JP6689147B2 - Thermoplastic resin - Google Patents

Description

  The present invention relates to a thermoplastic resin and an optical lens. More specifically, the present invention relates to a thermoplastic resin having a specific ester structure having a high balance of high refractive index, low birefringence and high heat resistance, and an optical lens made of the same.

  Optical glass or optical transparent resin is used as a material for an optical lens used in an optical system of various cameras such as a camera, a film-integrated camera, and a video camera. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., but has the problems of high material cost, poor moldability, and low productivity.

  On the other hand, an optical lens made of an optical resin has an advantage that it can be mass-produced by injection molding, and polycarbonate, polyester carbonate, polyester resin or the like is used as a high refractive index material for a camera lens. However, in recent years, development of a resin having a high refractive index has been required due to the light, thin, short and small products. Generally, when the refractive index of the optical material is high, a lens element having the same refractive index can be realized by a surface having a smaller curvature, so that the amount of aberration generated on this surface can be reduced, the number of lenses can be reduced, and It is possible to reduce the polarization sensitivity and reduce the lens thickness to reduce the weight.

  When an optical resin is used as an optical lens, heat resistance, transparency, low water absorption, chemical resistance, low birefringence and wet heat resistance are required in addition to the refractive index and Abbe number. Therefore, there is a weak point that the use place is limited by the balance of the characteristics of the resin. In particular, in recent years, a camera lens having high image-forming performance and lower birefringence has been demanded as the resolution is improved by increasing the number of pixels. In general, as a method of reducing birefringence, there is a method of canceling out birefringence between compositions having positive and negative birefringences having different signs. Therefore, the composition ratio of these materials having birefringence of opposite signs is very important.

  Patent Document 1 includes, as a monomer component, a biaryl compound that is bound by a bond axis capable of imparting internal rotational isomerism, and at least one aryl group has a π electron number of 4n + 6 (n is a natural number) with respect to the bond axis. A resin composition is disclosed, which has characteristics such as excellent transparency, low optical anisotropy, a high refractive index, and low moisture absorption. Materials for optical lenses having refraction have not been obtained yet.

JP 2001-72872 A

Then, the first object of the present invention is to provide a thermoplastic resin having a high refractive index, a low birefringence and a high heat resistance, and particularly excellent in optical characteristics.
In addition to the first object, a second object of the present invention is to provide a thermoplastic resin having excellent optical properties, which has a particularly well-balanced refractive index and heat resistance.

  The inventors of the present invention have conducted intensive studies to achieve this object, and as a result, found that the thermoplastic resin represented by the following general formula (1) and the following general formula (2) can solve the above problems. The present invention has been reached.

That is, the present invention is
1. A thermoplastic resin in which the total of repeating units represented by the following general formula (1) and the following general formula (2) is 70 mol% or more in all units.

（式（１）において、Ｒ^１およびＲ^２は夫々独立して、炭素原子数１〜１０の芳香族基を含んでもよい炭化水素基を示し、ｎおよびｍは夫々独立して０以上の整数を示す。Ｒ^３〜Ｒ^１０は夫々独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１〜１２の芳香族基を含んでいても良い炭化水素基を示す。Ｒ^１１およびＲ^１２は、夫々独立して、炭素原子数１〜１０の芳香族基を含んでも良い炭化水素基を示し、oおよびpは各々独立して０以上の整数を示す。Ｒ^１３およびＲ^１４は、夫々独立して、水素原子または炭素原子数１〜２０の芳香族基を含んでも良い炭化水素基を示す。）

(In Formula (1), R ¹ and R ² each independently represent a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, and n and m each independently represent an integer of 0 or more. R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. R ¹¹ and R ¹² are each independently represents an even better hydrocarbon group include an aromatic group having 1 to 10 carbon atoms, o and p is an integer of 0 or more each independently .R ¹³ and R ^14's each independently represent a hydrogen atom or a hydrocarbon group optionally containing an aromatic group having 1 to 20 carbon atoms.)

（式（２）において、Ｒ^１およびＲ^２は夫々独立して、炭素原子数１〜１０の芳香族基を含んでもよい炭化水素基を示し、ｎおよびｍは夫々独立して０以上の整数を示す。Ｒ^３〜Ｒ^１０は夫々独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１〜１２の芳香族基を含んでいても良い炭化水素基を示す。Ｒ^１５およびＲ^１６は夫々独立して、炭素原子数１〜１０の芳香族基を含んでもよい炭化水素基を示し、ｑおよびｒは夫々独立して０以上の整数を示す。Ｒ^１７〜Ｒ^2４は夫々独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１〜１２の芳香族基を含んでいても良い炭化水素基を示す。）

(In the formula (2), R ¹ and R ² each independently represent a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, and n and m each independently represent an integer of 0 or more. R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. R ¹⁵ and ^{R 16} each independently represents a hydrocarbon group which may include an aromatic group having 1 to 10 carbon atoms, q and r is an each independently an integer of 0 or more ^.R 17 to R ^Each of ²⁴ independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms.)

