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

Abstract

Provided is a thermoplastic resin composition or the like which can suppress changes in transmittance, particularly changes in transmittance in a short-wavelength region, even if an additive or the like is added. The above-mentioned problem is solved by a thermoplastic resin composition for an optical material, which contains a compounding agent represented by general formula (1). (In general formula (1), R1-R5 each independently represents a hydrogen atom or an optionally substituted alkyl group having 1-20 carbon atoms, R6-R9 each independently represents a hydrogen atom or an optionally substituted alkyl group having 1-20 carbon atoms, and R10 represents a hydrogen atom or an optionally substituted alkyl group having 1-5 carbon atoms) .

Description

[0001] This case is a divisional application filed on August 11, 2021, with application number 202180056154.0 (PCT / JP2021 / 029647), entitled "Thermoplastic Resin Composition for Optical Materials, Molded Article, Additive, Method for Manufacturing Thermoplastic Resin Composition and Method for Improving Transmittance". Technical Field

[0002] This invention relates to thermoplastic resin compositions, etc. In particular, this invention relates to thermoplastic resin compositions for optical materials, molded articles containing thermoplastic resin compositions, compounding agents added to thermoplastic resins, methods for manufacturing thermoplastic resin compositions, and methods for improving transmittance, etc. Background Technology

[0003] Currently, in thermoplastic resins used as optical materials, additives such as antioxidants and release agents are added to ensure stability and release properties during processing.

[0004] For example, it is known to add antioxidants to resins to improve their stability during processing (e.g., Patent Documents 1 and 2).

[0005] However, sometimes the addition of these additives can impair the original properties of the resin. For example, there is a problem where the addition of additives can lead to a decrease in the transmittance in the short wavelength region, which is extremely important for thermoplastic resins as optical materials.

[0006] Even small changes in the transmittance of thermoplastic resins in the short wavelength region, which are used as optical materials, can sometimes have a significant impact on practical products. Therefore, although there is a need for resin compositions that can maintain the original transmittance of thermoplastic resins as optical materials after the product is manufactured, resin compositions that can reliably suppress transmittance changes have not yet been realized.

[0007] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 7-233160 Patent Document 2: WO99 / 67232 Summary of the Invention

[0008] The problem that the invention aims to solve The main technical problem solved by the present invention is to provide a thermoplastic resin composition for optical materials that can suppress changes in transmittance, especially in the short wavelength region, even when additives are added for product manufacturing.

[0009] Technical solutions for solving the problem The inventors of this invention have discovered that thermoplastic resin compositions formulated with specific lactone compounds can maintain good transmittance, particularly in the short wavelength region, even in the presence of additives.

[0010] The present invention includes the following solutions.

[0011] <1> A thermoplastic resin composition containing a compounding agent represented by the following general formula (1). (in general formula (1), R1 to R5 each independently represent a hydrogen atom or an alkyl group with a total carbon number of 1 to 20 that may have substituents. R6 to R9 independently represent hydrogen atoms and alkyl groups with a total number of carbon atoms of 1 to 20, which may have substituents. R 10 (This refers to an alkyl group containing 1 to 5 hydrogen atoms or a total of 5 carbon atoms.) <2> The thermoplastic resin composition described in <1> above also contains an antioxidant.

[0012] <3> The thermoplastic resin composition described in <2> above, wherein the antioxidant is a phenolic antioxidant and / or a phosphite antioxidant.

[0013] <4> The thermoplastic resin composition described in <2> or <3> above, wherein, based on the total weight of the resin composition, it contains 1 ppm to 10,000 ppm of the antioxidant.

[0014] <5> The thermoplastic resin composition described in <4> above, wherein, based on the total weight of the resin composition, contains 1 to 3000 ppm by weight of the antioxidant.

[0015] <6> The thermoplastic resin composition of any one of <1> to <5> above, wherein, based on the total weight of the resin composition, it contains 1 ppm to 10,000 ppm of the compounding agent.

[0016] <7> The thermoplastic resin composition described in any one of <1> to <6> above, wherein the compounding agent is contained in 1 ppm to 2000 ppm by weight, based on the total weight of the resin composition.

[0017] <8> The thermoplastic resin composition described in any one of <1> to <7> above, wherein the transmittance (%) at wavelengths of 370 nm to 400 nm is 2.0% or more greater than that of the control resin composition having the same composition except that it does not contain the above-mentioned compounding agent.

[0018] <9> The thermoplastic resin composition described in any one of <1> to <8> above, wherein the transmittance (%) at wavelengths of 370 nm to 400 nm, as measured according to JIS K7105, is 1.1 times or more than that of a control resin composition having the same composition except that it does not contain the above-mentioned compounding agent.

[0019] <10> The thermoplastic resin composition described in any one of <1> to <9> above, wherein, compared with the control resin composition having the same composition except that it does not contain the above-mentioned compounding agent, the amount of volatile components generated when heated at 250°C for 5 minutes is less, wherein the volatile components are any one of formaldehyde, acetaldehyde, acetone, 2,3-butanedione, acetic acid and formic acid.

[0020] <11> The thermoplastic resin composition described in any one of <1> to <10> above, wherein the YI value measured according to JIS K7105 is 0.20 or more less than that of the control resin composition having the same composition except that it does not contain the above-mentioned compounding agent.

[0021] <12> The thermoplastic resin composition described in any one of <1> to <11> above, wherein in the above 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 It is a hydrogen atom.

[0022] <13> The thermoplastic resin composition of any one of <1> to <12> above, wherein, in the above general formula (1), the substituent is any one of halogen, cyano, alkenyl, alkynyl, and alkoxy.

[0023] <14> The thermoplastic resin composition described in any one of <1> to <13> above further contains a thermoplastic resin selected from polycarbonate resin, polyester resin, polyester carbonate resin, cycloolefin resin and acrylic resin.

[0024] <15> The thermoplastic resin composition described in <14> above, wherein the thermoplastic resin is a polycarbonate resin, polyester resin or polyester carbonate resin containing structural units (B) of monomers represented by the following general formula (2) and / or structural units (C) of monomers represented by the following general formula (3). (in general formula (2), R a and R bThe elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups having 6 to 20 carbon atoms that may have substituents containing one or more heterocyclic atoms selected from O, N, and S, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , R h This indicates an aryl group with 6 to 20 carbon atoms that may have substituents, or a heteroaryl group with 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N, and S. X represents a single bond or a fluorene group that can have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. m and n independently represent integers from 0 to 6. a and b independently represent integers from 0 to 10. (in general formula (3), R c and R d The groups are independently selected from hydrogen atoms, halogen atoms, alkyl groups with 1 to 20 carbon atoms that may have substituents, alkoxy groups with 1 to 20 carbon atoms that may have substituents, cycloalkyl groups with 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups with 5 to 20 carbon atoms that may have substituents, and aryl groups with 6 to 20 carbon atoms that may have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. p and q represent integers from 0 to 4 independently. a and b independently represent integers from 0 to 10. Y1 is a single bond, may be a fluorene group with substituents, or any of the structural formulas shown in the following general formulas (4) to (9) and (12) to (14). (In general formulas (4) to (9), R 21 and R 22 Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, or an aryl group with 6 to 30 carbon atoms that may have substituents, or represent R. 21 and R 22Carbon rings or heterocycles with 1 to 20 carbon atoms that can be formed by the combination of various elements and may have substituents. r and s independently represent integers from 0 to 5000. In general formulas (12) to (14), R 23 and R 24 Each can independently represent a hydrogen atom, fluorine, chlorine, bromine, or iodine, or can represent 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, which may have substituents. <16> The thermoplastic resin composition described in <14> or <15> above, wherein the weight-average molecular weight (Mw) of the thermoplastic resin converted from polystyrene is 10,000 to 300,000.

[0025] <17> The thermoplastic resin composition described in <15> or <16> above, wherein in the above general formula (2) and general formula (3), A and B respectively independently represent alkylene groups having 2 or 3 carbon atoms.

[0026] <18> The thermoplastic resin composition of any one of <14> to <17> above, wherein the thermoplastic resin contains at least a structural unit from any one of BPEF, BNE, BNEF and DPBHBNA.

[0027] <19> The thermoplastic resin composition described in any one of <1> to <18> above further contains a catalyst deactivator.

[0028] <20> The thermoplastic resin composition described in <19> above, wherein the catalyst deactivator contains dodecylbenzene sulfonate.

[0029] <21> The thermoplastic resin composition described in any one of <1> to <20> above further contains a release agent.

[0030] <22> The thermoplastic resin composition described in <21> above, wherein, based on the total weight of the resin composition, contains 1 ppm to 5000 ppm of the release agent.

[0031] <23> The thermoplastic resin composition of any one of <1> to <22> above, wherein the composition contains a compounding agent of the above general formula (1) having a peak at diffraction angle 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 rays.

[0032] <24> The thermoplastic resin composition described in any one of <1> to <23> above, which is used in optical materials.

[0033] <25> A thermoplastic resin composition containing a compounding agent of the following general formula (1) for increasing the transmittance (%) value in wavelengths from 370 nm to 400 nm. (in general formula (1), R1 to R5 each independently represent a hydrogen atom or an alkyl group with a total carbon number of 1 to 20 that may have substituents. R6 to R9 independently represent hydrogen atoms and alkyl groups with a total number of carbon atoms of 1 to 20, which may have substituents. R 10 (This refers to an alkyl group containing 1 to 5 hydrogen atoms or a total of 5 carbon atoms.) <26> A molded article comprising any one of the thermoplastic resin compositions described in <1> to <25> above.

[0034] <27> A compounding agent, which is a compounding agent shown in formula (10) or (11), and is a compounding agent added to the thermoplastic resin to increase the transmittance (%) value of the thermoplastic resin composition in the wavelength range of 370 nm to 400 nm. <28> A compounding agent, which is a compounding agent shown in the following formula (10) or (11), and which is a compounding agent added to the thermoplastic resin for the purpose of reducing the haze value of the thermoplastic resin composition. <29> The complexing agent described in <27> or <28> above, wherein it 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 the powder X-ray diffraction pattern using Cu-Kα rays.

