Thermoplastic resin, method for producing same, and optical lens

Abstract

Provided are: a thermoplastic resin having a high refractive index, a low b value, and high wet heat resistance; an optical lens using the thermoplastic resin; and the like. According to one embodiment, a thermoplastic resin containing a structural unit represented by general formula (1) is provided. (In formula (1), 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, 1, 2, 3 or 4 of the ring atoms are selected from nitrogen, sulfur and oxygen, the other ring atoms are carbon, and X, a and b are respectively described in the specification. )

Description

[0001] This case is filed on February 27, 2020 、Application No. 202080017426.1(PCT / JP2020 / 008193) 、The name of the invention is Thermoplastic resin, method for producing the same, and optical lens divisional application. Technical Field

[0002] The present invention relates to thermoplastic resins, particularly thermoplastic resins such as polyester resins, polyester carbonate resins, and polycarbonate resins, and methods for producing the same. The present invention also relates to optical lenses containing the thermoplastic resins. Background Art

[0003] Optical glass or optical resin is used as the material for optical lenses used in the optical systems of various cameras, including still cameras, film-integrated cameras, and video cameras. While optical glass offers excellent properties such as heat resistance, transparency, dimensional stability, and chemical resistance, it suffers from high material costs, poor moldability, and low productivity.

[0004] On the other hand, optical lenses made of optical resins have the advantage of being able to be mass-produced through injection molding. For example, thermoplastic resins are used in camera lenses. However, in recent years, as products have become thinner and smaller, there has been a need to develop resins with high refractive indexes (Patent Documents 1 to 4). 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 surface of smaller curvature, which can reduce the amount of aberration generated on the surface. As a result, the number of lenses can be reduced, the decentration sensitivity of the lens can be reduced, and the thickness of the lens can be reduced to achieve lightweighting.

[0005] Furthermore, generally speaking, lenses used in camera optical systems are required not only to have a high refractive index but also to maintain a certain b-value that is not too high, thereby suppressing chromatic aberration.

[0006] However, a thermoplastic resin and an optical lens having a sufficiently high refractive index and a low b value have not yet been provided.

[0007] Furthermore, in recent years, various electronic devices have been required to exhibit water resistance and heat resistance. As an environmental test to evaluate the water resistance and heat resistance of such electronic devices, the "PCT test" (pressure cooker test) is implemented. This test is a moisture and heat resistance test that evaluates the intrusion of water into the sample over a period of time. Therefore, optical lenses made of optical resin used in electronic devices are required not only to have a high refractive index and a low b-value, but also to exhibit high heat resistance and resistance to hydrolysis.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 2018-2893

[0011] Patent Document 2: Japanese Patent Application Laid-Open No. 2018-2894

[0012] Patent Document 3: Japanese Patent Application Laid-Open No. 2018-2895

[0013] Patent Document 4: Japanese Patent Application Laid-Open No. 2018-59074 Summary of the Invention

[0014] Technical problem to be solved by the invention

[0015] The technical problem to be solved by the present invention is to provide a thermoplastic resin having a high refractive index, a low b value, and high resistance to moisture and heat, in particular having a high refractive index. Furthermore, the present invention aims to provide an excellent optical lens by using the resin.

[0016] Technical solutions to technical problems

[0017] The inventors of the present invention have conducted intensive research to solve the above-mentioned technical problems and have found that the above-mentioned technical problems can be solved by the following thermoplastic resin and optical lens, thereby arriving at the present invention.

[0018] The present invention is as follows, for example.

[0019] [1] A thermoplastic resin comprising a structural unit represented by the following general formula (1):

[0020]

[0021] 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, 1, 2, 3 or 4 of the ring atoms are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon,

[0022] 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 CN, CH3, OCH3, O-phenyl, O-naphthyl, S-phenyl, S-naphthyl and halogen. a base,

[0023] Wherein, R1 and R2 are not all hydrogen,

[0024] 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,

[0025] The alkylene group and the cycloalkylene group may be substituted with a benzene ring, and a and b are integers of 1 to 10.

[0026] [2] The thermoplastic resin according to [1] above, wherein the thermoplastic resin is a polyester resin or a polyester carbonate resin.

[0027] [3] The thermoplastic resin according to [1] or [2] above, further comprising a structural unit represented by the following general formula (2).

[0028]

[0029] (In general formula (2), Q is represented by the following formula (2a).

[0030]

[0031] (In formula (2a), R C Each independently represents a single bond or an alkylene group bonded to the CO group in the above formula (2), the alkylene group may have a substituent, has a total carbon number of 1 to 10, and contains a bonding point to the CO group in the above formula (2) at the terminal.

[0032] [4] The thermoplastic resin according to [3] above, wherein Q is represented by the following formula (2b).

[0033]

[0034] (In formula (2b), n and m each independently represent an integer of 0 to 5,

[0035] p and k each independently represent an integer of 1 to 5,

[0036] R1 and R2 are the same as R1 and R2 in formula (1),

[0037] a and b each independently represent an integer from 0 to 6,

[0038] * represents the bonding point with the CO group in the above formula (2).

[0039] [5] The thermoplastic resin according to [4] above, which has at least a structural unit containing the above Q represented by the following formula (2c).

[0040]

[0041] (In formula (2c), * represents the bonding point to the CO group in formula (2).)

[0042] [6] The thermoplastic resin according to any one of [1] to [5] above, which contains more than 50 mol% of the structural unit represented by the general formula (1).

[0043] [7] The thermoplastic resin according to any one of [1] to [6] above, wherein at least one of R1 and R2 in the general formula (1) is an aryl group having 6 to 20 carbon atoms.

[0044] [8] The thermoplastic resin according to [7] above, wherein at least two of R1 and R2 in the general formula (1) are aryl groups having 6 to 14 carbon atoms.

[0045] [9] The thermoplastic resin according to any one of [1] to [8] 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),

[0046]

[0047]

[0048]

[0049]

[10] The thermoplastic resin according to any one of [1] to [9] above, further comprising at least one of the structural units represented by the following general formulas (3) and (4).

[0050]

[0051] (R'1~R' in formula (3) 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,

[0052] 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,

[0053] c and d are integers from 1 to 10 respectively.)

[0054]

[0055] (R1~R2 in formula (4) 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,

[0056] 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,

[0057] e and f are integers from 1 to 10 respectively.)

[0058]

[11] The thermoplastic resin according to 10] above, 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).

[0059]

[12] The thermoplastic resin according to

[11] above, wherein the copolymer further contains a structural unit represented by the following general formula (3-1):

[0060]

[0061]

[13] The thermoplastic resin according to

[10] above, comprising a copolymer containing at least the structural unit represented by the above general formula (1) and the structural unit represented by the above general formula (4).

[0062]

[14] The thermoplastic resin according to

[13] above, wherein the copolymer further contains a structural unit represented by the following general formula (4-1):

[0063]

[0064]

[15] The thermoplastic resin according to any one of [1] to

[14] , which contains 20 to 80 mol% in total of the structural units represented by the general formulas (3) and (4).

[0065]

[16] The thermoplastic resin according to [1] to

[15] above, further comprising at least one structural unit represented by the following general formula (5):

[0066]

[0067]

[17] The thermoplastic resin according to

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

[0068]

[18] The thermoplastic resin according to

[16] above, which contains at least a structural unit of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl.

[0069]

[19] The thermoplastic resin according to

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

[0070]

[20] The thermoplastic resin as described in any one of [1] to

[19] above, wherein the above-mentioned aromatic group is selected from 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 aromatic group having 6 to 16 carbon atoms.

[0071]

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

[20] above, wherein the refractive index of the thermoplastic resin is 1.655 or greater.

[0072]

[22] The thermoplastic resin according to any one of [1] to

[20] above, wherein the R1 is the same as the R2.

[0073]

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

[20] above, wherein

[0074] The above R1 and R2 are the same or different and are 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 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,

[0075] The monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group have no substituent.

[0076]

[24] The thermoplastic resin according to any one of [1] to

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

[0077] Azulene base;

[0078] An unsubstituted indenyl group or an indenyl group which may be substituted with two, three, four or five substituents selected from a phenyl group and a polycyclic aryl group, wherein the polycyclic aryl group has two, three or four benzene rings which may be bonded to each other via single bonds, may be directly condensed with each other, and / or may be condensed with a saturated or unsaturated 4-10 membered monocyclic or bicyclic hydrocarbon ring;

[0079] Phenyl with no substituents;

[0080] Phenyl substituted with 1 or 2 CN groups;

[0081] A phenyl group which may be substituted with two, three, four or five substituents selected from a phenyl group and a polycyclic aryl group, wherein the polycyclic aryl group has two, three or four phenyl 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;

[0082] A polycyclic aromatic group having two, three or four benzene rings that 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 has no substituent or may be substituted with one or two substituents selected from phenyl and a polycyclic aromatic group having two or three benzene rings, wherein the two or three benzene rings can be bonded to each other via a single bond, can be directly condensed with each other, and / or can be condensed with a saturated 4-10 membered monocyclic or bicyclic hydrocarbon ring, wherein the benzene ring of the polycyclic aromatic group has no substituent or has one or two substituents R a .

[0083]

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

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

[0084] Phenyl which is unsubstituted or may be substituted with 1, 2, 3, 4 or 5 phenyl groups;

[0085] Phenyl substituted with 1 or 2 CN groups;

[0086] Phenyl substituted with one or two polycyclic aromatic groups selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl and pyrenyl, and further substituted with one phenyl group;

[0087] an unsubstituted naphthyl group or a naphthyl group substituted with one or two substituents selected from the group consisting of CN, phenyl, and polycyclic aryl groups, wherein the polycyclic aryl group is selected from the group consisting of biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, and pyrenyl;

[0088] biphenylenyl;

[0089] triphenylenyl;

[0090] tetraphenylenyl;

[0091] Fiki;

[0092] pyrene;

[0093] 9H-fluorenyl;

[0094] dibenzo[a,e][8]annulyl;

[0095] perylene; and

[0096] 9,9'-Spirobi[9H-fluorenyl]yl.

[0097]

[26] The thermoplastic resin according to

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

[0098]

[27] The thermoplastic resin according to any one of [1] to

[23] above, wherein R1 and R2 are selected from the group consisting of:

[0099] a heteroaromatic monocyclic group 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;

[0100] A heteroaromatic polycyclic group having the above-mentioned heteroaromatic monocyclic ring and one, two, three, four or five additional 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, 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

[0101] A heteroaromatic polycyclic group having at least one saturated or partially unsaturated 5- or 6-membered heterocyclic ring containing one or two heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, and one, two, three, four or five additional aromatic rings selected from phenyl and the above-mentioned heteroaromatic monocyclic rings, wherein at least one additional aromatic ring is directly condensed with the saturated or partially unsaturated 5- or 6-membered heterocyclic group, and the other additional aromatic rings of the polycyclic heteroaryl aromatic ring may be 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.

[0102]

[28] The thermoplastic resin as described in

[27] above, wherein the above R1 and the above R2 are selected from the group consisting of furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, naphthofuranyl, benzothiophenyl, benzothiophenyl, benzothienyl, benzothrenyl, naphthofuranyl, benzothiophenyl, benzothienyl ... yl, furo[3,2-b]furyl, furo[2,3-b]furyl, furo[3,4-b]furyl, oxanthrenyl, indolyl, isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzo[cd]indolyl, 1H-benzo[g]indolyl, 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]quinolinyl, pyrido[2,3-b][1,8]naphthyridinyl, pyrrolo[3,2-b]pyridinyl, pteridinyl, purinyl, 9H-xanthenyl benzo[g]benzopyranyl, pyrrolo[3,2,1-hi]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl, and benzo[h]isoquinolyl.

[0103]

[29] The thermoplastic resin according to any one of [1] to

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

[0104]

[30] The thermoplastic resin according to any one of [1] to

[29] above, wherein the b value according to JIS K 7105 is 10 or less.

[0105]

[31] The thermoplastic resin according to any one of [1] to

[30] above, wherein the refractive index nD and the Abbe number ν satisfy the relationship -0.0002ν+1.6718<nD<-0.024ν+2.124.

[0106]

[32] The thermoplastic resin as described in

[31] above, wherein the refractive index nD and the Abbe number ν satisfy the relationship of -0.004v+1.744<nD<-0.024ν+2.124.

[0107]

[33] The thermoplastic resin as described in

[32] above, wherein the refractive index nD and the Abbe number ν satisfy the relationship of -0.02v+2.04<nD<-0.024ν+2.124.

[0108]

[34] An optical lens comprising the thermoplastic resin described in any one of [1] to

[33] above.

[0109]

[35] A method for producing a thermoplastic resin, for producing the thermoplastic resin described in any one of [1] to

[33] above, the method comprising the step of melt-polycondensing a dihydroxy compound represented by at least the following general formula (6) with at least one of a carboxylic acid, a carboxylic acid monoester, and a carboxylic acid diester.

[0110]

[0111] (In the general formula (6), 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,

[0112] 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 CN, CH3, OCH3, O-phenyl, O-naphthyl, S-phenyl, S-naphthyl and halogen. a base,

[0113] Wherein, R1 and R2 are not all hydrogen,

[0114] 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,

[0115] The above-mentioned alkylene group and the above-mentioned cycloalkylene group may be substituted to have a benzene ring,

[0116] a and b are integers from 1 to 10 respectively.)

[0117]

[36] A crystalline solvate of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl, wherein:

[0118] The crystals contain 0.3 to 1.2 mol of an organic solvent per 1 mol of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl.

[0119] The organic solvent is selected from methanol, toluene and methyl ethyl ketone.

[0120]

[37] The form of the crystalline solvate according to

[36] above, wherein the organic solvent is methanol.

[0121]

[38] The form of the crystalline solvate according to

[37] above, wherein

[0122] The X-ray powder diffraction pattern obtained by Cu Kα1 irradiation at 22°C is:

[0123] The following three reflection peaks are shown as 2θ values: 13.0±0.2°, 14.9±0.2°, and 21.5±0.2°.

[0124] As 2θ values, at least three of the following reflection peaks are shown: 6.2±0.2°, 9.0±0.2°, 10.6±0.2°, 16.9±0.2°, 18.2±0.2°, 18.5±0.2°, 19.2±0.2°, 19.6±0.2°, 20.9±0.2°, 22.7±0.2°, 24.3±0.2°, 24.9±0.2°, 26.2±0.2°, 28.7±0.2° and 30.5±0.2°.

[0125]

[39] The form of the crystalline solvate as described in

[37] or

[38] above, wherein, in differential scanning calorimetry (DSC) recorded in accordance with ISO 11357-3:2018 at a heating rate of 20 K / min (or 20°C / min, the same below), it shows an endothermic peak with an onset point in the range of 97 to 101°C, and the maximum value of the peak is in the range of 108 to 115°C.

[0126]

[40] The form of the crystalline solvate according to any one of

[37] to

[39] above, wherein the amount of methanol is 0.3 to 1.0 mol per 1 mol of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl.

[0127]

[41] The form of the crystalline solvate according to

[36] above, wherein the organic solvent is toluene.

[0128]

[42] The form of the crystalline solvate according to

[41] above, wherein

[0129] The X-ray powder diffraction pattern obtained by Cu Kα1 irradiation at 22°C is:

[0130] The following three reflection peaks are shown as 2θ values: 5.2±0.2°, 7.7±0.2°, and 21.6±0.2°.

[0131] At least three of the following reflection peaks are shown as 2θ values: 8.2±0.2°, 9.1±0.2°, 10.6±0.2°, 10.8±0.2°, 11.6±0.2°, 12.6±0.2°, 13.6±0.2°, 14.7±0.2°, 15.0±0.2°, 15.7±0.2°, 16.7±0.2°, 17.1±0.2°, 18. 8.0±0.2°, 18.5±0.2°, 19.4±0.2°, 19.9±0.2°, 20.8±0.2°, 21.0±0.2°, 22.2±0.2°, 22.7±0.2°, 24.1±0.2°, 25.0±0.2°, 25.7±0.2°, 26.5±0.2°, 27.1±0.2° and 27.6±0.2°.

[0132]

[43] The form of the crystalline solvate as described in

[41] or

[42] above, wherein, in differential scanning calorimetry (DSC) recorded in accordance with ISO 11357-3:2018 at a heating rate of 20 K / min, it shows an endothermic peak with an onset point in the range of 105 to 108°C, and the maximum value of the peak is in the range of 112 to 115°C.

[0133]

[44] The form of the crystalline solvate according to any one of

[41] to

[43] above, wherein the amount of toluene is 0.3 to 0.5 mol per 1 mol of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl.

[0134]

[45] A crystalline form A, which is a crystalline form A of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl, wherein:

[0135] The crystals contain less than 0.1 mol of an organic solvent per 1 mol of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl.

[0136] The X-ray powder diffraction pattern obtained by Cu Kα1 irradiation at 22°C is:

[0137] The following three reflection peaks are shown as 2θ values: 20.9±0.2°, 21.4±0.2°, and 23.7±0.2°.

[0138] At least three of the following reflection peaks are shown as 2θ values: 6.5±0.2°, 8.6±0.2°, 11.0±0.2°, 13.2±0.2°, 14.9±0.2°, 16.2±0.2°, 17.3±0.2°, 17.8±0.2°, 18.4±0.2°, and 19.0±0.2°.

[0139]

[46] The crystalline form as described in 45 above, wherein, in differential scanning calorimetry (DSC) recorded in accordance with ISO 11357-3:2018 at a heating rate of 20 K / min, an endothermic peak with an onset point in the range of 112 to 114°C is shown, and the maximum value of the peak is in the range of 124 to 126°C.

[0140]

[47] A crystalline form C, which is a crystalline form C of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl, wherein:

[0141] The crystals contain less than 0.1 mol of an organic solvent per 1 mol of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl.

[0142] The X-ray powder diffraction pattern obtained by Cu Kα1 irradiation at 22°C is:

[0143] The following three reflection peaks are shown as 2θ values: 5.1±0.2°, 7.6±0.2°, and 21.0±0.2°.

[0144] At least three of the following reflection peaks are shown as 2θ values: 8.2±0.2°, 9.2±0.2°, 10.4±0.2°, 10.8±0.2°, 11.6±0.2°, 12.8±0.2°, 13.4±0.2°, 14.5±0.2°, 15.2±0.2°, 15.6±0.2°, 16.6±0.2°, 17.4±0. .2°, 17.9±0.2°, 18.5±0.2°, 19.2±0.2°, 19.9±0.2°, 20.4±0.2°, 21.8±0.2°, 22.2±0.2°, 22.6±0.2°, 13.4±0.2°, 24.0±0.2°, 25.7±0.2°, 27.3±0.2° and 27.9±0.2°.

[0145]

[48] ​​The crystalline form as described in

[47] above, wherein, in differential scanning calorimetry (DSC) recorded in accordance with ISO11357-3:2018 at a heating rate of 20 K / min, an endothermic peak with an onset point in the range of 112 to 114°C is shown, and the maximum value of the peak is in the range of 124 to 126°C.

[0146]

[49] A crystalline form as described in any one of

[33] to

[48] above, wherein the crystal has an aspect ratio of at most 5:1.

[0147]

[50] An amorphous form B, which is an amorphous form B of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl, wherein

[0148] The crystals have a purity of at least 99.0% by weight based on organic matter, wherein the crystals contain less than 0.1 mol of an organic solvent per 1 mol of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl.

[0149] The X-ray powder diffraction pattern obtained by Cu Kα1 irradiation at 22°C is:

[0150] There is no reflection peak as a 2θ value at multiple diffraction angles within the range of 5° to 40°.

[0151] In differential scanning calorimetry (DSC) recorded in accordance with ISO 11357-3:2018 at a heating rate of 20 K / min, no endothermic peak was shown in the range of 80 to 200°C.

[0152]

[51] A 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl, wherein the total amount of impurities selected from 2-(2-hydroxyethoxy)-2′-hydroxy-6,6′-diphenyl-1,1′-binaphthyl, 2,2′-bishydroxy-6,6′-diphenyl-1,1′-binaphthyl and 2-(2-hydroxyethoxy)-2′-(2-(2-hydroxyethoxy)-ethoxy)-6,6′-diphenyl-1,1′-binaphthyl is less than 0.5% by weight, relative to 100% by weight of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl.

[0153]

[52] A 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl compound having at least one of the following characteristics:

[0154] i. A yellowness index (YI) of less than 3.0 as measured by a 5 w / w% dichloromethane solution of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl in accordance with ASTM E 313; and

[0155] ii. The haze measured using a 5 w / w% dichloromethane solution of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl is less than 1.0 ntu.

[0156]

[53] The 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl as described in

[51] or

[52] above, which exists in a crystalline form as described in any one of

[33] to

[49] above, or exists in an amorphous form as described in

[50] above.

[0157]

[54] The thermoplastic resin described in any one of [1] to

[33] above, which has structural units derived from the crystalline form described in

[33] to

[49] above and the amorphous form described in

[50] above.

