Polycarbonate resin, and optical lens and optical film using same

Abstract

The present invention can provide a polycarbonate resin comprising: a constituent unit (a) given by general formula (1-1A); a constituent unit (b) given by general formula (1-1A), but different from the constituent unit (a); a constituent unit (c-1) given by general formula (1-2A) or a constituent unit (c-2) given by general formula (3-1); and a constituent unit (d) given by general formula (2), wherein the content of the constituent unit (a) is 1-50 mol%, the content of the constituent unit (b) is 1-70 mol%, the content of the constituent unit (c-1) or (c-2) is 1-50 mol%, and the content of the constituent unit (d) is 1-30 mol%, in each case with reference to the total amount of the constituent units (a) to (d).

Description

Polycarbonate resin, and optical lens and optical film using the same

[0001] The present invention relates to a polycarbonate resin, and an optical lens and an optical film using the same. More specifically, the present invention relates to a polycarbonate resin that contains a structural unit having a specific binaphthyl skeleton and has excellent optical properties while improving the fluidity of the resin, and an optical lens and an optical film using the same.

[0002] Optical lenses are used in a variety of places, including not only eyeglasses but also the optical systems of various cameras, such as cameras, film cameras, and video cameras. Important physical properties of lens materials include the refractive index (nD) and Abbe number (ν). In the optical design of optical units, using a material with a high refractive index allows lens elements to be realized with surfaces of smaller curvature, thereby reducing the amount of aberration generated by these surfaces, and thus enabling a reduction in the number of lenses, the sensitivity of the lenses to decentering, and the size and weight of the lens system due to a reduction in lens thickness.

[0003] In the optical design of optical units, it is known to correct chromatic aberration by combining a plurality of lenses with different Abbe numbers. For example, chromatic aberration is corrected by combining a lens made of an alicyclic polyolefin resin with an Abbe number ν=45 to 60 with a lens made of a polycarbonate resin (nD=1.586, ν=30) containing bisphenol A, which has a low Abbe number.

[0004] Optical glass and optical transparent resins are widely used as lens materials. Optical transparent resins have the advantage of being injection molded to produce aspherical lenses and are suitable for mass production. Injection molding involves heating and softening plastic, forcing it into a mold under injection pressure, filling the mold, and then removing the molded product after allowing the resin to cool. While the higher the softening temperature, the better the resin's fluidity. However, the softening temperature is limited due to the susceptibility to resin decomposition and discoloration. While many molding machines maintain a constant mold temperature, general-purpose mold temperature controllers use pressurized water as a heat medium, limiting mold temperatures to approximately 150°C. As a result, when using this equipment to manufacture products with high surface precision, the glass transition temperature of the resin that can be used is limited to approximately 160°C.

[0005] Polycarbonate resins made from bisphenol A are widely used in optical lens applications, but as the applications of optical lenses expand, there is a demand for further improvements in refractive index. Furthermore, polycarbonate resins made from bisphenol A have the drawback of high birefringence, which limits their applications. For this reason, there has been extensive research into resins for optical lenses that combine high refractive index and low birefringence.

[0006] In order to improve the physical properties of bisphenol A polycarbonate resins, copolymerization with other types of polycarbonate resins has been carried out. In particular, Patent Document 1 discloses that copolymers with a structural unit represented by formula (a) have an improved refractive index.

[0007]

[0008] Furthermore, Patent Document 2 discloses a copolymer of bisphenol A and a polycarbonate resin containing a structural unit having a fluorene structure.

[0009] As a resin having an even higher refractive index, a copolymer in which bisphenol A polycarbonate or aromatic polycarbonate resin is replaced with the resin of formula (b) is disclosed in Patent Document 3. However, although this resin composition has a high refractive index, it is also disclosed that the glass transition point exceeds 160°C.

[0010]

[0011] Furthermore, polymers having a 1,1'-binaphthalene structure are described in Patent Documents 4 to 6. Specifically, Patent Documents 4 to 6 disclose polycarbonate resins having a 1,1'-binaphthalene structure, but there is still a demand for polycarbonate resins having flowability suitable for precision molding.

[0012] WO2007 / 142149 JP 6-25398 A JP 2010-132782 A JP 2000-302857 A JP 2000-302858 A JP 2015-166951 A

[0013] An object of the present invention is to provide a polycarbonate resin that has flowability suitable for molding while maintaining favorable physical properties as an optical material, and to provide an optical lens and an optical film using the polycarbonate resin.

