JP2018141084A - Thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin which has a high index of refraction and an excellent balance between heat resistance and moldability.SOLUTION: The thermoplastic resin is selected from poly(thio)carbonate resins, poly(thio)ester resins and poly(thio)ester (thio)carbonate resins including one or more selected from compounds represented by formula (1) and compounds in which a carbonyl group is further added to the compounds represented by formula (1) beyond the (L)side thioester with a further hydrocarbon group interposed therebetween.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin having a high refractive index and an excellent balance between 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 point 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

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

  The inventors of the present invention have intensively studied to achieve this object, and as a result, have found that the above-mentioned problems can be solved by the following thermoplastic resin, and have reached the present invention.

That is, the present invention
1. A thermoplastic resin containing at least one of the units represented by the following formulas (1) and (2).

(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.)

(In the formula, R _{9 to} R ₁₆ 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 ₃ and L ₄ each independently represents a divalent linking group, o and p each independently represents 0 or 1, X represents an alkylene group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. An alkoxylene group, a cycloalkylene group having 4 to 20 carbon atoms, a cycloalkoxylene group having 4 to 20 carbon atoms, and a thioalkylene group having 1 to 20 carbon atoms.)
2. 2. The thermoplastic resin as described in 1 above, which has a glass transition temperature of 130 to 160 ° C.
3. 3. The thermoplastic resin as described in 1 or 2 above, which has a refractive index of 1.671 or more.
4). The thermoplastic resin according to any one of 1 to 3, wherein the thermoplastic resin is at least one selected from the group consisting of a poly (thio) carbonate resin, a poly (thio) ester resin, and a poly (thio) ester (thio) carbonate resin. resin.
5. The thermoplastic resin according to any one of 1 to 4 above, wherein the unit represented by the formula (1) contains 30 mol% or more of all units.
6). The thermoplastic resin according to any one of 1 to 5, wherein the total of the unit represented by the formula (1) and the unit represented by the following formula (3) is 80 mol% or more in all units.

7). The thermoplastic resin according to any one of 1 to 6, wherein the molar ratio of the formula (1) and the formula (3) is 80:20 to 20:80.
8). The thermoplastic resin according to any one of 1 to 4 above, wherein the unit represented by the formula (2) contains 30 mol% or more of all units.
9. The thermoplastic resin according to any one of 1 to 4 and 8, wherein X in the formula (2) is an alkylene group having 2 to 4 carbon atoms.
10. The optical member which consists of a thermoplastic resin in any one of said 1-9.
11. An optical lens made of the thermoplastic resin according to any one of 1 to 10 above.

  Since the thermoplastic resin 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.
The thermoplastic resin of the present invention needs to contain at least one of the units represented by the formulas (1) and (2).

In the formulas (1) and (2), R _{1 to} R ₁₆ may each independently include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an aromatic group having 1 to 12 carbon atoms. A good hydrocarbon group is shown, preferably a hydrogen atom, a methyl group or a phenyl group.

In the formulas (1) and (2), L _{1 to} L ₄ each independently represent a divalent linking group, preferably a linking group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms. An aliphatic linking group, 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.

  In the above formulas (1) and (2), m, n, o, and p each independently represent 0 or 1, preferably 0.

  When the thermoplastic resin of the present invention includes the formula (1), the repeating unit represented by the formula (1) is preferably included in an amount of 30 mol% or more, more preferably 40 mol% or more, and more preferably 50 mol% or more. Even more preferably. When the formula (1) is within the above range, a high refractive index is preferable.

  When the thermoplastic resin of the present invention includes the formula (1) and the formula (3), the total of the unit represented by the formula (1) and the unit represented by the formula (3) is all units. It is preferable to contain 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more. The molar ratio of the formula (1) and the formula (3) is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and 65:35 to 35: 65 is even more preferable. It is preferable that the formula (1) and the formula (3) are in the above ranges because in addition to a high refractive index, the balance between heat resistance and moldability is excellent.

  When the thermoplastic resin of the present invention contains the formula (2), the unit represented by the formula (2) is preferably contained in an amount of 30 mol% or more, more preferably 40 mol% or more, more preferably 50 mol. It is even more preferable to contain at least%. When the formula (2) is within the above range, a high refractive index is preferable.

