Thermoplastic resin composition for optical materials, molded article, compounding agent, method for producing thermoplastic resin composition, and method for improving transmittance

Abstract

To provide a thermoplastic resin composition and the like which can suppress changes in transmittance, particularly transmittance in the short-wavelength region, even with the addition of additives or the like.SOLUTION: A thermoplastic resin composition for optical materials contains a compounding agent represented by the general formula (1) in the figure. (In the formula, R1 to R5 are independently H or an alkyl group having a total of 1-20 carbon atoms which may have a substituent; R6 to R9 are independently H or an alkyl group having a total of 1-20 carbon atoms which may have a substituent; R10 is H or an alkyl group having a total of 1-5 carbon atoms.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin composition, etc. In particular, the present invention relates to a thermoplastic resin composition for optical materials, a molded article containing the thermoplastic resin composition, a compounding agent added to a thermoplastic resin, a method for producing a thermoplastic resin composition, a method for improving transmittance, etc. [Background technology]

[0002] BACKGROUND ART Conventionally, in thermoplastic resins used as optical materials, additives such as antioxidants and mold release agents have been added to ensure stability during processing and mold releasability. For example, it is known that adding an antioxidant to a resin improves stability during processing (for example, Patent Documents 1 and 2). However, the addition of these additives can sometimes impair the inherent performance of the resin. For example, in thermoplastic resins used as optical materials, the addition of additives can reduce the transmittance in the short wavelength range, which is extremely important.

[0003] Even a slight change in the transmittance of a thermoplastic resin used as an optical material in the short wavelength region can have a significant impact on the product that it is put into practical use. For this reason, there has been a demand for a resin composition that can maintain the original transmittance of a thermoplastic resin used as an optical material even after commercialization, but no resin composition that can reliably suppress changes in transmittance has been realized. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 7-233160 [Patent Document 2] WO99 / 67232 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0005] A main object of the present invention is to provide a thermoplastic resin composition for optical materials that can suppress changes in transmittance, particularly changes in transmittance in the short wavelength range, even when additives are added for commercialization. [Means for solving the problem]

[0006] The present inventors have found that a thermoplastic resin composition containing a specific lactone compound maintains good transmittance, particularly in the short wavelength region, even in the presence of additives.

[0007] The present invention includes the following. <1> A thermoplastic resin composition comprising a compounding agent represented by the following general formula (1): [ka] (In general formula (1), R1 to R5 each independently represent a hydrogen atom or an alkyl group which may have a substituent and has a total of 1 to 20 carbon atoms; R6 to R9 each independently represent a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent; R 10 represents a hydrogen atom or an alkyl group having a total of 1 to 5 carbon atoms. <2> The above, further comprising an antioxidant. <1> The thermoplastic resin composition according to claim 1. <3> The antioxidant is a phenol-based antioxidant and / or a phosphite-based antioxidant. <2> The thermoplastic resin composition according to claim 1. <4> The antioxidant is contained in an amount of 1 ppm by weight to 10,000 ppm by weight based on the total weight of the resin composition. <2> or <3> The thermoplastic resin composition according to claim 1. <5> The antioxidant is contained in an amount of 1 ppm by weight to 3000 ppm by weight based on the total weight of the resin composition. <4> The thermoplastic resin composition according to claim 1. <6> The compounding agent is contained in an amount of 1 ppm by weight to 10,000 ppm by weight based on the total weight of the resin composition. <1> ~ <5> The thermoplastic resin composition according to any one of the preceding claims. <7> The compounding agent is contained in an amount of 1 ppm by weight to 2000 ppm by weight based on the total weight of the resin composition. <1> ~ <6> The thermoplastic resin composition according to any one of the preceding claims. <8> The transmittance (%) at a wavelength of 370 nm to 400 nm in accordance with JIS K7105 is 2.0 (%) or more higher than that of a target resin composition having the same composition except that it does not contain the compounding agent. <1> ~ <7> The thermoplastic resin composition according to any one of the preceding claims. <9> The transmittance (%) at a wavelength of 370 nm to 400 nm in accordance with JIS K7105 is 1.1 times or more as compared with a target resin composition having the same composition except that it does not contain the compounding agent. <1> ~ <8> The thermoplastic resin composition according to any one of the preceding claims. <10> Compared to a target resin composition having the same composition except that it does not contain the compounding agent, the amount of volatile components generated when heated at 250°C for 5 minutes is smaller, The volatile component is any one of formaldehyde, acetaldehyde, acetone, 2,3-butanedione, acetic acid, and formic acid. <1> ~ <9> The thermoplastic resin composition according to any one of the preceding claims. <11> the YI value according to JIS K7105 is 0.20 or more lower than that of a target resin composition having the same composition except that it does not contain the compounding agent; <1> ~ <10> The thermoplastic resin composition according to any one of the preceding claims. <12> In the general formula (1), Three of R1 to R5 are hydrogen atoms and two are alkyl groups; Two of R6 to R9 are hydrogen atoms and two are alkyl groups; R 10 is a hydrogen atom, <1> ~ <11> The thermoplastic resin composition according to any one of the preceding claims. <13> In the general formula (1), the substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group, and an alkoxy group. <1> ~ <12> The thermoplastic resin composition according to any one of the preceding claims. <14> The above-mentioned thermoplastic resin further comprises a thermoplastic resin selected from the group consisting of polycarbonate resin, polyester resin, polyester carbonate resin, cycloolefin resin, and acrylic resin. <1> ~ <13> The thermoplastic resin composition according to any one of claims 1 to 10. <15> The thermoplastic resin is a polycarbonate resin, a polyester resin, or a polyestercarbonate resin containing a structural unit (B) derived from a monomer represented by the following general formula (2) and / or a structural unit (C) derived from a monomer represented by the following general formula (3): <14> The thermoplastic resin composition according to claim 1. [ka] (In general formula (2), R a and R b each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡CR h selected from the group consisting of R h represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, X represents a single bond or an optionally substituted fluorene group; A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent; m and n each independently represent an integer of 0 to 6; a and b each independently represent an integer of 0 to 10. [ka] (In general formula (3), R c and R d are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent; A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent; p and q each independently represent an integer of 0 to 4, a and b each independently represent an integer of 0 to 10; Y1 represents a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following general formulae (4) to (9) and (12) to (14), [ka] (In general formulas (4) to (9), R 21 and R 22 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R 21 and R 22 are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; r and s each independently represent an integer of 0 to 5000, In general formulas (12) to (14), R 23 and R 24 each independently represents a hydrogen atom, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent. <16> The thermoplastic resin has a weight average molecular weight (Mw) of 10,000 to 300,000 in terms of polystyrene. <14> and <15> The thermoplastic resin composition according to any one of claims 1 to 10. <17> In the general formula (2) and the general formula (3), A and B each independently represent an alkylene group having 2 or 3 carbon atoms. <15> and <16> The thermoplastic resin composition according to any one of claims 1 to 10. <18> The thermoplastic resin contains at least a structural unit derived from any one of BPEF, BNE, BNEF, and DPBHBNA. <14> ~ <17> The thermoplastic resin composition according to any one of claims 1 to 10. <19> The above, further comprising a catalyst deactivator. <1> ~ <18> The thermoplastic resin composition according to any one of claims 1 to 10. <20> The catalyst deactivator comprises dodecylbenzenesulfonate. <19> The thermoplastic resin composition according to claim 1. <21> The above, further comprising a release agent. <1> ~ <20> The thermoplastic resin composition according to any one of claims 1 to 10. <22> The release agent is contained in an amount of 1 ppm by weight to 5000 ppm by weight based on the total weight of the resin composition. <21> The thermoplastic resin composition according to claim 1. <23> The compounding agent, which contains the compounding agent represented by the general formula (1), has peaks at diffraction angles 2θ of 6.7±0.2°, 10.4±0.2°, 11.1±0.2°, 12.7±0.2°, 13.2±0.2°, 15.2±0.2°, 16.1±0.2°, 17.3±0.2°, 20.8±0.2°, and 23.6±0.2° in a powder X-ray diffraction pattern using Cu-Kα radiation. <1> ~ <22> The thermoplastic resin composition according to any one of claims 1 to 10. <24> The above-mentioned is for optical materials. <1> ~ <23> The thermoplastic resin composition according to any one of claims 1 to 10. <25> A thermoplastic resin composition comprising an additive represented by the following general formula (1) for improving the transmittance (%) at wavelengths of 370 nm to 400 nm. [ka] (In general formula (1), R1 to R5 each independently represent a hydrogen atom or an alkyl group which may have a substituent and has a total of 1 to 20 carbon atoms; R6 to R9 each independently represent a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent; R 10 represents a hydrogen atom or an alkyl group having a total of 1 to 5 carbon atoms.

