JP2020117610A - Thermoplastic resin and optical member - Google Patents

Abstract

To provide a thermoplastic resin having a high refractive index and can balance heat resistance and moldability.SOLUTION: A thermoplastic resin includes a repeating unit represented by the following formula (1). In formula (1), ring Z and ring V each independently represent (the same or different) aromatic ring; R, R, Arand Areach independently represents a hydrogen atom, a halogen atom and a substituent having 1 to 12 carbon atoms that may contain an aromatic ring, and has at least one thiophene skeleton in any one of Z, V, R, R, Arand Ar; Land Leach independently represents a divalent connection group; j and k each independently represents an integer of 0 or larger; m and n each independently represents 0 or 1; and W is at least one selected from a carbonyl group and an α, ω-dicarbonyl group.SELECTED DRAWING: None

Description

The present invention relates to a thermoplastic resin having a high refractive index and capable of balancing heat resistance and moldability.

An imaging module is used for a camera, a video camera, a mobile phone with a camera, a videophone, an intercom with a camera, and the like. In recent years, the optical system used in this image pickup module is particularly required to be downsized. As the optical system becomes smaller, chromatic aberration of the optical system becomes a serious problem. Therefore, by combining a high-dispersion optical lens material with a high refractive index and a small Abbe number, and a low-dispersion optical lens material with a low refractive index and a large Abbe number, It is known that chromatic aberration can be corrected.

The glass conventionally used as a material for an optical system can realize various required optical characteristics and is excellent in environmental resistance, but has a problem of poor workability. On the other hand, a resin, which is cheaper than a glass material and is excellent in workability, has been used for an optical component. In particular, a resin having a fluorene skeleton or a binaphthalene skeleton is used because of its high refractive index. There is also an example in which sulfur, which is a hetero atom, is introduced in order to realize a high refractive index. For example, in Patent Documents 1 and 2, a high refractive index is realized with polythiocarbonate or polythioester. However, the 5% weight loss temperature, which is an index of heat resistance, is insufficient as a thermoplastic resin, and improvement of heat resistance is required to introduce sulfur into the polymer.

JP, 2008-141084, A JP, 2018-141085, A

Therefore, an object of the present invention is to provide a thermoplastic resin having a high refractive index and capable of balancing heat resistance and moldability.

The inventors of the present invention have conducted extensive studies to achieve this object, and as a result, a thermoplastic resin having a specific compound containing thiophene, which is a heterocyclic compound containing sulfur, has a specific weight loss temperature of 5%. They have found that they can be improved and have reached the present invention. It was also found that this thermoplastic resin can highly balance heat resistance and moldability while maintaining a high refractive index.
That is, the present invention is as follows.

1. A thermoplastic resin containing a repeating unit represented by the following formula (1).
(In the formula, ring Z and ring V each independently represent (the same or different) an aromatic ring, and R ¹ , R ² , Ar ¹ and Ar ² are each independently a hydrogen atom, a halogen atom or an aromatic group. A substituent having 1 to 12 carbon atoms, which may contain at least one thiophene skeleton in any of Z, V, R ¹ , R ² , Ar ¹ and Ar ² , and L ¹ and L ² each independently represents a divalent linking group, j and k each independently represent an integer of 0 or more, m and n each independently represent 0 or 1, and W represents the following formula (2) or (3 ) At least one selected from the group represented by).)
(In the formula, X represents a divalent linking group.)

2. 2. The thermoplastic resin as described in 1 above, which has at least two thiophene skeletons in the formula (1).
3. In the above formula (1), Ar ¹ and Ar ² each independently represent a hydrogen atom, a thienyl group, or a benzothienyl group.
4. In the above formula (1), the thermoplastic resin according to 3 above, wherein Z and V represent an aromatic hydrocarbon ring.
5. In the above formula (1), the thermoplastic resin according to 4 above, wherein Z and V represent benzene or naphthalene.
6. In the formula (1), R ¹ and R ² each independently represent a hydrogen atom, a methyl group, a phenyl group, a naphthyl group, a thienyl group, or a benzothienyl group. resin.
7. In the above formula (1), R ¹ and R ² represent a hydrogen atom or a methyl group, and the thermoplastic resin as described in 6 above.

8. X in the formula (3) is at least one selected from the group consisting of a phenylene group, a naphthalenediyl group, a group represented by the following formula (4) and a group represented by the following formula (5) as a repeating unit. The thermoplastic resin according to any one of 1 to 7 above.
(In the formula, R ³ and R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may include an aromatic group, or a halogen atom.)

9. 9. The thermoplastic resin as described in any one of 1 to 8 above, which contains at least one selected from the group consisting of units represented by the following formulas (6) to (8) as a repeating unit.
(In the formula, R ⁵ and R ⁶ are each independently a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, or a halogen atom.)
(In the formula, R ⁷ and R ⁸ are each independently a hydrogen atom, a substituent having 1 to 12 carbon atoms which may contain an aromatic group, or a halogen atom.)
(In the formula, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a substituent having 1 to 12 carbon atoms which may include an aromatic group, or a halogen atom, and U is a single bond or a divalent linking group. is there.)

10. The thermoplastic resin as described in any one of 1 to 9 above, which has a 10.5% weight loss temperature of 360°C or higher.
11. 11. The thermoplastic resin as described in 10 above, wherein the 5% weight loss temperature is 380° C. or higher. The thermoplastic resin according to any one of 1 to 11 above, which has a glass transition temperature of 130 to 180°C.
13. 13. The thermoplastic resin as described in any one of 1 to 12 above, which has a specific viscosity of 0.12 to 0.40.
14. The thermoplastic resin as described in any one of 1 to 13 above, which has a refractive index of 1.620 to 1.780.
15. An optical member comprising the thermoplastic resin according to any one of 1 to 14 above.
16. 16. The optical member as described in 15 above, which is an optical lens.

INDUSTRIAL APPLICABILITY The thermoplastic resin of the present invention has a high refractive index and can balance heat resistance and moldability, so that it has optical lenses, prisms, optical disks, transparent conductive substrates, optical cards, sheets, films, and optical fibers. It can be used as an optical member such as an optical film, an optical filter, and a hard coat film, and is extremely useful particularly for an optical lens. Therefore, the industrial effect produced by it is exceptional.

It is ¹ H NMR of 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-di(2-thienyl)fluorene obtained in Reference Example 1. 2 is ¹ H NMR of the polycarbonate resin obtained in Example 1.

The present invention will be described in more detail.
<Thermoplastic resin>
The thermoplastic resin of the present invention contains a repeating unit represented by the following formula (1).

(In the formula, ring Z and ring V each independently represent (the same or different) an aromatic ring, and R ¹ , R ² , Ar ¹ and Ar ² are each independently a hydrogen atom, a halogen atom or an aromatic group. A substituent having 1 to 12 carbon atoms, which may contain at least one thiophene skeleton in any of Z, V, R ¹ , R ² , Ar ¹ and Ar ² , and L ¹ and L ² each independently represents a divalent linking group, j and k each independently represent an integer of 0 or more, m and n each independently represent 0 or 1, and W represents the following formula (2) or (3 ) At least one selected from the group represented by).)

(In the formula, X represents a divalent linking group.)

Examples of the aromatic ring represented by the ring Z or the ring V in the formula (1) include an aromatic hydrocarbon ring, thiophene and benzothiophene, and the aromatic hydrocarbon ring includes at least a benzene ring in addition to benzene. Examples thereof include condensed polycyclic aromatic hydrocarbon rings having a skeleton, and preferable examples include condensed bicyclic hydrocarbon rings such as condensed bicyclic hydrocarbon rings and condensed tricyclic hydrocarbon rings.

As the condensed bicyclic hydrocarbon ring, those having 8 to 20 carbon atoms such as indene and naphthalene are preferable, and the condensed bicyclic hydrocarbon ring having 10 to 16 carbon atoms is more preferable. Further, as the condensed tricyclic hydrocarbon ring, anthracene, phenanthrene and the like are preferable.

Of ring Z, an aromatic hydrocarbon ring is preferable, benzene and naphthalene are more preferable, and benzene is further preferable.

Of ring V, an aromatic hydrocarbon ring and benzothiophene are preferable, benzene, naphthalene and benzothiophene are more preferable, benzene and naphthalene are further preferable, and benzene is even more preferable.

