Optical lenses containing thermoplastic resin

Abstract

According to the present invention, an optical lens comprising a thermoplastic resin having a constituent unit (A) derived from a monomer represented by the following general formula (1) and a constituent unit (B) derived from BPEF or BPPEF represented by the following structural formula, wherein the molar ratio (A:B) of the aforementioned constituent unit (A) and the aforementioned constituent unit (B) is 5:95 to 79:21. (In general formula (1), R1 to R4 are each independent and represent a hydrogen atom, a halogen atom, a branchable alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.)

Description

Technical Field

[0001] This invention relates to optical lenses containing thermoplastic resins. More specifically, this invention relates to optical lenses containing polycarbonate resins. Prior Technology

[0002] Optical lenses, used in the optical systems of various cameras such as cameras, thin-film cameras, and camcorders, are made of optical glass or optical resin. While optical glass has excellent heat resistance, transparency, dimensional stability, and chemical resistance, it also suffers from high material costs, poor formability, and low manufacturability.

[0003] On the other hand, optical lenses made of optical resins have the advantage of being mass-produced by injection molding. As a high refractive index material for camera lenses, polycarbonate, polyester carbonate, polyester resin, etc. are used.

[0004] When using optical resins as optical lenses, in addition to optical properties such as refractive index or Abbe number, properties such as heat resistance, transparency, low water absorption, chemical resistance, low birefringence, and resistance to damp heat are also sought. In recent years, in particular, there has been a pursuit of optical lenses with high refractive index and high heat resistance, leading to the development of various resins (Patent Documents 1-5).

[0005] Furthermore, thermoplastic resins made from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene possess excellent optical properties and can be used as various optical materials (Patent Document 6). However, with the expansion of various molding processes and usage environments, there is a pursuit to improve the rate of change in mass or size. [Previous Technical Documents] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2018-2893 [Patent Document 2] Japanese Patent Application Publication No. 2018-2894 [Patent Document 3] Japanese Patent Application Publication No. 2018-2895 [Patent Document 4] Japanese Patent Application Publication No. 2018-59074 [Patent Document 5] WO2017 / 078073 [Patent Document 6] WO2014 / 073496 Summary of the Invention

[0007] [The problem that the invention aims to solve]

[0008] The present invention relates to optical lenses made of thermoplastic resin that provide excellent optical properties such as refractive index or Abbe number, as well as excellent rates of change in mass or size. [Methods used to solve problems]

[0009] In order to solve previous problems, the inventors have diligently reviewed the results and discovered that by combining a specific amount of a diol compound with a specific structure, an optical lens containing thermoplastic resin can be obtained with excellent optical properties such as refractive index or Abbe number, as well as excellent mass change rate or dimensional change rate, thus completing the present invention.

[0010] That is, the present invention includes the following states. <1> An optical lens comprising a thermoplastic resin having a constituent unit (A) derived from a monomer represented by the following general formula (1) and a constituent unit (B) derived from a BPEF or BPPEF represented by the following structural formula. The molar ratio (A:B) between the aforementioned constituent unit (A) and the aforementioned constituent unit (B) is 5:95 to 79:21. (In general formula (1), R1 to R4 are independent and represent hydrogen atoms, halogen atoms, branchable alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, or aryl groups with 6 to 15 carbon atoms.) <2> As mentioned above <1> The optical lens described herein contains a constituent unit (C) derived from BCFL represented by the following structural formula. <3> As mentioned above <1> or <2> The optical lens described herein, wherein the proportion of the aforementioned constituent unit (A) in the total constituent units of the aforementioned thermoplastic resin is 5 to 50 moles. <4> As mentioned above <1> ~ <3> In any of the optical lenses described herein, the proportion of the aforementioned constituent unit (B) in the total constituent units of the aforementioned thermoplastic resin is 11 to 95 moles. <5> As mentioned above <2> The optical lens described herein, wherein the proportion of the aforementioned constituent unit (C) in the total constituent units of the aforementioned thermoplastic resin is 0 to 50 moles. <6> As mentioned above <1> ~ <5> The optical lens described in any one of the above, wherein the Tg of the aforementioned thermoplastic resin is 120℃~160℃. <7> As mentioned above <1> ~ <6> The optical lens described in any one of the above, wherein the refractive index (nD) of the aforementioned thermoplastic resin is 1.600 to 1.660. <8> As mentioned above <1> ~ <7> The optical lens described in any one of the above, wherein the Abbe number of the aforementioned thermoplastic resin is 21.0 to 27.0. <9> As mentioned above <1> ~ <8> The optical lens described in any one of the above, wherein the mass change rate of the aforementioned thermoplastic resin is less than 0.47%. <10> As mentioned above <1> ~ <9> The optical lens described in any one of the above, wherein the dimensional change rate of the aforementioned thermoplastic resin is 0.060% or less. [Effects of the Invention]

