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 resistance to moisture and heat. In one embodiment of the present invention, a polycarbonate resin containing a structural unit represented by the following general formula (1) is provided. (R1 and R2 in formula (1) 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, one, two, three or four 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 substituent, or may have one or two R selected from the group consisting of CN, CH3, OCH3, O-phenyl, O-naphthyl, S-phenyl, S-naphthyl and halogen a wherein R1 and R2 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 above-mentioned alkylene group and the above-mentioned cycloalkylene group may be substituted with a benzene ring; and a and b are integers of 1 to 10 respectively.

Description

[0001] (This application is a divisional application of application No. 201880056382.6, filed on August 29, 2018, entitled “Polycarbonate resin, method for producing the same and optical lens”) 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] Optical glass or optical resin is used as the material of optical lenses used in the optical systems of various cameras such as cameras, film-integrated cameras, and video cameras. Optical glass has excellent heat resistance, transparency, dimensional stability, and chemical resistance, but has problems such as high material cost, poor molding processability, and low production efficiency.

[0004] On the other hand, optical lenses made of optical resins have the advantage of being able to be mass-produced by injection molding. For example, polycarbonate resins are used in camera lenses. However, in recent years, as products have become thinner and smaller, it is necessary to develop resins with high refractive indexes. Generally speaking, when the refractive index of an optical material is high, a lens element with the same refractive index can be realized with a smaller curvature surface, thereby reducing the amount of aberration generated on the surface.

[0005] As a result, the number of lenses can be reduced, the decentering sensitivity of the lenses can be lowered, or the thickness of the lenses can be reduced to achieve weight reduction.

[0006] In general, in the optical system of a camera, aberration correction is performed by combining multiple concave lenses and convex lenses. That is, for 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 to cancel the chromatic aberration through synthesis.

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

[0008] For this reason, resins for optical lenses with high refractive index and low Abbe number have been developed. For example, Patent Document 1 discloses a solution that copolymers containing bisphenol A type polycarbonate structural units can increase the refractive index. The examples in Patent Document 1 record that the copolymers have a refractive index of 1.62 to 1.64 and an Abbe number of 23 to 26.

[0009] 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 state that the copolymer has a refractive index of 1.616 to 1.636. The polycarbonate copolymer disclosed in Patent Document 3 also fails to achieve a sufficiently high refractive index.

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

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

[0012] Prior art literature

[0013] Patent Literature

[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 Application Publication 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 resistance to moisture and heat, in particular, a high refractive index. In addition, the present invention also aims to provide an excellent optical lens by using the resin.

[0019] Technical solutions to solve problems

[0020] The present inventors have conducted intensive studies to solve the above-mentioned problems and, as a result, have found that the above-mentioned problems can be solved by using the following polycarbonate resin and optical lens, thereby completing the present invention.

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

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

[0023]

[0024] (R1 and R2 in formula (1) 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 heteroaryl group, one, two, three or four 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 substituent, or may have one or two R selected from the group consisting of CN, CH3, OCH3, O-phenyl, O-naphthyl, S-phenyl, S-naphthyl and halogen. a base,

[0026] Wherein, R1 and R2 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 be substituted with a benzene ring, and a and b are integers of 1 to 10.

[0029] [2] The polycarbonate resin according to [1] above, which contains more than 50 mol % of the structural unit represented by the general formula (1).

[0030] [3] The polycarbonate resin according to [1] or [2], wherein at least one of R1 and R2 in the general formula (1) is an aryl group having 6 to 20 carbon atoms.

[0031] [4] The polycarbonate resin according to [3] above, wherein at least two of R1 and R2 in the general formula (1) are aryl groups having 6 to 14 carbon atoms.

[0032] [5] The polycarbonate resin according to any one of [1] to [4] above, wherein the structural unit represented by the general formula (1) contains at least 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], further comprising at least one of the structural units represented by the following general formulas (2) and (3).

[0036]

[0037] (R'1~R' in formula (2) 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 integers from 1 to 10 respectively.)

[0040]

[0041] (R"1~R" in formula (3) 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 integers from 1 to 10 respectively.)

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

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

[0046]

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

[0048]

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

[0049]

[0050]

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

[10] , which contains 20 to 80 mol % in total of the structural units represented by the general formulae (2) and (3).

[0051]

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

[11] , further comprising at least one structural unit represented by the following general formula (4).

[0052]

[0053]

[0054]

[13] The polycarbonate resin according to

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

[0055]

[14] The polycarbonate resin according to

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

[0056]

[15] The polycarbonate resin according to

[12] , further comprising at least a BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene) structural unit.

[0057]

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

[15] above, wherein the aromatic group is selected from the group consisting of pyrenyl, furyl, benzodioxanyl, dihydrobenzofuranyl, piperonyl, benzofuranyl, dibenzofuranyl, pyrrolidinyl, isoquinolyl, 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 according to any one of [1] to

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

[0059]

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

[17] above, wherein R1 and R2 are the same.

[0060]

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

[17] , wherein R1 and R2 are the same or different and are monocyclic or polycyclic aryl groups having 6 to 36 carbon atoms or monocyclic or polycyclic heteroaryl groups having 5 to 36 ring atoms, wherein in the heteroaryl group, 1, 2, 3 or 4 ring atoms are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon,

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

[0062]

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

[19] , wherein R1 and R2 are selected from the following groups:

[0063] Azulene;

[0064] An unsubstituted indenyl group or an indenyl group which may be substituted with 2, 3, 4 or 5 substituents selected from phenyl groups and polycyclic aryl groups, wherein the polycyclic aryl groups have 2, 3 or 4 benzene rings which may be bonded to each other via single bonds, may be directly condensed to each other, and / or may be condensed with a saturated or unsaturated 4-10 membered monocyclic or bicyclic hydrocarbon ring;

[0065] Phenyl with no substituents;

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

[0067] A phenyl group which may be substituted with 2, 3, 4 or 5 substituents selected from a phenyl group and a polycyclic aryl group, 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 to each other, and / or may be condensed with a saturated or unsaturated 4-10 membered monocyclic or bicyclic hydrocarbon ring;

[0068] A polycyclic aromatic group having 2, 3 or 4 benzene rings which can be directly condensed with each other and / or condensed with a saturated or unsaturated 4-10-membered monocyclic or bicyclic hydrocarbon ring, wherein the polycyclic aromatic group may have no substituent or may be substituted with 1 or 2 substituents selected from phenyl and a polycyclic aromatic group having 2 or 3 benzene rings, wherein the 2 or 3 benzene rings may be bonded to each other via a single bond, may be directly condensed with each other and / or may be condensed with a saturated 4-10-membered monocyclic or bicyclic hydrocarbon ring, wherein the benzene ring of the polycyclic aromatic group may have no substituent or may have 1 or 2 substituents R a .

[0069]

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

[20] , wherein R1 and R2 are selected from the following groups:

[0070] unsubstituted phenyl or phenyl which may be substituted with 1, 2, 3, 4 or 5 phenyl groups,

[0071] Phenyl substituted with 1 or 2 CN groups,

[0072] substituted with one or two polycyclic aromatic groups selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl and pyrenyl, and phenyl which may be substituted with one phenyl, unsubstituted naphthyl or substituted with one or two substituents selected from CN, phenyl and polycyclic aromatic groups, wherein the polycyclic aromatic groups are selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl and pyrenyl,

[0073] Biphenylene,

[0074] Terphenylene,

[0075] Quaterphenylene,

[0076] Fiki,

[0077] Pyrene

[0078] 9H-fluorenyl,

[0079] Dibenzo[a,e][8]annulyl,

[0080] Perylene, and

[0081] 9,9'-Spirobi[9H-fluorenyl]yl.

[0082]

[22] The polycarbonate resin according to

[21] , wherein the R1 and R2 are selected from phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-naphthyl, 1-naphthyl and 9-naphthyl.