  When the thermoplastic resin of the present invention includes the formula (2), in the formula (2), X is an alkylene group having 1 to 20 carbon atoms, an alkoxylene group having 1 to 20 carbon atoms, or a carbon atom. A cycloalkylene group having 4 to 20 carbon atoms, a cycloalkoxylene group having 4 to 20 carbon atoms, and a thioalkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 20 carbon atoms, and more preferably Represents an alkylene group having 2 to 4 carbon atoms. It is preferable for X to be in the above-mentioned range because it has a high refractive index and is excellent in the balance between heat resistance and moldability.

  The refractive index of the thermoplastic resin of the present invention measured at 25 ° C. at a wavelength of 589 nm (hereinafter sometimes abbreviated as nD) is preferably 1.671 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.

  The thermoplastic resin of the present invention preferably has a glass transition point (hereinafter sometimes abbreviated as Tg) of 130 to 160 ° C, more preferably 135 to 160 ° C, and even more preferably 140 to 160 ° C. preferable. It is preferable for the glass transition point to be in the above-mentioned range because of excellent balance between heat resistance 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 for the specific viscosity to be in the above range since the balance between moldability and mechanical strength is excellent.

The Abbe number (ν) of the thermoplastic resin 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. The Abbe number 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.

  In the thermoplastic resin of the present invention, it is preferable that a molded test piece is sandwiched between two polarizing plates, light leakage is observed by a crossed Nicol method, and there is no light leakage.

  The thermoplastic resin 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 thermoplastic resin of the present invention preferably has a water absorption rate of 0.25% or less after being immersed at 23 ° C. for 24 hours, and 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 below.
<Di (thio) ol component of general formula (1) and (2)>
As the dithiol component used as a raw material of the general formulas (1) and (2) of the present invention, dithiol components represented by the following formulas (a) and (b) are preferably used.

In the general formulas (a) and (b), R _{1 to} R ₁₆ may each independently include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an aromatic group having 1 to 12 carbon atoms. A good hydrocarbon group is shown, preferably a hydrogen atom, a methyl group or a phenyl group.

L _{1 to} L ₄ each independently represent a divalent linking group, preferably a linking group having 1 to 10 carbon atoms, and more preferably an aliphatic linking group having 1 to 10 carbon atoms. More preferably, it represents an aliphatic linking group having 1 to 5 carbon atoms.

  Hereinafter, typical specific examples of the dithiol represented by the general formulas (a) and (b) are shown, but the raw materials used in the general formulas (1) and (2) of the present invention are limited by them. is not.

  The dithiol component used in the units represented by the formulas (1) and (2) of the thermoplastic resin of the present invention is 9,9-bis (4-mercaptophenyl) fluorene, 9,9-bis (4-mercapto- 2-methylphenyl) fluorene, 9,9-bis (4-mercapto-3-methylphenyl) fluorene, 9,9-bis (4-mercapto-2-ethylphenyl) fluorene, 9,9-bis (4-mercapto) -3-ethylphenyl) fluorene, 9,9-bis (4-mercapto-2-n-propylphenyl) fluorene, 9,9-bis (4-mercapto-3-n-propylphenyl) fluorene, 9,9- Bis (4-mercapto-2-isopropylphenyl) fluorene, 9,9-bis (4-mercapto-3-isopropylphenyl) fluorene, 9,9-bis 4-mercapto-2-n-butylphenyl) fluorene, 9,9-bis (4-mercapto-3-n-butylphenyl) fluorene, 9,9-bis (4-mercapto-2-sec-butylphenyl) fluorene 9,9-bis (4-mercapto-3-sec-butylphenyl) fluorene, 9,9-bis (4-mercapto-2-tert-butylphenyl) fluorene, 9,9-bis (4-mercapto-3) -Tert-butylphenyl) fluorene, 9,9-bis (4-mercapto-2-cyclohexylphenyl) fluorene, 9,9-bis (4-mercapto-3-cyclohexylphenyl) fluorene, 9,9-bis (4- Mercapto-2-phenylphenyl) fluorene, 9,9-bis (4-mercapto-3-phenylphenyl) fluorene 9,9-bis [4-mercapto-3- (3-methylphenyl) phenyl] fluorene, 9,9-bis (4- (2-mercaptoethoxy) phenyl) fluorene, 9,9-bis (4- (2-Mercaptoethoxy) -2-methylphenyl) fluorene, 9,9-bis (4- (2-mercaptoethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-mercaptoethoxy) 2-ethylphenyl) fluorene, 9,9-bis (4- (2-mercaptoethoxy) -3-ethylphenyl) fluorene, 9,9-bis (4- (2-mercaptoethoxy) -2-isopropylphenyl) Fluorene, 9,9-bis (4- (2-mercaptoethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-mercaptoeth Xyl) -2-isobutylphenyl) fluorene, 9,9-bis (4- (2-mercaptoethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-mercaptoethoxy) -2-tert -Butylphenyl) fluorene, 9,9-bis (4- (2-mercaptoethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-mercaptoethoxy) -2-cyclohexylphenyl) Fluorene, 9,9-bis (4- (2-mercaptoethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-mercaptoethoxy) -2-phenylphenyl) fluorene, 9,9- And bis (4- (2-mercaptoethoxy) -3-phenylphenyl) fluorene. Among them, 9,9-bis (4-mercapto-3-phenylphenyl) fluorene, 9,9-bis (4-mercapto-3-methylphenyl) fluorene, 9,9-bis (4-mercapto-3-phenylphenyl) ) Fluorene is preferred. These may be used alone or in combination of two or more.

