JP2018141085A - Poly (thio) carbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin that has a high refractive index, heat resistance and moldability in a balanced manner, has small birefringence, and has a scratch-proof surface.SOLUTION: A poly (thio) carbonate contains at least one selected from units represented by formula (1) and formula (2), as a repeating unit. Preferably, the poly (thio) carbonate further contains a diol component as a diol-derived repeating unit having a 9,9-bis(aryl) fluorene skeleton.SELECTED DRAWING: None

Description

  The present invention relates to a poly (thio) carbonate having an excellent balance of high refractive index, heat resistance and moldability.

  A conventional polycarbonate resin produced by reacting 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) with a carbonate-forming compound such as phosgene or diphenyl carbonate has high transparency, heat resistance, Since it has excellent impact resistance, it has been used for optical members such as optical disks. However, there are drawbacks such as large birefringence and the surface being easily damaged, and the usage is limited. As a method for reducing birefringence, the copolymerization of bisphenols having a fluorene structure in the side chain has been reported. (Patent Documents 1, 2, 3, 4). However, since the polycarbonate resins of Patent Document 1 and Patent Document 2 have a high glass transition temperature and extremely high viscosity when melted, it is difficult to mold an optical lens or an optical disk. Moreover, although the polycarbonate resin of patent document 3 and patent document 4 is a polycarbonate which has a melt viscosity which does not have a shaping | molding problem, and there exists description that it is suitable for an optical disk, refractive index is insufficient for using for an optical lens. Met.

JP-A-7-109342 JP 2010-53251 A JP-A-10-101786 JP-A-10-101787

  Accordingly, an object of the present invention is to provide a poly (thio) carbonate having an excellent balance of high refractive index, heat resistance and moldability.

  As a result of intensive studies aimed at achieving this object, the present inventors have found that the above problems can be solved by the following poly (thio) carbonates 1 to 9, and have reached the present invention.

That is, the present invention
1. Poly (thio) carbonate containing at least one selected from the group consisting of units represented by the following formula (1) and the following formula (2) as a repeating unit.

2. 2. The poly (thio) carbonate according to 1 above, wherein the total of the repeating units represented by the formula (1) and the formula (2) includes 30 mol% or more based on all repeating units.
3. 3. The poly (thio) carbonate according to the above 1 or 2, comprising a repeating unit represented by the following formula (3).

(In the formula, R _{1 to} R ₈ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. , L ₁ and L ₂ each independently represent a divalent linking group, and m and n each independently represents 0 or 1.)
4). 4. The poly of the above 3, wherein the molar ratio of the total of the repeating units represented by the formula (1) and the formula (2) and the repeating unit represented by the formula (3) is 80:20 to 20:80. (Thio) carbonate.
5. The poly (thio) carbonate according to any one of 2 to 4 above, wherein m and n in the formula (3) are 0.
6). The poly (thio) carbonate according to any one of 1 to 5 above, which has a glass transition temperature of 130 to 160 ° C.
7). 7. The poly (thio) carbonate according to any one of 1 to 6 above, which has a refractive index of 1.665 to 1.710.
8). An optical member comprising the poly (thio) carbonate according to any one of 1 to 7 above.
9. 9. The optical member according to 8, which is an optical lens.

  Since the poly (thio) carbonate of the present invention has a high refractive index and an excellent balance between heat resistance and moldability, the industrial effect is particularly remarkable.

It is proton NMR of the polyester resin obtained in Example 1 of the thermoplastic resin of this invention.

The present invention will be described in more detail.
<Poly (thio) carbonate>
The poly (thio) carbonate of the present invention must contain at least one selected from the group consisting of units represented by the formula (1) and the formula (2) as a repeating unit. The total of the repeating units represented by 1) and formula (2) is preferably 30 mol% or more, more preferably 40 mol% or more, and more preferably 50 mol% or more, based on all repeating units. More preferably. If the total of the repeating units represented by the formula (1) and the formula (2) is within the above range, a high refractive index is preferable.
On the other hand, the upper limit is not particularly limited, but it is preferably 80 mol% or less, more preferably 70 mol% or less. It is preferable that the total of the repeating units represented by the formula (1) and the formula (2) is in the above range because of excellent balance between heat resistance and moldability.

