Polycarbonate resin, method for producing the same, and optical lens

Abstract

The present invention provides a polycarbonate resin having a high refractive index, a low Abbe number, and high heat and humidity resistance. In one embodiment of the present invention, there is provided a polycarbonate resin containing a structural unit represented by the following general formula (1). (R in formula (1)) 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 36 carbon atoms, a monocyclic or polycyclic heteroaryl group having 5 to 36 ring atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, wherein in the above heteroaryl group, 1, 2, 3, or 4 of the ring atoms are selected from nitrogen, sulfur, and oxygen, and the other ring atoms are carbon; the above monocyclic or polycyclic aryl group and the above monocyclic or polycyclic heteroaryl group have no substituents, or may have 1 or 2 R 3 groups selected from CN, CH 3 , OCH a groups; wherein, R 1 and R 2 are not both hydrogen; X is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms; wherein the above alkylene group and the above cycloalkylene group may each be substituted to have a benzene ring; a and b are each an integer from 1 to 10.

Description

[0001] (This application is a divisional application of application No. 201880056382.6, titled "Polycarbonate Resin, Method for Producing the Same, and Optical Lens", filed on August 29, 2018) Technical Field

[0002] The present invention relates to a polycarbonate resin and a method for producing the same. In addition, the present invention also relates to an optical lens containing the polycarbonate resin. Background Art

[0003] As a material for an optical lens used in an optical system of various cameras such as a camera, an integrated camera, and a video camera, optical glass or an optical resin is used. Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., but has problems such as high material cost, poor moldability, and low production efficiency.

[0004] On the other hand, an optical lens made of an optical resin has the advantage of being mass-produced by injection molding. For example, in a camera lens, a polycarbonate resin or the like is used. However, in recent years, with the trend of products becoming thinner, lighter, shorter, and smaller, there is a need to develop a resin with a high refractive index. Generally, when the refractive index of an optical material is high, a lens element having the same refractive index can be realized with a surface having a smaller curvature, and thus the amount of aberration generated on this surface can be reduced.

[0005] As a result, it is possible to reduce the number of lens elements, reduce the eccentricity sensitivity of the lens, or reduce the lens thickness to achieve weight reduction.

[0006] In addition, generally, in an optical system of a camera, aberration correction is performed by combining a plurality of concave lenses and convex lenses. That is, for the chromatic aberration caused by a convex lens, a concave lens having a chromatic aberration with a sign opposite to that of the convex lens is combined, and the chromatic aberration is canceled by synthesis.

[0007] At this time, the concave lens is required to have a high dispersion (i.e., a low Abbe number).

[0008] For this reason, a resin for an optical lens having a high refractive index and a low Abbe number has been developed. For example, Patent Document 1 discloses a copolymer containing a polycarbonate structural unit such as a bisphenol A type, which can improve the refractive index. The examples of Patent Document 1 describe that the refractive index reaches 1.62 to 1.64 and the Abbe number reaches 23 to 26.

[0009] In addition, Patent Document 2 discloses a copolymer of a polycarbonate resin containing a structural unit having a fluorene structure and bisphenol A. The examples of this document describe that the refractive index reaches 1.616 to 1.636. In addition, a sufficiently high refractive index has not been achieved in the polycarbonate copolymer disclosed in Patent Document 3 either.

[0010] As described above, a polycarbonate resin and an optical lens having a high refractive index and a low Abbe number have not been provided yet.

[0011] Moreover, in recent years, water resistance and heat resistance have been required for various electronic devices. As an environmental test for evaluating the water resistance and heat resistance of such electronic devices, a "PCT test" (pressure cooker test) is carried out. This test is a damp heat resistance test, and the evaluation is performed by accelerating the intrusion of moisture into the sample from the time aspect. Therefore, in an optical lens formed of an optical resin for an electronic device, not only a high refractive index and a low Abbe number are required, but also the optical physical properties need to be maintained after the PCT test.

[0012] Prior art documents

[0013] Patent documents

[0014] Patent document 1: International Patent Publication No. 2007 / 142149

[0015] Patent document 2: Japanese Patent Laid-Open No. 6-25398

[0016] Patent document 3: Japanese Patent Laid-Open No. 2014-185325 Summary of the invention

[0017] Problems to be solved by the invention

[0018] The problem to be solved by the present invention is to provide a polycarbonate resin having a high refractive index, a low Abbe number, and high damp heat resistance, particularly having a high refractive index. In addition, an object of the present invention is to provide an excellent optical lens by using this resin.

[0019] Technical means for solving the problems

[0020] The inventors of the present invention have conducted intensive research to solve the above problems, and as a result, it has been found that the above problems can be solved by using the following polycarbonate resin and optical lens, and thus the present invention has been completed.

[0021] The present invention is, for example, as follows.

[0022] [1] A polycarbonate resin containing a structural unit represented by the following general formula (1).

[0023]

[0024] (In formula (1), R 1 and R 2Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 36 carbon atoms, a monocyclic or polycyclic heteroaryl group having 5 to 36 ring atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, wherein in the heteroaryl group, 1, 2, 3, or 4 of the ring atoms are selected from nitrogen, sulfur, and oxygen, and the other ring atoms are carbon;

[0025] The monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group have no substituents, or may have 1 or 2 R 3 groups selected from CN, CH 3 , OCH a , O-phenyl, O-naphthyl, S-phenyl, S-naphthyl, and halogen;

[0026] wherein R 1 and R 2 are not all hydrogen;

[0027] X is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms,

[0028] wherein the alkylene group and the cycloalkylene group may each be substituted to have a benzene ring, and a and b are each an integer from 1 to 10.)

[0029] [2] The polycarbonate resin as described in [1] above, wherein it contains more than 50 mol% of the structural unit represented by the above general formula (1).

[0030] [3] The polycarbonate resin as described in [1] or [2] above, wherein at least one of R 1 and R 2 in the above general formula (1) is an aryl group having 6 to 20 carbon atoms.

[0031] [4] The polycarbonate resin as described in [3] above, wherein at least two of R 1 and R 2 in the above general formula (1) are aryl groups having 6 to 14 carbon atoms.

[0032] [5] The polycarbonate resin as described in any one of [1] to [4] above, wherein the structural unit represented by the above general formula (1) contains at least any one of the structural units represented by the following general formulas (A-1) to (A-7).

[0033]

[0034]

[0035] [6] The polycarbonate resin according to any one of [1] to [5] above, further containing at least one of the structural units represented by the following general formulas (2) and (3).

[0036]

[0037] (In formula (2), R' 1 ~R' 20 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms,

[0038] Y is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms,

[0039] c and d are each an integer from 1 to 10.)

[0040]

[0041] (In formula (3), R” 1 ~R” 16 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms,

[0042] Z is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms,

[0043] e and f are each an integer from 1 to 10.)

[0044] [7] The polycarbonate resin according to [6] above, comprising a copolymer containing at least the structural unit represented by the above general formula (1) and the structural unit represented by the above general formula (2).

[0045] [8] The polycarbonate resin according to [7] above, wherein the copolymer further contains the structural unit represented by the following general formula (3-1).

[0046]

[0047] [9] The polycarbonate resin according to [6] above, comprising a copolymer containing at least the structural unit represented by the above general formula (1) and the structural unit represented by the above general formula (3).

[0048]

[10] The polycarbonate resin as described in [9] above, wherein the copolymer further contains a structural unit represented by the following general formula (2-1).

[0049]

[0050]

[11] The polycarbonate resin as described in any one of [1] to

[10] above, wherein the total content of the structural units represented by the above general formulas (2) and (3) is 20 to 80 mol%.

[0051]

[12] The polycarbonate resin as described in any one of [1] to

[11] above, wherein it further contains at least one of the structural units represented by the following general formula (4).

[0052]

[0053]

[0054]

[13] The polycarbonate resin as described in

[12] above, wherein it contains at least a structural unit of BNEF (9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene).

[0055]

[14] The polycarbonate resin as described in

[12] above, wherein it contains at least a structural unit of BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene).

[0056]

[15] The polycarbonate resin as described in

[12] above, wherein it further contains at least a structural unit of BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene).

[0057]

[16] The polycarbonate resin as described in any one of [1] to

[15] above, wherein the aryl group is selected from pyrenyl, furyl, benzodioxolyl, dihydrobenzofuranyl, piperonyl, benzofuranyl, dibenzofuranyl, pyrrolidinyl, isoquinolinyl, pyrimidinyl, and carbazolyl, which may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms.

[0058]

[17] The polycarbonate resin as described in any one of [1] to

[16] above, wherein the refractive index value of the polycarbonate resin is 1.655 or more.

[0059]

[18] The polycarbonate resin as described in any one of [1] to

[17] above, wherein the above R 1 and the above R 2 are the same.

[0060]

[19] The polycarbonate resin according to any one of [1] to

[17] above, wherein the above R 1 is the same as or different from the above R 2 and is a monocyclic or polycyclic aryl group having 6 to 36 carbon atoms or a monocyclic or polycyclic heteroaryl group having 5 to 36 ring atoms. Among them, in the above heteroaryl group, 1, 2, 3, or 4 of the ring atoms are selected from nitrogen, sulfur, and oxygen, and the other ring atoms are carbon.

[0061] The above monocyclic or polycyclic aryl group and the above monocyclic or polycyclic heteroaryl group have no substituents.

