JP6916026B2 - Thermoplastic resin - Google Patents

Description

The present invention relates to a thermoplastic resin having an excellent balance of high refractive index, low birefringence and moldability.

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

Glass, which has been conventionally used as a material for an optical system, can realize various required optical characteristics and has excellent environmental resistance, but has a problem of poor workability. On the other hand, resins that are cheaper than glass materials and have excellent workability have been used for optical components. In particular, a resin having a fluorene skeleton or a vinaphthalene skeleton is used because of its high refractive index and the like. For example, Patent Documents 1 and 2 describe a high refractive index resin having a refractive index of 1.64 using 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene. However, the refractive index is insufficient, and further increase in the refractive index is required. Further, Patent Document 3 describes a thermosetting resin composition having a benzofluorene skeleton. However, since the resin described in the patent document is a thermosetting resin, it is inferior in processability by injection molding.

WO2007 / 142149 Japanese Unexamined Patent Publication No. 7-1989901 Japanese Unexamined Patent Publication No. 2014-8057

Therefore, an object of the present invention is to provide a thermoplastic resin having an excellent balance of high refractive index, low birefringence and moldability.

As a result of diligent research to achieve this purpose, the present inventors have achieved high refractive index, low birefringence, and moldability by using a thermoplastic resin having a specific benzofluorene compound having an asymmetric structure and an optical member. We have arrived at the present invention by finding that it can be balanced.

（式中、Ｒ_１〜Ｒ_１６はそれぞれ独立に、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素原子数１〜１２の芳香族基を含んでいても良い炭化水素基を示し、Ｒ_９とＲ_１０、Ｒ_１０とＲ_１１、Ｒ_１１とＲ_１２、Ｒ_１３とＲ_１４、Ｒ_１４とＲ_１５およびＲ_１５とＲ_１６の組のうち、一組は互いに縮合して環を形成し、Ｌ_１およびＬ_２はそれぞれ独立に２価の連結基を示し、Ｗは下記式（２）または（３）で表される群より選ばれる少なくとも１つである。）

（式中、Ｘは２価の連結基を示す。） That is, the present invention
1. 1. A thermoplastic resin containing a repeating unit represented by the following formula (1).

(In the formula, R _{1 to} R ₁₆ each independently indicate a hydrocarbon group which may contain a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an aromatic group having 1 to 12 carbon atoms. , R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₄ and R ₁₅ and R ₁₅ and R ₁₆ one of which condenses with each other to form a ring. L ₁ and L ₂ each independently represent a divalent linking group, and W is at least one selected from the group represented by the following formula (2) or (3).

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

2. The thermoplastic resin according to 1 above, wherein the formula (1) is at least one selected from the group consisting of units represented by the following formulas (1A) to (1C).

3. 3. The thermoplastic resin according to 2 above, wherein the formula (1) is the formula (1B).
4. The thermoplastic resin according to any one of 1 to 3 above, wherein _{L 1} and L ₂ in the formula (1) are ethylene groups.
5. The thermoplastic resin according to any one of 1 to 4 above, wherein _{R 1 to} R ₈ in the formula (1) are hydrogen atoms.
6. The thermoplastic resin according to any one of 1 to 5 above, wherein X in the formula (3) is at least one selected from the group consisting of a phenylene group, a naphthalene diyl group, and a group represented by the following formula (4). ..

（式中、Ｒ_１７〜Ｒ_１８はそれぞれ独立して水素原子、炭素原子数１〜９の芳香族基を含んでもよい炭化水素基又はハロゲン原子である。）

（式中、Ｒ_１９〜Ｒ_２０はそれぞれ独立して水素原子、炭素原子数１〜９の芳香族基を含んでもよい炭化水素基又はハロゲン原子であり、Ｙは単結合または２価の連結基である。） 7. The thermoplastic resin according to any one of 1 to 6 above, which comprises at least one selected from the group consisting of units represented by the following formulas (5) to (7) as a repeating unit.

(In the formula, R _{17 to} R ₁₈ are each independently a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms.)

(In the formula, R _{19 to} R ₂₀ are each independently a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms, and Y is a single bond or a divalent linking group. Is.)

8. The thermoplastic resin according to any one of 1 to 7 above, wherein the thermoplastic resin is any one of polycarbonate, polyester, and polyester carbonate.
9. The thermoplastic resin according to any one of 1 to 8 above, which has a specific viscosity of 0.12 to 0.40.
10. The thermoplastic resin according to any one of 1 to 9 above, wherein the glass transition temperature is 130 to 180 ° C.
11. The thermoplastic resin according to any one of 1 to 10 above, which has a refractive index of 1.640 to 1.690.
12. An optical member made of the thermoplastic resin according to any one of 1 to 11 above.
13. The optical member according to the above 12, which is an optical lens.

Since the thermoplastic resin of the present invention has an excellent balance of high refractive index, low birefringence and moldability, the industrial effect exerted by the thermoplastic resin is exceptional.

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 formula (1), and the repeating unit represented by the formula (1) contains a lower limit of 5 mol% or more based on all the repeating units. It is preferable, it is more preferably contained in an amount of 20 mol% or more, and it is further preferably contained in an amount of 30 mol% or more. It is preferable that the repeating unit represented by the formula (1) is in the above range because of its high refractive index. 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 refractive index, birefringence, heat resistance and moldability is excellent.