2. The thermoplastic resin as described in 1 above, wherein the ratio of the units represented by the general formula (1) and the general formula (2) is 20 to 80:80 to 20.
3. In the general formula (1), R ¹¹ and R ¹² are each a hydrocarbon group having 1 to 4 carbon atoms, o and p are each 0 or 1, and R ¹³ and R ¹⁴ are each hydrogen. 3. The thermoplastic resin as described in 1 or 2 above, which is a hydrocarbon group which may contain an atom or an aromatic group having 1 to 12 carbon atoms.
4. In the above general formula (1), R ¹¹ and R ¹² each represent an ethylene group, o and p each represent 1, and R ¹³ and R ¹⁴ each represent a hydrogen atom or a phenyl group. The thermoplastic resin described.
5. In the general formula (2), R ¹⁵ and R ¹⁶ are each a hydrocarbon group having 1 to 4 carbon atoms, q and r are each 0 or 1, and R ^{17 to} R ²⁴ are each hydrogen. 3. The thermoplastic resin as described in 1 or 2 above, which is a hydrocarbon group which may contain an atom or an aromatic group having 1 to 12 carbon atoms.
6. In the general formula (2), R ¹⁵ and R ¹⁶ are each an ethylene group, q and r are each 1, and R ^{17 to} R ²⁴ are each a hydrogen atom. resin.
7. In the general formula (1) and the general formula (2), R ¹ and R ² are each a hydrocarbon group having 1 to 3 carbon atoms, n and m are 0 or 1, and R ³ -R10 is a thermoplastic resin as described in 1 or 2 above, wherein each R ¹⁰ is a hydrocarbon group which may contain a hydrogen atom or an aromatic group having 1 to 12 carbon atoms.
8. In the general formula (1) and the general formula (2), R ¹ and R ² are each a methylene group, n and m are each 1, and R ^{3 to} R ¹⁰ are hydrogen atoms. The thermoplastic resin according to.
9. The thermoplastic resin according to any one of 1 to 8 above, which has a refractive index of 1.650 to 1.700.
10. 10. The thermoplastic resin as described in any one of 1 to 9 above, which has a specific viscosity of 0.12 to 0.40.
11. The thermoplastic resin according to any one of 1 to 10 above, which has a glass transition temperature of 128 to 160 ° C.
12. 12. The thermoplastic resin as described in any one of 1 to 11 above, which has an orientation birefringence of 0 to 4 × 10 ⁻³ .
13. 13. The thermoplastic resin as described in any one of 1 to 12 above, which is a polyester or polyester carbonate resin.
14. An optical member comprising the thermoplastic resin according to any one of 1 to 13 above.
15. An optical lens comprising the thermoplastic resin according to any one of 1 to 13 above.

  Since the thermoplastic resin of the present invention has a high refractive index, a low birefringence and a high heat resistance, its industrial effect is exceptional.

The present invention will be described in more detail.
The thermoplastic resin of the present invention needs to contain 70 mol% or more of the repeating units represented by the general formula (1) and the general formula (2), and specific thermoplastic resin includes polyester resin or polyester. A carbonate resin is preferable, and a polyester resin is particularly preferable from the viewpoint of the effect of the present invention.

In the general formula (1), R ¹ and R ² each independently represent a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, and n and m each independently represent 0 or more. Indicates an integer. R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may include an aromatic group, and o and p each independently represent an integer of 0 or more. R ¹³ and R ¹⁴ each independently represent a hydrocarbon group which may contain a hydrogen atom or an aromatic group having 1 to 20 carbon atoms.

R ¹ and R ² preferably each independently represent a hydrocarbon group having 1 to 3 carbon atoms, and n and m preferably each independently represent an integer of 0 or 1. R ^{3 to} R ¹⁰ preferably each independently represent a hydrogen atom or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. R ¹¹ and R ¹² are preferably each independently a hydrocarbon group having 1 to 4 carbon atoms, o and p are each independently an integer of 0 or 1, and R ¹³ and R ¹⁴ are Each independently represents a hydrocarbon group which may contain a hydrogen atom or an aromatic group having 1 to 12 carbon atoms. Particularly preferably, R ¹ and R ² represent a methylene group, n and m represent 1, R ^{3 to} R ¹⁰ represent a hydrogen atom, R ¹¹ and R ¹² represent an ethylene group, and o and p Represents 1 and R ¹³ and R ¹⁴ represent a hydrogen atom or a phenyl group.

Further, R ¹ and R ² may be the same or different, n and m may be the same or different, and R ^{3 to} R ¹⁰ may be the same or different. R ¹¹ and R ¹² may be the same or different, o and p may be the same or different, and R ¹³ and R ¹⁴ may be the same or different. It may be.

In the general formula (2), R ¹ and R ² each independently represent a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, and n and m each independently represent 0 or more. Indicates an integer. R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. R ¹⁵ and R ¹⁶ each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may include an aromatic group, and q and r each independently represent an integer of 0 or more. R ^{17 to} R ²⁴ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms.

R ¹ and R ² preferably each independently represent a hydrocarbon group having 1 to 3 carbon atoms, and n and m preferably each independently represent an integer of 0 or 1. R ^{3 to} R ¹⁰ preferably each independently represent a hydrogen atom or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. R ¹⁵ and R ¹⁶ preferably each independently represent a hydrocarbon group having 1 to 4 carbon atoms, and q and r preferably each independently represent an integer of 0 or 1. R ^{17 to} R ²⁴ preferably each independently represent a hydrogen atom or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. Particularly preferably, R ¹ and R ² represent a methylene group, n and m represent 1, R ^{3 to} R ¹⁰ represent a hydrogen atom, R ¹⁵ and R ¹⁶ represent an ethylene group, and q and r. Represents 1 and R ^{17 to} R ²⁴ represent a hydrogen atom.

Further, R ¹ and R ² may be the same or different, n and m may be the same or different, and R ^{3 to} R ¹⁰ may be the same or different. R ¹⁵ and R ¹⁶ may be the same or different, q and r may be the same or different, and R ^{17 to} R ²⁴ are the same or different. It may be.