[0083]

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

[19] , wherein R1 and R2 are selected from:

[0084] a heteroaromatic monocyclic radical having 5 or 6 ring atoms, which has 1, 2, 3 or 4 nitrogen atoms, or has 1 oxygen atom and 0, 1, 2 or 3 nitrogen atoms, or has 1 sulfur atom and 0, 1, 2 or 3 nitrogen atoms, the other ring atoms being carbon atoms;

[0085] A heteroaromatic polycyclic group having the heteroaromatic monocyclic ring and 1, 2, 3, 4 or 5 other aromatic rings selected from phenyl and heteroaromatic monocyclic rings, wherein the (hetero) aromatic rings of the polycyclic heteroaromatic group may be bound to each other by covalent bonds or may be directly condensed with each other and / or may be condensed with a saturated or unsaturated 4-10 membered monocyclic or bicyclic hydrocarbon ring; and

[0086] A heteroaromatic polycyclic group having at least one saturated or partially unsaturated 5- or 6-membered heterocyclic ring having one or two heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, and one, two, three, four or five other aromatic rings selected from phenyl and the heteroaromatic monocyclic ring, at least one of the other aromatic rings being directly condensed with the saturated or partially unsaturated 5- or 6-membered heterocyclic group, and the other other aromatic rings of the polycyclic heteroaryl aromatic ring may be bound to each other via covalent bonds, may be directly condensed with each other, and / or may be condensed with a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0087]

[24] The polycarbonate resin according to

[23] , wherein R1 and R2 are selected from the group consisting of furyl, thiophenyl, 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, triazine, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, naphthyl, oxanthrenyl, indolyl, isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzo[cd]indolyl, 1H-benzo[g]indolyl, quinolyl, isoquinolyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, benzo[b][1, 5] naphthyridinyl, cinnolinyl, 1,5-naphthyridinyl, 1,8-naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, bipyridyl, phenylpyridinyl, naphthylpyridinyl, pyrido[4,3-b]indolyl, pyrido[3,2-b]indolyl, pyrido[3,2-g]quinolyl, pyrido[2,3-b][1,8]naphthyridinyl, pyrrolo[3,2-b]pyridinyl, pteridinyl, purinyl, 9H-xanthenyl enyl), 2H-benzopyranyl, phenanthridinyl, phenanthrolinyl, furo[3,2-f][1]benzofuranyl, furo[2,3-f][1]benzofuranyl, furo[3,2-g]quinolyl, furo[2,3-g]quinolyl, furo[2,3-g]quinoxalinyl, benzo[g]benzopyranyl, pyrrolo[3,2,1-hi]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl and benzo[h]isoquinolyl.

[0088]

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

[24] above, wherein X is an ethylene group.

[0089]

[26] An optical lens comprising the polycarbonate resin described in any one of [1] to

[25] above.

[0090]

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

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

[0091]

[0092] (In the general formula (5), R1 and R2 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,

[0093] The monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group have no substituent, or may have one or two R selected from the group consisting of CN, CH3, OCH3, O-phenyl, O-naphthyl, S-phenyl, S-naphthyl and halogen. a base,

[0094] Wherein, R1 and R2 are not all hydrogen,

[0095] 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,

[0096] The above alkylene group and the above cycloalkylene group may be substituted to have a benzene ring,

[0097] a and b are integers from 1 to 10 respectively.)

[0098] Effects of the Invention

[0099] The polycarbonate resin of the present invention has a high refractive index, a low Abbe number, and high resistance to moisture and heat, and particularly has a high refractive index. In addition, by using the resin, an excellent optical lens can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0100] Figure 1 The resin prepared in Example 2-B 1 H-NMR spectrum. DETAILED DESCRIPTION

[0101] Hereinafter, the present invention will be described in detail.

[0102] (1) Components (structural units) of polycarbonate resin

[0103] The polycarbonate resin of the present invention is a polycarbonate resin containing a structural unit represented by the following general formula (1).

[0104]

[0105] (R1 and R2 in formula (1) 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, one, two, three or four ring atoms are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon;

[0106] The monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group may have no substituent, or may have one or two R selected from the group consisting of CN, CH3, OCH3, O-phenyl, O-naphthyl, S-phenyl, S-naphthyl and halogen. a base,

[0107] Wherein, R1 and R2 are not all hydrogen,

[0108] 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,

[0109] The above alkylene group and the above cycloalkylene group may be substituted with a benzene ring, and a and b are integers of 1 to 10.

[0110] R1 and R2 in the general formula (1) 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. 10 At least one of them 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 R1 to R 10 At least two of them are preferably aryl groups having 6 to 14 carbon atoms, or more preferably aryl groups having 6 to 12 carbon atoms.

[0111] R1 and R2 are, for example, the same.

[0112] In addition, R1 and R2 may be the same or different, and may be selected from 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, wherein 1, 2, 3 or 4 of the ring atoms are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon. In addition, the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group may have no substituent.

[0113] R1 and R2 can be selected from the following groups.

[0114] Azulene;

[0115] An unsubstituted indenyl group or an indenyl group which may be substituted with 2, 3, 4 or 5 substituents selected from phenyl groups and polycyclic aryl groups, wherein the polycyclic aryl groups have 2, 3 or 4 benzene rings which may be bonded to each other via single bonds, may be directly condensed to each other, and / or may be condensed with a saturated or unsaturated 4-10 membered monocyclic or bicyclic hydrocarbon ring;

[0116] Phenyl with no substituents;

[0117] Phenyl substituted with 1 or 2 CN groups;

[0118] A phenyl group which may be substituted with 2, 3, 4 or 5 substituents selected from a phenyl group and a polycyclic aryl group, 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 to each other, and / or may be condensed with a saturated or unsaturated 4-10 membered monocyclic or bicyclic hydrocarbon ring;

[0119] A polycyclic aromatic group having 2, 3 or 4 benzene rings which can be directly condensed with each other and / or condensed with a saturated or unsaturated 4-10-membered monocyclic or bicyclic hydrocarbon ring, wherein the polycyclic aromatic group may have no substituent or may be substituted with 1 or 2 substituents selected from phenyl and a polycyclic aromatic group having 2 or 3 benzene rings, wherein the 2 or 3 benzene rings may be bonded to each other via a single bond, may be directly condensed with each other and / or may be condensed with a saturated 4-10-membered monocyclic or bicyclic hydrocarbon ring, wherein the benzene ring of the polycyclic aromatic group may have no substituent or may have 1 or 2 substituents R a .

[0120] In addition, R1 and R2 can be selected from the following groups, respectively. That is, selected from:

[0121] unsubstituted phenyl or phenyl which may be substituted with 1, 2, 3, 4 or 5 phenyl groups,

[0122] Phenyl substituted with 1 or 2 CN groups,

[0123] substituted with one or two polycyclic aromatic groups selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl and pyrenyl, and phenyl which may be substituted with one phenyl, unsubstituted naphthyl or substituted with one or two substituents selected from CN, phenyl and polycyclic aromatic groups, wherein the polycyclic aromatic groups are selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl and pyrenyl,

[0124] Biphenylene,

[0125] Terphenylene,

[0126] Quaterphenylene,

[0127] Fiki,

[0128] Pyrene

[0129] 9H-fluorenyl,

[0130] Dibenzo[a,e][8]annulyl,

[0131] Perylene, and

[0132] 9,9'-Spirobi[9H-fluorenyl]yl.

[0133] Among them, R1 and R2 are preferably selected from phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-naphthyl, 1-naphthyl and 9-naphthyl.