[0062]

[20] The polycarbonate resin according to any one of [1] to

[19] above, wherein the above R 1 and the above R 2 are selected from the following groups:

[0063] Azulenyl;

[0064] Indenyl without substituents or indenyl that may be substituted with 2, 3, 4, or 5 substituents selected from phenyl and polycyclic aryl groups. The above polycyclic aryl group has 2, 3, or 4 benzene rings that can be bonded to each other by single bonds, can be directly condensed with each other, and / or can be condensed with a saturated or unsaturated monocyclic or bicyclic hydrocarbon ring having 4 to 10 ring atoms;

[0065] Phenyl without substituents;

[0066] Phenyl substituted with 1 or 2 CN groups;

[0067] Phenyl that may be substituted with 2, 3, 4, or 5 substituents selected from phenyl and polycyclic aryl groups. The above polycyclic aryl group has 2, 3, or 4 benzene rings that can be bonded to each other by single bonds, can be directly condensed with each other, and / or can be condensed with a saturated or unsaturated monocyclic or bicyclic hydrocarbon ring having 4 to 10 ring atoms;

[0068] A polycyclic aryl group having 2, 3, or 4 benzene rings that can be directly condensed with each other and / or can be condensed with a saturated or unsaturated monocyclic or bicyclic hydrocarbon ring having 4 to 10 ring atoms. The above polycyclic aryl group may have no substituents, or may be substituted with 1 or 2 substituents selected from phenyl and a polycyclic aryl group having 2 or 3 benzene rings. The 2 or 3 above benzene rings can be bonded to each other by single bonds, can be directly condensed with each other, and / or can be condensed with a saturated monocyclic or bicyclic hydrocarbon ring having 4 to 10 ring atoms. The above benzene rings of the polycyclic aryl group may have no substituents, or may have 1 or 2 substituents R a .

[0069]

[21] The polycarbonate resin according to any one of [1] to

[20] above, wherein the above R 1 and the above R 2 are selected from the following groups:

[0070] A phenyl group without substituents or a phenyl group that may be substituted with 1, 2, 3, 4, or 5 phenyl groups,

[0071] A phenyl group substituted with 1 or 2 CN groups,

[0072] A phenyl group substituted with 1 or 2 polycyclic aryl groups selected from biphenyl, naphthyl, fluorenyl, anthryl, phenanthryl, and pyrenyl, and may also be substituted with 1 phenyl group,

[0073] A naphthyl group without substituents or a naphthyl group substituted with 1 or 2 substituents selected from CN, phenyl, and polycyclic aryl groups, and the above polycyclic aryl group is selected from biphenyl, naphthyl, fluorenyl, anthryl, phenanthryl, and pyrenyl,

[0074] Biphenylene,

[0075] Terphenylene,

[0076] Quaterphenylene,

[0077] Phenanthryl,

[0078] Pyrenyl,

[0079] 9H - Fluorenyl,

[0080] Dibenz[a,e][8]annulenyl,

[0081] Perylenyl, and

[0082] 9,9'-Spirobi[9H - fluorene]yl.

[0083]

[22] The polycarbonate resin according to

[21] above, wherein the above R 1 and the above R 2 are selected from phenyl, 2 - cyanophenyl, 3 - cyanophenyl, 4 - cyanophenyl, 2 - naphthyl, 1 - naphthyl, and 9 - naphthyl.

[0084]

[23] The polycarbonate resin according to any one of [1] to

[19] above, wherein the above R 1 and the above R 2 are selected from:

[0085] A heteroaromatic monocyclic group having 5 or 6 ring atoms, having 1, 2, 3, or 4 nitrogen atoms, or having 1 oxygen atom and 0, 1, 2, or 3 nitrogen atoms, or having 1 sulfur atom and 0, 1, 2, or 3 nitrogen atoms, and the other ring atoms are carbon atoms;

[0086] A heteroaromatic polycyclic group having the heteroaromatic monocyclic ring and one, two, three, four or five additional aromatic rings selected from a phenyl group and a heteroaromatic monocyclic ring, wherein the (hetero)aromatic rings of the polycyclic heteroaryl group may be bonded to each other by a covalent bond, may be directly condensed with each other, and / or may be condensed with a monocyclic or bicyclic hydrocarbon ring having 4 to 10 members which is saturated or unsaturated; and

[0087] A heterocyclic ring having at least one saturated or partially unsaturated 5- or 6-membered ring having one or two heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, and a heteroaromatic polycyclic group having one, two, three, four or five additional aromatic rings selected from a phenyl group and the heteroaromatic monocyclic ring, wherein at least one of the additional aromatic rings is directly condensed with the saturated or partially unsaturated 5- or 6-membered heterocyclic group, and the other additional aromatic rings of the polycyclic heteroaryl aromatic ring may be bonded to each other by a covalent bond, may be directly condensed with each other, and / or may be condensed with a monocyclic or bicyclic hydrocarbon ring having 4 to 10 members which is saturated or unsaturated.

[0088]

[24] The polycarbonate resin according to

[23] above, wherein the above R 1 and the above R 2Selected from: furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, benzofuryl, dibenzofuryl, benzothienyl, dibenzothienyl, thianthrenyl, naphthofuryl, furo[3,2-b]furyl, furo[2,3-b]furyl, furo[3,4-b]furyl, oxanthrenyl, indolyl, isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzo[cd]indolyl, 1H-benzo[g]indolyl, quinolinyl, isoquinolinyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, benzo[b][1,5]naphthyridinyl, cinnolinyl, 1,5-naphthyridinyl, 1,8-naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, dipyridyl, phenylpyridyl, naphthylpyridyl, pyrido[4,3-b]indolyl, pyrido[3,2-b]indolyl, pyrido[3,2-g]quinolinyl, pyrido[2,3-b][1,8]naphthyridinyl, pyrrolo[3,2-b]pyridyl, pteridinyl, purinyl, 9H-xanthenyl, 2H-benzopyranyl, phenanthridinyl, phenanthrolinyl, furo[3,2-f][1]benzofuryl, furo[2,3-f][1]benzofuryl, furo[3,2-g]quinolinyl, furo[2,3-g]quinolinyl, furo[2,3-g]quinoxalinyl, benzo[g]benzopyranyl, pyrrolo[3,2,1-hi]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl and benzo[h]isoquinolinyl.

[0089]

[25] The polycarbonate resin according to any one of the above [1] to

[24] , wherein X is an ethylene group.

[0090]

[26] An optical lens containing the polycarbonate resin according to any one of the above [1] to

[25] .

[0091]

[27] A method for producing the polycarbonate resin according to any one of the above [1] to

[25] , comprising a step of melt-polycondensing a dihydroxy compound represented by the following general formula (5) and a carbonic acid diester,

[0092]

[0093] (R in the general formula (5) 1 and R 2Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 36 carbon atoms, a monocyclic or polycyclic heteroaryl group having 5 to 36 ring atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. Among them, in the above heteroaryl group, 1, 2, 3, or 4 of the ring atoms are selected from nitrogen, sulfur, and oxygen, and the other ring atoms are carbon.

[0094] The monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group have no substituents, or may have 1 or 2 R 3 、OCH 3 、O-phenyl, O-naphthyl, S-phenyl, S-naphthyl, and halogen. a groups.

[0095] Among them, R 1 and R 2 are not all hydrogen.

[0096] X is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms.

[0097] Among them, the above alkylene group and the above cycloalkylene group may each be substituted to have a benzene ring.

[0098] a and b are each an integer from 1 to 10.)

[0099] Advantages of the Invention

[0100] The polycarbonate resin of the present invention exhibits a high refractive index, a low Abbe number, and high heat and humidity resistance, and particularly exhibits a high refractive index. In addition, by using this resin, excellent optical lenses can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0101] Figure 1 is the 1 H-NMR spectrum of the resin produced in Example 2-B. DETAILED DESCRIPTION OF THE INVENTION

[0102] Hereinafter, the present invention will be described in detail.

[0103] (1) Components (structural units) of the polycarbonate resin

[0104] The polycarbonate resin of the present invention is a polycarbonate resin containing a structural unit represented by the following general formula (1).

[0105]

[0106] (In formula (1), R 1 and R2 Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 36 carbon atoms, a monocyclic or polycyclic heteroaryl group having 5 to 36 ring atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. In the above heteroaryl group, 1, 2, 3, or 4 of the ring atoms are selected from nitrogen, sulfur, and oxygen, and the other ring atoms are carbon;

[0107] The above monocyclic or polycyclic aryl group and the above monocyclic or polycyclic heteroaryl group have no substituents, or may have 1 or 2 R 3 groups selected from CN, CH 3 、OCH a 、O-phenyl, O-naphthyl, S-phenyl, S-naphthyl, and halogen;

[0108] wherein R 1 and R 2 are not both hydrogen;

[0109] X is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms,

[0110] wherein the above alkylene group and the above cycloalkylene group may each be substituted to have a benzene ring,

[0111] a and b are each an integer from 1 to 10.)

[0112] In the above general formula (1), R 1 and R 2 are each preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and even more preferably an aryl group having 6 to 14 carbon atoms. In addition, at least one of R 1 to R 10 in the general formula (1) is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and in particular, at least two of R 1 to R 10 are preferably aryl groups having 6 to 14 carbon atoms or more preferably aryl groups having 6 to 12 carbon atoms.

[0113] R 1 and R 2 are, for example, the same.

[0114] In addition, R 1 and R 2They may be the same or different and may be selected from aryl groups having 6 to 36 carbon atoms which are monocyclic or polycyclic, or heteroaryl groups having 5 to 36 ring atoms which are monocyclic or polycyclic, wherein 1, 2, 3 or 4 of the ring atoms are selected from nitrogen, sulfur and oxygen and the remaining ring atoms are carbon. Additionally, the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group may have no substituents.

[0115] R 1 and R 2 may each independently be selected from the following groups. That is, selected from:

[0116] azulenyl;

[0117] indenyl having no substituents or indenyl which may be substituted with 2, 3, 4 or 5 substituents selected from phenyl and polycyclic aryl groups, wherein the polycyclic aryl group has 2, 3 or 4 benzene rings which may be bonded to each other via single bonds, may be directly condensed with each other, and / or may be condensed with a monocyclic or bicyclic hydrocarbon ring having 4 to 10 members which is saturated or unsaturated;

[0118] phenyl having no substituents;

[0119] phenyl substituted with 1 or 2 CN groups;

[0120] phenyl which may be substituted with 2, 3, 4 or 5 substituents selected from phenyl and polycyclic aryl groups, wherein the polycyclic aryl group has 2, 3 or 4 benzene rings which may be bonded to each other via single bonds, may be directly condensed with each other, and / or may be condensed with a monocyclic or bicyclic hydrocarbon ring having 4 to 10 members which is saturated or unsaturated;

[0121] a polycyclic aryl group having 2, 3 or 4 benzene rings which may be directly condensed with each other and / or may be condensed with a monocyclic or bicyclic hydrocarbon ring having 4 to 10 members which is saturated or unsaturated, the polycyclic aryl group may have no substituents, or may be substituted with 1 or 2 substituents selected from phenyl and a polycyclic aryl group having 2 or 3 benzene rings, the 2 or 3 benzene rings may be bonded to each other via single bonds, may be directly condensed with each other, and / or may be condensed with a monocyclic or bicyclic hydrocarbon ring having 4 to 10 members which is saturated, the benzene rings of the polycyclic aryl group may have no substituents, or may have 1 or 2 substituents R a .

