Polyester resin or polyester carbonate resin, and optical member using said resin

Abstract

To provide a polyester resin or polyester carbonate resin that has high refractive index, low birefringence, and excellent balance between heat resistance and moldability, as well as excellent color tone and moist heat resistance.SOLUTION: Provided is a polyester resin or a polyester carbonate resin that contains repeating unit typified by bishydroxynaphthylfluorene type monomer and bishydroxybinaphthyl type monomer, the ratio of these repeating units is 15:85 to 85:15, and the amount of terminal carboxylic acid is 0.8 equivalent / ton or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] 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, and further has excellent hue and moist heat resistance. [Background technology]

[0002] Imaging modules are used in cameras, video cameras, camera-equipped mobile phones, videophones, camera-equipped door phones, and the like. In recent years, there has been a particular demand for miniaturization of the optical systems used in these imaging 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.

[0003] Glass, which has traditionally been used as a material for optical systems, is capable of achieving various required optical properties and has excellent environmental resistance, but suffers from poor processability. In response to this, resins, which are less expensive and more processable than glass materials, have been used for optical components. Resins having a fluorene skeleton or a binaphthalene skeleton are particularly popular due to their high refractive index.

[0004] To achieve a high refractive index, polyester or polyester carbonate, which has less oxygen in the condensed portion, is more effective than polycarbonate.

[0005] In order to make a polyester resin or polyester carbonate resin have a high refractive index, it is necessary that both the monomers used in the diol portion and the carboxylic acid portion of the resin have a high refractive index.

[0006] It has been reported that high refractive index resins can be obtained by using a substance having a binaphthalene skeleton as the dicarboxylic acid moiety that constitutes the high refractive index resin. Among them, 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.

[0007] 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 having 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.

[0008] To solve these problems, Patent Document 5 describes a resin containing a specific 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. The terminal carboxylic acid has a negative effect on dry heat resistance and color. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 2017-171885 [Patent Document 2] Japanese Patent Application Publication No. 2018-002895 [Patent Document 3] Japanese Patent Application Publication No. 2018-002894 [Patent Document 4] Japanese Patent Application Publication No. 2018-002893 [Patent Document 5] International Publication No. 2019 / 176874 Summary of the Invention [Problem to be solved by the invention]

[0010] SUMMARY OF THE INVENTION An object of the present invention is to provide a polyester resin or polyester carbonate resin which has a high refractive index, low birefringence, and an excellent balance between heat resistance and moldability, and which also has excellent hue and moist heat resistance. [Means for solving the problem]

[0011] As a result of extensive research conducted by the inventors in order to achieve this objective, they discovered that polyester resins or polyester carbonate resins having a fluorene skeleton and a binaphthyl skeleton to which specific aromatic groups have been introduced, and further having a very low amount of terminal carboxylic acid, have a high refractive index and low birefringence, a high balance between heat resistance and moldability, and excellent hue and moist heat resistance, and thus arrived at the present invention.

[0012] 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.

[0013] [ka]

[0014] (In the formula, ring Z 1 , Z 2 each represents a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms, and R 1 , R 2 , R 7 and R 8each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and R 3 ~R 6 , R 9 ~R 16 represents 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.

[0015] [ka]

[0016] (In the formula, R 7 , R 8 , R 17 and R 18 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and R 9 ~R 16 , R 19 ~R 26 represents a hydrogen atom or an aliphatic or aromatic substituent, and r, s, t, and u each independently represent an integer of 0 or greater.

[0017] 2. Z in the formula (1) 1 and Z 2 2. The polyester resin or polyester carbonate resin according to 1 above, wherein is a naphthalenediyl group. 3. The polyester resin or polyester carbonate resin according to item 1 above, wherein the formula (1) comprises a unit represented by the following formula (3):

[0018] [ka]

[0019] (In the formula, R 1 , R 2 , R 7 and R 8 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and R 3 ~R 6 , R9 ~R 16 represents 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.

[0020] 4. The polyester resin or polyester carbonate resin according to 3 above, wherein the formula (3) is the following formula (4):

[0021] [ka]

[0022] (In the formula, R 1 , R 2 , R 7 and R 8 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group.

[0023] 5. R in the formula (3) or (4) 1 , R 2 is an ethylene group, R 7 and R 8 5. The polyester resin or polyester carbonate resin according to 3 or 4 above, wherein is a methylene group. 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. R in the formula (2) 9 ~R 16 , R 19 ~R 26 7. The polyester resin or polyester carbonate resin according to any one of 1 to 6 above, wherein is a hydrogen atom, and r, s, t and u are each 1. 8. R in the above formula (2) 7 , R 8 is a methylene group, R 17 and R 18 8. The polyester resin or polyester carbonate resin according to any one of 1 to 7 above, wherein is an ethylene group. 9. The polyester resin or polyester carbonate resin according to any one of the above items 1 to 8, wherein the repeating units represented by the formula (2) account for 20 mol % or more of all repeating units. 10. The polyester resin or polyester carbonate resin according to any one of 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 polyester carbonate resin according to any one of 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 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 absolute value of birefringence at 20°C and a wavelength of 589 nm for 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 ~5.0×10 -3 14. The polyester resin or polyester carbonate resin according to any one of 1 to 13 above, wherein 15. 1.0 g of the resin was dissolved in 5 mL of methylene chloride for spectroscopic analysis, and the solution was measured using CIE 1976 (L * a * b * ) color system b * 15. The polyester resin or polyester carbonate resin according to any one of items 1 to 14, wherein the value is 3.0 or less. 16. The polyester resin or polyestercarbonate resin according to any one of items 1 to 15, characterized in that the 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:

