CN118215702A

CN118215702A - Thermoplastic resin and optical lens comprising the same

Info

Publication number: CN118215702A
Application number: CN202280074108.8A
Authority: CN
Inventors: 加藤宣之; 西森克吏; 茂木笃志; 石原健太朗; 村田铃木章子; 新井雄太; 佐藤淳广
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2021-11-12
Filing date: 2022-11-10
Publication date: 2024-06-18

Abstract

According to the present invention, there can be provided a thermoplastic resin comprising 22 to 49 mol% of a structural unit (a) derived from a diol represented by the following general formula (1A), 40 to 75 mol% of a structural unit (B) derived from a diol represented by the following general formula (2A), and 0 to 15 mol% of a structural unit (C) derived from a diol represented by the following general formula (3A), based on the total amount (100 mol%) of the structural units in the resin.

Description

Thermoplastic resin and optical lens comprising the same

Technical Field

The present invention relates to a thermoplastic resin and an optical lens comprising the same. More particularly, the present invention relates to a polycarbonate resin and an optical lens comprising the same.

Background

As a material of an optical lens used in an optical system of various cameras such as a camera, a film-integrated camera, a video camera, and the like, an optical glass or an optical resin is used. The optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., 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 mass production can be performed by injection molding, and as a high refractive index material for a camera lens, polycarbonate, polyester carbonate, polyester resin, or the like is used.

When an optical resin is used as an optical lens, it is required to have heat resistance, transparency, low water absorption, chemical resistance, low birefringence, moist heat resistance, and the like in addition to optical characteristics such as refractive index and abbe number. In particular, in recent years, optical lenses having a high refractive index and high heat resistance have been demanded, and various resins have been developed (patent documents 1 to 5).

In addition, thermoplastic resins using 2,2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl as a raw material have excellent optical characteristics and are useful as various optical materials (patent document 6). However, due to the expansion of various molding processes and use environments, it is required to increase the birefringence in the lens surface.

In recent years, development of resins having a high refractive index has been demanded due to the thinness, shortness and smallness of the articles. In general, when the refractive index of the optical material is high, a lens element having the same refractive index can be realized with a surface having a smaller curvature, and thus the amount of aberration generated by the surface can be reduced. As a result, the number of lenses can be reduced, the decentering sensitivity of the lenses can be reduced, and the thickness of the lenses can be reduced, thereby realizing weight reduction.

In addition, in general, in an optical system of a camera, aberration correction is performed by combining a plurality of concave lenses and convex lenses. That is, for chromatic aberration generated by the convex lens, chromatic aberration is synthetically canceled by combining the convex lens with a concave lens having chromatic aberration of opposite sign. At this time, the concave lens is required to have high dispersion (i.e., low abbe number).

Therefore, a resin for an optical lens having a high refractive index and a low abbe number has been developed. For example, patent document 7 discloses that a copolymer of a bisphenol a type polycarbonate structural unit and a structural unit represented by the following formula (E) improves the refractive index. In the example of patent document 7, it is described that the refractive index reaches 1.62 to 1.64 and the abbe number reaches 23 to 26. Such an increase in refractive index is thought to be due to the structural unit represented by formula (E).

Further, patent document 8 discloses a copolymer of a polycarbonate resin having a structural unit having a fluorene structure and bisphenol a. Examples of this document describe refractive indices up to 1.616 to 1.636. The structural unit disclosed in this document is different from the formula (E).

As described above, polycarbonate resins and optical lenses having a high refractive index and a low abbe number have not been provided yet.

In recent years, a polycarbonate resin and an optical lens having a small absolute value of birefringence strength and a small in-plane birefringence have been demanded.

Prior art literature

Patent literature

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

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

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

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

Patent document 5: WO2017/078073

Patent document 6: WO2014/073496

Patent document 7: international publication No. 2007/142149

Patent document 8: japanese patent laid-open No. 6-25398

Disclosure of Invention

Technical problem to be solved by the invention

The technical problems to be solved by the invention are as follows: provided are a thermoplastic resin which has excellent optical characteristics such as refractive index, abbe number and haze and also has excellent birefringence in a lens surface, and an optical lens using the same. Moreover, the technical problems to be solved by the invention are as follows: provided are a polycarbonate resin having a high refractive index and a low Abbe number, and having a small absolute value of birefringence strength and a small in-plane birefringence, and an optical lens using the same.

Technical scheme for solving technical problems

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that: the present invention has been completed by adding a diol compound having a specific structure in a specific amount to obtain a thermoplastic resin having excellent optical characteristics such as refractive index, abbe number and haze and also excellent birefringence in the lens surface. It was also found that: the above technical problems can be solved by the following polycarbonate resin and optical lens, and the present invention has been completed.

That is, the present invention includes the following means.