[0008] <26> the above <1> ~ <25> A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 4. <27> A compounding agent represented by the following formula (10) or (11), which is added to a thermoplastic resin in order to improve the transmittance (%) of the thermoplastic resin composition at wavelengths of 370 nm to 400 nm. [ka] <28> A compounding agent represented by the following formula (10) or (11), which is added to a thermoplastic resin to reduce the haze value of the thermoplastic resin composition. [ka] <29> The powder X-ray diffraction pattern using Cu-Kα radiation has peaks at diffraction angles 2θ of 6.7±0.2°, 10.4±0.2°, 11.1±0.2°, 12.7±0.2°, 13.2±0.2°, 15.2±0.2°, 16.1±0.2°, 17.3±0.2°, 20.8±0.2° and 23.6±0.2°. <27> or <28> The combination agent described in <30> A method for producing a thermoplastic resin composition, comprising the step of adding a compounding agent represented by the following general formula (1) to a thermoplastic resin: [ka] (In general formula (1), R1 to R5 each independently represent a hydrogen atom or an alkyl group which may have a substituent and has a total of 1 to 20 carbon atoms; R6 to R9 each independently represent a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent; R10 represents a hydrogen atom or an alkyl group having a total of 1 to 5 carbon atoms. <31> A method for improving the transmittance of a thermoplastic resin composition, comprising the step of adding a compounding agent represented by the following general formula (1) to a thermoplastic resin: [ka] (In general formula (1), R1 to R5 each independently represent a hydrogen atom or an alkyl group which may have a substituent and has a total of 1 to 20 carbon atoms; R6 to R9 each independently represent a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent; R 10 represents a hydrogen atom or an alkyl group having a total of 1 to 5 carbon atoms. <32> A method for reducing haze in a thermoplastic resin composition, comprising the step of adding a compounding agent represented by the following general formula (1) to a thermoplastic resin: [ka] (In general formula (1), R1 to R5 each independently represent a hydrogen atom or an alkyl group which may have a substituent and has a total of 1 to 20 carbon atoms; R6 to R9 each independently represent a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent; R 10 represents a hydrogen atom or an alkyl group having a total of 1 to 5 carbon atoms. [Effects of the Invention]

[0009] As described above, the thermoplastic resin composition of the present invention contains the specified compounding agents and can maintain a good level of transmittance, particularly in the short wavelength region. For example, it has been revealed that the addition of antioxidants or mold release agents tends to decrease the transmittance of conventional thermoplastic resin compositions. However, the thermoplastic resin composition of the present invention can prevent a decrease in transmittance, particularly in the short wavelength region, even when additives are added. Such a thermoplastic resin composition is particularly suitable as an optical material. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 shows the powder X-ray diffraction pattern of the crystals of the combination drug used in Example 1. [Figure 2] FIG. 1 shows the powder X-ray diffraction pattern of a different sample of the crystals of the same compound as in the formulation of Example 1. [Figure 3] FIG. 1 shows the powder X-ray diffraction pattern of a different sample of crystals of the same compound as in the formulation of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0011] [1. Components of Thermoplastic Resin Composition] The components of the thermoplastic resin composition will be described below.

[0012] [1-1. Compounding Agents] The thermoplastic resin composition contains an additive represented by general formula (1). The additive represented by general formula (1) is used to improve the transmittance of the thermoplastic resin composition, particularly the transmittance at low wavelengths. Furthermore, by adding the compounding agent represented by general formula (1), it is possible to reduce the haze of the thermoplastic resin composition and improve the transparency. [ka] In general formula (1), R1 to R5 each independently represent a hydrogen atom or an optionally substituted alkyl group having a total of 1 to 20 carbon atoms. R1 to R5 are preferably a hydrogen atom or an optionally substituted alkyl group having a total of 1 to 10 carbon atoms, the total number of carbon atoms in the optionally substituted alkyl group is more preferably 1 to 5, and even more preferably 1 to 3, and the alkyl group is, for example, a methyl group. Of R1 to R5 in general formula (1), preferably, two to four are hydrogen atoms and one to three are alkyl groups, and more preferably, three are hydrogen atoms and two are alkyl groups.

[0013] In general formula (1), R6 to R9 each independently represent a hydrogen atom or an optionally substituted alkyl group having a total of 1 to 20 carbon atoms. R6 to R9 are preferably a hydrogen atom or an optionally substituted alkyl group having a total of 1 to 10 carbon atoms, the total number of carbon atoms of the optionally substituted alkyl group being more preferably 1 to 8, and even more preferably 1 to 5, and the alkyl group is, for example, a t-butyl group. Of R6 to R9 in general formula (1), it is preferable that 1 to 3 are hydrogen atoms and 1 to 3 are alkyl groups, and it is more preferable that 2 are hydrogen atoms and 2 are alkyl groups.

[0014] In general formula (1), R 10 represents a hydrogen atom or an alkyl group having a total of 1 to 5 carbon atoms. 10 is preferably a hydrogen atom or an alkyl group having a total of 1 to 3 carbon atoms which may have a substituent, and the total number of carbon atoms in the alkyl group which may have a substituent is more preferably 1 or 2. 10 is more preferably a hydrogen atom. In general formula (1), R 10 The carbon atom bonded to is an asymmetric carbon, but the compound of general formula (1) may be a racemic or optically active substance.

[0015] The substituent in the general formula (1) is, for example, any one of a halogen, a cyano group, an alkenyl group, an alkynyl group, and an alkoxy group. Specific examples of the compounding agent of general formula (1) include compounds of the following formulae (10) and (11) and mixtures thereof. [ka] [ka]

[0016] The thermoplastic resin composition may contain a compounding agent in a content of 1 ppm by weight to 10,000 ppm by weight, and the content of the compounding agent may be 1 ppm by weight to 8,000 ppm by weight, 1 ppm by weight to 6,000 ppm by weight, 1 ppm by weight to 4,000 ppm by weight, or 1 ppm by weight to 3,000 ppm by weight. The thermoplastic resin composition preferably contains the compounding agent in an amount of 1 ppm by weight to 2000 ppm by weight based on the total weight of the thermoplastic resin composition, more preferably 10 ppm by weight to 1000 ppm by weight, even more preferably 50 ppm by weight to 800 ppm by weight, particularly preferably 50 ppm by weight to 500 ppm by weight, and even more preferably 100 ppm by weight to 300 ppm by weight.

[0017] The compounding agent is preferably crystalline. For example, in the crystals of a 90:10 mixture of the compounds of the above formulas (10) and (11) (i.e., in general formula (1), two of R1 to R5 are methyl groups, the other two are hydrogen, and two of R6 to R9 are tertiary butyl groups, and the other two are hydrogen), the powder X-ray diffraction pattern using Cu-Kα radiation under the measurement conditions described in the examples has peaks at diffraction angles 2θ of 6.7°, 10.4°, 11.1°, 12.7°, 13.2°, 15.2°, 16.1°, 17.3°, 20.8°, and 23.6°. Of these, the peaks at 13.2°, 15.2°, and 20.8° have high relative intensities. As shown in the Examples section, when the peaks of the powder X-ray diffraction patterns using Cu-Kα radiation were measured for multiple samples of the same compound formulation, it was confirmed that all samples had the above-mentioned peak values ​​in common. However, a measurement error of about ±0.2° or ±0.1° may occur. Therefore, for the above-mentioned formulation, the diffraction angles 2θ of the powder X-ray diffraction pattern using Cu-Kα radiation have peaks at 6.7±0.2°, 10.4±0.2°, 11.1±0.2°, 12.7±0.2°, 13.2±0.2°, 15.2±0.2°, 16.1±0.2°, 17.3±0.2°, 20.8±0.2°, and 23.6±0.2°.

[0018] The thermoplastic resin composition may further contain the following additives in addition to the above-mentioned compounding ingredients. [1-2. Antioxidants] The thermoplastic resin composition preferably contains an antioxidant. The antioxidant is preferably at least one of a phenolic antioxidant and a phosphite antioxidant. Furthermore, a phenolic antioxidant and a phosphite antioxidant may be used in combination, and a thermoplastic resin composition containing both a phenolic antioxidant and a phosphite antioxidant is preferred. Phenolic antioxidants include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol, ocladecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and phenoxyethanol. Examples of the hydroxybenzoate include pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxospiro[5.5]undecane, and pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and preferably pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. Phosphite antioxidants include 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxy-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite, and Examples of the phosphite include tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra-C12-15-alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and preferably 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. As the antioxidant, any one of the above may be used alone, or a mixture of two or more may be used.

[0019] The thermoplastic resin composition may contain an antioxidant in a content of 1 ppm by weight to 10,000 ppm by weight, and the content of the antioxidant may be 1 ppm by weight to 8,000 ppm by weight, 1 ppm by weight to 6,000 ppm by weight, or 1 ppm by weight to 4,000 ppm by weight. The antioxidant is preferably contained in the thermoplastic resin composition in an amount of 1 ppm by weight to 3000 ppm by weight based on the total weight of the resin composition, more preferably 50 ppm by weight to 2500 ppm by weight, even more preferably 100 ppm by weight to 2000 ppm by weight, particularly preferably 150 ppm by weight to 1500 ppm by weight, and even more preferably 200 ppm by weight to 1200 ppm by weight. The above-mentioned ranges of the content of the antioxidants relate to the total amount of the antioxidants, but any one type of antioxidant may be used in a content within any of the above-mentioned ranges.

