Thermoplastic resin, method for manufacturing the same, and optical lens

Abstract

To provide a crystalline solvate form of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl.SOLUTION: According to one embodiment, a crystalline solvate form of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl is provided, which contains in its crystals from 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, where the organic solvent is selected from methanol, toluene, and methyl ethyl ketone.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin, particularly a polyester resin, a polyester carbonate resin, The present invention relates to a thermoplastic resin such as a polycarbonate resin, and a method for producing the same. The present invention also relates to optical lenses comprising thermoplastic resins. [Background technology]

[0002] Optical fibers used in the optical systems of various cameras, including cameras with integrated film and video cameras Optical glass or optical resin is used as the material for optical lenses. It has excellent heat resistance, transparency, dimensional stability, and chemical resistance, but the material cost is high and it is difficult to mold. This has the problem of poor workability and low productivity.

[0003] On the other hand, optical lenses made from optical resins can be mass-produced by injection molding. For example, thermoplastic resins are used in camera lenses. However, in recent years, the trend toward lighter, thinner, and smaller products has led to a demand for the development of resins with higher refractive indices. Generally, when the refractive index of an optical material is high, it is difficult to obtain a high refractive index from a lens having the same refractive index (Patent Documents 1 to 4). Since the lens element can be realized on a surface with a smaller curvature, the amount of aberration generated by this surface can be reduced. As a result, it is possible to reduce the number of lenses, reduce the sensitivity of the lenses to decentering, and This makes it possible to reduce the thickness and weight.

[0004] Generally, lenses used in camera optical systems have a high refractive index and a b value of It is required that the level is not too high and that chromatic aberration is suppressed. can be. However, thermoplastic resins with sufficiently high refractive index and low b-values ​​and optical The lens was not yet available.

[0005] Furthermore, in recent years, various electronic devices have been required to be water-resistant and heat-resistant. The "PCT test" (pressure cooker test) is an environmental test to evaluate the water resistance and heat resistance of equipment. This test is a moisture and heat resistance test, and measures the penetration of moisture into the sample. Therefore, the optical components made of optical resins used in electronic devices are evaluated. The lenses not only have a high refractive index and a low b value, but also high heat resistance and durability. It is also required to have water decomposability. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-2893 [Patent Document 2] Japanese Patent Application Publication No. 2018-2894 [Patent Document 3] Japanese Patent Application Publication No. 2018-2895 [Patent Document 4] Japanese Patent Application Publication No. 2018-59074 Summary of the Invention [Problem to be solved by the invention]

[0007] The problem to be solved by the present invention is to provide a film having a high refractive index, a low b value, and high resistance to humidity and heat, particularly high The object of the present invention is to provide a thermoplastic resin having a refractive index. Another object of the present invention is to provide an excellent optical lens. [Means for solving the problem]

[0008] As a result of extensive research into solving the above problems, the present inventors have discovered the following thermoplastic resin and optical The present inventors have found that the above problems can be solved by using an optical lens, and have arrived at the present invention.

[0009] The present invention is, for example, as follows. [1] A thermoplastic resin containing a structural unit represented by the following general formula (1): [ka] (R1 and R2 in formula (1) each independently represent a hydrogen atom, a fluorine atom, or a chlorine atom.) , bromine atom, iodine atom, alkyl group having 1 to 6 carbon atoms, monocyclic or polycyclic group having 6 carbon atoms and monocyclic or polycyclic heteroaryl groups having 5 to 36 ring atoms. where 1, 2, 3, or 4 of the ring atoms are selected from nitrogen, sulfur, and oxygen and the other ring atoms are Heteroaryl groups in which the atom is carbon, alkenyl groups with 2 to 6 carbon atoms, and alkynyl groups with 1 to 6 carbon atoms. represents an alkoxy group or an aralkyl group having 7 to 17 carbon atoms; The monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group are The aryl group may be unsubstituted or may be selected from the group consisting of CN, CH3, OCH3, O-phenyl, O -naphthyl, S-phenyl, S-naphthyl, and halogen; one or two R a may have a group, However, neither R1 nor R2 is hydrogen, X is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or a carbon an arylene group having a prime number of 6 to 20; However, the alkylene group and the cycloalkylene group each have a benzene ring. may be substituted so that a and b are each an integer of 1 to 10. [2] The thermoplastic resin is a polyester resin or a polyester carbonate resin. The thermoplastic resin according to [1] above. [3] Either of the above [1] or [2], further containing a constitutional unit represented by the following general formula (2): The thermoplastic resin according to any one of claims 1 to 4. [ka] (In general formula (2), Q is represented by the following formula (2a).) [ka] (In formula (2a), R C each independently represents a single bond to the CO group in the formula (2). The total number of carbon atoms in the formula (2) may be 1 to 10 and may have a bond or a substituent. represents an alkylene group containing a terminal bonding point to a CO group. [4] The thermoplastic resin according to the above [3], wherein Q is represented by the following formula (2b): [ka] (In formula (2b), n and m each independently represent an integer of 0 to 5, p and k each independently represent an integer of 1 to 5; R1 and R2 have the same meanings as R1 and R2 in formula (1), a and b each independently represent an integer of 0 to 6; * represents the point of attachment to the CO group in formula (2). [5] The above [4] having at least a structural unit containing Q represented by the following formula (2c): The thermoplastic resin according to claim 1. [ka] (In formula (2c), * represents the point of attachment to the CO group in formula (2).) [6] The above [1] to [3], wherein the structural unit represented by the general formula (1) is contained in an amount of more than 50 mol %. [5] The thermoplastic resin according to any one of [5]. [7] In the general formula (1), at least one of R1 and R2 has 6 to 20 carbon atoms. The thermoplastic resin according to any one of the above [1] to [6], which is an aryl group. [8] In the general formula (1), at least two of R1 and R2 have 6 to 14 carbon atoms. The thermoplastic resin according to the above [7], wherein the group is an aryl group. [9] The constitutional unit represented by the general formula (1) is represented by the following general formulas (A-1) to (A-7):

[0023] The thermal decomposition product according to any one of the above [1] to [8], which contains at least one of the structural units plastic resin. [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[10] Further containing at least one constitutional unit represented by the following general formulas (3) and (4): The thermoplastic resin according to any one of the above [1] to [9]. [ka] (R'1 to R' in formula (3) 20 are each independently a hydrogen atom, a fluorine atom, or a chlorine atom. Atom, bromine atom, iodine atom, alkyl group having 1 to 6 carbon atoms, 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 alkoxy group having 7 to 17 carbon atoms; represents an aralkyl group, Y is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or a an arylene group having 6 to 20 carbon atoms; c and d are each an integer of 1 to 10. [ka] (R''1 to R'' in Equation (4) 16 are each independently a hydrogen atom, a fluorine atom, Chlorine atom, bromine atom, iodine atom, alkyl group having 1 to 6 carbon atoms, 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 alkoxy group having 7 to 1 carbon atoms; 7 represents an aralkyl group, Z is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or a an arylene group having 6 to 20 carbon atoms; e and f are each an integer of 1 to 10.

[0010]

[11] A structural unit represented by the general formula (1) and a structural unit represented by the general formula (3) The thermoplastic resin according to

[10] above, comprising a copolymer containing at least

[12] The copolymer further contains a constitutional unit represented by the following general formula (3-1):

[11] The thermoplastic resin according to

[11] . [ka]

[13] A structural unit represented by the general formula (1) and a structural unit represented by the general formula (4) The thermoplastic resin according to

[10] above, comprising a copolymer containing at least

[14] The copolymer further contains a constitutional unit represented by the following general formula (4-1):

[13] The thermoplastic resin according to

[14] . [ka]

[15] The structural units represented by the general formulas (3) and (4) are contained in a total amount of 20 to 80 mol %. The thermoplastic resin according to any one of the above [1] to

[14] .

[16] The above [1] further contains at least one constitutional unit represented by the following general formula (5):

[16] The thermoplastic resin according to any one of

[15] to

[16] . [ka]

[17] At least BNEF (9,9-bis(6-(2-hydroxyethoxy)naphthalene) The thermoplastic resin according to

[16] above, which contains a structural unit of (a)benzo-2-ylfluorene.

[18] At least 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene The thermoplastic resin according to

[16] above, which contains a structural unit of

[19] At least BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3- The thermoplastic resin according to

[16] above, further comprising a structural unit of (phenylphenyl)fluorene. sex resin.

[20] The aryl group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a pyrenyl group, a furanyl group, or a phenyl group, which may be substituted with an aryl group having 6 to 16 carbon atoms. dihydrobenzofuranyl group, piperonyl group, benzofuranyl group, a benzoyl group, a dibenzofuranyl group, a pyrrolidinyl group, an isoquinolyl group, a pyrimidinyl group, and The thermoplastic resin according to any one of the above [1] to

[19] , wherein the carbazole group is selected from the group consisting of carbazole and carbazole groups. .

[21] The refractive index of the thermoplastic resin is 1.655 or more, as described in any one of [1] to

[20] above. The thermoplastic resin according to any one of the above.

[22] The thermal decomposition method according to any one of [1] to

[20] above, wherein R1 and R2 are the same. plastic resin.

[23] The R1 and R2 may be the same or different, and may be monocyclic or polycyclic. Cyclic aryl groups with 6 to 36 carbon atoms, monocyclic or polycyclic heterocyclic groups with 5 to 36 ring atoms Aryl groups in which one, two, three, or four of the ring atoms are selected from nitrogen, sulfur, and oxygen. and wherein the other ring atom is carbon; The monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group are The thermoplastic resin according to any one of the above [1] to

[20] , wherein the aryl group is unsubstituted. .

[24] The R1 and R2 are Azulenil, may be unsubstituted or may be bonded to each other by a phenyl and a single bond; They may be directly condensed with each other and / or may be saturated or unsaturated 4- to 10-membered single rings. Two, three, or four rings, optionally fused to a cyclic or bicyclic hydrocarbon ring Polycyclic aryls having 2, 3, 4, or more phenyl rings indenyl, optionally substituted by 1 or 5 substituents; unsubstituted phenyl, phenyl substituted by one or two CN groups; phenyl and may be bonded to each other by a single bond or may be directly fused to each other and / or saturated or unsaturated 4- to 10-membered monocyclic or bicyclic rings Polycyclic aromatic hydrocarbons having two, three, or four phenyl rings, which may be fused to a hydrocarbon ring. substituted by 2, 3, 4, or 5 substituents selected from cyclic aryl; Phenyl, They may be directly condensed with each other, and / or may be saturated or unsaturated 4- to 10-membered rings. Two, three, or four rings, optionally fused to a monocyclic or bicyclic hydrocarbon ring wherein the polycyclic aryl has a phenyl ring of the formula: or phenyl and polycyclic aryls having two or three phenyl rings; may be substituted by one or two substituents selected from the group consisting of The three phenyl rings may be bonded to each other by a single bond, or may be directly fused to each other. and / or saturated 4- to 10-membered monocyclic or bicyclic hydrocarbons. The phenyl ring of the polycyclic aryl may be unsubstituted or fused to a polycyclic aryl. , or one or two substituents R a Polycyclic aryl having the formula The thermoplastic resin according to any one of the above [1] to

[23] , selected from the group consisting of:

[25] The R1 and R2 are unsubstituted or substituted by 1, 2, 3, 4, or 5 phenyl groups optionally substituted phenyl, phenyl substituted by one or two CN groups; Biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, and pyrene substituted by one or two polycyclic aryl groups selected from aryl, phenyl, which may be further substituted by a phenyl group of the formula unsubstituted or substituted CN, phenyl and biphenyl, naphthyl, fluorenyl, polycyclic aryl selected from anthracenyl, phenanthryl, and pyrenyl; naphthyl substituted by one or two substituents, biphenylenyl, triphenylenyl, tetraphenylenyl, phenanthryl, pyrenyl, 9H-fluorenyl, dibenzo[a,e][8]annulenyl, Perylenyl, and 9,9'-Spirobi[9H-fluoren]yl The thermoplastic resin according to any one of the above [1] to

[24] , selected from the group consisting of:

[26] The R1 and R2 are phenyl, 2-cyanophenyl, 3-cyanophenyl, From the group consisting of 4-cyanophenyl, 2-naphthyl, 1-naphthyl, and 9-naphthyl The thermoplastic resin according to

[25] above, selected from the group consisting of:

[27] The R1 and R2 are Heteroaromatic monocyclic groups having 5 or 6 ring atoms, or 4 nitrogen atoms, or 1 oxygen atom and 0, 1, 2, or 3 nitrogen atoms a hydrogen atom or one sulfur atom and zero, one, two, or three nitrogen atoms; heteroaromatic monocyclic groups, the other ring atoms of which are carbon atoms; A heteroaromatic polycyclic group, which is a heteroaromatic monocyclic group and a ... polycyclic group, which is a heteroaromatic polycyclic group, and having one, two, three, four, or five additional aromatic rings selected from monocyclic and polycyclic rings. The (hetero)aromatic rings of a cyclic heteroaryl may be bonded to each other by a covalent bond. They may be directly condensed with each other, and / or may be saturated or unsaturated 4- to 10-membered rings. heteroaromatic polycyclic groups, which may be fused to a monocyclic or bicyclic hydrocarbon ring, Beauty, A heteroaromatic polycyclic group having ring atoms selected from oxygen, sulfur, and nitrogen. At least one saturated or partially unsaturated 5-membered heteroatom containing one or two heteroatoms Alternatively, a 6-membered heterocycle and one selected from phenyl and the above heteroaromatic monocycles , 2, 3, 4, or 5 additional aromatic rings, and at least one additional The aromatic ring is directly fused to a saturated or partially unsaturated 5- or 6-membered heterocyclic group. and other additional aromatic rings of the polycyclic heteroaryl aromatic ring are interconnected by covalent bonds. They may be bonded to each other, may be directly fused to each other, and / or may be saturated or may be fused to an unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring, heteroaromatic polycyclic groups, The thermoplastic resin according to any one of the above [1] to

[23] , selected from the group consisting of:

[28] The R1 and R2 are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, oxazolyl isoxazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl , pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, benzofuryl , dibenzofuranyl, benzothienyl, dibenzothienyl, thianthrenyl, naphthofuranyl furo[3,2-b]furanyl, furo[2,3-b]furanyl, furo[3,4-b]furanyl Ranyl, oxanthrenyl, indolyl, isoindolyl, carbazolyl , indolizinyl, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benz zo[cd]indolyl, 1H-benzo[g]indolyl, quinolinyl, isoquinolinyl, Acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, benzo Zo[b][1,5]naphthyldinyl, cinnolinyl, 1,5-naphthyridinyl, 1,8- Naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, dipyridinyl, phenylpyridinyl pyrido[4,3-b]indolyl, naphthylpyridinyl, pyrido[3,2-b]indolyl Andolyl, pyrido[3,2-g]quinolinyl, pyrido[2,3-b][1,8]naphthyl pyridinyl, pyrrolo[3,2-b]pyridinyl, pteridinyl, purinyl purinyl, 9H-xanthenyl, 2H-chromenyl, 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]chromenyl, pyrrolo[3,2,1- hi]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl, and benzo[h]isoquinolinyl, The thermoplastic resin according to

[27] above, selected from the group consisting of:

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

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

[30] Any of the above [1] to

[29] , whose b value according to JIS K 7105 is 10 or less. The thermoplastic resin according to any one of the preceding items.

[31] Between the refractive index nD and the Abbe number ν, -0.0002ν+1.6718 <nD<- The relationship 0.024ν+2.124 is satisfied, as described in any of [1] to

[30] above. Thermoplastic resin.

[32] Between the refractive index nD and the Abbe number ν, -0.004v+1.744 <nD<-0. The thermoplastic resin according to

[31] above, wherein the relationship of 024ν+2.124 is satisfied.

[33] Between the refractive index nD and the Abbe number ν, <nD<-0.0 The thermoplastic resin according to

[32] above, wherein the relationship of 24ν+2.124 is satisfied.

[0011]

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

[33] above.

[35] A method for producing a thermoplastic resin according to any one of the above [1] to

[33] , At least a dihydroxy compound represented by the following general formula (6), and a carboxylic acid and a carboxylic acid a step of melt polycondensing at least one of an acid monoester and a carboxylic acid diester; A method for producing a thermoplastic resin, comprising: [ka] (R1 and R2 in the general formula (6) each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, Br, iodine, alkyl group with 1 to 6 carbon atoms, monocyclic or polycyclic carbon atoms aryl groups having 6 to 36 ring atoms, monocyclic or polycyclic heteroaryl groups having 5 to 36 ring atoms; wherein one, two, three, or four of the ring atoms are selected from nitrogen, sulfur, and oxygen; Heteroaryl groups in which the ring atom is carbon, alkenyl groups having 2 to 6 carbon atoms, and alkenyl groups having 1 to 6 carbon atoms. represents an alkoxy group or an aralkyl group having 7 to 17 carbon atoms; The monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group are The aryl group may be unsubstituted or may be selected from the group consisting of CN, CH3, OCH3, O-phenyl, O -naphthyl, S-phenyl, S-naphthyl, and halogen; one or two R a may have a group, However, neither R1 nor R2 is hydrogen, X is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or a an arylene group having 6 to 20 carbon atoms; However, the alkylene group and the cycloalkylene group each have a benzene ring. may be substituted so that a and b are each an integer of 1 to 10.

[36] 2,2´-bis(2-hydroxyethoxy)-6,6´-diphenyl-1,1´ -binaphthalene in the form of a crystalline solvate containing 1 mole of 2,2'-bis(2-hydroxybenzoyl) (oxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene 0.3 to 1. The crystals contain 2 moles of organic solvent, The organic solvent is selected from methanol, toluene, and methyl ethyl ketone. Solvate form of benzophenone.

[37] The crystalline solvate according to

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

[38] The X-ray powder diffraction pattern by irradiation with Cu Kα radiation at 22°C is The following three reflection peaks as 2θ values: 13.0±0.2°, 14.9±0.2°, and 21.5±0.2°, The following reflection peaks as 2θ values: 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± The crystalline solvate form according to

[37] above, exhibiting at least three of the following: 0.2°.

[39] ISO 11 at a heating rate of 20 K / min (or 20 °C / min; the same applies below) 357-3:2018, the differential scanning calorimetry (DSC) recorded was 97-101°C. The peak exhibits an endothermic peak with an onset in the range of 108 to 115°C. The crystalline solvate form according to

[37] or

[38] above.

[40] The amount of methanol is 1 mole of 2,2'-bis(2-hydroxyethoxy)-6, The crystalline solvate form according to any one of

[0037] to

[39] , wherein the amount is 0.3 to 1.0 moles per 6'-diphenyl-1,1'-binaphthalene.

[41] The crystalline solvate form according to

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

[42] The X-ray powder diffraction pattern by Cu Kα radiation at 22°C is The following three reflection peaks as 2θ values: 5.2±0.2°, 7.7±0.2°, and 21 0.6±0.2°, The following reflection peaks 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°, 18.0±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 0.2°, 26.5±0.2°, 27.1±0.2° and 27.6±0.2° The crystalline solvate form according to

[41] above, which shows three forms.

[43] Recorded according to ISO 11357-3:2018 at a heating rate of 20 K / min The differential scanning calorimetry (DSC) showed an endothermic peak with an onset in the range of 105-108°C. The maximum peak value is in the range of 112-115°C, as shown in

[41] or

[42] above. 2. The crystalline solvate form according to claim 1.

[44] The amount of toluene is 1 mole of 2,2'-bis(2-hydroxyethoxy)-6,6 The crystalline solvate form according to any one of

[0041] to

[43] , wherein the amount of the solvate is 0.3 to 0.5 moles per 1,1'-diphenyl-1,1'-binaphthalene.

[45] 2,2´-bis(2-hydroxyethoxy)-6,6´-diphenyl-1,1´ -binaphthalene crystalline form A, containing 1 mole of 2,2'-bis(2-hydroxybenzoyl) less than 0.1 moles of organic per 1,1'-(2-hydroxy-6,6'-diphenyl-1,1'-binaphthalene) The solvent is contained in the crystals, The X-ray powder diffraction pattern by irradiation with Cu Kα1 radiation at 22°C is The following three reflection peaks as 2θ values: 20.9±0.2°, 21.4±0.2°, and 23.7±0.2°, The following reflection peaks 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 0.2°, 17.8±0.2°, 18.4±0.2° and 19.0±0.2° All three exhibit crystalline form A.

[46] Recorded according to ISO 11357-3:2018 at a heating rate of 20 K / min The differential scanning calorimetry (DSC) showed an endothermic peak with an onset in the range of 112-114°C. The crystalline material according to

[45] above, wherein the maximum value of the peak is in the range of 124 to 126°C. Form.

[47] 2,2´-bis(2-hydroxyethoxy)-6,6´-diphenyl-1,1´ -binaphthalene crystalline form C, containing 1 mole of 2,2'-bis(2-hydroxyethoxy) less than 0.1 moles of organic per 1,1'-(2-hydroxy-6,6'-diphenyl-1,1'-binaphthalene) The solvent is contained in the crystals, The X-ray powder diffraction pattern by irradiation with Cu Kα1 radiation at 22°C is The following three reflection peaks as 2θ values: 5.1±0.2°, 7.6±0.2°, and 21 0±0.2°, 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 0.2°, 27.3±0.2°, and 27.9±0.2°. Sexual form C.

[48] ​​Recorded according to ISO 11357-3:2018 at a heating rate of 20 K / min. The differential scanning calorimetry (DSC) showed an endothermic peak with an onset in the range of 112-114°C. The crystalline material according to

[47] above has a maximum peak value in the range of 124 to 126°C. form.

[49] The method according to any one of

[33] to

[48] above, wherein the crystal has an aspect ratio of at most 5:1. Any crystalline form as defined above.

[50] 2,2´-bis(2-hydroxyethoxy)-6,6´-diphenyl-1,1´ - amorphous form B of binaphthalene, at least 99.0% by weight based on organic matter and having a purity of 1 mole of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl The crystals contain less than 0.1 moles of organic solvent per 1,1'-nyl-binaphthalene, The X-ray powder diffraction pattern by irradiation with Cu Kα1 radiation at 22°C is No reflection peaks are observed as 2θ values ​​at multiple diffraction angles in the range of 5° to 40°. Recorded according to ISO 11357-3:2018 at a heating rate of 20 K / min Amorphous form in which differential scanning calorimetry (DSC) does not show an endothermic peak in the range of 80 to 200°C. Condition B.

[51] 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl- 1,1´-Binaphthalene, 2,2´-bishydroxy-6,6´-diphenyl-1,1´ -binaphthalene and 2-(2-hydroxyethoxy)-2'-(2-hydroxyethoxy)- (ethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthalene The total amount of selected impurities is 100% by weight of 2,2'-bis(2-hydroxyethoxy) )-6,6'-diphenyl-1,1'-binaphthalene is less than 0.5% by weight, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene Talen.

[52] 2,2'-bis(2-hydroxyethoxy)- ... CI)-6,6'-diphenyl-1,1'-binaphthalene. i. 5% w / w of 2,2'-bis(2-hydroxyethoxy) in dichloromethane -6,6'-diphenyl-1,1'-binaphthalene solution, measured according to ASTM E313 A yellowness index (YI) of less than 3.0 as defined above, and ii. 5 w / w% 2,2'-bis(2-hydroxyethoxy) )-6,6'-diphenyl-1,1'-binaphthalene solution measured at less than 1.0 ntu Haze.

[53] The compound according to any one of

[33] to

[49] above, which exists in a crystalline form or an amorphous form according to

[0050] above, ´-Bis(2-hydroxyethoxy)-6,6´-diphenyl-1,1´-binaphthalene .