  The repeating unit represented by the general formula (1) and the general formula (2) is 70 mol% or more, preferably 75 mol% or more, and more preferably 80 mol% or more in all repeating units. Within this range, the heat resistance is excellent.

  In the general formulas (1) and (2), the 1,1′-binaphthyl skeleton improves the heat resistance and the refractive index of the thermoplastic resin and is orthogonal to the bond axis connecting the two naphthalene rings. Since it has a different conformation, it has an effect of reducing birefringence.

The 1,1′-binaphthyl skeleton may be substituted with a substituent or may be condensed with each other. There are no particular restrictions on the substituent, and there are no particular limitations, but representative examples include alkyl, aryl, and the like. The alkyl group preferably has 1 to 12 carbon atoms and may be linear or branched. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group and the like.
The binaphthyl skeleton may be any of R-form, S-form and racemic form, and preferably the racemic form. The racemate, which does not require optical resolution, has a cost advantage.

A first object of the present invention is to provide a high refractive index and high heat resistance, and a refractive index (hereinafter, may be abbreviated as nD) at a measurement wavelength of 589 nm at 25 ° C. is 1.650 to 1.700. Is preferred, 1.655 to 1.695 is more preferred, and 1.657 to 1.686 is even more preferred.
The glass transition point (hereinafter sometimes abbreviated as Tg) is preferably 128 to 160 ° C, more preferably 130 to 158 ° C.
Further, the relational expression between nD and Tg calculated from the result of the present implementation is
Tg> -850nD + 1555 (1)
It is preferable that the relationship is satisfied.

  In addition to the first object, a second object of the present invention is to provide a particularly well-balanced high refractive index and heat resistance. ND is 1.665 to 1.680 and Tg is 138 to 150 ° C. is more preferable, nD is 1.668 to 1.677, and Tg is 140 to 147 ° C. is most preferable.

  The ratio of the units represented by the general formula (1) and the general formula (2) is 20 to 80:80 to 20, preferably 25 to 75:75 to 25, and more preferably 30 to 70:70 to 30. is there. Within this range, a high refractive index, a low birefringence and a high heat resistance can be provided, and a particularly high refractive index and heat resistance can be provided with good balance.

  The specific viscosity of the thermoplastic resin of the present invention is preferably 0.12 to 0.40, more preferably 0.15 to 0.35, and even more preferably 0.18 to 0.30. When the specific viscosity is within the above range, the moldability and mechanical strength are well balanced, which is preferable. Most preferably, it is 0.26 to 0.27.

The Abbe number (ν) of the thermoplastic resin of the present invention is preferably 17 to 25, and more preferably 17 to 23. The Abbe number is calculated from the refractive index at wavelengths of 486 nm, 589 nm and 656 nm measured at 25 ° C. using the following formula.
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: means a refractive index at a wavelength of 486 nm.

The absolute value of the orientation birefringence (Δn) of the thermoplastic resin of the present invention is preferably 0 to 4 × 10 ⁻³ , more preferably 0 to 2 × 10 ⁻³ . is there. The orientation birefringence (Δn) is measured at a wavelength of 589 nm when a cast film having a thickness of 100 μm obtained from the thermoplastic resin of the present invention is stretched 2 times at Tg + 10 ° C. When the orientation birefringence is within the above range, the optical strain of the lens becomes small, which is preferable.
Δn = Re / d
Δn: orientation birefringence
Re: Phase difference (nm)
d: Thickness (nm)
The repeating units of the general formulas (1) and (2) can be produced by reacting a diol component and a dicarboxylic acid component described below.

Specific raw materials will be described below.
<Dicarboxylic Acid Component of General Formula (1) and General Formula (2)>
As the dicarboxylic acid component, a compound represented by the following formula (a) or an ester-forming derivative thereof is preferably used.

In the above general formula (a) of the dicarboxylic acid as a raw material of the general formula (1) of the present invention and the general formula (2) of the present invention, R ¹ and R ² are each independently a C 1-10 carbon atom. It represents a hydrocarbon group which may contain an aromatic group, and n and m each independently represent an integer of 0 or more. R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. R ¹ and R ² preferably each independently represent a hydrocarbon group having 1 to 3 carbon atoms, and n and m preferably each independently represent an integer of 0 or 1. R ^{3 to} R ¹⁰ preferably each independently represent a hydrogen atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. Particularly preferably, R ¹ and R ² represent a methylene group, n and m represent 1, and R ^{3 to} R ¹⁰ represent hydrogen atoms. Further, R ¹ and R ² may be the same or different, n and m may be the same or different, and R ^{3 to} R ¹⁰ may be the same or different. Is also good.