[0020] [1-3. Release Agent] The thermoplastic resin composition preferably contains a mold release agent. Examples of the release agent include ester compounds, for example, glycerin fatty acid esters such as mono- and diglycerides of glycerin fatty acid, glycol fatty acid esters such as propylene glycol fatty acid esters and sorbitan fatty acid esters, higher alcohol fatty acid esters, full esters or mono-fatty acid esters of aliphatic polyhydric alcohols and aliphatic carboxylic acids, etc. When an ester of aliphatic polyhydric alcohols and aliphatic carboxylic acids is used as the release agent, either monoesters or full esters can be used, but other than full esters, such as monoesters, may also be used. Specific examples of the release agent include the following: namely, sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan tribehenate, sorbitan stearate, sorbitan tristearate, sorbitan caprylate, etc.; Propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate, and propylene glycol monopalmitate; higher alcohol fatty acid esters such as stearyl stearate; Glycerin fatty acid ester monoglycerides, including glycerin monohydroxystearates such as glycerin monostearate and glycerin mono 12-hydroxystearate, glycerin monooleate, glycerin monobehenate, glycerin monocaprylate, glycerin monocaprate, and glycerin monolaurate; and mono- and diglycerides such as glycerin monodistearate, glycerin monodistearate, glycerin monodibehenate, and glycerin monodiolate; Acetylated monoglycerides of glycerin fatty acid esters such as glycerin diacetomonolaurate; Glycerin fatty acid ester organic acid monoglycerides such as citric acid fatty acid monoglyceride, succinic acid fatty acid monoglyceride, and diacetyltartaric acid fatty acid monoglyceride; Examples of the fatty acid ester include polyglycerol fatty acid esters such as diglycerol stearate, diglycerol laurate, diglycerol oleate, diglycerol monostearate, diglycerol monolaurate, diglycerol monomyristate, diglycerol monooleate, tetraglycerol stearate, decaglycerol laurate, decaglycerol oleate, and polyglycerol polyricinoleate.

[0021] The thermoplastic resin composition preferably contains 1 ppm by weight to 5000 ppm by weight of the release agent based on the total weight of the resin composition. The content of the release agent in the thermoplastic resin composition is more preferably 50 ppm by weight to 4000 ppm by weight, even more preferably 100 ppm by weight to 3500 ppm by weight, particularly preferably 500 ppm by weight to 13000 ppm by weight, and even more preferably 1000 ppm by weight to 2500 ppm by weight. The release agent can be used in combination with other additives, for example, antioxidants, etc. The ranges of the content of the release agent described above relate to the total amount of the release agent, but any one type of release agent may be used in a content within any of the ranges described above.

[0022] [1-4. Catalyst deactivators] The thermoplastic resin composition preferably further contains a catalyst deactivator as an additive. The catalyst deactivator stops the polymerization reaction by deactivating the catalyst for polymerization of the resin composition. The addition of the catalyst deactivator can also prevent depolymerization of the polymer contained in the resin composition. Furthermore, the catalyst deactivator may not be used in order to prevent an increase in the thermal history of the resin composition due to the addition of the catalyst deactivator. Examples of catalyst deactivators include esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite; triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and li Suitable examples of suitable deactivators include phosphate esters such as monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonyl chloride; alkyl sulfates such as dimethyl sulfate; and organic halides such as benzyl chloride. From the standpoint of the deactivator's effectiveness and stability to the resin, tetrabutylphosphonium dodecylbenzenesulfonate, p-toluene, or butyl sulfonate are particularly preferred. These deactivators are used in an amount of 0.01 to 50 times, preferably 0.3 to 20 times, the molar amount of the catalyst. Less than 0.01 times the molar amount of the catalyst results in insufficient deactivation effect, which is undesirable. Furthermore, if the amount is more than 50 times the amount of the catalyst by mole, the heat resistance of the resin decreases and the molded product tends to be discolored, which is undesirable.

[0023] The catalyst deactivator content in the thermoplastic resin composition is preferably 1 ppm by weight to 1000 ppm by weight based on the total weight of the resin composition, more preferably 3 ppm by weight to 500 ppm by weight, even more preferably 5 ppm by weight to 100 ppm by weight, and particularly preferably 10 ppm by weight to 50 ppm by weight. The catalyst deactivator may be added to the thermoplastic resin composition preferably as a solution, for example, as an aqueous solution, or as a solution in an alcohol such as methanol or ethanol, or in an organic solvent such as a phenol solution.

[0024] [1-5. Other additives] In addition to the compounding agents, antioxidants, mold release agents, and catalyst deactivators, additives may be added to the thermoplastic resin composition, such as heat stabilizers, plasticizers, fillers, ultraviolet absorbers, rust inhibitors, dispersants, antifoaming agents, leveling agents, flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents, and clarifying agents. The content of additives other than compounding agents, antioxidants, mold release agents, and catalyst deactivators (hereinafter also referred to as additional additives) in the thermoplastic resin composition is preferably 10 ppm by weight to 5.0% by weight, more preferably 100 ppm by weight to 2.0% by weight, and even more preferably 1000 ppm by weight to 1.0% by weight, but is not limited thereto. The above-mentioned additives may adversely affect the transmittance, so it is preferable not to add them in excess, and for example, the total amount added is within the above-mentioned range.

[0025] [1-6.Thermoplastic resin] The thermoplastic resin composition includes a thermoplastic resin. The thermoplastic resin is preferably at least one of polycarbonate resin, polyester resin, polyester carbonate resin, cycloolefin resin, and acrylic resin. The thermoplastic resin preferably contains a polycarbonate resin, a polyester resin, or a polyestercarbonate resin having a structural unit (B) derived from a monomer represented by the following general formula (2). [ka] In general formula (2), R a and R b each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡CR h R h represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent. R a and R b is preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, more preferably a hydrogen atom, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferably a hydrogen atom, or an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0026] In general formula (2), X represents a single bond or an optionally substituted fluorene group, and is preferably a single bond or an optionally substituted fluorene group having a total of 12 to 20 carbon atoms. In the general formula (2), A and B each independently represent an alkylene group having 1 to 5 carbon atoms, which may have a substituent, and preferably an alkylene group having 2 or 3 carbon atoms. In the general formula (2), m and n each independently represent an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably 0 or 1. In the general formula (2), a and b each independently represent an integer of 0 to 10, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0027] Specific examples of the structural unit (B) include those derived from BNE, DPBHBNA, and the like. [ka]

[0028] The thermoplastic resin preferably contains a polycarbonate resin, a polyester resin, or a polyestercarbonate resin having a structural unit (C) derived from a monomer represented by the following general formula (3). [ka] In general formula (3), R c and R d are each independently selected from the group consisting of a halogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 5 to 20 carbon atoms, an optionally substituted cycloalkoxyl group having 5 to 20 carbon atoms, and an optionally substituted aryl group having 6 to 20 carbon atoms. R c and R d is preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, more preferably a hydrogen atom, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferably a hydrogen atom, or an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0029] In general formula (3), Y1 is a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following general formulae (4) to (9) and (12) to (14), and is preferably a single bond or the structural formula represented by the following general formula (4). [ka] In general formulas (4) and (9), R 21 and R 22 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R 21 and R 22 are bonded to each other to form a carbon ring or hetero ring having 1 to 20 carbon atoms which may have a substituent. In the general formulae (7) and (9), r and s each independently represent an integer of 0 to 5,000. In addition, in the general formulas (12) to (14), R 23 and R 24 are each independently a hydrogen atom, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent.

[0030] In the general formula (3), A and B each independently represent an alkylene group having 1 to 5 carbon atoms, which may have a substituent, and preferably an alkylene group having 2 or 3 carbon atoms. In the general formula (3), p and q each independently represent an integer of 0 to 4, and preferably 0 or 1. In the general formula (3), a and b each independently represent an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 0 to 2, for example, 0 or 1.

[0031] Specific examples of the structural unit (C) include BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene), bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol P-AP (4,4'-(1-phenylethylidene)bisphenol), bisphenol P-CDE (4,4'-cyclododecylidenebisphenol), bisphenol P-HTG (4,4'-(3,3,5-trimethylisothiazolinone)), and bisphenol P-HTG (4,4'-(3,3,5-trimethylisothiazolinone). Examples include those derived from bisphenol P-MIBK (4,4'-(1,3-dimethylbutylidene)bisphenol), bisphenol PEO-FL (bisphenoxyethanolfluorene), bisphenol P-3MZ (4-[1-(4-hydroxyphenyl)-3-methylcyclohexyl]phenol), bisphenol OC-FL (4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol), bisphenol Z, BP-2EO (2,2'-[[1,1'-biphenyl]-4,4'-diylbis(oxy)bisethanol), S-BOC (4,4'-(1-methylethylidene)bis(2-methylphenol), TrisP-HAP (4,4',4''-ethylidene trisphenol), etc. Thermoplastic resins such as polycarbonate resins having a structural unit (C) derived from a bisphenol compound such as bisphenol A or bisphenol AP have the advantage that many of them are of high purity and have good marketability. [ka]

[0032] The thermoplastic resin may be a polymer containing the structural unit (B) but not the structural unit (C), a polymer containing the structural unit (C) but not the structural unit (B), a copolymer containing the structural unit (B) and the structural unit (C), a mixture of a polymer containing only the structural unit (B) and a polymer containing only the structural unit (C), or a combination thereof. Examples of polymers containing the structural unit (C) but not the structural unit (B) include those having structural units of the following formulae (I-1) to (I-3), and examples of copolymers having the structural unit (B) and the structural unit (C) include those having structural units of the following formulae (II-1) to (II-4). Specific examples of polymers containing the structural unit (C) but not the structural unit (B) include those composed of only one or more of the above-mentioned BPEF, BPPEF, and bisphenols. [ka] (In formula (I-1), m and n each represent an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1, In formula (I-3), n is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1. Furthermore, as the polymer having multiple types of structural units, either a block copolymer in which the values ​​of m and n are large, for example, 100 or more, or a random copolymer can be used, but a random copolymer is preferred, and more preferably a random copolymer in which the values ​​of m and n are 1 is used. [ka] (In formulas (II-1) to (II-4), m and n each independently represent an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1.) Furthermore, as the polymer having multiple types of structural units, either a block copolymer in which the values ​​of m and n are large, for example, 100 or more, or a random copolymer can be used, but a random copolymer is preferred, and more preferably a random copolymer in which the values ​​of m and n are 1 is used. In the copolymer, the molar ratio of the structural unit (B) to the structural unit (C) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, even more preferably 15:85 to 85:15, and particularly preferably 30:70 to 70:30. In the mixture, the weight ratio of the polymer having only the structural unit (B) to the polymer having only the structural unit (C) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, even more preferably 15:85 to 85:15, and particularly preferably 30:70 to 70:30.