In the formula (1), Ar ¹ and Ar ² each independently represent a hydrogen atom, a halogen atom, or a substituent having 1 to 12 carbon atoms, which may include an aromatic group, and a hydrogen atom, a phenyl group, or a naphthyl group. A group, a thienyl group and a benzothienyl group are preferable, a hydrogen atom, a thienyl group and a benzothienyl group are more preferable, a thienyl group and a benzothienyl group are further preferable, and a thienyl group is even more preferable.

In the formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a substituent having 1 to 12 carbon atoms which may include an aromatic group, and a hydrogen atom, a methyl group, or phenyl. A group, a naphthyl group, a thienyl group and a benzothienyl group are preferable, a hydrogen atom, an ethyl group, a phenyl group and a naphthyl group are more preferable, a hydrogen atom and a methyl group are further preferable, and a hydrogen atom is even more preferable.

Further, as the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and the like are preferable.
Further, the substituent having 1 to 12 carbon atoms which may contain an aromatic group is preferably a phenyl group, a naphthyl group, a thienyl group, a benzothienyl group or the like.
Moreover, as a specific example of the naphthyl group, a 1-naphthyl group, a 2-naphthyl group, or the like is preferable.
Moreover, as a specific example of the thienyl group, a 2-thienyl group, a 3-thienyl group, or the like is preferable.
Further, as a specific example of the benzothienyl group, a 2-benzo[b]thienyl group, a 3-benzo[b]thienyl group, or the like is preferable.

In the formula (1), L ¹ and L ² each independently represent a divalent linking group, preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. Further, an ethylene group is more preferable. The glass transition temperature (Tg) of the resin can be adjusted by adjusting the length of the linking group of L ¹ and L ² .

In the above formula (1), W is at least one selected from the group represented by the above formula (2) or (3). When W is the formula (2), the formula (1) is a carbonate unit, and when W is the formula (3), the formula (1) is an ester unit.

The above formula (1) can be obtained from a dihydroxy compound and a carbonate precursor such as a carbonic acid ester, or a dihydroxy compound and a dicarboxylic acid or an ester-forming derivative thereof.

In the above formula (1), when the ring V is benzothiophene, it is preferable that the ring V is located symmetrically with respect to fluorene, and the 1,2-position and the 7,8-position, the 2,3-position, the 6,7-position and the 3-position. , 4th, 5th, and 6th positions are preferable, and 2,3rd and 6,7th positions are more preferable.

The number of thiophene skeletons is preferably at least two or more. The refractive index can be improved as the number of thiophene skeletons introduced increases.

The following can be considered as the reason why the high refractive index and the heat resistance, which are the effects of the present invention, can be balanced.

That is, from the relational expression between the molecular structure and the refractive index known as the Lorentz-Lorenz equation, it is known that the refractive index of a substance is increased by increasing the electron density of the molecule. Based on this theory, a resin having a sulfur atom, which is a conventional technique, has been made to have a high refractive index by introducing a sulfur atom into the molecule. In Patent Documents 1 and 2, the refractive index is improved by introducing a sulfur atom having a high electron density.

The present invention makes it possible to obtain a resin having both a high refractive index and excellent heat resistance, which cannot be achieved by these conventional techniques. The bond energy of the single bond between sulfur and carbon is smaller than the bond energy of the single bond between carbon and carbon, and the C—S bond site is easily cleaved by heat and has low heat resistance. By using a thiophene skeleton, sulfur is incorporated into and stabilized in the aromatic ring, so that the bond of C—S is strengthened and it is possible to realize both high refractive index and heat resistance due to sulfur. Conceivable.

The thiophene skeleton may be introduced in the main chain or the side chain, but by introducing it in the side chain, the conjugation is further spread, so that the electron density of the molecule is increased and it is possible to contribute to the high refractive index. Furthermore, since thiophene is a five-membered ring, steric hindrance due to hydrogen atoms is small when a single bond is formed with an aromatic ring, and the angle of the plane with the adjacent aromatic ring is smaller than that of a six-membered benzene or naphthalene ring. Therefore, it is considered that the conjugation is further expanded and the electron density can be increased.

Further, by introducing a thiophene ring, the electron density of the molecule becomes higher than that of a single sulfur atom, which can contribute to a higher refractive index.

The lower limit of the repeating unit represented by the formula (1) is preferably 5 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, based on the total repeating units. .. It is preferable that the repeating unit represented by the formula (1) has a high refractive index in the above range. The upper limit is preferably 100 mol% or less, more preferably 80 mol% or less, and further preferably 70 mol% or less. It is preferable that the repeating unit represented by the formula (1) is in the above range because the balance between the refractive index, heat resistance and moldability is excellent.

In the formula (3), X represents a divalent linking group, preferably a hydrocarbon group having 1 to 30 carbon atoms and optionally containing an aromatic group, such as a phenylene group, a naphthalenediyl group, and A group represented by formula (4) or formula (5) is more preferable.

In the thermoplastic resin of the present invention, when at least one selected from the group consisting of the units represented by the formulas (6) to (8) is included as a repeating unit, the repeating unit represented by the formula (1) The molar ratio of the repeating unit to the group consisting of the units represented by the formulas (6) to (8) is preferably 95:5 to 5:95, and more preferably 80:20 to 20:80. , 70:30 to 30:70 is more preferable. When the mol ratio of the repeating unit represented by the formula (1) and at least one repeating unit selected from the group consisting of the units represented by the formulas (6) to (8) is within the above range, In addition to having a refractive index, the balance of moldability is excellent, which is preferable.

The 5% weight loss temperature of the thermoplastic resin of the present invention is a 5% weight loss temperature at a temperature rising rate of 20°C/min in a nitrogen atmosphere, preferably 360°C or higher, and preferably 370°C or higher. More preferably, it is 380° C. or higher, even more preferably, and 390° C. or higher, most preferably. When the 5% weight loss temperature is 360°C or higher, the heat resistance is high.

The specific viscosity of the thermoplastic resin of the present invention is preferably 0.12 to 0.40, more preferably 0.14 to 0.35, and even more preferably 0.16 to 0.30. .. When the specific viscosity is within the above range, the moldability and the mechanical strength are well balanced, which is preferable. The specific viscosity is obtained by measuring at 20° C. using a solution prepared by dissolving 0.7 g of resin in 100 ml of methylene chloride.

The thermoplastic resin of the present invention has a refractive index (hereinafter, may be abbreviated as nD) at a wavelength of 589 nm measured at 25° C., preferably 1.620 to 1.780, and 1.640 to 1.780. Is more preferable, 1.650 to 1.780 is even more preferable, and 1.660 to 1.780 is most preferable. When the refractive index is equal to or higher than the lower limit, the spherical aberration of the optical lens can be reduced and the focal length of the optical lens can be shortened.

The thermoplastic resin of the present invention has a high refractive index, but preferably has a low Abbe number.
The Abbe number (ν) is preferably 10 to 21, more preferably 12 to 19, and even more preferably 12 to 16. 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 thermoplastic resin of the present invention preferably has an absolute value of orientation birefringence (|Δn|) of 0 to 10×10 ⁻³ , more preferably 0 to 5×10 ⁻³ , and further preferably 0 to 3. It is in the range of ×10 ⁻³ . Δn is obtained by the following formula by stretching a film having a thickness of 100 μm obtained from the thermoplastic resin of the present invention at a temperature of Tg+10° C. by 2 times and measuring the phase difference at a wavelength of 589 nm. It is preferable that |Δn| is within the above range because the optical distortion of the optical lens becomes small.
|Δn|=|Re/d|
Δn: orientation birefringence Re: retardation (nm)
d: Thickness (nm)

Tg of the thermoplastic resin of the present invention is preferably 130 to 180°C, more preferably 140 to 175°C, and further preferably 140 to 170°C. When the glass transition temperature is within the above range, the balance between heat resistance and moldability is excellent, which is preferable.

The thermoplastic resin of the present invention preferably has a water absorption rate of 0.25% by mass or less after being immersed in water at 23° C. for 24 hours, and more preferably 0.20% by weight or less. When the water absorption rate is within the above range, the change in optical characteristics due to water absorption is small, which is preferable.

Specific raw materials used for the thermoplastic resin of the present invention will be described below.
<Raw material monomer>
(Dihydroxy compound component of the above formula (1))
In the present invention, the dihydroxy compound component serving as the raw material of the formula (1) may be used alone or in combination of two or more kinds.

