Polyester resin or polyester carbonate resin and optical member using the same

文档序号：1145534 发布日期：2020-09-11 浏览：42次中文

阅读说明：本技术 聚酯树脂或聚酯碳酸酯树脂和使用该树脂的光学部件 (Polyester resin or polyester carbonate resin and optical member using the same ) 是由山田恭辅松井学柳田高恒小笠原一良布目和德佐藤敬介大山达也于 2019-03-11 设计创作，主要内容包括：本发明的目的在于提供高折射率且耐热性、低双折射的平衡优异的聚酯树脂或聚酯碳酸酯树脂。该聚酯树脂或聚酯碳酸酯树脂含有下式(1)和(2)表示的重复单元,下式(1)表示的重复单元与下式(2)表示的重复单元的比为15：85～85：15。(式(1)中,环Z1、Z2各自表示碳原子数9～20的多环芳香族烃基,R1、R2、R7和R8各自独立地表示碳原子数1～12的可含有芳香族基团的烃基,R3～R6、R9～R16表示氢原子、脂肪族或芳香族的取代基,j、k、r和s各自独立地表示0以上的整数,m、n、p和q各自独立地表示1或者2。)(式(2)中,R7、R8、R17和R18各自独立地表示碳原子数1～12的可含有芳香族基团的烃基,R9～R16、R19～R26表示氢原子、脂肪族或芳香族的取代基,r、s、t和u各自独立地表示0以上的整数。)<Image he="480" wi="700" file="DDA0002598075220000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The purpose of the present invention is to provide a polyester resin or a polyester carbonate resin having a high refractive index and an excellent balance between heat resistance and low birefringence. The polyester resin or polyester carbonate resin contains repeating units represented by the following formulae (1) and (2), and the ratio of the repeating unit represented by the following formula (1) to the repeating unit represented by the following formula (2) is 15: 85-85: 15. (in the formula (1), ring Z 1 、Z 2 Each represents a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms, R 1 、R 2 、R 7 And R 8 Each independently represents 1 to 12 carbon atomsHydrocarbon group which may contain aromatic group, R 3 ～R 6 、R 9 ～R 16 Represents a hydrogen atom, an aliphatic or aromatic substituent, j, k, r and s each independently represents an integer of 0 or more, and m, n, p and q each independently represents 1 or 2. ) (in the formula (2), R 7 、R 8 、R 17 And R 18 Each independently represents a C1-12 hydrocarbon group which may contain an aromatic group, R 9 ～R 16 、R 19 ～R 26 Represents a hydrogen atom, an aliphatic or aromatic substituent, and r, s, t and u each independently represents an integer of 0 or more. ))

1. A polyester resin or a polyestercarbonate resin comprising repeating units represented by the following formulae (1) and (2), wherein the ratio of the repeating unit represented by the following formula (1) to the repeating unit represented by the following formula (2) is 15: 85-85: 15,

in the formula (1), ring Z¹、Z²Each represents a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms, R¹、R²、R⁷And R⁸Each independently represents a C1-12 hydrocarbon group which may contain an aromatic group, R³～R⁶、R⁹～R¹⁶Represents a hydrogen atom, an aliphatic or aromatic substituent, j, k, r and s each independently represents an integer of 0 or more, m, n, p and q each independently represents 1 or 2,

in the formula (2), R⁷、R⁸、R¹⁷And R¹⁸Each independently represents a C1-12 hydrocarbon group which may contain an aromatic group, R⁹～R¹⁶、R¹⁹～R²⁶Represents a hydrogen atom, an aliphatic or aromatic substituent, and r, s, t and u each independently represents an integer of 0 or more.

2. The polyester resin or polyestercarbonate resin of claim 1, wherein Z of formula (1)¹And Z²Is naphthalenediyl.

3. The polyester resin or polyestercarbonate resin according to claim 1, wherein the formula (1) is composed of a unit represented by the following formula (3),

in the formula, R¹、R²、R⁷And R⁸Each independently represents a C1-12 hydrocarbon group which may contain an aromatic group, R³～R⁶、R⁹～R¹⁶Represents a hydrogen atom, an aliphatic or aromatic substituent, j, k, r and s each independently represents an integer of 0 or more, and m, n, p and q each independently represents 1 or 2.

4. The polyester resin or polyestercarbonate resin of claim 3, wherein R in the formula (3)³～R⁶、R⁹～R¹⁶Is a hydrogen atom, and j, k, r, s, m, n, p and q are 1.

5. The polyester resin or polyestercarbonate resin of claim 3 or 4, wherein R in the formula (3)¹、R²Is ethylene, R⁷And R⁸Is methylene.

6. The polyester resin or polyestercarbonate resin according to any one of claims 1 to 5, wherein the repeating unit represented by the formula (1) is 20 mol% or more of the total repeating units.