[0158]

[55] The thermoplastic resin described in any one of [1] to

[33] above, which has a structural unit derived from the 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl described in

[51] or

[52] above.

[0159]

[56] An optical lens comprising the thermoplastic resin described in

[54] or

[55] .

[0160] Effects of the Invention

[0161] The thermoplastic resin of the present invention exhibits a high refractive index, a low b value, and high resistance to moist heat, and particularly exhibits a high refractive index. Furthermore, by using such an excellent thermoplastic resin, an excellent optical lens can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0162] Figure 1 This is the H1-NMR spectrum of the resin (BINOL-2EO / BNEF=50 mol / 50 mol) produced in Example 2-B.

[0163] Figure 2 The X-ray powder diffraction pattern of Form A of 6,6′-DPBHBNA obtained in Example 21 is shown.

[0164] Figure 3 The NIR spectrum of Form A of 6,6′-DPBHBNA obtained in Example 21 is shown.

[0165] Figure 4The IR spectrum of Form A of 6,6′-DPBHBNA obtained in Example 21 is shown.

[0166] Figure 5 The DSC of Form A of 6,6'-DPBHBNA obtained in Example 21 is shown.

[0167] Figure 6 The X-ray powder diffraction pattern of the methanol solvate of 6,6′-DPBHBNA obtained in Example 22 is shown.

[0168] Figure 7 The NIR spectrum of the methanol solvate of 6,6′-DPBHBNA obtained in Example 22 is shown.

[0169] Figure 8 The NR spectrum of the methanol solvate of 6,6′-DPBHBNA obtained in Example 22 is shown.

[0170] Figure 9 The DSC of the methanol solvate of 6,6′-DPBHBNA obtained in Example 22 is shown.

[0171] Figure 10 The X-ray powder diffraction pattern of the crystalline material obtained in Example 23 is shown.

[0172] Figure 11 The NIR spectrum of the crystalline material obtained in Example 23 is shown.

[0173] Figure 12 The NR spectrum of the crystalline material obtained in Example 23 is shown.

[0174] Figure 13 The DSC of the crystalline material obtained in Example 23 is shown.

[0175] Figure 14 A microscopic photograph of the toluene solvate of 6,6′-DPBHBNA obtained in Example 24 is shown.

[0176] Figure 15 The X-ray powder diffraction pattern of the toluene solvate of 6,6′-DPBHBNA obtained in Example 24 is shown.

[0177] Figure 16 The NIR spectrum of the toluene solvate of 6,6′-DPBHBNA obtained in Example 24 is shown.

[0178] Figure 17 The NR spectrum of the toluene solvate of 6,6′-DPBHBNA obtained in Example 24 is shown.

[0179] Figure 18DSC of the toluene solvate of 6,6'-DPBHBNA obtained from Example 24.

[0180] Figure 19 Microphotograph of the MEK solvate of 6,6'-DPBHBNA obtained from Example 25.

[0181] Figure 20 NIR spectrum of the MEK solvate of 6,6'-DPBHBNA obtained from Example 25.

[0182] Figure 21 DSC of the MEK solvate of 6,6'-DPBHBNA obtained from Example 25.

[0183] Figure 22 X-ray powder diffraction pattern of the MEK solvate of 6,6'-DPBHBNA obtained from Example 25.

[0184] Figure 23 X-ray powder diffraction pattern of the amorphous Form B of 6,6'-DPBHBNA obtained from Example 26.

[0185] Figure 24 NIR spectrum of the amorphous Form B of 6,6'-DPBHBNA obtained from Example 26.

[0186] Figure 25 IR spectrum of the amorphous Form B of 6,6'-DPBHBNA obtained from Example 26.

[0187] Figure 26 X-ray powder diffraction pattern of Form C of 6,6'-DPBHBNA obtained from Example 27.

[0188] Figure 27 NIR spectrum of Form C of 6,6'-DPBHBNA obtained from Example 27.

[0189] Figure 28 IR spectrum of Form C of 6,6'-DPBHBNA obtained from Example 27.

[0190] Figure 29 DSC of Form C of 6,6'-DPBHBNA obtained from Example 27.

[0191] Figure 30 is a first graph in which Abbe number (v) of the thermoplastic resins of Examples and Comparative Examples is taken as a horizontal axis and refractive index (nD) is taken as a vertical axis.

[0192] Figure 31This is a second graph in which the Abbe number (v) of the thermoplastic resins of Examples and Comparative Examples is plotted on the horizontal axis and the refractive index (nD) is plotted on the vertical axis. DETAILED DESCRIPTION

[0193] Hereinafter, the present invention will be described in detail.

[0194] (1) Components (structural units) of thermoplastic resins

[0195] The thermoplastic resin of the present invention contains the structural unit represented by the following general formula (1). The type of thermoplastic resin is not particularly limited as long as it contains the following structural unit, but is preferably a polyester resin, polyester carbonate resin, polycarbonate resin, or a mixture of at least two of these.

[0196] Furthermore, among thermoplastic resins, polyester resins are resins having polyester structural units (repeating units) containing a (-RCO-O-) site but excluding polycarbonate structural units (repeating units) containing a (-RO-CO-O-) site; polycarbonate resins are resins having polycarbonate structural units (repeating units) containing a (-RO-CO-O-) site but excluding polyester structural units (repeating units) containing a (-RCO-O-) site; and polyester carbonate resins are resins having both polyester structural units (repeating units) containing a (-RO-CO-) site and polycarbonate structural units (repeating units) containing a (-RO-CO-O-) site (R in both cases is a hydrocarbon group, etc.).

[0197]

[0198] (In formula (1), 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,

[0199] 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 CN, CH3, OCH3, O-phenyl, O-naphthyl, S-phenyl, S-naphthyl and halogen. a base,

[0200] Wherein, R1 and R2 are not all hydrogen,

[0201] 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,

[0202] 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.

[0203] In the general formula (1), R1 and R2 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 particularly more preferably R1 to R 10 At least two of them are aryl groups having 6 to 14 carbon atoms or 6 to 12 carbon atoms.

[0204] R1 and R2 may be the same, for example.

[0205] Furthermore, 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 one, two, three, or four of the ring atoms in the heteroaryl group are selected from nitrogen, sulfur, and oxygen, and the remaining ring atoms are carbon. The monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group may be unsubstituted.

[0206] R1 and R2 can be selected from the following groups.

[0207] Azulene base;

[0208] An unsubstituted indenyl group or an indenyl group which may be substituted with two, three, four or five substituents selected from a phenyl group and a polycyclic aryl group, wherein the polycyclic aryl group has two, three or four benzene rings which may be bonded to each other via single bonds, may be directly condensed with each other, and / or may be condensed with a saturated or unsaturated 4-10 membered monocyclic or bicyclic hydrocarbon ring;

[0209] Phenyl with no substituents;

[0210] Phenyl substituted with 1 or 2 CN groups;

[0211] A phenyl group which may be substituted with two, three, four or five substituents selected from a phenyl group and a polycyclic aryl group, wherein the polycyclic aryl group has two, three or four phenyl 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;

[0212] A polycyclic aromatic group having two, three or four benzene rings that 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 has no substituent or may be substituted with one or two substituents selected from phenyl and a polycyclic aromatic group having two or three benzene rings, wherein the two or three benzene rings can be bonded to each other via a single bond, can be directly condensed with each other, and / or can be condensed with a saturated 4-10 membered monocyclic or bicyclic hydrocarbon ring, wherein the benzene ring of the polycyclic aromatic group has no substituent or has one or two substituents R a .

[0213] In addition, R1 and R2 can be selected from the following groups.

[0214] Phenyl which is unsubstituted or may be substituted with 1, 2, 3, 4 or 5 phenyl groups;

[0215] Phenyl substituted with 1 or 2 CN groups;

[0216] Phenyl substituted with one or two polycyclic aromatic groups selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl and pyrenyl, and further substituted with one phenyl group;

[0217] an unsubstituted naphthyl group or a naphthyl group substituted with one or two substituents selected from the group consisting of CN, phenyl, and polycyclic aryl groups, wherein the polycyclic aryl group is selected from the group consisting of biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, and pyrenyl;

[0218] biphenylene;

[0219] triphenylene;

[0220] tetraphenylene;

[0221] Fiki;

[0222] pyrene;

[0223] 9H-fluorenyl;

[0224] dibenzo[a,e][8]annulyl;

[0225] perylene; and

[0226] 9,9'-Spirobi[9H-fluorenyl]yl.

[0227] Among them, R1 and R2 are preferably selected from phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-naphthyl, 1-naphthyl and 9-naphthyl.

[0228] In addition, R1 and R2 can be selected from the following groups.

[0229] a heteroaromatic monocyclic group 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;

[0230] A heteroaromatic polycyclic group having the above-mentioned heteroaromatic monocyclic ring and one, two, three, four or five additional 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, 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

[0231] A heteroaromatic polycyclic group having at least one saturated or partially unsaturated 5- or 6-membered heterocyclic ring containing one or two heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, and one, two, three, four or five additional aromatic rings selected from phenyl and the above-mentioned heteroaromatic monocyclic rings, wherein at least one additional aromatic ring is directly condensed with the saturated or partially unsaturated 5- or 6-membered heterocyclic group, and the other additional aromatic rings of the polycyclic heteroaryl aromatic ring may be 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.

[0232] In addition, R1 and R2 may be independently selected from the following groups: furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, benzofuranyl, dibenzofuranyl, benzothienyl, dibenzothienyl, thianthrenyl, naphthofuryl, furo[3,2-b]furanyl, furo[2,3-b]furanyl, ] furanyl, furo[3,4-b]furanyl, oxanthrenyl, indolyl, isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzo[cd]indolyl, 1H-benzo[g]indolyl, quinolinyl, isoquinolinyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, benzo[b][1,5]naphthyridinyl, cinnolinyl, 1,5-naphthyridinyl, 1,8- naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, bipyridinyl, phenylpyridinyl, naphthylpyridinyl, pyrido[4,3-b]indolyl, pyrido[3,2-b]indolyl, pyrido[3,2-g]quinolinyl, pyrido[2,3-b][1,8]naphthyridinyl, pyrrolo[3,2-b]pyridinyl, pteridinyl, purinyl, 9H-xanthenyl, 2 H-benzopyranyl, phenanthridinyl, phenanthrolinyl, furo[3,2-f][1]benzofuranyl, furo[2,3-f][1]benzofuranyl, furo[3,2-g]quinolinyl, furo[2,3-g]quinolinyl, furo[2,3-g]quinoxalinyl, benzo[g]benzopyranyl, pyrrolo[3,2,1-hi]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl and benzo[h]isoquinolinyl.

[0233] X in the 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, such as ethylene.

[0234] In addition, a and b in the above general formula (1) are each preferably an integer of 1 to 6, more preferably 1 to 4, and particularly preferably 2 or 3.

[0235] The thermoplastic resin is, for example, a polyester resin or a polyester carbonate resin. Furthermore, the polyester resin or the polyester carbonate resin preferably further contains a structural unit represented by the following general formula (2).

[0236]

[0237] In the general formula (2), Q is represented by the following formula (2a).

[0238]

[0239] In formula (2a), R C Each independently represents a single bond to the CO group of formula (2), or an alkylene group which may have a substituent, has a total of 1 to 10 carbon atoms, and includes a bonding point to the CO group of formula (2) at a terminal. C It is preferably a single bond or an alkylene group having 1 to 3 carbon atoms in total.

[0240] Q in formula (2) is preferably represented by the following formula (2b).

[0241]

[0242] In formula (2b), n and m are each independently an integer of 0 to 5, preferably an integer of 1 to 3.

[0243] p and k are each independently an integer of 1-5, preferably an integer of 1-3.

[0244] R1 and R2 have the same meanings as R1 and R2 in formula (1).

[0245] a and b are each independently an integer of 0 to 6, preferably an integer of 1 to 3, and more preferably an integer of 1 or 2.

[0246] Furthermore, * represents a bonding point with the CO group in formula (2).

[0247] More preferably, Q in formula (2) is represented by the following formula (2c).

[0248]

[0249] In formula (2c), * is the bonding point with the CO group of formula (2).

[0250] The structural unit represented by the general formula (1) preferably includes at least one of the structural units represented by the following general formulae (A-1) to (A-7).

[0251]

[0252]

[0253] 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). at least one of a structural unit derived from (6,6′-bis(dibenzo[b,d]furan-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl) represented by the general formula (A-7); and a structural unit derived from (THI-BNA(6,6′-bis(dibenzo[b,d]thiophen-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl) represented by the general formula (A-8).

[0254] The thermoplastic resin of the present invention preferably contains more than 50 mol%, more preferably more than 60 mol%, even more preferably more than 70 mol%, particularly preferably more than 80 mol%, or preferably more than 90 mol%. The thermoplastic resin of the present invention may be composed solely of the structural unit represented by the general formula (1).

[0255] The thermoplastic 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.

[0256] Specifically, the thermoplastic resin of the present invention preferably further contains at least one of the structural units represented by general formulae (3) and (4).

[0257]

[0258] (R'1~R' in formula (3) 20each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms,

[0259] 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,

[0260] c and d are integers from 1 to 10 respectively.)

[0261] R'1 to R" in the above general formula (3) 20 Each of them is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and more preferably hydrogen.

[0262] Y in the above general formula (3) is preferably an alkylene group having 2 to 4 carbon atoms, a cycloalkylene group having 5 to 8 carbon atoms, or an arylene group having 6 to 14 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, a cycloalkylene group having 5 to 6 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and particularly preferably an alkylene group having 2 or 3 carbon atoms.

[0263] In addition, c and d 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.

[0264]

[0265] (R1~R2 in formula (4) 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,

[0266] 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,

[0267] e and f are integers from 1 to 10 respectively.)

[0268] R1 to R2 in the above general formula (4) 16 Each of them is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and more preferably a hydrogen atom or an aryl group having 6 to 10 carbon atoms.

[0269] Z in the above general formula (4) 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.

[0270] Furthermore, e and f in the general formula (4) are each preferably an integer of 1 to 6, more preferably 1 to 4, and particularly preferably 2 or 3.

[0271] The thermoplastic resin of the present invention preferably contains the structural unit (1) and, as the structural unit represented by the above-mentioned general formula (3) or (4), further contains at least one structural unit represented by the following general formula (5).

[0272]

[0273] That is, the thermoplastic resin of the present invention preferably contains, together with the structural unit (1), at least one of a structural unit derived from BNEF (9,9-bis(6-(2-hydroxyethoxy)naphth-2-yl)fluorene), 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) represented by the above general formula (5).

[0274] The thermoplastic resin of the present invention may contain 20 to 80 mol% of structural units other than the structural unit (1), preferably the structural units represented by the above-mentioned general formulae (3) and (4), in a total amount, for example, 25 to 75 mol%. The structural units represented by the above-mentioned general formulae (3) and (4) may be contained in the thermoplastic resin in an amount of, for example, 30 to 70 mol%, 35 to 65 mol%, or 40 to 60 mol%.

[0275] That is, the molar ratio of the structural unit (1) to the structural unit (3) represented by the general formula (3) in the thermoplastic resin composition of the present invention is, for example, 4:1 to 1:4 or 7:3 to 3:7. Furthermore, the molar ratio may be 65:35 to 35:65, 3:2 to 2:3, or 1:1. However, since the thermoplastic resin composition preferably contains more than 50 mol% of the structural unit (1), specific preferred examples of the molar ratio of the structural unit (1) to the structural unit (3) include 4:1 to 1:1, 7:3 to 1:1, 65:35 to 1:1, and 3:2 to 1:1.

[0276] The molar ratio of the structural unit (1) to the structural unit (4) represented by the general formula (4) is also the same as the molar ratio of the structural unit (1) to the structural unit (3).

[0277] The thermoplastic resin of the present invention may contain any structure of random, block, and alternating copolymer structures. Furthermore, the thermoplastic resin of the present invention may not contain all of the above-mentioned structural unit (1), structural unit (3), and structural unit (4) in the same polymer molecule. That is, as long as the above-mentioned structural unit is contained in a plurality of polymer molecules as a whole, the thermoplastic resin of the present invention may also be a blended resin. For example, as a thermoplastic resin containing all of the above-mentioned structural unit (1), structural unit (3), and structural unit (4), it may be a copolymer containing all of the structural units (1), (3), and (4), or a mixture of a homopolymer or copolymer containing structural unit (1), a homopolymer or copolymer containing structural unit (2), and a homopolymer or copolymer containing structural unit (4), or a blended resin of a copolymer containing structural units (1) and (3) and a copolymer containing structural units (1) and (4).

[0278] The thermoplastic resin of the present invention may be blended with other resins to produce a molded article. For example, when the thermoplastic resin is any of polyester, polyester carbonate, and polycarbonate, examples of the other resin include polyamide, polyacetal, a polycarbonate different from the thermoplastic resin, modified polyphenylene ether, polyethylene terephthalate, and polybutylene terephthalate.

[0279] Furthermore, the thermoplastic resin composition of the present invention preferably contains an antioxidant, a mold release agent, a processing stabilizer, an ultraviolet absorber, a fluidity modifier, a crystal nucleating agent, a reinforcing agent, a dye, an antistatic agent, or an antibacterial agent.

[0280] 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, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl) propionate. Examples of the antioxidant include butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid), diethyl 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate, 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 thermoplastic resin composition is preferably 0.001 to 0.3 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0281] The release agent preferably comprises at least 90% by weight of an ester of an alcohol and a fatty acid. Specifically, esters of alcohols and fatty acids include esters of monohydric alcohols and fatty acids, and partial or full esters of polyhydric alcohols and fatty acids. Preferred esters of monohydric alcohols and fatty acids are esters of monohydric alcohols having 1 to 20 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms. Furthermore, preferred partial or full esters of polyhydric alcohols and fatty acids are those of polyhydric alcohols having 1 to 25 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms.

[0282] Specifically, examples of esters of monohydric alcohols and saturated fatty acids include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Examples of partial or full esters of polyhydric alcohols and saturated fatty acids include stearyl monoglyceride, diglyceryl stearate, triglyceryl stearate, sorbitol monostearate, behenic monoglyceride, capric monoglyceride, lauric monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenyl ester, sorbitan monostearate, 2-ethylhexyl stearate, and full or partial esters of dipentaerythritol such as dipentaerythritol hexastearate. Among these, stearyl monoglyceride and lauric 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 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 thermoplastic resin.

[0283] 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, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite. , 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 diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, 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 thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0284] Examples of sulfur-based processing heat stabilizers include pentaerythritol tetrakis(3-laurylthiopropionate), pentaerythritol tetrakis(3-myristylthiopropionate), pentaerythritol tetrakis(3-stearylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate. The content of the sulfur-based processing heat stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight per 100 parts by weight of the thermoplastic resin.

[0285] The UV absorber is preferably at least one selected from the group consisting of benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, cyclic iminoester-based UV absorbers, and cyanoacrylate-based UV absorbers. Specifically, any one of the UV absorbers listed below may be used alone, or two or more may be used in combination.

[0286] Examples of the benzotriazole-based 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. di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-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.

[0287] 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 sulfonate benzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0288] Examples of the triazine-based ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol.

[0289] Examples of the cyclic urethane-based ultraviolet absorbers 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'-diphenylene)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), etc.

[0290] 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.

[0291] 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 per 100 parts by weight of the thermoplastic resin. Within this range, the thermoplastic resin composition can be provided with sufficient weather resistance depending on the intended use.

[0292] In thermoplastic resin compositions, such as polycarbonate resin compositions, impurities include phenols generated during production and unreacted carbonic acid diesters. The phenol content in the thermoplastic resin composition is preferably 0.1 to 3000 ppm, more preferably 0.1 to 2000 ppm, even more preferably 1 to 1000 ppm, 1 to 800 ppm, 1 to 500 ppm, or 1 to 300 ppm. Furthermore, the carbonic acid diester content in the thermoplastic resin composition is preferably 0.1 to 1000 ppm, more preferably 0.1 to 500 ppm, and particularly preferably 1 to 100 ppm. By adjusting the amounts of phenol and carbonic acid diester contained in the thermoplastic resin composition, a resin having properties suitable for the purpose can be obtained. The content of phenol and carbonic acid diester can be appropriately adjusted by changing the polycondensation conditions and equipment. Alternatively, it can be adjusted by adjusting the conditions of the extrusion process after polycondensation.

[0293] If 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, if the content of phenol or carbonic acid diester is below the above range, there is a concern that the plasticity of the resin when melted may be reduced.

[0294] (2) Properties of thermoplastic resins

[0295] The viscosity average molecular weight (Mv) of the thermoplastic resin of the present invention is preferably 8,000 to 20,000, more preferably 9,000 to 15,000, and even more preferably 10,000 to 14,000.

[0296] If the Mv value is less than 8,000, the molded product may become brittle. If the Mv value is greater than 20,000, the melt viscosity becomes high, making it difficult to remove the produced resin. Furthermore, the fluidity may deteriorate, making injection molding in the molten state difficult.