[0035] <30> A method for manufacturing a thermoplastic resin composition, comprising the step of adding a compounding agent represented by the following general formula (1) to a thermoplastic resin. (in general formula (1), R1 to R5 each independently represent a hydrogen atom or an alkyl group with a total carbon number of 1 to 20 that may have substituents. R6 to R9 independently represent hydrogen atoms and alkyl groups with a total number of carbon atoms of 1 to 20, which may have substituents. R 10 (This refers to an alkyl group containing 1 to 5 hydrogen atoms or a total of 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 the thermoplastic resin. (in general formula (1), R1 to R5 each independently represent a hydrogen atom or an alkyl group with a total carbon number of 1 to 20 that may have substituents. R6 to R9 independently represent hydrogen atoms and alkyl groups with a total number of carbon atoms of 1 to 20, which may have substituents. R 10 (This refers to an alkyl group containing 1 to 5 hydrogen atoms or a total of 5 carbon atoms.) <32> A method for reducing the haze of a thermoplastic resin composition, comprising the step of adding a compounding agent represented by the following general formula (1) to the thermoplastic resin. (in general formula (1), R1 to R5 each independently represent a hydrogen atom or an alkyl group with a total carbon number of 1 to 20 that may have substituents. R6 to R9 independently represent hydrogen atoms and alkyl groups with a total number of carbon atoms of 1 to 20, which may have substituents. R 10 (This refers to an alkyl group containing 1 to 5 hydrogen atoms or a total of 5 carbon atoms.) Invention Effects The thermoplastic resin composition of the present invention, as described above, contains the prescribed compounding agents and is particularly capable of maintaining a good level of transmittance in the low-wavelength region. While it is known that conventional thermoplastic resin compositions tend to exhibit a decrease in transmittance when antioxidants or mold release agents are added, for example, the thermoplastic resin composition of the present invention prevents this decrease in transmittance, particularly in the low-wavelength region, even with the addition of additives. Such a thermoplastic resin composition is particularly suitable as an optical material. Attached Figure Description

[0036] Figure 1 This is a powder X-ray diffraction pattern showing the crystallization of the complexing agent used in Example 1.

[0037] Figure 2 This is a diagram showing the powder X-ray diffraction pattern of a crystallized but different sample of the same compound as the complexing agent in Example 1.

[0038] Figure 3This is a diagram showing the powder X-ray diffraction pattern of a crystallized but different sample of the same compound as the complexing agent in Example 1. Detailed Implementation

[0039] [1. Composition of the thermoplastic resin composition] The composition of the thermoplastic resin composition is described below.

[0040] [1-1. Complexing agent] The thermoplastic resin composition contains a compounding agent represented by general formula (1). The compounding agent represented by general formula (1) is used to improve the transmittance of the thermoplastic resin composition, particularly to improve the transmittance value at low wavelengths.

[0041] Furthermore, by adding the compounding agent shown in general formula (1), it is possible to reduce the haze of the thermoplastic resin composition and improve its transparency. In general formula (1), R1 to R5 each independently represent a hydrogen atom or an alkyl group having a total carbon number of 1 to 20 that may have substituents. R1 to R5 are preferably hydrogen atoms or alkyl groups having a total carbon number of 1 to 10 that may have substituents, more preferably 1 to 5 that may have substituents, and even more preferably 1 to 3 that may have substituents, and the alkyl group is, for example, methyl.

[0042] In addition, in general formula (1), R1 to R5, preferably 2 to 4 are hydrogen atoms and 1 to 3 are alkyl groups, more preferably 3 are hydrogen atoms and 2 are alkyl groups.

[0043] In general formula (1), R6 to R9 independently represent hydrogen atoms and alkyl groups having a total carbon number of 1 to 20. R6 to R9 are preferably hydrogen atoms or alkyl groups having a total carbon number of 1 to 10, and the total carbon number of the alkyl groups having substituents is more preferably 1 to 8, and even more preferably 1 to 5. For example, the alkyl group is tert-butyl.

[0044] In addition, in general formula (1), R6 to R9 are preferably 1 to 3 hydrogen atoms and 1 to 3 alkyl atoms, and more preferably 2 hydrogen atoms and 2 alkyl atoms.

[0045] In general formula (1), R 10 R represents an alkyl group having 1 to 5 hydrogen atoms or a total number of carbon atoms. 10 Preferably, it is a hydrogen atom or an alkyl group having a total carbon number of 1 to 3, which may have substituents; more preferably, the total carbon number of the alkyl group having substituents is 1 or 2. 10 More preferably, it is a hydrogen atom.

[0046] In general formula (1), with R 10The carbon atom that is bonded is a chiral carbon, but the complexing agent of general formula (1) can be a racemic mixture or an optically active mixture.

[0047] The substituents in general formula (1) are, for example, any one of halogen, cyano, alkenyl, alkynyl, and alkoxy.

[0048] Specific examples of complexing agents of general formula (1) include compounds of formulas (10) and (11) and mixtures thereof. The thermoplastic resin composition may contain a compounding agent in an amount of 1 ppm to 10,000 ppm by weight. The content of the compounding agent may be 1 ppm to 8,000 ppm by weight, 1 ppm to 6,000 ppm by weight, 1 ppm to 4,000 ppm by weight, or 1 ppm to 3,000 ppm by weight.

[0049] In the thermoplastic resin composition, based on the total weight of the thermoplastic resin composition, it is preferable to contain a compounding agent of 1 to 2000 ppm by weight. More preferably, the content of the compounding agent in the thermoplastic resin composition is 10 to 1000 ppm by weight, even more preferably 50 to 800 ppm by weight, particularly preferably 50 to 500 ppm by weight, and even more preferably 100 to 300 ppm by weight.

[0050] The complexing agent is preferably crystalline. For example, in the crystallization of a 90:10 mixture of compounds of formulas (10) and (11) above (i.e., compounds in which two of R1 to R5 in general formula (1) are methyl and the other two are hydrogen, and two of R6 to R9 are tert-butyl and the other two are hydrogen), peaks are observed 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° using Cu-Kα rays under the measurement conditions described in the examples. Among these, the peaks at 13.2°, 15.2°, and 20.8° have relatively large intensities.

[0051] Furthermore, as shown in the examples section, when measuring the peaks of powder X-ray diffraction patterns using Cu-Kα rays on multiple samples of the same compound, it was found that all samples almost universally exhibited the aforementioned peak values. However, measurement errors of approximately ±0.2° or ±0.1° could occur. Therefore, in the aforementioned compounding agents, peaks were observed 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 the powder X-ray diffraction patterns using Cu-Kα rays.

[0052] In addition to the aforementioned compounding agents, the thermoplastic resin composition may also contain the following additives.

[0053] [1-2. Antioxidants] The thermoplastic resin composition preferably contains an antioxidant.

[0054] As an antioxidant, at least one of phenolic antioxidants and phosphite antioxidants is preferred. Furthermore, both phenolic antioxidants and phosphite antioxidants can be used simultaneously, and a thermoplastic resin composition containing both phenolic antioxidants and phosphite antioxidants is preferred.

[0055] Examples of 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 e-2,4,6(1H,3H,5H)-trione, 4,4',4''-(1-methylpropyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene di-m-cresol, and 3-(3,5-di-tert-butyl-4-hydroxybenzyl) ...-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2, Octadecyl methyl phenyl propionate, 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, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc., preferably pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0056] As phosphite-based antioxidants, 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxy-3,9-diphosspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane, and 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite Ester, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra-C12-15-alkyl(propane-2,2-dimethylbis(4,1-phenylene))bis(phosphite), 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane, etc., preferably 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane.

[0057] As antioxidants, any one of the above-mentioned agents can be used alone, or a mixture of two or more can be used.

[0058] The thermoplastic resin composition may contain an antioxidant in an amount of 1 ppm to 10,000 ppm by weight, or the antioxidant content may be 1 ppm to 8,000 ppm by weight, 1 ppm to 6,000 ppm by weight, or 1 ppm to 4,000 ppm by weight.

[0059] In the thermoplastic resin composition, based on the total weight of the resin composition, the antioxidant preferably contains 1 ppm to 3000 ppm by weight. More preferably, the antioxidant content in the thermoplastic resin composition is 50 ppm to 2500 ppm by weight, even more preferably 100 ppm to 2000 ppm by weight, particularly preferably 150 ppm to 1500 ppm by weight, and even more preferably 200 ppm to 1200 ppm by weight.

[0060] In addition, the above-mentioned range of antioxidant content refers to the total amount of antioxidants, but any antioxidant can be used at any of the above-mentioned ranges.

[0061] [1-3. Release agent] The thermoplastic resin composition preferably contains a mold release agent.

[0062] As a release agent, ester compounds can be listed, such as glycerol fatty acid esters such as mono- and diglycerides of glycerol fatty acids, propylene glycol fatty acid esters, diol fatty acid esters such as sorbitan fatty acid esters, higher alcohol fatty acid esters, and full esters or mono-fatty acid esters of aliphatic polyols and aliphatic carboxylic acids. When using esters of aliphatic polyols and aliphatic carboxylic acids as a release agent, both mono-esters and full esters can be used, but esters other than full esters, such as mono-esters, can also be used.

[0063] Specific examples of mold release agents can be listed below.

