Thermoplastic resin composition and optical member comprising same

Abstract

The purpose of the present invention is to provide a thermoplastic resin composition having a high refractive index and low birefringence and excellent long-term heat resistance. Another purpose of the present invention is to provide an excellent optical lens by using the thermoplastic resin composition. The thermoplastic resin composition contains a thermoplastic resin having a constituent unit represented by formula (1) and a release agent, and the content of an antioxidant in the thermoplastic resin composition is 0-300 ppm. (In formula (1), ring Z represents an aromatic hydrocarbon ring, L1 and L2 each independently represent a divalent linking group, o and p each independently represent an integer of 0 or more, R1, R2, R3 and R4 each independently represent a hydrogen atom or a C1-20 hydrocarbon group, and X is at least one selected from the group consisting of groups represented by formula (2) or (3). (In the formula, Y represents a divalent linking group) # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a thermoplastic resin composition and an optical component comprising the same. Background Art

[0002] Although the glass used as an optical system material has excellent optical properties, environmental resistance, and chromaticity, it has the problem of poor processability. On the other hand, optical resins, especially thermoplastic resin compositions, have the advantages of being affordable compared to glass materials, being able to mass-produce molded products by injection molding, and being easy to manufacture aspheric lenses. Therefore, it has been popularized so far mainly for constituting optical lenses of smartphone cameras. In recent years, as a new use, it is expected to be developed to the optical lenses of so-called vehicle-mounted cameras, such as vehicle-mounted sensor cameras and vehicle-mounted observation cameras, or optical lenses of AR / VR devices.

[0003] Under such circumstances, optical resins are required to have a higher refractive index in order to miniaturize and thin the optical system, and to have highly low distortion, i.e., low birefringence, in order for sensors or people to recognize images through optical lenses. In addition, in the case of automotive cameras, long-term heat resistance is important so that the color does not change over a long period of time at high temperatures due to the use environment.

[0004] In addition, in the use of AR / VR equipment, it is mainly for people to recognize the image, so the light of the display needs to be transmitted correctly. In order to allow the light in the visible light region to penetrate well-balanced and allow people to directly recognize the optical lens, it is required to have excellent appearance characteristics such as glass with a high-end feel.

[0005] Patent Document 1 describes that a polyester carbonate resin having a high refractive index of 1.635 to 1.650 and an orientation birefringence of 0 to 6×10 -3 A polyester carbonate resin having structural units represented by formula (M) and formula (N) and having excellent low birefringence.

[0006] [Chemical formula 1]

[0007]

[0008] [Chemical formula 2]

[0009]

[0010] (In formula (N), W is phenylene or naphthalene diyl.)

[0011] Patent Document 2 describes that the chromaticity of a polyester carbonate resin obtained by using a catalyst composed of an aluminum compound and a phosphorus compound is better than that obtained by using a titanium-based catalyst.

[0012] Patent Document 3 describes that a polycarbonate resin having a structure represented by formula (O) and excellent in high transparency, high Tg, high refractive index, and low birefringence can be obtained.

[0013] [Chemical formula 3]

[0014]

[0015] (In formula (O), T 1 and T 2 are each independently a hydrogen atom or a methyl group.)

[0016] Prior art literature

[0017] Patent Literature

[0018] Patent Document 1: International Publication No. 2011 / 010741

[0019] Patent Document 2: International Publication No. 2019 / 131841

[0020] Patent Document 3: Japanese Patent Application Publication No. 2010-189508 Summary of the invention

[0021] The above documents describe polycarbonate resins or polyester carbonate resins having high refractive index, low birefringence, high transparency, high Tg, and good chromaticity. However, the characteristics of the thermoplastic resin composition after extrusion and molding, especially the long-term heat resistance, are not described, and there is still room for improvement.

[0022] As described above, a polycarbonate resin composition, a polyester carbonate resin composition, and an optical lens having long-term heat resistance in addition to a high refractive index and a low birefringence have not been provided so far.

[0023] In addition, optical resin materials with high refractive index generally undergo thermal degradation and absorb light in the short wavelength region of visible light, thereby destroying the transmission balance of visible light, reducing transmittance, and causing the molded product after extrusion and molding to turn yellow and deteriorate in appearance. Although the above-mentioned documents describe polycarbonate resins or polyester carbonate resins that achieve high refractive index, low birefringence, high transparency, and good chromaticity, they do not describe the visible light transmission characteristics and appearance characteristics of thermoplastic resin compositions after extrusion and molding, especially the transmission balance and chromaticity, and there is still room for improvement.

[0024] As described above, a polycarbonate resin composition, a polyester carbonate resin composition, and an optical lens having excellent transmittance and chromaticity in addition to a high refractive index and a low birefringence have not been provided so far.

[0025] Therefore, an object of the present invention is to provide a thermoplastic resin composition having a high refractive index and low birefringence and excellent long-term heat resistance. In addition, another object of the present invention is to provide a thermoplastic resin composition having a high refractive index and low birefringence and excellent transmittance and excellent appearance. Furthermore, an object of the present invention is to provide an excellent optical lens by using the thermoplastic resin composition.

[0026] The present inventors have found that the above-mentioned problems can be solved by the present invention having the following aspects.

[0027] Method 1

[0028] A thermoplastic resin composition comprises a thermoplastic resin having a structural unit represented by the following formula (1) and a mold release agent, wherein the content of the antioxidant in the thermoplastic resin composition is 0 to 300 ppm.

[0029] [Chemical formula 4]

[0030]

[0031] {In formula (1), ring Z represents an aromatic hydrocarbon ring, L 1 and L 2 Each independently represents a divalent linking group, o and p each independently represent an integer greater than 0, R 1 , R 2 , R 3 and R 4 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X is at least one selected from the groups represented by the following formula (2) or (3).

[0032] [Chemical formula 5]

[0033]

[0034] [Chemical formula 6]

[0035]

[0036] {In the formula, Y represents a divalent linking group.}

[0037] Method 2

[0038] The thermoplastic resin composition according to Embodiment 1, wherein the mold release agent is contained in an amount of 1 to 4000 ppm in the thermoplastic resin composition.

[0039] Method 3

[0040] The thermoplastic resin composition according to aspect 1 or 2, wherein the content of the antioxidant in the thermoplastic resin composition is 0 to 50 ppm.

[0041] Method 4

[0042] The thermoplastic resin composition according to aspect 1 or 2, wherein dry heat yellowing ΔYI is 0.00 to 0.47.

[0043] Method 5

[0044] A thermoplastic resin composition comprises a thermoplastic resin having a structural unit represented by the following formula (4), a colorant and an antioxidant, wherein the content of the colorant in the thermoplastic resin composition is 0.01 to 4.00 ppm, and the content of the antioxidant is 50 to 3000 ppm.

[0045] [Chemical formula 7]

[0046]

[0047] {In formula (4), ring Z represents an aromatic hydrocarbon ring, L 1 and L 2 Each independently represents a divalent linking group, o and p each independently represent an integer greater than 0, R 1 , R 2 , R 3 and R 4 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X is at least one selected from the groups represented by the following formula (5) or (6).

[0048] [Chemical formula 8]

[0049]

[0050] [Chemical formula 9]

[0051]

[0052] {In the formula, Y represents a divalent linking group.}

[0053] Method 6

[0054] The thermoplastic resin composition according to Embodiment 5, wherein a 2 mm thick molded sheet of the thermoplastic resin composition has a chromaticity a* of -0.40 to 0.00 and a chromaticity b* of -0.50 to 1.25.

[0055] Method 7

[0056] The thermoplastic resin composition according to embodiment 5 or 6, wherein a 2 mm thick molded plate of the thermoplastic resin composition has a total light transmittance of 86.5% or more.

[0057] Method 8

[0058] The thermoplastic resin composition according to embodiment 5 or 6, wherein a 2 mm thick molded plate of the thermoplastic resin composition has a light transmittance at 400 nm of 81.0% or more.

[0059] Method 9

[0060] The thermoplastic resin composition according to embodiment 5 or 6, wherein a 2 mm thick molded plate of the thermoplastic resin composition has a light transmittance at 580 nm of 85.0% or more.

[0061] Method 10

[0062] The thermoplastic resin composition according to embodiment 1 or 5, wherein the ring Z in the formula (1) or (4) is a benzene ring.

[0063] Method 11

[0064] The thermoplastic resin composition according to embodiment 1 or 5, wherein the thermoplastic resin having the structural unit represented by formula (1) or (4) is a polycarbonate resin or a polyester carbonate resin.

[0065] Method 12

[0066] The thermoplastic resin composition according to Embodiment 11, wherein the thermoplastic resin having the structural unit represented by Formula (1) or Formula (4) is a polyester carbonate resin.

[0067] Method 13

[0068] An optical component comprising the thermoplastic resin composition according to embodiment 1 or 5.

[0069] Method 14

[0070] The optical component according to Mode 13 is an optical lens.

[0071] The thermoplastic resin composition of the present invention has a high refractive index, low birefringence, and excellent long-term heat resistance. Furthermore, by using the thermoplastic resin composition of the present invention, an excellent optical lens that can be used in a wide range of environments can be obtained. DETAILED DESCRIPTION

[0072] Hereinafter, the embodiment for carrying out the present invention will be described in detail, but the present invention is not limited to this embodiment, and various modifications can be made without departing from the gist of the present invention.

[0073] <Aspect I of the present invention>

[0074] Hereinafter, until the description of Embodiment II of the present invention, when describing the present invention, Embodiment I of the present invention is shown.

[0075] (1) Thermoplastic resin composition

[0076] The thermoplastic resin composition of the present invention comprises a thermoplastic resin having a predetermined structure and a release agent, wherein the content of the antioxidant in the thermoplastic resin composition is 0 to 300 ppm. The thermoplastic resin composition of the present invention has a high refractive index, low birefringence, and excellent long-term heat resistance due to such a configuration.

[0077] 《Thermoplastic Resins》

[0078] The thermoplastic resin used in the present invention has a structure represented by the above formula (1).

[0079] In the above formula (1), Z's are identical or different and represent an aromatic hydrocarbon ring, and examples thereof include a naphthalene ring and a benzene ring, and a benzene ring is preferred.

[0080] In the above formula (1), R 1 , R 2 , R 3 and R 4 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and examples of the hydrocarbon group include an alkyl group, a cycloalkyl group and an aryl group.

[0081] Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group and the like, and a methyl group is preferred.

[0082] Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and bicyclo[1.1.1]pentenyl.

[0083] Examples of the aryl group include phenyl, tolyl, naphthyl, and xylyl, and a phenyl group is preferred.

[0084] R 1 , R 2 , R 3 and R 4 Each independently is preferably a hydrogen atom, a methyl group, or a phenyl group, and more preferably a hydrogen atom.

[0085] In the above formula (1), L 1 and L 2 Each independently represents a divalent linking group, and examples thereof include an alkylene group having 1 to 4 carbon atoms, and preferably represents an ethylene group or a propylene group, and more preferably represents an ethylene group.

[0086] In the above formula (1), o and p each independently represent an integer of 0 or more, preferably 0 to 2, and more preferably 1.

[0087] In the above formula (1), X is at least one selected from the groups represented by the above formula (2) or (3).

[0088] In the above formula (3), Y represents a divalent linking group, and examples thereof include a hydrocarbon group having 1 to 25 carbon atoms, and examples of the hydrocarbon group include an olefin group, a cycloolefin group, and an arylene group.

