The polyester resin or polyestercarbonate resin according to any one of items 1 to 13, wherein the absolute value of birefringence at 20°C and a wavelength of 589 nm in a film stretched to 2 times its original size at a temperature 10°C higher than the glass transition temperature is 0.001 x 10 ^-3 to 5.0 x 10 ^-3 .
15. The polyester resin or polyestercarbonate resin according to any one of items 1 to 14, wherein 1.0 g of the resin is dissolved in 5 mL of methylene chloride for spectroscopic analysis, and the b ^* value of the solution measured according to the CIE 1976 ( ^L* a ^* b ^* ) color system is 3.0 or less.
16. The polyester resin or polyestercarbonate resin according to any one of items 1 to 15 above, characterized in that raw materials are compounds represented by the following formulas (a), (b), and (c), and optionally a carbonate-forming derivative, which are reacted by melt polymerization:

(In the formula, rings Z ¹ and Z ² each represent a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms; R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ³ to R ⁶ each represent a hydrogen atom or an aliphatic or aromatic substituent; j and k each independently represent an integer of 0 or greater; and m, n, p, and q each independently represent 1 or 2.)

(In the formula, R ¹⁷ and R ¹⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ¹⁹ to R ²⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; and t and u each independently represent an integer of 0 or greater.)

(In the formula, R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ⁹ to R ¹⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; r and s each independently represent an integer of 0 or greater; and R ²⁷ and R ²⁸ each independently represent a methyl group, an ethyl group, or a phenyl group.)

17. An optical member made of the polyester resin or polyester carbonate resin described in any one of 1 to 16 above.
18. The optical member according to 17 above, which is an optical lens.

The polyester resin or polyester carbonate resin of the present invention has a high refractive index, low birefringence, and an excellent balance between heat resistance and moldability, and also has excellent hue and moist heat resistance, making it an exceptionally effective industrial product.

The present invention will now be described in more detail.

<Polyester Resin or Polyester Carbonate Resin>
The polyester resin or polyester carbonate resin of the present invention contains repeating units represented by the following formulas (1) and (2), the ratio of the repeating units represented by the following formula (1) to the repeating units represented by the following formula (2) is 15:85 to 85:15, and the amount of terminal carboxylic acid is 0.8 equivalents/ton or less.

(In the formula, rings Z ¹ and Z ² each represent a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms; R ¹ , R ² , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ³ to R ⁶ and R ⁹ to R ¹⁶ each represent a hydrogen atom or an aliphatic or aromatic substituent; j, k, r and s each independently represent an integer of 0 or greater; and m, n, p and q each independently represent 1 or 2.)

(In the formula, R ⁷ , R ⁸ , R ¹⁷ and R ¹⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ⁹ to R ¹⁶ and R ¹⁹ to R ²⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; and r, s, t and u each independently represent an integer of 0 or greater.)

In a preferred embodiment of the polyester resin or polyester carbonate resin of the present invention, the polycyclic aromatic hydrocarbon group represented by rings ^Z1 and ^Z2 in formula (1) has at least 9 to 20 carbon atoms, and is preferably a fused polycyclic aromatic hydrocarbon ring having a benzene ring skeleton, with fused bicyclic hydrocarbon rings and fused tricyclic hydrocarbon rings being preferred. As the fused bicyclic hydrocarbon ring, an aromatic hydrocarbon ring having 9 to 20 carbon atoms, such as an indene ring or a naphthalene ring, is preferred, and a fused bicyclic hydrocarbon ring having 10 to 16 carbon atoms is more preferred. Furthermore, as the fused tricyclic hydrocarbon ring, an anthracene ring, a phenanthrene ring, or the like is preferred. These polycyclic aromatic hydrocarbon groups may have a substituent.

In a preferred embodiment of the polyester resin or polyester carbonate resin of the present invention, Z ¹ and Z ² in the formula (1) are naphthalenediyl groups.

In the above formula (1), the polycyclic aromatic hydrocarbon group represented by rings Z ¹ and Z ² is preferably a naphthalene-1,4-diyl group or a naphthalene-2,6-diyl group, more preferably a naphthalene-2,6-diyl group.

In a preferred embodiment of the polyester resin or polyester carbonate resin of the present invention, the formula (1) comprises units represented by the following formula (3):

(In the formula, R ¹ , R ² , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ³ to R ⁶ and R ⁹ to R ¹⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; j, k, r and s each independently represent an integer of 0 or greater; and m, n, p and q each independently represent 1 or 2.)

Preferable examples of R ³ to R ⁶ and R ⁹ to R ¹⁶ in the formula (3) include a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, and an aralkyloxy group, more preferably a hydrogen atom or an aryl group, and even more preferably a hydrogen atom.

Preferred halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms.

Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, and t-butyl groups. Alkyl groups having 1 to 4 carbon atoms are more preferred, and methyl or ethyl groups are even more preferred.

Specific examples of preferred cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecanyl, cyclododecanyl, and 4-tert-butylcyclohexyl groups, with cyclohexyl being more preferred.

Specific examples of aryl groups preferably include phenyl groups, alkylphenyl groups (mono- or dimethylphenyl groups such as tolyl, 2-methylphenyl, and xylyl), and naphthyl groups, with phenyl and naphthyl groups being more preferred, and phenyl groups being even more preferred.

Specific examples of aralkyl groups include benzyl and phenethyl groups, with benzyl being more preferred.

Specific examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups, with alkoxy groups having 1 to 4 carbon atoms being more preferred, and methoxy or ethoxy groups being even more preferred.

Preferred specific examples of the cycloalkyloxy group include a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.
A cyclohexyloxy group is more preferred.

Specific examples of aryloxy groups include phenoxy groups, alkylphenoxy groups (mono- or dimethylphenoxy groups), and naphthyloxy groups, with phenoxy groups and naphthyloxy groups being more preferred, and phenoxy groups being even more preferred.

Specific examples of aralkyloxy groups include benzyloxy and phenethyloxy groups, with benzyloxy being more preferred.

In formula (3), j, k, r, and s each independently represent an integer of 0 or greater, preferably 1 or 2, and more preferably 1.

In formula (3), m, n, p, and q each independently represent 1 or 2, preferably 1.

In a preferred embodiment of the polyester resin or polyester carbonate resin of the present invention, the formula (3) comprises units represented by the following formula (4):

R ¹ , R ² , R ⁷ , and R ⁸ in the formula (4) each independently represent a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms, and preferred examples thereof include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group, and arylene groups such as a phenylene group and a naphthalenediyl group. Of these, a methylene group and an ethylene group are preferred, and R ¹ and R ² are more preferably ethylene groups, and R ⁷ and R ⁸ are more preferably methylene groups.

More preferred examples of R ⁹ to R ¹⁶ and R ¹⁹ to R ²⁶ in the formula (2) include a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, and an aralkyloxy group, more preferred are a hydrogen atom and an aryl group, and even more preferred is a hydrogen atom.

Preferred specific examples of halogen atoms, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, cycloalkyloxy groups, aryloxy groups, and aralkyloxy groups are as described above.