[0122] Additionally, R 1 and R 2 may each independently be selected from the following groups. That is, selected from:

[0123] phenyl having no substituents or phenyl which may be substituted with 1, 2, 3, 4 or 5 phenyl groups,

[0124] a phenyl group substituted with one or two CN groups,

[0125] a phenyl group substituted with one or two polycyclic aryl groups selected from biphenyl, naphthyl, fluorenyl, anthryl, phenanthryl and pyrenyl and further optionally substituted with one phenyl group,

[0126] a naphthyl group having no substituent or a naphthyl group substituted with one or two substituents selected from CN, phenyl and polycyclic aryl groups, said polycyclic aryl group being selected from biphenyl, naphthyl, fluorenyl, anthryl, phenanthryl and pyrenyl,

[0127] biphenylene,

[0128] terphenyl-4,4'-diyl,

[0129] quaterphenyl-4,4'-diyl,

[0130] phenanthryl,

[0131] pyrenyl,

[0132] 9H-fluorenyl,

[0133] dibenzo[a,e][8]annulenyl,

[0134] perylenyl, and

[0135] 9,9'-spirobi[9H-fluorene]yl.

[0136] wherein R 1 and R 2 are preferably selected from phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-naphthyl, 1-naphthyl and 9-naphthyl.

[0137] In addition, R 1 and R 2 may each independently be selected from the following groups. That is,

[0138] a heteroaromatic monocyclic group having 5 or 6 ring atoms and having 1, 2, 3 or 4 nitrogen atoms, or having 1 oxygen atom and 0, 1, 2 or 3 nitrogen atoms, or having 1 sulfur atom and 0, 1, 2 or 3 nitrogen atoms, the remaining ring atoms being carbon atoms;

[0139] a heteroaromatic polycyclic group having the above heteroaromatic monocyclic ring and 1, 2, 3, 4 or 5 additional aromatic rings selected from phenyl and heteroaromatic monocyclic rings, the (hetero)aromatic rings of the polycyclic heteroaryl group may be covalently bonded to each other, may be directly condensed with each other, and / or may be condensed with a saturated or unsaturated monocyclic or bicyclic hydrocarbon ring having 4 to 10 ring atoms; and

[0140] A heterocyclic group having at least one saturated or partially unsaturated 5- or 6-membered ring with 1 or 2 heteroatoms selected from oxygen, sulfur, and nitrogen as ring atoms, and a heteroaromatic polycyclic group having 1, 2, 3, 4, or 5 additional aromatic rings selected from phenyl and the above-mentioned heteroaromatic monocyclic rings, at least one of the additional aromatic rings being directly condensed with the heterocyclic group of the saturated or partially unsaturated 5- or 6-membered ring, and the other additional aromatic rings of the polycyclic heteroaryl aromatic rings may be covalently bonded to each other, may be directly condensed with each other, and / or may be condensed with a monocyclic or bicyclic hydrocarbon ring of 4 to 10 members, saturated or unsaturated.

[0141] In addition, R 1 and R 2 may each independently be selected from the following groups. That is, selected from: furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, benzofuryl, dibenzofuryl, benzothienyl, dibenzothienyl, thianthrenyl, naphthofuryl, furo[3,2-b]furyl, furo[2,3-b]furyl, furo[3,4-b]furyl, oxanthrenyl, indolyl, isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzo[cd]indolyl, 1H-benzo[g]indolyl, quinolinyl, isoquinolinyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, benzo[b][1,5]naphthyridinyl, cinnolinyl, 1,5-naphthyridinyl, 1,8-naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, dipyridyl, phenylpyridyl, naphthylpyridyl, pyrido[4,3-b]indolyl, pyrido[3,2-b]indolyl, pyrido[3,2-g]quinolinyl, pyrido[2,3-b][1,8]naphthyridinyl, pyrrolo[3,2-b]pyridyl, pteridinyl, purinyl, 9H-xanthenyl, 2H-benzopyranyl, phenanthridinyl, phenanthrolinyl, furo[3,2-f][1]benzofuryl, furo[2,3-f][1]benzofuryl, furo[3,2-g]quinolinyl, furo[2,3-g]quinolinyl, furo[2,3-g]quinoxalinyl, benzo[g]benzopyranyl, pyrrolo[3,2,1-hi]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl, and benzo[h]isoquinolinyl.

[0142] X in the above general formula (1) is preferably an alkylene group having 2 to 4 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, or an arylene group having 6 to 14 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, a cycloalkylene group having 5 to 6 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and particularly preferably an alkylene group having 2 or 3 carbon atoms, for example, ethylene.

[0143] In addition, a and b in the above general formula (1) are each preferably an integer of 1 to 6, more preferably 1 to 4, and particularly preferably 2 or 3.

[0144] The structural unit represented by the above general formula (1) preferably contains at least any one of the structural units represented by the following general formulas (A-1) to (A-7).

[0145]

[0146]

[0147]

[0148] That is, the structural unit represented by the general formula (1) preferably contains the structural unit derived from (BINL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene)) represented by the general formula (A-1), the structural unit derived from (DNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-bis(naphthalen-1-yl)-1,1'-binaphthalene)) represented by the general formula (A-2), the structural unit derived from (2DNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-bis(naphthalen-2-yl)-1,1'-binaphthalene)) represented by the general formula (A-3), and the structural unit derived from (9DPNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-bis(phenanthren-9-yl)-1,1'-binaphthalene)) represented by the general formula (A-4), the structural unit derived from (CN-BNA (6,6'-di-(3-cyanophenyl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthalene)) represented by the general formula (A-5), the structural unit derived from (FUR-BNA (6,6'-di-(dibenzo[b,d]furan-4-yl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthalene)) represented by the general formula (A-6), and the structural unit derived from (THI-BNA (6,6'-di-(dibenzo[b,d]thiophen-4-yl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthalene)) represented by the general formula (A-7), at least any one of them.

[0149] In the polycarbonate resin of the present invention, the structural unit represented by the above general formula (1) is contained in an amount of more than 50 mol%, more preferably more than 60 mol%, still more preferably more than 70 mol%, particularly preferably more than 80 mol%, or more than 90 mol%. In addition, the polycarbonate resin of the present invention may be formed only of the structural unit represented by the above general formula (1).

[0150] In the polycarbonate resin of the present invention, in addition to the structural unit (structural unit (1)) represented by the above general formula (1), one or more other structural units may be contained. As the other structural units, fluorene derivative units and the like are preferred.

[0151] Specifically, the polycarbonate resin of the present invention preferably further contains at least one of the structural units represented by general formulas (2) and (3).

[0152]

[0153] (R'in formula (2) 1 ~R' 20 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms,

[0154] Y is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms,

[0155] and c and d are each an integer of 1 to 10.)

[0156] R'in the above general formula (2) 1 ~R'' 20 each is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and more preferably hydrogen.

[0157] Y in the above general formula (2) is preferably an alkylene group having 2 to 4 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, or an arylene group having 6 to 14 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, a cycloalkylene group having 5 to 6 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and particularly preferably an alkylene group having 2 or 3 carbon atoms.

[0158] In addition, c and d in the above general formula (2) are each preferably an integer of 1 to 6, more preferably 1 to 4, and particularly preferably 2 or 3.

[0159]

[0160] (R” in formula (3) 1 ~R” 16 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aralkyl group having 7 to 17 carbon atoms,

[0161] Z is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

[0162] and e and f are each an integer from 1 to 10.)

[0163] R” in the above general formula (3) 1 ~R” 16 each preferably represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, more preferably hydrogen or an aryl group having 6 to 10 carbon atoms.

[0164] Z in the above general formula (3) is preferably an alkylene group having 2 to 4 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms or an arylene group having 6 to 14 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, a cycloalkylene group having 5 to 6 carbon atoms or an arylene group having 6 to 10 carbon atoms, and particularly preferably an alkylene group having 2 or 3 carbon atoms.

[0165] In addition, e and f in the above general formula (3) are each preferably an integer from 1 to 6, more preferably from 1 to 4, and particularly preferably 2 or 3.

[0166] As the structural unit (1) in the polycarbonate resin of the present invention and the structural unit represented by the above general formula (2) or (3), it preferably further contains at least one structural unit represented by the following general formula (4).

[0167]

[0168] That is, in the polycarbonate resin of the present invention, while containing the structural unit (1), it preferably further contains at least any one of the structural unit derived from BNEF (9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene), the structural unit derived from BNE (2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene) and the structural unit derived from BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene) represented by the above general formula (4).

[0169] In the polycarbonate resin of the present invention, among the structural units other than the structural unit (1), it is preferable that the total of the structural units represented by the above general formulas (2) and (3) can be contained in an amount of 20 to 80 mol%, for example, 25 to 75 mol%. In the polycarbonate resin, the structural units represented by the above general formulas (2) and (3) can be contained, for example, in an amount of 30 to 70 mol%, 35 to 65 mol%, or 40 to 60 mol%.

[0170] That is, in the polycarbonate resin composition of the present invention, the molar ratio of the structural unit (1) to the structural unit (2) represented by the general formula (2) is, for example, 4:1 to 1:4, or 7:3 to 3:7. Moreover, the above molar ratio can also be 65:35 to 35:65, can also be 3:2 to 2:3, or can also be 1:1. Among them, in the polycarbonate resin composition, it is preferable to contain the above structural unit (1) in an amount of more than 50 mol%. Therefore, as the molar ratio of the structural unit (1) to the structural unit (2), specific preferable examples are 4:1 to 1:1, 7:3 to 1:1, 65:35 to 1:1, and 3:2 to 1:1, etc.

[0171] It should be noted that the molar ratio of the structural unit (1) to the structural unit (3) represented by the general formula (3) is the same as the molar ratio of the above structural unit (1) to the structural unit (2).