[0297] The refractive index (nD) of the thermoplastic resin of the present invention at 23°C and a wavelength of 589 nm is preferably 1.635 or more, more preferably 1.645 or more, even more preferably 1.655 or more, particularly preferably 1.665 or more, or greater than these values. For example, the refractive index of the thermoplastic resin of the present invention is preferably 1.640 to 1.710, more preferably 1.645 to 1.700, even more preferably 1.650 to 1.697, and particularly preferably 1.655 to 1.695. The thermoplastic resin of the present invention has a high refractive index (nD) and is suitable for optical lens materials. The refractive index can be measured using an Abbe refractometer according to JIS-K-7142 for a film with a thickness of 0.1 mm.

[0298] The Abbe number (ν) of the thermoplastic resin of the present invention is preferably 24 or less, more preferably 22 or less, and even more preferably 20 or less. The Abbe number can be calculated from the refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm at 23°C using the following formula.

[0299] ν=(nD-1) / (nF-nC)

[0300] nD: refractive index at a wavelength of 589 nm

[0301] nC: refractive index at a wavelength of 656nm

[0302] nF: refractive index at a wavelength of 486 nm

[0303] Considering the use for injection molding, the preferred glass transition temperature (Tg) of the thermoplastic resin of the present invention is 90 to 185°C, more preferably 95 to 180°C, and even more preferably 100 to 175°C. When Tg is lower than 90°C, the operating temperature range may be narrowed. In addition, when it exceeds 185°C, the melting temperature of the resin becomes high, and there is a concern that the resin is easily decomposed and colored. When the glass transition temperature of the resin is too high, the difference between the mold temperature and the glass transition temperature of the resin becomes large when using a conventional mold temperature controller. Therefore, in applications that require strict surface accuracy for products, it may be difficult to use resins with too high a glass transition temperature. 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.

[0304] The total light transmittance of an optical molded article obtained using the thermoplastic resin of the present invention is preferably 85% or higher, more preferably 87% or higher, and particularly preferably 88% or higher. A total light transmittance of 85% or higher is comparable to that of bisphenol A polycarbonate resins and the like.

[0305] The thermoplastic resin of the present invention has high resistance to moisture and heat. Resistance to moisture and heat can be evaluated by subjecting an optical molded body obtained using the thermoplastic resin to a "PCT test" (pressure cooker test) and measuring the total light transmittance of the optical molded body after the test. The PCT test can be performed by maintaining an injection molded body having a diameter of 50 mm and a thickness of 3 mm under conditions of 120°C, 0.2 MPa, 100% RH, and 20 hours. The total light transmittance of the thermoplastic resin of the present invention after the PCT test is 60% or more, preferably 70% or more, more preferably 75% or more, even more preferably 80% or more, and particularly preferably 85% or more. When the total light transmittance is 60% or more, it can be said that the optical molded body has high resistance to moisture and heat compared to existing thermoplastic resins.

[0306] The b value indicating the hue of the thermoplastic resin of the present invention is preferably not more than 5. A smaller b value indicates less yellowishness and better hue.

[0307] (3) Method for producing thermoplastic resin

[0308] When the thermoplastic resin having the structural unit represented by the general formula (1) is a polycarbonate resin, its production method includes, for example, the step of melt-polycondensing a dihydroxy compound represented by the following general formula (6) and a carbonic acid diester.

[0309]

[0310] (In the general formula (6), 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,

[0311] Wherein, R1 and R2 are not all hydrogen,

[0312] 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,

[0313] 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.

[0314] That is, a polycarbonate resin can be produced by using a compound represented by the general formula (6) as a dihydroxy component and reacting it with a carbonate precursor such as a carbonic acid diester. Specifically, the compound represented by the general formula (6) and a carbonate precursor such as a carbonic acid diester can be reacted in the presence of a basic compound catalyst or an ester exchange catalyst or a mixed catalyst containing both thereof, or in the absence of a catalyst, by a melt polycondensation method.

[0315] Furthermore, polyester carbonate resin and polyester resin can also be obtained by using the dihydroxy compound represented by the above general formula (6) as a raw material (monomer).

[0316] The polyester carbonate resin or polyester resin can be produced, for example, by subjecting the dihydroxy compound represented by the above-mentioned general formula (6) to melt polycondensation with at least one of carboxylic acid, carboxylic acid monoester, and carboxylic acid diester.

[0317] For example, specific examples of carboxylic acids, carboxylic acid monoesters, and carboxylic acid diesters include dicarboxylic acid, monocarboxylic acid monoesters, and diesters of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl (BINL-2EO), 9,9-fluorene-dipropionic acid, and 9,9-fluorene-dipropionic acid methyl ester (FDPM), which is a monoester and diester of 9,9-fluorene-dipropionic acid.

[0318] Specific examples of carboxylic acids, carboxylic acid monoesters, and carboxylic acid diesters include 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphth-1-yl)-1,1'-binaphthyl (DNBINOL-2EO), 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphth-2-yl)-1,1'-binaphthyl (2DNBINOL-2EO), 2,2'-bis(2-hydroxyethoxy)-6,6'-di(phenanthrene-9-yl)-1,1'-binaphthyl (9DPNBINO dicarboxylic acids, monocarboxylic acid monoesters, diesters, etc. of 6,6'-bis-(3-cyanophenyl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl (CN-BNA), 6,6'-bis-(dibenzo[b,d]furan-4-yl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl (FUR-BNA), and 6,6'-bis-(3-cyanophenyl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl (CN-BNA).

[0319] Examples of the compound of the general formula (6) include 2,2'-bis(hydroxy(poly)alkoxy)-diaryl-1,1'-binaphthyls and 2,2'-bis(hydroxy(poly)alkoxy)-dinaphthyl-1,1'-binaphthyls. For example, 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.

[0320] In addition, the monomer used to produce the thermoplastic resin may contain, as an impurity, a dihydroxy compound in which the values ​​of a and b in the general formula (6) are both 0, or a dihydroxy compound in which either a or b in the general formula (6) is 0, together with the dihydroxy compound represented by the general formula (6).

[0321] Thus, the total amount of dihydroxy compounds having a different value from at least any one of a and b in the above-mentioned general formula (6) is preferably contained in a monomer having the dihydroxy compound represented by the above-mentioned general formula (6) as the main component 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, and the total amount of dihydroxy compounds having a different value from at least any one of a and b in the above-mentioned general formula (6) in the above-mentioned monomer is preferably 50 ppm or less, and more preferably 20 ppm or less.

[0322] The compound of general formula (6) can be produced by various synthesis methods. For example, as described in Japanese Patent Application Laid-Open Nos. 2014-227387, 2014-227388, 2015-168658, and 2015-187098, it can be produced by: (a) reacting 1,1'-binaphthol with ethylene glycol monotoluenesulfonate, (b) reacting binaphthols with alkylene oxides, halogenated alkanols, or alkylene carbonates, (c) reacting 1,1'-binaphthol with ethylene carbonate, or (d) reacting 1,1'-binaphthol with ethylene carbonate.

[0323] The monomer of general formula (6) may contain impurities that may adversely affect the properties of the thermoplastic resin, particularly the optical properties. In particular, the monomer of general formula (6) may contain one or more of the following by-products of general formulas (6a) and (6b) as impurities generated during its production process.

[0324]

[0325] In one embodiment, the monomer of the general formula (6) may contain the following by-products of the general formula (6c) as impurities generated during the production process, in addition to or in place of the impurities of the formulae (6a) and (6b).

[0326] In formulae (6a), (6b), and (6c), substituents R1, R2, and X are the same as those defined in the monomer of formula (6). In formulae (6a) and (6c), as in the monomer of formula (6), a is an integer in the range of 1 to 10, preferably an integer in the range of 1 to 4, and more preferably 1, 2, or 3. In formulae (6c), variables b, c, and d are integers in the range of 1 to 10, preferably an integer in the range of 1 to 4, and more preferably 1, 2, or 3. In formulae (6a) and (6c), as in the monomer of formula (6), substituent X is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an ethylene group, i.e., 1,2-ethylenediyl or -CH2CH2-.

[0327] In formulae (6a), (6b) and (6c), as in the monomer of formula (6), the substituents R1 and R2 are preferably monocyclic or polycyclic aryl groups having 6 to 36 carbon atoms, or monocyclic or polycyclic heteroaryl groups having 6 to 36 ring atoms, more preferably monocyclic or polycyclic aryl groups having 6 to 20 carbon atoms, even more preferably aryl groups having 6 to 14 carbon atoms, and particularly preferably selected from phenyl, 1-naphthyl, 2-naphthyl, 9-phenanthrenyl, 4-dibenzo[b,d]furanyl and 4-dibenzo[b,d]thienyl.

[0328] The total weight of the impurities of formula (6a) and (6b) in the monomer of formula (6) used in the method of the present invention is preferably not more than 5000 ppm based on 1 part by weight of the monomer of formula (6). In particular, the total weight of the impurities of formula (6a) and (6b) is preferably not more than 4000 ppm, more preferably not more than 3000 ppm, and even more preferably not more than 2000 ppm, based on 1 part by weight of the monomer of formula (6). It is particularly preferred that the weight of each impurity of formula (6a) and (6b) is not more than 2000 ppm, more preferably not more than 1500 ppm, and even more preferably not more than 1000 ppm, based on 1 part by weight of the monomer of formula (6). If present, the amount of impurity (6c) is not more than 2000 ppm, and is usually not more than 1500 ppm, based on 1 part by weight of the monomer of formula (6).

[0329] In a specific embodiment of the invention relating to a thermoplastic resin produced by the method of the present invention, the variables (a) and (b) of the monomer of formula (6) are 1, and this is hereinafter referred to as monomer (6-1). Monomer (6-1) may contain one or more byproducts of the following formulas (6a-1), (6-2), and (6b), and may contain (6c-1) as an impurity.

[0330]

[0331] In formulas (6-1), (6a-1), (6-2), and (6c-1), the substituent X is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an ethylene group, i.e., 1,2-ethanediyl or -CH2CH2-. In formula (6-2), the variable e is defined as the variable a and can be 2 or 3, in particular. In formulae (6-1), (6a-1), (6-2), (6-b) and (6c-1), the substituents R1 and R2 are preferably monocyclic or polycyclic aryl groups having 6 to 36 carbon atoms, or monocyclic or polycyclic heteroaryl groups having 6 to 36 ring atoms, more preferably monocyclic or polycyclic aryl groups having 6 to 20 carbon atoms, even more preferably aryl groups having 6 to 14 carbon atoms, and particularly preferably selected from phenyl, 1-naphthyl, 2-naphthyl, 9-phenanthrenyl, 4-dibenzo[b,d]furanyl and 4-dibenzo[b,d]thienyl.

[0332] The total weight of impurities of formulae (6a-1), (6-2), and (6b) in the monomer of formula (6-1) used in the method of the present invention is preferably no more than 5000 ppm based on 1 part by weight of the monomer of formula (6). In particular, the total weight of impurities of formulae (6a-1), (6-2), and (6b) is preferably no more than 4000 ppm, more preferably no more than 3000 ppm, and even more preferably no more than 2000 ppm, based on 1 part by weight of the monomer of formula (6-1). In particular, the weight of each impurity of formulae (6a-1), (6-2), and (6b) is preferably no more than 2000 ppm, more preferably no more than 1500 ppm, and even more preferably no more than 1000 ppm, based on 1 part by weight of the monomer of formula (6-1). If present, the amount of impurity (6c-1) is no more than 2000 ppm, and is typically no more than 1500 ppm, based on 1 part by weight of the monomer of formula (6-1).

[0333] In a specific embodiment of the invention relating to a thermoplastic resin produced by the method of the present invention, the monomer of formula (6) is 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl (6,6'-diphenyl-2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl). That is, in formula (6), variables (a) and (b) are both 1, X is 1,2-ethanediyl, and the substituents R1 and R2 are both phenyl. Here and elsewhere in this specification, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl may also be abbreviated as 6,6'-DPBHBNA.

[0334] 6,6'-DPBHBNA may contain one or more impurities in which the substituent X in the above formulas (6a-1), (6-2), (6b) and (6c-1) is 1,2-ethanediyl, all R1 and R2 substituents are phenyl, and the variable e in formula (6-2) is 2 or 3, particularly 2.

[0335] In formula (6a-1), the chemical name of the compound in which the substituent X is 1,2-ethanediyl and the substituents of R1 and R2 are both phenyl is 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-binaphthyl.

[0336] In formula (6-2), the compound in which the substituent X is 1,2-ethanediyl, e is 2, and the substituents for R1 and R2 are both phenyl is chemically named 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthyl (6,6'-diphenyl-2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy)-1,1'-binaphthyl).

[0337] In formula (6b), the chemical name of the compound in which both R1 and R2 are phenyl groups is 2,2′-dihydroxy-6,6′-diphenyl-1,1′-binaphthyl.

[0338] In formula (6c-1), the chemical name of the compound in which the substituent X is 1,2-ethanediyl and all the substituents of R1 and R2 are phenyl is bis[2-[[1-[2-(2-hydroxyethoxy)-6-phenyl-1-naphthyl]-6-phenyl-2-naphthyl]-oxy]-ethyl] carbonate.

[0339] The total amount of impurities of formula (6a-1), (6-2) and (6b) in which X is 1,2-ethanediyl and the substituents of all R1and R2are phenyl, based on 1 part by weight of 6,6'-DPBHBNA, is preferably not more than 5000 ppm. In this way, 6,6'-DPBHBNA containing small amounts of the above-mentioned impurities is a novel substance, and therefore, it is also included in a part of the present application. In particular, the total amount of impurities of formula (6a-1), (6-2) and (6b) in which X is 1,2-ethanediyl and the substituents of all R1and R2are phenyl, based on 1 part by weight of 6,6'-DPBHBNA, is preferably not more than 4000 ppm, more preferably not more than 3000 ppm, and further preferably not more than 2000 ppm. In particular, the amount of each of the impurities of formula (6a-1), (6-2) and (6b) in which X is 1,2-ethanediyl and the substituents of all R1and R2are phenyl, based on 1 part by weight of 6,6'-DPBHBNA, is preferably not more than 2000 ppm, more preferably not more than 1500 ppm, and further preferably not more than 1000 ppm. If present, the amount of the impurity of formula (6c-1) in which X is 1,2-ethanediyl and the substituents of all R1and R2are phenyl, based on 1 part by weight of 6,6'-DPBHBNA, is usually not more than 2000 ppm, and generally not more than 1500 ppm.

[0340] 6,6'-DPBHBNA has a tendency to form solvates with certain organic solvents, in particular, a tendency to form solvates with methanol, toluene, anisole, xylene, chlorobenzene, tetrahydrofuran, and aliphatic ketones such as 2-butanone, also known as methyl ethyl ketone (MEK), and 4-methyl-2-pentanone, also known as methyl isobutyl ketone (MIBK). In these solvents, the amount of each organic solvent is generally in the range of 0.3 to 1.5 moles per 1 mole of 6,6'-DPBHBNA. Here and elsewhere in this specification, the term solvate is understood to mean a crystalline form that contains solvent in the crystal lattice. These solvates are often referred to as "pseudo polymorphs" as distinguished from polymorphs which are substantially free of solvent. In the crystalline solvates of 6,6'-DPBHBNA, the amount of solvent need not be stoichiometric with respect to the amount of 6,6'-DPBHBNA, but can vary. While not wishing to be bound by theory, the solvent molecules present in the crystalline solvates of 6,6'-DPBHBNA generally fill interstitial or void spaces in the crystal lattice formed by the molecules of 6,6'-DPBHBNA.

[0341] Among the above solvents, methanol, toluene, and methyl ethyl ketone are particularly preferred. Crystalline solvates formed with these solvents, such as 6,6'-DPBHBNA, typically form compact crystals with a low aspect ratio. These crystals tend to be free of mother liquor and contain high-purity 6,6'-DPBHBNA. Therefore, these crystalline solvates also form part of the present invention.

[0342] The solvate of 6,6'-DPBHBNA with an organic solvent selected from methanol, toluene and methyl ethyl ketone can increase the purity of 6,6'-DPBHBNA to more than 99%, particularly at least 99.5% or more, and further 99.7% or more.

[0343] In particular, unless otherwise specified, herein or in the context of solid forms of 6,6'-DPBHBNA, a purity exceeding 99% means that the total amount of organic impurities, i.e., the amount of organic compounds other than 6,6'-DPBHBNA and optionally present solvent, contained in the respective solid form of 6,6'-DPBHBNA is less than 1% by weight. Similarly, a purity of at least 99.5% or at least 99.7% means that the total amount of organic impurities, i.e., the amount of organic compounds other than 6,6'-DPBHBNA and optionally present solvent, contained in the respective solid form of 6,6'-DPBHBNA is a maximum of 0.5% or a maximum of 0.3% by weight.

[0344] In the crystalline solvate of 6,6'-DPBHBNA in the present invention, the total amount of impurities having a 1,1'-binaphthyl moiety selected from 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bishydroxy-6,6'-diphenyl-1,1'-binaphthyl, and 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthyl is generally at most 5000 ppm (0.50 wt%) or less, preferably at most 4000 ppm (0.40 wt%) or less, particularly preferably at most 3000 ppm (0.30 wt%) or less, and even more preferably at most 2000 ppm (0.20 wt%) or less, based on 1 part by weight of 6,6'-DPBHBNA contained in the crystals of the crystalline solvate. The weight of each of these impurities is particularly preferably no greater than 2000 ppm, more preferably no greater than 1500 ppm, and even more preferably no greater than 1000 ppm, based on 1 part by weight of 6,6'-DPBHBNA. If each solvate contains bis[2-[[1-[2-(2-hydroxyethoxy)-6-phenyl-1-naphthyl]-6-phenyl-2-naphthyl]-oxy]-ethyl] carbonate, the amount thereof is generally no greater than 2000 ppm, and may be no greater than 1500 ppm, based on 1 part by weight of 6,6'-DPBHBNA.

[0345] In the crystalline solvate of the present invention, the amount of the solvent may vary, but is generally in the range of 0.3 to 1.5 mol, particularly 0.3 to 1.2 mol, per mol of 6,6'-DPBHBNA.

[0346] A specific embodiment of the present invention relates to a crystalline solvate of 6,6'-DPBHBNA and methanol, which is hereinafter referred to as methanol solvate.

[0347] In the methanol solvate, the amount of methanol is generally in the range of 0.3 to 1.5 mol, particularly in the range of 0.4 to 1.2 mol, and further in the range of 0.6 to 1.1 mol per 1 mol of 6,6'-DPBHBNA.

[0348] In the X-ray powder diffraction pattern recorded by irradiation with Cu Kα1 rays at 22°C, the methanol solvate generally shows the following three reflection peaks as 2θ values, namely, 13.0±0.2°, 14.9±0.2°, and 21.5±0.2°;

[0349] showing as 2θ values ​​at least 3, in particular at least 5, at least 7 or all of the following reflection peaks: 6.2±0.2°, 9.0±0.2°, 10.6±0.2°, 16.9±0.2°, 18.2±0.2°, 18.5±0.2°, 19.2±0.2°, 19.6±0.2°, 20.9±0.2°, 22.7±0.2°, 24.3±0.2°, 24.9±0.2°, 26.2±0.2°, 28.7±0.2° and 30.5±0.2°; and

[0350] Optionally, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 reflection peaks are shown as 2θ values ​​among the following: 8.4±0.2°, 11.8±0.2°, 12.5±0.2°, 16.0±0.2°, 17.7±0.2°, 22.1±0.2°, 26.6±0.2°, 27.7±0.2°, 31.6±0.2° and 32.5±0.2°.

[0351] Methanol solvates can also be characterized by an endothermic peak indicating their decomposition. When methanol solvates are analyzed using a differential scanning calorimetry (DSC) analyzer recorded in accordance with ISO 11357-3:2018 at a heating rate of 20 K / min, methanol solvates generally exhibit an endothermic peak with an onset in the range of 97-101°C, and a peak maximum in the range of 108-115°C. Furthermore, the reaction point is generally in the range of 103-110°C. The reaction point is understood to be the inflection point on the lower side of the endothermic peak in the DSC curve. The above temperature can vary within the above range depending on the methanol content, and the temperature increases when the methanol content is high.