[0011] According to the present invention, an optical lens containing thermoplastic resin can be provided, which has excellent optical properties such as refractive index or Abbe number, and also excellent mass change rate or dimensional change rate. [Optimal Form of Invention Implementation]

[0012] The present invention will be described in detail below by way of examples of synthesis or embodiments, but the present invention is not limited to the examples of synthesis or embodiments shown. Any modifications can be made without significantly departing from the scope of the present invention.

[0013] <Thermoplastic Resins> The optical lens of the present invention comprises a thermoplastic resin containing a constituent unit (A) derived from a monomer represented by the following general formula (1) and a constituent unit (B) derived from BPEF (9,9-bis[4-(2-hydroxyethoxy)phenyl]fue) or BPPEF (9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fue) represented by the following structural formula.

[0014] [Constituting Unit (A)] In general formula (1), R1 to R4 are each independent and represent a hydrogen atom, a halogen atom, a branchable alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an alkoxy group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), or an aryl group having 6 to 15 carbon atoms (preferably 6 to 10 carbon atoms, more preferably 6 carbon atoms). R1 ​​to R4 are more preferably each independent and represent a hydrogen atom, a methyl group, or a phenyl group. In this invention, BPM (1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene), represented by the following structural formula, is particularly preferred as the monomer represented by the aforementioned general formula (1). This compound is also known as bisphenol M.

[0015] [Constituting Unit (B)] In this invention, the molar ratio (A:B) between the aforementioned constituent unit (A) and the aforementioned constituent unit (B) is 5:95 to 79:21, but preferably 8:92 to 77:23, and even more preferably 10:90 to 70:30. In this invention, BPEF and BPPEF can be commercially available or synthetic products.

[0016] [Constituent Unit (C)] In a preferred embodiment of the invention, the aforementioned thermoplastic resin further comprises a constituent unit (C) derived from BCFL (biscresolphite) represented by the following structural formula.

[0017] In a preferred embodiment of the present invention, the proportion of constituent unit (A) in the total constituent units of the aforementioned thermoplastic resin is 5-50 mol%, more preferably 8-48 mol%, the proportion of constituent unit (B) is 11-95 mol%, more preferably 14-92 mol%, and the proportion of constituent unit (C) is 0-50 mol%, more preferably 0-38 mol.

[0018] The thermoplastic resin used in the optical lens of the present invention is polyester resin, polycarbonate resin, polyester carbonate resin, epoxy resin, polyurethane resin, polyacrylate resin, polymethacrylate resin, etc., although not particularly limited, but polycarbonate resin, polyester resin or polyester carbonate resin is preferred, and polycarbonate resin is even more preferred.

[0019] In a preferred embodiment of the present invention, the proportion of the total number of constituent units (A), (B) and (C) in the thermoplastic resin is preferably 80-100 mol%, more preferably 90-100 mol%, and particularly preferably 100 mol%. That is, the thermoplastic resin used in this invention, in addition to the constituent units (A) to (C), may also include constituent units derived from aliphatic dihydroxy compounds or aromatic dihydroxy compounds that are generally used as constituent units of polycarbonate resin or polyester carbonate resin, without impairing the effectiveness of this invention. Specifically, various examples can be given for aliphatic dihydroxy compounds, but some examples include 1,4-cyclohexanediethanol, tricyclodecanediethanol, 1,3-adamantanediethanol, 2,2-bis(4-hydroxycyclohexyl)-propane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 2-(5-ethyl-5-hydroxymethyl-1,3-dioxane-2-yl)-2-methylpropane-1-ol, isosorbide, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. Regarding aromatic dihydroxy compounds, a wide variety of examples can be cited, but specific examples include 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkanes, bis(4-hydroxyphenyl)oxides, bis(4-hydroxyphenyl)sulfides, bis(4-hydroxyphenyl) sulfides, bis(4-hydroxyphenyl) sulfides, bis(4-hydroxyphenyl) sulfides, and bis(4-hydroxyphenyl) ketones, bisphenoxyethanol, etc.