[0033] The thermoplastic resin may be a cycloolefin-based resin or may contain a cycloolefin-based resin. Examples of the cycloolefin-based resin include those having the following structural units.

[0034] [ka]

[0035] In the above formula, X g each independently represents an alkylene group having 1 to 10 carbon atoms. Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, tert-butylene, and pentylene. Of these, methylene, ethylene, propylene, butylene, isobutylene, and sec-butylene are preferred, and methylene, ethylene, and propylene are more preferred.

[0036] R j , R k , and R leach independently represents a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, and -C≡CR i The R j , R k , and R l As for the above X a , X b , X c , X d , X e , and X f The same can be mentioned.

[0037] However, R j , R k , and R l may have a substituent. The substituent is not particularly limited, but examples thereof include a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyloxy group having 5 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, a cycloalkyloxycarbonyl group having 5 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 15 carbon atoms, an alkylcarbonyloxy group having 2 to 10 carbon atoms, a cycloalkylcarbonyloxy group having 5 to 10 carbon atoms, an arylcarbonyloxy group having 7 to 15 carbon atoms, a hydroxyalkylcarbonyl group having 2 to 10 carbon atoms, a glycidyloxycarbonyl group, a hydroxy group, a carboxy group, a cyano group, and an amido group having 1 to 10 carbon atoms.

[0038] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a pentyl group.

[0039] Examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a bicyclo[2.2.1]heptyl group, and a bicyclo[2.2.2]octyl group.

[0040] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a pentyloxy group.

[0041] Examples of the cycloalkyloxy group having 5 to 10 carbon atoms include a cyclopentyloxy group, a cyclohexyloxy group, a bicyclo[2.2.1]heptyloxy group, and a bicyclo[2.2.2]octyloxy group.

[0042] Examples of the alkyloxycarbonyl group having 2 to 10 carbon atoms include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, an isobutyloxycarbonyl group, a sec-butyloxycarbonyl group, and a tert-butyloxycarbonyl group.

[0043] Examples of the cycloalkyloxycarbonyl group having 5 to 10 carbon atoms include a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, a bicyclo[2.2.1]heptyloxycarbonyl group, and a bicyclo[2.2.2]octyloxycarbonyl group.

[0044] Examples of the aryloxycarbonyl group having 7 to 15 carbon atoms include a phenyloxycarbonyl group, a tolyloxycarbonyl group, a xylyloxycarbonyl group, a trimethylphenyloxycarbonyl group, a tetramethylphenyloxycarbonyl group, an ethylphenyloxycarbonyl group, an ethylmethylphenyloxycarbonyl group, a diethylphenyloxycarbonyl group, and a naphthyloxycarbonyl group.

[0045] Examples of the alkylcarbonyloxy group having 2 to 10 carbon atoms include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, and a butylcarbonyloxy group.

[0046] Examples of the cycloalkylcarbonyloxy group having 5 to 10 carbon atoms include a cyclopentylcarbonyloxy group, a cyclohexylcarbonyloxy group, a bicyclo[2.2.1]heptylcarbonyloxy group, and a bicyclo[2.2.2]octylcarbonyloxy group.

[0047] Examples of the arylcarbonyloxy group having 7 to 15 carbon atoms include a phenylcarbonyloxy group, a tolylcarbonyloxy group, a xylylcarbonyloxy group, a trimethylphenylcarbonyloxy group, a tetramethylphenylcarbonyloxy group, an ethylphenylcarbonyloxy group, an ethylmethylphenylcarbonyloxy group, a diethylphenylcarbonyloxy group, and a naphthylcarbonyloxy group.

[0048] Examples of the hydroxyalkylcarbonyl group having 2 to 10 carbon atoms include a hydroxymethylcarbonyl group, a hydroxyethylcarbonyl group, and a hydroxypropylcarbonyl group.

[0049] Examples of the amido group having 1 to 10 carbon atoms include a methylaminocarbonyl group, an ethylaminocarbonyl group, a dimethylaminocarbonyl group, and an acetylamino group.

[0050] The above-mentioned substituents may be present alone or in combination of two or more kinds.

[0051] R i represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S. i is the same as above.

[0052] Each p independently represents an integer of 0 or 1.

[0053] q, r, and s each independently represent an integer of 0 to 10, preferably 0 to 5, and more preferably 0 to 3.

[0054] t represents an integer of 1 to 3, and is preferably 1 or 2.

[0055] where q is 2 or more and two R j If two R are on adjacent carbon atoms, j may be joined together to form a ring structure. For example, when q is 2 and two R j When both R are substituted or unsubstituted alkyl groups, the general formula (20) becomes the following formula (20-1), where q is 2 and two R j When is a substituted or unsubstituted alkyl and a substituted or unsubstituted cycloalkyl, general formula (20) can be the following formula (20-2), (20-3), or (20-4).

[0056] [ka]

[0057] In the above formula, X g and p is as described above.

[0058] R n is the above-mentioned substituent, and specific examples thereof include a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyloxy group having 5 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, a cycloalkyloxycarbonyl group having 5 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 15 carbon atoms, an alkylcarbonyloxy group having 2 to 10 carbon atoms, a cycloalkylcarbonyloxy group having 5 to 10 carbon atoms, an arylcarbonyloxy group having 7 to 15 carbon atoms, a hydroxyalkylcarbonyl group having 2 to 10 carbon atoms, a glycidyloxycarbonyl group, a hydroxy group, a carboxy group, a cyano group, and an amido group having 1 to 10 carbon atoms.

[0059] Although z is not particularly limited, it is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 or 1.

[0060] u represents an integer of 1 to 3, preferably 1 or 2.

[0061] Also, if r is 2 or more, and two R k If two R are on adjacent carbon atoms, k may be joined together to form a ring structure. For example, when r is 2, two R k When both R are substituted or unsubstituted alkyl groups, the general formula (21) becomes the following formula (21-1) or (21-2), where r is 2 and the two R k When is a substituted or unsubstituted alkyl and a substituted or unsubstituted cycloalkyl, general formula (21) can be the following formula (21-3):

[0062] [ka]

[0063] In the above formula, X g ,p,R n , z, and u are as described above.

[0064] Furthermore, if s is 2 or more and two R l If two R are on adjacent carbon atoms, l may be joined together to form a ring structure. For example, when s is 2 and two R l are both substituted or unsubstituted alkyl groups, the general formula (22) becomes the following formula (22-1) or (22-2), where s is 2 and two R l When is a substituted or unsubstituted alkyl and a substituted or unsubstituted cycloalkyl, general formula (22) can be the following formula (22-3) or (22-4).

[0065] [ka]

[0066] In the above formula, X g ,p,R n , z, and u are as described above.

[0067] R m represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms is not particularly limited, but examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

[0068] Specific examples of cycloolefin resins include those containing at least one selected from the group consisting of structural units represented by the following formulas 1 to 8.

[0069] [ka]

[0070] The above-mentioned structural units may be contained alone in the cycloolefin resin, or two or more of them may be contained in combination. Furthermore, the above-mentioned structural units may be combined with structural units of other cyclic polyolefins, or with structural units of other resins (polyolefin resins, polyester resins), etc.

[0071] The weight average molecular weight (Mw) of the cycloolefin resin is not particularly limited, but is preferably 1,000 to 3,000,000, more preferably 10,000 to 3,000,000, further preferably 20,000 to 1,000,000, and particularly preferably 30,000 to 500,000.

[0072] In addition to the above-mentioned cycloolefin resin, a resin (polymer) having a structural unit containing an aliphatic ring may be used as the thermoplastic resin. For example, a thermoplastic resin having at least one structural unit selected from the group consisting of a structural unit derived from isosorbide, a structural unit derived from pentacyclopentadecanedimethanol (PCPMD), a structural unit derived from cyclohexanedimethanol, and a structural unit derived from spiroglycol may be used as the structural unit represented by the following formula (23): [ka] (In general formula (23), Rp represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[0073] Furthermore, a copolymer or blend of the above-mentioned cycloolefin resin or a resin having a structural unit containing an aliphatic ring and a structural unit represented by the following general formula (24) may be used as the thermoplastic resin. Specific examples of such thermoplastic resins include copolymers or blends of the above-mentioned general formula (23) and a structural unit represented by the following general formula (24). [ka] (In general formula (24), Rq and Rs each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms; and A and B each independently represent an alkylene group having 1 to 4 carbon atoms.)

[0074] The thermoplastic resin may contain an acrylic resin, which is not particularly limited, but may be, for example, a homopolymer of various (meth)acrylic acid esters such as polymethyl methacrylate (PMMA) or methyl methacrylate (MMA), or a copolymer of PMMA or MMA with one or more other monomers, or a mixture of two or more of these resins.

[0075] The weight average molecular weight (Mw) of the thermoplastic resin in terms of polystyrene is preferably 10,000 to 300,000, more preferably 15,000 to 100,000, and even more preferably 20,000 to 50,000. The viscosity average molecular weight (Mv) of the thermoplastic resin is preferably 5,000 to 200,000, more preferably 7,000 to 70,000, and even more preferably 10,000 to 30,000.