[0352] The methanol solvate can be obtained by crystallizing 6,6'-DPBHBNA from a hot methanol solution or a hot methanol-toluene mixture of 6,6'-DPBHBNA. To obtain the desired methanol solvate, the 6,6'-DPBHBNA to be crystallized must have a purity of at least 97% by weight relative to organic matter other than the solvent. The 6,6'-DPBHBNA with a purity of at least 97% by weight is preferably dissolved in hot methanol or a hot methanol-toluene mixture. The methanol content in the mixture is preferably at least 50 w / w% and no more than 90 w / w%, based on the total weight of the solvent (mixture). In other words, the volume ratio of methanol to toluene is 1:1 to 9:1, particularly preferably 6:4 to 8:2, for example 7:3. Typically, the temperature of the high-temperature solution of 6,6'-DPBHBNA is at least 45°C, and can be as high as reflux temperature, particularly when the methanol content is high. The concentration of 6,6'-DPBHBNA in the high-temperature solution can vary depending on the amount of methanol used for crystallization. When the amount of methanol is high, a lower 6,6'-DPBHBNA concentration is generally acceptable. The concentration of 6,6'-DPBHBNA generally does not exceed 30% by weight, typically ranging from 2 to 25% by weight. Crystallization of the methanol solvate from the high-temperature solution is typically achieved by cooling the high-temperature solution to a temperature below 40°C, for example, from -10°C to below 40°C, or from -5 to 30°C. Seed crystals can be added at a temperature below 40°C, for example, from -5 to 30°C. The amount of seed crystals is typically 0.05 to 2% by weight, particularly 0.1 to 1% by weight, based on the amount of 6,6'-DPBHBNA crystallized as the methanol solvate. The time required to complete crystallization of the methanol solvate varies depending on the concentration of 6,6'-DPBHBNA and the temperature used, but is typically in the range of 4 to 24 hours. Crystallization of the methanol solvate can also be achieved by concentrating the high-temperature solution, or by a combination of concentration and cooling. Concentration of the solution can be achieved by distilling off a portion of the solvent.

[0353] Methanol solvates can be obtained by crystallization as compact crystals with a low aspect ratio. The aspect ratio of methanol solvates is typically less than 5, more specifically, within the range of 1 to 4. The crystal size typically ranges from 5 to 200 μm. The solvate crystal size, like the unsolvated crystal size, can be determined by visual inspection at 100x magnification using an optical microscope. The size ranges given here refer to the longest dimension of the crystal.

[0354] Crystallization of the methanol solvate tends not to enclose a significant amount of mother liquor. Therefore, the crystalline solvate of 6,6'-DPBHBNA with methanol can increase the purity of 6,6'-DPBHBNA to at least 99%, further to at least 99.5% or higher, and more preferably to 99.7% or higher. This means that, as described above, the total amount of impurities other than methanol in the methanol solvate does not exceed 1% by weight, particularly 0.5% by weight, and more preferably, does not exceed 0.3% by weight.

[0355] On the other hand, the methanol solvate crystals described above are very easily decomposed by prolonged drying. While drying at high temperatures is preferred, they can be decomposed at temperatures below the melting point of the methanol solvate. Therefore, a new crystalline polymorph of 6,6'-DPBHBNA can be obtained that is essentially free of organic solvent and cannot be obtained by crystallization from a solution of 6,6'-DPBHBNA. This crystalline polymorph is hereinafter referred to as crystalline Form A of 6,6'-DPBHBNA, or simply Form A. Form A, because it does not contain a significant amount of solvent, is particularly useful in the production of the thermoplastic resin of the present invention.

[0356] Form A typically contains no more than 0.1 mol of organic solvent per mol of 6,6'-DPBHBNA, and particularly no more than 0.05 mol of solvent. The total amount of organic solvent in Form A is typically less than 1 wt%. Furthermore, the amount of methanol in Form A is typically less than 0.1 wt%.

[0357] In the X-ray powder diffraction pattern recorded by irradiation with Cu Kα1 rays at 22°C, Form A generally shows the following six reflection peaks as 2θ values, namely, 13.0±0.2°, 14.9±0.2°, 20.9±0.2°, 21.4±0.2°, 21.5±0.2°, and 23.7±0.2°;

[0358] showing as 2θ values ​​at least 5, in particular at least 7, at least 9 or all of the following reflection peaks: 6.5±0.2°, 8.6±0.2°, 11.0±0.2°, 13.2±0.2°, 14.9±0.2°, 16.2±0.2°, 17.3±0.2°, 17.8±0.2°, 18.4±0.2° and 19.0±0.2°; and

[0359] Optionally, 1, 2, 3, 4, 5, 6, 7, 8 or 9 reflection peaks are shown as 2θ values ​​among the following: 9.4±0.2°, 10.4±0.2°, 15.5±0.2°, 22.5±0.2°, 22.9±0.2°, 24.5±0.2°, 25.9±0.2°, 27.8±0.2° and 30.8±0.2°.

[0360] Form A can also be characterized by an endothermic peak indicating its dissolution. When analyzed by DSC according to ISO 11357-3:2018 at a heating rate of 20 K / min, Form A typically exhibits an endothermic peak with an onset in the range of 112-114°C and a peak maximum in the range of 124-126°C. Furthermore, the reaction point is typically in the range of 117-120°C.

[0361] Form A can be obtained by decomposition of a methanol solvate as a compact crystalline form with a low aspect ratio. The aspect ratio of the crystals of Form A is generally less than 5, and more specifically in the range of 1 to 4. The crystal size of Form A is generally in the range of 5 to 200 μm, and the crystal size of the solvate form can be obtained by visual inspection using an optical microscope at 100 times magnification. The decomposition of the methanol solvate generally occurs by long-term drying. Although drying is preferably performed at a high temperature, decomposition can occur at a temperature lower than the melting point of the methanol solvate. Typically, drying is performed until the amount of methanol in the obtained 6,6'-DPBHBNA is less than 0.1% by weight. Drying is performed at a temperature range of 30°C to 95°C, and in particular can be performed at 30°C to 70°C.

[0362] Crystals of Form A of 6,6'-DPBHBNA typically have a purity of at least 99%, further preferably at least 99.5% or higher, and further preferably 99.7% or higher. As described above, this means that the total amount of impurities other than the solvent in Form A does not exceed 1% by weight, particularly not more than 0.5% by weight, and further not more than 0.3% by weight. Particularly in Form A, the total amount of impurities selected from 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bishydroxy-6,6'-diphenyl-1,1'-binaphthyl, and 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthyl is generally 5000 ppm or less, preferably 4000 ppm or less, particularly preferably 3000 ppm or less, and even more preferably 2000 ppm or less, based on 1 part by weight of 6,6'-DPBHBNA contained in the crystals of Form A. In particular, the weight of each of these impurities is 2000 ppm or less, more preferably 1500 ppm or less, and even more preferably 1000 ppm or less, based on 1 part by weight of 6,6'-DPBHBNA contained in the crystals of Form A. When Form A contains bis[2-[[1-[2-(2-hydroxyethoxy)-6-phenyl-1-naphthyl]-6-phenyl-2-naphthyl]-oxy]-ethyl] carbonate, the amount thereof is usually not more than 2000 ppm, and may be a maximum of 1500 ppm or less, based on 1 part by weight of 6,6'-DPBHBNA contained in the crystals of Form A.

[0363] In addition, a specific embodiment of the present invention relates to a crystalline 6,6'-DPBHBNA, which is a mixture of a crystalline methanol solvate of 6,6'-DPBHBNA and form A. The mixture is usually obtained by incomplete decomposition of the methanol solvate. The mixture is characterized by showing reflection peaks of both the methanol solvate and form A in the X-ray powder diffraction pattern. In particular, the mixture shows the following three reflection peaks as 2θ values ​​in the X-ray powder diffraction pattern recorded by irradiation with Cu Kα1 rays at 22°C, namely, 20.9±0.2°, 21.4±0.2° and 23.7±0.2°; and

[0364] at least 5, at least 7, at least 9 of the following: 6.2 ± 0.2°, 6.5 ± 0.2°, 8.6 ± 0.2°, 9.0 ± 0.2°, 10.6 ± 0.2°, 11.0 ± 0.2°, 13.2 ± 0.2°, 14.9 ± 0.2°, 16.2 ± 0.2°, 16.9 ± 0.2°, 17.3 ± 0.2°, 17.8 ± 0.2°, 18.2 ± 0.2°, 18.4 ± 0.2°, 18.5 ± 0.2°, 19.0 ± 0.2°, 19.2 ± 0.2°, 19.6 ± 0.2°, 20.9 ± 0.2°, 22.7 ± 0.2°, 24.3 ± 0.2°, 24.9 ± 0.2°, 26.2 ± 0.2°, 28.7 ± 0.2°, and 30.5 ± 0.2°;

[0365] The other reflection peaks described above observed in the methanol solvate and Form A can also be arbitrarily shown.

[0366] For a mixture of the methanol solvate and Form A, when analyzed using DSC recorded in accordance with ISO 11357-3:2018 at a temperature increase rate of 20 K / minute, generally, 2 endothermic peaks are observed. One peak has an onset point in the range of 97 to 101°C, and a peak maximum in the range of 108 to 115°C, and the second peak has an onset point in the range of 112 to 114°C, and a peak maximum in the range of 124 to 126°C.

[0367] The mixture of the methanol solvate and Form A generally has a purity of at least 99%, further at least 99.5% or more, still further 99.7% or more. In the mixture, the total amount of impurities selected from 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-dihydroxy-6,6'-diphenyl-1,1'-binaphthyl, and 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthyl, based on 1 part by weight of 6,6'-DPBHBNA contained in the mixture of the methanol solvate and Form A, is generally at most 5000 ppm or less, preferably at most 4000 ppm or less, particularly preferably at most 3000 ppm or less, further preferably at most 2000 ppm or less.

[0368] Another specific mode of the present application relates to a crystalline solvate of 6,6'-DPBHBNA with toluene, which is referred to as toluene solvate hereinafter.

[0369] In the toluene solvate, the amount of toluene is generally in the range of 0.3 to 1.5 mol, particularly in the range of 0.3 to 1.2 mol, and further in the range of 0.3 to 0.5 mol per 1 mol of 6,6'-DPBHBNA.

[0370] In the X-ray powder diffraction pattern recorded by irradiation with Cu Kα1 rays at 22°C, the toluene solvate generally shows the following three reflection peaks as 2θ values, namely, 5.2±0.2°, 7.7±0.2°, and 21.6±0.2°; and

[0371] The 2θ values ​​of the present invention include at least three, particularly at least five, at least seven or all of the following reflection peaks: 8.2±0.2°, 9.1±0.2°, 10.6±0.2°, 10.8±0.2°, 11.6±0.2°, 12.6±0.2°, 13.6±0.2°, 14.7±0.2°, 15.0±0.2°, 15.7±0.2°, 16.7±0.2°, 17. .1±0.2°, 18.0±0.2°, 18.5±0.2°, 19.4±0.2°, 19.9±0.2°, 20.8±0.2°, 21.0±0.2°, 22.2±0.2°, 22.7±0.2°, 24.1±0.2°, 25.0±0.2°, 25.7±0.2°, 26.5±0.2°, 27.1±0.2° and 27.6±0.2°.

[0372] Toluene solvates can also be characterized by an endothermic peak indicating their decomposition. When analyzed by DSC according to ISO 11357-3:2018 at a heating rate of 20 K / min, toluene solvates typically exhibit an endothermic peak with an onset in the range of 105-108°C and a peak maximum in the range of 112-115°C. Furthermore, the reaction point is typically in the range of 109-112°C.

[0373] Toluene solvates can be obtained by crystallizing 6,6'-DPBHBNA from a hot toluene solution containing no more than 5% by weight of other organic solvents, particularly no more than 1% by weight of methanol. To obtain the desired toluene solvate, the 6,6'-DPBHBNA to be crystallized must have a purity of at least 97% by weight with respect to organic matter other than the solvent. Preferably, 6,6'-DPBHBNA with a purity of at least 97% by weight is dissolved in hot toluene. The hot solution of 6,6'-DPBHBNA is typically at least 60°C, and can be as high as reflux. The concentration of 6,6'-DPBHBNA in the hot solution is typically no more than 50% by weight, typically ranging from 10 to 40% by weight. Crystallization of the toluene solvate from the hot solution is typically achieved by cooling the hot solution to a temperature below 50°C, for example, from -10°C to below 50°C, or from -5 to 40°C. Seed crystals may be added at a temperature below 50°C, for example, from -5 to 40°C. The amount of seed crystals is typically 0.05 to 2% by weight, particularly 0.1 to 1% by weight, based on the amount of 6,6'-DPBHBNA crystallized as a toluene solvate. The time required to complete the crystallization of the toluene solvate varies depending on the concentration of 6,6'-DPBHBNA and the temperature used, but is typically in the range of 4 to 24 hours. Crystallization of the toluene solvate can also be achieved by concentrating the high-temperature solution, or by a combination of concentration and cooling. Concentration of the solution can be achieved by distilling off some of the toluene.

[0374] Toluene solvates can be obtained by crystallization in the form of compact crystals with a low aspect ratio. The aspect ratio of toluene solvates is typically less than 5, more specifically, in the range of 1 to 4. The crystal size is typically in the range of 5 to 300 μm. Crystals of toluene solvates tend not to enclose significant amounts of mother liquor. Therefore, crystalline solvates of 6,6'-DPBHBNA and toluene can increase the purity of 6,6'-DPBHBNA to at least 99%, further to at least 99.5%, or even higher, and further to 99.7% or higher.

[0375] Another specific embodiment of the present invention relates to a crystalline solvate of 6,6'-DPBHBNA and methyl ethyl ketone (MEK), which is hereinafter referred to as MEK solvate.

[0376] In the MEK solvate, the amount of MEK is generally in the range of 0.3 to 1.5 mol, particularly in the range of 0.4 to 1.0 mol, and further in the range of 0.5 to 0.8 mol per 1 mol of 6,6'-DPBHBNA.

[0377] In an X-ray powder diffraction pattern recorded by irradiation with Cu Kα1 rays at 22°C, MEK solvate generally shows the following three reflection peaks as 2θ values, namely, 7.0±0.2°, 16.8±0.2°, and 23.4±0.2°; and

[0378] The invention also shows at least three, in particular at least five, at least seven or all of the following reflection peaks as 2θ values: 5.0±0.2°, 7.5±0.2°, 12.6±0.2°, 13.4±0.2°, 14.5±0.2°, 15.4±0.2°, 15.7±0.2°, 18.3±0.2°, 19.4±0.2°, 20.6±0.2°, 21.5±0.2°, 22.7±0.2°, 24.1±0.2°, 25.6±0.2°, 26.2±0.2°, 26.6±0.2° and 30.8±0.2°.

[0379] MEK solvates can also be characterized by an endothermic peak indicating their decomposition. When analyzed by DSC according to ISO 11357-3:2018 at a heating rate of 20 K / min, MEK solvates typically exhibit an endothermic peak with an onset in the range of 87-91°C and a peak maximum in the range of 95-100°C. Furthermore, the reaction point is typically in the range of 94-98°C.

[0380] MEK solvates can be obtained by crystallizing 6,6'-DPBHBNA from a hot MEK solution containing no more than 5% by weight of other organic solvents, particularly no more than 0.5% by weight of methanol. To obtain the desired MEK solvate, the 6,6'-DPBHBNA to be crystallized must have a purity of at least 97% by weight with respect to organic matter other than the solvent. 6,6'-DPBHBNA with a purity of at least 97% by weight is preferably dissolved in hot MEK. The hot solution of 6,6'-DPBHBNA is typically at least 60°C, and can be as high as reflux. The concentration of 6,6'-DPBHBNA in the hot solution is typically no more than 50% by weight, typically ranging from 10 to 40% by weight. Crystallization of the MEK solvate from the hot solution is typically achieved by cooling the hot solution to a temperature below 50°C, for example, to a temperature ranging from -10°C to below 50°C, or from -5 to 40°C. Seed crystals may be added at a temperature below 50°C, for example, in the range of -5 to 40°C. The amount of seed crystals is typically 0.05 to 2% by weight, particularly 0.1 to 1% by weight, based on the amount of 6,6'-DPBHBNA crystallized as the MEK solvate. The time required to complete the crystallization of the MEK solvate varies depending on the concentration of 6,6'-DPBHBNA and the temperature used, but is typically in the range of 4 to 24 hours. Crystallization of the MEK solvate can also be achieved by concentrating the high-temperature solution, or by a combination of concentration and cooling. Concentration of the solution can be achieved by distilling off a portion of the MEK.

[0381] MEK solvates can be obtained by crystallization in the form of compact crystals with a low aspect ratio. The aspect ratio of MEK solvates is typically less than 5, more specifically, in the range of 1 to 4. The size of the crystals is typically in the range of 1 to 300 μm. Crystals of MEK solvates tend not to enclose significant amounts of mother liquor. Therefore, the crystalline solvate of 6,6'-DPBHBNA and MEK can increase the purity of 6,6'-DPBHBNA to at least 99%, further to at least 99.5% or higher, and further to 99.7% or higher.

[0382] Although the above-mentioned crystalline forms of 6,6'-DPBHBNA have high purity, they can also be converted into amorphous form B. Amorphous form B is stable and has no tendency to crystallize even after long-term storage or after being crushed by grinding. Amorphous form B is prepared by melting any crystalline form and then rapidly cooling it. Preferably, each crystalline form is heated to a temperature at least 5K higher than its melting point until it is completely melted to obtain a clear melt. If a solvate is used as a starting material to prepare the melt, it is preferably that all the solvent is removed by vacuuming. Thereafter, the melt is preferably rapidly cooled at a cooling rate of at least 5K / min, for example, at a cooling rate of 5 to 50K / min. In this way, form B can be obtained as a solid amorphous (glass). To obtain a powder, the amorphous can be crushed by, for example, grinding. To prevent crystallization, the comminution operation is carried out at a temperature significantly lower than 100°C, for example, in the range of 5 to 40°C. In this powder, the particles still exist in the amorphous form B.

[0383] In the X-ray powder diffraction pattern recorded by irradiation with Cu Kα1 rays at 22°C, Form B generally does not show reflection peaks as 2θ values ​​at multiple diffraction angles in the range of 5° to 40°. Instead, a broad halo is observed, indicating that there is substantially no crystalline layer.

[0384] Form B is also characterized by not exhibiting an endothermic peak in the 80-200°C range when analyzed by DSC according to ISO 11357-3:2018 at a heating rate of 20 K / min. In contrast, amorphous Form B exhibits a glass transition temperature of 105-125°C under these conditions.

[0385] Amorphous Form B of 6,6'-DPBHBNA typically has a purity of at least 99%, further preferably at least 99.5% or higher, and more preferably at least 99.7%. As described above, this means that the total amount of impurities other than the solvent in Form B does not exceed 1% by weight, particularly not more than 0.5% by weight, and further not more than 0.3% by weight. In particular, in Form B, the total amount of impurities selected from 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bishydroxy-6,6'-diphenyl-1,1'-binaphthyl, and 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthyl is generally 5000 ppm or less, preferably 4000 ppm or less, particularly preferably 3000 ppm or less, and even more preferably 2000 ppm or less, based on 1 part by weight of 6,6'-DPBHBNA contained in the crystals of Form B. In particular, the weight of each of these impurities is 2000 ppm or less, more preferably 1500 ppm or less, and even more preferably 1000 ppm or less, based on 1 part by weight of 6,6'-DPBHBNA contained in the crystals of amorphous Form B. When the amorphous form B contains bis[2-[[1-[2-(2-hydroxyethoxy)-6-phenyl-1-naphthyl]-6-phenyl-2-naphthyl]-oxy]-ethyl] carbonate, the amount thereof is usually not more than 2000 ppm based on 1 part by weight of 6,6'-DPBHBNA contained in the crystals of the amorphous form B, and may be a maximum of 1500 ppm or less.

[0386] Surprisingly, crystallization from an ethanol solution of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl yielded not an ethanol solvate of 6,6′-DPBHBNA, but a novel polymorph of 6,6′-DPBHBNA, hereinafter referred to as Form C. Form C, because it does not contain a significant amount of solvent, is particularly useful in the production of the thermoplastic resin of the present invention.

[0387] Form C typically does not contain more than 0.1 mol of organic solvent per mol of 6,6'-DPBHBNA, and particularly does not contain more than 0.05 mol of solvent. The total amount of organic solvent in Form C is typically less than 1 wt%, particularly a maximum of 0.5 wt%, or a maximum of 0.1 wt%.

[0388] In the X-ray powder diffraction pattern recorded by irradiation with Cu Kα1 rays at 22°C, Form C generally shows the following three reflection peaks as 2θ values, namely, 5.1±0.2°, 7.6±0.2°, and 21.0±0.2°; and

[0389] The invention shows at least three, particularly preferably at least five, at least seven or all of the following reflection peaks as 2θ values: 8.2±0.2°, 9.2±0.2°, 10.4±0.2°, 10.8±0.2°, 11.6±0.2°, 12.8±0.2°, 13.4±0.2°, 14.5±0.2°, 15.2±0.2°, 15.6±0.2°, 16.6±0. 2°, 17.4±0.2°, 17.9±0.2°, 18.5±0.2°, 19.2±0.2°, 19.9±0.2°, 20.4±0.2°, 21.8±0.2°, 22.2±0.2°, 22.6±0.2°, 13.4±0.2°, 24.0±0.2°, 25.7±0.2°, 27.3±0.2° and 27.9±0.2°.

[0390] The X-ray powder diffraction pattern of Form C is substantially the same as that of the toluene solvate, indicating that the molecules of 6,6′-DPBHBNA in Form C and the toluene solvate have the same arrangement in the crystal lattice.