[0064] That is, sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan trisorbitate, sorbitan stearate, sorbitan trisorbitate, and sorbitan caprylate. Propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monosorbitate, propylene glycol monolaurate, and propylene glycol monopalmitate; Higher alcohol fatty acid esters such as stearyl stearate; This includes monoglycerides such as glyceryl monostearate, glyceryl mono-12-hydroxystearate, glyceryl monooleate, glyceryl monosuccinate, glyceryl monocaprylate, glyceryl monodecanoate, and glyceryl monolaurate; and mono- and diglycerides such as glyceryl mono-distearate, glyceryl mono- and distearate, and glyceryl mono- and dioleate. Acetylated monoglycerides of glycerol fatty acid esters such as diacetyl monolaurate; Citric acid fatty acid monoglycerides, succinic acid fatty acid monoglycerides, diacetyl tartaric acid fatty acid monoglycerides, and other glycerol fatty acid esters and organic acid monoglycerides; Diglyceride stearate, diglyceride laurate, diglyceride oleate, diglyceride monostearate, diglyceride monolaurate, diglyceride monomyristate, diglyceride monooleate, tetraglyceride stearate, decaglyceride laurate, decaglyceride oleate, polyglycerol polycastor oil ester, and other polyglycerol fatty acid esters.

[0065] In the thermoplastic resin composition, the release agent preferably contains 1 ppm to 5000 ppm by weight, based on the total weight of the resin composition. More preferably, the content of the release agent in the thermoplastic resin composition is 50 ppm to 4000 ppm by weight, even more preferably 100 ppm to 3500 ppm by weight, particularly preferably 500 ppm to 13000 ppm by weight, and even more preferably 1000 ppm to 2500 ppm by weight.

[0066] Release agents can be used simultaneously with other additives, such as antioxidants. Furthermore, the above-mentioned content ranges for release agents refer to the total dosage range of the release agent; however, any release agent can be used within any of the above-mentioned ranges.

[0067] [1-4. Catalyst deactivators] In thermoplastic resin compositions, a catalyst deactivator is preferably also included as an additive. The catalyst deactivator deactivates the catalyst used for polymerization of the resin composition, thereby stopping the polymerization reaction. By adding a catalyst deactivator, depolymerization of the polymer contained in the resin composition can also be prevented. Alternatively, to prevent an increase in the thermal process of the resin composition due to the addition of a catalyst deactivator, the catalyst deactivator may not be used.

[0068] As catalyst deactivators, esters such as butyl benzoate are preferred; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonates such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphite esters 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; and phosphite esters such as triphenyl phosphate, diphenyl phosphate, and phosphoric acid. Phosphate esters such as monophenyl ester, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonates such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonate esters such as diethyl phenylphosphonate; phosphine derivatives such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboronic acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organohalides such as stearoyl chloride, benzoyl chloride, and p-toluenesulfonyl chloride; alkyl sulfuric acid such as dimethyl sulfuric acid; and organohalides such as benzyl chloride. From the viewpoint of the effectiveness of the deactivator and its impact on resin stability, tetrabutylphosphonium dodecylbenzenesulfonate, p-toluene, or butyl sulfonate are particularly preferred. These deactivators are preferably used at 0.01 to 50 moles relative to the catalyst amount, and more preferably at 0.3 to 20 moles. When the amount is less than 0.01 moles relative to the catalyst amount, the deactivation effect becomes insufficient and is therefore not preferred. In addition, when the amount of catalyst is more than 50 times the molar amount, the heat resistance of the resin decreases and the molded body becomes more easily colored, which is therefore not preferred.

[0069] In the thermoplastic resin composition, the catalyst deactivator preferably contains 1 to 1000 ppm by weight, based on the total weight of the resin composition. More preferably, the content of the catalyst deactivator in the thermoplastic resin composition is 3 to 500 ppm by weight, even more preferably 5 to 100 ppm by weight, and particularly preferably 10 to 50 ppm by weight.

[0070] The catalyst deactivator is preferably added to the thermoplastic resin composition in solution form, such as in aqueous solution. Alternatively, the catalyst deactivator may also be added to the thermoplastic resin composition in the form of an alcohol solution such as methanol or ethanol, or in the form of an organic solvent solution such as phenol.

[0071] [1-5. Other additives] In addition to the aforementioned compounding agents, antioxidants, release agents, and catalyst deactivators, additives may also be added to the thermoplastic resin composition. Examples of additives that may be included in a thermoplastic resin composition include heat stabilizers, plasticizers, fillers, ultraviolet absorbers, rust inhibitors, dispersants, defoamers, leveling agents, flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents, and transparentizing agents.

[0072] The content of additives (hereinafter also referred to as additional additives) other than compounding agents, antioxidants, release agents and catalyst deactivators in the thermoplastic resin composition is preferably 10 ppm to 5.0 wt%, more preferably 100 ppm to 2.0 wt%, and even more preferably 1000 ppm to 1.0 wt%, but not limited thereto.

[0073] Since the above-mentioned additives may have an adverse effect on transmittance, it is preferable to add them in moderation, for example, the total amount added should be within the range mentioned above.

[0074] [1-6. Thermoplastic resins] The thermoplastic resin composition contains thermoplastic resin.

[0075] The thermoplastic resin is preferably any one or more of polycarbonate resin, polyester resin, polyester carbonate resin, cycloolefin resin and acrylic resin.

[0076] The thermoplastic resin preferably contains a polycarbonate resin, a polyester resin or a polyester carbonate resin having a structural unit (B) derived from a monomer of the following general formula (2). In general formula (2), R a and R b The elements are independently selected from halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups having 6 to 20 carbon atoms that may have substituents containing one or more heterocyclic atoms selected from O, N, and S, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h R hIt refers to an aryl group with 6 to 20 carbon atoms that may have substituents, or a heteroaryl group with 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N and S.

[0077] R a and R b Preferably, it is a hydrogen atom, an aryl group with 6 to 20 carbon atoms that may have substituents, or a heteroaryl group with 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N, and S. More preferably, it is a hydrogen atom, an aryl group with 6 to 20 carbon atoms that may have substituents, and even more preferably, it is a hydrogen atom, an aryl group with 6 to 12 carbon atoms that may have substituents.

[0078] In general formula (2), X represents a single bond or a fluorene group that may have substituents. X is preferably a single bond or a fluorene group that may have substituents and has a total number of carbon atoms of 12 to 20.

[0079] In general formula (2), A and B are each independently an alkylene group having 1 to 5 carbon atoms that may have substituents, preferably an alkylene group having 2 or 3 carbon atoms.

[0080] In general formula (2), m and n are independent integers from 0 to 6, preferably integers from 0 to 3, and more preferably 0 or 1.

[0081] In general formula (2), a and b are independent integers from 0 to 10, preferably integers from 1 to 3, and more preferably 1 or 2.

[0082] As a specific example of structural unit (B), structural units from BNE, DPBHBNA, etc. can be listed. The thermoplastic resin preferably contains a polycarbonate resin, a polyester resin or a polyester carbonate resin having a structural unit (C) derived from a monomer of the following general formula (3). In general formula (3), R c and R d The substituents are independently selected from halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents.

[0083] R c and R dPreferably, it is a hydrogen atom, an aryl group with 6 to 20 carbon atoms that may have substituents, or a heteroaryl group with 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N, and S. More preferably, it is a hydrogen atom, an aryl group with 6 to 20 carbon atoms that may have substituents, and even more preferably, it is a hydrogen atom, an aryl group with 6 to 12 carbon atoms that may have substituents.

[0084] In general formula (3), Y1 is a single bond, may be a fluorene group with substituents, or any of the structural formulas shown in general formulas (4) to (9) and (12) to (14) below, preferably a single bond or represented by the structural formula of general formula (4) below. In general formulas (4) and (9), R 21 and R 22 Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, or an aryl group with 6 to 30 carbon atoms that may have substituents, or represent R. 21 and R 22 Carbon rings or heterocycles formed by the combination of various elements can have 1 to 20 carbon atoms and may have substituents.

[0085] In general formulas (7) and (9), r and s are independent integers from 0 to 5000.

[0086] In addition, in general formulas (12) to (14), R 23 and R 24 Each of the following can be independently hydrogen, fluorine, chlorine, bromine or iodine, or can be 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, which may have substituents respectively.

[0087] In the above general formula (3), A and B are each independently an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms. In the above general formula (3), p and q are each independently an integer from 0 to 4, preferably 0 or 1. In addition, in the above general formula (3), a and b are each independently an integer from 0 to 10, preferably an integer from 0 to 5, more preferably an integer from 0 to 2, for example 0 or 1.

[0088] Specific examples of structural unit (C) include those derived from 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'-cyclohexylenebisphenol), and bisphenol P-HTG (4,4'-(3,3,5-trimethylcyclohexylene)). Bisphenol), Bisphenol P-MIBK (4,4'-(1,3-dimethylbutylene)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'-dimethylbis(oxy)bisethanol), S-BOC (4,4'-(1-methylethylidene)bis(2-methylphenol),) TrisP-HAP (4,4',4''-ethylidene triphenol), etc.

[0089] In addition, thermoplastic resins such as polycarbonate resin, which have structural units derived from bisphenol compounds such as bisphenol A and bisphenol AP as structural units (C), have the advantages of producing a wide variety of high-purity products and having good market circulation. Thermoplastic resins can be polymers containing structural unit (B) but not structural unit (C), polymers containing structural unit (C) but not structural unit (B), copolymers containing both structural unit (B) and structural unit (C), mixtures of polymers containing only structural unit (B) and polymers containing only structural unit (C), and combinations thereof. Examples of polymers containing structural unit (C) but not structural unit (B) include polymers having structural units of formulas (I-1) to (I-3). Examples of copolymers containing both structural unit (B) and structural unit (C) include copolymers having structural units of formulas (II-1) to (II-4). Furthermore, specific examples of polymers containing structural unit (C) but not structural unit (B) include polymers composed of only one or more of the above-mentioned BPEF, BPPEF, and bisphenols. In formula (I-1), m and n are integers from 1 to 10, preferably integers from 1 to 5, and more preferably 1. In equation (I-3), n is an integer from 1 to 10, preferably an integer from 1 to 5, and more preferably 1. In addition, although block copolymers and random copolymers with large values ​​of m and n (e.g., 100 or more) can be used as polymers having multiple structural units, random copolymers are preferred, and random copolymers with a value of m and n of 1 are even more preferred. (In equations (II-1) to (II-4), m and n are independent integers from 1 to 10, preferably integers from 1 to 5, and more preferably 1.) In addition, although block copolymers and random copolymers with large values ​​of m and n (e.g., 100 or more) can be used as polymers having multiple structural units, random copolymers are preferred, and random copolymers with a value of m and n of 1 are even more preferred.