[0076] Thermoplastic resins such as polycarbonate resins, polyester resins, polyester carbonate resins, cycloolefin resins, and acrylic resins in the thermoplastic resin composition are produced by known methods. Examples of methods for producing thermoplastic resins include interfacial polymerization, melt transesterification, and condensation polymerization. Examples of methods for producing polycarbonate resins include ring-opening polymerization using a cyclic carbonate compound, the pyridine method, and solid-phase transesterification of a prepolymer. Polycarbonate resins, polyester resins, polyestercarbonate resins, and the like produced by interfacial polymerization using a terminal terminator contain terminal structures derived from the terminal terminator. For example, the thermoplastic resin may have terminal groups such as para-tert-butylphenyl groups, para-tert-octylphenyl groups, and p-benzoic acid hexadecane groups, which correspond to phenolic compounds such as para-tert-butylphenol, para-tert-octylphenol, and parahydroxybenzoic acid hexadecane, respectively, used as terminal terminators in interfacial polymerization. These terminal structures can improve the fluidity of thermoplastic resins such as polycarbonate resins.

[0077] [2. Properties of Thermoplastic Resin Composition] The thermoplastic resin composition of the present invention containing the compounding agent can maintain a high level of transmittance (%) compared to a thermoplastic resin composition not containing the compounding agent.

[0078] For example, the thermoplastic resin composition has a transmittance (%) of 2.0% or more greater at wavelengths of 370 nm to 400 nm as measured in JIS K7105 than a resin composition for a target object having the same composition but without adding additives. That is, when the transmittance (%) of a resin composition for a target object that does not contain additives as measured in JIS K7105 at wavelengths of 370 nm to 400 nm as measured in JIS K7105 for the thermoplastic resin composition of the present invention is compared at the same wavelength, the transmittance of the thermoplastic resin composition is higher, achieving a difference of 2.0% or more. Preferably, the transmittance of the thermoplastic resin composition is greater than the transmittance of the resin composition for a target object by 3.0% or more, more preferably by 4.0% or more.

[0079] Furthermore, for example, the thermoplastic resin composition has a transmittance (%) of 370 to 400 nm as measured in JIS K7105 that is 1.1 times or more higher than that of a resin composition for a target application having the same composition but without the addition of additives. That is, when the transmittance (%) of a resin composition for a target application that does not contain additives as measured in JIS K7105 as that of a thermoplastic resin composition of the present invention as measured in JIS K7105 as that of a thermoplastic resin composition for a target application at the same wavelength is compared, the transmittance (%) of the thermoplastic resin composition is higher than that of the resin composition for a target application by 1.1 times or more. Preferably, the transmittance of the thermoplastic resin composition is 1.3 times or more, more preferably 1.5 times or more, of the resin composition for a target application.

[0080] When additives such as a mold release agent or an antioxidant are added to the thermoplastic resin composition of the present invention, the transmittance value of the resulting thermoplastic resin composition tends to decrease. However, when the thermoplastic resin composition contains the above-mentioned compounding agents, the decrease in the transmittance value can be prevented or suppressed.

[0081] Furthermore, the thermoplastic resin composition of one embodiment has a lower haze value in accordance with JIS K-7361 and JIS K-7136 than a target resin composition having the same composition as the thermoplastic resin composition except that it does not contain the compounding agent, with a difference in haze value of 0.03 or more being observed. Thus, the compounding agent described above is also effective in improving the transparency of the thermoplastic resin composition. The difference between the haze value of the thermoplastic resin composition and the haze value of the resin composition for the target is preferably 0.05 or more, more preferably 0.07 or more, even more preferably 0.10 or more, and particularly preferably 0.12 or more. In one embodiment, the thermoplastic resin composition has a haze value that is 0.15 or more lower than the haze value of the resin composition for the target, and the thermoplastic resin composition preferably has a haze value that is 0.18 or more lower than the haze value of the resin composition for the target, or 0.20 or more lower than the haze value of the resin composition for the target.

[0082] Furthermore, the thermoplastic resin composition of one embodiment has a lower YI value than a target resin composition having the same composition as the thermoplastic resin composition except for the absence of the additive. Specifically, the YI value of a thermoplastic resin composition containing the additive, for example, the YI value according to JIS K 7105, can be 0.20 or more lower than the YI value of a thermoplastic resin composition having the same components but without the additive. The difference in these YI values ​​can be, for example, 0.50 or more, 0.80 or more, 0.90 or more, 1.0 or more, or even 1.1 or more.

[0083] As described above, the thermoplastic resin composition of the present invention, which enables the maintenance of high transmittance and the improvement of hue indicated by a low YI value, is suitable for use as an optical material, etc. The thermoplastic resin composition of the present invention is particularly suitable for use as an optical material. Furthermore, the thermoplastic resin composition of the present invention has high heat resistance and transparency, and is expected to have the effect of reducing the amount of volatile components. In particular, the polyester resin composition among the thermoplastic resin compositions of the present invention has been confirmed to have the effect of reducing the amount of volatile components at high temperatures, as will be described in detail below, and can suppress odors generated during heating. Therefore, the thermoplastic resin composition of the present invention, mainly the polyester resin composition, is also useful as a plastic for food container packaging, for example. For example, a thermoplastic resin composition according to an embodiment has the same or better effect of suppressing volatile components as a target resin composition having the same composition as the thermoplastic resin composition except that it does not contain any additives, as will be described in detail later. That is, the thermoplastic resin composition can suppress the amount of volatile components generated under specific conditions, such as heating at 250°C for 5 minutes, as will be described later. Specific examples of volatile components include formaldehyde, acetaldehyde, acetone, 2,3-butanedione, acetic acid, and formic acid.

[0084] [3. Method for producing thermoplastic resin composition] The method for producing a thermoplastic resin composition for optical materials of the present invention includes a step of adding the compounding agent to a thermoplastic resin, which allows the transmittance of the thermoplastic resin, particularly at low wavelengths, to be maintained at a good level compared to a thermoplastic resin to which the compounding agent is not added.

[0085] [4. Method for improving transmittance of thermoplastic resin composition] The method of the present invention for improving the transmittance of a thermoplastic resin composition for optical materials includes the step of adding the above-mentioned compounding agent to a thermoplastic resin. By adding the compounding agent to a thermoplastic resin, the transmittance of the thermoplastic resin, particularly the transmittance value at low wavelengths, can be improved. In particular, a thermoplastic resin composition to which a compounding agent has been further added can have an improved transmittance value compared to a thermoplastic resin to which an additive different from the compounding agent has been added.

[0086] [5. Method for reducing haze of thermoplastic resin composition] The method for reducing the haze of a thermoplastic resin composition for optical materials of the present invention includes adding the above-described additive to a thermoplastic resin. Adding the additive to a thermoplastic resin can reduce the haze value of the thermoplastic resin, particularly the haze value according to JIS K-7361 and JIS K-7136. That is, the haze value of the thermoplastic resin composition is smaller than the haze value of a target resin composition having the same composition as the thermoplastic resin composition but without the additive. The difference between these haze values ​​may be, for example, 0.03 or more, 0.05 or more, 0.07 or more, 0.10 or more, 0.12 or more, 0.15 or more, 0.18 or more, 0.20 or more, or even 0.30 or more, 0.40 or more, as described above.

[0087] [6. Molded body] The thermoplastic resin composition of the present invention can be used for extrusion molding, blow molding, injection molding, and the like. The molded articles obtained include extrusion molded articles, hollow molded articles, precision parts, and thin injection molded articles. The thermoplastic resin composition of the present invention can maintain a good transmittance value. Therefore, the thermoplastic resin composition of the present invention is particularly suitable as an optical material. Molded articles produced using such a thermoplastic resin composition include optical lenses, optical films, transparent conductive substrates used in liquid crystal displays, organic EL displays, solar cells, etc., optical disks, liquid crystal panels, optical cards, sheets, films such as retardation films, optical fibers, connectors, vapor-deposited plastic reflectors, displays, touch panels, etc. These optical molded articles have high transmittance even when they contain additives added for various applications. Specific examples of molded articles using the thermoplastic resin of the present invention as optical materials and in related fields include optical media products such as compact discs, digital video discs, minidiscs, and magneto-optical discs; optical communication media such as optical fiber; optical components such as car headlamp lenses and camera lenses; siren light covers, lighting lamp covers, window glass replacements for trains and automobiles; window glass replacements for homes; lighting components such as sunroofs and greenhouse roofs; goggles, sunglasses, eyeglass lenses and housings; housings for office automation equipment such as copiers, facsimiles, and personal computers; housings for home appliances such as televisions and microwave ovens; and electronic component applications such as connectors and IC trays. Furthermore, protective equipment such as helmets, protectors, and protective masks; household products such as baby bottles, tableware, and trays; medical products such as dialysis cases and dentures; miscellaneous goods such as packaging materials, writing implements, and stationery can also be mentioned, but are not limited to these. Particularly preferred examples of molded articles obtainable from the thermoplastic resin composition of the present invention include the following, which require high heat resistance and high transparency: automobile components such as headlamp lenses, meter panels, and sunroofs, as well as glass window replacements and exterior panel parts; various films for liquid crystal displays and the like, light guide plates, optical disk substrates, and housings for electronic devices such as smartphones; and building materials such as transparent sheets. Even in the case of molded articles that do not require the excellent transparency of the thermoplastic resin composition of the present invention, the high transparency of the raw material resin composition has the advantage that it is easier to control the degree of coloration with colorants such as pigments and dyes.

[0088] Furthermore, if necessary, a coating layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical molded body. The antireflection layer may be a single layer or a multilayer, and may be made of either an organic or inorganic material, but is preferably made of an inorganic material. Specific examples include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride.