7. The polyester resin or polyestercarbonate resin according to any of claims 1 to 6, wherein R in the formula (2)⁹～R¹⁶、R¹⁹～R²⁶Is a hydrogen atom, and r, s, t and u are 1.

8. The polyester resin or polyestercarbonate resin according to any of claims 1 to 7, wherein R in the formula (2)⁷、R⁸Is methylene, R¹⁷And R¹⁸Is an ethylene group.

9. The polyester resin or polyestercarbonate resin according to any one of claims 1 to 8, wherein the repeating unit represented by the formula (2) is 20 mol% or more of the total repeating units.

10. The polyester resin or polyestercarbonate resin of any 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: 75-75: 25.

11. the polyester resin or polyestercarbonate resin according to any of claims 1 to 10, wherein the refractive index is 1.680 to 1.695.

12. The polyester resin or polyestercarbonate resin of any of claims 1 to 11, wherein the glass transition temperature is 140 to 155 ℃.

13. The polyester resin or polyestercarbonate resin of any of claims 1 to 12, wherein the fluorenone content is 1 to 500 ppm.

14. An optical member comprising the polyester resin or polyester carbonate resin according to any one of claims 1 to 13.

15. The optical component of claim 14, being an optical lens.

Technical Field

The present invention relates to a polyester resin or a polyester carbonate resin having a high refractive index, low birefringence, and an excellent balance between heat resistance and moldability.

Background

Camera modules are used in cameras, video cameras, mobile phones with cameras, video phones, door phones with cameras, and the like. In recent years, miniaturization of an optical system used in the image pickup module is particularly demanded. Chromatic aberration of an optical system becomes a big problem if the optical system is miniaturized. Therefore, it is known that chromatic aberration can be corrected by combining an optical lens material which has a high dispersion by increasing the refractive index of the optical lens and decreasing the abbe number and an optical lens material which has a low dispersion by decreasing the refractive index and increasing the abbe number.

Glass, which has been conventionally used as a material for optical systems, has a problem of poor processability, although it can achieve various optical properties required and has excellent environmental resistance. On the other hand, resins that are less expensive than glass materials and have excellent processability have been used for optical members. In particular, resins having a fluorene skeleton or a binaphthyl skeleton are used for reasons such as a high refractive index. For example, patent document 1 describes a polycarbonate using 2,2 '-bis (2-hydroxyethoxy) -1, 1' -binaphthyl. Patent document 2 describes a thermoplastic resin using 9, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene. Patent document 3 describes a resin using 9, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene and 2,2 '-bis (2-hydroxyethoxy) -1, 1' -binaphthyl. These resins have a refractive index of 1.64 to 1.67, and still have room for improvement. Patent document 4 describes a polyester resin using 2,2 '-bis (ethoxycarbonylmethoxy) -1, 1' -binaphthyl and 9, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene, and patent documents 5 and 6 describe a polycarbonate using 9, 9-bis [6- (2-hydroxyethoxy) -2-naphthyl ] fluorene, and disclose a resin having a refractive index of 1.65 to 1.69. Patent document 7 describes the use of a polycarbonate such as 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] -2, 3-benzofluorene. The contents of these documents are incorporated by reference into the present specification. However, although these resins have high refractive indices, the balance between birefringence and heat resistance and moldability is insufficient, and there is still room for improvement.

Disclosure of Invention

Accordingly, an object of the present invention is to provide a polyester resin or a polyester carbonate resin having a high refractive index, low birefringence, and an excellent balance between heat resistance and moldability.

The present inventors have conducted intensive studies to achieve the object, and as a result, have found that a polyester resin or a polyester carbonate resin having a fluorene skeleton and a binaphthyl skeleton into which a specific aromatic group is introduced has a high refractive index and low birefringence, and can have a high balance between heat resistance and moldability, thereby completing the present invention.

Namely, the present invention is as follows.

(in the formula, ring Z¹、Z²Each represents a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms, R¹、R²、R⁷And R⁸Each independently represents a C1-12 hydrocarbon group which may contain an aromatic group, R³～R⁶、R⁹～R¹⁶Represents a hydrogen atom, an aliphatic or aromatic substituent, j, k, r and s each independently represents an integer of 0 or more, and m, n, p and q each independently represents 1 or 2. )

(in the formula, R⁷、R⁸、R¹⁷And R¹⁸Each independently represents a C1-12 hydrocarbon group which may contain an aromatic group, R⁹～R¹⁶、R¹⁹～R²⁶Represents a hydrogen atom, an aliphatic or aromatic substituent, and r, s, t and u each independently represents an integer of 0 or more. )

2. The polyester resin or polyester carbonate resin according to the above 1, wherein Z of the above formula (1)¹And Z²Is naphthalenediyl.

3. The polyester resin or polyestercarbonate resin according to 1, wherein the formula (1) is a unit represented by the following formula (3).