[54] The crystalline form according to

[33] to

[49] above and the amorphous form according to

[50] above

[0033] Any of the above [1] to

[33] , which has a structural unit derived from any of the following forms: Thermoplastic resin.

[55] The 2,2'-bis(2-hydroxyethoxy) (ii)-6,6'-diphenyl-1,1'-binaphthalene-derived structural units The thermoplastic resin according to any one of [1] to

[33] .

[56] An optical lens comprising the thermoplastic resin according to

[54] or

[55] above. [Effects of the Invention]

[0012] The thermoplastic resin of the present invention has a high refractive index, a low b value, and high resistance to moisture and heat, and in particular, a high refractive index. Furthermore, by using such excellent thermoplastic resins, it is possible to produce excellent optical lenses. can be obtained. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a H1-NMR chart of the resin (BINOL-2EO / BNEF=50 mol / 50 mol) produced in Example 2-B. [Figure 2] 1 shows the X-ray powder diffraction pattern of Form A of 6,6′-DPBHBNA obtained from Example 21. [Figure 3] 1 shows the NIR spectrum of Form A of 6,6′-DPBHBNA obtained from Example 21. [Figure 4] 1 shows the IR spectrum of Form A of 6,6′-DPBHBNA obtained from Example 21. [Figure 5] 1 shows the DSC of Form A of 6,6′-DPBHBNA obtained from Example 21. [Figure 6] 1 shows the X-ray powder diffraction pattern of the methanol solvate of 6,6′-DPBHBNA obtained from Example 22. [Figure 7] 1 shows the NIR spectrum of the methanol solvate of 6,6′-DPBHBNA obtained from Example 22. [Figure 8] 1 shows the NR spectrum of the methanol solvate of 6,6′-DPBHBNA obtained from Example 22. [Figure 9] 1 shows the DSC of the methanol solvate of 6,6′-DPBHBNA obtained from Example 22. [Figure 10] 1 shows the X-ray powder diffraction pattern of the crystalline material obtained from Example 23. [Figure 11] 1 shows the NIR spectrum of the crystalline material obtained from Example 23. [Figure 12] 1 shows the NR spectrum of the crystalline material obtained from Example 23. [Figure 13] 1 shows the DSC of the crystalline material obtained from Example 23. [Figure 14] 1 shows a microphotograph of toluene solvation of 6,6′-DPBHBNA obtained from Example 24. [Figure 15] 1 shows the X-ray powder diffraction pattern of the toluene solvate of 6,6′-DPBHBNA obtained from Example 24. [Figure 16]1 shows the NIR spectrum of the toluene solvate of 6,6′-DPBHBNA obtained from Example 24. [Figure 17] 1 shows the NR spectrum of the toluene solvate of 6,6′-DPBHBNA obtained from Example 24. [Figure 18] 1 shows the DSC of the toluene solvate of 6,6′-DPBHBNA obtained from Example 24. [Figure 19] 1 shows a microphotograph of the MEK solvation of 6,6′-DPBHBNA obtained from Example 25. [Figure 20] 1 shows the NIR spectrum of the MEK solvate of 6,6′-DPBHBNA obtained from Example 25. [Figure 21] 1 shows the DSC of the MEK solvate of 6,6′-DPBHBNA obtained from Example 25. [Figure 22] 1 shows the X-ray powder diffraction pattern of the MEK solvate of 6,6′-DPBHBNA obtained from Example 25. [Figure 23] 1 shows the X-ray powder diffraction pattern of amorphous Form B of 6,6′-DPBHBNA obtained from Example 26. [Figure 24] 1 shows the NIR spectrum of amorphous Form B of 6,6′-DPBHBNA obtained from Example 26. [Figure 25] 1 shows the IR spectrum of amorphous Form B of 6,6′-DPBHBNA obtained from Example 26. [Figure 26] 1 shows the X-ray powder diffraction pattern of Form C of 6,6′-DPBHBNA obtained from Example 27. [Figure 27] 1 shows the NIR spectrum of Form C of 6,6′-DPBHBNA obtained from Example 27. [Figure 28] 1 shows the IR spectrum of Form C of 6,6′-DPBHBNA obtained from Example 27. [Figure 29] 1 shows the DSC of Form C of 6,6′-DPBHBNA obtained from Example 27. [Figure 30] 1 is a first graph in which the horizontal axis represents the Abbe number (v) of the thermoplastic resins of Examples and Comparative Examples, and the vertical axis represents the refractive index (nD). [Figure 31] 2 is a second graph in which the horizontal axis represents the Abbe number (v) of the thermoplastic resins of the examples and comparative examples, and the vertical axis represents the refractive index (nD). DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention will be described in detail below. (1) Thermoplastic resin components (structural units) The thermoplastic resin of the present invention contains a structural unit represented by the following general formula (1): The type of the copolymer is not particularly limited as long as it has the following structural units, but polyester copolymers are preferred. resin, polyester carbonate resin, polycarbonate resin, or at least Both are mixtures of two or more. Among thermoplastic resins, polyester resin is a type of polyolefin containing the (-RCO-O-) moiety. Polycarbonate having an ester structural unit (repeating unit) and containing a (-RO-CO-O-) moiety The polycarbonate resin does not contain a carbonate structural unit (repeating unit), and the polycarbonate resin is -RO-CO-O-) moiety-containing polycarbonate structural unit (repeating unit), ( does not contain polyester structural units (repeating units) containing the -RCO-O- moiety. The polyester carbonate resin is a polyester structure containing (-RO-CO-) moieties. Polycarbonate structure containing units (repeating units) and (-RO-CO-O-) moieties The R's are hydrocarbon groups or the like. [ka] (R1 and R2 in formula (1) each independently represent a hydrogen atom, a fluorine atom, or a chlorine atom.) , bromine atom, iodine atom, alkyl group having 1 to 6 carbon atoms, monocyclic or polycyclic group having 6 carbon atoms and monocyclic or polycyclic heteroaryl groups having 5 to 36 ring atoms. Thus, one, two, three, or four of the ring atoms are selected from nitrogen, sulfur, and oxygen, and other ring atoms are Heteroaryl groups in which the atom is carbon, alkenyl groups with 2 to 6 carbon atoms, and alkynyl groups with 1 to 6 carbon atoms. represents an alkoxy group or an aralkyl group having 7 to 17 carbon atoms; The monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group are The aryl group may be unsubstituted or may be selected from the group consisting of CN, CH3, OCH3, O-phenyl, O -naphthyl, S-phenyl, S-naphthyl, and halogen; one or two R a may have a group, However, neither R1 nor R2 is hydrogen, X is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or a an arylene group having 6 to 20 carbon atoms; However, the alkylene group and the cycloalkylene group each have a benzene ring. may be substituted so that a and b are each an integer of 1 to 10.

[0015] In the general formula (1), R1 and R2 are each preferably a hydrogen atom, a group having 1 carbon atom, or a group having 1 carbon atom. alkyl groups with 6 to 30 carbon atoms, alkenyl groups with 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 It is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms. In addition, R1 to R2 in general formula (1) 10 At least one of the aryl groups has 6 to 20 carbon atoms. Preferably, it is an aryl group, more preferably an aryl group having 6 to 14 carbon atoms. In particular, R1~R 10 At least two of these have 6 to 14 carbon atoms or 6 to 12 carbon atoms. It is more preferably a methyl group.

[0016] R1 and R2 are, for example, the same. R1 and R2 may be the same or different and may be monocyclic or polycyclic carbon atoms. Aryl groups with 6 to 36 prime atoms, monocyclic or polycyclic heteroaryl groups with 5 to 36 ring atoms group, wherein one, two, three, or four of the ring atoms are selected from nitrogen, sulfur, and oxygen. The other ring atoms may be selected from heteroaryl groups, where the other ring atoms are carbon. The monocyclic or polycyclic aryl groups and the monocyclic or polycyclic heteroaryl groups may be substituted. It doesn't have to be.

[0017] R1 and R2 may each be selected from the following group: Azulenil, may be unsubstituted or may be bonded to each other by a phenyl and a single bond; They may be directly condensed with each other and / or may be saturated or unsaturated 4- to 10-membered single rings. Two, three, or four rings, optionally fused to a cyclic or bicyclic hydrocarbon ring Polycyclic aryls having 2, 3, 4, or more phenyl rings indenyl, optionally substituted by 1 or 5 substituents; unsubstituted phenyl, phenyl substituted by one or two CN groups; phenyl and may be bonded to each other by a single bond or may be directly fused to each other and / or saturated or unsaturated 4- to 10-membered monocyclic or bicyclic rings Polycyclic aromatic hydrocarbons having two, three, or four phenyl rings, which may be fused to a hydrocarbon ring. substituted by 2, 3, 4, or 5 substituents selected from cyclic aryl; Phenyl, They may be directly condensed with each other, and / or may be saturated or unsaturated 4- to 10-membered rings. Two, three, or four rings, optionally fused to a monocyclic or bicyclic hydrocarbon ring wherein the polycyclic aryl has a phenyl ring of the formula: or phenyl and polycyclic aryls having two or three phenyl rings; may be substituted by one or two substituents selected from the group consisting of The three phenyl rings may be bonded to each other by a single bond, or may be directly fused to each other. and / or saturated 4- to 10-membered monocyclic or bicyclic hydrocarbons. The phenyl ring of the polycyclic aryl may be unsubstituted or fused to a polycyclic aryl. , or one or two substituents R a and polycyclic aryl having the formula: do.

[0018] Additionally, R1 and R2 may each be selected from the following group: unsubstituted or substituted by 1, 2, 3, 4, or 5 phenyl groups optionally substituted phenyl, phenyl substituted by one or two CN groups; Biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, and pyrene substituted by one or two polycyclic aryl groups selected from aryl, phenyl, which may be further substituted by a phenyl group of the formula unsubstituted or substituted CN, phenyl and biphenyl, naphthyl, fluorenyl, polycyclic aryl selected from anthracenyl, phenanthryl, and pyrenyl; naphthyl substituted by one or two substituents, biphenylenyl, triphenylenyl, tetraphenylenyl, phenanthryl, pyrenyl, 9H-fluorenyl, dibenzo[a,e][8]annulenyl, Perylenyl, and The group consists of 9,9'-spirobi[9H-fluoren]yl. Here, R1 and R2 are phenyl, 2-cyanophenyl, 3-cyanophenyl, 4- -cyanophenyl, 2-naphthyl, 1-naphthyl, and 9-naphthyl; It is preferable to select

[0019] Additionally, R1 and R2 may each be selected from the following group: Heteroaromatic monocyclic groups having 5 or 6 ring atoms, or 4 nitrogen atoms, or 1 oxygen atom and 0, 1, 2, or 3 nitrogen atoms a hydrogen atom or one sulfur atom and zero, one, two, or three nitrogen atoms; heteroaromatic monocyclic groups, the other ring atoms of which are carbon atoms; A heteroaromatic polycyclic group, which is a heteroaromatic monocyclic group and a ... polycyclic group, which is a heteroaromatic polycyclic group, and having one, two, three, four, or five additional aromatic rings selected from monocyclic and polycyclic rings. The (hetero)aromatic rings of a cyclic heteroaryl may be bonded to each other by a covalent bond. They may be directly condensed with each other, and / or may be saturated or unsaturated 4- to 10-membered rings. heteroaromatic polycyclic groups, which may be fused to a monocyclic or bicyclic hydrocarbon ring, Beauty, A heteroaromatic polycyclic group having ring atoms selected from oxygen, sulfur, and nitrogen. At least one saturated or partially unsaturated 5-membered heteroatom containing one or two heteroatoms Alternatively, a 6-membered heterocycle and one selected from phenyl and the above heteroaromatic monocycles , 2, 3, 4, or 5 additional aromatic rings, and at least one additional The aromatic ring is directly fused to a saturated or partially unsaturated 5- or 6-membered heterocyclic group. and other additional aromatic rings of the polycyclic heteroaryl aromatic ring are interconnected by covalent bonds. They may be bonded to each other, may be directly fused to each other, and / or may be saturated or may be fused to an unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring, Heteroaromatic polycyclic groups.

[0020] Additionally, R1 and R2 may each be selected from the following group: frill, Thienyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2, 4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, 1,3,4-oxazolyl Oxadiazolyl, 1,2,4-oxadiazolyl, pyridinyl, pyrazinyl, pyridazinyl , pyrimidinyl, triazinyl, benzofuryl, dibenzofuranyl, benzothienyl, di Benzothienyl, thianthrenyl, naphthofuryl, furo[3,2-b]furanyl, furo[ 2,3-b]furanyl, furo[3,4-b]furanyl, oxanthrenyl , indolyl, isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzo[g]indolyl, benzoxazolyl, benzo[cd]indolyl, 1H-benzo[g ]indolyl, quinolinyl, isoquinolinyl, acridinyl, phenazinyl, quinazolinyl quinoxalinyl, phenoxazinyl, benzo[b][1,5]naphthyldinyl, cinnamyl Naphthyridinyl, 1,5-naphthyridinyl, 1,8-naphthyridinyl, phenylpyrrolyl, naphthyridinyl thylpyrrolyl, dipyridinyl, 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 yl), 2H-chromenyl, 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, be Benzo[g]chromenyl, pyrrolo[3,2,1-hi]indolyl, benzo[g]quinoxa quinoxalinyl, benzo[f]quinoxalinyl, and benzo[h]isoquinolinyl be.

[0021] In the general formula (1), X is preferably an alkylene group having 2 to 4 carbon atoms, a cycloalkylene group having 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 a group having An arylene group having 6 to 10 carbon atoms is particularly preferred, and an alkylene group having 2 or 3 carbon atoms, e.g. For example, an ethylene group. In addition, a and b in the above general formula (1) are each preferably an integer of 1 to 6. More preferably, it is 1 to 4, and particularly preferably 2 or 3.

[0022] The thermoplastic resin is, for example, a polyester resin or a polyester carbonate resin. The polyester resin or polyester carbonate resin is represented by the following general formula: It is preferable that the polymer further contains a structural unit represented by (2). [ka] In the general formula (2), Q is represented by the following formula (2a). [ka] In formula (2a), R C each independently binds to a CO group in formula (2) A single bond or a substituent may be present, and the total number of carbon atoms is 1 to 10, and the formula (2) It is an alkylene group containing a terminal bond to a CO group. C is preferably a single bond, or It is an alkylene group having a total of 1 to 3 carbon atoms. Q in formula (2) is preferably represented by the following formula (2b). [ka] In formula (2b), n and m each independently represent an integer of 0 to 5, and preferably An integer between 1 and 3. p and k each independently represent an integer of 1 to 5, and preferably an integer of 1 to 3. R1 and R2 have the same meanings as R1 and R2 in formula (1). a and b each independently represent an integer of 0 to 6, preferably an integer of 1 to 3, more preferably Preferably, it is an integer of 1 or 2. Also, * represents the point of attachment to the CO group in formula (2). It is more preferable that Q in formula (2) is represented by the following formula (2c). [ka] In formula (2c), * represents the point of attachment to the CO group in formula (2).

[0023] The structural unit represented by the general formula (1) is preferably a structural unit represented by the following general formulae (A-1) to (A- 7) contains at least one of the structural units represented by the formula (I). [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0024] That is, the structural unit represented by general formula (1) is (BIN L-2EO(2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1, 1'-binaphthalene)-derived structural unit, DNBINOL-2 represented by general formula (A-2) EO(2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-1-yl) a structural unit derived from (1,1'-binaphthalene), 2DNB represented by general formula (A-3) INOL-2EO (2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene) A structural unit derived from (1,1'-binaphthalene-2-yl)-1,1'-binaphthalene, and a structural unit derived from (1,1'-binaphthalene-2-yl)-1,1'-binaphthalene, 9DPNBINOL-2EO (2,2'-bis(2-hydroxyethoxy)- Building blocks derived from 6,6'-di(phenanthrene-9-yl)-1,1'-binaphthalene , (CN-BNA(6,6'-di-(3-cyanophenyl) -2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthalene Unit, (FUR-BNA (6,6'-di-(dibenzo[b, d]furan-4-yl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-bi naphthalene)-derived structural unit and (THI-BNA(6) represented by general formula (A-7) ,6'-di-(dibenzo[b,d]thien-4-yl)-2,2'-bis-(2-hydro (oxyethoxy)-1,1'-binaphthalene)-derived structural units. It is preferable to do so.

[0025] The thermoplastic resin of the present invention contains more than 50 mol % of the structural unit represented by the general formula (1). It is preferable that the content is 100% by mole, more preferably 60% by mole, even more preferably 70% by mole, and particularly Preferably, the content is more than 80 mol %, or more than 90 mol %. The thermoplastic resin may be formed solely from the structural unit represented by the general formula (1).

[0026] The thermoplastic resin of the present invention contains at least one structural unit represented by the general formula (1) (structural unit (1)). In addition, one or more other structural units may be contained. Derivative units are preferred.

[0027] Specifically, the thermoplastic resin of the present invention is a resin having structural units represented by general formulas (3) and (4): It is preferred to further include at least one of the following: [ka] (R'1 to R' in formula (3) 20 are each independently a hydrogen atom, a fluorine atom, or a chlorine atom. Atom, bromine atom, iodine atom, alkyl group having 1 to 6 carbon atoms, 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 alkoxy group having 7 to 17 carbon atoms; represents an aralkyl group, Y is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or a an arylene group having 6 to 20 carbon atoms; c and d are each an integer of 1 to 10.

[0028] R'1 to R'' in the above general formula (3) 20 are preferably hydrogen atoms, carbon atoms, 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 is more preferred. Mostly hydrogen.

[0029] Y in the above general formula (3) is preferably an alkylene group having 2 to 4 carbon atoms, a cycloalkylene group having 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 a group having An arylene group having 6 to 10 carbon atoms is particularly preferred, and an alkylene group having 2 or 3 carbon atoms is particularly preferred. do. In addition, c and d in the general formula (3) are each preferably an integer of 1 to 6. More preferably, it is 1 to 4, and particularly preferably 2 or 3.

[0030] [ka] (R''1 to R'' in Equation (4) 16 are each independently a hydrogen atom, a fluorine atom, Chlorine atom, bromine atom, iodine atom, alkyl group having 1 to 6 carbon atoms, 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 alkoxy group having 7 to 1 carbon atoms; 7 represents an aralkyl group, Z is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or a an arylene group having 6 to 20 carbon atoms; e and f are each an integer of 1 to 10.

[0031] R"1 to R" in the above general formula (4) 16 are each preferably a hydrogen atom, Alkyl groups with 1 to 4 carbon atoms, aryl groups with 6 to 12 carbon atoms, and alkenyl groups with 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 Preferably, it is hydrogen or an aryl group having 6 to 10 carbon atoms.

[0032] In the general formula (4), Z is preferably an alkylene group having 2 to 4 carbon atoms, a cycloalkylene group having 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 a group having An arylene group having 6 to 10 carbon atoms is particularly preferred, and an alkylene group having 2 or 3 carbon atoms is particularly preferred. do. In addition, e and f in the general formula (4) are each preferably an integer of 1 to 6. More preferably, it is 1 to 4, and particularly preferably 2 or 3.

[0033] The thermoplastic resin of the present invention comprises a structural unit (1) and a copolymer represented by the general formula (3) or (4) above. The structural unit to be contained further includes at least one structural unit represented by the following general formula (5): It is preferable that the compound is included in the formula (I). [ka] That is, the thermoplastic resin of the present invention comprises, together with the structural unit (1), a structural unit represented by the above general formula (5): BNEF (9,9-bis(6-(2-hydroxyethoxy)naphthalene-2-yl) BNE (2,2'-bis(2-hydroxyethoxy)fluorene) is a structural unit derived from BPPEF (9,9-bis(trimethylsilyl)-1,1'-binaphthalene) and (4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene) It is preferable that the polymer further contains at least one of the following structural units.

[0034] The thermoplastic resin of the present invention contains a structural unit other than the structural unit (1), preferably a structural unit represented by the above general formula (3 ) and (4) may be contained in a total amount of 20 to 80 mol %, for example, The thermoplastic resin may contain 25 to 75 mol % of the compounds represented by the above general formulas (3) and (4). The structural units to be used are, for example, 30 to 70 mol %, 35 to 65 mol %, or 40 to 60 mol %include. That is, the thermoplastic resin composition of the present invention comprises a structural unit (1) and a structural unit represented by general formula (3): The molar ratio of the structural unit (3) to the structural unit (4) 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, However, in the thermoplastic resin composition, the ratio of the structural unit ( Since it is preferable that the structural unit (1) is contained in an amount of more than 50 mol %, the structural unit (1) and the structural unit ( 3) The molar ratio is preferably 4:1 to 1:1, 7:3 to 1:1, or 65:3. 5 to 1:1, and 3:2 to 1:1, etc. The molar ratio of the structural unit (1) to the structural unit (4) represented by general formula (4) is The molar ratio of the structural unit (1) to the structural unit (3) is the same as that described above.

[0035] The thermoplastic resin of the present invention may include any of random, block and alternating copolymer structures. In the thermoplastic resin of the present invention, the above-mentioned structural unit (1) may be present in the same polymer molecule. ), structural unit (3), and structural unit (4) may not all be contained. If the above-mentioned structural units are contained in the entire polymer molecule of the present invention, the thermoplastic polymer of the present invention can be used. The polymeric resin may be a blend resin. For example, the polymeric resin may be a blend resin of the above-mentioned structural unit (1), structural unit (3), The thermoplastic resin containing both the structural unit (1) and the structural unit (4) is preferably a resin containing the structural unit (1), (3) Even if the copolymer contains both the structural unit (1) and (4), it is not a homopolymer containing the structural unit (1) or A copolymer and a homopolymer containing the structural unit (2) or a copolymer and a homopolymer containing the structural unit (4). It may be a mixture of polymers or copolymers, and may contain structural units (1) and (3). Even in the case of a blend resin of a copolymer containing the structural units (1) and (4) good.

[0036] The thermoplastic resin of the present invention can be blended with other resins to produce molded articles. For example, thermoplastic resins such as polyester, polyester carbonate, and polycarbonate In the case where the resin is any one of the above, examples of the other resin include polyamide, polyacetal, Polycarbonate, modified polyphenylene ether, polyethylene, and other types of thermoplastic resins Examples include polybutylene terephthalate and polybutylene terephthalate.

[0037] Furthermore, the thermoplastic resin composition of the present invention may contain additives such as antioxidants, mold release agents, processing stabilizers, ultraviolet absorbers, Adding absorbents, flow improvers, nucleating agents, strengthening agents, dyes, antistatic agents, antibacterial agents, etc. It is preferable.

[0038] Antioxidants include triethylene glycol-bis[3-(3-tert-butyl- 5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol- Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] ], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxybenzoate] hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl ethyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6 -tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N -Hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate) amide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-di Ethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)iso Socyanurate and 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl ethyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4, 8,10-tetraoxaspiro(5,5)undecane, etc. , pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxybenzoate The content of antioxidants in thermoplastic resin compositions is preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, The content is preferably 0.001 to 0.3 parts by weight per 100 parts by weight of the thermoplastic resin. It's nice.

[0039] As a release agent, 90% or more by weight of which is made up of an ester of alcohol and fatty acid The ester of alcohol and fatty acid is preferably a monohydric alcohol and a fatty acid. Examples include esters with fatty acids, partial esters or full esters of polyhydric alcohols and fatty acids. The esters of the monohydric alcohol and fatty acid include monohydric alcohols having 1 to 20 carbon atoms. Esters of polyhydric alcohols and saturated fatty acids having 10 to 30 carbon atoms are preferred. As a partial or complete ester of alcohol and fatty acid, it has 1 to 25 carbon atoms. Partial or complete ester of polyhydric alcohol and saturated fatty acid having 10 to 30 carbon atoms Ru is preferred.