[0391] Form C can also be characterized by an endothermic peak indicating its dissolution. When analyzed by DSC according to ISO 11357-3:2018 at a heating rate of 20 K / min, Form C typically exhibits an endothermic peak with an onset in the range of 115-118°C and a peak maximum in the range of 124-126°C. Furthermore, the reaction point is typically in the range of 120-122°C.

[0392] Form C can be obtained by crystallizing 6,6'-DPBHBNA from hot ethanol. To obtain the desired Form C, the 6,6'-DPBHBNA to be crystallized typically must have a purity of at least 97% by weight, including organic matter other than the solvent. Preferably, 6,6'-DPBHBNA with a purity of at least 97% by weight is dissolved in hot ethanol. The hot 6,6'-DPBHBNA solution is typically at least 45°C, and can be as high as reflux. The concentration of 6,6'-DPBHBNA in the hot solution typically does not exceed 30% by weight, typically ranging from 2 to 25% by weight. Crystallization of Form C from the hot solution is typically achieved by cooling the hot solution to a temperature below 40°C, for example, from -10°C to below 40°C, or from -5 to 30°C. Seed crystals may be added at a temperature below 40°C, for example, from -5 to 30°C. The amount of seed crystals is typically 0.05 to 2% by weight, particularly 0.1 to 1% by weight, based on the amount of 6,6'-DPBHBNA crystallized as Form C. The time required to complete the crystallization of Form C varies depending on the concentration of 6,6'-DPBHBNA and the temperature used, but is typically in the range of 4 to 24 hours. Crystallization of Form C can also be achieved by concentrating the high-temperature solution, or by a combination of concentration and cooling. Concentration of the solution can be achieved by distilling off a portion of the solvent.

[0393] Form C can be obtained by crystallization as compact crystals with a low aspect ratio. The aspect ratio of Form C is typically less than 5, and is generally in the range of 1 to 4. The crystal size is generally in the range of 2 to 250 μm.

[0394] Form C crystals tend not to contain a significant amount of mother liquor. Therefore, Form C crystals of 6,6'-DPBHBNA can increase the purity of 6,6'-DPBHBNA to at least 99%, further at least 99.5% or higher, and more preferably at least 99.7% or higher. As described above, this means that the total amount of impurities other than solvent in Form C does not exceed 1% by weight, particularly 0.5% by weight, and more preferably, does not exceed 0.3% by weight. In particular, in Form C, the total amount of impurities selected from 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bishydroxy-6,6'-diphenyl-1,1'-binaphthyl, and 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthyl is generally 5000 ppm or less, preferably 4000 ppm or less, particularly preferably 2000 ppm or less, and even more preferably 1000 ppm or less, based on 1 part by weight of 6,6'-DPBHBNA contained in the Form C crystals. In particular, the weight of each of these impurities is 2000 ppm or less, more preferably 1500 ppm or less, and even more preferably 1000 ppm or less, based on 1 part by weight of 6,6'-DPBHBNA contained in the Form C crystals. When Form C contains bis[2-[[1-[2-(2-hydroxyethoxy)-6-phenyl-1-naphthyl]-6-phenyl-2-naphthyl]-oxy]-ethyl] carbonate, the amount thereof is usually not more than 2000 ppm based on 1 part by weight of 6,6'-DPBHBNA contained in the Form C crystals, and may be a maximum of 1500 ppm or less.

[0395] The solid forms of 6,6'-DPBHBNA of the present invention, namely, the methanol solvate, toluene solvate, methyl ethyl ketone solvate, and crystalline Forms A and C, similar to amorphous Form B, also have a yellowness index (YI) as low as typically less than 3.0, sometimes less than 2.5 or less than 2.0, particularly less than 1.5, further less than 1.0 or less than 0.75, and even less than 0.5. All YI values ​​are measured using a 5 w / w% dichloromethane solution of 6,6'-DPBHBNA in accordance with ASTM E 313.

[0396] The solid form of 6,6'-DPBHBNA of the present invention typically has a low haze of less than 1.0 ntu, and sometimes less than 0.8 ntu or less than 0.6 ntu, when measured using a 5 w / w% dichloromethane solution of 6,6'-DPBHBNA. Turbidity is measured using a 5 w / w% dichloromethane solution of 6,6'-DPBHBNA and expressed in nephelometric turbidity units (ntu). The haze of the crystalline solid of 6,6'-DPBHBNA of the present invention can be further reduced to, for example, 0.4 ntu, less than 0.35 ntu, less than 0.30 ntu, and can even be as low as 0.2 ntu or less.

[0397] The thermoplastic resin of the present invention, ie, polyester resin, polyester carbonate resin, polycarbonate resin, or a mixture of at least two of these resins, is preferably produced from a monomer having a predetermined amount of impurities, purity, and the like.

[0398] For example, if the dihydroxy compound represented by the general formula (6) is in the form of a crystalline solvate, it is preferable to use an organic solvent containing 0.3 to 1.2 moles per 1 mole of the dihydroxy compound in the crystals to produce the thermoplastic resin. Examples of the organic solvent include methanol, toluene, and methyl ethyl ketone.

[0399] When a monomer containing an organic solvent in an appropriate content range as described above is used as the monomer of formula (6), a thermoplastic resin can be efficiently produced. For example, when a monomer containing an organic solvent in an amount of about 0.3 to 1.2 mol, 0.3 to 1.0 mol, or 0.3 to 0.5 mol per 1 mol of the dihydroxy compound is used to produce a thermoplastic resin, scattering of the monomer can be prevented, and a high-purity thermoplastic resin can be produced.

[0400] When the dihydroxy compound represented by the general formula (6) is in a crystalline form, a compound containing less than 0.1 mol of an organic solvent in the crystals may be used to produce a thermoplastic resin.

[0401] Among the dihydroxy compounds in crystalline form, those having an aspect ratio of at most 5:1 can be used. For example, crystals having an aspect ratio of at most 3:1 or at most 1:1 can be used.

[0402] As the dihydroxy compound represented by the general formula (6), a compound having a purity of at least 99.0% by weight (or higher) based on an organic substance is preferably used, preferably a compound having a purity of 99.5% by weight or higher, and particularly preferably a compound having a purity of 99.7% by weight. Furthermore, a thermoplastic resin can be produced using the dihydroxy compound of the general formula (6) containing less than 0.1 mol of an organic solvent, for example, less than 0.05 mol of an organic solvent, and preferably less than 0.03 mol of an organic solvent.

[0403] The dihydroxy compound represented by general formula (6) preferably has a yellowness index (YI) value of less than 3.0, more preferably less than 2.0, and even more preferably less than 1.0, as measured using a 5 w / w % dichloromethane solution according to ASTM E313.

[0404] The dihydroxy compound represented by the general formula (6) preferably has a haze measured using a 5 w / w% dichloromethane solution of less than 1.0 ntu, more preferably less than 0.7 ntu, and even more preferably less than 0.5 ntu.

[0405] When a thermoplastic resin is produced using any dihydroxy compound represented by general formula (6), the total amount of impurities such as dihydroxy compounds other than the dihydroxy compound, for example, impurities having a similar molecular structure, is preferably less than 0.5% by weight, more preferably less than 0.3% by weight, and even more preferably less than 0.1% by weight, based on the weight of the dihydroxy compound.

[0406] For example, when 6-6'DPBHBNA is used as a monomer, the total amount of impurities such as 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bishydroxy-6,6'-diphenyl-1,1'-binaphthyl, and 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthyl is preferably less than 0.5% by weight, more preferably less than 0.3% by weight, and even more preferably less than 0.1% by weight, based on the weight of 6-6'DPBHBNA.

[0407] When the impurity content of a specific dihydroxy compound is 0.5% by mass or more, the reaction efficiency may be reduced, and the final molecular weight may be reduced. In addition, when the impurity contains a large number of hydroxyethoxy groups and a large number of repeating impurities, the refractive index of the resulting thermoplastic resin tends to be reduced.

[0408] On the other hand, the impurities in the specific dihydroxy compound are less than 0.5% by mass. When contained, a structure similar to the basic structure is contained in the resin, and the moldability is improved by reducing the melt viscosity, that is, there is a tendency for the flow of the resin to become better, and the impact resistance of the molded body such as the optical lens to be improved.

[0409] For example, the impurities are preferably contained in an amount not exceeding 1 ppb to 5000 ppm based on 1 part by weight of the monomer of formula (6).

[0410] In addition, it is preferred to use a monomer of formula (6) having an impurity content of less than 0.5% by mass, for example, to use a monomer containing a structural unit derived from an impurity selected from 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-dihydroxy-6,6'-diphenyl-1,1'-binaphthyl and 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthyl in an amount of less than 0.5% by weight, to produce a resin, a resin composition, an optical lens, an optical film, etc.

[0411] Furthermore, the thermoplastic resin preferably has properties particularly suitable for optical applications, for example, preferably a good balance between refractive index and Abbe number. Specifically, the thermoplastic resin preferably has a refractive index higher than 1.660, more preferably higher than 1.668, and an Abbe number lower than 19, for example, 13 or higher and lower than 19, or 15 or higher and lower than 19. Furthermore, in addition to satisfying the above-mentioned refractive index and Abbe number conditions, it is preferred that the refractive index nD and the Abbe number ν also satisfy the relationship: -0.0002ν + 1.6718 < nD < -0.024ν + 2.124. It is more preferred that the refractive index nD and the Abbe number ν also satisfy the relationship: -0.004ν + 1.744 < nD < -0.024ν + 2.124. It is even more preferred that the refractive index nD and the Abbe number ν also satisfy the relationship: -0.02ν + 2.04 < nD < -0.024ν + 2.124.

[0412] In the thermoplastic resin having the structural unit represented by the general formula (1) of the present invention, in addition to the compound represented by the general formula (6), an aromatic dihydroxy compound or an aliphatic dihydroxy compound (e.g., a dihydroxy compound having a fluorene skeleton or binaphthols) can be used as a dihydroxy component.

[0413] The thermoplastic resin of the present invention can preferably be produced by using, in addition to the compound represented by the above-mentioned general formula (6), a compound represented by the following general formula (7) and / or a compound represented by the following general formula (8) as a dihydroxy component.

[0414]

[0415] Among them, R'1~R' in formula (7) 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,

[0416] 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,

[0417] c and d are integers of 1 to 10 respectively.

[0418] In addition, R1 to R2 in formula (8) 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,

[0419] 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,

[0420] e and f are integers of 1 to 10 respectively.

[0421] Examples of the dihydroxy compound represented by formula (7) include 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(3-hydroxypropyloxy)-1,1'-binaphthyl, and 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthyl. Among these, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl is preferred. These can be used alone or in combination of two or more.

[0422] Examples of the dihydroxy compound represented by formula (8) 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-isopropylphenyl]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 can be used alone or in combination of two or more.

[0423] For example, examples of the dihydroxy compound represented by formula (7) or (8) include compounds represented by the following general formula (9).

[0424]

[0425] In addition, the monomer used to produce the thermoplastic resin may contain, together with the dihydroxy compound represented by the above general formula (6), a dihydroxy compound in which the values ​​of c and d in the above general formula (6) are both 0, or a dihydroxy compound in which either one of c and d in the above general formula (6) is 0 as an impurity.

[0426] Thus, the total amount of dihydroxy compounds in which the value of at least any one of c and d is different from that of the above-mentioned general formula (6) is preferably 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 content of dihydroxy compounds in which the value of at least any one of c and d is different from that of the above-mentioned general formula (6) in the above-mentioned monomer is preferably 50 ppm or less, and more preferably 20 ppm or less.

[0427] The content of impurities related to the general formula (6) is also the same in the dihydroxy compound represented by the general formula (7) or (8). That is, together with the dihydroxy compound represented by the general formula (7) or (8), a dihydroxy compound in which both the values ​​of e and f in the general formula (7) or (8) are 0, or a dihydroxy compound in which either one of e and f in the general formula (7) or (8) is 0 may be contained as an impurity.

[0428] Furthermore, the total amount of these impurities in the monomer having the dihydroxy compound represented by the above-mentioned general formula (7) or (8) as the main component is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 200 ppm or less, and particularly preferably 100 ppm or less. Moreover, the total content of the above-mentioned impurities in the above-mentioned monomer is preferably 50 ppm or less, and more preferably 20 ppm or less.

[0429] The compounds of the general formulae (7) and (8) can be produced by various synthetic methods. For example, as described in Japanese Patent No. 5442800 and Japanese Patent Application Laid-Open No. 2014-028806, 9,9-bis(hydroxynaphthyl)fluorenes are 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 an alkylthiol), (c) reacting fluorenones with hydroxynaphthalenes in the presence of hydrochloric acid and a thiol (such as mercaptocarboxylic acid), and (d) reacting fluorenones with hydroxynaphthalenes in the presence of sulfuric acid and a thiol (such as mercaptocarboxylic acid) followed by crystallization using a crystallization solvent composed of a hydrocarbon and a polar solvent. These can be produced by reacting these with a compound corresponding to the [XO]a group and the [XO]b group (such as an alkylene oxide and a haloalkanol). 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.

[0430] 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.

[0431] (Vinyl terminal group amount)

[0432] The thermoplastic polyester resin, polyester carbonate resin, and polycarbonate resin of the present invention are obtained by using compounds represented by the above-mentioned general formulas (6) to (9) as dihydroxy components and reacting them with carbonate precursors such as carbonic acid diesters. However, during the polymerization process for producing thermoplastic resins such as polycarbonates, impurities may be generated in which one or both of the terminal -OROH groups of the compounds represented by the above-mentioned general formulas (6) to (9) are converted into vinyl terminal groups, such as -OC=CH groups.

[0433] For example, an impurity having a vinyl group represented by the following formula (v-1) may be present in the monomer, resin, resin composition, optical lens, and optical film described in the specification of the present application.

[0434]

[0435] (Where, * represents a polymer chain, and Hp represents a hydrogen atom)

[0436] (V-1)

[0437] These vinyl groups can be generated and contained in monomers during monomer synthesis and refining. Alternatively, they can be generated and increased during resin polymerization and additive mixing. While these vinyl groups are believed to contribute to polymer coloration, they can also, at trace levels, improve the flexural strength and impact resistance of the resin.

[0438] The amount of impurities having such a vinyl terminal structure is usually very small, and the produced polymer can be used as a thermoplastic resin without purification.

[0439] For example, the amount of vinyl groups in the polycarbonate resin can be determined by performing the following calculations as described in <9. Amount of vinyl terminal groups in polycarbonate resin>. 1 The content is determined by the integrated ratio of the following formula (A) in H-NMR measurement: The amount of terminal vinyl groups is preferably 0.0001 to 5.0, more preferably 0.01 to 3.0, and even more preferably 0.1 to 1.0.

[0440]

[0441] However, Hk in the above formula (A) refers to Hk in the following formula (v-2) corresponding to the above formula (v-1).

[0442]

[0443] (where Hk represents a hydrogen atom)

[0444] (V-2)

[0445] In addition, in the resin of the present application, sometimes an oligomer with a molecular weight (Mw) of less than 1000 or a cyclic structure formed by two or more monomers bonded to each other by carbonates is formed. Such oligomers and cyclic bodies can be analyzed by LC-MS etc., and for example, preferably contain less than 2.5% by mass, more preferably contain less than 2.0% by mass, and even more preferably contain less than 1.0% by mass in total.

[0446] Regarding the metals contained in the monomer, the total amount of Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn is preferably 1000 wtppm or less (e.g., 100 wtppm, 10 wtppm).

[0447] Regarding the metals in the obtained resin or resin composition, the total content of Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn, and Sn is preferably 1000 ppm by weight or less.

[0448] When the metal concentration is 1000 ppm by weight or less, the resulting resin exhibits minimal coloration, minimizing concerns about decreased catalyst activity during polymerization. Furthermore, by preferably containing 1 ppb by weight or more (more preferably 1 ppm by weight or more), catalyst addition can be omitted. By utilizing the catalytic effect, the amount of catalyst added may be reduced, potentially leading to lower production costs. Such metal concentrations can be measured, for example, by the following method.

[0449] <Metal Analysis>

[0450] After carbonization of the sample with sulfuric acid, the metal concentration was measured by ICP-MS.

[0451] Specifically, 2g of the sample was weighed into a synthetic quartz measuring cup. 2.5ml of sulfuric acid was added immediately before carbonization. During carbonization, 0.1ml of sulfuric acid was added and carbonized on a hot plate. The sample was then covered with a quartz dish and heated in an electric furnace at 500°C for 10 hours to achieve carbonization. Sulfuric acid was then added, heated to dry and solidify, and nitric acid was added, heated to dry and solidify, thereby performing thermal acid decomposition. A nitric acid aqueous solution was added to make up to 50ml, heated to 50°C, and quantitative analysis was performed using ICP-MS.

[0452] ICP-MS equipment: Shimadzu Corporation: ICPE-9000

[0453] Examples of carbonic acid diesters used in the production of polycarbonate resins and polyester carbonate resins include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresol carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Among these, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate used is preferably 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, relative to 1 mol of the total dihydroxy compound.

[0454] Furthermore, the dicarboxylic acid, monocarboxylic acid monoester, and diester compounds that can be used in the production of polyester resins and polyester carbonate resins are preferably used in a ratio of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, per 1 mol of the total dihydroxy compound.

[0455] Among the above-mentioned transesterification catalysts used in the production of thermoplastic resins, examples of basic compound catalysts include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.

[0456] Examples of the alkali metal compound used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylborate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium, dipotassium, dicesium, or dilithium salts of bisphenol A, and sodium, potassium, cesium, or lithium salts of phenol can be used.

[0457] Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds. 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, and magnesium phenylphosphate can be used.

[0458] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides and salts thereof, and amines. Specifically, quaternary ammonium hydroxides having an alkyl group, an aryl group, or the like, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine; secondary amines such as diethylamine and dibutylamine; primary amines such as propylamine and butylamine; imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; or bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0459] As the transesterification catalyst, salts of titanium, zinc, tin, zirconium, lead, etc. are preferably used, and these can be used alone or in combination.

[0460] Specifically, the transesterification catalyst that can be used includes alkoxytitanium such as tetrabutoxytitanium, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxy, zirconium acetylacetonate, zirconium oxyacetate, tetrabutoxyzirconium, lead (II) acetate, lead (IV) acetate, and the like.

[0461] These catalysts are used in an amount of 10 to 1 mol of the total dihydroxy compound. －9 ~10 －3 The molar ratio is preferably 10 －7 ~10 －4Molar ratios were used.

[0462] The melt polycondensation method is a method in which the above-mentioned raw materials and a catalyst are used to carry out melt polycondensation under heating and further under normal pressure or reduced pressure while removing by-products by an ester exchange reaction.

[0463] In the melt polycondensation of this composition system, it is desired to melt the compound represented by general formula (6) and the carbonic acid diester in a reaction vessel and then react under a state where the by-product monohydroxy compound is retained. In order to retain it, the reaction apparatus can be closed, or pressure can be controlled by decompression or pressurization. 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-product monohydroxy compound is distilled and removed immediately after its generation, the content of the high molecular weight body in the thermoplastic resin finally obtained is small. However, when the by-product monohydroxy compound is retained in the reaction vessel for a certain period of time, a resin with a high content of the high molecular weight body in the thermoplastic resin finally obtained can be obtained.

[0464] The melt polycondensation reaction can be carried out in a continuous or batch manner. The reaction apparatus used for the reaction can be a vertical type equipped with an anchor-type stirring paddle, a MAXBLEND stirring paddle, a ribbon-type stirring paddle, etc., or a horizontal type equipped with a paddle blade, a grid blade, a spectacle-type blade, etc., or an extruder type equipped with a screw. In addition, it is preferred to use a reaction apparatus formed by appropriately combining these reaction apparatuses in consideration of the viscosity of the polymer.

[0465] In the production method of the thermoplastic resin used in the present application, the catalyst can be removed or deactivated after the polymerization reaction in order to maintain thermal stability and hydrolytic stability. The method of deactivating the catalyst by adding a known acidic substance can be appropriately performed. 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, hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid; phosphite esters such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, mono-octyl phosphite; phosphoric acid esters such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, mono-octyl phosphate; phosphonic acids such as diphenyl phosphonic acid, dioctyl phosphonic acid, dibutyl phosphonic acid; phosphonic acid esters such as diethyl phenyl phosphonate; phosphines such as triphenyl phosphine, bis(diphenylphosphino)ethane; boronic acids such as boric acid, phenylboronic acid; aromatic sulfonic acid salts such as dodecylbenzenesulfonic acid tetrabutylphosphonium salt; organic halides such as stearoyl chloride, benzoyl chloride, p-toluenesulfonyl chloride; alkyl sulfates such as dimethyl sulfate; and organic halides such as benzyl chloride can be used. These deactivators are used in a range of 0.01 to 50 times the molar amount of the catalyst, and preferably in a range of 0.3 to 20 times the molar amount of the catalyst. When the amount of the deactivator is less than 0.01 times the molar amount of the catalyst, the deactivating effect is insufficient, and thus is not preferred. When the amount of the deactivator is more than 50 times the molar amount of the catalyst, the heat resistance of the resin is reduced, and the molded body tends to be colored, and thus is not preferred.