In formula (2), r, s, t, and u are each independently an integer of 0 or greater, preferably 1 or 2, and more preferably 1.

R ⁷ , R ⁸ , R ¹⁷ , and R ¹⁸ in the formula (2) each independently represent a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms, and preferred examples thereof include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group, and arylene groups such as a phenylene group and a naphthalenediyl group. Of these, a methylene group and an ethylene group are preferred, and R ⁷ and R ⁸ are more preferably methylene groups, and R ¹⁷ and R ¹⁸ are more preferably ethylene groups.

The relationship between molecular structure and refractive index, traditionally known as the Lorentz-Lorenz equation, has shown that increasing the electron density of a molecule and decreasing its molecular volume increases the refractive index of the material. Based on this theory, resins with fluorene or binaphthalene skeletons have a high refractive index achieved by introducing many aromatic groups into the molecule. However, although these resins have a high refractive index, they lack an adequate balance between birefringence and heat resistance/formability.

The specific ester structure represented by formula (1) of the present invention has a high refractive index and low birefringence, contributing to high heat resistance, while the specific ester structure represented by formula (2) has a lower refractive index than formula (1), but a high refractive index and low birefringence, lowering the glass transition temperature of the resin and contributing to moldability. Therefore, polyester resins or polyester carbonate resins containing repeating units represented by formulas (1) and (2) have a high refractive index and can balance birefringence with heat resistance and moldability.

The resin composition ratio in this invention refers to the molar ratio of the monomer structures introduced into the resin, based on the number of moles of all monomer units. Note that the total number of monomer units does not include carbonic acid components.

In this invention, a repeating unit refers to the smallest unit connected by an ester bond and/or a carbonate bond. A repeating unit of an ester bond refers to a structural unit formed from a diol component and a dicarboxylic acid component, and a repeating unit of a carbonate bond refers to a structural unit formed from a diol derivative and a carbonic acid component.

The molar ratio of the repeating unit represented by formula (1) to the repeating unit represented by formula (2) in the polyester resin or polyester carbonate resin of the present invention is 15:85 to 85:15.

The molar ratio of the repeating units represented by formula (1) to the repeating units represented by formula (2) is preferably 25:75 to 75:25, and more preferably 30:70 to 70:30. A ratio within this range provides an excellent balance between high refractive index and birefringence.

A preferred embodiment of the polyester resin or polyester carbonate resin of the present invention is
The specific viscosity is preferably 0.12 to 0.40, more preferably 0.15 to 0.35, and even more preferably 0.18 to 0.30. A specific viscosity within the above range is preferable because it provides an excellent balance between moldability and mechanical strength. The specific viscosity is the specific viscosity (η _{sp )} measured at 20°C using a solution in which the resin is dissolved in methylene chloride at 0.53% by mass (a solution in which 0.7 g of resin is dissolved in 100 mL of methylene chloride).

A preferred embodiment of the polyester resin or polyester carbonate resin of the present invention is
The refractive index (hereinafter sometimes abbreviated as nD) at a wavelength of 589 nm measured at 25° C. is preferably 1.660 to 1.695, more preferably 1.670 to 1.695, even more preferably 1.675 to 1.695, and particularly preferably 1.680 to 1.695. If the refractive index is equal to or greater than the lower limit, the spherical aberration of the lens can be reduced, and the focal length of the lens can be shortened.

The polyester resin or polyester carbonate resin of the present invention has a high refractive index, but preferably also has a low Abbe number. The Abbe number (ν) is preferably 15.0 to 21.0, more preferably 16.0 to 20.0, even more preferably 16.0 to 19.0, and particularly preferably 17.0 to 19.0. The Abbe number is calculated using the following formula from the refractive indexes at wavelengths of 486 nm, 589 nm, and 656 nm measured at 25°C.

ν=(nD-1)/(nF-nC)
In the present invention,
nD: refractive index at a wavelength of 589 nm,
nC: refractive index at a wavelength of 656 nm,
nF: refers to the refractive index at a wavelength of 486 nm.

A preferred embodiment of the polyester resin or polyester carbonate resin of the present invention has a glass transition temperature (Tg) of 140 to 160°C, more preferably 140 to 155°C, and even more preferably 140 to 150°C. A glass transition temperature within the above range is preferred because it provides an excellent balance between heat resistance and moldability.

In a preferred embodiment of the polyester resin or polyester carbonate resin of the present invention, the absolute value of orientation birefringence (|Δn|) is preferably in the range of 0.001×10 ⁻³ to 10.0×10 ⁻³ , more preferably 0.001×10 ⁻³ to 5.0×10 ⁻³ , even more preferably 0.001×10 ⁻³ to 4.0×10 ⁻³ , particularly preferably 0.001×10 ⁻³ to 3.5×10 ⁻³ , and most preferably 0.001×10 ⁻³ to 3.0×10 ⁻³ .

|Δn| is calculated using the following formula by stretching a 100 μm thick film obtained from the polyester resin or polyester carbonate resin of the present invention to 2 times its original size in one direction at a temperature of Tg + 10°C, measuring the phase difference at a wavelength of 589 nm, and then using the formula below. It is preferable for |Δn| to be within the above range, as this reduces the optical distortion of the lens.

|Δn|=|Re/d|
Δn: orientational birefringence
Re: phase difference (nm)
d: thickness (nm)

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention have a total light transmittance at a thickness of 1 mm of preferably 80% or more, more preferably 85% or more, and even more preferably 88% or more. A total light transmittance within the above range is suitable for use as an optical component. Total light transmittance was measured using a 1 mm thick molded piece using an NDH-300A manufactured by Nippon Denshoku Industries Co., Ltd.

A preferred embodiment of the polyester resin or polyester carbonate resin of the present invention is that it has ^a low degree of coloration, particularly ^a low yellowish tint.
The b ^* value of the CIE 1976 (L*a ^*b* ) color system is preferably 4.0 or less. The b ^* value is more preferably 3.0 or less, even more preferably 2.0 or less, particularly preferably 1.6 or less, and most preferably 1.4 or less. This b ^* value is a value of the CIE 1976 (L ^* a ^* b ^*) color system measured with a spectrophotometer for a solution in which 1.0 g of the compound is dissolved in 5 mL of methylene chloride (a solution dissolved in methylene chloride at 13% by mass).

A preferred embodiment of the polyester resin or polyester carbonate resin of the present invention is one in which the water absorption rate after immersion at 23°C for 24 hours is 0.25% by mass or less, and more preferably 0.20% by mass or less. A water absorption rate within the above range is preferred because changes in optical properties due to water absorption are minimal.