The thermoplastic resin of the present invention is preferably any one of a polycarbonate resin, a polyester resin, and a polyester carbonate resin.

In the above formula (1), R _{1 to} R ₁₆ may independently contain a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an aromatic group having 1 to 12 carbon atoms. Of the groups R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₄ and R ₁₅ and R ₁₅ and R ₁₆ , one set is fused to each other. To form a ring. One set in the present invention means only one set not including two or more sets.
It is preferable that the ring formed by condensation is an aromatic ring, and it is more preferable _{that a set thereof is R 10} and R _{11. R 1 to} R ₁₆ that do not form the ring are preferably a hydrogen atom or a phenyl group, and more preferably a hydrogen atom.

In the formula (1), L ₁ and L ₂ each independently represent a divalent linking group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an ethylene group.

In the formula (1), W is at least one selected from the group represented by the 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.

In the above formula (3), X represents a divalent linking group, preferably a hydrocarbon group which may contain an aromatic group having 1 to 30 carbon atoms, and a phenylene group, a naphthalenediyl group, the above. It is more preferable that the group is represented by the formula (4).

In the thermoplastic resin of the present invention, when at least one selected from the group consisting of the units represented by the formulas (5) to (7) is included as a repeating unit, the repeating unit represented by the formula (1) is used. The mol ratio of the repeating unit to the group consisting of the units represented by the formulas (5) to (7) 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 (5) to (7) is in the above range, it is high. In addition to having a refractive index, it is preferable because it has an excellent balance between low birefringence and moldability.

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. .. It is preferable that the specific viscosity is within the above range because the balance between moldability and mechanical strength is excellent. The specific viscosity can be measured by a conventional method.

The refractive index of the thermoplastic resin of the present invention at a wavelength of 589 nm measured at 25 ° C. (hereinafter, may be abbreviated as nD) is preferably 1.640 to 1.690, preferably 1.650 to 1.690. More preferably, 1.660 to 1.690 is even more preferable, and 1.670 to 1.690 is most preferable. When the refractive index is at least the lower limit, the spherical aberration of the lens can be reduced, and the focal length of the lens can be shortened.

The Abbe number (ν) of the thermoplastic resin of the present invention is preferably 17 to 23, more preferably 17 to 21, and even more preferably 17 to 20. The Abbe number is calculated from the refractive indexes of wavelengths 486 nm, 589 nm, and 656 nm measured at 25 ° C. using the following formula.
ν = (nD-1) / (nF-nC)
In the present invention, it should be noted.
nD: Refractive index at wavelength 589 nm,
nC: Refractive index at wavelength 656 nm,
nF: means the 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 5 × 10 ^-3 , more preferably 0 to 3 × 10 ^-3 , and even more preferably 0 to 2 × 10. It is in the range of ^-3. The orientation birefringence (Δn) is calculated by the following formula by stretching a film having a thickness of 100 μm obtained from the thermoplastic resin of the present invention twice at a temperature of Tg + 10 ° C. and measuring the phase difference at a wavelength of 589 nm. When the orientation birefringence is within the above range, the optical distortion of the lens is reduced, which is preferable.
Δn = Re / d
Δn: orientation birefringence
Re: Phase difference (nm)
d: Thickness (nm)

The thermoplastic resin of the present invention preferably has a glass transition point (Tg) of 130 to 180 ° C, more preferably 130 to 170 ° C, and even more preferably 135 to 155 ° C. When the glass transition point is within the above range, the balance between heat resistance and moldability is excellent, which is preferable.

The thermoplastic resin of the present invention has a total light transmittance of 1 mm thickness of preferably 80% or more, more preferably 85% or more, still more preferably 88% or more. When the total light transmittance is within the above range, it is suitable as an optical member.

The thermoplastic resin of the present invention preferably has a water absorption rate of 0.25% or less, more preferably 0.20% or less, after being immersed at 23 ° C. for 24 hours. 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>
(Glycol component of the above formula (1))
The diol component used as a raw material of the formula (1) of the present invention is mainly a diol component represented by the formula (a), and may be used alone or in combination of two or more.

In the general formula (a), R _{1 to} R ₁₆ and L _{1 to} L ₂ can be said to be the same as those described in the above formula (1).

Hereinafter, typical specific examples of the diol component represented by the formula (a) will be shown, but the raw materials used in the formula (1) of the present invention are not limited thereto.

9,9-bis (4- (2-hydroxyethoxy) phenyl) -1,2-benzofluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) -1,2-benzo Fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) -1,2-benzofluorene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) -2,3 -Benzofluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) -2,3-benzofluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenyl) Phenyl) -2,3-benzofluorene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) -3,4-benzofluorene, 9,9-bis (4- (2-hydroxyethoxy) -3) -Methylphenyl) -3,4-benzofluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) -3,4-benzofluorene and the like are preferably mentioned. Among them, 9,9-bis (4-hydroxyphenyl) -1,2-benzofluorene and 9,9-bis (4- (2-hydroxyethoxy) phenyl) -2 represented by the following formulas (a1) to (a3). , 3-Benzofluorene, 9,9-bis (4-hydroxyphenyl) -3,4-benzofluorene are more preferred, and 9,9-bis (4- (2-hydroxyethoxy) phenyl) -2,3-benzo Fluorene is more preferred. These may be used alone or in combination of two or more.