[0024] [ka]

[0025] (In the formula, ring Z 1 , Z 2 each represents a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms, and R 1 , R 2 are each independently a hydrocarbon having 1 to 12 carbon atoms which may contain an aromatic group. represents a group, and R 3 ~R 6 represents 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.

[0026] [ka]

[0027] (In the formula, R 17 , R 18 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and R 19 ~R 26 represents a hydrogen atom or an aliphatic or aromatic substituent, and t and u each independently represent an integer of 0 or greater.

[0028] [ka]

[0029] (In the formula, R 7 , R 8 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and R 9 ~R 16 represents a hydrogen atom or an aliphatic or aromatic substituent, r and s each independently represent an integer of 0 or more, and R 27 , R 28 represents a methyl group, an ethyl group, or a phenyl group.

[0030] 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 element according to 17 above, which is an optical lens. [Effects of the Invention]

[0031] 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 further has excellent hue and moist heat resistance, so that it has exceptional industrial effects. DETAILED DESCRIPTION OF THE INVENTION

[0032] The present invention will now be described in more detail.

[0033] <Polyester resin or polyester carbonate resin> The polyester resin or polyester carbonate resin of the present invention is represented by the following formula (1) and 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.

[0034] [ka]

[0035] (In the formula, ring Z 1 , Z 2 each represents a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms, and R 1 , R 2 , R 7 and R 8 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and R 3 ~R 6 , R 9 ~R 16represents 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.

[0036] [ka]

[0037] (In the formula, R 7 , R 8 , R 17 and R 18 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and R 9 ~R 16 , R 19 ~R 26 represents a hydrogen atom or an aliphatic or aromatic substituent, and r, s, t, and u each independently represent an integer of 0 or greater.

[0038] A preferred embodiment of the polyester resin or polyester carbonate resin of the present invention is a polyester resin or polyester carbonate resin represented by the formula (1) above, wherein the ring Z 1 , Z 2 The polycyclic aromatic hydrocarbon group represented by the formula (I) may have 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, with a fused bicyclic hydrocarbon ring having 10 to 16 carbon atoms being 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.

[0039] A preferred embodiment of the polyester resin or polyester carbonate resin of the present invention is a resin having Z in the formula (1). 1 and Z 2 is a naphthalenediyl group.

[0040] In the above formula (1), ring Z 1 , Z2 Examples of the polycyclic aromatic hydrocarbon group represented by the formula A naphthalene-1,4-diyl group or a naphthalene-2,6-diyl group is preferred, and a naphthalene-2,6-diyl group is more preferred.

[0041] In a preferred embodiment of the polyester resin or polyester carbonate resin of the present invention, the formula (1) comprises a unit represented by the following formula (3):

[0042] [ka]

[0043] (In the formula, R 1 , R 2 , R 7 and R 8 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and R 3 ~R 6 , R 9 ~R 16 represents 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.

[0044] R in the formula (3) 3 ~R 6 , R 9 ~R 16 is preferably 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, an aralkyloxy group, or the like, more preferably a hydrogen atom or an aryl group, and even more preferably a hydrogen atom.

[0045] The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or the like.

[0046] Specific preferred examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group, with an alkyl group having 1 to 4 carbon atoms being more preferred, and a methyl group or an ethyl group being even more preferred.

[0047] Specific preferred examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a 4-tert-butylcyclohexyl group, with a cyclohexyl group being more preferred.

[0048] Specific preferred examples of the aryl group include a phenyl group, an alkylphenyl group (a mono- or dimethylphenyl group such as a tolyl group, a 2-methylphenyl group, or a xylyl group), and a naphthyl group, with a phenyl group and a naphthyl group being more preferred, and a phenyl group being even more preferred.

[0049] Specific preferred examples of the aralkyl group include a benzyl group and a phenethyl group, with a benzyl group being more preferred.

[0050] Specific preferred examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group, with an alkoxy group having 1 to 4 carbon atoms being more preferred, and a methoxy group or an ethoxy group being even more preferred.

[0051] 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.

[0052] Specific preferred examples of the aryloxy group include a phenoxy group, an alkylphenoxy group (mono- or dimethylphenoxy group), and a naphthyloxy group, with a phenoxy group and a naphthyloxy group being more preferred, and a phenoxy group being even more preferred.

[0053] Specific preferred examples of the aralkyloxy group include a benzyloxy group and a phenethyloxy group, with a benzyloxy group being more preferred.

[0054] In the formula (3), j, k, r and s each independently represent an integer of 0 or more, preferably 1 or 2, and more preferably 1.