The poly (thio) carbonate of the present invention preferably further has a repeating unit represented by the formula (3). When the repeating unit represented by the formula (3) is included, R _{1 to} R ₈ of the repeating unit represented by the formula (3) are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Represents a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms, preferably a hydrogen atom, a methyl group or a phenyl group.

In the poly (thio) carbonate of the present invention, when the repeating unit represented by the formula (3) is included, L _{1 to} L ₂ of the repeating unit represented by the formula (3) are each independently a divalent linkage. Group, preferably a linking group having 1 to 10 carbon atoms, more preferably an aliphatic linking group having 1 to 10 carbon atoms, and still more preferably an aliphatic linking group having 1 to 5 carbon atoms. . Examples include methylene, ethylene, propylene, butylene, oxyethylene, oxybutylene, thioethylene, thiobutylene, aminomethylene, aminobutylene, carbonylene and the like, preferably an oxyethylene group.

  When the poly (thio) carbonate of the present invention contains a repeating unit represented by the formula (3), m and n of the repeating unit represented by the formula (3) each independently represent 0 or 1, Preferably it is 0.

  When the poly (thio) carbonate of the present invention contains the repeating unit represented by the formula (3), the total of the repeating units represented by the formula (1) and the formula (2) and the formula (3) Is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 65:35 to 35:65. When the molar ratio of the repeating unit represented by the formula (1) and the repeating unit represented by (2) and the repeating unit represented by the formula (3) is within the above range, a high refractive index. In addition to the above, it is preferable because of excellent balance between heat resistance and moldability.

  The poly (thio) carbonate of the present invention preferably has a refractive index with a wavelength of 589 nm (hereinafter sometimes abbreviated as nD) measured at 25 ° C. of 1.665 to 1.710. When the refractive index is equal to or higher than the lower limit, the spherical aberration of the lens can be reduced, and the focal length of the lens can be shortened. Moreover, when a refractive index is below an upper limit, it is excellent in the balance of heat resistance and a moldability.

  The poly (thio) carbonate of the present invention preferably has a glass transition temperature (hereinafter sometimes abbreviated as Tg) of 130 to 160 ° C, more preferably 135 to 160 ° C, and 140 to 160 ° C. Even more preferable. It is preferable for the glass transition temperature to be in the above range since the balance between heat resistance and moldability is excellent.

  The specific viscosity of the poly (thio) carbonate of the present invention is preferably 0.12 to 0.40, more preferably 0.15 to 0.35, and more preferably 0.18 to 0.30. Even more preferable. It is preferable for the specific viscosity to be in the above range since the balance between moldability and mechanical strength is excellent. The specific viscosity can be measured by a conventional method.

The Abbe number (ν) of the poly (thio) carbonate of the present invention is calculated from the refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm measured at 25 ° C. using the following formula. In the present invention, the Abbe number calculated by the following formula is preferably in the range of 20-30.
v = (nD-1) / (nF-nC)
In the present invention,
nD: refractive index at a wavelength of 589 nm,
nC: refractive index at a wavelength of 656 nm,
nF: Refractive index at a wavelength of 486 nm.

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

  The poly (thio) carbonate of the present invention preferably has a water absorption rate of 0.25% or less after being immersed at 23 ° C. for 24 hours, more preferably 0.20% or less. It is preferable for the water absorption rate to be within the above range since the change in optical properties due to water absorption is small.

Specific raw materials will be described.
<Raw material monomer>
(Dithiol component of the above formulas (1) and (2))
As the dithiol component for deriving the repeating units of the formulas (1) and (2) of the present invention, dithiol components represented by the following formulas (a) and (b) are preferably used.

(Diol component of formula (3))
A diol component represented by the following formula (c) is preferably used as the diol component for deriving the repeating unit of the formula (3) of the present invention.

In the general formula (c), R _{1 to} R _8, L _{1 to} L _2, m, and n can be said to be the same as described in the formula (3).