The polyester resin or polyestercarbonate resin of the present invention has a terminal carboxylic acid content of 0.8 equivalents/ton or less, more preferably 0.5 equivalents/ton or less, and even more preferably 0.3 equivalents/ton or less. A terminal carboxylic acid content of 0.8 equivalents/ton or less can prevent the terminal carboxylic acid from acting as a catalyst for the hydrolysis of ester bonds, improving moist heat resistance. Furthermore, the carboxylic acid can be prevented from causing decarboxylation or side reactions that result in the production of colored components, improving the hue. That is, a terminal carboxylic acid content of 0.8 equivalents/ton or less results in excellent moist heat resistance and hue. The terminal carboxylic acid content can be measured by dissolving 0.1 g of resin in 10 mL of methylene chloride at room temperature under a nitrogen atmosphere, adding 3 mL of acetone, and titrating the resulting mixture.

The moist heat resistance of the polyester resin or polyester carbonate resin of the present invention can be evaluated by treating the resin in an environment of 85°C and 85% relative humidity for a predetermined period of time and comparing the specific viscosity of the resin before and after the treatment. Specifically, the moist heat resistance can be calculated using the following formula.
Moisture and heat resistance (%) = [specific viscosity of resin after treatment] / [specific viscosity of resin before treatment] × 100
The wet heat resistance after 500 hours of treatment is preferably 95% or more, more preferably 97% or more, and even more preferably 98% or more.

Specific raw materials used in the polyester resin or polyester carbonate resin of the present invention are described below.

<Raw material monomer>
(Diol component of the formula (1))
The diol component used as the raw material of the formula (1) of the present invention is mainly a diol component represented by the following formula (a), and may be used alone or in combination of two or more kinds.

In the formula (a), rings Z ¹ and Z ² each represent a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, R ³ to R ⁶ each represent a hydrogen atom or an aliphatic or aromatic substituent, j and k each independently represent an integer of 0 or greater, and m, n, p, and q each independently represent 1 or 2.

In the formula (a), the preferred values of Z ¹ , Z ² , R ¹ to R ⁶ , j, k, m, n, p and q are the same as those in the formula (1).

Representative examples of the diol component represented by formula (a) are shown below, but the raw materials used in formula (1) of the present invention are not limited to these.

Specifically, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)-1-naphthyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene, 9,9-
Preferred examples include bis(6-(2-hydroxypropoxy)-2-naphthyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)fluorene, and 9,9-bis(6-hydroxy-2-naphthyl)fluorene. Among these, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)fluorene, and 9,9-bis(6-hydroxy-2-naphthyl)fluorene are more preferred, and 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)fluorene and 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene are particularly preferred.

These may be used alone or in combination of two or more.

(Diol component of the formula (2))
The diol component serving as a raw material of the formula (2) of the present invention is mainly a diol component represented by the following formula (b), and may be used alone or in combination of two or more kinds.

In the formula (b), R ¹⁷ and R ¹⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, R ¹⁹ to R ²⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent, and t and u each independently represent an integer of 0 or greater.

In the formula (b), the preferred values of R ¹⁷ to R ²⁶ , t, and u are the same as those in the formula (2).

Representative examples of the diol component represented by formula (b) are shown below, but the raw materials used in formula (2) of the present invention are not limited to these.

Specific examples include 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-3,3'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-7,7'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-3,3'-dimethyl-1,1'-binaphthyl, 2 Preferred examples include 2,2'-bis(2-hydroxyethoxy)-6,6'-dimethyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-7,7'-dimethyl-1,1'-binaphthyl, 1,1'-bi-2-naphthol, 2,2'-dihydroxy-3,3'-diphenyl-1,1'-binaphthyl, 2,2'-dihydroxy-6,6'-diphenyl-1,1'-binaphthyl, and 2,2'-dihydroxy-7,7'-diphenyl-1,1'-binaphthyl. Of these, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl and 1,1'-bi-2-naphthol are more preferred, and 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl is even more preferred.

These may be used alone or in combination of two or more.

(Diol components other than those of the formula (1) and the formula (2))
The polyester resin or polyester carbonate resin of the present invention may be copolymerized with other diol components to the extent that the properties of the present invention are not impaired. The amount of other diol components is preferably less than 30 mol % of all repeating units.

Other diol components that can be used in the polyester resin or polyester carbonate resin of the present invention include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, tricyclo[5.2.1.0 ^2,6 ]Decanedimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spiroglycol, isosorbide, isomannide, isoidide, hydroquinone, resorcinol, dihydroxynaphthalene, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl) 9,9-bis(4-hydroxyphenyl)sulfide, biphenol, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)- Examples include 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, bis(4-hydroxyphenyl)sulfone, bis(4-(2-hydroxyethoxy)phenyl)sulfone, and 10,10-bis(4-hydroxyphenyl)anthrone, and these may be used alone or in combination of two or more.

(Dicarboxylic acid components of the formula (1) and the formula (2))
As the dicarboxylic acid component monomer forming the units represented by the formula (1) and the formula (2) of the polyester resin or polyester carbonate resin of the present invention, a dicarboxylic acid ester represented by the following formula (c) is used.

In the formula (c), R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, R ⁹ to R ¹⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent, r and s each independently represent an integer of 0 or greater, and R ²⁷ and R ²⁸ each independently represent a methyl group, an ethyl group, or a phenyl group.

In the formula (c), the preferred values of R ⁷ to R ¹⁶ , r, and s are the same as those in the formula (1).

Representative examples of dicarboxylic esters represented by formula (c) are shown below, but the raw materials used in formula (c) of the present invention are not limited to these.

Specific examples include dimethyl 2,2'-biphenyldicarboxylate, diethyl 2,2'-biphenyldicarboxylate, diphenyl 2,2'-biphenyldicarboxylate, 2,2'-bis(ethoxycarboxymethoxy)-1,1'-binaphthyl, 2,2'-bis(2-ethoxycarboxyethoxy)-1,1'-binaphthyl, 2,2'-bis(3-ethoxycarboxypropoxy)-1,1'-binaphthyl, 2,2'-bis(3-ethoxycarboxy-2-methylpropoxy)-1,1'-binaphthyl, 2,2'-bis(4-ethoxycarboxyphenylmethoxy)-1,1'-binaphthyl, and 2,2'-biphenyldicarboxylic acid. Preferred examples include 2,2'-bis(methoxycarboxymethoxy)-1,1'-binaphthyl, 2,2'-bis(2-methoxycarboxyethoxy)-1,1'-binaphthyl, 2,2'-bis(3-methoxycarboxypropoxy)-1,1'-binaphthyl, 2,2'-bis(3-methoxycarboxy-2-methylpropoxy)-1,1'-binaphthyl, and 2,2'-bis(4-methoxycarboxyphenylmethoxy)-1,1'-binaphthyl, with 2,2'-bis(ethoxycarboxymethoxy)-1,1'-binaphthyl and 2,2'-bis(methoxycarboxymethoxy)-1,1'-binaphthyl being more preferred.

In addition, mixed dicarboxylic acid esters, rather than the same esters within the molecule, can also be used without any problems. A specific example is an asymmetric ester such as 2-(ethoxycarboxymethoxy)-2'-(methoxycarboxymethoxy)-1,1'-binaphthyl.

These may be used alone or in combination of two or more.