<Copolymerization component other than general formulas (1) and (2)>
The thermoplastic resin of the present invention may be copolymerized with other di (thiol) 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, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9 -Bis (4-hydroxy-3-cyclohexylphenyl) fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, 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, 1,1-bi-2-naphthol, 2,2- (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, dimercaptonaphthalene, bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane And the like. Of these, bis (2-mercaptoethyl) sulfide is preferable. These may be used alone or in combination of two or more.

<Dicarboxylic acid component of general formula (2)>
As the dicarboxylic acid component used in the unit represented by the formula (2) of the thermoplastic resin of the present invention, a dicarboxylic acid represented by the following formula (c) or an ester-forming derivative thereof is preferably used.

  In the general formula (c), X is an alkylene group having 1 to 20 carbon atoms, an alkoxylene group having 1 to 20 carbon atoms, a cycloalkylene group having 4 to 20 carbon atoms, or a cyclohexane having 4 to 20 carbon atoms. An alkoxylen group is shown.

Hereinafter, typical specific examples of the dicarboxylic acid represented by the general formula (c) or an ester-forming derivative thereof are shown, but the raw materials used in the general formula (1) of the present invention are not limited thereto. Absent.

  Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, methylmalonic acid, ethylmalonic acid, methylsuccinic acid, 2,2- Dimethyl succinic acid, 2,3-dimethyl succinic acid, 3-methyl glutaric acid, 3,3 dimethyl glutaric acid cyclohexane dicarboxylic acid, decalin dicarboxylic acid, norbornane dicarboxylic acid, tricyclodecane dicarboxylic acid, pentacyclododecanedicarboxylic acid, adamantane dicarboxylic acid Examples of the acid include succinic acid, glutaric acid, and adipic acid having 2 to 4 carbon atoms in the general formula (a). These dicarboxylic acids may be used as derivatives such as esters, acid anhydrides, and acid halides. Moreover, you may use these individually or in combination of 2 or more types.

  The thermoplastic resin of the present invention is, for example, a method in which a di (thi) ol component is reacted with a carbonate precursor such as phosgene or a carbonic acid diester, a method in which a di (thi) ol component is reacted with a dicarboxylic acid or an ester-forming derivative thereof, etc. Manufactured by. Specific examples are shown below.

<Method for producing poly (thio) carbonate resin>
The poly (thio) carbonate resin of the present invention is 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.

  The poly (thio) carbonate resin of the present invention can use monofunctional phenols which are usually used as a terminal terminator 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.

<Manufacture of poly (thio) ester resin>
The poly (thio) ester resin of the present invention is obtained by subjecting a di (thio) ol component and a dicarboxylic acid or an ester-forming derivative thereof to an esterification reaction or an ester exchange reaction, and subjecting the obtained reaction product to a polycondensation reaction. A high molecular weight substance having a molecular weight of

  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. Particularly preferred.

  In the case of using the interfacial polymerization method, a solution (organic phase) in which dicarboxylic acid chloride is dissolved in an organic solvent incompatible with water is mixed with an alkaline aqueous solution (aqueous phase) containing an aromatic diol and a polymerization catalyst, and 50 ° C. Hereinafter, a method in which the polymerization reaction is performed with stirring at a temperature of preferably 25 ° C. or lower for 0.5 to 8 hours may be mentioned.

  As the solvent used in the organic phase, a solvent that is not compatible with water and dissolves the polyester resin of the present invention is preferable. Examples of such a solvent include chlorinated solvents such as methylene chloride, 1,2-dichloroethane, chloroform and chlorobenzene, and aromatic hydrocarbon 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.