[0055] In the formula (3), m, n, p and q each independently represent 1 or 2, and preferably 1.

[0056] In a preferred embodiment of the polyester resin or polyester carbonate resin of the present invention, the formula (3) comprises a unit represented by the following formula (4):

[0057] [ka]

[0058] R in the formula (4) 1 , R 2 , R 7 , R 8 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and preferred examples thereof include alkylene groups such as methylene, ethylene, propylene, and butylene, and arylene groups such as phenylene and naphthalenediyl. Of these, methylene and ethylene groups are preferred, and R 1 , R 2 is more preferably an ethylene group, and R 7 , R 8 is more preferably a methylene group.

[0059] R in the formula (2) 9 ~R 16 , R 19 ~R 26 is more preferably 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, an aralkyloxy group, and the like, more preferably a hydrogen atom or an aryl group, and even more preferably a hydrogen atom.

[0060] Preferable specific examples of the halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, cycloalkyloxy group, aryloxy group and aralkyloxy group are as described above.

[0061] In the formula (2), r, s, t and u each independently represent an integer of 0 or more, preferably 1 or 2, and more preferably 1.

[0062] R in the formula (2) 7 , R 8 , R 17 , R 18 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and preferred examples thereof include alkylene groups such as methylene, ethylene, propylene, and butylene, and arylene groups such as phenylene and naphthalenediyl. Of these, methylene and ethylene groups are preferred, and R 7 , R 8 is more preferably a methylene group, and R 17 , R 18 is more preferably an ethylene group.

[0063] From the relationship between molecular structure and refractive index, traditionally known as the Lorentz-Lorenz equation, it is known that the refractive index of a substance increases by increasing the electron density of the molecule and decreasing the molecular volume. Based on this theory, resins with fluorene or binaphthalene skeletons have a high refractive index by introducing many aromatic groups into the molecule. However, although these resins have a high refractive index, they lack an adequate balance between birefringence, heat resistance, and moldability.

[0064] The specific ester structure of the present invention represented by formula (1) 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. Thus, 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.

[0065] The composition ratio of the resin in the present invention is expressed as the molar ratio of the monomer structures introduced into the resin based on the number of moles of all monomer units, which does not include the carbonic acid component.

[0066] In the present invention, the repeating unit refers to the minimum unit connected by an ester bond and / or a carbonate bond. The repeating unit of an ester bond refers to a structural unit formed from a diol component and a dicarboxylic acid component, and the repeating unit of a carbonate bond refers to a structural unit formed from a diol derivative and a carbonic acid component.

[0067] The molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (2) in the polyester resin or polyester carbonate resin of the present invention is 15:85 to 85:15.

[0068] The molar ratio of the repeating unit represented by formula (1) to the repeating unit represented by formula (2) is preferably 25:75 to 75:25, more preferably 30:70 to 70:30. When the molar ratio is within the above range, an excellent balance between a high refractive index and birefringence is achieved.

[0069] 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. The specific viscosity within the above range is preferable because it provides an excellent balance between moldability and mechanical strength. The specific viscosity is 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). sp )

[0070] 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.

[0071] The polyester resin or polyester carbonate resin of the present invention has a high refractive index, but preferably 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. .

[0072] 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: Refractive index at a wavelength of 486 nm.

[0073] In a preferred embodiment of the polyester resin or polyester carbonate resin of the present invention, the glass transition temperature (Tg) is preferably 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.

[0074] A preferred embodiment of the polyester resin or polyester carbonate resin of the present invention is The absolute value of orientation birefringence (|Δn|) is preferably 0.001×10 -3 ~10.0×10 -3 , more preferably 0.001 × 10 -3 ~5.0×10 -3 , and more preferably 0.001 × 10 -3 ~4.0×10 -3 , and particularly preferably 0.001 × 10 -3 ~3.5×10 -3 , most preferably 0.001 x 10 -3 ~3.0×10 -3 The range is.

[0075] |Δn| is calculated by the following formula after 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. and measuring the retardation at a wavelength of 589 nm. |Δn| is preferably within the above range because it reduces the optical distortion of the lens.

[0076] |Δn|=|Re / d| Δn: Orientation birefringence Re: Phase difference (nm) d: thickness (nm)

[0077] In a preferred embodiment of the polyester resin or polyester carbonate resin of the present invention, the total light transmittance at a thickness of 1 mm is preferably 80% or more, more preferably 85% or more, and even more preferably 88% or more. When the total light transmittance is within the above range, the resin is suitable for use as an optical component. The total light transmittance was measured using an NDH-300A model manufactured by Nippon Denshoku Industries Co., Ltd. using a molded piece having a thickness of 1 mm.

[0078] A preferred embodiment of the polyester resin or polyester carbonate resin of the present invention is one in which the degree of coloration, particularly yellowness, is light. * a * b * ) color system b * A value of 4.0 or less is preferable. * The 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. * The values ​​were measured using a spectrophotometer in accordance with CIE 1976 (L) for a solution of 1.0 g dissolved in 5 mL of methylene chloride (a solution dissolved in methylene chloride at 13% by mass). * a * b * ) color system values.