[0172] The polycarbonate resin of the present invention can contain any of the random, block, and alternating copolymerization structures. In addition, in the polycarbonate resin of the present invention, it is not necessary to contain all of the above structural unit (1), structural unit (2), and structural unit (3) within the same polymer molecule. That is, as long as the above structural units are contained in the whole of a plurality of polymer molecules, the polycarbonate resin of the present invention can also be a blended resin. For example, as the polycarbonate resin containing any of the above structural unit (1), structural unit (2), and structural unit (3), it can be a copolymer containing all of the structural units (1), (2), and (3), or a mixture of a homopolymer or copolymer containing the structural unit (1), a homopolymer or copolymer containing the structural unit (2), and a homopolymer or copolymer containing the structural unit (3). In addition, it can also be a blended resin of a copolymer containing the structural units (1) and (2) and a copolymer containing the structural units (1) and (3), etc.

[0173] Other resins can be blended in the polycarbonate resin of the present invention for the manufacture of molded articles. As other resins, for example, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, etc. can be exemplified.

[0174] Moreover, in the polycarbonate resin composition of the present invention, it is preferable to add an antioxidant, a mold release agent, a processing stabilizer, an ultraviolet absorber, a fluidity modifier, a nucleating agent, a reinforcing agent, a dye, an antistatic agent, an antibacterial agent, or the like.

[0175] Examples of the antioxidant 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 - tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate / salt, 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-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate - diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 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. Among these, pentaerythritol - tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is preferable. The content of the antioxidant in the polycarbonate resin composition is preferably 0.001 to 0.3 parts by weight relative to 100 parts by weight of the polycarbonate resin.

[0176] As the mold release agent, it is preferable that 90% by weight or more thereof is composed 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, a partial ester or a full ester of a polyhydric alcohol and a fatty acid. As the ester of the monohydric alcohol and the fatty acid, an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable. In addition, as the partial ester or the full ester of the polyhydric alcohol and the fatty acid, a partial ester or a full ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable.

[0177] Specifically, as esters of monohydric alcohols and saturated fatty acids, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. can be cited. As partial esters or full esters of polyhydric alcohols and saturated fatty acids, monoglyceryl stearate, diglyceryl stearate, triglycerin stearate, sorbitan monostearate, monoglyceryl behenate, monoglyceryl caprate, monoglyceryl laurate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetranonanoate, propylene glycol monostearate, biphenyl dicarboxylate, sorbitol monostearate, 2-ethylhexyl stearate, and full esters or partial esters of dipentaerythritol such as dipentaerythritol hexastearate, etc. can be cited. Among these, monoglyceryl stearate and monoglyceryl laurate are particularly preferred. The content of these mold release agents is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight, and even more preferably in the range of 0.02 to 0.5 parts by weight based on 100 parts by weight of the polycarbonate resin.

[0178] As processing stabilizers, phosphorus-based processing heat stabilizers, sulfur-based processing heat stabilizers, etc. can be cited. As phosphorus-based processing heat stabilizers, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, etc. can be cited. Specifically, triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tris(octadecyl) phosphite, diphenylmonooctyl phosphite, diphenyldidecyl phosphite, diphenyldiisopropyl phosphite, monophenyldibutyl phosphite, monophenyldidecyl 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, distearylpentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenylmono(o-terphenyl) phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, tetra(2,4-di-tert-butylphenyl)-4,4'-biphenyldiphosphonate, tetra(2,4-di-tert-butylphenyl)-4,3'-biphenyldiphosphonate, tetra(2,4-di-tert-butylphenyl)-3,3'-biphenyldiphosphonate, bis(2,4-di-tert-butylphenyl)-4-phenylphenylphosphonate and bis(2,4-di-tert-butylphenyl)-3-phenylphenylphosphonate, etc. Among these, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is preferred. The content of the phosphorus-based processing heat stabilizer in the polycarbonate resin composition is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the polycarbonate resin.

[0179] As sulfur-based processing heat stabilizers, pentaerythritol-tetra(3-laurylthiopropionate), pentaerythritol-tetra(3-myristylthiopropionate), pentaerythritol-tetra(3-stearylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc. can be cited. The content of the sulfur-based processing heat stabilizer in the polycarbonate resin composition is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the polycarbonate resin.

[0180] As the ultraviolet absorber, it is preferably at least one ultraviolet absorber selected from 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 can be used alone or in combination of two or more.

[0181] As the benzotriazole-based ultraviolet absorber, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-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-benzotriazolylphenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, etc. can be cited.

[0182] As the benzophenone-based ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfonate benzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. can be cited.

[0183] As the triazine-based ultraviolet absorber, 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, etc. can be cited.

[0184] Examples of the cyclic iminoester-based ultraviolet absorbers include 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-p-phenylene bis(3,1-benzoxazin-4-one), 2,2'-m-phenylene bis(3,1-benzoxazin-4-one), 2,2'-(4,4'-biphenylene) bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthalene) bis(3,1-benzoxazin-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), etc.

[0185] Examples of the cyanoacrylate-based ultraviolet absorbers include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyloxy)]-2,2-bis[(2-cyano-3,3-diphenylacryloyloxy)methyl]propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyloxy)]benzene, etc.

[0186] The content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and still more preferably 0.05 to 0.8 parts by weight, based on 100 parts by weight of the polycarbonate resin. As long as it is within the range of this compounding amount, the polycarbonate resin composition can be given sufficient weather resistance according to the use.

[0187] In the polycarbonate resin composition, phenol generated during production and unreacted residual carbonic acid diester are present as impurities. The phenol content in the polycarbonate resin composition is preferably 0.1 to 3000 ppm, more preferably 0.1 to 2000 ppm, still more preferably 1 to 1000 ppm, 1 to 800 ppm, 1 to 500 ppm, or 1 to 300 ppm. In addition, the carbonic acid diester content in the polycarbonate resin composition is preferably 0.1 to 1000 ppm, more preferably 0.1 to 500 ppm, and particularly preferably 1 to 100 ppm. By adjusting the amounts of phenol and carbonic acid diester contained in the polycarbonate resin composition, a resin having physical properties suitable for the purpose can be obtained. The adjustment of the contents of phenol and carbonic acid diester can be carried out by appropriately changing the polycondensation conditions and equipment. In addition, it can also be adjusted by controlling the conditions of the extrusion process after polycondensation.

[0188] When the content of phenol or carbonic acid diester is higher than the above range, there may be problems such as a decrease in the strength of the obtained resin molded body and the generation of odor. On the other hand, when the content of phenol or carbonic acid diester is lower than the above range, there is a concern about a decrease in the plasticity during resin melting.

[0189] (2) Properties of the polycarbonate resin

[0190] The preferred viscosity-average molecular weight (Mv) of the polycarbonate resin of the present invention is 8,000 to 20,000, more preferably 9,000 to 15,000, and even more preferably 10,000 to 14,000.

[0191] When the value of Mv is less than 8,000, the molded body may become brittle. In addition, when the value of Mv is greater than 20,000, it is difficult to take out the resin after manufacturing due to the high melt viscosity, and there is also a concern that the fluidity becomes poor and it is difficult to perform injection molding in a molten state.

[0192] The refractive index (nD) of the polycarbonate resin of the present invention at 23 °C and a wavelength of 589 nm is preferably 1.635 or more, more preferably 1.645 or more, even more preferably 1.655 or more, and particularly preferably 1.665 or more, or greater than these values. For example, the refractive index of the polycarbonate resin of the present invention is preferably 1.640 to 1.710, more preferably 1.645 to 1.700, even more preferably 1.650 to 1.697, and particularly preferably 1.655 to 1.695. The polycarbonate resin of the present invention has a high refractive index and is suitable for optical lens materials. The refractive index can be measured by the method of JIS-K-7142 using an Abbe refractometer for a film with a thickness of 0.1 mm.

[0193] The Abbe number (ν) of the polycarbonate resin of the present invention is preferably 24 or less, more preferably 22 or less, and even more preferably 20 or less. The Abbe number can be calculated from the refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm at 23 °C by the following formula.

[0194] ν = (nD - 1) / (nF - nC)

[0195] nD: Refractive index at a wavelength of 589 nm

[0196] nC: Refractive index at a wavelength of 656 nm

[0197] nF: Refractive index at a wavelength of 486 nm

[0198] Regarding the preferred glass transition temperature (Tg) of the polycarbonate resin of the present invention, considering injection molding, it is preferably 90 to 185°C, more preferably 95 to 180°C, and even more preferably 100 to 175°C. When Tg is lower than 90°C, there is a possibility that the usable temperature range becomes narrow. In addition, when it exceeds 185°C, there is a concern that the melting temperature of the resin becomes high and resin decomposition and coloring are likely to occur. When the glass transition temperature of the resin is too high, the difference between the mold temperature and the resin glass transition temperature becomes too large in a conventional mold temperature control machine. Therefore, in applications with strict surface accuracy requirements for products, there is a possibility that it becomes difficult to use the resin when the glass transition temperature is too high. In addition, from the viewpoints of molding fluidity and molding heat resistance, the lower limit value of Tg is preferably 130°C, more preferably 135°C, and the upper limit value of Tg is preferably 185°C, more preferably 175°C.

[0199] The total light transmittance of the optical molded article obtained using the polycarbonate resin of the present invention is preferably 85% or more, more preferably 87% or more, and particularly preferably 88% or more. As long as the total light transmittance is 85% or more, it is comparable to bisphenol A polycarbonate resin and the like.

[0200] The polycarbonate resin of the present invention has high heat and humidity resistance. The heat and humidity resistance can be evaluated by performing a "PCT test" (pressure cooker test) on the optical molded article obtained using the polycarbonate resin and measuring the total light transmittance of the optical molded article after the test. The PCT test can be carried out using an injection molded article with a diameter of 50 mm and a thickness of 3 mm under the conditions of 120°C, 0.2 Mpa, and 100% RH for 20 hours. The total light transmittance of the polycarbonate resin of the present invention after the PCT test is 60% or more, preferably 70% or more, more preferably 75% or more, even more preferably 80% or more, and particularly preferably 85% or more. As long as the total light transmittance is 60% or more, it can be said that it has high heat and humidity resistance compared to existing polycarbonate resins.