[0090] In the copolymer, the molar ratio of structural unit (B) to 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. Furthermore, in the mixture, the weight ratio of the polymer containing only structural unit (B) to the polymer containing only 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.

[0091] Thermoplastic resins can be cycloolefin resins or resins containing cycloolefins. Examples of cycloolefin resins include those having the following structural units. In the above formula, X g Each of these can be independently represented as an alkylene group having 1 to 10 carbon atoms. Examples of alkylene groups having 1 to 10 carbon atoms include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, tert-butylene, and pentylene. Among these, methylene, ethylene, propylene, butylene, isobutylene, and sec-butylene are preferred, and methylene, ethylene, and propylene are more preferred.

[0092] R j R k and R lEach of the following is independently selected from halogen atoms, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 5 to 20 carbon atoms, substituted or unsubstituted cycloalkoxy groups having 5 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 20 carbon atoms containing one or more heterocyclic atoms selected from O, N, and S, substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms, and -C≡C-R i As for the aforementioned R j R k and R l Examples of X can be listed above. a X b X c X d X e and X f The same example.

[0093] Among them, R j R k and R l It may also have substituents. There are no particular restrictions on the substituents, and examples include halogen atoms, alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 5 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, cycloalkyloxy groups with 5 to 10 carbon atoms, alkyloxycarbonyl groups with 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups with 5 to 10 carbon atoms, aryloxycarbonyl groups with 7 to 15 carbon atoms, alkylcarbonyloxy groups with 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups with 5 to 10 carbon atoms, arylcarbonyloxy groups with 7 to 15 carbon atoms, hydroxyalkylcarbonyl groups with 2 to 10 carbon atoms, glycidyloxycarbonyl groups, hydroxyl groups, carboxyl groups, cyano groups, and amide groups with 1 to 10 carbon atoms.

[0094] Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, etc.

[0095] Examples of cycloalkyl groups with 5 to 10 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, and bicyclo[2.2.2]octyl.

[0096] Examples of alkoxy groups with 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentoxy.

[0097] Examples of cycloalkyloxy groups with 5 to 10 carbon atoms include cyclopentyloxy, cyclohexyloxy, bicyclo[2.2.1]heptyloxy, and bicyclo[2.2.2]octyloxy.

[0098] Examples of alkyloxycarbonyl groups with 2 to 10 carbon atoms include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, and tert-butyloxycarbonyl.

[0099] Examples of cycloalkyloxycarbonyl groups with 5 to 10 carbon atoms include cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, bicyclo[2.2.1]heptyloxycarbonyl, and bicyclo[2.2.2]octyloxycarbonyl.

[0100] Examples of aryloxycarbonyl groups with 7 to 15 carbon atoms include phenoxycarbonyl, tolyloxycarbonyl, xyloxycarbonyl, trimethylphenyloxycarbonyl, tetramethylphenyloxycarbonyl, ethylphenyloxycarbonyl, ethylmethylphenyloxycarbonyl, diethylphenyloxycarbonyl, naphthoxycarbonyl, etc.

[0101] Examples of alkyl carbonyloxy groups with 2 to 10 carbon atoms include methyl carbonyloxy, ethyl carbonyloxy, propyl carbonyloxy, isopropyl carbonyloxy, and butyl carbonyloxy.

[0102] Examples of cycloalkyl carbonyloxy groups with 5 to 10 carbon atoms include cyclopentyl carbonyloxy, cyclohexyl carbonyloxy, bicyclo[2.2.1]heptyl carbonyloxy, and bicyclo[2.2.2]octyl carbonyloxy.

[0103] Examples of aryl carbonyloxy groups with 7 to 15 carbon atoms include phenyl carbonyloxy, tolyl carbonyloxy, xylyl carbonyloxy, trimethylphenyl carbonyloxy, tetramethylphenyl carbonyloxy, ethylphenyl carbonyloxy, ethylmethylphenyl carbonyloxy, diethylphenyl carbonyloxy, and naphthyl carbonyloxy.

[0104] Examples of hydroxyalkyl carbonyl groups with 2 to 10 carbon atoms include hydroxymethyl carbonyl, hydroxyethyl carbonyl, and hydroxypropyl carbonyl.

[0105] Examples of amide groups with 1 to 10 carbon atoms include methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, and acetamido.

[0106] The above-mentioned substituents may be present individually or in combination of two or more.

[0107] R i This refers to an aryl group with 6 to 20 carbon atoms, or a heteroaryl group with 3 to 20 carbon atoms containing one or more heterocyclic atoms selected from O, N, and S. The above R... i Same as above.

[0108] p represents an integer that is either 0 or 1, each independently.

[0109] q, r and s each independently represent an integer from 0 to 10, preferably from 0 to 5, and more preferably from 0 to 3.

[0110] t represents an integer from 1 to 3, preferably 1 or 2.

[0111] Here, when q is 2 or more and there are 2 R's j When present in adjacent carbon atoms, 2 R j They can also form a ring structure together. For example, when q is 2 and there are 2 R... j When all are substituted or unsubstituted alkyl groups, the general formula (20) is the following formula (20-1), where q is 2 and there are 2 R groups. j In the case of substituted or unsubstituted alkyl and substituted or unsubstituted cycloalkyl, the general formula (20) can be (20-2), (20-3) or (20-4). In the above formula, X g And p is the same as above.

[0112] R n The substituents mentioned above can specifically include halogen atoms, alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 5 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, cycloalkyloxy groups with 5 to 10 carbon atoms, alkyloxycarbonyl groups with 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups with 5 to 10 carbon atoms, aryloxycarbonyl groups with 7 to 15 carbon atoms, alkylcarbonyloxy groups with 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups with 5 to 10 carbon atoms, arylcarbonyloxy groups with 7 to 15 carbon atoms, hydroxyalkylcarbonyl groups with 2 to 10 carbon atoms, glycidyloxycarbonyl groups, hydroxyl groups, carboxyl groups, cyano groups, and amide groups with 1 to 10 carbon atoms.

[0113] z is not particularly limited, but is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 or 1.

[0114] u represents an integer from 1 to 3, preferably 1 or 2.

[0115] Additionally, when r is 2 or more and there are 2 R's k When present in adjacent carbon atoms, 2 R k They can also form a ring structure together. For example, when r is 2 and there are 2 R... k When all are substituted or unsubstituted alkyl groups, general formula (21) can become formula (21-1) or (21-2), where r is 2 and there are 2 R groups. k In the case of substituted or unsubstituted alkyl and substituted or unsubstituted cycloalkyl, the general formula (21) can be the following formula (21-3). In the above formula, Xg p, R n z and u are the same as above.

[0116] Moreover, when s is 2 or more and there are 2 Rs l When present in adjacent carbon atoms, 2 R l They can also form a ring structure together. For example, when s is 2 and there are 2 R... l When all are substituted or unsubstituted alkyl groups, the general formula (22) can be (22-1) or (22-2) as follows, where s is 2 and there are 2 R groups. l In the case of substituted or unsubstituted alkyl and substituted or unsubstituted cycloalkyl, the general formula (22) can be (22-3) or (22-4). In the above formula, X g p, R n z and u are the same as above.

[0117] R m This refers to an alkyl group having 1 to 3 carbon atoms or hydrogen atoms. There are no particular limitations on the alkyl group having 1 to 3 carbon atoms mentioned above; examples include methyl, ethyl, propyl, and isopropyl.

[0118] As a specific example of a cycloolefin resin, a resin containing at least one of the structural units selected from the following formulas 1 to 8 can be cited. The aforementioned structural units can be contained individually in cyclic olefin resins, or in combination of two or more. Furthermore, they can be combined with structural units of other cyclic polyolefins, or with structural units of other resins (polyolefin resins, polyester resins, etc.).

[0119] The weight-average molecular weight (Mw) of the cyclic olefin resin is not particularly limited, but is preferably 1,000 to 3,000,000, more preferably 10,000 to 3,000,000, even more preferably 20,000 to 1,000,000, and particularly preferably 30,000 to 500,000.

[0120] In addition to the cyclic olefin resins mentioned above, resins (polymers) having structural units containing aliphatic rings can also be used as thermoplastic resins. For example, thermoplastic resins having at least one of the structural units shown in the following formula (23), structural units derived from isosorbide as a monomer, structural units derived from pentacyclic pentadecanediethanol (PCPMD), structural units derived from cyclohexanediethanol, and structural units derived from spirocyclic diol can be used. (In general formula (23), Rp represents an alkyl group with 1 to 4 hydrogen atoms.) In addition, copolymers or blends containing any of the above-mentioned cyclic olefin resins or resins having aliphatic ring structural units, and structural units shown in the following general formula (24) can be used as thermoplastic resins. As specific examples of such thermoplastic resins, copolymers or blends having structural units of the above-mentioned general formula (23) and structural units of the following general formula (24) can be listed. (In general formula (24), Rq and Rs independently represent hydrogen atom, alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms, cycloalkyl group with 5 to 20 carbon atoms, cycloalkoxy group with 5 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms, or aryloxy group with 6 to 20 carbon atoms, respectively, and A and B independently represent alkylene group with 1 to 4 carbon atoms.) Thermoplastic resins may contain acrylic resins. There are no particular limitations on acrylic resins, such as homopolymers of various (meth)acrylates represented by polymethyl methacrylate (PMMA) and methyl methacrylate (MMA), or copolymers of PMMA or MMA with one or more other monomers, and mixtures of various mixtures of these resins can also be mentioned.