  When producing the poly (thio) ester resin of the present invention, an end-capping agent may be used for adjusting the molecular weight and improving the thermal stability. Examples of the end-capping agent include monohydric phenol, monohydric acid chloride, monohydric alcohol, and monohydric carboxylic acid. Examples of the monohydric phenol include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol [PTBP], o-phenylphenol, m-phenylphenol, p-phenylphenol, and o-methoxyphenol. M-methoxyphenol, p-methoxyphenol, 2,3,6-trimethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2-phenyl-2- (4-hydroxyphenyl) propane, 2-phenyl-2- (2-hydroxyphenyl) propane, 2-phenyl-2- (3-hydroxyphenyl) propane and the like It is done. Examples of the monovalent acid chloride include benzoyl chloride, benzoic acid chloride, methanesulfonyl chloride, phenyl chloroformate and the like. Examples of the monohydric alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, phenethyl alcohol and the like. Examples of the monovalent carboxylic acid include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid, and p-methoxyphenylacetic acid. Of these, PTBP is preferred because of its high reactivity and thermal stability.

  In producing the poly (thio) ester resin of the present invention, an antioxidant may be used to improve the resin hue. Examples of the antioxidant include hydrosulfite sodium, L-ascorbic acid, erythorbic acid, catechin, tocophenol, and butylhydroxyanisole, and hydrosulfite sodium is preferable because it quickly dissolves in water.

  In the reaction by the melt polymerization method, a di (thio) ol component and a dicarboxylic acid component or a diester thereof are usually mixed and usually reacted at 120 to 350 ° C., preferably 150 to 300 ° C. The degree of vacuum is changed stepwise, and finally, water or alcohol produced at 0.13 kPa or less is distilled out of the system, and the reaction time is usually about 1 to 10 hours.

In addition, a polymerization catalyst can be used to increase the polymerization rate in the melting method. As the transesterification catalyst, a catalyst known per se can be employed. For example, a compound containing manganese, magnesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium, or a lead element can be used. Specific examples 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, alcoholates and the like are preferable from the viewpoints of melt stability of the thermoplastic resin, hue, and a small amount of polymer-insoluble foreign matter. Further, manganese, magnesium and titanium compounds are preferable. These compounds can be used in combination of two or more. A polymerization catalyst known per se can be employed as the polymerization catalyst, 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. These compounds can be used in combination of two or more. Among these, tin, titanium, and a germanium compound are preferable from the viewpoint of melt stability of the thermoplastic resin and hue. The usage-amount of a catalyst has the preferable range of 1 * 10 < ^-8 > -1 * 10 < ^-3 > mol with respect to 1 mol of dicarboxylic acid components, for example.

  The thermoplastic resin of the present invention may contain a copolymer component other than a di (thi) ol component and dicarboxylic acid or an ester-forming derivative thereof. For example, when a poly (thio) ester carbonate resin is used, it is produced by reacting a carbonate precursor such as phosgene or carbonic acid diester in addition to a di (thi) ol component and dicarboxylic acid or an ester-forming derivative thereof. Can do.

  The thermoplastic resin of the present invention can be used as 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, and an ultraviolet absorber. Additives such as agents and mold release agents can be blended.

  The thermoplastic resin 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 for optical members such as optical cards, sheets, films, optical fibers, optical lenses, prisms, optical films, substrates, optical filters, and hard coat films.

<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 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 lens made of the thermoplastic resin in the optical lens of the present invention is molded by an arbitrary method such as mold forming, cutting, polishing, laser processing, electric discharge processing, 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.
(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) 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 the polymerization was measured with a DSC-60A manufactured by Shimadzu Corporation at 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.

Production Example 1 (Production of 9,9-bis (4-mercapto-3-methylphenyl) fluorene)
A three-necked flask equipped with a glass stirrer and a temperature controller was charged with 295.2 parts of methanol and cooled in an ice-water bath, and then 16.8 parts of potassium hydroxide was added and completely dissolved. Further, 49.2 parts of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and 35.4 parts of NN dimethylthiocarbamoyl chloride were added, the ice water bath was removed, and the mixture was stirred for 1 hour. A solid precipitated out. Furthermore, it heated up at 60 degreeC and stirred for 3 hours. The reaction solution was cooled to room temperature, and crystals and mother liquor were separated by suction filtration. The obtained crystals were washed with a 1: 1 mixture of methanol and water, dissolved in 305 parts of chloroform, washed with 305 parts of water and separated. After washing with water three times in the same manner, the organic phase was dehydrated with anhydrous sodium sulfate and concentrated to obtain 47.2 parts of a white solid (A-1).

