Thermoplastic resin, method for producing the same, and optical lens containing the thermoplastic resin

Abstract

The present invention provides a thermoplastic resin having a high refractive index, high heat resistance, and a low YI value, a method for producing the same, and an optical lens containing the thermoplastic resin. [Solution] A method for producing a thermoplastic resin by reacting a composition containing a dicarboxylic acid represented by the following formula (1) and a metal derived from the dicarboxylic acid. The metal contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn, and Sn in a total amount of 10,000 ppb or less. TIFF2026090640000018.tif57168 (R1 and R2 are independently H, F, Cl, Br, I, alkyl groups, aryl groups, etc.)

Description

Technical Field

[0001] The present invention relates to a thermoplastic resin, a method for producing the same, and an optical lens containing the thermoplastic resin. More specifically, the present invention relates to a thermoplastic resin having a high refractive index, high heat resistance, and a low YI value, and an optical lens containing the same.

Background Art

[0002] As materials for optical lenses used in the optical systems of various cameras such as cameras, film-integrated cameras, and video cameras, optical glass or optical resins are used. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., but has problems such as high material cost, poor molding processability, and low productivity.

[0003] On the other hand, optical lenses made of optical resins have the advantage of being mass-produced by injection molding, and polycarbonate, polyester carbonate, polyester resins, etc. are used as high refractive index materials for camera lenses. However, in recent years, with the trend of making products thinner, lighter, and more compact, the development of resins with a high refractive index has been demanded. Generally, when the refractive index of an optical material is high, a lens element with the same refractive index can be realized with a surface having a smaller curvature. Therefore, the amount of aberration generated on this surface can be reduced, the number of lens sheets can be reduced, the polarization sensitivity of the lens can be reduced, or the lens thickness can be reduced to achieve weight reduction.

[0004] When an optical resin is used as an optical lens, in addition to the refractive index and Abbe number, heat resistance, transparency, low water absorption, chemical resistance, low birefringence, and resistance to wet heat are required. Especially in recent years, high refractive index and Optical lenses with high heat resistance are in demand, and various resins are being developed ( References 1-4) show that there is a need for optical lenses with even better refractive index and high heat resistance. That is the current situation. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2018-2893 [Patent Document 2] Japanese Patent Publication No. 2018-2894 [Patent Document 3] Japanese Patent Publication No. 2018-2895 [Patent Document 4] Japanese Patent Publication No. 2018-59074 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The present invention relates to a thermoplastic resin having a high refractive index, high heat resistance, and a low YI value, and the manufacturing process thereof. The objective is to provide a manufacturing method and an optical lens containing the thermoplastic resin. [Means for solving the problem]

[0007] As a result of diligent research, the inventors have found a dicarboxylic acid containing a specific metal in a specific amount. We found that the above problems can be solved by using this method to manufacture thermoplastic resins. And thus arrived at the present invention.

[0008] In other words, the present invention is as follows: <1> At a minimum, a dicarboxylic acid represented by the following formula (1) and a substance derived from said dicarboxylic acid. A method for producing a thermoplastic resin by reacting a composition containing a metal, The metal contains Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn, and Sn in a total amount of 1000 ppb or less, and it is a manufacturing method.

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0009] The thermoplastic resin of the present invention has a high refractive index, high heat resistance, and a low YI value, and is particularly suitable for optical lenses. It can produce excellent results when used. [Brief explanation of the drawing]

[0010] [Figure 1] Figure 1 shows the NMR measurement results of the polyester resin obtained in Example 1. [Modes for carrying out the invention]