(Glycol component of the above formulas (5) to (7))
The diol components used as the raw materials of the formulas (5) to (7) of the present invention are shown below, and these may be used alone or in combination of two or more.
The diol component used as a raw material of the formula (5) of the present invention is 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthyl.

The diol component used as the raw material of the formula (6) of the present invention is 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 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, etc. Is exemplified, and 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is particularly preferable. These may be used alone or in combination of two or more.

The diol component used as the raw material of the formula (7) of the present invention is 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-. Bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 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) 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, Examples include 9-bis (4-hydroxy-3-phenylphenyl) fluorene, bis (4-hydroxyphenyl) sulfone, 10,10-bis (4-hydroxyphenyl) antron, and 2,2-bis (4-hydroxyphenyl). Phenyl) propane and bis (4-hydroxyphenyl) sulfide are particularly preferred. These may be used alone or in combination of two or more.

(Copolymerization components other than the general formulas (1) to (7))
The thermoplastic resin of the present invention may be copolymerized with other diol components to the extent that the characteristics of the present invention are impaired. The other diol component is preferably less than 30 mol% in all repeating units.

Other diol components used in the thermoplastic resin of the present invention, ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, tricyclo [5.2.1.0 ^{2 , 6} ] Decandimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecanemethanol, cyclopentane-1,3-dimethanol, spiroglycol, isosorbide, Examples thereof include isomannide, isoidide, hydroquinone, resorsinol, bis (4- (2-hydroxyethoxy) phenyl) sulfone, 1,1'-bi-2-naphthol, dihydroxynaphthalene, bis (2-hydroxyethoxy) naphthalene and the like. May be used alone or in combination of two or more types.

前記式（ｂ）において、Ｘは、２価の連結基を示す。 (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, the dicarboxylic acid represented by the formula (b) or an ester-forming derivative thereof is preferably used.

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

Hereinafter, typical specific examples of the dicarboxylic acid represented by the general formula (b) or an ester-forming derivative thereof will be shown, but the raw materials used in the general formula (b) of the present invention are not limited thereto. do not have.

Examples of the dicarboxylic acid component used in the thermoplastic resin of the present invention include aliphatic dicarboxylic acid components such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelliic acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid. , Monocyclic aromatic dicarboxylic acid components such as phthalic acid, isophthalic acid, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid. Acid, 1,8-naphthalenedicarboxylic acid, anthracendicarboxylic acid, phenanthenedenedicarboxylic acid, 2,2'-bis (carboxymethoxy) -1,1'-binaphthyl, 9,9-bis (carboxymethyl) fluorene, 9,9 -Bis (2-carboxyethyl) 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- Polycyclic aromatic dicarboxylic acid component such as bis (2-carboxy-1-methylbutyl) fluorene, 9,9-bis (5-carboxypentyl) fluorene, 9,9-bis (carboxycyclohexyl) fluorene, 2,2' Examples include biphenyldicarboxylic acid components such as −biphenyldicarboxylic acid, alicyclic dicarboxylic acid components such as 1,4-cyclohexanedicarboxylic acid and 2,6-decalindicarboxylic acid, and isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid. Acid, 2,2'-bis (carboxymethoxy) -1,1'-binaphthyl is preferred. These may be used alone or in combination of two or more. Further, as the ester-forming derivative, acid chloride or esters such as methyl ester, ethyl ester and phenyl ester may be used.

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

<Manufacturing method of thermoplastic resin>
(Manufacturing method of polycarbonate resin)
The polycarbonate resin which is the thermoplastic resin of the present invention is obtained by reacting a diol component with a carbonate precursor by an interfacial polymerization method or a melt polymerization method. In producing the polycarbonate resin, a catalyst, a terminal terminator, an antioxidant or the like may be used, if necessary.

The reaction by the interfacial polymerization method is usually a reaction between a diol component and phosgene, and the reaction 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, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, in order to promote the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound may be used. can. At that time, it is preferable to keep the reaction temperature at 0 to 40 ° C., the reaction time at about 10 minutes to 5 hours, and the pH during the reaction at 9 or more.

The reaction by the melt polymerization method is usually a transesterification reaction between a diol component and a carbonate ester, and a hydroxy compound such as phenol produced by mixing the diol component and the carbonate ester while heating in the presence of an inert gas. It is done by the method of distilling. 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 system is reduced in pressure to about 1000 to 1 Pa to facilitate distillation of the produced hydroxy compound. The reaction time is usually about 1 to 8 hours.

Examples of the carbonate ester include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, and an alkyl group having 1 to 4 carbon atoms which may be substituted. Specific examples thereof include diphenyl carbonate, ditril carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like, and among them, diphenyl carbonate. Is preferable.