  Hereinafter, typical specific examples of the diol represented by the general formula (c) are shown, but the raw materials used in the general formula (c) of the present invention are not limited thereto.

  The diol component used for the unit represented by the formula (3) of the poly (thio) carbonate of the present invention is 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-2-). Methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-2-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3) -Ethylphenyl) fluorene, 9,9-bis (4-hydroxy-2-n-propylphenyl) fluorene, 9,9-bis (4-hydroxy-3-n-propylphenyl) fluorene, 9,9-bis ( 4-hydroxy-2-isopropylphenyl) fluorene, 9,9-bis (4-hydroxy-3-isopropylphenyl) fluorene, 9,9-bis ( -Hydroxy-2-n-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-n-butylphenyl) fluorene, 9,9-bis (4-hydroxy-2-sec-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-sec-butylphenyl) fluorene, 9,9-bis (4-hydroxy-2-tert-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3- tert-butylphenyl) fluorene, 9,9-bis (4-hydroxy-2-cyclohexylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, 9,9-bis (4-hydroxy) -2-phenylphenyl) fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene 9,9-bis [4-hydroxy-3- (3-methylphenyl) phenyl] fluorene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- ( 2-hydroxyethoxy) -2-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy)- 2-ethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-ethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -2-isopropylphenyl) fluorene 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) Ii) -2-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -2-tert -Butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -2-cyclohexylphenyl) Fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -2-phenylphenyl) fluorene, 9,9- Bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene and the like can be mentioned. Of these, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene are preferable. These may be used alone or in combination of two or more.

(Copolymerization component other than general formulas (1) to (3))
The poly (thio) carbonate of the present invention may be copolymerized with other di (thio) ol components to such an extent that the characteristics of the present invention are not impaired. The other di (thi) ol component is preferably less than 30 mol% in all repeating units. Other diol components include hydroquinone, resorcinol, 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, α, α'-bis (4-hydroxyphenyl)- m-diisopropylbenzene, 1,1-bis (4-hydroxyphenyl) decane, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, 1 , 1-Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohex Sun, 1,1-bis (4-hydroxyphenyl) cyclohexane, biphenol, 1,1-bi-2-naphthol, 2,2-bis (2-hydroxyethoxy) -1,1-binaphthyl, dihydroxynaphthalene, 10, 10-bis (4-hydroxyphenyl) anthrone, 2,2-bis (4-mercaptophenyl) propane, 2,2-bis (3-methyl-4-mercaptophenyl) propane, bis (4-mercaptophenyl) sulfide, Bis (4-mercapto-3-methylphenyl) sulfide, 1,1-bis (4-mercaptophenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-mercaptophenyl) cyclohexane, 1,1 -Bi-2-thionaphthol, 2,2-bis (2-mercaptoethoxy) -1,1-binaphthyl Dimercapto naphthalene, 1,4-dithiane-2,5-di (methanethiol), and the like, 1,1-bi-2-naphthol is particularly preferable. These may be used alone or in combination of two or more.

  The poly (thio) carbonate of the present invention is produced, for example, by a method of reacting a di (thi) ol component with a carbonate precursor such as phosgene or carbonic acid diester. Specific examples are shown below.

<Method for producing poly (thio) carbonate>
The poly (thio) carbonate of the present invention can be obtained by reacting a di (thio) ol component and a carbonate precursor by an interfacial polymerization method or a melt polymerization method. In producing the poly (thio) carbonate resin, a catalyst, a terminal terminator, an antioxidant and the like may be used as necessary.

  The reaction by the interfacial polymerization method is usually a reaction between a di (thio) ol component and phosgene, and is allowed to react 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. In order to accelerate the reaction, 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. it can. In that case, it is preferable to keep reaction temperature normally 0-40 degreeC, reaction time about 10 minutes-about 5 hours, and pH during reaction at 9 or more.

  The reaction by the melt polymerization method is usually a transesterification reaction between the di (thi) ol component and the carbonate ester, and the di (thi) ol component and the carbonate ester are mixed with heating in the presence of an inert gas. The alcohol or phenol produced is distilled off. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system is evacuated to about 1000 to 1 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 8 hours.