[0201] The b value representing the hue of the polycarbonate resin of the present invention is preferably 5 or less. The smaller the b value, the weaker the yellowish tint and the better the hue.

[0202] (3) Method for manufacturing polycarbonate resin

[0203] The method for manufacturing a polycarbonate resin having a structural unit represented by the above general formula (1) according to the present invention includes a step of melt polycondensing a dihydroxy compound represented by the following general formula (5) with a carbonic acid diester.

[0204]

[0205] (In general formula (5), R 1 and R2 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 36 carbon atoms, a monocyclic or polycyclic heteroaryl group having 5 to 36 ring atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, wherein in the above-mentioned heteroaryl group, 1, 2, 3, or 4 of the ring atoms are selected from nitrogen, sulfur, and oxygen, and the other ring atoms are carbon,

[0206] wherein, R 1 and R 2 are not both hydrogen,

[0207] X is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms,

[0208] wherein the above-mentioned alkylene group and the above-mentioned cycloalkylene group may each be substituted to have a benzene ring,

[0209] a and b are each an integer from 1 to 10.)

[0210] That is, by using the compound represented by the above general formula (5) as the dihydroxy component and reacting it with a carbonate precursor such as a dicarbonate, a polycarbonate resin can be produced. Specifically, the compound represented by the general formula (5) and a carbonate precursor such as a dicarbonate can be reacted by melt polycondensation in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst containing both, or in the absence of a catalyst.

[0211] In addition, by using the above-mentioned dihydroxy compound represented by the general formula (5) as a raw material (monomer), polymers other than polycarbonate resins, such as polyester carbonates and polyesters, can also be obtained.

[0212] Examples of the compound of the general formula (5) include 2,2'-bis(hydroxy(poly)alkoxy)-diaryl-1,1'-binaphthalenes and 2,2'-bis(hydroxy(poly)alkoxy)-dinaphthyl-1,1'-binaphthalenes. Preferred are 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-bis(naphthalen-1-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxymethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(2-hydroxymethoxy)-6,6'-bis(naphthalen-1-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxypropoxy)-6,6'-diphenyl-1,1'-binaphthalene, and 2,2'-bis(2-hydroxypropoxy)-6,6'-bis(naphthalen-1-yl)-1,1'-binaphthalene. These can be used alone or in combination of two or more.

[0213] It should be noted that, among the monomers used for manufacturing polycarbonate resins, together with the dihydroxy compounds represented by the above general formula (5), as impurities, dihydroxy compounds in which both a and b in the above general formula (5) are 0 or dihydroxy compounds in which either a or b in the above general formula (5) is 0 may be contained.

[0214] Thus, regarding the total of dihydroxy compounds having values different from at least any one of a and b in the above general formula (5), in the monomer having the dihydroxy compound represented by the above general formula (5) as the main component, it is preferably contained in an amount of 1000 ppm or less, more preferably 500 ppm or less, still more preferably 200 ppm or less, and particularly preferably 100 ppm or less. Moreover, regarding the total content of dihydroxy compounds having values different from at least any one of a and b in the above general formula (5) in the above monomer, it is desirable to be 50 ppm or less, and more desirably 20 ppm or less.

[0215] The compound of general formula (5) can be manufactured by various synthesis methods. For example, as described in Japanese Patent Laid-Open No. 2014-227387, Japanese Patent Laid-Open No. 2014-227388, Japanese Patent Laid-Open No. 2015-168658, and Japanese Patent Laid-Open No. 2015-187098, (a) a method of reacting 1,1'-binaphthol with ethylene glycol monotosylate, (b) a method of reacting binaphthol compounds with alkylene oxides, haloalkanol, or alkylene carbonates, (c) a method of reacting 1,1'-binaphthol with ethylene carbonate, (d) a method of reacting 1,1'-binaphthol with ethylene carbonate, etc. are used for manufacturing.

[0216] In the polycarbonate resin having a structural unit represented by general formula (1) of the present invention, in addition to the compound of general formula (5), aromatic dihydroxy compounds and aliphatic dihydroxy compounds (for example, dihydroxy compounds having a fluorene skeleton, binaphthol compounds) can be used simultaneously as the dihydroxy component.

[0217] Preferably, in the polycarbonate resin of the present invention, in addition to the compound represented by the above general formula (5), the compound represented by the following general formula (6) and / or the compound represented by the following general formula (7) can be used as the dihydroxy component for manufacturing.

[0218]

[0219] Among them, R' in formula (6) 1 ~R' 20each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aralkyl group having 7 to 17 carbon atoms

[0220] Y is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms

[0221] c and d are each an integer from 1 to 10

[0222] In addition, R” in formula (7) 1 ~R” 16 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aralkyl group having 7 to 17 carbon atoms

[0223] Z is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms

[0224] e and f are each an integer from 1 to 10

[0225] Examples of the dihydroxy compound represented by formula (6) include 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(3-hydroxypropoxy)-1,1'-binaphthyl, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthyl, etc. Among them, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl is preferred. These can be used alone or in combination of two or more.

[0226] Examples of the dihydroxy compound represented by formula (7) include 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-tert-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-(isopropyl)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, etc. Among them, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene are preferred. These can be used alone or in combination of two or more.

[0227] For example, as an example of the dihydroxy compound represented by the formula (6) or (7), a compound represented by the following general formula (8) can be cited.

[0228]

[0229] It should be noted that in the monomers used for manufacturing polycarbonate resins, together with the dihydroxy compound represented by the above general formula (6), as impurities, a dihydroxy compound in which both c and d in the above general formula (6) are 0 or a dihydroxy compound in which either c or d in the above general formula (6) is 0 may also be contained.

[0230] Thus, regarding the total of dihydroxy compounds having values different from at least any one of c and d in the above general formula (6), in the monomer having the dihydroxy compound represented by the above general formula (6) as the main component, it is preferably contained in an amount of 1000 ppm or less, more preferably 500 ppm or less, still more preferably 200 ppm or less, and particularly preferably 100 ppm or less. Moreover, the total content of dihydroxy compounds having values different from at least any one of c and d in the above general formula (6) in the above monomer is desirably 50 ppm or less, and more desirably 20 ppm or less.

[0231] Regarding the content of impurities related to the above general formula (6), the same applies to the dihydroxy compound represented by the formula (7). That is, together with the dihydroxy compound represented by the above general formula (7), as impurities, a dihydroxy compound in which both e and f in the above general formula (7) are 0 or a dihydroxy compound in which either e or f in the above general formula (7) is 0 is contained.

[0232] The total of these impurities is preferably contained in an amount of 1000 ppm or less, more preferably 500 ppm or less, still more preferably 200 ppm or less, and particularly preferably 100 ppm or less in the monomer having the dihydroxy compound represented by the above general formula (7) as the main component. Moreover, the total content of the above impurities in the above monomer is desirably 50 ppm or less, and more desirably 20 ppm or less.

[0233] The compounds of general formulas (6) and (7) can be manufactured by various synthetic methods. For example, as described in Japanese Patent No. 5442800 and Japanese Patent Application Laid-Open No. 2014-028806, methods such as (a) reacting fluorenones with hydroxynaphthalenes in the presence of hydrogen chloride gas and mercapto carboxylic acid, (b) reacting 9-fluorenone with hydroxynaphthalenes in the presence of an acid catalyst (and alkyl mercaptan), (c) reacting fluorenones with hydroxynaphthalenes in the presence of hydrochloric acid and thiols (such as mercapto carboxylic acid), (d) reacting fluorenones with hydroxynaphthalenes in the presence of sulfuric acid and thiols (such as mercapto carboxylic acid), and crystallizing hydrocarbons with a crystallization solvent composed of a polar solvent to manufacture binaphthol fluorene, etc. are used to obtain 9,9-bis(hydroxynaphthyl)fluorenes, and then reacting them with compounds corresponding to the [XO]a group and the [XO]b group (such as alkylene oxides, haloalkanol, etc.) to manufacture. For example, 9,9-bis[6-(2-hydroxyethoxy)naphthyl]fluorene can be obtained by reacting 9,9-bis[6-hydroxynaphthyl]fluorene with 2-chloroethanol under alkaline conditions.

[0234] Examples of aromatic dihydroxy compounds that can be used simultaneously other than the above can include, for example, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z, etc.

[0235] (Amount of vinyl end groups)

[0236] The polycarbonate resin of the present invention is obtained by reacting a compound represented by the above general formulas (5) to (8), etc. as a dihydroxy component with a carbonate precursor substance such as a dicarbonate. However, in the polymer chemical process for manufacturing the polycarbonate resin, there may be impurities in which one or both of the terminal -OROH groups in the compounds of the above general formulas (5) to (8) are converted into vinyl end groups such as -OC=CH groups.

[0237] However, the amount of such impurities having a vinyl end structure is usually trace, and the manufactured polymer can be used as a polycarbonate resin without purification.

[0238] Examples of the dicarbonate used in the present invention include diphenyl carbonate, dimethylxylene carbonate, bis(chlorophenyl) carbonate, m-tolyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. Among these, diphenyl carbonate is particularly preferred. Relative to 1 mole in total of the dihydroxy compounds, diphenyl carbonate is preferably used in a proportion of 0.97 to 1.20 moles, and more preferably in a proportion of 0.98 to 1.10 moles.

[0239] In addition, among the above-mentioned transesterification catalysts for the production of polycarbonate resins, as basic compound catalysts, alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, etc. can be particularly mentioned.

[0240] Examples of the alkali metal compounds used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, or alkoxides of alkali metals, etc. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, 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 benzyldiborate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, or dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, or lithium salt of phenol, etc. can be used.

[0241] Examples of the alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, or alkoxides of alkaline earth metal compounds, etc. Specifically, 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, magnesium phenylphosphate, etc. can be used.

[0242] Examples of the nitrogen-containing compounds include quaternary ammonium hydroxides and their salts, amines, etc. Specifically, quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, etc. having alkyl groups, aryl groups, etc.; tertiary amines such as triethylamine, dimethylbenzylamine, triphenylamine, etc.; secondary amines such as diethylamine, dibutylamine, etc.; primary amines such as propylamine, butylamine, etc.; imidazoles such as 2-methylimidazole, 2-phenylimidazole, benzimidazole, etc.; or bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate, etc. can be used.