[0134] In addition, R1 and R2 can be selected from the following groups. That is,

[0135] a heteroaromatic monocyclic radical having 5 or 6 ring atoms, which has 1, 2, 3 or 4 nitrogen atoms, or has 1 oxygen atom and 0, 1, 2 or 3 nitrogen atoms, or has 1 sulfur atom and 0, 1, 2 or 3 nitrogen atoms, the other ring atoms being carbon atoms;

[0136] A heteroaromatic polycyclic group having the above-mentioned heteroaromatic monocyclic ring and 1, 2, 3, 4 or 5 other aromatic rings selected from phenyl and heteroaromatic monocyclic rings, wherein the (hetero) aromatic rings of the polycyclic heteroaromatic group may be bound to each other via covalent bonds or may be directly condensed with each other and / or may be condensed with a saturated or unsaturated 4-10 membered monocyclic or bicyclic hydrocarbon ring; and

[0137] A heteroaromatic polycyclic group having at least one saturated or partially unsaturated 5- or 6-membered heterocyclic ring having one or two heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, and one, two, three, four or five other aromatic rings selected from phenyl and the above-mentioned heteroaromatic monocyclic rings, at least one of the above-mentioned other aromatic rings is directly condensed with the saturated or partially unsaturated 5- or 6-membered heterocyclic group, and the other other aromatic rings of the polycyclic heteroaryl aromatic ring may be bound to each other via a covalent bond or may be directly condensed with each other, and / or may be condensed with a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0138] In addition, R1 and R2 may be selected from the following groups, respectively. That is, selected from the group consisting of furanyl, 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, benzofuranyl, dibenzofuranyl, benzothienyl, dibenzothienyl, thianthrenyl, naphthofuranyl, furano[3,2-b]furanyl, furano[3,2-b]furanyl, furano[ 2,3-b]furanyl, furano[3,4-b]furanyl, oxanthrenyl, indolyl, isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzo[cd]indolyl, 1H-benzo[g]indolyl, quinolyl, isoquinolyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, benzo[b][1,5]naphthyridinyl, cinnolinyl, 1,5-naphthyridinyl 1,8-naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, bipyridinyl, phenylpyridinyl, naphthylpyridinyl, pyrido[4,3-b]indolyl, pyrido[3,2-b]indolyl, pyrido[3,2-g]quinolyl, pyrido[2,3-b][1,8]naphthyridinyl, pyrrolo[3,2-b]pyridinyl, pteridinyl, purinyl, 9H-xanthenyl, 2H -benzopyranyl, phenanthridinyl, phenanthrolinyl, furo[3,2-f][1]benzofuranyl, furo[2,3-f][1]benzofuranyl, furo[3,2-g]quinolyl, furo[2,3-g]quinolyl, furo[2,3-g]quinoxalinyl, benzo[g]benzopyranyl, pyrrolo[3,2,1-hi]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl and benzo[h]isoquinolyl.

[0139] 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.

[0140] In addition, a and b in the general formula (1) are each preferably an integer of 1 to 6, more preferably 1 to 4, and particularly preferably 2 or 3.

[0141] The structural unit represented by the general formula (1) preferably contains at least one of the structural units represented by the following general formulae (A-1) to (A-7).

[0142]

[0143]

[0144]

[0145] That is, the structural unit represented by the general formula (1) preferably contains a structural unit derived from (BINL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl) represented by the general formula (A-1), a structural unit derived from DNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-1-yl)-1,1'-binaphthyl) represented by the general formula (A-2), a structural unit derived from 2DNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-2-yl)-1,1'-binaphthyl) represented by the general formula (A-3), and a structural unit derived from 9DPNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-2-yl)-1,1'-binaphthyl) represented by the general formula (A-4). The present invention further comprises at least one of a structural unit derived from (CN-BNA (6,6′-di-(3-cyanophenyl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl) represented by the general formula (A-5), a structural unit derived from (FUR-BNA (6,6′-di-(dibenzo[b,d]furan-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl) represented by the general formula (A-6), and a structural unit derived from (THI-BNA (6,6′-di-(dibenzo[b,d]thiophen-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl) represented by the general formula (A-7).

[0146] In the polycarbonate resin of the present invention, the structural unit represented by the general formula (1) is contained in an amount of more than 50 mol%, more preferably more than 60 mol%, 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 by the structural unit represented by the general formula (1).

[0147] The polycarbonate resin of the present invention may contain one or more other structural units in addition to the structural unit represented by the general formula (1) (structural unit (1)). As the other structural unit, a fluorene derivative unit is preferred.

[0148] Specifically, the polycarbonate resin of the present invention preferably further contains at least one of the structural units represented by the general formulae (2) and (3).

[0149]

[0150] (R'1~R' in formula (2) 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,

[0151] 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,

[0152] c and d are integers from 1 to 10 respectively.)

[0153] In the above general formula (2), R'1 to R" 20 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 are preferred, and hydrogen is more preferred.

[0154] In the above general formula (2), Y 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.

[0155] In the general formula (2), c and d are each preferably an integer of 1 to 6, more preferably 1 to 4, and particularly preferably 2 or 3.

[0156]

[0157] (R"1~R" in formula (3)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,

[0158] 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,

[0159] e and f are integers from 1 to 10 respectively.)

[0160] In the above general formula (3), R1 to R 16 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 are preferred, and hydrogen or an aryl group having 6 to 10 carbon atoms is more preferred.

[0161] In the above general formula (3), Z 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.

[0162] In addition, e and f in the above general formula (3) are each preferably an integer of 1 to 6, more preferably 1 to 4, and particularly preferably 2 or 3.

[0163] As the structural unit (1) and the structural unit represented by the above general formula (2) or (3) in the polycarbonate resin of the present invention, it is preferred that the polycarbonate resin further contain at least one structural unit represented by the following general formula (4).

[0164]

[0165] That is, the polycarbonate resin of the present invention preferably contains, in addition to the structural unit (1), at least one of a structural unit derived from BNEF (9,9-bis(6-(2-hydroxyethoxy)naphth-2-yl)fluorene) represented by the above general formula (4), a structural unit derived from BNE (2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl) and a structural unit derived from BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene).

[0166] In the polycarbonate resin of the present invention, among the structural units other than the structural unit (1), the structural units represented by the general formulae (2) and (3) may preferably be contained in an amount of 20 to 80 mol%, for example, 25 to 75 mol%. The polycarbonate resin may contain the structural units represented by the general formulae (2) and (3), for example, 30 to 70 mol%, 35 to 65 mol%, or 40 to 60 mol%.

[0167] 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. The molar ratio may be 65:35 to 35:65, 3:2 to 2:3, or 1:1. In particular, the polycarbonate resin composition preferably contains the structural unit (1) in an amount of more than 50 mol%, and therefore, specific preferred examples of the molar ratio of the structural unit (1) to the structural unit (2) are 4:1 to 1:1, 7:3 to 1:1, 65:35 to 1:1, and 3:2 to 1:1.

[0168] 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 structural unit (1) to the structural unit (2) described above.

[0169] The polycarbonate resin of the present invention may contain any of random, block and alternating copolymer structures. In addition, the polycarbonate resin of the present invention does not necessarily contain all of the above-mentioned structural units (1), structural units (2) and structural units (3) in the same polymer molecule. That is, as long as the above-mentioned structural units are contained in a plurality of polymer molecules as a whole, the polycarbonate resin of the present invention may be a blended resin. For example, the polycarbonate resin containing any of the above-mentioned structural units (1), structural units (2) and structural units (3) may 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 may be a blended resin of a copolymer containing the structural units (1) and (2) and a copolymer containing the structural units (1) and (3).

[0170] The polycarbonate resin of the present invention may be blended with other resins for the production of a molded article. Examples of other resins include polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, and polybutylene terephthalate.

[0171] Furthermore, it is preferred 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, or an antibacterial agent to the polycarbonate resin composition of the present invention.

[0172] 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-tetrakis[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- The antioxidant may be 1,4-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid amide), 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-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is preferred. The content of the antioxidant in the polycarbonate resin composition is preferably 0.001 to 0.3 parts by weight based on 100 parts by weight of the polycarbonate resin.

[0173] As a release agent, it is preferred that 90% by weight or more of the release agent is composed of an ester of an alcohol and a fatty acid. As the ester of an alcohol and a fatty acid, specifically, there can be mentioned an ester of a monohydric alcohol and a fatty acid, and a partial ester or full ester of a polyhydric alcohol and a fatty acid. As the ester of the monohydric alcohol and a fatty acid, it is preferred that it is an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. In addition, as the partial ester or full ester of a polyhydric alcohol and a fatty acid, it is preferred that it is 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.

