Thermoplastic resin and optical lens comprising same

Abstract

The present invention can provide a thermoplastic resin that contains a structural unit (A) derived from a diol represented by general formula (1), a structural unit (B) derived from a diol represented by general formula (2), and a structural unit (C) derived from a diol represented by general formula (3). (In general formula (1), Re and Rf each independently represent a hydrogen atom, a halogen atom, and so forth; Y2 represents a single bond, a possibly substituted fluorene group, and so forth; E2 and F2 each independently represent a possibly substituted C1-5 alkylene group; t and u each independently represent an integer from 0 to 4; and e and f each independently represent an integer from 0 to 10.) (In general formula (2), R represents a hydrogen atom or a C1-4 alkyl group.) (In general formula (3), Rz and Rx each independently represent a hydrogen atom or a C1-3 alkyl group, i represents an integer from 2 to 16, and p represents an integer from 1 to 600.)

Description

Thermoplastic resin and optical lens containing same

[0001] The present invention relates to a thermoplastic resin and an optical lens containing the same. More particularly, the present invention relates to a polycarbonate resin, a polyester carbonate resin, or a polyester resin, and an optical lens containing the same.

[0002] Optical glass or optical resin is used as a material for optical lenses used in the optical systems of various cameras, such as cameras with integrated film, video cameras, etc. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., but has problems such as high material costs, poor moldability, and low productivity.

[0003] On the other hand, optical lenses made of optical resins have the advantage that they can be mass-produced by injection molding, and polycarbonate, polyester carbonate, polyester resin, etc. are used as high refractive index materials for camera lenses.

[0004] When an optical resin is used as an optical lens, in addition to optical properties such as refractive index and Abbe number, it is required to have heat resistance, transparency, low water absorption, chemical resistance, low birefringence, moist heat resistance, etc. In particular, in recent years, there has been a demand for optical lenses with high refractive index and high heat resistance, and various resins have been developed (Patent Documents 1 to 5).

[0005] JP 2018-2893 A JP 2018-2894 A JP 2018-2895 A JP 2018-59074 A WO2017 / 078073

[0006] An object of the present invention is to provide a thermoplastic resin that has low orientation birefringence while maintaining heat resistance sufficient for use, and an optical lens using the same.

[0007] As a result of extensive research to solve the problems of the past, the inventors discovered that by combining three types of monomers having specific structures as raw materials, a thermoplastic resin can be obtained that has orientation birefringence close to 0 (the absolute value of orientation birefringence is close to 0) while maintaining heat resistance sufficient for use, and thus completed the present invention.

[0008] That is, the present invention includes the following aspects: <1> A thermoplastic resin including a structural unit (A) derived from a diol represented by the following general formula (1), a structural unit (B) derived from a diol represented by the following general formula (2), and a structural unit (C) derived from a diol represented by the following general formula (3): (In general formula (1), R ｅ and R ｆ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent; ２ represents a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following formulae (8) to (15): (In formulas (8) to (15), R ６１ , R ６２ , R ７１ , R ７２ , R ８１ and R ８２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R ６１ and R ６２ , or R ７１ and R ７２ are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent, and r and s each independently represent an integer of 0 to 5,000. ２ and F ２ each independently represents an alkylene group having 1 to 5 carbon atoms which may have a substituent; t and u each independently represent an integer of 0 to 4; and e and f each independently represent an integer of 0 to 10. (In general formula (2), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) (In general formula (3), Rz and Rx each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, i represents an integer of 2 to 16, and p represents an integer of 1 to 600.) <2> The thermoplastic resin according to <1> above, wherein the proportion of the structural unit (A) among all structural units in the thermoplastic resin is 5 to 99 mol %. <3> The thermoplastic resin according to <1> above, wherein the proportion of the structural unit (B) among all structural units in the thermoplastic resin is 0.1 to 90 mol %. <4> The thermoplastic resin according to <1> above, wherein the proportion of the structural unit (C) among all structural units in the thermoplastic resin is 0.1 to 90 mol %. <5> The thermoplastic resin according to <1> above, wherein the Tg of the thermoplastic resin is 85°C to 135°C. <6> The thermoplastic resin according to <1>, wherein the weight average molecular weight (Mw) of the thermoplastic resin is 10,000 to 100,000. <7> The orientation birefringence Δn of the thermoplastic resin is −5.00×10 －５ ~5.00 x 10 －５ <8> The thermoplastic resin according to <7> above, wherein the sign of the orientation birefringence is positive. <9> The thermoplastic resin according to <1> above, wherein the thermoplastic resin is polycarbonate, polyester carbonate, or polyester. <10> An optical lens comprising the thermoplastic resin according to any one of <1> to <9> above.