[0011] The present invention will be described in more detail. The present invention provides a method for producing thermoplastic resins, comprising at least a dicarbon represented by the following formula (1). A thermoplastic resin is produced by reacting a composition containing an acid and a metal derived from the dicarboxylic acid. A method for producing, wherein the metal is Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and S It contains n in a total amount of 10,000 ppb or less. [ka] In formula (1), R1 and R2 are, independently, a hydrogen atom, a fluorine atom, and a chlorine atom. , bromine atom, iodine atom, alkyl group having 1 to 6 carbon atoms, or selected from O, N and S A C6-C20 aryl group may contain a heterocyclic atom, and a C2-C6 aryl group may also contain a heterocyclic atom. This represents a kenyl group, an alkoxy group with 1 to 6 carbon atoms, or an aralkyl group with 7 to 17 carbon atoms. Preferably, R1 and R2 are each independently a hydrogen atom, a phenyl group, and a naphthyl group. This represents a group or a substituent selected from the group consisting of the following. [ka] a and b each independently represent integers from 0 to 5, preferably independently 0 Alternatively, it represents 1. Among the compounds represented by formula (1), 2,2'-bis(hydroxycarbonylmethoxy (C)-1,1'-binaphthyl and compounds represented by the following structural formula are preferred, and 2,2'- Bis(hydroxycarbonylmethoxy)-1,1'-binaphthyl is particularly preferred. [ka]

[0012] In formula (1) above, the 1,1'-binaphthyl skeleton provides the heat resistance and refractive index of the thermoplastic resin. In addition to improving the conformation, the bond axis connecting the two naphthalene rings is perpendicular to the conformation. Therefore, it has the effect of reducing birefringence. Furthermore, the binaphthyl skeleton may be R-isomer, S-isomer, or racemic, and preferably racemic. A racemic mixture is preferable. Racemic mixtures that do not require optical resolution offer cost advantages.

[0013] In the present invention, the metal derived from the dicarboxylic acid represented by formula (1) is the same as the metal of formula ( This refers to metal components that are introduced as impurities during the production of the dicarboxylic acid represented by 1). Examples of such metals include Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn, Sn, V, Mn, and Co Examples include Cu, Ge, Sr, Zr, Mo, Ag, Cd, Sb, Ba, W, Pb, etc., but among these, V, For Mn, Co, Cu, Ge, Sr, Zr, Mo, Ag, Cd, Sb, Ba, W, and Pb, the detection limit is <0.0 Since it is 0.5 μg / g or less, in this invention, Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni The total content of Zn and Sn is measured. In this invention, the metal derived from the dicarboxylic acid represented by formula (1) is Li, Na, Mg, Al It is characterized by containing K, Ca, Ti, Cr, Fe, Ni, Zn, and Sn in a total amount of 10,000 ppb or less. It contains, more preferably, 5870 ppb or less, and particularly preferably 3738 ppb. The present inventors have identified Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn as follows: Thermoplastic resins are produced by reacting dicarboxylic acids in an amount of 10,000 ppb or less in total. By doing so, a thermoplastic resin with a remarkably high refractive index, high heat resistance, and low YI value is produced. They discovered that fat could be obtained from it. Furthermore, in the present invention, the metal derived from the dicarboxylic acid represented by formula (1) is Li, Na, It is preferable that the total amount of Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn, and Sn be 54 ppb or more. It seems so.

[0014] In the present invention, the metal derived from the dicarboxylic acid represented by formula (1) is Fe with 20 to It is preferable to include it in an amount of 3000 ppb. Also, Li should be 1 to 100 ppb and Na 2 to 50 ppb. 0 ppb, Mg 1-1000 ppb, Al 5-500 ppb, K 20-3000 ppb Ca 5-1000 ppb, Ti 1-100 ppb, Cr 5-500 ppb, Ni 1-1 It is preferable to include 00 ppb of Zn, 2 to 100 ppb of Sn, and 1 to 100 ppb of Zn. Table 1 below shows the more preferable content and the upper limit of the particularly preferable content for each metal component. .

[0015] [Table 1]

[0016] The thermoplastic resin of the present invention obtained by the manufacturing method described above is represented by the following formula (3). A thermoplastic resin comprising a constituent unit and a metal derived from the dicarboxylic acid constituting the constituent unit. The aforementioned metals include Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn, and Sn in total. It is contained in amounts of 0000 ppb or less. [ka] In equation (3), R5, R6, e, and f are R1, R2, in equation (1), respectively. a and b are synonymous. Specific thermoplastic resins include polyester resin or polyethylene resin. It is preferable that the material be a polyester carbonate resin, and in particular, polyester is preferred in terms of the effects of the present invention. It is preferable that it be made of resin.