Hereinafter, typical specific examples of the dicarboxylic acid represented by the general formula (a) or an ester-forming derivative thereof will be described. Are not limited thereby.
2,2′-dicarboxy-1,1′-binaphthyl, 2,2′-bis (carboxymethoxy) -1,1′-binaphthyl, 2,2′-bis (2-carboxyethoxy) -1,1 ′ -Binaphthyl, 2,2'-bis (3-carboxypropoxy) -1,1'-binaphthyl, 2,2'-dimethoxycarbonyl-1,1'-binaphthyl, 2,2'-bis (methoxycarbonylmethoxy)- 1,1′-binaphthyl, 2,2′-bis (2-methoxycarbonylethoxy) -1,1′-binaphthyl, 2,2′-bis (3-methoxycarbonylpropoxy) -1,1′-binaphthyl, 2 , 2'-diethoxycarbonyl-1,1'-binaphthyl, 2,2'-bis (ethoxycarbonylmethoxy) -1,1'-binaphthyl, 2,2'-bis (2-ethoxycarbonylethoxy) -1, 1'-binaphthi , 2,2'-bis (3-ethoxycarbonylpropoxy) -1,1'-binaphthyl, 2,2'-diphenoxycarbonyl-1,1'-binaphthyl, 2,2'-bis (phenoxycarbonylmethoxy)- 1,1′-binaphthyl, 2,2′-bis (2-phenoxycarbonylethoxy) -1,1′-binaphthyl, 2,2′-bis (3-phenoxycarbonylpropoxy) -1,1′-binaphthyl, 2 , 2'-Ditert-butoxycarbonyl-1,1'-binaphthyl, 2,2'-bis (tert-butoxycarbonylmethoxy) -1,1'-binaphthyl, 2,2'-bis (2-tert-butoxy Carbonyl ethoxy) -1,1'-binaphthyl, 2,2'-bis (3-tert-butoxycarbonylpropoxy) -1,1'-binaphthyl and the like. Of these, R ¹ and R ² in the general formula (a) are methylene groups, o and p are 1, and R ^{3 to} R ¹⁰ are hydrogen atoms, 2,2′-bis (carboxymethoxy) Most preferred is -1,1'-binaphthyl (hereinafter sometimes abbreviated as BCMB) or an ester-forming derivative thereof.
<The diol component of the general formula (1)>
As the diol component, a compound mainly represented by the general formula (b) is preferably used.

In the general formula (b) of the diol component as the raw material of the general formula (1), R ¹¹ and R ¹² are each independently a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms. And o and p each independently represent an integer of 0 or more. R ¹³ and R ¹⁴ each independently represent a hydrocarbon group which may contain a hydrogen atom or an aromatic group having 1 to 20 carbon atoms. R ¹¹ and R ¹² preferably each independently represent a hydrocarbon group having 1 to 4 carbon atoms, and o and p each independently represent an integer of 0 or 1. Particularly preferably, R ¹¹ and R ¹² represent an ethylene group, o and p represent 1, and R ¹³ and R ¹⁴ represent a hydrogen atom or a phenyl group. Further, R ¹¹ and R ¹² may be the same or different, o and p may be the same or different, and R ¹³ and R ¹⁴ may be the same or different. May be.

Formula specifically ^(b), the a R ^{11, R 12} is an ethylene group, o and p are the ^{1, R 13,} R ¹⁴ is a hydrogen atom of 9,9-bis [4- ( 2-Hydroxyethoxy) phenyl] fluorene (hereinafter sometimes abbreviated as BPEF) and 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl in which R ¹³ and R ¹⁴ are phenyl groups. ] Fluorene (hereinafter sometimes abbreviated as OPBPEF) or biscresolfluorene in which o and p are 0 and R ¹³ and R ¹⁴ are methyl groups is more preferable.
<The diol component of the general formula (2)>
As the diol component, a compound mainly represented by the general formula (c) is preferably used.

In the general formula (c) of the diol component as the raw material of the general formula (2), R ¹⁵ and R ¹⁶ are each independently a hydrocarbon group having 1 to 10 carbon atoms which may include an aromatic group. Q and r each independently represent an integer of 0 or more. R ^{17 to} R ²⁴ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. R ¹⁵ and R ¹⁶ preferably each represent a hydrocarbon group having 1 to 4 carbon atoms, and q and r each preferably represent an integer of 0 or 1. R ^{17 to} R ²⁴ preferably each independently represent a hydrogen atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. Particularly preferably, R ¹⁵ and R ¹⁶ represent an ethylene group, q and r represent 1, and R ^{17 to} R ²⁴ represent a hydrogen atom. Further, R ¹⁵ and R ¹⁶ may be the same or different, o and p may be the same or different, and R ^{17 to} R ²⁴ may be the same or different. Is also good.

Specifically, in the general formula (c), R ¹⁵ and R ¹⁶ are ethylene groups, q and r are 1, and R ^{17 to} R ²⁴ are hydrogen atoms 2,2′-bis (2- Hydroxyethoxy) -1,1′-binaphthyl (hereinafter sometimes abbreviated as BHEB), q and r are 0, and R ^{17 to} R ²⁴ are 1,1′-bi-2-naphthol which is a hydrogen atom. It is more preferable that there is.

<Copolymerization component other than general formula (1) and general formula (2)>
The thermoplastic resin in the present invention has the repeating unit represented by the general formula (1) and the general formula (2), but may contain a copolymerization component separately. As the copolymerization component, a dicarboxylic acid component other than the compound represented by the general formula (a), a diol component other than the compounds represented by the general formula (b) and the general formula (c), a repeating unit having a carbonate bond, etc. Is exemplified.

  Specific examples of the dicarboxylic acid component as the copolymerization component include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, ethylmalonic acid and other aliphatic dicarboxylic acid components, Monocyclic aromatic dicarboxylic acid components such as phthalic acid, isophthalic acid and terephthalic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid , Polycyclic aromatic dicarboxylic acid components such as anthracene dicarboxylic acid and phenanthrene dicarboxylic acid, biphenyl dicarboxylic acid components such as 2,2′-biphenyldicarboxylic acid, 1,4-cyclodicarboxylic acid and 2,6-decalindicarboxylic acid Alicyclic dicarboxylic acid component of. You may use these individually or in combination of 2 or more types. Moreover, you may use acid chloride and ester as these derivatives. Among these, a monocyclic aromatic dicarboxylic acid component, a polycyclic aromatic dicarboxylic acid component, and a biphenyldicarboxylic acid component are preferable because they are likely to have higher heat resistance and a higher refractive index.