<1> A thermoplastic resin comprising, relative to the total amount (100 mol%) of structural units in the resin, 22 to 49 mol% of structural units (A) derived from a diol represented by the following general formula (1A), 40 to 75 mol% of structural units (B) derived from a diol represented by the following general formula (2A), and 0 to 15 mol% of structural units (C) derived from a diol represented by the following general formula (3A),

In the general formula (1A), R _a、R_b、R_aa and R _bb are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxy group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which may have a substituent and contains 1 or more hetero ring atoms selected from O, N and S, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and-C.ident.C-R _h,

R _h represents an aryl group having 6 to 20 carbon atoms which may have a substituent or a heteroaryl group having 6 to 20 carbon atoms which may have a substituent and contains 1 or more hetero ring atoms selected from O, N and S,

X each independently represents an alkylene group having 1 to 5 carbon atoms which may have a substituent,

A and b each independently represent an integer of 0 to 10,

In the general formula (2A), R _c and R _d are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxy group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, a heteroaryl group having 6 to 30 carbon atoms which may have a substituent and contains 1 or more hetero ring atoms selected from O, N and S, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and-C.ident.C-R _h,

C and d each independently represent an integer of 0 to 10,

In the general formula (3A), R _e and R _f are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxy group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which may have a substituent and contains 1 or more hetero ring atoms selected from O, N and S, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and-C.ident.C-R _h,

E and f each independently represent an integer of 0 to 10.

<2> The thermoplastic resin according to the above <1>, wherein the proportion of the structural unit (A) derived from the diol represented by the above general formula (1A) is 24 to 47 mol%, the proportion of the structural unit (B) derived from the diol represented by the above general formula (2A) is 45 to 70 mol%, and the proportion of the structural unit (C) derived from the diol represented by the above general formula (3A) is 0 to 8 mol%, based on the total amount (100 mol%) of the structural units in the resin.

<3> The thermoplastic resin according to the above <1> or <2>, wherein the diol represented by the above general formula (1) comprises a diol represented by the following structural formula,

<4> The thermoplastic resin according to any one of the above <1> to <3>, wherein the diol represented by the above general formula (2A) comprises at least one of the diols represented by the following structural formulas,

<5> The thermoplastic resin according to any one of the above <1> to <4>, wherein the diol represented by the above general formula (3A) comprises a diol represented by the following structural formula,

<6> The thermoplastic resin according to any one of the above <1> to <5>, wherein the thermoplastic resin is a polycarbonate resin.

<7> The thermoplastic resin according to any one of the above <1> to <6>, wherein the thermoplastic resin further comprises a structural unit derived from at least one monomer selected from the group consisting of,

In the above formula, R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group or an ethyl group, and R ₃ and R ₄ each independently represent a hydrogen atom, a methyl group, an ethyl group or an alkylene glycol having 2 to 5 carbon atoms.

<8> The thermoplastic resin according to any one of <1> to <7>, wherein the thermoplastic resin has an in-lens-surface birefringence of 1 to 21.

<9> The thermoplastic resin according to any one of <1> to <8>, wherein the weight average molecular weight (Mw) of the thermoplastic resin in terms of polystyrene is 10,000 ～ 100,000.

<10> The thermoplastic resin according to any one of <1> to <9>, wherein the refractive index (nD) of the thermoplastic resin is 1.650 to 1.695.

<11> The thermoplastic resin according to any one of <1> to <10>, wherein the thermoplastic resin has an Abbe number (. Nu.) of 16.0 to 21.0.

<12> The thermoplastic resin according to any one of <1> to <11>, wherein the glass transition temperature of the thermoplastic resin is 130 to 190 ℃.

<13> The thermoplastic resin according to any one of <1> to <12>, wherein the thermoplastic resin has a melt volume flow rate (MVR) of 20 to 55.

<14> The thermoplastic resin according to any one of <1> to <13>, wherein the thermoplastic resin has a haze of 0.01 to 1.00.

<15> An optical member comprising the thermoplastic resin according to any one of the above <1> to <14 >.

<16> An optical lens comprising the thermoplastic resin according to any one of the above <1> to <14 >.

<17> An optical film comprising the thermoplastic resin according to any one of the above <1> to <14 >.

<18> A polycarbonate resin comprising a structural unit represented by the following general formula (1B), a structural unit represented by the following general formula (2B) and a structural unit represented by the following general formula (3B),

The proportion of the structural unit represented by the following general formula (1B) is 1 mol% or more and less than 10 mol%,

The proportion of the structural unit represented by the following general formula (2B) is 10 to 60 mol%,

The proportion of the structural unit represented by the following general formula (3B) is 5 to 80 mol%,

In the general formula (1B), X represents an alkylene group having 1 to 4 carbon atoms, and a and B each independently represent an integer of 1 to 10;

In the general formula (2B), Y represents an alkylene group having 1 to 4 carbon atoms, and c and d each independently represent an integer of 1 to 10;

in the general formula (3B),

Z represents an alkylene group having 1 to 4 carbon atoms,

R ₁～R₆ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms,

E and f each independently represent an integer of 0 to 5.

<19> The polycarbonate resin as described in <18> above, wherein,

The proportion of the structural unit represented by the above general formula (1B) is 2 to 9 mol%,

The proportion of the structural unit represented by the general formula (2B) is 20 to 60 mol%,

The proportion of the structural unit represented by the general formula (3B) is 30 to 70 mol%.

<20> An optical lens comprising the polycarbonate resin according to <18> or <19 >.

Effects of the invention

According to the present invention, it is possible to provide a thermoplastic resin excellent in optical characteristics such as refractive index, abbe number and haze and also excellent in-plane birefringence, and an optical lens comprising the same. Further, according to the present invention, there can be provided a polycarbonate resin having a high refractive index and a low abbe number, and having a small absolute value of birefringence and a small in-plane birefringence, and an optical lens comprising the same.

Detailed Description

The present invention will be described in detail by way of examples, and the like, but the present invention is not limited to the examples, and the like, and can be modified to any method without significantly departing from the scope of the present invention.