(in the formula, R¹、R²、R⁷And R⁸Each independently represents a C1-12 hydrocarbon group which may contain an aromatic group, R³～R⁶、R⁹～R¹⁶Represents a hydrogen atom, an aliphatic or aromatic substituent, j, k, r and s each independently represents an integer of 0 or more, and m, n, p and q each independently represents 1 or 2. )

4. The polyester resin or polyestercarbonate resin according to 3, wherein R in the formula (3)³～R⁶、R⁹～R¹⁶Is a hydrogen atom, and j, k, r, s, m, n, p and q are 1.

5. The polyester resin or polyestercarbonate resin according to 3 or 4, wherein R in the formula (3)¹、R²Is ethylene, R⁷And R⁸Is methylene.

6. The polyester resin or polyestercarbonate resin according to any one of the above 1 to 5, wherein the repeating unit represented by the above formula (1) is 20 mol% or more of the total repeating units.

7. The polyester resin or polyester carbonate resin according to any one of the above 1 to 6, wherein R in the above formula (2)⁹～R¹⁶、R¹⁹～R²⁶Is a hydrogen atom, and r, s, t and u are 1.

8. The polyester resin or polyester carbonate resin according to any one of the above 1 to 7, whereinR in the formula (2)⁷、R⁸Is methylene, R¹⁷And R¹⁸Is an ethylene group.

9. The polyester resin or polyestercarbonate resin according to any one of the above 1 to 8, wherein the repeating unit represented by the above formula (2) is 20 mol% or more of the total repeating units.

10. The polyester resin or polyestercarbonate resin according to any one of the above 1 to 9, wherein the ratio of the repeating unit represented by the above formula (1) to the repeating unit represented by the above formula (2) is 25: 75-75: 25.

11. the polyester resin or polyestercarbonate resin according to any one of 1 to 10, wherein the specific viscosity measured on a solution dissolved in methylene chloride at 0.53 mass% is 0.12 to 0.40.

12. The polyester resin or polyester carbonate resin according to any one of the above 1 to 11, wherein the refractive index is 1.680 to 1.695.

13. The polyester resin or polyester carbonate resin according to any one of the above 1 to 12, wherein the glass transition temperature is 140 to 155 ℃.

14. The polyester resin or polyestercarbonate resin according to any of the above 1 to 13, wherein the absolute value of birefringence at 20 ℃ and a wavelength of 589nm of a film stretched at a temperature 10 ℃ higher than the glass transition temperature by a factor of 2 is 0.001 × 10^-3～5×10^-3。

15. The polyester resin or polyestercarbonate resin according to any of the above 1 to 14, wherein the amount of the terminal carboxylic acid is 10 equivalents/ton or less.

16. The polyester resin or polyester carbonate resin according to any one of the above 1 to 15, wherein the fluorenone content is 1 to 500 ppm.

17. The polyester carbonate resin according to any one of 1 to 16, wherein the phenol content is 1 to 500 ppm.

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

19. The optical component according to 18 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 therefore exhibits a remarkable industrial effect.

Drawings

FIG. 1 is a drawing showing a process for producing a polyestercarbonate resin obtained in example 6¹H NMR。

Detailed Description

The present invention will 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 formulae (1) and (2), and the ratio of the repeating unit represented by the following formula (1) to the repeating unit represented by the following formula (2) is 15: 85-85: 15.

The polyester resin or polyester carbonate resin of the present inventionThe preferred form of (A) is: as ring Z in the above formula (1)¹、Z²The polycyclic aromatic hydrocarbon group represented by (a) is not particularly limited as long as the number of carbon atoms is 9 to 20, and a fused polycyclic aromatic hydrocarbon ring having a benzene ring skeleton is preferable, and a fused bicyclic hydrocarbon ring, a fused tricyclic hydrocarbon ring, and the like are preferable. The fused bicyclic hydrocarbon ring is preferably an aromatic hydrocarbon ring having 9 to 20 carbon atoms such as an indene ring and a naphthalene ring, and more preferably a fused bicyclic hydrocarbon ring having 10 to 16 carbon atoms. Further, as the fused tricyclic hydrocarbon ring, an anthracene ring, a phenanthrene ring, or the like is preferable. These polycyclic aromatic hydrocarbon groups may have a substituent.

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention are: z in the above formula (1)¹And Z²Is naphthalenediyl.

As ring Z in the above formula (1)¹、Z²The polycyclic aromatic hydrocarbon group is preferably naphthalene-1, 4-diyl or naphthalene-2, 6-diyl, and more preferably naphthalene-2, 6-diyl.

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention are: the formula (1) is composed of a unit represented by the following formula (3).

R in the above formula (3)³～R⁶、R⁹～R¹⁶More preferably, a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, etc., and still more preferably a hydrogen atom.

