Thermoplastic resin, method for producing same, and optical lens

文档序号：118939 发布日期：2021-10-19 浏览：20次中文

阅读说明：本技术 热塑性树脂、其制造方法和光学透镜 (Thermoplastic resin, method for producing same, and optical lens ) 是由池田慎也加藤宣之平川学 K·罗伊特 V·安德鲁什科 M·坎托尔 F·施托尔茨于 2020-02-27 设计创作，主要内容包括：本发明提供一种具有高折射率、低b值和高耐湿热性的热塑性树脂、使用这种热塑性树脂的光学透镜等。根据一个实施方式,提供含有下述通式(1)所示的结构单元的热塑性树脂。(式(1)中的R-(1)和R-(2)分别独立地表示氢原子、氟原子、氯原子、溴原子、碘原子、碳原子数1～6的烷基、单环式或多环式的碳原子数6～36的芳基、单环式或多环式的环原子数5～36的杂芳基、碳原子数2～6的烯基、碳原子数1～6的烷氧基或碳原子数7～17的芳烷基,上述杂芳基中,环原子中的1、2、3或4个选自氮、硫和氧,其他的环原子为碳,X、a和b分别如本申请说明书所述。)(The invention provides a thermoplastic resin having a high refractive index, a low b value and a high moist heat resistance, and an optical lens and the like using the same. According to one embodiment, a thermoplastic resin containing a structural unit represented by the following general formula (1) is provided. (R in the formula (1)) 1 And R 2 Independently represent hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, alkyl group of 1-6 carbon atoms, monocyclic or polycyclic 6-C36 aryl, monocyclic or polycyclic heteroaryl having 5 to 36 ring atoms, alkenyl having 2 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms or aralkyl having 7 to 17 carbon atoms, wherein 1,2,3 or 4 of the ring atoms in the heteroaryl are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon atoms, and X, a and b are as defined in the specification. ))

1. A thermoplastic resin characterized by:

contains a structural unit represented by the following general formula (1),

r in the formula (1)₁And R₂Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 36 carbon atoms in a monocyclic or polycyclic ring form, a heteroaryl group having 5 to 36 carbon atoms in a monocyclic or polycyclic ring form, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, wherein 1,2,3 or 4 of the ring atoms in the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon,

the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group have no substituent, or may have a substituent selected from CN, CH₃、OCH₃1 or 2R of O-phenyl, O-naphthyl, S-phenyl, S-naphthyl and halogen^aThe base group is a group of a compound,

wherein R is₁And R₂The total amount of the hydrogen is not all hydrogen,

x is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

wherein each of the alkylene group and the cycloalkylene group may be substituted to have a benzene ring,

a and b are respectively integers of 1-10.

2. The thermoplastic resin of claim 1, wherein:

the thermoplastic resin is a polyester resin or a polyester carbonate resin.

3. The thermoplastic resin according to claim 1 or 2, wherein:

further comprising a structural unit represented by the following general formula (2),

in the general formula (2), Q is represented by the following formula (2a),

in the formula (2a), R_CEach independently represents a single bond or an alkylene group which may have a substituent and has 1 to 10 carbon atoms in total, and which is bonded to the CO group in the formula (2) and contains a bonding point to the CO group in the formula (2) at the terminal.

4. The thermoplastic resin of claim 3, wherein:

q is represented by the following formula (2b),

in the formula (2b), n and m independently represent an integer of 0 to 5,

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

R₁and R₂And R in the formula (1)₁And R₂In the same way, the first and second,

a and b each independently represent an integer of 0 to 6,

represents a binding site to the CO group in the formula (2).

5. The thermoplastic resin according to claim 4, wherein:

at least has a structural unit containing Q represented by the following formula (2c),

in formula (2c), a represents a bonding point to the CO group in formula (2).

6. The thermoplastic resin according to any one of claims 1 to 5, wherein:

contains more than 50 mol% of the structural unit represented by the general formula (1).

7. The thermoplastic resin according to any one of claims 1 to 6, wherein:

r of the general formula (1)₁And R₂At least 1 of the (a) groups is an aryl group having 6 to 20 carbon atoms.

8. The thermoplastic resin of claim 7, wherein:

r of the general formula (1)₁And R₂At least 2 of the (a) groups are aryl groups having 6 to 14 carbon atoms.

9. The thermoplastic resin according to any one of claims 1 to 8, wherein:

the structural unit represented by the general formula (1) contains at least one of structural units represented by the following general formulae (A-1) to (A-7),

10. the thermoplastic resin according to any one of claims 1 to 9, wherein:

further comprising at least 1 of the structural units represented by the following general formulae (3) and (4),

r 'in the formula (3)'₁～R’₂₀Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkane having 1 to 6 carbon atomsA C6-12 aryl group, a C2-6 alkenyl group, a C1-6 alkoxy group or a C7-17 aralkyl group,

y is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

c and d are each an integer of 1 to 10,

r in the formula (4) "₁～R”₁₆Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aralkyl group having 7 to 17 carbon atoms,

z is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

e and f are integers of 1-10 respectively.

11. The thermoplastic resin of claim 10, wherein:

comprises a copolymer containing at least a structural unit represented by the general formula (1) and a structural unit represented by the general formula (3).

12. The thermoplastic resin of claim 11, wherein:

the copolymer further contains a structural unit represented by the following general formula (3-1),

13. the thermoplastic resin of claim 10, wherein:

comprises a copolymer containing at least a structural unit represented by the general formula (1) and a structural unit represented by the general formula (4).

14. The thermoplastic resin of claim 13, wherein:

the copolymer further contains a structural unit represented by the following general formula (4-1),

15. the thermoplastic resin according to any one of claims 1 to 14, wherein:

the total content of the structural units represented by the general formulae (3) and (4) is 20 to 80 mol%.

16. The thermoplastic resin according to claim 1 to 15, wherein:

further comprising at least 1 of the structural units represented by the following general formula (5),

17. the thermoplastic resin of claim 16, wherein:

contains at least a structural unit of BNEF (9, 9-bis (6- (2-hydroxyethoxy) naphthalene-2-yl) fluorene).

18. The thermoplastic resin of claim 16, wherein:

contains at least the structural unit of 2,2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl.

19. The thermoplastic resin of claim 16, wherein:

at least contains a structural unit of BPPEF (9, 9-bis (4- (2-hydroxyethoxy) -3-phenyl) fluorene).

20. The thermoplastic resin according to any one of claims 1 to 19, wherein:

the aryl group is selected from pyrenyl, furyl, benzodioxanyl, dihydrobenzofuryl, piperonyl, benzofuryl, dibenzofuryl, pyrrolidinyl, isoquinolinyl, pyrimidinyl and carbazolyl groups which can be substituted by alkyl groups having 1-6 carbon atoms, alkoxy groups having 1-6 carbon atoms or aryl groups having 6-16 carbon atoms.

21. The thermoplastic resin according to any one of claims 1 to 20, wherein:

the thermoplastic resin has a refractive index of 1.655 or more.

22. The thermoplastic resin according to any one of claims 1 to 21, wherein:

the R is₁And said R₂The same is true.

23. The thermoplastic resin according to any one of claims 1 to 21, wherein:

the R is₁And said R₂The same or different, selected from monocyclic or polycyclic aryl with 6-36 carbon atoms, monocyclic or polycyclic heteroaryl with 5-36 ring atoms, wherein in the heteroaryl, 1,2,3 or 4 ring atoms are selected from nitrogen, sulfur and oxygen, and other ring atoms are carbon,

the aryl group of monocyclic or polycyclic and the heteroaryl group of monocyclic or polycyclic have no substituent.

24. The thermoplastic resin according to any one of claims 1 to 23, wherein:

the R is₁And said R₂Selected from the following groups:

azulene groups;

an indenyl group having no substituent or an indenyl group which may be substituted with 2,3, 4 or 5 substituents selected from a phenyl group and a polycyclic aryl group having 2,3 or 4 benzene rings which may be bonded to each other by a single bond, may be directly condensed with each other, and/or may be condensed with a monocyclic or bicyclic hydrocarbon ring of a saturated or unsaturated 4-to 10-membered ring;

phenyl without substituents;

phenyl substituted with 1 or 2 CN groups;

a phenyl group which may be substituted with 2,3, 4 or 5 substituents selected from a phenyl group and a polycyclic aryl group having 2,3 or 4 benzene rings which may be bonded to each other by a single bond, may be directly condensed with each other, and/or may be condensed with a monocyclic or bicyclic hydrocarbon ring of a saturated or unsaturated 4 to 10-membered ring;

polycyclic aromatic groups having 2,3 or 4 benzene rings which may be directly condensed with each other and/or may be condensed with a monocyclic or bicyclic hydrocarbon ring of a saturated or unsaturated 4-to 10-membered ring, said polycyclic aromatic groups having no substituent or may be substituted with 1 or 2 substituents selected from phenyl and polycyclic aromatic groups having 2 or 3 benzene rings, 2 or 3 of said benzene rings may be bonded to each other by a single bond and may be directly condensed with each other, and/or may be condensed with a monocyclic or bicyclic hydrocarbon ring of a saturated 4-to 10-membered ring, said benzene rings of polycyclic aromatic groups having no substituent or may have 1 or 2 substituents R^a。

25. The thermoplastic resin according to any one of claims 1 to 24, wherein:

the R is₁And said R₂Selected from the following groups:

phenyl which has no substituent or phenyl which may be substituted with 1,2,3, 4 or 5 phenyl groups;

phenyl substituted with 1 or 2 CN groups;

a phenyl group substituted with 1 or 2 polycyclic aryl groups selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, and pyrenyl, and further substituted with 1 phenyl group;

naphthyl having no substituent or naphthyl substituted with 1 or 2 substituents selected from CN, phenyl and polycyclic aryl selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl and pyrenyl;

a biphenylene group;

triphenylene;

tetraphenylene;

phenanthryl;

pyrenyl;

9H-fluorenyl;

dibenzo [ a, e ] [8] annulenyl;

a perylene group; and

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

26. The thermoplastic resin of claim 25, wherein:

the R is₁And said R₂Selected from the group consisting of phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-naphthyl, 1-naphthyl and 9-naphthyl.

27. The thermoplastic resin according to any one of claims 1 to 23, wherein:

the R is₁And said R₂Selected from:

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

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

a heteroaromatic polycyclic group having at least 1 saturated or partially unsaturated 5-or 6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms and 1,2,3, 4 or 5 additional aromatic rings selected from phenyl and the heteroaromatic monocyclic ring, wherein at least 1 additional aromatic ring is directly condensed with a heterocyclic group of a saturated or partially unsaturated 5-or 6-membered ring, and the other additional aromatic rings of the polycyclic heteroaryl aromatic ring may be bonded to each other by a covalent bond, may be directly condensed with each other, and/or may be condensed with a monocyclic or bicyclic hydrocarbon ring of a saturated or unsaturated 4-to 10-membered ring.

28. The thermoplastic resin of claim 27, wherein:

the R is₁And said R₂Selected from: furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, 1,3, 4-oxadiazolyl, 1,2, 4-oxadiazolyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, benzofuranyl, dibenzofuranyl, benzothienyl, dibenzothienyl, thianthrenyl, naphthofuranyl, furo [3, 2-b ] o]Furyl, furo [2, 3-b ]]Furyl, furo [3, 4-b ]]Furyl, oxanthrenyl, indolyl, isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzo [ cd)]Indolyl, 1H-benzo [ g ]]Indolyl, quinolyl, isoquinolyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, benzo [ b ]][1,5]Naphthyridinyl, cinnolinyl, 1, 5-naphthyridinyl, 1, 8-naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, bipyridyl, phenylpyridinyl, naphthylpyridinyl, pyrido [4, 3-b ]]Indolyl, pyrido [3, 2-b ]]Indolyl, pyrido [3, 2-g ]]Quinolyl, pyrido [2, 3-b ]][1,8]Naphthyridinyl, pyrrolo [3, 2-b ] s]Pyridyl, pteridinyl (pteridinyl), purinyl (purinyl), 9H-xanthenyl (xanthenyl), 2H-benzopyranyl, phenanthridinyl, phenanthrolinyl, furo [3, 2-f)][1]Benzofuranyl, furo [2, 3-f ]][1]Benzofuranyl, furo [3, 2-g ]]Quinolyl, furo [2, 3-g ]]Quinolyl, furo [2, 3-g ]]Quinoxalinyl, benzo [ alpha ], [ beta ], [ alpha ], [ beta ]g]Benzopyranyl, pyrrolo [3,2, 1-hi]Indolyl, benzo [ g ]]Quinoxalinyl, benzo [ f)]Quinoxalinyl and benzo [ h ]]An isoquinolinyl group.

29. The thermoplastic resin according to any one of claims 1 to 28, wherein:

and X is ethylene.

30. The thermoplastic resin according to any one of claims 1 to 29, wherein:

the b value according to JIS K7105 is 10 or less.

31. The thermoplastic resin according to any one of claims 1 to 30, wherein:

the refractive index nD and the Abbe number nu meet the relation of-0.0002 nu +1.6718 < nD < -0.024 nu + 2.124.

32. The thermoplastic resin of claim 31, wherein:

the refractive index nD and the Abbe number nu meet the relation of-0.004 v +1.744 < nD < -0.024 nu + 2.124.

33. The thermoplastic resin of claim 32, wherein:

the refractive index nD and the Abbe number nu meet the relation of-0.02 v +2.04 < nD < -0.024 nu + 2.124.

34. An optical lens, characterized in that:

comprising the thermoplastic resin according to any one of claims 1 to 33.

35. A method for producing the thermoplastic resin according to any one of claims 1 to 33, the method comprising:

a step of melt-polycondensing at least a dihydroxy compound represented by the following general formula (6) with at least one of a carboxylic acid, a carboxylic acid monoester and a carboxylic acid diester,

r in the general formula (6)₁And R₂Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 36 carbon atoms in a monocyclic or polycyclic ring form, a heteroaryl group having 5 to 36 carbon atoms in a monocyclic or polycyclic ring form, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, wherein 1,2,3 or 4 of the ring atoms in the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon,

wherein R is₁And R₂The total amount of the hydrogen is not all hydrogen,

x is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

wherein each of the alkylene group and the cycloalkylene group may be substituted to have a benzene ring,

a and b are respectively integers of 1-10.

36. A crystalline solvate form of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl, characterized in that:

the crystals contain 0.3 to 1.2 moles of an organic solvent per 1 mole of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl,

the organic solvent is selected from methanol, toluene and methyl ethyl ketone.

37. The crystalline solvate form of claim 36, wherein:

the organic solvent is methanol.

38. A crystalline solvate form according to claim 37, wherein:

in an X-ray powder diffraction pattern obtained by irradiation with Cu Ka 1 radiation at 22 ℃,

the following 3 reflection peaks are shown as 2 θ values: 13.0 +/-0.2 degrees, 14.9 +/-0.2 degrees and 21.5 +/-0.2 degrees,

at least 3 of the following reflection peaks are shown as 2 θ values: 6.2 +/-0.2 degrees, 9.0 +/-0.2 degrees, 10.6 +/-0.2 degrees, 16.9 +/-0.2 degrees, 18.2 +/-0.2 degrees, 18.5 +/-0.2 degrees, 19.2 +/-0.2 degrees, 19.6 +/-0.2 degrees, 20.9 +/-0.2 degrees, 22.7 +/-0.2 degrees, 24.3 +/-0.2 degrees, 24.9 +/-0.2 degrees, 26.2 +/-0.2 degrees, 28.7 +/-0.2 degrees and 30.5 +/-0.2 degrees.

39. A crystalline solvate form according to claim 37 or claim 38, wherein:

at a temperature rise rate of 20K/min in accordance with ISO 11357-3: 2018, and shows an endothermic peak having an onset point in a range of 97 to 101 ℃ and a maximum value of the peak in a range of 108 to 115 ℃.

40. A crystalline solvate form of any one of claims 37 to 39, wherein:

the amount of methanol is 0.3 to 1.0 mole per 1 mole of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl.

41. The crystalline solvate form of claim 36, wherein:

the organic solvent is toluene.

42. A crystalline solvate form according to claim 41, wherein:

in an X-ray powder diffraction pattern obtained by irradiation with Cu Ka 1 radiation at 22 ℃,

the following 3 reflection peaks are shown as 2 θ values: 5.2 +/-0.2 degrees, 7.7 +/-0.2 degrees and 21.6 +/-0.2 degrees,

at least 3 of the following reflection peaks are shown as 2 θ 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 °.

43. A crystalline solvate form according to claim 41 or 42, wherein: at a temperature rise rate of 20K/min in accordance with ISO 11357-3: 2018, and shows an endothermic peak having an onset point in a range of 105 to 108 ℃ and a maximum value of the peak in a range of 112 to 115 ℃.

44. A crystalline solvate form according to any one of claims 41 to 43, wherein:

the amount of toluene is 0.3 to 0.5 mol per 1mol of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl.

45. A crystalline form a of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl, characterized by:

the crystals contain less than 0.1 mole of an organic solvent per 1 mole of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl,

in an X-ray powder diffraction pattern obtained by irradiation with Cu Ka 1 radiation at 22 ℃,

the following 3 reflection peaks are shown as 2 θ values: 20.9 +/-0.2 degrees, 21.4 +/-0.2 degrees and 23.7 +/-0.2 degrees,

at least 3 of the following reflection peaks are shown as 2 θ values: 6.5 +/-0.2 degrees, 8.6 +/-0.2 degrees, 11.0 +/-0.2 degrees, 13.2 +/-0.2 degrees, 14.9 +/-0.2 degrees, 16.2 +/-0.2 degrees, 17.3 +/-0.2 degrees, 17.8 +/-0.2 degrees, 18.4 +/-0.2 degrees and 19.0 +/-0.2 degrees.

46. The crystalline form of claim 45, wherein:

at a temperature rise rate of 20K/min in accordance with ISO 11357-3: 2018, and shows an endothermic peak having an onset point in a range of 112 to 114 ℃ and a maximum value of the peak in a range of 124 to 126 ℃.

47. A crystalline form C of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl, characterized by:

the crystals contain less than 0.1 mole of an organic solvent per 1 mole of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl,

in an X-ray powder diffraction pattern obtained by irradiation with Cu Ka 1 radiation at 22 ℃,

the following 3 reflection peaks are shown as 2 θ values: 5.1 +/-0.2 degrees, 7.6 +/-0.2 degrees and 21.0 +/-0.2 degrees,

at least 3 of the following reflection peaks are shown as 2 θ 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 °.

48. The crystalline form of claim 47, wherein:

49. The crystalline form of any one of claims 33 to 48, wherein: the crystals have an aspect ratio of at most 5: 1.

50. An amorphous form B of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl, characterized in that:

having a purity of at least 99.0% by weight with respect to the organic substance, which contains less than 0.1 mole of organic solvent per 1 mole of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl,

in an X-ray powder diffraction pattern obtained by irradiation with Cu Ka 1 radiation at 22 ℃,

does not show a reflection peak as a 2 theta value at a plurality of diffraction angles in the range of 5 DEG to 40 DEG,

at a temperature rise rate of 20K/min in accordance with ISO 11357-3: 2018, and shows no endothermic peak in a range of 80 to 200 ℃ in a Differential Scanning Calorimetry (DSC).

51. 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl, wherein the total amount of impurities selected from the group consisting of 2- (2-hydroxyethoxy) -2 ' -hydroxy-6, 6' -diphenyl-1, 1' -binaphthyl, 2 ' -dihydroxy-6, 6' -diphenyl-1, 1' -binaphthyl, and 2- (2-hydroxyethoxy) -2 ' - (2- (2-hydroxyethoxy) -ethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl is less than 0.5% by weight relative to 100% by weight of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl.

52. A 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl having at least 1 of the following characteristics:

i. a yellowness (Y.I.) of less than 3.0 measured according to ASTM E313 using a 5 w/w% solution of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl in methylene chloride; and

haze of less than 1.0ntu measured using a 5 w/w% solution of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl in methylene chloride.

53. 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl according to claim 51 or 52, wherein:

in a crystalline form as claimed in any one of claims 33 to 49 or in an amorphous form as claimed in claim 50.

54. The thermoplastic resin according to any one of claims 1 to 33, wherein:

structural units having a crystalline form according to claims 33 to 49 and an amorphous form according to claim 50.

55. The thermoplastic resin according to any one of claims 1 to 33, wherein:

having structural units derived from 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl as claimed in any one of claims 51 to 53.

56. An optical lens, characterized in that:

a thermoplastic resin composition comprising the thermoplastic resin of claim 54 or claim 55.

Technical Field

The present invention relates to a thermoplastic resin, particularly to a thermoplastic resin such as a polyester resin, a polyester carbonate resin, or a polycarbonate resin, and a method for producing the same. The present invention also relates to an optical lens containing the thermoplastic resin.

Background

As a material of an optical lens used in an optical system of various cameras such as a camera, a film-integrated camera, and a video camera, optical glass or an optical resin is used. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance and the like, but has problems of high material cost, poor molding processability and low productivity.

On the other hand, an optical lens made of an optical resin has an advantage that it can be mass-produced by injection molding. For example, a thermoplastic resin or the like is used for a camera lens. However, in recent years, as products have become thinner and smaller, it has been required to develop resins having a high refractive index (patent documents 1 to 4). In general, when the refractive index of an optical material is high, a lens element having the same refractive index can be realized with a surface having a smaller curvature, and the amount of aberration generated on the surface can be reduced. As a result, the number of lenses can be reduced, the decentering sensitivity of the lens can be reduced, and the thickness of the lens can be reduced to reduce the weight.

In addition to the high refractive index, the lens used in the optical system of the camera is generally required to have a b value not higher than a certain level and to suppress chromatic aberration.

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

In recent years, various electronic devices are required to have water resistance and heat resistance. As an environmental test for evaluating the water resistance and heat resistance of such electronic devices, a "PCT test" (pressure cooker test) is performed. This test is a moist heat resistance test, and the penetration of moisture into the sample is accelerated over time and evaluated. Therefore, optical lenses made of optical resins used in electronic devices are required to have not only a high refractive index and a low b value but also high heat resistance and resistance to water decomposition.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2018-2893

Patent document 2: japanese patent laid-open publication No. 2018-2894

Patent document 3: japanese patent laid-open publication No. 2018-2895

Patent document 4: japanese patent laid-open publication No. 2018-59074

Disclosure of Invention

Technical problem to be solved by the invention

The invention aims to provide a thermoplastic resin with high refractive index, low b value and high moist heat resistance, in particular with high refractive index. Further, it is also an object to provide an excellent optical lens by using the resin.