In the formula (a), the ring Z, the ring V, R ¹ , R ² , Ar ¹ , Ar ² , L ¹ , L ² , j, k, m and n are the same as those in the formula (1). Is.
Hereinafter, typical specific examples of the dihydroxy compound represented by the formula (a) will be shown, but the raw material used in the formula (1) of the present invention is not limited thereto.

When the ring V is benzene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-di(represented by the following formulas (a-1) and (a-2) is represented. 2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-1,8-di(2-thienyl)fluorene, 9,9-bis(4-(2- Hydroxyethoxy)-3-phenylphenyl)-1,8-di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-1,8-di(2- Thienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-1,8-di(2-thienyl)fluorene, 9,9-bis(4-hydroxyphenyl)-1, 8-di(2-thienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-1,8-di(2-thienyl)fluorene, 9,9-bis(4-hydroxy-3-) Phenylphenyl)-1,8-di(2-thienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-1,8-di(2-thienyl)fluorene, 9,9-bis(6 -Hydroxy-2-naphthyl)-1,8-di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-di(3-thienyl)fluorene, 9 ,9-Bis(4-(2-hydroxyethoxy)-3-methylphenyl)-1,8-di(3-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenyl Phenyl)-1,8-di(3-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-1,8-di(3-thienyl)fluorene, 9,9 -Bis(6-(2-hydroxyethoxy)-2-naphthyl)-1,8-di(3-thienyl)fluorene, 9,9-bis(4-hydroxyphenyl)-1,8-di(3-thienyl) ) Fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-1,8-di(3-thienyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-1,8 -Di(3-thienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-1,8-di(3-thienyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl) -1,8-Di(3-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)- 1,8-di(2-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-1,8-di(2-benzothienyl)fluorene, 9,9 -Bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1,8-di(2-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl) -1,8-Di(2-benzothienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-1,8-di(2-benzothienyl)fluorene, 9,9 -Bis(4-hydroxyphenyl)-1,8-di(2-benzothienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-1,8-di(2-benzothienyl)fluorene ,9,9-bis(4-hydroxy-3-phenylphenyl)-1,8-di(2-benzothienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-1,8-di (2-Benzothienyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-1,8-di(2-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)) Phenyl)-1,8-di(3-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-1,8-di(3-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1,8-di(3-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1 -Naphthyl)-1,8-di(3-benzothienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-1,8-di(3-benzothienyl)fluorene, 9,9-bis(4-hydroxyphenyl)-1,8-di(3-benzothienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-1,8-di(3-benzo Thienyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-1,8-di(3-benzothienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-1, 8-di(3-benzothienyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-1,8-di(3-benzothienyl)fluorene, 9,9-bis(4-(2- Hydroxyethoxy)phenyl)-2,7- Di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-2,7-di(2-thienyl)fluorene, 9,9-bis(4-( 2-Hydroxyethoxy)-3-phenylphenyl)-2,7-di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-2,7-di( 2-thienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-di(2-thienyl)fluorene, 9,9-bis(4-hydroxyphenyl)- 2,7-di(2-thienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-2,7-di(2-thienyl)fluorene, 9,9-bis(4-hydroxy-) 3-phenylphenyl)-2,7-di(2-thienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-2,7-di(2-thienyl)fluorene, 9,9-bis (6-Hydroxy-2-naphthyl)-2,7-di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-di(3-thienyl)fluorene , 9,9-Bis(4-(2-hydroxyethoxy)-3-methylphenyl)-2,7-di(3-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3. -Phenylphenyl)-2,7-di(3-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-2,7-di(3-thienyl)fluorene, 9 ,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-di(3-thienyl)fluorene, 9,9-bis(4-hydroxyphenyl)-2,7-di(3 -Thienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-2,7-di(3-thienyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-2 ,7-Di(3-thienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-2,7-di(3-thienyl)fluorene, 9,9-bis(6-hydroxy-2-) Naphthyl)-2,7-di(3-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-di(2-benzothienyl)fluorene, 9,9-bis (4-(2-hydroxyethoxy)-3-methylphenyl)-2,7-di(2-benzothi) Enyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-di(2-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxy) Ethoxy)-1-naphthyl)-2,7-di(2-benzothienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-di(2-benzo Thienyl)fluorene, 9,9-bis(4-hydroxyphenyl)-2,7-di(2-benzothienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-2,7-di (2-Benzothienyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-2,7-di(2-benzothienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl) )-2,7-Di(2-benzothienyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(2-benzothienyl)fluorene, 9,9-bis(4 -(2-Hydroxyethoxy)phenyl)-2,7-di(3-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-2,7-di( 3-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-di(3-benzothienyl)fluorene, 9,9-bis(4-( 2-hydroxyethoxy)-1-naphthyl)-2,7-di(3-benzothienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-di( 3-benzothienyl)fluorene, 9,9-bis(4-hydroxyphenyl)-2,7-di(3-benzothienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-2, 7-di(3-benzothienyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-2,7-di(3-benzothienyl)fluorene, 9,9-bis(4-hydroxy-) 1-naphthyl)-2,7-di(3-benzothienyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(3-benzothienyl)fluorene, 9,9- Bis(4-(2-hydroxyethoxy)phenyl)-3,6-di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-3,6- Di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-3,6-di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1- Naphthyl)-3,6-di(2-thienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-3,6-di(2-thienyl)fluorene, 9,9 -Bis(4-hydroxyphenyl)-3,6-di(2-thienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-3,6-di(2-thienyl)fluorene, 9 ,9-bis(4-hydroxy-3-phenylphenyl)-3,6-di(2-thienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-3,6-di(2- Thienyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-3,6-di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-3, 6-di(3-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-3,6-di(3-thienyl)fluorene, 9,9-bis(4 -(2-Hydroxyethoxy)-3-phenylphenyl)-3,6-di(3-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-3,6- Di(3-thienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-3,6-di(3-thienyl)fluorene, 9,9-bis(4-hydroxyphenyl) )-3,6-Di(3-thienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-3,6-di(3-thienyl)fluorene, 9,9-bis(4- Hydroxy-3-phenylphenyl)-3,6-di(3-thienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-3,6-di(3-thienyl)fluorene, 9,9 -Bis(6-hydroxy-2-naphthyl)-3,6-di(3-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-3,6-di(2-benzo Thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-3,6-di(2-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxy Ethoxy)-3-phenylphenyl)-3,6-di(2-benzothienyl)fluorene, 9 ,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-3,6-di(2benzo-thienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl )-3,6-Di(2-benzothienyl)fluorene, 9,9-bis(4-hydroxyphenyl)