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention are: r in the above formulae (1) and (2)¹、R²、R⁷、R⁸、R¹⁷And R¹⁸Each independently represents a hydrocarbon group which may contain an aromatic group and has 1 to 12 carbon atoms, and preferable examples thereof include an alkylene group such as a methylene group, an ethylene group, a propylene group and a butylene group, and an arylene group such as a phenylene group and a naphthalenediyl group. Among them, methylene and ethylene are more preferable. In particular R¹、R²、R¹⁷、R¹⁸Ethylene is preferred. Further, R7 and R8 are preferably methylene groups.

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention are: in the above formulae (1) and (2), R³～R⁴Preferred are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group and the like, and among them, a hydrogen atom is more preferred.

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention are: r in the above formulae (1) and (2)⁵～R⁶、R⁹～R¹⁶And R¹⁹～R²⁶The substituent is preferably a hydrogen atom, and specific examples thereof include a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, and an aralkyloxy group.

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

Specific examples of the alkyl group include preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, etc., more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group.

Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, and 4-tert-butylcyclohexyl, and cyclohexyl is more preferable.

Specific 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), a naphthyl group, etc., more preferably a phenyl group or a naphthyl group, and still more preferably a phenyl group.

Specific examples of the aralkyl group include a benzyl group and a phenethyl group, and a benzyl group is more preferable.

Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and the like, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group.

Specific examples of the cycloalkoxy group include cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group and the like, and cyclohexyloxy group is more preferable.

Specific examples of the aryloxy group include a phenoxy group, an alkylphenoxy group (a mono-or dimethylphenoxy group), a naphthoxy group, and the like, more preferably a phenoxy group and a naphthoxy group, and still more preferably a phenoxy group.

Specific examples of the aralkyloxy group include a benzyloxy group, a phenethyloxy group and the like, and a benzyloxy group is more preferable.

Based on the relational expression between the molecular structure and the refractive index, which is conventionally known as the Lorentz-Lorenz equation, it is known that the refractive index of a substance is improved by increasing the electron density of a molecule to reduce the molecular volume. Based on the theory, the resins having a fluorene skeleton and a binaphthyl skeleton disclosed in patent documents 1 to 6 have a high refractive index by introducing a large amount of aromatic groups into the molecule. However, although these resins have high refractive indices, the balance between birefringence and heat resistance and moldability is insufficient.

The specific ester structure represented by the above formula (1) of the present invention has a high refractive index and a low birefringence, and contributes to high heat resistance, and the specific ester structure represented by the above formula (2) has a lower refractive index than the above formula (1), but has a high refractive index and a low birefringence, and can lower the glass transition temperature of the resin, and contribute to moldability. Thus, the polyester resin or polyester carbonate resin containing the repeating units represented by the above formulae (1) and (2) has a high refractive index and can balance birefringence with heat resistance and moldability.

The composition ratio of the resin in the present invention is expressed by the molar ratio of the monomer structure introduced into the resin based on the number of moles of all the monomer units. All of the monomer units mentioned herein do not include a carbonic acid component used in the production of the polyester carbonate resin.

The repeating unit in the present invention means the smallest unit formed by ester bonds and/or carbonate bonds. The repeating unit of the ester bond means a structural unit formed by a diol component and a dicarboxylic acid component, and the repeating unit of the carbonate bond means a structural unit formed by a diol derivative and a carbonic acid component.

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

the molar ratio of the repeating unit represented by the above formula (1) to the repeating unit represented by the above formula (2) is preferably 25: 75-75: 25, more preferably 30: 70-70: 30. when the refractive index is within the above range, the balance between the high refractive index and the birefringence is excellent.

In the resin of the present invention, each of the repeating units represented by the above formula (1) and the above formula (2) may be present in an amount of 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more, or may be present in an amount of 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, or 40 mol% or less. For example, each of these repeat units may be present in the resin at 20 mole% to 80 mole%, or 30 mole% to 70 mole%.

In particular, when the resin of the present invention is a polyester carbonate resin, the resin may further contain a repeating unit utilizing a carbonate bond in addition to the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2). The repeating unit utilizing a carbonate bond may be a repeating unit in which a part of the ester bond of the repeating unit represented by the above formulas (1) to (3) is changed to a carbonate bond. In the polyester carbonate resin of the present invention, the repeating unit utilizing a carbonate bond may be present in an amount of 5 mol% or more, 10 mol% or more, 15 mol% or more, or 20 mol% or more, and may be present in an amount of 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less. For example, the repeating unit is present in the resin at 5 to 50 mol%, or 10 to 30 mol%.

In the resin of the present invention, the repeating units other than the repeating units represented by the above formulae (1) and (2) and the repeating units in which a part of the ester bond is changed to a carbonate bond may be absent, may be present in an amount of more than 0 mol%, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and may be present in an amount of 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less.