By using dicarboxylic acid esters as raw monomers for the dicarboxylic acid component, the polymer ends in esters. This makes it possible to reduce the amount of terminal carboxylic acid, thereby reducing the effects of terminal carboxylic acid, such as deterioration of color and moist heat resistance.

(Dicarboxylic acid components other than those of the formula (1) and the formula (2))
The dicarboxylic acid component used in the polyester resin or polyester carbonate resin of the present invention may be copolymerized with other dicarboxylic acid components to the extent that the properties of the present invention are not impaired. The amount of the other dicarboxylic acid components is preferably less than 30 mol % of all repeating units.

Other dicarboxylic acid components that can be used in the polyester resin or polyester carbonate resin of the present invention 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 acid components such as phthalic acid, isophthalic acid, and terephthalic acid; 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, anthracenedicarboxylic acid, phenanthrenedicarboxylic acid, 9,9-bis(carboxymethyl)fluorene, and 9,9-bis(2-carboxyethyl)fluorene. Preferred are polycyclic aromatic dicarboxylic acid components such as 9,9-bis(1-carboxyethyl)fluorene, 9,9-bis(1-carboxypropyl)fluorene, 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, as well as alicyclic dicarboxylic acid components such as 1,4-cyclohexanedicarboxylic acid and 2,6-decalindicarboxylic acid. These raw materials may be carboxylic acids or may be in the form of esters. Furthermore, they may be used alone or in combination of two or more.

The method for producing the polyester resin or polyester carbonate resin of the present invention is described below.

<Method of producing polyester resin>
The polyester resin of the present invention may be prepared by using a diol component and a diester as a dicarboxylic acid component, subjecting the resulting reaction product to a transesterification reaction, and then subjecting the resulting reaction product to a polycondensation reaction to produce a polymer having a desired molecular weight.

The ethylene glycol component is preferably 0 to 50 mol% of the total diol components. This range is preferred because it provides an excellent balance between heat resistance and moldability.

As a polymerization method, a known melt polymerization method such as transesterification can be carried out to produce the resin.
In the polyester polymerization method of the present invention, a diol component and a diester of a dicarboxylic acid component are mixed and reacted at preferably 120 to 350°C, more preferably 150 to 300°C, and even more preferably 180 to 270°C. The degree of reduced pressure is gradually changed, and finally reduced to 0.13 kPa or less, so that the produced alcohol, hydroxy compounds such as phenol, etc. can be distilled out of the system. The reaction time is usually preferably about 1 to 10 hours.

In addition, a catalyst can be used to increase the polymerization rate in the melt polymerization method. For example, alkali metal compounds such as lithium acetate, sodium hydroxide, potassium hydroxide, and sodium and potassium salts of dihydric phenols; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide, and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine; alkoxides of alkali metals and alkaline earth metals; organic acid salts of alkali metals and alkaline earth metals; zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, magnesium compounds, titanium compounds, cobalt compounds, and zirconium compounds, which are commonly used in esterification and transesterification reactions, can be preferably used. Among these, from the viewpoint of the melt stability and color of the resin, aluminum, tin, titanium, and germanium compounds are more preferred, and aluminum compounds are even more preferred.

The amount of the polymerization catalyst used is preferably in the range of 1×10 ⁻⁸ to 1×10 ⁻³ moles per mole of the total of all monomer units.

The polyester resin of the present invention may contain an end-capping agent to adjust molecular weight and improve thermal stability. Preferred end-capping agents include monofunctional hydroxy compounds, epoxy compounds, oxazoline compounds, isocyanate compounds, carbodiimide compounds, and ketenimine compounds.

The polyester resin of the present invention may contain copolymer components other than the diol component and dicarboxylic ester.

<Method for producing polyester carbonate resin>
The polyester carbonate resin of the present invention can be obtained by reacting a diol component and a dicarboxylic acid ester with a carbonate-forming derivative such as a carbonic acid diester by a melt polymerization method, and a catalyst, a terminal terminator, an antioxidant, etc. may be used as necessary.

The reaction using the melt polymerization method is typically a transesterification reaction between a diol component, a dicarboxylic acid ester, and a carbonate-forming derivative. It is carried out by mixing the diol component, dicarboxylic acid ester, and carbonate-forming derivative while heating them in the presence of an inert gas, and then distilling off the resulting alcohols and hydroxy compounds such as phenols.

The reaction temperature varies depending on the diol component used, but is preferably 120 to 350° C., more preferably 150 to 300° C., and even more preferably 180 to 270° C. The degree of reduced pressure is changed stepwise, and finally reduced to 0.13 kPa or less to distill off the produced alcohol and hydroxy compounds such as phenol from the system.
The reaction time is usually preferably about 1 to 10 hours.

In the initial stage of the reaction, it is preferable to carry out the reaction at a relatively low temperature of around 180-220°C to distill off low-molecular-weight alcohols. If the distillation column is equipped with a reflux unit, low-molecular-weight alcohols can be selectively distilled off by increasing the reflux ratio.

Preferred carbonate-forming derivatives include esters of optionally substituted aryl groups having 6 to 10 carbon atoms, aralkyl groups, or alkyl groups having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate, with diphenyl carbonate being more preferred.

In addition, a catalyst can be used to increase the polymerization rate in the melt polymerization method. For example, alkali metal compounds such as lithium acetate, sodium hydroxide, potassium hydroxide, and sodium and potassium salts of dihydric phenols; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide, and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine; alkoxides of alkali metals and alkaline earth metals; organic acid salts of alkali metals and alkaline earth metals; zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, magnesium compounds, titanium compounds, cobalt compounds, and zirconium compounds, which are commonly used in esterification and transesterification reactions, can be preferably used. Among these, from the viewpoint of the melt stability and color of the resin, aluminum, tin, titanium, and germanium compounds are more preferred, and aluminum compounds are even more preferred.

The catalyst may be used alone or in combination of two or more, or may be used in combination with another compound as a co-catalyst. The amount of these polymerization catalysts used is preferably in the range of 1×10 ⁻⁸ to 1×10 ⁻³ mol per 1 mol of the total of all monomer units.

Aluminum or its compounds, which are preferably used as catalysts, have catalytic activity for polymerizing polyester carbonate resins by transesterification. In particular, they act as catalysts for the carbonate-forming reaction in polymerizations using diol components, dicarboxylic acid components, and carbonate-forming derivatives as raw material monomers.

Preferred examples of such aluminum or compounds thereof include metallic aluminum, aluminum salts, aluminum chelate compounds, organic aluminum compounds, and inorganic aluminum compounds.

Preferred examples of aluminum salts include organic and inorganic aluminum salts. Examples of organic aluminum salts include aluminum carboxylates, and specific examples of preferred aluminum salts include 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. Preferred examples of inorganic aluminum salts include aluminum chloride, aluminum hydroxide, aluminum carbonate, aluminum phosphate, and aluminum phosphonate.

Preferred examples of aluminum chelate compounds include aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, and aluminum ethylacetoacetate diso-propoxide.