  Examples of the carbonate ester include esters such as an optionally substituted 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, and dibutyl carbonate. Is preferred.

In addition, a polymerization catalyst can be used to increase the polymerization rate in the melting method. Examples of such a polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol, potassium salt, 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, alkali metal and alkaline earth metal alkoxides , 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, man Emission compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. A catalyst may be used independently and may be used in combination of 2 or more types. 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 di (thio) ol component.

  In the poly (thio) carbonate of the present invention, monofunctional phenols usually used as a terminal terminator can be used in the polymerization reaction. Especially in the case of reactions using phosgene as a carbonate precursor, monofunctional phenols are generally used as end-capping agents for molecular weight control, and the polymers obtained are based on groups based on monofunctional phenols. Since it is blocked by, it is superior in thermal stability compared to other cases.

  The poly (thio) carbonate of the present invention is a heat stabilizer, a plasticizer, a light stabilizer, a polymerized metal deactivator, a flame retardant, a lubricant, an antistatic agent, a surfactant, an antibacterial agent, if necessary and necessary. Additives such as ultraviolet absorbers and mold release agents can be blended and used as a resin composition.

  The poly (thio) carbonate of the present invention can be molded and processed by any method such as injection molding, compression molding, injection compression molding, melt extrusion molding, melt extrusion film formation, casting film formation, etc. It is suitable as an optical member such as a conductive substrate, optical card, sheet, film, optical fiber, optical lens, prism, optical film, substrate, optical filter, and hard coat film.

<Optical lens>
The poly (thio) carbonate of the present invention is suitable for optical members, particularly optical lenses.
When the poly (thio) carbonate optical lens of the present invention is produced by injection molding, it is preferably molded under conditions of a cylinder temperature of 240 to 350 ° C. and a mold temperature of 70 to 160 ° C. More preferably, molding is preferably performed under conditions of a cylinder temperature of 260 to 300 ° C and a mold temperature of 100 to 150 ° C. When the cylinder temperature is higher than 350 ° C., the thermoplastic resin is decomposed and colored, and when it is lower than 240 ° C., the melt viscosity is high and the molding tends to be difficult. When the mold temperature is higher than 160 ° C., it is difficult to take out a molded piece made of a 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 during molding, making it difficult to control the shape of the molded piece, or sufficiently transferring the molding attached to the mold. Tends to be difficult.

  The optical lens of the present invention is preferably implemented using an aspherical lens shape as necessary. Since an aspheric lens can substantially eliminate spherical aberration with a single lens, it is not necessary to remove spherical aberration with a combination of a plurality of spherical lenses, thus reducing weight and reducing molding costs. It becomes possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.

  Further, the optical lens of the present invention is particularly useful as a material for an optical lens having a thin and small size and a complicated shape because of high molding fluidity. 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 still more preferably 0.1 to 2.0 mm. Moreover, a diameter is 1.0 mm-20.0 mm, More preferably, it is 1.0-10.0 mm, More preferably, it is 3.0-10.0 mm. In addition, it is preferably a meniscus lens having a convex surface on one side and a concave surface on the other side.

  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, die molding is more preferable from the viewpoint of manufacturing cost.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The evaluation was performed by the following method.

Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
(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, it was dried at a temperature of 120 ° C. or lower for 8 hours to prepare a cast film having a thickness of about 100 μm.
(B) Molded piece The obtained resin was vacuum hot-pressed with a vacuum compression molding machine SFV-10 manufactured by Shinto Metal Industry Co., Ltd. to produce a 1 mm thick molded piece. The mold temperature was the glass transition temperature of the resin + 30 ° C.
(1) Resin composition: The resin obtained after completion of polymerization was measured using proton NMR of JNM-AL400 manufactured by JEOL Ltd.
(2) Refractive index (nD), Abbe number (ν): A film prepared by the method of (a) above using a DR-M2 Abbe refractometer manufactured by ATAGO, the refractive index at 25 ° C. (wavelength: 589 nm) and Abbe number (wavelength: 589 nm, 656 nm, 486 nm) was measured.
(3) Glass transition temperature: The resin obtained after completion of polymerization was measured by DSC-60A manufactured by Shimadzu Corporation at a sample rate of 15 mg and a heating rate of 20 ° C./min.
(4) Specific viscosity: The resin obtained after the completion of polymerization was sufficiently dried, and the specific viscosity (η _sp ) at 20 ° C. of the solution was measured from a solution obtained by dissolving 0.7 g of the resin in 100 ml of methylene chloride.