Phenyl)-3,6-di(2-benzothienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-3,6-di(2-benzothienyl)fluorene, 9,9-bis (4-Hydroxy-3-phenylphenyl)-3,6-di(2-benzothienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-3,6-di(2-benzothienyl) Fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-3,6-di(2-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-3,6 -Di(3-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-3,6-di(3-benzothienyl)fluorene, 9,9-bis( 4-(2-hydroxyethoxy)-3-phenylphenyl)-3,6-di(3-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-3, 6-di(3-benzothienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-3,6-di(3-benzothienyl)fluorene, 9,9-bis( 4-hydroxyphenyl)-3,6-di(3-benzothienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-3,6-di(3-benzothienyl)fluorene, 9, 9-bis(4-hydroxy-3-phenylphenyl)-3,6-di(3-benzothienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-3,6-di(3- Benzothienyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-3,6-di(3-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)- 4,5-di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-4,5-di(2-thienyl)fluorene, 9,9-bis (4-(2-hydroxyethoxy)-3-phenylphenyl)-4,5-di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-4, 5-di(2-thienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-4,5-di(2-thienyl)fluorene, 9,9-bis(4- Hydroxyphenyl)-4,5-di(2-thienyl)phenyl Ruolene, 9,9-bis(4-hydroxy-3-methylphenyl)-4,5-di(2-thienyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-4,5- Di(2-thienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-4,5-di(2-thienyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)- 4,5-di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-4,5-di(3-thienyl)fluorene, 9,9-bis(4-( 2-hydroxyethoxy)-3-methylphenyl)-4,5-di(3-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-4,5-di (3-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-4,5-di(3-thienyl)fluorene, 9,9-bis(6-(2- Hydroxyethoxy)-2-naphthyl)-4,5-di(3-thienyl)fluorene, 9,9-bis(4-hydroxyphenyl)-4,5-di(3-thienyl)fluorene, 9,9-bis (4-Hydroxy-3-methylphenyl)-4,5-di(3-thienyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-4,5-di(3-thienyl)fluorene ,9,9-bis(4-hydroxy-1-naphthyl)-4,5-di(3-thienyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-4,5-di(3 -Thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-4,5-di(2-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)- 3-Methylphenyl)-4,5-di(2-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-4,5-di(2-benzothienyl) ) Fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-4,5-di(2-benzothienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)) 2-naphthyl)-4,5-di(2-benzothienyl)fluorene, 9,9-bis(4-hydroxyphenyl)-4,5-di(2-benzothienyl)fluorene, 9,9-bis( 4-hydroxy-3-methylphenyl)-4,5-di(2-benzothienyl) ) Fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-4,5-di(2-benzothienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-4,5 -Di(2-benzothienyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-4,5-di(2-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxy) Ethoxy)phenyl)-4,5-di(3-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-4,5-di(3-benzothienyl) Fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-4,5-di(3-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)) -1-Naphthyl)-4,5-di(3-benzothienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-4,5-di(3-benzothienyl) Fluorene, 9,9-bis(4-hydroxyphenyl)-4,5-di(3-benzothienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-4,5-di(3 -Benzothienyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-4,5-di(3-benzothienyl)fluorene, 9,9-bis(4-hydroxy-1-naphthyl)- Preferred are 4,5-di(3-benzothienyl)fluorene and 9,9-bis(6-hydroxy-2-naphthyl)-4,5-di(3-benzothienyl)fluorene.

(In the formula, Ar represents a thienyl group or a benzothienyl group, and the substitution position is any of 1,8-position, 2,7-position, 3,6-position and 4,5-position of fluorene.)

(In the formula, Ar represents a thienyl group or a benzothienyl group, and the substitution position is any of 1,8-position, 2,7-position, 3,6-position, and 4,5-position.)

When the ring Z is benzene and the ring V is benzothiophene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)- represented by the following formulas (a-3) and (a-4): Dithieno[2,3-a:2′,3′-i]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-dithieno[2,3-a:2′, 3'-i]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-dithieno[2,3-a:2',3'-i]fluorene, 9,9- Bis(4-(2-hydroxyethoxy)phenyl)-dithieno[3,2-a:3',2'-i]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl )-Dithieno[3,2-a:3′,2′-i]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-dithieno[3,2-a:3 ',2'-i]fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-dithieno[2,3-b:2',3'-h]fluorene, 9,9-bis( 4-(2-hydroxyethoxy)-3-methylphenyl)-dithieno[2,3-b:2',3'-h]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3- Phenylphenyl)-dithieno[2,3-b:2',3'-h]fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-dithieno[3,2-b:3', 2'-h]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-dithieno[3,2-b:3',2'-h]fluorene, 9,9- Bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-dithieno[3,2-b:3',2'-h]fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl )-Dithieno[2,3-c:2′,3′-g]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-dithieno[2,3-c:2 ',3'-g]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-dithieno[2,3-c:2',3'-g]fluorene, 9, 9-bis(4-(2-hydroxyethoxy)phenyl)-dithieno[3,2-c:3',2'-g]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3- Methylphenyl)-dithieno[ 3,2-c:3',2'-g]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-dithieno[3,2-c:3',2' -G]fluorene, 9,9-bis(4-hydroxyphenyl)-dithieno[2,3-a:2',3'-i]fluorene, 9,9-bis(4-hydroxy-3-methylphenyl) -Dithieno[2,3-a:2',3'-i]fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-dithieno[2,3-a:2',3'-i ] Fluorene, 9,9-bis(4-hydroxyphenyl)-dithieno[3,2-a:3',2'-i]fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-dithieno [3,2-a:3′,2′-i]fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-dithieno[3,2-a:3′,2′-i]fluorene ,9,9-bis(4-hydroxyphenyl)-dithieno[2,3-b:2′,3′-h]fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-dithieno[2 ,3-b:2′,3′-h]fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-dithieno[2,3-b:2′,3′-h]fluorene, 9 ,9-Bis(4-hydroxyphenyl)-dithieno[3,2-b:3′,2′-h]fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-dithieno[3,2 -B:3',2'-h]fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-dithieno[3,2-b:3',2'-h]fluorene, 9,9 -Bis(4-hydroxyphenyl)-dithieno[2,3-c:2',3'-g]fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-dithieno[2,3-c : 2',3'-g]fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-dithieno[2,3-c:2',3'-g]fluorene, 9,9-bis (4-Hydroxyphenyl)-dithieno[3,2-c:3',2'-g]fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-dithieno[3,2-c:3 Preferred examples include',2'-g]fluorene and 9,9-bis(4-hydroxy-3-phenylphenyl)-dithieno[3,2-c:3',2'-g]fluorene.

When ring Z is naphthalene and ring V is benzothiophene, 9,9-bis(4-(2-hydroxyethoxy)-1-represented by the following formulas (a-5) and (a-6): Naphthyl)-dithieno[2,3-a:2',3'-i]fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-dithieno[2,3-a:2 ',3'-i]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-dithieno[3,2-a:3',2'-i]fluorene, 9,9 -Bis(6-(2-hydroxyethoxy)-2-naphthyl)-dithieno[3,2-a:3',2'-i]fluorene, 9,9-bis(4-(2-hydroxyethoxy)- 1-naphthyl)-dithieno[2,3-b:2′,3′-h]fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-dithieno[2,3-b : 2',3'-h]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-dithieno[3,2-b:3',2'-h]fluorene, 9 ,9-Bis(6-(2-hydroxyethoxy)-2-naphthyl)-dithieno[3,2-b:3′,2′-h]fluorene, 9,9-bis(4-(2-hydroxyethoxy) )-1-Naphthyl)-dithieno[2,3-c:2′,3′-g]fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-dithieno[2,3 -C:2',3'-g]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-dithieno[3,2-c:3',2'-g]fluorene ,9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-dithieno[3,2-c:3',2'-g]fluorene, 9,9-bis(4-hydroxy-1) -Naphtyl)-dithieno[2,3-a:2',3'-i]fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-dithieno[2,3-a:2',3' -I]fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-dithieno[3,2-a:3',2'-i]fluorene, 9,9-bis(6-hydroxy-2-) Naphthyl)-dithieno[3,2-a:3',2'-i]fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-dithieno[2,3-b:2',3'- h]fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-dithieno[2,3-b:2′,3′ -H]fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-dithieno[3,2-b:3',2'-h]fluorene, 9,9-bis(6-hydroxy-2-) Naphthyl)-dithieno[3,2-b:3',2'-h]fluorene, 9,9-bis(4-hydroxy-1-naphthyl)-dithieno[2,3-c:2',3'- g]fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-dithieno[2,3-c:2′,3′-g]fluorene, 9,9-bis(4-hydroxy-1-naphthyl) )-Dithieno[3,2-c:3′,2′-g]fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-dithieno[3,2-c:3′,2′-g ] Fluorene is preferred.