[0089] [6-1. Optical Lenses] Optical lenses produced using the thermoplastic resin composition of the present invention have excellent transmittance characteristics. Furthermore, optical lenses produced using the polycarbonate resin of the present invention have a high refractive index, a low Abbe number, and high humidity and heat resistance. Therefore, they are extremely useful in fields where expensive high-refractive-index glass lenses have traditionally been used, such as telescopes, binoculars, and television projectors. If necessary, they are preferably used in the form of aspherical lenses. Aspherical lenses can essentially eliminate spherical aberration with a single lens, eliminating the need to combine multiple spherical lenses to eliminate spherical aberration, thereby enabling weight reduction and reduced production costs. Therefore, aspherical lenses are particularly useful as camera lenses, among other optical lenses. Optical lenses are molded by any method, such as injection molding, compression molding, injection compression molding, etc. The present invention makes it possible to more easily obtain high refractive index, low birefringence aspherical lenses, which are technically difficult to process using glass lenses. To prevent foreign matter from getting into the optical lens as much as possible, the molding environment must also be a low-dust environment, preferably class 6 or less, and more preferably class 5 or less.

[0090] The optical lens produced using the thermoplastic resin composition of the present invention can be obtained by injection molding the polycarbonate copolymer of the present invention into a lens shape using an injection molding machine or an injection compression molding machine. The molding conditions for injection molding are not particularly limited, but the molding temperature is preferably 180 to 280°C. The injection pressure is preferably 50 to 1700 kg / cm. 2 is. To prevent foreign matter from getting into the optical lens as much as possible, the molding environment must also be a low-dust environment, preferably class 1000 or less, and more preferably class 100 or less. The optical lens containing the thermoplastic resin composition of the present invention is preferably used in the form of an aspherical lens, if necessary. Since an aspherical lens can substantially eliminate spherical aberration with a single lens, it is not necessary to eliminate spherical aberration by combining multiple spherical lenses, which enables weight reduction and reduced production costs. Therefore, aspherical lenses are particularly useful as camera lenses, among other optical lenses. The astigmatism of the aspherical lens is preferably 0 to 15 mλ, more preferably 0 to 10 mλ. The thickness of the optical lens produced using the thermoplastic resin composition of the present invention can be set over a wide range depending on the application and is not particularly limited, but is preferably 0.01 to 30 mm, more preferably 0.1 to 15 mm. If necessary, a coating layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical lens of the present invention. The antireflection layer may be a single layer or a multilayer, and may be made of either an organic or inorganic material, but is preferably an inorganic material. Specific examples of the antireflection layer include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride. Among these, silicon oxide and zirconium oxide are more preferred, and a combination of silicon oxide and zirconium oxide is even more preferred. Regarding the antireflection layer, the combination of single layer / multilayer, or the combination of their components and thicknesses is not particularly limited, but a two-layer or three-layer structure is preferred, and a three-layer structure is particularly preferred. The antireflection layer as a whole is preferably formed to a thickness of 0.00017 to 3.3% of the thickness of the optical lens, specifically 0.05 to 3 μm, and particularly preferably 1 to 2 μm.

[0091] [6-2. Optical Film] The optical film produced using the thermoplastic resin composition of the present invention has excellent transparency and heat resistance, and is therefore suitable for use as a film for liquid crystal substrates, optical memory cards, and the like. To prevent foreign matter from getting into the optical film as much as possible, the molding environment must also be a low-dust environment, preferably class 6 or less, more preferably class 5 or less. [Example]

[0092] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples and can be practiced with any modifications within the scope of the present invention.

[0093] [Evaluation Method 1] The evaluation methods used in the examples and comparative examples using polycarbonate resin, which will be described in detail later, are as follows. (1-1) Transmittance [%] Pellets of the thermoplastic resin composition obtained by the method described below were dried in a hot air circulating dryer at 120°C for 5 hours, and then molded into flat plate-shaped test specimens measuring 40 mm wide, 40 mm long, and 3 mm thick using an injection molding machine (ROBOSHOT S-2000i30A manufactured by Fanuc Corporation) under conditions of a resin temperature of 260°C, a mold temperature of 130°C, and a molding cycle of 30 seconds. The transmittance (%) of a 3 mm-thick portion of the flat plate-shaped test specimen was measured at wavelengths of 370 nm, 380 nm, and 400 nm using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) in accordance with JIS K7105.

[0094] (1-2-1) Mass average molecular weight (Mw) The mass average molecular weight of the resin and resin composition was measured by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene. The apparatus, column, and measurement conditions used are as follows: GPC equipment: Tosoh Corporation, HLC-8420GPC Column: Tosoh Corporation, TSKgel SuperHM-M × 3 Tosoh Corporation, TSKgel guardcolumn SuperH-H x 1 Tosoh Corporation, TSKgel SuperH-RC x 1 Detector: RI detector Standard polystyrene: Tosoh Corporation, Standard Polystyrene Kit PStQuick C Sample solution: 0.2% by mass tetrahydrofuran solution Eluent: tetrahydrofuran ·Eluent flow rate: 0.6mL / min Column temperature: 40℃ (1-2-2) Viscosity average molecular weight (Mv) The viscosity average molecular weight (Mv) of a thermoplastic resin can be calculated using the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 Mv 0.83 It is calculated from Here, the value of the intrinsic viscosity [η] (unit: dL / g) is calculated by the following formula.

number

[0095] <Synthesis of thermoplastic resin: PC1> As raw materials, 20.86 kg (47.56 mol) of 9,9-bis[4-(2-hydroxyethoxy)-phenyl]fluorene (BPEF), 10.5 kg (49.02 mol) of diphenyl carbonate (DPC), and 2.5 × 10 -2 16 ml (4.0 x 10 mol / L) of sodium bicarbonate solution -4 mole, i.e., 8.4 × 10 per mole of the total of dihydroxy compounds -6(mol) was placed in a 50L reactor equipped with a stirrer and distillation device and heated to 180°C under a nitrogen atmosphere of 760 mmHg. Complete dissolution of the raw materials was confirmed 30 minutes after the start of heating, and stirring was continued for 120 minutes under the same conditions. The vacuum was then adjusted to 200 mmHg, and the temperature was raised to 200°C at a rate of 60°C / hr. During this time, the start of distillation of by-product phenol was confirmed. The reaction was then continued at 200°C for 20 minutes. The temperature was then raised to 230°C at a rate of 75°C / hr. After 10 minutes of heating, the temperature was maintained at this temperature while the vacuum was reduced to 1 mmHg or less over 2 hours. The temperature was then raised to 245°C at a rate of 60°C / hr, and stirring was continued for another 40 minutes. After the reaction was completed, nitrogen was introduced into the reactor to return to normal pressure, and the resulting resin was pelletized and removed to obtain a thermoplastic polycarbonate resin (PC1). [ka]

[0096] <Synthesis of thermoplastic resin: PC2> The raw materials were 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE) 14.978 kg (40.000 mol), 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene (BNEF) 24.239 kg (45.000 mol), DPBHBNA 7.899 kg (15.000 mol), DPC 22.236 kg (103.800 mol), and sodium bicarbonate 5.09 × 10 -2 g (6.06 × 10 -4 The same procedure as in Synthesis Example 1 was carried out except that the amount of methylcellulose was changed to 1.5 moles, thereby obtaining a polycarbonate resin (PC2) which was a thermoplastic resin. [ka]

[0097] <Examples 1 to 3, etc.> PC1 obtained in Synthesis Example 1, additives (mold release agent, antioxidant), and compounding ingredients were dry-mixed using a tumbler in the mass ratios shown in Table 1 below, and the mixture was melt-kneaded using a twin-screw extruder (IPEC Corporation, IPT-type 35 mm co-rotating twin-screw extruder, L / D=38) at a cylinder temperature of 250°C, a vent pressure of 25 Torr, and a discharge rate of 20 kg / hour, and extruded as strands to obtain a polycarbonate resin composition as a thermoplastic resin in the form of pellets. The transmittance of the obtained resin composition was measured, and the results are shown in Table 1. [Table 1] Antioxidant AO-60: Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADEKA AO-60) Antioxidant PEP-36: 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (ADEKA PEP-36) Release agent S-100A: Stearic acid monoglyceride (S-100A, manufactured by Riken Vitamin Co., Ltd.) Compounding agent: the mixture of the following formula (a 90:10 mixture of 3,4-dimethyl and 2,4-dimethyl compounds), a commercially available product manufactured by Tokyo Chemical Industry Co., Ltd., was used. [ka]

[0098] <Examples 4 to 7, etc.> A polycarbonate resin composition, which is a thermoplastic resin in pellet form, was obtained by the same procedure as in Example 1, except that PC2 obtained in Synthesis Example 2, additives (mold release agent, antioxidant), compounding ingredients, and an aqueous solution of catalyst deactivator were used in the mass ratios shown in Table 2. The transmittance of the obtained resin composition was measured, and the results are shown in Table 2. Among the abbreviations in Table 2, those shown in the margin of Table 1 are those other than MGA, which represents tetrabutylphosphonium dodecylbenzenesulfonate. [Table 2]

[0099] (1-3) Total light transmittance and haze Measurements were carried out in accordance with JIS K-7361 and JIS K-7136 for samples of the resin compositions of the following Examples and Comparative Examples, which were molded to a thickness of 3 mm. Measuring equipment: Spectroscopic haze meter SH7000 manufactured by Nippon Denshoku Industries Co., Ltd. (1-4)YI A sample molded to a thickness of 3 mm was measured using a spectroscopic haze meter in accordance with JIS K-7105. Measuring equipment: Spectroscopic haze meter SH7000 manufactured by Nippon Denshoku Industries Co., Ltd.