[0243] As the transesterification catalyst, salts of zinc, tin, zirconium, lead, etc. are preferably used, and these can be used alone or in combination.

[0244] Specifically, as the transesterification catalyst, 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, tetrabutoxyzirconium, lead(II) acetate, lead(IV) acetate, etc. can be used.

[0245] These catalysts are used in a proportion of 10 －9 to 10 －3 moles, preferably 10 －7 to 10 －4 moles, per 1 mole in total of the dihydroxy compound.

[0246] The melt polycondensation method uses the above raw materials and catalysts, and under heating, and additionally under normal pressure or reduced pressure, while removing the by-products generated from the transesterification reaction, melt polycondensation is carried out.

[0247] In the melt polycondensation in this composition system, it is preferred to melt the compound represented by the general formula (5) and the carbonic acid diester in a reaction vessel and carry out the reaction in a state where the by-produced monohydroxy compound is retained. In order to achieve retention, the reaction apparatus can be closed, or pressure control such as reduced pressure or increased pressure can be carried out. The reaction time for this step is 20 minutes or more and 240 minutes or less, preferably 40 minutes or more and 180 minutes or less, and particularly preferably 60 minutes or more and 150 minutes or less. At this time, if the by-produced monohydroxy compound is immediately distilled off after being generated, the content of the high molecular weight polymer in the finally obtained polycarbonate resin is small. However, when the by-produced monohydroxy compound is retained in the reaction vessel for a certain period of time, a polymer with a large content of the high molecular weight polymer in the finally obtained polycarbonate resin can be obtained.

[0248] The melt polycondensation reaction can be carried out continuously or batchwise. The reaction apparatus used for the reaction can be a vertical apparatus equipped with an anchor type stirring paddle, a MAXBLEND stirring paddle, a ribbon type stirring paddle, etc., or a horizontal apparatus equipped with paddle type blades, lattice blades, spectacle type blades, etc., or an extruder type equipped with a screw. In addition, it is preferred to use a reaction apparatus obtained by appropriately combining these reaction apparatuses in consideration of the viscosity of the polymer.

[0249] In the method for manufacturing the polycarbonate resin used in the present invention, after the polymerization reaction is completed, in order to maintain thermal stability and hydrolysis stability, the catalyst can be removed or deactivated. A method of deactivating the catalyst by adding a known acidic substance can be preferably implemented. Specifically, as the acidic substance, 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; phosphate esters such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonate esters such as diethyl phenylphosphonate; 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 stearyl chloride, benzoyl chloride, and p-toluenesulfonyl chloride; alkyl sulfates such as dimethyl sulfate; organic halides such as benzyl chloride, etc. These deactivators are used in an amount of 0.01 to 50 times the molar amount relative to the amount of the catalyst, preferably 0.3 to 20 times the molar amount. When the amount is less than 0.01 times the molar amount relative to the amount of the catalyst, the deactivation effect may sometimes be insufficient, so it is not preferred. In addition, when the amount is more than 50 times the molar amount relative to the amount of the catalyst, the heat resistance of the resin is likely to decrease and the molded article is likely to be colored, so it is not preferred.

[0250] After the catalyst is deactivated, a step of removing volatile low-boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350 °C can be provided. In this step, a horizontal stirring device equipped with a paddle blade, a grid blade, a spectacle blade, etc., which has excellent surface renewal ability, or a thin-film evaporator can be preferably used.

[0251] The polycarbonate resin of the present invention preferably has as little foreign matter content as possible, and filtration of the molten raw material, filtration of the catalyst solution, etc. are preferably implemented. The mesh of the filter is preferably 5 μm or less, more preferably 1 μm or less. Moreover, it is preferable to filter the produced resin using a polymer filter. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. In addition, the step of collecting the resin pellets naturally needs to be carried out in a low-dust environment, preferably class 6 or less, more preferably class 5 or less.

[0252] It should be noted that as the molding method of the polycarbonate resin, in addition to injection molding, compression molding, casting, roll processing, extrusion molding, stretching, etc. can be exemplified, but it is not limited to these.

[0253] (4) Optical molded article

[0254] An optical molded article can be manufactured using the polycarbonate resin of the present invention. Any method such as injection molding, compression molding, extrusion molding, solution casting method, etc. can be used for molding. Since the polycarbonate resin of the present invention has excellent moldability and heat resistance, it can be particularly advantageously used in optical lenses that require injection molding. During molding, the polycarbonate resin of the present invention can be used after being mixed with other resins such as other polycarbonate resins and polyester resins. In addition, additives such as antioxidants, processing stabilizers, light stabilizers, polymerization metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, mold release agents, ultraviolet absorbers, plasticizers, compatibilizers, etc. can also be mixed in.

[0255] Examples of the antioxidant include diethylene 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 - tetra[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-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate - diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 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, etc. The content of the antioxidant in the polycarbonate resin is preferably 0.001 to 0.3 parts by weight relative to 100 parts by weight of the polycarbonate resin.

[0256] As processing stabilizers, phosphorus-based processing heat stabilizers, sulfur-based processing heat stabilizers, etc. can be cited. As phosphorus-based processing heat stabilizers, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, etc. can be cited. Specifically, triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tris(octadecyl) phosphite, diphenylmonophenyl phosphite, dioctylmonophenyl phosphite, diisopropylmonophenyl phosphite, monophenyldiphenyl 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, distearylpentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenylmono(o-biphenylyl) phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, tetra(2,4-di-tert-butylphenyl)-4,4'-biphenyldiphosphonate, tetra(2,4-di-tert-butylphenyl)-4,3'-biphenyldiphosphonate, tetra(2,4-di-tert-butylphenyl)-3,3'-biphenyldiphosphonate, bis(2,4-di-tert-butylphenyl)-4-phenylphenylphosphonate and bis(2,4-di-tert-butylphenyl)-3-phenylphenylphosphonate, etc. The content of the phosphorus-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the polycarbonate resin.

[0257] As sulfur-based processing heat stabilizers, pentaerythritol-tetra(3-laurylthiopropionate), pentaerythritol-tetra(3-myristylthiopropionate), pentaerythritol-tetra(3-stearylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc. can be cited. The content of the sulfur-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the polycarbonate resin.

[0258] As a mold release agent, preferably, more than 90% by weight thereof is composed of an ester of an alcohol and a fatty acid. As the ester of an alcohol and a fatty acid, specifically, an ester of a monohydric alcohol and a fatty acid, a partial ester or a full ester of a polyhydric alcohol and a fatty acid can be cited. As the above-mentioned ester of a monohydric alcohol and a fatty acid, an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferred. In addition, as the partial ester or full ester of a polyhydric alcohol and a fatty acid, a partial ester or full ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferred.

[0259] Specifically, as the ester of a monohydric alcohol and a saturated fatty acid, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. can be cited. As the partial ester or full ester of a polyhydric alcohol and a saturated fatty acid, monoglyceryl stearate, monoglyceryl stearate, diglyceryl stearate, triglycerin stearate, sorbitan monostearate, monoglyceryl behenate, monoglyceryl caprate, monoglyceryl laurate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetraisononanoate, propylene glycol monostearate, biphenyl benzoate, sorbitol monostearate, 2-ethylhexyl stearate, and full esters or partial esters of dipentaerythritol such as dipentaerythritol hexastearate, etc. can be cited. The content of these mold release agents is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight, and still more preferably in the range of 0.02 to 0.5 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

[0260] As the ultraviolet absorber, at least one ultraviolet absorber selected from benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers is preferred. That is, any one of the following-mentioned ultraviolet absorbers can be used alone, or two or more thereof can be used in combination.

[0261] As benzotriazole-based ultraviolet absorbers, examples 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-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-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-benzotriazolylphenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, and the like.

[0262] As benzophenone-based ultraviolet absorbers, examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfonate benzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like.

[0263] As triazine-based ultraviolet absorbers, examples 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 the like.

[0264] Examples of the cyclic iminoester-based ultraviolet absorbers include 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-p-phenylene bis(3,1-benzoxazin-4-one), 2,2'-m-phenylene bis(3,1-benzoxazin-4-one), 2,2'-(4,4'-biphenylene) bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthalene) bis(3,1-benzoxazin-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).

[0265] Examples of the cyanoacrylate-based ultraviolet absorbers include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyloxy)]-2,2-bis[(2-cyano-3,3-diphenylacryloyloxy)methyl]propane, and 1,3-bis-[(2-cyano-3,3-diphenylacryloyloxy)]benzene.

[0266] The content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and even more preferably 0.05 to 0.8 parts by weight with respect to 100 parts by weight of the polycarbonate resin. As long as it is within the range of this compounding amount, sufficient weather resistance suitable for the use can be imparted to the polycarbonate resin.

[0267] The polycarbonate resin of the present invention has a high refractive index and a low Abbe number. Moreover, in addition to optical lenses, it can also be preferably used as a structural material or functional material for optical molded articles applicable to transparent conductive substrates, optical discs, liquid crystal panels, optical memory cards, sheets, films, optical fibers, connectors, vapor-deposited plastic mirrors, displays, etc. such as liquid crystal displays, organic EL displays, and solar cells.

[0268] On the surface of the optical molded article, a coating such as an antireflection layer or a hard coat may be provided as needed. The antireflection layer can be a single layer or a multilayer, and can be an organic substance or an inorganic substance, but an inorganic substance is preferred. Specifically, oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride can be exemplified.

[0269] (5) Optical lens

[0270] The optical lenses made of the polycarbonate resin of the present invention have a high refractive index, a low Abbe number, and high heat and humidity resistance, and can be used in fields such as telescopes, binoculars, and television projectors, which currently use expensive high refractive index glass lenses, and are extremely useful. As needed, it is preferably used in the form of an aspherical lens. The aspherical lens can substantially make the spherical aberration zero with one lens, so there is no need to combine multiple spherical lenses to eliminate the spherical aberration, and weight reduction and cost reduction of production can be achieved. Therefore, the aspherical lens is a lens that is useful especially as a camera lens among optical lenses.