[0009] According to the present invention, it is possible to provide a thermoplastic resin having orientation birefringence close to 0 (the absolute value of orientation birefringence close to 0) while maintaining heat resistance sufficient for use, and an optical lens using the same.

[0010] Hereinafter, embodiments of the present invention will be described in detail. <Thermoplastic Resin> One embodiment of the present invention is a thermoplastic resin containing a structural unit (A) derived from a diol represented by the following general formula (1), a structural unit (B) derived from a diol represented by the following general formula (2), and a structural unit (C) derived from a diol represented by the following general formula (3).

[0011] <Structural Unit (A)> The structural unit (A) contained in the thermoplastic resin of the present invention is a structural unit derived from a diol (dihydroxy compound) represented by the following general formula (1). In general formula (1), R ｅ and R ｆ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N, and S and which may have a substituent. ｅ and R ｆ is preferably selected from the group consisting of a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, more preferably selected from the group consisting of a hydrogen atom and an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferably selected from the group consisting of a hydrogen atom and an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0012] In the general formula (1), Y ２ represents a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following formulas (8) to (15), and is preferably a fluorene group which may have a substituent. In formulas (8) to (15), R ６１ , R ６２ , R ７１ , R ７２ , R ８１ and R ８２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R ６１ and R ６２ , or R ７１ and R ７２are bonded to each other to form a carbon ring or hetero ring having 1 to 20 carbon atoms, which may have a substituent. In formulas (8) to (15), r and s each independently represent an integer of 0 to 5,000.

[0013] In general formula (1), E ２ and F ２ each independently represents an alkylene group having 1 to 5 carbon atoms which may have a substituent, and is preferably an alkylene group having 2 or 3 carbon atoms. In general formula (1), t and u each independently represent an integer of 0 to 4, and is preferably 0 or 1. In general formula (1), e and f each independently represent an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 0 to 2, for example, 0 or 1.

[0014] Specific examples of the dihydroxy compound represented by general formula (1) include BCFL (9,9-bis(4-hydroxy-3-methylphenyl)fluorene), BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene), BNEF (9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]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 (BPM), bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol P-AP (4,4'-(1-phenylethylidene)bisphenol), and bisphenol P-CD. E (4,4'-cyclododecylidene bisphenol), bisphenol P-HTG (4,4'-(3,3,5-trimethylcyclohexylidene) bisphenol), bisphenol P-MIBK (4,4'-(1,3-dimethylbutylidene) bisphenol), bisphenol PEO-FL (bisphenoxyethanol fluorene), bisphenol P-3MZ (4-[1-(4-hydroxyphenyl)-3-methylcyclohexyl]phenol), bisphenol Examples of suitable dihydroxy compounds include bisphenol Z, BP-2EO (2,2'-[[1,1'-biphenyl]-4,4'-diylbis(oxy)bisethanol), S-BOC (4,4'-(1-methylethylidene)bis(2-methylphenol), TrisP-HAP (4,4',4''-ethylidene trisphenol), and the like. Among these, preferred dihydroxy compounds represented by general formula (1) include BPEF, BNEF, BPM, and BCFL.

[0015] <Structural Unit (B)> The structural unit (B) contained in the thermoplastic resin of the present invention is a structural unit derived from a diol (dihydroxy compound) represented by the following general formula (2). In general formula (2), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom.