Preferred examples of organic aluminum compounds include aluminum alkoxides, such as trialkylaluminum, dialkylaluminum alkoxides, alkylaluminum dialkoxides, aluminum trialkoxides, and hydrolyzates thereof. Specific examples include aluminum alkoxides such as aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, and aluminum tert-butoxide, as well as trimethylaluminum, triethylaluminum, and hydrolyzates thereof. Preferred examples of inorganic aluminum compounds include aluminum oxide.

Aluminum carboxylates, inorganic acid salts, and chelate compounds are particularly preferred, with aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetonate being more preferred.

These aluminum compounds may be used in combination with other compounds as co-catalysts, and in particular, phosphorus compounds can improve the catalytic activity of aluminum or its compounds in the polymerization reaction of polyester carbonate resins.

Examples of such phosphorus compounds include phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphineous 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 even more preferred.

Examples of 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, diethyl p-methylbenzylphosphonate, dihexyl p-methylbenzylphosphonate, dioctyl p-methylbenzylphosphonate, diphenyl p-methylbenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, Preferred examples include dimethyl sulfonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dihexyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, and diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, and more preferred are dimethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dihexyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, and diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.

The molar ratio of the amount of phosphorus compound used to the amount of aluminum or its compound used is preferably in the range of 0.5 to 10, more preferably in the range of 1 to 5, and even more preferably in the range of 1.5 to 3.

The form in which the catalyst is added is not particularly limited; it may be added to the monomer in a powder form, or in the form of a dispersion or solution in a solvent. Furthermore, a premix of aluminum or its compound and a phosphorus compound may be added, or aluminum or its compound and the phosphorus compound may be added separately.

The polyester carbonate resin of the present invention may contain a copolymerization component of a diol component and a diol component other than a dicarboxylic acid or an ester-forming derivative thereof.

<Impurities>
(residual phenol)
The residual phenol content of the polyester carbonate resin of the present invention is preferably 1 to 500 ppm, more preferably 1 to 400 ppm, and even more preferably 1 to 300 ppm.

The phenol content is preferably adjusted by the reaction time at a pressure of 1.3 kPa or less. If the reaction is not carried out at a vacuum of 1.3 kPa or less, the phenol content will be high. Also, if the reaction time is too long, too much phenol will be distilled off from the resin.

Alternatively, the phenol content may be adjusted after the polyester carbonate resin of the present invention is obtained, for example, by dissolving the polyester carbonate resin of the present invention in an organic solvent and washing the organic solvent layer with water, or by removing volatile components using a commonly used kneading device such as a single-screw or twin-screw extruder or various kneaders at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320°C.

The residual phenol content in the polyester carbonate resin of the present invention can improve molding flowability without impairing heat resistance. However, if it exceeds 500 ppm, the resin will have poor thermal stability when heated and melted, and will undesirably cause severe mold contamination during resin injection molding. Furthermore, phenol has the property of becoming discolored when oxidized, which deteriorates the hue of the polyester carbonate resin. If it is less than 1 ppm, molding flowability will be poor, which is also undesirable.

(Residual fluorenone)
The residual fluorenone content of the polyester resin or polyester carbonate resin of the present invention is preferably 1 to 500 ppm, more preferably 1 to 300 ppm, even more preferably 1 to 100 ppm, and particularly preferably 1 to 50 ppm.

If the residual fluorenone content in the polyester resin or polyester carbonate resin of the present invention exceeds 500 ppm, the resin will become significantly discolored, which is undesirable.

<Additives>
The polyester resin or polyester carbonate resin of the present invention (hereinafter sometimes referred to as the resin of the present invention) can be used by appropriately adding additives such as a mold release agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a bluing agent, an antistatic agent, a flame retardant, a plasticizer, and a filler, as needed.

Preferably, the release agent is one that consists of 90% by weight or more of an ester of alcohol and fatty acid. Specific examples of the ester of alcohol and fatty acid include esters of monohydric alcohol and fatty acid and/or partial or full esters of polyhydric alcohol and fatty acid. The ester of monohydric alcohol and fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Furthermore, the partial or full ester of a polyhydric alcohol and fatty acid is preferably a partial or full ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Specific examples of the ester of a monohydric alcohol and saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate, with stearyl stearate being preferred.

Specific examples of partial or full esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, and full or partial esters of dipentaerythritol such as dipentaerythritol hexastearate. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and mixtures of stearic acid triglyceride and stearyl stearate are preferred.

The amount of the ester in the release agent is preferably 90% by weight or more, and more preferably 95% by weight or more, when the release agent is taken as 100% by weight.

The release agent to be blended into the resin of the present invention is preferably in the range of 0.005 to 2.0 parts by weight, more preferably 0.01 to 0.6 parts by weight, and even more preferably 0.02 to 0.5 parts by weight, per 100 parts by weight of the resin.

Heat stabilizers include phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and hindered phenol-based heat stabilizers. Trivalent phosphorus compounds are preferred because they not only have a heat stabilizing effect but also act as antioxidants.

Phosphorus-based heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and their esters. Specific examples include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, and monobutyl diphenyl phosphite. phosphite, monodecyldiphenyl phosphite, monooctyldiphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, Examples of suitable phosphate diphosphates include 2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-t-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-t-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite.

Among these, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-t-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-t-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite are preferably used. Particularly preferred are tris(2,4-di-tert-butylphenyl)phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite.

The content of phosphorus-based heat stabilizer is preferably 0.001 to 0.2 parts by weight per 100 parts by weight of resin.

Examples of sulfur-based heat stabilizers include pentaerythritol-tetrakis(3-laurylthiopropionate), pentaerythritol-tetrakis(3-myristylthiopropionate), pentaerythritol-tetrakis(3-stearylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate. Of these, pentaerythritol-tetrakis(3-laurylthiopropionate), pentaerythritol-tetrakis(3-myristylthiopropionate), dilauryl-3,3'-thiodipropionate, and dimyristyl-3,3'-thiodipropionate are preferred. Pentaerythritol-tetrakis(3-laurylthiopropionate) is particularly preferred.

The content of sulfur-based heat stabilizer is preferably 0.001 to 0.2 parts by weight per 100 parts by weight of resin.

Hindered phenol-based heat stabilizers include triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t Examples of suitable hydroxybenzoates include N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane. Among these, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] are particularly preferred.

The content of the hindered phenol-based heat stabilizer is preferably 0.001 to 0.3 parts by weight per 100 parts by weight of resin.

Phosphorus-based heat stabilizers and hindered phenol-based heat stabilizers can also be used in combination.

Preferably, the ultraviolet absorber is at least one ultraviolet absorber selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers.

Of the benzotriazole-based ultraviolet absorbers, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole and 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] are more preferred.

Examples of benzophenone-based ultraviolet absorbers include 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

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

2,2'-p-phenylenebis(3,1-benzoxazin-4-one) is particularly suitable as a cyclic imino ester UV absorber.