[0089] Preferred examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferred.

[0090] In the above formula (1), the presence of an aromatic hydrocarbon ring has an effect of increasing the refractive index, and the presence of a cardo structure has an effect of reducing the birefringence.

[0091] Examples of the thermoplastic resin of the present invention include polycarbonate, polyester carbonate and polyester, preferably polycarbonate and polyester carbonate, and more preferably polyester carbonate.

[0092] <<Diol component used for the thermoplastic resin having the structure represented by the above formula (1)>>

[0093] The diol component used in the structural unit represented by the above formula (1) of the thermoplastic resin of the present invention is mainly a compound represented by the formula (a).

[0094] [Chemical formula 10]

[0095]

[0096] In the above formula (a) of the diol component, Z, L 1 , L 2 ,o,p,R 1 , R 2 , R 3 and R 4 The same as the above formula (1).

[0097] Representative specific examples of the diol component represented by the above formula (a) are shown below, but the raw material used for the above formula (a) in the present invention is not limited thereto.

[0098] Specific examples include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(hydroxymethoxy)phenyl)fluorene, 9,9-bis(4-(hydroxymethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(hydroxymethoxy)-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-phenylphenyl)fluorene, 9,9-bis(4-(3-hydroxypropoxy)phenyl)fluorene, 9,9-bis(4-(3-hydroxypropoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(3 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-dimethylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene, 9,9-bis(6-(2-hydroxymethoxy)-2-naphthyl)fluorene, 9,9-bis(6-(2-hydroxymethoxy)-2-naphthyl)fluorene, )-2,7-dimethylfluorene, 9,9-bis(6-(2-hydroxymethoxy)-2-naphthyl)-2,7-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-dimethylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-diphenylfluorene,

[0099] 9,9-bis(6-(3-hydroxypropoxy)-2-naphthyl)fluorene, 9,9-bis(6-(3-hydroxypropoxy)-2-naphthyl)-2,7-dimethylfluorene, 9,9-bis(6-(3-hydroxypropoxy)-2-naphthyl)-2,7-diphenylfluorene.

[0100] These may be used alone or in combination of two or more.

[0101] Among them, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, and 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene are preferred, and 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene is more preferred. 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene has a structure that contributes to high refractive index and low birefringence, and has a structure that is highly stable against oxidation, and is also advantageous in exhibiting long-term heat resistance.

[0102] <<Diol components other than the above formula (a)>>

[0103] The thermoplastic resin of the present invention has the structure of the above formula (1) derived from the diol component represented by the above formula (a), but may contain structures derived from other diol components within a range that does not impair the effects of the present invention. In the thermoplastic resin of the present invention, the diol component represented by the above formula (a) preferably accounts for 70 mol% or more of the total diol components, and more preferably 80 mol% or more.

[0104] Examples of other diol components include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, tricyclo[5.2.1.0 2,6 ]Decanedimethanol, cyclohexane-1,4-dimethanol, decahydronaphthalene-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spirodiol, isosorbide, isomannide, isoidide, hydroquinone, resorcinol, dihydroxynaphthalene, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1 , 1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, biphenol, 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(3-hydroxypropoxy)-1,1'-binaphthyl, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthyl, 1,1'-bin-2-naphthol, etc., which can be used alone or in combination of two or more.

[0105] <<Dicarboxylic acid component used in the thermoplastic resin having the structure represented by the above formula (1)>>

[0106] When the thermoplastic resin of the present invention is polyester carbonate, polyester or the like, the dicarboxylic acid component used is mainly a compound represented by formula (b) or an ester-forming derivative thereof.

[0107] [Chemical formula 11]

[0108]

[0109] In the above formula (b), Y is the same as in the above formula (3).

[0110] Representative specific examples of the dicarboxylic acid represented by the above formula (b) or its ester-forming derivative are shown below, but the raw material used for the above formula (b) of the present invention is not limited thereto.

[0111] Examples of the dicarboxylic acid component include aliphatic dicarboxylic acid components such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid; monocyclic aromatic dicarboxylic acid components such as phthalic acid, isophthalic acid, and terephthalic acid; 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, 9,9-bis(carboxymethyl)fluorene, 9,9-bis(2-carboxyethyl)fluorene, 9,9-bis(1-carboxyethyl)fluorene, 9,9-bis(1 The present invention also comprises a polycyclic aromatic dicarboxylic acid component such as 9,9-bis(2-carboxypropyl)fluorene, 9,9-bis(2-carboxypropyl)fluorene, 9,9-bis(2-carboxy-1-methylethyl)fluorene, 9,9-bis(2-carboxy-1-methylpropyl)fluorene, 9,9-bis(2-carboxybutyl)fluorene, 9,9-bis(2-carboxy-1-methylbutyl)fluorene, 9,9-bis(5-carboxypentyl)fluorene, and 9,9-bis(carboxycyclohexyl)fluorene; and an alicyclic dicarboxylic acid component such as 1,4-cyclohexanedicarboxylic acid and 2,6-decalinizedicarboxylic acid, preferably 2,6-naphthalenedicarboxylic acid and terephthalic acid, and more preferably terephthalic acid. In addition, as ester-forming derivatives, esters such as acid chloride, methyl ester, ethyl ester, and phenyl ester can be used, preferably dimethyl 2,6-naphthalene dicarboxylate and dimethyl terephthalate, and more preferably dimethyl terephthalate. Dimethyl terephthalate has a strong stable structure against oxidation and is advantageous in exhibiting long-term heat resistance. These can be used alone or in combination of two or more.

[0112] 《Production method of polycarbonate resin》

[0113] The polycarbonate resin can be obtained by a reaction method known per se, for example, by reacting a dihydroxy compound component with a carbonate precursor by a surface polymerization method or a melt polymerization method. When manufacturing the polycarbonate resin, a catalyst, a capping agent, an antioxidant, etc. can be used as required. It can be manufactured with reference to the record of International Publication No. 2017 / 078070.

[0114] In the melt polymerization method, a polymerization catalyst may be used to accelerate the polymerization rate, and examples of the polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, etc. As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alcoholates, quaternary ammonium hydroxides, etc. of alkali metals or alkaline earth metals are preferably used, and these compounds may be used alone or in combination.

[0115] Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt, dipotassium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, lithium salt of phenol, and the like. Preferred are sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, and lithium carbonate, and more preferred is sodium hydrogen carbonate.

[0116] 《Production method of polyester carbonate resin》

[0117] The polyester carbonate resin can be produced by a known reaction method, for example, by reacting a dihydroxy compound component with a dicarboxylic acid or an ester-forming derivative thereof, and a carbonate precursor such as phosgene or carbonate. The polyester carbonate resin can be produced by referring to the descriptions of Patent Documents 1 and 2.

[0118] In the melt polymerization method, a polymerization catalyst may be used to accelerate the polymerization rate. As the polymerization catalyst, aluminum or a catalyst composed of an aluminum compound and a phosphorus compound may be used. In this case, the amount may be 80 μmol or more, 90 μmol or more, or 100 μmol or less, or 1000 μmol or less, or 800 μmol or less, or 600 μmol or less relative to 1 mol of the total monomer units used.

[0119] As aluminum salts, organic acid salts and inorganic acid salts of aluminum can be cited. As organic acid salts of aluminum, for example, carboxylates of aluminum can be cited, specifically, aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, and aluminum salicylate can be cited. As inorganic acid salts of aluminum, for example, aluminum chloride, aluminum hydroxide, aluminum hydroxide chlorohydrate, aluminum carbonate, aluminum phosphate, and aluminum phosphonate can be cited. As aluminum chelate compounds, for example, aluminum acetylacetonate, aluminum acetoacetate, ethyl acetoacetate aluminum, and ethyl acetoacetate aluminum diisopropylate can be preferably cited, and aluminum acetylacetonate is further preferred.

[0120] Examples of phosphorus compounds include phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphinous acid compounds, phosphinous acid compounds, and phosphine compounds. Among these, phosphonic acid compounds, phosphinous acid compounds, and phosphine oxide compounds are particularly preferred, and phosphonic acid compounds are particularly preferred.

[0121] 《Production method of polyester resin》

[0122] In the case of a polyester resin, a high molecular weight body of a desired molecular weight can be formed by a known reaction method, for example, by subjecting a dihydroxy compound component to an esterification reaction or an ester exchange reaction with a dicarboxylic acid or an ester-forming derivative thereof, and subjecting the obtained reaction product to a polycondensation reaction. The production can be carried out with reference to the description of Japanese Patent Publication No. 2016-69643.

[0123] Release agent

[0124] The thermoplastic resin composition of the present invention contains a release agent. As the content of the release agent, it is preferred that the thermoplastic resin composition contains 1 to 4000 ppm, more preferably 10 to 3500 ppm, further preferably 50 to 3000 ppm, further preferably 80 to 2500 ppm, particularly preferably 300 to 2000 ppm, and most preferably 700 ppm to 2000 ppm. The inventors have found that by adding a release agent within the above range, not only the demolding property is improved, but also a higher long-term heat resistance can be exerted. It is believed that the long-term heat resistance is improved by suppressing oxidative degradation. Therefore, it is speculated that by allowing the release agent to exist in the resin, the polymer chain is protected from friction during resin mixing and molding processing to reduce the load, and the generation of unstable structures such as free radicals and peroxides that cause oxidative degradation can be suppressed, so that the long-term heat resistance is improved. In addition, by suppressing oxidative degradation during resin mixing and molding processing, the initial chromaticity is also improved.

[0125] Furthermore, within the above range, it is possible to suppress a decrease in the refractive index, a decrease in the total light transmittance, and dirt adhered to the metal mold due to an excessive amount of the release agent. It should be noted that in this specification, "ppm" means "ppm by mass".

[0126] As the release agent, one type of release agent may be used, or a plurality of release agents may be combined. When a plurality of release agents are used, the total amount of the release agents may be adjusted so as to fall within the above numerical range.

[0127] As the release agent used in the present invention, the release agent described in International Publication No. 2011 / 010741 can be preferably cited. As a particularly preferred release agent, a mixture of stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, stearic acid triglyceride and stearyl stearate can be preferably used. In addition, when the release agent is set to 100% by mass, the amount of the above ester in the release agent is preferably 90% by mass or more, more preferably 95% by mass or more.

[0128] Antioxidants

[0129] In the thermoplastic resin composition of the present invention, the content of the antioxidant contained in the thermoplastic resin composition is 0 to 300 ppm. The amount of the antioxidant contained in the thermoplastic resin composition is preferably 0 to 200 ppm, more preferably 0 to 100 ppm, further preferably 0 to 50 ppm, further preferably 0 to 10 ppm, particularly preferably 0 to 1 ppm, and most preferably 0 ppm. By making the antioxidant within the above range, long-term heat resistance is excellent. Since long-term heat resistance is improved by suppressing oxidative degradation, long-term heat resistance can be improved by reducing structures that can easily change, such as antioxidants, and adopting a chemical structure that is strongly stable to oxidation to construct a thermoplastic resin composition.

[0130] Specific examples of the antioxidant include those described in International Publication No. 2011 / 010741, including phosphorus-based antioxidants, sulfur-based antioxidants, and hindered phenol-based antioxidants.