[0017] One of the characteristics of the thermoplastic resin of the present invention is its high refractive index, and the measurement wavelength at 25°C The refractive index at 589 nm (hereinafter sometimes abbreviated as "nD") is between 1.650 and 1.720. It is preferable that it be such, more preferably 1.660 to 1.710, and 1.670 to 1 It is even more preferable if it is 0.700. Furthermore, one of the characteristics of the thermoplastic resin of the present invention is its high heat resistance, and glass transition The temperature point (hereinafter sometimes abbreviated as "Tg") is preferably 130-160°C. A temperature of 140-155°C is more preferable. Furthermore, one of the characteristics of the thermoplastic resin of the present invention is that it has a low YI value. The value is preferably between 7 and 40, and more preferably between 9 and 38. Furthermore, the thermoplastic resin of the present invention preferably has a weight-average molecular weight (Mw) of 10,000~ The weight-average numerator is 50,000, and more preferably 15,000 to 40,000. The method for measuring the quantity (Mw) can be the method described in the examples below. .

[0018] The thermoplastic resin of the present invention comprises a dicarboxylic acid represented by formula (1) and the dicarboxylic acid It is not particularly limited as long as it is obtained by reacting a composition containing a metal derived from that metal. Instead, any of the diol compounds may be used as raw materials. In the present invention, the dicarboxylic acid represented by formula (1) and the dicarboxylic acid derived therefrom are used. A composition containing a metal is reacted with a diol compound represented by the following formula (2). It is preferable. [ka] In formula (2), R3 and R4 are, independently, a hydrogen atom, a fluorine atom, and a chlorine atom. , bromine atom, iodine atom, alkyl group having 1 to 6 carbon atoms, or selected from O, N and S A C6-C20 aryl group may contain a heterocyclic atom, and a C2-C6 aryl group may also contain a heterocyclic atom. This represents a kenyl group, an alkoxy group with 1 to 6 carbon atoms, or an aralkyl group with 7 to 17 carbon atoms. Preferably, R3 and R4 are each independently a hydrogen atom, a phenyl group, and a naphthyl group. This represents a group or a substituent selected from the group consisting of the following. [ka] c and d each independently represent integers from 0 to 5, preferably independently 0 Alternatively, it represents 1.

[0019] <Other copolymer components> The thermoplastic resin in the present invention has a constituent unit represented by formula (3), and preferably It has a constituent unit derived from the diol compound represented by formula (2) above, but separately from that, It may contain polymerization components. Copolymer components other than those shown in formula (1) above may be used. The ammonium acid component, the diol component other than that shown in formula (2) above, and the carbonate bond Examples of repeating units are given.

[0020] Specific dicarboxylic acid components that can be used as copolymers include malonic acid, succinic acid, and gluta. Azelaic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, ethyl malonic acid Aliphatic dicarboxylic acid components such as ronic acid, monocyclic compounds such as phthalic acid, isophthalic acid, and terephthalic acid Aromatic dicarboxylic acid components, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid Bonic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, anthracite Polycyclic aromatic dicarboxylic acid components such as cededicarboxylic acid and phenantradiocarboxylic acid, 2 ,2'-biphenyldicarboxylic acid and other biphenyldicarboxylic acid components, 1,4-cyclodical Examples include alicyclic dicarboxylic acid components such as rubonic acid and 2,6-decalindicarboxylic acid. These may be used individually or in combination of two or more types. Furthermore, derivatives of these include... Acid chlorides and esters may also be used. Among these, those with higher heat resistance and refractive index Because they are inexpensive, monocyclic aromatic dicarboxylic acid components, polycyclic aromatic dicarboxylic acid components, biphenyls A nyl dicarboxylic acid component is preferred.