When ring Z is benzene and ring V is naphthalene, 9,9-bis(4-(2-hydroxyethoxy)-3-(represented by the following formulas (a-7) and (a-8)) 2-thienyl)phenyl)-dibenzo[a,i]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-(3-thienyl)phenyl)-dibenzo[a,i]fluorene, 9, 9-bis(4-(2-hydroxyethoxy)-3-(2-benzothienyl)phenyl)-dibenzo[a,i]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-( 3-benzothienyl)phenyl)-dibenzo[a,i]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-(2-thienyl)phenyl)-dibenzo[b,h]fluorene, 9 , 9-bis(4-(2-hydroxyethoxy)-3-(3-thienyl)phenyl)-dibenzo[b,h]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-( 2-benzothienyl)phenyl)-dibenzo[b,h]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-(3-benzothienyl)phenyl)-dibenzo[b,h]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-(2-thienyl)phenyl)-dibenzo[c,g]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3- (3-thienyl)phenyl)-dibenzo[c,g]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-(2-benzothienyl)phenyl)-dibenzo[c,g]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-(3-benzothienyl)phenyl)-dibenzo[c,g]fluorene, 9,9-bis(4-(2-hydroxy)-3- (2-thienyl)phenyl)-dibenzo[a,i]fluorene, 9,9-bis(4-(2-hydroxy)-3-(3-thienyl)phenyl)-dibenzo[a,i]fluorene, 9, 9-bis(4-(2-hydroxy)-3-(2-benzothienyl)phenyl)-dibenzo[a,i]fluorene, 9,9-bis(4-(2-hydroxy)-3-(3- Benzothienyl)phenyl)-dibenzo[a,i]fluorene, 9,9-bis(4-(2-hydroxy)-3-(2-thienyl)phenyl)-dibenzo[b,h]fluorene, 9,9- Bis(4-(2-hydroxy)-3-(3-thienyl)phenyl )-Dibenzo[b,h]fluorene, 9,9-bis(4-(2-hydroxy)-3-(2-benzothienyl)phenyl)-dibenzo[b,h]fluorene, 9,9-bis(4 -(2-Hydroxy)-3-(3-benzothienyl)phenyl)-dibenzo[b,h]fluorene, 9,9-bis(4-(2-hydroxy)-3-(2-thienyl)phenyl)- Dibenzo[c,g]fluorene, 9,9-bis(4-(2-hydroxy)-3-(3-thienyl)phenyl)-dibenzo[c,g]fluorene, 9,9-bis(4-(2 -Hydroxy)-3-(2-benzothienyl)phenyl)-dibenzo[c,g]fluorene, 9,9-bis(4-(2-hydroxy)-3-(3-benzothienyl)phenyl)-dibenzo[ Preferred are c, g] fluorene.

(In the formula, R represents a thienyl group or a benzothienyl group.)

(In the formula, R represents a thienyl group or a benzothienyl group.)

Among them, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methyl Phenyl)-2,7-di(2-thienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-di(2-thienyl)fluorene, 9, 9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-2,7-di(2-thienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)- 2,7-di(2-thienyl)fluorene, 9,9-bis(4-hydroxyphenyl)-2,7-di(2-thienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl) )-2,7-Di(2-thienyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-2,7-di(2-thienyl)fluorene, 9,9-bis(4- Hydroxy-1-naphthyl)-2,7-di(2-thienyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(2-thienyl)fluorene, 9,9- Bis(4-(2-hydroxyethoxy)phenyl)-2,7-di(2-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-2,7 -Di(2-benzothienyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-di(2-benzothienyl)fluorene, 9,9-bis( 4-(2-hydroxyethoxy)-1-naphthyl)-2,7-di(2-benzothienyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7 -Di(2-benzothienyl)fluorene, 9,9-bis(4-hydroxyphenyl)-2,7-di(2-benzothienyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl) -2,7-di(2-benzothienyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-2,7-di(2-benzothienyl)fluorene, 9,9-bis(4 -Hydroxy-1-naphthyl)-2,7-di(2-benzothienyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(2-benzothienyl)fluorene, 9 , 9-bis(4-(2-hydroxyethoxy)-3-(2-thio) (Enyl)phenyl)-dibenzo[b,h]fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-(2-benzothienyl)phenyl)-dibenzo[b,h]fluorene, 9,9 -Bis(4-(2-hydroxy)-3-(2-thienyl)phenyl)-dibenzo[b,h]fluorene, 9,9-bis(4-(2-hydroxy)-3-(2-benzothienyl) )Phenyl)-dibenzo[b,h]fluorene is more preferred.

Among them, the following formula (1-1) represented by the following formulas (1-1) to (1-6): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-di(2 -Thienyl)fluorene, the following formula (1-2): 9,9-bis(4-hydroxyphenyl)-2,7-di(2-thienyl)fluorene, the following formula (1-3): 9,9-bis (6-(2-hydroxyethoxy)-2-naphthyl)-2,7-di(2-thienyl)fluorene, the following formula (1-4): 9,9-bis(6-hydroxy-2-naphthyl)- 2,7-di(2-thienyl)fluorene, the following formula (1-5): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-di(2-benzothienyl)fluorene, The following formula (1-6): 9,9-bis(4-hydroxyphenyl)-2,7-di(2-benzothienyl)fluorene is more preferable, and the following formula (1-1): 9,9- is particularly preferable. Bis(4-(2-hydroxyethoxy)phenyl)-2,7-di(2-thienyl)fluorene, the following formula (1-3): 9,9-bis(6-(2-hydroxyethoxy)-2- Naphthyl)-2,7-di(2-thienyl)fluorene is more preferred. These may be used alone or in combination of two or more.

(Dicarboxylic acid component of the above formula (1))
As the dicarboxylic acid component used in the unit represented by the formula (1) of the thermoplastic resin of the present invention, a dicarboxylic acid represented by the formula (b) or an ester-forming derivative thereof is preferably used mainly.

In the above formula (b), X represents a divalent linking group, and the same as described in the above formula (3) can be said.
Hereinafter, typical specific examples of the dicarboxylic acid represented by the formula (b) or an ester-forming derivative thereof will be shown. However, the raw material used in the formula (b) of the present invention is not limited thereto. Absent.

Examples of the dicarboxylic acid component used in the thermoplastic resin of the present invention include 2,2′-bis(carboxymethoxy)-1,1′-binaphthyl and 6,6′-diphenyl-2, which are raw materials of the formula (4). ,2′-bis(carboxymethoxy)-1,1′-binaphthyl, 6,6′-dibromo-2,2′-bis(carboxymethoxy)-1,1′-binaphthyl, the raw material of the formula (5) In addition to 9,9-bis(2-carboxyethyl)fluorene, aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid. Component, monocyclic aromatic dicarboxylic acid component such as phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalene Dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, 9,9-bis(carboxymethyl)fluorene, 9,9-bis(1-carboxyethyl)fluorene, 9,9-bis(1 -Carboxypropyl)fluorene, 9,9-bis(2-carboxypropyl)fluorene, 9,9-bis(2-carboxy-1-methylethyl)fluorene, 9,9-bis(2-carboxy-1-methylpropyl) ) Fluorene, 9,9-bis(2-carboxybutyl)fluorene, 9,9-bis(2-carboxy-1-methylbutyl)fluorene, 9,9-bis(5-carboxypentyl)fluorene, 9,9-bis Polycyclic aromatic dicarboxylic acid component such as (carboxycyclohexyl)fluorene, biphenyldicarboxylic acid component such as 2,2′-biphenyldicarboxylic acid, alicyclic ring such as 1,4-cyclohexanedicarboxylic acid and 2,6-decalindicarboxylic acid Group dicarboxylic acid components, such as isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,2′-bis(carboxymethoxy)-1,1′-binaphthyl, 9,9-bis(2-carboxyethyl) ) Fluorene is preferable, and 2,6-naphthalenedicarboxylic acid, 2,2′-bis(carboxymethoxy)-1,1′-binaphthyl, 9,9-bis(2-carboxyethyl)fluorene is more preferable. You may use these individually or in combination of 2 or more types. As the ester-forming derivative, acid chloride or esters such as methyl ester, ethyl ester and phenyl ester may be used.

(Carbonate component of the above formula (1))
Examples of the carbonate component used in the unit represented by the above formula (1) of the thermoplastic resin of the present invention include phosgene and carbonate ester. Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and among them, diphenyl carbonate. Is preferred.

(Components of the above formulas (6) to (8))
The thermoplastic resin of the present invention may further have repeating units of the above formulas (6) to (8), and the dihydroxy compound component as a raw material of the above formulas (6) to (8) is shown below. These may be used alone or in combination of two or more.

The dihydroxy compound component as the raw material of the above formula (6) of the present invention is 2,2′-bis(2-hydroxyethoxy)-3,3′-diphenyl-1,1′-binaphthyl, 2,2′-bis. (2-Hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-7,7'-diphenyl-1,1'-binaphthyl, 2, 2'-bis(2-hydroxyethoxy)-3,3'-dimethyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-dimethyl-1,1'- Examples thereof include binaphthyl and 2,2′-bis(2-hydroxyethoxy)-7,7′-dimethyl-1,1′-binaphthyl.

The dihydroxy compound component as the raw material of the above formula (7) of the present invention includes 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and 9,9-bis(4-(2-hydroxyethoxy)- 3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene And the like, and 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene are particularly preferable. These may be used alone or in combination of two or more.