Further, in the melting method, a polymerization catalyst can be used to increase the polymerization rate, and the polymerization catalyst includes, for example, sodium hydroxide, potassium hydroxide, an alkali metal compound such as a sodium salt of dihydric phenol, a 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, and alkoxides of alkali metals and alkaline earth metals. , Organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds, Alkali usually used for esterification reaction and ester exchange reaction such as manganese compounds, titanium compounds and zirconium compounds can be used. The catalyst may be used alone or in combination of two or more. The amount of these polymerization catalysts used is preferably in the range of ^{1 × 10 -8} to 1 × 10 ^-3 mol with respect to 1 mol of the diol component of the raw material.

As the polycarbonate resin which is the thermoplastic resin of the present invention, a monofunctional hydroxy compound usually used as a terminal terminator may be used in the polymerization reaction. Monofunctional phenols are commonly used as end-stoppers for molecular weight regulation, especially in reactions using phosgen as a carbonate precursor, and the resulting polymers are groups whose ends are based on monofunctional phenols. Because it is blocked by, it has better thermal stability than those that do not.

(Polyester resin manufacturing method)
In the polyester resin which is the thermoplastic resin of the present invention, a diol 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 molecular weight. It may be a high molecular weight substance.

The ethylene glycol component is preferably 0 to 50 mol% with respect to the total diol component. The above range is preferable because the balance between heat resistance and moldability is excellent.

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) in which dicarboxylic acid chloride is dissolved in an organic solvent that is incompatible with water is mixed with an alkaline aqueous solution (aqueous phase) containing an aromatic diol and a polymerization catalyst, and the temperature is 50 ° C. or lower. A method of carrying out the polymerization reaction while stirring at a temperature of 25 ° C. or lower for 0.5 to 8 hours can be mentioned.

As the solvent used for the organic phase, a solvent that is incompatible with water and dissolves the polyester resin of the present invention is preferable. 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 for 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 to mix a diol component and a dicarboxylic acid component or a diester thereof and react them at 120 to 350 ° C., preferably 150 to 300 ° C., more preferably 180 to 270 ° C. The degree of decompression is changed stepwise, and finally, hydroxy compounds such as water and alcohol produced at 0.13 kPa or less are distilled off from the system, and the reaction time is usually about 1 to 10 hours.

Further, in the melting method, a transesterification catalyst and a polymerization catalyst can be used to increase the polymerization rate. As the transesterification catalyst, a catalyst known per se can be adopted, and for example, a compound containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium and lead elements can be used. Specific examples thereof include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates and sulfates containing these elements. 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 a small amount of polymer insoluble foreign substances. Two or more of these compounds can be used in combination. As the polymerization catalyst, a catalyst known per se can be adopted, and for example, an antimony compound, a titanium compound, a germanium compound, a tin compound or an aluminum compound is preferable. Examples of such compounds include antimony, titanium, germanium, tin, aluminum oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, sulfates and the like. In addition, these compounds can be used in combination of two or more. Among these, 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 preferably in the range of ^{1 × 10 -8} to 1 × 10 ^-3 mol with respect to 1 mol of the dicarboxylic acid component, for example.

For the polyester resin of the present invention, an end sealant may be used for adjusting the molecular weight and improving the thermal stability. Examples of the terminal encapsulant include monofunctional hydroxy compounds, epoxy compounds, oxazoline compounds, isocyanate compounds, carbodiimide compounds, ketenimine compounds and the like.

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

(Manufacturing method of polyester carbonate resin)
The polyester carbonate resin, which is the thermoplastic resin of the present invention, can be produced by reacting a carbonate precursor such as phosgene or carbonic acid diester in addition to a diol component and a dicarboxylic acid or an ester-forming derivative thereof.

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

As the release agent, it is preferable that 90% by weight or more thereof is composed of an ester of alcohol and a fatty acid. Specific examples of the ester of the alcohol and the fatty acid include an ester of a monohydric alcohol and a fatty acid and / or a partial ester or a total ester of a polyhydric alcohol and a fatty acid. The ester of the monohydric alcohol and the fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. The partial ester or total ester of the polyhydric alcohol and the fatty acid is preferably a partial ester or the total ester of the polyhydric alcohol having 1 to 25 carbon atoms and the saturated fatty acid having 10 to 30 carbon atoms. Specific examples of the monohydric alcohol, the saturated fatty acid and the ester include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like, and stearyl stearate is preferable.

Specifically, as a partial ester or total ester of polyhydric alcohol and saturated fatty acid, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetra All esters or portions of dipentaerythritol such as stearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenylbiphenylate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate. Examples include ester. 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, when the release agent is 100% by weight.

The release agent to be blended in the thermoplastic resin composition is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight with respect to 100 parts by weight of the thermoplastic resin. The range of 0.02 to 0.5 parts by weight is preferable, and the range of 0.02 to 0.5 parts by weight is more preferable.

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

Examples of the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, Tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphos Fight, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (nonylphenyl) ) Pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, Tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, tetrakis (2,4-) Di-t-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-) t-Butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) ) -3-Phenyl-Phenylphosphonite and the like.

Among them, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-) tert-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3' -Biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphospho Nite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite are preferably used. Particularly preferred are tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-). tert-Butylphenyl) -4,4'-biphenylenediphosphonite 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.