First embodiment

< Thermoplastic resin >

The first embodiment of the present invention is a thermoplastic resin comprising 22 to 49 mol% of a structural unit (a) derived from a diol represented by the following general formula (1A), 40 to 75 mol% of a structural unit (B) derived from a diol represented by the following general formula (2A), and 0 to 15 mol% of a structural unit (C) derived from a diol represented by the following general formula (3A), based on the total amount (100 mol%) of the structural units in the resin.

[ Structural Unit (A) derived from a diol represented by the general formula (1A) ]

In the general formula (1A), R _a、R_b、R_aa and R _bb are each independently selected from a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), an alkyl group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 6 carbon atoms) which may have a substituent, an alkoxy group having 1 to 20 carbon atoms (preferably an alkoxy group having 1 to 6 carbon atoms) which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms (preferably a cycloalkyl group having 5 to 10 carbon atoms) which may have a substituent, a cycloalkoxy group having 5 to 20 carbon atoms (preferably a cycloalkoxy group having 5 to 10 carbon atoms) which may have a substituent, an aryl group having 6 to 20 carbon atoms (preferably an aryl group having 6 to 12 carbon atoms) which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms (preferably a heteroaryl group having 6 to 12 carbon atoms) which may have a heterocyclic atom selected from O, N and S, an aryloxy group having 6 to 20 carbon atoms (preferably a c≡c) which may have a substituent, and an aryloxy group having a c≡c _h.

Preferably, R _a and R _b each independently represent a hydrogen atom, a methyl group, an ethyl group or a phenyl group, and R _aa and R _bb each independently represent a hydrogen atom or a phenyl group.

R _h in the above-mentioned-C.ident.C-R _h represents an aryl group having 6 to 20 carbon atoms (preferably an aryl group having 6 to 12 carbon atoms) which may have a substituent or a heteroaryl group having 6 to 20 carbon atoms (preferably a heteroaryl group having 6 to 12 carbon atoms) which contains 1 or more hetero ring atoms selected from O, N and S and may have a substituent.

X independently represents an alkylene group having 1 to 5 carbon atoms (preferably an alkylene group having 1 to 3 carbon atoms, more preferably an ethylene group) which may have a substituent.

A and b each independently represent an integer of 0 to 10, preferably an integer of 1 to 3, and more preferably 1.

In the present specification, examples of the substituent "which may have a substituent" include halogen, cyano, alkyl having 1 to 20 carbon atoms, and aryl having 6 to 12 carbon atoms.

In one embodiment of the present invention, the structural unit (A) derived from the diol represented by the above general formula (1A) is

When used as an optical lens, it is preferable because of good balance between refractive index and Abbe number.

The above structural units are derived from BPEF (9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene) represented by the following structural formula and OPPFL (9, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene) represented by the following structural formula, respectively, and in the present invention, commercially available products or synthetic products may be used.

[ Structural Unit (B) derived from a diol represented by the general formula (2A) ]

C and d each independently represent an integer of 0 to 10.

R _c and R _d in the general formula (2A) are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and still more preferably an aryl group having 6 to 14 carbon atoms. It is preferable that at least one of R _c and R _d in the general formula (2A) is an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and particularly preferably both of R _c and R _d are aryl groups having 6 to 14 carbon atoms or 6 to 12 carbon atoms.

R _c and R _d may be the same or different and may be selected from a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms or a monocyclic or polycyclic heterocyclic aryl group having 5 to 36 ring atoms, wherein 1,2, 3 or 4 ring atoms of the heterocyclic aryl group are selected from nitrogen, sulfur and oxygen, and the other ring atoms are carbon. Wherein the mono-or polycyclic aryl group and the mono-or polycyclic heteroaryl group may be unsubstituted.

R _c and R _d are each selected from the group described below. That is to say,

Azulene group (azulenyl);

an unsubstituted indenyl group, or an indenyl group which may be substituted with 2, 3, 4 or 5 substituents selected from phenyl groups and polycyclic aryl groups 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 saturated or unsaturated 4 to 10 membered ring monocyclic or bicyclic hydrocarbon ring and have 2, 3 or 4 benzene rings;

Unsubstituted phenyl;

Phenyl which may be substituted by 1 or 2 CN groups;

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

Polycyclic aryl groups which may be directly condensed with each other and/or may be condensed with saturated or unsaturated 4-to 10-membered monocyclic or bicyclic hydrocarbon rings and which have 2,3 or 4 benzene rings may be unsubstituted or substituted with 1 or 2 substituents selected from phenyl groups and polycyclic aryl groups having 2 or 3 benzene rings, 2 or 3 of the benzene rings may be bonded to each other by a single bond, may be directly condensed with each other and/or may be condensed with saturated 4-to 10-membered monocyclic or bicyclic hydrocarbon rings, and the benzene rings of polycyclic aryl groups may be unsubstituted or have 1 or 2 substituents R ^a.

In addition, R _c and R _d may be each selected from the following group. That is to say,

Unsubstituted phenyl, or phenyl which may be substituted by 1,2, 3, 4 or 5 phenyl groups;

phenyl substituted with 1 or 2 CN groups;

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

Unsubstituted naphthyl, or naphthyl substituted with 1 or 2 substituents selected from CN, phenyl, polycyclic aryl selected from biphenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, and pyrenyl;

A biphenyl group; a triphenyl group; tetraphenyl; phenanthryl; pyrenyl; 9H-fluorenyl; dibenzo [ a, e ] [8] cycloalkenyl, perylene, and 9,9' -spirodi [ 9H-fluorene ] groups.