[0131] Examples of the phosphorus antioxidant include tris(2,4-di-tert-butylphenyl)phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, distearylpentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, cycloneopentanatetraylbis(2,6-di-tert-butyl-4-methylphenylphosphite), and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite.

[0132] In addition, examples of sulfur-based antioxidants include pentaerythritol-tetrakis (3-laurylthiopropionate).

[0133] Examples of hindered phenol antioxidants include octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,

[0134] N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-cinnamic acid amide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane.

[0135] As long as the total amount of the antioxidants is within the above numerical range, a plurality of antioxidants may be contained.

[0136] 《Optional Additives》

[0137] The thermoplastic resin composition of the present invention may be used as a resin composition by appropriately adding additives such as ultraviolet absorbers, antistatic agents, flame retardants, plasticizers, fillers, lubricants, surfactants, antimicrobial agents, polymeric metal deactivators, compatibilizers, and colorants as needed.

[0138] The ultraviolet absorber is preferably at least one ultraviolet absorber selected from the group consisting of benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, cyclic imino ester ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers.

[0139] Among the benzotriazole-based ultraviolet absorbers, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole and 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] are more preferred.

[0140] Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

[0141] Examples of the triazine ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol.

[0142] As the cyclic iminoester-based ultraviolet absorber, 2,2′-p-phenylenebis(3,1-benzoxazin-4-one) is particularly preferred.

[0143] Examples of the cyanoacrylate ultraviolet absorber include 1,3-bis-[(2′-cyano-3′,3′-diphenylacryl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryl)oxy]benzene.

[0144] The amount of the ultraviolet absorber added is preferably 1,000 to 30,000 ppm based on the thermoplastic resin composition. Within the above range, sufficient durability can be imparted to a molded article of the thermoplastic resin composition depending on the intended use.

[0145] 《Method for producing thermoplastic resin composition》

[0146] The thermoplastic resin composition of the present invention is produced by adding a mold release agent and other additives to a thermoplastic resin having a structure represented by formula (1), and performing melt kneading.

[0147] The method for adding various additives is not particularly limited, and any method can be used. For example, it can be added in the polymerization stage of the thermoplastic resin, or it can be added after the thermoplastic resin is polymerized. When adding various additives to the thermoplastic resin, the additives can be added to the container containing the thermoplastic resin, or the thermoplastic resin can be added to the container pre-filled with the additives, or the thermoplastic resin and the additives can be added to the same container at the same time. Specifically, a drum mixer, Henschel mixer, ribbon blender, super mixer, roll mixer or drum mixer can be used to attach the additives to the granular thermoplastic resin. According to such a method of adding, the additives can be uniformly dispersed in the thermoplastic resin, so it is preferred. In addition, the granular thermoplastic resin and a part of the thermoplastic resin can be mixed with each other with particles formed by melt-kneading the additives at a high concentration. After adding various additives to the thermoplastic resin, the method for melt-kneading these is not particularly limited, and any method can be used. For example, melt kneading can be performed by a known kneading method such as a uniaxial or biaxial extruder, a Banbury mixer, a static mixer, etc. The pelletizing method is not particularly limited, and any method can be used.

[0148] 《Characteristics of thermoplastic resin compositions》

[0149] The thermoplastic resin composition of the present invention has excellent long-term heat resistance. In this specification, "excellent long-term heat resistance" means that the injection molded product has less yellowing before and after long-term high temperature exposure. Long-term heat resistance can be evaluated as follows: the thermoplastic resin composition is injection molded, and the obtained molded product is subjected to a dry heat test in a dry atmosphere at 120°C for 500 hours, and the color change before and after the test, i.e., the dry heat yellowing ΔYI, is measured. The dry heat yellowing ΔYI of a 2 mm thick molded product of the thermoplastic resin composition of the present invention is preferably 0.00 to 0.47, more preferably 0.00 to 0.40, further preferably 0.00 to 0.35, further preferably 0.00 to 0.30, further preferably 0.00 to 0.21, and most preferably 0.00 to 0.15. If the dry heat yellowing ΔYI is within the above range, the scope of use as various transparent parts is not limited, so it is preferred.

[0150] The thermoplastic resin composition of the present invention has a high refractive index nd and a low Abbe number νd. When the refractive index nd of the thermoplastic resin composition of the present invention is measured at a temperature of 20°C and a wavelength of 589 nm, it is 1.600 or more, and may be 1.610 or more, 1.620 or more, or 1.630 or more, or 1.680 or less, 1.670 or less, 1.660 or less, or 1.650 or less. For example, the refractive index nd of the thermoplastic resin of the present invention is 1.635 to 1.650, preferably 1.635 to 1.648, more preferably 1.635 to 1.646, further preferably 1.636 to 1.644, particularly preferably 1.636 to 1.642, and most preferably 1.636 to 1.641. When the refractive index is within the above range, the spherical aberration of the optical lens can be reduced, and the focal length of the optical lens can be shortened.

[0151] The Abbe number νd of the thermoplastic resin composition of the present invention may be 17.0 or more, 18.0 or more, 19.0 or more, 20.0 or more, or 21.0 or more, or 30.0 or less, 29.0 or less, 28.0 or less, 27.0 or less, 26.0 or less, or 25.0 or less. For example, the Abbe number νd of the thermoplastic resin composition of the present invention may be 21.0 to 26.0, 21.5 to 25.5, or 22.0 to 25.0.

[0152] Here, the Abbe number νd is calculated from the refractive index at temperature: 20°C, wavelength: 486.13nm, 587.56nm, 656.27nm using the following formula:

[0153] νd=(nd-1) / (nF-nC)

[0154] Meaning

[0155] nd: refractive index at a wavelength of 587.56nm,

[0156] nF: refractive index at a wavelength of 486.13nm,

[0157] nC: refractive index at a wavelength of 656.27nm.

[0158] The thermoplastic resin composition of the present invention has low orientation birefringence |Δn|. The absolute value of the orientation birefringence |Δn| of the thermoplastic resin composition of the present invention is preferably 6.0×10 -3 Below, more preferably 5.0×10 -3 Below, more preferably 4.0×10 -3 Below, the most preferred is 3.0×10 -3Below. If the orientation birefringence |Δn| is within the above range, the chromatic aberration will not be greatly affected, so the same performance as the optical design can be maintained. The orientation birefringence |Δn| is obtained by stretching a 100 μm thick cast film obtained from the thermoplastic resin by 2 times at Tg+10°C and then measuring the phase difference value at a wavelength of 589 nm and the film thickness.

[0159] The viscosity average molecular weight Mv of the thermoplastic resin composition of the present invention, when measured by the method described in the Examples, may be 5000 or more, 6000 or more, or 7000 or less, or 25000 or less, 20000 or less, or 15000 or less. For example, the viscosity average molecular weight Mv of the thermoplastic resin composition of the present invention may be 6000 to 20000, or 7000 to 15000.

[0160] The initial chromaticity YI can be evaluated by injection molding the thermoplastic resin composition and measuring the YI of the obtained molded product. The initial chromaticity YI of the 2 mm thick molded product of the thermoplastic resin composition of the present invention is preferably 7.0 or less, more preferably 6.0 or less, further preferably 5.5 or less, particularly preferably 5.0 or less, and most preferably 4.5 or less. If the initial chromaticity YI is within the above range, the scope of use as various transparent parts is not limited, so it is preferred.

[0161] <Mode II of the Invention>

[0162] Hereinafter, when describing the present invention, this refers to Embodiment II of the present invention.

[0163] (1) Thermoplastic resin composition

[0164] The thermoplastic resin composition of the present invention comprises a thermoplastic resin having a predetermined structure, a colorant and an antioxidant, wherein the content of the colorant in the thermoplastic resin composition is 0.01 to 4.00 ppm and the content of the antioxidant is 50 to 3000 ppm. The thermoplastic resin composition of the present invention has a high refractive index, low birefringence, and excellent transmittance and appearance due to such a configuration.

[0165] 《Thermoplastic Resins》

[0166] The thermoplastic resin used in the present invention has a structure represented by the above formula (4).

[0167] In the above formula (4), Z's are identical or different and represent an aromatic hydrocarbon ring, and examples thereof include a naphthalene ring and a benzene ring, and a benzene ring is preferred.

[0168] In the above formula (4), R 1 , R 2 , R3 and R 4 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and examples of the hydrocarbon group include an alkyl group, a cycloalkyl group and an aryl group.

[0169] Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group and the like, and a methyl group is preferred.

[0170] Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and bicyclo[1.1.1]pentenyl.

[0171] Examples of the aryl group include phenyl, tolyl, naphthyl, and xylyl, and a phenyl group is preferred.

[0172] R 1 , R 2 , R 3 and R 4 Each independently is preferably a hydrogen atom, a methyl group or a phenyl group, and more preferably a hydrogen atom.

[0173] In the above formula (4), L 1 and L 2 Each independently represents a divalent linking group, and examples thereof include an alkylene group having 1 to 4 carbon atoms, and preferably represents an ethylene group or a propylene group, and more preferably represents an ethylene group.

[0174] In the above formula (4), o and p each independently represent an integer of 0 or more, preferably 0 to 2, and more preferably 1.

[0175] In the above formula (4), X is at least one selected from the groups represented by the above formula (5) or (6).

[0176] In the above formula (6), Y represents a divalent linking group, and examples thereof include a hydrocarbon group having 1 to 25 carbon atoms, and examples of the hydrocarbon group include an olefin group, a cycloolefin group, and an arylene group.

[0177] Preferred examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferred.

[0178] In the above formula (4), the presence of an aromatic hydrocarbon ring has an effect of increasing the refractive index, and the presence of a cardo structure has an effect of reducing the birefringence.

[0179] Examples of the thermoplastic resin in the present invention include polycarbonate resins, polyester carbonate resins, and polyester resins. Polycarbonate resins and polyester carbonate resins are preferred, and polyester carbonate resins are more preferred.

[0180] The thermoplastic resin as a constituent component of the thermoplastic resin composition of the present invention preferably contains 50 mol% or more of the following formula (7) in the repeating unit represented by the above formula (4), more preferably 60 mol% or more, further preferably 70 mol% or more, and particularly preferably 80 mol% or more, based on the above formula (3).

[0181] [Chemical formula 12]

[0182]

[0183] In the above formula (4), Z, L 1 , L 2 ,o,p,R 1 , R 2 , R 3 and R 4 The same as the above formula (1).

[0184] <<Diol component used for the thermoplastic resin having the structure represented by the above formula (4)>>

[0185] The diol component used in the structural unit represented by the above formula (4) of the thermoplastic resin of the present invention is mainly a compound represented by the formula (a).

[0186] [Chemical formula 13]

[0187]

[0188] In the above formula (4) of the diol component, Z, L 1 , L 2 ,o,p,R 1 , R 2 , R 3 and R 4 The same as the above formula (4).

[0189] Representative specific examples of the diol component represented by the above formula (a) are shown below, but the raw material used for the above formula (a) in the present invention is not limited thereto.