[0021] Furthermore, specific diol components used as copolymers include ethylene glycol and protamine. Panediol, butanediol, pentanediol, hexanediol, heptanediol Aliphatic diol components such as octanediol, nonanediol, and tricyclo[5.2. 1.02,6] Decanedimethanol, cyclohexane-1,4-dimethanol, decalli n-2,6-dimethanol, norbornanedimethanol, pentacyclopentadecanedimethanol Thanol, cyclopentane-1,3-dimethanol, spiroglycol, isosorbide, etc. The alicyclic diol component, hydroquinone, resorcinol, 2,2-bis(4-hydroxy Phenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-Bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl) Phenyl)diphenylmethane, 1,3-bis(2-(4-hydroxyphenyl)-2-p Ropyrbenzene, bis(4-hydroxyphenyl)sulfone, bis(4-(2-hydro) Xyethoxy(phenyl)sulfone, bis(4-hydroxyphenyl)sulfide, 1, 1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1 -Bis(4-hydroxyphenyl)cyclohexane, biphenol, 2,2'-bis(2 -hydroxyethoxy)-1,1'-binaphthyl, 1,1'-bi-2-naphthol, dihy droxynaphthalene, bis(2-hydroxyethoxy)naphthalene, 10,10-bis( Examples include aromatic diol components such as 4-hydroxyphenyl)antrone. They may be used individually or in combination of two or more types. Among these, while improving moldability, Because it is easy to suppress the decrease in thermal properties and refractive index, ethylene glycol and 2,2'-bis(2-H) Droxyethoxy)-1,1'-binaphthyl is preferred.

[0022] Furthermore, as specific copolymer components, repeating units having carbonate bonds include: The diol component exemplified in formula (2) and the diol component exemplified as the copolymer component mentioned above One example is a compound in which the molecules are bonded together with carbonate.

[0023] The thermoplastic resin of the present invention is a dicarboxylic acid and diol compound represented by the above formula (1). A substance is subjected to an esterification or transesterification reaction, and the resulting reaction product is subjected to a polycondensation reaction. Therefore, it is sufficient to use a high molecular weight product with the desired molecular weight.

[0024] Specifically, for example, in the presence of an inert gas, the diol component and the dicarboxylic acid component or The diester is mixed and heated under reduced pressure, usually at 120-350°C, preferably 150-300°C. It is preferable to carry out the reaction at °C. The degree of reduced pressure should be changed in stages, ultimately reaching 0.13 kPa. The water or alcohols produced as described below are removed from the system by distillation, and the reaction time is usually 1 to 10 It takes about an hour.

[0025] As polymerization catalysts, known ones can be used, for example, antimony compounds, titan A tin compound, germanium compound, tin compound, or aluminum compound is preferred. Examples of such compounds include antimony, titanium, germanium, tin, and aluminum. Oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, sulfur Examples include salts and the like. Furthermore, two or more of these compounds can be used in combination. Among these, tin, titanium, and germanium stand out from the perspective of melt stability and hue of thermoplastic resins. Compounds are preferred.

[0026] As the transesterification catalyst, any known catalyst can be used, such as manganese or magnesium. Nesium, titanium, zinc, aluminum, calcium, cobalt, sodium, lithium , or compounds containing lead can be used. Specifically, compounds containing these elements Oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, sulfuric acids Examples include salts, etc. Among these, the melt stability of thermoplastic resins, hue, and polymer properties are important. From the perspective of minimizing dissolved foreign matter, manganese, magnesium, zinc, titanium, and cobalt oxides are used. Compounds such as acetates and alkoxides are preferred. Furthermore, manganese, magnesium, and titanium compounds are preferred. Compounds are preferred. Two or more of these compounds can be used in combination.

[0027] Furthermore, as described above, the thermoplastic resin of the present invention is other than the constituent unit represented by formula (3). Copolymer components may be included. For example, if polyester carbonate resin is used, In addition to the diol and dicarboxylic acid components, dicarboxylic acid chlorides and phosgene are reacted. Alternatively, the diol, dicarboxylic acid and biaryl carbonate may be reacted. It can be manufactured by doing so.

[0028] Specific examples of biaryl carbonates include diphenyl carbonate and di-p-tolyl Carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate Examples include diphenyl carbonate and dinaphthyl carbonate. Bonate is preferred.

[0029] The content of the dicarboxylic acid chloride, phosgene, or biaryl carbonate component is Preferably less than 42 ml, and more preferably, relative to 100 ml of the dicarboxylic acid component. The concentration is less than 30 moles, and more preferably less than 20 moles.

[0030] <Additives> The thermoplastic resin of the present invention may optionally contain a heat stabilizer, antioxidant, mold release agent, plasticizer, The thermoplastic resin composition is used by adding appropriate additives such as fillers and ultraviolet absorbers. It is possible.