[0466] After the catalyst is deactivated, a step of removing low-boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350°C can be provided. In this step, a horizontal device equipped with a stirring blade having excellent surface renewal ability such as a paddle blade, a lattice blade, and a spectacle blade, or a thin film evaporator is suitably used.

[0467] The thermoplastic resin of the present application is desired to have as little foreign matter content as possible, and thus filtration of the molten raw material, filtration of the catalyst solution, and the like are suitably performed. The pore size of the filter is preferably 5 μm or less, and more preferably 1 μm or less. Furthermore, filtration of the produced resin through a polymer filter is suitably performed. The pore size of the polymer filter is preferably 100 μm or less, and more preferably 30 μm or less. In addition, the step of collecting the resin pellets must of course be performed in a low-dust environment, and is preferably at a level of 6 or less, and more preferably at a level of 5 or less.

[0468] In addition, as the molding method of the polycarbonate resin, in addition to injection molding, compression molding, casting, roll processing, extrusion molding, stretching, and the like can be exemplified, but are not limited thereto.

[0469] (4) Optical molded body

[0470] The thermoplastic resin of the present invention can be used to manufacture optical molded bodies. For example, it can be molded using any method such as injection molding, compression molding, extrusion molding, solution casting, etc. The thermoplastic resin of the present invention has excellent moldability and heat resistance, and therefore can be used particularly advantageously in optical lenses that require injection molding. During molding, the thermoplastic resin of the present invention can be mixed with other resins such as polycarbonate resins and polyester resins. In addition, additives such as antioxidants, processing stabilizers, light stabilizers, polymer metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, release agents, ultraviolet absorbers, plasticizers, and compatibilizers can also be mixed.

[0471] 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, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl) propionate. The antioxidant may be an ester of butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid), diethyl 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate, 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 thermoplastic resin is preferably 0.001 to 0.3 parts by weight based on 100 parts by weight of the thermoplastic resin.

[0472] 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, 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 diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, etc. The content of the phosphorus-based processing heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0473] Examples of sulfur-based process heat stabilizers include pentaerythritol tetrakis(3-laurylthiopropionate), pentaerythritol tetrakis(3-myristylthiopropionate), pentaerythritol tetrakis(3-stearylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate. The content of the sulfur-based process heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.2 parts by weight per 100 parts by weight of the thermoplastic resin.

[0474] The release agent preferably comprises at least 90% by weight of an ester of an alcohol and a fatty acid. Specifically, examples of the ester of an alcohol and a fatty acid include esters of monohydric alcohols and fatty acids, and partial or full esters of polyhydric alcohols and fatty acids. Preferred esters of monohydric alcohols and fatty acids are esters of monohydric alcohols having 1 to 20 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms. Furthermore, preferred partial or full esters of polyhydric alcohols and fatty acids are partial or full esters of polyhydric alcohols having 1 to 25 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms.

[0475] Specifically, examples of esters of monohydric alcohols and saturated fatty acids include octadecyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Examples of partial or full esters of polyhydric alcohols and saturated fatty acids include monoglyceryl stearate, monoglyceryl stearate, diglyceryl stearate, triglyceryl stearate, sorbitol monostearate, monoglyceryl behenate, monoglyceryl caprate, monoglyceryl laurate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenyl ester, sorbitan monostearate, 2-ethylhexyl stearate, and full or partial esters of dipentaerythritol such as dipentaerythritol hexastearate. 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 thermoplastic resin.

[0476] The UV absorber is preferably at least one selected from the group consisting of benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, cyclic imine-based UV absorbers, and cyanoacrylate-based UV absorbers. Specifically, any one of the UV absorbers listed below may be used alone, or two or more may be used in combination.

[0477] Examples of the benzotriazole-based 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. di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-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.

[0478] 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 sulfonate benzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0479] Examples of the triazine-based ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol.

[0480] Examples of the cyclic urethane-based ultraviolet absorbers 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'-diphenylene)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), etc.

[0481] 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.

[0482] 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 per 100 parts by weight of the thermoplastic resin. Within this range, the thermoplastic resin can be given sufficient weather resistance depending on the intended use.

[0483] The thermoplastic resin of the present invention has a high refractive index and a low Abbe number. Furthermore, in addition to optical lenses, it can also be preferably used as a structural or functional material for optical components such as transparent conductive substrates used in 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 mirrors, and displays.

[0484] The surface of the optical molded article may be provided with a coating such as an antireflection layer or a hard coat, as needed. The antireflection layer may be a single layer or multiple layers and may be organic or inorganic, preferably inorganic. Specific examples include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride.

[0485] (5) Optical lens

[0486] The optical lens that uses thermoplastic resin of the present invention to make has high refractive index, low Abbe number, and has high resistance to moisture and heat, therefore can be used in the field of telescope, binoculars, television projector etc., use expensive high refractive index glass lens at present, very useful.As required, preferably use with the form of aspheric lens.Aspheric lens can utilize 1 lens to make spherical aberration become zero in fact, therefore does not need to eliminate spherical aberration by combining multiple spherical lenses, can realize the reduction of lightweight and production cost.Therefore, aspheric lens is particularly useful as camera lens in optical lens.

[0487] The optical lens can be formed by any method such as injection molding, compression molding, injection compression molding, etc. The present invention can more easily produce a high refractive index low birefringence aspheric lens that is technically difficult to process using a glass lens.

[0488] In order to avoid foreign matter from entering the optical lens as much as possible, the molding environment must of course also be a low-dust environment, preferably below level 6, and more preferably below level 5.

[0489] (6) Optical film

[0490] The optical film produced using the thermoplastic resin of the present invention has excellent transparency and heat resistance and is therefore suitable for use in films for liquid crystal substrates, optical memory cards, and the like.

[0491] In order to minimize the mixing of foreign matter into the optical film, the molding environment must of course be a low-dust environment, preferably level 6 or lower, more preferably level 5 or lower.

[0492] [Abbreviation]

[0493] 6,6'-DPBHBNA: Bis-2,2'-(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-bisnaphthyl; 6,6'-DPMHBNA: 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-bisnaphthyl;

[0494] 6,6'-DPTHBNA: 2-(2-hydroxyethoxy)-2'-[(2-hydroxyethoxy)ethoxy]-6,6'-diphenyl-1,1'-bisnaphthyl;

[0495] %bw:% by weight;

[0496] DSC: differential scanning calorimetry;

[0497] LOD: Loss on drying;

[0498] mp: melting point;

[0499] MeOH: Methanol;

[0500] NaOH: sodium hydroxide;

[0501] NIR: near infrared;

[0502] PXRD: powder X-ray diffraction;

[0503] TLC: thin layer chromatography;

[0504] UPLC: Ultra Performance Liquid Chromatography.

[0505] [Example]

[0506] <1. Method for measuring weight average molecular weight (Mw)>

[0507] The polystyrene-equivalent weight-average molecular weight was determined based on a pre-prepared calibration curve for standard polystyrene according to JIS K 7252-3. Specifically, a calibration curve was created using a standard polystyrene (PStQuick MP-M, manufactured by Tosoh Corporation) with a known molecular weight (molecular weight distribution = 1). The elution time and molecular weight values ​​of each peak measured from the standard polystyrene were plotted, and a cubic approximation was performed to create a calibration curve. Mw was calculated using the following formula.

[0508] Mw=Σ(Wi×Mi)÷Σ(Wi)

[0509] Here, i represents the i-th cutoff point when dividing the molecular weight M, Wi represents the weight of the i-th unit, and Mi represents the molecular weight of the i-th unit. The molecular weight M refers to the polystyrene molecular weight value at the corresponding dissolution time on the calibration curve. The GPC apparatus used was a Tosoh Corporation HLC-8320GPC. A single TSK guardcolumn Super MPHZ-M guard column was used, and a column consisting of three TSK gel SuperMultipore HZ-M units connected in series was used as the analytical column. Other conditions are as follows.

[0510] Solvent: HPLC grade tetrahydrofuran

[0511] Injection volume: 10 μL

[0512] Sample concentration: 0.2w / v% HPLC grade chloroform solution

[0513] Solvent flow rate: 0.35ml / min

[0514] Measurement temperature: 40°C

[0515] Detector: RI

[0516] <2. Glass transition temperature (Tg)>

[0517] The measurement was performed using a differential scanning calorimeter (DSC) in accordance with JIS K7121-1987. Hitachi High-Technologies X-DSC7000 was used as the analyzer.

[0518] <3. Refractive Index (nD)>

[0519] The 0.1 mm-thick film composed of the resin produced in the Examples was measured using an Abbe refractometer in accordance with the method of JIS-K-7142.

[0520] <4. Abbe number (ν)>

[0521] The refractive index of a 0.1 mm thick film made of the resin produced in Examples at wavelengths of 486 nm, 589 nm, and 656 nm was measured at 23° C. using an Abbe refractometer, and the Abbe number was calculated using the following formula.

[0522] ν=(nD-1) / (nF-nC)

[0523] nD: refractive index at a wavelength of 589 nm

[0524] nC: refractive index at a wavelength of 656nm

[0525] nF: Refractive index at a wavelength of 486nm <5.b value>

[0526] The produced resin was vacuum-dried at 120°C for 4 hours and then injection-molded using an injection molding machine (FANUC ROBOSHOTα-S30iA) at a cylinder temperature of 270°C and a mold temperature of Tg-10°C to produce disc-shaped test plaques with a diameter of 50 mm and a thickness of 3 mm. These plaques were used to measure the b value according to JIS K7105. A smaller b value indicates less yellowishness and better hue. The molded plaques were measured using a Nippon Denshoku Industries SE2000 spectrophotometer.

[0527] <6. Pressure Cooker Test (PCT Test)>

[0528] The produced resin was vacuum-dried at 120°C for 4 hours and then injection-molded using an injection molding machine (FANUC ROBOSHOTα-S30iA) at a cylinder temperature of 270°C and a mold temperature set at 10°C below the resin's Tg. This yielded a disc-shaped test plaque with a diameter of 50 mm and a thickness of 3 mm. This plaque was then stored at 130°C and a relative humidity of 85% for 48 hours.

[0529] <7. Total light transmittance>

[0530] The plates before and after the PCT test were measured using a spectrophotometer SE2000 manufactured by Nippon Denshoku Industries, Ltd., in accordance with the method of JIS-K-7361-1.

[0531] <8. Total light transmittance retention rate (%)>

[0532] The total light transmittance was determined according to the following formula using the value of the total light transmittance measured by the above method.

[0533] Total light transmittance retention (%) = total light transmittance after PCT test / total light transmittance before PCT test × 100

[0534] <9. Vinyl terminal group content of polycarbonate resin>

[0535] 1 H-NMR measurement was performed under the following conditions.

[0536] · 1 H-NMR measurement conditions

[0537] Device: Bruker AVANZE III HD 500MHz

[0538] Tipping angle: 30 degrees

[0539] Waiting time: 1 second

[0540] Cumulative times: 500 times

[0541] Measurement temperature: room temperature (298K)

[0542] Concentration: 5wt%

[0543] Solvent: deuterated chloroform

[0544] Internal standard substance: tetramethylsilane (TMS) 0.05wt%

[0545] <10. Measurement of Phenol and Diphenyl Carbonate (DPC) Amounts in Polycarbonate Resin>

[0546] Dissolve 0.5 g of the sample from Example 1 (described in detail later) in 50 ml of tetrahydrofuran (THF) to prepare the sample solution. Use the pure products of each compound as standards to create a calibration curve. Quantify 2 μL of the sample solution using LC-MS under the following measurement conditions. The detection limit under these measurement conditions is 0.01 ppm.

[0547] LC-MS assay conditions:

[0548] Measurement device (LC part): Agilent Infinity 1260LC System

[0549] Chromatographic column: ZORBAX Eclipse XDB-18, and guard column

[0550] Mobile phase:

[0551] A: 0.01 mol / L ammonium acetate aqueous solution

[0552] B: 0.01 mol / L ammonium acetate methanol solution

[0553] C:THF

[0554] Gradient program of mobile phase:

[0555] 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 at the time indicated in the Time (minutes) column.

[0556] [Table 1]

[0557]

[0558] Flow rate: 0.3 ml / min

[0559] Column temperature: 45°C

[0560] Detector: UV (225nm)

[0561] Measurement device (MS part): Agilent 6120 single quad LCMS System

[0562] Ionization source: ESI

[0563] Polarity: Positive (DPC) & Negative (PhOH)

[0564] Fragmentation voltage: 70V

[0565] Drying gas: 10L / min, 350℃

[0566] Atomizer: 50psi

[0567] Capillary voltage: 3000V (Positive), 2500V (Negative)

[0568] Measured ions:

[0569] [Table 2]

[0570] monomer Ion type m / z PhOH [MH]- 93.1 DPC [M+NH4]+ 232.1

[0571] Sample injection volume: 2μL

[0572] Monomer analysis method

[0573] <11. Powder X-ray Diffraction (PXRD)>

[0574] Powder X-ray diffraction (PXRD) patterns were recorded using a D8 Discover X-ray diffractometer (Bragg Brentano, Germany) from Bruker AXS GmbH, using Cu Kα1 radiation (40 kV, 40 mA) as the X-ray source. Data were collected at room temperature over the range of 2θ-5.0° to 2θ-80.0° with a resolution of 0.025° and a measurement time of 0.5 s / step.

[0575] <12.DSC measurement>

[0576] DSC measurement was performed using a Linseis Chip-DSC 10. The heating rate was 20°C / min.

[0577] <13. Determination of Melting Point>

[0578] The melting point was measured by a capillary method using a Büchi Melting Point B-545 apparatus at a heating rate of 1 K / min.

[0579] <14. Near-infrared analysis>

[0580] Near infrared analyses were recorded by means of a Bruker FT-NIR spectrometer Matrix F spectrometer, Bruker Opus 5.5 software and a reflection immersible probe head.

[0581] <15. Determination of Purity>

[0582] Purity was determined by UPLC using the following system and operating conditions.

[0583] Waters Acquity UPLC H-Class system; columns

[0584] Acquity UPLC BEH C18, 1.7 μm, 2 x 100 mm; column temperature: 40 °C,

[0585] Gradient: acetonitrile / water (acetonitrile; ACN: 48% at 0 min, 50% at 21 min, 100% at 26 min, 100% at 28 min, 48% at 28.1 min, 48% at 32 min);

[0586] Injection volume: 0.8 μl; flow rate 0.6 ml / min; detection at 210 nm.

[0587] <16. Determination of Volatile Solvents>

[0588] The amount of volatile solvents was determined by gas chromatography using a Shimadzu GC 14B and Class VP 4.3 software, an AOC-20i autoinjector, an AOC-20s autosampler, and an FID detector.

[0589] As a chromatography column, PE 624 20 (Perkin Elmer) having the following dimensions was used. Gas chromatography was performed under the following operating conditions.

[0590] Carrier gas: hydrogen

[0591] Pressure: 0.3 bar

[0592] Injection temperature: 250℃

[0593] Detection temperature: 300℃

[0594] Column temperature: 40°C (2 minutes), 20°C / min, 200°C (2 minutes)

[0595] Concentration: C = 20 mg / ml

[0596] Injection volume: 0.2-2 μl

[0597] As an internal standard, a solution of 100 mg of naphthalene in 10 ml of dimethylformamide was used. Samples were prepared by dissolving 20 mg of the compound in a 0.1 mM internal standard solution and adding 0.9 ml of dimethylformamide. The amount of medium was calculated using the following formula.

[0598] S Solv *M St *100 / (S St *M Sample *RRF)

[0599] M St : The amount of internal standard in the sample solution

[0600] M Sample : The weight of the sample

[0601] S Solv : Area of ​​solvent peak

[0602] S St :Standard area

[0603] RRF: Relative sensitivity factor of solvent <17. Determination of yellowness>

[0604] The yellowness index YI of 6,6'-DPBHBNA was measured according to the following protocol with reference to ASTM E 313.

[0605] One gram of 6,6'-DPBHBNA was dissolved in 19 g of dichloromethane. The solution was transferred to a 50 mm cuvette, and the transmittance was measured in the range of 300 to 800 nm using a Shimadzu UV-Visible spectrophotometer UV-1650PC. Dichloromethane was used as a control. From the spectrum, the yellowness index was calculated according to ASTM E308 (Standard practice for computing the colors of objects by using the CIE System) and ASTM E 313 (Standard practice for calculating yellowness and whiteness indices from instrumentally measured color coordinates) using the software RCA-software UV2DAT.

[0606] <18. Measurement of Haze>

[0607] As for the haze, it was determined by measuring the transmittance at 860 nm of a 5% dichloromethane solution of 6,6'-DPBHBNA using a standard nephelometer.

[0608] <19. Microscopy>

[0609] As for the images of the microscopy, a Nikon microscope Eclipse TS100 was used, and the photographing was performed using a 100-fold magnification provided by a Nikon photographing unit Digital Sight DS-U1. From these microscope photographs, the width (W), the length (L), and the aspect ratio (L / W ratio) were confirmed.

[0610] [Production of Polycarbonate Resin]

[0611] (Example 1)

[0612] As the raw materials, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl (hereinafter sometimes abbreviated as "BINL-2EO") 31.6 kg (60.0 moles), diphenyl carbonate (hereinafter sometimes abbreviated as "DPC") 13.5 kg (63.0 moles), and sodium bicarbonate 0.074 g (8.8 x 10 －4mol) was placed in a 50L reactor equipped with a stirrer and a distillation device and heated to 180°C under a nitrogen atmosphere of 760 mmHg. 20 minutes after the start of heating, the raw materials were confirmed to be completely dissolved, and then stirred under the same conditions for 120 minutes. Thereafter, the pressure was adjusted to 200 mmHg while the temperature was raised to 200°C at a rate of 60°C / hr. At this time, it was confirmed that the by-product phenol began to distill. Thereafter, the temperature was maintained at 200°C for 40 minutes to allow the reaction to proceed. Thereafter, the temperature was raised to 240°C at a rate of 75°C / hr. 10 minutes after the temperature was raised, the temperature was maintained while the pressure was reduced to below 1 mmHg over 1 hour. Thereafter, the temperature was raised to 245°C at a rate of 60°C / hr and stirred for another 30 minutes. After the reaction was completed, nitrogen was introduced into the reactor to return it 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. As a result, 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.

[0613] The physical properties of the obtained resin are shown in Table 3 below.

[0614] (Example 2-A)

[0615] 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.

[0616] (Example 2-B)

[0617] 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.

[0618] (Example 2-C)

[0619] 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.

[0620] The physical properties of the obtained resin are shown in Table 3. The NMR spectrum of the resin (BINOL-2EO / BNEF=50 mol / 50 mol) obtained in Example 2-B is shown in Table 3. Figure 1 .

[0621] (Example 3-A)

[0622] The same procedures as in Example 1 were 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 resulting resin are shown in Table 3.

[0623] (Example 3-B)

[0624] The same procedures as in Example 1 were 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 resulting resin are shown in Table 3.

[0625] (Example 3-C)

[0626] The same procedures as in Example 1 were 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 resulting resin are shown in Table 3.

[0627] (Example 4-A)

[0628] 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. The physical properties of the obtained resin are shown in Table 3.

[0629] (Example 4-B)

[0630] 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. The physical properties of the obtained resin are shown in Table 3.

[0631] (Example 4-C)

[0632] 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. The physical properties of the obtained resin are shown in Table 3.

[0633] (Example 5)

[0634] The same procedures as in Example 1 were 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(naphthalen-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 resulting resin are shown in Table 3.

[0635] (Example 6-A)

[0636] The same procedures as in Example 1 were carried out 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 resulting resin are shown in Table 3.

[0637] (Example 6-B)

[0638] 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. The physical properties of the obtained resin are shown in Table 3.

[0639] (Example 6-C)

[0640] 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, 6.9 kg (12.0 mol) of BPPEF, 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.

[0641] The BINL-2EO used in Examples 1, 2-A to 2-C, 3-A to 3-C, 4-A to 3-C, and 6-A to 3-C is the “Form A” obtained in Example 21 described in detail later.

[0642] (Example 6-D)

[0643] The same operation as in Example 1 was carried out 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.

[0644] (Example 6-E)

[0645] The same operation as in Example 1 was carried out 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. The physical properties of the obtained resin are shown in Table 3.

[0646] (Example 6-F)

[0647] The same operation as in Example 1 was carried out 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. The physical properties of the obtained resin are shown in Table 3.

[0648] (Example 7)

[0649] The same procedures as in Example 1 were carried out 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.

[0650] (Example 7-A)

[0651] The same procedures as in Example 1 were carried out 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.

[0652] (Example 7-B)

[0653] The same procedures as in Example 1 were carried out 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.