Technical solution for solving technical problem

The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by the following thermoplastic resins and optical lenses, and have reached the present invention.

The present invention is as follows, for example.

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

the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group may have no substituent, or may have a substituent selected from CN and CH₃、OCH₃1 or 2R of O-phenyl, O-naphthyl, S-phenyl, S-naphthyl and halogen^aThe base group is a group of a compound,

wherein R is₁And R₂The total amount of the hydrogen is not all hydrogen,

x is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

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

a and b are respectively integers of 1-10.

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

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

(in the general formula (2), Q is represented by the following formula (2 a))

(in the formula (2a), R_CEach independently represents a single bond or an alkylene group which is bonded to the CO group in the formula (2), may have a substituent, has 1 to 10 carbon atoms in total, and has a bonding point to the CO group in the formula (2) at the terminal. )

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

(in the 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,

R₁and R₂And R in the formula (1)₁And R₂In the same way, the first and second,

a and b each independently represent an integer of 0 to 6,

indicates a bonding point to the CO group in the above formula (2). )

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

(in the formula (2c),. phi.

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

[7]As described above [1]～[6]The thermoplastic resin according to any one of the above items, wherein R in the above general formula (1)₁And R₂At least 1 of the (a) groups is an aryl group having 6 to 20 carbon atoms.

[8]As described above [7]The thermoplastic resin, wherein R is represented by the general formula (1)₁And R₂At least 2 of the (a) groups are aryl groups having 6 to 14 carbon atoms.

[9] The thermoplastic resin according to any one of the above [1] to [8], wherein the structural unit represented by the above general formula (1) contains at least one of the structural units represented by the following general formulae (A-1) to (A-7),

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

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

y is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

c and d are integers of 1-10 respectively. )

(R in the formula (4)) "₁～R”₁₆Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aralkyl group having 7 to 17 carbon atoms,

z is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

e and f are integers of 1-10 respectively. )

[11] The thermoplastic resin according to the above item 10, which comprises a copolymer containing at least a structural unit represented by the above general formula (1) and a structural unit represented by the above general formula (3).

[12] The thermoplastic resin according to [11], wherein the copolymer further contains a structural unit represented by the following general formula (3-1),

[13] the thermoplastic resin according to [10], which comprises a copolymer containing at least a structural unit represented by the above general formula (1) and a structural unit represented by the above general formula (4).

[14] The thermoplastic resin according to [13], wherein the copolymer further contains a structural unit represented by the following general formula (4-1),

[15] the thermoplastic resin according to any one of the above [1] to [14], which contains 20 to 80 mol% of the structural units represented by the above general formulae (3) and (4) in total.

[16] The thermoplastic resin according to the above [1] to [15], further comprising at least 1 of the structural units represented by the following general formula (5),

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

[18] The thermoplastic resin according to [16], which contains at least a structural unit of 2,2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl.

[19] The thermoplastic resin according to [16], further comprising at least a structural unit of BPPEF (9, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene).

[20] The thermoplastic resin according to any one of the above [1] to [19], wherein the aryl group is selected from the group consisting of pyrenyl, furyl, benzodioxanyl, dihydrobenzofuryl, piperonyl, benzofuryl, dibenzofuryl, pyrrolidinyl, isoquinolinyl, pyrimidinyl and carbazolyl groups, which may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 16 carbon atoms.

[21] The thermoplastic resin according to any one of the above [1] to [20], wherein a refractive index of the thermoplastic resin is 1.655 or more.

[22]As described above [1]～[20]The thermoplastic resin of, wherein R is₁And the above-mentioned R₂The same is true.

[23] The thermoplastic resin according to any one of the above [1] to [20], wherein,

r is as defined above₁And the above-mentioned R₂The same or different, selected from monocyclic or polycyclic aryl group having 6 to 36 carbon atoms, monocyclic or polycyclic heteroaryl group having 5 to 36 ring atoms, wherein in the heteroaryl group, 1,2,3 or 4 ring atoms are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon,

the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group have no substituent.

[24]As described above [1]～[23]The thermoplastic resin of, wherein R is₁And the above R₂Selected from the following groups:

azulene groups;

phenyl without substituents;

phenyl substituted with 1 or 2 CN groups;

polycyclic aromatic groups having 2,3 or 4 benzene rings which may be directly condensed with each other and/or may be condensed with a monocyclic or bicyclic hydrocarbon ring of a saturated or unsaturated 4-to 10-membered ring, wherein the polycyclic aromatic groups have no substituent or may be substituted with 1 or 2 substituents selected from phenyl and polycyclic aromatic groups having 2 or 3 benzene rings, and 2 or 3 of the benzene rings may be bonded to each other by a single bond and may be directly condensed with each other, and/or may be condensed with a monocyclic or bicyclic hydrocarbon ring of a saturated 4-to 10-membered ring, wherein the benzene rings of the polycyclic aromatic groups have no substituent or may have 1 or 2 substituentsRadical R^a。

[25]As described above [1]～[24]The thermoplastic resin of, wherein R is₁And the above R₂Selected from the following groups:

phenyl which has no substituent or phenyl which may be substituted with 1,2,3, 4 or 5 phenyl groups;

phenyl substituted with 1 or 2 CN groups;

a phenyl group substituted with 1 or 2 polycyclic aryl groups selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, and pyrenyl, and further substituted with 1 phenyl group;

biphenylene (biphenylene);

triphenylene (triphenylenyl);

tetraphenylene (tetraphenylene);

phenanthryl;

pyrenyl;

9H-fluorenyl;

dibenzo [ a, e ] [8] annulenyl;

a perylene group; and

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

[26]As described above [25 ]]The thermoplastic resin, wherein R is₁And the above R₂Selected from the group consisting of phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-naphthyl, 1-naphthyl and 9-naphthyl.

[27]As described above [1]～[23]The thermoplastic resin of, wherein R is₁And the above R₂Selected from:

a heteroaromatic polycyclic group having the above heteroaromatic monocyclic ring and 1,2,3, 4 or 5 additional aromatic rings selected from the group consisting of phenyl and heteroaromatic monocyclic rings, wherein the (hetero) aromatic rings of the polycyclic heteroaryl group may be bonded to each other by a covalent bond, may be directly condensed with each other, and/or may be condensed with a monocyclic or bicyclic hydrocarbon ring of a saturated or unsaturated 4-to 10-membered ring; and

[28]As described above [27 ]]The thermoplastic resin, wherein R is₁And the above R₂Selected from: furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, 1,3, 4-oxadiazolyl, 1,2, 4-oxadiazolyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, benzofuranyl, dibenzofuranyl, benzothienyl, dibenzothienyl, thianthrenyl, naphthofuranyl, furo [3, 2-b ] o]Furyl, furo [2, 3-b ]]Furyl, furo [3, 4-b ]]Furyl, oxanthrenyl, indolyl, isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzo [ cd)]Indolyl, 1H-benzo [ g ]]Indolyl, quinolyl, isoquinolyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, benzo [ b ]][1,5]Naphthyridinyl, cinnolinyl, 1, 5-naphthyridinyl, 1, 8-naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, bipyridyl, phenylpyridinyl, naphthylpyridinyl, pyrido [4, 3-b ]]Indolyl, pyrido [3, 2-b ]]Indolyl radicalPyrido [3, 2-g]Quinolyl, pyrido [2, 3-b ]][1,8]Naphthyridinyl, pyrrolo [3, 2-b ] s]Pyridyl, pteridinyl (pteridinyl), purinyl (purinyl), 9H-xanthenyl (xanthenyl), 2H-benzopyranyl, phenanthridinyl, phenanthrolinyl, furo [3, 2-f)][1]Benzofuranyl, furo [2, 3-f ]][1]Benzofuranyl, furo [3, 2-g ]]Quinolyl, furo [2, 3-g ]]Quinolyl, furo [2, 3-g ]]Quinoxalinyl, benzo [ g ]]Benzopyranyl, pyrrolo [3,2, 1-hi]Indolyl, benzo [ g ]]Quinoxalinyl, benzo [ f)]Quinoxalinyl and benzo [ h ]]An isoquinolinyl group.

[29] The thermoplastic resin according to any one of the above [1] to [28], wherein X is an ethylene group.

[30] The thermoplastic resin according to any one of the above [1] to [29], wherein a b value according to JIS K7105 is 10 or less.

[31] The thermoplastic resin according to any one of the above [1] to [30], wherein the refractive index nD and the Abbe number v satisfy a relationship of-0.0002 v +1.6718 < nD < -0.024 v + 2.124.

[32] The thermoplastic resin according to [31], wherein the refractive index nD and the Abbe number v satisfy a relationship of-0.004 v +1.744 < nD < -0.024 v + 2.124.

[33] The thermoplastic resin according to the above [32], wherein the relation between the refractive index nD and the Abbe number v is-0.02 v +2.04 < nD < -0.024 v + 2.124.

[34] An optical lens comprising the thermoplastic resin according to any one of [1] to [33 ].

[35] A method for producing a thermoplastic resin according to any one of the above [1] to [33], the method comprising: and (2) melt-polycondensing at least a dihydroxy compound represented by the following general formula (6) with at least one of a carboxylic acid, a carboxylic acid monoester and a carboxylic acid diester.

(R in the general formula (6))₁And R₂Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 36 carbon atoms in a monocyclic or polycyclic ring form, a heteroaryl group having 5 to 36 carbon atoms in a monocyclic or polycyclic ring form, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, wherein 1,2,3 or 4 of the ring atoms in the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon,

wherein R is₁And R₂The total amount of the hydrogen is not all hydrogen,

x is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

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

a and b are respectively integers of 1-10. )

[36] A crystalline solvate in the form of a crystalline solvate of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl, wherein,

the crystals contain 0.3 to 1.2 moles of an organic solvent per 1 mole of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl,

the organic solvent is selected from methanol, toluene and methyl ethyl ketone.

[37] The crystalline solvate form according to [36], wherein the organic solvent is methanol.

[38] The crystalline solvate according to [37] above, wherein,

in an X-ray powder diffraction pattern obtained by irradiation with Cu Ka 1 radiation at 22 ℃,

the following 3 reflection peaks are shown as 2 θ values: 13.0 +/-0.2 degrees, 14.9 +/-0.2 degrees and 21.5 +/-0.2 degrees,

[39] The crystalline solvate form according to [37] or [38] above, wherein the crystalline solvate form is prepared in accordance with ISO 11357-3: 2018, and shows an endothermic peak having an onset point in a range of 97 to 101 ℃ and a maximum value of the peak in a range of 108 to 115 ℃.

[40] The crystalline solvate form according to any one of [37] to [39], wherein the amount of methanol is 0.3 to 1.0 mol per 1mol of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl.

[41] The crystalline solvate form according to [36], wherein the organic solvent is toluene.

[42] The crystalline solvate according to [41] above, wherein,

in an X-ray powder diffraction pattern obtained by irradiation with Cu Ka 1 radiation at 22 ℃,

the following 3 reflection peaks are shown as 2 θ values: 5.2 +/-0.2 degrees, 7.7 +/-0.2 degrees and 21.6 +/-0.2 degrees,

[43] The crystalline solvate form according to the above [41] or [42], wherein the crystalline solvate form is prepared at a temperature rise rate of 20K/min in accordance with ISO 11357-3: 2018, and shows an endothermic peak having an onset point in a range of 105 to 108 ℃ and a maximum value of the peak in a range of 112 to 115 ℃.

[44] The crystalline solvate form according to any one of [41] to [43], wherein the amount of toluene is 0.3 to 0.5 mol per 1mol of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl.

[45] A crystalline form A of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl, wherein,

the crystals contain less than 0.1 mole of an organic solvent per 1 mole of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl,

in an X-ray powder diffraction pattern obtained by irradiation with Cu Ka 1 radiation at 22 ℃,

the following 3 reflection peaks are shown as 2 θ values: 20.9 +/-0.2 degrees, 21.4 +/-0.2 degrees and 23.7 +/-0.2 degrees,

[46] The crystalline form as claimed in 45, wherein the molar ratio of the compound (I) to the compound (II) is in accordance with ISO 11357-3 at a temperature rise rate of 20K/min: 2018, and shows an endothermic peak having an onset point in a range of 112 to 114 ℃ and a maximum value of the peak in a range of 124 to 126 ℃.

[47] A crystalline form C of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl, wherein,

the crystals contain less than 0.1 mole of an organic solvent per 1 mole of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl,

in an X-ray powder diffraction pattern obtained by irradiation with Cu Ka 1 radiation at 22 ℃,

the following 3 reflection peaks are shown as 2 θ values: 5.1 +/-0.2 degrees, 7.6 +/-0.2 degrees and 21.0 +/-0.2 degrees,

[48] The crystalline form according to [47], wherein the crystal is crystallized at a temperature rise rate of 20K/min in accordance with ISO 11357-3: 2018, and shows an endothermic peak having an onset point in a range of 112 to 114 ℃ and a maximum value of the peak in a range of 124 to 126 ℃.

[49] The crystal form according to any one of [33] to [48], wherein the crystal has an aspect ratio of at most 5: 1.

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

in an X-ray powder diffraction pattern obtained by irradiation with Cu Ka 1 radiation at 22 ℃,

does not show a reflection peak as a 2 theta value at a plurality of diffraction angles in the range of 5 DEG to 40 DEG,

at a temperature rise rate of 20K/min in accordance with ISO 11357-3: 2018, and shows no endothermic peak in a range of 80 to 200 ℃ in a Differential Scanning Calorimetry (DSC).

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

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

i. a yellowness (Y.I.) of less than 3.0 measured according to ASTM E313 using a 5 w/w% solution of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl in methylene chloride; and

haze of less than 1.0ntu measured using a 5 w/w% solution of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl in methylene chloride.

[53] The 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl according to [51] or [52], which exists in one of the crystal forms according to any one of [33] to [49], or exists in an amorphous form according to [50 ].

[54] The thermoplastic resin according to any one of the above [1] to [33], which has structural units derived from the crystal form according to the above [33] to [49] and the amorphous form according to the above [50 ].

[55] The thermoplastic resin according to any one of the above [1] to [33], which has a structural unit derived from the 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl according to the above [51] or [52 ].

[56] An optical lens comprising the thermoplastic resin according to [54] or [55 ].

ADVANTAGEOUS EFFECTS OF INVENTION

The thermoplastic resin of the present invention exhibits a high refractive index, a low b value and high moist heat resistance, particularly a high refractive index. By using such an excellent thermoplastic resin, an excellent optical lens can be obtained.

Drawings

Fig. 1 is an H1-NMR spectrum of the resin produced in example 2-B (BINOL-2 EO/BNEF ═ 50 moles/50 moles).

Fig. 2 shows the X-ray powder diffraction pattern of form a of 6,6' -DPBHBNA obtained from example 21.

FIG. 3 shows NIR spectra of form A of 6,6' -DPBHBNA obtained from example 21.

FIG. 4 shows the IR spectrum of form A of 6,6' -DPBHBNA obtained in example 21.

FIG. 5 shows the DSC of form A of 6,6' -DPBHBNA obtained in example 21.

Figure 6 shows the X-ray powder diffraction pattern of the methanol solvate of 6,6' -DPBHBNA obtained from example 22.

FIG. 7 shows the NIR spectrum of the methanol solvate of 6,6' -DPBHBNA obtained from example 22.

FIG. 8 shows the NR spectrum of the methanol solvate of 6,6' -DPBHBNA obtained from example 22.

FIG. 9 shows the DSC of methanol solvate of 6,6' -DPBHBNA obtained from example 22.

Fig. 10 shows the X-ray powder diffraction pattern of the crystalline substance obtained in example 23.

Fig. 11 shows an NIR spectrum of the crystalline substance obtained in example 23.

Fig. 12 shows an NR spectrum of the crystalline substance obtained in example 23.

Fig. 13 shows DSC of the crystalline substance obtained in example 23.

FIG. 14 shows a photomicrograph of the toluene solvate of 6,6' -DPBHBNA obtained from example 24.

Fig. 15 shows the X-ray powder diffraction pattern of the toluene solvate of 6,6' -DPBHBNA obtained from example 24.

Figure 16 shows the NIR spectrum of the toluene solvate of 6,6' -DPBHBNA obtained from example 24.

FIG. 17 shows the NR spectrum of the toluene solvate of 6,6' -DPBHBNA obtained from example 24.

FIG. 18 shows the DSC of the toluene solvate of 6,6' -DPBHBNA obtained from example 24.

Fig. 19 shows a photomicrograph of the MEK solvate of 6,6' -DPBHBNA obtained from example 25.

Figure 20 shows the NIR spectrum of the MEK solvate of 6,6' -DPBHBNA obtained from example 25.

Figure 21 shows the DSC of the MEK solvate of 6,6' -DPBHBNA obtained from example 25.

Figure 22 shows the X-ray powder diffraction pattern of the MEK solvate of 6,6' -DPBHBNA obtained from example 25.

Fig. 23 shows the X-ray powder diffraction pattern of amorphous form B of 6,6' -DPBHBNA obtained from example 26.

Fig. 24 shows the NIR spectrum of amorphous form B of 6,6' -DPBHBNA obtained from example 26.

FIG. 25 shows the IR spectrum of amorphous form B of 6,6' -DPBHBNA obtained from example 26.

Fig. 26 shows the X-ray powder diffraction pattern of form C of 6,6' -DPBHBNA obtained from example 27.

FIG. 27 shows the NIR spectrum of form C of 6,6' -DPBHBNA obtained from example 27.

FIG. 28 shows the IR spectrum of form C of 6,6' -DPBHBNA obtained in example 27.

FIG. 29 shows a DSC of form C of 6,6' -DPBHBNA obtained in example 27.

FIG. 30 is a graph of FIG. 1 with the Abbe number (v) of the thermoplastic resins of examples and comparative examples on the horizontal axis and the refractive index (nD) on the vertical axis.

Fig. 31 is a graph of fig. 2 with the abbe number (v) of the thermoplastic resins of the examples and comparative examples as the horizontal axis and the refractive index (nD) as the vertical axis.

Detailed Description

The present invention will be described in detail below.

(1) Components (structural units) of thermoplastic resin

The thermoplastic resin of the present invention contains a structural unit represented by the following general formula (1). The type of the thermoplastic resin is not particularly limited as long as it has the following structural unit, and is preferably a polyester resin, a polyester carbonate resin, a polycarbonate resin, or a mixture of at least 2 of these.

The thermoplastic resin is a resin having a polyester structural unit (repeating unit) having a (-RCO-O-) site, but not including a polycarbonate structural unit (repeating unit) having a (-RO-CO-O-) site, the polycarbonate resin is a resin having a polycarbonate structural unit (repeating unit) having a (-RO-CO-O-) site but not including a polyester structural unit (repeating unit) having a (-RCO-O-) site, and the polyester carbonate resin is a resin having both a polyester structural unit (repeating unit) having a (-RO-CO-) site and a polycarbonate structural unit (repeating unit) having a (-RO-CO-O-) site (R is a hydrocarbon group, etc.).

(R in the formula (1))₁And R₂Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 36 carbon atoms in a monocyclic or polycyclic ring form, a heteroaryl group having 5 to 36 carbon atoms in a monocyclic or polycyclic ring form, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, wherein 1,2,3 or 4 of the ring atoms in the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon,

wherein R is₁And R₂The total amount of the hydrogen is not all hydrogen,

x is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

wherein the alkylene group and the cycloalkylene group may be substituted with benzene rings, and a and b are integers of 1 to 10, respectively. )

R in the above general formula (1)₁And R₂Each of which is preferably a hydrogen atom or a carbon atom having 1 to 4The alkyl group, the aryl group having 6 to 30 carbon atoms, the alkenyl group having 2 to 4 carbon atoms, the alkoxy group having 1 to 4 carbon atoms or the aralkyl group having 7 to 12 carbon atoms, more preferably the aryl group having 6 to 20 carbon atoms, and still more preferably the aryl group having 6 to 14 carbon atoms. In addition, R of the general formula (1)₁～R₁₀At least 1 of them is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and particularly preferably R₁～R₁₀At least 2 of them are aryl groups having 6 to 14 carbon atoms or 6 to 12 carbon atoms.

R₁And R₂For example, may be the same.

In addition, R₁And R₂The aryl group may be selected from monocyclic or polycyclic aryl groups having 6 to 36 carbon atoms and monocyclic or polycyclic heteroaryl groups having 5 to 36 carbon atoms, wherein 1,2,3 or 4 of the ring atoms in the heteroaryl groups are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon. Wherein the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group may have no substituent.

R₁And R₂Each may be selected from the following groups. Namely:

azulene groups;

phenyl without substituents;

phenyl substituted with 1 or 2 CN groups;

has the advantages ofPolycyclic aromatic groups having 2,3 or 4 benzene rings, which are directly condensed with each other and/or which are condensed with a monocyclic or bicyclic hydrocarbon ring having 4 to 10 saturated or unsaturated ring members, wherein the polycyclic aromatic groups have no substituent or may be substituted with 1 or 2 substituents selected from phenyl and polycyclic aromatic groups having 2 or 3 benzene rings, and 2 or 3 of the benzene rings may be bonded to each other by a single bond and may be directly condensed with each other, and/or may be condensed with a monocyclic or bicyclic hydrocarbon ring having 4 to 10 saturated ring members, wherein the benzene rings of the polycyclic aromatic groups have no substituent or have 1 or 2 substituents R^a。

In addition, R₁And R₂Each may be selected from the following groups. Namely:

phenyl which has no substituent or phenyl which may be substituted with 1,2,3, 4 or 5 phenyl groups;

phenyl substituted with 1 or 2 CN groups;

a phenyl group substituted with 1 or 2 polycyclic aryl groups selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, and pyrenyl, and further substituted with 1 phenyl group;

a biphenylene group;

triphenylene;

tetraphenylene;

phenanthryl;

pyrenyl;

9H-fluorenyl;

dibenzo [ a, e ] [8] annulenyl;

a perylene group; and

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

Wherein R is₁And R₂Preferably selected from phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-naphthyl, 1-naphthyl and 9-naphthyl.