[0040] Specifically, examples of esters of monohydric alcohols and saturated fatty acids include stearyl stearyl alcohol and esters of saturated fatty acids. Palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate Partial or complete esters of polyhydric alcohols and saturated fatty acids. Stearic acid monoglyceride, stearic acid diglyceride, stearic acid Triglyceride, Stearic Acid Monosorbate, Behenic Acid Monoglyceride, Caprylic / Capric Triglyceride Acid monoglyceride, lauric acid monoglyceride, pentaerythritol monostearate , Pentaerythritol tetrastearate, Pentaerythritol tetrapelargone , propylene glycol monostearate, biphenyl biphenate, sorbitan mono Stearate, 2-Ethylhexyl Stearate, Dipentaerythritol Hexastearate Examples of the dipentaerythritol include full or partial esters of dipentaerythritol such as esters of dipentaerythritol. Among these, stearic acid monoglyceride and lauric acid monoglyceride are particularly preferred. The content of these release agents is 0.005 to 2.0 parts by weight per 100 parts by weight of the thermoplastic resin. The range of 0.01 to 0.6 parts by weight is preferred, and the range of 0.02 to 0. A range of 5 parts by weight is more preferred.

[0041] Examples of the processing stabilizer include phosphorus-based processing heat stabilizers and sulfur-based processing heat stabilizers. The heat-processing stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and the like. esters, etc. Specifically, triphenyl phosphite, tris(nonyl phenoxy) tris(2,4-di-tert-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, Tris(2,6-di-tert-butylphenyl)phosphite, tridecylphosphite , trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl Phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite Phosphite, Monobutyldiphenylphosphite, Monodecyldiphenylphosphite, Octyldiphenylphosphite, bis(2,6-di-tert-butyl-4-methyl phenyl) pentaerythritol diphosphite, 2,2-methylenebis(4,6-di- tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol Thuritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol di Phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol di Phosphite, Distearyl Pentaerythritol Diphosphite, Tributyl Phosphite phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, Diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, benzenephosphonic acid diethyl benzenephosphonate, dipropyl benzenephosphonate, tetrakis(2,4-di-t-butylphenyl) tetrakis(2,4-di-t-butyl)-4,4'-biphenylene diphosphonite phenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-t-b Bis(2,4-di-tert-phenyl)-3,3'-biphenylene diphosphonite -butylphenyl)-4-phenyl-phenylphosphonite and bis(2,4-di-t (ert-butylphenyl)-3-phenyl-phenylphosphonite, etc. Among these, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol The phosphorus-based heat-processing stabilizer in the thermoplastic resin composition is preferably ethylenediamine diphosphite. The amount is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0042] Sulfur-based heat stabilizers include pentaerythritol-tetrakis(3-laurylthio) propionate), pentaerythritol-tetrakis(3-myristylthiopropionate) Pentaerythritol-tetrakis(3-stearylthiopropionate), di Lauryl-3,3'-thiodipropionate, Dimyristyl-3,3'-thiodipropionate ester, distearyl-3,3'-thiodipropionate, etc. Thermoplastic resins The content of the sulfur-based heat processing stabilizer in the composition is 0.00 with respect to 100 parts by weight of the thermoplastic resin. The amount is preferably 1 to 0.2 parts by weight.

[0043] UV absorbers include benzotriazole-based UV absorbers and benzophenone-based UV absorbers. absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyano At least one ultraviolet absorber selected from the group consisting of acrylate-based ultraviolet absorbers is preferred. That is, the ultraviolet absorbers listed below may be used alone or in combination of two or more. The above may be used in combination.

[0044] Benzotriazole-based UV absorbers include 2-(2-hydroxy-5-methylphenyl) Nyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl) Benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzol Zotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetrachlorobenzotriazole] tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole , 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-( 2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebi bis(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. It can be obtained.

[0045] Benzophenone-based UV absorbers include 2,4-dihydroxybenzophenone, 2- Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone Non, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy 5-sulfoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5 -sulfonic acid hydrate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2' ,4,4'-Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-di Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiol sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl) (phenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy 4-methoxy-2'-carboxybenzophenone and the like.

[0046] Triazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazine). 2-(4,6-bis(2-(2-yl)-5-[(hexyl)oxy]-phenol) ,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl) hydroxy]-phenol and the like.

[0047] Cyclic iminoester UV absorbers include 2,2'-bis(3,1-benzoxa) 2,2'-p-phenylenebis(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-benzoxazin-4-one), 2,2'- (1,5-naphthalene)bis(3,1-benzoxazin-4-one), 2,2'-(2 -methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'- (2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one) and 2 ,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one) Examples include:

[0048] Cyanoacrylate-based UV absorbers include 1,3-bis-[(2'-cyano-3' ,3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-di phenylacryloyl)oxy]methyl)propane, and 1,3-bis-[(2-cyano) and benzo[(3,3-diphenylacryloyl)oxy]benzene.

[0049] The content of the ultraviolet absorber is preferably 0.01 to 100 parts by weight of the thermoplastic resin. 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and even more preferably The blending amount is 0.05 to 0.8 parts by weight. Within this blending amount range, the thermoplastic resin can be used depending on the application. It is possible to impart sufficient weather resistance to the resin composition.

[0050] Thermoplastic resin compositions, such as polycarbonate resin compositions, contain oxidizing agents that are generated during production. Phenol and unreacted diester carbonate are present as impurities. The phenol content in the oil composition is preferably 0.1 to 3000 ppm, and more preferably 0.1 More preferably, the concentration is 1 to 1000 ppm, 1 to 800 ppm, It is more preferable that the content is 1 to 500 ppm, or 1 to 300 ppm. The content of the carbonic acid diester in the resin composition is preferably 0.1 to 1000 ppm, It is more preferably 0.1 to 500 ppm, and particularly preferably 1 to 100 ppm. It is preferable to adjust the amounts of phenol and carbonic acid diester contained in the thermoplastic resin composition. By doing so, it is possible to obtain a resin with the properties required for the intended purpose. The content of the acid diester can be adjusted appropriately by changing the polycondensation conditions and equipment. It can also be adjusted by the conditions of the extrusion step after polycondensation.

[0051] If the content of phenol or carbonic acid diester exceeds the above range, the resulting resin molding may have a problem. Problems such as a decrease in strength and the generation of odor may occur. If the ester content is below the above range, the plasticity of the resin may decrease when melted.

[0052] (2) Properties of thermoplastic resin The preferred viscosity average molecular weight (Mv) of the thermoplastic resin of the present invention is 8,000 to 20,000. 0, more preferably 9,000 to 15,000, and even more preferably 10,000 to 14,000. More preferable.

[0053] If the Mv value is less than 8,000, the molded body may become brittle. If it is greater than 20,000, the melt viscosity will be high, making it difficult to remove the resin after production. Furthermore, the fluidity may be deteriorated, making it difficult to perform injection molding in a molten state.

[0054] The refractive index (nD) of the thermoplastic resin of the present invention at 23°C and a wavelength of 589 nm is preferably is 1.635 or more, more preferably 1.645 or more, and even more preferably 1.655 or more, Particularly preferably, the t-value is 1.665 or more, or greater than these values. The refractive index of the plastic resin is preferably 1.640 to 1.710, more preferably 1.645 to 1.700, more preferably 1.650 to 1.697, and particularly preferably 1.65 The thermoplastic resin of the present invention has a high refractive index (nD) and is suitable for use as an optical lens material. The refractive index is measured using an Abbe refractometer for a 0.1 mm thick film. It can be measured according to the method of JIS-K-7142.

[0055] The Abbe number (ν) of the thermoplastic resin of the present invention is preferably 24 or less, more preferably 22 The Abbe number is 5 at a wavelength of 486 nm and 5 at 23°C. It can be calculated from the refractive indices at 89 nm and 656 nm using the following formula: ν=(nD-1) / (nF-nC) nD: Refractive index at a wavelength of 589 nm nC: Refractive index at a wavelength of 656 nm nF: Refractive index at a wavelength of 486 nm

[0056] The preferred glass transition temperature (Tg) of the thermoplastic resin of the present invention is such that it can be used for injection molding. Considering this, the temperature is 90 to 185°C, more preferably 95 to 180°C, and even more preferably Preferably, it is 100 to 175°C. If Tg is lower than 90°C, the usable temperature range may be narrowed. If the temperature exceeds 185°C, the melting point of the resin will increase, which may cause decomposition or discoloration of the resin. If the glass transition temperature of the resin is too high, it may be difficult to control the temperature with a general-purpose mold temperature controller. The difference between the mold temperature and the resin glass transition temperature becomes large. In applications where surface precision is required, it becomes difficult to use resins with too high a glass transition temperature. In addition, from the viewpoint of molding flowability and molding heat resistance, the lower limit of Tg is 130°C. The upper limit of Tg is preferably 185°C, more preferably 175°C. is more preferred.

[0057] The optically molded article obtained using the thermoplastic resin of the present invention has a total light transmittance of 85% or more. It is preferable that the ratio is 87% or more, more preferable that the ratio is 88% or more. It is preferable that the total light transmittance is 85% or more. It is comparable to fat.

[0058] The thermoplastic resin of the present invention has high resistance to moisture and heat. The obtained optical molded body is subjected to a "PCT test" (pressure cooker test). The PCT test can be evaluated by measuring the total light transmittance of the optical molded article after the test. , 50mm diameter, 3mm thick injection molded product, 120℃, 0.2Mpa, 100%RH, The thermoplastic resin of the present invention can be subjected to the PCT test by maintaining the temperature at 20°C for 20 hours. The total light transmittance after the test is 60% or more, preferably 70% or more, and more preferably 75% or more. It is more preferable that the ratio is 80% or more, and even more preferable that the ratio is 85% or more. It is particularly preferable that the total light transmittance is 60% or more. It can be said that it has high resistance to moisture and heat.

[0059] The b value, which indicates the hue of the thermoplastic resin of the present invention, is preferably 5 or less. This indicates that the yellow color is weak and the hue is good.

[0060] (3) Manufacturing method of thermoplastic resin The thermoplastic resin having the structural unit represented by the general formula (1) is a polycarbonate resin. In this case, the production method thereof includes, for example, a method for producing a dihydroxy compound represented by the following general formula (6): and a carbonic acid diester. [ka] (R1 and R2 in the general formula (6) each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, Br, iodine, alkyl group with 1 to 6 carbon atoms, monocyclic or polycyclic carbon atoms aryl groups having 6 to 36 ring atoms, monocyclic or polycyclic heteroaryl groups having 5 to 36 ring atoms; wherein one, two, three, or four of the ring atoms are selected from nitrogen, sulfur, and oxygen; Heteroaryl groups in which the ring atom is carbon, alkenyl groups having 2 to 6 carbon atoms, and alkenyl groups having 1 to 6 carbon atoms. represents an alkoxy group or an aralkyl group having 7 to 17 carbon atoms; However, neither R1 nor R2 is hydrogen, X is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or a an arylene group having 6 to 20 carbon atoms; However, the alkylene group and the cycloalkylene group each have a benzene ring. may be substituted so that a and b are each an integer of 1 to 10. That is, the compound represented by the above general formula (6) is used as a dihydroxy component, and carbonate Reacting with carbonate precursors such as diesters to produce polycarbonate resins Specifically, the compound represented by the general formula (6) and carbonic acid diesters can be used. The carbonate precursor is catalyzed by a basic compound or a transesterification catalyst or both. The polymer is produced by reacting the polymer by a melt polycondensation method in the presence of a mixed catalyst comprising the following or in the absence of a catalyst: It is possible. In addition, the dihydroxy compound represented by the above general formula (6) is used as a raw material (monomer) to produce poly(vinyl alcohol). It is also possible to obtain ester carbonate resins and polyester resins. The polyester carbonate resin or polyester resin may be, for example, a resin represented by the above general formula (6 ) and a dihydroxy compound represented by the formula (I), a carboxylic acid, a carboxylic acid monoester, and a carboxylic acid It can be produced by a process of melt polycondensation with at least one of a diester.

[0061] For example, specific examples of carboxylic acids, carboxylic acid monoesters, and carboxylic acid diesters include: 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1' -Dicarboxylic acid, monocarboxylic acid monoester, di-binaphthalene (BINL-2EO) Ester, 9,9-fluorene-dipropionic acid, 9,9-fluorene-dipropionic acid 9,9-fluorene-dipropionate methyl ester (FDP) M) and others. Further, specific examples of carboxylic acids, carboxylic acid monoesters, and carboxylic acid diesters include: 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-1- 2,2'-bis(2-hydroxybenzoyl)-1,1'-binaphthalene (DNBINOL-2EO) (hydroxyethoxy)-6,6'-di(naphthalen-2-yl)-1,1'-binaphthalene (2DNBINOL-2EO), 2,2'-bis(2-hydroxyethoxy)-6,6' -Di(phenanthrene-9-yl)-1,1'-binaphthalene (9DPNBINOL-2 EO), 6,6'-di-(3-cyanophenyl)-2,2'-bis-(2- hydroxyethoxy)-1,1'-binaphthyl(CN-BNA), 6 ,6'-di-(dibenzo[b,d]furan-4-yl)-2,2'-bis -(2-hydroxyethoxy)-1,1'-binaphthyl(FUR-B NA), 6,6'-di-(3-cyanophenyl)-2,2'-bis-(2- hydroxyethoxy)-1,1'-binaphthyl(CN-BNA), Also included are dicarboxylic acids, monocarboxylic acid monoesters, diesters, and the like.

[0062] The compound of general formula (6) includes 2,2'-bis(hydroxy(poly)alkoxy)- Diaryl-1,1'-binaphthalenes, 2,2'-bis(hydroxy(poly)alkoxy) For example, 2,2'-bis( 2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2' -Bis(2-hydroxyethoxy)-6,6'-di(naphthalen-1-yl)-1,1'- Binaphthalene, 2,2'-bis(2-hydroxymethoxy)-6,6'-diphenyl-1 ,1'-binaphthalene, 2,2'-bis(2-hydroxymethoxy)-6,6'-di(naphthalene) phthalen-1-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxypropyl) (epoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(2-hydroxy (6,6'-di(naphthalen-1-yl)-1,1'-binaphthalene These may be used alone or in combination of two or more.

[0063] In addition, among the monomers for producing the thermoplastic resin, the monomer represented by the above general formula (6) In addition to the dihydroxy compound, the values ​​of a and b in the general formula (6) are both 0. A dihydroxy compound, or one of a and b in the above general formula (6) Dihydroxy compounds having an OH group of 0 may be contained as impurities. Thus, the dihydride having at least one value of a and b different from that of the general formula (6) is The dihydroxy compound is a monomer having a dihydroxy compound represented by the above general formula (6) as a main component. In total, the content is preferably 1000 ppm or less, more preferably 500 ppm or less, and Preferably, the amount is 200 ppm or less, particularly preferably 100 ppm or less. In addition, a dihydroxy compound having a different value of at least one of a and b from that of the general formula (6) is The total content of the above-mentioned monomers is preferably 50 ppm or less, and more preferably 20 ppm or less. It is more desirable that it be less than m.

[0064] The compound of general formula (6) can be produced by various synthesis methods. -227387, JP 2014-227388, JP 2015-168658, and JP 2015-187098 As described above, (a) 1,1'-binaphthol and ethylene glycol monotosylate (b) a method of reacting a binaphthol with an alkylene oxide or a halogenoalkanoic acid. (c) a method of reacting 1,1'-binaphthol or alkylene carbonate with (d) a method of reacting 1,1'-binaphthol with ethylene carbonate; It can be produced by a method of reacting it with ethylene carbonate.

[0065] The monomer of general formula (6) contains an undesirable component that can adversely affect the properties of the thermoplastic resin, particularly the optical properties. In particular, the monomer of general formula (6) may contain impurities resulting from the manufacturing process thereof. The compound may contain one or more of the following by-products of general formula (6a) and (6b) as pure compounds: It's okay to be. [ka]

[0066] In one embodiment, the monomer of general formula (6) is also free from impurities of formulas (6a) and (6b). In addition, or instead of them, impurities arising from the manufacturing process include compounds of the general formula (6c) The following by-products may be included: In formulae (6a), (6b) and (6c), the substituents R1, R2 and X are each independently selected from the group consisting of the groups of formula (6) The monomers of formula (6) and formula (6a) are the same as those defined in the monomers of formula (6). In (6c) and (6d), a is an integer ranging from 1 to 10, preferably from 1 to 4. is an integer, more preferably 1, 2 or 3. In formula (6c), the variables b, c and d is an integer ranging from 1 to 10, preferably an integer ranging from 1 to 4, more preferably The monomers of formula (6) are 1, 2, or 3. In formulas (6a) and (6c), Each of the substituents X is preferably an alkylene group having 1 to 4 carbon atoms, more preferably The most common is an ethylene group, i.e., 1,2 ethanediyl or -CH2CH2-. In the monomer of formula (6), as well as in the monomers of formula (6a), (6b) and (6c), the substituent R R1 and R2 are preferably a monocyclic or polycyclic aryl group having 6 to 36 carbon atoms, and preferably a monocyclic or polycyclic heteroaryl group having 6 to 36 ring atoms. or polycyclic aryl groups having 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms. aryl groups, particularly phenyl, 1-naphthyl, 2-naphthyl, 9-phenanthyl from the group consisting of 4-dibenzo[b,d]furanyl and 4-dibenzo[b,d]thienyl are selected.

[0067] Preferably, the monomer of formula (6) used in the process of the present invention is a monomer of formula (6a) and ( The total weight of the impurities of 6b) is 5000 ppm based on 1 part by weight of the monomer of formula (6). In particular, the total weight of impurities of formula (6a) and (6b) does not exceed the weight of the monomer of formula (6) Based on 1 part by weight, the maximum is 4000 ppm or less, and further, the maximum is 3000 ppm or less, and more preferably at most 2000 ppm or less. The weight of each of the impurities of formula (6a) and (6b) is based on 1 part by weight of the monomer of formula (6). As a standard, the maximum is 2000 ppm or less, and even more so, the maximum is 1500 ppm or less. If present, it is preferable that the maximum concentration is 1000 ppm or less. The amount of impurity (6c) is 2000 ppm based on 1 part by weight of the monomer of formula (6). It does not exceed this level, and is often no more than 1500 ppm.

[0068] In a specific embodiment of the invention relating to the thermoplastic resin produced by the method of the present invention, The variables (a) and (b) of the monomer (6) are 1, and this will be referred to as monomer (6-1) below. The monomer (6-1) is one of the following formulae (6a-1), (6-2), and (6b): It may contain one or more by-products, and may optionally contain (6c-1) as an impurity. That's fine. [ka]

[0069] In formulae (6-1), (6a-1), (6-2) and (6c-1), the substituent X is Each of them is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an ethylene group. That is, 1,2-ethanediyl or -CH2CH2-. In formula (6-2), The variable e is defined as the variable a, and is particularly 2 or 3. In (6a-1), (6-2), (6-b) and (6c-1), the substituents R1 and R2 is preferably a monocyclic or polycyclic aryl group having 6 to 36 carbon atoms, It is a polycyclic heteroaryl group having 6 to 36 ring atoms, and more preferably a monocyclic or A polycyclic aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms. In particular, phenyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl, 4-diphenyl benzo[b,d]furanyl and 4-dibenzo[b,d]thienyl do.

[0070] Preferably, the monomer of formula (6-1) used in the method of the present invention is a monomer of formula (6a-1 The total weight of impurities (6-1), (6-2) and (6b) is based on 1 part by weight of the monomer of formula (6). In particular, the impurities of the formulae (6a-1), (6-2) and (6b) The total weight of the pure material is at most 4000 parts by weight based on 1 part by weight of the monomer of formula (6-1). pm or less, and even at most 3000 ppm or less, and even at most 200 It is particularly preferable that the amount of the cations represented by the formulas (6a-1), (6-2) and (6b) is 0 ppm or less. The weight of each impurity is at most 2 parts by weight based on 1 part by weight of the monomer of formula (6-1). 000 ppm or less, and even a maximum of 1500 ppm or less, and even a maximum of If present, the impurity of (6c-1) is preferably 1000 ppm or less. The amount of the substance does not exceed 2000 ppm based on 1 part by weight of the monomer of formula (6-1), and The maximum is often less than 1500 ppm.

[0071] In a specific embodiment of the invention relating to the thermoplastic resin produced by the method of the present invention, The monomer (6) is 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl 6,6'-diphenyl-2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene phthyl), i.e., in formula (6), variables (a) and (b) are both 1 and X is 1,2-ethanediyl, and the substituents of R1 and R2 are both phenyl. Here and elsewhere in this specification, 2,2'-bis(2-hydroxyethyl) (oxy)-6,6'-diphenyl-1,1'-binaphthalene is 6,6'-DPBHBNA It is also abbreviated as .

[0072] 6,6'-DPBHBNA can be prepared by the above-mentioned formulas (6a-1), (6-2), (6b) and (6 In c-1), the substituent X is 1,2-ethanediyl, and all of the substituents of R1 and R2 are phenyl, and the variable e in formula (6-2) is 2 or 3, particularly 2; It may contain impurities. In formula (6a-1), the substituent X is 1,2-ethanediyl, and the substituents R1 and R2 are The chemical name for the compound in which both substituents are phenyl is 2-(2-hydroxyethoxy)-2 '-Hydroxy-6,6'-diphenyl-1,1'-binaphthalene (6,6'-diphenyl-2-( 2-hydroxyethoxy)-2'-hydroxy-1,1'-binaphthyl). In formula (6-2), the substituent X is 1,2-ethanediyl, e is 2, and R1 The chemical name of the compound in which both R and R2 are phenyl is 2-(2-hydroxyethoxy)-2-phenyl. (2-(2-hydroxyethoxy)-ethoxy)-6,6'-diphenyl 1,1'-binaphthalene (6,6'-diphenyl-2-(2-hydroxyethoxy)-2'-(2-hydroxy (ethoxy)-ethoxy)-1,1'-binaphthyl). In formula (6b), the chemical name of the compound in which both R1 and R2 are phenyl is 2,2'-bishydroxy-6,6'-diphenyl-1,1'-binaphthalene (6,6 '-diphenyl-2,2'-bishydroxy-1,1'-binaphthyl). In formula (6c-1), the substituent X is 1,2-ethanediyl, and all of R and R The chemical name for the compound in which both substituents of 2 are phenyl is bis[2-[[1-[2-(2 -hydroxyethoxy)-6-phenyl-1-naphthyl]-6-phenyl-2-naphthyl ]-oxy]-ethyl] carbonate (bis[2-[[1-[2-(2-hydroxyethoxy)-6-phenyl-1-naphthyl] thyl]-6-phenyl-2-naphthyl]-oxy]-ethyl]carbonate).

[0073] Preferably, the 6,6'-DPBHBNA of the formula (6a- Impurities of (1), (6-2) and (6b), wherein the substituent X is 1,2-ethanediyl. The total weight of impurities in which all R1 and R2 substituents are phenyl is 6,6'-DP It does not exceed 5000 ppm based on 1 part by weight of BHBNA. The 6,6'-DPBHBNA containing the above-mentioned impurities is novel, and therefore also Particularly, in formulas (6a-1), (6-2) and (6b), An impure compound in which the group X is 1,2-ethanediyl and all R1 and R2 substituents are phenyl The total weight of the pure substance is at most 400 parts by weight based on 1 part by weight of 6,6'-DPBHBNA. 0 ppm or less, and even at most 3000 ppm or less, and even at most 2 000 ppm or less. In particular, the formulas (6a-1), (6-2) and (6b ) wherein the substituent X is 1,2-ethanediyl and all of the R1 and R2 substituents are fluoro. The weight of each of the phenyl impurities is 1 part by weight of the 6,6'-DPBHBNA monomer. Based on this standard, the maximum concentration is 2000 ppm or less, and even more so, the maximum concentration is 1500 ppm or less. It is preferable that the maximum concentration is 1000 ppm or less. In this case, in formula (6c-1), the substituent X is 1,2-ethanediyl, and all of R1 and The amount of the impurity in which the R2 substituent is phenyl is usually 6,6'-DPBHBNA. Not exceeding 2000 ppm by volume, and often no more than 1500 ppm .