[0100] <Examples 8 to 10, etc.> PC3 (cyclic olefin copolymer "APEL (registered trademark)" brand: APL5014CL manufactured by Mitsui Chemicals, Inc.), additives (mold release agent, antioxidant), and compounding ingredients were dry-mixed using a tumbler in the mass ratios shown in Table 3, and the mixture was melt-kneaded at a cylinder temperature of 260°C using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., product name "TEM18ss") and extruded as strands to obtain a polycarbonate resin composition, which is a thermoplastic resin in the form of pellets. The physical properties of the resulting resin composition were measured, and the results are shown in Table 3. The molecular structure of the cyclic olefin copolymer PC3 is as shown in the formula (22).

[0101] [Table 3]

[0102] In Examples 8 to 10, which used a cyclic olefin copolymer having the above-mentioned molecular structure, the effect of reducing transmittance in the low wavelength range was not as significant as in other Examples, but the haze characteristics were improved. Furthermore, the polycarbonate resin compositions of Examples 8 to 10 also had low YI values, confirming that they had excellent hue.

[0103] (1-5) Powder X-ray Diffraction The conditions for measuring powder X-ray diffraction of each crystal of the above-mentioned compound used in Example 1 etc. (a 90:10 mixture of 3,4-dimethyl and 2,4-dimethyl forms of the compound represented by general formula (1) in which two of R1 to R5 are methyl groups and the other two are hydrogen, and two of R6 to R9 are tert-butyl groups and the other two are hydrogen) are as follows: An appropriate amount of the crystal to be measured was filled into the sample filling section of a glass test plate, and measurement was carried out using a powder X-ray diffractometer (MiniFlex600, manufactured by Rigaku Corporation) under the following conditions. X-ray: CuKα (40kV, 15mA) Kβ filter: Ni filter 0.015mm x 1 Scan speed: 10° / min Step width: 0.02° Scan axis: 2θ / θ Scan range: 5°~90° Entrance slit (DS): 1.25° Length limit slit (IHS): 10.0 mm Receiving slit 1 (SS): 8.0 mm Receiving slit 2 (RS): 13.0 mm

[0104] Powder X-ray diffraction measurements were performed on three different lots of the above compounding agent (Samples 1 to 3). Sample 1 was the one actually used in Example 1, while Samples 2 and 3 were the same compound as Sample 1 but were produced separately. As a result of the measurements, in addition to the main peaks at 13.2°, 15.2°, and 20.8°, it was confirmed that there were also peaks at 6.7°, 10.4°, 11.1°, 12.7°, 16.1±0.2°, 17.3±0.2°, 20.8°, and 23.6° (see Table 4 and Figures 1 to 3 below). As is clear from Table 4 below, although different samples show roughly the same peak values, a measurement error of about ±0.2° or ±0.1° may occur. [Table 4]

[0105] [Evaluation method 2] The evaluation methods used in the examples of the polyester resins and polyester resin compositions described in detail below are as follows.

[0106] (2-1) Ratio of diol units having a cyclic acetal skeleton and alicyclic diol units The ratio of the units derived from the diol having a cyclic acetal skeleton and the units derived from the alicyclic diol in the polyester resin is 1 Calculations were made by H-NMR measurement. Measurements were made using an Ascend™500 measuring device manufactured by Bruker BioSpin KK. Deuterated chloroform was used as the solvent.

[0107] (2-2) Glass transition temperature The glass transition temperature (Tg) of the polyester resin was measured using a differential scanning calorimeter (model: DSC / TA-50WS) manufactured by Shimadzu Corporation. Approximately 10 mg of the sample was placed in an unsealed aluminum container and measured in a nitrogen gas (30 ml / min) stream at a temperature rise rate of 20°C / min. The glass transition temperature was determined as the temperature at which the temperature changed by half the difference in the baseline before and after the transition of the DSC curve.

[0108] (2-3) YI value of pellets Measurements were made using a "ZE2000" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K-7105.

[0109] (2-4) Volatile component content when pellets are melted The relative value of the peak area of ​​the low molecular weight compounds (volatile components) obtained by GC-MS (headspace) converted per unit weight of the sample, i.e., the relative value of the peak area of ​​the volatile components in the corresponding other Examples when the value of the peak area of ​​the volatile components in Comparative Example 5 or Comparative Example 8 described below is taken as 100%, was taken as the amount of volatile components (%). Specifically, the following applies: 0.3 g of dried pellets were placed in an HS vial and septum-sealed under air. After heating at 250°C for 5 minutes in a block heater, analysis using a headspace GC-MS system was immediately initiated. For the analysis, a mass chromatogram was extracted using characteristic ions for each compound, and the peak area per unit weight of each sample was calculated. The equipment and measurement conditions used were as follows: [HS] Agilent G1888 Heating temperature and time: 250℃ 5min (external incubator) +230℃ 1min Loop temperature:240℃ TR LINE Temperature: 250℃ Vial equilibration: 1 min, vial pressurization: 0.5 min (15 psi) Loop filling: 0.2 min, loop equilibration: 0.2 min, injection: 0.1 min GC cycle: analysis 35min + equilibration 10min Carrier pressure: 16.5psi [GC] Agilent 8890 Column:DB-WAX(Φ0.25mm×60×t0.5μm) Oven temperature: 40℃5min~10℃ / min~240℃(10min) Column flow: He 1.0 ml / min Split ratio: 1 / 10 Injection temperature: 240℃ MSD transfer line: 240℃ [MS] Agilent 5977B MSD Gain Factor: 1 Scan range: m / z = 29 to 700

[0110] <Examples 11 to 14, etc.> Examples 11 to 14, etc., in which polyester resin was used, will be explained below. <Production example> [Synthesis of polyester resins (PEs-1 and PEs-2)] A 30 L polyester production apparatus equipped with a packed column rectification column, partial condenser, total condenser, cold trap, agitator, heater, and nitrogen inlet tube was charged with the raw material monomers listed in Table 5 below. 0.005 mol % tetra-n-butoxytitanium and 0.02 mol % potassium acetate were added relative to the dicarboxylic acid component, and the temperature was raised to 225°C under a nitrogen atmosphere to carry out a transesterification reaction. After the reaction conversion of the dicarboxylic acid component reached 90% or more, 0.025 mol % germanium dioxide and 0.05 mol % triethyl phosphate were added relative to the dicarboxylic acid component. The temperature was gradually raised and the pressure was gradually reduced, and polycondensation was finally carried out at 280°C and 0.1 kPa or less. The reaction was terminated when an appropriate melt viscosity was achieved, and polyester resins PEs-1 and PEs-2 were synthesized, respectively.

[0111] [Table 5]

[0112] The meanings of the abbreviations in Table 5 are as follows: DMT: dimethyl terephthalate NDCM: 2,6-naphthalenedicarboxylic acid dimethyl EG: Ethylene glycol SPG: 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane CHDM: 1,4-cyclohexanedimethanol

[0113] (Preparation of mixed pellets) Using a twin-screw extruder (Technovel Corporation, model KZW15TW-30MG-NH(-700), screw diameter: 15 mm, L / D: 30), polyester resins PEs-1 and PEs-2 synthesized in the above-mentioned production examples were dry-blended with an antioxidant at a predetermined ratio and charged into the extruder through a hopper. Strands were extruded at a cylinder temperature of 210-280°C, a die temperature of 280°C, a screw rotation speed of 60 rpm, and a throughput of 1.4 kg / h. After air cooling, the extruded strands were pelletized to obtain polyester resin pellets and additive-mixed pellets. The types and amounts of additives are shown in Tables 6 and 7, respectively.

[0114] The additives used are as follows: Antioxidant Irganox 1330: 3,3',3",5,5',5"-Hexa-tert-butyl-.alpha,.alpha',.alpha"-(mesitylene-2,4,6-triyl)tri-p-cresol (Irganox 1330, manufactured by BASF Japan) Antioxidant PEP-36: 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane (ADEKA PEP-36) Compounding agent: the mixture of the following formula (a 90:10 mixture of 3,4-dimethyl and 2,4-dimethyl compounds), a commercially available product manufactured by Tokyo Chemical Industry Co., Ltd., was used. [ka]

[0115] [Table 6]

[0116] [Table 7]

[0117] In the polyester resin compositions containing the compounding agents according to Examples 11 to 14, the effect of reducing the YI of the pellets after kneading and the effect of reducing the amount of volatile components were observed, compared to the polyester resin compositions containing no compounding agents according to Comparative Examples 7 to 11. Furthermore, in these examples, the effect of reducing the amount of volatile components was roughly the same as in the comparative examples (Example 12 and Comparative Example 9), but the reduction effect due to the addition of compounding agents was confirmed.

[0118] <Examples 15 to 18, etc.> Examples 15 to 18, etc., in which a bisphenol-based polycarbonate resin was used, will be described below. A polycarbonate resin composition, which is a thermoplastic resin in pellet form, was obtained in the same manner as in Example 1, except that the polycarbonate resin, additives (mold release agent, antioxidant), and compounding ingredients shown below were used in the mass ratios shown in Tables 8 to 11. The obtained physical property values ​​are as shown in Tables 8 to 11.