The dihydroxy compound component as the raw material of the above formula (8) of the present invention includes 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1 -Bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,1-bis(4-hydroxyphenyl)-3,3 ,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxyphenyl)sulfide, Bis(4-hydroxy-3-methylphenyl)sulfide, biphenol, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis (4-Hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, bis(4-hydroxyphenyl)sulfone,10,10-bis(4-hydroxyphenyl)anthrone And the like, and 2,2-bis(4-hydroxyphenyl)propane and bis(4-hydroxyphenyl)sulfide are particularly preferable. These may be used alone or in combination of two or more.

(Copolymerization component other than the above formulas (1) to (8))
The thermoplastic resin of the present invention may be copolymerized with other dihydroxy compound components to the extent that the characteristics of the present invention are not impaired. The content of the other dihydroxy compound component is preferably less than 30 mol% in all repeating units.

Other dihydroxy compound components used in the thermoplastic resin of the present invention include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol and tricyclo[5.2.1.0]. ^2,6 ] Decanedimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornanedimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spiroglycol, isosorbide , Isomannide, isoidide, hydroquinone, resorcinol, bis(4-(2-hydroxyethoxy)phenyl)sulfone, 1,1′-bi-2-naphthol, dihydroxynaphthalene, bis(2-hydroxyethoxy)naphthalene, and the like, You may use these individually or in combination of 2 or more types.

The thermoplastic resin of the present invention is produced by, for example, a method of reacting a dihydroxy compound component with a carbonate precursor such as phosgene or carbonic acid diester, a method of reacting a diol component with a dicarboxylic acid or an ester-forming derivative thereof. Specific examples are shown below.

<Method for producing thermoplastic resin>
(Method for producing polycarbonate resin)
When the thermoplastic resin of the present invention is a polycarbonate resin, it is obtained by reacting a dihydroxy compound component and a carbonate precursor by an interfacial polymerization method or a melt polymerization method. In producing the polycarbonate resin, a catalyst, a terminal terminating agent, an antioxidant and the like may be used if necessary.

The reaction by the interfacial polymerization method is usually a reaction between a diol component and phosgene, which is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. It is also possible to use a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, a quaternary ammonium compound, a quaternary phosphonium compound, etc., for promoting the reaction. it can. At that time, it is preferable that the reaction temperature is usually 0 to 40° C., the reaction time is about 10 minutes to 5 hours, and the pH during the reaction is 9 or more.

The reaction by the melt polymerization method is usually a transesterification reaction between a dihydroxy compound component and a carbonate ester, and the dihydroxy compound component and the carbonate ester are heated and mixed in the presence of an inert gas to produce a phenol or the like. It is carried out by a method of distilling a hydroxy compound. The reaction temperature varies depending on the diol component used, but is usually in the range of 120 to 350°C, preferably 150 to 300°C, and more preferably 180 to 270°C. In the latter stage of the reaction, the pressure of the system is reduced to about 1000 to 1 Pa to facilitate the distillation of the produced hydroxy compound. The reaction time is usually about 1 to 8 hours.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and among them, diphenyl carbonate. Is preferred.

Further, in the melting method, a polymerization catalyst can be used to accelerate the polymerization rate, and examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol, alkali metal compounds such as potassium salt, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkoxides of alkali metals and alkaline earth metals , Organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds, It is possible to use a catalyst such as a manganese compound, a titanium compound or a zirconium compound which is usually used for an esterification reaction or a transesterification reaction. The catalyst may be used alone or in combination of two or more kinds. The amount of these polymerization catalysts used is preferably in the range of 1×10 ⁻⁸ to 1×10 ⁻³ mol per 1 mol of the raw material diol component.

The polycarbonate resin, which is the thermoplastic resin of the present invention, may use a monofunctional hydroxy compound which is usually used as an end terminating agent in the polymerization reaction. Especially in the case of reactions using phosgene as a carbonate precursor, monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the polymers obtained are also based on monofunctional phenol-based groups. Because it is blocked by, it has better thermal stability than those that do not.

(Method for producing polyester resin)
When the thermoplastic resin of the present invention is a polyester resin, a dihydroxy compound component and a dicarboxylic acid or an ester-forming derivative thereof are subjected to an esterification reaction or a transesterification reaction, and the obtained reaction product is subjected to a polycondensation reaction to obtain a desired product A high molecular weight polymer having the molecular weight of

The ethylene glycol component is preferably 0 to 50 mol% with respect to the total dihydroxy compound component. Within the above range, the balance between heat resistance and moldability is excellent, which is preferable.

As the polymerization method, an appropriate method can be selected from known methods such as a direct polymerization method, a melt polymerization method such as a transesterification method, a solution polymerization method, and an interfacial polymerization method. When the interfacial polymerization method is used, a solution (organic phase) prepared by dissolving dicarboxylic acid chloride in an organic solvent incompatible with water is mixed with an alkaline aqueous solution (aqueous phase) containing an aromatic dihydroxy compound and a polymerization catalyst, and the mixture is heated at 50° C. Hereinafter, a method of carrying out the polymerization reaction while stirring at a temperature of preferably 25° C. or less for 0.5 to 8 hours can be mentioned.

The solvent used in the organic phase is preferably a solvent which is incompatible with water and dissolves the polyester resin of the present invention. Examples of such a solvent include chlorine-based solvents such as methylene chloride, 1,2-dichloroethane, chloroform and chlorobenzene, and aromatic hydrocarbon-based solvents such as toluene, benzene and xylene, which are easy to use in production. Therefore, methylene chloride is preferable.

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

In the reaction by the melt polymerization method, it is usually preferable that a diol component and a dicarboxylic acid component or a diester thereof are mixed and reacted at usually 120 to 350°C, preferably 150 to 300°C, more preferably 180 to 270°C. The degree of pressure reduction is changed stepwise, and finally, a hydroxy compound such as 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.

Further, in the melting method, an ester exchange catalyst and a polymerization catalyst can be used to accelerate the polymerization rate. As the transesterification catalyst, one known per se can be adopted, and for example, a compound containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium, or lead element can be used. Specific examples include oxides containing these elements, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, sulfates and the like. Among 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 low amount of polymer-insoluble foreign matter. These compounds can be used in combination of two or more kinds. 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 them, tin, titanium and germanium compounds are preferable from the viewpoint of melt stability and hue of the thermoplastic resin. The amount of the catalyst used is, for example, preferably in the range of 1×10 ⁻⁸ to 1×10 ⁻³ mol with respect to 1 mol of the dicarboxylic acid component.

The polyester resin of the present invention may use an end-capping agent in order to adjust the molecular weight and improve thermal stability. Examples of the terminal blocking agent include monofunctional hydroxy compounds, epoxy compounds, oxazoline compounds, isocyanate compounds, carbodiimide compounds, ketene imine compounds and the like.

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

(Method for producing polyester carbonate resin)
When the thermoplastic resin of the present invention is a polyester carbonate resin, it can be produced by reacting a dihydroxy compound component and a dicarboxylic acid or an ester-forming derivative thereof with a carbonate precursor such as phosgene or a carbonate ester. As the polymerization method, the same method as the above-mentioned polycarbonate resin or polyester resin can be used.

<Additive>
To the thermoplastic resin of the present invention, if necessary, additives such as a release agent, a heat stabilizer, an ultraviolet absorber, a bluing agent, an antistatic agent, a flame retardant, a plasticizer and a filler are appropriately added. Can be used.
Specific examples of the releasing agent and heat stabilizer include those described in International Publication No. 2011/010741.

As a particularly preferable releasing agent, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used. Further, the amount of the ester in the release agent is preferably 90% by mass or more, and more preferably 95% by mass or more, based on 100% by mass of the releasing agent. Moreover, as a mold release agent mix|blended with a thermoplastic resin composition, the range of 0.005-2.0 mass parts is preferable with respect to 100 mass parts of thermoplastic resins, and the range of 0.01-0.6 mass parts. Are more preferable, and the range of 0.02-0.5 mass part is still more preferable.

Examples of the heat stabilizer include phosphorus-based heat stabilizers, sulfur-based heat stabilizers and hindered phenol-based heat stabilizers.