[0074] 6,6'-DPBHBNA tends to form solvates with certain organic solvents, especially Methanol, toluene, anisole, xylene, chlorobenzene, tetrahydrofuran 2-butanone and methyl isobutyl ether, also known as methyl ethyl ketone (MEK), Solvated with aliphatic ketones such as 4-methyl-2-pentanone, also known as ketone (MIBK) In these solvents, the amount of each organic solvent is usually 6 The amount of hydroxybenzoates is in the range of 0.3 to 1.5 moles per mole of 6'-DPBHBNA. and elsewhere in this specification, the term solvate refers to a compound that contains a solvent within the crystal lattice of a crystalline form. These solvates are often referred to as "pseudo polymorphs" These are called "polymorphs" and are distinguished from "polymorphisms" which essentially do not involve solvent.6 In the crystalline solvate of 6,6'-DPBHBNA, the amount of solvent is It does not have to be stoichiometric with respect to the amount of BNA, but it can vary. However, the solvent molecules present in the crystalline solvates of 6,6'-DPBHBNA are generally Usually, gaps or holes are formed in the crystal lattice by the 6,6'-DPBHBNA molecules. Fill in.

[0075] Among the above-mentioned solvents, methanol, toluene and methyl ethyl ketone are particularly preferred. The crystalline solvates they form with 6,6'-DPBHBNA usually have low aspartic acid. The crystals are obtained as compact crystals with a high aspect ratio. These crystals do not adhere to the mother liquor. These crystalline solvents tend to have high purity 6,6'-DPBHBNA. Solvates may also be part of the invention.

[0076] with an organic solvent selected from the group consisting of methanol, toluene and methyl ethyl ketone The solvate of 6,6'-DPBHBNA is more than 99% (or more) of 6,6'-DPBHBNA. In particular, all products with a purity of at least 99.5% or more, and even 99.7% or more This allows for improved purity of 6,6'-DPBHBNA.

[0077] Unless otherwise specified herein, the solid form of 6,6'-DPBHBNA In the context of the present invention, purity of greater than 99% refers to the purity of each solid of 6,6'-DPBHBNA. The total amount of organic impurities contained in the form, i.e., 6,6'-DPBHBNA and and the amount of organic compounds other than solvents that may optionally be present is less than 1% by weight. Similarly, purity of at least 99.5% or at least 99.7% means that the organic The total amount of impurities, i.e., in each solid form of 6,6'-DPBHBNA Amount of organic compounds other than 6,6'-DPBHBNA and solvents that may be optionally present This means that the amount is at most 0.5% by weight, or at most 0.3% by weight.

[0078] In the crystalline solvate of 6,6'-DPBHBNA of the present invention, 2-(2- Hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-binaphthalene 2,2'-bishydroxy-6,6'-diphenyl-1,1'-binaphthalene, and and 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy)-ethoxy 1,1'-binaphthalene, 1,1'-diphenyl-2,2'-diphenyl- ... The total amount of impurities containing 1,1'-binaphthyl moieties is 6 contained in the crystals of the crystalline solvate. , based on 1 part by weight of 6'-DPBHBNA, often at most 5000 ppm ( 0.50% by weight or less, preferably at most 4000 ppm (0.40% by weight) or less, in particular, at most 3000 ppm (0.30% by weight) or less, and further The maximum concentration is 2000 ppm (0.20% by weight). The weight of each component is at most 2000 parts by weight based on 1 part by weight of 6,6'-DPBHBNA. m or less, and even at most 1500 ppm or less, and even at most 1000 It is preferable that the concentration of each solvate is bis[2-[[1-[ 2-(2-hydroxyethoxy)-6-phenyl-1-naphthyl]-6-phenyl-2- If naphthyl]-oxy]-ethyl] carbonate is included, the amount thereof is usually 6,6'- Not exceeding 2000 ppm based on 1 part by weight of DPBHBNA, and often not exceeding 15 ppm 00ppm or less.

[0079] In the crystalline solvates of the present invention, the amount of solvent varies but is generally 6,6'-DP The range is 0.3 to 1.5 moles per mole of BHBNA, and in particular, 0.3 to 1.2 moles. This is the range of

[0080] A particular embodiment of the present invention is a crystalline solvate of 6,6'-DPBHBNA with methanol. and hereinafter relates to a methanol solvate.

[0081] In the methanol solvate, the amount of methanol is 1 mole of 6,6'-DPBHBNA. The amount is usually in the range of 0.3 to 1.5 mol, particularly in the range of 0.4 to 1.2 mol, per and more particularly, in the range of 0.6 to 1.1 moles.

[0082] In the X-ray powder diffraction pattern recorded using Cu Kα radiation at 22°C, The ethanol solvate usually has the following three reflection peaks at 2θ values: ±0.2°, 14.9±0.2° and 21.5±0.2°; At least three, particularly at least five, at least seven of the following 2θ values: Or all 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 Optionally, one, two, three, four, five, six, seven of the following as 2θ values: , 8, 9, or 10 reflection peaks: 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° Shows.

[0083] The methanol solvate is also characterized by an endothermic peak indicating its decomposition. Methanol solvate was measured at a heating rate of 20 K / min according to ISO 11357-3:2018 The differential scanning calorimetry (DSC) recorded along When analyzed by DSC (Differential Scanning Calorimetry), the methanol solvate typically exhibits a 97-101 It exhibits an endothermic peak with an onset in the range of 108 to 115°C, and the peak maximum is in the range of 108 to 115°C. The reaction point is usually in the range of 103 to 110°C. The stress point is understood to be the inflection point below the endothermic peak in the DSC curve. It can be said that the value can vary within the above range depending on the content of methanol, and the content of methanol The higher the temperature, the higher the

[0084] The methanol solvate is a hot methanol solution of 6,6'-DPBHBNA, or , 6,6'-DPBHBNA from a solution of 6,6'-DPBHBNA in a mixture of methanol and toluene at high temperature The desired methanoic acid is obtained by crystallization of α-DPBHBNA. To obtain the diol solvate, the target of crystallization, 6,6'-DPBHBNA, must be dissolved in a solvent other than the solvent. It has a purity of at least 97% by weight with respect to organic matter. 6,6'-DPBHBNA, which has Preferably, the methanol content in the mixture is Preferably at least 50 w / w% and 90 w / w% based on the total weight of the solvent (mixture). / w% or less, i.e., the volume ratio of methanol to toluene is 1:1 to 9:1, In particular, it is 6:4 to 8:2, for example, 7:3. Usually, 6,6'-DPBHBNA The temperature of the hot solution is at least 45°C, especially if the methanol content is high. The concentration of 6,6'-DPBHBNA in the hot solution can be as high as reflux temperature. This may vary depending on the amount of methanol used in the crystallization. Usually, low concentrations of 6,6'-DPBHBNA are tolerated. The concentration usually does not exceed 30% by weight, and is usually between 2 and 25% by weight. The crystallization of the diol solvate is usually carried out at a temperature below 40°C, for example, from -10 to below 40°C, for example, from -5 This is achieved by cooling the hot solution to a temperature in the range of 0 to 30°C. Seed crystals may be added at a temperature in the range of -5 to 30°C. The amount of seed crystals is usually Based on the amount of 6,6'-DPBHBNA crystallized as the ethanol solvate, 2% by weight, particularly 0.1 to 1% by weight. The time may vary depending on the concentration of 6,6'-DPBHBNA and the temperature applied. The crystallization of the methanol solvate occurs after a concentrated solution of the solution at high temperature. Concentration of the solution can also be achieved by condensation or a combination of concentration and cooling. This can be achieved by distilling off a portion of the

[0085] The methanol solvate crystallizes into compact crystals with low aspect ratios. The aspect ratio of the methanol solvate is usually less than 5, and The crystal size is usually in the range of 5 to 200 μm. Here, the crystal size of the solvated form, as well as the unsolvated crystalline form, can be measured via optical microscopy. obtained by silent visual inspection under 100x magnification, where the range of sizes given is , refers to the longest dimension of the crystal.

[0086] Crystals of the methanol solvate tend not to entrap significant amounts of mother liquor. The crystalline solvate of 6'-DPBHBNA with methanol is at least 99%, and is at least 99.5% or more, and even up to 99.7% or more, with 6,6'-D This allows for improved purity of PBHBNA. As mentioned above, this is due to the fact that the methanol solvate The total amount of impurities other than methanol in the It also means that it does not exceed 0.3% by weight.

[0087] Apart from this, the crystals of the above-mentioned methanol solvate can be easily obtained by long-term drying. which can be decomposed into methanol solvate, preferably by drying at high temperatures. Therefore, it is basically free of organic solvents and can decompose at temperatures lower than the melting point of the substance. A new 6,6'-DPBHBNA that cannot be obtained by crystallization from a solvent A new crystalline polymorph was obtained. This crystalline polymorph will be referred to as the crystalline polymorph of 6,6'-DPBHBNA hereinafter. Form A, or simply Form A. Form A does not contain significant amounts of solvent and is therefore not suitable for use in the present invention. It is particularly useful in the production of thermoplastic resins in

[0088] Form A typically contains more than 0.1 moles of 6,6'-DPBHBNA per mole of 6,6'-DPBHBNA. The total amount of organic solvent in Form A is: The amount of methanol in Form A is usually less than 1% by weight. is less than %.

[0089] In the X-ray powder diffraction pattern recorded using Cu Kα radiation at 22°C, the shape Form A usually has the following six reflection peaks as 2θ values: 13.0±0.2°, 14.9±0.2°, 20.9±0.2°, 21.4±0.2°, 21.5±0.2° and and 23.7±0.2°; At least five, particularly at least seven, at least nine of the following 2θ values: Or all 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 Optionally, one, two, three, four, five, six, seven of the following as 2θ values: , 8 or 9 reflection peaks: 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°.

[0090] Form A is also characterized by an endothermic peak indicating its melting. DSC recorded according to ISO 11357-3:2018 with a heating rate of 0 K / min When analyzed by The maximum value of the peak is in the range of 124 to 126°C. The on point is usually in the range of 117 to 120°C.

[0091] Form A is a methanol solvated form of compact crystals with a low aspect ratio. The aspect ratio of the crystals of Form A is usually less than 5, and The crystal size of Form A is usually in the range of 5-200 μm. The crystal size of the solvate form was measured by optical microscopy at 100x magnification. Decomposition of the methanol solvate usually occurs with prolonged drying. This is preferably achieved by drying at high temperatures, but not below the melting point of the methanol solvate. Drying usually occurs at a temperature lower than that of the resulting 6,6'-DPBHBNA. Drying is carried out until the alcohol content is less than 0.1% by weight. Drying is carried out at temperatures ranging from 30°C to 95°C. The reaction may be carried out at a temperature ranging from 30°C to 70°C.

[0092] Form A crystals of 6,6'-DPBHBNA are typically at least 99% pure, and even less The purity is at least 99.5% or more, and even 99.7% or more. This means that the total amount of impurities other than the solvent in Form A does not exceed 1% by weight, particularly This means that the amount of the hydroxybenzoates does not exceed 0.5% by weight, and even 0.3% by weight. 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1, 1´-Binaphthalene, 2,2´-bishydroxy-6,6´-diphenyl-1,1´-bi Naphthalene and 2-(2-hydroxyethoxy)-2'-(2-hydroxyethoxy) (ethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthalene The total amount of the selected impurities is 1 wt. of 6,6'-DPBHBNA contained in the crystals of Form A. On a part by part basis, it is often at most 5000 ppm or less, preferably at most 4000 ppm or less, in particular, a maximum of 3000 ppm or less, and furthermore, a maximum of In particular, the weight of each of these impurities is less than 2000 ppm. Based on 1 part by weight of 6,6'-DPBHBNA contained in the crystals, the maximum is 2000pp m or less, and even at most 1500 ppm or less, and even at most 1000 If Form A is bis[2-[[1-[2-(2-hydroxybenzoyl) hydroxyethoxy)-6-phenyl-1-naphthyl]-6-phenyl-2-naphthyl]- If the crystals contain [hydroxy]-ethyl] carbonate, the amount is usually less than that contained in the crystals of Form A. Not exceeding 2000 ppm based on 1 part by weight of 6,6'-DPBHBNA, The maximum is 1500 ppm or less.

[0093] Furthermore, a specific embodiment of the present invention is a method for producing crystalline 6,6'-DPBHBNA in a methanol solvent. The present invention relates to crystalline 6,6'-DPBHBNA, which is a mixture of the solvate and Form A. This mixture is often obtained by incomplete decomposition of the methanol solvate. The X-ray powder diffraction patterns of both the ethanol solvate and Form A show distinct reflex peaks. In particular, the mixture was recorded using CuKα radiation at 22°C. In the X-ray powder diffraction pattern obtained, the following three reflection peaks are observed as 2θ values: 20. 9±0.2°, 21.4±0.2° and 23.7±0.2°; and At least three, particularly at least five, at least seven of the following 2θ values: At least nine reflection peaks: 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°; Optionally, the additional reflections noted above observed for the methanol solvate and Form A. The peaks may further be shown.

[0094] A mixture of methanol solvate and Form A was heated at a rate of 20 K / min according to ISO 11 When analyzed by DSC recorded along the Thermal peaks are observed. One peak has an onset in the range of 97-101°C. The maximum value is in the range of 108-115°C, and the second peak is in the range of 112-114°C. The temperature ranges from 124 to 126°C, with an onset in the range of 124 to 126°C.

[0095] The mixture of methanol solvate and Form A is typically at least 99%, and even less. Both have a purity of 99.5% or more, and even 99.7% or more. In the present invention, 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl -1,1´-binaphthalene, 2,2´-bishydroxy-6,6´-diphenyl-1,1 '-Binaphthalene and 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy) (oxyethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthalene The total amount of impurities selected from the group consisting of 6 and 10 is contained in the mixture of methanol solvate and Form A. Based on 1 part by weight of 6'-DPBHBNA, it is often at most 5000 ppm or more. Preferably, the maximum is 4000 ppm or less, and in particular, the maximum is 3000 ppm or less. pm or less, and even more so, the maximum is 2000 ppm or less.

[0096] A further specific embodiment of the present invention is a crystalline solution of 6,6'-DPBHBNA with toluene. The solvate is referred to below as the toluene solvate.

[0097] In the toluene solvate, the amount of toluene is 1 mole of 6,6'-DPBHBNA. and the amount is usually in the range of 0.3 to 1.5 mol, particularly in the range of 0.3 to 1.2 mol. Furthermore, it is in the range of 0.3 to 0.5 moles.

[0098] In the X-ray powder diffraction pattern recorded using Cu Kα radiation at 22°C, The ruthenium solvate usually has the following three reflection peaks as 2θ values: 0.2°, 7.7±0.2° and 21.6±0.2°; and At least three, particularly at least five, at least seven of the following 2θ values: Or all 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°;

[0099] The toluene solvate is also characterized by an endothermic peak indicating its decomposition. The benzene solvate was analyzed according to ISO 11357-3:2018 at a heating rate of 20 K / min. When analyzed by DSC recorded at 100°C, the toluene solvate typically exhibits a 105-10 It shows an endothermic peak with an onset in the range of 112 to 115°C, and the peak maximum is in the range of 112 to 115°C. The reaction point is usually in the range of 109 to 112°C.

[0100] Toluene solvate is a hot toluene solvate of 6,6'-DPBHBNA, 5% by weight 6,6 from a solution of toluene containing more than 1% by weight of other organic solvents, in particular methanol. To obtain the desired toluene solvate, The 6,6'-DPBHBNA that is the subject of the analysis has been analyzed using at least 97 organic compounds other than solvents. 6,6'-DPBHBNA having a purity of at least 97% by weight. It is preferable that the 6,6'-DPBHBNA is dissolved in hot toluene. The temperature of the hot solution is at least 60°C and may be as high as reflux temperature. The concentration of 6,6'-DPBHBNA in the solution usually does not exceed 50% by weight, and is usually 10 to 40% by weight. The crystallization of the toluene solvate from a hot solution is usually carried out at a temperature below 50°C, e.g. For example, this can be achieved by cooling the hot solution to temperatures ranging from -10 to below 50°C, or from -5 to 40°C. Seed crystals are added at temperatures below 50°C, for example, in the range of -5 to 40°C. The amount of seed crystals is usually determined based on the amount of 6,6'-DPBHB crystallized as a toluene solvate. The content is 0.05 to 2% by weight, particularly 0.1 to 1% by weight, based on the amount of NA. Toluene solvent The time required to complete the crystallization of the monohydrate depends on the concentration of 6,6'-DPBHBNA and the applied This can vary depending on the temperature, but typically ranges from 4 to 24 hours. Crystallization of the product can also be achieved by concentrating the hot solution or by a combination of concentration and cooling. Concentration of the solution can be achieved by distilling off a portion of the toluene.

[0101] The toluene solvate crystallizes into compact crystals with low aspect ratios. The aspect ratio of the toluene solvate is usually less than 5, and even less than 1. The crystal size is usually in the range of 5 to 300 μm. Crystals of the 6,6'-D solvate tend not to trap significant amounts of mother liquor. The crystalline solvate of PBHBNA with toluene is at least 99%, and even at least 99.5% or more, even up to 99.7% or more, 6,6'-DPBHBNA This allows for improved purity.

[0102] A further specific embodiment of the present invention is a method for producing a mixture of 6,6'-DPBHBNA and methyl ethyl ketone (M EK), which is hereinafter referred to as MEK solvate.

[0103] In the MEK solvate, the amount of MEK per mole of 6,6'-DPBHBNA is It is usually in the range of 0.3 to 1.5 mol, particularly in the range of 0.4 to 1.0 mol, and more particularly in the range of 0.4 to 1.0 mol. The amount of hydroxybenzoates is in the range of 0.5 to 0.8 moles.

[0104] In the X-ray powder diffraction pattern recorded using Cu Kα radiation at 22 °C, M The EK solvate typically has the following three reflection peaks at 2θ values: 7.0±0. 2°, 16.8±0.2° and 23.4±0.2°; and At least three, particularly at least five, at least seven of the following 2θ values: Or all reflection peaks: 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°;

[0105] The MEK solvate is also characterized by an endothermic peak indicating its decomposition. K solvate was measured according to ISO 11357-3:2018 at a heating rate of 20 K / min. When analyzed by DSC, the MEK solvate typically exhibits a temperature range of 87-91 °C. It shows an endothermic peak with an onset point at 95 to 100°C, and the maximum value of the peak is in the range of 95 to 100°C. The reaction point is usually in the range of 94 to 98°C.

[0106] The MEK solvate is a high temperature MEK solvate of 6,6'-DPBHBNA containing more than 5% by weight of 6,6' from solutions of other organic solvents, especially MEK, which does not contain more than 0.5% by weight of methanol. To obtain the desired MEK solvate, the crystallization step The target 6,6'-DPBHBNA is at least 97% by weight of organic matter other than solvents. % purity. 6,6'-DPBHBNA having a purity of at least 97% by weight is It is preferably dissolved in hot MEK. Usually, a hot solution of 6,6'-DPBHBNA The temperature of the solution is at least 60°C and may be as high as reflux. The concentration of 6'-DPBHBNA usually does not exceed 50% by weight, and is usually between 10 and 40% by weight. Crystallization of MEK solvates from hot solutions is usually carried out at temperatures below 50°C, e.g., -1 This is achieved by cooling the hot solution to a temperature ranging from 0 to less than 50°C, from -5 to 40°C. Seed crystals may be added at temperatures below 50°C, for example in the range of -5 to 40°C. The amount of seed crystals is usually determined based on the amount of 6,6'-DPBHBNA to be crystallized as the MEK solvate. Based on the above, the concentration is 0.05 to 2% by weight, particularly 0.1 to 1% by weight. The time to completion depends on the concentration of 6,6'-DPBHBNA and the temperature applied. The crystallization time can vary, but is typically in the range of 4 to 24 hours. This can also be achieved by concentrating the hot solution or by a combination of concentrating and cooling. Condensation can be achieved by distilling off a portion of the MEK.

[0107] The MEK solvate crystallizes into compact crystals with low aspect ratios. The aspect ratio of the MEK solvate is usually less than 5, and even between 1 and 5. The crystal size is usually in the range of 1-300 μm. MEK solvent Crystals of the dihydrate tend not to trap significant amounts of mother liquor. The crystalline solvate of BNA with MEK has a solubility of at least 99%, and even at least 99.5%. % or more, even up to 99.7% or more, to improve the purity of 6,6'-DPBHBNA Makes the above possible.

[0108] Despite the high purity of the crystalline forms of 6,6'-DPBHBNA mentioned above, they are amorphous. It can be converted to (amorphous) Form B. Amorphous Form B is stable and remains stable even after long-term storage. Even after being broken down by grinding, it does not tend to crystallize. Amorphous Form B can be obtained by dissolving either of the crystalline forms and then rapidly cooling them. Preferably, each crystalline form is completely melted to form a clear solution. It is heated to a temperature at least 5 K above its melting point until a liquid is obtained. When a solvate is used as a starting material for the preparation, preferably any solvent The solution is preferably subjected to a vacuum of at least 5 K / min. The cooling rate is rapid, for example, at a rate of 5 to 50 K / min. is obtained as a solid amorphous (glass). This amorphous material can be used to obtain a powder, e.g. It can be crushed by grinding, etc. To prevent crystallization, ) is carried out at temperatures significantly lower than 100°C, for example in the range of 5 to 40°C. In this powder, the particles are still present as amorphous Form B.

[0109] In the X-ray powder diffraction pattern recorded using Cu Kα radiation at 22°C, the shape Form B usually exhibits reflection peaks as 2θ values ​​at multiple diffraction angles in the range of 5° to 40°. Rather, a broad halo was observed, indicating the substantial absence of a crystalline layer. will be done.

[0110] Form B also conforms to ISO 11357-3:2018 at a heating rate of 20 K / min. When analyzed by DSC using the same method, it was found that no endothermic peak was observed in the range of 80 to 200°C. Rather, under these conditions, amorphous Form B is characterized by a 105 to 150% solubility in water. It may exhibit a glass transition temperature of 125°C.

[0111] The amorphous form B of 6,6'-DPBHBNA is typically at least 99%, and even less. The purity of the above-mentioned fluorine-containing compound is at least 99.5% or more, and even 99.7% or more. This means that the total amount of impurities other than the solvent in Form B does not exceed 1% by weight. In particular, it means that the content does not exceed 0.5% by weight, and even more particularly 0.3% by weight. 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1 ,1´-Binaphthalene, 2,2´-bishydroxy-6,6´-diphenyl-1,1´- Binaphthalene and 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxy (ethoxy)-ethoxy)-6,6'-diphenyl-1,1'-binaphthalene The total amount of impurities selected from the above is the single 6,6'-DPBHBNA contained in the crystals of Form B. On a parts by weight basis, it is often at most 5000 ppm or less, preferably at most The maximum concentration is 4000 ppm or less, and in particular, the maximum concentration is 3000 ppm or less. In particular, the weight of each of these impurities is less than 2000 ppm at most. Based on 1 part by weight of 6,6'-DPBHBNA contained in the crystals of Form B, at most 2 000 ppm or less, and even a maximum of 1500 ppm or less, and even a maximum of Preferably, the content of the amorphous form B is 1000 ppm or less. 1-[2-(2-hydroxyethoxy)-6-phenyl-1-naphthyl]-6-phenyl If it contains amorphous 2-naphthyloxyethyl carbonate, the amount is usually Based on 1 part by weight of 6,6'-DPBHBNA contained in the crystals of Form B, ppm, and often a maximum of 1500 ppm or less.