  Specific examples of the diol component as a copolymerization component include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and other aliphatic diol components, and tricyclo [5.2]. .1.02,6] decanedimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornanedimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spiro Alicyclic diol components such as glycol and isosorbide, hydroquinone, resorcinol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyl Phenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, bis (4-hydroxyphenyl) sulfone, bis (4 -(2-hydroxyethoxy) phenyl) sulfone, bis (4-hydroxyphenyl) sulfide, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy) Examples thereof include aromatic diol components such as phenyl) cyclohexane, biphenol, dihydroxynaphthalene, bis (2-hydroxyethoxy) naphthalene, and 10,10-bis (4-hydroxyphenyl) anthrone. You may use these individually or in combination of 2 or more types. Among these, ethylene glycol is preferable because it is easy to suppress deterioration in heat resistance and refractive index while improving moldability.

  As the repeating unit having a carbonate bond as a specific copolymerization component, the diol component exemplified by the general formulas (b) and (c) and the diol component exemplified by the above-mentioned copolymerization component are carbonates. Among them, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, since it is easy to suppress lowering of heat resistance and refractive index while enhancing moldability, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, biscresolfluorene, 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthyl, 1,1'-bi -2-Naphthol is preferred.

  The thermoplastic resin of the present invention is produced by subjecting the raw materials represented by the above-mentioned general formulas (a), (b) and (c) to an esterification reaction or a transesterification reaction, and subjecting the obtained reaction product to a polycondensation reaction to obtain a desired product. A high molecular weight polymer having the molecular weight of

  Specifically, for example, it is preferable to mix the diol component and the dicarboxylic acid component or its diester in the presence of an inert gas, and to react under reduced pressure, usually at 120 to 350 ° C, preferably at 150 to 300 ° C. . The degree of pressure reduction is changed stepwise, and finally water or alcohol produced at 0.13 kPa or less is distilled out of the system, and the reaction time is usually about 1 to 10 hours.

  As the polymerization catalyst, those known per se can be adopted, and for example, antimony compounds, titanium compounds, germanium compounds, tin compounds or aluminum compounds are preferable. Examples of such compounds include antimony, titanium, germanium, tin, aluminum oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates and sulfates. Moreover, these compounds can be used in combination of 2 or more types. Among these, tin, titanium and germanium compounds are preferable from the viewpoints of melt stability and hue of the thermoplastic resin.

As the transesterification catalyst, those known per se can be adopted, and for example, compounds containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium, lead elements, etc. can be used. Specific examples thereof include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates and sulfates containing these elements. Of these, compounds such as manganese, magnesium, zinc, titanium, cobalt oxides, acetates, and alcoholates are preferable from the viewpoints of melt stability of the thermoplastic resin, hue, and small amount of polymer-insoluble foreign matter. Further, manganese, magnesium and titanium compounds are preferable. These compounds can be used in combination of two or more kinds.
The amount of the catalyst used is, for example, about 0.01 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol, preferably about 0.1 × 10 ⁻⁴ to 40 × 10 ⁻⁴ mol, per 1 mol of the dicarboxylic acid component. It may be.

  As described above, the thermoplastic resin of the present invention may contain a copolymer component other than the repeating units of the general formula (1) and the general formula (2). For example, in the case of using a polyester carbonate resin, it can be produced by reacting with a dicarboxylic acid chloride or phosgene in addition to a diol component and a dicarboxylic acid component, or by reacting a diol, a dicarboxylic acid and a biaryl carbonate.

  Specific examples of the biaryl carbonate include carbonic acid diesters such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Of these, diphenyl carbonate is preferred.

  The content of the dicarboxylic acid chloride, phosgene, or biaryl carbonate component is preferably less than 42 mol%, more preferably less than 30 mol%, and further preferably less than 20 mol% with respect to 100 mol% of the dicarboxylic acid component.

<Additives>
To the thermoplastic resin of the present invention, if necessary, additives such as a heat stabilizer, an antioxidant, a release agent, a plasticizer, a filler, and an ultraviolet absorber are appropriately added to obtain a thermoplastic resin composition. Can be used.

  As the release agent, those having 90% by weight or more thereof consisting of alcohol and fatty acid ester are preferable. Specific examples of the ester of alcohol and fatty acid include ester of monohydric alcohol and fatty acid and / or partial ester or total ester of polyhydric alcohol and fatty acid. The ester of monohydric alcohol and fatty acid is preferably an ester of monohydric alcohol having 1 to 20 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms. The partial ester or total ester of polyhydric alcohol and fatty acid is preferably a partial ester or total ester of polyhydric alcohol having 1 to 25 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms. Specific examples of monohydric alcohols, saturated fatty acids and esters include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate and isopropyl palmitate, with stearyl stearate being preferred.

Specific examples of the partial or total ester of polyhydric alcohol and saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetraglyceride. All or partial ester of dipentaerythritol such as stearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate. Esters and the like can be mentioned. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used.

The amount of the ester in the release agent is preferably 90% by weight or more, more preferably 95% by weight or more, based on 100% by weight of the release agent.
The release agent to be added to the thermoplastic resin composition is preferably 0.005 to 2.0 parts by weight, more preferably 0.01 to 0.6 parts by weight, based on 100 parts by weight of the thermoplastic resin. A range of 0.02 to 0.5 parts by weight is more preferable.
Examples of the heat stabilizer include phosphorus-based heat stabilizers, sulfur-based heat stabilizers and hindered phenol-based heat stabilizers.