[0016] In one embodiment of the present invention, -CH in the general formula (2) ２ An isomer in which the OH group is bonded to the 6-position (2,6-position isomer) and —CH ２ It is preferable to use a mixture with an isomer in which the OH group is bonded to the 7-position (2,7-position isomer). In one embodiment of the present invention, the mass ratio of these isomers is 2,6-isomer:2,7-isomer = 0.1:99.9 to 99.9:0.1. From the viewpoint of resin physical properties such as resin strength, tensile elongation, and appearance of molded articles, the mass ratio of 2,6-isomer:2,7-isomer is preferably 1.0:99.0 to 99.0:1.0, more preferably 2,6-isomer:2,7-isomer = 20:80 to 80:20, and particularly preferably 2,6-isomer:2,7-isomer = 50:50 to 80:20.

[0017] <Structural Unit (C)> The structural unit (C) contained in the thermoplastic resin of the present invention is a structural unit derived from a diol (dihydroxy compound) represented by the following general formula (3). In general formula (3), R ｚ and R ｘ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; i represents an integer of 2 to 16; and p represents an integer of 1 to 600.

[0018] In a preferred embodiment of the present invention, in general formula (3), i is an integer of 2 to 14, 2 to 12, 2 to 10, 2 to 8, 2 to 6, 2 to 4, 4 to 16, 4 to 14, 4 to 12, 4 to 10, 4 to 8, 4 to 6, 6 to 16, 6 to 14, 6 to 12, 6 to 10, or 6 to 8, and p is an integer of 1 to 500, 1 to 400, 1 to 300, 1 to 200, 1 to 100, 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 15, 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, or 2 to 3. Preferred examples of the dihydroxy compound represented by general formula (3) include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and poly-n-propylene glycol. Preferred examples of poly-n-propylene glycol include polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, polypentamethylene glycol, and polyhexamethylene glycol. Commercially available polytrimethylene glycols include those sold under the trade name "VELVETOL" by Allessa. In the present invention, the structural unit (C) is more preferably a structural unit derived from a compound selected from the group consisting of diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol, and is particularly preferably a structural unit derived from 1,12-dodecanediol.

[0019] In the present invention, the proportion of the structural unit (A) in all structural units in the thermoplastic resin is preferably 5 to 99 mol%, more preferably 50 to 90 mol%, and particularly preferably 60 to 80 mol%. In the present invention, the proportion of the structural unit (B) in all structural units in the thermoplastic resin is preferably 0.1 to 90 mol%, more preferably 1 to 70 mol%, even more preferably 5 to 50 mol%, and particularly preferably 5 to 30 mol%. In the present invention, the proportion of the structural unit (C) in all structural units in the thermoplastic resin is preferably 0.1 to 90 mol%, more preferably 1 to 70 mol%, even more preferably 5 to 50 mol%, and particularly preferably 5 to 30 mol%.

[0020] In a thermoplastic resin according to one embodiment of the present invention, the total proportion of the structural units (A), (B), and (C) in all structural units is preferably 80 to 100 mol %, more preferably 90 to 100 mol %, and particularly preferably 100 mol %. In other words, in addition to the structural units (A), (B), and (C), the thermoplastic resin according to one embodiment of the present invention can contain structural units derived from an aliphatic dihydroxy compound or a structural unit derived from an aromatic dihydroxy compound, which are generally used as structural units in polycarbonate resins and polyester carbonate resins. Specific examples of aliphatic dihydroxy compounds include, but are not limited to, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 1,3-adamantanedimethanol, 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-dioxan-2-yl)-2-methylpropan-1-ol, isosorbide, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. Examples of aromatic dihydroxy compounds include various compounds, particularly 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)cycloalkane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bisphenoxyethanolfluorene, and the like.

[0021] The thermoplastic resin of the present invention is not particularly limited and may be a polyester resin, a polycarbonate resin, a polyester carbonate resin, an epoxy resin, a polyurethane resin, a polyacrylic acid ester resin, a polymethacrylic acid ester resin, or the like, but is preferably a polycarbonate resin, a polyester carbonate resin, or a polyester resin.