[0079] In a preferred embodiment of the polyester resin or polyester carbonate resin of the present invention, the water absorption rate after immersion for 24 hours at 23° C. is preferably 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 small.

[0080] The polyester resin or polyester carbonate resin of the present invention has a terminal carboxylic acid amount of 0.8 equivalents / ton or less, more preferably 0.5 equivalents / ton or less, and even more preferably The terminal carboxylic acid content is 0.3 equivalents / ton or less. When the terminal carboxylic acid content is 0.8 equivalents / ton or less, the terminal carboxylic acid is prevented from acting as a catalyst for the hydrolysis of the ester bond, improving moist heat resistance. Furthermore, the color is improved because the carboxylic acid is prevented from causing decarboxylation or side reactions that would result in the production of colored components. In other words, when the terminal carboxylic acid content is 0.8 equivalents / ton or less, moist heat resistance and color are excellent. 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.

[0081] The moist heat resistance of the polyester resin or polyester carbonate resin of the present invention can be evaluated by subjecting it to a moist heat resistance environment of 85°C and 85% relative humidity for a specified period of time and comparing the specific viscosity of the resin before and after the treatment. Specifically, 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] x 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.

[0082] Specific raw materials used for the polyester resin or polyester carbonate resin of the present invention will be described below.

[0083] <Raw material monomer> (Diol component of the above formula (1)) The diol component serving 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.

[0084] [ka]

[0085] In the formula (a), ring Z 1 , Z 2 each represents a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms, and R1 , R 2 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and R 3 ~R 6 represents a hydrogen atom or an aliphatic or aromatic substituent; j and k each independently represent an integer of 0 or greater; m, n, p, and q each independently represent 1 or 2.

[0086] In the formula (a), Z 1 , Z 2 , R 1 ~R 6 The preferred values ​​of j, k, m, n, p, and q are the same as those of the respective formulae in the formula (1).

[0087] Representative examples of the diol component represented by the formula (a) are shown below, but the raw materials used in the formula (1) of the present invention are not limited to these.

[0088] 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.

[0089] These may be used alone or in combination of two or more.

[0090] (Diol component of the above formula (2)) The diol component serving as the 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.

[0091] [ka]

[0092] In the formula (b), R 17 , R 18 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and R 19 ~R 26 represents a hydrogen atom or an aliphatic or aromatic substituent, and t and u each independently represent an integer of 0 or more.

[0093] In the formula (b), R 17 ~R 26 The preferred values ​​of t and u are the same as those of the respective formulae in the formula (2).

[0094] Representative examples of the diol component represented by the formula (b) are shown below, but the raw materials used in the formula (2) of the present invention are not limited to these.

[0095] Specifically, 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 thereof 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, 2,2'-dihydroxy-7,7'-diphenyl-1,1'-binaphthyl, etc. Among 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.

[0096] These may be used alone or in combination of two or more.

[0097] (Diol Components Other Than Formula (1) and 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.

[0098] 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]diol, and the like. 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.

[0099] (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.

[0100] [ka]

[0101] In the formula (c), R 7 , R 8 each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, and R 9 ~R 16 represents a hydrogen atom or an aliphatic or aromatic substituent, r and s each independently represent an integer of 0 or more, and R 27 , R 28 represents a methyl group, an ethyl group, or a phenyl group.

[0102] In the formula (c), R 7 ~R 16 The preferred values ​​of r and s are the same as those of the respective formulae in the formula (1).

[0103] Representative examples of the dicarboxylic ester represented by the formula (c) are shown below, but the raw materials used in the formula (c) of the present invention are not limited to these.

[0104] Specifically, 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, 2,2'-biphenyldicarboxylic acid , 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, 2,2'-bis(4-methoxycarboxyphenylmethoxy)-1,1'-binaphthyl, and the like are preferred, and 2,2'-bis(ethoxycarboxymethoxy)-1,1'-binaphthyl and 2,2'-bis(methoxycarboxymethoxy)-1,1'-binaphthyl are more preferred.

[0105] In addition, mixed dicarboxylic acid esters, rather than identical 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.

[0106] These may be used alone or in combination of two or more.

[0107] By using a dicarboxylic acid ester as a raw material monomer for the dicarboxylic acid component, the polymer ends in an ester, which reduces the amount of terminal carboxylic acid and reduces the effects of terminal carboxylic acid, such as deterioration of color and moist heat resistance.

[0108] (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.

[0109] Other dicarboxylic acid components 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, 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.

[0110] The method for producing the polyester resin or polyester carbonate resin of the present invention will be described below.

[0111] <Method of manufacturing 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.

[0112] The ethylene glycol component is preferably 0 to 50 mol % relative to the total diol component, which is preferable because the above range provides an excellent balance between heat resistance and moldability.

[0113] 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.

[0114] 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, ammonium compounds, and the like can be used. Catalysts that are typically used in esterification reactions and transesterification reactions, such as thimon compounds, manganese compounds, magnesium compounds, titanium compounds, cobalt compounds, zirconium compounds, etc., 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.