[0031] As a release agent, those consisting of 90% or more by weight of alcohol and fatty acid esters are used. Preferred. Specifically, esters of alcohols and fatty acids include monohydric alcohols and fatty acids. Esters of and / or partial or total esters of polyhydric alcohols and fatty acids Examples include the esters of monohydric alcohols and fatty acids, which have 1 to 20 carbon atoms. Esters of alcohols with saturated fatty acids having 10 to 30 carbon atoms are preferred. Also, polyhydric alcohols Partial or total esters of ethanol and fatty acids are polyvalent esters with 1 to 25 carbon atoms. Partial or total esters of alcohols and saturated fatty acids with 10 to 30 carbon atoms are preferred. It seems so. Specifically, as an ester of a monohydric alcohol and a saturated fatty acid, stearyl stearyl Palmitate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl Examples include lupalmitate, with stearyl stearate being preferred.

[0032] Specifically, as partial or total esters of polyhydric alcohols and saturated fatty acids, Thearic acid monoglyceride, stearate diglyceride, stearate triglyceride, Monosorbite stearate, monoglyceride behenate, pentaerythritol mono Stearate, Pentaerythritol Tetra Stearate, Pentaerythritol Tetra Pelargonate, propylene glycol monostearate, biphenyl biphenate, so Rubitan monostearate, 2-ethylhexyl stearate, dipentaerythritol Examples include whole or partial esters of dipentaerythultol such as hexastearate. Among these esters, stearic acid monoglyceride, stearic acid Liglycerides, pentaerythritol tetrastearate, triglyceride stearate A mixture of stearyl stearate is preferably used.

[0033] The amount of the ester in the release agent is preferably 90% by weight or more, when the total release agent is considered to be 100% by weight. It is preferable that the content be 95% by weight or more. As a release agent to be incorporated into a thermoplastic resin composition, the amount per 100 parts by weight of thermoplastic resin is A range of 0.005 to 2.0 parts by weight is preferred, and a range of 0.01 to 0.6 parts by weight is more preferred. Furthermore, a range of 0.02 to 0.5 parts by weight is even more preferable.

[0034] Examples of heat stabilizers include phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and hindered phenol-based heat stabilizers. Stabilizers are one example. In phosphorus-based heat stabilizers, tetrakis(2,4-di-tert-butylphenyl) is preferred. Nyl)-4,4'-biphenylenediphosphonite is used. The content of the phosphorus-based heat stabilizer in the thermoplastic resin is as follows: per 100 parts by weight of the thermoplastic resin 0.001 to 0.2 parts by weight is preferred.

[0035] In hindered phenol-based heat stabilizers, octadecyl-3-(3,5-di-ter t-butyl-4-hydroxyphenyl)propionate is particularly preferred. The content of hindered phenol-based heat stabilizers in thermoplastic resins is as follows: 0.001 to 0.3 parts by weight per 00 parts by weight is preferable.

[0036] Examples of UV absorbers include benzotriazole-based UV absorbers and benzophenone-based UV absorbers. UV absorbers, triazine-based UV absorbers, cyclic iminoester-based UV absorbers and cyanoates At least one ultraviolet absorber selected from the group consisting of acrylate-based agents is preferred.

[0037] In benzotriazole-based ultraviolet absorbers, more preferably 2-(2-hydroxy -5-tert-octylphenyl)benzotriazol, 2,2'-methylenebis[4 -(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-i) It is a phenol. Benzophenone-based UV absorbers include 2-hydroxy-4 -n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carbbox Cibenzophenone is one example. As for triazine-based UV absorbers, 2-(4,6-di Phenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-pheno 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2) Examples include -yl)-5-[(octyl)oxy]phenol, etc. Cyclic iminoeste As for UV absorbers, in particular 2,2'-p-phenylenebis(3,1-benzox) Zin-4-one is preferred.

[0038] The amount of UV absorber added is preferably 0.01 to 3 parts by weight of thermoplastic resin. It is 0.0 parts by weight, and within this range of blending amounts, depending on the application, it is sufficient for thermoplastic resin molded products. It is possible to impart sufficient weather resistance.