[0022] <Physical Properties of Thermoplastic Resin> The glass transition temperature (Tg) of the thermoplastic resin of the present invention is preferably 85°C to 135°C, more preferably 100 to 130°C, even more preferably 110 to 130°C, and particularly preferably 110 to 120°C. If the Tg is lower than 85°C, the operating temperature range of lenses and cameras becomes narrow, which is not preferred. Also, if the Tg exceeds 135°C, the molding conditions during injection molding become strict, which is not preferred. The glass transition temperature (Tg) in the present invention can be measured by the method described in the examples below.

[0023] The weight-average molecular weight (Mw) of the thermoplastic resin of the present invention is preferably 10,000 to 100,000, more preferably 10,000 to 50,000, and particularly preferably 20,000 to 50,000. By increasing Mw above the lower limit, the strength of the resin can be maintained. Furthermore, by decreasing Mw below the upper limit, the melt viscosity can be prevented from becoming excessively high, making it easier to extract the resin after production and improving its fluidity, making it easier to handle in a molten state. The weight-average molecular weight (Mw) in the present invention can be measured by the method described in the Examples below.

[0024] The orientation birefringence Δn, which is a measure of the amount of birefringence of the thermoplastic resin of the present invention, is −5.00×10 －５ ~5.00 x 10 －５ It is preferable that the －５ ~3.00 x 10 －５ , −1.00×10 －５ ~1.00 x 10 －５ , −0.80×10 －５ ~0.80 x 10 －５ , −0.30×10 －５ ~0.30 x 10－５ More preferably, it is −0.20×10 －５ ~0.20 x 10 －５ More preferably, it is −0.10×10 －５ ~0.10 x 10 －５ It is particularly preferable that the orientation birefringence Δn of the film is −5.00×10 －５ ~5.00 x 10 －５ Within this range, when a lens is made (when thickened), the image passing through the lens is advantageously sharp and clear. The orientation birefringence Δn in the present invention can be measured by the method described in the Examples below. In a preferred embodiment of the present invention, the sign of the orientation birefringence is positive. However, as long as the absolute value of the orientation birefringence Δn is close to "0", the sign of the orientation birefringence may be "negative". The sign of the birefringence Δn is expressed by the following formula, and when Δn is positive, it is called positive birefringence, and when it is negative, it is called negative birefringence.

[0025] <Method for Producing Polycarbonate Resin> A method for producing a polycarbonate resin, which is a preferred embodiment of the present invention, will now be described. The method for producing a polycarbonate resin is not particularly limited. For example, the dihydroxy compounds constituting the structural units (A) to (C), and other dihydroxy compounds as needed, can be produced by melt polycondensation in the presence of a carbonate diester and a catalyst. The catalyst can be a basic compound catalyst, a transesterification catalyst, or a mixed catalyst comprising both.

[0026] Examples of the carbonate diester include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Among these, diphenyl carbonate is particularly preferred. Diphenyl carbonate is preferably used in a ratio of 0.90 to 1.15 moles, more preferably 0.95 to 1.10 moles, and even more preferably 1.00 to 1.10 moles, per mole of the dihydroxy compound.

[0027] Examples of the basic compound catalyst include alkali metal compounds and / or alkaline earth metal compounds, nitrogen-containing compounds, and the like.

[0028] Examples of alkali metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. Specific examples include 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 phenylborohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium, dipotassium, dicesium, and dilithium salts of bisphenol A, and sodium, potassium, cesium, and lithium salts of phenol. Among these, sodium bicarbonate is preferred.

[0029] Examples of alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds. Specific examples include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, and magnesium phenylphosphate.

[0030] Examples of the nitrogen-containing compound include quaternary ammonium hydroxides and their salts, amines, etc. Specific examples include quaternary ammonium hydroxides having an alkyl or aryl group, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines, such as triethylamine, dimethylbenzylamine, and triphenylamine; secondary amines, such as diethylamine and dibutylamine; primary amines, such as propylamine and butylamine; imidazoles, such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; and bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0031] As the transesterification catalyst, zinc, tin, zirconium, and lead salts are preferably used, and these can be used alone or in combination. Specific examples include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead(II) acetate, and lead(IV) acetate. These catalysts are used in an amount of 1×10 per mole of the total of the dihydroxy compounds. －９ ~1 x 10 －３ In terms of molar ratio, preferably 1 × 10 －７ ~1 x 10 －４ Used in molar ratios.