[0020] In one embodiment of the present invention, the thermoplastic resin is preferably a constituent unit comprising at least one monomer selected from the group of monomers described below. (In the above formula, R1 and R2 are independent and represent hydrogen atoms, methyl or ethyl groups, and R3 and R4 are independent and represent hydrogen atoms, methyl groups, ethyl groups, or alkyldiols with 2 to 5 carbon atoms.)

[0021] In a preferred embodiment of the present invention, the polycarbonate resin contains impurities such as phenolic compounds generated as byproducts during manufacturing, unreacted diol components, or diester carbonates. Impurities such as phenolic compounds, alcoholic compounds, or diester carbonates can reduce the strength of molded products or cause odor, so the lower the content of these, the better.

[0022] The content of residual phenolic compounds, relative to 100% by mass of polycarbonate resin, is preferably less than 3000 ppm by mass, more preferably less than 1000 ppm by mass, and even more preferably less than 300 ppm by mass. The content of residual diol components, relative to 100% by mass of polycarbonate resin, is preferably less than 1000 ppm by mass, more preferably less than 100 ppm by mass, and even more preferably less than 10 ppm by mass. The residual diester content, relative to 100% by mass of polycarbonate resin, is preferably less than 1000 ppm by mass, more preferably less than 100 ppm by mass, and even more preferably less than 10 ppm by mass. In particular, the content of compounds such as phenols and t-butylphenols is preferably in small amounts, and these compounds are preferably within the above-mentioned range.

[0023] The content of residual phenolic compounds in polycarbonate resin can be determined by analyzing the phenolic compounds extracted from the polycarbonate resin using gas chromatography. The content of residual alcohol compounds in polycarbonate resin can also be determined by analyzing the alcohol compounds extracted from the polycarbonate resin using gas chromatography. The content of residual diols and diesters in polycarbonate resins can also be determined by extracting these compounds from the polycarbonate resins and analyzing them using gas chromatography.

[0024] The content of byproducts such as phenolic compounds, alcohols, glycols, and diesters can be reduced to undetectable levels. However, from a production standpoint, small amounts are acceptable without compromising effectiveness. Furthermore, even in very small quantities, the resin can maintain good plasticity during melting.

[0025] The content of residual phenolic compounds, glycol components, or diesters, relative to 100% by mass of polycarbonate resin, may be, for example, 0.01 ppm or more, 0.1 ppm or more, or 1 ppm or more. The content of residual alcohol compounds, relative to 100% by mass of polycarbonate resin, may be, for example, 0.01 ppm or more, 0.1 ppm or more, or 1 ppm or more.

[0026] Furthermore, the content of byproducts such as phenolic compounds, alcohols, glycols, and diesters in polycarbonate resin can be adjusted to the aforementioned range by appropriately adjusting the polycondensation conditions or equipment settings. Additionally, the content can also be adjusted by the conditions of the extrusion step after polycondensation.

[0027] For example, the residual amount of alcohol compounds, byproducts of phenolic compounds, is related to the type of diester used in the polymerization of polycarbonate resin, as well as the polymerization temperature and pressure. By adjusting these factors, the residual amount of alcohol compounds, byproducts of phenolic compounds, can be reduced.