[0039] <Optical Lenses> The thermoplastic resin of the present invention is suitable for optical components, particularly optical lenses. When manufacturing an optical lens containing the thermoplastic resin of the present invention by injection molding, the cylinder temperature is 2 It is preferable to mold the product at a temperature of 60-350°C and a mold temperature of 90-170°C. The molding process is performed under the following conditions: cylinder temperature 270-320°C and mold temperature 100-160°C. It is preferable to do so. If the cylinder temperature is higher than 350°C, the thermoplastic resin will decompose. When colored and at temperatures below 260°C, the melt viscosity is high, making molding difficult. If the temperature is higher than 170°C, the molded piece made of thermoplastic resin will not come out of the mold. This tends to become difficult. On the other hand, if the mold temperature is below 90°C, the resin inside the mold during molding will not be as fast. If it hardens too much, it becomes difficult to control the shape of the molded piece, or the molded form applied to the mold is not sufficiently transferred. It tends to become difficult to do.

[0040] The optical lens of the present invention may preferably be in the form of an aspherical lens as needed. Aspherical lenses make it possible to virtually eliminate spherical aberration with a single lens. Therefore, there is no need to eliminate spherical aberration by combining multiple spherical lenses, resulting in weight reduction and molding. Cost reduction becomes possible. Therefore, aspherical lenses are particularly important among optical lenses. It is useful as a lens.

[0041] Furthermore, because the optical lens of the present invention has high molding fluidity, it is thin-walled, small, and has a complex shape. It is particularly useful as a material for academic lenses. Specifically, the thickness of the center is 0 Preferably 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and further Preferably, the diameter is 0.1 to 2.0 mm. Preferably, 1.0 to 10.0 mm, and even more preferably 3.0 to 1 It is 0.0 mm. Furthermore, its shape is that of a meniscus lens, with one side convex and the other concave. It is preferable to have one.

[0042] The optical lenses of this invention are manufactured using methods such as mold forming, cutting, polishing, laser processing, electrical discharge machining, and etching. They are formed by any method, such as those listed above. Among these, mold forming is preferred from the standpoint of manufacturing costs. It's nice. [Examples]

[0043] The present invention will be further described below with reference to examples, but the present invention is not limited thereto. No. Furthermore, the measurement of each physical property was performed using the following method.

[0044] <Metal analysis> After sulfuric acid carbonization of the sample, the metal concentration was measured by ICP-MS. Specifically, 2g of the sample is weighed into a synthetic quartz beaker, and 2.5ml of sulfuric acid is added during carbonization, and 0.1ml of sulfuric acid is added before carbonization. It was heated on a hot plate and carbonized. Next, it was covered with a quartz dish and placed in an electric furnace for 500°C. The material was heated at ℃ for 10 hours to carbonize it. Then, sulfuric acid was added and heated to dryness, and nitric acid was added and heated to dryness. By doing so, heat acid decomposition was carried out. Nitric acid aqueous solution was added to make a total volume of 50 mL, and the mixture was heated to 50°C, and ICP- Quantitative analysis was performed using MS. ICP-MS device: Shimadzu Corporation: ICPE-9000

[0045] <Method for measuring weight-average molecular weight (Mw)> The weight-average molecular weight equivalent to polystyrene was determined from a pre-prepared calibration curve of standard polystyrene. That is, standard polystyrene with a known molecular weight (molecular weight distribution = 1) (manufactured by Tosoh Corporation, "PStQ") A calibration curve was created using uick MP-M"), and the elution of each peak from the measured standard polystyrene was analyzed. Time and molecular weight were plotted, and a cubic equation was used for approximation to obtain a calibration curve. Mw is as follows: This was calculated using the following formula. Mw = Σ(Wi × Mi) ÷ Σ(Wi) Here, i is the i-th division point when dividing the molecular weight M, Wi is the i-th weight, and Mi is the i-th molecular weight. The molecular weight M represents the polystyrene molecular weight value at the same elution time of the calibration curve. As the GPC device, HLC-8320GPC manufactured by Tosoh Corporation was used. As the guard column, one TSKguardcolumn SuperMPHZ-M was used, and as the analytical column, three TSKgel SuperMultiporeHZ-M columns connected in series were used. Other conditions are as follows. Solvent: HPLC grade tetrahydrofuran Injection volume: 10 μL Sample concentration: 0.2 w / v% HPLC grade chloroform solution Solvent flow rate: 0.35 ml / min Measurement temperature: 40 °C Detector: RI

[0046] <Method for measuring refractive index (nD, νd)> The obtained resin was press-molded into a 40φ, 3 mm thick disc (molding conditions: 200 °C, 100 kgf / cm 2 for 2 minutes), cut out at a right angle, and the refractive index at a measurement wavelength of 589 nm was measured at 25 °C using a KPR-200 manufactured by Carl Zeiss.