[0032] The melt polycondensation method uses the above-mentioned raw materials and a catalyst to carry out melt polycondensation under heating at normal or reduced pressure while removing by-products through a transesterification reaction. The reaction is generally carried out in two or more multi-stage steps.

[0033] In the melt polycondensation using this composition, the dihydroxy compound and the carbonate diester constituting the structural units (A) to (C) may be melted in a reaction vessel, and the reaction may be carried out in a state in which the monohydroxy compound by-produced is retained without being distilled off. In such a case, the reaction time in a state in which the monohydroxy compound by-produced is retained without being distilled off is 20 to 240 minutes, preferably 40 to 180 minutes, and particularly preferably 60 to 150 minutes. In this case, if the monohydroxy compound by-produced is distilled off immediately after its production, the content of high molecular weight compounds in the final polycarbonate resin will be low. The above reaction times are merely examples, and the preferred reaction time may vary depending on the reaction scale.

[0034] Such a reaction may be carried out continuously or batchwise. The reaction apparatus used may be a vertical type equipped with an anchor-type impeller, a Maxblend impeller, a helical ribbon-type impeller, or the like, a horizontal type equipped with a paddle impeller, a lattice impeller, a spectacle impeller, or the like, or an extruder type equipped with a screw, and these may be used in appropriate combination taking into consideration the viscosity of the polymer.

[0035] In the method for producing a polycarbonate resin, it is preferable to use a catalyst without deactivating it. However, if necessary, the catalyst may be removed or deactivated after completion of the polymerization reaction in order to maintain thermal stability and hydrolytic stability. When deactivating the catalyst, a method of deactivating the catalyst by adding a known acidic substance can be preferably carried out. Specific examples of the acidic substance include esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; 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; triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate. Phosphate esters of the above; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonic acid chloride; alkyl sulfates such as dimethyl sulfate; and organic halides such as benzyl chloride are preferably used, with butyl p-toluenesulfonate being more preferred. These deactivators are used in an amount of 0.01 to 50 times, preferably 0.3 to 20 times, the molar amount of the catalyst. Less than 0.01 times the molar amount of the catalyst results in an insufficient deactivation effect, which is undesirable. Furthermore, more than 50 times the molar amount of the catalyst results in a decrease in the heat resistance of the resin and increased discoloration of the molded product, which is undesirable.

[0036] After catalyst deactivation, a step of removing low-boiling compounds in the polymer by volatilization at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350° C. may be provided. For this step, a horizontal apparatus equipped with stirring blades with excellent surface renewal ability, such as paddle blades, lattice blades, or spectacle blades, or a thin-film evaporator is preferably used.

[0037] It is desirable that the polycarbonate resin contain as little foreign matter as possible, and therefore filtration of the molten raw material, filtration of the catalyst solution, etc. are preferably carried out. The mesh of the filter is preferably 5 μm or less, more preferably 1 μm or less. Furthermore, filtration of the produced resin through a polymer filter is preferably carried out. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Furthermore, the process of collecting resin pellets must naturally be carried out in a low-dust environment, preferably class 6 or less, more preferably class 5 or less.

[0038] Furthermore, to the polycarbonate resin which is a preferred embodiment of the present invention, antioxidants, catalyst deactivators, processing stabilizers, mold release agents, ultraviolet absorbers, flow modifiers, crystal nucleating agents, reinforcing agents, dyes, antistatic agents, antibacterial agents, etc. may be added as needed. In the present invention, it is preferable to contain an antioxidant and a catalyst deactivator. In this specification, the polycarbonate resin of the present invention to which the above-mentioned additives have been added is also called a "polycarbonate resin," but strictly speaking it is a "polycarbonate resin composition."

[0039] <Optical Lens> An optical lens, which is one embodiment of the present invention, can be obtained by injection molding the thermoplastic resin of the present invention into a lens shape using an injection molding machine or an injection compression molding machine. The molding conditions for injection molding are not particularly limited, but the molding temperature is preferably 180 to 280°C. The injection pressure is preferably 50 to 1700 kg / cm. 2 is.