Sulfur-based heat stabilizers include pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), and so on. Dilauryl-3, 3'-thiodipropionate, dimyristyl-3, 3'-thiodipropionate, disstearyl-3, 3'-thiodipropionate and the like can be mentioned. Among them, pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), dilauryl-3, 3'-thiodipropionate, dimyristyl-3, 3'-thio Dipropionate is preferred. Particularly preferred is pentaerythritol-tetrakis (3-laurylthiopropionate).

The content of the sulfur-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.

Examples of the hindered phenol-based heat stabilizer include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [3- (3). , 5-Di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3, 5-Di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5) -Di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {1,1-dimethyl-2-[β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] Ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane and the like. Among them, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and pentaerythritol-tetrakis [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.
Phosphorus-based heat stabilizers and hindered phenol-based heat stabilizers can also be used in combination.

The UV absorber is at least one UV absorber selected from the group consisting of benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, cyclic iminoester-based UV absorbers, and cyanoacrylate-based UV absorbers. Is preferable.

Among benzotriazole-based UV absorbers, more preferably 2- (2-hydroxy-5-tert-octylphenyl) benzotriazol, 2,2'-methylenebis [4- (1,1,3,3-tetramethyl) Butyl) -6- (2H-benzotriazole-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 triazine-based UV absorbers include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] -phenol and 2- (4,6-bis (4,6-bis). 2.4-Dimethylphenyl) -1,3,5-triazine-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-benzoxazine-4-one) is particularly preferable.

Examples of cyanoacrylate-based ultraviolet absorbers include 1,3-bis-[(2'-cyano-3', 3'-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenyl). Examples thereof include acryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

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, and within the range of such blending amount, it can be used as a thermoplastic resin molded product 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, particularly optical lenses.

When the thermoplastic resin optical lens of the present invention is manufactured by injection molding, it is preferably molded under the conditions of a cylinder temperature of 230 to 350 ° C. and a mold temperature of 70 to 170 ° 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 160 ° C. When the cylinder temperature is higher than 350 ° C., the thermoplastic resin is decomposed and colored, and when the cylinder temperature is lower than 230 ° C., the melt viscosity is high and molding tends to be difficult. Further, when the mold temperature is higher than 170 ° C., it tends to be difficult to remove the molded piece made of the thermoplastic resin from the mold. On the other hand, if the mold temperature is less than 70 ° C, the resin hardens 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. Tends to be difficult.

As the optical lens of the present invention, it is preferably carried out in the form of an aspherical lens, if necessary. Since it is possible to eliminate spherical aberration with a single lens in an aspherical lens, it is not necessary to remove spherical aberration by combining a plurality of spherical lenses, resulting in weight reduction and reduction in molding cost. It 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 high molding fluidity, it is particularly useful as a material for an optical lens having a thin wall, a small size, and 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 even more preferably 3.0 to 10.0 mm. Further, it is preferable that the shape is a meniscus lens having one side convex and one side concave.

The lens made of a thermoplastic resin in the optical lens of the present invention is molded by an arbitrary method such as mold molding, cutting, polishing, laser processing, electric discharge machining, and etching. Among these, mold 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.

(A) Film 3 g of the obtained resin is dissolved in 50 ml of methylene chloride and cast on a glass petri dish. After sufficiently drying at room temperature, the film was dried at a temperature of 120 ° C. or lower for 8 hours to prepare a 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 polymerization was measured by using proton NMR of JNM-AL400 manufactured by JEOL Ltd.
(2) Specific Viscosity: The resin obtained after the completion of polymerization was sufficiently dried, and the specific viscosity (η _sp ) of the solution at 20 ° C. was measured from a solution in which 0.7 g of the resin was dissolved in 100 ml of methylene chloride.
(3) Glass transition temperature: The pellets obtained after melt-kneading were measured with a DSC-60A manufactured by Shimadzu Corporation at a heating rate of 20 ° C./min.
(4) Refractive index (nD): The film produced by the method of (a) is subjected to the refractive index (wavelength: 589 nm) and Abbe number (wavelength: 486 nm, 589 nm) at 25 ° C. using a DR-M2 Abbe refractometer manufactured by ATAGO. , Calculated from the refractive index at 656 nm).
(5) Absolute value of orientation birefringence (| Δn |): A cast film having a thickness of 100 μm prepared by the method of (a) was stretched twice at Tg + 10 ° C., and an ellipsometer M-220 manufactured by JASCO Corporation was used. The phase difference (Re) at 589 nm was measured using the above formula, and the absolute value of the orientation birefringence was obtained from the following formula.
| Δn | = | Re / d |
Δn: orientation birefringence
Re: Phase difference (nm)
d: Thickness (nm)