The polyester resin or polyester carbonate resin of the present invention preferably has a specific viscosity of 0.12 to 0.40, more preferably 0.15 to 0.35, and even more preferably 0.18 to 0.30. if the specific viscosity is within the above range, the moldability is excellent in balance with the mechanical strength, and therefore, it is preferable that the specific viscosity is a specific viscosity (η) measured at 20 ℃ using a solution of 0.53 mass% dissolved in methylene chloride (a solution of 0.7g of the resin dissolved in 100ml of methylene chloride)_sp)。

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention are: the refractive index measured at 25 ℃ and having a wavelength of 589nm (hereinafter occasionally abbreviated as nD) is preferably 1.660 to 1.695, more preferably 1.670 to 1.695, even more preferably 1.680 to 1.695, even more preferably 1.685 to 1.695, and most preferably 1.688 to 1.695. When the refractive index is not less than the lower limit, spherical aberration of the lens can be reduced, and the focal length of the lens can be further shortened.

The polyester resin or polyester carbonate resin of the present invention has a high refractive index, but a low abbe number is more preferable. The Abbe number (v) is preferably 15 to 21, more preferably 15 to 20, and still more preferably 15 to 18. Abbe number is calculated from refractive indices measured at 25 ℃ at wavelengths of 486nm, 589nm, and 656nm by the following formula.

ν＝(nD－1)/(nF－nC)

In the present invention, it should be noted that,

nD: refers to a refractive index of 589nm wavelength,

nC: refers to the refractive index at a wavelength of 656nm,

nF: refers to a refractive index at a wavelength of 486 nm.

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention are: the glass transition temperature (Tg) is preferably 140 to 160 ℃, more preferably 140 to 155 ℃, and still more preferably 140 to 150 ℃. When the glass transition temperature is within the above range, the balance between heat resistance and moldability is excellent, and therefore, such a range is preferable.

The polyester resin or polyester carbonate resin of the present invention is preferably in a form in which the absolute value of the orientation birefringence (| Deltan |) is preferably 0.001 × 10^-3～10×10^-3More preferably 0.001 × 10^-3～5×10^-3More preferably 0.001 × 10^-3～4×10^-3The range of (1).

The | Δ n | is obtained by stretching a film having a thickness of 100 μm obtained from the polyester resin or the polyestercarbonate resin of the present invention 2 times at a temperature of Tg +10 ℃ and measuring a phase difference at a wavelength of 589nm and the following equation. If | Δ n | is within the above range, the optical distortion of the lens becomes small, which is preferable.

|Δn|＝|Re/d|

Δ n: oriented birefringence

Re: phase difference (nm)

d: thickness (nm)

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention are: the total light transmittance at a thickness of 1mm is preferably 80% or more, more preferably 85% or more, and further preferably 88% or more. If the total light transmittance is within the above range, it is suitable as an optical member. The total light transmittance was measured by measuring a 1mm thick molded sheet using NDH-300A manufactured by Nippon Denshoku industries Co., Ltd.

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention are: the degree of coloration is particularly preferably light yellow. In particular CIE1976 (L)^＊a^＊b^＊) B of the color system^＊The value is preferably 10.0 or less, 8.0 or less, 6.0 or less, or 4.0 or less. b^＊The value is more preferably 3.0 or less, and still more preferably 2.0 or less. B is^＊The value is CIE1976 (L) determined spectrophotometrically for a solution of 1.0g dissolved in 5ml of methylene chloride (solution dissolved in methylene chloride at 13 mass%)^＊a^＊b^＊) Value of the color system.

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention are: the water absorption after immersion at 23 ℃ for 24 hours is preferably 0.25 mass% or less, more preferably 0.20 mass% or less. When the water absorption rate is within the above range, the change in optical properties due to water absorption is small, which is preferable.

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention are: the amount of the terminal carboxylic acid may be 12 equivalents/ton or less, 10 equivalents/ton or less, 6 equivalents/ton or less, or 3 equivalents/ton or less, and preferably 1 equivalent/ton or less. If the amount of the terminal carboxylic acid is more than 12 equivalents/ton, the terminal carboxylic acid functions as a catalyst for hydrolysis of the ester bond, and the moist heat resistance may be deteriorated. It is preferable that the amount of the terminal carboxylic acid is 12 equivalents/ton or less because the moist heat resistance is excellent. The amount of the terminal carboxylic acid can be determined by a titration method after dissolving 0.1g of the resin in 20ml of benzyl alcohol at 200 ℃ under a nitrogen atmosphere.

Preferred embodiments of the polyester resin or polyester carbonate resin of the present invention are: the moist heat resistance can be evaluated by treating the resin at 85 ℃ and 85% relative humidity for a predetermined time and comparing the specific viscosities of the resin before and after the treatment. Specifically, the moist heat resistance can be calculated from the following equation.