[0112] Surprisingly, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl Crystallization of 6,6'-DPBHBNA from ethanol solution of 1,1'-binaphthalene It is not an ethanol solvate, but a novel polymorph of 6,6'-DPBHBNA. This gave rise to a polymorph, hereinafter referred to as Form C. Form C does not contain significant amounts of solvent and is therefore suitable for use in the present invention. It is particularly useful in the production of thermoplastic resins in the light.

[0113] Form C typically contains more than 0.1 moles of 6,6'-DPBHBNA per mole of 6,6'-DPBHBNA. The total amount of organic solvent in Form C is: It is usually less than 1% by weight, in particular at most 0.5% by weight or at most 0.1% by weight. %.

[0114] In the X-ray powder diffraction pattern recorded using Cu Kα radiation at 22°C, the shape Form C usually has the following three reflection peaks at 2θ values: 5.1±0.2°, 7 0.6±0.2° and 21.0±0.2°; and At least three, particularly at least five, at least seven of the following 2θ values: Or all reflection peaks: 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°;

[0115] The X-ray powder diffraction pattern of Form C is comparable to that of the toluene solvate. The pattern was almost identical to that of the 6,6'-DPBHBNA in Form C. This shows that the molecules are arranged in the same way as in the crystal lattice in the toluene solvate.

[0116] Form C is also characterized by an endothermic peak indicating its melting. DSC recorded according to ISO 11357-3:2018 with a heating rate of K / min When analyzed, Form C typically exhibits an endothermic peak with an onset in the range of 115-118°C. The maximum value of the peak is in the range of 124 to 126°C. The temperature (temperature point) is usually in the range of 120 to 122°C.

[0117] Form C is the 6,6'-DPBHB produced by the hot ethanol treatment of 6,6'-DPBHBNA. To obtain the desired Form C, the 6,6'-NA is crystallized. DPBHBNA typically has a purity of at least 97% by weight with respect to organic matter other than the solvent. 6,6'-DPBHBNA having a purity of at least 97% by weight is obtained by high-temperature ethanol It is preferable that the 6,6'-DPBHBNA solution is dissolved in a solution of 1000 kJ / L. The temperature is at least 45°C and may be as high as reflux. The concentration of BHBNA usually does not exceed 30% by weight, and is usually between 2 and 25% by weight. Crystallization of Form C from a solution is typically carried out at temperatures below 40°C, e.g., from -10 to below 40°C, e.g., - This is achieved by cooling the hot solution to a temperature in the range of 5 to 30°C. Seed crystals may be added at a temperature in the range of -5 to 30°C. The amount of seed crystals is usually 0.05 to 2% by weight based on the amount of 6,6'-DPBHBNA crystallized as Form C; In particular, it is 0.1 to 1 wt. %. The time to complete the crystallization of Form C is 6,6'-D Typically, 4-24 h is used, although this may vary depending on the concentration of PBHBNA and the temperature applied. The crystallization of Form C occurs by concentrating a hot solution or by a combination of concentration and cooling. Concentration of the solution can also be achieved by evaporating off part of the solvent. It can be done.

[0118] Form C is obtained by crystallization as a compact crystalline form with a low aspect ratio. The aspect ratio of Form C is typically less than 5 and even in the range of 1 to 4. The crystal size is usually in the range of 2-250 μm.

[0119] Form C crystals tend not to trap significant amounts of mother liquor. The crystalline form C of BHBNA is at least 99%, and even at least 99.5%. or more, and even up to at least 99.7% or more of 6,6'-DPB As mentioned above, this allows for an improvement in the purity of the HBNA. The total amount of impurities should not exceed 1% by weight, in particular 0.5% by weight, and even more particularly 0.3% by weight. In particular, in Form C, 2-(2-hydroxyethoxy)-2' -Hydroxy-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bishydro 6,6'-diphenyl-1,1'-binaphthalene and 2-(2-hydroxyethoxy) (2-(2-hydroxyethoxy)-ethoxy)-6,6'-diphenyl The total amount of impurities selected from the group consisting of 1,1'-dibenzo-1,1'-binaphthalene in the crystals of Form C is Based on 1 part by weight of the 6,6'-DPBHBNA contained, it is often at most 500 0 ppm or less, preferably at most 4000 ppm or less, in particular at most The maximum concentration is 2000 ppm or less, and even 1000 ppm or less. The weight of each of these impurities is 1 / 2 of the weight of 6,6'-DPBHBNA contained in the crystals of Form C. On a weight basis, the maximum is 2000 ppm or less, and even more so, the maximum is 1500 ppm pm or less, and preferably at most 1000 ppm. However, bis[2-[[1-[2-(2-hydroxyethoxy)-6-phenyl-1-naphthyl phenyl-6-phenyl-2-naphthyl-oxy-ethyl carbonate, The amount is usually based on 1 part by weight of 6,6'-DPBHBNA contained in the crystals of Form C. It usually does not exceed 2000 ppm and is often at most 1500 ppm or less.

[0120] The solid forms of 6,6'-DPBHBNA in the present invention, i.e., amorphous form B and Similarly, methanol solvate, toluene solvate, methyl ethyl ketone solvate, and Crystalline forms A and C also usually have a molecular weight of less than 3.0, often less than 2.5 or even less than 2.0, In particular, it is low, even below 1.5, below 1.0, below 0.75, or even below 0.5. Yellowness Index (YI). All YI values ​​here are based on 5 in dichloromethane. Measured in w / w% 6,6'-DPBHBNA solution according to ASTM E 313 is.

[0121] The solid form of 6,6'-DPBHBNA in the present invention is 5 in dichloromethane. Less than 1.0 ntu, often 0.0, measured in w / w% 6,6'-DPBHBNA solution. It typically has a low haze of less than 8 ntu or even less than 0.6 ntu. Turbidity was measured using 5% w / w of 6,6'-DPBHBNA in dichloromethane. It is measured in solution and expressed as nephelometric turbidity units (ntu). The haze of the crystalline solid of 6,6'-DPBHBNA in the present invention is , for example, less than 0.4 ntu, less than 0.35 ntu, or less than 0.30 ntu, etc. can be even lower, such as as low as 0.2 ntu or less.

[0122] Thermoplastic resins of the present invention, i.e., polyester resins and polyester carbonate resins and polycarbonate resin, or a mixture of at least two thereof, It is preferable that the polymer is produced using a monomer having a certain amount of impurities, purity, etc. For example, the dihydroxy compound represented by the above general formula (6) may be in the form of a crystalline solvate. If so, add 0.3 to 1.2 moles of organic solvent to the crystals per mole of dihydroxy compound. It is preferable to use an organic solvent containing methanol to produce a thermoplastic resin. Examples of suitable solvents include alcohol, toluene, and methyl ethyl ketone.

[0123] As the monomer of formula (6), a monomer containing an organic solvent in an appropriate range of content as described above is used. The use of dihydroxy compound 1 can enable efficient production of thermoplastic resins. Per mole, about 0.3 to 1.2 moles, 0.3 to 1.0 moles, or 0.3 to 0.5 moles When thermoplastic resins are produced using materials containing organic solvents, the monomers may fly off. This may enable the production of a high-purity thermoplastic resin while preventing the deterioration of the thermoplastic resin.

[0124] When the dihydroxy compound represented by the general formula (6) is in a crystalline form, The thermoplastic resin may be produced using a material containing less than 0.1 mole of an organic solvent in its crystals. . In the crystalline form of the dihydroxy compound, the aspect ratio is at most 5: 1, for example, crystals with aspect ratios of up to 3:1, or even up to 1:1. It may be used.

[0125] As the dihydroxy compound represented by the general formula (6), at least 99% based on an organic substance 0.0% by weight (or 99.0% by weight or more) purity, preferably 99.5% by weight The purity of the cellulose acetate solution is preferably 99.7% by weight or more. It is also preferable that the amount of the organic solvent is less than 0.1 mole, for example, less than 0.05 mole. a dihydroxy compound of general formula (6) containing a solvent, preferably less than 0.03 moles of an organic solvent; may be used to produce the thermoplastic resin.

[0126] As a dihydroxy compound represented by the general formula (6), 5 w / w in dichloromethane Yellowness Index (YI) value of less than 3.0 measured according to ASTM E 313 in a % solution More preferably, the yellowness index is less than 2.0, and even more preferably, it is less than 1.0. is less than. In addition, as a dihydroxy compound represented by the general formula (6), 5-hydroxybenzophenone in dichloromethane Preferably, the haze measured on a w / w% solution is less than 1.0 ntu, more preferably Preferably, it is less than 0.7 ntu, and more preferably less than 0.5 ntu.

[0127] A thermoplastic resin is produced using any of the dihydroxy compounds represented by general formula (6). In this case, impurities such as dihydroxy compounds other than the dihydroxy compound in question, e.g. The total amount of impurities having a similar molecular structure is based on the weight of the dihydroxy compound. It is preferably less than 0.5% by weight, more preferably less than 0.3% by weight, More preferably, it is less than 0.1% by weight. For example, when 6-6'DPBHBNA is used as a monomer, hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-binaphthalene 2,2'-bishydroxy-6,6'-diphenyl-1,1'-binaphthalene, and , 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy) The total amount of impurities of 6,6'-diphenyl-1,1'-binaphthalene is 6-6'D Preferably, it is less than 0.5% by weight based on the weight of PBHBNA, more preferably is less than 0.3% by weight, and more preferably less than 0.1% by weight.

[0128] When the impurity content of a specific dihydroxy compound is 0.5% by mass or more, the reaction efficiency is reduced. The rate of polymerization may decrease, and the molecular weight may decrease. If a large amount of impurities are contained, the refractive index of the resulting thermoplastic resin tends to decrease. There is. On the other hand, when the impurity of a specific dihydroxy compound is contained in an amount of less than 0.5% by mass, The resin contains a structure similar to the basic structure, which reduces the melt viscosity. This improves moldability, i.e., improves the flow of resin, and also makes it more shock-resistant for molded products such as optical lenses. There is a tendency for attack to improve. For example, the concentration should not exceed 1 ppb to 5000 ppm based on 1 part by weight of the monomer of formula (6). It is preferable that the impurities are contained within a small range. Also, the monomer of formula (6), such as 2-(2-hydroxybenzoyl)-2-hydroxybenzoyl ... (2'-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-binaphthalene , 2,2'-bishydroxy-6,6'-diphenyl-1,1'-binaphthalene and 2- (2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy)-ethoxy)- Derived from impurities selected from the group consisting of 6,6'-diphenyl-1,1'-binaphthalene A resin, a resin composition, an optical lens, and the like are prepared by using a monomer containing less than 0.5% by weight of a structural unit having the above structure. It is preferable to produce an optical film or the like.

[0129] The thermoplastic resin preferably has properties particularly suitable for optical applications, such as: A material having a good balance between the refractive index and the Abbe number is preferred. Specifically, a thermoplastic resin The refractive index is higher than 1.660, more preferably higher than 1.668, and Abbe number less than 19, for example, 13 or more but less than 19, or 15 or more but less than 19 Furthermore, it is preferable that the refractive index nD and Abbe number requirements be satisfied as described above. Between the Abbe number ν, -0.0002ν + 1.6718 < nD < -0.024ν + 2.12 It is preferable that the relationship of 4 is satisfied. Between the refractive index nD and the Abbe number ν, -0.004 v + 1.744 < nD < -0.024ν + 2.124 relationship is more preferably satisfied Preferably, between the refractive index nD and the Abbe number ν,, -0.02v + 2.04 < nD < -0.02 4ν + 2.124 relationship is even more preferably satisfied.

[0130] The thermoplastic resin having a structural unit represented by the general formula (1) according to the present invention is represented by the general formula (6) In addition to the compound of, an aromatic dihydroxy compound or an aliphatic dihydroxy compound (for example, a dihydroxy compound having a fluorene skeleton or binaphthols) can be used as a dihydroxy component and used in combination. It can be used in combination.

[0131] Preferably, the thermoplastic resin of the present invention is, in addition to the compound represented by the general formula (6) above, the following The compound represented by the general formula (7) and / or the compound represented by the following general formula (8) can be used as a dihydroxy component and used in the production.

Chemical formula

[0132] An example of a dihydroxy compound represented by formula (7) is 2,2'-bis(1-hydroxy 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-1, 1'-Binaphthyl, 2,2'-bis(3-hydroxypropyloxy)-1,1'-binaphthyl butyl, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthyl, etc. Among them, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl is preferred. These may be used alone or in combination of two or more.

[0133] An example of a dihydroxy compound represented by formula (8) is 9,9-bis[4-(2-hydroxybenzoyl)-2-methylbenzoyl] 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 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, 9,9-bis[4-(2-hydroxyethyl Among them, 9,9-bis[4- (2-hydroxyethoxy)phenyl]fluorene and 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene

[0033] (3-ethoxy-3-phenylphenyl)fluorene is preferred. or two or more of them may be used in combination.

[0134] For example, examples of dihydroxy compounds represented by formula (7) or (8) include the following general compounds: One example is that expressed by equation (9). [ka]

[0135] In addition, among the monomers for producing the thermoplastic resin, the monomer represented by the above general formula (6) In addition to the dihydroxy compound, the values ​​of c and d in the general formula (6) are both 0. A dihydroxy compound, or one of c and d in the above general formula (6) Dihydroxy compounds having an OH group of 0 may be contained as impurities. Thus, the dihydride having at least one value of c and d different from that of the general formula (6) is The dihydroxy compound is a monomer having a dihydroxy compound represented by the above general formula (6) as a main component. In total, the content is preferably 1000 ppm or less, more preferably 500 ppm or less, and Preferably, the amount is 200 ppm or less, particularly preferably 100 ppm or less. and a dihydroxy group having a different value of at least one of c and d from that of the general formula (6). The total content of silicon compounds in the above monomers is preferably 50 ppm or less, and It is more desirable that it be 0 ppm or less. Regarding the content of impurities related to the above general formula (6), The same applies to the dihydroxy compounds represented by the general formula (7) or (8). ), together with a dihydroxy compound represented by the general formula (7) or (8), and f are both 0, or a dihydroxy compound represented by the above general formula (7) or (8). In this case, a dihydroxy compound in which either e or f is 0 is contained as an impurity. It's okay to have it. These impurities are then removed by dihydroxy compounds represented by the general formula (7) or (8). In the monomer mainly composed of the above, the total amount is preferably 1000 ppm or less, more preferably 5 00 ppm or less, more preferably 200 ppm or less, particularly preferably 100 ppm or less Furthermore, the total content of the above impurities in the above monomers is 50 ppm or less. It is desirable that the concentration is less than 20 ppm, and more desirable that the concentration is less than 20 ppm.

[0136] The compounds of general formulas (7) and (8) can be prepared by various synthetic methods. As described in Japanese Patent Publication No. 5442800 and Japanese Patent Application Laid-Open No. 2014-028806, (a) hydrogen chloride gas and fluorenones and hydroxynaphthalenes are reacted in the presence of mercaptocarboxylic acid. (b) a method of reacting 9-fluorenone with 9-fluorenone in the presence of an acid catalyst (and an alkyl mercaptan); (c) a method of reacting with hydrochloric acid and thiols (mercaptocarbons), a method of reacting fluorenones with hydroxynaphthalenes in the presence of carboxylic acids, etc. (d) in the presence of sulfuric acid and thiols (such as mercaptocarboxylic acids), It is reacted with hydroxynaphthalenes and crystallized in a solvent consisting of hydrocarbons and polar solvents. 9,9-bis(hydroxybenzoate) is produced by crystallizing bisnaphtholfluorene. [XO]a group and [XO]b group. It can be produced by reacting alkylene oxides and haloalkanols. For example, 9,9-bis[6-(2-hydroxyethoxy)naphthyl]fluoro The compound is a mixture of 9,9-bis[6-hydroxynaphthyl]fluorene and 2-chloroethanol. may be obtained by reacting under alkaline conditions.

[0137] In addition to the above, examples of aromatic dihydroxy compounds that can be used in combination include bisphene Bisphenol A, Bisphenol AP, Bisphenol AF, Bisphenol B, Bisphenol Bisphenol BP, Bisphenol C, Bisphenol E, Bisphenol F, Bisphenol G, Bisphenol M, Bisphenol S, Bisphenol P, Bisphenol PH, Bisphenol Examples include phenol TMC and bisphenol Z.

[0138] (Amount of vinyl end groups) The thermoplastic polyester resin, polyester carbonate resin, and Polycarbonate resins are prepared by subjecting the compounds represented by the above general formulas (6) to (9) to dihydroxybenzoates. It is used as a component and is obtained by reacting it with a carbonate precursor such as a carbonic acid diester. However, in the polymerization process for producing thermoplastic resins such as polycarbonate, In the compound of the general formula (6) to (9), one of the terminal -OROH groups is impurities in which either or both are converted to vinyl end groups, e.g., represented as -OC=CH groups, It can be born. For example, the impurity having a vinyl group represented by the following formula (v-1) can be used in the present specification. The compound may be present in a monomer, a resin, a resin composition, an optical lens, or an optical film. [ka] The vinyl group may be generated during the monomer synthesis and purification process and may be contained in the monomer. These vinyl groups can also be generated and increased during the polymerization and kneading stages of additives. This may be one of the reasons, but on the other hand, if the content is small, it may affect the bending strength and impact resistance of the resin. The attacking power may be improved. The amount of impurities having such vinyl terminal structures is usually small, and the amount of impurities in the produced polymer is The mer can be used as a thermoplastic resin without purification. For example, the amount of vinyl groups in polycarbonate resin is as follows: <9. Polycarbonate resin Vinyl end group amount 1 H-NMR measurement was performed, and the content was calculated using the integral ratio of the following formula (A). The amount of vinyl terminal groups is preferably 0.0001 to 5.0, and more preferably is 0.01 to 3.0, and more preferably 0.1 to 1.0.

number

[0139] The metals contained in the monomer are Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn. The total amount is preferably 1000 ppm by weight or less (for example, 100 ppm by weight, 10 wt ppm). The metals in the resulting resin and resin composition are Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn is preferably 1000 ppm by weight or less in total. When the metal content is 1000 ppm by weight or less, the resulting resin is less colored, and the catalyst is not easily discolored during polymerization. There is little risk of the activity decreasing. In addition, it is preferably 1 ppb by weight or more (more preferably 1 By including 100 ppm or more by weight, the trouble of adding a catalyst can be eliminated and the catalytic effect can be exerted. This may allow for a reduction in the amount of catalyst added, which may lead to lower production costs. The metal concentration is measured, for example, by the following method. <Metal analysis> After carbonizing the samples with sulfuric acid, the metal concentrations were measured by ICP-MS. That is, 2 g of sample was weighed into a synthetic quartz beaker, and 2.5 ml of sulfur dioxide was added immediately before carbonization and 0.1 ml of sulfur dioxide was added during carbonization. Acid was added and the mixture was heated on a hot plate to carbonize. Then, the mixture was covered with a quartz dish and heated in an electric furnace for 50 minutes. It was heated at 0°C for 10 hours and carbonized. Then, sulfuric acid was added and heated to dryness, and nitric acid was added and heated to dryness. A nitric acid solution was added to make 50 mL, and the mixture was heated to 50°C. Quantitative analysis was performed by P-MS. ICP-MS equipment: Shimadzu Corporation: ICPE-9000

[0140] Carbonate diester used in the production of polycarbonate resin and polyester carbonate resin The esters include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) m-cresyl carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate ester, dibutyl carbonate, dicyclohexyl carbonate, etc. Among these, diphenyl carbonate is particularly preferred. It is preferable to use the compound in a ratio of 0.97 to 1.20 moles per mole of the total of the hydroxy compounds. The molar ratio is preferably 0.98 to 1.10, and more preferably 0.98 to 1.10.

[0141] Also, dicarboxylic acids that can be used in the production of polyester resins and polyester carbonate resins The total of carboxylic acids, monocarboxylic acid monoesters, and diester compounds is dihydroxy compounds. It is preferable to use it in a ratio of 0.97 to 1.20 moles per mole of the alcohol, and more preferably The molar ratio is usually 0.98 to 1.10.

[0142] In addition, among the above-mentioned transesterification catalysts used in the production of thermoplastic resins, basic compounds Examples of the catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds. etc.

[0143] The alkali metal compound used in the present invention includes, for example, an organic acid salt of an alkali metal, Examples of the inorganic salt include inorganic salts, oxides, hydroxides, hydrides, and alkoxides. Sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate Sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, vinegar Potassium stearate, Cesium acetate, Lithium acetate, Sodium stearate, Potassium stearate Calcium, Cesium stearate, Lithium stearate, Sodium borohydride, Pheny Sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, benzo Lithium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate , disodium phenylphosphate, disodium salt, dipotassium salt of bisphenol A, Dicesium salt or dilithium salt, sodium salt, potassium salt of phenol, cesium For example, a salt or a lithium salt is used.

[0144] Examples of alkaline earth metal compounds include organic acid salts and inorganic salts of alkaline earth metal compounds. , oxides, hydroxides, hydrides, alkoxides, etc. Magnesium, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate Nesium, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate Nesium, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, vinegar Calcium acetate, Strontium acetate, Barium acetate, Magnesium stearate, Stearic acid Calcium phosphate, calcium benzoate, magnesium phenylphosphate, etc. are used.

[0145] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides and their salts, and amines. Specifically, tetramethylammonium hydroxide, tetraethyl Ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide alkyl groups such as ammonium hydroxide, trimethylbenzylammonium hydroxide, etc. , quaternary ammonium hydroxides having aryl groups, etc.; triethylamine, dimethyl Tertiary amines such as benzylamine and triphenylamine; diethylamine, dibutylamine secondary amines such as propylamine, butylamine, and other primary amines; 2-methylimide imidazoles such as imidazole, 2-phenylimidazole, and benzimidazole; or Ammonia, tetramethylammonium borohydride, tetrabutylammonium ammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenyl A base or a basic salt such as ammonium tetraphenylborate is used.

[0146] The transesterification catalyst is preferably a salt of titanium, zinc, tin, zirconium, lead, or the like. These may be used alone or in combination.

[0147] Specific examples of the transesterification catalyst include 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 oxalate Iodide, dibutyltin dimethoxide, zirconium acetylacetonate, dimethyl oxyacetate lead(II) acetate, lead(IV) acetate, etc. are used. .

[0148] These catalysts were used in an amount of 10 moles per mole of the total of dihydroxy compounds. -9 ~10 -3 mole Preferably in a ratio of 10 -7 ~10 -4 Used in molar ratios.

[0149] The melt polycondensation method uses the above-mentioned raw materials and catalyst under heating and further under atmospheric pressure or reduced pressure. This involves carrying out melt polycondensation while removing by-products from the transesterification reaction.

[0150] In the melt polycondensation of this composition, a compound represented by general formula (6) and a carbonate diester are After melting in the reaction vessel, the reaction is carried out while retaining the monohydroxy compound produced as a by-product. To retain the gas, it is desirable to avoid blocking the reactor or reducing or pressurizing it. The reaction time in this step is 20 minutes or more and 240 minutes or less. The heating time is preferably 40 minutes or more and 180 minutes or less, and particularly preferably 60 minutes or more and 150 minutes or less. In this case, if the by-product monohydroxy compound is distilled off immediately after it is produced, the final heat Plastic resins contain a small amount of high molecular weight compounds. However, the by-product monohydroxy compounds are reacted. When the mixture is allowed to remain in the reaction vessel for a certain period of time, the content of polymers in the final thermoplastic resin increases. You can get a lot of them.