Cyanoacrylate UV absorbers include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

The amount of UV absorber to be added is preferably 0.01 to 3.0 parts by weight per 100 parts by weight of resin. This amount range can provide sufficient weather resistance to the resin molded product depending on the application.

Examples of bluing agents include Bayer's Macrolex Violet B and Macrolex Blue RR, and Clariant's Polythrem Blue RLS. Bluing agents are effective in eliminating the yellow tinge of resin. In particular, in the case of weather-resistant resin compositions, a certain amount of UV absorber is blended, and the resin composition is prone to taking on a yellow tinge due to the "effect and color of the UV absorber." Therefore, the incorporation of a bluing agent is extremely effective in imparting a natural transparency to lenses.

The amount of bluing agent added is preferably 0.05 to 1.5 ppm, and more preferably 0.1 to 1.2 ppm, per 100 parts by weight of resin.

<Optical lenses>
The polyester resin or polyester carbonate resin of the present invention is suitable for optical members, particularly optical lenses.

When optical lenses made from the polyester resin or polyester carbonate resin of the present invention are manufactured by injection molding, molding is preferably performed under conditions of a cylinder temperature of 230 to 350°C and a mold temperature of 70 to 180°C. More preferably, molding is performed under conditions of a cylinder temperature of 250 to 300°C and a mold temperature of 80 to 170°C. If the cylinder temperature is higher than 350°C, the resin will decompose and discolor, and if it is lower than 230°C, the melt viscosity will be high, making molding difficult. Furthermore, if the mold temperature is higher than 180°C, it will be difficult to remove a molded piece made of the resin from the mold. On the other hand, if the mold temperature is lower than 70°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 fully transfer the shape applied to the mold.

The optical lens of the present invention is preferably implemented in the form of an aspherical lens, if necessary. Because a single aspherical lens can eliminate spherical aberration, there is no need to combine multiple spherical lenses to eliminate spherical aberration, which allows for weight reduction and reduced molding costs. Therefore, aspherical lenses are particularly useful as camera lenses, among other optical lenses.

Furthermore, because the polyester resin or polyester carbonate resin 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. Specific lens sizes include 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. Furthermore, the diameter is 1.0 mm 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 convex surface and one concave surface.

The optical lens of the present invention, which is made of polyester resin or polyester carbonate resin, can be formed by any method, such as mold molding, cutting, polishing, laser processing, electrical discharge processing, or etching. Of these, mold molding is more preferable in terms of manufacturing costs.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
(1) Copolymerization ratio: After the polymerization was completed, the resin obtained was subjected to ¹ H NMR measurement using JNM-ECZ400S/L1 manufactured by JEOL Ltd. to determine the copolymerization ratio.
(2) Specific viscosity: After the polymerization was completed, the resin obtained was thoroughly dried, and 0.7 g of the resin was dissolved in 100 mL of methylene chloride to measure the specific viscosity (η _sp ) of the solution at 20° C. In this measurement, the transit time between the marked lines of an Ostwald viscosity tube was measured in a thermostatic bath at 20±0.01° C., and the specific viscosity (η _sp ) of the solution at 20° C. was calculated using the following formula:
η _sp = (t ₁ - _{t 0} )/t ₀
t ₁ : Passage time of resin solution between the gauge lines t ₀ : Passage time of methylene chloride between the gauge lines

(3) Amount of Terminal Carboxylic Acid Under a nitrogen atmosphere, 0.1 g of resin was completely dissolved in 10 mL of methylene chloride at 25°C, and then 3 mL of acetone was added to the resulting mixture, which was then titrated to measure the number of terminal carboxylic acid groups (equivalents/ton) as the number of equivalents per ton of resin. Phenol red was used as an indicator.
(4) Glass transition temperature (Tg): The resin obtained after melt-kneading was measured by a DSC-60A manufactured by Shimadzu Corporation at a temperature rise rate of 20° C./min.
(5) Refractive index (nD): 3 g of the obtained resin was dissolved in 50 mL of methylene chloride, cast onto a glass petri dish, and thoroughly dried at room temperature, followed by drying for 8 hours at a temperature of 120°C or lower to prepare a film with a thickness of approximately 100 μm. The refractive index (wavelength: 589 nm) and Abbe number (calculated using the following formula from the refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm) of this film were measured using an ATAGO DR-M2 Abbe refractometer.
ν=(nD-1)/(nF-nC)
In the present invention,
nD: refractive index at a wavelength of 589 nm,
nC: refractive index at a wavelength of 656 nm,
nF: refers to the refractive index at a wavelength of 486 nm.

(6) Absolute value of orientation birefringence (|Δn|): The 100 μm thick film prepared in (5) was stretched twice in one direction at Tg+10° C., and the retardation (Re) at 589 nm was measured using an Ellipsometer M-220 manufactured by JASCO Corporation, and the absolute value of orientation birefringence was calculated by the following formula.
|Δn|=|Re/d|
Δn: orientational birefringence
Re: phase difference (nm)
d: thickness (nm)
(7) Color: 1.0 g of the obtained resin was dissolved in 5 mL of methylene chloride for spectroscopic analysis, and the b ^* value (yellowness) of the solution was measured using a spectrophotometer U-3310 manufactured by Hitachi.
(8) Moisture and heat resistance: The obtained resin pellets were treated in an environment of 85°C and 85% relative humidity for 500 hours, and the moisture and heat resistance was evaluated according to the following formula.
Moisture and heat resistance (%) = [specific viscosity of resin after treatment] / [specific viscosity of resin before treatment] × 100
(9) Moldability: After vacuum drying the resin pellets at 120°C for 8 hours, lenses with a thickness of 0.3 mm, a convex radius of curvature of 5 mm, a concave radius of curvature of 4 mm, and a diameter of 5 mm were injection molded using an SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. at a molding temperature of Tg+110°C and a mold temperature of Tg-10°C. 500 lenses were molded and visually evaluated for filling defects, molding defects, mold deposits, etc., and the moldability was evaluated as follows: if the probability of defective products was less than 5%, moldability was evaluated as ◯; if it was 5% or more but less than 20%, moldability was evaluated as △; and if it was 20% or more, moldability was evaluated as ×.

[Example 1]
53.3 parts by mass of 2,2'-bis(ethoxycarboxymethoxy)-1,1'-binaphthyl (hereinafter sometimes abbreviated as BECMB), 31.4 parts by mass of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (hereinafter sometimes abbreviated as BNEF), 21.8 parts by mass of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (hereinafter sometimes abbreviated as BHEB), and 4.0 × 10 tetrabutoxytitanium(IV) ^Three parts by mass of the raw materials were placed in a reactor equipped with a stirrer and a distillation device. After three nitrogen substitutions, the jacket was heated to 200°C to melt the raw materials. After complete dissolution, the pressure was reduced to 40 kPa over 20 minutes. The jacket was then heated to 260°C at a rate of 60°C/hr to carry out a transesterification reaction. Subsequently, while maintaining the jacket at 260°C, the pressure was reduced to 0.13 kPa over 50 minutes, and a polymerization reaction was carried out until a predetermined stirring torque was reached under conditions of 260°C and 0.13 kPa or less. After completion of the reaction, the resulting resin was pelletized and extracted to obtain polyester resin pellets. The resulting polyester resin was analyzed by ^1H NMR, and it was confirmed that 50 mol% of the BECMB component, 25 mol% of the BNEF component, and 25 mol% of the BHEB component were incorporated relative to the total monomer components. The evaluation results of the resulting polyester resin are listed in Table 1.