Further, particularly preferable phosphorus-based heat stabilizers are tris(2,4-di-tert-butylphenyl)phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite. Phyto, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite is used. Further, the content of the phosphorus-based heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.2 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

Further, a particularly preferable sulfur heat stabilizer is pentaerythritol-tetrakis(3-laurylthiopropionate). Further, the content of the sulfur-based heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.2 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

Further, as preferable hindered phenol heat stabilizers, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol-tetrakis[3-(3,5-di-tert) are used. -Butyl-4-hydroxyphenyl)propionate].

The content of the hindered phenolic heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.3 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

The phosphorus heat stabilizer and the hindered phenol heat stabilizer can be used in combination.

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 UV 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 imino ester-based ultraviolet absorber, 2,2'-p-phenylene bis(3,1-benzoxazin-4-one) is particularly preferable.

Examples of the cyanoacrylate-based ultraviolet absorber include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenyl). Acryloyl)oxy]methyl)propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene and the like can be mentioned.

The blending amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin, and if the blending amount is in the range, the thermoplastic resin molded article may be used depending on the application. It is possible to impart sufficient weather resistance.

Examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer, and Polycinthremble-RLS manufactured by Clariant. The bluing agent is effective for eliminating the yellow tint of the thermoplastic resin. In particular, in the case of a thermoplastic resin composition imparted with weather resistance, there is a fact that the resin composition tends to be yellowish due to "action and color of the ultraviolet absorber" because a certain amount of the ultraviolet absorber is blended. The addition of a bluing agent is very effective for giving a natural transparent feeling to an optical lens.

The blending amount of the bluing agent is preferably 0.05 to 1.5 ppm, and more preferably 0.1 to 1.2 ppm, relative to 100 parts by mass of the thermoplastic resin.

<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 230 to 350°C and a mold temperature of 70 to 180°C. More preferably, molding is performed under the conditions of a cylinder temperature of 250 to 300°C and a mold temperature of 80 to 170°C. If the cylinder temperature is higher than 350°C, the thermoplastic resin is decomposed and colored, and if it is lower than 230°C, the melt viscosity is high and molding tends to be difficult. Further, if the mold temperature is higher than 180° C., it tends to be difficult to take out the molded piece made of the thermoplastic resin from the mold. On the other hand, when the mold temperature is lower than 70° C., the resin is hardened too quickly in the mold at the time of molding and the shape of the molded piece is difficult to control, or the mold attached to the mold is sufficiently transferred. It is easy to be difficult.

The optical lens of the present invention is preferably implemented in the form of an aspherical lens, if necessary. With an aspherical lens, spherical aberration can be reduced to substantially zero with a single optical lens, so there is no need to remove spherical aberration with a combination of multiple spherical lenses, which reduces weight and reduces molding costs. Will be possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.

Further, since the thermoplastic resin of the present invention has a high molding fluidity, it is particularly useful as a material for an optical lens that is thin and 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 obtained resin was evaluated by the following methods.
(1) Copolymerization ratio: The obtained resin was determined by ¹ H NMR measurement using JNM-ECZ400S/L1 manufactured by JEOL Ltd. The solvent used was _{DMSO-d 6.}
(2) Specific viscosity: The obtained resin 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 temperature (Tg): The obtained resin was measured with a Discovery DSC25Auto model manufactured by TA Instruments Japan Co., Ltd. at a temperature rising rate of 20° C./min. Samples were measured at 5-10 mg.
(4) 5% weight loss temperature: The obtained resin was measured at a temperature rising rate of 20° C./min under a nitrogen atmosphere by a differential thermal/thermogravimetric simultaneous measurement device DTG-60A manufactured by Shimadzu Corporation, The 5% weight loss temperature was measured. Samples were measured at 5-10 mg.
(5) Refractive index and Abbe number: 3 g of the obtained resin was dissolved in 50 ml of methylene chloride, cast on a glass petri dish, sufficiently dried at room temperature, and then dried at a temperature of 120° C. or lower for 8 hours. The refractive index (wavelength: 589 nm) (nD) at 25° C. was measured by using the DR-M2 Abbe refractometer manufactured by ATAGO with the film having a thickness of about 100 μm.

[Reference Example 1] Synthesis of 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-di(2-thienyl)fluorene (BPDT2) A stirrer, a cooler, and a thermometer were provided. To a 1 L separable flask, 122 g of toluene as a solvent and 5.47 g of 12 tungst (VI) phosphoric acid n-hydrate H ₃ [PW ₁₂ O ₄₀ ].nH ₂ O were charged, and the mixture was subjected to azeotropic dehydration under toluene reflux. After cooling the content, 33.80 g (0.10 mol) of 2,7-dibromofluorenone (hereinafter sometimes abbreviated as DBFN), 55.27 g (0.40 mol) of 2-phenoxyethanol, and 38 g of toluene were added, and toluene was added. The reaction was carried out by stirring under reflux for 18 hours while discharging water produced by the reaction from the system. The progress of the reaction was confirmed by HPLC, and it was confirmed that the residual amount of 2,7-dibromofluorenone was 0.1% or less, and the reaction was terminated. The resulting 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dibromofluorene (hereinafter sometimes abbreviated as BPDB) was used in the reaction of the next step without isolation and purification. I moved to.

After cooling the reaction solution obtained in the above step to room temperature, 58 mL of 4 mol/L potassium carbonate aqueous solution and 26.87 g (0.21 mol) of 2-thiopheneboronic acid, and further 1.12 g of tetrakis(triphenylphosphine)palladium. 0.97 mmol) was added and the reaction was carried out by stirring at 80° C. for 2 hours. The progress of the reaction was confirmed by HPLC, and it was confirmed that the residual amount of BPDB was 0.1% or less, and the reaction was terminated.

The obtained reaction solution was returned to room temperature, and 300 g of diethyl ether was added for crystallization to remove the crude product. The obtained solid was purified with a silica gel column using an eluent of methanol/chloroform (1/1) to obtain 35 g of a target, yellow crystal of BPDT2 in a yield of about 67%. In addition, the obtained yellow crystals were analyzed by ¹ H NMR and confirmed to be the target substance (FIG. 1). The solvent used was _{DMSO-d 6.}

The HPLC measurement was carried out by using a column: ACQUITY UPLC BEH C18 1.7 μm manufactured by Waters Co., Ltd., a solvent: a mixed solution of N,N-dimethylformamide and 0.15% trifluoroacetic acid/ultra pure water at 7:3, Detection was carried out using UV-270 nm at a flow rate of 1 mL/min.

[Example 1]
BPDT2 synthesized in Reference Example 1 was 9.04 parts by mass (20 mol part), 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter, may be abbreviated as BPEF) 26.31 parts by mass. Parts (80 mol parts), diphenyl carbonate (hereinafter sometimes abbreviated as DPC) 16.23 parts by mass (110 mol parts), and sodium hydrogen carbonate as a catalyst at a concentration of 60 mmol/L of 3.19×10 ^−5. A mass part (5.07x10 < ^-4 >mol part) was added and it heated at 180 degreeC in nitrogen atmosphere, and was made to fuse|melt. Then, the degree of pressure reduction was adjusted to 20 kPa over 10 minutes. The temperature was raised to 250°C at a heating rate of 60°C/hr, the pressure was reduced to 20 kPa/hr after the outflow amount of phenol reached 70%, and the polymerization reaction was performed until a predetermined electric power was reached, and the reaction was completed. The resin was taken out from the rear flask. The obtained polycarbonate resin was analyzed by ¹ H NMR, and it was confirmed that 20 mol% of the BPDT2 component was introduced with respect to all the monomers. Using the polycarbonate resin, the copolymerization ratio, refractive index, Tg and 5% weight loss temperature were evaluated, and the results are shown in Table 1.

[Example 2]
A polycarbonate resin was produced in the same manner as in Example 1 except that the ratios of BPDT2 and BPEF were changed to those shown in Table 1. Using the polycarbonate resin, the copolymerization ratio, refractive index, Tg and 5% weight loss temperature were evaluated, and the results are shown in Table 1.

[Example 3]
A polycarbonate resin was produced in the same manner as in Example 1 except that BPDT2 was changed to the ratio shown in Table 1. Using the polycarbonate resin, the copolymerization ratio, refractive index, Tg and 5% weight loss temperature were evaluated, and the results are shown in Table 1.