In the phosphorus-based heat stabilizer, preferably tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite is used.
The content of the phosphorus-based heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
Among the hindered phenol heat stabilizers, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is particularly preferably used.
The content of the hindered phenolic heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.3 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

  As the UV absorber, at least one UV absorber selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic iminoester UV absorbers and cyanoacrylate UV absorbers. Is preferred.

In the benzotriazole type ultraviolet absorber, more preferably, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethyl) Butyl) -6- (2H-benzotriazol-2-yl) phenol].
Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Examples of the triazine-based ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and 2- (4,6-bis ( 2.4-Dimethylphenyl) -1,3,5-triazin-2-yl) -5-[(octyl) oxy] -phenol and the like can be mentioned.
As the cyclic iminoester-based ultraviolet absorber, 2,2'-p-phenylenebis (3,1-benzoxazin-4-one) is particularly preferable.

The blending amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If the blending amount is within the above range, the thermoplastic resin molded article may be used depending on the application. It is possible to impart sufficient weather resistance.
<Optical lens>
The thermoplastic resin of the present invention is suitable for optical members, especially optical lenses.

  When the optical lens of the thermoplastic resin of the present invention is manufactured by injection molding, it is preferable to mold under the conditions of a cylinder temperature of 260 to 350 ° C and a mold temperature of 90 to 170 ° C. More preferably, molding is performed under the conditions of a cylinder temperature of 270 to 320 ° C. and a mold temperature of 100 to 160 ° C. If the cylinder temperature is higher than 350 ° C, the thermoplastic resin is decomposed and colored, and if it is lower than 260 ° C, the melt viscosity is high and molding tends to be difficult. Further, if the mold temperature is higher than 170 ° C., it tends to be difficult to take out the molded piece made of the thermoplastic resin from the mold. On the other hand, if the mold temperature is lower than 90 ° C, the resin may harden too quickly in the mold at the time of molding, making it difficult to control the shape of the molded piece, or sufficiently transferring the mold attached to the mold. Is likely to be difficult.

  The optical lens of the present invention is preferably implemented in the form of an aspherical lens, if necessary. Since it is possible to reduce the spherical aberration to substantially zero with a single aspherical lens, it is not necessary to remove the spherical aberration by combining a plurality of spherical lenses, and it is possible to reduce the weight and the molding cost. It will be possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.

  Further, since the optical lens of the present invention has high molding fluidity, it is particularly useful as a material for an optical lens that is thin, small, and has a complicated shape. As a specific lens size, the thickness of the central portion is 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and further preferably 0.1 to 2.0 mm. The diameter is 1.0 mm to 20.0 mm, more preferably 1.0 to 10.0 mm, and further preferably 3.0 to 10.0 mm. Further, it is preferable that the meniscus lens has a convex shape on one side and a concave shape on one side.

  The lens made of the thermoplastic resin in the optical lens of the present invention is molded by any method such as mold molding, cutting, polishing, laser machining, electric discharge machining, and etching. Among these, die molding is more preferable from the viewpoint of manufacturing cost.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The evaluation was performed by the following method.
(A) Film 3 g of the obtained resin is dissolved in 50 ml of methylene chloride and cast on a glass petri dish. After being sufficiently dried at room temperature, it was dried at a temperature of 120 ° C. or lower for 8 hours to prepare a cast film having a thickness of about 100 μm.

The evaluation was performed by the following method.
(1) Copolymerization ratio: The resin obtained after the completion of the polymerization was measured using proton NMR of JNM-AL400 manufactured by JEOL Ltd.
(2) Specific viscosity: The resin obtained after the completion of the polymerization was sufficiently dried, and the specific viscosity (η _sp ) of the solution at 20 ° C. was measured from a solution prepared by dissolving 0.7 g of the resin in 100 ml of methylene chloride.
(3) Glass transition point: Pellets obtained after melt-kneading were measured by Shimadzu DSC-60A at a temperature rising rate of 20 ° C / min.
(4) Refractive index (nd): The film prepared by the method of (a) was measured for the refractive index (wavelength: 589 nm) at 25 ° C. using an Abbe refractometer of DR-M2 manufactured by ATAGO.
(5) Orientation birefringence (Δn): A cast film having a thickness of 100 μm prepared by the method of (a) was stretched 2 times at Tg + 10 ° C., and the position at 589 nm was measured using an ellipsometer M-220 manufactured by JASCO Corporation. The phase difference (Re) was measured, and the orientation birefringence (Δn) was calculated from the following formula.
Δn = Re / d
Δn: orientation birefringence
Re: Phase difference (nm)
d: Thickness (nm)
◯: 0 or more, 2 × 10 ⁻³ or less Δ: 2 × 10 ^{−3 or} more, 4 × 10 ⁻³ or less ×: 4 × 10 ^{−3 or} more

Example 1
2,2'-bis (carboxymethoxy) -1,1'-binaphthyl (BCMB) 16.90 parts by weight, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF) 12.72 parts by weight Parts, 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthyl (BHEB) 10.86 parts by weight, diphenyl carbonate (DPC) 3.64 parts by weight and tetrabutoxy titanium 17.0 × 10 ^{−. 3} parts by weight was placed in a reaction kettle equipped with a stirrer and a distillation device, heated to 180 ° C. under a normal pressure of nitrogen atmosphere and stirred for 20 minutes. Then, the temperature was gradually raised and the pressure was reduced, and finally, the temperature was raised to 260 ° C. and 0.13 kPa or less and the pressure was reduced to carry out a transesterification / polycondensation reaction. After reaching a predetermined stirring torque, the content was taken out of the reactor to obtain pellets of polyester carbonate resin. When the obtained pellets were analyzed by NMR, the dicarboxylic acid component introduced into the polyester resin was 42 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 58 mol% with respect to all the monomer components (all dicarboxylic acid components + all diol components), 29 mol% was derived from BPEF, and 29 mol% was derived from BHEB. The polyester resin obtained had a specific viscosity of 0.26, a glass transition temperature Tg of 141 ° C., and a refractive index of 1.669.