[0040] To prevent foreign matter from getting into the optical lens as much as possible, the molding environment must naturally be a low-dust environment, preferably class 1000 or less, and more preferably class 100 or less.

[0041] The optical lens of the present invention is preferably used in the form of an aspherical lens, if necessary. Since an aspherical lens can substantially eliminate spherical aberration with a single lens, it is not necessary to eliminate spherical aberration by combining multiple spherical lenses, which enables weight reduction and reduced production costs. Therefore, aspherical lenses are particularly useful as camera lenses, among other optical lenses. The astigmatism of the aspherical lens is preferably 0 to 15 mλ, more preferably 0 to 10 mλ.

[0042] The thickness of the optical lens of the present invention can be set over a wide range depending on the application and is not particularly limited, but is preferably 0.01 to 30 mm, more preferably 0.1 to 15 mm. If necessary, a coating layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical lens of the present invention. The antireflection layer may be a single layer or a multilayer, and may be made of either an organic or inorganic material, but is preferably an inorganic material. Specific examples include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride. Of these, silicon oxide and zirconium oxide are more preferred, and a combination of silicon oxide and zirconium oxide is even more preferred. Furthermore, the antireflection layer is not particularly limited in terms of the single-layer / multilayer combination, or the combination of their components and thicknesses, but is preferably a two-layer or three-layer configuration, and particularly preferably a three-layer configuration. The antireflection layer as a whole is preferably formed to a thickness of 0.00017 to 3.3% of the thickness of the optical lens, specifically 0.05 to 3 μm, and particularly preferably 1 to 2 μm.

[0043] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The values ​​in the examples were measured using the following methods or devices.

[0044] Example 1 As raw materials, 27.4902 g (0.0627 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) represented by the following structural formula, 2.1247 g (0.0096 mol) of decahydro-1,4:5,8-dimethanonaphthalene-2,6-dimethanol and decahydro-1,4:5,8-dimethanonaphthalene-2,7-dimethanol (D-NDM), 3.1224 g (0.0154 mol) of 1,12-dodecanediol, 19.3459 g (0.0903 mol) of diphenyl carbonate (DPC), and 0.7365×10 sodium hydrogen carbonate were used. －４ g(0.8767×10 －６ (mol) was placed in a 300 mL reactor equipped with a stirrer and a distillation device, and the system was set to a nitrogen atmosphere of 101.3 kPa. The reactor was immersed in an oil bath heated to 200 ° C to initiate the transesterification reaction. Stirring was started 5 minutes after the start of the reaction, and after 20 minutes, the pressure was reduced from 101.3 kPa to 26.66 kPa over 10 minutes. The temperature was heated to 210 ° C while reducing the pressure, and the temperature was raised to 220 ° C over 60 minutes after the start of the reaction. After 80 minutes, the pressure was reduced to 20.00 kPa over 10 minutes, and the temperature was raised to 240 ° C while reducing the pressure to 0 kPa and maintained for 30 minutes. Nitrogen gas was then introduced into the reaction system, and the pressure was returned to 101.3 kPa, and a polycarbonate resin was obtained. The physical properties of the resulting polycarbonate resin are shown in Table 1.

[0045] Example 2 As raw materials, 25.7096 g (0.0586 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) represented by the above structural formula, 2.5345 g (0.0114 mol) of decahydro-1,4:5,8-dimethanonaphthalene-2,6-dimethanol and decahydro-1,4:5,8-dimethanonaphthalene-2,7-dimethanol (D-NDM), 2.3067 g (0.0114 mol) of 1,12-dodecanediol, 17.9672 g (0.0839 mol) of diphenyl carbonate (DPC), and 0.6841 × 10 sodium hydrogen carbonate were used. －４ g(0.8143×10 －６(mol) was placed in a 300 mL reactor equipped with a stirrer and a distillation device, and the system was set to a nitrogen atmosphere of 101.3 kPa. The reactor was immersed in an oil bath heated to 200 ° C to initiate the transesterification reaction. Stirring was started 5 minutes after the start of the reaction, and after 20 minutes, the pressure was reduced from 101.3 kPa to 26.66 kPa over 10 minutes. The temperature was heated to 210 ° C while reducing the pressure, and the temperature was raised to 220 ° C over 60 minutes after the start of the reaction. After 80 minutes, the pressure was reduced to 20.00 kPa over 10 minutes, and the temperature was raised to 240 ° C while reducing the pressure to 0 kPa and maintained for 30 minutes. Nitrogen gas was then introduced into the reaction system, and the pressure was returned to 101.3 kPa, and a polycarbonate resin was obtained. The physical properties of the resulting polycarbonate resin are shown in Table 1.