Among them, R _c and R _d are preferably selected from phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-naphthyl, 1-naphthyl and 9-naphthyl.

In addition, R _c and R _d may be each selected from the following groups. That is to say,

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

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

A heteroaromatic polycyclic group having: a heterocyclic ring containing 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 further aromatic rings selected from phenyl and the above heteroaromatic monocyclic rings, at least 1 further of the above aromatic rings being directly condensed with a saturated or partially unsaturated 5-or 6-membered heterocyclic group, the other further aromatic rings of the polycyclic heteroaryl aromatic rings being bonded to each other by covalent bonds or being directly condensed with each other and/or being condensed with a saturated or unsaturated 4-to 10-membered mono-or bi-cyclic hydrocarbon ring.

In addition, R _c and R _d may be each selected from the following groups. That is to say, 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 ] furanyl, furo [2,3-b ] furanyl, furo [3,4-b ] furanyl, oxazolyl (oxanthrenyl), indolyl, isoindolyl, carbazolyl, indolizinyl, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzo [ cd ] indolyl, 1H-benzo [ g ] indolyl, quinolinyl, isoquinolinyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl phenoxazinyl, benzo [ b ] [1,5] naphthyridinyl, cinnolinyl, 1, 5-naphthyridinyl, 1, 8-naphthyridinyl, phenylpyrrolyl, naphthyridinyl, bipyridinyl, phenylpyridinyl, naphthyridinyl, pyrido [4,3-b ] indolyl, pyrido [3,2-g ] quinolinyl, pyrido [2,3-b ] [1,8] naphthyridinyl, pyrrolo [3,2-b ] pyridinyl, 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 ] quinolinyl, furo [2,3-g ] pyrrolyl, benzoo [3, 3-g ] benzopyranyl, benzoo [3,2-g ] pyrrolyl, benzopyrrolyl (xanthenyl), benzo [ g ] quinoxalinyl, benzo [ f ] quinoxalinyl and benzo [ h ] isoquinolinyl.

X in the general formula (2A) is independently preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, particularly preferably an ethylene group.

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

The diol represented by the above general formula (2A) preferably contains at least one of the diols represented by the following structural formulas.

[ Structural Unit (C) derived from a diol represented by the general formula (3A) ]

In the general formula (3A), R _e and R _f are each independently selected from a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), an alkyl group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 6 carbon atoms) which may have a substituent, an alkoxy group having 1 to 20 carbon atoms (preferably an alkoxy group having 1 to 6 carbon atoms) which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms (preferably a cycloalkyl group having 5 to 10 carbon atoms) which may have a substituent, a cycloalkoxy group having 5 to 20 carbon atoms (preferably a cycloalkoxy group having 5 to 10 carbon atoms) which may have a substituent, an aryl group having 6 to 20 carbon atoms (preferably an aryl group having 6 to 12 carbon atoms) which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms (preferably a heteroaryl group having 6 to 12 carbon atoms) which may have 1 or more hetero atoms selected from O, N and S, an aryloxy group having 6 to 20 carbon atoms (preferably a C.ident.6 to 20 carbon atoms) which may have a substituent, and a C. _h aryl group having C.ident.,

Preferably, R _e and R _f each independently represent a hydrogen atom or a phenyl group.

E and f each independently represent an integer of 0 to 10, preferably an integer of 1 to 3, more preferably 1.

In one embodiment of the present invention, it is particularly preferable that the diol represented by the above general formula (3A) is NOLE (9, 9-bis [6- (2-hydroxyethoxy) -2-naphthyl ] fluorene) represented by the following structural formula, and in the present invention, a commercially available product or a synthetic product may be used.

One embodiment of the present invention is a thermoplastic resin containing 22 to 49 mol% (preferably 22 to 47 mol%, more preferably 26 to 45 mol%) of a structural unit (a) derived from a diol represented by the above general formula (1A), 40 to 75 mol% (preferably 45 to 70 mol%, more preferably 40 to 65 mol%) of a structural unit (B) derived from a diol represented by the above general formula (2A), and 0 to 15 mol% (preferably 0 to 8 mol%, more preferably 0 to 6 mol%) of a structural unit (C) derived from a diol represented by the above general formula (3A) with respect to the total amount (100 mol%) of the structural units in the resin.

The thermoplastic resin according to one embodiment of the present invention may be a polyester resin, a polycarbonate resin, a polyester carbonate resin, an epoxy resin, a polyurethane resin, a polyacrylate resin, a polymethacrylate resin, or the like, but is not particularly limited, and is preferably a polycarbonate resin, a polyester resin, or a polyester carbonate resin, and more preferably a polycarbonate resin.

In the thermoplastic resin according to an embodiment of the present invention, the proportion of the total of the structural units (a), (B) and (C) in the total of the structural units is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, and particularly preferably 100 mol% of the total of the structural units.

That is, the thermoplastic resin according to one embodiment of the present invention may contain, in addition to the structural units (a) to (C), structural units derived from an aliphatic dihydroxy compound and/or structural units derived from an aromatic dihydroxy compound, which are generally used as structural units of a polycarbonate resin and/or a polyester carbonate resin, within a range that does not impair the effects of the present invention.