Reference Example 1 (Synthesis of 9,9-bis [4- (2-hydroxyethoxy) phenyl] -2,3-benzofluorene (hereinafter, may be abbreviated as BPE23B))
(1-1) Synthesis of 2,3-benzofluorenone In a 300 ml three-necked flask, 30.0 g of 1-indanone, 36.3 g of phthalaldehyde, and 90 ml of super-dehydrated methanol were charged and dissolved. Further, 38.7 g of potassium hydroxide and 60 ml of super-dehydrated methanol were charged into the dropping funnel and dissolved. While stirring the reaction solution at 60 ° C., a potassium hydroxide methanol solution was added dropwise to the reaction solution over 30 minutes, and the reaction solution was further stirred for 3 hours. A yellow solid was precipitated in the reaction solution. The reaction mixture was concentrated under reduced pressure to 90 ml and then filtered to obtain 23.4 g of yellow crystals (2,3-benzofluorenone).
(1-2) Synthesis of 9,9-bis (4-hydroxyphenyl) -2,3-benzofluoren In a 300 ml eggplant flask, 22.5 g of 2,3-benzofluorenone, 1.5 g of concentrated sulfuric acid, and 112.5 g of phenol , 2.3 g of toluene and 2.3 ml of mercaptopropionic acid were added, and the mixture was stirred at 55 ° C. for 4 hours. The reaction solution was dissolved in 2M aqueous sodium hydroxide solution and extracted with diethyl ether. The organic phase was washed twice with 2M aqueous sodium hydroxide solution. The organic phase was dried over anhydrous sodium sulfate and then concentrated to give a pale yellow solid. The pale yellow solid was washed 4 times with a mixed solvent of chloroform / hexane (1/3) to give 38 g of a white solid (9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene). ..
(1-3) Synthesis of BPE23B To a 300 ml three-necked flask, 25.0 g of 9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene, 17.5 g of potassium carbonate, and 250 ml of N, N-dimethylformamide were added. .. The reaction mixture was stirred at 80 ° C. for 10 minutes, and then 31.0 g of 2-bromoethanol was added dropwise over 10 minutes. Then, the reaction solution was heated to 140 ° C. and stirred for 4 hours. The reaction solution was added dropwise to 2.5 L of a 2 M aqueous sodium hydroxide solution to precipitate a white solid. The white solid was recovered by filtration and purified on a silica gel column using an eluent of ethyl acetate / hexane (1/1) to obtain 22.5 g of the target product, BPE23B.

Reference Example 2 (Synthesis of 9,9-bis [4- (2-hydroxyethoxy) phenyl] -1,2-benzofluorene (hereinafter, may be abbreviated as BPE12B))
1,2-Benzofluorenone was obtained by the method described in Agewandte Chemie, 48 (10), 1849-852, 2009. Then, BPE12B was obtained in the same manner as in 1-2 and 1-3 above except that 2,3-benzofluorenone was changed to 1,2-benzofluorenone.

Example 1
9.76 parts of BPE23B synthesized in Reference Example 1, 35.08 parts of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (hereinafter sometimes abbreviated as BPEF), diphenyl carbonate (hereinafter "DPC"" 21.64 parts and 8.40 × ^10-5 parts of sodium hydrogen carbonate are placed in a reaction vessel equipped with a stirrer and a distiller, nitrogen substitution is performed 3 times, and then the jacket is cooled to 180 ° C. The raw material was melted. After complete dissolution, the pressure was reduced to 20 kPa over 5 minutes, and at the same time, the jacket was heated to 260 ° C. at a rate of 60 ° C./hr, and a transesterification reaction was carried out. Then, while keeping the jacket at 260 ° C., the pressure was reduced to 0.13 kPa over 50 minutes, and the polymerization reaction was carried out under the conditions of 260 ° C. and 0.13 kPa or less until a predetermined torque was reached. After completion of the reaction, the produced resin was extracted while pelletizing to obtain pellets. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 1. Further, after drying the obtained resin at 120 ° C. for 4 hours, 0.05% by weight of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite was added based on the weight of the resin. , Glycerin monostearate was added in an amount of 0.10% by weight, and pelletized using a φ15 mm twin-screw extruder with a vent. The pellet was dried at 120 ° C. for 4 hours and then injection molded at a cylinder temperature of 280 ° C. and a mold temperature of 130 ° C. to obtain a lens having a thickness of 0.3 mm, a convex radius of curvature of 5 mm and a concave radius of curvature of 4 mm.

Example 2
Pellets were obtained in the same manner as in Example 1 except that the BPE23B of Example 1 was 24.41 parts and the BPEF was 21.93 parts. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 1.

Example 3
Pellets were obtained in the same manner as in Example 1 except that BPE23B of Example 1 was 48.82 parts and BPEF was 0 parts. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 1.

Example 4
BPE23B of Example 1 was changed to 24.41 parts, BPEF was changed to 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthyl (hereinafter, may be abbreviated as BHEB), and 18.72. Pellets were obtained in the same manner as in Example 1 except for the parts. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 1.

Example 5
Pellets were obtained in the same manner as in Example 4 except that BPE23B of Example 1 was 14.65 parts and BHEB was 26.21 parts. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, and glass transition point were measured, and the results are shown in Table 1.

Example 6
Pellets were obtained in the same manner as in Example 1 except that BPE23B of Example 1 was changed to 29.29 parts and BPEF was changed to bisphenol A (hereinafter, may be abbreviated as BPA) to 9.12 parts. rice field. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 1.