Wet heat resistance (%) [ specific viscosity of resin after treatment ]/[ specific viscosity of resin before treatment ] × 100

The wet heat resistance after 500 hours of the treatment is preferably 76% or more, more preferably 90% or more, and still more preferably 98% or more.

The following is a description of the polyester resin or polyester carbonate resin of the present invention using specific raw materials.

< raw Material monomer >

(diol component of the above formula (1))

The diol component which is the raw material of the above 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.

In the above formula (a), Z¹、Z²、R¹～R⁶J, k, m, n, p, q are the same as in the above formula (1).

Representative specific examples of the diol component represented by the above formula (a) will be described below, and the raw material used in the above formula (1) of the present invention is not limited to these examples.

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

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

(diol component of the above formula (2))

The diol component which is the raw material of the above 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.

In the above formula (b), R¹⁷～R²⁶T and u are the same as those in the above formula (2).

Representative specific examples of the diol component represented by the above formula (b) will be described below, and the raw material used in the above formula (2) of the present invention is not limited to these examples.

Specifically, preferred examples thereof include 2,2 '-bis (2-hydroxyethoxy) -1, 1' -binaphthyl, 2 '-bis (2-hydroxyethoxy) -3, 3' -diphenyl-1, 1 '-binaphthyl, 2' -bis (2-hydroxyethoxy) -6,6 '-diphenyl-1, 1' -binaphthyl, 2 '-bis (2-hydroxyethoxy) -7, 7' -diphenyl-1, 1 '-binaphthyl, 2' -bis (2-hydroxyethoxy) -3,3 '-dimethyl-1, 1' -binaphthyl, 2 '-bis (2-hydroxyethoxy) -6, 6' -dimethyl-1, 1 '-binaphthyl, 2' -bis (2-hydroxyethoxy) -7,7 '-dimethyl-1, 1' -binaphthyl, 1 '-bi-2-naphthol, 2' -dihydroxy-3, 3 '-diphenyl-1, 1' -binaphthyl, 2 '-dihydroxy-6, 6' -diphenyl-1, 1 '-binaphthyl, 2' -dihydroxy-7, 7 '-diphenyl-1, 1' -binaphthyl, and the like. Among these, 2 ' -bis (2-hydroxyethoxy) -1,1 ' -binaphthyl and 1,1 ' -bi-2-naphthol are more preferable, and 2,2 ' -bis (2-hydroxyethoxy) -1,1 ' -binaphthyl is further preferable.

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

(diol component other than the above formula (1) and the above formula (2))

The polyester resin or polyester carbonate resin of the present invention may have other diol components copolymerized therein to the extent that the characteristics of the present invention are not impaired. Preferably, the other diol component is less than 30 mole percent of the total repeating units.

As other diol components that can be used in the polyester resin or polyester carbonate resin of the present invention, there can be used those known in the art, and examples thereof include, in addition to the diols described in [0040] of patent document 7, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, 9-bis (4-hydroxy-3-phenylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 10-bis (4-hydroxyphenyl) anthrone, and the like, and these may be used alone or in combination of two or more.

(dicarboxylic acid component of the above formula (1) and the above formula (2))

In the polyester resin or polyester carbonate resin of the present invention, the dicarboxylic acid component used in the units represented by the above formulae (1) and (2) is preferably a dicarboxylic acid represented by the following formula (c) or an ester-forming derivative thereof.

In the above formula (c), R⁷～R¹⁶R and s are the same as in the above formula (1).

Representative examples of the dicarboxylic acid represented by the above formula (c) or an ester-forming derivative thereof will be described below, and the raw material used in the above formula (c) of the present invention is not limited to these examples.

Specifically, 2 ' -biphenyldicarboxylic acid, 2 ' -bis (carboxymethoxy) -1,1 ' -binaphthyl, 2 ' -bis (2-carboxyethoxy) -1,1 ' -binaphthyl, 2 ' -bis (3-carboxypropoxy) -1,1 ' -binaphthyl, 2 ' -bis (3-carboxy-2-methylpropoxy) -1,1 ' -binaphthyl, 2 ' -bis (4-carboxyphenylmethoxy) -1,1 ' -binaphthyl, and the like are preferable, and 2,2 ' -bis (carboxymethoxy) -1,1 ' -binaphthyl is more preferable.

These may be used alone or in combination of two or more. As the ester-forming derivative, esters such as acid chloride, methyl ester, ethyl ester, and phenyl ester can be used.

(dicarboxylic acid component other than the above formula (1) and formula (2))

As the dicarboxylic acid component used in the polyester resin or polyester carbonate resin of the present invention, other dicarboxylic acid components may be copolymerized to the extent that the characteristics of the present invention are not impaired. The other dicarboxylic acid component is preferably less than 30 mol% in the total repeating units.