Example 2
Polymerization was performed in the same manner as in Example 1 except that BCMB was 20.12 parts by weight, BPEF was 10.96 parts by weight, BHEB was 9.36 parts by weight, and DPC was 0 part by weight. When the obtained pellets were analyzed by NMR, the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was The content was 50 mol% with respect to all the monomer components (all dicarboxylic acid components + all diol components), 25 mol% was derived from BPEF, and 25 mol% was derived from BHEB. Moreover, the specific viscosity of the obtained polyester resin was 0.26, the glass transition temperature Tg was 143 ° C., and the refractive index was 1.672.

Example 3
Polymerization was performed in the same manner as in Example 1 except that BCMB was 20.12 parts by weight, BPEF was 10.96 parts by weight, BHEB was 5.62 parts by weight, ethylene glycol (EG) was 3.72 parts by weight, and DPC was 0 parts by weight. When the obtained pellets were analyzed by NMR, the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was The content was 50 mol% with respect to all monomer components (all dicarboxylic acid components + all diol components), 25 mol% was BPEF, 15 mol% was derived from BHEB, and 10 mol% was derived from EG. The polyester resin obtained had a specific viscosity of 0.26, a glass transition temperature Tg of 141 ° C., and a refractive index of 1.670.

Example 4
16.90 parts by weight of BCMB, 17.13 parts by weight of 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene (OPBPEF), 10.86 parts by weight of BHEF, and 3.64 parts by weight of DPC. Was polymerized in the same manner as in Example 1. When the obtained pellets were analyzed by NMR, the dicarboxylic acid component introduced into the polyester resin was 42 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 58 mol% with respect to all monomer components (all dicarboxylic acid components + all diol components), 29 mol% was OPBPEF, and 29 mol% was derived from BHEB. The polyester resin obtained had a specific viscosity of 0.27, a glass transition temperature Tg of 144 ° C., and a refractive index of 1.673.

Example 5
Polymerization was performed in the same manner as in Example 1 except that BCMB was 20.12 parts by weight, OPBPEF was 14.77 parts by weight, BHEB was 9.36 parts by weight, and DPC was 0 parts by weight. When the obtained pellets were analyzed by NMR, the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was The content was 50 mol% with respect to all monomer components (all dicarboxylic acid components + all diol components), 25 mol% was derived from OPBPEF, and 25 mol% was derived from BHEB. The polyester resin obtained had a specific viscosity of 0.27, a glass transition temperature Tg of 145 ° C., and a refractive index of 1.675.

Example 6
Polymerization was performed in the same manner as in Example 1 except that BCMB was 20.12 parts by weight, OPBPEF was 11.81 parts by weight, BHEB was 7.49 parts by weight, ethylene glycol (EG) was 3.72 parts by weight, and DPC was 0 parts by weight. When the obtained pellets were analyzed by NMR, the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was It was 50 mol% with respect to all monomer components (all dicarboxylic acid components + all diol components), 20 mol% was OPBPEF, 20 mol% was derived from BHEB, and 10 mol% was derived from EG. The polyester resin obtained had a specific viscosity of 0.27, a glass transition temperature Tg of 141 ° C., and a refractive index of 1.675.

Example 7
Example 2, except that 2,2′-bis (ethoxycarbonylmethoxy) -1,1′-binaphthyl (BECMB) 20.93 parts by weight, BPEF 10.96 parts by weight, BHEB 9.36 parts by weight, and DPC 0 parts by weight. Polymerized in the same manner as. When the obtained pellets were analyzed by NMR, the diester component introduced into the polyester resin was 50 mol% with respect to all the monomer components (all diester components + all diol components), and the diol component introduced into the polyester resin was all monomers. The content was 50 mol% with respect to the components (all ester components + all diol components), 25 mol% was derived from BPEF, and 25 mol% was derived from BHEB. Moreover, the specific viscosity of the obtained polyester resin was 0.26, the glass transition temperature Tg was 143 ° C., and the refractive index was 1.672.

Comparative Example 1
Polymerization was performed in the same manner as in Example 1 except that BCMB was 20.12 parts by weight, BHEB was 11.23 parts by weight, and EG was 4.34 parts by weight. When the obtained pellets were analyzed by NMR, the dicarboxylic acid component introduced into the polyester resin was 50 mol% with respect to the total monomer components (total dicarboxylic acid component + total diol component), and the diol component introduced into the polyester resin was The content was 50 mol%, 30 mol% was derived from BHEB, and 20 mol% was derived from EG with respect to all monomer components (all dicarboxylic acid components + all diol components). The specific viscosity of the obtained polyester resin was 0.27, the glass transition temperature Tg was 128 ° C., and the refractive index was 1.677.

Comparative example 2
Polymerization was conducted in the same manner as in Example 1 except that dimethyl terephthalate (DMT) was 9.71 parts by weight, BHEB was 18.72 parts by weight, and diphenyl carbonate (DPC) was 0 parts by weight. When the obtained pellets were analyzed by NMR, the diester component introduced into the polyester resin was 50 mol% with respect to the total monomer components (all diester components + all diol components), and the diol component introduced into the polyester resin was all monomers. It was 50 mol% with respect to the components (all diester components + all diol components). The polyester resin obtained had a specific viscosity of 0.25, a glass transition temperature Tg of 127 ° C., and a refractive index of 1.658.