Specifically, examples of the aliphatic dihydroxy compound include various compounds, particularly 1, 4-cyclohexanedimethanol, tricyclodecanedimethanol, 1, 3-adamantanedimethanol, 2-bis (4-hydroxycyclohexyl) -propane, 3, 9-bis (2-hydroxy-1, 1-dimethylethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane, 2- (5-ethyl-5-hydroxymethyl-1, 3-dioxane-2-yl) -2-methylpropan-1-ol, isosorbide, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, and the like.

Examples of the aromatic dihydroxy compound include various compounds, particularly 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 4' -dihydroxybiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, diphenoxyglycolfluorene and the like.

The thermoplastic resin according to one embodiment of the present invention also preferably further contains a structural unit derived from at least one monomer selected from the following monomer groups.

In the polycarbonate resin according to a preferred embodiment of the present invention, alcohol compounds such as phenol compounds that are produced as by-products during production, unreacted and residual diol components or carbonic acid diester may be present as impurities.

Since alcohol compounds such as phenol compounds and carbonic acid diesters as impurities also cause a decrease in strength after forming a molded article and an odor, the content of these compounds is preferably as small as possible.

The content of the remaining phenolic compound is preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less, and particularly preferably 300 mass ppm or less, based on 100 mass% of the polycarbonate resin.

The content of the residual diol component is preferably 1000 mass ppm or less, more preferably 100 mass ppm or less, and particularly preferably 10 mass ppm or less, based on 100 mass% of the polycarbonate resin.

The content of the residual carbonic acid diester is preferably 1000 mass ppm or less, more preferably 100 mass ppm or less, and particularly preferably 10 mass ppm or less, based on 100 mass% of the polycarbonate resin.

In particular, the content of the compounds such as phenol and tert-butylphenol is preferably small, and these compounds are preferably within the above-mentioned range.

The content of the remaining phenolic compound in the polycarbonate resin can be measured by a method of analyzing the phenolic compound extracted from the polycarbonate resin by using gas chromatography.

The content of the alcohol compound remaining in the polycarbonate resin can also be measured by a method of analyzing the alcohol compound extracted from the polycarbonate resin by using gas chromatography.

The content of the diol component and the carbonic acid diester remaining in the polycarbonate resin can also be measured by extracting these compounds from the polycarbonate resin and analyzing them by gas chromatography.

The content of the by-product alcohol compound such as the phenol compound, the diol component and the carbonic acid diester can be reduced to an undetectable level, but may be contained in a small amount within a range that does not impair the effect from the viewpoint of productivity. In addition, if the amount is small, the plasticity can be improved when the resin is melted.

The content of each of the residual phenolic compound, diol component and carbonic acid diester may be, for example, 0.01 mass ppm or more, 0.1 mass ppm or more, or 1 mass ppm or more with respect to 100 mass ppm of the polycarbonate resin.

The content of the remaining alcohol compound may be, for example, 0.01 mass ppm or more, 0.1 mass ppm or more, or 1 mass ppm or more with respect to 100 mass% of the polycarbonate resin.

The content of the by-product alcohol compound such as the phenol compound, the diol component, and the carbonic acid diester in the polycarbonate resin can be adjusted to the above range by appropriately adjusting the polycondensation conditions, the setting of the apparatus, and the like. In addition, the conditions of the extrusion process after polycondensation may be adjusted.

For example, the residual amount of the by-product alcohol compound such as the phenol compound is related to the type of carbonic acid diester used in the polymerization of the polycarbonate resin, the polymerization temperature, the polymerization pressure, and the like. By adjusting these conditions, the residual amount of the by-product alcohol compound such as the phenol compound can be reduced.

For example, when a polycarbonate resin is produced using a dialkyl carbonate such as diethyl carbonate, the molecular weight tends to be less likely to increase, and the content of a by-product alkyl alcohol compound tends to increase because a low molecular weight polycarbonate is formed. Such an alkyl alcohol has high volatility, and once it remains in the polycarbonate resin, the moldability of the resin tends to be deteriorated. In addition, when the residual amount of the by-product alcohol compound such as the phenol compound is large, there is a possibility that a problem of odor generation occurs during resin molding or a cleavage reaction of the resin skeleton occurs during compounding, resulting in a decrease in molecular weight. Accordingly, the content of the by-product alcohol compound remaining in the obtained polycarbonate resin is preferably 3000 mass ppm or less with respect to the polycarbonate resin (100 mass%). The content of the remaining alcohol compound is preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less, and particularly preferably 300 mass ppm or less, based on 100 mass% of the polycarbonate resin.

< Physical Properties of thermoplastic resin >

(1) Refractive index (nD)

In one embodiment of the present invention, one of the characteristics of the thermoplastic resin is a high refractive index, preferably 1.650 to 1.695, more preferably 1.660 to 1.690, particularly preferably 1.662 to 1.689. In the present invention, the refractive index can be measured by the method described in examples described below.

(2) Abbe number (v)

In one embodiment of the present invention, the thermoplastic resin has an Abbe number of preferably 16.0 to 21.0, more preferably 16.3 to 20.5, particularly preferably 16.6 to 20.2. In the present invention, the Abbe number can be measured by the method described in examples described below.

(3) Glass transition temperature (Tg)

In one embodiment of the present invention, one of the characteristics of the thermoplastic resin is high heat resistance, and the glass transition temperature (Tg) is preferably 130 to 190 ℃, more preferably 135 to 180 ℃, particularly preferably 140 to 165 ℃. In the present invention, the glass transition temperature can be measured by the method described in examples described below.