[Example 2]
57.5 parts by mass of BECMB, 33.8 parts by mass of BNEF, 14.1 parts by mass of BHEB, 16.0 parts by mass of ethylene glycol (hereinafter sometimes abbreviated as EG), and 4.3 x 10 ^-3 parts by mass of tetrabutoxytitanium (IV) were placed in a reactor equipped with a stirrer and a distillation device, and the same procedure as in Example 1 was then carried out to obtain polyester resin pellets. It was confirmed that the obtained polyester resin contained 50 mol% of the BECMB component, 25 mol% of the BNEF component, 15 mol% of the BHEB component, and 10 mol% of the EG component. The evaluation results of the obtained polyester resin are shown in Table 1.

[Example 3]
Polyester resin pellets were obtained in the same manner as in Example 1, except that the amounts of BECMB, BNEF, BHEB, and tetrabutoxytitanium (IV) were changed to 51.4 parts by mass, 42.3 parts by mass, 12.6 parts by mass, and 3.8 x ^{10 parts} by mass, respectively. It was confirmed that the resulting polyester resin contained 50 mol% of the BECMB component, 35 mol% of the BNEF component, and 15 mol% of the BHEB component. The evaluation results of the resulting polyester resin are shown in Table 1.

[Example 4]
44.4 parts by mass of BECMB, 36.0 parts by mass of BNEF, 25.0 parts by mass of BHEB, and 8.7 parts by mass of diphenyl carbonate (hereinafter sometimes abbreviated as DPC) were placed in a reactor equipped with a stirrer and a distillation device, and after nitrogen substitution three times, the jacket was heated to 200°C to melt the raw materials. After complete dissolution, the pressure was reduced to 40 kPa over 20 minutes. The jacket was heated to 260°C at a rate of 60°C/hr, and then, while maintaining the jacket at 260°C, the pressure was reduced to 26 kPa over 20 minutes. Thereafter, 22.4 × ^10-3 parts by mass of aluminum acetylacetonate (hereinafter sometimes abbreviated as Al(acac) ₃ ), 3.5
49.3 x 10 ^-3 parts by mass of diethyl 4-di-tert-butyl-hydroxybenzylphosphonate (hereinafter sometimes abbreviated as DEBHBP) was added to the reactor. Thereafter, while maintaining the jacket at 260°C, the pressure was reduced to 0.13 kPa over 70 minutes, and a polymerization reaction was carried out under conditions of 260°C and 0.13 kPa or less until a predetermined stirring torque was reached. After completion of the reaction, the produced resin was pelletized and extracted to obtain polyester carbonate resin pellets. It was confirmed that the resulting polyester carbonate resin contained 42 mol% of the BECMB component, 29 mol% of the BNEF component, and 29 mol% of the BHEB component. The evaluation results of the resulting polyester carbonate resin are shown in Table 1.

[Example 5]
Polyester carbonate resin pellets were obtained in the same manner as in Example 4, except that the amounts of BECMB, BNEF, BHEB, DPC, Al(acac) ₃ , and DEBHBP were changed to 50.1 parts by mass, 19.6 parts by mass, 36.4 parts by mass, 5.7 parts by mass, 23.6 x ^10-3 parts by mass, and 52.0 x ^10-3 parts by mass, respectively. It was confirmed that the resulting polyester carbonate resin contained 45 mol% of the BECMB component, 15 mol% of the BNEF component, and 40 mol% of the BHEB component. The evaluation results of the resulting polyester carbonate resin are shown in Table 1.

[Example 6]
Polyester carbonate resin pellets were obtained in the same manner as in Example 4, except that the amounts of BECMB, BNEF, BHEB, DPC, Al(acac) ₃ , and DEBHBP were 48.2 parts by mass, 31.5 parts by mass, 26.2 parts by mass, 5.5 parts by mass, 22.7 x ^10-3 parts by mass, and 50.0 x ^10-3 parts by mass, respectively. It was confirmed that the resulting polyester carbonate resin contained 45 mol% of the BECMB component, 25 mol% of the BNEF component, and 30 mol% of the BHEB component. The evaluation results of the resulting polyester carbonate resin are shown in Table 1.

[Example 7]
Polyester carbonate resin pellets were obtained in the same manner as in Example 4, except that the amounts of BECMB, BNEF, BHEB, DPC, Al(acac) ₃ , and DEBHBP were changed to 45.6 parts by mass, 47.6 parts by mass, 5.2 parts by mass, 21.5 x ^10-3 parts by mass, and 47.2 x ^10-3 parts by mass, respectively. It was confirmed that the resulting polyester carbonate resin contained 45 mol% of the BECMB component, 40 mol% of the BNEF component, and 15 mol% of the BHEB component. The evaluation results of the resulting polyester carbonate resin are shown in Table 1.

[Comparative Example 1]
Polyester resin pellets were obtained by the same procedure as in Example 1, except that 46.8 parts by mass of 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl (hereinafter sometimes abbreviated as BCMB) was used instead of BECMB in Example 1. The obtained polyester resin was analyzed by ^1H NMR, and it was confirmed that the BCMB component, BNEF component, and BHEB component were incorporated in amounts of 50 mol%, 25 mol%, and 25 mol%, respectively, based on the total monomer components. The evaluation results of the obtained polyester resin are shown in Table 1.

[Comparative Example 2]
Polyester resin pellets were obtained by the same procedure as in Example 2, except that 50.5 parts by mass of BCMB was used instead of the BECMB used in Example 2. It was confirmed that the resulting polyester resin contained 50 mol % of BCMB, 25 mol % of BNEF, 15 mol % of BHEB, and 10 mol % of EG. The evaluation results of the resulting polyester resin are shown in Table 1.

[Comparative Example 3]
Polyester resin pellets were obtained by using 45.1 parts by mass of BCMB instead of BECMB in Example 3. It was confirmed that the resulting polyester resin contained 50 mol % of BCMB, 35 mol % of BNEF, and 15 mol % of BHEB. The evaluation results of the resulting polyester resin are shown in Table 1.

[Comparative Example 4]
Polyester carbonate resin pellets were obtained by the same procedure as in Example 4, except that 39.0 parts by mass of BCMB was used instead of the BECMB used in Example 4. It was confirmed that the resulting polyester carbonate resin contained 42 mol% of BCMB, 29 mol% of BNEF, and 29 mol% of BHEB. The evaluation results of the resulting polyester carbonate resin are shown in Table 1.