[0028] For example, when using dialkyl carbonates such as diethyl carbonate to manufacture polycarbonate resins, the molecular weight may be difficult to increase, resulting in low molecular weight polycarbonate, and the content of byproduct alkyl alcohol compounds may easily increase. These alkyl alcohols are highly volatile, and if they remain in the polycarbonate resin, the resin's formability tends to deteriorate. Furthermore, a high residual amount of byproduct alcohol compounds such as phenolic compounds may lead to odor problems during resin molding or, during compounding, the resin skeleton may undergo a cracking reaction, resulting in a decrease in molecular weight. Therefore, the residual byproduct alcohol compound content in the obtained polycarbonate resin is preferably below 3000 ppm (by mass) relative to the polycarbonate resin (100% by mass). The residual alcohol compound content, relative to 100% by mass of the polycarbonate resin, is preferably below 3000 ppm (by mass), more preferably below 1000 ppm (by mass), and even more preferably below 300 ppm (by mass).

[0029] A preferred embodiment of the polycarbonate resin of the present invention can be manufactured in the presence of an alkaline compound catalyst, an ester exchange catalyst, or a mixture thereof as a polycondensation catalyst.

[0030] In terms of alkaline compound catalysts, examples include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.

[0031] Regarding alkali metal compounds, examples include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, or alcohols of alkali metals. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium borophenylide, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, sodium hydrogen phosphate, potassium hydrogen phosphate, lithium hydrogen phosphate, sodium phenyl phosphate, sodium bisphenol A (sodium, potassium, cesium, and lithium salts), and sodium, potassium, cesium, and lithium salts of phenols are preferred. From the perspectives of catalytic effect, price, circulation volume, and influence on resin color, sodium carbonate and sodium bicarbonate are the best choices.

[0032] Regarding alkaline earth metal compounds, examples include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, or alcohols. Specifically, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, and magnesium phenyl phosphate are examples.

[0033] Regarding nitrogen-containing compounds, examples include quaternary ammonium hydroxides and their salts, amines, etc. Specifically, quaternary ammonium hydroxides containing alkyl or aryl groups, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines, such as triethylamine, dimethylbenzylamine, and triphenylamine; tertiary amines, such as diethylamine and dibutylamine; primary amines, such as propylamine and butylamine; imidazoles, such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; or bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0034] For transesterification catalysts, salts of zinc, tin, zirconium, and lead are preferred, and these can be used alone or in combination. They can also be used in combination with the aforementioned alkali metal compounds or alkaline earth metal compounds.

[0035] In terms of transesterification catalysts, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethyl oxide, zirconium acetoacetone, zirconium oxyacetate, zirconium tetrabutoxide, lead(II) acetate, lead(IV) acetate, etc. can be used.

[0036] These catalysts are preferably used at a ratio of 1×10⁻⁹ to 1×10⁻³ mol relative to the total 1 mol of the diol compound, and more preferably at a ratio of 1×10⁻⁷ to 1×10⁻⁴ mol.

[0037] <Physical Properties of Thermoplastic Resins> (1) Refractive index (nD) In one embodiment of the present invention, the thermoplastic resin is characterized by a high refractive index, preferably 1.600~1.660, and more preferably 1.610~1.650. The refractive index in the present invention can be determined by the method described in the examples below.

[0038] (2) Abbe number (ν) In one embodiment of the present invention, the Abbe number of the thermoplastic resin is preferably 21.0 to 27.0, and more preferably 22.0 to 26.5. The Abbe number in the present invention can be determined by the method described in the examples below.

[0039] (3) Glass transition temperature (Tg) In one embodiment of the present invention, the thermoplastic resin is characterized by high heat resistance, and the glass transition temperature (Tg) is preferably 120~160℃, and more preferably 125~155℃. The glass transition temperature in the present invention can be determined by the method described in the examples below.

[0040] (4) Converted weight average molecular weight of polystyrene (Mw) In one embodiment of the present invention, the polystyrene of the thermoplastic resin has a weight-average molecular weight of 10,000 to 100,000, is more preferably 20,000 to 70,000, and is particularly preferably 30,000 to 60,000.

[0041] (5) Rate of change in quality (%) In one embodiment of the present invention, a low rate of mass change of the thermoplastic resin is one of its characteristics, preferably below 0.47%, and more preferably below 0.43%. While not particularly limited, the lower limit is approximately 0.20%. The rate of mass change in the present invention can be determined by the method described in the examples below.