[0190] Specific examples include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(hydroxymethoxy)phenyl)fluorene, 9,9-bis(4-(hydroxymethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(hydroxymethoxy)-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-phenylphenyl)fluorene, 9,9-bis(4-(3-hydroxypropoxy)phenyl)fluorene, 9,9-bis(4-(3-hydroxypropoxy)-3-methylphenyl)fluorene, 9,9-bis(4 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-dimethylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene, 9,9-bis(6-(hydroxymethoxy)-2-naphthyl)fluorene, 9,9-bis(6-(hydroxymethoxy)-2-naphthyl)fluorene, )-2,7-dimethylfluorene, 9,9-bis(6-(hydroxymethoxy)-2-naphthyl)-2,7-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-dimethylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-diphenylfluorene,

[0191] 9,9-bis(6-(3-hydroxypropoxy)-2-naphthyl)fluorene, 9,9-bis(6-(3-hydroxypropoxy)-2-naphthyl)-2,7-dimethylfluorene, 9,9-bis(6-(3-hydroxypropoxy)-2-naphthyl)-2,7-diphenylfluorene.

[0192] These may be used alone or in combination of two or more.

[0193] Among them, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, and 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene are preferred, and 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene is more preferred. 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene has a structure that contributes to high refractive index and low birefringence, and has a highly stable structure against thermal load, and is also advantageous in suppressing absorption in the short wavelength region of visible light due to thermal degradation.

[0194] <<Diol components other than the above formula (a)>>

[0195] The thermoplastic resin of the present invention has the structure of the above formula (4) derived from the diol component represented by the above formula (a), but may contain structures derived from other diol components within the range that does not impair the effects of the present invention. In the thermoplastic resin of the present invention, the diol component represented by the above formula (a) preferably accounts for 70 mol% or more of the total diol components, and more preferably 80 mol% or more.

[0196] Examples of other diol components include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, tricyclo[5.2.1.0 2，6 ]Decanedimethanol, cyclohexane-1,4-dimethanol, decahydronaphthalene-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spirodiol, isosorbide, isomannide, isoidide, hydroquinone, resorcinol, dihydroxynaphthalene, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1 bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, biphenol, 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(3-hydroxypropoxy)-1,1'-binaphthyl, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthyl, 1,1'-bin-2-naphthol, etc. These may be used alone or in combination of two or more.

[0197] <<Dicarboxylic acid component used in the thermoplastic resin having the structure represented by the above formula (4)>>

[0198] When the thermoplastic resin of the present invention is a polyester carbonate resin, a polyester resin or the like, the dicarboxylic acid component used is mainly a compound represented by formula (b) or an ester-forming derivative thereof.

[0199] [Chemical formula 14]

[0200]

[0201] In the above formula (b), Y is the same as in the above formula (6).

[0202] Representative specific examples of the dicarboxylic acid represented by the above formula (b) or its ester-forming derivative are shown below, but the raw material used for the above formula (b) of the present invention is not limited thereto.

[0203] Examples of the dicarboxylic acid component include aliphatic dicarboxylic acid components such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid; monocyclic aromatic dicarboxylic acid components such as phthalic acid, isophthalic acid, and terephthalic acid; 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, 9,9-bis(carboxymethyl)fluorene, 9,9-bis(2-carboxyethyl)fluorene, 9,9-bis(1-carboxyethyl)fluorene, 9,9-bis(1 The present invention also comprises a polycyclic aromatic dicarboxylic acid component such as 9,9-bis(2-carboxypropyl)fluorene, 9,9-bis(2-carboxypropyl)fluorene, 9,9-bis(2-carboxy-1-methylethyl)fluorene, 9,9-bis(2-carboxy-1-methylpropyl)fluorene, 9,9-bis(2-carboxybutyl)fluorene, 9,9-bis(2-carboxy-1-methylbutyl)fluorene, 9,9-bis(5-carboxypentyl)fluorene, and 9,9-bis(carboxycyclohexyl)fluorene; and an alicyclic dicarboxylic acid component such as 1,4-cyclohexanedicarboxylic acid and 2,6-decalinizedicarboxylic acid, preferably 2,6-naphthalenedicarboxylic acid and terephthalic acid, and more preferably terephthalic acid. In addition, as ester-forming derivatives, esters such as acid chloride, methyl ester, ethyl ester, and phenyl ester can be used, preferably dimethyl 2,6-naphthalene dicarboxylate and dimethyl terephthalate, and more preferably dimethyl terephthalate. Dimethyl terephthalate has a strong thermally stable structure, which is beneficial for suppressing the absorption of the visible light short wavelength region around 400nm caused by thermal degradation. These can be used alone or in combination of two or more.

[0204] 《Production method of polycarbonate resin》

[0205] The polycarbonate resin can be obtained by a reaction method known per se, such as reacting a dihydroxy compound component with a carbonate precursor by a surface polymerization method or a melt polymerization method. When manufacturing the polycarbonate resin, a catalyst, a capping agent, an antioxidant, etc. can be used as needed. It can be manufactured with reference to the record of International Publication No. 2017 / 078070.

[0206] In the melt polymerization method, a polymerization catalyst may be used to accelerate the polymerization rate, and examples of the polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, etc. As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alcoholates, quaternary ammonium hydroxides, etc. of alkali metals or alkaline earth metals may be preferably used, and these compounds may be used alone or in combination.

[0207] Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt, dipotassium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, lithium salt of phenol, and the like. Preferred are sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, and lithium carbonate, and more preferred is sodium hydrogen carbonate.

[0208] 《Production method of polyester carbonate resin》

[0209] The polyester carbonate resin can be produced by a known reaction method, for example, by reacting a dihydroxy compound component with a dicarboxylic acid or an ester-forming derivative thereof and a carbonate precursor such as phosgene or a carbonate ester. The polyester carbonate resin can be produced by referring to the descriptions of Patent Documents 1 and 2.

[0210] In the melt polymerization method, a polymerization catalyst may be used to accelerate the polymerization rate. As the polymerization catalyst, a catalyst composed of aluminum or a compound thereof and a phosphorus compound may be used. In this case, the amount may be 80 μmol or more, 90 μmol or more, or 100 μmol or less, or 1000 μmol or less, or 800 μmol or less, or 600 μmol or less relative to 1 mol of the total monomer units used.

[0211] As aluminum salts, organic acid salts and inorganic acid salts of aluminum can be cited. As organic acid salts of aluminum, for example, carboxylates of aluminum can be cited, specifically, aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, and aluminum salicylate can be cited. As inorganic acid salts of aluminum, for example, aluminum chloride, aluminum hydroxide, aluminum hydroxide chlorohydrate, aluminum carbonate, aluminum phosphate, and aluminum phosphonate can be cited. As aluminum chelate compounds, for example, aluminum acetylacetonate, aluminum acetoacetate, ethyl acetoacetate aluminum, and ethyl acetoacetate aluminum diisopropylate can be preferably cited, and aluminum acetylacetonate is more preferably cited.

[0212] Examples of phosphorus compounds include phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphinous acid compounds, phosphinous acid compounds, and phosphine compounds. Among these, phosphonic acid compounds, phosphinous acid compounds, and phosphine oxide compounds are particularly preferred, and phosphonic acid compounds are particularly preferred.

[0213] 《Production method of polyester resin》

[0214] In the case of a polyester resin, a high molecular weight body of a desired molecular weight can be formed by a known reaction method, for example, by subjecting a dihydroxy compound component to an esterification reaction or an ester exchange reaction with a dicarboxylic acid or an ester-forming derivative thereof, and subjecting the obtained reaction product to a polycondensation reaction. The preparation can be made with reference to the description of Japanese Patent Publication No. 2016-69643.

[0215] Colorants

[0216] The thermoplastic resin composition of the present invention contains a colorant. As the content of the colorant, it is preferred that the thermoplastic resin composition contains 0.01 to 4.00 ppm, more preferably 0.50 to 3.50 ppm, further preferably 0.80 to 3.00 ppm, further preferably 1.00 to 2.75 ppm, particularly preferably 1.20 to 2.50 ppm, and most preferably 1.40 to 2.25 ppm. The inventors have found that by adding a colorant within the above range, it is possible to achieve high transmission of visible light with good balance (400 nm light transmittance, 580 nm light transmittance, and high total light transmittance) and eliminate the yellow hue peculiar to high refractive index optical resins, thereby presenting an excellent appearance of a blue-green system color like glass.

[0217] Furthermore, within the above range, it is possible to suppress the degradation of the transmission balance of visible light and the reduction of transmittance due to an excessive amount of the colorant. In addition, in this specification, "ppm" means "ppm by mass".

[0218] As the colorant, one colorant may be used, or a combination of a plurality of colorants may be used. When a plurality of colorants are used, the total amount of the colorants may be adjusted so as to fall within the above numerical range.

[0219] As the colorant, any colorant that is used for polycarbonate, polyester carbonate, or polyester can be used without any particular problem.

[0220] As the colorant used in the present invention, anthraquinone dyes are preferred, and specific examples thereof include Solvent Violet 13 (CA No. 60725; trade name: Macrolex Violet B manufactured by LANXESS), Solvent Violet 36 (trade name: Macrolex Violet 3R manufactured by LANXESS), Solvent Blue 97 (CA No. 615290; trade name: Macrolex Blue RR manufactured by LANXESS), and Solvent Blue 45 (trade name: Polysynthren Blue 50 manufactured by Clariant). RLS (Polysynthren Blue RLS)"], etc., and more preferably Solvent Blue 45 (trade name: "Polysynthren Blue RLS (Polysynthren Blue RLS)" manufactured by Clariant) is a common name.

[0221] The generic name Solvent Blue 45 [trade name: "Polysynthren Blue RLS" manufactured by Clariant] has a high thermal decomposition temperature and does not fade during extrusion and molding. Even if it is added during the polymerization stage of the resin, it does not affect the reaction and can color the thermoplastic resin composition in a balanced manner. In this coloring, the yellow hue of the thermoplastic resin composition can be suppressed and a blue-green system color like glass can be presented, and the appearance is excellent. On the other hand, since it absorbs light in the wavelength region of visible light near 580nm, a large amount of addition will cause a decrease in the 580nm light transmittance and a decrease in the total light transmittance.

[0222] Antioxidants

[0223] In the thermoplastic resin composition of the present invention, the content of the antioxidant contained in the thermoplastic resin composition is 50 to 3000 ppm. The amount of the antioxidant contained in the thermoplastic resin composition is preferably 50 to 3000 ppm, more preferably 100 to 2500 ppm, further preferably 200 to 2000 ppm, further preferably 300 to 1500 ppm, particularly preferably 400 to 1200 ppm, and most preferably 500 to 1000 ppm. By making the antioxidant within the above range, thermal degradation can be effectively prevented, and the transmittance reduction in the visible light short wavelength region near 400 nm can be suppressed to maintain high transmittance, while yellowing of chromaticity can be prevented. In addition, if it is within the above range, the reduction in refractive index, the reduction in transmittance, and the adhesion of dirt to the metal mold caused by excessive amount of antioxidant can be suppressed.

[0224] Specific examples of the antioxidant include those described in International Publication No. 2011 / 010741, including phosphorus-based antioxidants, sulfur-based antioxidants, and hindered phenol-based antioxidants.

[0225] Examples of the phosphorus antioxidant include tris(2,4-di-tert-butylphenyl)phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, distearylpentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, cycloneopentanatetraylbis(2,6-di-tert-butyl-4-methylphenylphosphite), and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite.

[0226] In addition, examples of sulfur-based antioxidants include pentaerythritol-tetrakis (3-laurylthiopropionate).

[0227] Examples of hindered phenol antioxidants include octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris(3, 5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-cinnamic acid), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane.