[0271] The optical lens is formed by any method such as an injection molding method, a compression molding method, an injection compression molding method, etc. By using the present invention, a high refractive index and low birefringence aspherical lens, which is technically difficult to process for glass lenses, can be obtained more easily.

[0272] In order to avoid foreign matter from mixing into the optical lens as much as possible, the molding environment must of course be a low dust environment, preferably below class 6, and more preferably below class 5.

[0273] (6) Optical film

[0274] The optical film made of the polycarbonate resin of the present invention has excellent transparency and heat resistance, and is therefore preferably used for films for liquid crystal substrates, optical memory cards, etc.

[0275] In order to avoid foreign matter from mixing into the optical film as much as possible, the molding environment must of course be a low dust environment, preferably below class 6, and more preferably below class 5.

[0276] Examples

[0277] 2) Refractive index (nD): For a 0.1 mm thick film containing the polycarbonate resin manufactured in the examples, an Abbe refractometer was used to measure it by the method of JIS-K-7142.

[0278] 3) Abbe number (ν): For a 0.1 mm thick film containing the polycarbonate resin manufactured in the examples, an Abbe refractometer was used to measure the refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm at 23 °C, and the Abbe number was further calculated using the following formula.

[0279] ν = (nD - 1) / (nF - nC)

[0280] nD: Refractive index at a wavelength of 589 nm

[0281] nC: Refractive index at a wavelength of 656 nm

[0282] nF: Refractive index at a wavelength of 486 nm

[0283] 4) Glass transition temperature (Tg): Measured using a differential scanning calorimeter (DSC).

[0284] 5) Total light transmittance: For a 3-mm-thick plate made of polycarbonate resin prepared for measuring the following b value, it was measured by the method of JIS-K-7361-1 using a SE2000 spectral color difference meter manufactured by Nippon Denshoku Industries Co., Ltd.

[0285] 6) b value: After drying the manufactured resin at 120 °C for 4 hours, injection molding was carried out using an injection molding machine (FANUC ROBOSHOTα-S30iA) at a barrel temperature of 270 °C and a mold temperature of Tg - 10 °C to obtain a disc-shaped test plate with a diameter of 50 mm and a thickness of 3 mm. Using this plate, the b value was measured with reference to JIS K7105. The smaller the b value, the weaker the yellowing and the better the hue. The measurement of the molded plate was carried out using a SE2000 spectral color difference meter manufactured by Nippon Denshoku Industries Co., Ltd.

[0286] 7) Vinyl end group amount: 1 The measurement of 1H-NMR was carried out under the following conditions.

[0287] · 1 1H-NMR measurement conditions

[0288] Apparatus: Bruker AVANZE III HD 500 MHz

[0289] Inclination angle: 30 degrees

[0290] Waiting time: 1 second

[0291] Number of accumulations: 500 times

[0292] Measurement temperature: Room temperature (298 K)

[0293] Concentration: 5 wt%

[0294] Solvent: Deuterochloroform

[0295] Internal standard substance: Tetramethylsilane (TMS) 0.05 wt%

[0296] 8) Determination of the amounts of phenol and diphenyl carbonate (DPC) in the polycarbonate resin

[0297] 0.5 g of the sample of Example 1 described below was dissolved in 50 ml of tetrahydrofuran (THF) to prepare a sample solution. As a standard, a calibration curve was prepared from pure compounds, and 2 μL of the sample solution was quantified by LC-MS under the following measurement conditions. It should be noted that the detection limit value under these measurement conditions is 0.01 ppm.

[0298] LC-MS measurement conditions:

[0299] Measurement device (LC part): Agilent Infinity 1260 LC System

[0300] Chromatographic column: ZORBAX Eclipse XDB-18, and guard column

[0301] Mobile phase:

[0302] A: 0.01 mol / L - ammonium acetate aqueous solution

[0303] B: 0.01 mol / L - methanol solution of ammonium acetate

[0304] C: THF

[0305] Gradient program of the mobile phase:

[0306] As shown in Table 1, use the mixture of A to C above as the mobile phase, and while switching the composition of the mobile phase at the time indicated in the time (minute) column, pass the mobile phase through the chromatographic column for 30 minutes.

[0307] [Table 1]

[0308]

[0309] Flow rate: 0.3 ml / min

[0310] Chromatographic column temperature: 45 °C

[0311] Detector: UV (225 nm)

[0312] Measurement device (MS part): Agilent 6120 single quad LCMS System

[0313] Ionization source: ESI

[0314] Polarity: Positive (DPC) & Negative (PhOH)

[0315] Fragmentation voltage: 70 V

[0316] Drying gas: 10 L / min, 350 °C

[0317] Nebulizer: 50 psi

[0318] Capillary voltage: 3000 V (Positive), 2500 V (Negative)

[0319] Measured ions:

[0320] [Table 2]

[0321] monomer ion species m / z PhOH [M-H]- 93.1 DPC [M+NH4]+ 232.1

[0322] Sample injection volume: 2 μL

[0323] [Manufacture of Polycarbonate Resin]

[0324] (Example 1)

[0325] As raw materials, 31.6 kg (60.0 moles) of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene (hereinafter sometimes abbreviated as "BINL-2EO"), 13.5 kg (63.0 moles) of diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"), and 0.074 g (8.8×10 －4 moles) of sodium bicarbonate were placed in a 50 L reactor equipped with a stirrer and a distillation separation device, and heated to 180 °C under 760 mmHg in a nitrogen atmosphere. After 20 minutes from the start of heating, it was confirmed that the raw materials were completely dissolved, and then stirred for 120 minutes under the same conditions. After that, the degree of vacuum was adjusted to 200 mmHg, and at the same time, the temperature was raised to 200 °C at a rate of 60 °C / hr. At this time, the by-product phenol separated by distillation was started to be confirmed. After that, the reaction was allowed to proceed while maintaining at 200 °C for 40 minutes. After that, the temperature was raised to 240 °C at a rate of 75 °C / hr, and 10 minutes after the end of the temperature rise, while maintaining this temperature, the degree of vacuum was brought to 1 mmHg or less over 1 hour. After that, the temperature was raised to 245 °C at a rate of 60 °C / hr, and stirring was carried out for another 30 minutes. After the reaction was completed, nitrogen was introduced into the reactor, and the pressure was restored to normal pressure. The polycarbonate resin produced was granulated and taken out. The amounts of phenol and diphenyl carbonate (DPC) as impurities in the obtained polycarbonate resin were measured in the above-described manner, and it was found that the phenol in the resin was 100 mass ppm and the DPC was 300 mass ppm.

[0326] The physical property values of the obtained resin are shown in Table 3 below.

[0327] (Example 2-A)

[0328] Except that BINL-2EO 7.9 kg (15.0 moles), BNEF 24.2 kg (45.0 moles), and DPC 13.5 kg (63.0 moles) were used as raw materials, the same operations as in Example 1 were carried out.

[0329] (Example 2-B)

[0330] Except that 15.8 kg (30.0 moles) of BINL-2EO, 16.2 kg (30.0 moles) of BNEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out.

[0331] (Example 2-C)

[0332] Except that 23.7 kg (45.0 moles) of BINL-2EO, 8.1 kg (15.0 moles) of BNEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out.

[0333] The physical property values of the obtained resin are shown in Table 3. In addition, the NMR spectrum of the resin (BINOL-2EO / BNEF = 50 mol / 50 mol) obtained in Example 2-B is shown in Figure 1 .

[0334] (Example 3-A)

[0335] Except that 7.9 kg (15.0 moles) of BINL-2EO, 19.0 kg (45.0 moles) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter sometimes abbreviated as "BPEF"), and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0336] (Example 3-B)

[0337] Except that 15.8 kg (30.0 moles) of BINL-2EO, 12.7 kg (30.0 moles) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter sometimes abbreviated as "BPEF"), and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0338] (Example 3-C)

[0339] Except that 23.7 kg (45.0 moles) of BINL-2EO, 6.3 kg (15.0 moles) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter sometimes abbreviated as "BPEF"), and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0340] (Example 4-A)

[0341] Except that 7.9 kg (15.0 moles) of BINL-2EO, 25.9 kg (45.0 moles) of BPPEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0342] (Example 4-B)

[0343] Except that 15.8 kg (30.0 moles) of BINL-2EO, 17.2 kg (30.0 moles) of BPPEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0344] (Example 4-C)

[0345] Except that 23.7 kg (45.0 moles) of BINL-2EO, 8.6 kg (15.0 moles) of BPPEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0346] (Example 5)

[0347] Except that 7.6 kg (18.0 moles) of BPEF, 26.3 kg (42.0 moles) of 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalen-1-yl)-1,1'-binaphthalene (hereinafter sometimes abbreviated as "DNBINOL-2EO"), and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0348] (Example 6-A)

[0349] Except that 7.9 kg (15.0 moles) of BINL-2EO, 9.7 kg (18.0 moles) of BNEF, 10.1 kg (27.0 moles) of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (hereinafter sometimes abbreviated as "BNE"), and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0350] (Example 6-B)

[0351] Except for using 19.0 kg (36.0 moles) of BINL-2EO, 4.5 kg (12.0 moles) of BNE, 5.1 kg (12.0 moles) of BPEF, and 13.5 kg (63.0 moles) of DPC as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0352] (Example 6-C)

[0353] Except for using 19.0 kg (36.0 moles) of BINL-2EO, 4.5 kg (12.0 moles) of BNE, 6.9 kg (12.0 moles) of BPPEF, and 13.5 kg (63.0 moles) of DPC as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0354] (Example 6-D)

[0355] Except for using 11.3 kg (21.0 moles) of BNEF, 11.2 kg (30.0 moles) of BNE, 5.6 kg (9.0 moles) of DNBINOL-2EO, and 13.5 kg (63.0 moles) of DPC as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0356] (Example 6-E)

[0357] Except for using 6.7 kg (18.0 moles) of BNE, 17.2 kg (30.0 moles) of BPPEF, 7.5 kg (12.0 moles) of DNBINOL-2EO, and 13.5 kg (63.0 moles) of DPC as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0358] (Example 6-F)

[0359] Except for using 6.7 kg (18.0 moles) of BNE, 10.1 kg (24.0 moles) of BPEF, 11.3 kg (18.0 moles) of DNBINOL-2EO, and 13.5 kg (63.0 moles) of DPC as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0360] (Example 7)

[0361] Except that 32.0 kg (51.0 moles) of 2,2'-bis(2-hydroxyethoxy)-6,6'-bis(naphthalen-2-yl)-1,1'-binaphthalene (2DNBINOL-2EO), 3.8 kg (9.0 moles) of BPEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0362] (Example 7-A)

[0363] Except that 18.8 kg (30.0 moles) of 2,2'-bis(2-hydroxyethoxy)-6,6'-bis(naphthalen-2-yl)-1,1'-binaphthalene (2DNBINOL-2EO), 12.7 kg (30.0 moles) of BPEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0364] (Example 7-B)

[0365] Except that 5.6 kg (9.0 moles) of 2,2'-bis(2-hydroxyethoxy)-6,6'-bis(naphthalen-2-yl)-1,1'-binaphthalene (2DNBINOL-2EO), 21.5 kg (51.0 moles) of BPEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0366] (Example 8)

[0367] Except that 37.1 kg (51.0 moles) of 2,2'-bis(2-hydroxyethoxy)-6,6'-bis(phenanthren-9-yl)-1,1'-binaphthalene (9DPNBINOL-2EO), 3.8 kg (9.0 moles) of BPEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 1.