[0042] (6) Dimensional change rate (%) In one embodiment of the present invention, a low dimensional change rate of the thermoplastic resin is one of its characteristics; preferably, the dimensional change rate is below 0.060%, and more preferably below 0.050%. While not particularly limited to a lower limit, it is approximately 0.010%. The dimensional change rate in the present invention can be measured using the method described in the embodiments below.

[0043] <Thermoplastic Resin Composition> The optical lens of the present invention may contain a thermoplastic resin composition comprising the aforementioned thermoplastic resin and additives. Without compromising the desired effects of the present embodiment, the thermoplastic resin composition may be made from resins other than those containing the aforementioned constituent units (A) and (B), or constituent units (A), (B), and (C). Such resins are not particularly limited, but examples include at least one resin selected from the group consisting of polycarbonate resin, polyester resin, polyester carbonate resin, (meth)acrylic resin, polyamide resin, polystyrene resin, cycloolefin resin, acrylonitrile-butadiene-styrene copolymer resin, vinyl chloride resin, polyphenylene ether resin, polyurethane resin, polyacetal resin, and methmethacrylate-styrene copolymer resin. Various known resins may be used, and one or more may be added to the thermoplastic resin composition alone.

[0044] [Antioxidants] Thermoplastic resin composition, as the above-mentioned additive, preferably contains an antioxidant. Regarding antioxidants, those containing at least one of phenolic antioxidants and phosphite antioxidants are preferred. In the realm of phenolic antioxidants, examples 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-methyl-3-propylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene di-m-cresol, and octadecyl 3- ...benzyl)-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-hydroxybenzene), 1,3,5-tris(3,5-di-tert-butyl-4 Pentaerythritol tetra[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-tetraoxyspiro[5.5]undecane, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc., preferably pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. Regarding phosphite-based antioxidants, examples include 2-ethylhexyl diphenyl phosphite, isodeyl 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. The preferred formulations include 2,4-ditert-butylphenyl) phosphite, 2,4-nonylphenyl) phosphite, tetra-C12-15-alkyl(propane-2,2-diylbis(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, with 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane being preferred. Regarding antioxidants, any one of the above types may be used, or a mixture of two or more types may be used.

[0045] In thermoplastic resin compositions, the antioxidant content is preferably 1 ppm to 3000 ppm by weight, based on the total weight of the resin composition. More preferably, the antioxidant content in the thermoplastic resin composition is 50 ppm to 2500 ppm by weight; further preferably, 100 ppm to 2000 ppm by weight; even more preferably, 150 ppm to 1500 ppm by weight; and still more preferably, 200 ppm to 1200 ppm by weight.

[0046] [Mold Release Agent] Thermoplastic resin composition, as the above-mentioned additive, preferably contains a mold release agent. Regarding mold release agents, examples include ester compounds, such as glycerol fatty acid esters (e.g., mono- and diglycerides of glycerol fatty acids), propylene glycol fatty acid esters, sorbitan fatty acid esters, higher alcohol fatty acid esters, and full or mono-fatty acid esters of aliphatic polyols and aliphatic carboxylic acids. When using esters of aliphatic polyols and aliphatic carboxylic acids as mold release agents, either mono-esters or full-esters can be used, but other than full-esters such as mono-esters are also acceptable. Specific examples of mold release agents include the following. That is, sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan trihexylenate, sorbitan stearate, sorbitan tristearate, and sorbitan caprylate; Propylene glycol fatty acid esters, including propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate, and propylene glycol monopalmitate; Higher alcohol fatty acid esters such as stearyl stearate; Monoglycerides including glycerol monostearate, glycerol mono-12-hydroxystearate, glycerol monooleate, glycerol mono-behenate, glycerol monocaprylate, glycerol monodecanoate, glycerol monolaurate, etc.; mono- and diglycerides including glycerol mono- and distearate, glycerol mono- and dibehenate, glycerol mono- and dioleate, etc.; and glycerol fatty acid ester monoglycerides. 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 polyricinoleate, and other polyglycerol fatty acid esters.

[0047] In thermoplastic resin compositions, the release agent is preferably present at a concentration of 1 ppm to 5000 ppm by weight, based on the total weight of the resin composition. More preferably, the release agent content in the thermoplastic resin composition is 50 ppm to 4000 ppm by weight; further preferably, 100 ppm to 3500 ppm by weight; even more preferably, 500 ppm to 13000 ppm by weight; and still more preferably, 1000 ppm to 2500 ppm by weight.