[0654] (Example 8)

[0655] The same procedures as in Example 1 were carried out 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 3.

[0656] (Example 8-A)

[0657] The same procedures as in Example 1 were carried out 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.

[0658] (Example 8-B)

[0659] The same procedures as in Example 1 were carried out 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.

[0660] (Example 9)

[0661] The same procedures as in Example 1 were carried out except that 10.4 kg (18.0 mol) of 6,6'-bis(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.

[0662] (Example 10)

[0663] The same operation as in Example 1 was conducted, except that 6,6'-bis(dibenzo[b,d]furan-4-yl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl (FUR-BNA) 12.7 kg (18.0 moles), BPEF 18.4 kg (42.0 moles), DPC 13.5 kg (63.0 moles) were used as raw materials. The physical property values of the obtained resin are shown in Table 3.

[0664] (Example 11)

[0665] The same operation as in Example 1 was conducted, except that 6,6'-bis(dibenzo[b,d]furan-4-yl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl (FUR-BNA) 12.7 kg (18.0 moles), BPEF 18.4 kg (42.0 moles), DPC 13.5 kg (63.0 moles) were used as raw materials. The physical property values of the obtained resin are shown in Table 3.

[0666] (Comparative Example 1)

[0667] The same operation as in Example 1 was conducted, except that BNE 22.5 kg (60.0 moles), DPC 13.5 g (63.0 moles) were used as raw materials. The physical property values of the obtained resin are shown in Table 3.

[0668] [Table 3]

[0669]

[0670] Example:

[0671] BINL-2EO 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl

[0672] BNEF 9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene

[0673] BNE 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl

[0674] BPEF 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene

[0675] BPPEF 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene

[0676] DNBINOL-2EO 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalen-1-yl)-1,1'-binaphthyl

[0677] 2DNBINOL-2EO 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-2-yl)-1,1'-binaphthyl

[0678] 9DPNBINOL-2EO 2,2'-bis(2-hydroxyethoxy)-6,6'-di(phenanthrene-9-yl)-1,1'-binaphthyl

[0679] CN-BNA 6,6'-bis(3-cyanophenyl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl

[0680] FUR-BNA 6,6′-bis(dibenzo[b,d]furan-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl

[0681] THI-BNA6,6′-bis(dibenzo[b,d]thiophen-4-yl)-2,2′-bis-(2-hydroxyethoxy)-1,1′-binaphthyl

[0682] Comparative Example:

[0683] BNE 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl

[0684] [Moldability]

[0685] A: The molded sheet has no gaps and no surface undulations.

[0686] B: There are gaps in the molded sheet.

[0687] C: The surface of the molded piece has undulations.

[0688] D: The molded piece has gaps and the surface is deformed.

[0689]

[0690] [Manufacture of polyester and polyester carbonate resins]

[0691] (Example 12)

[0692] 0.090 mol of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl (BINL-2EO) as a diol compound, 0.010 mol of 9,9-fluorene-dipropionic acid methyl ester (FDPM) as a carboxylic acid dialkyl ester, 0.120 mol of ethylene glycol (EG), and 0.001 mol of tetrabutoxytitanium as an ester exchange catalyst were placed in a reactor equipped with a Nakamura Scientific Instruments Co., Ltd. Sealing Mixer UZU with a half-moon-shaped stirring blade and a distillation device. The mixture was heated to 180°C under a nitrogen atmosphere and atmospheric pressure, and stirred for 30 minutes. The temperature was then raised to 250°C over 1 hour, and the pressure was reduced to 0.13 kPa to allow polymerization to proceed. After maintaining the pressure at 250°C and 0.13 kPa for 1 hour, the contents were removed from the reactor to obtain a polyester resin. The physical properties of the resulting polyester resin are shown in Table 3.

[0693] (Examples 13 to 18, Comparative Example 2)

[0694] A polyester resin was obtained in the same manner as in Example 12 except that the diol compound listed in Table 3 was used as the diol compound. Table 3 shows the physical properties of the obtained polyester resin.

[0695] (Example 19)

[0696] 0.110 mol of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl (BINL-2EO) as a diol compound, 0.100 mol of 9,9-fluorene-dipropionic acid methyl ester (FDPM) as a carboxylic acid dialkyl ester, 0.010 mol of diphenyl carbonate, and 0.001 mol of tetrabutoxytitanium as an ester exchange catalyst were placed in a reactor equipped with a Nakamura Scientific Instruments Co., Ltd. Sealing Mixer UZU with a half-moon-shaped stirring blade and a distillation device. The mixture was heated to 180°C under a nitrogen atmosphere and stirred for 60 minutes. Phenol and methanol distillation was observed. The temperature was then raised to 240°C over 1 hour, and the pressure was reduced to 0.13 kPa to allow polymerization to proceed. After maintaining the temperature at 240°C and 0.13 kPa for 1 hour, the contents were removed from the reactor to obtain a polyester carbonate resin. Table 3 shows the physical properties of the obtained polyester carbonate resin.

[0697] (Example 20)

[0698] A reactor equipped with a stirrer and a distillation device was charged with 0.10 mol of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl (BINL-2EO) as a diol compound, 0.06 mol of ethylene glycol (EG), 0.12 mol of 2,2'-bis(hydroxycarbonylmethoxy)-1,1'-binaphthyl (BINOL-DC) as a dicarboxylic acid, and 0.001 mol of tetrabutoxytitanium as a catalyst. The mixture was heated to 180°C under a nitrogen atmosphere and atmospheric pressure, and stirred for 30 minutes. The temperature was then raised to 255°C and the pressure was reduced to below 0.13 kPa to allow polymerization to proceed. After maintaining the pressure at 255°C and 0.13 kPa for 1 hour, the contents were removed from the reactor to obtain a polyester resin. The physical properties of the resulting polyester resin are shown in Table 4.

[0699] [Table 4]

[0700]

[0701]

[0702] Dihydroxy compounds that may be further added

[0703]

[0704] [Manufacturing of single units]

[0705] (Example 21: Preparation of Form A)

[0706] Step 1: Hydroxyethylation of 6,6'-dibromo-1,1'-bis(2-naphthol)

[0707] A nitrogen-purged vessel was charged with 1053 kg of anisole, 157.6 kg of 6,6'-dibromo-1,1'-bis(2-naphthol) (commercially available), 14.6 kg of potassium carbonate, and 97 kg of ethylene carbonate. After the addition of the starting materials was complete, the vessel was heated to an internal temperature of 125-135°C. As indicated by gas evolution, the reaction began at approximately 80-90°C. The reaction mixture was maintained at 125-135°C for 40 hours until TLC showed complete conversion. The reaction mixture was cooled to an internal temperature of 75°C. 145 kg of water was slowly added. The mixture was heated to 80°C and stirred at this temperature for an additional 30 minutes. After stirring was stopped, the layers separated after 25 minutes. After the layers separated, the lower aqueous layer was removed. 164 kg of 20% (w / w) sodium hydroxide solution was added to the organic layer remaining in the vessel, and the mixture was stirred at 90°C for 2 hours (with a reflux condenser). After 2 hours, the container was cooled to 80°C and stirring was stopped. After 25 minutes, the layers separated. The lower, substantially aqueous layer was removed. The organic layer was further washed with 160 kg of water and 25 kg of sodium chloride (80°C, 30 minutes), and then the layers were separated for 20 minutes. The aqueous layer was removed.

[0708] The anisole solution of the target 2,2'-bis(2-hydroxyethoxy)-6,6'-dibromo-1,1'-binaphthyl in the organic layer thus obtained was used directly in the next step without isolating the compound.

[0709] Step 2: Preparation of 6,6'-DPBHBNA using Suzuki coupling

[0710] 84 g of tris-(o-tolyl)phosphine and 15 g of palladium (II) acetate were dissolved in 1.5 kg of anisole to prepare a catalyst solution.

[0711] In a first reaction vessel, heat the anisole solution of 2,2'-bis(2-hydroxyethoxy)-6,6'-dibromo-1,1'-binaphthyl obtained in Step 1 to 60°C and add 93.4 kg of phenylboronic acid. Stir the mixture for 15 minutes until the phenylboronic acid is completely dissolved. Then, cool the mixture to 40°C to 50°C.

[0712] In the second reaction vessel, 520 kg of a 31% (w / w) aqueous solution of tripotassium phosphate is heated to 50°C. Then, the pre-prepared catalyst solution is slowly added. As a result, the overall temperature rises by about 15°C. After adding the catalyst, the mixture is stirred at 60-70°C for 1 hour. Then, the remaining 70% from container 1 is slowly added to the reaction vessel at 55-75°C. After the addition is completed, the mixture is stirred at 60°C for another hour. TLC shows that the conversion is complete. After 30 minutes at 50-60°C, the layers separate. Remove the lower aqueous layer. To the organic layer, 186 kg of water and 125 kg of a 20 wt% aqueous sodium hydroxide solution are added. The mixture is stirred at 55°C for 40 minutes. After that, the mixture separates into layers and the substantially lower aqueous layer is removed.

[0713] Then, 182 kg of 2M hydrochloric acid was added to the organic layer, and the mixture was stirred at 50-60°C for 30 minutes. The layers were separated and the acidic aqueous layer on the lower side was removed. The organic layer was further washed with 182 kg of 25% by weight salt water at 50-60°C. The residual organic layer was stirred at 60-70°C with 10 kg of activated carbon ( DX Ultra) and 50 kg of sodium sulfate were stirred for 90 minutes. The mixture was then filtered through a pressure filter at 60-70°C to prevent precipitation of the product. (Although 6,6'-DPBHBNA can be crystallized from anisole to form polyhedral crystals, the crystals do not have a specific composition, resulting in a low yield.)

[0714] The filtrate (approximately 2500 L) is then transferred to a distiller. Anisole is distilled off at a temperature exceeding 80°C and 90 mbar until approximately 200 L of residue remains. Anisole can be recovered and reused. After releasing the vacuum, the residue is cooled to 55°C. At this temperature, 140 kg of methanol and 60 kg of toluene are added. The mixture is heated to 60-65°C while stirring until the precipitate dissolves and the solution becomes homogeneous. After the mixture reaches complete homogeneity, the container is cooled to 20°C. At a temperature of approximately 35-40°C, 40 g of 6,6'-DPBHBNA is added to the solution as seed crystals to initiate crystallization. The mixture is cooled to 20°C and stirred at 20°C for 4 hours. The precipitate is then recovered by centrifugation, and the filter cake is washed with two 10 kg bottles of methanol.

[0715] This yielded 162 kg of 6,6'-DPBHBNA (loss on drying: 15%), representing 137 kg of dry 6,6'-DPBHBNA. The yield over two steps was equivalent to 74%. UPLC analysis revealed a chemical purity of 98% for the resulting 6,6'-DPBHBNA.

[0716] Step 3: Purification / recrystallization of 6,6'-DPBHBNA

[0717] 6,6'-DPBHBNA (142 kg, 270 mol; purity: 98.0%) obtained by the method in Step 2 was dissolved in a mixture of methanol and toluene (7:3 (v / v); 827 kg). The solution was treated with activated carbon (8 kg) at 55°C for 2 hours. The activated carbon was removed by filtration, and the filtrate was cooled to 0°C over 4 hours while stirring, and then stirred at 0°C for another hour. This resulted in crystallization of 6,6'-DPBHBNA. The 6,6'-DPBHBNA crystals were collected by filtration and washed with methanol to yield 154 kg of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl (LOD: 14%; 252 mol; UPLC chemical purity: 98.8%).

[0718] The resulting 6,6'-DPBHBNA was dissolved in a mixture of methanol and toluene (7:3 (v / v); 772 kg). The solution was then treated again with activated carbon (7 kg) at 55°C for 2 hours. The activated carbon was removed by filtration, and the filtrate was cooled to 0°C over 5 hours while stirring, and then stirred at 0°C for another hour. The solid was collected by filtration and washed with methanol to yield 131.4 kg of 6,6'-DPBHBNA (LOD: 14%; 220 mol; UPLC chemical purity: 99%). PXRD confirmed the product to be a methanol solvate.

[0719] Step 4: Conversion of the methanol solvate of 6,6'-DPBHBNA to Form A

[0720] The obtained 48 kg of crystalline 6,6′-DPBHBNA methanol solvate was dried at 40° C. in air for 5 days to obtain 41.3 kg of crystalline 6,6′-DPBHBNA in the form of compact crystals with a size ranging from 5 to 200 μm.

[0721] GC measurement showed that the product obtained in step 4 contained 0.03% bw of methanol and 0.3% bw of toluene as solvent components, that is, based on the weight of 6,6'-DPBHBNA (2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl) (relative to 100% by weight of 6,6'-DPBHBNA), it contained 0.03% by weight of methanol and 0.3% by weight of toluene as solvent components.

[0722] The product of step 4 was analyzed by PXRD. Figure 2 As shown, this clearly indicates that the crystalline form is Form A. The following reflection peaks were observed.

[0723] [Table 5]

[0724] 2-θ(Theta) ％＊ 6.52 8.07 8.61 22.93 9.42 8.71 10.44 8.04 11.01 24.95 13.19 26.54 14.94 38.29 15.46 16.41 16.19 29.40 17.35 24.87 17.79 25.59 18.43 24.31 18.97 28.39 20.88 100 21.45 45.06 22.50 15.27 22.92 15.41 23.69 20.41 24.49 17.30 25.89 17.46 27.75 15.03 30.82 12.46

[0725] *Indicates relative strength.

[0726] UPLC confirmed that the product of step 4 contained 99.1% bw of 6,6'-DPBHBNA, 0.06% bw (0.06 wt%) of 6,6'-DPMHBNA, and 0.19% bw (0.19 wt%) of 6,6'-DPTHBNA.

[0727] The product of step 4 had a yellowness YI of 3.9 and a haze of 0.5 ntu.

[0728] The product of step 4 is analyzed by IR and NIR. Figure 3 As shown, IR Figure 4 In the NIR, around 7000 and 4500 cm -1 The habit of is characteristic of Form A, showing a clear distinction from the solvate.

[0729] The DSC of the product of step 4 showed an endothermic peak with an onset at 113.6°C, a peak maximum at 124.4°C, and a reaction point at 112.9°C. The melting point was immediately determined and the melting points shown were 127.0°C, 126.5°C, and 126.8°C. Figure 5 shown.

[0730] (Example 22: Preparation of methanol solvate of 6,6'-DPBHBNA)

[0731] 20 g of 6,6'-DPBHBNA (UPLC chemical purity; >99%) obtained in Step 4 of Example 21 was dissolved in 600 ml of pure methanol and heated under reflux. When the homogeneous solution was slowly cooled to 22°C, 6,6'-DPBHBNA crystals precipitated as compact crystals with a size range of 10 to 200 μm. The crystals were collected by filtration, washed with methanol, and air-dried at 25° C. for 2 days to obtain 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl containing 5.98% bw of methanol, corresponding to a 6,6′-DPBHBNA:methanol molar ratio of approximately 1:1 (i.e., 6,6′-DPBHBNA containing 5.98% by weight of methanol based on the weight of 6,6′-DPBHBNA (2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl) (relative to 100% by weight of 6,6′-DPBHBNA)).

[0732] The product thus obtained was analyzed using PXRD. Figure 6 As shown, it was found that the product had a crystalline form different from Form A and Form C, and the following reflection peaks were observed.

[0733] [Table 6]

[0734] 2-θ(Theta) ％＊ 6.23 16.29 8.45 3.99 9.03 50.21 10.59 61.47 11.79 8.13 12.51 11.36 13.00 41.31 14.87 85.66 16.02 8.34 16.93 26.66 17.69 7.31 18.21 22.01 18.45 32.77 19.20 49.49 19.56 53.32 20.86 59.04 21.54 100 22.11 17.86 22.72 20.60 24.29 44.09 24.86 23.58 26.18 22.33 26.65 11.83 27.66 16.59 28.67 12.87 30.48 15.82 31.61 9.93 32.47 8.349

[0735] *Indicates relative strength.

[0736] The product thus obtained was analyzed using IR and NIR. Figure 7 As shown, IR Figure 8 In the NIR, around 4500 and 4300 cm -1 The habit of is characteristic of methanol solvate, showing clear distinction from Form A and other solvates.

[0737] The DSC of the product thus obtained showed an endothermic peak having an onset at 100.9° C., a peak maximum at 113.4° C., and a reaction point at 108.3° C. The melting point was immediately determined and the melting points shown were 107.4° C., 108.7° C., and 107.7° C. Figure 9 shown.

[0738] (Example 23: Preparation of a mixture of Form A and methanol solvate)

[0739] Step 1: Hydroxyethylation of 6,6′-dibromo-1,1′-bis(2-naphthol)

[0740] A 2L, three-necked flask equipped with a stirrer, a water separator, a reflux condenser, a thermometer, and a bubble counter was charged with 89.7g of 6,6′-dibromo-1,1′-bis(2-naphthol), 573g of anisole, 8.3g of K2CO3, and 52.8g of ethylene carbonate. The reaction mixture was heated under reflux (internal temperature 125-135°C) and stirred for 6 hours. Some gas evolution was observed. The progress of the reaction was monitored by TLC. After the reaction was completed, the reaction mixture was cooled to 70-80°C, 75g of water and 25g of brine were added, and the mixture was stirred at this temperature for an additional 20 minutes. After separation, 15% bw aqueous NaOH (110g) was added to the organic layer, and the mixture was stirred at 95°C for 3 hours. After separation, the organic layer was washed with an aqueous solution prepared from 110g of water and 25g of brine. The organic layer obtained after separation was used directly in the next step without isolating the compound.

[0741] Step 2: Preparation of 6,6'-DPBHBNA using Suzuki coupling

[0742] A 2L, three-necked flask equipped with a stirrer, reflux condenser, and thermometer was filled with the organic solution obtained in step 1. 50.0g of phenylboronic acid, 93.4g of K3PO4, and 210g of water were added, and the mixture was heated to an internal temperature of 60°C. Then, 49mg of tris-(o-tolyl)phosphine and 9mg of palladium(II) acetate were added with vigorous stirring. The reaction mixture was slowly heated to reflux, and the progress of the reaction was monitored by TLC. After the reaction was completed (30 minutes to 1 hour later), the mixture was cooled to 70°C, and the aqueous layer was separated and removed. The organic layer was washed successively with 150ml of 10% bw aqueous NaOH, 87.5ml of 2M aqueous HCl, and again with brine (75ml). The organic layer was then treated with 2.5g of activated carbon and dried over sodium sulfate (12.5g). After filtration, the solvent was evaporated under vacuum and the residue was crystallized from a mixture of methanol (77 g) and toluene (33 g). This gave a crystalline product which was collected by filtration.

[0743] This yielded 110 g of wet 6,6'-DPBHBNA (loss on drying: 15%), which in turn yielded 93.5 g of dry 6,6'-DPBHBNA, equivalent to an 89% yield over two steps. UPLC analysis revealed a chemical purity of 98% for the resulting 6,6'-DPBHBNA.

[0744] Step 3: Purification / recrystallization of 6,6'-DPBHBNA

[0745] 107 g of 6,6'-DPBHBNA (purity: 98.0%) obtained by the method in step 2 was dissolved in a mixture of methanol / toluene (7:3 (v / v); 535 g). The solution was treated with activated carbon (5.4 g) at 55°C for 2 hours. The activated carbon was removed by filtration, and the filtrate was cooled to 0°C while stirring and stirred at 0°C for 1 hour and 30 minutes. This resulted in the crystallization of 6,6'-DPBHBNA as compact crystals with a size range of 5 to 150 μm. The solid was collected by filtration, washed with methanol, and dried in air at room temperature overnight to yield 85.0 g of 6,6'-DPBHBNA with a chemical purity of 99.89% (UPLC) and a yellowness index (YI) of 2.1.

[0746] GC measurement showed that the product obtained in step 3 contained a solvent component of 2.4% bw of methanol, 0.1% bw of toluene, and 0.002% bw of anisole (i.e., it was 6,6'-DPBHBNA containing a solvent component of 2.4% by weight of methanol, 0.1% by weight of toluene, and 0.002% by weight of anisole, based on the weight of 6,6'-DPBHBNA (2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl) (relative to 100% by weight of 6,6'-DPBHBNA)).

[0747] The product of step 3 is analyzed by PXRD. Figure 10 As shown, the crystalline form of the product was confirmed to be a mixture of Form A and methanol solvate. The following reflection peaks were observed.

[0748] [Table 7]

[0749] 2-θ(Theta) ％＊ 6.25 10.87 8.61 58.88 8.98 33.71 9.47 16.41 10.59 41.40 11.82 9.716 12.95 36.20 13.25 22.35 14.82 100 16.02 11.65 16.27 11.10 17.03 26.14 18.43 37.00 19.31 57.83 19.60 48.99 20.83 91.68 21.47 90.71 22.28 23.42 22.62 34.69 24.39 51.81 24.96 27.86 26.13 34.43 27.61 18.75 28.93 14.31 30.28 14.82 30.67 14.72 31.68 11.82 32.47 12.43

[0750] *Indicates relative strength.