[0228] As long as the total amount of the antioxidants is within the above-mentioned numerical range, a plurality of antioxidants may be contained.

[0229] Among them, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, distearylpentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, cyclic neopentanetetraylbis(2,6-di-tert-butyl-4-methylphenylphosphite), and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite are preferred, and cyclic neopentanetetraylbis(2,6-di-tert-butyl-4-methylphenylphosphite is more preferred. Cyclic neopentanetetraylbis(2,6-di-tert-butyl-4-methylphenylphosphite) has excellent oxygen capture capability from peroxides and can suppress a decrease in transmittance in the visible light short wavelength region of around 400 nm due to thermal degradation of the thermoplastic resin composition even in a small amount.

[0230] 《Optional Additives》

[0231] The thermoplastic resin composition of the present invention may be used as a resin composition by appropriately adding additives such as a release agent, ultraviolet absorber, antistatic agent, flame retardant, plasticizer, filler, lubricant, surfactant, antibacterial agent, polymer metal deactivator, compatibilizer, and colorant as needed.

[0232] As the release agent used in the present invention, the release agent described in International Publication No. 2011 / 010741 can be preferably cited. As particularly preferred release agents, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate can be preferably used. In addition, when the release agent is set to 100% by mass, the amount of the above ester in the release agent is preferably 90% by mass or more, and more preferably 95% by mass or more.

[0233] As the ultraviolet absorber, at least one ultraviolet absorber selected from the group consisting of benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, cyclic imino ester ultraviolet absorbers and cyanoacrylate ultraviolet absorbers is preferred.

[0234] Among the benzotriazole-based ultraviolet absorbers, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole and 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] are more preferred.

[0235] Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

[0236] Examples of the triazine ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol.

[0237] As the cyclic iminoester-based ultraviolet absorber, 2,2′-p-phenylenebis(3,1-benzoxazin-4-one) is particularly preferred.

[0238] Examples of the cyanoacrylate ultraviolet absorber include 1,3-bis-[(2′-cyano-3′,3′-diphenylacryl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryl)oxy]benzene.

[0239] The amount of the ultraviolet absorber added is preferably 1,000 to 30,000 ppm based on the thermoplastic resin composition. Within the above range, sufficient durability can be imparted to a molded article of the thermoplastic resin composition depending on the intended use.

[0240] 《Method for producing thermoplastic resin composition》

[0241] The thermoplastic resin composition of the present invention can be produced by adding a colorant, an antioxidant and other additives to a thermoplastic resin having a structure represented by formula (4) and melt-kneading the mixture.

[0242] The method for adding various additives is not particularly limited, and any method can be used. For example, it can be added in the polymerization stage of the thermoplastic resin, or it can be added after the thermoplastic resin is polymerized. When adding various additives to the thermoplastic resin, the additive can be added to the container containing the thermoplastic resin, or the thermoplastic resin can be added to the container pre-filled with the additive, or the thermoplastic resin and the additive can be added to the same container simultaneously. Specifically, a drum mixer, Henschel mixer, ribbon blender, super mixer, roll mixer or drum mixer can be used to attach the additive to the granular thermoplastic resin. According to such a method of adding, the additive can be uniformly dispersed in the thermoplastic resin, so it is preferred. In addition, the granular thermoplastic resin and a part of the thermoplastic resin can be mixed with each other with particles formed by melt-kneading the additive at a high concentration. After adding various additives to the thermoplastic resin, the method for melt-kneading these is not particularly limited, and any method can be used. For example, melt kneading can be performed by a known kneading method such as a uniaxial or biaxial extruder, a Banbury mixer, a static mixer, etc. The pelletizing method is not particularly limited, and any method can be used.

[0243] The addition of the colorant in the polymerization step is preferred because a uniform thermoplastic resin composition free of color unevenness can be obtained.

[0244] 《Characteristics of thermoplastic resin compositions》

[0245] The thermoplastic resin composition of the present invention has a high refractive index and low birefringence, and has excellent transmittance and excellent appearance. In this specification, "excellent transmittance" means that the transmittance of visible light is high and the transmittance balance is well-balanced, and "excellent appearance" means that there is no yellow tint but a blue-green system color like glass.

[0246] The height of the transmittance of visible light can be evaluated by measuring the total light transmittance of the molded body obtained by injection molding the thermoplastic resin composition. The total light transmittance of the 2 mm thick molded product of the thermoplastic resin composition of the present invention is preferably 86.5% or more, more preferably 87.0% or more, further preferably 87.2% or more, particularly preferably 87.4% or more, further preferably 87.6% or more, and most preferably 87.8% or more. If the total light transmittance is within the above range, the scope of use as various transparent parts is not limited, so it is preferred. For example, in the case of an optical part such as an optical lens, the brightness of the image formed will become brighter, so it is preferred.

[0247] Transmission balance can be evaluated by measuring the light transmittance at 400 nm in the short wavelength region of visible light that changes due to thermal degradation and the light transmittance at 580 nm in the medium wavelength region of visible light that changes due to absorption of the colorant for the molded body obtained by injection molding of the thermoplastic resin composition. The light transmittance at 400 nm of a 2 mm thick molded plate of the thermoplastic resin composition of the present invention is preferably 81.0% or more, more preferably 81.2% or more, further preferably 81.4% or more, further preferably 81.6% or more, further preferably 81.8% or more, and most preferably 82.0% or more. The light transmittance at 580 nm of a 2 mm thick molded plate of the thermoplastic resin composition of the present invention is preferably 85.0% or more, more preferably 85.4% or more, further preferably 85.8% or more, further preferably 86.0% or more, further preferably 86.2% or more, and most preferably 86.4% or more. If the light transmittance at 400nm and 580nm is within the above range, the transmittance in both the short-wavelength region and the medium- and long-wavelength region of visible light is high and the transmittance balance is excellent, and the scope of use as various transparent components is not limited. Therefore, it is preferred. For example, in the case of optical components such as optical lenses, it is preferred because there is no loss of specific wavelengths and light can be transmitted correctly.

[0248] The chromaticity can be evaluated by measuring the color of a molded body obtained by injection molding the thermoplastic resin composition and using a* and b* in the CIE (1976) L*a*b* color space. The a* of a 2 mm thick molded plate of the thermoplastic resin composition of the present invention is preferably -0.40 to 0.00, more preferably -0.35 to -0.05, further preferably -0.30 to -0.10, further preferably -0.25 to -0.15, further preferably -0.24 to -0.16, and most preferably -0.23 to -0.17.

[0249] The b* of a 2 mm thick molded plate of the thermoplastic resin composition of the present invention is preferably -0.50 to 1.25, more preferably -0.30 to 1.10, further preferably -0.10 to 1.00, further preferably 0.20 to 0.90, further preferably 0.30 to 0.85, and most preferably 0.40 to 0.80.

[0250] If a* and b* are within the above ranges, the excellent appearance of a blue-green system color like glass without a yellow tint will be achieved, thereby expanding the use of various transparent parts. For example, in the case of optical parts such as optical lenses, especially in uses where people directly recognize the parts, the excellent appearance can give a good impression, so it is preferred.

[0251] The thermoplastic resin composition of the present invention has a high refractive index nd and a low Abbe number νd. The refractive index nd of the thermoplastic resin composition of the present invention is 1.600 or more when measured at a temperature of 20°C and a wavelength of 589 nm, and may be 1.610 or more, 1.620 or more, or 1.630 or less, 1.680 or less, 1.670 or less, 1.660 or less, or 1.650 or less. For example, the refractive index nd of the thermoplastic resin of the present invention is 1.635 to 1.650, preferably 1.635 to 1.648, more preferably 1.635 to 1.646, further preferably 1.636 to 1.644, particularly preferably 1.636 to 1.642, and most preferably 1.636 to 1.641. When the refractive index is within the above range, the spherical aberration of the optical lens can be reduced, and the focal length of the optical lens can be shortened.

[0252] The Abbe number νd of the thermoplastic resin composition of the present invention may be 17.0 or more, 18.0 or more, 19.0 or more, 20.0 or more, or 21.0 or more, or 30.0 or less, 29.0 or less, 28.0 or less, 27.0 or less, 26.0 or less, or 25.0 or less. For example, the Abbe number νd of the thermoplastic resin composition of the present invention may be 21.0 to 26.0, 21.5 to 25.5, or 22.0 to 25.0.

[0253] Here, the Abbe number νd is calculated from the refractive index at a temperature of 20°C and wavelengths of 486.13 nm, 587.56 nm, and 656.27 nm using the following formula:

[0254] νd=(nd-1) / (nF-nC)

[0255] Meaning

[0256] nd: refractive index at a wavelength of 587.56nm,

[0257] nF: refractive index at a wavelength of 486.13nm,

[0258] nC: refractive index at a wavelength of 656.27nm.

[0259] The thermoplastic resin composition of the present invention has low orientation birefringence |Δn|. The absolute value of the orientation birefringence |Δn| of the thermoplastic resin composition of the present invention is preferably 6.0×10 -3 Below, more preferably 5.0×10 -3 Below, more preferably 4.0×10 -3 Below, the most preferred is 3.0×10 -3If the orientation birefringence |Δn| is within the above range, the chromatic aberration will not be greatly affected, so the same performance as the optical design can be maintained. The orientation birefringence |Δn| is obtained by stretching a 100 μm thick cast film obtained from the thermoplastic resin by 2 times at Tg+10°C and then measuring the phase difference value at a wavelength of 589 nm and the film thickness.

[0260] The viscosity average molecular weight Mv of the thermoplastic resin composition of the present invention, when measured by the method described in the Examples, may be 5000 or more, 6000 or more, or 7000 or less, or 25000 or less, 20000 or less, or 15000 or less. For example, the viscosity average molecular weight Mv of the thermoplastic resin composition of the present invention may be 6000 to 20000, or 7000 to 15000.

[0261] The chromaticity L* of a 2 mm thick molded plate of the thermoplastic resin composition of the present invention is preferably 90.0% or more, more preferably 91.0% or more, further preferably 92.0% or more, further preferably 94.0% or more, further preferably 94.5% or more, and most preferably 95.0% or more. When L* is within the above range, the color tone is bright and the appearance is good, and the range of use as various transparent parts is not limited, so it is preferred.

[0262] The yellowness index YI of a 2 mm thick molded plate of the thermoplastic resin composition of the present invention is preferably 3.0 or less, more preferably 2.8 or less, further preferably 2.6 or less, further preferably 2.4 or less, further preferably 2.2 or less, and most preferably 2.0 or less. If the YI is within the above range, the yellow tint is small and the appearance is good, and the use as various transparent parts is not limited, so it is preferred.

[0263] <Optical component and optical lens according to aspects I and II of the present invention>

[0264] (2) Optical components

[0265] The optical component of the embodiment I or embodiment II of the present invention comprises the above-mentioned thermoplastic resin composition, respectively. As such an optical component, there is no particular limitation as long as the above-mentioned thermoplastic resin composition can be used for useful optical purposes, and examples thereof include optical lenses, light guide plates, optical disks, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, hard coating films, and the like.

[0266] In addition, the optical component of mode I or mode II of the present invention can be composed of a resin composition comprising the above-mentioned thermoplastic resin composition, and additives such as heat stabilizers, antioxidants, plasticizers, light stabilizers, polymer metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, and release agents can be added to the resin composition as needed.