(4) Weight average molecular weight (Mw) in terms of polystyrene

In one embodiment of the present invention, the weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably 10,000 ～ 100,000, more preferably 20,000 ～ 70,000, particularly preferably 30,000 ～ 60,000.

(5) Melt volume flow Rate (MVR)

In one embodiment of the present invention, the thermoplastic resin preferably has a melt volume flow rate (MVR) of 20 to 55, more preferably 25 to 50, particularly preferably 30 to 45. In the present invention, the melt volume flow rate (MVR) can be measured by the method described in examples described below.

(6) Haze degree

In one embodiment of the present invention, the haze of the thermoplastic resin is preferably 0.01 to 1.00, more preferably 0.05 to 0.50, and particularly preferably 0.10 to 0.30. In the present invention, haze can be measured by the method described in examples described below.

(7) Internal birefringence of lens face

In one embodiment of the present invention, the thermoplastic resin preferably has an in-lens-surface birefringence of 1 to 21, more preferably 2 to 15, and particularly preferably 2 to 13. In the present invention, the transparent in-plane birefringence can be measured by the method described in examples described below.

< Thermoplastic resin composition >

Another embodiment of the present invention is a thermoplastic resin composition containing the above thermoplastic resin and an additive. The thermoplastic resin composition of the present embodiment may be used in combination with a resin other than the thermoplastic resin of the present invention containing the above-mentioned structural units (a), (B) and (C) within a range that does not impair the intended effects of the present embodiment. The resin is not particularly limited, and examples thereof include at least one resin selected from the group consisting of polycarbonate resins, polyester carbonate resins, (meth) acrylic resins, polyamide resins, polystyrene resins, cycloolefin resins, acrylonitrile-butadiene-styrene copolymer resins, vinyl chloride resins, polyphenylene ether resins, polysulfone resins, polyacetal resins, and methyl methacrylate-styrene copolymer resins. These resins may be used in various known products, and may be added to the thermoplastic resin composition singly or in combination of two or more.

[ Antioxidant ]

The thermoplastic resin composition preferably contains an antioxidant as the above additive.

The antioxidant preferably contains at least one of a phenolic antioxidant and a phosphite antioxidant.

Examples of the phenolic antioxidants include 1,3, 5-tris (3, 5-di-t-butyl-4-hydroxyphenylmethyl) -2,4, 6-trimethylbenzene, 1,3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 4' - (1-methylpropanoyl-3-ylidene) tris (6-t-butylm-cresol), 6' -di-t-butyl-4, 4' -butylidenemethyl phenol, 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate octadecyl ester, pentaerythritol-tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 3, 9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1, 1-dimethylethyl } -2,4,8, 10-tetraoxaspiro [5.5] undecyl ] pentaerythritol-tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] pentaerythritol-tetrakis [3, 5-di-t-butyl-4-hydroxyphenyl ] propionate.

Examples of the phosphite-based antioxidant include 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, 3, 9-bis (octadecylacyloxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, 3, 9-bis (2, 6-di-tert-butyl-4-methylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, 2' -methylenebis (4, 6-di-tert-butylphenyl) 2-ethylhexyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, and tetra-C12-15 alkyl (propane-2, 2-diylbis (4, 1-phenylene)) bisphosphite, and 3, 9-bis (2, 6-di-tert-butyl-4-methylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane are preferable.

As the antioxidant, only any one of the above-mentioned may be used, or a mixture of two or more kinds may be used.

In the present invention, 5, 7-di-t-butyl-3- (3, 4-dimethylphenyl) -3H-benzofuran-2-one may be used as an antioxidant other than a phenol-based antioxidant and a phosphite-based antioxidant.

The antioxidant is preferably contained in the thermoplastic resin composition in an amount of 1 to 3000 ppm by weight based on the total weight of the resin composition. The content of the antioxidant in the thermoplastic resin composition is more preferably 50 to 2500 ppm by weight, still more preferably 100 to 2000 ppm by weight, particularly preferably 150 to 1500 ppm by weight, still more preferably 200 to 1500 ppm by weight.

[ Release agent ]

The thermoplastic resin composition preferably contains a release agent as the above additive.

Examples of the release agent include ester compounds, for example, fatty acid glycerides such as monoglycerides and diglycerides of glycerin fatty acid, glycol fatty acid esters such as propylene glycol fatty acid esters and sorbitan fatty acid esters, higher alcohol fatty acid esters, full esters of aliphatic polyhydric alcohols and aliphatic carboxylic acids, and mono fatty acid esters. When an ester of an aliphatic polyol and an aliphatic carboxylic acid is used as the release agent, any of a monoester, a full ester, and the like may be used, and for example, an ester other than the full ester such as a monoester may be used.

Specific examples of the release agent include the following.