As the other dicarboxylic acid component used in the polyester resin or polyester carbonate resin of the present invention, a carboxylic acid component known in the art can be used, and for example, the carboxylic acid component described in [0043] of the above patent document 7 can be used.

The polyester resin of the present invention can be produced by a known production method in the art, and for example, the production methods described in [0051] to [0060] of patent document 7 can be used.

< 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 component or an ester-forming derivative thereof with a carbonate-forming derivative such as phosgene or a carbonic acid diester by an interfacial polymerization method or a melt polymerization method, and if necessary, a catalyst, a chain terminator, an antioxidant, or the like can be used.

In the case of the interfacial polymerization method, a solution (organic phase) obtained by dissolving dicarboxylic acid chloride in a water-immiscible organic solvent is mixed with an alkaline aqueous solution (aqueous phase) containing an aromatic diol and a polymerization catalyst, and the resulting mixture is further reacted with phosgene. Preferably, the polymerization is carried out by stirring at a reaction temperature of 0 to 40 ℃ and preferably 25 ℃ or lower for 0.5 to 8 hours.

The solvent used in the organic phase is preferably a solvent which is incompatible with water and can dissolve the polyester resin of the present invention. Examples of such solvents include chlorine-based solvents such as dichloromethane, 1, 2-dichloroethane, chloroform and chlorobenzene, aromatic hydrocarbon-based solvents such as toluene, benzene and xylene, and dichloromethane is more preferable from the viewpoint of ease of use in production.

Examples of the alkaline aqueous solution used in the aqueous phase include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, and the like.

To accelerate the reaction, for example, triethylamine, tetra-n-butylammonium bromide may be used

Etc. tertiary amines, quaternary ammonium compounds, quaternary phosphonium compoundsCompounds, and the like.

The reaction by the melt polymerization method is usually an ester exchange reaction between a diol component and a dicarboxylic acid or an ester-forming derivative thereof and a carbonate-forming derivative, and is carried out by a method of mixing the diol component and the dicarboxylic acid or the ester-forming derivative thereof and the carbonate-forming derivative in the presence of an inert gas while heating, and distilling off the produced water, alcohol, phenol, or other hydroxyl compound.

In particular, in the polymerization of the diol component, the dicarboxylic acid component and the carbonate-forming derivative as the raw material monomers, the following is preferred. The ester condensation reaction of the diol component and the dicarboxylic acid component is first carried out in a first stage. In this reaction, water is produced as a by-product, and the reaction can be carried out without a catalyst. After removing water from the system, in the second-stage polycondensation, a transesterification reaction with a carbonate-forming derivative is carried out, preferably in the presence of a catalyst described later, to form a polyester carbonate while by-producing a hydroxy compound such as an alcohol or phenol.

The reaction temperature varies depending on the diol component used, and is preferably 120 to 350 ℃, more preferably 150 to 300 ℃, and still more preferably 180 to 270 ℃. The reduced pressure was varied stepwise to finally set the pressure to 0.13kPa or lower, and the produced water, alcohol, phenol and other hydroxyl compounds were distilled out of the system. The reaction time is preferably about 1 to 10 hours.

The carbonate-forming derivative is preferably an ester of an aryl group having 6 to 10 carbon atoms, an aralkyl group, an alkyl group having 1 to 4 carbon atoms, or the like, which may be substituted. Specific examples thereof include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, etc., and diphenyl carbonate is more preferable among them.

In the melt polymerization method, a catalyst may be used to increase the polymerization rate. For example, catalysts generally used in esterification reactions and ester exchange reactions, such as lithium acetate, sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium salts 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, alkanols 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, organotin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, magnesium compounds, titanium compounds, cobalt compounds and zirconium compounds, can be preferably used. Among these, aluminum, tin, titanium, and germanium compounds are more preferable, and aluminum compounds are further more preferable, from the viewpoint of melt stability and color tone of the resin.

The catalyst may be used alone, or 2 or more kinds may be used in combination, or other compounds may be used in combination as a co-catalyst, and the amount of the catalyst used is preferably 1 × 10 based on 1 mol of the total of all monomer units^-8～1×10^-3The molar range.

Aluminum or a compound thereof preferably used as a catalyst has activity as a catalyst for polymerizing a polyestercarbonate resin by transesterification. In particular, the catalyst functions as a catalyst for a carbonate formation reaction in polymerization of a diol component, a dicarboxylic acid component and a carbonate-forming derivative as raw material monomers.

Examples of such aluminum or its compound include metallic aluminum, aluminum salt, aluminum chelate compound, organoaluminum compound, and inorganic aluminum compound.

Preferred examples of the aluminum salt include organic acid salts and inorganic acid salts of aluminum. Examples of the organic acid salt of aluminum include carboxylic acid salts of aluminum, and specific examples thereof 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. Examples of the inorganic acid salt of aluminum include aluminum chloride, aluminum hydroxide, aluminum carbonate, aluminum phosphate, and aluminum phosphonate.