[0115] The amount of polymerization catalyst used is 1 × 10 per mole of all monomer units. -8 ~1×10 -3 Molar ranges are preferred.

[0116] The polyester resin of the present invention may contain a terminal blocking agent for adjusting the molecular weight or improving the thermal stability. Preferred examples of the terminal blocking agent include monofunctional hydroxy compounds, epoxy compounds, oxazoline compounds, isocyanate compounds, carbodiimide compounds, and ketenimine compounds.

[0117] The polyester resin of the present invention may contain a copolymerization component other than the diol component and the dicarboxylic ester.

[0118] <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.

[0119] The reaction by the melt polymerization method is usually a transesterification reaction between a diol component, a dicarboxylic acid ester, and a carbonate-forming derivative, and is carried out by mixing the diol component, the dicarboxylic acid ester, and the carbonate-forming derivative with heating in the presence of an inert gas, and distilling off the resulting alcohol and hydroxy compounds such as phenol.

[0120] 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.

[0121] In the initial stage of the reaction, it is preferable to carry out the reaction at a relatively low temperature of about 180 to 220° C. to distill off low molecular weight alcohols. If the distillation column has a reflux device, the reflux ratio can be increased to selectively distill off low molecular weight alcohols.

[0122] Preferred examples of carbonate-forming derivatives include esters of optionally substituted aryl groups or aralkyl groups having 6 to 10 carbon atoms, or alkyl groups having 1 to 4 carbon atoms. Specific preferred 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.

[0123] 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, alkali metal and alkaline earth metal alkoxides, and alkali metal and alkaline earth metal alkoxides are usable. Catalysts typically used in esterification reactions and transesterification reactions can be preferably used, such as organic acid salts of 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, zirconium compounds, etc. Among these, aluminum, tin, titanium, and germanium compounds are more preferred, with aluminum compounds being even more preferred, from the viewpoint of the melt stability and color of the resin.

[0124] The catalyst may be used alone or in combination of two or more kinds, or may be used in combination with another compound as a co-catalyst. The amount of these polymerization catalysts used is 1 × 10 per mole of the total of all monomer units. -8 ~1×10 -3 Molar ranges are preferred.

[0125] Aluminum or a compound thereof preferably used as a catalyst has catalytic activity for polymerizing polyester carbonate resins by transesterification, particularly acting as a catalyst for the carbonate-forming reaction in polymerization using a diol component, a dicarboxylic acid component, and a carbonate-forming derivative as raw material monomers.

[0126] Preferred examples of such aluminum or compounds thereof include metallic aluminum, aluminum salts, aluminum chelate compounds, organic aluminum compounds, and inorganic aluminum compounds.

[0127] Preferred examples of aluminum salts include organic and inorganic salts of aluminum. Preferred examples of organic 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. Preferred examples of inorganic salts of aluminum include aluminum chloride, aluminum hydroxide, aluminum carbonate, aluminum phosphate, and aluminum phosphonate.

[0128] Preferred examples of the aluminum chelate compound include aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, and aluminum ethylacetoacetate di-isopropoxide.

[0129] Preferred examples of the organic aluminum compound include aluminum alkoxides such as trialkylaluminum, dialkylaluminum alkoxides, alkylaluminum dialkoxides, aluminum trialkoxides, and hydrolysates thereof, and specific examples thereof include aluminum alkoxides such as aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, and aluminum tert-butoxide, trimethylaluminum, triethylaluminum, and hydrolysates thereof. Preferred examples of the inorganic aluminum compound include aluminum oxide.

[0130] In particular, aluminum carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are more preferred.

[0131] These aluminum compounds may be used in combination with other compounds as co-catalysts. In particular, phosphorus compounds are used to prevent the reaction of aluminum or its compounds with the polyester carbonate resin in the polymerization reaction. The catalytic activity of the material can be improved.

[0132] 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, and phosphonic acid compounds are particularly more preferred.

[0133] 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 thereof 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, of which 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 are more preferred.

[0134] The ratio of the amount of the phosphorus compound used to the amount of aluminum or a compound thereof 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, in molar ratio.

[0135] The form of the catalyst when added is not particularly limited, and it may be added to the monomer in the form of a powder or the like, or in the form of a dispersion or solution in a solvent. Also, a mixture of aluminum or a compound thereof and a phosphorus compound may be added in advance, or aluminum or a compound thereof and a phosphorus compound may be added separately.

[0136] The polyester carbonate resin of the present invention may contain a copolymer component of a diol component other than a diol component and a dicarboxylic acid or an ester-forming derivative thereof.

[0137] <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.

[0138] 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.

[0139] Furthermore, even if the phenol content is adjusted after the polyester carbonate resin of the present invention is obtained, For example, a method of dissolving the polyester carbonate resin of the present invention in an organic solvent and washing the organic solvent layer with water, or a method of removing volatile components by 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 may be used.