[0014] As a result of extensive research aimed at solving the above problems, the present inventors have discovered that the above problems can be solved by using a polycarbonate resin containing the structural units (a) to (d) described below, and have arrived at the present invention. <1> A polycarbonate resin comprising a structural unit (a) represented by the following general formula (1-1A), a structural unit (b) represented by the following general formula (1-1A) that is different from the structural unit (a), a structural unit (c-1) represented by the following general formula (1-2A) or a structural unit (c-2) represented by the following general formula (3-1), and a structural unit (d) represented by the following general formula (2), wherein, relative to the total amount of the structural units (a) to (d), the content of the structural unit (a) is 1 to 50 mol %, the content of the structural unit (b) is 1 to 70 mol %, the content of the structural unit (c-1) or (c-2) is 1 to 50 mol %, and the content of the structural unit (d) is 1 to 30 mol %. In formula (1-1A), R ａ and R ｂeach independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, an aryloxy group having 6 to 20 carbon atoms, and —C≡C—R ｈ is selected from R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; and a and b each independently represent an integer of 0 to 10. In formula (1-2A), R ａ and R ｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, and an aryloxy group having 6 to 20 carbon atoms, as well as -C≡C-R ｈ is selected from R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; and a and b each independently represent an integer of 0 to 10. In formula (3-1), R ａ and R ｂare each independently selected from hydrogen, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms; Y represents a fluorene group; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 0 to 4; and a and b each independently represent an integer of 1 to 10. In formula (2), 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. <2> The structural unit (a) is a structural unit derived from 2DNBINOL-2EO (6,6'-di-(2-naphthyl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl) represented by the following structural formula, the structural unit (b) is a structural unit derived from DPBHBNA (6,6'-diphenyl-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl) represented by the following structural formula, and the structural unit (c-1) is a structural unit derived from BNEF (9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene) represented by the following structural formula. The polycarbonate resin according to <1> above, wherein the structural unit (c-2) is a structural unit derived from BPPEF (9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene) represented by the following structural formula, and the structural unit (d) is 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. <3> The polycarbonate resin according to <1> or <2> above, which contains an antioxidant and a catalyst deactivator. <4> The polycarbonate resin according to <3> above, in which the antioxidant is pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and the catalyst deactivator is dodecylbenzenesulfonic acid tetrabutylphosphonium salt. <5> The polycarbonate resin according to any one of <1> to <4> above, in which the refractive index (nD) of the polycarbonate resin is 1,685 to 1.800. <6> The polycarbonate resin according to any one of <1> to <5> above, wherein the Abbe number (ν) of the polycarbonate resin is 14.0 to 18.0. <7> The polycarbonate resin according to any one of <1> to <6> above, wherein the glass transition temperature of the polycarbonate resin is 130 to 160°C. <8> The polycarbonate resin according to any one of <1> to <6> above, wherein the melt volume-flow rate (MVR) of the polycarbonate resin is 30 to 100 cm ３ <9> The polycarbonate resin according to any one of <1> to <8> above, wherein the water absorption rate of the polycarbonate resin is less than 0.11%. <10> An optical lens comprising the polycarbonate resin according to any one of <1> to <9> above. <11> An optical film comprising the polycarbonate resin according to any one of <1> to <9> above.

[0015] According to the present invention, it is possible to obtain a polycarbonate resin that has a high refractive index, a low Abbe number, and fluidity suitable for molding while maintaining physical properties favorable for an optical material. Furthermore, according to the present invention, optical lenses and optical films can be precisely molded from this resin.

[0016] (Polycarbonate Resin) The polycarbonate resin of the present invention contains a structural unit (a) represented by the following general formula (1-1A), a structural unit (b) represented by the following general formula (1-1A) that is different from the structural unit (a), a structural unit (c-1) represented by the following general formula (1-2A) or a structural unit (c-2) represented by the following general formula (3-1), and a structural unit (d) represented by the following general formula (2).

[0017] <Structural Unit (a) and Structural Unit (b)> In formula (1-1A), R ａ and R ｂ each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, an aryloxy group having 6 to 20 carbon atoms, and —C≡C—R ｈ is selected from R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; and a and b each independently represent an integer of 0 to 10.