[0048] [Other Additives] In addition to the antioxidants and release agents mentioned above, other additives may also be added to thermoplastic resin compositions. Examples of additives that may be included in thermoplastic resin compositions include: synergists, catalyst deactivators, heat stabilizers, plasticizers, fillers, UV absorbers, rust inhibitors, dispersants, defoamers, leveling agents, flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents, and transparentizing agents. The content of additives other than antioxidants and release agents 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. The above-mentioned additives may have a negative impact on the permeability, so it is best not to add them in excess, for example, the total amount added should be within the range mentioned above.

[0049] In the method for manufacturing the thermoplastic resin composition used in this invention, after the polymerization reaction is complete, the catalyst can be removed or deactivated in order to maintain thermal stability and hydrolytic stability, but deactivation is not always necessary. When deactivation is required, it is preferable to add a known acidic substance to deactivate the catalyst. Specifically, acidic substances such as esters like butyl benzoate; 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; phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, din-propyl phosphite, din-butyl phosphite, din-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite; and phosphites such as triphenyl phosphate, diphenyl phosphate, and phosphoric acid. Phosphate esters such as monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids 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; organohalogen compounds such as stearyl chloride, benzoyl chloride, and p-toluenesulfonate; alkyl sulfuric acid such as dimethyl sulfuric acid; and organohalogen compounds such as benzyl chloride. From the viewpoint of resin stability, p-toluene or butyl sulfonate is particularly effective as a deactivator. The dosage of these deactivators relative to the catalyst is preferably 0.01 to 50 moles, or more preferably 0.3 to 20 moles. If the amount of catalyst is less than 0.01 moles, the deactivation effect is insufficient and unsatisfactory. Conversely, if the amount of catalyst is more than 50 moles, the heat resistance of the resin decreases, and the molded body is prone to coloring, resulting in unsatisfactory performance. The kneading of the deactivating agent can be carried out immediately after the polymerization reaction is complete, or after the polymerized resin has been granulated. Furthermore, other additives besides the deactivating agent can also be added using the same method.

[0050] <Optical Lenses> The optical lens of the present invention comprises the above-mentioned thermoplastic resin or thermoplastic resin composition (hereinafter simply referred to as "resin composition"). When manufacturing optical lenses containing the aforementioned resin composition by injection molding, it is preferable to perform molding at a cylinder temperature of 200-350°C and a mold temperature of 90-200°C. More preferably, molding should be performed at a cylinder temperature of 230-300°C and a mold temperature of 100-180°C. Particularly preferred is a mold temperature of 110-170°C. When the cylinder temperature is higher than 350°C, the resin composition decomposes and colors; when it is lower than 200°C, the melt viscosity is high, making molding difficult. Furthermore, when the mold temperature is higher than 200°C, it becomes difficult to remove the molded sheet made of the resin composition from the mold. On the other hand, if the mold temperature is below 90°C, the resin hardens too quickly within the mold during molding, making it difficult to control the shape of the molded sheet and to fully transfer the pattern applied to the mold.

[0051] Optical lenses made from the above-mentioned resin composition are highly useful in fields such as telescopes, binoculars, and television projectors, where expensive high-refractive-index glass lenses were previously used due to their high refractive index and excellent heat resistance. For example, in the lens of a smartphone, a lens formed of thermoplastic resin containing the aforementioned constituent units (A) and (B), or constituent units (A), (B) and (C), can be combined with, or (In the above formula, R1 and R2 are independent and represent hydrogen atoms, methyl or ethyl groups, and R3 and R4 are independent and represent hydrogen atoms, methyl groups, ethyl groups, or alkyldiols with 2 to 5 carbon atoms.) Lenses formed from resins containing constituent units derived from any of the monomers in the above formula are superimposed and used as lens units.

[0052] The optical lens of this invention is preferably in the shape of an aspherical lens, which is necessary. Because an aspherical lens can make spherical aberration virtually zero with a single lens, it eliminates the need for multiple spherical lenses to remove spherical aberration, resulting in weight reduction and lower manufacturing costs. Therefore, aspherical lenses are particularly suitable for use as camera lenses in optical applications.