In addition, R₁And R₂May be selected from the following groups, respectively. Namely:

a heteroaromatic polycyclic group having a heterocyclic ring having at least 1 saturated or partially unsaturated 5-or 6-membered ring containing 1 or 2 heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms and 1,2,3, 4 or 5 additional aromatic rings selected from phenyl and the above heteroaromatic monocyclic ring, wherein at least 1 additional aromatic ring is directly condensed with a heterocyclic group of a saturated or partially unsaturated 5-or 6-membered ring, and the other additional aromatic rings of the polycyclic heteroaryl aromatic ring may be bonded to each other by a covalent bond, may be directly condensed with each other, and/or may be condensed with a monocyclic or bicyclic hydrocarbon ring of a saturated or unsaturated 4-to 10-membered ring.

In addition, R₁And R₂May be selected from the following groups, respectively. Namely: furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, tetrazolyl, oxazolyl, isoxazolyl, 1,3, 4-oxadiazolyl, 1,2, 4-oxadiazolyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, benzofuranyl, dibenzofuranyl, benzothienyl, dibenzothienyl, thianthrenyl, naphthofuranyl, furo [3, 2-b ] o]Furyl, furo [2, 3-b ]]Furyl, furo [3, 4-b ]]Furyl, oxanthrenyl, indolyl, isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzo [ cd)]Indolyl, 1H-Benzo [ g ]]Indolyl, quinolyl, isoquinolyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, benzo [ b ]][1,5]Naphthyridinyl, cinnolinyl, 1, 5-naphthyridinyl, 1, 8-naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, bipyridyl, phenylpyridinyl, naphthylpyridinyl, pyrido [4, 3-b ]]Indolyl, pyrido [3, 2-b ]]Indolyl, pyrido [3, 2-g ]]Quinolyl, pyrido [2, 3-b ]][1,8]Naphthyridinyl, pyrrolo [3, 2-b ] s]Pyridyl, pteridinyl (pteridinyl), purinyl (purinyl), 9H-xanthenyl (xanthenyl), 2H-benzopyranyl, phenanthridinyl, phenanthrolinyl, furo [3, 2-f)][1]Benzofuranyl, furo [2, 3-f ]][1]Benzofuranyl, furo [3, 2-g ]]Quinolyl, furo [2, 3-g ]]Quinolyl, furo [2, 3-g ]]Quinoxalinyl, benzo [ g ]]Benzopyranyl, pyrrolo [3,2, 1-hi]Indolyl, benzo [ g ]]Quinoxalinyl, benzo [ f)]Quinoxalinyl and benzo [ h ]]An isoquinolinyl group.

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

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

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

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

In the formula (2a), R_CEach independently represents a single bond to the CO group of the formula (2) or an alkylene group which may have a substituent, has 1 to 10 carbon atoms in total, and has a bonding point to the CO group of the formula (2) at the terminal. R_CPreferably a single bond or an alkylene group having 1 to 3 carbon atoms in total.

Q in formula (2) is preferably represented by formula (2b) below.

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

p and k are each independently an integer of 1 to 5, preferably 1 to 3.

R₁And R₂With R in the formula (1)₁And R₂The same is true.

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

And represents a bonding point to the CO group of formula (2).

Q in formula (2) is more preferably represented by formula (2c) below.

In formula (2c), a is a bonding site to the CO group of formula (2).

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

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

The thermoplastic resin of the present invention preferably contains more than 50 mol% of the structural unit represented by the above general formula (1), more preferably more than 60 mol%, still more preferably more than 70 mol%, particularly preferably more than 80 mol%, or preferably more than 90 mol%. The thermoplastic resin of the present invention may be formed only of the structural unit represented by the above general formula (1).

The thermoplastic resin of the present invention may contain 1 or more kinds of other structural units in addition to the structural unit represented by the above general formula (1) (structural unit (1)). As the other structural unit, a fluorene derivative unit or the like is preferable.

Specifically, the thermoplastic resin of the present invention preferably further contains at least 1 kind of the structural units represented by the general formulae (3) and (4).

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

y is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

c and d are integers of 1-10 respectively. )

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

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

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

z is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

e and f are integers of 1-10 respectively. )

Of the above general formula(4) R in (1) "₁～R”₁₆Each of which is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, and more preferably a hydrogen atom or an aryl group having 6 to 10 carbon atoms.

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

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

The thermoplastic resin of the present invention preferably contains at least 1 kind of the structural unit represented by the following general formula (5) as the structural unit represented by the above general formula (3) or (4) and the structural unit (1).

That is, the thermoplastic resin of the present invention preferably further contains at least one of a structural unit derived from BNEF (9, 9-bis (6- (2-hydroxyethoxy) naphthalen-2-yl) fluorene), a structural unit derived from BNE (2,2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl), and a structural unit derived from BPPEF (9, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene) as represented by the above general formula (5) together with the structural unit (1).

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

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

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

The thermoplastic resin of the present invention may have any structure of random, block and alternating copolymer structures. In the thermoplastic resin of the present invention, all of the structural unit (1), the structural unit (3) and the structural unit (4) may not be contained in the same polymer molecule. That is, the thermoplastic resin of the present invention may be a blend resin as long as the structural unit is contained in the entire plurality of polymer molecules. For example, the thermoplastic resin containing all of the structural unit (1), the structural unit (3) and the structural unit (4) may be a copolymer containing all of the structural units (1), (3) and (4), a mixture of a homopolymer or copolymer containing the structural unit (1), a homopolymer or copolymer containing the structural unit (2) and a homopolymer or copolymer containing the structural unit (4), a blend resin of a copolymer containing the structural units (1) and (3) and a copolymer containing the structural units (1) and (4), or the like.

The thermoplastic resin of the present invention may be blended with another resin to be used for production of molded articles. For example, when the thermoplastic resin is any of polyester, polyester carbonate and polycarbonate, examples of the other resin include polyamide, polyacetal, polycarbonate different from the thermoplastic resin, modified polyphenylene ether, polyethylene terephthalate, and polybutylene terephthalate.

Further, in the thermoplastic resin composition of the present invention, an antioxidant, a mold release agent, a processing stabilizer, an ultraviolet absorber, a fluidity modifier, a crystal nucleating agent, a reinforcing agent, a dye, an antistatic agent, an antibacterial agent, or the like is preferably added.

As the antioxidant, triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], pentaerythritol-tetrakis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, N-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3, 5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3, 9-bis {1, 1-dimethyl-2- [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl } -2,4,8, 10-tetraoxaspiro (5,5) undecane, and the like. Among these, pentaerythritol-tetrakis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] is preferred. The content of the antioxidant in the thermoplastic resin composition is preferably 0.001 to 0.3 parts by weight based on 100 parts by weight of the thermoplastic resin.

The release agent is preferably an ester of an alcohol and a fatty acid in an amount of 90% by weight or more. Specific examples of the ester of an alcohol and a fatty acid include an ester of a monohydric alcohol and a fatty acid, and a partial or full ester of a polyhydric alcohol and a fatty acid. The ester of a monohydric alcohol and a fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. The partial or full ester of a polyhydric alcohol and a fatty acid is preferably a partial or full ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

Specifically, examples of the ester of a monohydric alcohol and a saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Examples of the partial esters or full esters of polyhydric alcohols and saturated fatty acids include full esters or partial esters of dipentaerythritol such as stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid sorbitan ester, behenic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl ester, sorbitan monostearate, 2-ethylhexyl stearate, and dipentaerythritol hexastearate. Among these, stearic acid monoglyceride and lauric acid monoglyceride are particularly preferable. The content of the release agent is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight, and still more preferably in the range of 0.02 to 0.5 parts by weight, based on 100 parts by weight of the thermoplastic resin.

Examples of the processing stabilizer include a phosphorus-based processing heat stabilizer, a sulfur-based processing heat stabilizer, and the like. Examples of the phosphorus-based processing heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2, 6-di-t-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecylmonophenyl phosphite, dioctylmonophenyl phosphite, diisopropyl monophenyl phosphite, monobutyldiphenyl phosphite, monodecyl diphenyl phosphite, monooctyldiphenyl phosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl mono-o-biphenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, tetrakis (2, 4-di-tert-butylphenyl) -4, 4 ' -biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -4, 3 ' -biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -3, 3 ' -biphenylene diphosphonite, bis (2, 4-di-tert-butylphenyl) -4-phenyl phosphonite, bis (2, 4-di-tert-butylphenyl) -3-phenyl phosphonite and the like. Of these, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is preferred. The content of the phosphorus-based processing heat stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 part by weight based on 100 parts by weight of the thermoplastic resin.

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

The ultraviolet absorber is preferably at least 1 ultraviolet absorber selected from benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic imino ester-based ultraviolet absorbers and cyanoacrylate-based ultraviolet absorbers. That is, the ultraviolet absorbers listed below may be used alone or in combination of 2 or more.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2' -methylenebis [ 4- (1,1,3, 3-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-pentylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) benzotriazole, and mixtures thereof, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) benzotriazole, 2 '-methylenebis (4-cumyl-6-benzotriazolylphenyl), 2' -p-phenylenebis (1, 3-benzoxazin-4-one), 2- [ 2-hydroxy-3- (3,4,5, 6-tetrahydrophthalimidomethyl) -5-methylphenyl ] benzotriazole and the like.

Examples of the benzophenone-based ultraviolet absorber include 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate, 2 '-dihydroxy-4-methoxybenzophenone, 2', 4,4 '-tetrahydroxybenzophenone, 2' -dihydroxy-4, 4 '-dimethoxybenzophenone, 2' -dihydroxy-4, 4 '-dimethoxy-5-sodium sulfobenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2' -carboxybenzophenone, and the like.

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

As the cyclic imide-based ultraviolet absorbers, 2 '-bis (3, 1-benzoxazin-4-one), 2' -p-phenylenebis (3, 1-benzoxazin-4-one), 2 '-m-phenylenebis (3, 1-benzoxazin-4-one), 2' - (4,4 '-diphenylene) bis (3, 1-benzoxazin-4-one), 2' - (2, 6-naphthalene) bis (3, 1-benzoxazin-4-one), 2 '- (1, 5-naphthalene) bis (3, 1-benzoxazin-4-one), 2' - (2-methyl-p-phenylene) bis (3, 1-benzoxazin-4-one), 2 '- (2-nitro-p-phenylene) bis (3, 1-benzoxazin-4-one), and 2, 2' - (2-chloro-p-phenylene) bis (3, 1-benzoxazine-4-one), and the like.

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

The content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 part by weight, and still more preferably 0.05 to 0.8 part by weight, based on 100 parts by weight of the thermoplastic resin. Within the range of the blending amount, sufficient weather resistance can be imparted to the thermoplastic resin composition depending on the application.

In a thermoplastic resin composition, for example, a polycarbonate resin composition, phenol generated during production and a carbonic acid diester remaining unreacted are present as impurities. The phenol content in the thermoplastic resin composition is preferably 0.1 to 3000ppm, more preferably 0.1 to 2000ppm, still more preferably 1 to 1000ppm, 1 to 800ppm, 1 to 500ppm or 1 to 300 ppm. The content of the carbonic acid diester in the thermoplastic resin composition is preferably 0.1 to 1000ppm, more preferably 0.1 to 500ppm, and particularly preferably 1 to 100 ppm. By adjusting the amounts of the phenol and the carbonic acid diester contained in the thermoplastic resin composition, a resin having physical properties suitable for the purpose can be obtained. The content of the phenol and the carbonic acid diester can be adjusted as appropriate by changing the conditions and the apparatus for the polycondensation. Further, the conditions of the extrusion step after polycondensation can be adjusted.

When the content of the phenol or the carbonic acid diester exceeds the above range, there is a possibility that the strength of the obtained resin molded article is lowered and odor is generated. On the other hand, when the content of the phenol or the carbonic acid diester is less than the above range, plasticity at the time of melting the resin may be reduced.

(2) Properties of thermoplastic resin

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

When the value of Mv is less than 8,000, the molded article may become brittle. When the value of Mv is more than 20,000, the melt viscosity becomes high, which may make it difficult to take out the resin after production, and the fluidity may be poor, which may make it difficult to perform injection molding in a molten state.

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

The abbe number (ν) of the thermoplastic resin of the present invention is preferably 24 or less, more preferably 22 or less, and still more preferably 20 or less. Abbe number can be calculated from refractive indices at 23 ℃ at wavelengths of 486nm, 589nm, and 656nm by the following formula.

ν＝(nD－1)/(nF－nC)

nD: refractive index at wavelength of 589nm

nC: refractive index at wavelength 656nm

nF: refractive index at wavelength of 486nm

In view of the use in injection molding, the thermoplastic resin of the present invention preferably has a glass transition temperature (Tg) of 90 to 185 ℃, more preferably 95 to 180 ℃, and still more preferably 100 to 175 ℃. When Tg is less than 90 ℃, the usable temperature range may be narrowed. If the temperature exceeds 185 ℃, the melting temperature of the resin increases, and the resin may be easily decomposed or colored. When the glass transition temperature of the resin is too high, the difference between the mold temperature and the glass transition temperature of the resin becomes large when a conventional mold temperature regulator is used. Therefore, in applications where strict surface precision is required for products, it may be difficult to use a resin having an excessively high glass transition temperature. From the viewpoint of molding flowability and molding heat resistance, the lower limit of Tg is preferably 130 ℃, more preferably 135 ℃, and the upper limit of Tg is preferably 185 ℃, more preferably 175 ℃.

The optical molded article obtained using the thermoplastic resin of the present invention has a total light transmittance of preferably 85% or more, more preferably 87% or more, and particularly preferably 88% or more. When the total light transmittance is 85% or more, it is also comparable to bisphenol A polycarbonate resin and the like.

The thermoplastic resin of the present invention has high moist heat resistance. The moist heat resistance can be evaluated by performing a "PCT test" (pressure cooker test) on an optical molded article obtained using a thermoplastic resin, and measuring the total light transmittance of the optical molded article after the test. The PCT test can be carried out by holding an injection-molded article having a diameter of 50mm and a thickness of 3mm at 120 ℃ under 0.2MPa at 100% RH for 20 hours. The thermoplastic resin of the present invention has a total light transmittance after PCT test of 60% or more, preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, and particularly preferably 85% or more. When the total light transmittance is 60% or more, it can be said that the resin has high moist heat resistance compared with conventional thermoplastic resins.

The b value indicating the hue of the thermoplastic resin of the present invention is preferably 5 or less. A smaller b value indicates a lower yellowing, and the hue is better.

(3) Method for producing thermoplastic resin

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

wherein R is₁And R₂The total amount of the hydrogen is not all hydrogen,

x is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

wherein the alkylene group and the cycloalkylene group may be substituted with benzene rings, and a and b are integers of 1 to 10, respectively. )

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

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

The polyester carbonate resin or the polyester resin can be produced, for example, by a step of melt-polycondensing a dihydroxy compound represented by the above general formula (6) with at least one of a carboxylic acid, a carboxylic acid monoester and a carboxylic acid diester.

Specific examples of the carboxylic acid, carboxylic acid monoester and carboxylic acid diester include dicarboxylic acid, monocarboxylic acid monoester and diester, 9-fluorene-dipropionic acid, and 9, 9-fluorene-dipropionic acid methyl ester (FDPM) which is a monoester or diester of 9, 9-fluorene-dipropionic acid of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl (BINL-2 EO).

Specific examples of the carboxylic acid, the carboxylic acid monoester and the carboxylic acid diester include 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -bis (naphthalen-1-yl) -1,1' -binaphthyl (DNBINOL-2 EO), 2 ' -bis (2-hydroxyethoxy) -6, 6' -bis (naphthalen-2-yl) -1,1' -binaphthyl (2 DNBINOL-2 EO), 2 ' -bis (2-hydroxyethoxy) -6, 6' -bis (phenanthren-9-yl) -1,1' -binaphthyl (9 DPNBINOL-2 EO), 6' -bis- (3-cyanophenyl) -2,2 ' -bis- (2-hydroxyethoxy) -1,1' -binaphthyl (CN-BNA), 6' -bis- (dibenzo [ b, d ] furan-4-yl) -2,2 ' -bis- (2-hydroxyethoxy) -1,1' -binaphthyl (R-BNA), Dicarboxylic acids, monocarboxylic monoesters, and diesters of 6,6' -bis- (3-cyanophenyl) -2,2 ' -bis- (2-hydroxyethoxy) -1,1' -binaphthyl (CN-BNA).

Examples of the compound of the general formula (6) include 2,2 '-bis (hydroxy (poly) alkoxy) -diaryl-1, 1' -binaphthyl and 2,2 '-bis (hydroxy (poly) alkoxy) -dinaphthyl-1, 1' -binaphthyl. For example, 2 '-bis (2-hydroxyethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl, 2' -bis (2-hydroxyethoxy) -6,6 '-bis (naphthalen-1-yl) -1,1' -binaphthyl, 2 '-bis (2-hydroxymethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl, 2' -bis (2-hydroxymethoxy) -6,6 '-bis (naphthalen-1-yl) -1,1' -binaphthyl, 2 '-bis (2-hydroxypropoxy) -6, 6' -diphenyl-1,1 '-binaphthyl, and 2, 2' -bis (2-hydroxypropoxy) -6,6 '-bis (naphthalen-1-yl) -1,1' -binaphthyl are preferable. These may be used alone, or two or more kinds may be used in combination.

In addition, in the monomer for producing the thermoplastic resin, the dihydroxy compound represented by the general formula (6) may contain, as impurities, a dihydroxy compound in which a and b in the general formula (6) have both a value of 0 or a dihydroxy compound in which either one of a and b in the general formula (6) is 0.

As described above, the total amount of dihydroxy compounds having a value different from at least either of a and b in the general formula (6) is preferably 1000ppm or less, more preferably 500ppm or less, still more preferably 200ppm or less, and particularly preferably 100ppm or less in the monomer containing the dihydroxy compound represented by the general formula (6) as the main component, and the total amount of dihydroxy compounds having a value different from at least either of a and b in the general formula (6) is preferably 50ppm or less, and more preferably 20ppm or less.

The compound of formula (6) can be produced by various synthetic methods. For example, as described in Japanese patent laid-open Nos. 2014-227387, 2014-227388, 2015-168658, and 2015-187098, it is possible to: (a) a method of reacting 1,1' -binaphthol with ethylene glycol monotoluene sulfonate, (b) a method of reacting binaphthol with an alkylene oxide, a halogenated alkyl alcohol, or an alkylene carbonate, (c) a method of reacting 1,1' -binaphthol with ethylene carbonate, and (d) a method of reacting 1,1' -binaphthol with ethylene carbonate.

The monomer of the general formula (6) may contain impurities which may adversely affect the properties of the thermoplastic resin, particularly the optical properties. In particular, the monomer of the general formula (6) may contain 1 or 2 or more of the following by-products of the general formulae (6a) and (6b) as impurities generated from the production process thereof.

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

In the formulae (6a), (6b) and (6c), the substituent R₁、R₂And X is the same as defined in the monomer of formula (6). In the formulae (6a) and (6c), a is an integer in the range of 1 to 10, preferably an integer in the range of 1 to 4, and more preferably 1,2 or 3, as in the monomer of formula (6). In formula (6c), the variables b, c and d are integers in the range of 1 to 10, preferably integers in the range of 1 to 4, and more preferably 1,2 or 3. In the formulae (6a) and (6c), as in the monomer of formula (6), the substituents X are each preferably an alkylene group having 1 to 4 carbon atoms, more preferably an ethylene group, i.e., 1, 2-ethanediyl or-CH₂CH₂－。

In the formulae (6a), (6b) and (6c), the substituent R is the same as in the monomer of formula (6)₁And R₂Preferably monocyclic or polycyclic aryl group having 6 to 36 carbon atoms, monocyclic or polycyclic heteroaryl group having 6 to 36 ring atoms, more preferably monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, still more preferably monocyclic or polycyclic aryl group having 6 to 14 carbon atomsAryl, particularly preferably from phenyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl, 4-dibenzo [ b, d ]]Furyl and 4-dibenzo [ b, d ]]A thienyl group.

The total weight of the impurities of the formulae (6a) and (6b) in the monomer of the formula (6) used in the process of the present invention is preferably not more than 5000ppm based on 1 part by weight of the monomer of the formula (6). In particular, the total weight of the impurities of the formulae (6a) and (6b) is preferably 4000ppm or less, more preferably 3000ppm or less, and still more preferably 2000ppm or less, based on 1 part by weight of the monomer of the formula (6). The weight of each impurity of the formulae (6a) and (6b) is particularly preferably at most 2000ppm or less, more preferably at most 1500ppm or less, and still more preferably at most 1000ppm or less, based on 1 part by weight of the monomer of the formula (6). If present, the amount of impurities of (6c) is not more than 2000ppm, usually not more than 1500ppm, based on 1 part by weight of the monomer of formula (6).

In a specific embodiment group of the invention relating to the thermoplastic resin produced by the method of the present invention, variables (a) and (b) of the monomer of formula (6) are 1, and hereinafter referred to as monomer (6-1). The monomer (6-1) may contain 1 or 2 or more by-products of the following formulae (6 a-1), (6-2) and (6b), and may contain (6 c-1) as an impurity in some cases.

In the formulae (6-1), (6 a-1), (6-2) and (6 c-1), the substituent X is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an ethylene group, i.e., 1, 2-ethanediyl or-CH₂CH₂-. In the formula (6-2), the variable e is a variable defined as the variable a, and may be 2 or 3 in particular. In the formulae (6-1), (6 a-1), (6-2), (6-b) and (6 c-1), the substituent R₁And R₂Preferably monocyclic or polycyclic aryl group having 6 to 36 carbon atoms, monocyclic or polycyclic heteroaryl group having 6 to 36 ring atoms, more preferably monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, still more preferably aryl group having 6 to 14 carbon atoms, particularly preferably selected from phenyl group, 1-naphthyl group, and,2-naphthyl, 9-phenanthryl, 4-dibenzo [ b, d ]]Furyl and 4-dibenzo [ b, d ]]A thienyl group.