That is, sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan tribehenate, sorbitan stearate, sorbitan tristearate, and sorbitan caprylate;

propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate and propylene glycol monopalmitate;

Higher alcohol fatty acid esters such as stearyl stearate;

Glycerol fatty acid ester monoglycerides including glycerol monostearate, glycerol mono-hydroxystearate and glycerol mono-12-hydroxystearate, glycerol monooleate, glycerol monobehenate, glycerol monocaprylate, glycerol monocaprate, monoglycerides such as glycerol monolaurate, glycerol mono/distearate, glycerol mono/dibuch, glycerol mono/dioleate and glycerol mono/diglycerol esters such as glycerol mono/dioleate;

acetylated monoglycerides of glycerol fatty acid esters such as diacetyl monolaurate;

Organic acid monoglycerides such as citric acid fatty acid monoglyceride, succinic acid fatty acid monoglyceride, diacetyl tartaric acid fatty acid monoglyceride, and the like;

Polyglyceryl fatty acid esters such as diglyceryl stearate, diglyceryl laurate, diglyceryl oleate, diglyceryl monostearate, diglyceryl monolaurate, diglyceryl monomyristate, diglyceryl monooleate, tetraglyceryl stearate, decaglyceryl laurate, decaglyceryl oleate, polyglyceryl polyricinoleate, and the like.

Among them, glycerol monostearate is preferable as the release agent.

The release agent is preferably contained in the thermoplastic resin composition in an amount of 1 to 5000 ppm by weight based on the total weight of the resin composition. The content of the release agent in the thermoplastic resin composition is more preferably 50 to 4000 ppm by weight, still more preferably 100 to 3500 ppm by weight, particularly preferably 500 to 13000 ppm by weight, still more preferably 1000 to 2500 ppm by weight.

[ Other additives ]

In addition to the above-mentioned antioxidant and release agent, other additives may be added to the thermoplastic resin composition. Examples of the additives that may be contained in the thermoplastic resin composition include complexing agents, catalyst deactivators, heat stabilizers, plasticizers, fillers, ultraviolet absorbers, rust inhibitors, dispersants, defoamers, leveling agents, flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents, clarifying agents, and the like.

The content of the antioxidant and the additive other than the release agent in the thermoplastic resin composition is preferably 10 to 5.0 wt%, more preferably 100 to 2.0 wt%, still more preferably 1000 to 1.0 wt%, but is not limited thereto.

The above additives may adversely affect the transmittance, and therefore are preferably excessively added, for example, the total amount added is within the above range.

In the method for producing a thermoplastic resin composition of the present invention, the catalyst may be removed or deactivated after completion of the polymerization reaction in order to maintain thermal stability and hydrolytic stability, but it is not necessarily deactivated. In order to deactivate the catalyst, a method of deactivating the catalyst by adding a known acidic substance may be suitably carried out. Esters such as butyl benzoate are particularly suitable for use as the acidic substance; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonates 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; phosphate esters such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, and the like; phosphonates such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis (diphenylphosphine) ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearoyl chloride, benzoyl chloride and p-toluenesulfonyl chloride; alkyl sulfates such as dimethyl sulfate; organic halides such as benzyl chloride, and the like. From the viewpoints of the effect of the inactivating agent, stability against resin, and the like, p-toluene or butyl sulfonate or tetrabutylphosphonium dodecylbenzenesulfonate is particularly preferable. These deactivators are used in an amount of 0.01 to 50 mol, preferably 0.3 to 20 mol, based on the amount of the catalyst. When the amount is less than 0.01 times by mol, the deactivation effect is insufficient, which is not preferable. When the amount is more than 50 times by mole based on the amount of the catalyst, the heat resistance of the resin is lowered, and the molded article is liable to be colored, which is not preferable.

The kneading of the deactivator may be performed immediately after completion of the polymerization reaction, or may be performed after granulating the polymerized resin. In addition, other additives other than the deactivator may be added by the same method.

< Optical Member >

The thermoplastic resin or thermoplastic resin composition (hereinafter simply referred to as "resin composition") of the present invention can be applied to an optical member. In one embodiment of the present invention, there is provided an optical member containing the resin composition of the present invention. In one embodiment of the present invention, the optical member includes, but is not limited to, an optical disc, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, a lens, a prism, an optical film, a base, an optical filter, a hard coat film, and the like. The resin composition of the present invention is particularly suitable for producing a thin optical member because it has high flowability and can be molded by a casting method. In a preferred embodiment of the present invention, the optical member manufactured using the resin composition of the present invention may be an optical lens. In another preferred embodiment of the present invention, the optical member manufactured using the resin composition of the present invention may be an optical film.

When an optical member containing the resin composition of the present invention is produced by injection molding, it is preferable to mold it under the conditions of a cylinder temperature of 260 to 350℃and a mold temperature of 90 to 170 ℃. More preferably, the molding is performed at a cylinder temperature of 270 to 320℃and a mold temperature of 100 to 160 ℃. When the barrel temperature is higher than 350 ℃, cracking and coloring of the resin composition occur; when the temperature is less than 260 ℃, the melt viscosity increases, which tends to cause difficulty in molding. Further, when the mold temperature is higher than 170 ℃, it is easy to cause difficulty in removing a molded article made of the resin composition from the mold. On the other hand, when the mold temperature is lower than 90 ℃, the resin is cured prematurely in the mold at the time of molding, resulting in difficulty in controlling the shape of the molded sheet or in sufficiently transferring the shape attached to the mold.

< Optical lens >

In one embodiment of the present invention, the resin composition can be applied to an optical lens. The optical lens produced using the resin composition of the present invention has a high refractive index and excellent heat resistance, and therefore can be used in the field of conventional expensive high refractive index glass lenses such as telescopes, binoculars, television projectors, and the like, and is therefore extremely useful.

For example, in the lens of a smart phone, it is possible to mold a lens from a thermoplastic resin containing the structural units (A), (B) and (C), or a lens from a thermoplastic resin containing a thermoplastic resin derived from the structural units (A), (B) and (C)

Resin molded lens stacks of structural units of any one of the above formulas, in which R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group or an ethyl group, and R ₃ and R ₄ each independently represent a hydrogen atom, a methyl group, an ethyl group or an alkylene glycol having 2 to 5 carbon atoms, are used as lens units.