[0047] <Method for measuring YI value> 6 g of the obtained resin was dissolved in 60 ml of methylene chloride, and using a spectroscopic color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SE-2000") with a cell having an optical path length of 6 cm, the YI value was measured based on JIS 7373.

[0048] (Example 1) 50.29 g (0.12 mol) of 2,2'-bis(hydroxycarbonylmethoxy)-1,1'-binaphthyl (hereinafter referred to as "BINOL-DC") represented by the following structural formula, ​The structural formula shown is 2,2'-bis(2-hydroxyethoxy)-6,6'diphenyl- 1,1'-Binaphthalene (hereinafter referred to as "DP-BHBNA") 52.66g (0.10 mol), ethylene glycol (hereinafter referred to as "EG") 3.49g (0.06mol) , and 0.011 g of tetrabutoxytitanium as a catalyst, in a reaction with a stirrer and distillation apparatus. The mixture was placed in a vessel, heated to 180°C under atmospheric pressure and nitrogen, and stirred for 30 minutes. Afterward, it was heated to 250°C. The polymerization reaction was carried out by raising the temperature to below 0.13 kPa and reducing the pressure. The contents were then placed in the reactor. Polyester resin was obtained by extracting it from the resin. Analysis of the obtained polyester resin by NMR revealed that the components introduced into the polyester resin were Of the diol components, 80 mol% are derived from DP-BHBNA and 20 mol% are derived from EG, 100 mol% of the carboxylic acid component introduced into the ester resin was derived from BINOL-DC. The NMR measurement results are shown in Figure 1. The physical properties of the obtained polyester resin are shown in Table 2.

[0049] [ka] [ka]

[0050] (Example 2) Different batches of 2,2'-bis(hydroxycarbonylmethoxy)-1,1'-binaf A polyester resin was obtained in the same manner as in Example 1, except that chill was used. Table 2 shows the physical properties of the resin of Tel. Note that in Table 2, the 2,2'-bis(Hy) used in Example 1 is shown. (Droxycarbonylmethoxy)-1,1'-binaphthyl is designated as BINOL-DC-A. The 2,2'-bis(hydroxycarbonylmethoxy)-1,1'-binaphthi used in Example 2 The code was changed to BINOL-DC-B.

[0051] (Example 3) Furthermore, different lots of 2,2'-bis(hydroxycarbonylmethoxy)-1,1'-bis A polyester resin was obtained in the same manner as in Example 1, except that naphthyl was used. The physical properties of the ester resin are shown in Table 2. Note that in Table 2, the 2,2'-bis used in Example 3 is shown. (Hydroxycarbonylmethoxy)-1,1'-binaphthyl is designated as BINOL-DC-C. Ta.

[0052] (Example 4) The 2,2'-bis(hydroxycarbonylmethoxy)-1,1'-bina used in Example 1 Phthyl (BINOL-DC-A) 50.29g (0.12mol), represented by the following structural formula 9,9'-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) 164.41g (0.37mol), diphenyl carbonate 55.95g (0.26m (ol), and 0.015 g of tetrabutoxytitanium as a catalyst, with a stirrer and distillation apparatus. It was placed in the reaction vessel, heated to 180°C under atmospheric pressure and nitrogen, and stirred for 30 minutes. Then, 1 The temperature was gradually raised to 255°C and 0.13kPa, then the pressure was reduced, and then the temperature was continued at 255°C and 0.13kPa. The polymerization reaction was carried out by stirring at Pa for 1 hour. The contents were removed from the reactor and the polyester Polycarbonate resin was obtained. The physical properties of the obtained polyester carbonate resin are shown in Table 2. . [ka]

[0053] (Comparative example) 2,2'-bis(hydroxycarbonylmethoxy)-1, containing the metal amounts shown in Table 2 below A polyester resin was obtained in the same manner as in Example 1, except that 1'-binaphthyl was used. Table 2 shows the physical properties of the polyester resin.