[0053] Furthermore, the optical lens of this invention, due to its high formability, is particularly suitable for materials used in thin, small, and complex-shaped optical lenses. Specifically, regarding lens dimensions, the central thickness is preferably 0.05~3.0 mm, more preferably 0.05~2.0 mm, and even more preferably 0.1~2.0 mm. Also, the diameter is preferably 1.0 mm~20.0 mm, more preferably 1.0~10.0 mm, and even more preferably 3.0~10.0 mm. Furthermore, regarding its shape, a meniscus lens with one convex side and one concave side is preferred. The optical lens of this invention can be formed by any method such as mold forming, cutting, grinding, laser processing, electrical discharge machining, or etching. Among these methods, mold forming is preferred from a manufacturing cost perspective. Implementation

[0054] [Example]

[0055] The following describes embodiments and comparative examples of the present invention, which will disclose the invention in detail, but the present invention is not limited to these embodiments.

[0056] 1) Refractive index (nD) According to JIS B 7071-2:2018, polycarbonate resin was molded to obtain V-ends, and test pieces were made. The refractive index was measured at 23°C using the following refractive index meter. Refractometer: Shimadzu KPR-3000

[0057] 2) Abbe number (ν) Using the same test piece (V-ended) as used by the refractive index meter, measure the refractive index at wavelengths of 486 nm, 589 nm, and 656 nm at 23 °C using the following refractive index meter, and calculate the Abbe number using the following formula. Refractometer: Shimadzu KPR-3000 ν=(nD-1) / (nF-nC) nD: Refractive index at a wavelength of 589nm nC: Refractive index at a wavelength of 656 nm nF: Refractive index at a wavelength of 486 nm

[0058] 3) Glass transition temperature (Tg) According to JIS K7121-1987, measurements were performed using the differential scanning calorimeter described below, with a temperature ramping program of 10 °C / min. Differential scanning calorimeter: Hitachi High-Tech Science X-DSC7000

[0059] 4) Rate of change in quality (%) [] The polycarbonate resin was dried at 120°C for 8 hours for injection molding to obtain a circular test piece with a diameter of 50 mm and a thickness of 2 mm. Forming conditions; Injection molding machine: FANUC S-2000i30A (30 tons) injection molding machine manufactured by FANUC AG. Forming conditions: Cylinder temperature; Tg of polycarbonate resin +135℃ Mold temperature; Tg of polycarbonate resin -15℃ The weight of the obtained test piece was measured and recorded as M0. Next, after being stored in a constant temperature and humidity chamber set at 85°C and 85% for 72 hours, the weight of the test piece was measured again and recorded as M1. The rate of change in mass (%) was calculated using the following formula. Mass change rate (%) = (M1 - M0) / M0 × 100 M1: The quality of the test piece after storage at 85℃ and 85% humidity for 72 hours. M0: The quality of the test piece before storage at 85℃ and 85% humidity for 72 hours.

[0060] 5) Dimensional change rate (%) The polycarbonate resin was dried at 120°C for 8 hours for injection molding to obtain a circular test piece with a diameter of 50 mm and a thickness of 2 mm. Injection molding machine: FANUC S-2000i30A (30 tons) injection molding machine manufactured by FANUC AG. Forming conditions: Cylinder temperature; Tg of polycarbonate resin +135℃ Mold temperature; Tg of polycarbonate resin -15℃ The length of the test piece from the forming gate to the reverse gate, measured using an image dimension measuring instrument, is denoted as L0. Next, the test piece is stored in a constant temperature and humidity chamber set at 85°C and 85% for 72 hours. The length of the test piece from the forming gate to the reverse gate is then measured again using an image dimension measuring instrument and denoted as L1. The dimensional change rate (%) is calculated using the following formula. Dimensional change rate (%) = (L1 - L0) / L0 × 100 L1: The length of the test piece from the forming gate to the reverse gate after storage at 85℃ and 85% humidity for 72 hours. L0: The length of the test piece from the forming gate to the reverse gate before storage at 85℃ and 85% humidity for 72 hours. Image size measuring instrument: Keyence AG, Inc. Image size measuring instrument Head LM-1100