Example 7
Pellets were prepared in the same manner as in Example 1 except that BPE23B of Example 1 was changed to 34.17 parts and BPEF was changed to thiodiphenol (hereinafter, may be abbreviated as TDP) to 6.54 parts. Obtained. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 1.

Example 8
Pellets were obtained in the same manner as in Example 1 except that BPE23B of Example 1 was changed to BPE12B to 24.41 parts and BPEF was changed to 21.93 parts. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 1.

Comparative Example 1
43.85 parts of BPEF, 21.21 parts of DPC, and 4.20 × ^10-6 parts of sodium hydrogen carbonate were placed in a reaction vessel equipped with a stirrer and a distiller, nitrogen substitution was performed 3 times, and then the jacket was heated to 180 ° C. And the raw material was melted. After complete dissolution, the pressure was reduced to 20 kPa over 5 minutes, and at the same time, the jacket was heated to 260 ° C. at a rate of 60 ° C./hr, and a transesterification reaction was carried out. Then, while keeping the jacket at 260 ° C., the pressure was reduced to 0.13 kPa over 50 minutes, and the polymerization reaction was carried out under the conditions of 260 ° C. and 0.13 kPa or less until a predetermined torque was reached. After completion of the reaction, the produced resin was extracted while pelletizing to obtain pellets. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 1.

Example 9
BPE23B 24.41 parts, 2,2'-bis (carboxymethoxy) -1,1'-binaphthyl (hereinafter sometimes abbreviated as BCMB) 20.12 parts, and titanium tetrabutoxide 3.40 x 10 ^-3 parts Was placed in a reaction vessel equipped with a stirrer and a distiller, and after performing nitrogen substitution three times, the jacket was heated to 180 ° C. to melt the raw materials. Then, the pressure was reduced to 40 kPa over 20 minutes, and at the same time, the jacket was heated to 260 ° C. at a rate of 60 ° C./hr, and a transesterification reaction was carried out. Then, the pressure was reduced to 0.13 kPa over 70 minutes, and then the polymerization reaction was carried out under the conditions of 0.13 kPa or less until a predetermined torque was reached. After completion of the reaction, the produced resin was extracted while pelletizing to obtain pellets. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 2.

Example 10
9.76 parts of BPE23B, 11.23 parts of BHEB, 20.12 parts of BCMB, and 3.40 × ^10-3 parts of titanium tetrabutoxide were placed in a reaction vessel equipped with a stirrer and a distiller, and after nitrogen substitution was performed three times, the jacket was used. Was heated to 180 ° C. to melt the raw material. Then, the pressure was reduced to 40 kPa over 20 minutes, and at the same time, the jacket was heated to 260 ° C. at a rate of 60 ° C./hr, and a transesterification reaction was carried out. Then, the pressure was reduced to 0.13 kPa over 70 minutes, and then the polymerization reaction was carried out under the conditions of 0.13 kPa or less until a predetermined torque was reached. After completion of the reaction, the produced resin was extracted while pelletizing to obtain pellets. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 2. Further, after drying the obtained resin at 120 ° C. for 4 hours, 0.05% by weight of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite was added based on the weight of the resin. , Glycerin monostearate was added in an amount of 0.10% by weight, and pelletized using a φ15 mm twin-screw extruder with a vent. The pellet was dried at 120 ° C. for 4 hours and then injection molded at a cylinder temperature of 280 ° C. and a mold temperature of 130 ° C. to obtain a lens having a thickness of 0.3 mm, a convex radius of curvature of 5 mm and a concave radius of curvature of 4 mm.

Example 11
12.21 parts of BPE23B, 4.66 parts of ethylene glycol (hereinafter sometimes abbreviated as EG), 20.12 parts of BCMB, and 3.40 x ^10-3 parts of titanium tetrabutoxide in a reaction vessel with a stirrer and a distiller. After the nitrogen substitution was performed 3 times, the jacket was heated to 180 ° C. to melt the raw materials. Then, the jacket was heated to 230 ° C. at a rate of 60 ° C./hr, a transesterification reaction was carried out, and a predetermined amount of water was distilled off. Then, the jacket was heated to 260 ° C. and reduced to 0.13 kPa over 80 minutes, and then the polymerization reaction was carried out under the conditions of 0.13 kPa or less until a predetermined torque was reached. After completion of the reaction, the produced resin was extracted while pelletizing to obtain pellets. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 2.

Example 12
Pellets were obtained in the same manner as in Example 11 except that BPE23B was 17.09 parts, EG was 4.03 parts, and dimethyl terephthalate (hereinafter, may be abbreviated as DMT) was 9.71 parts. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 2.