[Example 4]
BPDT2,2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthyl (hereinafter sometimes abbreviated as BHEB), 2,2′-bis(carboxymethoxy)-1,1′-binaphthyl (Hereinafter, may be abbreviated as BCMB) in the ratios shown in Table 1, DPC was changed to 9.3 parts by mass (11 mol parts), and titanium tetrabutoxide 3.4× as a catalyst. except for using 10 ^-3 parts by weight (2.5 × ^{10 -3} mоl portion) in the same manner as in example 1 to produce a polyester carbonate resin. Using the polyester carbonate resin, the copolymerization ratio, refractive index, Tg and 5% weight loss temperature were evaluated, and the results are shown in Table 1.

[Example 5]
BPDT2, BHEB, and dimethyl naphthalenedicarboxylate (hereinafter sometimes abbreviated as NDCM) were used in the ratios shown in Table 1, DPC was changed to 47 parts by mass (55 mol parts), and titanium was used as a catalyst. A polyester carbonate resin was produced in the same manner as in Example 1 except that 3.4×10 ⁻³ parts by mass of tetrabutoxide (2.5×10 ⁻³ mol part) was used. Using the polyester carbonate resin, the copolymerization ratio, refractive index, Tg and 5% weight loss temperature were evaluated, and the results are shown in Table 1.

[Example 6]
A polycarbonate resin was produced in the same manner as in Example 1 except that BPDT2,2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as BPA) was used in the ratios shown in Table 1. did. Using the polycarbonate resin, the copolymerization ratio, refractive index, Tg and 5% weight loss temperature were evaluated, and the results are shown in Table 1.

[Example 7]
Except that BPDT2, BHEB, and BCMB were used in the ratios shown in Table 1 and that 3.4×10 ⁻³ parts by mass of titanium tetrabutoxide (2.5×10 ⁻³ mol parts) was used as a catalyst. A polyester resin was produced in the same manner as in Example 1. The polyester resin was used to evaluate the copolymerization ratio, refractive index, Tg and 5% weight loss temperature, and the results are shown in Table 1.

[Comparative Example 1]
According to the method described in Example 1 of JP-A-2018-141085, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene (hereinafter sometimes abbreviated as OPPFL) and bis(2-mercapto). A polythiocarbonate resin which is a polycondensation product of ethyl) sulfide (hereinafter sometimes abbreviated as BMES) and thiophosgene was obtained. Copolymerization ratio, refractive index, Tg, and 5% weight loss temperature were evaluated using the polythiocarbonate resin, and the results are shown in Table 1.

[Comparative example 2]
According to the method described in Example 3 of JP-A-2018-141084, 9,9-bis(4-mercapto-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as BCFSH) and BMES and thiophosgene A polythiocarbonate resin which is a polycondensate was obtained. Copolymerization ratio, refractive index, Tg, and 5% weight loss temperature were evaluated using the polythiocarbonate resin, and the results are shown in Table 1.

[Comparative Example 3]
A polythioester resin, which is a polycondensate of BCFSH and adipic acid chloride (hereinafter sometimes abbreviated as ACl), was obtained by the method described in Example 1 of JP-A-2018-141084. Using the polythioester resin, the copolymerization ratio, refractive index, Tg and 5% weight loss temperature were evaluated, and the results are shown in Table 1.

[Comparative Example 4]
According to the method described in Example 3 of JP-A-2018-141085, 1,4-dithiane-2,5-di(methanethiol) (hereinafter, sometimes abbreviated as BMMD) and 9,9-bis A polythiocarbonate resin which is a polycondensation product of (4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as BCF) and thiophosgene was obtained. Copolymerization ratio, refractive index, Tg, and 5% weight loss temperature were evaluated using the polythiocarbonate resin, and the results are shown in Table 1.

Results for polycarbonate and poly(thio)carbonate resins, or polythioester resins are shown in Table 1.

BPDT 2:9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-di(2-thienyl)fluorene BMES: bis(2-mercaptoethyl)sulfide BCFSH: 9,9-bis(4- Mercapto-3-methylphenyl)fluorene BMMD: 1,4-dithian-2,5-di(methanethiol)
BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene OPPFL: 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene BCF: 9,9-bis(4-hydroxy-3) -Methylphenyl)fluorene BHEB:2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl BPA:2,2-bis(4-hydroxyphenyl)propane BCMB:2,2'-bis(carboxy) Methoxy)-1,1'-binaphthyl NDCM: dimethyl naphthalenedicarboxylate ACl: adipic acid chloride

The thermoplastic resins obtained in Examples 1 to 7 have a high refractive index, a high 5% weight loss temperature of 390° C. or higher, and a Tg of 130 to 180° C., so that the moldability is balanced. Excellent Excellent as an optical lens. On the other hand, the thermoplastic resin of the comparative example has a high refractive index and a Tg between 130° C. and 180° C., but has a low 5% weight loss temperature, and therefore has a problem in heat resistance.

Compared to the C—S bond in which sulfur is contained in the aliphatic group, the C—S bond in which sulfur is contained in the aromatic group such as BPDT2 is stabilized by resonance and the bond is strong, so It is effective for heat resistance.

The thermoplastic resin of the present invention is used as an optical material, and is used as an optical member such as an optical lens, a prism, an optical disk, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, an optical film, an optical filter, a hard coat film. In particular, it is extremely useful as an optical lens.

Claims (16)

A thermoplastic resin containing a repeating unit represented by the following formula (1).
(In the formula, ring Z and ring V each independently represent (the same or different) an aromatic ring, and R ¹ , R ² , Ar ¹ and Ar ² are each independently a hydrogen atom, a halogen atom or an aromatic group. A substituent having 1 to 12 carbon atoms, which may contain at least one thiophene skeleton in any of Z, V, R ¹ , R ² , Ar ¹ and Ar ² , and L ¹ and L ² each independently represents a divalent linking group, j and k each independently represent an integer of 0 or more, m and n each independently represent 0 or 1, and W represents the following formula (2) or (3 ) At least one selected from the group represented by).)
(In the formula, X represents a divalent linking group.) The thermoplastic resin according to claim 1, which has at least two thiophene skeletons in the formula (1). The thermoplastic resin according to claim 1, wherein Ar ¹ and Ar ^{2 in the} formula (1) each independently represent a hydrogen atom, a thienyl group, or a benzothienyl group. The thermoplastic resin according to claim 3, wherein Z and V in the formula (1) each represent an aromatic hydrocarbon ring. The thermoplastic resin according to claim 4, wherein Z and V in the formula (1) represent benzene or naphthalene. In the formula (1), R ¹ and R ² each independently represent a hydrogen atom, a methyl group, a phenyl group, a naphthyl group, a thienyl group, or a benzothienyl group. Plastic resin. The thermoplastic resin according to claim 6, wherein R ¹ and R ^{2 in the} formula (1) represent a hydrogen atom or a methyl group. X in the formula (3) is at least one selected from the group consisting of a phenylene group, a naphthalenediyl group, a group represented by the following formula (4) and a group represented by the following formula (5) as a repeating unit. The thermoplastic resin according to any one of claims 1 to 7, which comprises.
(In the formula, R ³ and R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may include an aromatic group, or a halogen atom.)
The thermoplastic resin according to claim 1, comprising at least one selected from the group consisting of units represented by the following formulas (6) to (8) as a repeating unit.
(In the formula, R ⁵ and R ⁶ are each independently a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group, or a halogen atom.)
(In the formula, R ⁷ and R ⁸ are each independently a hydrogen atom, a substituent having 1 to 12 carbon atoms which may contain an aromatic group, or a halogen atom.)
(In the formula, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a substituent having 1 to 12 carbon atoms which may include an aromatic group, or a halogen atom, and U is a single bond or a divalent linking group. is there.) The thermoplastic resin according to any one of claims 1 to 9, which has a 5% weight loss temperature of 360°C or higher. The thermoplastic resin according to claim 10, wherein the 5% weight loss temperature is 380°C or higher. The thermoplastic resin according to any one of claims 1 to 11, which has a glass transition temperature of 130 to 180°C. The thermoplastic resin according to any one of claims 1 to 12, which has a specific viscosity of 0.12 to 0.40. The thermoplastic resin according to any one of claims 1 to 13, which has a refractive index of 1.620 to 1.780. An optical member comprising the thermoplastic resin according to claim 1. The optical member according to claim 15, which is an optical lens.