[0140] The residual phenol content in the polyester carbonate resin of the present invention can improve molding flowability without impairing heat resistance. However, if it is higher than 500 ppm, the thermal stability when heated and melted is poor and mold contamination during resin injection molding is severe, which is undesirable. Furthermore, phenol has the property of becoming discolored when oxidized, which deteriorates the color of the polyester carbonate resin. Also, if it is less than 1 ppm, molding flowability is poor, which is undesirable.

[0141] (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, still more preferably 1 to 100 ppm, and particularly preferably 1 to 50 ppm.

[0142] If the content of residual fluorenone in the polyester resin or polyester carbonate resin of the present invention is higher than 500 ppm, the resin will be significantly colored, which is undesirable.

[0143] <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.

[0144] The release agent is preferably one that comprises 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 complete 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 complete ester of a polyhydric alcohol and fatty acid is preferably a partial or complete 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, isopropyl palmitate, etc., with stearyl stearate being preferred.

[0145] 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 preferably used.

[0146] 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.

[0147] The release agent to be blended in 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.

[0148] Examples of the heat stabilizer include phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and hindered phenol-based heat stabilizers. Trivalent phosphorus compounds are preferred because they have an antioxidant effect in addition to their heat stabilizing effect.

[0149] Examples of phosphorus-based heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, 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, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl 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 phosphates 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.

[0150] 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 preferably used 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.

[0151] The content of the phosphorus-based heat stabilizer is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the resin.

[0152] Sulfur-based heat stabilizers include pentaerythritol-tetrakis(3-laurylthiopropionate) and pentaerythritol-tetrakis(3-myristylthiopropionate). ), pentaerythritol-tetrakis(3-stearylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc. Among these, pentaerythritol-tetrakis(3-laurylthiopropionate), pentaerythritol-tetrakis(3-myristylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate are preferred. Pentaerythritol-tetrakis(3-laurylthiopropionate) is particularly preferred.

[0153] The content of the sulfur-based heat stabilizer is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the resin.

[0154] Hindered phenolic 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, and 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.

[0155] The content of the hindered phenol-based heat stabilizer is preferably 0.001 to 0.3 parts by weight relative to 100 parts by weight of the resin.

[0156] The phosphorus-based heat stabilizer and the hindered phenol-based heat stabilizer can also be used in combination.

[0157] The ultraviolet absorber is preferably 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.

[0158] 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.

[0159] Benzophenone-based ultraviolet absorbers include 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0160] Triazine-based UV 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.

[0161] As the cyclic iminoester-based ultraviolet absorber, 2,2'-p-phenylenebis(3,1-benzoxazin-4-one) is particularly suitable.

[0162] Examples of cyanoacrylate ultraviolet 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.

[0163] The amount of ultraviolet absorber to be added is preferably 0.01 to 3.0 parts by weight per 100 parts by weight of resin, and within this range of addition, it is possible to impart sufficient weather resistance to the resin molded product depending on the application.

[0164] Examples of bluing agents include Bayer's Macrolex Violet B and Macrolex Blue RR, and Clariant's Polythremble 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.

[0165] The blending amount of the bluing agent is preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm, based on 100 parts by weight of the resin.

[0166] <Optical lenses> The polyester resin or polyester carbonate resin of the present invention is suitable for optical members, particularly optical lenses.

[0167] When an optical lens made of the polyester resin or polyester carbonate resin of the present invention is produced 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 sufficiently transfer the shape of the molded piece.

[0168] The optical lens of the present invention is preferably implemented as an aspherical lens, if necessary. Since a single aspherical lens can substantially eliminate spherical aberration, it is not necessary 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.

[0169] Furthermore, the polyester resin or polyester carbonate resin of the present invention has high molding fluidity and is therefore 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 shape of the lens is a meniscus lens with one convex surface and one concave surface. It is preferable that there is.

[0170] The optical lens of the present invention made of polyester resin or polyester carbonate resin is formed by any method such as mold molding, cutting, polishing, laser processing, electrical discharge processing, etching, etc. Among these, mold molding is more preferred from the viewpoint of production costs. [Example]

[0171] The present invention will be further described below with reference to examples, but the present invention is not limited thereto. (1) Copolymerization ratio: After polymerization, the resin obtained was mixed with JNM-ECZ400S / L1 manufactured by JEOL Ltd. 1 1 H NMR was measured. (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 obtain a solution, and the specific viscosity (η sp In this measurement, the time it took for the solution to pass between the marked lines of an Ostwald viscosity tube in a thermostatic bath at 20±0.01°C was measured, and the specific viscosity (ηsp ) was sought. η sp =(t1-t0) / t0 t1: Passage time of resin solution between the gauge lines t0: Time for methylene chloride to pass between the gauge lines

[0172] (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. The resulting mixture was titrated to measure the number of carboxylic acid end groups (equivalents / ton) as 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 with 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. After that, it was dried at a temperature of 120°C or less for 8 hours to produce 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: Refractive index at a wavelength of 486 nm.