[0046] (Example 3) As raw materials, 26.5344 g (0.0605 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) represented by the above structural formula, 3.5500 g (0.0160 mol) of decahydro-1,4:5,8-dimethanonaphthalene-2,6-dimethanol and decahydro-1,4:5,8-dimethanonaphthalene-2,7-dimethanol (D-NDM), 1.5305 g (0.0076 mol) of 1,12-dodecanediol, 18.5436 g (0.0866 mol) of diphenyl carbonate (DPC), and 0.7060 × 10 sodium hydrogen carbonate were used. －４ g(0.8404×10 －６ (mol) was placed in a 300 mL reactor equipped with a stirrer and a distillation device, and the system was set to a nitrogen atmosphere of 101.3 kPa. The reactor was immersed in an oil bath heated to 200 ° C to initiate the transesterification reaction. Stirring was started 5 minutes after the start of the reaction, and after 20 minutes, the pressure was reduced from 101.3 kPa to 26.66 kPa over 10 minutes. The temperature was heated to 210 ° C while reducing the pressure, and the temperature was raised to 220 ° C over 60 minutes after the start of the reaction. After 80 minutes, the pressure was reduced to 20.00 kPa over 10 minutes, and the temperature was raised to 240 ° C while reducing the pressure to 0 kPa and maintained for 30 minutes. Nitrogen gas was then introduced into the reaction system, and the pressure was returned to 101.3 kPa, and a polycarbonate resin was obtained. The physical properties of the resulting polycarbonate resin are shown in Table 1.

[0047] Comparative Example 1 As raw materials, 27.6746 g (0.0631 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) represented by the above structural formula, 7.228 g (0.0325 mol) of decahydro-1,4:5,8-dimethanonaphthalene-2,6-dimethanol and decahydro-1,4:5,8-dimethanonaphthalene-2,7-dimethanol (D-NDM), 21.0987 g (0.0985 mol) of diphenyl carbonate (DPC), and 0.8033 × 10 sodium hydrogen carbonate were used. －４ g(0.9562×10 －６ (mol) was placed in a 300 mL reactor equipped with a stirrer and a distillation device, and the system was set to a nitrogen atmosphere of 101.3 kPa. The reactor was immersed in an oil bath heated to 200 ° C to initiate the transesterification reaction. Stirring was started 5 minutes after the start of the reaction, and after 20 minutes, the pressure was reduced from 101.3 kPa to 26.66 kPa over 10 minutes. The temperature was heated to 210 ° C while reducing the pressure, and the temperature was raised to 220 ° C over 60 minutes after the start of the reaction. After 80 minutes, the pressure was reduced to 20.00 kPa over 10 minutes, and the temperature was raised to 240 ° C while reducing the pressure to 0 kPa and maintained for 30 minutes. Nitrogen gas was then introduced into the reaction system, and the pressure was returned to 101.3 kPa, and a polycarbonate resin was obtained. The physical properties of the resulting polycarbonate resin are shown in Table 1.

[0048] Comparative Examples 2 to 4 Polycarbonate resins were obtained in the same manner as in Example 1, except that the raw materials were changed to those shown in Table 1. The physical properties of the obtained polycarbonate resins are shown in Table 1.