[0121] The weight-average molecular weight (Mw) of the thermoplastic resin converted from polystyrene is preferably 10,000 to 300,000, more preferably 15,000 to 100,000, and even more preferably 20,000 to 50,000.

[0122] In addition, 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.

[0123] Thermoplastic resins such as polycarbonate resin, polyester resin, polyester-carbonate resin, cyclic olefin resin, and acrylic resin in thermoplastic resin compositions can be manufactured using known methods. Examples of methods for manufacturing thermoplastic resins include interfacial polymerization, melt transesterification, and condensation polymerization. Examples of methods for manufacturing polycarbonate resins include ring-opening polymerization using cyclic carbonate compounds, pyridine polymerization, and solid-phase transesterification of prepolymers.

[0124] Polycarbonate resins, polyester resins, and polyester-carbonate resins manufactured using interfacial polymerization with chain terminators contain end-group structures derived from the chain terminators. For example, thermoplastic resins may have end groups such as p-tert-butylphenyl, p-tert-octylphenyl, and p-hexadecyl benzoate, respectively, corresponding to phenolic compounds used as chain terminators in interfacial polymerization, such as p-tert-butylphenol, p-tert-octylphenol, and p-hexadecyl benzoate. These end-group structures can improve the flowability of thermoplastic resins such as polycarbonate resins.

[0125] [2. Properties of the thermoplastic resin composition] The thermoplastic resin compositions of the present invention containing a compounding agent are able to maintain a high level of transmittance (%) compared to thermoplastic resin compositions without a compounding agent.

[0126] For example, compared to a control resin composition having the same composition except for the absence of a compounding agent, the transmittance (%) of the thermoplastic resin composition at wavelengths of 370 nm to 400 nm, as measured according to JIS K7105, is at least 2.0% higher. That is, when comparing the transmittance (%) at the same wavelength between the control resin composition without compounding agents and the thermoplastic resin composition of the present invention, as measured according to JIS K7105, at the same wavelength, the transmittance of the thermoplastic resin composition is higher, and the difference between these values ​​can be at least 2.0%. Preferably, the transmittance of the thermoplastic resin composition is at least 3.0% higher than that of the control resin composition, more preferably at least 4.0%.

[0127] Furthermore, for example, compared to a control resin composition having the same composition except for the absence of a compounding agent, the transmittance (%) of the thermoplastic resin composition at wavelengths of 370 nm to 400 nm, as measured according to JIS K7105, is at least 1.1 times higher. That is, when comparing the transmittance (%) at the same wavelength between the control resin composition without compounding agents and the thermoplastic resin composition of the present invention, as measured according to JIS K7105, the transmittance (%) of the thermoplastic resin composition is higher than that of the control resin composition, and is at least 1.1 times higher. Preferably, the transmittance of the thermoplastic resin composition is at least 1.3 times that of the control resin composition, more preferably at least 1.5 times higher.

[0128] When additives, such as mold release agents and antioxidants, are added to the thermoplastic resin composition of the present invention, there is a tendency for the transmittance value of the resulting thermoplastic resin composition to decrease. However, in the thermoplastic resin composition containing the above-mentioned compounding agents, the decrease in transmittance value can be prevented and suppressed.

[0129] Furthermore, compared to a control resin composition with the same composition except for the absence of a compounding agent, one type of thermoplastic resin composition exhibited a lower haze value measured according to JIS K-7361 and JIS K-7136, with a haze value difference exceeding 0.03. This confirms that the aforementioned compounding agent also has the effect of improving the transparency of the thermoplastic resin composition.

[0130] The difference between the haze value of the thermoplastic resin composition and the haze value of the control resin composition 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. Furthermore, one embodiment of the thermoplastic resin composition has a haze value that is 0.15 or more lower than that of the control resin composition; preferably, the thermoplastic resin composition has a haze value that is 0.18 or more lower than that of the control resin composition, or 0.20 or more lower than that of the control resin composition.

[0131] Furthermore, a thermoplastic resin composition of one embodiment has a lower YI value compared to a control resin composition having the same composition as the thermoplastic resin composition except for the absence of a compounding agent. Specifically, the YI value of the thermoplastic resin composition containing the aforementioned compounding agent, for example, the YI value measured according to JIS K 7105, can be 0.20 or lower than the YI value of the thermoplastic resin composition with the same composition except for the absence of a compounding agent. These differences in YI values ​​can be, for example, 0.50 or higher, 0.80 or higher, 0.90 or higher, 1.0 or higher, or even 1.1 or higher.

[0132] As described above, the thermoplastic resin composition of the present invention, which can achieve the maintenance of high transmittance and the improvement of hue as expressed by a low YI value, is suitable for use in optical materials and the like. The thermoplastic resin composition of the present invention is particularly suitable for use as an optical material.

[0133] Furthermore, the thermoplastic resin composition of the present invention exhibits high heat resistance and transparency, and is expected to reduce the amount of volatile components. In particular, the polyester resin composition in the thermoplastic resin composition of the present invention, as detailed later, has been shown to reduce the amount of volatile components at high temperatures, and can suppress odors generated during heating. Therefore, the thermoplastic resin composition of the present invention, mainly the polyester resin composition, is also very useful as, for example, plastics for food container packaging.

[0134] For example, a thermoplastic resin composition of one manner exhibits an equal or better suppression effect on volatile components compared to a control resin composition having the same composition except for the absence of a compounding agent. That is, the thermoplastic resin composition is able to suppress the amount of volatile components generated under specified conditions, such as heating at 250°C for 5 minutes, as described later.

[0135] Specific examples of volatile components include formaldehyde, acetaldehyde, acetone, 2,3-butanedione, acetic acid, and formic acid.

[0136] [3. Method for manufacturing thermoplastic resin composition] The method for manufacturing the thermoplastic resin composition for optical materials of the present invention includes a step of adding the aforementioned compounding agent to a thermoplastic resin. By adding the compounding agent to the thermoplastic resin, the transmittance of the thermoplastic resin, especially the transmittance value at low wavelengths, can be well maintained compared with the thermoplastic resin without the addition of the compounding agent.

[0137] [4. Methods for improving the transmittance of thermoplastic resin compositions] The method for improving the transmittance of a thermoplastic resin composition for optical materials according to the present invention includes a step of adding the aforementioned compounding agent to a thermoplastic resin. By adding the compounding agent to the thermoplastic resin, the transmittance of the thermoplastic resin can be improved, particularly the transmittance value at low wavelengths. Specifically, compared to thermoplastic resins with additives different from the compounding agent, the transmittance value can be improved in thermoplastic resin compositions with further added compounding agents.

[0138] [5. Method for reducing haze of thermoplastic resin compositions] The method for reducing the haze of the thermoplastic resin composition for optical materials according to the present invention includes a step of adding the aforementioned compounding agent to the thermoplastic resin. By adding the compounding agent to the thermoplastic resin, the haze value of the thermoplastic resin can be reduced, particularly the haze value measured 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 control resin composition having the same composition as the thermoplastic resin composition except that it does not contain the compounding agent, and the difference between these haze values ​​is, 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, and may also be 0.30 or more, or 0.40 or more.

[0139] [6. Molded body] The thermoplastic resin composition of the present invention can be used in extrusion molding, blow molding, injection molding, etc.

[0140] Examples of the resulting molded products include extruded products, hollow products, precision parts, and thin-walled injection molded products.

[0141] 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. Examples of molded articles manufactured using such a thermoplastic resin composition include transparent conductive substrates used in optical lenses, optical films, liquid crystal displays, organic EL displays, solar cells, optical discs, liquid crystal panels, optical cards, sheets, phase refraction films, optical fibers, connectors, vapor-deposited plastic mirrors, displays, touch panels, etc. These optical molded articles have high transmittance even when containing additives added for their respective uses.

[0142] Specific examples of molded articles using the thermoplastic resin of this invention in optical materials and related fields include optical media such as compact optical discs, digital video optical discs, mini-discs, and magneto-optical discs; optical communication media such as optical fibers; optical components such as headlight lenses for vehicles and lenses for cameras; hazard light covers; lighting covers; substitutes for window glass for vehicles such as trams or automobiles; substitutes for window glass for homes; lighting components for roofs of skylights or greenhouses; goggles or sunglasses; lenses or frames for eyeglasses; housings for copiers or fax machines and OA equipment such as personal computers; housings for home appliances such as televisions or microwave ovens; electronic components such as connectors or IC trays; and applications such as protective gear such as helmets, protective gear, and protective masks; household items such as nursing bottles, tableware, and trays; medical supplies such as dialysis machines or dentures; packaging materials; notebooks; stationery; and other miscellaneous goods, but not limited to these.

[0143] As molded articles obtained from the thermoplastic resin composition of the present invention, the following items that require high heat resistance and high transparency are particularly preferred: namely, headlight lenses, dashboards, sunroofs, etc., automotive parts, as well as substitutes or outer panel parts for glass windows; various films for liquid crystal displays, light guide plates, optical disc substrates, housings for electronic devices such as smartphones; and building materials such as transparent sheets.

[0144] Furthermore, even for molded articles where the excellent transparency of the thermoplastic resin composition of the present invention is not required, the advantage of easily controlling the degree of coloring using colorants such as pigments and dyes has been confirmed since the resin composition of the raw material is highly transparent.

[0145] Furthermore, an anti-reflective layer or a hard coating may be applied to the surface of the optically shaped body as needed. The anti-reflective layer can be a single layer or multiple layers, and can be organic or inorganic, preferably inorganic. Specific examples include oxides or fluorides of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride.

[0146] [6-1. Optical Lenses] Optical lenses manufactured using the thermoplastic resin composition of the present invention not only possess excellent transmittance characteristics, but optical lenses manufactured using the polycarbonate resin of the present invention also exhibit high refractive index, low Abbe number, and high resistance to damp heat. Therefore, they are highly useful in fields currently using expensive high-refractive-index glass lenses, such as telescopes, binoculars, and television projectors. Preferably, they are used in the form of aspherical lenses. Since aspherical lenses can achieve virtually zero spherical aberration using a single lens, it eliminates the need to combine multiple spherical lenses to eliminate spherical aberration, enabling weight reduction and lower production costs. Therefore, aspherical lenses are particularly useful in optical lenses, especially as camera lenses.