[0018] In a preferred embodiment of the present invention, in formula (1-1A), R ａ and R ｂ each independently represents an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, an aryloxy group having 6 to 20 carbon atoms, and —C≡C—R ｈ and R ｈrepresents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S. The aryl group more preferably has 6 to 18 carbon atoms, even more preferably has 6 to 14 carbon atoms, and particularly preferably has 6 to 10 carbon atoms. The heteroaryl group more preferably has 6 to 18 carbon atoms, even more preferably has 8 to 16 carbon atoms, and particularly preferably has 10 to 14 carbon atoms. The aryloxy group more preferably has 6 to 18 carbon atoms, even more preferably has 6 to 16 carbon atoms, and particularly preferably has 6 to 14 carbon atoms.

[0019] In a preferred embodiment of the present invention, in formula (1-1A), R ａ and R ｂ may each independently be selected from the group consisting of a phenyl group, a naphthyl group, or

[0020] In the present invention, it is particularly preferred that the structural unit (a) is a structural unit derived from 2DNBINOL-2EO (6,6'-di-(2-naphthyl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl) represented by the following structural formula, and that the structural unit (b) is a structural unit derived from DPBHBNA (6,6'-diphenyl-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl) represented by the following structural formula.

[0021] <Structural Unit (c-1)> In formula (1-2A), R ａ and R ｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C≡C-R ｈ is selected from R ｈrepresents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; and a and b each independently represent an integer of 0 to 10.

[0022] In a preferred embodiment of the present invention, in formula (1-2A), R ａ and R ｂ each independently represents an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, an aryloxy group having 6 to 20 carbon atoms, and —C≡C—R ｈ and R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S. The aryl group more preferably has 6 to 18 carbon atoms, even more preferably has 6 to 14 carbon atoms, and particularly preferably has 6 to 10 carbon atoms. The heteroaryl group more preferably has 6 to 18 carbon atoms, even more preferably has 8 to 16 carbon atoms, and particularly preferably has 10 to 14 carbon atoms. The aryloxy group more preferably has 6 to 18 carbon atoms, even more preferably has 6 to 16 carbon atoms, and particularly preferably has 6 to 14 carbon atoms.

[0023] In a preferred embodiment of the present invention, in formula (1-2A), R ａ and R ｂ may each independently be selected from the group consisting of a hydrogen atom, a phenyl group, a naphthyl group, or

[0024] In the present invention, it is particularly preferable that the structural unit (c-1) is a structural unit derived from BNEF (9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene) represented by the following structural formula.

[0025] <Structural Unit (c-2)> In formula (3-1), R ａ and Rｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; Y represents a fluorene group; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 0 to 4; and a and b each independently represent an integer of 1 to 10.

[0026] In the present invention, it is particularly preferable that the structural unit (c-2) is a structural unit derived from BPPEF (9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene) represented by the following structural formula:

[0027] <Structural Unit (d)> In formula (2), 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.

[0028] In a preferred embodiment of the present invention, in formula (2), 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 aliphatic dihydroxy compound related to the structural unit (d) represented by formula (2) 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, poly-n-propylene glycol, etc. Preferred examples of the poly-n-propylene glycol include polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, polypentamethylene glycol, polyhexamethylene glycol, etc. Additionally, an example of a commercially available polytrimethylene glycol is the trade name "VELVETOL" manufactured by Allessa, Inc. In the present invention, the structural unit (d) 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.

[0029] In the polycarbonate resin of the present invention, the content of the structural unit (a) is 1 to 50 mol%, preferably 1 to 40 mol%, more preferably 2 to 35 mol%, and particularly preferably 30 to 34 mol%, based on the total amount of the structural units (a) to (d). The content of the structural unit (b) is 1 to 70 mol%, preferably 10 to 60 mol%, more preferably 20 to 60 mol%, and particularly preferably 30 to 36 mol%, based on the total amount of the structural units (a) to (d). The content of the structural unit (c-1) or (c-2) is 1 to 50 mol%, preferably 5 to 40 mol%, more preferably 15 to 30 mol%, and particularly preferably 20 to 26 mol%, based on the total amount of the structural units (a) to (d). The content of the structural unit (d) is 1 to 30 mol %, preferably 5 to 20 mol %, and more preferably 10 to 15 mol %, based on the total amount of the structural units (a) to (d).

[0030] The polystyrene-equivalent average molecular weight (Mw) of the polycarbonate resin is preferably 1,000 to 100,000, more preferably 5,000 to 80,000, even more preferably 10,000 to 80,000, and particularly preferably 10,000 to 70,000. 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.