[0368] (Example 8-A)

[0369] Except that 21.8 kg (30.0 moles) of 2,2'-bis(2-hydroxyethoxy)-6,6'-bis(phenanthren-9-yl)-1,1'-binaphthalene (9DPNBINOL-2EO), 12.7 kg (30.0 moles) of BPEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0370] (Example 8-B)

[0371] Except that 6.5 kg (9.0 moles) of 2,2'-bis(2-hydroxyethoxy)-6,6'-bis(phenanthren-9-yl)-1,1'-binaphthalene (9DPNBINOL-2EO), 21.5 kg (51.0 moles) of BPEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0372] (Example 9)

[0373] Except that 10.4 kg (18.0 moles) of 6,6'-bis-(3-cyanophenyl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthalene (CN-BNA), 18.4 kg (42.0 moles) of BPEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0374] (Example 10)

[0375] Except that 12.7 kg (18.0 moles) of 6,6'-bis-(dibenzo[b,d]furan-4-yl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthalene (FUR-BNA), 18.4 kg (42.0 moles) of BPEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0376] (Example 11)

[0377] Except that 13.3 kg (18.0 moles) of 6,6'-bis-(dibenzo[b,d]thiophen-4-yl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthalene (THI-BNA), 18.4 kg (42.0 moles) of BPEF, and 13.5 kg (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0378] (Comparative Example 1)

[0379] Except that 22.5 kg (60.0 moles) of BNE and 13.5 g (63.0 moles) of DPC were used as raw materials, the same operations as in Example 1 were carried out. The physical property values of the obtained resin are shown in Table 3.

[0380] [Table 3]

[0381]

[0382] Examples:

[0383] BINL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene)

[0384] BNEF (9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene)

[0385] BNE (2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene)

[0386] BPEF (9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene)

[0387] BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene)

[0388] DNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalen-1-yl)-1,1'-binaphthalene)

[0389] 2DNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalen-2-yl)-1,1'-binaphthalene)

[0390] 9DPNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-di(phenanthren-9-yl)-1,1'-binaphthalene)

[0391] CN-BNA (6,6'-di-(3-cyanophenyl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthalene)

[0392] FUR-BNA (6,6'-di-(dibenzo[b,d]furan-4-yl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthalene)

[0393] THI-BNA (6,6'-di-(dibenzo[b,d]thiophen-4-yl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthalene)

[0394] Comparative Examples:

[0395] BNE (2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene)

[0396] [Moldability]

[0397] The molded sheet A has no voids and no waves on the surface

[0398] The molded sheet B has voids

[0399] The surface of the C-shaped sheet has waves

[0400] The D-shaped sheet has voids and its surface is deformed

[0401] 2,2’-Bis(2-hydroxyethoxy)-6,6’-diphenyl-1,1’-binaphthalene

[0402] 9,9-Bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene

[0403] 2,2’-Bis(2-hydroxyethoxy)-1,1’-binaphthalene

[0404] 9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorene

[0405] 9,9-Bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene

[0406] 2,2’-Bis(2-hydroxyethoxy)-6,6’-di(naphthalen-1-yl)-1,1’-binaphthalene 2,2’-Bis(2-hydroxyethoxy)-6,6’-di(naphthalen-2-yl)-1,1’-binaphthalene 2,2’-Bis(2-hydroxyethoxy)-6,6’-di(phenanthren-9-yl)-1,1’-binaphthalene

[0407]

[0408]

[0409]

Claims

1. A polycarbonate resin, characterized in that, it is a polycarbonate resin containing more than 50 mol% of the structural unit represented by the following general formula (1) and having a refractive index value of 1.655 or more, R in formula (1) 1 and R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 36 carbon atoms, or a monocyclic or polycyclic heteroaryl group having 5 to 36 ring atoms, where one, two, three, or four of the ring atoms in the heteroaryl group are selected from sulfur and oxygen, and the other ring atoms are carbon; the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group have no substituents, or have 1 or 2 substituents selected from CN, O-phenyl, O-naphthyl, S-phenyl, and S-naphthyl, wherein, R 1 and R 2 are not all hydrogen, X is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms, wherein the alkylene group and the cycloalkylene group are each optionally substituted in a manner having a benzene ring, a and b are each an integer from 1 to 10.

2. The polycarbonate resin according to claim 1, characterized in that, it contains more than 60 mol% of the structural unit represented by the general formula (1).

3. The polycarbonate resin according to claim 1 or 2, characterized in that, R in the general formula (1) 1 and R 2 At least one of them is an aryl group having 6 to 20 carbon atoms.

4. The polycarbonate resin according to claim 3, characterized in that, R in the general formula (1) 1 and R 2 At least one of them is an aryl group having 6 to 14 carbon atoms.

5. The polycarbonate resin according to claim 1 or 2, characterized in that, the structural unit represented by the general formula (1) contains at least any one of the structural units represented by the following general formulas (A-1) to (A-7), 6. The polycarbonate resin according to claim 1, characterized in that, it further contains at least one of the structural units represented by the following general formulas (2) and (3), R' in formula (2) 1 ~R' 20 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms Y is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms, c and d are each an integer from 1 to 10; R” in formula (3) 1 ~R” 16 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms Z is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms, e and f are each an integer from 1 to 10.

7. The polycarbonate resin according to claim 6, characterized in that, it comprises a copolymer containing at least the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2).

8. The polycarbonate resin according to claim 7, characterized in that, the copolymer further contains the structural unit represented by the following general formula (3-1), 9. The polycarbonate resin according to claim 6, characterized in that, it comprises a copolymer containing at least the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3).

10. The polycarbonate resin according to claim 9, characterized in that, the copolymer further contains the structural unit represented by the following general formula (2-1), 11. The polycarbonate resin according to claim 6, characterized in that, the molar ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (2) or (3) is 4:1 to 1:

1.

12. The polycarbonate resin according to claim 1 or 2, characterized in that, it further contains at least one of the structural units represented by the following general formula (4), 13. The polycarbonate resin according to claim 12, characterized in that, it contains at least the structural unit of BNEF, i.e., 9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene.

14. The polycarbonate resin according to claim 12, characterized in that, It contains at least a structural unit of 2,2’-bis(2-hydroxyethoxy)-1,1’-binaphthalene.

15. The polycarbonate resin according to claim 12, characterized in that it further contains at least a structural unit of BPPEF, i.e., 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene.

16. The polycarbonate resin according to claim 1 or 2, characterized in that the aryl group or the heteroaryl group in the general formula (1) is selected from an optionally substituted phenyl group, naphthyl group, benzofuranyl group, phenanthryl group, cyanobenzyl group, and benzothienyl group.

17. The polycarbonate resin according to claim 1 or 2, characterized in that the refractive index value of the polycarbonate resin is 1.665 or more.

18. The polycarbonate resin according to claim 1 or 2, characterized in that The said R 1 is the same as the said R 2 .

19. The polycarbonate resin according to claim 1 or 2, characterized in that The R 1 is the same as or different from the R 2 and is an aryl group having 6 to 36 carbon atoms which is monocyclic or polycyclic, or a heteroaryl group having 5 to 36 ring atoms which is monocyclic or polycyclic. In the heteroaryl group, 1, 2, 3 or 4 of the ring atoms are selected from sulfur and oxygen, and the other ring atoms are carbon. the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group have no substituents.

20. The polycarbonate resin according to claim 1 or 2, characterized in that Said R 1 and said R 2 are selected from phenyl without substituents and phenyl substituted with one CN group.

21. The polycarbonate resin according to claim 1, characterized in that The said R 1 and the said R 2 are selected from phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-naphthyl, 1-naphthyl and 9-naphthyl.

22. The polycarbonate resin according to claim 1 or 2, characterized in that X is an ethylene group.

23. An optical lens, characterized in that it contains the polycarbonate resin according to any one of claims 1 to 22.

24. A method for manufacturing a polycarbonate resin for manufacturing the polycarbonate resin according to any one of claims 1 to 22, the manufacturing method is characterized in that it includes: a step of melt polycondensing a dihydroxy compound represented by the following general formula (5) with a carbonic acid diester, R in general formula (5) 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 36 carbon atoms, or a monocyclic or polycyclic heteroaryl group having 5 to 36 ring atoms, where one, two, three, or four of the ring atoms in the heteroaryl group are selected from sulfur and oxygen and the remaining ring atoms are carbon the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group have no substituents, or have 1 or 2 substituents selected from CN, O-phenyl, O-naphthyl, S-phenyl, and S-naphthyl, wherein, R 1 and R 2 are not all hydrogen, X is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms, wherein the alkylene group and the cycloalkylene group are each optionally substituted in a manner having a benzene ring, a and b are each an integer from 1 to 10.

Images