[0174] Specifically, as the ester of monohydric alcohol and saturated fatty acid, stearyl stearate, limonyl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. can be cited. As the partial ester or full ester of polyhydric alcohol and saturated fatty acid, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitol ester, behenic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenylate, sorbitol monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, etc. can be cited. Among these, stearic acid monoglyceride and lauric acid monoglyceride are particularly preferred. The content of these release agents is preferably in the range of 0.005 to 2.0 parts by 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.

[0175] Examples of the processing stabilizer include phosphorus-based processing heat stabilizers, sulfur-based processing heat stabilizers, etc. Examples of the phosphorus-based processing heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl 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 Acid ester, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl mono-o-biphenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonate, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonate, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonate, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonate and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonate, 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 based on 100 parts by weight of the polycarbonate resin.

[0176] Examples of the sulfur-based processing heat stabilizer include pentaerythritol-tetrakis (3-lauryl thiopropionate), pentaerythritol-tetrakis (3-myristyl thiopropionate), pentaerythritol-tetrakis (3-stearyl thiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate. 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.

[0177] As the ultraviolet absorber, at least one ultraviolet absorber selected from benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, cyclic iminoester ultraviolet absorbers and cyanoacrylate ultraviolet absorbers is preferred. That is, the ultraviolet absorbers listed below can be used alone or in combination of two or more.

[0178] Examples of the benzotriazole ultraviolet absorber include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, and 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole. 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-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, etc.

[0179] Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 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 sulfonatebenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0180] Examples of the triazine-based ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-[(octyl)oxy]-phenol.

[0181] Examples of the cyclic imidoester ultraviolet absorber include 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-biphenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthalene)bis(3 ,1-benzoxazine-4-one), 2,2'-(1,5-naphthalene)bis(3,1-benzoxazine-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazine-4-one) and 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazine-4-one).

[0182] Examples of the cyanoacrylate-based ultraviolet absorber include 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0183] 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 relative to 100 parts by weight of the polycarbonate resin. Within this range, the polycarbonate resin composition can be provided with sufficient weather resistance depending on the application.

[0184] In the polycarbonate resin composition, phenol generated during the manufacture and unreacted and 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, and 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 amount of phenol and carbonic acid diester contained in the polycarbonate resin composition, a resin having physical properties that meet the purpose can be obtained. The adjustment of the content of phenol and carbonic acid diester can be carried out by appropriately changing the conditions and devices of the polycondensation. In addition, it can also be adjusted by controlling the conditions of the extrusion process after the polycondensation.

[0185] When the content of phenol or carbonic acid diester exceeds the above range, there may be problems such as reduced strength of the obtained resin molded product and generation of odor. On the other hand, when the content of phenol or carbonic acid diester is below the above range, there is a concern that the plasticity of the resin when it is melted may be reduced.

[0186] (2) Properties of polycarbonate resin

[0187] The polycarbonate resin of the present invention preferably has a viscosity average molecular weight (Mv) of 8,000 to 20,000, more preferably 9,000 to 15,000, and even more preferably 10,000 to 14,000.

[0188] When the Mv value is less than 8,000, the molded product may become brittle. When the Mv value is greater than 20,000, the melt viscosity becomes high, making it difficult to remove the produced resin, and the fluidity may deteriorate, making it difficult to perform injection molding in a molten state.

[0189] 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, more preferably 1.655 or more, 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, more preferably 1.650 to 1.697, particularly preferably 1.655 to 1.695. The polycarbonate resin of the present invention has a high refractive index (nD) and is suitable for optical lens materials. The refractive index can be measured by using an Abbe refractometer for a film having a thickness of 0.1 mm according to the method of JIS-K-7142.

[0190] The Abbe number (ν) of the polycarbonate resin of the present invention is preferably 24 or less, more preferably 22 or less, and further preferably 20 or less. The Abbe number can be calculated from the refractive index at 23° C. for wavelengths of 486 nm, 589 nm, and 656 nm by the following formula.

[0191] ν=(nD-1) / (nF-nC)

[0192] nD: refractive index at a wavelength of 589nm

[0193] nC: refractive index at a wavelength of 656nm

[0194] nF: refractive index at a wavelength of 486nm

[0195] The preferred glass transition temperature (Tg) of the polycarbonate resin of the present invention is preferably 90 to 185°C, more preferably 95 to 180°C, and even more preferably 100 to 175°C, in consideration of use for injection molding. When Tg is lower than 90°C, there is a possibility that the use 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 the resin is easily decomposed and colored. When the glass transition temperature of the resin is too high, the difference between the metal mold temperature and the glass transition temperature of the resin becomes too large in a conventional metal mold temperature controller. Therefore, in applications where strict surface accuracy requirements are placed on products, there is a possibility that the use of the resin becomes difficult when the glass transition temperature is too high. In addition, from the viewpoint of molding fluidity and molding heat resistance, the lower limit of Tg is preferably 130°C, more preferably 135°C, and the upper limit of Tg is preferably 185°C, more preferably 175°C.

[0196] The total light transmittance of the optical molded body obtained by using the polycarbonate resin of the present invention is preferably 85% or more, more preferably 87% or more, and particularly preferably 88% or more. If the total light transmittance is 85% or more, it is comparable to bisphenol A type polycarbonate resin and the like.

[0197] The polycarbonate resin of the present invention has high resistance to moisture and heat. Resistance to moisture and heat can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molded body obtained using the polycarbonate resin and measuring the total light transmittance of the optical molded body after the test. The PCT test can be performed using an injection molded body with a diameter of 50 mm and a thickness of 3 mm, at 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 above 60%, preferably above 70%, more preferably above 75%, more preferably above 80%, and particularly preferably above 85%. As long as the total light transmittance is above 60%, it can be said that it has high resistance to moisture and heat relative to existing polycarbonate resins.

[0198] The b value indicating the hue of the polycarbonate resin of the present invention is preferably not more than 5. A smaller b value indicates less yellowishness and better hue.

[0199] (3) Method for producing polycarbonate resin

[0200] The method for producing a polycarbonate resin having a structural unit represented by the general formula (1) according to the present invention comprises the step of melt-polycondensing a dihydroxy compound represented by the following general formula (5) and a carbonic acid diester.

[0201]

[0202] (In the general formula (5), R1 and R2 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,

[0203] Wherein, R1 and R2 are not both hydrogen,

[0204] 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,

[0205] The above alkylene group and the above cycloalkylene group may be substituted to have a benzene ring,

[0206] a and b are integers from 1 to 10 respectively.)

[0207] That is, use the compound shown in the above-mentioned general formula (5) as dihydroxy component, make it react with carbonate precursor materials such as carbonic acid diester, can manufacture polycarbonate resin.Specifically, the carbonate precursor materials of the compound shown in the general formula (5) and carbonic acid diester etc. in the presence of basic compound catalyst or transesterification catalyst or containing its both sides' mixed catalyst, or under the situation of catalyst-free, can utilize melt polycondensation method to react and manufacture.

[0208] Furthermore, by using the dihydroxy compound represented by the above general formula (5) as a raw material (monomer), polymers other than polycarbonate resins, such as polyester carbonate and polyester, can be obtained.

[0209] Examples of the compound of the general formula (5) include 2,2'-bis(hydroxy(poly)alkoxy)-diaryl-1,1'-binaphthyls and 2,2'-bis(hydroxy(poly)alkoxy)-dinaphthyl-1,1'-binaphthyls. Preferred are 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphth-1-yl)-1,1'-binaphthyl, 2,2'-bis(2-hydroxymethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxymethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxymethoxy)-6,6'-di(naphth-1-yl)-1,1'-binaphthyl, 2,2'-bis(2-hydroxypropoxy)-6,6'-diphenyl-1,1'-binaphthyl, and 2,2'-bis(2-hydroxypropoxy)-6,6'-di(naphth-1-yl)-1,1'-binaphthyl. These may be used alone or in combination of two or more.