Example 1
In a reactor equipped with a thermometer and a stirrer, 3,789 parts of sodium carbonate was dissolved in 28,008 parts of ion-exchanged water under a flow of nitrogen, and then 9,9-bis (4-hydroxy-) was added thereto. 1,953 parts of 3-phenylphenyl) fluorene (hereinafter sometimes abbreviated as OPPFL), 18 parts of p-tert-butylphenol, and 7 parts of hydrosulfite were charged. Thereafter, 11,880 parts of methylene chloride, 600 parts of bis (2-mercaptoethyl) sulfide (hereinafter sometimes abbreviated as BMES) and 39 parts of triethylamine were charged, and phosgene 1,230 at 15 to 25 ° C. with stirring. The part was blown in over 60 minutes. After completion of the phosgene blowing, 2,487 parts of 25% aqueous sodium hydroxide solution was added, and after emulsification, 157 parts of triethylamine was added and stirred at 30 ° C. for 2 hours to complete the reaction. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. A methylene chloride solution was obtained. Subsequently, this solution was dropped into warm water, and poly (thio) carbonate was flaked while distilling off methylene chloride. Thereafter, the poly (thio) carbonate was dried at 120 ° C. for 12 hours. Poly (thio) carbonate was used to evaluate the resin composition, refractive index, glass transition temperature, and specific viscosity, and the results are shown in Table 1.

Example 2
In a reactor equipped with a thermometer and a stirrer, 4,032 parts of sodium carbonate was dissolved in 26,826 parts of ion-exchanged water under a flow of nitrogen, and then, 2,078 parts of OPPFL, 1,178 bead. 118 parts of 2-naphthol (hereinafter sometimes abbreviated as BINOL), 19 parts of p-tert-butylphenol, and 7 parts of hydrosulfite were charged. Thereafter, 9,109 parts of methylene chloride, 574 parts of BMES, and 42 parts of triethylamine were charged, and then 7 parts of 15 to 25 minites were blown over 309 parts over 60 minutes with stirring. After the completion of phosgene blowing, 2,647 parts of 25% aqueous sodium hydroxide solution was added, and after emulsification, 168 parts of triethylamine was added, and after 30 blows of triethylamine 1, the aqueous 25% sodium hydroxide solution was added to 2, lium and washed with water. Further, washing with water was repeated until the electric conductivity of the aqueous phase became substantially the same as that of ion-exchanged water to obtain a poly (thio) carbonate methylene chloride solution in which the resin remained. Subsequently, this solution was dropped into warm water, and poly (thio) carbonate was flaked while distilling off methylene chloride. Thereafter, the resin composition, the refractive index, the glass transition temperature, and the specific viscosity were evaluated using 120 (o) carbonate for poly (thio) carbonate and then poly (thio) carbonate, and the results are shown in Table 1.