[0147] Optical lenses can be formed by any method, such as injection molding, compression molding, or injection compression molding. Using this invention, high-refractive-index, low-birefractive-index aspherical lenses, which are technically difficult to manufacture with glass lenses, can be obtained more easily.

[0148] To minimize the risk of foreign matter entering the optical lens, the forming environment must be a low-dust environment, preferably level 6 or lower, and more preferably level 5 or lower.

[0149] Optical lenses manufactured 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 injection molding conditions are not particularly limited, but the molding temperature is preferably 180–280°C. Furthermore, the injection pressure is preferably 50–1700 kg / cm². 2 .

[0150] To minimize the risk of foreign matter entering the optical lens, the forming environment must be a low-dust environment, preferably with a dust level of 1000 or lower, and more preferably with a dust level of 100 or lower.

[0151] Optical lenses containing the thermoplastic resin composition of the present invention are suitable for use as aspherical lenses as needed. Since aspherical lenses can achieve substantially zero spherical aberration using a single lens, it eliminates the need for combining multiple spherical lenses to eliminate spherical aberration, thus enabling weight reduction and lower production costs. Therefore, aspherical lenses are particularly useful in optical lenses, especially as camera lenses. The astigmatism of the aspherical lens is preferably 0–15 mλ, more preferably 0–10 mλ.

[0152] The thickness of the optical lens manufactured using the thermoplastic resin composition of the present invention can be set to a wide range depending on the application, and is not particularly limited, preferably 0.01 to 30 mm, more preferably 0.1 to 15 mm. An anti-reflective layer or a hard coating may also be provided on the surface of the optical lens of the present invention, as needed. The anti-reflective layer can be a single layer or multiple layers, and can be organic or inorganic, preferably inorganic. Examples include oxides or fluorides of 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. Furthermore, the anti-reflective layer can be a combination of single and multiple layers, and there are no particular limitations on the combination of their components and thicknesses; it is preferably composed of two or three layers, and particularly preferably three layers. Additionally, the anti-reflective 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.

[0153] [6-2. Optical film] The optical film manufactured using the thermoplastic resin composition of the present invention has excellent transparency and heat resistance, and is therefore suitable for use in films for liquid crystal substrates, optical memory cards, etc.

[0154] To minimize the ingress of foreign matter into the optical film, the molding environment must be a low-dust environment, preferably level 6 or lower, and more preferably level 5 or lower.

[0155] Example The following embodiments illustrate the present invention in more detail. However, the present invention is not limited to the following embodiments, and can be implemented with any modifications without departing from the spirit of the invention.

[0156] [Evaluation Method 1] The evaluation methods for the examples and comparative examples using polycarbonate resins, which are detailed below, are as follows.

[0157] (1-1) Transmittance [%) The granules of the thermoplastic resin composition obtained by the following method were dried in a hot air circulating dryer at 120°C for 5 hours. Then, they were molded into flat test pieces with a width of 40 mm, a length of 40 mm, and a thickness of 3 mm using an injection molding machine (FANUC ROBOSHOT S-2000i30A) at a resin temperature of 260°C, a mold temperature of 130°C, and a molding cycle of 30 seconds. The transmittance (%) of the 3 mm thick portion of the flat test piece was measured using a spectrophotometer (Hitachi High-Tech U-4100) at wavelengths of 370 nm, 380 nm, and 400 nm, according to JIS K7105.

[0158] (1-2-1) Mass-average molecular weight (Mw) The mass-average molecular weight of the resin and resin composition was determined by gel permeation chromatography (GPC) and converted to standard polystyrene. The apparatus, column, and determination conditions are as follows.

[0159] ·GPC device: Made by Tosoh Corporation, HLC-8420GPC; • Chromatographic column: TSKgel SuperHM-M×3, manufactured by Tosoh Corporation; Made by Tosoh Co., Ltd., TSKgel guardcolumn SuperH-H×1 piece; Made by Tosoh Co., Ltd., TSKgel SuperH-RC×1 piece; • Detector: RI detector; • Standard polystyrene: Manufactured by Tosoh Corporation, Standard Polystyrene Set PStQuick C; • Sample solution: 0.2% by mass tetrahydrofuran solution; • Eluent: Tetrahydrofuran; • Elution buffer flow rate: 0.6 mL / min; • Column temperature: 40℃.

[0160] (1-2-2) Viscosity-average molecular weight (Mv) The viscosity-average molecular weight (Mv) of thermoplastic resins is calculated using Schnell's viscosity formula, η = 1.23 × 10⁻⁶. －4 Mv 0.83 Figure it out.

[0161] The intrinsic viscosity [η] (unit: dL / g) is calculated using the following formula. The specific viscosity [η] in the above formula sp The value of η is the specific viscosity of samples of various concentrations [C] (g / dL) prepared by dissolving the resin in dichloromethane solvent, measured at 25°C using an Ubbelohde viscometer. sp The intrinsic viscosity [η] (unit dL / g) is calculated from the values ​​of [C] and [C] using the above formula.

[0162] <Thermoplastic Resin: Synthesis of PC1> The raw materials used were 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 × 10⁻⁶ mol of... －2 16 mL of sodium bicarbonate aqueous solution (4.0 × 10⁻⁶ mol / L)－4 One mole, that is, the total amount of the dihydroxy compound, is 8.4 × 10⁻⁶ moles. －6 The phenol byproduct (mol) was placed into a 50L reactor equipped with a stirrer and distillation removal device, and heated to 180°C under a nitrogen atmosphere of 760 mmHg. After 30 minutes of heating, the raw material was confirmed to be completely dissolved, and then stirred for 120 minutes under the same conditions. The pressure was then adjusted to 200 mmHg, and the temperature was increased to 200°C at a rate of 60°C / hr. At this point, distillation to remove the byproduct phenol was confirmed. The reaction was then maintained at 200°C for 20 minutes. Further, the temperature was increased to 230°C at a rate of 75°C / hr, and after 10 minutes of heating, this temperature was maintained for 2 hours to bring the pressure down to below 1 mmHg. Then, the temperature was increased to 245°C at a rate of 60°C / hr, and stirred for another 40 minutes. After the reaction was complete, nitrogen was introduced into the reactor to restore atmospheric pressure, and the resulting resin was granulated and removed to obtain polycarbonate resin (PC1) as a thermoplastic resin. <Thermoplastic Resin: Synthesis of PC2> The raw materials were changed to 14.978 kg (40,000 mol) of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE), 24.239 kg (45,000 mol) of 9,9-bis[6-(2-hydroxyethoxy)naphthyl-2-yl]fluorene (BNEF), 7.899 kg (15,000 mol) of DPBHBNA, 22.236 kg (103,800 mol) of DPC, and 5.09 × 10⁻⁶ sodium bicarbonate. － 2 g (6.06×10 －4 Except for the molars), the same operation as in Synthesis Example 1 was performed to obtain polycarbonate resin (PC2) as a thermoplastic resin. <Examples 1-3, etc.> The PC1 obtained in Synthesis Example 1 was dry-mixed with additives (release agent, antioxidant) and compounding agents using a rotary drum at the mass ratios shown in Table 1 below. The mixture was then melt-mixed using a twin-screw extruder (IPEC Corporation, IPT type 35mm co-directional twin-screw extruder, L / D = 38) at a barrel temperature of 250°C, a discharge pressure of 25 Torr, and a discharge rate of 20 kg / h. The mixture was extruded into granules to obtain a polycarbonate resin composition in the form of thermoplastic resin. The transmittance of the obtained resin composition was measured, and the results are shown in Table 1.

[0163] [Table 1] Antioxidant AO-60: Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (AO-60 manufactured by ADEKA). Antioxidant PEP-36: 3,9-Bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (PEP-36, manufactured by ADEKA). Release agent S-100A: Glyceryl stearate (Rikken Vitamin Co., Ltd. S-100A); Complexing agent: The following mixture (a 90:10 mixture of 3,4-dimethyl body and 2,4-dimethyl body) is used, and is a commercially available product manufactured by Tokyo Chemical Industry Co., Ltd. <Examples 4-7, etc.> Except for using the PC2 obtained in Synthesis Example 2 with the additives (release agent, antioxidant), compounding agent, and catalyst deactivator aqueous solution at the mass ratios shown in Table 2, the same operation as in Example 1 was performed to obtain a granular thermoplastic polycarbonate resin composition. The transmittance of the obtained resin composition was measured, and the results are shown in Table 2. In the abbreviations shown in Table 2, except that tetrabutylphosphonium dodecylbenzenesulfonate is represented as MGA, they are the same as those shown in the columns of Table 1.

[0164] [Table 2] (1-3) Total light transmittance and haze Samples of the resin compositions of the following examples and comparative examples, molded to a thickness of 3 mm, were measured according to JIS K-7361 and JIS K-7136.

[0165] Measuring instrument: SH7000 spectrophotometer manufactured by Nippon Denshoku Kogyo Co., Ltd.

[0166] (1-4)YI The sample, which was shaped to a thickness of 3 mm, was measured using a spectrophotometer in accordance with JIS K-7105.

[0167] Measuring instrument: SH7000 spectrophotometer manufactured by Nippon Denshoku Kogyo Co., Ltd.

[0168] <Examples 8-10, etc.> In addition to dry mixing PC3 (a cyclic olefin copolymer manufactured by Mitsui Chemicals Co., Ltd., trade name "APEL (registered trademark)" APL5014CL), additives (release agent, antioxidant) and compounding agents in a rotary drum according to the mass ratio shown in Table 3, the mixture was melt-mixed using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., trade name "TEM18ss") at a barrel temperature of 260°C and extruded into granules to obtain a polycarbonate resin composition of granular thermoplastic resin.