[0267] (3) Optical lens

[0268] As the optical component of the mode I or mode II of the present invention, an optical lens can be particularly mentioned. Such an optical lens can be mentioned as an imaging lens used in mobile phones, smart phones, tablet terminals, personal computers, digital cameras, video cameras, car cameras, surveillance cameras, etc.; sensor cameras such as TOF cameras; and lenses used in AR / VR devices represented by smart glasses and head-mounted displays.

[0269] When the optical lens of mode I or mode II of the present invention is manufactured by injection molding, it is preferably molded under the conditions of a cylinder temperature of 230 to 350°C and a metal mold temperature of 70 to 180°C. It is further preferred that the molding is performed under the conditions of a cylinder temperature of 250 to 300°C and a metal mold temperature of 80 to 170°C. When the cylinder temperature is higher than 350°C, the thermoplastic resin composition will decompose and color, and when it is lower than 230°C, the melt viscosity is high and it becomes difficult to mold. In addition, when the metal mold temperature is higher than 180°C, the molded sheet composed of the thermoplastic resin composition becomes difficult to remove from the metal mold. On the other hand, if the metal mold temperature is less than 70°C, the resin in the metal mold during molding will quickly become too hard and it will become difficult to control the shape of the molded sheet, and it will become difficult to fully transfer the shaping given by the metal mold.

[0270] The optical lens of mode I or mode II of the present invention is preferably implemented in the form of using an aspherical lens as required. Since the aspherical lens can make the spherical aberration substantially zero with one lens, it is not necessary to remove the spherical aberration by combining multiple spherical lenses, thereby becoming lightweight and reducing molding costs.

[0271] In addition, the thermoplastic resin composition of the mode I or mode II of the present invention has high molding fluidity and is therefore particularly useful as a material for an optical lens of a complex shape. As a specific lens size, the thickness of the center portion is 0.05 to 10.0 mm, more preferably 0.05 to 8.0 mm, and further preferably 0.1 to 6.0 mm. In addition, the diameter is 1.0 mm to 100.0 mm, more preferably 1.0 to 80.0 mm, and further preferably 1.0 to 60.0 mm. In addition, as its shape, it is preferably a meniscus lens with one side convex and one side concave.

[0272] The lens made of thermoplastic resin according to aspect I or aspect II of the present invention can be molded by any method such as metal mold molding, cutting, grinding, laser processing, electrical discharge machining, etching, etc. Among them, metal mold molding is more preferred from the viewpoint of production cost.

[0273] Example

[0274] The present invention will be further specifically described with reference to the following examples, but the present invention is not limited thereto.

[0275] Evaluation Method

[0276] 〈Refractive index nd〉

[0277] A 3 mm thick plate of each thermoplastic resin composition was prepared, cut and polished, and then the refractive index nd (587.56 nm) was measured using a Kalneur precision refractometer KPR-2000 manufactured by Shimadzu Corporation.

[0278] 〈Abbe number νd〉

[0279] The measurement wavelength of the Abbe number is calculated using the following formula from the refractive indices at 486.13 nm, 587.56 nm, and 656.27 nm.

[0280] νd=(nd-1) / (nF-nC)

[0281] Meaning

[0282] nd: refractive index at a wavelength of 587.56nm,

[0283] nF: refractive index at a wavelength of 486.13nm,

[0284] nC: refractive index at a wavelength of 656.27nm.

[0285] 〈Initial Chroma YI〉

[0286] A 2 mm thick plate of each thermoplastic resin composition was prepared, and the YI was measured using a color and turbidity simultaneous measuring device COH 400 (D65 light source, 10° field of view) manufactured by Nippon Denshoku Industries Co., Ltd.

[0287] 〈Dry heat yellowing ΔYI〉

[0288] A 2 mm thick plate of each thermoplastic resin composition was prepared and subjected to a dry heat test in a dry atmosphere at 120° C. for 500 hours. The YI before and after the test was measured using a color and turbidity simultaneous measuring device COH 400 (D65 light source, 10° field of view) manufactured by Nippon Denshoku Industries Co., Ltd., and the dry heat yellowing ΔYI was calculated using the following formula.

[0289] Dry heat yellowing ΔYI = YI after dry heat test - YI before dry heat test

[0290] 〈Chroma L*, a*, b*〉

[0291] A 2 mm thick plate of the thermoplastic resin composition was prepared, and L*, a*, and b* were measured using a color and turbidity simultaneous measuring device COH 400 (D65 light source, 10° viewing field) manufactured by Nippon Denshoku Industries Co., Ltd.

[0292] 〈Yellowness YI〉

[0293] A 2 mm thick plate of the thermoplastic resin composition was prepared, and the YI was measured using a color and turbidity simultaneous measuring device COH 400 (D65 light source, 10° viewing field) manufactured by Nippon Denshoku Industries Co., Ltd.

[0294] 〈Total light transmittance Tt〉

[0295] A 2 mm thick plate of the thermoplastic resin composition was prepared, and Tt (%) was measured using a color and turbidity simultaneous measuring instrument COH 400 (D65 light source, 10° field of view) manufactured by Nippon Denshoku Industries Co., Ltd. <400 nm light transmittance and 580 nm light transmittance>

[0296] A 2 mm thick plate of the thermoplastic resin composition was prepared, and the transmittance (%) of light at 400 nm and the transmittance (%) of light at 580 nm were measured using an ultraviolet-visible-near-infrared spectrophotometer V-770EX manufactured by JASCO Corporation.

[0297] 〈Viscosity average molecular weight Mv〉

[0298] The viscosity average molecular weight of the thermoplastic resin composition was measured by the following method: 0.7 g of the thermoplastic resin composition was dissolved in 100 ml of dichloromethane, and the specific viscosity (ηsp) of the solution at 20° C. Then, Mv calculated by the following formula was defined as the viscosity average molecular weight.

[0299] ηsp / c=[η]+0.45×[η] 2 c

[0300] [η] = 1.23 × 10 -4 Mv 0.83

[0301] ηsp: specific viscosity

[0302] η: intrinsic viscosity

[0303] c: constant (=0.7)

[0304] Mv: viscosity average molecular weight

[0305] 〈Absolute value of orientation birefringence |Δn|〉

[0306] The thermoplastic resin composition was dissolved in dichloromethane, cast on a glass petri dish and dried thoroughly to prepare a cast film with a thickness of 100 μm. The film was stretched 2 times at Tg+10°C, and the phase difference (Re) at 589 nm was measured using an ellipsometer M-220 manufactured by JASCO Corporation, and the absolute value of the oriented birefringence (|Δn|) was calculated using the following formula.

[0307] |Δn|=|Re / d|

[0308] Δn: Orientation birefringence

[0309] Re: Phase difference (nm)

[0310] d: thickness (nm)

[0311] <Aspect I of the present invention>

[0312] <Synthesis Example 1> (Production of polyester carbonate resin (PEC1))

[0313] 82.0 mol of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (hereinafter, sometimes referred to as BPEF), 18.0 mol of dimethyl terephthalate (hereinafter, sometimes referred to as DMT), 71.0 mol of diphenyl carbonate (hereinafter, sometimes referred to as DPC), 1.5×10 -2 mol and 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester (hereinafter, sometimes referred to as Cat.P) 3.0×10 -2 mol was added into a reaction kettle equipped with a stirrer and a distillation device, and after nitrogen substitution three times, the jacket was heated to 200°C to melt the raw materials.

[0314] After complete dissolution, the pressure was reduced to 40 kPa over 20 minutes. The temperature was then raised to 260°C, the pressure was reduced to below 0.13 kPa, and the polymerization reaction was carried out until the specified stirring torque was reached. After the reaction was completed, the generated resin was granulated and extracted to obtain particles of polyester carbonate resin (PEC1). The Mv of the obtained polyester carbonate resin (PEC1) was 10100.

[0315] <Synthesis Example 2> (Production of polyester carbonate resin (PEC2))

[0316] Referring to Example 4 of Patent Document 1, 90.0 mol of BPEF, 10.0 mol of DMT, 84.0 mol of DPC, and 1.0×10 -2mol was added into a reaction kettle equipped with a stirrer and a distillation device, and after nitrogen substitution three times, the jacket was heated to 180°C to melt the raw materials.

[0317] After complete dissolution, the pressure was reduced to 30 kPa over 20 minutes. The temperature was then raised to 250°C, the pressure was reduced to below 0.13 kPa, and the polymerization reaction was carried out until the specified stirring torque was reached. After the reaction was completed, the generated resin was granulated and extracted to obtain particles of polyester carbonate resin (PEC2). The Mv of the obtained polyester carbonate resin (PEC2) was 10,800.

[0318] <Synthesis Example 3> (Production of polycarbonate resin (PC1))

[0319] BPEF 100.0 mol, DPC 104.0 mol and sodium bicarbonate (hereinafter, sometimes referred to as Cat.Na) 6.0×10 - 4 mol (sodium bicarbonate is added in the form of a 0.1 wt% aqueous solution) was added to a reactor equipped with a stirrer and a distillation device, and after nitrogen substitution was performed three times, the jacket was heated to 200°C to melt the raw materials.

[0320] After complete dissolution, the pressure was reduced to 40 kPa over 20 minutes. The temperature was then raised to 240°C, the pressure was reduced to below 0.13 kPa, and the polymerization reaction was carried out until the specified stirring torque was reached. After the reaction was completed, the generated resin was granulated and extracted to obtain particles of polycarbonate resin (PC1). The Mv of the obtained polycarbonate resin (PC1) was 9800.

[0321] <Example 1>

[0322] The polyester carbonate resin (PEC1) obtained in Synthesis Example 1 and stearic acid monoglyceride [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent are mixed in the mass ratio shown in Table 1, and after being fully mixed, melt-kneaded at 270°C and exhaust pressure of 30 mmHg using an extruder (TEX30α30mmφ twin-screw extruder manufactured by Nippon Steel Works). After the thermoplastic resin composition obtained by melt kneading is extruded into a filament bundle, it is pelletized using a pelletizer to obtain pellets of the thermoplastic resin composition. The Mv of the pellets is 9800. The pellets are injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body is transparent. The evaluation results are shown in Table 1.

[0323] <Example 2>

[0324] The polyester carbonate resin (PEC1) obtained in Synthesis Example 1 and the release agent Rikemal S-100A are mixed in the mass ratio shown in Table 1, and after being fully mixed, melt-kneading is performed at 270°C and an exhaust pressure of 30 mmHg using an extruder (TEX30α30mmφ twin-screw extruder manufactured by Nippon Steel Works). After the thermoplastic resin composition obtained by melt kneading is extruded into a filament bundle, it is granulated using a granulator to obtain particles of the thermoplastic resin composition. The Mv of the particles is 9800. The particles are injection molded at 280°C to obtain 2 mm thick and 3 mm thick plate-shaped molded sheets. The molded body is transparent. The evaluation results are shown in Table 1.

[0325] <Example 3>

[0326] The polyester carbonate resin (PEC1) obtained in Synthesis Example 1 and the release agent Rikemal S-100A are mixed in the mass ratio shown in Table 1, and after being fully mixed, melt-kneading is performed at 270°C and an exhaust pressure of 30 mmHg using an extruder (TEX30α30mmφ twin-screw extruder manufactured by Nippon Steel Works). After the thermoplastic resin composition obtained by melt kneading is extruded into a filament bundle, it is granulated using a granulator to obtain particles of the thermoplastic resin composition. The Mv of the particles is 9900. The particles are injection molded at 280°C to obtain 2 mm thick and 3 mm thick plate-shaped molded pieces. The molded body is transparent. The evaluation results are shown in Table 1.