[0210] It should be noted that the monomer used to produce the polycarbonate resin may contain, as an impurity, a dihydroxy compound in which the values ​​of a and b in the general formula (5) are both 0 or a dihydroxy compound in which either one of a and b in the general formula (5) is 0, together with the dihydroxy compound represented by the general formula (5).

[0211] Thus, the total amount of dihydroxy compounds having different values ​​from at least any one of a and b in the above-mentioned general formula (5) is preferably contained in an amount of less than 1000 ppm, more preferably less than 500 ppm, more preferably less than 200 ppm, and particularly preferably less than 100 ppm in the monomer having the dihydroxy compound represented by the above-mentioned general formula (5) as the main component, and the total amount of dihydroxy compounds having different values ​​from at least any one of a and b in the above-mentioned general formula (5) in the above-mentioned monomer is desirably less than 50 ppm, more desirably less than 20 ppm.

[0212] The compound of the general formula (5) can be produced 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 monotoluenesulfonate, (b) a method of reacting binaphthols with alkylene oxides, halogenated alkanols 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.

[0213] In the polycarbonate resin having the structural unit represented by the general formula (1) of the present invention, an aromatic dihydroxy compound or an aliphatic dihydroxy compound (for example, a dihydroxy compound having a fluorene skeleton or binaphthols) can be used as a dihydroxy component in addition to the compound represented by the general formula (5).

[0214] The polycarbonate resin of the present invention can be preferably produced by using, in addition to the compound represented by the above general formula (5), a compound represented by the following general formula (6) and / or a compound represented by the following general formula (7) as a dihydroxy component.

[0215]

[0216] Among them, R'1~R' in formula (6) 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,

[0217] 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,

[0218] c and d are integers of 1 to 10 respectively.

[0219] In addition, R"1~R" in formula (7) 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,

[0220] 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,

[0221] e and f are integers of 1 to 10 respectively.

[0222] 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, and 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthyl. Among them, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl is preferred. These may be used alone or in combination of two or more.

[0223] 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, and 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene. Among them, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene are preferred. These may be used alone or in combination of two or more.

[0224] For example, examples of the dihydroxy compound represented by the formula (6) or (7) include compounds represented by the following general formula (8).

[0225]

[0226] It should be noted that the monomer used to produce the polycarbonate resin may contain, together with the dihydroxy compound represented by the general formula (6), as an impurity, a dihydroxy compound in which the values ​​of c and d in the general formula (6) are both 0 or a dihydroxy compound in which either of c and d in the general formula (6) is 0.

[0227] Thus, the total amount of dihydroxy compounds having a value different from at least any one of c and d in the above-mentioned general formula (6) is preferably contained in an amount of 1000 ppm or less, more preferably 500 ppm or less, even more preferably 200 ppm or less, and particularly preferably 100 ppm or less in the monomer having the dihydroxy compound represented by the above-mentioned general formula (6) as the main component, and the total amount of dihydroxy compounds having a value different from at least any one of c and d in the above-mentioned general formula (6) in the above-mentioned monomer is desirably 50 ppm or less, and more desirably 20 ppm or less.

[0228] The content of impurities related to the general formula (6) is the same for the dihydroxy compound represented by the general formula (7). That is, together with the dihydroxy compound represented by the general formula (7), a dihydroxy compound in which the values ​​of e and f in the general formula (7) are both 0 or a dihydroxy compound in which either one of e and f in the general formula (7) is 0 is contained as an impurity.

[0229] The total amount of these impurities in the monomer having the dihydroxy compound represented by the above general formula (7) as the main component is preferably contained in an amount of less than 1000 ppm, more preferably less than 500 ppm, more preferably less than 200 ppm, and particularly preferably less than 100 ppm. Moreover, the total amount of the above impurities in the above monomer is preferably less than 50 ppm, and more preferably less than 20 ppm.

[0230] The compounds of the general formulae (6) and (7) can be produced by various synthesis methods. For example, as described in Japanese Patent No. 5442800 and Japanese Patent Application Laid-Open No. 2014-028806, 9,9-bis(hydroxynaphthyl)fluorene is obtained by (a) reacting fluorenones with hydroxynaphthalenes in the presence of hydrogen chloride gas and mercaptocarboxylic acid, (b) reacting 9-fluorenones with hydroxynaphthalenes in the presence of an acid catalyst (and alkyl mercaptan), (c) reacting fluorenones with hydroxynaphthalenes in the presence of hydrochloric acid and mercaptans (such as mercaptocarboxylic acid), (d) reacting fluorenones with hydroxynaphthalenes in the presence of sulfuric acid and mercaptans (such as mercaptocarboxylic acid), and crystallizing hydrocarbons with a crystallization solvent consisting of a polar solvent to produce bis-naphthol fluorene. The 9,9-bis(hydroxynaphthyl)fluorene is then reacted with a compound corresponding to the [XO]a group and the [XO]b group (such as an alkylene oxide and a halogenated alkanol). 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.

[0231] Examples of aromatic dihydroxy compounds other than those mentioned above that can be used simultaneously include 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.

[0232] (Vinyl terminal group amount)

[0233] The polycarbonate resin of the present invention is obtained by using compounds represented by the above general formulas (5) to (8) as dihydroxy components and reacting them with carbonate precursors such as carbonic acid diesters. However, in the polymerization process for producing the polycarbonate resin, impurities may be generated 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 terminal groups represented by, for example, -OC=CH groups.

[0234] However, the amount of impurities having such a vinyl terminal structure is usually very small, and the produced polymer can be used as a polycarbonate resin without purification.

[0235] As the carbonic acid diester used in the present invention, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-tolyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. can be mentioned. Among these, diphenyl carbonate is particularly preferred. Relative to 1 mol of the total of the dihydroxy compounds, diphenyl carbonate is preferably used in a ratio of 0.97 to 1.20 mol, more preferably in a ratio of 0.98 to 1.10 mol.

[0236] Among the above-mentioned transesterification catalysts used in the production of the polycarbonate resin, examples of the basic compound catalysts include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.

[0237] As the alkali metal compound used in the present invention, for example, organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkali metals can be mentioned. 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 phenylborate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt, dipotassium salt, dicesium salt or dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt or lithium salt of phenol can be used.

[0238] As the alkaline earth metal compound, for example, organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkaline earth metal compounds can be mentioned. 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 and the like can be used.

[0239] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides and their salts, amines, etc. Specifically, quaternary ammonium hydroxides having alkyl groups, aryl groups, etc., such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, 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.

[0240] As the transesterification catalyst, salts of zinc, tin, zirconium, lead or the like are preferably used, and these can be used alone or in combination.

[0241] Specific examples of the transesterification catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyldimethoxytin, zirconium acetylacetonate, zirconium oxyacetate, tetrabutoxyzirconium, lead (II) acetate, and lead (IV) acetate.

[0242] These catalysts are used at 10 moles per mole of the total dihydroxy compound. －9 ~10 －3 The molar ratio is preferably 10 －7 ~10 －4 Molar ratios were used.

[0243] The melt polycondensation method is a method of using the above-mentioned raw materials and catalysts, and carrying out melt polycondensation under heating and at normal pressure or reduced pressure while removing by-products generated by the transesterification reaction.

[0244] In the melt polycondensation of the present composition system, the compound represented by the general formula (5) and the carbonic acid diester are preferably melted in a reaction vessel, and then reacted in a state where the by-produced monohydroxy compound is retained. In order to achieve retention, the reaction device can be closed, or pressure control such as decompression and pressurization can be performed. The reaction time of this process is more than 20 minutes and less than 240 minutes, preferably more than 40 minutes and less than 180 minutes, and particularly preferably more than 60 minutes and less than 150 minutes. At this time, if the by-produced monohydroxy compound is distilled and removed immediately after generation, the content of high molecular weight polymer in the polycarbonate resin finally obtained is small. However, when the by-produced monohydroxy compound is retained in the reaction vessel for a certain period of time, a polymer having a high content of high molecular weight polymer in the polycarbonate resin finally obtained can be obtained.