[0169] The physical properties of the obtained resin composition were determined, and the results are shown in Table 3.

[0170] The molecular structure of the cyclic olefin copolymer of PC3 is shown in formula (22) above.

[0171] [Table 3] In Examples 8-10, which employed cyclic olefin copolymers having the aforementioned molecular structure, the reduction in transmittance in the low-wavelength region was not significant compared to other examples, but haze characteristics were improved. Furthermore, in the polycarbonate resin compositions of Examples 8-10, it was also confirmed that the YI value was controlled to be low, resulting in excellent hue.

[0172] (1-5) Powder X-ray diffraction The powder X-ray diffraction conditions for each crystal of the complexing agent used in Example 1, etc. (a mixture of 90:10 of 3,4-dimethyl and 2,4-dimethyl forms in which two of R1 to R5 in general formula (1) are methyl and the other two are hydrogen, and two of R6 to R9 are tert-butyl and the other two are hydrogen) are as follows.

[0173] An appropriate amount of the crystallized object to be measured was filled into the sample filling part of the glass test plate, and the measurement was performed using a powder X-ray diffraction apparatus (RIGAKU MiniFlex600, Ltd.) under the following conditions.

[0174] X-ray: CuKα (40kV, 15mA); Kβ filter: Ni filter 0.015mm×1 piece; Scanning speed: 10° / min; Step width: 0.02°; Scan axis: 2θ / θ; Scanning range: 5°~90°; Entrance slit (DS): 1.25°; Long side limiting slit (IHS): 10.0 mm; Light-receiving slit 1 (SS): 8.0 mm; Light-receiving slit 2 (RS): 13.0 mm.

[0175] Powder X-ray diffraction was performed on three batches of the above-mentioned complexing agent (samples 1-3). Sample 1 was the one actually used in Example 1, while samples 2 and 3, although containing the same compound as sample 1, were separately manufactured.

[0176] The measurement results, in addition to the main peaks at 13.2°, 15.2°, and 20.8°, also confirmed 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 below). Figures 1-3 ).

[0177] In addition, as shown in Table 4 below, roughly the same peak values ​​will be displayed between different samples, but there may be a measurement error of about ±0.2° or ±0.1°.

[0178] [Table 4] [Evaluation Method 2] The evaluation methods in the examples of polyester resins and polyester resin compositions detailed below are as follows.

[0179] (2-1) The ratio of diol units with cyclic acetal skeletons to alicyclic diol units The ratio of units from diols with a cyclic acetal backbone and units from alicyclic diols in polyester resins is determined by... 1 The results were obtained by ¹H-NMR spectroscopy. The measuring apparatus was a Bruker BioSpin KK Ascend TM500. Deuterated chloroform was used as the solvent.

[0180] (2-2) Glass transition temperature The glass transition temperature (Tg) of polyester resin was determined using a differential scanning calorimeter (model: DSC / TA-50WS) manufactured by Shimadzu Corporation. Approximately 10 mg of sample was placed in an aluminum unsealed container and heated at a rate of 20 °C / min in a nitrogen (30 ml / min) gas stream. The temperature at which only half of the difference between the baselines before and after the transition of the DSC curve changed was taken as the glass transition temperature.

[0181] (2-3) YI value of granules The measurements were performed according to JIS K-7105 and using the “ZE2000” manufactured by Nippon Denshoku Kogyo Co., Ltd.

[0182] (2-4) Volatile component content during pellet melting The relative value of the peak area of ​​the low molecular weight compound (volatile component) obtained by GC-MS (headspace) per unit weight of the sample is taken as the volatile component amount (%). That is, the relative value of the peak area of ​​the volatile component in other examples, etc., corresponding to the value of 100% of the peak area of ​​the volatile component in Comparative Example 5 or Comparative Example 8 described later, is taken as the volatile component amount (%).

[0183] The details are as follows.

[0184] 0.3 g of dried granules was placed in an HS sample vial and sealed with a rubber stopper under air. After heating in a dry heater at 250 °C for 5 minutes, analysis was immediately initiated using a headspace-GC-MS apparatus. During analysis, the peak area per unit weight of each sample was determined using characteristic ion extraction mass spectrometry for each compound. The apparatus and measurement conditions are as follows.

[0185] [HS] Agilent G1888 Heating temperature and time: 250℃ for 5 minutes (external thermostat) +230℃ for 1 min; Loop temperature: 240℃; TR LINE Temperature: 250℃; In-bottle equilibration: 1 min; In-bottle pressurization: 0.5 min (15 psi); Ring filling: 0.2 min, ring equilibration: 0.2 min, injection: 0.1 min; GC cycle: 35 min analysis + 10 min equilibration; Carrier gas pressure: 16.5 psi.

[0186] [GC] Agilent 8890 Column: DB-WAX (Φ0.25mm×60×t0.5μm); Furnace temperature: 40℃ for 5 min ~ 10℃ / min ~ 240℃ (10 min); Column flow: He 1.0ml / min; Split ratio: 1 / 10; Injection temperature: 240℃; MSD transfer line: 240℃.

[0187] [MS] Agilent 5977B MSD Gain coefficient: 1; Scan range: m / z = 29 to 700.

[0188] <Examples 11-14, etc.> Examples 11 to 14, etc., using polyester resin will be described below.

[0189] <Manufacturing Example> Synthesis of polyester resins (PEs-1 and PEs-2) A 30L polyester manufacturing unit, equipped with a packed column distillation column, a partial condenser, a total condenser, a cold trap, a stirrer, a heating device, and a nitrogen inlet pipe, was introduced with the raw material monomers listed in Table 5 below. Tetra-n-butoxytitanium and potassium acetate (0.005 mol%) were added relative to the dicarboxylic acid composition. The mixture was heated to 225°C under a nitrogen atmosphere to carry out a transesterification reaction. After the conversion rate of the dicarboxylic acid composition reached over 90%, germanium dioxide (0.025 mol%) and triethyl phosphate (0.05 mol%) were added relative to the dicarboxylic acid composition. The temperature was gradually increased and the pressure reduced, ultimately undergoing polycondensation at 280°C and below 0.1 kPa. The reaction was terminated when a suitable melt viscosity was reached, synthesizing polyester resins PEs-1 and PEs-2, respectively.

[0190] [Table 5] The meanings of the abbreviations in Table 5 are as follows.

[0191] DMT: Dimethyl terephthalate; NDCM: Dimethyl 2,6-naphthalenedicarboxylate; EG: Ethylene glycol; SPG: 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; CHDM: 1,4-cyclohexanediethanol.

[0192] (Preparation of mixed granules) Using a twin-screw compounding extruder (TECHNOVEL Co., Ltd., model: KZW15TW-30MG-NH(-700), screw diameter: 15mmφ, L / D: 30), the polyester resins PEs-1 and PEs-2 synthesized in the above manufacturing example were dry-blended with antioxidants in a specified ratio and fed into the hopper. The extrusion was carried out under the conditions of barrel temperature 210–280°C, die temperature 280°C, screw speed 60 rpm, and discharge rate 1.4 kg / h. After air cooling, the extruded material was granulated to obtain pure polyester resin extruded granules and additive compounded granules. The types and amounts of additives are shown in Tables 6 and 7, respectively.

[0193] The additives used are as described below.

[0194] Antioxidant Irganox 1330: 3,3',3'',5,5',5''-Hexa-tert-butyl-α,α',α''-(mesitylene-2,4,6-triyl)tri-p-cresol (3,3',3'',5,5',5''-Hexa-tert-butyl-.alpha,.alpha',.alpha''-(mesitylene-2,4,6-triyl)tri-p-cresol) (BASF JAPAN Irganox 1330); Antioxidant PEP-36: 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphospha[5,5]undecane (PEP-36 manufactured by ADEKA). Complexing agent: The following mixture (a 90:10 mixture of 3,4-dimethyl and 2,4-dimethyl) was used, which is a commercially available product manufactured by Tokyo Chemical Industry Co., Ltd. [Table 6] [Table 7] Compared with the polyester resin compositions without compounding agents in Comparative Examples 7-11, the polyester resin compositions with added compounding agents in Examples 11-14 showed that the YI reduction effect and the volatile component reduction effect of the mixed granules were achieved.

[0195] In addition, although the reduction effect of volatile component content was approximately the same as that of the comparative examples (Example 12 and Comparative Example 9) in these embodiments, the reduction effect brought about by the addition of the complexing agent was confirmed.

[0196] <Examples 15-18, etc.> Examples 15 to 18, etc., using bisphenol-based polycarbonate resins will be described below.

[0197] Except for changing the use of the polycarbonate resin, additives (release agent, antioxidant), and compounding agents shown in Tables 8-11 below at the mass ratios shown below, the same operation as in Example 1 was performed to obtain a granular thermoplastic polycarbonate resin composition. The obtained physical property values ​​are shown in Tables 8-11.

[0198] Example 15 PCa: Bisphenol A type aromatic polycarbonate is used, which is the trade name Iupizeta T-3840 (viscosity average molecular weight Mv: 13,500) manufactured by Mitsubishi Gas Chemical Co., Ltd. with the terminal structure of p-tert-octylphenyl.

[0199] [Table 8] Example 16 PCb: Bisphenol A type aromatic polycarbonate is used, which is the trade name Iupizeta T-3700 (viscosity average molecular weight Mv: 17,500) manufactured by Mitsubishi Gas Chemical Co., Ltd. with the terminal structure of p-tert-octylphenyl.

[0200] [Table 9] Example 17 PCc: Bisphenol A type aromatic polycarbonate is used, which is the trade name Iupizeta T-1380 (viscosity average molecular weight Mv: 25,500) manufactured by Mitsubishi Gas Chemical Co., Ltd. with a terminal structure of hexadecyl terebenzoate.