[0031] (Method for Producing Polycarbonate Resin) The method for producing the polycarbonate resin is not particularly limited. For example, the dihydroxy compounds constituting the structural units (a) to (d) 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.

[0032] The polycarbonate resin of the present invention may contain structural units derived from dihydroxy compounds other than the dihydroxy compounds that constitute the structural units (a) to (d). Examples of other dihydroxy compounds include alicyclic dihydroxy compounds such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantanedimethanol, 1,4:3,6-dianhydrosorbitol, and 3,9-bis(1,1-dimethyl-2-dihydroxyethyl)-2,4,8,10-tetraoxaspiro-(5,5)-undecane; 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene, 2,2-bis(4-hydroxyphenyl)propane [=bisphenol A], 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)methane aromatic dihydroxy compounds such as 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-2-methylphenyl)fluorene;

[0033] The amount of the other dihydroxy compounds is preferably 20 mol % or less, and more preferably 10 mol % or less, relative to 100 mol % of the dihydroxy compounds constituting the structural units (a) to (d).Within this range, a high refractive index can be maintained.

[0034] 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.

[0035] Examples of the basic compound catalyst include alkali metal compounds and / or alkaline earth metal compounds, nitrogen-containing compounds, and the like.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] In the melt polycondensation using this composition, the dihydroxy compound and the carbonate diester constituting the structural units (a) to (d) may be melted in a reaction vessel, and the reaction may be carried out in a state in which the by-product monohydroxy compound is retained without being distilled off. In such a case, the reaction time in a state in which the by-product monohydroxy compound 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 by-product monohydroxy compound is distilled off immediately after 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] Furthermore, to the polycarbonate resin 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."

[0047] Antioxidants include triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), and 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl. ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane, and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4, 8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, among which pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane are preferred. The content of the antioxidant in the polycarbonate resin is preferably 0.001 to 0.3 parts by mass, and more preferably 0.01 to 0.2 parts by mass, per 100 parts by mass of the polycarbonate resin.

[0048] Specific examples of catalyst deactivators include esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; 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; Suitable examples of suitable catalysts include phosphate esters such as diethyl phosphate and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonyl chloride; alkyl sulfates such as dimethyl sulfate; and organic halides such as benzyl chloride. From the viewpoints of catalyst deactivator effect, stability against resins, and the like, tetrabutylphosphonium dodecylbenzenesulfonate is particularly preferred. The content of the catalyst deactivator in the polycarbonate resin is preferably 0.0001 to 0.3 parts by mass, more preferably 0.001 to 0.1 parts by mass, and particularly preferably 0.001 to 0.01 parts by mass, per 100 parts by mass of the polycarbonate resin. The catalyst deactivator may be kneaded immediately after the polymerization reaction is completed, or may be kneaded after the polymerized resin is pelletized. In addition to the catalyst deactivator, other additives may also be added in a similar manner.

[0049] Examples of the processing stabilizer include phosphorus-based processing heat stabilizers and sulfur-based processing heat stabilizers. Examples of the phosphorus-based processing heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, phosphite, monodecyldiphenyl phosphite, monooctyldiphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, Examples of the bis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite are mentioned.The content of the phosphorus-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.3 parts by mass, and more preferably 0.001 to 0.2 parts by mass, per 100 parts by mass of the polycarbonate resin.

[0050] Examples of sulfur-based processing heat stabilizers include pentaerythritol-tetrakis(3-laurylthiopropionate), pentaerythritol-tetrakis(3-myristylthiopropionate), pentaerythritol-tetrakis(3-stearylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc. The content of the sulfur-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.3 parts by mass, and more preferably 0.001 to 0.2 parts by mass, per 100 parts by mass of the polycarbonate resin.

[0051] Preferably, the release agent is one that comprises 90% by mass or more of an ester of an alcohol and a fatty acid. Specific examples of the ester of an alcohol and a fatty acid include an ester of a monohydric alcohol and a fatty acid, and a partial or complete ester of a polyhydric alcohol and a fatty acid. The ester of a monohydric alcohol and a fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Furthermore, the partial or complete ester of a polyhydric alcohol and a fatty acid is preferably a partial or complete ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

[0052] Specific examples of esters of monohydric alcohols and saturated fatty acids include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. Examples of partial or full esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride (glycerin monostearate), stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, and full or partial esters of dipentaerythritol such as dipentaerythritol hexastearate. Among these, stearic acid monoglyceride and lauric acid monoglyceride are particularly preferred. The content of these release agents is preferably in the range of 0.005 to 2.0 parts by mass, more preferably in the range of 0.01 to 0.6 parts by mass, and even more preferably in the range of 0.02 to 0.5 parts by mass, per 100 parts by mass of the polycarbonate resin.