  A three-necked flask equipped with a stirrer and a temperature controller was charged with 50 parts of the white solid (A-1) and 250 parts of diphenyl ether, and stirred at 255 ° C. for 3 hours in a nitrogen atmosphere. After cooling the reaction solution to 150 ° C., the pressure was reduced to 1 kPa to distill off diphenyl ether. The reaction product was cooled to room temperature and chloroform was added to completely dissolve the solution. The solution was then added dropwise to hexane, and the precipitate was filtered to obtain a white solid. The white solid was dissolved in 75 parts of chloroform at 65 ° C., 395 parts of methanol was added, and recrystallization was performed three times. Then, it filtered and dried and obtained 30.5 parts of white solid (B-1).

  An eggplant flask was charged with 65 parts of a white solid (B-1), 66 parts of potassium hydroxide, 260 parts of tetrahydrofuran, and 247 parts of methanol, and stirred at 65 ° C. for 40 minutes in a nitrogen atmosphere. The reaction solution was filtered to remove insolubles and then distilled off under reduced pressure. 1500 parts of water was added and neutralized with 20% aqueous hydrochloric acid. The precipitated white solid was filtered and dried to obtain 45 parts of 9,9-bis (4-mercapto-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as BCF-SH). The purity of the obtained BCF-SH was 99.3%.

Production Example 2 (Production of 9,9-bis (4-mercaptophenyl) fluorene)
A three-necked flask equipped with a glass stirrer and a temperature controller was charged with 160 parts of methanol and cooled in an ice-water bath, and then 5.2 parts of potassium hydroxide was added and completely dissolved. Furthermore, 14 parts of 9,9-bis (4-hydroxyphenyl) fluorene and 10.9 parts of NN dimethylthiocarbamoyl chloride were added, the ice-water bath was removed, and the mixture was stirred for 1 hour, whereby a white solid was precipitated. Furthermore, it heated up at 60 degreeC and stirred for 3 hours. The reaction solution was cooled to room temperature, and crystals and mother liquor were separated by suction filtration. The obtained crystals were washed with a 1: 1 mixture of methanol and water, dissolved in 94.1 parts of chloroform, washed with 94.1 parts of water, and separated. After washing with water three times in the same manner, the organic phase was dehydrated with anhydrous sodium sulfate and concentrated to obtain 17.4 parts of a white solid (A-2).

  In a three-necked flask equipped with a stirrer and a temperature controller, 2.6 parts of the white solid (A-2) and 30 parts of diphenyl ether were charged, and stirred at 255 ° C. for 3 hours in a nitrogen atmosphere. After cooling the reaction solution to 150 ° C., the pressure was reduced to 1 kPa to distill off diphenyl ether. The reaction product was cooled to room temperature and chloroform was added to completely dissolve the solution. The solution was then added dropwise to hexane, and the precipitate was filtered to obtain a white solid. The white solid was dissolved in 3.9 parts of chloroform at 65 ° C., 21 parts of methanol was added, and recrystallization was performed 3 times. Then, it filtered and dried and obtained 2.6 parts of white solid (B-2).

  In a recovery flask, 2.6 parts of a white solid (B-2), 2.7 parts of potassium hydroxide, 26 parts of tetrahydrofuran, and 25.7 parts of methanol were charged and stirred at 65 ° C. for 40 minutes in a nitrogen atmosphere. The reaction solution was filtered to remove insolubles and then distilled off under reduced pressure. 140 parts of water was added and neutralized with 20% aqueous hydrochloric acid. The precipitated white solid was filtered and dried to obtain 2.5 parts of 9,9-bis (4-mercapto-phenyl) fluorene (hereinafter sometimes abbreviated as BPF-SH). The purity of the obtained BPF-SH was 99.5%.

Example 1
A reactor equipped with a thermometer and a stirrer was charged with 422 parts of a 48% aqueous sodium hydroxide solution and 7,233 parts of ion-exchanged water under a nitrogen flow, and 1,000 parts of BCF-SH obtained in Production Example 1 were added thereto. 2 parts of hydrosulfite and 9 parts of tetrabutylammonium bromide were dissolved, and a solution prepared by dissolving 455 parts of adipic acid chloride in 4,347 parts of methylene chloride was added dropwise over 30 minutes at 10 to 20 ° C. with stirring. did. After completion of dropping, the reaction was completed by stirring for 1 hour. 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 solution was obtained. Subsequently, this solution was dropped into warm water, and the polythioester resin was flaked while distilling off methylene chloride. Thereafter, the polythioester resin was dried at 120 ° C. for 12 hours. Using the polythioester resin, the resin composition, refractive index, glass transition temperature, and specific viscosity were evaluated, and the results are shown in Table 1.