Example 13
9.76 parts of BPE23B, 13.11 parts of BHEB, 18.11 parts of BCMB, 2.57 parts of DPC, and 3.40 × ^10-3 parts of titanium tetrabutoxide were placed in a reaction vessel equipped with a stirrer and a distiller, and nitrogen substitution was performed 3 times. After that, the jacket was heated to 180 ° C. to melt the raw materials. Then, the pressure was reduced to 40 kPa over 20 minutes, and at the same time, the jacket was heated to 260 ° C. at a rate of 60 ° C./hr, and a transesterification reaction was carried out. Then, the pressure was reduced to 0.13 kPa over 70 minutes, and then the polymerization reaction was carried out under the conditions of 0.13 kPa or less until a predetermined torque was reached. After completion of the reaction, the produced resin was extracted while pelletizing to obtain pellets. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 2. Further, after drying the obtained resin at 120 ° C. for 4 hours, 0.05% by weight of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite was added based on the weight of the resin. , Glycerin monostearate was added in an amount of 0.10% by weight, and pelletized using a φ15 mm twin-screw extruder with a vent. The pellet was dried at 120 ° C. for 4 hours and then injection molded at a cylinder temperature of 280 ° C. and a mold temperature of 130 ° C. to obtain a lens having a thickness of 0.3 mm, a convex radius of curvature of 5 mm and a concave radius of curvature of 4 mm.

Example 14
Pellets were obtained in the same manner as in Example 13 except that BPE23B was 19.53 parts, BHEB was 13.11 parts, BCMB was 10.06 parts, and DPC was 11.14 parts. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 2.

Example 15
BPE23B was changed to 24.41 parts, BHEB was changed to 14.98 parts, BCMB was changed to dimethyl naphthalenedicarboxylic acid (hereinafter, may be abbreviated as NDCM) to 2.44 parts, and DPC was changed to 17.57 parts. Pellets were obtained in the same manner as in Example 13. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 2.

Comparative Example 2
A polyester resin was obtained under the conditions described in Example 1 of JP-A-7-1989901. Using the obtained resin, the specific viscosity, copolymerization ratio, refractive index, Abbe number, glass transition point, and orientation birefringence were measured, and the results are shown in Table 2.

BPE23B: 9,9-bis [4- (2-hydroxyethoxy) phenyl] -2,3-benzofluorene BPE12B: 9,9-bis [4- (2-hydroxyethoxy) phenyl] -1,2-benzofluorene BPEF: 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene BHEB: 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthyl BPA: bisphenol A
TDP: Thiodiphenol EG: Ethylene glycol BCMB: 2,2'-bis (carboxymethoxy) -1,1'-binaphthyl DMT: Dimethyl terephthalate NDCM: Dimethyl naphthalene dicarboxylic acid

The thermoplastic resins obtained in Examples 1 to 15 can be easily injection-molded by injection molding and have a high bending rate. On the other hand, the thermoplastic resins of Comparative Examples 1 and 2 have a low refractive index.

The thermoplastic resin of the present invention can be used for optical members such as optical disks, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, and hard coat films, and in particular. Extremely useful for lenses.

Claims (11)

A thermoplastic resin containing at least one selected from the group consisting of units represented by the following formulas (1A) to (1C) as a repeating unit.

(In the formula, R _{1 to} R ₈ are hydrogen atoms, and R _{11 to} R ₁₆ are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and aromatic groups having 1 to 12 carbon atoms. Indicates a hydrocarbon group that may contain, L ₁ and L ₂ each independently represent a divalent linking group, and W is at least one selected from the group represented by the following formula (2) or (3). One.)

(In the formula, R _{1 to} R ₈ are hydrogen atoms, and R _{9 and} R _{12 to} R ₁₆ are independently hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and carbon atoms 1 to 12. Indicates a hydrocarbon group that may contain an aromatic group, L ₁ and L ₂ each independently indicate a divalent linking group, and W is selected from the group represented by the following formula (2) or (3). At least one.)

(In the formula, R _{1 to} R ₈ are hydrogen atoms, and R _9, R _{10, and} R _{13 to} R ₁₆ are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, and carbon atom number 1. Indicates a hydrocarbon group that may contain up to 12 aromatic groups, L ₁ and L ₂ each independently represent a divalent linking group, and W is represented by the following formula (2) or (3). At least one selected from the group)

(In the formula, X represents a divalent linking group.) The thermoplastic resin according to claim 1, wherein the repeating unit is the formula (1B). The thermoplastic resin according to claim 1 or 2, _{wherein L 1} and L ₂ in the repeating unit are ethylene groups. The thermoplastic according to any one of claims 1 to 3, wherein X in the formula (3) is at least one selected from the group consisting of a phenylene group, a naphthalene diyl group, and a group represented by the following formula (4). resin.

The thermoplastic resin according to any one of claims 1 to 4, which contains at least one selected from the group consisting of units represented by the following formulas (5) to (7) as a repeating unit.

(In the formula, R _{17 to} R ₁₈ are each independently a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms.)

(In the formula, R _{19 to} R ₂₀ are each independently a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms, and Y is a single bond or a divalent linking group. Is.) The thermoplastic resin according to any one of claims 1 to 5, wherein the thermoplastic resin is any one of polycarbonate, polyester, and polyester carbonate. The thermoplastic resin according to any one of claims 1 to 6, which has a specific viscosity of 0.12 to 0.40. The thermoplastic resin according to any one of claims 1 to 7, wherein the glass transition temperature is 130 to 180 ° C. The thermoplastic resin according to any one of claims 1 to 8, which has a refractive index of 1.640 to 1.690. An optical member made of the thermoplastic resin according to any one of claims 1 to 9. The optical member according to claim 10, which is an optical lens.