Examples of the Aluminum chelate compound include Aluminum acetylacetonate, Aluminum acetoacetate, Aluminum ethylacetoacetate, and Aluminum diisopropylacetoacetate (Aluminum ethyl acetate).

The organoaluminum compound is preferably an aluminum alkoxide such as trialkylaluminum, dialkylaluminum alkoxide, alkyldialkylaluminum alkoxide, aluminum trialkoxide, or a hydrolysate thereof, and specifically, it is preferably an aluminum alkoxide such as aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum isopropoxide, aluminum n-butoxide, or aluminum t-butoxide, or trimethylaluminum, triethylaluminum, or a hydrolysate thereof. Preferred examples of the inorganic aluminum compound include alumina and the like.

Particularly preferred are carboxylates, inorganic acid salts and chelates of aluminum, and of these, particularly more preferred are aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum chlorohydrate (hydrochloric acid salt, or salt of アルミニウム), and aluminum acetylacetonate.

These aluminum compounds may be used in combination with other compounds as a co-catalyst, and particularly phosphorus compounds, can enhance the catalytic activity of aluminum or its compounds in the polymerization of the polyestercarbonate resin.

Examples of such phosphorus compounds include phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. Among these, particularly preferred are phosphonic acid-based compounds, phosphinic acid-based compounds, and phosphine oxide-based compounds, and more preferred are phosphonic acid-based compounds.

As the phosphonic acid-based compound, for example, 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, dimethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, dihexyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctyl ester, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid diphenyl ester, etc., more preferably 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid dimethyl ester, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid dihexyl ester, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctyl ester, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid diphenyl ester.

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

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

The polyester carbonate resin of the present invention may use a monofunctional hydroxyl compound, which is generally used, as a chain terminator in its polymerization reaction. In particular, in the case of a reaction using phosgene as a carbonate precursor, a monofunctional phenol is generally used as a chain terminator for adjusting the molecular weight, and the terminal of the obtained resin is blocked with a group based on a monofunctional phenol, and therefore, the resin is more excellent in thermal stability than a resin not blocked with such a monofunctional phenol. As other blocking agents, epoxy compounds, and the like are preferably mentioned,

Oxazoline compounds, isocyanate compounds, carbodiimide compounds, ketene imine compounds, and the like.

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

< impurities >

(residual phenol)

The polyester carbonate resin of the present invention preferably has a residual phenol content of 1 to 500ppm, more preferably 1 to 400ppm, and still more preferably 1 to 300 ppm.

The phenol content is preferably adjusted by means of the reaction time under a pressure of 1.3kPa or less. When the reaction is not performed in a vacuum of 1.3kPa or less, the content of phenol increases. In addition, if the reaction time is long, too much distillation from the resin occurs.

In addition, the phenol content can be adjusted after the polyestercarbonate resin of the present invention is obtained. For example, the following method may be used: a method of dissolving the polyester carbonate resin of the present invention in an organic solvent, and washing the organic solvent layer with water; a method of devolatilizing and removing the volatile matter at a pressure of 133 to 13.3Pa and a temperature of 200 to 320 ℃ by using a kneading apparatus such as a single-screw or twin-screw extruder or various kneaders which are generally used.

The content of residual phenol in the polyester carbonate resin of the present invention can improve molding flowability without impairing heat resistance. However, if it exceeds 500ppm, the thermal stability at the time of heating and melting is insufficient, and the mold contamination at the time of resin injection molding becomes serious, which is not preferable. Further, phenol has a property of being colored by oxidation, and the color tone of the polyester carbonate resin is deteriorated. On the other hand, when the amount is less than 1ppm, the molding flowability is not preferable.

(residual fluorenone)

The polyester resin or polyester carbonate resin of the present invention preferably has a residual fluorenone content of 1 to 500ppm, more preferably 1 to 300ppm, even more preferably 1 to 100ppm, and particularly preferably 1 to 50ppm or 1 to 40 ppm.

If the content of residual fluorenone in the polyester resin or polyestercarbonate resin of the present invention is more than 500ppm, the resin is remarkably colored, and thus it is not preferable.

< additive >

Additives such as a mold release agent, a heat stabilizer, an ultraviolet absorber, a bluing agent, an antistatic agent, a flame retardant, a plasticizer, and a filler may be added to the polyester resin or the polyester carbonate resin of the present invention as needed. These additives can be added by known methods to known additives in the art, and for example, refer to [0062] to [0081] of patent document 7.

< optical lens >

The polyester resin or polyester carbonate resin of the present invention is suitable for optical parts, particularly optical lenses. The method of using the resin of the present invention for an optical component, particularly an optical lens, can employ a known use method, and for example, refer to the descriptions in [0082] to [0086] of the above patent document 7.

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Polyester resin or polyester carbonate resin and optical member using the same

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