[0151] The melt polycondensation reaction may be carried out in a continuous manner or in a batch manner. The reactors used in this process include anchor-type impellers, Maxblend impellers, and helical ribbon impellers. Whether it is a vertical type equipped with agitating blades, etc., or a horizontal type equipped with paddle blades, lattice blades, spectacle blades, etc. It may be an extruder equipped with a screw or a similar extruder, taking into consideration the viscosity of the polymer. It is preferable to use a reaction apparatus in which these reaction apparatuses are appropriately combined.

[0152] In the method for producing the thermoplastic resin used in the present invention, after the polymerization reaction is completed, the thermostability and hydrolysis To maintain cracking stability, the catalyst may be removed or deactivated. The method of deactivating the catalyst by adding an acidic substance can be preferably carried out. Esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid; p- Aromatic sulfonates such as butyl toluenesulfonate and hexyl p-toluenesulfonate Phosphoric acid, phosphoric acid, phosphonic acid, and other phosphoric acids; triphenyl phosphite, phosphorous acid Monophenyl, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, phosphite Di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite phosphates such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate phosphate esters such as dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; Phosphonic acids such as phenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; triphenylphosphine, bis( Phosphines such as diphenylphosphinoethane; boric acids such as boric acid and phenylboric acid Aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; Organic compounds such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonic acid chloride Halides; alkyl sulfates such as dimethyl sulfate; organic halides such as benzyl chloride, etc. These deactivators are preferably used in an amount of 0.01 to 50 times by mole relative to the amount of the catalyst, When the amount is less than 0.01 moles relative to the amount of catalyst, the deactivation effect is low. Furthermore, if the amount is more than 50 times the amount of the catalyst, the resin will not be able to withstand the heat. This is undesirable because it reduces heat resistance and makes the molded article more susceptible to coloration.

[0153] After catalyst deactivation, the low boiling point compounds in the polymer are separated by a pressure of 0.1 to 1 mmHg and a temperature of 200 to 35 A step of devolatilization at a temperature of 0°C may be provided. This step may be performed using a paddle blade, a lattice blade, a mega blade, or the like. A horizontal device equipped with stirring blades with excellent surface renewal ability, such as a Ne blade, or a thin film evaporator is preferably used. can be done.

[0154] The thermoplastic resin of the present invention is desired to have as little foreign matter content as possible, and the filtration and catalysis of the molten raw material are necessary. The medium is preferably filtered. The mesh of the filter is preferably 5 μm or less. Preferably, the particle size is 1 μm or less, and more preferably 1 μm or less. The mesh of the polymer filter is preferably 100 μm or less. It is preferable that the particle size is 30 μm or less, and more preferably 30 μm or less. The process must be carried out in a low-dust environment, preferably class 6 or less. Preferably it is class 5 or lower.

[0155] In addition to injection molding, methods for molding polycarbonate resin include compression molding, casting, and Examples of such methods include, but are not limited to, molding, extrusion, and stretching.

[0156] (4) Optical molded body The thermoplastic resin of the present invention can be used to produce optical molded articles. For example, injection molding, compression molding The thermoplastic resin of the present invention can be molded by any method, such as a molding method, an extrusion molding method, or a solution casting method. Plastic resins have excellent moldability and heat resistance, making them ideal for optical lenses that require injection molding. In molding, the thermoplastic resin of the present invention can be used particularly advantageously in other polymers. It can be used in combination with other resins such as carbonate resins and polyester resins. Also, antioxidants, processing stabilizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents Additives such as antibacterial agents, surfactants, antibacterial agents, release agents, UV absorbers, plasticizers, and compatibilizers are mixed in. It's okay to do so.

[0157] Antioxidants include triethylene glycol-bis[3-(3-tert-butyl- 5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol- Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] ], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxybenzoate] hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl ethyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6 -tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N -Hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate) amide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-di Ethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)iso Socyanurate and 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl {4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8 , 10-tetraoxaspiro(5,5)undecane, etc. The content of the antioxidant is 0.001 to 0.3 parts by weight per 100 parts by weight of the thermoplastic resin. It is preferable that there is.

[0158] Examples of the processing stabilizer include phosphorus-based processing heat stabilizers and sulfur-based processing heat stabilizers. The heat-processing stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and their esters. esters, etc. Specifically, triphenyl phosphite, tris(nonylphenyl) tris(2,4-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, Tris(2,6-di-tert-butylphenyl)phosphite, Tridecylphosphite , trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite Phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite Phosphite, Monobutyldiphenylphosphite, Monodecyldiphenylphosphite, Mono Octyldiphenylphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) phenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-t (ert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol Pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite Sulfite, Bis(2,4-ditert-butylphenyl)pentaerythritol diphosphate Phosphite, distearyl pentaerythritol diphosphite, tributyl phosphate phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, di Phenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, benzenephosphonic acid Diethyl, dipropyl benzenephosphonate, tetrakis(2,4-di-t-butylphenyl) Tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphonite, phenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-t-butyl Bis(2,4-di-tert- butylphenyl)-4-phenyl-phenylphosphonite and bis(2,4-di-tert-butylphenyl) t-butylphenyl)-3-phenyl-phenylphosphonite, etc. The content of phosphorus-based heat processing stabilizer in the resin is 0.001 for 100 parts by weight of thermoplastic resin. Preferably, it is up to 0.2 parts by weight.

[0159] Sulfur-based heat stabilizers include pentaerythritol-tetrakis(3-laurylthio) propionate), pentaerythritol-tetrakis(3-myristylthiopropionate) Pentaerythritol-tetrakis(3-stearylthiopropionate), di Lauryl-3,3'-thiodipropionate, Dimyristyl-3,3'-thiodipropionate ester, distearyl-3,3'-thiodipropionate, etc. Thermoplastic resins The content of sulfur-based heat processing stabilizer in the thermoplastic resin is 0.001 to 0.001 parts by weight. 0.2 parts by weight is preferred.

[0160] As a release agent, 90% or more by weight of which is made up of an ester of alcohol and fatty acid The ester of alcohol and fatty acid is preferably a monohydric alcohol and a fatty acid. Examples include esters with fatty acids, partial esters or full esters of polyhydric alcohols and fatty acids. The esters of the monohydric alcohol and fatty acid include monohydric alcohols having 1 to 20 carbon atoms. Esters of polyhydric alcohols and saturated fatty acids having 10 to 30 carbon atoms are preferred. As a partial or complete ester of alcohol and fatty acid, it has 1 to 25 carbon atoms. Partial or complete ester of polyhydric alcohol and saturated fatty acid having 10 to 30 carbon atoms is preferred.

[0161] Specifically, examples of esters of monohydric alcohols and saturated fatty acids include stearyl stearyl alcohol and esters of saturated fatty acids. Palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate Partial or complete esters of polyhydric alcohols and saturated fatty acids. Examples of stearic acid monoglyceride include stearic acid monoglyceride, stearic acid monoglyceride, stearic acid Diglyceride, stearic acid triglyceride, stearate monosorbitate, behenin Acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, pentaerythritol Pentaerythritol Monostearate, Pentaerythritol Tetrastearate, Pentaerythritol Lithol tetrapelargonate, propylene glycol monostearate, biphenyl bicarbonate Phenate, Sorbitan Monostearate, 2-Ethylhexyl Stearate, Dipenta Dipentaerythritol full esters or partial esters such as erythritol hexastearate The content of these release agents is 0.01% by weight based on 100 parts by weight of thermoplastic resin. The range of 0.005 to 2.0 parts by weight is preferred, and the range of 0.01 to 0.6 parts by weight is more preferred. The range of 0.02 to 0.5 parts by weight is more preferable.

[0162] UV absorbers include benzotriazole-based UV absorbers and benzophenone-based UV absorbers. absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyanoacrylates At least one ultraviolet absorber selected from the group consisting of acrylate-based ultraviolet absorbers is preferred. That is, any of the ultraviolet absorbers listed below may be used alone, or two or more kinds may be used in combination. You can also use a combination of the above.

[0163] Benzotriazole-based UV absorbers include 2-(2-hydroxy-5-methylphenyl) Nyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl) Benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzol Zotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetrachlorobenzotriazole] tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole , 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-( 2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebi bis(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. It can be obtained.

[0164] Benzophenone-based UV absorbers include 2,4-dihydroxybenzophenone, 2- Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone Non, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy 5-sulfoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5 -sulfonic acid hydrate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2' ,4,4'-Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-di Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiol sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl) (phenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy 4-methoxy-2'-carboxybenzophenone and the like.

[0165] Triazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazine). 2-(4,6-bis(2-(2-yl)-5-[(hexyl)oxy]-phenol) ,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl) hydroxy]-phenol and the like.

[0166] Cyclic iminoester UV absorbers include 2,2'-bis(3,1-benzoxa) 2,2'-p-phenylenebis(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-benzoxazin-4-one), 2,2'- (1,5-naphthalene)bis(3,1-benzoxazin-4-one), 2,2'-(2 -methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'- (2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one) and 2, 2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one) Examples include:

[0167] Cyanoacrylate-based UV absorbers include 1,3-bis-[(2'-cyano-3' ,3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-di phenylacryloyl)oxy]methyl)propane, and 1,3-bis-[(2-cyano -3,3-diphenylacryloyl)oxy]benzene and the like.

[0168] The content of the ultraviolet absorber is preferably 0.01 to 100 parts by weight of the thermoplastic resin. 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and even more preferably The blending amount is 0.05 to 0.8 parts by weight. Within this blending amount range, the thermoplastic resin can be used depending on the application. It is possible to give the oil sufficient weather resistance.

[0169] The thermoplastic resin of the present invention has a high refractive index and a low Abbe number. Transparent conductive substrates used in LCD displays, organic EL displays, solar cells, etc. , optical discs, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors , vapor-deposited plastic reflectors, structural or functional materials for optical components such as displays It can be advantageously used as a suitable optical molded article.

[0170] The surface of the optical molded product may be coated with a coating such as an anti-reflection layer or a hard coat layer as required. The anti-reflection layer may be a single layer or a multi-layer, and may be an organic The material may be either organic or inorganic, but is preferably inorganic. Silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, acid Examples of the oxides include magnesium oxide and magnesium fluoride.

[0171] (5) Optical lenses The optical lens manufactured using the thermoplastic resin of the present invention has a high refractive index and a low Abbe number. It is highly resistant to humidity and heat, making it suitable for telescopes, binoculars, television projectors, and other devices that were previously expensive. The present invention is extremely useful as it can be used in fields where high refractive index glass lenses have been used. If necessary, it is preferable to use it in the form of an aspherical lens. Since spherical aberration can be virtually eliminated with a single lens, the combination of multiple spherical lenses is This eliminates the need to eliminate spherical aberration, making it possible to reduce weight and production costs. Therefore, aspherical lenses are particularly useful as camera lenses among optical lenses. The optical lens can be manufactured by any method such as injection molding, compression molding, or injection compression molding. The present invention allows the production of high refractive index, low birefringence, non-crystalline lenses, which are technically difficult to produce with glass lenses. A spherical lens can be obtained more easily.

[0172] To prevent foreign matter from getting into the optical lens as much as possible, the molding environment must be a low-dust environment. It is not necessary, and it is preferably class 6 or less, and more preferably class 5 or less.

[0173] (6) Optical film The optical film produced using the thermoplastic resin of the present invention has excellent transparency and heat resistance. Therefore, it is suitable for use in films for liquid crystal substrates, optical memory cards, etc.

[0174] To prevent foreign matter from getting into the optical film as much as possible, the molding environment must be a low-dust environment. It must be class 6 or less, and more preferably class 5 or less.

[0175] [Abbreviation] 6,6'-DPBHBNA: 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-bina Phthalene (Bis-2,2'-(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-bisnaphthyl) 6,6'-DPMHBNA: 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1 ´-Binaphthalene(2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1'-bisnaphth yl) 6,6'-DPTHBNA: 2-(2-hydroxyethoxy)-2'-[2-hydroxyethoxy(ethoxy)]- 6,6'-Diphenyl-1,1'-binaphthalene (2-(2-hydroxyethoxy)-2'-[(2-hydrox yethoxy)ethoxy]-6,6'-diphenyl-1,1'-bisnaphthyl) % bw: % by weight DSC: Differential scanning calorimetry LOD: Loss on drying mp: melting point MeOH: Methanol NaOH: sodium hydroxide NIR: near infrared PXRD: powder X-ray diffraction TLC: thin layer chromatography UPLC: Ultra Performance Liquid Chromatography

[0176] [Example] <1. Measurement method of weight average molecular weight (Mw)> Based on JIS K 7252-3, the polystyrene was calculated from the calibration curve of the standard polystyrene prepared in advance. The weight average molecular weight converted to polyethylene was calculated. A calibration curve was created using polyethylene (Tosoh Corporation, "PStQuick MP-M"), and the measured standard The elution time and molecular weight of each peak from the quasi-polystyrene were plotted and a cubic approximation was performed. This was used as a calibration curve. Mw was calculated using the following formula: Mw = Σ(Wi × Mi) ÷ Σ(Wi) where i is the i-th division point when dividing the molecular weight M, Wi is the i-th weight, and Mi is the i The molecular weight M is the molecular weight of polystyrene at the same elution time on the calibration curve. The GPC device used was a Tosoh HLC-8320GPC. One TSKguardcolumn SuperMPHZ-M was used as the analytical column, and one TSKgel SuperMul Three tiporeHZ-Ms connected in series were used. Other conditions were as follows: Solvent: HPLC grade tetrahydrofuran Injection volume: 10μL Sample concentration: 0.2 w / v% HPLC grade chloroform solution Solvent flow rate: 0.35 ml / min Measurement temperature: 40℃ Detector: RI 2. Glass transition temperature (Tg) Measured using a differential scanning calorimeter (DSC) based on JIS K7121-1987 The analyzer used was a Hitachi High-Tech Science X-DSC7000. 3. Refractive index (nD) The 0.1 mm thick film made of the resin produced in the example was measured using an Abbe refractometer. The measurement was carried out according to the method of JIS-K-7142. <4. Abbe number (ν)> The 0.1 mm thick film made of the resin produced in the example was measured using an Abbe refractometer. The refractive index was measured at wavelengths of 486 nm, 589 nm and 656 nm at 23°C. The Abbe number was calculated using the formula below. ν=(nD-1) / (nF-nC) nD: Refractive index at a wavelength of 589 nm nC: Refractive index at a wavelength of 656 nm nF: Refractive index at a wavelength of 486 nm <5.b value> The resin was vacuum dried at 120°C for 4 hours and then injected into an injection molding machine (FANUC ROBOSHOT α-S3 0iA) at a cylinder temperature of 270°C and a mold temperature of Tg-10°C. A disc-shaped test plate with a diameter of 1 mm and a thickness of 3 mm was obtained. The b value was measured according to 7105. The smaller the b value, the weaker the yellowness and the better the hue. The measurement of the molded plate was carried out using a Nippon Denshoku Industries SE2000 spectrophotometer. A meter was used. <6. Pressure Cooker Test (PCT Test)> The produced resin was vacuum dried at 120°C for 4 hours, and then injected into an injection molding machine (FANUC ROBOSHOT α- Injection was performed using the S30iA with the cylinder temperature set at 270°C and the mold temperature set at Tg-10°C of the resin. The plate was molded to obtain a disc-shaped test plate piece having a diameter of 50 mm and a thickness of 3 mm. The sample was exposed to 30°C and a relative humidity of 85% for 48 hours. <7.Total light transmittance> The plate pieces before and after the PCT test were measured using the SE2000 model manufactured by Nippon Denshoku Industries Co., Ltd. Measurement was carried out using a spectrophotometer according to the method of JIS-K-7361-1. <8. Total light transmittance retention rate (%)> The total light transmittance was calculated from the following formula using the total light transmittance measured by the above method. Total light transmittance retention rate (%) = Total light transmittance after PCT test / Total light transmittance before PCT test Rate x 100

[0177] 9. Amount of vinyl end groups in polycarbonate resin 1H-NMR measurements were carried out under the following conditions. ·1H-NMR measurement conditions Equipment: Bruker AVANZE III HD 500MHz Flip angle: 30 degrees Wait time: 1 second Accumulation count: 500 times Measurement temperature: room temperature (298K) Concentration: 5wt% Solvent: deuterated chloroform Internal standard: tetramethylsilane (TMS) 0.05 wt% <10. The amount of phenol and diphenyl carbonate (DPC) in polycarbonate resin Measurement> 0.5 g of the sample from Example 1, which will be described in detail later, was dissolved in 50 ml of tetrahydrofuran (THF). A calibration curve was prepared using the pure compounds of each compound as a standard, and 2 μL of the sample solution was added. was quantified by LC-MS under the following measurement conditions. The detection limit under these measurement conditions was 0 It is .01 ppm. LC-MS measurement conditions: Measurement device (LC part): Agilent Infinity 1260 LC System Column: ZORBAX Eclipse XDB-18 and guard cartridge Mobile phase: A: 0.01mol / L ammonium acetate aqueous solution B: 0.01 mol / L ammonium acetate solution in methanol C:THF Mobile phase gradient program: As shown in Table 1, the mixture of A to C was used as the mobile phase, and the composition of the mobile phase was changed over time ( The mobile phase was run on the column for 30 minutes, switching between phases at the times shown in the column (minutes). [Table 1] Flow rate: 0.3ml / min Column temperature: 45℃ Detector: UV (225 nm) Measurement equipment (MS part): Agilent 6120 single quad LCMS System Ionization source: ESI Polarity: Positive (DPC) & Negative (PhOH) Fragmenter: 70V Dry gas: 10 L / min, 350°C Nebulizer: 50 psi Capillary voltage: 3000V (Positive), 2500V (Negative) Measurement ions: [Table 2]

[0178] Monomer analysis method 11. Powder X-ray Diffraction (PXRD) Powder X-ray diffraction (PXRD) patterns were obtained using a D8 Discover X-ray from Bruker AXS GmbH, Germany. The diffraction measurement instrument (D8 Discover X-ray diffractometer) used Cu Kα1 ray ( The data were recorded in a Bragg-Brentano reflection configuration using a voltage of 40 kV and 40 mA. At room temperature, the resolution is 0.025° and the measurement range is from -5.0° 2θ to -80.0° 2θ. The data were collected at a constant time of 0.5 seconds per step.

[0179] <12.DSC measurement> DSC measurements were performed using a Linseis Chip-DSC 10. The heating rate was 2 The temperature was 0°C / min.

[0180] <13. Melting Point Measurement> The melting point is Buchi Melting Point B-545 at a heating rate of 1K / min. The measurement was carried out by the capillary method using the device.

[0181] <14.Near infrared analysis> Near-infrared analysis was performed using a Bruker FT-NIR spectrometer Matrix Fspectrometer, Bruker Opus 5. 5 Software and reflection immersible probe head The data were recorded using the following method.

[0182] 15. Purity determination Purity was determined by UPLC using the following system and operating conditions: Waters Acquity UPLC H-Class System; Columns Acquity UPLC BEH C18, 1.7 μm, 2 x 100 mm; column temperature: 40°C Gradient: acetonitrile / water (acetonitrile; ACN: 48% in 0 min, 50% in 21 min, 26 min) 100%, 28 min 100%, 28.1 min 48%, 32 min 48%); Injection volume: 0.8 μl; flow rate 0.6 ml / min; detection at 210 nm.

[0183] <16. Measurement of volatile solvents> The amount of volatile solvent was measured using a Shimadzu GC 14 B with Class VP 4.3 software, AOC-20i automatic injection. The sample was analyzed by gas chromatography using an AOC-20s autosampler and an FID detector. The measurements were taken.

[0184] The column used was a PE 624 20 (Perkin Elmer) with the following dimensions: The graphing was carried out under the following operating conditions: Carrier gas: Hydrogen Pressure: 0.3 bar Injection temperature: 250℃ Detection temperature: 300℃ Column temperature: 40°C (2 min), 20°C / min, 200°C (2 min) Concentration: C=20mg / ml Injection volume: 0.2~2μl

[0185] As an internal standard, a solution of 100 mg of naphthalene in 10 ml of dimethylformamide was used. The sample was prepared by dissolving 20 mg of the compound in a 0.1 mM internal standard solution and then diluting it with 0.9 mM water. The amount of solvent was calculated using the following formula: S Solv *M St *100 / (S St *M Sample *RRF) M St : Amount of internal standard in the sample solution M Sample : sample weight SSolv : Solvent peak area S St :Standard area RRF: Relative sensitivity factor of solvent

[0186] <17. Yellowness measurement> The yellowness index (YI) of 6,6'-DPBHBNA is as follows according to ASTM E 313: Measurements were taken according to protocol. 1 g of 6,6'-DPBHBNA was dissolved in 19 g of dichloromethane. The solution was diluted to 50 ml The solution was transferred to a cuvette and measured using a Shimadzu UV-Visible spectrophotometer UV-1650PC (spectrophotometer). The transmittance was measured in the range of 300 to 800 nm using a fluororesin. From the spectrum, the yellowness index was calculated according to ASTM E308 (CIE spectrum). Standard practice for calculating the color of an object using a stem ice for computing the colors of objects by using theCIE System) and ASTM E 31 3 (Standard Practice for Calculating Yellowness and Whiteness from Instrumentally Measured Color Coordinates) Standard practice for calculating yellowness and whiteness indices from instr The software RCA-software UV2DAT It is calculated using

[0187] <18. Haze Measurement> Haze was measured using a standard nephelometer (turbidimeter) measuring 6,6'-D By measuring the transmittance of a 5% dichloromethane solution of PBHBNA at 860 nm, It was decided that

[0188] 19. Microscopy The images for the microscopic examination were taken using a Nikon microscope, EclipseTS 100, and the images were taken with a Nikon camera. The image was taken with a 100x magnification provided by the DigitalSight DS-U1 shadow unit. From these micrographs, the width (W), length (L), and aspect ratio (L / W ratio) were determined. I was criticized.

[0189] [Manufacturing of polycarbonate resin] Example 1 As a raw material, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1 ,1'-binaphthalene (hereinafter sometimes abbreviated as "BINL-2EO") 31.6 kg (60.0 mol), diphenyl carbonate (hereinafter abbreviated as "DPC") 1 3.5 kg (63.0 mol) and 0.074 g (8.8 × 10 -4 The resulting mixture (mol) was placed in a 50 L reactor equipped with a stirrer and a distillation device, and the resulting mixture was placed in a nitrogen atmosphere of 760 mmHg. The mixture was heated to 180°C under the same conditions. After 20 minutes of heating, the raw materials were confirmed to be completely dissolved. Stirring was carried out for 120 minutes, after which the pressure was reduced to 200 mmHg and the temperature was increased to 60°C. The temperature was raised to 200°C at a rate of 1 / hr. After that, the reaction was carried out by holding the temperature at 200°C for 40 minutes. The temperature was raised to 240°C at 10°C, and after 10 minutes the temperature was maintained at that level while the temperature was reduced over 1 hour. The pressure was set to 1 mmHg or less. Then, the temperature was increased to 245°C at a rate of 60°C / hr. After the reaction was completed, nitrogen was introduced into the reactor to return the pressure to normal, and the resulting The polycarbonate resin was pelletized and taken out. The amounts of phenol and diphenyl carbonate (DPC), which are impurities in the When measured, the phenol content in the resin was 100 ppm by mass and the DPC content was 300 ppm by mass. It was. The physical properties of the resulting resin are shown in Table 3 below.