The total weight of the impurities of the formulae (6 a-1), (6-2) and (6b) in the monomer of the formula (6-1) used in the process of the present invention is preferably not more than 5000ppm based on 1 part by weight of the monomer of the formula (6). In particular, the total weight of the impurities of the formulae (6 a-1), (6-2) and (6b) is preferably at most 4000ppm, more preferably at most 3000ppm, still more preferably at most 2000ppm, based on 1 part by weight of the monomer of the formula (6-1). In particular, the weight of each impurity of the formulae (6 a-1), (6-2) and (6b) is preferably at most 2000ppm, more preferably at most 1500ppm, and still more preferably at most 1000ppm, based on 1 part by weight of the monomer of the formula (6-1). If present, the amount of impurities of (6 c-1) is not more than 2000ppm, usually not more than 1500ppm, based on 1 part by weight of the monomer of formula (6-1).

In a specific embodiment of the present invention relating to the thermoplastic resin produced by the method of the present invention, the monomer of formula (6) is 2,2 '-bis (2-hydroxyethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl (6,6' -diphenyl-2,2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl), that is, in formula (6), both variables (a) and (b) are 1, X is 1, 2-ethanediyl, R is ethylene glycol₁And R₂All substituents of (A) are phenyl groups. Here and elsewhere in this specification, 2 '-bis (2-hydroxyethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl is sometimes abbreviated as 6,6' -DPBHBNA.

The 6,6' -DPBHBNA may contain the substituents X in the above-mentioned formulae (6 a-1), (6-2), (6b) and (6 c-1) as 1, 2-ethanediyl, all R₁And R₂The substituent(s) is phenyl, 1 or 2 or more impurities of the formula (6-2) in which the variable e is 2 or 3, particularly 2.

In the formula (6 a-1), the substituent X is a 1, 2-ethanediyl group, R₁And R₂The chemical name of the compound with phenyl substituents is 2- (2-hydroxyethoxy) -2 '-hydroxy-6, 6' -diphenyl-1,1 '-binaphthyl (6,6' -diphenyl-2- (2-hydroxyethoxy) -2 '-hydroxy-1, 1' -binaphthyl).

In the formula (6-2), the substituent X is 1, 2-ethanediyl, e is 2, R₁And R₂The chemical name of the compound with the substituents of phenyl is 2- (2-hydroxyethoxy) -2 '- (2- (2-hydroxyethoxy) -ethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl (6,6' -diphenyl-2- (2-hydroxyethoxy) -2 '- (2- (2-hydroxyethoxy) -ethoxy) -1,1' -binaphthyl).

In the formula (6b), R₁And R₂The chemical name of the compound with the substituents of phenyl is 2,2 '-dihydroxy-6, 6' -diphenyl-1,1 '-binaphthyl (6,6' -diphenyl-2,2 '-bishydroxy-1, 1' -binaphtyl).

In the formula (6 c-1), the substituent X is a 1, 2-ethanediyl group or all R₁And R₂The chemical name of the compound of which the substituents are all phenyl is bis [2- [ [1- [2- (2-hydroxyethoxy) -6-phenyl-1-naphthyl)]-6-phenyl-2-naphthyl]-oxy radical]-ethyl radical]Carbonate (bis [2- [ [1- [2- (2-hydroxyethanethoxy) -6-phenyl-1-naphthyl)]-6-phenyl-2-naphth yl]-oxy]-ethyl]carbonate)。

In the 6,6' -DPBHBNA used in the method of the invention, the substituents X are 1, 2-ethanediyl and all R as impurities of the formulae (6 a-1), (6-2) and (6b)₁And R₂The total weight of the impurities in which the substituent(s) is a phenyl group is preferably not more than 5000ppm based on 1 part by weight of 6,6' -DPBHBNA. Thus, 6' -DPBHBNA containing a small amount of the above impurities is a novel substance and, therefore, is also included in the present invention. In particular in the formulae (6 a-1), (6-2) and (6b) the substituents X are 1, 2-ethanediyl, all R₁And R₂The total weight of the impurities in which the substituent(s) is a phenyl group is preferably at most 4000ppm, more preferably at most 3000ppm, and still more preferably at most 2000ppm, based on 1 part by weight of 6,6' -DPBHBNA. In particular in the formulae (6 a-1), (6-2) and (6b) the substituents X are 1, 2-ethanediyl, all R₁And R₂The weight of each of the impurities in which the substituent(s) is a phenyl group is preferably at most 2000ppm, more preferably at most 1500ppm, and still more preferably at most 1000ppm, based on 1 part by weight of the 6,6' -DPBHBNA monomer. If present, in the formulaIn (6 c-1), the substituent X is a 1, 2-ethanediyl group, all R₁And R₂The amount of the impurity whose substituent is a phenyl group is usually not more than 2000ppm, and usually not more than 1500ppm based on 1 part by weight of 6,6' -DPBHBNA.

6,6' -DPBHBNA tends to form solvates with certain organic solvents, particularly aliphatic ketones such as methanol, toluene, anisole, xylene, chlorobenzene, tetrahydrofuran, and 2-butanone known as Methyl Ethyl Ketone (MEK), and 4-methyl-2-pentanone known as methyl isobutyl ketone (MIBK). The amount of each organic solvent is usually in the range of 0.3 to 1.5 moles per 1 mole of 6,6' -DPBHBNA among these solvents. Here and elsewhere in the specification of the present application, the term solvate is understood to mean a crystalline form containing a solvent in the crystal lattice of the crystalline form. These solvates are generally referred to as pseudopolymorphs ("pseudopolymorphs") to distinguish them from polymorphs ("polymorphisms") that are substantially free of solvent. In the crystalline solvate of 6,6 '-DPBHBNA, the amount of solvent need not be a stoichiometric amount relative to the amount of 6,6' -DPBHBNA, but may vary. While not bound by theory, the solvent molecules present in the crystalline solvate of 6,6 '-DPBHBNA typically fill gaps or pores in the crystal lattice formed by the molecules of 6,6' -DPBHBNA.

Among the above solvents, methanol, toluene and methyl ethyl ketone are particularly preferable, and these crystal solvates formed together with 6,6' -DPBHBNA are generally obtained in the form of compact crystals having a low aspect ratio. Such crystals tend to be highly pure 6,6' -DPBHBNA without adhering to the mother liquor. Thus, these crystalline solvates also form part of the present invention.

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

In particular, without further description, a purity of more than 99% in this context or in the context of the solid form of 6,6' -DPBHBNA means that the total amount of organic impurities contained in each solid form of 6,6' -DPBHBNA, i.e. the amount of organic compounds other than 6,6' -DPBHBNA and optionally solvents, is less than 1% by weight. Likewise, a purity of at least 99.5% or at least 99.7% means the total amount of organic impurities, i.e. the amount of organic compounds other than 6,6 '-DPBHBNA and optionally solvents contained in each solid form of 6,6' -DPBHBNA, is at most 0.5% by weight or at most 0.3% by weight.

In the crystalline solvate of 6,6 '-DPBHBNA in the present invention, the total amount of impurities having a 1,1' -binaphthyl moiety selected from 2- (2-hydroxyethoxy) -2 '-hydroxy-6, 6' -diphenyl-1,1 '-binaphthyl, 2' -bishydroxy-6, 6 '-diphenyl-1, 1' -binaphthyl, and 2- (2-hydroxyethoxy) -2 '- (2- (2-hydroxyethoxy) -ethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl is usually not more than 5000ppm (0.50 wt%) based on 1 part by weight of 6,6' -DPBHBNA contained in the crystal of the crystalline solvate, preferably not more than 4000ppm (0.40 wt%), particularly preferably not more than 3000ppm (0.30 wt%), and further preferably not more than 2000ppm (0.20 wt%). The weight of each of these impurities is particularly preferably at most 2000ppm, more preferably at most 1500ppm, and still more preferably at most 1000ppm, based on 1 part by weight of 6,6' -DPBHBNA. If each solvate contains bis [2- [ [1- [2- (2-hydroxyethoxy) -6-phenyl-1-naphthyl ] -6-phenyl-2-naphthyl ] -oxy ] -ethyl ] carbonate, the amount thereof is usually not more than 2000ppm, in some cases not more than 1500ppm, based on 1 part by weight of 6,6' -DPBHBNA.

The amount of the solvent in the crystalline solvate of the present invention may vary, but is usually in the range of 0.3 to 1.5 moles, particularly 0.3 to 1.2 moles, per 1 mole of 6,6' -DPBHBNA.

A particular embodiment of the present invention relates to a crystalline solvate of 6,6' -DPBHBNA with methanol, which is referred to as methanol solvate hereinafter.

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

In an X-ray powder diffraction pattern recorded by irradiation with Cu ka 1 ray at 22 ℃, the methanol solvate generally shows 3 reflection peaks, i.e., 13.0 ± 0.2 °, 14.9 ± 0.2 °, and 21.5 ± 0.2 °, as 2 θ values;

at least 3, in particular at least 5, at least 7 or all of the following reflection peaks are shown as 2 θ 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 +/-0.2 °; and

optionally, 1,2,3, 4,5,6, 7, 8, 9 or 10 reflection peaks among the following are shown as 2 θ values: 8.4 +/-0.2 degrees, 11.8 +/-0.2 degrees, 12.5 +/-0.2 degrees, 16.0 +/-0.2 degrees, 17.7 +/-0.2 degrees, 22.1 +/-0.2 degrees, 26.6 +/-0.2 degrees, 27.7 +/-0.2 degrees, 31.6 +/-0.2 degrees and 32.5 +/-0.2 degrees.

The methanol solvate can also be characterized by an endothermic peak indicating its decomposition. For methanol solvates, the reaction is carried out using a reaction at a temperature rise rate of 20K/min according to ISO 11357-3: 2018, the methanol solvate usually shows an endothermic peak having an onset in the range of 97 to 101 ℃ and a maximum value of the peak in the range of 108 to 115 ℃. The reaction point (reaction point) is usually in the range of 103 to 110 ℃. The reaction point is understood to be an inflection point on the lower side of the endothermic peak in the DSC curve. The temperature may vary within the above range depending on the content of methanol, and the temperature may be increased when the content of methanol is high.

The methanol solvate can be obtained by crystallization (crystallization) of 6,6' -DPPBHBNA from a high-temperature methanol solution of 6,6' -DPPBHBNA or a high-temperature solution of a mixture of methanol and toluene of 6,6' -DPPBHBNA. In order to obtain a desired methanol solvate, 6' -DPBHBNA to be crystallized has a purity of at least 97% by weight with respect to organic substances other than the solvent. 6,6' -DPBHBNA having a purity of at least 97% by weight, preferably dissolved in methanol at elevated temperature, or a mixture of methanol and toluene at elevated temperature. In the mixture, the content of methanol is preferably at least 50 w/w% and 90 w/w% or less based on the total weight of the solvent (mixture), i.e., 1: 1 to 9: 1, more preferably 6: 4 to 8: 2, for example, 7: 3, in terms of a volume ratio of methanol to toluene. Typically, the temperature of the high temperature solution of 6,6' -DPBHBNA is at least 45 ℃, especially in the case of high methanol content, up to reflux temperature. The concentration of 6,6' -DPBHBNA in the high temperature solution may vary depending on the amount of methanol used for crystallization. In the case of a large amount of methanol, the concentration of 6,6' -DPBHBNA is generally allowed to be low. The concentration of 6,6' -DPBHBNA is usually not more than 30% by weight, and usually 2-25% by weight. Crystallization from the methanol solvate in the high-temperature solution is usually achieved by cooling the high-temperature solution to a temperature of less than 40 ℃, for example, a temperature in the range of-10 to less than 40 ℃, -5 to 30 ℃. The seed crystal may be added at a temperature lower than 40 ℃, for example, in the range of-5 to 30 ℃. The amount of the seed crystal is usually 0.05 to 2% by weight, particularly 0.1 to 1% by weight, based on the amount of 6,6' -DPBHBNA crystallized as a methanol solvate. The time for completing the crystallization of the methanol solvate may vary depending on the concentration of 6,6' -DPBHBNA and the temperature applied, and is typically in the range of 4 to 24 hours. Crystallization of the methanol solvate can also be achieved by concentration of the high temperature solution, or a combination of concentration and cooling. Concentration of the solution may be achieved by distilling off part of the solvent.

The methanol solvate can be obtained in the form of a compact crystal having a low aspect ratio by crystallization. The aspect ratio of the methanol solvate is usually less than 5, and more specifically, in the range of 1 to 4. The size of the crystals is usually in the range of 5 to 200. mu.m. Among them, the crystal size of the solvate form can be obtained by visual inspection at a magnification of 100 times by an optical microscope, similarly to the crystal form of the non-solvate form. The size ranges given herein are the longest dimension of the crystals.

The crystals of the methanol solvate tend not to be enclosed in a significant amount of the mother liquor. Therefore, the crystalline solvate of 6,6 '-DPBHBNA with methanol can increase the purity of 6,6' -DPBHBNA to at least 99%, further to at least 99.5% or more, further to 99.7% or more. This means that the total amount of impurities other than methanol in the methanol solvate is not more than 1% by weight, particularly not more than 0.5% by weight, and further not more than 0.3% by weight, as described above.

On the other hand, the crystals of the methanol solvate are very easily decomposed by drying for a long time, and are preferably dried at a high temperature, but decomposed at a temperature lower than the melting point of the methanol solvate. Thus, a novel crystalline polymorph of 6,6 '-DPBHBNA, which is substantially free of organic solvents and is not obtainable by crystallization from a solution of 6,6' -DPBHBNA, can be obtained. This crystalline polymorph is hereinafter referred to as crystalline form a of 6,6' -DPBHBNA or simply as form a. Form a is particularly useful in the production of the thermoplastic resin of the present invention because it does not contain a significant amount of solvent.

In form a, the organic solvent is usually not contained in an amount exceeding 0.1 mole, particularly not contained in an amount exceeding 0.05 mole per 1 mole of 6,6' -DPBHBNA. The total amount of organic solvent in form a is typically less than 1 wt%. In addition, the amount of methanol in form a is generally less than 0.1 wt%.

In an X-ray powder diffraction pattern recorded with irradiation of Cu K α 1 ray at 22 ℃, form a generally shows 6 reflection peaks, i.e., 13.0 ± 0.2 °, 14.9 ± 0.2 °, 20.9 ± 0.2 °, 21.4 ± 0.2 °, 21.5 ± 0.2 ° and 23.7 ± 0.2 °, as 2 θ values;

at least 5, in particular at least 7, at least 9 or all of the following reflection peaks are shown as 2 θ values: 6.5 +/-0.2 degrees, 8.6 +/-0.2 degrees, 11.0 +/-0.2 degrees, 13.2 +/-0.2 degrees, 14.9 +/-0.2 degrees, 16.2 +/-0.2 degrees, 17.3 +/-0.2 degrees, 17.8 +/-0.2 degrees, 18.4 +/-0.2 degrees and 19.0 +/-0.2 degrees; and

optionally, 1,2,3, 4,5,6, 7, 8 or 9 reflection peaks among the following are shown as 2 θ values: 9.4 +/-0.2 degrees, 10.4 +/-0.2 degrees, 15.5 +/-0.2 degrees, 22.5 +/-0.2 degrees, 22.9 +/-0.2 degrees, 24.5 +/-0.2 degrees, 25.9 +/-0.2 degrees, 27.8 +/-0.2 degrees and 30.8 +/-0.2 degrees.

Form a can also be characterized by an endothermic peak indicating its dissolution. For form a, the temperature was measured at a rate of 20K/min according to ISO 11357-3: 2018, form A generally shows an endothermic peak having an onset point in the range of 112 to 114 ℃ and a maximum value of the peak in the range of 124 to 126 ℃. The reaction point (reaction point) is usually in the range of 117 to 120 ℃.

Form a can be obtained by decomposition of the methanol solvate, which is a compact crystalline form with a low aspect ratio. The aspect ratio of the crystal of form a is usually less than 5, and more specifically, in the range of 1 to 4. The crystal size of form A is usually in the range of 5 to 200. mu.m, and the crystal size of the solvate form can be obtained by visual inspection at a magnification of 100 times by an optical microscope. The decomposition of the methanol solvate generally occurs by drying for a long time, and although it is preferable to perform drying at a high temperature, the decomposition can occur at a temperature lower than the melting point of the methanol solvate. Typically, drying is carried out until the amount of methanol in the resulting 6,6' -DPBHBNA is less than 0.1 wt%. The drying is carried out at a temperature in the range from 30 ℃ to 95 ℃ and can in particular be carried out at from 30 ℃ to 70 ℃.

The crystals of form a of 6,6' -DPBHBNA generally have a purity of at least 99%, further at least 99.5% or more, further at least 99.7%. As described above, this means that the total amount of impurities other than the solvent in form a is not more than 1% by weight, particularly not more than 0.5% by weight, further not more than 0.3% by weight. In particular, in form a, the total amount of impurities selected from the group consisting of 2- (2-hydroxyethoxy) -2 '-hydroxy-6, 6' -diphenyl-1,1 '-binaphthyl, 2' -bishydroxy-6, 6 '-diphenyl-1, 1' -binaphthyl, and 2- (2-hydroxyethoxy) -2 '- (2- (2-hydroxyethoxy) -ethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl is usually not more than 5000ppm, preferably not more than 4000ppm, particularly preferably not more than 3000ppm, and further preferably not more than 2000ppm, based on 1 part by weight of 6,6' -DPBHBNA contained in the crystals of form a. In particular, the respective weights of these impurities are not more than 2000ppm, more preferably not more than 1500ppm, and still more preferably not more than 1000ppm, based on 1 part by weight of 6,6' -DPBHBNA contained in the form A crystals. If form A contains bis [2- [ [1- [2- (2-hydroxyethoxy) -6-phenyl-1-naphthyl ] -6-phenyl-2-naphthyl ] -oxy ] -ethyl ] carbonate, the amount thereof is usually not more than 2000ppm, and sometimes not more than 1500ppm, based on 1 part by weight of 6,6' -DPBHBNA contained in the crystals of form A.

In addition, a specific embodiment of the present invention relates to crystalline 6,6 '-DPBHBNA which is a mixture of a crystalline methanol solvate of 6,6' -DPBHBNA and form a. This mixture is usually obtained by incomplete decomposition of the methanol solvate. The mixture was characterized by reflection peaks showing X-ray powder diffraction patterns of both methanol solvate and form a. In particular, the mixture shows the following 3 reflection peaks, i.e., 20.9 ± 0.2 °, 21.4 ± 0.2 ° and 23.7 ± 0.2 °, as 2 θ values in an X-ray powder diffraction pattern recorded by irradiation with Cu K α 1 rays at 22 ℃; and

at least 3, in particular at least 5, at least 7, at least 9 reflection peaks out of the following are shown as 2 θ values: 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 °;

the other reflection peaks observed in the methanol solvate and form a can be optionally shown.

For the mixture of methanol solvate with form a, the mixture was prepared using a thermal gradient according to ISO 11357-3: 2018, 2 endothermic peaks are usually observed. One peak has an onset in the range of 97 to 101 ℃ and the maximum of the peak is in the range of 108 to 115 ℃, and the second peak has an onset in the range of 112 to 114 ℃ and the maximum of the peak is in the range of 124 to 126 ℃.

The mixture of methanol solvate and form a generally has a purity of at least 99%, further at least 99.5% or more, further at least 99.7% or more. In the mixture, the total amount of impurities selected from the group consisting of 2- (2-hydroxyethoxy) -2 '-hydroxy-6, 6' -diphenyl-1,1 '-binaphthyl, 2' -bishydroxy-6, 6 '-diphenyl-1, 1' -binaphthyl, and 2- (2-hydroxyethoxy) -2 '- (2- (2-hydroxyethoxy) -ethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl is usually not more than 5000ppm, preferably not more than 4000ppm, particularly preferably not more than 3000ppm, and further preferably not more than 2000ppm, based on 1 part by weight of 6,6' -DPBHBNA contained in the mixture of the methanol solvate and form a.

Another particular embodiment of the present invention relates to a crystalline solvate of 6,6' -DPBHBNA with toluene, which is referred to as toluene solvate hereinafter.

The amount of toluene in the toluene solvate is usually in the range of 0.3 to 1.5 mol, particularly in the range of 0.3 to 1.2 mol, and further in the range of 0.3 to 0.5 mol per 1mol of 6,6' -DPBHBNA.

In an X-ray powder diffraction pattern recorded with irradiation of Cu K α 1 ray at 22 ℃, the toluene solvate generally shows 3 reflection peaks, i.e., 5.2 ± 0.2 °, 7.7 ± 0.2 °, and 21.6 ± 0.2 °, as 2 θ values; and

at least 3, in particular at least 5, at least 7 or all of the following reflection peaks are shown as 2 θ 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 °.

The toluene solvate can also be characterized by an endothermic peak showing its decomposition. For the toluene solvate, the temperature was adjusted using a temperature ramp rate of 20K/min according to ISO 11357-3: 2018, the toluene solvate generally shows an endothermic peak having an onset point in a range of 105 to 108 ℃ and a maximum value of the peak in a range of 112 to 115 ℃. The reaction point (reaction point) is usually in the range of 109 to 112 ℃.