[0119] Example 15 PCa: A bisphenol A type aromatic polycarbonate having a terminal structure of a pt-octylphenyl group, trade name Iupizeta T-3840 (viscosity average molecular weight Mv: 13,500) manufactured by Mitsubishi Gas Chemical Company, Inc. was used. [Table 8]

[0120] Example 16 PCb: Bisphenol A type aromatic polycarbonate having a terminal structure of a pt-octylphenyl group, trade name Iupizeta T-3700 (viscosity average molecular weight Mv: 17,500) manufactured by Mitsubishi Gas Chemical Company, Inc. was used. [Table 9]

[0121] Example 17 PCc: A bisphenol A type aromatic polycarbonate having a terminal structure of a p-benzoic acid hexadecane group, trade name Iupizeta T-1380 (viscosity average molecular weight Mv: 25,500) manufactured by Mitsubishi Gas Chemical Company, Inc. was used. [Table 10]

[0122] Example 18 PCd: FPC-0210 (viscosity average molecular weight Mv: 11,500) manufactured by Mitsubishi Gas Chemical Company, Inc., was used. This aromatic polycarbonate was obtained by interfacial polymerization using bisphenol AP as the starting material and para-tert-butylphenol as the end terminator. [Table 11]

[0123] In the polycarbonate resin compositions of Examples 15 to 18, although it was not necessarily possible to improve the transmittance, reduce the YI value, or reduce the haze value compared to the corresponding comparative examples, generally better properties were observed.

Claims

1. A thermoplastic resin composition comprising a compounding agent represented by the following general formula (1): 【Chemical 1】 (In general formula (1), R １ ~R ５ each independently represents a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent, R ６ ~R ９ each independently represents a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent, R １０ represents a hydrogen atom or an alkyl group having a total of 1 to 5 carbon atoms.

2. The thermoplastic resin composition of claim 1 further comprising an antioxidant.

3. The thermoplastic resin composition according to claim 2, wherein the antioxidant is a phenol-based antioxidant and / or a phosphite-based antioxidant.

4. 4. The thermoplastic resin composition according to claim 2, wherein the antioxidant is contained in an amount of 1 ppm by weight to 10,000 ppm by weight based on the total weight of the resin composition.

5. 5. The thermoplastic resin composition according to claim 4, wherein the antioxidant is contained in an amount of 1 ppm by weight to 3000 ppm by weight based on the total weight of the resin composition.

6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the compounding agent is contained in an amount of 1 ppm by weight to 10,000 ppm by weight based on the total weight of the resin composition.

7. 7. The thermoplastic resin composition according to claim 6, wherein the compounding agent is contained in an amount of 1 ppm by weight to 2000 ppm by weight based on the total weight of the resin composition.

8. The thermoplastic resin composition according to any one of claims 1 to 7, which has a transmittance (%) at a wavelength of 370 nm to 400 nm in accordance with JIS K7105 that is 2.0 (%) or more higher than that of a target resin composition having the same composition except that it does not contain the compounding agent.

9. The thermoplastic resin composition according to any one of claims 1 to 8, wherein the transmittance (%) at wavelengths of 370 nm to 400 nm in accordance with JIS K7105 is 1.1 times or more as compared to a target resin composition having the same composition except that it does not contain the compounding agent.

10. Compared to a target resin composition having the same composition except that it does not contain the compounding agent, the amount of volatile components generated when heated at 250°C for 5 minutes is smaller, The thermoplastic resin composition according to any one of claims 1 to 9, wherein the volatile component is any one of formaldehyde, acetaldehyde, acetone, 2,3-butanedione, acetic acid, and formic acid.

11. The thermoplastic resin composition according to any one of claims 1 to 10, which has a YI value in accordance with JIS K7105 that is 0.20 or more lower than that of a target resin composition having the same composition except that it does not contain the compounding agent.

12. In the general formula (1), R １ ~R ５ three of which are hydrogen atoms and two of which are alkyl groups, R ６ ~R ９ two of which are hydrogen atoms and two of which are alkyl groups, R １０ The thermoplastic resin composition according to any one of claims 1 to 11, wherein is a hydrogen atom.

13. The thermoplastic resin composition according to any one of claims 1 to 12, wherein in the general formula (1), the substituent is any one of a halogen, a cyano group, an alkenyl group, an alkynyl group, and an alkoxy group.

14. The thermoplastic resin composition according to any one of claims 1 to 13, further comprising a thermoplastic resin selected from the group consisting of polycarbonate resins, polyester resins, polyester carbonate resins, cycloolefin resins, and acrylic resins.

15. The thermoplastic resin composition according to claim 14, wherein the thermoplastic resin is a polycarbonate resin, a polyester resin, or a polyestercarbonate resin containing a structural unit (B) derived from a monomer represented by the following general formula (2) and / or a structural unit (C) derived from a monomer represented by the following general formula (3): 【Chemistry 2】 (In general formula (2), R ａ and R ｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ selected from the group consisting of R ｈ represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, X represents a single bond or an optionally substituted fluorene group; A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent; m and n each independently represent an integer of 0 to 6; a and b each independently represent an integer of 0 to 10. 【Chemistry 3】 (In general formula (3), R ｃ and R ｄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 5 to 20 carbon atoms, an optionally substituted cycloalkoxyl group having 5 to 20 carbon atoms, and an optionally substituted aryl group having 6 to 20 carbon atoms; A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent; p and q each independently represent an integer of 0 to 4; a and b each independently represent an integer of 0 to 10; Y １ represents a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following general formulae (4) to (9) and (12) to (14), 【Chemistry 4】 (In general formulas (4) to (9), R ２１ and R ２２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R ２１ and R ２２ are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent; r and s each independently represent an integer of 0 to 5000; In general formulas (12) to (14), R ２３ and R ２４ each independently represents a hydrogen atom, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent.

16. The thermoplastic resin composition according to any one of claims 14 and 15, wherein the thermoplastic resin has a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 to 300,000.

17. 17. The thermoplastic resin composition according to claim 15, wherein in the general formula (2) and the general formula (3), A and B each independently represent an alkylene group having 2 or 3 carbon atoms.

18. The thermoplastic resin composition according to any one of claims 14 to 17, wherein the thermoplastic resin contains at least a structural unit derived from any one of BPEF, BNE, BNEF, and DPBHBNA.

19. The thermoplastic resin composition according to any one of claims 1 to 18, further comprising a catalyst deactivator.

20. 20. The thermoplastic resin composition of claim 19, wherein the catalyst deactivator comprises dodecylbenzene sulfonate.

21. The thermoplastic resin composition according to any one of claims 1 to 20, further comprising a mold release agent.

22. The thermoplastic resin composition according to claim 21, wherein the release agent is contained in an amount of 1 ppm by weight to 5000 ppm by weight based on the total weight of the resin composition.

23. The thermoplastic resin composition according to any one of claims 1 to 22, comprising a compounding agent represented by general formula (1) having peaks at diffraction angles 2θ of 6.7 ± 0.2 °, 10.4 ± 0.2 °, 11.1 ± 0.2 °, 12.7 ± 0.2 °, 13.2 ± 0.2 °, 15.2 ± 0.2 °, 16.1 ± 0.2 °, 17.3 ± 0.2 °, 20.8 ± 0.2 °, and 23.6 ± 0.2 ° in a powder X-ray diffraction pattern using Cu-Kα radiation.

24. The thermoplastic resin composition according to any one of claims 1 to 23, which is for use as an optical material.

25. A thermoplastic resin composition comprising an additive represented by the following general formula (1) for improving the transmittance (%) in the wavelength range of 370 nm to 400 nm: 【Chemistry 5】 (In general formula (1), R １ ~R ５ each independently represents a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent, R ６ ~R ９ each independently represents a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent, R １０ represents a hydrogen atom or an alkyl group having a total of 1 to 5 carbon atoms.

26. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 25.

27. A compounding agent represented by the following formula (10) or (11), which is added to a thermoplastic resin in order to improve the transmittance (%) of the thermoplastic resin composition at wavelengths of 370 nm to 400 nm: 【Chemistry 6】

28. A compounding agent represented by the following formula (10) or (11), which is added to a thermoplastic resin to reduce the haze value of the thermoplastic resin composition. 【Chemistry 7】

29. The compounding agent according to claim 27 or 28, wherein the powder X-ray diffraction pattern using Cu-Kα radiation has peaks at diffraction angles 2θ of 6.7±0.2°, 10.4±0.2°, 11.1±0.2°, 12.7±0.2°, 13.2±0.2°, 15.2±0.2°, 16.1±0.2°, 17.3±0.2°, 20.8±0.2°, and 23.6±0.2°.

30. A method for producing a thermoplastic resin composition for optical materials, comprising the step of adding a compounding agent represented by the following general formula (1) to a thermoplastic resin: 【Chemistry 8】 (In general formula (1), R １ ~R ５ each independently represents a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent, R ６ ~R ９ each independently represents a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent, R １０ represents a hydrogen atom or an alkyl group having a total of 1 to 5 carbon atoms.

31. A method for improving the transmittance of a thermoplastic resin composition, comprising the step of adding a compounding agent represented by the following general formula (1) to a thermoplastic resin: 【Chemistry 9】 (In general formula (1), R １ ~R ５ each independently represents a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent, R ６ ~R ９ each independently represents a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent, R １０ represents a hydrogen atom or an alkyl group having a total of 1 to 5 carbon atoms.

32. A method for reducing haze in a thermoplastic resin composition, comprising the step of adding a compounding agent represented by the following general formula (1) to a thermoplastic resin: 【Chemistry 10】 (In general formula (1), R １ ~R ５ each independently represents a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent, R ６ ~R ９ each independently represents a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent, R １０ represents a hydrogen atom or an alkyl group having a total of 1 to 5 carbon atoms.

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