[0327] <Example 4>

[0328] The polyester carbonate resin (PEC1) obtained in Synthesis Example 1 and the release agent Rikemal S-100A are mixed in the mass ratio shown in Table 1, and after being fully mixed, melt-kneading is performed at 270°C and an exhaust pressure of 30 mmHg using an extruder (TEX30α30mmφ twin-screw extruder manufactured by Nippon Steel Works). After the thermoplastic resin composition obtained by melt kneading is extruded into a filament bundle, it is granulated using a granulator to obtain particles of the thermoplastic resin composition. The Mv of the particles is 9800. The particles are injection molded at 280°C to obtain 2 mm thick and 3 mm thick plate-shaped molded sheets. The molded body is transparent. The evaluation results are shown in Table 1.

[0329] <Example 5>

[0330] The polycarbonate resin (PC1) obtained in Synthesis Example 3 and the release agent Rikemal S-100A are mixed in the mass ratio shown in Table 1, and after being fully mixed, melt-kneading is performed at 270°C and an exhaust pressure of 30 mmHg using an extruder (TEX30α30mmφ twin-screw extruder manufactured by Nippon Steel Works). After the thermoplastic resin composition obtained by melt kneading is extruded into a filament bundle, it is pelletized using a pelletizer to obtain pellets of the thermoplastic resin composition. The Mv of the pellets is 9600. The pellets are injection molded at 280°C to obtain 2 mm thick and 3 mm thick plate-shaped molded sheets. The molded body is transparent. The evaluation results are shown in Table 1.

[0331] <Example 6>

[0332] The polyester carbonate resin (PEC1) obtained in Synthesis Example 1, the release agent Rikemal S-100A, and the cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant were mixed in the mass ratio shown in Table 1, and then melt-kneaded at 270°C and an exhaust pressure of 30 mmHg using an extruder (TEX30α30mmφ twin-screw extruder manufactured by Nippon Steel Works). After the thermoplastic resin composition obtained by melt kneading is extruded into a filament bundle, it is pelletized using a pelletizer to obtain pellets of the thermoplastic resin composition. The Mv of the pellets is 9900. The pellets are injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body is transparent. The evaluation results are shown in Table 1.

[0333] <Comparative Example 1>

[0334] The polyester carbonate resin (PEC1) obtained in Synthesis Example 1, the release agent Rikemal S-100A and the antioxidant PEP-36 are mixed in the mass ratio shown in Table 1, and after being fully mixed, melt-kneaded at 270°C and an exhaust pressure of 30 mmHg using an extruder (TEX30α30mmφ twin-screw extruder manufactured by Nippon Steel Works). After the thermoplastic resin composition obtained by melt kneading is extruded into a filament bundle, it is granulated using a granulator to obtain pellets of the thermoplastic resin composition. The Mv of the pellets is 9900. The pellets are injection molded at 280°C to obtain 2 mm thick and 3 mm thick plate-shaped molded sheets. The molded body is transparent. The evaluation results are shown in Table 1.

[0335] <Comparative Example 2>

[0336] The polycarbonate resin (PC1) obtained in Synthesis Example 3, the release agent Rikemal S-100A and the antioxidant PEP-36 are mixed in the mass ratio shown in Table 1, and after being fully mixed, melt-kneaded at 270°C and an exhaust pressure of 30 mmHg using an extruder (TEX30α30mmφ twin-screw extruder manufactured by Nippon Steel Works). After the thermoplastic resin composition obtained by melt kneading is extruded into a filament bundle, it is pelletized using a pelletizer to obtain pellets of the thermoplastic resin composition. The Mv of the pellets is 9700. The pellets are injection molded at 280°C to obtain 2 mm thick and 3 mm thick plate-shaped molded sheets. The molded body is transparent. The evaluation results are shown in Table 1.

[0337] <Comparative Example 3>

[0338] With reference to Example 4 of Patent Document 1, the polyester carbonate resin (PEC2) obtained in Synthesis Example 2, pentaerythritol tetrastearate as a mold release agent, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite as an antioxidant are blended in the mass ratio shown in Table 1, and after being fully mixed, melt-kneaded at 270°C and exhaust pressure 30 mmHg using an extruder (TEX30α30mmφ twin-screw extruder manufactured by Nippon Steel Works). After the thermoplastic resin composition obtained by melt kneading is extruded into a filament bundle, it is pelletized using a pelletizer to obtain pellets of the thermoplastic resin composition. The Mv of the pellets is 10600. The pellets are injection molded at 280°C to obtain plate-shaped molded sheets of 2 mm thickness and 3 mm thickness. The molded body is transparent. The evaluation results are shown in Table 1.

[0339]

[0340] From the results shown in Table 1, it can be seen that the thermoplastic resin compositions of Examples 1 to 6 have a high refractive index, low birefringence, and excellent optical properties, and also have excellent long-term heat resistance compared to the thermoplastic resin compositions of Comparative Examples 1 to 3. The thermoplastic resin composition of Embodiment I of the present invention has excellent optical properties and is therefore extremely useful as an optical material, particularly as an optical lens, and can be used in a wide range of environments due to its excellent long-term heat resistance.

[0341] <Aspect II of the present invention>

[0342] [Synthesis example]

[0343] <Synthesis Example 4> (Production of polyester carbonate resin (PEC3))

[0344] 30.00 parts by mass of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (hereinafter, sometimes referred to as BPEF), 2.92 parts by mass of dimethyl terephthalate (hereinafter, sometimes referred to as DMT), 12.69 parts by mass of diphenyl carbonate (hereinafter, sometimes referred to as DPC), 4.05×10 -3 Mass parts, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester (hereinafter, sometimes referred to as Cat.P) 8.91×10 -3 parts by mass and Solvent Blue 45 [Product name: Polysynthren Blue RLS manufactured by Clariant] (hereinafter, sometimes referred to as PB) as a colorant 9.97×10 -5 10 parts by weight were added to a reaction kettle equipped with a stirrer and a distillation device, and after nitrogen substitution three times, the jacket was heated to 200° C. to melt the raw materials.

[0345] After complete dissolution, the pressure was reduced to 40 kPa over 20 minutes. The temperature was then raised to 260°C, the pressure was reduced to below 0.13 kPa, and the polymerization reaction was carried out until the specified stirring torque was reached. After the reaction was completed, the generated resin was granulated and extracted to obtain particles of polyester carbonate resin (PEC3). The Mv of the obtained polyester carbonate resin (PEC3) was 10300.

[0346] <Synthesis Example 5> (Production of polyester carbonate resin (PEC4))

[0347] In addition, the amount of PB used in Synthesis Example 4 was changed to 8.31×10 -5 Pellets of a polyester carbonate resin (PEC4) were synthesized in the same manner as in Synthesis Example 4 except for the differences in parts by mass. The Mv of the obtained polyester carbonate resin (PEC4) was 10,300.

[0348] <Synthesis Example 6> (Production of polyester carbonate resin (PEC5))

[0349] In addition, the amount of PB used in Synthesis Example 4 was changed to 6.65×10 -5 Pellets of a polyester carbonate resin (PEC5) were synthesized in the same manner as in Synthesis Example 4 except for the differences in parts by mass. The Mv of the obtained polyester carbonate resin (PEC5) was 10,400.

[0350] <Synthesis Example 7> (Production of polyester carbonate resin (PEC6))

[0351] In addition, the amount of PB used in Synthesis Example 4 was changed to 4.99×10 -5Pellets of polyester carbonate resin (PEC6) were synthesized in the same manner as in Synthesis Example 4 except for the differences in parts by mass. The Mv of the obtained polyester carbonate resin (PEC6) was 10,400.

[0352] <Synthesis Example 8> (Production of polyester carbonate resin (PEC7))

[0353] In addition, the amount of PB used in Synthesis Example 4 was changed to 3.32×10 -5 Pellets of polyester carbonate resin (PEC7) were synthesized in the same manner as in Synthesis Example 4 except for the differences in parts by mass. The Mv of the obtained polyester carbonate resin (PEC7) was 10,400.

[0354] <Synthesis Example 9> (Production of polyester carbonate resin (PEC8))

[0355] In addition, the amount of PB used in Synthesis Example 4 was changed to 1.66×10 -5 Pellets of a polyester carbonate resin (PEC8) were synthesized in the same manner as in Synthesis Example 4 except for the differences in parts by mass. The Mv of the obtained polyester carbonate resin (PEC8) was 10,400.

[0356] <Synthesis Example 10> (Production of polyester carbonate resin (PEC9))

[0357] Pellets of a polyester carbonate resin (PEC9) were obtained by synthesis in the same manner as in Synthesis Example 4 except that PB in Synthesis Example 4 was not included. The Mv of the obtained polyester carbonate resin (PEC9) was 10,400.

[0358] <Synthesis Example 11> (Production of polyester carbonate resin (PEC10))

[0359] In addition, the amount of PB used in Synthesis Example 4 was changed to 1.66×10 -4 Pellets of a polyester carbonate resin (PEC10) were synthesized in the same manner as in Synthesis Example 4 except for the differences in parts by mass. The Mv of the obtained polyester carbonate resin (PEC10) was 10,200.

[0360] <Synthesis Example 12> (Production of polyester carbonate resin (PEC11))

[0361] Referring to Example 4 of Patent Document 1, 30.00 parts by mass of BPEF, 1.48 parts by mass of DMT, 13.68 parts by mass of DPC and 2.59×10 -3 10 parts by weight were added to a reaction kettle equipped with a stirrer and a distillation device, and nitrogen substitution was performed three times. Then, the jacket was heated to 180° C. to melt the raw materials.

[0362] After complete dissolution, the pressure was reduced to 30 kPa over 20 minutes. The temperature was then raised to 250°C, the pressure was reduced to below 0.13 kPa, and the polymerization reaction was carried out until the specified stirring torque was reached. After the reaction was completed, the generated resin was granulated and extracted to obtain particles of polyester carbonate resin (PEC11). The Mv of the obtained polyester carbonate resin (PEC11) was 10,800.

[0363] <Synthesis Example 13> (Production of polycarbonate resin (PC2))

[0364] 30.00 parts by mass of BPEF, 15.24 parts by mass of DPC, 3.45×10 -5 mass parts (sodium bicarbonate is added in the form of 0.1wt% aqueous solution) and PB4.80×10 -5 10 parts by weight were added to a reaction kettle equipped with a stirrer and a distillation device, and after nitrogen substitution three times, the jacket was heated to 200° C. to melt the raw materials.

[0365] After complete dissolution, the pressure was reduced to 40 kPa over 20 minutes. Then, the temperature was raised to 240°C, the pressure was reduced to below 0.13 kPa, and the polymerization reaction was carried out until the specified stirring torque was reached. After the reaction was completed, the generated resin was granulated and extracted to obtain particles of polycarbonate resin (PC2). The Mv of the obtained polycarbonate resin (PC2) was 9800.

[0366] <Synthesis Example 14> (Production of polycarbonate resin (PC3))

[0367] Pellets of a polycarbonate resin (PC3) were obtained by synthesis in the same manner as in Synthesis Example 13 except that PB in Synthesis Example 13 was not included. The Mv of the obtained polycarbonate resin (PC3) was 9,800.