The toluene solvate can be obtained by crystallization of 6,6 '-DPBHBNA from a high temperature toluene solution of 6,6' -DPBHBNA which does not contain more than 5% by weight of other organic solvents, in particular does not contain more than 1% by weight of methanol. In order to obtain a desired toluene solvate, 6' -DPBHBNA to be crystallized has a purity of at least 97% by weight with respect to organic substances other than the solvent. Preferably, 6' -DPBHBNA having a purity of at least 97 wt.% is dissolved in toluene at elevated temperature. Typically, the temperature of the high temperature solution of 6,6' -DPBHBNA is at least 60 ℃, possibly up to reflux temperature. The concentration of 6,6' -DPBHBNA in the high temperature solution is usually not more than 50% by weight, usually 10-40% by weight. Crystallization of toluene solvate from the high temperature solution is typically achieved by cooling the high temperature solution to a temperature below 50 ℃, for example a temperature in the range of-10 to below 50 ℃, -5 to 40 ℃. At temperatures below 50 deg.C, for example in the range of-5 to 40 deg.C, seed crystals may be added. The amount of the seed crystal is usually 0.05 to 2% by weight, particularly 0.1 to 1% by weight, based on the amount of 6,6' -DPBHBNA crystallized as a toluene solvate. The time for completing the crystallization of the toluene solvate may vary depending on the concentration of 6,6' -DPBHBNA and the applicable temperature, but is typically in the range of 4 to 24 hours. Crystallization of the toluene solvate can also be achieved by concentration of the high temperature solution, or a combination of concentration and cooling. Concentration of the solution can be achieved by distilling off part of the toluene.

The toluene solvate can be obtained in the form of a compact crystal having a low aspect ratio by crystallization. The aspect ratio of the toluene solvate is usually less than 5, further in the range of 1 to 4. The size of the crystals is usually in the range of 5 to 300. mu.m. The crystals of the toluene solvate tend not to enclose a significant amount of the mother liquor. Therefore, the crystalline solvate of 6,6 '-DPBHBNA and toluene can increase the purity of 6,6' -DPBHBNA to at least 99%, further to at least 99.5% or more, further to 99.7% or more.

Yet another particular embodiment of the present invention relates to a crystalline solvate of 6,6' -DPBHBNA with Methyl Ethyl Ketone (MEK), hereinafter referred to as MEK solvate.

The amount of MEK in the MEK solvate 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 0.5 to 0.8 mol per 1mol of 6,6' -DPBHBNA.

MEK solvate generally shows the following 3 reflection peaks, i.e., 7.0 ± 0.2 °, 16.8 ± 0.2 ° and 23.4 ± 0.2 °, as 2 θ values in an X-ray powder diffraction pattern recorded by irradiation with Cu K α 1 ray at 22 ℃; and

at least 3, in particular at least 5, at least 7 or all of the following reflection peaks are shown as 2 θ values: 5.0 +/-0.2 degrees, 7.5 +/-0.2 degrees, 12.6 +/-0.2 degrees, 13.4 +/-0.2 degrees, 14.5 +/-0.2 degrees, 15.4 +/-0.2 degrees, 15.7 +/-0.2 degrees, 18.3 +/-0.2 degrees, 19.4 +/-0.2 degrees, 20.6 +/-0.2 degrees, 21.5 +/-0.2 degrees, 22.7 +/-0.2 degrees, 24.1 +/-0.2 degrees, 25.6 +/-0.2 degrees, 26.2 +/-0.2 degrees, 26.6 +/-0.2 degrees and 30.8 +/-0.2 degrees.

MEK solvates may also be characterized by endothermic peaks indicative of their decomposition. For MEK solvates, the use of a solvent at a temperature rise rate of 20K/min according to ISO 11357-3: 2018, the MEK solvate generally shows an endothermic peak with an onset point in the range of 87-91 ℃ and a maximum value in the range of 95-100 ℃. The reaction point (reaction point) is usually in the range of 94 to 98 ℃.

MEK solvates may be obtained by crystallization of 6,6 '-DPBHBNA from a high temperature MEK solution of 6,6' -DPBHBNA which is free of more than 5 wt.% of other organic solvents, in particular free of more than 0.5 wt.% of methanol. In order to obtain the desired MEK solvate, the 6,6' -DPBHBNA to be crystallized has a purity of at least 97% by weight with respect to an organic substance other than the solvent. Preferably, 6' -DPBHBNA having a purity of at least 97 wt.% is dissolved in MEK at elevated temperature. Typically, the temperature of the high temperature solution of 6,6' -DPBHBNA is at least 60 ℃, possibly up to reflux temperature. The concentration of 6,6' -DPBHBNA in the high temperature solution is usually not more than 50% by weight, usually 10-40% by weight. Crystallization of MEK solvate from the high temperature solution is typically achieved by cooling the high temperature solution to a temperature below 50 ℃, for example a temperature in the range of from-10 to below 50 ℃, -5 to 40 ℃. At temperatures below 50 deg.C, for example in the range of-5 to 40 deg.C, seed crystals may be added. The amount of the seed crystal is usually 0.05 to 2% by weight, particularly 0.1 to 1% by weight, based on the amount of 6,6' -DPBHBNA crystallized as a MEK solvate. The time for completing the crystallization of the MEK solvate may vary depending on the concentration of 6,6' -DPBHBNA and the temperature applied, but is typically in the range of 4 to 24 hours. Crystallization of MEK solvates may also be achieved by concentration of the high temperature solution, or a combination of concentration and cooling. Concentration of the solution can be achieved by distilling off part of the MEK.

MEK solvates may be obtained by crystallization in the form of compact crystals with a low aspect ratio. The aspect ratio of MEK solvates is typically below 5, further in the range of 1 to 4. The size of the crystals is usually in the range of 1 to 300. mu.m. Crystallization of MEK solvate tends not to seal in a significant amount of mother liquor. Therefore, the crystalline solvate of 6,6 '-DPBHBNA and MEK can increase the purity of 6,6' -DPBHBNA to at least 99%, further to at least 99.5% or more, further to 99.7% or more.

The crystalline forms of 6,6' -DPBHBNA described above, although of high purity, can also be converted into the amorphous (amophorus) form B. The amorphous form B is stable and does not tend to crystallize even after long-term storage or crushing (grinding). Amorphous form B is prepared by melting an arbitrary crystalline form and then rapidly cooling it. Preferably, each crystalline form is heated to a temperature at least 5K above its melting point until it is completely melted to give a clear melt. If, for the preparation of the melt, solvates are used as starting materials, it is preferred that all solvents are removed by subjecting them to vacuum. Then, the melt is preferably rapidly cooled at a cooling rate of at least 5K/min, for example, at a cooling rate of 5 to 50K/min. Thereby, form B can be obtained as a solid amorphous (glass). This amorphous form can be broken by, for example, grinding (pulverization) to obtain a powder. In order to prevent crystallization, the crushing operation (conditioning) is carried out at a temperature substantially lower than 100 ℃, for example, in the range of 5 to 40 ℃. In this powder, the particles are still present in amorphous form B.

In an X-ray powder diffraction pattern recorded by irradiation with Cu K α 1 rays at 22 ℃, form B does not generally show a reflection peak as a 2 θ value at a plurality of diffraction angles in the range of 5 ° to 40 °, and on the contrary, a broad halo (halo) showing substantially no crystal layer can be observed.

Form B is also characterized by a temperature increase rate of 20K/min in accordance with ISO 11357-3: 2018, shows no endothermic peak at 80 to 200 ℃. In contrast, under such conditions, amorphous form B may exhibit a glass transition temperature of 105 to 125 ℃.

The amorphous form B of 6,6' -DPBHBNA generally has a purity of at least 99%, further at least 99.5% or more, further 99.7% or more. As described above, this means that the total amount of impurities other than the solvent in form B is not more than 1% by weight, particularly not more than 0.5% by weight, further not more than 0.3% by weight. In particular, in form B, the total amount of impurities selected from the group consisting of 2- (2-hydroxyethoxy) -2 '-hydroxy-6, 6' -diphenyl-1,1 '-binaphthyl, 2' -bishydroxy-6, 6 '-diphenyl-1, 1' -binaphthyl and 2- (2-hydroxyethoxy) -2 '- (2- (2-hydroxyethoxy) -ethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl is usually at most 5000ppm or less, preferably at most 4000ppm or less, particularly preferably at most 3000ppm or less, and further preferably at most 2000ppm or less, based on 1 part by weight of 6,6' -DPBHBNA contained in the crystals of form B. In particular, the respective weights of these impurities are not more than 2000ppm, more preferably not more than 1500ppm, and still more preferably not more than 1000ppm, based on 1 part by weight of 6,6' -DPBHBNA contained in the crystal of amorphous form B. If amorphous form B contains bis [2- [ [1- [2- (2-hydroxyethoxy) -6-phenyl-1-naphthyl ] -6-phenyl-2-naphthyl ] -oxy ] -ethyl ] carbonate, the amount thereof is usually not more than 2000ppm, and sometimes not more than 1500ppm, based on 1 part by weight of 6,6' -DPBHBNA contained in the crystals of amorphous form B.

Surprisingly, instead of the ethanolic solvate of 6,6' -DPBHBNA, crystallized from an ethanolic solution of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl, a further novel polymorph of 6,6' -DPBHBNA was obtained, which is referred to as form C below. Form C is particularly useful in the production of the thermoplastic resin of the present invention because it does not contain a significant amount of solvent.

In form C, the organic solvent is usually not contained in an amount exceeding 0.1 mole, particularly not contained in an amount exceeding 0.05 mole per 1 mole of 6,6' -DPBHBNA. The total amount of organic solvent in form C is generally less than 1 wt.%, in particular at most 0.5 wt.%, or at most 0.1 wt.%.

In an X-ray powder diffraction pattern recorded by irradiation with Cu K α 1 ray at 22 ℃, form C generally shows 3 reflection peaks, i.e., 5.1 ± 0.2 °, 7.6 ± 0.2 °, and 21.0 ± 0.2 °, as 2 θ values; and

at least 3, particularly preferably at least 5, at least 7 or all of the following reflection peaks are shown as 2 θ 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 °.

The pattern of the X-ray powder diffraction of form C is approximately the same as the pattern of the X-ray powder diffraction of toluene solvate, indicating that the 6,6' -DPBHBNA in form C has the same arrangement of the molecules and the crystal lattice of toluene solvate.

Form C can also be characterized by an endothermic peak indicating its dissolution. For form C, the temperature was measured at a rate of 20K/min according to ISO 11357-3: 2018, form C generally shows an endothermic peak having an onset in the range of 115 to 118 ℃ and a maximum value in the range of 124 to 126 ℃. The reaction point (reaction point) is usually in the range of 120 to 122 ℃.

Form C can be obtained by crystallization of 6,6 '-DPBHBNA from high temperature ethanol of 6,6' -DPBHBNA. In order to obtain the desired form C, the 6,6' -DPBHBNA to be crystallized generally has a purity of at least 97% by weight with respect to organic substances other than the solvent. 6,6' -DPBHBNA having a purity of at least 97% by weight is preferably dissolved in ethanol at elevated temperature. Typically, the temperature of the high temperature solution of 6,6' -DPBHBNA is at least 45 ℃, and may be as high as reflux temperature. The concentration of 6,6' -DPBHBNA in the high temperature solution is typically no more than 30 wt%, typically 2 to 25 wt%. Crystallization of form C from the high temperature solution is typically achieved by cooling the high temperature solution to a temperature below 40 ℃, for example a temperature in the range of-10 to below 40 ℃, -5 to 30 ℃. Seed crystals may be added at a temperature below 40 deg.c, for example in the range of-5 to 30 deg.c. The amount of the seed crystal is usually 0.05 to 2% by weight, particularly 0.1 to 1% by weight, based on the amount of 6,6' -DPBHBNA crystallized as form C. The time for completing the crystallization of form C may vary depending on the concentration of 6,6' -DPBHBNA and the temperature applied, but is typically in the range of 4 to 24 hours. The crystallization of form C may also be achieved by concentration of the high temperature solution, or a combination of concentration and cooling. Concentration of the solution may be achieved by distilling off part of the solvent.

Form C can be obtained by crystallization in the form of compact crystals having a low aspect ratio. The aspect ratio of form C is usually lower than 5, further in the range of 1 to 4. The size of the crystals is usually in the range of 2 to 250. mu.m.

The crystal of form C tends not to enclose a significant amount of mother liquor. Therefore, the crystalline form C of 6,6 '-DPBHBNA can increase the purity of 6,6' -DPBHBNA to at least 99%, further at least 99.5% or more, further at least 99.7% or more. As described above, this means that the total amount of impurities other than the solvent in form C is not more than 1% by weight, particularly not more than 0.5% by weight, and further not more than 0.3% by weight. In particular, in form C, the total amount of impurities selected from the group consisting of 2- (2-hydroxyethoxy) -2 '-hydroxy-6, 6' -diphenyl-1,1 '-binaphthyl, 2' -bishydroxy-6, 6 '-diphenyl-1, 1' -binaphthyl and 2- (2-hydroxyethoxy) -2 '- (2- (2-hydroxyethoxy) -ethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl is usually at most 5000ppm or less, preferably at most 4000ppm or less, particularly preferably at most 2000ppm or less, and further preferably at most 1000ppm or less, based on 1 part by weight of 6,6' -DPBHBNA contained in the crystals of form C. In particular, the respective weights of these impurities are not more than 2000ppm, more preferably not more than 1500ppm, and still more preferably not more than 1000ppm, based on 1 part by weight of 6,6' -DPBHBNA contained in the crystal of form C. If form C contains bis [2- [ [1- [2- (2-hydroxyethoxy) -6-phenyl-1-naphthyl ] -6-phenyl-2-naphthyl ] -oxy ] -ethyl ] carbonate, the amount thereof is usually not more than 2000ppm, and sometimes not more than 1500ppm, based on 1 part by weight of 6,6' -DPBHBNA contained in the form C crystals.

The solid form of 6,6' -DPBHBNA of the present invention, i.e., methanol solvate, toluene solvate, methyl ethyl ketone solvate, and crystalline forms a and C, as well as amorphous form B, also have a yellowness (Y.I.) as low as usually less than 3.0, sometimes less than 2.5 or less than 2.0, particularly less than 1.5, further less than 1.0 or less than 0.75, further less than about 0.5. Wherein all y.i. values are values measured according to ASTM E313 using a 5 w/w% dichloromethane solution of 6,6' -DPBHBNA.

The solid forms of 6,6 '-DPBHBNA of the present invention typically have a haze as low as less than 1.0ntu, sometimes less than 0.8ntu, or less than 0.6ntu when measured using a 5 w/w% solution of 6,6' -DPBHBNA in methylene chloride. Wherein turbidity (turbidity) is a value measured using a 5 w/w% dichloromethane solution of 6,6' -DPBHBNA and shown in nephelometric turbidity units (ntu). The haze of the crystalline solid of 6,6' -DPBHBNA of the present invention may be further reduced to, for example, 0.4ntu, less than 0.35ntu, less than 0.30ntu, or even less than 0.2 ntu.

The thermoplastic resin of the present invention, that is, the polyester resin, the polyester carbonate resin and the polycarbonate resin or the mixture of at least 2 or more of these resins is preferably produced from a monomer having a prescribed impurity amount, purity, etc.

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

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

When the dihydroxy compound represented by the general formula (6) is in the form of crystals, a thermoplastic resin can be produced using a compound containing less than 0.1 mol of an organic solvent in the crystals.

In the dihydroxy compound in the crystalline form, the aspect ratio can be at most 5: 1, for example, at most 3: 1 or at most 1: 1.

As the dihydroxy compound represented by the general formula (6), a compound having a purity of at least 99.0 wt% (or 99.0 wt% or more) relative to the organic substance is preferably used, a compound having a purity of 99.5 wt% or more is preferable, and a compound having a purity of 99.7 wt% is particularly preferable. The dihydroxy compound of the general formula (6) containing less than 0.1 mol of an organic solvent, for example, less than 0.05 mol of an organic solvent, and preferably less than 0.03 mol of an organic solvent may be used to produce the thermoplastic resin.

As the dihydroxy compound represented by formula (6), it is preferable that the value of the yellowness index (Y.I.) measured according to ASTM E313 using a 5 w/w% dichloromethane solution is less than 3.0, more preferably the value of the yellowness index is less than 2.0, still more preferably less than 1.0.

Further, as the dihydroxy compound represented by the general formula (6), the haze measured with a 5 w/w% dichloromethane solution is preferably less than 1.0ntu, more preferably less than 0.7ntu, and still more preferably less than 0.5 ntu.

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

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

When the content of impurities in the specific dihydroxy compound is 0.5% by mass or more, the reaction efficiency may be reduced, and the molecular weight may be reduced. In particular, in the case of a large amount of repeating impurities containing a large amount of hydroxyethoxy groups, the refractive index of the resulting thermoplastic resin tends to decrease.

On the other hand, when the amount of the impurity in the specific dihydroxy compound is less than 0.5% by mass, the resin contains a structure having a similar basic structure, and the melt viscosity is reduced, whereby moldability is improved, that is, the flow of the resin is improved, and impact resistance of a molded article such as an optical lens tends to be improved.

For example, it is preferable that the impurity is contained in a range of not more than 1ppb to 5000ppm based on 1 part by weight of the monomer of formula (6).

Further, it is preferable to use the monomer of formula (6) having less than 0.5 mass% of impurities, for example, a monomer containing less than 0.5 mass% of a structural unit derived from an impurity selected from the group consisting of 2- (2-hydroxyethoxy) -2 ' -hydroxy-6, 6' -diphenyl-1, 1' -binaphthyl, 2 ' -dihydroxy-6, 6' -diphenyl-1, 1' -binaphthyl, and 2- (2-hydroxyethoxy) -2 ' - (2- (2-hydroxyethoxy) -ethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl, to produce a resin, a resin composition, an optical lens, an optical film, and the like.

The thermoplastic resin preferably has properties particularly suitable for optical applications, and for example, the balance between the refractive index and the abbe number is preferably good. Specifically, the thermoplastic resin preferably has a refractive index of higher than 1.660, more preferably higher than 1.668, and an abbe number of lower than 19, for example, 13 or more and lower than 19, or 15 or more and lower than 19. Further, it is preferable that the refractive index nD and the Abbe number v satisfy the above-mentioned conditions of the refractive index and Abbe number, and further satisfy a relationship of-0.0002 v +1.6718 < nD < -0.024 v +2.124, more preferably a relationship of-0.004 v +1.744 < nD < -0.024 v +2.124, and still more preferably a relationship of-0.02 v +2.04 < nD < -0.024 v + 2.124.

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

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

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

y is an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

c and d are integers of 1-10 respectively.

In addition, R in the formula (8) "₁～R”₁₆Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aralkyl group having 7 to 17 carbon atoms,

z is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or an arylene group having 6 to 20 carbon atoms,

e and f are integers of 1-10 respectively.

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

Examples of the dihydroxy compound represented by formula (8) include 9, 9-bis [ 4- (2-hydroxyethoxy) phenyl ] fluorene, 9-bis [ 4- (2-hydroxyethoxy) -3-methylphenyl ] fluorene, 9-bis [ 4- (2-hydroxyethoxy) -3-tert-butylphenyl ] fluorene, 9-bis [ 4- (2-hydroxyethoxy) -3-isopropylphenyl ] fluorene, 9-bis [ 4- (2-hydroxyethoxy) -3-cyclohexylphenyl ] fluorene, and 9, 9-bis [ 4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene. Among them, 9-bis [ 4- (2-hydroxyethoxy) phenyl ] fluorene and 9, 9-bis [ 4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene are preferable. These may be used alone or in combination of two or more.

For example, as examples of the dihydroxy compound represented by formula (7) or (8), compounds represented by the following general formula (9) can be cited.

In addition, in the monomer for producing the thermoplastic resin, the dihydroxy compound represented by the general formula (6) may contain, as impurities, a dihydroxy compound in which both values of c and d in the general formula (6) are 0 or a dihydroxy compound in which either one of c and d in the general formula (6) is 0.

In this manner, the dihydroxy compound having at least any one of c and d different from the above general formula (6) is contained in an amount of preferably 1000ppm or less, more preferably 500ppm or less, still more preferably 200ppm or less, and particularly preferably 100ppm or less in total in the monomer containing the dihydroxy compound represented by the above general formula (6) as a main component, and the total content of the dihydroxy compound having at least any one of c and d different from the above general formula (6) in the monomer is preferably 50ppm or less, more preferably 20ppm or less.

The same applies to the content of the impurity of the general formula (6) in the dihydroxy compound represented by the general formula (7) or (8). That is, the dihydroxy compound represented by the general formula (7) or (8) may contain, as impurities, a dihydroxy compound in which both e and f in the general formula (7) or (8) have a value of 0 or a dihydroxy compound in which either e or f in the general formula (7) or (8) has a value of 0.

The total content of these impurities in the monomer containing the dihydroxy compound represented by the general formula (7) or (8) as a main component is preferably 1000ppm or less, more preferably 500ppm or less, still more preferably 200ppm or less, and particularly preferably 100ppm or less, and the total content of the impurities in the monomer is preferably 50ppm or less, more preferably 20ppm or less.

The compounds of the general formulae (7) and (8) can be produced by various synthetic methods. For example, as described in Japanese patent No. 5442800 and Japanese patent application laid-open No. 2014-028806, 9-bis (hydroxynaphthyl) fluorenes are obtained by reacting (a) a method of reacting fluorenones with hydroxynaphthalenes in the presence of hydrogen chloride gas and mercaptocarboxylic acid, (b) a method of reacting 9-fluorenones with hydroxynaphthalenes in the presence of an acid catalyst (and an alkylthiol), (c) a method of reacting fluorenones with hydroxynaphthalenes in the presence of hydrochloric acid and thiols (mercaptocarboxylic acid, etc.), (d) a method of producing bisnaphthofluorene by reacting fluorenones with hydroxynaphthalenes in the presence of sulfuric acid and thiols (mercaptocarboxylic acid, etc.) and crystallizing with a crystallization solvent composed of a hydrocarbon and a polar solvent, and the like, and are reacted with a compound (alkylene oxide, halogenoalkanol, etc.) corresponding to the XO group and the [ XO ] b group, thereby enabling manufacturing. For example, 9, 9-bis [ 6- (2-hydroxyethoxy) naphthyl ] fluorene can be obtained by reacting 9, 9-bis [ 6-hydroxynaphthyl ] fluorene with 2-chloroethanol under basic conditions.

Examples of the aromatic dihydroxy compound which can be used simultaneously other than the above-mentioned compounds include bisphenol a, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z.