Comparative Example 3
Polymerization was conducted in the same manner as in Example 1 except that 21.93 parts by weight of BPEF, 18.72 parts by weight of BHEB, and 21.85 parts by weight of DPC. When the obtained pellets were analyzed by NMR, it was found that 50 mol% was derived from BPEF and 50 mol% was derived from BHEB with respect to all the monomer components introduced into the polycarbonate resin. The specific viscosity of the obtained polycarbonate resin was 0.23, the glass transition temperature Tg was 135 ° C., and the refractive index was 1.649.

Comparative Example 4
Polymerization was carried out in the same manner as in Example 1 except that 43.85 parts by weight of BPEF and 21.85 parts by weight of DPC were used. When the obtained pellet was analyzed by NMR, 100 mol% of the diol component introduced into the polycarbonate resin was derived from BPEF. The specific viscosity of the obtained polycarbonate resin was 0.24, the glass transition temperature Tg was 147 ° C., and the refractive index was 1.638.

The value of Formula (1) + Formula (2) in Table 1 is the ratio of the repeating units represented by Formula (1) and Formula (2) when the total of all repeating units is 100 mol%.
The polyester or polyester carbonate resin obtained in Examples 1 to 7 in Table 1 is a resin having a high refractive index, low birefringence and high heat resistance, and is excellent as an optical lens. In contrast, Comparative Example 1 has a high refractive index and a low birefringence, but has lower heat resistance than the polymer. Since the birefringence of Comparative Example 2 is not sufficiently canceled, the birefringence obtained from the polymer is large and the heat resistance is poor. Comparative Example 3 is a polycarbonate copolymer in which the 1,1′-binaphthalene structure is used as the diol component BHEB and is copolymerized with BPEF, but has a lower refractive index than the polymer.

The thermoplastic resin of the present invention has a high refractive index, a low birefringence, and a high heat resistance, and therefore, an optical disc, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, a lens, a prism, an optical film, a substrate, and an optical element. It can be used as an optical member such as a filter and a hard coat film, and is particularly useful for a lens.

Claims (15)

A thermoplastic resin in which the total of repeating units represented by the following general formula (1) and the following general formula (2) is 70 mol% or more in all units.

(In Formula (1), R ¹ and R ² each independently represent a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, and n and m each independently represent an integer of 0 or more. R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. R ¹¹ and R ¹² are each independently represents an even better hydrocarbon group include an aromatic group having 1 to 10 carbon atoms, o and p is an integer of 0 or more each independently .R ¹³ and R ^14's each independently represent a hydrogen atom or a hydrocarbon group optionally containing an aromatic group having 1 to 20 carbon atoms.)

(In the formula (2), R ¹ and R ² each independently represent a hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, and n and m each independently represent an integer of 0 or more. R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. R ¹⁵ and R ¹⁶ each independently represents a hydrocarbon group which may include an aromatic group having 1 to 10 carbon atoms, o and p is an each independently an integer of 0 or more .R ¹⁷ to R ^Each of ²⁴ independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms.)   The thermoplastic resin according to claim 1, wherein the ratio of the units represented by the general formula (1) and the general formula (2) is 20 to 80:80 to 20. In the general formula (1), R ¹¹ and R ¹² are each a hydrocarbon group having 1 to 4 carbon atoms, o and p are each 0 or 1, and R ¹³ and R ¹⁴ are each hydrogen. The thermoplastic resin according to claim 1 or 2, which is a hydrocarbon group which may contain an atom or an aromatic group having 1 to 12 carbon atoms. In the general formula (1), R ¹¹ and R ¹² are each an ethylene group, o and p are each 1, and R ¹³ and R ¹⁴ are each a hydrogen atom or a phenyl group. The thermoplastic resin according to. In the general formula (2), R ¹⁵ and R ¹⁶ are each a hydrocarbon group having 1 to 4 carbon atoms, q and r are each 0 or 1, and R ^{17 to} R ²⁴ are each hydrogen. The thermoplastic resin according to claim 1 or 2, which is a hydrocarbon group which may contain an atom or an aromatic group having 1 to 12 carbon atoms. In the general formula (2), R ¹⁵ and R ¹⁶ are each an ethylene group, q and r are each 1, and R ^{17 to} R ²⁴ are each a hydrogen atom. Plastic resin. In the general formula (1) and the general formula (2), R ¹ and R ² are each a hydrocarbon group having 1 to 3 carbon atoms, n and m are 0 or 1, and R ³ to R ¹⁰ is a thermoplastic resin according to claim 1 or 2 also include each hydrogen atom or an aromatic group having 1 to 12 carbon atoms which is a good hydrocarbon group. In the general formula (1) and the general formula (2), R ¹ and R ² are each a methylene group, n and m are each 1, and R ^{3 to} R ¹⁰ are hydrogen atoms. 7. The thermoplastic resin according to 7.   The thermoplastic resin according to any one of claims 1 to 8, which has a refractive index of 1.650 to 1.700.   The thermoplastic resin according to any one of claims 1 to 9, which has a specific viscosity of 0.12 to 0.40.   The thermoplastic resin according to any one of claims 1 to 10, which has a glass transition temperature of 128 to 160 ° C. The thermoplastic resin according to claim 1, which has an orientation birefringence of 0 to 4 × 10 ⁻³ .   The thermoplastic resin according to any one of claims 1 to 12, wherein the thermoplastic resin is a polyester or polyester carbonate resin.   An optical member comprising the thermoplastic resin according to claim 1. An optical lens comprising the thermoplastic resin according to claim 1.