Example 3
In a reactor equipped with a thermometer and a stirrer, 7,973 parts of 25% aqueous sodium hydroxide solution was dissolved in 11,673 parts of ion-exchanged water under a flow of nitrogen, and then 9,9-bis ( 4-hydroxy-3-methylphenyl) fluorene (1,886 parts) and hydrosulfite (22 parts) were charged. Thereafter, 14,812 parts of methylene chloride and 1,600 parts of 1,4-dithian-2,5-di (methanethiol) (hereinafter sometimes abbreviated as BMMD) were added, and then stirred at 15 to 25 ° C. Then, 1,602 parts of phosgene was blown in over 60 minutes. After completion of the phosgene blowing, 399 parts of a 25% aqueous sodium hydroxide solution and 28 parts of p-tert-butylphenol were added and stirred, and then 32 parts of triethylamine was added and emulsified. Thereafter, 32 parts of triethylamine and 8,464 parts of methylene chloride were added and stirred at 30 ° C. for 2 hours to complete the reaction. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. A methylene chloride solution was obtained. Subsequently, this solution was dropped into warm water, and poly (thio) carbonate was flaked while distilling off methylene chloride. Thereafter, the poly (thio) carbonate was dried at 120 ° C. for 12 hours. Poly (thio) carbonate was used to evaluate the resin composition, refractive index, glass transition temperature, and specific viscosity, and the results are shown in Table 1.

Comparative Example 1
It is a polycondensate of 2,2-bis (4-hydroxyphenyl) propane, 9,9-bis (4-hydroxyphenyl) fluorene and thiophosgene according to the method described in Example 1 of JP 2010-53251 A A polythiocarbonate resin (R-3) was obtained. Using the polythiocarbonate resin, the resin composition, refractive index, birefringence, glass transition temperature, and thermal decomposition temperature were evaluated, and the results are shown in Table 1.

Comparative Example 2
It is a polycondensate of 9,9-bis (4-mercaptophenyl) fluorene and 2,2-bis (4-mercaptophenyl) propane and thiophosgene according to the method described in Example 1 of JP-A-2010-53251. A polythiocarbonate resin (R-4) was obtained. Using the polythiocarbonate resin, the resin composition, refractive index, glass transition temperature and specific viscosity were evaluated, and the results are shown in Table 1.

BMES: bis (2-mercaptoethyl) sulfide BMMD: 1,4-dithian-2,5-di (methanethiol)
OPPFL: 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene BINOL: 1,1′-bi-2-naphthol BCF: 9,9-bis (4-hydroxy-3-methylphenyl) fluorene BPF: 9,9-bis (4-hydroxyphenyl) fluorene BPA: 2,2-bis (4-hydroxyphenyl) propane BPF-SH: 9,9-bis (4-mercaptophenyl) fluorene BPA-SH: 2,2- Bis (4-mercaptophenyl) propane

  The thermoplastic resins obtained in Examples 1 to 3 have a high refractive index and an excellent balance between heat resistance and moldability. On the other hand, the thermoplastic resin of Comparative Example 1 has a low refractive index and a high glass transition point, and thus is difficult to mold. The thermoplastic resin of Comparative Example 2 has a high refractive index, but is difficult to mold because of its high glass transition point.

  The thermoplastic resin of the present invention is used as an optical member such as an optical disk, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, an optical lens, a prism, an optical film, a substrate, an optical filter, a refractive index adjustment layer, and a hard coat film. Suitable, especially for optical lenses.

Claims (9)

Poly (thio) carbonate containing at least one selected from the group consisting of units represented by the following formula (1) and the following formula (2) as a repeating unit.
  The poly (thio) carbonate of Claim 1 in which the sum total of the repeating unit represented by the said Formula (1) and the said Formula (2) contains 30 mol% or more on the basis of all the repeating units. The poly (thio) carbonate in any one of Claim 1 or 2 containing the repeating unit represented by following formula (3).
(In the formula, R _{1 to} R ₈ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms. , L ₁ and L ₂ each independently represent a divalent linking group, and m and n each independently represents 0 or 1.)   The molar ratio of the sum of the repeating units represented by the formula (1) and the formula (2) and the repeating unit represented by the formula (3) is 80:20 to 20:80. Poly (thio) carbonate.   The poly (thio) carbonate according to claim 3 or 4, wherein m and n in the formula (3) are 0.   Glass transition temperature is 130-160 degreeC, The poly (thio) carbonate in any one of Claims 1-5.   The poly (thio) carbonate according to any one of claims 1 to 6, which has a refractive index of 1.665 to 1.710.   An optical member comprising the poly (thio) carbonate according to any one of claims 1 to 7.   The optical member according to claim 8, wherein the optical member is an optical lens.