[0054] [Table 2] [Industrial applicability]

[0055] The thermoplastic resin of the present invention has a high refractive index, high heat resistance, and a low YI value, and therefore is suitable for optical discs. Transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, light It can be used in optical components such as optical films, substrates, optical filters, and hard coat films, and in particular, This invention is extremely useful for camera lenses in smartphones, DSCs, and automotive cameras. By using plastic resin, it is possible to make lens units used in telephoto lenses and the like thinner. It becomes possible.

Claims

1. At least a dicarboxylic acid represented by the following formula (1) and gold derived from the dicarboxylic acid. A method for producing a thermoplastic resin by reacting a composition containing the genus, The aforementioned metals are Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn, and Sn, totaling 1000 units. A manufacturing method that includes the substance in an amount of 0 ppb or less. 【Chemistry 1】 (In formula (1), R １ and R ２ These are, independently, a hydrogen atom, a fluorine atom, and a chlorine atom. , bromine atom, iodine atom, alkyl group having 1 to 6 carbon atoms, or selected from O, N and S A C6-C20 aryl group may contain a heterocyclic atom, and a C2-C6 aryl group may also contain a heterocyclic atom. This represents a kenyl group, an alkoxy group with 1 to 6 carbon atoms, or an aralkyl group with 7 to 17 carbon atoms. (a and b each independently represent integers from 0 to 5.)

2. The aforementioned metals Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn, and Sn total 54 ppb The manufacturing method according to claim 1, comprising the above amount.

3. The manufacturing method according to claim 1 or 2, wherein the metal contains Fe in an amount of 20 to 3000 ppb. Law.

4. The aforementioned metals are Li at 1 to 100 ppb, Na at 2 to 500 ppb, and Mg at 1 to 1000 ppb. Al at 5-500 ppb, K at 20-3000 ppb, Ca at 5-1000 ppb, Ti at 1 ~100 ppb, Cr 5-500 ppb, Ni 1-100 ppb, Zn 2-100 ppb A manufacturing method according to any one of claims 1 to 3, comprising Sn in an amount of 1 to 100 ppb.

5. The dicarboxylic acid represented by formula (1) and a metal derived from the dicarboxylic acid are included. The composition is reacted with a diol compound represented by the following formula (2), any one of claims 1 to 4. The manufacturing method described in item 1. 【Chemistry 2】 (In formula (2), R ３ and R ４ These are, independently, a hydrogen atom, a fluorine atom, and a chlorine atom. , bromine atom, iodine atom, alkyl group having 1 to 6 carbon atoms, or selected from O, N and S A C6-C20 aryl group may contain a heterocyclic atom, and a C2-C6 aryl group may also contain a heterocyclic atom. This represents a kenyl group, an alkoxy group with 1 to 6 carbon atoms, or an aralkyl group with 7 to 17 carbon atoms. c and d each independently represent integers from 0 to 5.

6. Claim 1, wherein the thermoplastic resin is polyester or polyester carbonate. The manufacturing method described in any one of items ~5.

7. A constituent unit represented by the following formula (3), and gold derived from the dicarboxylic acid constituting the constituent unit. A thermoplastic resin containing the genus, The aforementioned metals are Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn, and Sn, totaling 1000 units. Thermoplastic resin containing 0 ppb or less. 【Transformation 3】 (In formula (3), R ５ and R ６ These are, independently, a hydrogen atom, a fluorine atom, and a chlorine atom. , bromine atom, iodine atom, alkyl group having 1 to 6 carbon atoms, or selected from O, N and S A C6-C20 aryl group may contain a heterocyclic atom, and a C2-C6 aryl group may also contain a heterocyclic atom. This represents a kenyl group, an alkoxy group with 1 to 6 carbon atoms, or an aralkyl group with 7 to 17 carbon atoms. e and f each independently represent integers from 0 to 5.

8. The thermoplastic resin according to claim 7, wherein the thermoplastic resin has a YI value of 7 to 40.

9. An optical lens comprising the thermoplastic resin described in claim 7 or 8.

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