[0190] Example 2-A As raw materials, 7.9 kg (15.0 mol) of BINL-2EO and 24.2 kg ( The same procedure as in Example 1 was carried out except that 13.5 kg (45.0 mol) of DPC and 13.5 kg (63.0 mol) of DPC were used. The operation was performed. Example 2-B As raw materials, BINL-2EO 15.8 kg (30.0 mol) and BNEF 16.2 kg The same procedure as in Example 1 was repeated except that 13.5 kg (63.0 mol) of DPC was used. The operation was performed. (Example 2-C) As raw materials, BINL-2EO23.7 kg (45.0 mol) and BNEF8.1 kg ( The same procedure as in Example 1 was carried out except that 13.5 kg (63.0 mol) of DPC was used. The operation was performed.

[0191] The physical properties of the resin obtained are shown in Table 3. The resin obtained in Example 2-B (BINOL The NMR chart of the compound (2EO / BNEF = 50 mol / 50 mol) is shown in Figure 1.

[0192] Example 3-A As raw materials, BINL-2EO 7.9 kg (15.0 mol), 9,9-bis[4-( 2-hydroxyethoxy)phenyl]fluorene (hereinafter abbreviated as "BPEF" 19.0 kg (45.0 mol) of HCl and 13.5 kg (63.0 mol) of DPC were used. The same procedure as in Example 1 was carried out. The physical properties of the obtained resin are shown in Table 3. Example 3-B As raw materials, BINL-2EO 15.8 kg (30.0 mol), 9,9-bis[4-( 2-hydroxyethoxy)phenyl]fluorene (hereinafter abbreviated as "BPEF") 12.7 kg (30.0 mol) of HCl and 13.5 kg (63.0 mol) of DPC were used. The same procedure as in Example 1 was carried out. The physical properties of the obtained resin are shown in Table 3. Example 3-C As raw materials, BINL-2EO23.7 kg (45.0 mol), 9,9-bis[4-( 2-hydroxyethoxy)phenyl]fluorene (hereinafter abbreviated as "BPEF") The other components were used: 6.3 kg (15.0 mol) of HCl and 13.5 kg (63.0 mol) of DPC. The same procedure as in Example 1 was carried out. The physical properties of the obtained resin are shown in Table 3.

[0193] Example 4-A As raw materials, BINL-2EO 7.9 kg (15.0 mol) and BPPEF 25.9 The same procedure as in Example 1 was repeated except that 13.5 kg (45.0 mol) of HCl and 13.5 kg (63.0 mol) of DPC were used. The same procedure was repeated. The physical properties of the resulting resin are shown in Table 3. Example 4-B The raw materials were BINL-2EO 15.8 kg (30.0 mol) and BPPEF 17. Example 1 except that 2 kg (30.0 mol) of HCl and 13.5 kg (63.0 mol) of DPC were used. The physical properties of the resulting resin are shown in Table 3. Example 4-C As raw materials, BINL-2EO 23.7 kg (45.0 mol) and BPPEF 8.6 The same procedure as in Example 1 was repeated except that 13.5 kg (63.0 mol) of DPC was used. The same procedure was repeated. The physical properties of the resulting resin are shown in Table 3.

[0194] Example 5 As raw materials, 7.6 kg (18.0 mol) of BPEF, 2,2'-bis(2-hydroxybenzoyl) (6,6'-di(naphthalen-1-yl)-1,1'-binaphthalene (hereinafter " DNBINOL-2EO (sometimes abbreviated as "DNBINOL-2EO") 26.3 kg (42.0 mol), DP The same procedure as in Example 1 was carried out except that 13.5 kg (63.0 mol) of C was used. The physical properties of the resin are shown in Table 3.

[0195] (Example 6-A) As raw materials, 7.9 kg (15.0 mol) of BINL-2EO and 9.7 kg ( 18.0 mol), 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (hereinafter referred to as "BNE") 10.1 kg (27.0 mol), DPC 13. The same procedure as in Example 1 was carried out except that 5 kg (63.0 mol) of the resin was used. The physical properties are shown in Table 3. (Example 6-B) As raw materials, BINL-2EO 19.0 kg (36.0 mol) and BNE 4.5 kg (12.0 mol), BPEF 5.1 kg (12.0 mol), DPC 13.5 kg (6 The same procedure as in Example 1 was carried out except that 3.0 mol) of ethylenediaminetetraacetic acid was used. The physical properties of the resulting resin are shown in the table below. Shown in 3. (Example 6-C) As raw materials, BINL-2EO 19.0 kg (36.0 mol) and BNE 4.5 kg (12.0 mol), BPPEF 6.9 kg (12.0 mol), DPC 13.5 kg ( The same procedure as in Example 1 was carried out except that 63.0 mol) of ethylenediaminetetraacetic acid was used. The physical properties of the obtained resin were Shown in Table 3. In addition, the above-mentioned Example 1, Example 2-A to C, Example 3-A to C, Example 4-A to C, and BINL-2EO used in Examples 6-A to 6-C was the same as that obtained in Example 21, the details of which will be described later. Form A. (Example 6-D) As raw materials, 11.3 kg (21.0 mol) of BNEF and 11.2 kg (30 0.0 mol), DNBINOL-2EO 5.6 kg (9.0 mol), DPC 13.5 kg The same procedure as in Example 1 was carried out except that 100 g (63.0 mol) of the resin was used. The values ​​are shown in Table 3. Example 6-E As raw materials, 6.7 kg (18.0 mol) of BNE and 17.2 kg (30 0.0 mol), DNBINOL-2EO 7.5 kg (12.0 mol), DPC 13.5 The same procedure as in Example 1 was carried out except that 100 kg (63.0 mol) of the resin was used. The performance values ​​are shown in Table 3. (Example 6-F) The raw materials were 6.7 kg (18.0 mol) of BNE and 10.1 kg (24. 0 mol), DNBINOL-2EO 11.3 kg (18.0 mol), DPC 13.5 The same procedure as in Example 1 was carried out except that 100 kg (63.0 mol) of the resin was used. The performance values ​​are shown in Table 3.

[0196] Example 7 As a raw material, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene -2-yl)-1,1'-binaphthalene (2DNBINOL-2EO) 32.0 kg (5 1.0 mol), BPEF 3.8 kg (9.0 mol), DPC 13.5 kg (63.0 The same procedure as in Example 1 was carried out except that a 100% hydroxypropyl methylcellulose (100%) was used. The physical properties of the resulting resin are shown in Table 3. vinegar. Example 7-A As a raw material, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene -2-yl)-1,1'-binaphthalene (2DNBINOL-2EO) 18.8 kg (3 0.0 mol), BPEF 12.7 kg (30.0 mol), DPC 13.5 kg (63 The same procedure as in Example 1 was carried out, except that a 1.0 mol (0.0 mol) of ethylenediaminetetraacetic acid was used. The physical properties of the resulting resin are shown in Table 3. Shown below. (Example 7-B) As a raw material, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene -2-yl)-1,1'-binaphthalene (2DNBINOL-2EO) 5.6 kg (9. 0 mol), BPEF 21.5 kg (51.0 mol), DPC 13.5 kg (63.0 The same procedure as in Example 1 was carried out except that a 100% hydroxypropyl methylcellulose (100%) was used. The physical properties of the resulting resin are shown in Table 3. vinegar.

[0197] Example 8 As a raw material, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(phenanthroline) 9DPNBINOL-2EO) 37.1kJ g (51.0 mol), BPEF 3.8 kg (9.0 mol), DPC 13.5 kg (6 The same procedure as in Example 1 was carried out except that 3.0 mol) of ethylenediaminetetraacetic acid was used. The physical properties of the resulting resin are shown in the table below. Shown in 3. (Example 8-A) As a raw material, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(phenanthroline) 9DPNBINOL-2EO) 21.8kJ g (30.0 mol), BPEF 12.7 kg (30.0 mol), DPC 13.5 kg The same procedure as in Example 1 was carried out except that (63.0 mol) was used. Physical properties of the obtained resin is shown in Table 3. (Example 8-B) As a raw material, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(phenanthroline) 9DPNBINOL-2EO) 6.5kg (9.0 mol), BPEF 21.5 kg (51.0 mol), DPC 13.5 kg (6 The same procedure as in Example 1 was carried out except that 3.0 mol) of ethylenediaminetetraacetic acid was used. The physical properties of the resulting resin are shown in the table below. Shown in 3.

[0198] Example 9 As a raw material, 6,6'-di-(3-cyanophenyl)-2,2'-bis- (2-hydroxyethoxy)-1,1'-binaphthyl(CN-BNA ) 10.4 kg (18.0 mol), BPEF 18.4 kg (42.0 mol), DPC The same procedure as in Example 1 was carried out except that 13.5 kg (63.0 mol) of the product was used. The physical properties of the resin are shown in Table 3.

[0199] Example 10 As a raw material, 6,6'-di-(dibenzo[b,d]furan-4-yl)- 2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphth yl(FUR-BNA) 12.7 kg (18.0 mol), BPEF 18.4 kg (4 The same procedure as in Example 1 was repeated except that 13.5 kg (63.0 mol) of DPC was used. The physical properties of the resulting resin are shown in Table 3.

[0200] Example 11 As a raw material, 6,6'-di-(dibenzo[b,d]thien-4-yl)- 2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphth yl(THI-BNA) 13.3 kg (18.0 mol), BPEF 18.4 kg (4 The same procedure as in Example 1 was repeated except that 13.5 kg (63.0 mol) of DPC was used. The physical properties of the resulting resin are shown in Table 3.

[0201] (Comparative Example 1) As raw materials, 22.5 kg (60.0 mol) of BNE and 13.5 g (63.0 mol) of DPC were used. The same procedure as in Example 1 was carried out except that the resin obtained was used. The physical properties of the resulting resin are shown in Table 3.

[0202] [Table 3]

[0203] [ka]

[0204] [Production of polyester and polyester carbonate resins] Example 12 As a diol compound, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl 1,1'-binaphthalene (BINL-2EO) 0.090 mol, dicarboxylic acid Alkyl methyl 9,9-fluorenedipropionate (FDPM) 0.010m ol, ethylene glycol (EG) 0.120 mol, and as a transesterification catalyst 0.001 mol of tetrabutoxytitanium was added to a Nakamura Scientific Instruments Industry Co., Ltd. agitator equipped with a half-moon-shaped agitating blade. The reactor was equipped with a UZU agitator and a distillation device, and nitrogen was added. The mixture was heated to 180°C under atmospheric pressure and stirred for 30 minutes. The temperature was raised to 250°C and the pressure was reduced to 0.13 kPa to carry out the polymerization reaction. After holding at 0.13 kPa for 1 hour, the contents were removed from the reactor to obtain a polyester resin. The physical properties of the obtained polyester resin are shown in Table 3.

[0205] (Examples 13 to 18, Comparative Example 2) The same procedure as in Example 12 was repeated except that the diol compounds shown in Table 3 were used. The physical properties of the polyester resin obtained are shown in Table 3.

[0206] Example 19 As a diol compound, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl 1,1'-binaphthalene (BINL-2EO) 0.110 mol, dicarboxylic acid Alkyl methyl 9,9-fluorenedipropionate (FDPM) 0.100m ol, diphenyl carbonate 0.010 mol, and tetrahydrofuran as a transesterification catalyst. 0.001 mol of ruthoxytitanium was added to a Nakamura Scientific Instruments Co., Ltd. agitator equipped with a half-moon-shaped agitator blade. The mixture was placed in a reactor equipped with a company-manufactured agitator, a ceiling mixer UZU, and a distillation device, and placed under a nitrogen atmosphere. The mixture was heated to 180°C under atmospheric pressure and stirred for 60 minutes. After that, the temperature was raised to 240°C over 1 hour, and the pressure was reduced to 0.13 kPa. The contents were then heated at 240°C and 0.13 kPa for 1 hour, and then the contents were heated. The mixture was taken out of the reactor to obtain a polyester carbonate resin. The physical properties of the nate resin are shown in Table 3.

[0207] Example 20 As a diol compound, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl 1,1'-binaphthalene (BINL-2EO) 0.10 mol, ethylene glycol (EG) 0.06 mol, 2,2'-bis(hydroxycarbonyl) as dicarboxylic acid 0.12 mol of 1,1'-binaphthyl methoxy (BINOL-DC) and a catalyst. 0.001 mol of tetrabutoxytitanium was placed in a reaction vessel equipped with a stirrer and a distillation device. The mixture was heated to 180°C under nitrogen atmosphere and normal pressure, and stirred for 30 minutes. The temperature was raised and the pressure was reduced to 0.13 kPa or less to carry out the polymerization reaction. After holding at 55°C and 0.13 kPa for 1 hour, the contents were removed from the reactor and The polyester resin was removed from the reactor and the physical properties of the polyester resin are shown in Table 4. show.

[0208] [Table 4]

[0209] [ka] [ka]

[0210] [Monomer production] Example 21: Preparation of Form A Step 1: 6,6'-dibromo-1,1'-bis(2-naphthol) Hydroxyethylation of 1,1'-bis(2-naphthol) A nitrogen-purged container was filled with 1053 kg of anisole and 157.6 kg of 6,6' -dibromo-1,1'-bis(2-naphthol) (commercially available), 14.6 kg Potassium carbonate and 97 kg of ethylene carbonate were charged. After that, the vessel was heated to an internal temperature of 125-135°C. As shown, the reaction started at about 80-90°C. The reaction was continued until TLC showed complete conversion. The mixture was maintained at 125-135°C for 40 hours. The internal temperature of the reaction mixture was adjusted to 75°C. The mixture was cooled. 145 kg of water was slowly added. The mixture was heated to 80°C. The mixture was stirred at that temperature for another 30 minutes. After stirring was stopped, layer separation occurred 25 minutes later. After completion, the lower aqueous layer was removed. The organic layer remaining in the vessel was added with 164 kg of sodium hydroxide. Thorium solution (20% (w / w)) was added and the mixture was stirred at 90°C for 2 hours. After 2 hours, the vessel was cooled to 80°C, stirring was stopped, and layers were separated in 25 minutes. The lower, substantially aqueous layer was removed. The organic layer was washed with an additional 160 kg of water and 25 kg of chloride. Wash with sodium hydroxide (80°C, 30 min) and allow to separate for 20 min. Remove the aqueous layer. did.

[0211] The organic layer thus obtained is the target 2,2'-bis(2-hydroxyethoxy)- A solution of 6,6'-dibromo-1,1'-binaphthalene in anisole was prepared without isolating the compound. It was used directly in the next step.

[0212] Step 2: Suzuki coupling of 6,6'-DPBHBNA preparation 84 g of tris-(o-tolyl)phosphine and 15 g of palladium A catalyst solution was prepared by dissolving ammonium(II) acetate in 1.5 kg of anisole.

[0213] In a first reaction vessel, 2,2'-bis(2-hydroxyethoxy) A solution of 1,1'-6,6'-dibromo-binaphthalene in anisole was heated to 60°C. 93.4 kg of phenylboronic acid was added. The mixture was stirred for 15 minutes until the phenylboronic acid was completely dissolved. Cool to 50°C.

[0214] In a second reaction vessel, 3 parts of 520 kg of tripotassium phosphate The 1% (w / w) aqueous solution was heated to 50°C, and the catalyst solution prepared in advance was gradually added. This resulted in an overall temperature increase of approximately 15°C. After the catalyst was added, the mixture was The remaining 70% from vessel 1 was stirred at 55-75°C for 1 hour. After the addition was complete, the mixture was heated at 60°C for an additional hour. The mixture was stirred for 30 minutes at 50-60°C. TLC showed complete conversion. The layers were separated. The aqueous layer on the side was removed. The organic layer was added with 186 kg of water and 125 kg of 20% by weight sodium hydroxide. An aqueous solution of sodium was added. The mixture was stirred at 55°C for 40 minutes. The layers were separated and the lower, substantially aqueous layer was removed.

[0215] Further, 182 kg of 2 M hydrochloric acid was added to the organic layer, and the mixture was heated at 50 to 60°C for 30 minutes. The layers were allowed to separate and the lower acidic aqueous layer was removed. The organic layer was then added to an additional 182 kg of The organic layer was washed with 25% by weight of brine at 50-60°C. The organic layer was then heated at 60-70°C for 90 minutes. 10 kg of activated carbon (Norit® DX Ultra) and 50 kg of sodium sulfate were mixed under stirring. The mixture was then passed through a pressure strainer at 60-70°C to prevent precipitation of the product. The mixture was filtered (6,6'-DPBHBNA crystallized from anisole to give polyhedral crystals). Although crystals are produced, they do not have a specific composition and the yield is low.

[0216] The filtrate (approximately 2500 L) was then transferred to a still. Anisole was added to approximately 200 L of Distillation was carried out at temperatures above 80° C. and 90 mbar until a residue remained. can be recovered and reused. After releasing the vacuum, the residue was cooled to 55°C. At this temperature, 140 kg of methanol and 60 kg of toluene were added. This mixture was used to dissolve the precipitate. The mixture was heated to 60-65°C while stirring until the solution became homogeneous. Once the temperature reached 35-40°C, the container was cooled to 20°C. The solution was seeded with -DPBHBNA and crystallization was initiated. The mixture was cooled to 20°C and The mixture was stirred at rt for 4 hours, and the precipitate was collected by centrifugation and filtered. was washed with two 10 kg portions of methanol.

[0217] In this way, 162 kg of 6,6'-DPBHBNA (loss on drying: 15%) was obtained. This resulted in 137 kg of dry 6,6'-DPBHBNA and a yield of 7.5% over both steps. The chemical purity of the obtained 6,6'-DPBHBNA was 98.4% by UPLC. It was measured as %.

[0218] Step 3: Purification / recrystallization of 6,6'-DPBHBNA 6,6'-DPBHBNA (142 kg, 270 mol; pure) obtained in step 2 98.0% in a mixture of methanol / 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. The filtrate was cooled to 0°C over 4 hours with stirring, and then stirred at 0°C for an additional hour. As a result, 6,6'-DPBHBNA was crystallized. The crystals were collected by filtration and washed with methanol, revealing 154 kg of 2,2'-bis(2- Hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene (Bis-2,2'-(2 (-hydroxyethoxy)-6,6'-diphenyl-1,1'-bisnaphthyl) was obtained (LOD: 14%; 252 Molar; UPLC chemical purity; 98.8%).

[0219] The thus obtained 6,6'-DPBHBNA was dissolved in methanol / toluene (7:3 (v / v The solution was again heated at 55°C with activated carbon (7 kg) for 2 hours. The activated carbon was removed by filtration, and the filtrate was cooled to 0°C for 5 hours with stirring. The mixture was stirred for another hour at 0°C. The solid was collected by filtration and washed with methanol. As a result, 131.4 kg of 6,6'-DPBHBNA was obtained (LOD: 14%; 220 mol; UPLC chemical purity: 99%. The product was determined to be a methanol solvate by PXRD. Identified.

[0220] Step 4: Conversion of 6,6'-DPBHBNA to methanol solvate form A The resulting 48 kg of crystalline 6,6'-DPBHBNA methanol solvate was heated at 40°C. The mixture was dried under air at RT for 5 days to form compact crystals with sizes ranging from 5 to 200 μm. As a result, 41.3 kg of crystalline 6,6'-DPBHBNA was obtained.

[0221] The product obtained in step 4 was dissolved in 0.03% bw methanol and 0.3% bw toluol. The solvent component of the ene, i.e., 6,6'-DPBHBNA (2,2'-bis(2-hydroxybenzoyl) Based on the weight of (6,6'-diphenyl-1,1'-binaphthalene) 6,6'-DPBHBNA 100 wt%), 0.03 wt% methanol and 0. It was determined by GC to contain a solvent content of 3 wt% toluene.

[0222] The product of step 4 was analyzed by PXRD, which is shown in Figure 2. This confirmed that the crystalline form was Form A. The following reflection peaks were observed: was done. [Table 5]

[0223] UPLC showed that the product of step 4 was 6,6'-DPBHBNA with 99.1% bw. 0.06% bw (0.06% by weight) 6,6'-DPMHBNA and 0.19% bw It was found to contain 0.19 wt% 6,6'-DPTHBNA.

[0224] The yellowness index YI of the product of Step 4 was 3.9 and the haze was 0.5 ntu.

[0225] The product of step 4 was analyzed by IR and NIR. The NIR is shown in Figure 3 and the IR is In the NIR, the peaks at approximately 7000 and 4500 cm are shown in Figure 4. -1 The habit of It is characteristic of Form A and clearly distinguishes it from the solvate.

[0226] The DSC of the product from step 4 showed an onset at 113.6°C and a peak maximum at 124.4°C. The melting point was immediately measured and showed an endothermic peak with a reaction point of 112.9°C. The melting points shown were 127.0°C, 126.5°C, and 126.8°C. DSC was shown in Figure 5. As shown in.

[0227] Example 22: Preparation of methanol solvate of 6,6'-DPBHBNA 20 g of 6,6'-DPBHBNA obtained in Step 4 of Example 21 (UPLC chemistry) Purity: >99%) was dissolved in 600 ml of pure methanol and heated at reflux. When the solution was gradually cooled to 22°C, 6,6'-DPBHBNA was dissolved in 10-20% water. 6,6'-DPBHBN as a form of compact crystals with sizes in the 0 μm range The crystals were collected by filtration, washed with methanol, and then heated at 25°C for 2 days in air. and the molar ratio of 6,6'-DPBHBNA to methanol is about 1:1. The corresponding 2,2'-bis(2-hydroxyethoxy) 6,6'-diphenyl-1,1'-binaphthalene (i.e., 6,6'-DPBH BNA (2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1' -binaphthalene) (based on 100% by weight of 6,6'-DPBHBNA) ) and 6,6'-DPBHBNA)) containing 5.98 wt% methanol were obtained.

[0228] The product thus obtained was analyzed by PXRD, the PXRD of which is shown in Figure 6. This demonstrates that the crystalline form is different from Form A and Form C. The following reflection peaks were observed:

[0229] [Table 6]

[0230] The product thus obtained was analyzed by IR and NIR. The NIR is shown in Figure 7, and the I R is shown in Figure 8. In the NIR, the R is approximately 4500 and 4300 cm -1 Habit is characteristic of the methanol solvate and clearly distinguishes it from Form A and other solvates. .

[0231] The DSC of the product thus obtained showed an onset at 100.9°C and a peak at 113.4°C. The melting point was immediately measured. The melting points were 107.4°C, 108.7°C, and 107.7°C. Shown in Figure 9.

[0232] Example 23: Preparation of a mixture of Form A and methanol solvate Step 1: Hydroxybenzoates of 6,6'-dibromo-1,1'-bis(2-naphthol) Chilling A 2 L three-neck flask equipped with a stirrer, water separator, reflux condenser, thermometer, and bubble counter 89.7 g of 6,6'-dibromo-1,1'-bis(2-naphthol), 573 g of Nisole, 8.3 g of K2CO3, and 52.8 g of ethylene carbonate were charged and the reaction The mixture was heated to reflux (internal temperature 125-135°C) and stirred for 6 hours. The reaction was monitored by TLC. After the reaction was completed, the reaction mixture was Cool to 70-80°C, add 75g of water and 25g of salt water, and keep the mixture at that temperature for a further After stirring for 20 minutes, the layers were separated and 15% by weight of aqueous NaOH (110 g) was added to the organic layer. The mixture was stirred at 95° C. for 3 hours. After layer separation, the organic layer was diluted with 110 g of water. The resulting organic layer was washed with an aqueous solution prepared from 25 g of brine. It was used directly in the next step without isolation.