(amount of vinyl terminal group)

The thermoplastic polyester resin, polyester carbonate resin and polycarbonate resin of the present invention are obtained by using compounds represented by the above general formulae (6) to (9) and the like as dihydroxy components and reacting them with a carbonate precursor such as a carbonic acid diester. However, in the polymerization step for producing a thermoplastic resin such as polycarbonate, impurities are generated in which one or both of the terminal — OROH groups of the compounds of the general formulae (6) to (9) are converted into a vinyl terminal group represented by, for example, a — OC ═ CH group.

For example, impurities having a vinyl group represented by the following formula (v-1) may be present in the monomer, the resin composition, the optical lens, and the optical film described in the present specification.

The vinyl group may be generated in the stage of synthesizing and purifying the monomer and contained in the monomer. In addition, the amount of the additive may be increased or generated in the stage of polymerization of the resin or kneading of the additive. This vinyl group is considered to be one of the causes of coloring of the polymer, but when the content is small, the flexural strength and impact resistance of the resin may be improved.

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

For example, the amount of vinyl groups in the polycarbonate resin can be determined by the procedure described in < 9 > amount of vinyl terminal groups in the polycarbonate resin¹H-NMR measurement was carried out, and the content was determined by integrating the following formula (A). The amount of the vinyl terminal group is preferably 0.0001 to 5.0, more preferably 0.01 to 3.0, and still more preferably 0.1 to 1.0.

Wherein Hk in the above formula (A) means Hk in the following formula (v-2) corresponding to the above formula (v-1).

In the resin of the present application, an oligomer having a molecular weight (Mw) of 1000 or less and a cyclic structure in which 2 or more monomers are bonded to each other with carbonate may be formed. Such oligomers and cyclic compounds can be analyzed by LC-MS or the like, and are contained in a total amount of preferably 2.5 mass% or less, more preferably 2.0 mass% or less, and still more preferably 1.0 mass% or less, for example.

The metal contained in the monomer is preferably an amount of not more than 1000ppm by weight (for example, 100ppm by weight or 10 ppm by weight) in total of Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn.

The total of Li, Na, Mg, Al, K, Ca, Ti, Cr, Fe, Ni, Zn and Sn is preferably 1000ppm by weight or less with respect to the metal in the resin or resin composition obtained.

When the metal content is 1000ppm by weight or less, the obtained resin is less colored and the catalyst activity is less likely to be lowered during polymerization. Further, by containing preferably 1ppb by weight or more (more preferably 1ppm by weight or more), the operation of adding the catalyst can be omitted, and by exerting the catalytic effect, the amount of the catalyst to be added can be reduced, and the production cost can be reduced. Such a metal concentration is measured, for example, by the following method.

< analysis of metals >

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

That is, 2g of a sample was weighed in a synthetic quartz cuvette, 2.5ml of sulfuric acid was added immediately before carbonization, 0.1ml of sulfuric acid was added during carbonization, and the sample was carbonized by heating on a hot plate. Thereafter, the resultant was covered with a quartz dish, heated at 500 ℃ for 10 hours in an electric furnace, and carbonized. Then, sulfuric acid is added, and the mixture is heated, dried and solidified, and then nitric acid is added, and heated, dried and solidified, whereby heated acid decomposition is performed. An aqueous nitric acid solution was added to 50mL, the mixture was heated to 50 ℃ and subjected to quantitative analysis by ICP-MS.

ICP-MS apparatus: shimadzu corporation: ICPE-9000

Examples of the carbonic acid diester used for producing the polycarbonate resin and the polyester carbonate resin include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like. Of these, diphenyl carbonate is particularly preferred. Diphenyl carbonate is preferably used in an amount of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, based on 1mol of the total of dihydroxy compounds.

The dicarboxylic acid, monocarboxylic acid monoester, and diester compound that can be used for producing the polyester resin and the polyester carbonate resin are preferably used in a proportion of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, based on 1mol of the total of the dihydroxy compounds.

Among the above-mentioned transesterification catalysts used for the production of thermoplastic resins, the basic compound catalyst may be, in particular, an alkali metal compound, an alkaline earth metal compound, a nitrogen-containing compound, and the like.

Examples of the alkali metal compound used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides of alkali metals, and the like. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylboronate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogenphosphate, dipotassium hydrogenphosphate, dilithium hydrogenphosphate, 2 sodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, or dilithium salt of bisphenol a, a sodium salt, a potassium salt, a cesium salt, or a lithium salt of phenol, and the like can be used.

Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, and the like of the alkaline earth metal compound. Specifically, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogencarbonate, calcium hydrogencarbonate, strontium hydrogencarbonate, barium hydrogencarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium benzoate, magnesium phenylphosphate, and the like can be used.

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

As the transesterification catalyst, salts of titanium, zinc, tin, zirconium, lead, and the like are preferably used, and they may be used alone or in combination.

Specific examples of the transesterification catalyst include titanium alkoxides such as tetrabutoxytitanium, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxytin, zirconium acetylacetonate, zirconyl acetate, tetrabutoxyzirconium, lead (II) acetate, and lead (IV) acetate.

These catalysts are used in an amount of 10mol based on 1mol of the total of dihydroxy compounds^－9～10^－3The molar ratio is preferably 10^－7～10^－4Molar ratios are used.

The melt polycondensation method is a method of performing melt polycondensation by using the above-mentioned raw materials and a catalyst under heating and further under normal pressure or reduced pressure through an ester exchange reaction while removing by-products.

In the melt polycondensation of the present composition system, it is desirable that the compound represented by the general formula (6) and the carbonic acid diester are melted in the reaction vessel and then reacted in a state where the by-produced monohydroxy compound is retained. The reaction apparatus may be closed for retention, or the pressure may be controlled by reducing or increasing the pressure. The reaction time in this step is 20 minutes to 240 minutes, preferably 40 minutes to 180 minutes, and particularly preferably 60 minutes to 150 minutes. In this case, if the by-produced monohydroxy compound is distilled off immediately after its production, the content of the high molecular weight material in the thermoplastic resin finally obtained is small. However, when the by-produced monohydroxy compound is allowed to remain in the reaction vessel for a certain period of time, a resin having a large content of the high molecular weight material in the thermoplastic resin finally obtained can be obtained.

The melt polycondensation reaction may be carried out continuously or batchwise. The reaction apparatus used for carrying out the reaction may be a vertical type equipped with an anchor paddle, a MAXBLEND paddle, a ribbon paddle or the like, a horizontal type equipped with a paddle blade, a lattice blade, a spectacle blade or the like, or an extruder type equipped with a screw. Further, it is preferable to use a reaction apparatus in which these reaction apparatuses are appropriately combined in consideration of the viscosity of the polymer.

In the method for producing a thermoplastic resin used in the present invention, after completion of the polymerization reaction, the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolytic stability. A method of deactivating the catalyst by adding a known acidic substance can be appropriately performed. As the acidic substance, specifically, esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, etc.; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid and phosphonic acid; phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite; phosphoric acid esters such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane; boric acids such as boric acid and phenylboronic acid; aromatic sulfonic acid salts such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearoyl chloride, benzoyl chloride, p-toluenesulfonyl chloride and the like; alkyl sulfuric acids such as dimethyl sulfuric acid; and organic halides such as benzyl chloride. The amount of the deactivator is 0.01 to 50 times by mol, preferably 0.3 to 20 times by mol, based on the amount of the catalyst. When the amount of the catalyst is less than 0.01 times by mol, the deactivation effect is not sufficient, which is not preferable. Further, if the amount of the catalyst is more than 50 times by mol, the heat resistance of the resin is lowered, and the molded article is liable to be colored, which is not preferable.

After the catalyst is deactivated, a step of removing the low boiling point compounds in the polymer by devolatilization under a pressure of 0.1 to 1mmHg at a temperature of 200 to 350 ℃ may be provided. In this step, a horizontal apparatus or a thin film evaporator equipped with a stirring paddle having excellent surface renewal properties such as a paddle blade, a lattice blade, and a spectacle blade is suitably used.

The thermoplastic resin of the present invention is desired to have a content of foreign matter as small as possible, and is suitable for filtration of a molten raw material, filtration of a catalyst solution, and the like. The pore size of the filter is preferably 5 μm or less, more preferably 1 μm or less. Further, filtration of the produced resin through a polymer filter is suitably carried out. The pore diameter of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. The step of collecting the resin pellets is, of course, required to be performed in a low-dust environment, and is preferably no greater than class 6, and more preferably no greater than class 5.

Examples of the molding method of the polycarbonate resin include, but are not limited to, compression molding, casting, roll processing, extrusion molding, and stretching, in addition to injection molding.

(4) Optical molded body

The thermoplastic resin of the present invention can be used to produce an optical molded article. For example, the resin composition can be molded by any method such as injection molding, compression molding, extrusion molding, and solution casting. The thermoplastic resin of the present invention is excellent in moldability and heat resistance, and therefore can be used particularly advantageously in an optical lens requiring injection molding. The thermoplastic resin of the present invention can be used in combination with other resins such as other polycarbonate resins and polyester resins in molding. Further, additives such as an antioxidant, a processing stabilizer, a light stabilizer, a polymeric metal deactivator, a flame retardant, a lubricant, an antistatic agent, a surfactant, an antibacterial agent, a mold release agent, an ultraviolet absorber, a plasticizer, and a compatibilizer may be blended.

As the antioxidant, triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], pentaerythritol-tetrakis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, N-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3, 5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3, 9-bis {1, 1-dimethyl-2- [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl } -2,4,8, 10-tetraoxaspiro (5,5) undecane, and the like. The content of the antioxidant in the thermoplastic resin is preferably 0.001 to 0.3 parts by weight based on 100 parts by weight of the thermoplastic resin.

Examples of the processing stabilizer include a phosphorus-based processing heat stabilizer, a sulfur-based processing heat stabilizer, and the like. Examples of the phosphorus-based processing heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2, 6-di-t-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecylmonophenyl phosphite, dioctylmonophenyl phosphite, diisopropyl monophenyl phosphite, monobutyldiphenyl phosphite, monodecyl diphenyl phosphite, monooctyldiphenyl phosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl mono-o-biphenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, tetrakis (2, 4-di-tert-butylphenyl) -4, 4 ' -biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -4, 3 ' -biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -3, 3 ' -biphenylene diphosphonite, bis (2, 4-di-tert-butylphenyl) -4-phenyl phosphonite, bis (2, 4-di-tert-butylphenyl) -3-phenyl phosphonite and the like. The content of the phosphorus-based processing heat stabilizer in the thermoplastic resin is preferably 0.001 to 0.2 part by weight based on 100 parts by weight of the thermoplastic resin.

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

Specifically, examples of the ester of a monohydric alcohol and a saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Examples of the partial esters or full esters of polyhydric alcohols and saturated fatty acids include full esters or partial esters of dipentaerythritol such as stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid sorbitan ester, behenic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl ester, sorbitan monostearate, 2-ethylhexyl stearate, and dipentaerythritol hexastearate. The content of the release agent is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight, and still more preferably in the range of 0.02 to 0.5 parts by weight, based on 100 parts by weight of the thermoplastic resin.

The ultraviolet absorber is preferably at least 1 ultraviolet absorber selected from benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic imino ester-based ultraviolet absorbers and cyanoacrylate-based ultraviolet absorbers. That is, the following ultraviolet absorbers may be used alone, or 2 or more of them may be used in combination.

The thermoplastic resin of the present invention has a high refractive index and a low abbe number. In addition to optical lenses, optical molded articles can be preferably used as structural materials or functional materials for use as optical members suitable for liquid crystal displays, organic EL displays, solar cells, and the like, transparent conductive substrates, optical disks, liquid crystal panels, optical memory cards, sheets, films, optical fibers, connectors, vapor-deposited plastic mirrors, displays, and the like.

If necessary, a coating layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical molded body. The antireflection layer may be a single layer or a plurality of layers, and may be organic or inorganic, and is preferably inorganic. Specifically, oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride can be exemplified.

(5) Optical lens

Since the optical lens produced using the thermoplastic resin of the present invention has a high refractive index, a low abbe number, and high moist heat resistance, it can be used in the field where expensive high refractive index glass lenses are used, such as a telescope, a binocular, and a television projector, and is very useful. It is preferably used in the form of an aspherical lens as needed. Since the aspherical lens can substantially zero spherical aberration by using 1 lens, it is not necessary to combine a plurality of spherical lenses to eliminate spherical aberration, and weight reduction and reduction in production cost can be achieved. Therefore, the aspherical lens is useful as an optical lens, particularly a camera lens.

The optical lens can be molded by any method such as injection molding, compression molding, and injection compression molding. The present invention can provide a high-refractive-index low-birefringence aspherical lens which is difficult to process technically when using a glass lens, more easily.

In order to avoid the contamination of foreign substances into the optical lens as much as possible, the molding environment must be a low-dust environment, and is preferably class 6 or less, and more preferably class 5 or less.

(6) Optical film

The optical film produced using the thermoplastic resin of the present invention is excellent in transparency and heat resistance, and therefore is suitably used for films for liquid crystal substrates, optical memory cards, and the like.

In order to avoid the contamination of foreign substances into the optical film as much as possible, the molding environment must be a low-dust environment, and is preferably class 6 or less, and more preferably class 5 or less.

[ shorthand ]

6,6' -DPBHBNA: 2,2 '-Bis (2-hydroxyethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl (Bis-2, 2' - (2-hydroxyethoxy) -6,6 '-diphenyl-1, 1' -bisnaphyl);

6,6' -DPMHBNA: 2- (2-hydroxyethoxy) -2 '-hydroxy-6, 6' -diphenyl-1,1 '-binaphthyl (2- (2-hydroxyethoxy) -2' -hydroxy-6,6 '-diphenyl-1, 1' -bisnaphyl);

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

% b.w.: weight% (% by weight);

DSC: differential scanning calorimetry (differential scanning calorimetry);

LOD: loss on drying (Loss on drying);

m.p.: melting point (melting point);

MeOH: methanol (Methanol);

NaOH: sodium hydroxide (sodium hydroxide);

NIR: near infrared (near infrared);

PXRD: powder X-ray diffraction (powder X-ray diffraction);

TLC: thin layer chromatography (thin layer chromatography);

and (3) UPLC: high Performance Liquid Chromatography (Ultra Performance Liquid Chromatography).

[ examples ]

< 1. method for measuring weight average molecular weight (Mw) >

The polystyrene-equivalent weight average molecular weight was determined from a calibration curve of standard polystyrene prepared in advance in accordance with JIS K7252-3. That is, a calibration curve was prepared using a standard polystyrene (PStQuick MP-M, product of tokyo co., ltd.) having a known molecular weight (molecular weight distribution of 1), and the elution time and the molecular weight of each peak were plotted from the measured standard polystyrene, followed by approximation with a 3-fold equation to obtain a calibration curve. Mw is calculated by the following equation.

Mw＝Σ(Wi×Mi)÷Σ(Wi)

Where i represents the ith division point at which the molecular weight M is divided, Wi represents the weight of the ith, and Mi represents the molecular weight of the ith. And molecular weight M refers to the polystyrene molecular weight value at that dissolution time of the calibration curve. As a GPC apparatus, HLC-8320 GPC available from Tosoh corporation was used, 1 TSK guard column SuperMPHZ-M was used as a guard column, and 3 TSK gel SuperMultipore HZ-M were connected in series as an analytical column. Other conditions are as follows.

Solvent: HPLC grade tetrahydrofuran

Injection amount: 10 μ L

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

Flow rate of solvent: 0.35ml/min

Measuring temperature: 40 deg.C

A detector: RI (Ri)

< 2. glass transition temperature (Tg) >

The measurement was carried out by a Differential Scanning Calorimetry (DSC) instrument in accordance with JIS K7121-1987. As the analyzer, Hitachi high New science X-DSC 7000 was used.

< 3. refractive index (nD) >

A film having a thickness of 0.1mm and made of the resin produced in the examples was measured by the method of JIS-K-7142 using an Abbe refractometer.

Abbe number (v) > < 4

The refractive indices at wavelengths of 486nm, 589nm and 656nm of a film having a thickness of 0.1mm and comprising the resin produced in the examples were measured at 23 ℃ by an Abbe refractometer, and the Abbe number was calculated by the following formula.

ν＝(nD－1)/(nF－nC)

nD: refractive index at wavelength of 589nm

nC: refractive index at wavelength 656nm

nF: refractive index < 5. b-value > at a wavelength of 486nm

The resin thus produced was vacuum-dried at 120 ℃ for 4 hours, and then injection-molded by an injection molding machine (FANUC ROBOSHOT. alpha. -S30iA) at a cylinder temperature of 270 ℃ and a mold temperature of Tg-10 ℃ to obtain a disk-shaped test piece having a diameter of 50mm and a thickness of 3 mm. Using the sheet, the b value was measured in accordance with JIS K7105. A smaller b value indicates a lower yellowing, and the hue is better. For the measurement of the molded plate, a spectroscopic color difference meter model SE2000 manufactured by Nippon Denshoku industries Co., Ltd was used.

< 6. pressure cooker test (PCT test) >

< 7. Total light transmittance >

The sheet pieces before and after the PCT test were measured by a method of JIS-K-7361-1 using a spectroscopic color difference meter SE2000 model manufactured by Nippon Denshoku industries Co., Ltd.

< 8. Total light transmittance Retention ratio (%) >

The total light transmittance measured by the above method was calculated from the following equation.

Total light transmittance retention (%) full light transmittance after PCT test/full light transmittance before PCT test × 100

< 9. amount of vinyl terminal group of polycarbonate resin >

¹The H-NMR measurement was carried out under the following conditions.

·¹H-NMR measurement conditions

The device comprises the following steps: bruker AVANZE III HD 500MHz

Pouring angle: 30 degree

Waiting time: 1 second

And (4) accumulating times: 500 times (times)

Measuring temperature: room temperature (298K)

Concentration: 5 wt.%

Solvent: deuterated chloroform

Internal standard substance: tetramethylsilane (TMS)0.05 wt%

< 10. measurement of phenol and Diphenyl carbonate (DPC) amount in polycarbonate resin >

In detail, 0.5g of a sample of example 1 described later was dissolved in 50ml of Tetrahydrofuran (THF) to prepare a sample solution. As a standard, a calibration curve was prepared using a pure product of each compound, and 2. mu.L of the sample solution was quantified by LC-MS under the following measurement conditions. The limit value of detection under the measurement conditions was 0.01 ppm.

LC-MS measurement conditions:

measurement apparatus (LC part): agilent Infinity 1260LC System

A chromatographic column: ZORBAX Eclipse XDB-18, and guard column

Mobile phase:

a: 0.01mol/L ammonium acetate aqueous solution

B: 0.01 mol/L-ammonium acetate in methanol

C：THF

Gradient program of mobile phase:

as shown in table 1, the mixture of a to C was used as a mobile phase, and the mobile phase was passed through the column for 30 minutes while switching the composition of the mobile phase when the time indicated in the column of time (minutes) elapsed.

[ Table 1]

Flow rate: 0.3 ml/min

Temperature of the column: 45 deg.C

A detector: UV (225nm)

Measurement apparatus (MS part): agilent 6120single quad LCMS System

An ionization source: ESI

Polarity: positive (DPC) & negative (PhOH)

Fragmentation voltage: 70V

Drying gas: 10L/min, 350 deg.C

An atomizer: 50psi

Capillary voltage: 3000V (Positive), 2500V (negqative)

And (3) ion determination:

[ Table 2]

Monomer	Ion species	m/z
			PhOH	[M-H]-	93.1
DPC	[M+NH4]+	232.1

Sample injection amount: 2 μ L

Method for analyzing monomer

<11. powder X-ray diffraction (PXRD) >

Powder X-ray diffraction (PXRD) patterns were recorded using a D8 Discover X-ray diffractometer (D8 Discover X-ray diffractometer) from Bruker AXS GmbH, germany, by using as X-ray source a reflection configuration (Bragg Brentano) of Cu ka 1 radiation (40kV, 40 ma). Data were collected at room temperature for a range of 2 theta-5.0 deg. to 2 theta-80.0 deg. with a resolution of 0.025 deg. and a measurement time of 0.5 seconds per step.

< 12.DSC measurement >

DSC measurement was performed using Linsei Chip-DSC 10. The temperature rise rate was 20 ℃ per minute.

< 13. determination of melting Point >

The Melting Point was measured by the capillary method using a Buchi Melting Point B-545 apparatus at a temperature rise rate of 1K/min.

< 14. near Infrared analysis >

Near infrared analysis was recorded by means of using a Bruker FT-NIR spectrometer Matrix F spectrometer, Bruker Optis 5.5 software and a reflectance immersion probe (reflectance immersion probe head).

< 15. determination of purity >

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

A Waters Acquity UPLC H-Class system; chromatographic column

Acquity UPLC BEH C18,1.7 μm,2 × 100 mm; temperature of the column: at a temperature of 40 c,

gradient: acetonitrile/water (acetonitrile; ACN: 0 min 48%, 21 min 50%, 26 min 100%, 28 min 100%, 28.1 min 48%, 32 min 48%);

injection amount: 0.8 μ l; flow rate 0.6 ml/min; detection was at 210 nm.

< 16. determination of volatile solvent >

Regarding the amount of volatile solvent, it was determined by gas chromatography using Shimadzu GC 14B and Class VP 4.3 software, AOC-20i auto-injector, AOC-20s auto-sampler, and FID detector.

As the column, PE 62420 (Perkin Elmer) having the following dimensions was used. The gas chromatography was carried out under the following operating conditions.

Carrier gas: hydrogen

Pressure: 0.3bar

Injection temperature: 250 deg.C

Detecting the temperature: 300 deg.C

Temperature of the column: 40 deg.C (2 min), 20 deg.C/min, 200 deg.C (2 min)

Concentration: c20 mg/ml

Injection amount: 0.2 to 2. mu.l

As an internal standard, 100mg of naphthalene in 10ml of dimethylformamide are used. Samples were prepared by dissolving 20mg of the compound in 0.1mm internal standard solution, adding 0.9ml of dimethylformamide. The amount of the medium is calculated by the following equation.

S_Solv＊M_St＊100/(S_St＊M_Sample＊RRF)

M_St: amount of internal standard in sample solution

M_Sample: weight of sample

S_Solv: area of solvent peak

S_St: standard area of

RRF: relative sensitivity coefficient of solvent

< 17. measurement of yellowness >

The yellowness YI of 6,6' -DPBHBNA was measured by the following protocol (protocol) with reference to ASTM E313.