[0201] [Table 10] Example 18 PCd: FPC-0210 (viscosity-average molecular weight Mv: 11,500) manufactured by Mitsubishi Gas Chemical Co., Ltd., which uses bisphenol AP as the starting material and p-tert-butylphenol as the chain terminator to obtain an aromatic polycarbonate by interfacial polymerization.

[0202] [Table 11] In the polycarbonate resin compositions of Examples 15-18, compared with the corresponding comparative examples, not all of the increases in transmittance, decreases in YI value, and decreases in haze value were achieved, but good properties were generally observed.

Claims

1. A thermoplastic resin composition, characterized in that: Contains a compounding agent and a thermoplastic resin as shown in the following general formula (1), The thermoplastic resin includes polycarbonate resin, polyester resin, or polyester carbonate resin containing structural units derived from spirocyclic diols. In general formula (1), R1 to R5 each independently represent a hydrogen atom, or an alkyl group with or without substituents, having a total carbon number of 1 to 20. R6 to R9 each independently represent a hydrogen atom, or an alkyl group with or without substituents, having a total of 1 to 20 carbon atoms. R 10 An alkyl group representing 1 to 5 hydrogen atoms or a total number of carbon atoms.

2. The thermoplastic resin composition according to claim 1, characterized in that: It also contains antioxidants.

3. The thermoplastic resin composition according to claim 2, characterized in that: The antioxidant is a phenolic antioxidant and / or a phosphite antioxidant.

4. The thermoplastic resin composition according to claim 2 or 3, characterized in that: Based on the total weight of the resin composition, it contains 1 ppm to 10,000 ppm of the antioxidant.

5. The thermoplastic resin composition according to claim 4, characterized in that: Based on the total weight of the resin composition, it contains 1 to 3000 ppm by weight of the antioxidant.

6. The thermoplastic resin composition according to claim 1 or 2, characterized in that: Based on the total weight of the resin composition, it contains 1 ppm to 10,000 ppm of the compounding agent.

7. The thermoplastic resin composition according to claim 6, characterized in that: Based on the total weight of the resin composition, it contains 1 to 2000 ppm by weight of the compounding agent.

8. The thermoplastic resin composition according to claim 1 or 2, characterized in that: Compared with a control resin composition having the same composition except that it does not contain the aforementioned compounding agent, the transmittance % value in the wavelength range of 370 nm to 400 nm, as measured according to JIS K7105, is more than 2.0% greater.

9. The thermoplastic resin composition according to claim 1 or 2, characterized in that: Compared with a control resin composition having the same composition except that it does not contain the aforementioned compounding agent, the transmittance % value in the wavelength range of 370 nm to 400 nm, as measured according to JIS K7105, is more than 1.1 times higher.

10. The thermoplastic resin composition according to claim 1 or 2, characterized in that: 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 It is a hydrogen atom.

11. The thermoplastic resin composition according to claim 1 or 2, characterized in that: In the general formula (1), the substituent is any one of halogen, cyano, alkenyl, alkynyl, and alkoxy.

12. The thermoplastic resin composition according to claim 1 or 2, characterized in that: It also contains thermoplastic resins selected from cycloolefin resins and acrylic resins.

13. The thermoplastic resin composition according to claim 1 or 2, characterized in that: The thermoplastic resin also contains structural unit (B), which is derived from a monomer represented by the following general formula (2). In general formula (2), R a and R b The atoms are independently selected from hydrogen atoms, halogen atoms, alkyl groups with or without substituents having 1 to 20 carbon atoms, alkoxy groups with or without substituents having 1 to 20 carbon atoms, cycloalkyl groups with or without substituents having 5 to 20 carbon atoms, cycloalkoxy groups with or without substituents having 5 to 20 carbon atoms, aryl groups with or without substituents having 6 to 20 carbon atoms, heteroaryl groups with or without substituents having 6 to 20 carbon atoms containing one or more heterocyclic atoms selected from O, N, and S, aryloxy groups with or without substituents having 6 to 20 carbon atoms, and -C≡C-R. h , R h This refers to an aryl group with 6 to 20 carbon atoms, with or without substituents, or a heteroaryl group with 6 to 20 carbon atoms, with or without substituents, containing one or more heterocyclic atoms selected from O, N, and S. X represents a single bond or a fluorene group with or without substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms, with or without substituents. m and n independently represent integers from 0 to 6. a and b represent integers from 0 to 10 independently.

14. The thermoplastic resin composition according to claim 1 or 2, characterized in that: The thermoplastic resin also contains structural units (C) derived from monomers represented by the following general formula (3). In general formula (3), R c and R d The atoms are independently selected from hydrogen atoms, halogen atoms, alkyl groups with or without substituents having 1 to 20 carbon atoms, alkoxy groups with or without substituents having 1 to 20 carbon atoms, cycloalkyl groups with or without substituents having 5 to 20 carbon atoms, cycloalkoxy groups with or without substituents having 5 to 20 carbon atoms, and aryl groups with or without substituents having 6 to 20 carbon atoms. A and B independently represent alkylene groups with 1 to 5 carbon atoms, with or without substituents. p and q represent integers from 0 to 4 independently. a and b independently represent integers from 0 to 10. Y1 is a fluorene group with or without substituents, or any of the structural formulas shown in general formulas (4) to (9) and (12) to (14) below. In general formulas (4) to (9), R 21 and R 22 Each of the following can independently represent a hydrogen atom, a halogen atom, an alkyl group with or without substituents and having 1 to 20 carbon atoms, or an aryl group with or without substituents and having 6 to 30 carbon atoms, or R. 21 and R 22 Carbon rings or heterocycles with 1 to 20 carbon atoms, with or without substituents, formed by the combination of various elements. r and s independently represent integers from 0 to 5000. In general formulas (12) to (14), R 23 and R 24 Each can independently represent a hydrogen atom, fluorine, chlorine, bromine, or iodine, or can represent an alkyl group with 1 to 9 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, an alkenyl group with 2 to 12 carbon atoms, or an aryl group with 6 to 12 carbon atoms, with or without substituents.

15. The thermoplastic resin composition according to claim 1 or 2, characterized in that: The weight-average molecular weight (Mw) of the thermoplastic resin converted from polystyrene is 10,000 to 300,000.

16. The thermoplastic resin composition according to claim 14, characterized in that: In the general formulas (2) and (3), A and B independently represent alkylene groups having 2 or 3 carbon atoms, respectively.

17. The thermoplastic resin composition according to claim 1 or 2, characterized in that: The thermoplastic resin contains at least structural units from any of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 9,9-bis[6-(2-hydroxyethoxy)naphth-2-yl]fluorene, and DPBHBNA as shown below. 。 18. The thermoplastic resin composition according to claim 1 or 2, characterized in that: It also contains a catalytic deactivator.

19. The thermoplastic resin composition according to claim 18, characterized in that: The catalytic deactivator contains dodecylbenzene sulfonate.

20. The thermoplastic resin composition according to claim 1 or 2, characterized in that: It also contains a mold release agent.

21. The thermoplastic resin composition according to claim 20, characterized in that: Based on the total weight of the resin composition, it contains 1 ppm to 5000 ppm of the release agent.

22. The thermoplastic resin composition according to claim 1 or 2, characterized in that: The complexing agent of the general formula (1) contains a peak 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 rays.

23. The thermoplastic resin composition according to claim 1 or 2, characterized in that: It is used in optical materials.

24. The thermoplastic resin composition according to claim 1 or 2, characterized in that: The complexing agent represented by general formula (1) is a complexing agent represented by formula (10) or (11). 。 25. A molded body, characterized in that: A thermoplastic resin composition comprising any one of claims 1 to 24.

26. The use of a compounding agent represented by the following general formula (1) in a thermoplastic resin composition, wherein the compounding agent is used to increase the transmittance % of the thermoplastic resin composition in the wavelength range of 370 nm to 400 nm, characterized in that: The thermoplastic resin composition contains a thermoplastic resin, which comprises a polycarbonate resin, a polyester resin, or a polyester carbonate resin containing structural units derived from spirocyclic diols. In general formula (1), R1 to R5 each independently represent a hydrogen atom, or an alkyl group with or without substituents, having a total carbon number of 1 to 20. R6 to R9 each independently represent a hydrogen atom, or an alkyl group with or without substituents, having a total of 1 to 20 carbon atoms. R 10 An alkyl group representing 1 to 5 hydrogen atoms or a total number of carbon atoms.

27. The application as described in claim 26, characterized in that: The complexing agent represented by general formula (1) is a complexing agent represented by formula (10) or (11). 。 28. The application as described in claim 26 or 27, characterized in that: Peaks are observed 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 the powder X-ray diffraction pattern using Cu-Kα rays.

29. A method for manufacturing a thermoplastic resin composition for optical materials, characterized in that: The process includes adding a compounding agent of the following general formula (1) to a thermoplastic resin. The thermoplastic resin includes polycarbonate resin, polyester resin, or polyester carbonate resin containing structural units derived from spirocyclic diols. In general formula (1), R1 to R5 each independently represent a hydrogen atom, or an alkyl group with or without substituents, having a total carbon number of 1 to 20. R6 to R9 each independently represent a hydrogen atom, or an alkyl group with or without substituents, having a total of 1 to 20 carbon atoms. R 10 An alkyl group representing 1 to 5 hydrogen atoms or a total number of carbon atoms.

30. A method for improving the transmittance of a thermoplastic resin composition, characterized in that: The process includes adding a compounding agent of the following general formula (1) to a thermoplastic resin. The thermoplastic resin includes polycarbonate resin, polyester resin, or polyester carbonate resin containing structural units derived from spirocyclic diols. In general formula (1), R1 to R5 each independently represent a hydrogen atom, or an alkyl group with or without substituents, having a total carbon number of 1 to 20. R6 to R9 each independently represent a hydrogen atom, or an alkyl group with or without substituents, having a total of 1 to 20 carbon atoms. R 10 An alkyl group representing 1 to 5 hydrogen atoms or a total number of carbon atoms.

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