[0053] The ultraviolet absorber is preferably at least one ultraviolet absorber selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. That is, the ultraviolet absorbers listed below may be used alone or in combination of two or more.

[0054] Examples of benzotriazole-based ultraviolet absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, and 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole. phenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, and the like.

[0055] Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Examples of triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0056] Examples of cyclic iminoester-based ultraviolet absorbers include 2,2'-bis(3,1-benzoxazine-4-one), 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-m-phenylenebis(3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2,6-naphthalene)bis(3,1-benzoxazine-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazine-4-one). 2,2'-(1,5-naphthalene)bis(3,1-benzoxazin-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one), and 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one).

[0057] Examples of cyanoacrylate ultraviolet absorbers include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0058] The content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by mass, more preferably 0.02 to 1.0 part by mass, and even more preferably 0.05 to 0.8 parts by mass, relative to 100 parts by mass of the polycarbonate resin. Within this range of blending amount, it is possible to impart sufficient weather resistance to the polycarbonate resin depending on the application.

[0059] (Method for producing molded article) A molded article can be produced using the polycarbonate resin of the present invention. For example, it can be molded by any method such as injection molding, compression molding, extrusion molding, solution casting, etc. The polycarbonate resin of the present invention has excellent moldability (good fluidity) and heat resistance (high glass transition temperature), so it can be particularly advantageously used in optical lenses and optical films that require injection molding.

[0060] (Physical Properties of Polycarbonate Resin) The polycarbonate resin of the present invention preferably has a glass transition point (Tg) of 130°C to 160°C, more preferably 135°C to 155°C, and particularly preferably 148°C to 155°C.

[0061] The refractive index of a molded article made from the polycarbonate resin of the present invention is preferably 1.685 to 1.800, more preferably 1.690 to 1.750, and even more preferably 1.695 to 1.720.

[0062] The molded article made from the polycarbonate resin of the present invention preferably has an Abbe number of 14.0 to 18.0, more preferably 14.5 to 17.0, and even more preferably 15.0 to 16.5.

[0063] The polycarbonate resin of the present invention has a melt volume flow rate (MVR) of 30 to 100 cm ３ / 10 min, and 35 to 95 cm ３ / 10 min is more preferable, and 40 to 90 cm ３ It is more preferable that the time is 10 min. / 10 min.

[0064] The polycarbonate resin of the present invention preferably has a water absorption rate of less than 0.11%, more preferably 0.10% or less, and even more preferably 0.09% or less.

[0065] (Optical Lenses) Optical lenses produced using the polycarbonate resin of the present invention have a high refractive index and excellent heat resistance, making them extremely useful in fields where expensive high-refractive index glass lenses have traditionally been used, such as telescopes, binoculars, and television projectors. If necessary, they are preferably used in the form of aspherical lenses. Aspherical lenses can essentially eliminate spherical aberration with a single lens, eliminating the need to combine multiple spherical lenses to eliminate spherical aberration, thereby enabling weight reduction and reduced production costs. Therefore, aspherical lenses are particularly useful as camera lenses. Furthermore, optical lenses can be molded by any method, such as injection molding, compression molding, or injection-compression molding. The present invention makes it possible to more easily obtain high-refractive index, low-birefringence aspherical lenses, which are technically difficult to process using glass lenses.

[0066] 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 6 or less, more preferably class 5 or less.

[0067] (Optical Film) The optical film produced using the polycarbonate resin of the present invention is excellent in transparency and heat resistance, and is therefore suitable for use as a film for liquid crystal substrates, optical memory cards, and the like.

[0068] In order to prevent foreign matter from being mixed into the optical film as much as possible, the molding environment must naturally be a low-dust environment, preferably class 6 or less, more preferably class 5 or less.

[0069] 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.