[0245] The melt polycondensation reaction can be carried out in a continuous manner or in a batch manner. The reaction apparatus used during 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 a paddle blade, a lattice blade, a glasses-type blade, etc., or an extruder type equipped with a screw. In addition, it is preferred to use a reaction apparatus that appropriately combines these reaction apparatuses in consideration of the viscosity of the polymer for implementation.

[0246] In the method for producing the polycarbonate resin used in the present invention, after the polymerization reaction is completed, the catalyst may be removed or inactivated in order to maintain thermal stability and hydrolytic stability. A method of deactivating the catalyst by adding a known acidic substance can be preferably implemented. As the acidic substance, specifically, 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; phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite; triphenyl phosphate, diphenyl phosphate Phosphates such as monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonates 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 stearoyl chloride, benzoyl chloride, and p-toluenesulfonyl chloride; alkylsulfuric acid such as dimethylsulfuric acid; organic halides such as benzyl chloride, etc. These deactivators are used in an amount of 0.01 to 50 times the amount of the catalyst, preferably 0.3 to 20 times the amount of the catalyst. When the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is sometimes insufficient, so it is not preferred. In addition, when the amount is more than 50 times the amount of the catalyst, the heat resistance of the resin is easily reduced, and the molded body is easily colored, so it is not preferred.

[0247] After the catalyst is deactivated, a step of removing low boiling point compounds in the polymer by devolatilization 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 paddle device or a thin film evaporator having excellent surface renewal performance, such as a paddle blade, a lattice blade, or a spectacled blade, can be preferably used.

[0248] The polycarbonate resin of the present invention is expected to have as little foreign matter as possible, and it is preferred to filter the molten raw material, filter the catalyst solution, etc. The mesh of the filter is preferably 5 μm or less, and more preferably 1 μm or less. In addition, it is preferred to filter the generated resin using a polymer filter. The mesh of the polymer filter is preferably 100 μm or less, and more preferably 30 μm or less. In addition, the process of collecting the resin pellets must of course be in a low-dust environment, preferably 6 or less, and more preferably 5 or less.

[0249] In addition, as a molding method of a polycarbonate resin, compression molding, casting, roll processing, extrusion molding, stretching, etc. can be exemplified in addition to injection molding, but it is not limited to these.

[0250] (4) Optical molding

[0251] The polycarbonate resin of the present invention can be used to manufacture optical molded bodies. Any method such as injection molding, compression molding, extrusion molding, solution casting, 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 mixed with other polycarbonate resins, polyester resins, and other resins for use. In addition, additives such as antioxidants, processing stabilizers, light stabilizers, polymer metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, mold release agents, ultraviolet absorbers, plasticizers, and compatibilizers can also be mixed.

[0252] 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-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid amide), 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. 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.

[0253] Examples of the processing stabilizer include phosphorus-based processing heat stabilizers, sulfur-based processing heat stabilizers, etc. Examples of the phosphorus-based processing heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tri(octadecyl) phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl 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 Phosphate, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl mono-o-biphenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonate, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonate, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonate, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonate and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonate, etc. The content of the phosphorus-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by weight based on 100 parts by weight of the polycarbonate resin.

[0254] Examples of the sulfur-based processing heat stabilizer include pentaerythritol-tetrakis (3-lauryl thiopropionate), pentaerythritol-tetrakis (3-myristyl thiopropionate), pentaerythritol-tetrakis (3-stearyl thiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate. 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.

[0255] As a release agent, it is preferred that 90% by weight or more of the release agent is composed of an ester of an alcohol and a fatty acid. As the ester of an alcohol and a fatty acid, specifically, there can be mentioned an ester of a monohydric alcohol and a fatty acid, and a partial ester or full ester of a polyhydric alcohol and a fatty acid. As the ester of the 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 a 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.

[0256] Specifically, examples of the esters of monohydric alcohols and saturated fatty acids include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. Examples of partial or full esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitol, behenic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenylate, sorbitol monostearate, 2-ethylhexyl stearate, full or partial esters of dipentaerythritol such as dipentaerythritol hexastearate, etc. The content of these release agents is preferably in the range of 0.005 to 2.0 parts by weight, more preferably 0.01 to 0.6 parts by weight, and even more preferably 0.02 to 0.5 parts by weight, based on 100 parts by weight of the polycarbonate resin.

[0257] As the ultraviolet absorber, at least one ultraviolet absorber selected from benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, cyclic iminoester ultraviolet absorbers and cyanoacrylate ultraviolet absorbers is preferred. That is, any one of the ultraviolet absorbers listed below may be used alone, or two or more may be used in combination.

[0258] Examples of the benzotriazole ultraviolet absorber include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, and 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole. 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-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, etc.

[0259] Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 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 sulfonatebenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0260] Examples of the triazine-based ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-[(octyl)oxy]-phenol.

[0261] Examples of the cyclic imidoester ultraviolet absorber include 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-biphenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthalene)bis(3 ,1-benzoxazine-4-one), 2,2'-(1,5-naphthalene)bis(3,1-benzoxazine-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazine-4-one) and 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazine-4-one).

[0262] Examples of the cyanoacrylate-based ultraviolet absorber include 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0263] 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, based on 100 parts by weight of the polycarbonate resin. Within this range, sufficient weather resistance suitable for the intended use can be imparted to the polycarbonate resin.

[0264] The polycarbonate resin of the present invention has a high refractive index and a low Abbe number. In addition to optical lenses, it can also be preferably used as an optical molded body for use as a structural material or functional material for optical parts such as transparent conductive substrates for liquid crystal displays, organic EL displays, and solar cells, optical disks, liquid crystal panels, optical memory cards, sheets, films, optical fibers, connectors, vapor-deposited plastic reflectors, and displays.

[0265] The surface of the optical molded body may be provided with a coating such as an anti-reflection layer or a hard coating layer as required. The anti-reflection layer may be a single layer or a multilayer, and may be an organic substance or an inorganic substance, but is preferably an inorganic substance. Specifically, oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride may be exemplified.

[0266] (5) Optical lens

[0267] The optical lens manufactured using the polycarbonate resin of the present invention has high refractive index, low Abbe number, high resistance to moisture and heat, and can be used in the fields of telescopes, binoculars, television projectors, etc., which are currently using expensive high-refractive index glass lenses, and is extremely useful. According to the needs, it is preferably used in the form of an aspheric lens. The aspheric lens can utilize one lens to substantially reduce the spherical aberration to zero, so there is no need to combine multiple spherical lenses to eliminate the spherical aberration, and it is possible to achieve lightweight and reduced production costs. Therefore, the aspheric lens is a lens useful as a camera lens among optical lenses.

[0268] The optical lens is molded by any method such as injection molding, compression molding, injection compression molding, etc. According to the present invention, a high-refractive-index low-birefringence aspheric lens which is technically difficult to process with a glass lens can be obtained more easily.

[0269] 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 level 6, and more preferably below level 5.

[0270] (6) Optical film

[0271] The optical film produced using the polycarbonate resin of the present invention has excellent transparency and heat resistance and is therefore preferably used in a film for a liquid crystal substrate, an optical memory card, and the like.

[0272] In order to avoid foreign matter from being mixed into the optical film as much as possible, the molding environment must of course be a low-dust environment, preferably below level 6, more preferably below level 5.

[0273] Example

[0274] 2) Refractive index (nD): The refractive index of a film having a thickness of 0.1 mm and containing the polycarbonate resin produced in the examples was measured using an Abbe refractometer in accordance with the method of JIS-K-7142.

[0275] 3) Abbe number (ν): The refractive index of a 0.1 mm thick film containing the polycarbonate resin produced in the examples at wavelengths of 486 nm, 589 nm and 656 nm at 23° C. was measured using an Abbe refractometer, and the Abbe number was calculated using the following formula.

[0276] ν=(nD-1) / (nF-nC)

[0277] nD: refractive index at a wavelength of 589nm

[0278] nC: refractive index at a wavelength of 656nm

[0279] nF: refractive index at a wavelength of 486nm

[0280] 4) Glass transition temperature (Tg): measured using a differential scanning calorimeter (DSC).