[Comparative Example 5]
Polyester carbonate resin pellets were obtained by the same procedure as in Example 7, except that 40.0 parts by mass of BCMB was used instead of BECMB. It was confirmed that the resulting polyester carbonate resin contained 45 mol % of BCMB, 40 mol % of BNEF, and 15 mol % of BHEB. The evaluation results of the resulting polyester carbonate resin are shown in Table 1.

The polyester resins or polyester carbonate resins obtained in Examples 1 to 7 have physical properties such as refractive index, Abbe number, and heat resistance equivalent to those of Comparative Examples 1 to 5. The amount of terminal carboxylic acid is 0.8 equivalents/ton or less, and it can be confirmed that the color and moist heat resistance are superior to those of Comparative Examples 1 to 5.

The polyester resin or polyester carbonate resin of the present invention is used in optical materials and can be used for optical components such as lenses, prisms, optical disks, transparent conductive substrates, optical cards, sheets, films, optical fibers, optical films, optical filters, and hard coat films, and is particularly useful for lenses.

Claims (18)

A polyester carbonate resin comprising a compound represented by formula (a), a compound represented by formula (b), a compound represented by formula (c), and repeating units derived from a carbonate-forming derivative, the polyester carbonate resin comprising repeating units represented by the following formulas (1) and (2), wherein the ratio of the repeating units represented by formula (1) to the repeating units represented by formula (2) is 15:85 to 85:15, and the amount of terminal carboxylic acid is 0.8 equivalents/ton or less.

(In formula (a), rings Z ¹ and Z ² each represent a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms; R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ³ to R ⁶ each represent a hydrogen atom or an aliphatic or aromatic substituent; j and k each independently represent an integer of 0 or greater; and m, n, p, and q each independently represent 1 or 2.)
(In formula (b), R ¹⁷ and R ¹⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ¹⁹ to R ²⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; and t and u each independently represent an integer of 0 or greater.)
(In formula (c), R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ⁹ to R ¹⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; r and s each independently represent an integer of 0 or greater; and R ²⁷ and R ²⁸ each independently represent a methyl group, an ethyl group, or a phenyl group.)
(In the formula, rings Z ¹ and Z ² each represent a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms; R ¹ , R ² , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ³ to R ⁶ and R ⁹ to R ¹⁶ each represent a hydrogen atom or an aliphatic or aromatic substituent; j, k, r and s each independently represent an integer of 0 or greater; and m, n, p and q each independently represent 1 or 2.)
(In the formula, R ⁷ , R ⁸ , R ¹⁷ and R ¹⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ⁹ to R ¹⁶ and R ¹⁹ to R ²⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; and r, s, t and u each independently represent an integer of 0 or greater.) 2. The polyester carbonate resin according to claim 1, wherein ^Z1 and ^Z2 in the formula (1) are naphthalenediyl groups. The polyester carbonate resin according to claim 1, wherein the formula (1) comprises a unit represented by the following formula (3):
(In the formula, R ¹ , R ² , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ³ to R ⁶ and R ⁹ to R ¹⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; j, k, r and s each independently represent an integer of 0 or greater; and m, n, p and q each independently represent 1 or 2.) The polyester carbonate resin according to claim 3, wherein the formula (3) is the following formula (4):
(In the formula, R ¹ , R ² , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group.) 5. The polyester carbonate resin according to claim 3, wherein R ¹ and R ² in the formula (3) or (4) are ethylene groups, and R ⁷ and R ⁸ are methylene groups. The polyester carbonate resin according to any one of claims 1 to 5, wherein the repeating units represented by formula (1) account for 20 mol% or more of all repeating units. 7. The polyester carbonate resin according to claim 1, wherein R ⁹ to R ¹⁶ and R ¹⁹ to R ²⁶ in the formula (2) are hydrogen atoms, and r, s, t, and u are each 1. 8. The polyester carbonate resin according to claim 1, wherein R ⁷ and R ⁸ in the formula (2) are methylene groups, and R ¹⁷ and R ¹⁸ are ethylene groups. The polyester carbonate resin according to any one of claims 1 to 8, wherein the repeating units represented by formula (2) account for 20 mol% or more of all repeating units. The polyester carbonate resin according to any one of claims 1 to 9, wherein the ratio of the repeating units represented by formula (1) to the repeating units represented by formula (2) is 25:75 to 75:25. The polyester carbonate resin according to any one of claims 1 to 10, having a specific viscosity of 0.12 to 0.40 measured in a solution dissolved in methylene chloride at 0.53% by mass. The polyester carbonate resin according to any one of claims 1 to 11, having a refractive index of 1.675 to 1.695. The polyester carbonate resin according to any one of claims 1 to 12, having a glass transition temperature of 140 to 155°C. The polyester carbonate resin according to any one of claims 1 to 13, wherein the absolute value of birefringence at 20°C and a wavelength of 589 nm in a film stretched to 2 times its original size at a temperature 10°C higher than the glass transition temperature is 0.001 x ^10-3 to 5.0 x ^10-3 . The polyester carbonate resin according to any one of claims 1 to 14, wherein 1.0 g of the resin is dissolved in 5 mL of methylene chloride for spectroscopic analysis, and the b ^* value of the solution measured using the CIE 1976 (L ^* a ^* b ^* ) color system is 3.0 or less. A method for producing a polyester carbonate resin, characterized by reacting compounds represented by the following formulas (a), (b), and (c) as raw materials with a carbonate-forming derivative by melt polymerization , the method for producing a polyester carbonate resin containing repeating units represented by the following formulas (1) and (2), the ratio of the repeating units represented by the following formula (1) to the repeating units represented by the following formula (2) being 15:85 to 85:15, and the amount of terminal carboxylic acid being 0.8 equivalents/ton or less .
(In the formula, rings Z ¹ and Z ² each represent a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms; R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ³ to R ⁶ each represent a hydrogen atom or an aliphatic or aromatic substituent; j and k each independently represent an integer of 0 or greater; and m, n, p, and q each independently represent 1 or 2.)
(In the formula, R ¹⁷ and R ¹⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ¹⁹ to R ²⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; and t and u each independently represent an integer of 0 or greater.)
(In the formula, R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ⁹ to R ¹⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; r and s each independently represent an integer of 0 or greater; and R ²⁷ and R ²⁸ each independently represent a methyl group, an ethyl group, or a phenyl group.)
(In the formula, rings Z ¹ and Z ² each represent a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms; R ¹ , R ² , R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ³ to R ⁶ and R ⁹ to R ¹⁶ each represent a hydrogen atom or an aliphatic or aromatic substituent; j, k, r and s each independently represent an integer of 0 or greater; and m, n, p and q each independently represent 1 or 2.)
(In the formula, R ⁷ , R ⁸ , R ¹⁷ and R ¹⁸ each independently represent a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; R ⁹ to R ¹⁶ and R ¹⁹ to R ²⁶ each independently represent a hydrogen atom or an aliphatic or aromatic substituent; and r, s, t and u each independently represent an integer of 0 or greater.) An optical component made from the polyester carbonate resin described in any one of claims 1 to 15. The optical element according to claim 17, which is an optical lens.