[0061] (Example 1) Regarding the raw materials, 8000g (18.24 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]benzene (BPEF) represented by the following structural formula, 550g (1.59 mol) of 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (BPM) represented by the following structural formula, 4375g (20.42 mol) of diphenyl carbonate (DPC), and 1.2ml (2.2×10⁻⁴ mol, i.e., 1 mol of the total dihydroxy compounds is 6.0×10⁻⁶ mol) of sodium bicarbonate aqueous solution at 0.10 mol / L were placed into a 50-liter reactor equipped with a stirrer and a distillation device. The mixture was heated to 215°C and stirred for 1 hour under a nitrogen atmosphere of 760 Torr. Then, after 15 minutes, the pressure was adjusted to 150 Torr, and the transesterification reaction was carried out at 215°C and 150 Torr for 20 minutes. The temperature was then further increased to 240°C at a rate of 37.5°C / hr, and maintained at 240°C and 150 Torr for 10 minutes. After that, after 10 minutes, the pressure was adjusted to 120 Torr, and maintained at 240°C and 120 Torr for 70 minutes. After that, after 10 minutes, the pressure was adjusted to 100 Torr, and maintained at 240°C and 100 Torr for 10 minutes. Finally, after 40 minutes, the pressure was reduced to below 1 Torr, and the polymerization reaction was carried out at 240°C and below 1 Torr with stirring for 10 minutes. After the reaction was complete, nitrogen was introduced into the reactor and pressurized, causing the generated polycarbonate resin to be granulated and pulled out simultaneously. The evaluation results of the obtained resin are shown in Table 1 below. The obtained resin was dried at 100°C for more than 12 hours using an ADVANTEC DRM420DD constant temperature dryer. Then, it was injection molded using a FANUC S-2000i30A injection molding machine with the cylinder temperature set at 260°C and the mold temperature 10°C lower than the glass transition temperature of the resin to obtain a lens with a diameter of 5mm.

[0062]

[0063] (Examples 2-7, Comparative Examples 1-5) Polycarbonate resin was obtained in the same manner as in Example 1, except that the raw materials shown in Table 2 below were used. The evaluation results of the obtained resins are shown in Table 1 below. Also, in Comparative Examples 2-4, the Tg was low, and the rate of change in mass and size could not be measured.

[0064]

Claims

1. An optical lens comprising a thermoplastic resin having a constituent unit (A) derived from a monomer represented by the following general formula (1), a constituent unit (B) derived from BPEF or BPPEF represented by the following structural formula, and a constituent unit (C) derived from BCFL represented by the following structural formula, wherein the molar ratio (A:B) of the aforementioned constituent unit (A) to the aforementioned constituent unit (B) is 5:95 to 79:21, (in the general formula (1), R1 to R4 are each independent and represent a hydrogen atom, a halogen atom, a branchable alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms).

2. The optical lens as described in claim 1, wherein, In the aforementioned thermoplastic resin, the proportion of the aforementioned constituent unit (A) is 5 to 50 moles.

3. The optical lens as described in claim 1 or 2, wherein, In the aforementioned thermoplastic resin, the proportion of the aforementioned constituent unit (B) is 11 to 95 moles.

4. The optical lens as described in claim 1 or 2, wherein, In the aforementioned thermoplastic resin, the proportion of the aforementioned constituent unit (C) is 38-50 moles.

5. The optical lens as described in claim 1 or 2, wherein, The Tg of the aforementioned thermoplastic resin is 120℃~160℃.

6. The optical lens as described in claim 1 or 2, wherein, The refractive index (nD) of the aforementioned thermoplastic resin is 1.600~1.

660.

7. The optical lens as described in claim 1 or 2, wherein, The Abbe number of the aforementioned thermoplastic resin is 21.0 to 27.

0.

8. The optical lens as described in claim 1 or 2, wherein, The mass change rate of the aforementioned thermoplastic resin is less than 0.47%.

9. The optical lens as described in claim 1 or 2, wherein, The dimensional change rate of the aforementioned thermoplastic resin is less than 0.060%.