[0281] 5) Total light transmittance: A 3 mm thick plate made of a polycarbonate resin prepared for measuring the b value described below was measured using a SE2000 spectrophotometer manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with the method of JIS-K-7361-1.

[0282] 6) b value: After the manufactured resin was dried at 120°C for 4 hours, it was injection molded using an injection molding machine (FANUC ROBOSHOTα-S30iA) at a barrel temperature of 270°C and a metal 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 in accordance with JIS K7105. The smaller the b value, the weaker the yellowish color and the better the hue. The SE2000 spectrophotometer manufactured by Nippon Denshoku Industries Co., Ltd. was used for the measurement of the molded plate.

[0283] 7) Vinyl terminal group amount: 1 H-NMR measurement was performed under the following conditions.

[0284] · 1 H-NMR measurement conditions

[0285] Device: Bruker AVANZE III HD 500MHz

[0286] Inclination: 30 degrees

[0287] Waiting time: 1 second

[0288] Total times: 500 times

[0289] Measurement temperature: room temperature (298K)

[0290] Concentration: 5wt%

[0291] Solvent: deuterated chloroform

[0292] Internal standard substance: tetramethylsilane (TMS) 0.05wt%

[0293] 8) Determination of phenol and diphenyl carbonate (DPC) content in polycarbonate resin

[0294] 0.5 g of the sample of Example 1 described below was dissolved in 50 ml of tetrahydrofuran (THF) as a sample solution. A calibration curve was prepared from each pure compound as a standard, and 2 μL of the sample solution was quantified using LC-MS under the following measurement conditions. It should be noted that the detection limit under the measurement conditions was 0.01 ppm.

[0295] LC-MS assay conditions:

[0296] Measurement device (LC part): Agilent Infinity 1260LC System

[0297] Chromatographic column: ZORBAX Eclipse XDB-18, and guard column

[0298] Mobile Phase:

[0299] A: 0.01 mol / L ammonium acetate aqueous solution

[0300] B: 0.01mol / L ammonium acetate methanol solution

[0301] C:THF

[0302] Gradient program of mobile phase:

[0303] As shown in Table 1, the mixture of A to C was used as the mobile phase, and the mobile phase was passed through the column for 30 minutes while switching the composition of the mobile phase when the time shown in the time (minutes) column elapsed.

[0304] [Table 1]

[0305]

[0306] Flow rate: 0.3ml / min

[0307] Column temperature: 45°C

[0308] Detector: UV (225nm)

[0309] Measurement device (MS part): Agilent 6120 single quad LCMS System

[0310] Ionization source: ESI

[0311] Polarity: Positive (DPC) & Negative (PhOH)

[0312] Fragmentation voltage: 70V

[0313] Drying gas: 10L / min, 350℃

[0314] Atomizer: 50psi

[0315] Capillary voltage: 3000V (Positive), 2500V (Negqative)

[0316] Measured ions:

[0317] [Table 2]

[0318] monomer Ion type m / z PhOH [MH]- 93.1 DPC [M+NH4]+ 232.1

[0319] Sample injection volume: 2 μL

[0320] [Manufacture of polycarbonate resin]

[0321] (Example 1)

[0322] As raw materials, 31.6 kg (60.0 mol) of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl (hereinafter sometimes abbreviated as "BINL-2EO"), 13.5 kg (63.0 mol) of diphenyl carbonate (hereinafter sometimes abbreviated as "DPC") and 0.074 g (8.8 × 10 －4 mol) was placed in a 50L reactor with a stirrer and a distillation separation device, and heated to 180°C under a nitrogen atmosphere of 760mmHg. After 20 minutes from the start of heating, it was confirmed that the raw material was completely dissolved, and then stirred for 120 minutes under the same conditions. After that, the reduced pressure was adjusted to 200mmHg, and the temperature was raised to 200°C at a rate of 60°C / hr. At this time, phenol, a by-product separated by distillation, began to be confirmed. After that, the reaction was carried out by keeping it 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 temperature was raised, the temperature was maintained while the reduced pressure was reduced to less than 1mmHg for 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 to return to normal pressure, and the generated polycarbonate resin was pelletized and taken out. The amounts of phenol and diphenyl carbonate (DPC) as impurities in the obtained polycarbonate resin were measured as described above, and the amount of phenol in the resin was 100 ppm by mass, and the amount of DPC in the resin was 300 ppm by mass.

[0323] The physical property values ​​of the obtained resin are shown in Table 3 below.

[0324] (Example 2-A)

[0325] The same operation as in Example 1 was carried out except that 7.9 kg (15.0 mol) of BINL-2EO, 24.2 kg (45.0 mol) of BNEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials.

[0326] (Example 2-B)

[0327] The same operation as in Example 1 was carried out except that 15.8 kg (30.0 mol) of BINL-2EO, 16.2 kg (30.0 mol) of BNEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials.

[0328] (Example 2-C)

[0329] The same operation as in Example 1 was carried out except that 23.7 kg (45.0 mol) of BINL-2EO, 8.1 kg (15.0 mol) of BNEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials.

[0330] The physical properties 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 .

[0331] (Example 3-A)

[0332] The same operation as in Example 1 was performed except that 7.9 kg (15.0 mol) of BINL-2EO, 19.0 kg (45.0 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter sometimes abbreviated as "BPEF"), and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0333] (Example 3-B)

[0334] The same operation as in Example 1 was performed except that 15.8 kg (30.0 mol) of BINL-2EO, 12.7 kg (30.0 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter sometimes abbreviated as "BPEF"), and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0335] (Example 3-C)

[0336] The same operation as in Example 1 was performed except that 23.7 kg (45.0 mol) of BINL-2EO, 6.3 kg (15.0 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter sometimes abbreviated as "BPEF"), and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0337] (Example 4-A)

[0338] The same operation as in Example 1 was carried out except that 7.9 kg (15.0 mol) of BINL-2EO, 25.9 kg (45.0 mol) of BPPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. Table 3 shows the physical properties of the obtained resin.

[0339] (Example 4-B)

[0340] The same operation as in Example 1 was carried out except that 15.8 kg (30.0 mol) of BINL-2EO, 17.2 kg (30.0 mol) of BPPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. Table 3 shows the physical properties of the obtained resin.

[0341] (Example 4-C)

[0342] The same operation as in Example 1 was carried out except that 23.7 kg (45.0 mol) of BINL-2EO, 8.6 kg (15.0 mol) of BPPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. Table 3 shows the physical properties of the obtained resin.

[0343] (Example 5)

[0344] The same operation as in Example 1 was performed except that 7.6 kg (18.0 mol) of BPEF, 26.3 kg (42.0 mol) of 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-1-yl)-1,1'-binaphthyl (hereinafter sometimes abbreviated as "DNBINOL-2EO"), and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0345] (Example 6-A)

[0346] The same operation as in Example 1 was performed except that 7.9 kg (15.0 mol) of BINL-2EO, 9.7 kg (18.0 mol) of BNEF, 10.1 kg (27.0 mol) of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (hereinafter sometimes abbreviated as "BNE"), and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0347] (Example 6-B)

[0348] The same operation as in Example 1 was carried out except that 19.0 kg (36.0 mol) of BINL-2EO, 4.5 kg (12.0 mol) of BNE, 5.1 kg (12.0 mol) of BPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. Table 3 shows the physical properties of the obtained resin.

[0349] (Example 6-C)

[0350] The same operation as in Example 1 was performed except that 19.0 kg (36.0 mol) of BINL-2EO, 4.5 kg (12.0 mol) of BNE, 6.9 kg (12.0 mol) of BPPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. Table 3 shows the physical properties of the obtained resin.

[0351] (Example 6-D)

[0352] The same operation as in Example 1 was performed except that 11.3 kg (21.0 mol) of BNEF, 11.2 kg (30.0 mol) of BNE, 5.6 kg (9.0 mol) of DNBINOL-2EO, and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0353] (Example 6-E)

[0354] The same operation as in Example 1 was performed except that 6.7 kg (18.0 mol) of BNE, 17.2 kg (30.0 mol) of BPPEF, 7.5 kg (12.0 mol) of DNBINOL-2EO, and 13.5 kg (63.0 mol) of DPC were used as raw materials. Table 3 shows the physical properties of the obtained resin.