[0173] (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 phase difference (Re) at 589 nm was measured using an Ellipsometer M-220 manufactured by JASCO Corporation. The absolute value of orientation birefringence was calculated using the following formula. |Δn|=|Re / d| Δn: Orientation birefringence Re: Phase difference (nm) d: thickness (nm) (7) Color: Dissolve 1.0 g of the obtained resin in 5 mL of methylene chloride for spectroscopic analysis. * The value (yellowness) was measured using a Hitachi U-3310 spectrophotometer. (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 using the following formula. Moisture and heat resistance (%) = [specific viscosity of resin after treatment] / [specific viscosity of resin before treatment] x 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 curvature radius of 5 mm, a concave curvature radius 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 good; if it was 5% or more but less than 20%, moldability was evaluated as fair; and if it was 20% or more, moldability was evaluated as bad.

[0174] [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) -3 The mass parts 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 then heated to 260°C at a rate of 60°C / hr to carry out an ester exchange reaction. Then, 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 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 resin pellets. The resulting polyester resin was 1Analysis by H NMR confirmed that the BECMB component, BNEF component, and BHEB component were incorporated at 50 mol%, 25 mol%, and 25 mol%, respectively, relative to the total monomer components. The evaluation results of the obtained polyester resin are shown in Table 1.

[0175] [Example 2] BECMB 57.5 parts by mass, BNEF 33.8 parts by mass, BHEB 14.1 parts by mass, ethylene glycol (hereinafter sometimes abbreviated as EG) 16.0 parts by mass, tetrabutoxytitanium(IV) 4.3 x 10 -3 The resulting mixture was 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 resulting polyester resin contained 50 mol% of BECMB components, 25 mol% of BNEF components, 15 mol% of BHEB components, and 10 mol% of EG components. The evaluation results of the resulting polyester resin are shown in Table 1.

[0176] [Example 3] 51.4 parts by mass of BECMB of Example 1, 42.3 parts by mass of BNEF, 12.6 parts by mass of BHEB, 3.8 × 10 tetrabutoxytitanium (IV) -3 Polyester resin pellets were obtained in the same manner as in Example 1, except that the amounts were changed to parts by mass. 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.

[0177] [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 and the raw materials were melted. 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. Then, 22.4 x 10% aluminum acetylacetonate (hereinafter sometimes abbreviated as Al(acac)3) was added. -3 Parts by mass, 3,5 -Di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester (hereinafter abbreviated as DEBHBP) 49.3 × 10 -3 Parts by mass were added to the reactor. Then, while the jacket was maintained at 260°C, the pressure was reduced to 0.13 kPa over 70 minutes, and the polymerization reaction was carried out under conditions of 260°C and 0.13 kPa or less until the specified stirring torque was reached. After the reaction was completed, the resulting resin was pelletized and extracted to obtain polyester carbonate resin pellets. It was confirmed that the resulting polyester carbonate resin contained 42 mol% of BECMB components, 29 mol% of BNEF components, and 29 mol% of BHEB components. The evaluation results of the resulting polyester carbonate resin are shown in Table 1.

[0178] [Example 5] 50.1 parts by mass of BECMB in Example 4, 19.6 parts by mass of BNEF, 36.4 parts by mass of BHEB, 5.7 parts by mass of DPC, 23.6 × 10 Al(acac) -3 Parts by mass: DEBHBP 52.0 x 10 -3 Polyester carbonate resin pellets were obtained in the same manner as in Example 4, except that the amounts were changed to parts by mass. It was confirmed that the obtained polyester carbonate resin contained 45 mol% of BECMB components, 15 mol% of BNEF components, and 40 mol% of BHEB components. The evaluation results of the obtained polyester carbonate resin are shown in Table 1.

[0179] [Example 6] 48.2 parts by mass of BECMB in Example 4, 31.5 parts by mass of BNEF, 26.2 parts by mass of BHEB, 5.5 parts by mass of DPC, and 22.7 × 10 Al(acac) -3 Parts by mass: DEBHBP 50.0 x 10 -3 Polyester carbonate resin pellets were obtained in the same manner as in Example 4, except that the amounts were changed to parts by mass. It was confirmed that the obtained 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 obtained polyester carbonate resin are shown in Table 1.

[0180] [Example 7] 45.6 parts by mass of BECMB of Example 4, 47.6 parts by mass of BNEF, 12.4 parts by mass of BHEB, 5.2 parts by mass of DPC, 21.5 × 10 Al(acac) -3 Parts by mass of DEBHBP: 47.2 x 10 -3 Polyester carbonate resin pellets were obtained in the same manner as in Example 4, except that the amounts were changed to parts by mass. It was confirmed that the obtained polyester carbonate resin contained 45 mol% of BECMB components, 40 mol% of BNEF components, and 15 mol% of BHEB components. The evaluation results of the obtained polyester carbonate resin are shown in Table 1.

[0181] [Comparative Example 1] The same procedure as in Example 1 was carried out 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, to obtain polyester resin pellets. 1 Analysis by H NMR confirmed that the BCMB component, BNEF component, and BHEB component were incorporated at 50 mol%, 25 mol%, and 25 mol%, respectively, relative to the total monomer components. The evaluation results of the obtained polyester resin are shown in Table 1.

[0182] 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 the BCMB 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 resulting polyester resin are shown in Table 1.