[0368] <Example 7>

[0369] The polyester carbonate resin (PEC3) obtained in Synthesis Example 4, glyceryl monostearate as a release agent [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.], and cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) as an antioxidant [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] were mixed in the mass ratio shown in Table 1, and then melt-kneaded by an extruder (TEX30α 30mmφ twin-screw extruder manufactured by Nippon Steel Works) at 270°C and an exhaust pressure of 4.0 kPa. After the thermoplastic resin composition obtained by melt kneading was extruded into a filament bundle, it was pelletized using a pelletizer to obtain pellets of the thermoplastic resin composition. The Mv of the pellets was 10000. The pellets were injection molded at 280°C to obtain plate-shaped molded pieces with a thickness of 2 mm and 3 mm. The molded body was transparent. Table 2 shows the evaluation results.

[0370] <Example 8>

[0371] Except that the polyester carbonate resin (PEC4) obtained in Synthesis Example 5 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant are mixed in the mass ratio shown in Table 2, melt kneading and pelletization are carried out in the same manner as in Example 7 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets is 10000. The pellets are injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body is transparent. The evaluation results are shown in Table 2.

[0372] <Example 9>

[0373] Except that the polyester carbonate resin (PEC5) obtained in Synthesis Example 6 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant are mixed in the mass ratio shown in Table 2, melt kneading and pelletization are carried out in the same manner as in Example 7 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets is 10100. The pellets are injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body is transparent. The evaluation results are shown in Table 2.

[0374] <Example 10>

[0375] Except that the polyester carbonate resin (PEC6) obtained in Synthesis Example 7 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant are mixed in the mass ratio shown in Table 2, melt kneading and pelletization are carried out in the same manner as in Example 7 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets is 10100. The pellets are injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body is transparent. The evaluation results are shown in Table 2.

[0376] <Example 11>

[0377] Except that the polyester carbonate resin (PEC7) obtained in Synthesis Example 8 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetraylbis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant were blended in the mass ratio shown in Table 2, melt-kneading and pelletizing were performed in the same manner as in Example 7 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets was 10200. The pellets were injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body was transparent. The evaluation results are shown in Table 2.

[0378] <Example 12>

[0379] Except that the polyester carbonate resin (PEC8) obtained in Synthesis Example 9 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetraylbis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant were mixed in the mass ratio shown in Table 2, melt kneading and pelletization were carried out in the same manner as in Example 7 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets was 10100. The pellets were injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body was transparent. The evaluation results are shown in Table 2.

[0380] <Example 13>

[0381] Except that the polyester carbonate resin (PEC6) obtained in Synthesis Example 7 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant are mixed in the mass ratio shown in Table 2, melt kneading and pelletization are carried out in the same manner as in Example 7 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets is 10100. The pellets are injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body is transparent. The evaluation results are shown in Table 2.

[0382] <Example 14>

[0383] Except that the polyester carbonate resin (PEC6) obtained in Synthesis Example 7 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant are mixed in the mass ratio shown in Table 2, melt kneading and pelletization are carried out in the same manner as in Example 7 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets is 10100. The pellets are injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body is transparent. The evaluation results are shown in Table 2.

[0384] <Example 15>

[0385] The polycarbonate resin (PC2) obtained in Synthesis Example 13 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant were blended in the mass ratio shown in Table 2. Melt kneading and pelletization were performed in the same manner as in Example 7 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets was 9500. The pellets were injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body was transparent. The evaluation results are shown in Table 2.

[0386] <Comparative Example 4>

[0387] The polyester carbonate resin (PEC9) obtained in Synthesis Example 10 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent are mixed in the mass ratio shown in Table 2, and after being fully mixed, melt-kneaded at 270°C and exhaust pressure 4.0 kPa using an extruder (TEX30α30mmφ twin-screw extruder manufactured by Nippon Steel Works). After the thermoplastic resin composition obtained by melt kneading is extruded into a filament bundle, it is pelletized using a pelletizer to obtain pellets of the thermoplastic resin composition. The Mv of the pellets is 9900. The pellets are injection molded at 280°C to obtain 2 mm thick and 3 mm thick plate-shaped molded sheets. The molded body is transparent. The evaluation results are shown in Table 2.

[0388] <Comparative Example 5>

[0389] Except that the polyester carbonate resin (PEC5) obtained in Synthesis Example 6 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent were blended in the mass ratio shown in Table 1, melt kneading and pelletization were performed in the same manner as in Comparative Example 4 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets was 10100. The pellets were injection molded at 280°C to obtain plate-shaped molded pieces with a thickness of 2 mm and a thickness of 3 mm. The molded body was transparent. The evaluation results are shown in Table 2.

[0390] <Comparative Example 6>

[0391] Except that the polyester carbonate resin (PEC9) obtained in Synthesis Example 10 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant were blended in the mass ratio shown in Table 2, melt kneading and pelletization were performed in the same manner as in Comparative Example 4 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets was 10000. The pellets were injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body was transparent. The evaluation results are shown in Table 2.

[0392] <Comparative Example 7>

[0393] Except that the polyester carbonate resin (PEC10) obtained in Synthesis Example 11 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant were blended in the mass ratio shown in Table 2, melt-kneading and pelletizing were performed in the same manner as in Comparative Example 4 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets was 9700. The pellets were injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body was transparent. The evaluation results are shown in Table 2.

[0394] <Comparative Example 8>

[0395] Except that the polyester carbonate resin (PEC9) obtained in Synthesis Example 10 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant were blended in the mass ratio shown in Table 2, melt kneading and pelletization were carried out in the same manner as in Comparative Example 4 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets was 10300. The pellets were injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body was transparent. The evaluation results are shown in Table 2.

[0396] <Comparative Example 9>

[0397] Except that the polyester carbonate resin (PEC9) obtained in Synthesis Example 10 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant were blended in the mass ratio shown in Table 2, melt kneading and pelletization were carried out in the same manner as in Comparative Example 4 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets was 10300. The pellets were injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body was transparent. The evaluation results are shown in Table 2.

[0398] <Comparative Example 10>

[0399] With reference to Example 4 of Patent Document 1, except that the polyester carbonate resin (PEC11) obtained in Synthesis Example 12, pentaerythritol tetrastearate as a release agent, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite as an antioxidant were blended in the mass ratio shown in Table 2, melt-kneaded and pelletized in the same manner as in Comparative Example 4 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets was 10600. The pellets were injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body was transparent. The evaluation results are shown in Table 2.

[0400] <Comparative Example 11>

[0401] Except that the polycarbonate resin (PC3) obtained in Synthesis Example 14 and glyceryl monostearate [product name: Rikemal S-100A manufactured by Riken Vitamin Co., Ltd.] as a release agent and cyclic neopentane tetrayl bis (2,6-di-tert-butyl-4-methylphenyl phosphite) [product name: Adekastab PEP-36 manufactured by ADEKA Co., Ltd.] as an antioxidant were blended in the mass ratio shown in Table 2, melt kneading and pelletization were performed in the same manner as in Comparative Example 4 to obtain pellets of a thermoplastic resin composition. The Mv of the pellets was 9700. The pellets were injection molded at 280°C to obtain plate-shaped molded pieces of 2 mm thickness and 3 mm thickness. The molded body was transparent. The evaluation results are shown in Table 2.

[0402] [Table 2-1]

[0403]

[0404] [Table 2-2]

[0405] From the results shown in Table 2, it can be seen that the thermoplastic resin compositions of Examples 7 to 15 have a high refractive index, low birefringence, and excellent optical properties. In addition, compared with the thermoplastic resin compositions of Comparative Examples 4 to 11, the visible light transmittance is high, the transmission balance is good, and the chromaticity is also excellent. The thermoplastic resin composition of Aspect II of the present invention has excellent optical properties and is therefore extremely useful as an optical material, especially as an optical lens, and has an excellent appearance and can be used in a wide range of fields.

[0406] Industrial Applicability

[0407] The thermoplastic resin composition of the present invention has a high refractive index, low birefringence and long-term heat resistance, and can be suitably used for optical materials such as lenses and films. In addition, the thermoplastic resin composition of the present invention has a high refractive index, low birefringence and excellent transmittance and appearance, and can be suitably used for optical materials such as lenses and films.

Claims

1. A thermoplastic resin composition comprising: a thermoplastic resin having a constituent unit represented by the following formula (1), and a mold release agent, wherein the content of the antioxidant in the thermoplastic resin composition is 0 to 300 ppm, In formula (1), ring Z represents an aromatic hydrocarbon ring, L 1 and L 2 Each independently represents a divalent linking group, o and p each independently represent an integer greater than 0, R 1 , R 2 , R 3 and R 4 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X is at least one selected from the group represented by the following formula (2) or (3), In the formula, Y represents a divalent linking group.

2. The thermoplastic resin composition according to claim 1, wherein The release agent is included in an amount of 1 to 4000 ppm in the thermoplastic resin composition.

3. The thermoplastic resin composition according to claim 1 or 2, wherein The content of the antioxidant in the thermoplastic resin composition is 0 to 50 ppm.

4. The thermoplastic resin composition according to claim 1 or 2, wherein Dry heat yellowing ΔYI is 0.00~0.

47.

5. A thermoplastic resin composition comprising: a thermoplastic resin having a constituent unit represented by the following formula (4), a colorant, and an antioxidant, wherein the content of the colorant in the thermoplastic resin composition is 0.01 to 4.00 ppm, and the content of the antioxidant is 50 to 3000 ppm. In formula (4), ring Z represents an aromatic hydrocarbon ring, L 1 and L 2 Each independently represents a divalent linking group, o and p each independently represent an integer greater than 0, R 1 , R 2 , R 3 and R 4 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X is at least one selected from the group represented by the following formula (5) or (6), In the formula, Y represents a divalent linking group.

6. The thermoplastic resin composition according to claim 5, wherein A 2 mm thick molded plate of the thermoplastic resin composition has a chromaticity a* of -0.40 to 0.00 and a chromaticity b* of -0.50 to 1.

25.

7. The thermoplastic resin composition according to claim 5 or 6, wherein The total light transmittance of a 2 mm thick molded plate of the thermoplastic resin composition is 86.5% or more.

8. The thermoplastic resin composition according to claim 5 or 6, wherein The 2 mm thick molded plate of the thermoplastic resin composition has a 400 nm light transmittance of 81.0% or more.

9. The thermoplastic resin composition according to claim 5 or 6, wherein The 2 mm thick molded plate of the thermoplastic resin composition has a 580 nm light transmittance of 85.0% or more.

10. The thermoplastic resin composition according to claim 1 or 5, wherein The ring Z in the formula (1) or (4) is a benzene ring.

11. The thermoplastic resin composition according to claim 1 or 5, wherein The thermoplastic resin having the structural unit represented by formula (1) or formula (4) is a polycarbonate resin or a polyester carbonate resin.

12. The thermoplastic resin composition according to claim 11, wherein The thermoplastic resin having the structural unit represented by formula (1) or formula (4) is a polyester carbonate resin. 13 . An optical component comprising the thermoplastic resin composition according to claim 1 or 5 . The optical component according to claim 13 , which is an optical lens.

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