[0233] Step 2: Suzuki coupling of 6,6'-DPBHBNA preparation In a 2 L three-neck flask equipped with a stirrer, reflux condenser, and thermometer, add the HCl solution obtained in step 1. The organic solution was charged with 50.0 g of phenylboronic acid, K3 PO4 (93.4 g) and water (210 g) were added, and the mixture was heated to an internal temperature of 60°C. Then, 49 mg of tris-(o-tolyl)phosphine was added. hine) and 9 mg of palladium(II) acetate were added under vigorous stirring. The mixture was slowly heated to reflux and the reaction progress was monitored by TLC. After 10 minutes to 1 hour, the mixture was cooled to 70°C and the aqueous layer was separated and removed. ml of 10% bw aqueous NaOH, 2 M aqueous HCl (87.5 ml), and again The organic layer was then treated with 2.5 g of activated carbon and sulfuric acid. After filtration, the solvent was evaporated in vacuo and the residue was dissolved in methylpropional. The crystalline product was crystallized from a mixture of ethanol (77 g) and toluene (33 g). of product was obtained and collected by filtration.

[0234] This resulted in 110 g of wet 6,6'-DPBHBNA (loss on drying: 15%). This resulted in 93.5 g of dry 6,6'-DPBHBNA and the yields from both steps. The chemical purity of the obtained 6,6'-DPBHBNA was confirmed by UPLC. It was measured at 98%.

[0235] Step 3: Purification / recrystallization of 6,6'-DPBHBNA 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). Solution The mixture 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 The mixture was cooled to 0°C while stirring, and stirred at 0°C for 1.5 hours. 6,6'-DPBHBNA as a form of compact crystals with sizes in the µm range This solid was collected by filtration, washed with methanol, and left overnight in air at room temperature. Upon drying, it has a chemical purity of 99.89% (UPLC) and a yellowness index (YI) of 2.1. 85.0 g of 6,6'-DPBHBNA was obtained.

[0236] The product obtained in step 3 was dissolved in 2.4% bw of methanol, 0.1% bw of toluene. and 0.002% bw of the solvent components of anisole (i.e., 6,6'-D PBHBNA (2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1 ,1'-binaphthalene) (based on the weight of 6,6'-DPBHBNA 100% by weight) % of methanol, 0.1% of toluene, and 0.002% of toluene. 6,6'-DPBHBNA) containing % of the solvent component of anisole was determined by GC. It was.

[0237] The product of Step 3 was analyzed by PXRD, which is shown in Figure 10. This revealed that the crystalline form was a mixture of Form A and a methanol solvate. The following reflection peaks were observed:

[0238] [Table 7]

[0239] The product of step 3 was analyzed by IR and NIR. The NIR is shown in Figure 11 and the IR is shown in Figure 12. In the NIR, at approximately 4500 and 4300 cm -1 Habit is characteristic of the methanol solvate.

[0240] The DSC of the product from Step 3 showed an onset at 97.3°C, a peak maximum at 109.8°C, and a first endothermic peak with a reaction point of 109.8 ° C, and an onset at 118.9 ° C, It showed a peak maximum at 24.4°C and a second peak with a reaction point at 121.4°C. The melting points were immediately determined and were 118.6°C, 119.4°C, and 116.7°C. ° C. The DSC is shown in FIG.

[0241] Example 24: Preparation of toluene solvate of 6,6'-DPBHBNA 20 g of 6,6'-DPBHBNA obtained in Step 4 of Example 21 (UPLC chemistry) Purity: >99.0%) was dissolved in 60 ml of pure toluene and heated at reflux. When the solution was gradually cooled to 22°C, 6,6'-DPBHBNA was dissolved in water for 20-25 minutes. 6,6'-DPBHBN as a form of compact crystals with sizes in the 0 μm range The crystals were collected by filtration, washed with methanol, and then heated at 25°C for 2 days in air. and dried by 6,6'-DPBHBNA:toluene molar ratio of about 2.95:1. 2,2'-bis(2-hydroxyethoxy)- ... 1)-6,6'-diphenyl-1,1'-binaphthalene was obtained. The photomicrograph is shown in FIG.

[0242] The product thus obtained was analyzed by PXRD, the PXRD of which is shown in Figure 15. This reveals that the crystalline form is different from Form A, and A reflection peak of [Table 8]

[0243] The product thus obtained was analyzed by IR and NIR. The NIR is shown in Figure 16. The IR is shown in Figure 17. In the NIR, the peaks at approximately 7000 and 4700 cm -1 The phase of habi t) is characteristic of the toluene solvate and differentiates it from Form A, Form B, and other solvates. Make it clear.

[0244] The DSC of the product thus obtained showed an onset at 106.5°C and a peak at 113.6°C. The melting point was immediately measured. The melting points shown are 103-107.9°C, 104.0-106.8°C, and 104.8°C. ~107.6°C. The DSC is shown in Figure 18.

[0245] Example 25: Preparation of MEK solvate of 6,6'-DPBHBNA 100 g of 6,6'-DPBHBNA (UPLC) obtained in Step 4 of Example 21 Chemical purity: >99.0%) was dissolved in 300 ml of pure MEK and heated at reflux. The homogeneous solution was gradually cooled to 22°C, and 6,6'-DPBHBNA was dissolved in 20-2 6,6'-DPBHB as a form of compact crystals with sizes in the 00 µm range The crystals were collected by filtration, washed with MEK, and then exposed to air at 25°C for 2 days. The mixture was further dried and then heated at 50°C for 1 hour to obtain 6,6'-DPBHBNA:MEK. 2,2'-bis(2,2'-biphenyl)-2,2'-diol containing 8.5% bw MEK, corresponding to a molar ratio of about 1.5:1. bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene was obtained. A micrograph of the crystals thus obtained is shown in FIG.

[0246] The product thus obtained was analyzed by NIR, and the NIR is shown in Figure 20. At 4600 cm -1 is characteristic of the MEK solvate, and Form A and clearly shows the difference from other solvates.

[0247] The DSC of the product thus obtained showed an onset at 89.4°C and a peak maximum at 97.6°C. The melting point was immediately measured and showed an endothermic peak with a reaction point of 95.5°C. The melting points observed were 105.9° C. and 105.8° C. The DSC is shown in FIG.

[0248] The product of Example 25 thus obtained was analyzed by PXRD. 22, which shows that the crystalline forms differ from Form A and Form B. The following reflection peaks were observed: [Table 9] Example 26: Preparation of amorphous form B of 6,6'-DPBHBNA 100 g of 6,6'-DPBHBNA (UPLC) obtained in Step 4 of Example 21 The molten material (chemical purity: >99.0%) was heated to 130°C to obtain a clear melt. It was cooled to 22°C within 2 minutes, which gave an amorphous (glassy) solid. The solid was crushed into small pieces and crushed in a mortar to obtain a powder.

[0249] The product thus obtained was analyzed by PXRD, the PXRD of which is shown in Figure 23. This is evidenced by the absence of reflection peaks in the 2θ range of 5° to 40°. As shown in Fig. 1, no crystalline layer was observed. A broad halo was observed.

[0250] The product thus obtained was analyzed by IR and NIR. The NIR is shown in Figure 24. The IR is shown in FIG.

[0251] The DSC of the product thus obtained (not shown) showed that in the temperature range of 80 to 200°C No endothermic peak was observed. Rather, the glass transition point was in the range of 109 to 110°C. A corresponding step was observed.

[0252] Example 27: Preparation of Form C of 6,6'-DPBHBNA Example 27a 20 g of 6,6'-DPBHBNA obtained in Step 4 of Example 21 (UPLC chemistry) Purity: >99.0%) was dissolved in 300 ml of 96% ethanol and heated to reflux. The homogeneous solution was gradually cooled to 22°C, and 6,6'-DPBHBNA was converted into 2-1 6,6'-DPBHB in the form of compact crystals with sizes in the 50 μm range The crystals were collected by filtration, washed with MEK, and then exposed to air at 25°C for 2 days. and dried at 50°C for 1 hour, resulting in 100% ethanol-free samples. 5.8g of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1 ´-Binaphthalene was obtained.

[0253] Example 27b 30 g of 6,6'-DPBHBNA obtained in Step 4 of Example 21 (UPLC chemistry) Purity: >99.0%) was dissolved in 250 ml of anisole at 100°C. When cooled very slowly to 22°C, 6,6'-DPBHBNA was dissolved in 10-3 6,6'-DPBHB as a form of compact crystals with sizes in the 00 µm range The crystals were collected by filtration, washed with cold anisole, and stirred for 19 hours. Dry in a rotary evaporator at 80 °C to remove a small amount of anisole (approximately 0.1 wt. %) and no other solvents. -6,6'-diphenyl-1,1'-binaphthalene was obtained.

[0254] The product obtained in Example 27a was analyzed by PXRD. The PXRD is shown in Figure 2. 6, which shows that its crystalline form is similar to the PXRD of the toluene solvate. It is clear that, unlike Form A and other solvates, the following reflection peaks are observed: I did. [Table 10]

[0255] The product obtained in Example 27b was analyzed by PXRD. It shows the same reflection peaks and habit as the product obtained in Example 27a. It was confirmed that the crystals obtained in Example 27b and Example 27c were of the same crystalline form.

[0256] The product obtained in Example 27a was analyzed by IR and NIR. The NIR is shown in Figure 27. The IR is shown in Figure 28. In the NIR, the peaks at approximately 7000 and 4700 cm -1 of The habit is characteristic of Form C, which is different from Forms A and B and the toluene solvate. The difference between the solvates and the non-solvates is clearly shown. The product was analyzed by IR and NIR. These spectra were the same as those obtained in Example 27a. The phase was the same as that of the product.

[0257] The DSC of the product obtained in Example 27a showed an onset at 116.6°C and a peak at 125.0°C. It showed an endothermic peak with a peak maximum and a reaction point of 121.0° C. Example 27a The DSC of the product obtained in Example 27b is shown in Figure 29. SC has an onset at 115.4°C, a peak maximum at 124.0°C, and a reaction point at 120.0°C. An endothermic peak with a reaction point was observed.

[0258] [Production of polycarbonate resin composition using the monomers of the above examples] Example 28 As a starting material, BINL-2EO, "Form A" obtained in Example 21, i.e., 6,6' -DPBHBNA 7.9 kg (15.0 mol), BNE 16.8 kg (45.0 mol) , BNEF 21.5 kg (40.0 mol), DPC 22.1 kg (103.0 mol) and and sodium bicarbonate 0.117g (13.9 x 10 -4 mol), a stirrer and distillate The mixture was scooped into a 50 L reactor equipped with a hopper. Nitrogen was introduced into the reactor, the inside of the reactor was pressurized to 780 mmHg, and after holding for 3 minutes, the nitrogen was discharged from the exhaust port. Nitrogen was again introduced into the reactor, and after 3 minutes, nitrogen was released from the exhaust port. The pressure was then evacuated to 760 mmH. Nitrogen was then introduced into the reactor again, and after 3 minutes, the pressure was evacuated. Nitrogen was exhausted from the vent to return the pressure to 760 mmH. Then, under a nitrogen atmosphere of 760 mmHg, The mixture was heated to 180°C. After 20 minutes of heating, the raw materials were confirmed to be completely dissolved. Stirring was carried out for 20 minutes, and then the pressure was reduced to 200 mmHg and the temperature was increased to 60°C / The temperature was raised to 200°C at a rate of 1 / 2 hour. At this time, the start of distillation of the by-product phenol was confirmed. The reaction was then continued at 200°C for 40 minutes. The temperature was raised to 240°C, and 10 minutes after the temperature was raised, the pressure was reduced over 1 hour while maintaining the temperature. The temperature was then raised to 245°C at a rate of 60°C / hr, and then After the reaction was completed, nitrogen was introduced into the reactor to return the pressure to normal, and the resulting poly The recarbonate resin was pelletized and taken out. The Mw of the pellets was 27,500. It was.

[0259] The obtained polycarbonate resin pellets were dried at 100°C for 3 hours to determine the moisture content of the pellets. The dry pellets were then washed with water and the resulting solution was washed with water. As an additive, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl (4-hydroxyphenyl)propionate (ADEKA AO-60: antioxidant) 100 0 ppm, stearic acid monoglyceride (Riken Vitamin Co., Ltd. S-100A: mold release agent) 15 00 ppm, and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetramethylphenoxy Oxa-3,9-diphosphaspiro[5.5]undecane (ADEKA PEP-36: antioxidant) 30 The additive was then added to the dried pellets. The mixture was melt-kneaded and pelletized under a reduced pressure of 40 mmHg.

[0260] The refractive index of the obtained polycarbonate resin composition was 1.680, the Abbe number was 18.1, and the T g is 147℃, Mv is 11900, Mw is 27000, b value is 3.9, formability is A, total light The light transmittance was 89%, and the total light transmittance after the PCT test was 89%. The physical properties of the polycarbonate resin obtained in Example 28 were compared with those of the resins in other Examples. These are also shown in Table 11. [ka] (BINL-2EO, i.e., 6,6'-DPBHBNA)

[0261] Example 29 The raw materials were BINL-2EO 12.6 kg (24.0 mol) and BNE 11.1 kJ. g(30.0mol), BNEF 17.8kg(33.0mol), 2DNBINOL -2EO 8.1 kg (13.0 mol), DPC 22.1 kg (103.0 mol) and Sodium bicarbonate 0.117g (13.9 x 10 -4 Example 28 except that 1,2-dimethyl-2,4-dichloro-1,4-dichloro ... In the same manner as above, a polycarbonate resin and a polycarbonate composition were obtained.

[0262] The refractive index of the obtained polycarbonate resin composition was 1.690, the Abbe number was 16.7, and the T g is 155℃, Mv is 11900, Mw is 27000, b value is 3.9, formability is A, total light The light transmittance was 89%, and the total light transmittance after the PCT test was 89%. The physical properties of the polycarbonate resin obtained in Example 29 are shown in Table 11. [ka] (2DNBINOL-2EO) [Table 11]

[0263] Examples 30 to 36 The raw material was BINL-2EO, i.e., 6,6'-DPBHBNA 78, as shown in the table below. 99g (0.15 mol), BNE 168.50g (0.45 mol), BNEF 215.4 5g (0.40 mol), DPC 220.64g (1.030 mol) and sodium bicarbonate 1.2 mg (1.39 × 10 -5 (mol / aqueous solution) was added, and a stirrer and distillation equipment were used. The mixture was poured into a 1 L reactor equipped with a separator through a funnel. The inside was pressurized to 780mmHg, and after holding for 3 minutes, nitrogen was discharged from the exhaust port to 760mmH. Nitrogen was again introduced into the reactor, and after 3 minutes of holding, the nitrogen was exhausted from the exhaust port and The temperature was returned to H. Nitrogen was then introduced into the reactor again, and after 3 minutes, the nitrogen was exhausted from the exhaust port. The pressure was then returned to 760 mmH. After that, the mixture was 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 then stirring was continued for 120 minutes under the same conditions. After that, the degree of vacuum was adjusted to 200 mmHg, and the temperature was increased to 200°C / hr. The temperature was raised to 40 °C. At this time, the start of distillation of by-produced phenol was confirmed. The reaction was carried out by holding the temperature at 200°C for 1 minute. The temperature was then increased to 240°C at a rate of 75°C / hr. After 10 minutes of heating, reduce the pressure to 1mmHg or less over 1 hour while maintaining the temperature. After that, the temperature was raised to 245°C at a rate of 60°C / hr, and stirring was continued for another 30 minutes. After the reaction was completed, nitrogen was introduced into the reactor to return it to normal pressure, and the produced polycarbonate resin was The optical properties of the resin obtained were the same as those of Example 28, but the molecular weight reached was slightly different. There were differences. [Table 12]

[0264] (Reference example) In step 3 of Example 23, "washed with methanol and dried overnight in air at room temperature" When the drying time was shortened, 1 mole of 2,2'-bis(2-hydroxyethylene) 1.3 moles of methanol per (6,6'-diphenyl-1,1'-binaphthalene) BINL-2EO containing 6,6'-DPBHBNA was obtained. Additional Example 1 except for replacing the main ingredient with INL-2EO (6,6'-DPBHBNA) The same reaction was attempted. As a result, when the raw material is poured into the reactor through the hopper with a scoop, it can be poured in smoothly. The reaction proceeded slowly, and the pellets obtained were less resistant to the reaction than those obtained in Example 28. In comparison, the Mw was low at 24,500.

[0265] Among the properties of the thermoplastic resins obtained in each example and comparative example, the Abbe number (v) is on the horizontal axis, and the bending moment (f) is on the Graphs with the refractive index (nD) on the vertical axis are shown in FIGS. The specific ranges shown in these graphs, e.g. The line nD=-0.02v+1.96 and the line nD=-0.02v+2.04 in Figure 30 Between, or The line nD=-0.0002ν+1.6718 and the line nD=-0.024ν+2 in Figure 31 .124, or between the line nD=-0.004v+1.744 and the line y=-0.0 Since many points of the examples are plotted between 2x and 2.04, In this case, a thermoplastic resin that has a good balance between the Abbe number and the refractive index and is suitable for optical applications is required. It was confirmed that this was achieved.

[0266] For example, in FIG. 31, the refractive index is higher than 1.660 and the Abbe number is less than 19. is 19 or less, for example, in the range 13 to 19 or 15 to 19, and The line nD=-0.0002ν+1.6718 and the line nD=-0.024ν+2.124 It is plotted in the region between -0.0002ν+1.6718 <nd<-0.0Polycarbonate resins that satisfy the relationship of 24ν+2.124 have preferable properties. Between the line nD=-0.004v+1.744 and the line nD=-0.024ν+2.124 It is plotted in the region between -0.004v+1.744 <nd<-0.024ν+Polycarbonate resins that satisfy the relationship 2.124 have more desirable properties. Between the line nD=-0.02v+2.04 and the line nD=-0.024ν+2.124 It is plotted in the region -0.02v+2.04 <nd<-0.024ν+2.12 It can be said that a polycarbonate resin that satisfies the relationship 4 has more preferable properties.< / nd<-0.024ν+2.12

Claims

1. 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-bina A crystalline solvate form of phthalene, containing 1 mole of 2,2'-bis(2-hydroxyphthalene) 0.3 to 1.2 moles per ethoxy)-6,6'-diphenyl-1,1'-binaphthalene containing an organic solvent in the crystals, The organic solvent is selected from methanol, toluene, and methyl ethyl ketone. Solvate form of benzophenone.

2. 2. The crystalline solvate form of claim 1, wherein the organic solvent is methanol.

3. The X-ray powder diffraction pattern by irradiation with Cu Kα1 radiation at 22°C is The following three reflection peaks as 2θ values: 13.0±0.2°, 14.9±0.2°, and 21.5±0.2°, The following reflection peaks as 2θ values: 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± 3. The crystalline solvate form of claim 2, exhibiting at least three of 0.2°.

4. Recorded according to ISO 11357-3:2018 at a heating rate of 20 K / min Differential scanning calorimetry (DSC) shows an endothermic peak with an onset in the range of 97-101°C; The crystalline solvent according to claim 2 or 3, wherein the maximum value of the peak is in the range of 108 to 115°C. Form of solubility.

5. The amount of methanol is 1 mole of 2,2'-bis(2-hydroxyethoxy)-6,6'- 0.3 to 1.0 mol per diphenyl-1,1'-binaphthalene according to claims 2 to 4.

2. The crystalline solvate form according to any one of claims 1 to 11.

6. 2. The crystalline solvate form of claim 1, wherein the organic solvent is toluene.

7. The X-ray powder diffraction pattern by irradiation with Cu Kα1 radiation at 22°C is The following three reflection peaks as 2θ values: 5.2±0.2°, 7.7±0.2°, and 21 .6±0.2°, The following reflection peaks 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°，１８．０±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° 7. The crystalline solvate form of claim 6, wherein:

8. Recorded according to ISO 11357-3:2018 at a heating rate of 20 K / min Differential scanning calorimetry (DSC) showed an endothermic peak with an onset in the range of 105-108°C. The crystalline polymer according to claim 6 or 7, wherein the maximum value of the peak is in the range of 112 to 115°C. Solvate forms.

9. The amount of toluene is 1 mole of 2,2'-bis(2-hydroxyethoxy)-6,6'-di 9. The amount of the phenyl-1,1'-binaphthalene is 0.3 to 0.5 mol per phenyl-1,1'-binaphthalene according to claims 6 to 8. Any crystalline solvate form as described herein.

10. 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-bina Crystalline Form A of phthalene, containing 1 mole of 2,2'-bis(2-hydroxyethoxy) )-6,6'-diphenyl-1,1'-binaphthalene with less than 0.1 mole of organic solvent The crystals contain The X-ray powder diffraction pattern by irradiation with Cu Kα1 radiation at 22°C is The following three reflection peaks as 2θ values: 20.9±0.2°, 21.4±0.2°, and 23.7±0.2°, The following reflection peaks 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° All three exhibit crystalline form A.

11. Recorded according to ISO 11357-3:2018 at a heating rate of 20 K / min Differential scanning calorimetry (DSC) showed an endothermic peak with an onset in the range of 112-114°C.

11. The crystalline form of claim 10, wherein the peak maximum is in the range of 124 to 126°C.

12. 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-bina Crystalline Form C of phthalene, containing 1 mole of 2,2'-bis(2-hydroxyethoxy) )-6,6'-diphenyl-1,1'-binaphthalene with less than 0.1 mole of organic solvent The crystals contain The X-ray powder diffraction pattern by irradiation with Cu Kα1 radiation at 22°C is The following three reflection peaks as 2θ values: 5.1±0.2°, 7.6±0.2°, and 21 .0±0.2°, 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°, Sexual form C.

13. Recorded according to ISO 11357-3:2018 at a heating rate of 20 K / min Differential scanning calorimetry (DSC) showed an endothermic peak with an onset in the range of 112-114°C.

13. The crystalline form of claim 12, wherein the peak maximum is in the range of 124 to 126°C.

14. 14. The method of claim 1, wherein the crystals have an aspect ratio of at most 5:

1. crystalline form of.

15. 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-bina Amorphous form B of phthalene, at least 99.0% by weight pure based on organic matter and 1 mole of 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl- The crystals contain less than 0.1 moles of organic solvent per mole of 1,1'-binaphthalene; The X-ray powder diffraction pattern by irradiation with Cu Kα1 radiation at 22°C is does not exhibit reflection peaks as 2θ values ​​at multiple diffraction angles in the range of 5° to 40°; Recorded according to ISO 11357-3:2018 at a heating rate of 20 K / min Amorphous form in which differential scanning calorimetry (DSC) does not show an endothermic peak in the range of 80 to 200°C B.

16. 2-(2-hydroxyethoxy)-2'-hydroxy-6,6'-diphenyl-1,1 '-binaphthalene, 2,2'-bishydroxy-6,6'-diphenyl-1,1'-bina Phthalene and 2-(2-hydroxyethoxy)-2'-(2-(2-hydroxyethoxy) )-ethoxy)-6,6'-diphenyl-1,1'-binaphthalene The total amount of impurities contained in the 2,2'-bis(2-hydroxyethoxy)-6 less than 0.5% by weight based on 2,2,6'-diphenyl-1,1'-binaphthalene '-Bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene 。

17. 2,2'-bis(2-hydroxyethoxy)- having at least one of the following characteristics: 6,6'-diphenyl-1,1'-binaphthalene. i. 5% w / w of 2,2'-bis(2-hydroxyethoxy) in dichloromethane -6,6'-diphenyl-1,1'-binaphthalene solution according to ASTM E313 a yellowness index (Y.I.) of less than 3.0 as determined by the ii. 5% w / w of 2,2'-bis(2-hydroxyethoxy)methylpropional in dichloromethane ) Less than 1.0 ntu measured in 6,6'-diphenyl-1,1'-binaphthalene solution Haze.

Images