[0183] 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 components, 35 mol% of BNEF components, and 15 mol% of BHEB components. The evaluation results of the resulting polyester resin are shown in Table 1.

[0184] 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 BECMB in Example 4. It was confirmed that the resulting polyester carbonate resin contained 42 mol% of BCMB components, 29 mol% of BNEF components, and 29 mol% of BHEB components. The evaluation results of the resulting polyester carbonate resin are shown in Table 1.

[0185] 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.

[0186] [Table 1]

[0187] 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. [Industrial Applicability]

[0188] The polyester resin or polyester carbonate resin of the present invention is used in optical materials, and is suitable for use in lenses, prisms, optical disks, transparent conductive substrates, optical cards, sheets, films, optical It can be used for optical components such as fibers, optical films, optical filters, and hard coat films, and is particularly useful for lenses.

Claims

1. 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. 【Chemistry 1】 (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.) 【Chemistry 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.) 【Transformation 3】 (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.) 【Chemistry 4】 (In the formula, ring Z １ , Z ２ each represents a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms, and R １ , R ２ , R ７ and R ８ each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, R ３ ~R ６ , R ９ ~R １６ represents a hydrogen atom or an aliphatic or aromatic substituent, j, k, r, and s each independently represent an integer of 0 or more, and m, n, p, and q each independently represent 1 or 2. 【Transformation 5】 (In the formula, R ７ , R ８ , R １７ and R １８ each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, R ９ ~R １６ , R １９ ~R ２６ represents a hydrogen atom or an aliphatic or aromatic substituent, and r, s, t, and u each independently represent an integer of 0 or more.

2. Z in the formula (1) １ and Z ２ 2. The polyester carbonate resin according to claim 1, wherein is a naphthalenediyl group.

3. The polyester carbonate resin according to claim 1, wherein the formula (1) comprises a unit represented by the following formula (3): 【Transformation 6】 (In the formula, R １ , R ２ , R ７ and R ８ each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, R ３ ~R ６ , R ９ ~R １６ represents a hydrogen atom or an aliphatic or aromatic substituent, j, k, r, and s each independently represent an integer of 0 or more, and m, n, p, and q each independently represent 1 or 2.

4. The polyester carbonate resin according to claim 3, wherein the formula (3) is the following formula (4): 【Transformation 7】 (In the formula, R １ , R ２ , R ７ and R ８ each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group.

5. R in the formula (3) or (4) １ , R ２ is an ethylene group, R ７ and R ８ 5. The polyester carbonate resin according to claim 3, wherein is a methylene group.

6. 6. The polyester carbonate resin according to claim 1, wherein the repeating units represented by formula (1) account for 20 mol % or more of all repeating units.

7. R in the formula (2) ９ ~R １６ , R １９ ~R ２６ The polyester carbonate resin according to any one of claims 1 to 6, wherein is a hydrogen atom, and r, s, t, and u are each 1.

8. R in the formula (2) ７ , R ８ is a methylene group, R １７ and R １８ The polyester carbonate resin according to any one of claims 1 to 7, wherein is an ethylene group.

9. 9. The polyester carbonate resin according to claim 1, wherein the repeating units represented by formula (2) account for 20 mol % or more of all repeating units.

10. The polyester carbonate resin according to any one of claims 1 to 9, 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. 11. The polyester carbonate resin according to claim 1, wherein the specific viscosity measured for a 0.53% by mass solution in methylene chloride is 0.12 to 0.

40.

12. The polyester carbonate resin according to any one of claims 1 to 11, which has a refractive index of 1.675 to 1.

695.

13. The polyester carbonate resin according to any one of claims 1 to 12, which has a glass transition temperature of 140 to 155°C.

14. The absolute value of birefringence at 20°C and a wavelength of 589 nm for 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 ~5.0 x 10 －３ The polyester carbonate resin according to any one of claims 1 to 13, wherein

15. 1.0 g of the resin was dissolved in 5 mL of methylene chloride for spectroscopic analysis, and the solution was measured using CIE 1976 (L ＊ a ＊ b ＊ ) color system b ＊ The polyestercarbonate resin according to any one of claims 1 to 14, wherein the value is 3.0 or less.

16. 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. 【Transformation 8】 (In the formula, ring Z １ , Z ２ each represents a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms, and R １ , R ２ each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, R ３ ~R ６ represents 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. 【Chemistry 9】 (In the formula, R １７ , R １８ each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, R １９ ~R ２６ represents a hydrogen atom or an aliphatic or aromatic substituent, and t and u each independently represent an integer of 0 or more. 【Chemistry 10】 (In the formula, R ７ , R ８ each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, R ９ ~R １６ represents a hydrogen atom or an aliphatic or aromatic substituent; r and s each independently represent an integer of 0 or more; R ２７ , R ２８ represents a methyl group, an ethyl group, or a phenyl group.) 【Chemistry 11】 (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.) 【Chemistry 12】 (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.)

17. An optical member comprising the polyester carbonate resin according to any one of claims 1 to 15.

18. The optical member according to claim 17, which is an optical lens.

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