[0070] 1) Glass transition temperature (Tg): The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC). The specific conditions were as follows: Apparatus: Hitachi High-Tech Science DSC7000X, Sample amount: 5 mg, Atmosphere: Nitrogen gas atmosphere, Heating rate: 10°C / min

[0071] 2) Refractive index (nD): A 0.1 mm thick film made of polycarbonate resin produced in the following examples was measured using an Abbe refractometer according to the method of JIS-K-7142.

[0072] 3) Abbe number (νd): For a 0.1 mm thick film made of polycarbonate resin produced in the following examples, the refractive indexes at wavelengths of 486 nm, 589 nm, and 656 nm at 23°C were measured using an Abbe refractometer according to the method of JIS-K-7142, and the Abbe number was calculated using the following formula: νd=(nD-1) / (nF-nC), where nD is the refractive index at a wavelength of 589 nm, nC is the refractive index at a wavelength of 656 nm, and nF is the refractive index at a wavelength of 486 nm.

[0073] 4) Weight-average molecular weight (Mw) The weight-average molecular weight of the 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

[0074] 5) Melt volume flow rate: MVR (cm ３ / 10 min) Measurement was performed in accordance with ISO 1133 at 260°C and a load of 2.16 kg. Measuring equipment: Melt Indexer T-111 (manufactured by Toyo Seiki Seisakusho, Ltd.)

[0075] 6) Water absorption (%) This was measured according to the method of JIS K7209. Specifically, a test piece with a diameter of 50 mm and a thickness of 3 mm obtained by injection molding was dried in a hot air dryer at 50°C for 24 hours. Thereafter, the mass of the test piece was measured and designated as M0. Next, this test piece was immersed in water controlled at a temperature of 23°C ± 2°C (21°C to 25°C). After 24 hours, the test piece was removed, the water adhering to the surface was wiped off, and the mass was measured and designated as Mt. The water absorption (%) was calculated using the following formula: Water absorption (%) = (Mt - M0) / M0 × 100. The mass was measured in an environment controlled at 23°C ± 2°C (21°C to 25°C).

[0076] Example 1 As raw materials, 5342.4 g (8.52 mol) of 2DNBINOL-2EO (molecular weight: 626.8) represented by the following structural formula, 4629.2 g (8.79 mol) of DPBHBNA (molecular weight: 526.6) represented by the following structural formula, 3300.0 g (6.13 mol) of BNEF (molecular weight: 538.6) represented by the following structural formula, and 646.8 g (3.20 mol) of 1,12-dodecanediol (molecular weight: 202.3) were placed in a 50-liter reactor equipped with a stirrer and a distillation device, followed by 5877.4 g (27.4 mol) of diphenyl carbonate (DPC) and 2.24 × 10 sodium hydrogen carbonate. －２ g (2.66 x 10 －４ Thereafter, the reaction system was purged with nitrogen, and the mixture was heated to 180° C. over 30 minutes under a nitrogen atmosphere of 760 Torr and stirred. After the raw materials were completely dissolved, the temperature was raised to 190°C over 20 minutes, and then the reduced pressure was adjusted to 200 Torr. The mixture was maintained at 190°C and 200 Torr for 20 minutes to carry out a transesterification reaction. The temperature was then raised to 220°C at a rate of 30°C / hr, and the reduced pressure was adjusted to 150 Torr. The temperature was then raised to 240°C at a rate of 60°C / hr, and the reduced pressure was adjusted to 100 Torr. The pressure was then reduced to 1 Torr or less over 40 minutes, and a polymerization reaction was carried out with stirring for 30 minutes at 240°C and 1 Torr. After completion of the reaction, nitrogen was introduced into the reactor, pressurization was applied, and the resulting polycarbonate resin was pelletized using a pelletizer and withdrawn. The obtained polycarbonate resin pellets were dried at 100°C for 3 hours, and the following compounds were added to the polycarbonate resin: pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADEKA STAB AO-60; manufactured by ADEKA Corporation); 1000 ppm relative to the polycarbonate resin; 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (ADEGASTABE PEP-36; manufactured by ADEKA Corporation); 300 ppm relative to the polycarbonate resin; dodecylbenzenesulfonic acid tetrabutylphosphonium salt (MGA-614; manufactured by Takemoto Oil & Fat Co., Ltd.); 15 ppm relative to the polycarbonate resin; Glycerin monostearate (stearic acid monoglyceride, S-100; manufactured by Riken Vitamin Co., Ltd.) was added to the polycarbonate resin so as to give a concentration of 1,500 ppm, and the mixture was kneaded in a twin-screw extruder. The details of the extrusion are as follows. The physical properties of the resulting polycarbonate resin are shown in Table 1. Twin-screw extruder: TEM-18SS manufactured by Shibaura Machine Co., Ltd. Resin temperature: 260°C Screw rotation speed: 200 rpm