1g of 6,6' -DPBHBNA was dissolved in 19g of methylene chloride. The solution was transferred to a 50mm measuring cell, and the transmittance in the range of 300 to 800nm was measured using a Shimadzu UV-Visible spectrophotometer UV-1650PC (spectrophotometer). Dichloromethane was used as a control. The yellowness index (yellowness index) was calculated from the spectra using the software RCA-software UV2DAT according to ASTM E308 (Standard procedure for calculating the colors of objects by using the CIE System; Standard practice for calculating the colors of objects by using the CIE System) and ASTM E313 (Standard procedure for calculating the yellowness and whiteness from the color coordinates measured with an instrument; Standard practice for calculating the yellowness and whiteness from the coordinates measured with an instrument).

< 18. measurement of haze >

Haze was determined by measuring the transmission at 860nm of a 5% dichloromethane solution of 6,6' -DPBHBNA using a standard turbidimeter (nephelometer).

< 19. microscopic examination

The image for microscopic examination was captured at a magnification of 100 times that of Digital Sight DS-U1, a capturing unit of Nikon, using Eclipse TS 100, a microscope of Nikon. From these photomicrographs, the width (W), length (L), and aspect ratio (L/W ratio) were confirmed.

[ production of polycarbonate resin ]

(example 1)

As raw materials, 31.6kg (60.0 mol) of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl (hereinafter, may be abbreviated as "BINL-2 EO"), 13.5kg (63.0 mol) of diphenyl carbonate (hereinafter, may be abbreviated as "DPC"), and 0.074g (8.8X 10) of sodium hydrogencarbonate were added^－4Molal) was charged into a 50-liter reactor equipped with a stirrer and a distilling device, and heated to 180 ℃ under a nitrogen atmosphere of 760 mmHg. After heating was started for 20 minutes, complete dissolution of the starting material was confirmed, and then stirring was carried out under these conditions for 120 minutes. Thereafter, the temperature was raised to 200 ℃ at a rate of 60 ℃/hr while the reduced pressure was adjusted to 200 mmHg. At this time, it was confirmed that the by-produced phenol started to distill off. Thereafter, the reaction was carried out at 200 ℃ for 40 minutes. Then, the temperature was increased to 240 ℃ at a rate of 75 ℃/hr, and after the completion of the temperature increase for 10 minutes, the reduced pressure was maintained at 1mmHg or less for 1 hour while maintaining the temperature. Then, the temperature was raised to 245 ℃ at a rate of 60 ℃/hr, and the mixture was stirred for 30 minutes. After the reaction, nitrogen was introduced into the reactor and the pressure was returned to normal pressure, and the produced polycarbonate resin was taken out while being pelletized. As a result of measuring the amounts of phenol and diphenyl carbonate (DPC) as impurities in the obtained polycarbonate resin as described above, the phenol content in the resin was 100 mass ppm and the DPC content was 300 mass ppm.

The physical property values of the obtained resin are shown in table 3 below.

(example 2-A)

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

(example 2-B)

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

(example 2-C)

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

The physical property values of the obtained resin are shown in table 3. An NMR spectrum of the resin obtained in example 2-B (BINOL-2 EO/BNEF 50mol/50mol) is shown in fig. 1.

(example 3-A)

The same procedures as in example 1 were carried out except for using, as raw materials, BINL-2EO 7.9kg (15.0 mol), 9-bis [ 4- (2-hydroxyethoxy) phenyl ] fluorene (hereinafter, may be abbreviated as "BPEF") 19.0kg (45.0 mol), and DPC 13.5kg (63.0 mol). The physical property values of the obtained resin are shown in table 3.

(example 3-B)

The same procedures as in example 1 were carried out except for using, as raw materials, 12.7kg (30.0mol) of BINL-2EO 15.8kg (30.0mol), 9-bis [ 4- (2-hydroxyethoxy) phenyl ] fluorene (hereinafter sometimes abbreviated as "BPEF"), and 13.5kg (63.0 mol) of DPC. The physical property values of the obtained resin are shown in table 3.

(example 3-C)

The same procedures as in example 1 were carried out except for using, as raw materials, BINL-2EO 23.7kg (45.0 mol), 9-bis [ 4- (2-hydroxyethoxy) phenyl ] fluorene (hereinafter, sometimes abbreviated as "BPEF") 6.3kg (15.0 mol), and DPC 13.5kg (63.0 mol). The physical property values of the obtained resin are shown in table 3.

(example 4-A)

The same operation as in example 1 was carried out except that BINL-2EO 7.9kg (15.0 mol), BPPEF 25.9kg (45.0 mol) and DPC 13.5kg (63.0 mol) were used as raw materials. The physical property values of the obtained resin are shown in table 3.

(example 4-B)

The same operation as in example 1 was carried out except that BINL-2EO 15.8kg (30.0mol), BPPEF 17.2kg (30.0mol) and DPC 13.5kg (63.0 mol) were used as raw materials. The physical property values of the obtained resin are shown in table 3.

(example 4-C)

The same operation as in example 1 was carried out except that BINL-2EO 23.7kg (45.0 mol), BPPEF 8.6kg (15.0 mol) and DPC 13.5kg (63.0 mol) were used as raw materials. The physical property values of the obtained resin are shown in table 3.

(example 5)

The same operation as in example 1 was carried out except for using 7.6kg (18.0 moles) of BPEF, 26.3kg (42.0 moles) of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -di (naphthalen-1-yl) -1,1' -binaphthyl (hereinafter, sometimes abbreviated to "DNBINOL-2 EO") and 13.5kg (63.0 moles) of DPC as raw materials. The physical property values of the obtained resin are shown in table 3.

(example 6-A)

The same operation as in example 1 was carried out except for using 7.9kg (15.0 mol) of BINL-2EO, 9.7kg (18.0 mol) of BNEF, 10.1kg (27.0 mol) of 2,2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl (hereinafter, sometimes abbreviated as "BNE") and 13.5kg (63.0 mol) of DPC as raw materials. The physical property values of the obtained resin are shown in table 3.

(example 6-B)

The same operation as in example 1 was carried out except that BINL-2EO 19.0kg (36.0 mol), BNE 4.5kg (12.0 mol), BPEF 5.1kg (12.0 mol), and DPC 13.5kg (63.0 mol) were used as raw materials. The physical property values of the obtained resin are shown in table 3.

(example 6-C)

The same operation as in example 1 was carried out except for using 19.0kg (36.0 mol) of BINL-2EO, 4.5kg (12.0 mol) of BNE, 6.9kg (12.0 mol) of BPPEF, and 13.5kg (63.0 mol) of DPC as raw materials. The physical property values of the obtained resin are shown in table 3.

BINL-2EO used in the above-mentioned examples 1, 2-A to C, 3-A to C, 4-A to C and 6-A to C is "form A" obtained in example 21 described in detail later.

(example 6-D)

The same operation as in example 1 was carried out except for using 11.3kg (21.0 mol) of BNEF, 11.2kg (30.0mol) of BNE, 5.6kg (9.0 mol) of DNBINOL-2 EO and 13.5kg (63.0 mol) of DPC as raw materials. The physical property values of the obtained resin are shown in table 3.

(example 6-E)

The same operation as in example 1 was carried out except for using, as raw materials, BNE 6.7kg (18.0 moles), BPPEF 17.2kg (30.0 moles), DNBINOL-2 EO 7.5kg (12.0 moles), and DPC 13.5kg (63.0 moles). The physical property values of the obtained resin are shown in table 3.

(example 6-F)

The same operation as in example 1 was carried out except for using BNE 6.7kg (18.0 moles), BPEF 10.1kg (24.0 moles), DNBINOL-2 EO 11.3kg (18.0 moles), and DPC 13.5kg (63.0 moles) as raw materials. The physical property values of the obtained resin are shown in table 3.

(example 7)

The same procedures as in example 1 were carried out except for using 32.0kg (51.0 mol) of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -di (naphthalen-2-yl) -1,1' -binaphthyl (2 DNBINOL-2 EO), 3.8kg (9.0 mol) of BPEF, and 13.5kg (63.0 mol) of DPC as a raw material. The physical property values of the obtained resin are shown in table 3.

(example 7-A)

The same procedures as in example 1 were carried out except for using 18.8kg (30.0mol) of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -di (naphthalen-2-yl) -1,1' -binaphthyl (2 DNBINOL-2 EO), 12.7kg (30.0mol) of BPEF, and 13.5kg (63.0 mol) of DPC as a raw material. The physical property values of the obtained resin are shown in table 3.

(example 7-B)

The same operation as in example 1 was carried out except for using 5.6kg (9.0 mol) of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -di (naphthalen-2-yl) -1,1' -binaphthyl (2 DNBINOL-2 EO), 21.5kg (51.0 mol) of BPEF, and 13.5kg (63.0 mol) of DPC as a raw material. The physical property values of the obtained resin are shown in table 3.

(example 8)

The same procedures as in example 1 were carried out except for using 37.1kg (51.0 mol) of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -bis (phenanthren-9-yl) -1,1' -binaphthyl (9 DPNBINOL-2 EO), 3.8kg (9.0 mol) of BPEF, and 13.5kg (63.0 mol) of DPC as a raw material. The physical property values of the obtained resin are shown in table 3.

(example 8-A)

The same procedures as in example 1 were carried out except for using 21.8kg (30.0mol) of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -bis (phenanthren-9-yl) -1,1' -binaphthyl (9 DPNBINOL-2 EO), 12.7kg (30.0mol) of BPEF, and 13.5kg (63.0 mol) of DPC as a raw material. The physical property values of the obtained resin are shown in table 3.

(example 8-B)

The same procedures as in example 1 were carried out except for using 6.5kg (9.0 mol) of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -bis (phenanthren-9-yl) -1,1' -binaphthyl (9 DPNBINOL-2 EO), 21.5kg (51.0 mol) of BPEF, and 13.5kg (63.0 mol) of DPC as a raw material. The physical property values of the obtained resin are shown in table 3.

(example 9)

The same operation as in example 1 was carried out except for using 10.4kg (18.0 mol) of 6,6' -bis (3-cyanophenyl) -2,2 ' -bis (2-hydroxyethoxy) -1,1' -binaphthyl (CN-BNA), 18.4kg (42.0 mol) of BPEF, and 13.5kg (63.0 mol) of DPC as raw materials. The physical property values of the obtained resin are shown in table 3.

(example 10)

The same operation as in example 1 was carried out except for using 12.7kg (18.0 mol) of 6,6' -bis (dibenzo [ b, d ] furan-4-yl) -2,2 ' -bis- (2-hydroxyethoxy) -1,1' -binaphthyl (FUR-BNA), 18.4kg (42.0 mol) of BPEF, and 13.5kg (63.0 mol) of DPC as a raw material. The physical property values of the obtained resin are shown in table 3.

(example 11)

The same operation as in example 1 was carried out except for using 13.3kg (18.0 mol) of 6,6' -bis (dibenzo [ b, d ] thiophen-4-yl) -2,2 ' -bis- (2-hydroxyethoxy) -1,1' -binaphthyl (THI-BNA), 18.4kg (42.0 mol) of BPEF, and 13.5kg (63.0 mol) of DPC as a raw material. The physical property values of the obtained resin are shown in table 3.

Comparative example 1

The same operation as in example 1 was carried out except that BNE 22.5kg (60.0 moles) and DPC 13.5g (63.0 moles) were used as raw materials. The physical property values of the obtained resin are shown in table 3.

[ Table 3]

Example (b):

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

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

BNE 2,2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl

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

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

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

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

9 DPNBINOL-2 EO 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -bis (phenanthren-9-yl) -1,1' -binaphthyl

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

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

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

Comparative example:

BNE 2,2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl

[ formability ]

A: the molded plate has no gap and no surface fluctuation.

B: the molding plate has a gap.

C: the surface of the molding plate has undulation.

D: the molding sheet has a gap and a surface deformation.

[ production of polyester/polyester carbonate resin ]

(example 12)

0.090mol of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl (BINL-2EO) as a diol compound, 0.010mol of 9, 9-fluorene-dipropionic acid methyl ester (FDPM) as a dialkyl carboxylate, 0.120mol of Ethylene Glycol (EG), and 0.001mol of titanium tetrabutoxide as a transesterification catalyst were put into a reaction vessel equipped with a mixer Sealing mixer UZU manufactured by Miura scientific and instruments industries, which is equipped with a half-moon-shaped stirring paddle, and a distillation apparatus, and heated to 180 ℃ under normal pressure in a nitrogen atmosphere, and stirred for 30 minutes. Thereafter, the temperature was raised to 250 ℃ over 1 hour, and the pressure was reduced to 0.13kPa, to carry out polymerization. Thereafter, the reaction mixture was held at 250 ℃ and 0.13kPa for 1 hour, and then the contents were taken out of the reactor to obtain a polyester resin. The physical property values of the obtained polyester resin are shown in table 3.

(examples 13 to 18, comparative example 2)

A polyester resin was obtained in the same manner as in example 12, except that the diol compounds shown in table 3 were used as the diol compounds. The physical property values of the obtained polyester resin are shown in table 3.

(example 19)

0.110mol of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl (BINL-2EO) as a diol compound, 0.100mol of 9, 9-fluorene-dipropionic acid methyl ester (FDPM) as a dialkyl carboxylate, 0.010mol of diphenyl carbonate, and 0.001mol of titanium tetrabutoxide as a transesterification catalyst were charged into a reaction vessel equipped with a stirring mixer Sealing mixer UZU manufactured by Mitsu scientific and instruments, Inc. having a half-moon-shaped stirring paddle and a distillation apparatus, and heated to 180 ℃ under a nitrogen atmosphere and stirred for 60 minutes. Distillation of phenol and methanol was confirmed. Thereafter, the temperature was raised to 240 ℃ over 1 hour, and the pressure was reduced to 0.13kPa, to carry out polymerization. Thereafter, after keeping at 240 ℃ under 0.13kPa for 1 hour, the contents were taken out of the reactor to obtain a polyestercarbonate resin. The physical property values of the obtained polyester carbonate resin are shown in table 3.

(example 20)

0.10mol of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl (BINL-2EO) as a diol compound, 0.06mol of Ethylene Glycol (EG), 0.12mol of 2,2 ' -bis (hydroxycarbonylmethoxy) -1,1' -binaphthyl (BINOL-DC) as a dicarboxylic acid, and 0.001mol of titanium tetrabutoxide as a catalyst were charged into a reaction vessel equipped with a stirrer and a distillation apparatus, heated to 180 ℃ under normal pressure in a nitrogen atmosphere, and stirred for 30 minutes. Thereafter, the temperature was raised to 255 ℃ and the pressure was reduced to 0.13kPa or less, thereby carrying out the polymerization reaction. Thereafter, the reaction mixture was held at 255 ℃ and 0.13kPa for 1 hour, and then the contents were taken out of the reactor to obtain a polyester resin. The physical property values of the obtained polyester resin are shown in table 4.

[ Table 4]

Dihydroxy Compound which can be further added

[ production of monomer ]

Example 21 preparation of form A

Step 1: hydroxyethylation of 6,6'-dibromo-1,1' -bis (2-naphthol) (6,6'-dibromo-1,1' -bis (2-naphthol))

A nitrogen-purged vessel was charged with 1053kg of anisole, 157.6kg of 6,6'-dibromo-1,1' -bis (2-naphthol) (commercially available), 14.6kg of potassium carbonate and 97kg of ethylene carbonate. After the addition of the starting material was completed, the vessel was heated in such a way that the internal temperature reached 125-135 ℃. The reaction starts at about 80-90 ℃ as indicated by the generation of gas. The reaction mixture was maintained at 125-135 ℃ for 40 hours until TLC indicated complete conversion. The reaction mixture was cooled in such a way that the internal temperature reached 75 ℃. 145kg of water was slowly added. The mixture was heated to 80 ℃ and stirred at this temperature for a further 30 minutes. After stirring was stopped, layer separation occurred after 25 minutes. After the layer separation was completed, the lower aqueous layer was removed. To the organic layer remaining in the vessel was added 164kg of sodium hydroxide solution (20% (w/w)), and the mixture was stirred at 90 ℃ for 2 hours (reflux condenser). After 2 hours, the vessel was cooled to 80 ℃ and stirring was stopped, after 25 minutes layer separation occurred. The lower, substantially aqueous layer is removed. The organic layer was further washed with 160kg of water and 25kg of sodium chloride (80 ℃, 30 minutes), and then the layer was separated for 20 minutes. The aqueous layer was removed.

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

Step 2: preparation of 6,6' -DPBHBNA Using Suzuki coupling (Suzuki coupling)

A catalyst solution was prepared by dissolving 84g of tri-o-tolylphosphine (tris- (o-tolyl) phosphine) and 15g of palladium (II) acetate in 1.5kg of anisole.

In the first reaction vessel, the anisole solution of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -dibromo-1,1' -binaphthyl obtained in step 1 was heated to 60 ℃ and 93.4kg of phenylboronic acid (phenylboronic acid) was added. The mixture was stirred for 15 minutes until the phenylboronic acid was completely dissolved. Thereafter, the mixture was cooled to 40 ℃ to 50 ℃.

In a second reaction vessel, 520kg of a 31% (w/w) aqueous solution of tripotassium phosphate (tripotassium phosphate) was heated to 50 ℃. Thereafter, a catalyst solution prepared in advance was gradually added. This causes a temperature rise of about 15 ℃ as a whole. After the catalyst was added, the mixture was stirred at 60 to 70 ℃ for 1 hour. Thereafter, the remaining 70% of the reaction mixture from vessel 1 was slowly added to the reaction vessel at 55-75 ℃. After the end of the addition, the mixture was stirred at 60 ℃ for a further 1 hour. TLC showed the conversion was complete. Layer separation occurs after 30 minutes at 50-60 ℃. The lower aqueous layer was removed. To the organic layer, 186kg of water and 125kg of a 20 wt% aqueous solution of sodium hydroxide were added. The mixture was stirred at 55 ℃ for 40 minutes. Thereafter, the mixture was subjected to layer separation, and the lower substantially aqueous layer was removed.

Further, 182kg of 2M hydrochloric acid was added to the organic layer, and the mixture was stirred at 50 to 60 ℃ for 30 minutes. Layer separation occurs and the lower acidic aqueous layer is removed. The organic layer was further washed with 182kg of 25 wt% brine at 50 to 60 ℃. Mixing the organic layer of the residue with 10kg of activated carbon (C) at 60-70 ℃DX Ultra) was treated with 50kg of sodium sulfate while stirring for 90 minutes. In order to prevent precipitation of the product, the mixture is filtered through a pressure filter at 60 to 70 ℃ (6,6' -DPBHBNA can form polyhedral crystals by crystallization from anisole, but the crystals do not have a specific composition and the yield is low).

After that, the filtrate (about 2500L) was transferred to a distiller. Anisole was distilled off at a temperature of over 80 ℃ and 90 millibar (mbar) until approximately 200L of residue remained. The anisole can be recycled. After the vacuum was released, the residue was cooled to 55 ℃. At this temperature, 140kg of methanol and 60kg of toluene were added. And heating the mixture to 60-65 ℃ while stirring until the precipitate is dissolved and the solution is uniform. After the mixture reached complete homogeneity, the vessel was cooled to 20 ℃. At a temperature of about 35 to 40 ℃, 40g of 6,6' -DPBHBNA was added to the solution as a seed crystal to start crystallization. The mixture was cooled to 20 ℃ and stirred at 20 ℃ for 4 hours. Thereafter, the precipitate was recovered by centrifugation, and the filter cake (filter cake) was washed with 210 kg of methanol.

Thus, 162kg of 6,6 '-DPBHBNA (loss on drying: 15%) was obtained, which was 137kg of dried 6,6' -DPBHBNA, and the yield by two steps corresponded to 74%. The chemical purity of the obtained 6,6' -DPBHBNA was 98% as determined by UPLC.

And step 3: purification/recrystallization of 6,6' -DPBHBNA

6,6' -DPBHBNA (142kg, 270 mol; purity; 98.0%) obtained by the method of step 2 was dissolved in a mixture of methanol/toluene (7: 3 (v/v); 827 kg). The solution was treated with activated carbon (8kg) at 55 ℃ for 2 hours. The activated carbon was removed by filtration, and the filtrate was cooled to 0 ℃ over 4 hours with stirring, and further stirred at 0 ℃ for 1 hour. This crystallized 6,6' -DPBHBNA. The crystals of 6,6' -DPBHBNA were collected by filtration and washed with methanol to give 154kg of 2,2 ' -Bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl (Bis-2,2 ' - (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -bisnaphyl) (LOD: 14%; 252 mol; UPLC chemical purity; 98.8%).

The 6,6' -DPBHBNA thus obtained was dissolved in a mixture of methanol/toluene (7: 3 (v/v); 772kg), and the solution was treated again with activated carbon (7kg) at 55 ℃ for 2 hours. The activated carbon was removed by filtration, and the filtrate was cooled to 0 ℃ over 5 hours with stirring, and further stirred at 0 ℃ for 1 hour. The solid was collected by filtration and washed with methanol to give 131.4kg of 6,6' -DPBHBNA (LOD: 14%; 220 mol; UPLC chemical purity; 99%). The product was identified as methanol solvate by PXRD.

And 4, step 4: conversion of methanol solvate of 6,6' -DPBHBNA to form A

The obtained 48kg of methanol solvate of crystalline 6,6 '-DPBHBNA was dried at 40 ℃ for 5 days in air to obtain 41.3kg of crystalline 6,6' -DPBHBNA in the form of compact crystals having a size in the range of 5 to 200 μm.

The product obtained in step 4 contained a solvent composition of 0.03% b.w. methanol and 0.3% b.w. toluene, as determined by GC, i.e., a solvent composition of 0.03% by weight methanol and 0.3% by weight toluene based on the weight of 6,6' -DPBHBNA (2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl) (100% by weight relative to 6,6' -DPBHBNA).

The product of step 4 was analyzed using PXRD. The PXRD is shown in fig. 2, which identifies the crystalline form as form a. The following reflection peaks were observed.