Example 2
A polythioester resin was obtained in the same manner as in Example 1 except that 1,000 parts of BCF-SH in Example 1 were changed to 950 parts in BCF-SH and 5 parts in BPF-SH. Using the polythioester resin, the resin composition, refractive index, glass transition temperature, and specific viscosity were evaluated, and the results are shown in Table 1.

Example 3
A reactor equipped with a thermometer and a stirrer was charged with 5,200 parts of a 25% aqueous sodium hydroxide solution and 8,700 parts of ion-exchanged water under a flow of nitrogen, to which 2,287 parts of BCF-SH, bis (2 -Mercaptoethyl) After dissolving 16 parts of sulfide (hereinafter sometimes abbreviated as BMES) and hydrosulfite, 11,040 parts of methylene chloride was added and 45% of 1,194 parts of phosgene was added at 15 to 20 ° C. with stirring. Infused over a minute. After completion of the phosgene blowing, 34.9 parts of p-tert-butylphenol and 297 parts of 25% aqueous sodium hydroxide solution were added. After emulsification, 23.5 parts of triethylamine was added and stirred at 27 ° C. for 1 hour, followed by 23.5 parts of triethylamine. And 297 parts of a 25% aqueous sodium hydroxide solution were added and stirred at 27 ° C. for 1 hour 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. Got. Next, this solution was dropped into warm water, and the polyester resin was flaked while distilling off methylene chloride. Thereafter, the polyester resin was dried at 120 ° C. for 12 hours. 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.

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.

Comparative Example 3
In the method described in Example 6 of JP-A-2003-292591, bis (2-mercaptoethyl) sulfide and tetracyclo [4.4.0.1 ^2,5 . The polythioester resin (1-A-2) which is a polycondensation product with a ^1,7,10 ] dodecanedicarboxylic acid dimethyl ester was obtained.

BCF-SH: 9,9-bis (4-mercapto-3-methylphenyl) fluorene BPF-SH: 9,9-bis (4-mercaptophenyl) fluorene ACl: adipic acid chloride BMES: bis (2-mercaptoethyl) Sulfide BPA: 2,2-bis (4-hydroxyphenyl) propane BPF: 9,9-bis (4-hydroxyphenyl) fluorene BPA-SH: 2,2-bis (4-mercaptophenyl) propane TCD-DM: tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanedicarboxylic acid dimethyl ester

  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. Since the thermoplastic resin of Comparative Example 3 has a low refractive index and a low glass transition point, it has poor heat resistance.

  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 (11)

A thermoplastic resin containing at least one of the units represented by the following formulas (1) and (2).
(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.)
(In the formula, R _{9 to} R ₁₆ 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 ₃ and L ₄ each independently represents a divalent linking group, o and p each independently represents 0 or 1, X represents an alkylene group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. An alkoxylene group, a cycloalkylene group having 4 to 20 carbon atoms, a cycloalkoxylene group having 4 to 20 carbon atoms, and a thioalkylene group having 1 to 20 carbon atoms.)   The thermoplastic resin according to claim 1, which has a glass transition temperature of 130 to 160 ° C.   3. The thermoplastic resin according to claim 1, having a refractive index of 1.671 or more.   The heat according to any one of claims 1 to 3, wherein the thermoplastic resin is at least one selected from the group consisting of a poly (thio) carbonate resin, a poly (thio) ester resin and a poly (thio) ester (thio) carbonate resin. Plastic resin.   The thermoplastic resin in any one of Claims 1-4 which contains 30 mol% or more of units represented by the said Formula (1) in all units. The thermoplastic resin according to any one of claims 1 to 5, wherein the total of the unit represented by the formula (1) and the unit represented by the following formula (3) is 80 mol% or more in all units.
  The thermoplastic resin according to any one of claims 1 to 6, wherein a molar ratio of the formula (1) and the formula (3) is 80:20 to 20:80.   The thermoplastic resin in any one of Claims 1-4 which contains 30 mol% or more of units represented by said Formula (2) in all units.   The thermoplastic resin according to any one of claims 1 to 4, wherein X in the formula (2) is an alkylene group having 2 to 4 carbon atoms.   An optical member made of the thermoplastic resin according to claim 1. An optical lens made of the thermoplastic resin according to claim 1.