[0077] Example 2 A polycarbonate resin was obtained in the same manner as in Example 1, except that the raw materials used were 663.1 g (1.06 mol) of 2DNBINOL-2EO, 6017.7 g (11.4 mol) of DPBHBNA, 3500.0 g (5.92 mol) of BPPEF (molecular weight: 590.7) represented by the structural formula below, 556.6 g (2.75 mol) of 1,12-dodecanediol, and 4669.1 g (21.8 mol) of DPC. The physical properties of the obtained polycarbonate resin are shown in Table 1.

[0078] Comparative Example 1 A polycarbonate resin was obtained in the same manner as in Example 1, except that the raw materials used were 5,000.0 g (13.4 mol) of BNE (molecular weight: 374.4) represented by the following structural formula, 2,344.1 g (4.45 mol) of DPBHBNA, 6,393.4 g (11.9 mol) of BNEF, and 6,547.5 g (30.6 mol) of DPC. The physical properties of the obtained polycarbonate resin are shown in Table 1.

[0079]

Claims

1. A polycarbonate resin comprising a structural unit (a) represented by the following general formula (1-1A), a structural unit (b) represented by the following general formula (1-1A) different from the structural unit (a), a structural unit (c-1) represented by the following general formula (1-2A) or a structural unit (c-2) represented by the following general formula (3-1), and a structural unit (d) represented by the following general formula (2): The polycarbonate resin, wherein, based on the total amount of the structural units (a) to (d), the content of the structural unit (a) is 1 to 50 mol %, the content of the structural unit (b) is 1 to 70 mol %, the content of the structural unit (c-1) or (c-2) is 1 to 50 mol %, and the content of the structural unit (d) is 1 to 30 mol %. 【Chemical 1】 In formula (1-1A), R ａ and R ｂ each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, an aryloxy group having 6 to 20 carbon atoms, and —C≡C—R ｈ is selected from R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; a and b each independently represent an integer of 0 to 10. 【Chemistry 2】 In formula (1-2A), R ａ and R ｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, and an aryloxy group having 6 to 20 carbon atoms, as well as -C≡C-R ｈ is selected from R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; a and b each independently represent an integer of 0 to 10. 【Chemistry 3】 In formula (3-1), R ａ and R ｂ are each independently selected from hydrogen, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms; Y represents a fluorene group; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 0 to 4; a and b each independently represent an integer of 1 to 10; 【Chemistry 4】 In formula (2), 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.

2. The structural unit (a) is a structural unit derived from 2DNBINOL-2EO (6,6'-di-(2-naphthyl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl) represented by the following structural formula, the structural unit (b) is a structural unit derived from DPBHBNA (6,6'-diphenyl-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl) represented by the following structural formula, and the structural unit (c-1) is BNEF (9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene) represented by the following structural formula. the structural unit (c-2) is a structural unit derived from BPPEF (9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene) represented by the following structural formula; and the structural unit (d) is 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. 【Chemistry 5】

3. 10. The polycarbonate resin of claim 1, further comprising an antioxidant and a catalyst deactivator.

4. 4. The polycarbonate resin according to claim 3, wherein the antioxidant is pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and the catalyst deactivator is dodecylbenzenesulfonic acid tetrabutylphosphonium salt.

5. 2. The polycarbonate resin according to claim 1, wherein the refractive index (nD) of the polycarbonate resin is 1,685 to 1,800.

6. 2. The polycarbonate resin according to claim 1, wherein the polycarbonate resin has an Abbe number (ν) of 14.0 to 18.

0.

7. 2. The polycarbonate resin according to claim 1, wherein the polycarbonate resin has a glass transition temperature of 130 to 160°C.

8. The melt volume flow rate (MVR) of the polycarbonate resin is 30 to 100 cm ３ 2. The polycarbonate resin according to claim 1, wherein the melting point is 1000 rpm.

9. 2. The polycarbonate resin of claim 1, wherein the polycarbonate resin has a water absorption rate of less than 0.11%.

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

11. An optical film comprising the polycarbonate resin according to any one of claims 1 to 9.

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