[0355] (Example 6-F)

[0356] The same operation as in Example 1 was performed except that 6.7 kg (18.0 mol) of BNE, 10.1 kg (24.0 mol) of BPEF, 11.3 kg (18.0 mol) of DNBINOL-2EO, and 13.5 kg (63.0 mol) of DPC were used as raw materials. Table 3 shows the physical properties of the obtained resin.

[0357] (Example 7)

[0358] The same operation as in Example 1 was performed except that 32.0 kg (51.0 mol) of 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-2-yl)-1,1'-binaphthyl (2DNBINOL-2EO), 3.8 kg (9.0 mol) of BPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0359] (Example 7-A)

[0360] The same operation as in Example 1 was performed except that 18.8 kg (30.0 mol) of 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-2-yl)-1,1'-binaphthyl (2DNBINOL-2EO), 12.7 kg (30.0 mol) of BPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0361] (Example 7-B)

[0362] The same operation as in Example 1 was performed except that 5.6 kg (9.0 mol) of 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-2-yl)-1,1'-binaphthyl (2DNBINOL-2EO), 21.5 kg (51.0 mol) of BPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0363] (Example 8)

[0364] The same operation as in Example 1 was performed except that 37.1 kg (51.0 mol) of 2,2'-bis(2-hydroxyethoxy)-6,6'-di(phenanthrene-9-yl)-1,1'-binaphthyl (9DPNBINOL-2EO), 3.8 kg (9.0 mol) of BPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 1.

[0365] (Example 8-A)

[0366] The same operation as in Example 1 was performed except that 21.8 kg (30.0 mol) of 2,2'-bis(2-hydroxyethoxy)-6,6'-di(phenanthrene-9-yl)-1,1'-binaphthyl (9DPNBINOL-2EO), 12.7 kg (30.0 mol) of BPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0367] (Example 8-B)

[0368] The same operation as in Example 1 was performed except that 6.5 kg (9.0 mol) of 2,2'-bis(2-hydroxyethoxy)-6,6'-di(phenanthrene-9-yl)-1,1'-binaphthyl (9DPNBINOL-2EO), 21.5 kg (51.0 mol) of BPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0369] (Example 9)

[0370] The same operation as in Example 1 was performed except that 10.4 kg (18.0 mol) of 6,6′-di-(3-cyanophenyl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (CN-BNA), 18.4 kg (42.0 mol) of BPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0371] (Example 10)

[0372] The same operation as in Example 1 was performed except that 12.7 kg (18.0 mol) of 6,6′-di-(dibenzo[b,d]furan-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (FUR-BNA), 18.4 kg (42.0 mol) of BPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0373] (Example 11)

[0374] The same operation as in Example 1 was performed except that 13.3 kg (18.0 mol) of 6,6′-di-(dibenzo[b,d]thiophen-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl (THI-BNA), 18.4 kg (42.0 mol) of BPEF, and 13.5 kg (63.0 mol) of DPC were used as raw materials. The physical properties of the obtained resin are shown in Table 3.

[0375] (Comparative Example 1)

[0376] The same operation as in Example 1 was carried out except that 22.5 kg (60.0 mol) of BNE and 13.5 g (63.0 mol) of DPC were used as raw materials. Table 3 shows the physical properties of the obtained resin.

[0377] [Table 3]

[0378]

[0379] Example:

[0380] BINL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl)

[0381] BNEF (9,9-bis(6-(2-hydroxyethoxy)naphthalene-2-yl)fluorene)

[0382] BNE (2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl)

[0383] BPEF (9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene)

[0384] BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene)

[0385] DNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-1-yl)-1,1'-binaphthyl)

[0386] 2DNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-2-yl)-1,1'-binaphthyl)

[0387] 9DPNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-di(phenanthrene-9-yl)-1,1'-binaphthyl)

[0388] CN-BNA (6,6′-bis-(3-cyanophenyl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl)

[0389] FUR-BNA (6,6′-di-(dibenzo[b,d]furan-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl)

[0390] THI-BNA (6,6′-di-(dibenzo[b,d]thiophene-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl)

[0391] Comparative Example:

[0392] BNE (2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl)

[0393] [Moldability]

[0394] A The formed piece has no gaps and no waves on the surface

[0395] B The molded piece has gaps

[0396] C The surface of the molded piece has waves

[0397] D The molded piece has gaps and the surface is deformed

[0398]

Claims

1. A polycarbonate resin, characterized in that It is a polycarbonate resin containing a structural unit represented by the following general formula (1) and having an Abbe number of 20 or less, In formula (1), R1 and R2 each independently represent a monocyclic or polycyclic aromatic group having 6 to 20 carbon atoms, The R1 is the same as the R2, The monocyclic or polycyclic aryl group has no substituent, or has one or two groups selected from the group consisting of CN, CH3, OCH3, O-phenyl, O-naphthyl, S-phenyl, S-naphthyl and halogen, 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 arbitrarily substituted in a manner of having a benzene ring, a and b are integers of 1 to 10 respectively.

2. The polycarbonate resin according to claim 1, characterized in that The structural unit represented by the general formula (1) is contained in an amount of more than 50 mol%.

3. The polycarbonate resin according to claim 1 or 2, characterized in that In the general formula (1), R1 and R2 are aryl groups having 6 to 14 carbon atoms.

4. The polycarbonate resin according to claim 1, wherein It also contains at least one of the structural units represented by the following general formulae (2) and (3), R'1~R' in formula (2) 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 integers from 1 to 10 respectively; R"1~R" in formula (3) 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 integers of 1 to 10 respectively.

5. The polycarbonate resin according to claim 4, characterized in that The present invention comprises a copolymer containing at least a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2).

6. The polycarbonate resin according to claim 5, characterized in that The copolymer further contains a structural unit represented by the following general formula (3-1):

7. The polycarbonate resin according to claim 4, characterized in that The present invention comprises a copolymer containing at least a structural unit represented by the general formula (1) and a structural unit represented by the general formula (3).

8. The polycarbonate resin according to claim 7, wherein The copolymer further contains a structural unit represented by the following general formula (2-1):

9. The polycarbonate resin according to claim 4, characterized in that The structural units represented by the general formulae (2) and (3) are contained in an amount of 20 to 80 mol% in total.

10. The polycarbonate resin according to claim 1 or 2, characterized in that It also contains at least one structural unit represented by the following general formula (4), 11. The polycarbonate resin according to claim 10, wherein The present invention contains at least a structural unit of BNEF, ie, 9,9-bis(6-(2-hydroxyethoxy)naphthalene-2-yl)fluorene.

12. The polycarbonate resin according to claim 10, wherein The present invention contains at least a structural unit of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl.

13. The polycarbonate resin according to claim 10, wherein It also contains at least a structural unit of BPPEF, ie, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene.

14. The polycarbonate resin according to claim 1 or 2, characterized in that The refractive index of the polycarbonate resin is 1.655 or more.

15. The polycarbonate resin according to claim 1 or 2, characterized in that The R1 and the R2 have no substituent.

16. The polycarbonate resin according to claim 1 or 2, characterized in that The R1 and R2 are phenyl groups without substituents.

17. The polycarbonate resin according to claim 1 or 2, characterized in that The R1 and R2 are selected from the following groups: Unsubstituted phenyl, Phenyl substituted with 1 or 2 CN groups, an unsubstituted naphthyl group or a naphthyl group substituted with one or two substituents selected from the group consisting of CN and phenyl, Biphenylene, Terphenylene, Fiki, Pyrene 9H-fluorenyl, dibenzo[a,e][8]annulyl, and Perylene.

18. The polycarbonate resin according to claim 1 or 2, characterized in that The R1 and R2 are selected from phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-naphthyl, 1-naphthyl and 9-naphthyl.

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

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