[0751] The product of step 3 is analyzed by IR and NIR. Figure 11 As shown, IR Figure 12 In the NIR, around 4500 and 4300 cm -1 The habit is characteristic of methanol solvates.

[0752] The DSC of the product of step 3 showed a first endothermic peak with an onset at 97.3°C, a peak maximum at 109.8°C, and a reaction point at 109.8°C, and a second peak with an onset at 118.9°C, a peak maximum at 124.4°C, and a reaction point at 121.4°C. The melting point was immediately determined and the melting points shown were 118.6°C, 119.4°C, and 116.7°C. DSC is as shown in FIG. Figure 13 shown.

[0753] (Example 24: Preparation of Toluene Solvate of 6,6'-DPBHBNA)

[0754] 20 g of 6,6'-DPBHBNA (UPLC chemical purity; >99.0%) obtained in step 4 of Example 21 was dissolved in 60 ml of pure toluene and heated under reflux. When the homogeneous solution was slowly cooled to 22°C, 6,6'-DPBHBNA crystallized as a compact crystalline form with a size ranging from 20 to 250 μm. The crystals were collected by filtration, washed with methanol, and air-dried at 25°C for 2 days to obtain 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl containing 5.6% bw of toluene, which was equivalent to a substance with a molar ratio of 6,6'-DPBHBNA:toluene of approximately 2.95:1. A microscopic photograph of the crystals obtained in this way is shown in FIG. Figure 14 .

[0755] The product thus obtained was analyzed using PXRD. Figure 15 As shown, it was found that the product had a crystalline form different from Form A, and the following reflection peaks were observed.

[0756] [Table 8]

[0757] 2-θ(Theta) ％＊ 5.17 24.19 7.75 78.65 8.24 24.20 9.15 24.11 10.57 30.11 10.84 17.41 11.63 44.87 12.61 36.65 13.59 20.23 14.70 79.90 15.04 37.68 15.65 26.32 16.68 41.77 17.15 27.95 18.03 44.69 18.52 59.36 19.36 77.80 19.95 35.92 20.83 87.49 20.98 91.79 21.59 100 22.23 42.26 22.67 35.50 24.15 85.68 24.96 33.01 25.69 32.43 26.45 25.74 27.14 28.79 27.63 29.19

[0758] *Indicates relative strength.

[0759] The product thus obtained was analyzed using IR and NIR. Figure 16 As shown, IR Figure 17 In the NIR, around 7000 and 4700 cm －1 The habit of α-acetaminophen is characteristic of a toluene solvate, showing clear differences from Form A, Form B and other solvates.

[0760] The DSC of the product thus obtained showed an endothermic peak with an onset at 106.5°C, a peak maximum at 113.6°C and a reaction point at 110.7°C. The melting point was immediately determined and the melting points shown were 103-107.9°C, 104.0-106.8°C and 104.8-107.6°C. Figure 18 shown.

[0761] (Example 25: Preparation of MEK Solvate of 6,6'-DPBHBNA)

[0762] 100 g of 6,6'-DPBHBNA (UPLC chemical purity; >99.0%) obtained in step 4 of Example 21 was dissolved in 300 ml of pure MEK and heated under reflux. When the homogeneous solution was slowly cooled to 22°C, 6,6'-DPBHBNA crystallized as a compact crystalline form with a size ranging from 20 to 200 μm. The crystals were collected by filtration, washed with MEK, air-dried at 25°C for 2 days, and then dried at 50°C for 1 hour to obtain 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl containing 8.5% bw of MEK, which was equivalent to a substance with a molar ratio of 6,6'-DPBHBNA:MEK of approximately 1.5:1. A microscopic photograph of the crystals obtained in this way is shown in FIG. Figure 19 .

[0763] The product thus obtained was analyzed using NIR. Figure 20 In the NIR, 4600 cm －1 The habit of α-β- ...

[0764] The DSC of the product thus obtained showed an endothermic peak with an onset at 89.4°C, a peak maximum at 97.6°C and a reaction point at 95.5°C. The melting point was immediately determined and the melting points shown were 105.9°C and 105.8°C. Figure 21 shown.

[0765] The product of Example 25 thus obtained was analyzed using PXRD. Figure 22 As shown, it was found that the product had a crystalline form different from Form A and Form B, and the following reflection peaks were observed.

[0766] [Table 9]

[0767] 2-θ(Theta) ％＊ 5.0 24.9 7.0 100 7.5 14.4 12.6 20.1 13.4 14.9 14.5 30.4 15.4 27.9 15.7 44.5 16.8 76.6 18.3 33.8 19.4 17.6 20.6 35.7 21.5 59.5 22.7 21.7 23.4 37.5 24.1 51.9 25.6 24.1 26.2 19.5 26.6 17.0 29.1 13.7 30.8 11.1

[0768] *Indicates relative strength.

[0769] (Example 26: Preparation of Amorphous Form B of 6,6'-DPBHBNA)

[0770] 100 g of 6,6'-DPBHBNA (UPLC chemical purity; >99.0%) obtained in Step 4 of Example 21 was heated to 130°C to obtain a clear melt. This melt was immediately cooled to 22°C over 2 minutes to obtain an amorphous (glassy) solid. This amorphous solid was crushed into small pieces and ground in a mortar to obtain a powder.

[0771] The product thus obtained was analyzed using PXRD. Figure 23 As shown, the absence of a crystal layer is evident from the absence of a reflection peak in the range of 5° to 40° at 2θ. Instead, a broad halo is observed in this range of 2θ.

[0772] The product thus obtained was analyzed using IR and NIR. Figure 24 As shown, IR Figure 25 shown.

[0773] The DSC (not shown) of the product thus obtained showed no endothermic peak in the temperature range of 80 to 200° C. Instead, a step corresponding to the glass transition temperature was observed in the range of 109 to 110° C.

[0774] (Example 27: Preparation of Form C of 6,6'-DPBHBNA)

[0775] Example 27a

[0776] 20 g of 6,6'-DPBHBNA (UPLC chemical purity; >99.0%) obtained in Step 4 of Example 21 was dissolved in 300 ml of 96% ethanol and heated under reflux. When the homogeneous solution was slowly cooled to 22°C, 6,6'-DPBHBNA crystals precipitated as compact crystals ranging in size from 2 to 150 μm. The crystals were collected by filtration, washed with MEK, and air-dried at 25°C for 2 days, followed by drying at 50°C for 1 hour, yielding 15.8 g of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, free of detectable ethanol.

[0777] Example 27b

[0778] 30 g of 6,6'-DPBHBNA (UPLC chemical purity; >99.0%) obtained in Step 4 of Example 21 was dissolved in 250 ml of anisole at 100°C. When the homogeneous solution was very slowly cooled to 22°C, 6,6'-DPBHBNA crystals precipitated as compact crystals ranging in size from 10 to 300 μm. The crystals were collected by filtration, washed with cooled anisole, and dried in a rotary evaporator at 80°C for 19 hours, yielding 11.4 g of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, containing a very small amount of anisole (approximately 0.1% by weight) and no other solvent.

[0779] The product obtained in Example 27a was analyzed using PXRD. Figure 26 As shown, it was found that the crystalline form of the product was the same as that of the toluene solvate by PXRD, but different from Form A and other solvates, and showed the following reflection peaks.

[0780] [Table 10]

[0781] 2-θ(Theta) ％＊ 5.1 35.0 7.6 86.3 8.2 26.2 9.2 27.3 10.4 20.7 10.8 31.5 11.4 48.0 11.6 43.9 12.8 35.6 13.4 22.8 14.5 53.2 15.2 64.4 15.6 40.6 16.6 41.5 17.4 34.1 17.9 43.3 18.5 58.2 19.2 63.4 19.9 48.2 20.4 44.8 21.0 100.0 21.8 64.7 22.2 82.4 22.6 40.6 23.4 33.7 24.0 71.1 24.9 34.1 25.7 34.2 27.3 26.9 27.9 28.5

[0782] *Indicates relative strength.

[0783] The product obtained in Example 27b was analyzed by PXRD. This PXRD showed the same reflection peaks and habit as those of the product obtained in Example 27a, confirming that the crystals obtained in Examples 27a and 27b had the same crystalline morphology.

[0784] The product obtained in Example 27a was analyzed using IR and NIR. Figure 27 As shown, IR Figure 28 In the NIR, around 7000 and 4700 cm -1 The phase (habit) of is characteristic of Form C, which shows a clear difference from Forms A and B and solvates other than toluene solvate. The product obtained in Example 27b was also analyzed by IR and NIR. These spectra showed the same phase as the product obtained in Example 27a.

[0785] The DSC of the product obtained in Example 27a showed an endothermic peak having an onset at 116.6°C, a peak maximum at 125.0°C, and a reaction point at 121.0°C. Figure 29 DSC of the product obtained in Example 27b showed an endothermic peak having an onset at 115.4°C, a peak maximum at 124.0°C, and a reaction point at 120.0°C.

[0786] [Production of a polycarbonate resin composition using the monomers of the above examples]

[0787] (Example 28)

[0788] As raw materials, BINL-2EO as "Form A" obtained in Example 21, namely 7.9 kg (15.0 mol) of 6,6'-DPBHBNA, 16.8 kg (45.0 mol) of BNE, 21.5 kg (40.0 mol) of BNEF, 22.1 kg (103.0 mol) of DPC and 0.117 g (13.9 × 10 －4 mol) and was added to a 50L reactor equipped with a stirrer and a distillation device through a hopper with a shovel. Then, nitrogen was added to the reactor and the pressure inside the reactor was increased to 780 mmHg. After maintaining it for 3 minutes, nitrogen was discharged from the exhaust port to return it to 760 mmHg. Nitrogen was added to the reactor again and maintained for 3 minutes, and nitrogen was discharged from the exhaust port to return it to 760 mmHg. Then, nitrogen was added to the reactor again and maintained for 3 minutes, and nitrogen was discharged from the exhaust port to return it to 760 mmHg. Then, under a nitrogen atmosphere of 760 mmHg, heating was carried out to 180°C. 20 minutes after the start of heating, it was confirmed that the raw materials were completely dissolved, and then stirring was carried out under the same conditions for 120 minutes. Then, while adjusting the degree of decompression to 200 mmHg, the temperature was raised to 200°C at a rate of 60°C / hr. At this time, it was confirmed that the by-product phenol began to distill. Then, the reaction was carried out by maintaining it at 200°C for 40 minutes. The temperature was then raised to 240°C at a rate of 75°C / hr. Ten minutes after the temperature was raised, the pressure was reduced to below 1 mmHg over 1 hour while maintaining this temperature. The temperature was then raised to 245°C at a rate of 60°C / hr and stirred for an additional 30 minutes. After the reaction was complete, nitrogen was introduced into the reactor to return it to atmospheric pressure, and the resulting polycarbonate resin was pelletized and removed. The Mw of these pellets was 27,500.

[0789] The resulting polycarbonate resin pellets were dried at 100°C for 3 hours, and the moisture content in the pellets was confirmed to be 1% using a Karl Fischer meter. The dried pellets were then mixed with additives: 1000 ppm of pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (AO-60 manufactured by ADEKA: antioxidant), 1500 ppm of stearic acid monoglyceride (S-100A manufactured by Riken Vitamin Co., Ltd.: mold release agent), and 300 ppm of 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (PEP-36 manufactured by ADEKA: antioxidant). The additives were then applied to the dried pellets. The pellets were then melt-kneaded in a twin-screw extruder while reducing the pressure to 40 mmHg, resulting in pelletization.

[0790] The obtained polycarbonate resin composition had a refractive index of 1.680, an Abbe number of 18.1, a Tg of 147°C, an Mv of 11900, an Mw of 27000, a b value of 3.9, moldability A, a total light transmittance of 89%, and a total light transmittance after a PCT test of 89%.

[0791] The physical properties of the polycarbonate resin obtained in Example 28 are shown in Table 11 together with the physical properties of the resins in other Examples and the like.

[0792]

[0793] (BINL-2EO, i.e. 6,6'-DPBHBNA)

[0794] (Example 29)

[0795] As raw materials, BINL-2EO 12.6 kg (24.0 mol), BNE 11.1 kg (30.0 mol), BNEF 17.8 kg (33.0 mol), 2DNBINOL-2EO 8.1 kg (13.0 mol), DPC 22.1 kg (103.0 mol) and sodium bicarbonate 0.117 g (13.9 × 10 －4 mol), a polycarbonate resin and a polycarbonate composition were obtained in the same manner as in Example 28, except for the above.

[0796] The obtained polycarbonate resin composition had a refractive index of 1.690, an Abbe number of 16.7, a Tg of 155°C, an Mv of 11900, an Mw of 27000, a b value of 3.9, moldability of A, a total light transmittance of 89%, and a total light transmittance after a PCT test of 89%.

[0797] Table 11 shows the physical properties of the polycarbonate resin obtained in Example 29.

[0798]

[0799] (2DNBINOL-2EO) [Table 11]

[0800]

[0801] (Examples 30 to 36)

[0802] As raw materials, BINL-2EO shown in the table below, namely 6,6′-DPBHBNA 78.99 g (0.15 mol), BNE 168.50 g (0.45 mol), BNEF 215.45 g (0.40 mol), DPC 220.64 g (1.030 mol) and sodium bicarbonate 1.2 mg (1.39×10 －5 mol / mol (added as an aqueous solution) and added via a funnel to a 1L reactor equipped with a stirrer and a distillation device. Nitrogen was then introduced into the reactor, pressurized to 780 mmHg. After maintaining for 3 minutes, nitrogen was discharged from the vent to return the pressure to 760 mmHg. Nitrogen was again introduced into the reactor, maintained for 3 minutes, and then nitrogen was discharged from the vent to return the pressure to 760 mmHg. Nitrogen was again introduced into the reactor, maintained for 3 minutes, and then nitrogen was discharged from the vent to return the pressure to 760 mmHg. Nitrogen was then introduced into the reactor again, maintained for 3 minutes, and then nitrogen was discharged from the vent to return the pressure to 760 mmHg. The mixture was then heated to 180°C under a nitrogen atmosphere of 760 mmHg. Complete dissolution of the raw materials was confirmed 20 minutes after the start of heating, and stirring was then continued under the same conditions for 120 minutes. The pressure was then adjusted to 200 mmHg while the temperature was raised to 200°C at a rate of 60°C / hr. At this point, by-product phenol began to distill. The reaction was then continued at 200°C for 40 minutes. The temperature was then raised to 240°C at a rate of 75°C / hr. Ten minutes after the temperature was raised, the pressure was reduced to below 1 mmHg over 1 hour while maintaining this temperature. The temperature was then raised to 245°C at a rate of 60°C / hr and stirred for an additional 30 minutes. After the reaction was complete, nitrogen was introduced into the reactor to return it to atmospheric pressure, and the resulting polycarbonate resin was removed. The optical properties of the resulting resin were identical to those of Example 28, but the final molecular weight was slightly different.

[0803] [Table 12]

[0804]

[0805] (Reference example)

[0806] In step 3 of Example 23, when washing with methanol and drying overnight in air at room temperature, the drying time was shortened to obtain BINL-2EO (6,6'-DPBHBNA) containing 1.3 mol of methanol per mol of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl. The reaction was repeated in the same manner as in the additional Example 1, except that the main raw material was replaced with the BINL-2EO (6,6'-DPBHBNA obtained in this manner.)

[0807] As a result, the raw materials could not be smoothly added to the reactor through the hopper using a shovel, resulting in poor operability and slow reaction progress. The Mw of the obtained pellets was lower than that of Example 28, being 24,500.

[0808] The properties of the thermoplastic resins obtained in the examples and comparative examples are shown in a graph with the Abbe number (v) as the horizontal axis and the refractive index (nD) as the vertical axis. Figure 30 and 31 .

[0809] These graphs show specific ranges, e.g.

[0810] exist Figure 30 Between the straight line nD=-0.02v+1.96 and the straight line nD=-0.02v+2.04, or

[0811] exist Figure 31 The points of multiple embodiments are marked between the straight line nD = -0.0002ν + 1.6718 and the straight line nD = -0.024ν + 2.124, or between the straight line nD = -0.004v + 1.744 and the straight line y = -0.02x + 2.04. From this, it can be confirmed that in each embodiment, the balance between the Abbe number and the refractive index is good, and a thermoplastic resin suitable for optical applications is achieved.

[0812] For example, in Figure 31 The refractive index is higher than 1.660, the Abbe number is lower than 19 or is 19 or less, for example, in the range of 13 to 19 or 15 to 19, and

[0813] In the region between the straight line nD = -0.0002ν + 1.6718 and the straight line nD = -0.024ν + 2.124, a polycarbonate resin satisfying the relationship -0.0002ν + 1.6718 < nD < -0.024ν + 2.124 has preferable properties.

[0814] In the region between the straight line nD = -0.004v + 1.744 and the straight line nD = -0.024v + 2.124, a polycarbonate resin satisfying the relationship -0.004v + 1.744 < nD < -0.024v + 2.124 has more preferable properties.

[0815] In the region between the straight line nD=-0.02v+2.04 and the straight line nD=-0.024v+2.124, a polycarbonate resin satisfying the relationship -0.02v+2.04<nD<-0.024v+2.124 has further preferred properties.

Claims

1. A thermoplastic resin, characterized in that: The thermoplastic resin contains at least a structural unit derived from any of the crystalline form A and crystalline form C described below and the amorphous form B described below, The thermoplastic resin contains a structural unit represented by the following general formula (1), The crystal form A is a crystal form A of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl, wherein the crystal contains less than 0.1 mol of an organic solvent per 1 mol of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl. The X-ray powder diffraction pattern obtained by Cu Kα1 irradiation at 22°C is: The following three reflection peaks are shown as 2θ values: 20.9±0.2°, 21.4±0.2°, and 23.7±0.2°. At least three of the following reflection peaks are shown as 2θ values: 6.5±0.2°, 8.6±0.2°, 11.0±0.2°, 13.2±0.2°, 14.9±0.2°, 16.2±0.2°, 17.3±0.2°, 17.8±0.2°, 18.4±0.2°, and 19.0±0.2°; The crystal form C is a crystal form C of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl, wherein the crystal contains less than 0.1 mol of an organic solvent per 1 mol of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl. The X-ray powder diffraction pattern obtained by Cu Kα1 irradiation at 22°C is: The following three reflection peaks are shown as 2θ values: 5.1±0.2°, 7.6±0.2°, and 21.0±0.2°. At least three of the following reflection peaks are shown as 2θ values: 8.2±0.2°, 9.2±0.2°, 10.4±0.2°, 10.8±0.2°, 11.6±0.2°, 12.8±0.2°, 13.4±0.2°, 14.5±0.2°, 15.2±0.2°, 15.6±0.2°, 16.6±0.2°, 17.4±0. .2°, 17.9±0.2°, 18.5±0.2°, 19.2±0.2°, 19.9±0.2°, 20.4±0.2°, 21.8±0.2°, 22.2±0.2°, 22.6±0.2°, 23.4±0.2°, 24.0±0.2°, 25.7±0.2°, 27.3±0.2°, and 27.9±0.2°; The amorphous form B is an amorphous form B of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl, having a purity of at least 99.0% by weight based on organic matter, wherein the amorphous form B contains less than 0.1 mol of an organic solvent per 1 mol of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl. The X-ray powder diffraction pattern obtained by Cu Kα1 irradiation at 22°C is: There is no reflection peak as a 2θ value at multiple diffraction angles within the range of 5° to 40°. In differential scanning calorimetry (DSC) recorded in accordance with ISO 11357-3:2018 at a heating rate of 20 K / min, no endothermic peak is shown in the range of 80 to 200°C; 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, 1, 2, 3 or 4 of the ring atoms are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon, The monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group have no substituent, or have one or two substituents R selected from 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 alkylene group and the cycloalkylene group may be substituted with a benzene ring, a and b are integers of 1 to 10 respectively.

2. A thermoplastic resin, characterized in that: The thermoplastic resin contains a structural unit derived from 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl described in any one of the following: 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl containing less than 0.5% by weight of the total amount of impurities selected from 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bishydroxy-6,6'-diphenyl-1,1'-binaphthyl, and 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthyl, based on 100% by weight of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl; and 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl having at least one of the following characteristics i. and ii., i. A yellowness index (YI) of less than 3.0 as measured by ASTM E 313 using a 5 w / w% dichloromethane solution of 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl; and ii. The haze measured using a 5 w / w % dichloromethane solution of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl is less than 1.0 ntu; The thermoplastic resin contains a structural unit represented by the following general formula (1), 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, 1, 2, 3 or 4 of the ring atoms are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon, The monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group have no substituent, or have one or two substituents R selected from 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 alkylene group and the cycloalkylene group may be substituted with a benzene ring, a and b are integers of 1 to 10 respectively.

3. An optical lens, characterized in that: Contains the thermoplastic resin according to claim 1 or claim 2.

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