[ Table 5]

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

Denotes relative intensity.

As evident by UPLC, the product of step 4 contains 99.1% b.w. 6,6' -DPBHBNA, 0.06% b.w. (0.06 wt.%) 6,6' -DPMHBNA, and 0.19% b.w. (0.19 wt.%) 6,6' -DPTHBNA.

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

The product of step 4 was analyzed using IR and NIR. NIR is shown in FIG. 3 and IR is shown in FIG. 4. In the NIR, approximately 7000 and 4500cm^-1The phase (hibit) of (a) is characteristic of form a, showing clear differences from solvates.

The DSC of the product of step 4 shows an endothermic peak with an onset point at 113.6 ℃, a peak maximum at 124.4 ℃, and a reaction point at 112.9 ℃. Melting points were measured immediately, and the melting points shown were 127.0 ℃, 126.5 ℃ and 126.8 ℃. DSC is shown in FIG. 5.

Example 22 preparation of methanol solvate of 6,6' -DPBHBNA

20g of 6,6' -DPBHBNA (UPLC chemical purity; > 99%) obtained in step 4 of example 21 were dissolved in 600ml of pure methanol and heated under reflux. When the homogeneous solution is slowly cooled to 22 ℃,6, 6 '-DPBHBNA is crystallized to precipitate 6,6' -DPBHBNA having a compact crystal form with a size in the range of 10 to 200 μm. The crystals were collected by filtration, washed with methanol, and air-dried at 25 ℃ for 2 days to obtain 2,2 '-bis (2-hydroxyethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl containing 5.98% b.w. of methanol, which was equivalent to a molar ratio of 6,6' -DPBHBNA to methanol of about 1: 1 (i.e., 6 '-DPBHBNA (2, 2' -bis (2-hydroxyethoxy) -6,6 '-diphenyl-1, 1' -binaphthyl) (i.e., 6 '-dpbha containing 5.98% by weight of methanol based on 100% by weight of 6,6' -dpbha)).

The product thus obtained was analyzed by PXRD. As shown in fig. 6, this PXRD clearly shows that the product is a substance having a crystal form different from form a and form C, and the following reflection peaks are observed.

[ Table 6]

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

Denotes relative intensity.

The product thus obtained was analyzed by IR and NIR. NIR is shown in FIG. 7 and IR is shown in FIG. 8. In the NIR, about 4500 and 4300cm^-1The phase (hibit) of (a) is characteristic of methanol solvates, showing clear differences from form a and other solvates.

The DSC of the product thus obtained showed an endothermic peak having an onset point at 100.9 ℃, a peak maximum at 113.4 ℃ and a reaction point at 108.3 ℃. Melting points were measured immediately, and melting points indicated were 107.4 ℃, 108.7 ℃ and 107.7 ℃. DSC is shown in FIG. 9.

Example 23 preparation of a mixture of form A and methanol solvate

Step 1: hydroxyethylation of 6,6'-dibromo-1,1' -bis (2-naphthol)

A2L 3-necked flask equipped with a stirrer, a water separator, a reflux condenser, a thermometer and a bubble counter was charged with 89.7g of 6,6'-dibromo-1,1' -bis (2-naphthol), 573g of anisole and 8.3g of K₂CO₃And 52.8g of ethylene carbonate, the reaction mixture was heated under reflux (internal temperature 125 ℃ C.) and stirred for 6 hours. It was confirmed that a certain amount of gas was generated. The progress of the reaction was monitored by TLC. After the reaction was completed, the reaction mixture was cooled to 70 to 80 ℃, 75g of water and 25g of brine were added, and the mixture was stirred at that temperature for another 20 minutes. After layer separation, 15% b.w. aqueous NaOH (110g) was added to the organic layer and the mixture was stirred at 95 ℃ for 3 hours. After layer separation, the organic layer was washed with an aqueous solution prepared from 110g of water and 25g of brine. The organic layer obtained after layer separation was used directly in the following step without isolation of the compound.

Step 2: preparation of 6,6' -DPBHBNA Using Suzuki coupling (Suzuki coupling)

In a 2L 3-neck flask equipped with a stirrer, a reflux condenser and a thermometer, the organic solution obtained in the previous step 1 was charged, and 50.0g of phenylboronic acid (phenylboronic acid), K₃PO₄(93.4g) and water (210g) and the mixture was heated to an internal temperature of 60 ℃. Thereafter, 49mg of tri-o-tolylphosphine (tris- (o-tolyl) phosphine) and 9mg of palladium (II) acetate were added with vigorous stirring. The reaction mixture was slowly heated to reflux and the progress of the reaction was monitored by TLC. After the reaction was complete (after 30 minutes to 1 hour), the mixture was cooled to 70 ℃ and the aqueous layer was separated and removed. The organic layer was washed successively with 150ml of 10% b.w. aqueous NaOH, 2M aqueous HCl (87.5ml), and again with brine (75 ml). Thereafter, the organic layer was treated with 2.5g of activated carbon and dried over sodium sulfate (12.5 g). After filtration, the solvent was evaporated in vacuo and the residue was crystallized from a mixture of methanol (77g) and toluene (33 g). Thus, a crystalline product is obtainedThe material was collected by filtration.

Thus, 110g of wet 6,6 '-DPBHBNA (loss on drying: 15%) was obtained, which was 93.5g of dry 6,6' -DPBHBNA, and the yield by two steps corresponded to 89%. The chemical purity of the obtained 6,6' -DPBHBNA was 98% as determined by UPLC.

And step 3: purification/recrystallization of 6,6' -DPBHBNA

107g of 6,6' -DPBHBNA (purity; 98.0%) obtained by the method of step 2 were dissolved in a mixture of methanol/toluene (7: 3 (v/v); 535 g). The solution was treated with activated carbon (5.4g) at 55 ℃ for 2 hours. The activated carbon was removed by filtration, and the filtrate was cooled to 0 ℃ with stirring, and stirred at 0 ℃ for 1 hour and 30 minutes. As a result, 6' -DPBHBNA is crystallized in a compact crystal form having a size in the range of 5 to 150 μm. The solid was collected by filtration, washed with methanol, and dried evening-out in air at room temperature to give 85.0g of 6,6' -DPBHBNA with a chemical purity (UPLC) of 99.89% and a yellowness YI of 2.1.

The product obtained in step 3 contained 2.4% b.w. of methanol, 0.1% b.w. of toluene and 0.002% b.w. of anisole as a solvent component (i.e., 6 '-DPBHBNA containing 2.4% by weight of methanol, 0.1% by weight of toluene and 0.002% by weight of anisole based on the weight of 6,6' -DPBHBNA (2,2 '-bis (2-hydroxyethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl) (relative to 100% by weight of 6,6' -DPBHBNA)), as determined by GC.

The product of step 3 was analyzed using PXRD. The PXRD pattern is shown in figure 10, confirming that the crystalline form of the product is a mixture of form a and methanol solvate. The following reflection peaks were observed.

[ Table 7]

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

Denotes relative intensity.

The product of step 3 was analyzed using IR and NIR. NIR is shown in FIG. 11 and IR is shown in FIG. 12. In the NIR, about 4500 and 4300cm^-1The phase (hibit) of (a) is characteristic of methanol solvate.

The DSC of the product of step 3 shows a first endothermic peak with an onset at 97.3 ℃, a peak maximum at 109.8 ℃ and a reaction point at 109.8 ℃, and a second peak with an onset at 118.9 ℃, a peak maximum at 124.4 ℃ and a reaction point at 121.4 ℃. Melting points were measured immediately, and the indicated melting points were 118.6 ℃, 119.4 ℃ and 116.7 ℃. The DSC is shown in FIG. 13.

Example 24 preparation of toluene solvate of 6,6' -DPBHBNA

20g of 6,6' -DPBHBNA (UPLC chemical purity; > 99.0%) obtained in step 4 of example 21 were dissolved in 60ml of pure toluene and heated under reflux. When the homogeneous solution is slowly cooled to 22 ℃,6, 6 '-DPBHBNA is crystallized to precipitate 6,6' -DPBHBNA having a compact crystal form with a size in the range of 20 to 250 μm. The crystals were collected by filtration, washed with methanol and air-dried at 25 ℃ for 2 days to give a solution corresponding to 6,6' -DPBHBNA: toluene molar ratio of about 2.95: 1,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl containing 5.6% b.w. toluene. A micrograph of the thus-obtained crystal is shown in fig. 14.

The product thus obtained was analyzed by PXRD. As shown in fig. 15, this PXRD clearly shows that the product is a substance having a crystal form different from form a, and the following reflection peaks are observed.

[ Table 8]

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

Denotes relative intensity.

The product thus obtained was analyzed by IR and NIR. NIR is shown in FIG. 16 and IR is shown in FIG. 17. In the NIR, approximately 7000 and 4700cm^－1Phase (hibit) of (a) is characteristic of toluene solvate, showing clear differences from form a, form B and other solvates.

The DSC of the product thus obtained showed an endothermic peak having an onset point at 106.5 ℃, a peak maximum at 113.6 ℃ and a reaction point at 110.7 ℃. The melting points were measured immediately, and the melting points were 103 to 107.9 ℃, 104.0 to 106.8 ℃ and 104.8 to 107.6 ℃. DSC is shown in FIG. 18.

Example 25 preparation of MEK solvate of 6,6' -DPBHBNA

100g of 6,6' -DPBHBNA (UPLC chemical purity; > 99.0%) obtained in step 4 of example 21 were dissolved in 300ml of pure MEK and heated under reflux. When the homogeneous solution is slowly cooled to 22 ℃,6, 6 '-DPBHBNA is crystallized to precipitate 6,6' -DPBHBNA having a compact crystal form with a size in the range of 20 to 200 μm. The crystals were collected by filtration, washed with MEK, air-dried at 25 ℃ for 2 days, and then dried at 50 ℃ for 1 hour to obtain 2,2 '-bis (2-hydroxyethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl containing 8.5% b.w. MEK as the substance at a molar ratio of 6,6' -DPBHBNA to MEK of about 1.5: 1. A micrograph of the thus-obtained crystal is shown in fig. 19.

The product thus obtained was analyzed by NIR. NIR is shown in FIG. 20. In the NIR, 4600cm^－1Phase (hibit) of (a) is characteristic of MEK solvates, showing clear differences from form a and other solvates.

The DSC of the product thus obtained showed an endothermic peak having an onset at 89.4 ℃, a peak maximum at 97.6 ℃ and a reaction point at 95.5 ℃. Melting points were measured immediately, and the melting points shown were 105.9 ℃ and 105.8 ℃. DSC is shown in FIG. 21.

The product of example 25 thus obtained was analyzed by PXRD. As shown in fig. 22, this PXRD clearly shows that the product is a substance having a crystal form different from form a and form B, and the following reflection peaks are observed.

[ Table 9]

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

Denotes relative intensity.

Example 26 preparation of amorphous form B of 6,6' -DPBHBNA

100g of 6,6' -DPBHBNA (UPLC chemical purity; > 99.0%) obtained in step 4 of example 21 were heated to 130 ℃ to obtain a clear melt. The melt was immediately cooled to 22 ℃ within 2 minutes, thereby obtaining an amorphous (glass) solid. The amorphous solid was crushed to form small pieces, and the pieces were ground with a mortar to obtain powder.

The product thus obtained was analyzed by PXRD. As shown in fig. 23, PXRD clearly shows that no crystalline layer exists as evidenced by the absence of reflection peaks in the range of 5 ° to 40 ° of 2 θ. In contrast, a wide halo (halo) is observed in this 2 θ range.

The product thus obtained was analyzed by IR and NIR. NIR is shown in FIG. 24 and IR is shown in FIG. 25.

The DSC (not shown) of the product thus obtained shows no endothermic peak at a temperature of 80 to 200 ℃. In contrast, a step (step) corresponding to the glass transition temperature was observed in the range of 109 to 110 ℃.

Example 27 preparation of form C of 6,6' -DPBHBNA

Example 27a

20g of 6,6' -DPBHBNA (UPLC chemical purity; > 99.0%) obtained in step 4 of example 21 were dissolved in 300ml of 96% ethanol and heated under reflux. When the homogeneous solution is slowly cooled to 22 ℃,6, 6 '-DPBHBNA is crystallized to precipitate 6,6' -DPBHBNA having a compact crystal form with a size in the range of 2 to 150 μm. The crystals were collected by filtration, washed with MEK, and dried at 25 ℃ for 2 days using air, followed by drying at 50 ℃ for 1 hour to give 15.8g of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl containing no detectable amount of ethanol.

Example 27b

30g of 6,6' -DPBHBNA (UPLC chemical purity; > 99.0%) obtained in step 4 of example 21 were dissolved in 250ml of anisole at 100 ℃. When the homogeneous solution is cooled very slowly to 22 ℃,6, 6 '-DPBHBNA crystallizes out 6,6' -DPBHBNA having a compact crystalline form with a size in the range of 10 to 300 μm. The crystals were collected by filtration, washed with cooled anisole and dried in a rotary evaporator at 80 ℃ over 19 hours to give 11.4g of 2,2 ' -bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1' -binaphthyl containing a very small amount of anisole (about 0.1% by weight) and no other solvents.

The product obtained in example 27a was analyzed using PXRD. As shown in fig. 26, the PXRD of the product clearly showed the following reflection peak, which is the same as PXRD of the toluene solvate but different from form a and other solvates.

[ Table 10]

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

Denotes relative intensity.

The product obtained in example 27b was analyzed using PXRD. The PXRD showed the same reflection peak and phase (sign) as the product obtained in example 27a, confirming that the crystals obtained in example 27a and example 27b are the same crystal morphology.

The product obtained in example 27a was analyzed using IR and NIR. NIR is shown in FIG. 27 and IR is shown in FIG. 28. In the NIR, approximately 7000 and 4700cm^-1Is characteristic of form C, showing clear differences from forms a and B and solvates other than toluene solvate. The product obtained in example 27b was also analyzed using IR and NIR. These spectra show the same phase as the product obtained in example 27 a.

DSC of the product obtained in example 27a shows an endothermic peak with an onset at 116.6 ℃, a peak maximum at 125.0 ℃ and a reaction point at 121.0 ℃. The DSC of the product obtained in example 27a is shown in figure 29. DSC of the product obtained in example 27b shows an endothermic peak with an onset point at 115.4 ℃, a peak maximum at 124.0 ℃ and a reaction point at 120.0 ℃.

[ production of polycarbonate resin composition Using monomers of the above examples ]

(example 28)

As the starting material, BINL-2EO as "form A" obtained in example 21, namely 6, 6-7.9kg (15.0 moles) of DPBHBNA, 16.8kg (45.0 moles) of BNE, 21.5kg (40.0 moles) of BNEF, 22.1kg (103.0 moles) of DPC and 0.117g (13.9X 10 mol) of sodium bicarbonate^－4Molal) was charged into a 50-liter reactor equipped with a stirrer and a distillation apparatus via a hopper with a spatula. Thereafter, the reactor was charged with nitrogen, the pressure in the reactor was increased to 780mmHg, the pressure was maintained for 3 minutes, and then nitrogen was discharged from the vent port to return to 760 mmHg. The reactor was again charged with nitrogen, and after 3 minutes, nitrogen was purged through the vent and returned to 760 mmHg. After that, the reactor was charged with nitrogen again, and after keeping for 3 minutes, the nitrogen was purged through the vent and returned to 760 mmHg. Thereafter, the mixture was heated to 180 ℃ under a nitrogen atmosphere of 760 mmHg. After the completion of the dissolution of the starting material was confirmed after 20 minutes from the initiation of heating, the mixture was stirred under these conditions for 120 minutes. Thereafter, the temperature was raised to 200 ℃ at a rate of 60 ℃/hr while the reduced pressure was adjusted to 200 mmHg. At this time, it was confirmed that the by-produced phenol started to distill off. Thereafter, the reaction was carried out at 200 ℃ for 40 minutes. Then, the temperature was increased to 240 ℃ at a rate of 75 ℃/hr, and after the completion of the temperature increase for 10 minutes, the reduced pressure was maintained at 1mmHg or less for 1 hour while maintaining the temperature. Then, the temperature was raised to 245 ℃ at a rate of 60 ℃/hr, and the mixture was stirred for 30 minutes. After the reaction, nitrogen was introduced into the reactor and the pressure was returned to normal pressure, and the polycarbonate resin produced was taken out while being pelletized. The Mw of the pellets was 27500.

The obtained polycarbonate resin pellets were dried at 100 ℃ for 3 hours, and it was confirmed that the water content in the pellets reached 1% by a Karl Fischer meter. The dried pellets were mixed with 1000ppm of pentaerythritol-tetrakis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (AO-60: antioxidant manufactured by ADEKA Co., Ltd.), 1500ppm of glycerol monostearate (S-100A: mold release agent manufactured by Rikawa vitamin Co., Ltd.) and 300ppm of 3, 9-bis (2, 6-di-tert-butyl-4-methylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane (PEP-36: antioxidant manufactured by ADEKA Co., Ltd.) as additives, and the additives were added to the dried pellets. Thereafter, the mixture was melt-kneaded and pelletized by a twin-screw extruder under reduced pressure of 40 mmHg.

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

The physical properties of the polycarbonate resin obtained in example 28 are shown in table 11 together with the physical properties of the resins of other examples and the like.

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

(example 29)

As raw materials, BINL-2EO 12.6kg (24.0mol), BNE 11.1kg (30.0mol), BNEF 17.8kg (33.0mol), 2 DNBINOL-2 EO 8.1kg (13.0mol), DPC 22.1kg (103.0 mol) and sodium hydrogen carbonate 0.117g (13.9X 10 mol)^－4Moles) of the polycarbonate resin, a polycarbonate composition was obtained in the same manner as in example 28.

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

The physical properties of the polycarbonate resin obtained in example 29 are shown in table 11.

(2DNBINOL－2EO)

[ Table 11]

(examples 30 to 36)

As the raw materials, BINL-2EO shown in the following table, that is, 6' -DPBHBNA 78.99g (0.15 mol), BNE 168.50g (0.45 mol), BNEF 215.45g (0.40 mol), DPC 220.64g (1.030 mol), and sodium hydrogencarbonate 1.2mg (1.3 mg)9×10^－5Mols/made into an aqueous solution) was charged through a funnel into a 1-liter reactor equipped with a stirrer and a distillation apparatus. Thereafter, the reactor was charged with nitrogen, the pressure in the reactor was increased to 780mmHg, the pressure was maintained for 3 minutes, and then nitrogen was discharged from the vent port to return to 760 mmHg. The reactor was again charged with nitrogen, and after 3 minutes, nitrogen was purged through the vent and returned to 760 mmHg. After that, the reactor was charged with nitrogen again, and after keeping for 3 minutes, the nitrogen was purged through the vent and returned to 760 mmHg. Thereafter, the mixture was heated to 180 ℃ under a nitrogen atmosphere of 760 mmHg. After the completion of the dissolution of the starting material was confirmed after 20 minutes from the initiation of heating, the mixture was stirred under these conditions for 120 minutes. Thereafter, the temperature was raised to 200 ℃ at a rate of 60 ℃/hr while the reduced pressure was adjusted to 200 mmHg. At this time, it was confirmed that the by-produced phenol started to distill off. Thereafter, the reaction was carried out at 200 ℃ for 40 minutes. Then, the temperature was increased to 240 ℃ at a rate of 75 ℃/hr, and after the completion of the temperature increase for 10 minutes, the reduced pressure was maintained at 1mmHg or less for 1 hour while maintaining the temperature. Then, the temperature was raised to 245 ℃ at a rate of 60 ℃/hr, and the mixture was stirred for 30 minutes. After the reaction, nitrogen was introduced into the reactor to return to normal pressure, and the produced polycarbonate resin was taken out. The optical properties of the obtained resin were the same as those of example 28, but the molecular weights reached were slightly different.

[ Table 12]

(reference example)

In step 3 of example 23, "after-evening-out was dried in air at room temperature by washing with methanol", the drying time was shortened to obtain BINL-2EO containing 1.3 moles of methanol per 1 mole of 2,2 '-bis (2-hydroxyethoxy) -6, 6' -diphenyl-1,1 '-binaphthyl, that is, 6' -DPBHBNA. The reaction was attempted in the same manner as in additional example 1, except that the main raw material was replaced with the thus-obtained BINL-2EO (6,6' -DPBHBNA).

As a result, when the raw material was charged into the reactor through the hopper with a spatula, smooth charging was not easy, the operability was poor, the progress of the reaction was slow, and Mw was as low as 2450 as that of example 28, which is the pellet obtained.

Fig. 30 and 31 show graphs in which abbe number (v) is plotted on the horizontal axis and refractive index (nD) is plotted on the vertical axis, among properties of the thermoplastic resins obtained in examples and comparative examples.

The particular ranges shown in these graphs may be, for example,

between line nD-0.02 v +1.96 and line nD-0.02 v +2.04 in fig. 30, or

In fig. 31, a plurality of examples were marked between the straight line nD of-0.0002 ν +1.6718 and the straight line nD of-0.024 ν +2.124, or between the straight line nD of-0.004 v +1.744 and the straight line y of-0.02 x +2.04, and it was confirmed that in each example, the balance between the abbe number and the refractive index was good, and a thermoplastic resin suitable for optical use was realized.

For example, in FIG. 31, the refractive index is higher than 1.660, the Abbe number is lower than 19 or less, for example, in the region of 13 to 19 or 15 to 19, and

the polycarbonate resin which is plotted in a region between a straight line nD of-0.0002 v +1.6718 and a straight line nD of-0.024 v +2.124 and satisfies a relationship of-0.0002 v +1.6718 < nD < -0.024 v +2.124 has a preferable shape,

the polycarbonate resin which satisfies the relationship of-0.004 v +1.744 < nD < -0.024 v +2.124, plotted in the region between the straight line nD-0.004 v +1.744 and the straight line nD-0.024 v +2.124, has a more preferable property,

the polycarbonate resin which is plotted in the region between the straight line nD-0.02 v +2.04 and the straight line nD-0.024 v +2.124 and satisfies the relationship of-0.02 v +2.04 < nD < -0.024 v +2.124 has more preferable properties.

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