[0049] <Glass Transition Temperature (Tg)> The glass transition temperature (Tg) of the obtained resin was measured using a differential scanning calorimeter with a temperature increase program of 10°C / min in accordance with JIS K7121-1987. Differential scanning calorimeter: X-DSC7000 manufactured by Hitachi High-Tech Science Corporation

[0050] <Weight-average molecular weight (Mw)> The weight-average molecular weight of the obtained resin was measured by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene. The apparatus, column, and measurement conditions used were as follows: GPC apparatus: HLC-8420GPC, manufactured by Tosoh Corporation; Columns: TSKgel Super HM-M x 3, manufactured by Tosoh Corporation; TSKgel guard column Super H-H x 1, manufactured by Tosoh Corporation; TSKgel Super H-RC x 1, manufactured by Tosoh Corporation; Detector: RI detector; Standard polystyrene: Standard polystyrene kit PStQuick C, manufactured by Tosoh Corporation; Sample solution: 0.2% by mass tetrahydrofuran solution; Eluent: tetrahydrofuran; Eluent flow rate: 0.6 mL / min; Column temperature: 40°C.

[0051] <Orientation Birefringence (Δn)> A 0.1 mm thick cast film was cut into a 5.0 cm square, and then both ends of the film were clamped with chucks (chuck distance 3.0 cm) and stretched 1.5 times at Tg of the polycarbonate resin + 20°C. The phase difference (Re) at 550 nm was measured using an Ellipsometer M-220 manufactured by JASCO Corporation, and the orientation birefringence (Δn) was calculated using the following formula: Δn = Re / d Δn: orientation birefringence Re: phase difference d: thickness The birefringence sign was determined using an Ellipsometer M-220 manufactured by JASCO Corporation, where the in-plane direction of the stretched film was the maximum refractive index, and the birefringence sign was determined from the relationship with the stretching direction. When the birefringence sign was positive, the stretching direction was the direction in which the in-plane refractive index was the maximum. When the birefringence sign was negative, the stretching direction was the direction perpendicular to the in-plane direction of the film where the refractive index was the maximum.

[0052]

Claims

1. A thermoplastic resin comprising a structural unit (A) derived from a diol represented by the following general formula (1), a structural unit (B) derived from a diol represented by the following general formula (2), and a structural unit (C) derived from a diol represented by the following general formula (3): (In general formula (1), R ｅ and R ｆ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent; ２ represents a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following formulae (8) to (15): (In formulas (8) to (15), R ６１ , R ６２ , R ７１ , R ７２ , R ８１ and R ８２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R ６１ and R ６２ , or R ７１ and R ７２ are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent, and r and s each independently represent an integer of 0 to 5,000. ２ and F ２ each independently represents an alkylene group having 1 to 5 carbon atoms which may have a substituent; t and u each independently represent an integer of 0 to 4; and e and f each independently represent an integer of 0 to 10. (In general formula (2), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) (In general formula (3), Rz and Rx each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, i represents an integer of 2 to 16, and p represents an integer of 1 to 600.) 2. The thermoplastic resin according to claim 1, wherein the proportion of the structural unit (A) in all structural units in the thermoplastic resin is 5 to 99 mol %.

3. The thermoplastic resin according to claim 1, wherein the proportion of the structural unit (B) in all structural units in the thermoplastic resin is 0.1 to 90 mol %.

4. The thermoplastic resin according to claim 1, wherein the proportion of the structural unit (C) in all structural units in the thermoplastic resin is 0.1 to 90 mol %.

5. The thermoplastic resin according to claim 1, wherein the Tg of the thermoplastic resin is 85°C to 135°C.

6. The thermoplastic resin according to claim 1, wherein the weight average molecular weight (Mw) of the thermoplastic resin is 10,000 to 100,000.

7. The orientation birefringence Δn of the thermoplastic resin is −5.00×10 －５ ~5.00 x 10 －５ The thermoplastic resin according to claim 1, wherein 8. The thermoplastic resin according to claim 7, wherein the sign of the orientation birefringence is positive.

9. The thermoplastic resin of claim 1, wherein the thermoplastic resin is a polycarbonate, polyester carbonate, or polyester.

10. An optical lens comprising the thermoplastic resin according to any one of claims 1 to 9.

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