The optical lens of the present invention can be realized by using an aspherical lens form as needed. Since the aspherical lens can realize substantially zero spherical aberration with one lens, it is not necessary to combine a plurality of spherical lenses to eliminate spherical aberration, and it is possible to reduce the weight and the molding cost. Therefore, an aspherical lens is useful as an optical lens, particularly as a camera lens.

Further, since the optical lens of the present invention has high molding fluidity, it is particularly useful as a material for thin, small and complex optical lenses. The thickness of the center portion is preferably 0.05 to 3.0mm, more preferably 0.05 to 2.0mm, and still more preferably 0.1 to 2.0mm, as a specific lens size. The diameter is preferably 1.0 to 20.0mm, more preferably 1.0 to 10.0mm, and still more preferably 3.0 to 10.0mm. In addition, a meniscus lens having a convex surface and a concave surface is preferable as the shape.

The optical lens of the present invention may be molded by any method such as mold molding, cutting, grinding, laser processing, electric discharge processing, etching, and the like. Among them, mold molding is more preferable in terms of manufacturing cost.

< Optical film >

In one embodiment of the present invention, the resin composition can be applied to an optical film. In particular, the optical film produced using the polycarbonate resin of the present invention is excellent in transparency and heat resistance, and therefore can be suitably used for a film for a liquid crystal substrate, an optical memory card, and the like.

In order to avoid the contamination of foreign matter into the optical film as much as possible, the molding environment is of course also required to be a low-dust environment, preferably 6 or less, more preferably 5 or less.

Second embodiment

< Polycarbonate resin >

The second embodiment of the present invention is a polycarbonate resin containing a structural unit represented by the following general formula (1B), a binaphthyl derivative unit represented by the following general formula (2B), and a fluorene derivative unit represented by the following general formula (3B).

In the general formula (3B), Z represents an alkylene group having 1 to 4 carbon atoms, R ₁～R₆ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, and e and f each independently represent an integer of 0 to 5.

The polycarbonate resin of the present invention is preferably substantially composed of structural units represented by the general formulae (1B) to (3B). In the present specification, "substantially consist of" means that the polycarbonate resin of the present invention may contain other structural units within a range that does not impair the effects of the present invention. For example, in the structural unit of the polycarbonate resin of the present invention, the structural unit represented by the general formulae (1B) to (3B) is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more.

In the polycarbonate resin of the present invention, the proportion of the structural unit represented by the general formula (1B) is 1 mol% or more and less than 10 mol%, the proportion of the structural unit represented by the general formula (2B) is 10 to 60 mol%, and the proportion of the structural unit represented by the general formula (3B) is 5 to 80 mol%. In addition, since a resin having a small absolute value of the birefringence strength and a small birefringence index in the lens surface can be obtained, the ratio of the structural unit represented by the general formula (1B) is preferably 2 to 9 mol%, the ratio of the structural unit represented by the general formula (2B) is preferably 20 to 60 mol%, the ratio of the structural unit represented by the general formula (3B) is preferably 30 to 70 mol%, the ratio of the structural unit represented by the general formula (1B) is particularly preferably 3 to 8 mol%, the ratio of the structural unit represented by the general formula (2B) is preferably 30 to 60 mol%, and the ratio of the structural unit represented by the general formula (3B) is preferably 40 to 60 mol%.

The polycarbonate resin of the present invention is not particularly limited as to how the structural units represented by the general formulae (1B) to (3B) are contained in the resin. In one embodiment of the present invention, the polycarbonate resin may contain a copolymer containing structural units represented by the general formulae (1B) to (3B), or may be a ternary resin containing a homopolymer formed of each structural unit. Or may be a blend of a copolymer comprising structural units represented by the general formulae (1B) and (2B) and a homopolymer comprising structural units represented by the general formula (3B), or may be a blend of a copolymer comprising structural units represented by the general formulae (1B) and (2B) and a copolymer comprising structural units represented by the general formulae (1B) and (3B).

The polycarbonate resin of the present invention may comprise any of random, block and alternating copolymer structures.

The polycarbonate resin of the present invention preferably has a weight average molecular weight (Mw) of 20,000 ～ 200,000 in terms of polystyrene. The weight average molecular weight (Mw) in terms of polystyrene is more preferably 25,000 ～ 120,000, still more preferably 28,000 ～ 55,000, particularly preferably 30,000 ～ 45,000.

When the Mw is less than 20,000, the molded body becomes brittle, and is thus not preferable; if the Mw exceeds 200,000, the melt viscosity increases, which is not preferable because the resin after production is difficult to take out and the fluidity is poor, and injection molding is difficult to achieve in a molten state.

The refractive index (nD) of the polycarbonate resin of the present invention at 23℃and a wavelength of 589nm is preferably 1.635 to 1.695, more preferably 1.640 to 1.690, still more preferably 1.645 to 1.685, and particularly preferably 1.650 to 1.680. The polycarbonate resin of the present invention has a high refractive index (nD) and is suitable for use as an optical lens material. The refractive index may be measured by Abbe refractometer according to JIS B7071-2: 2018 was measured on a film having a thickness of 0.1 mm.

The Abbe number (. Nu.) of the polycarbonate resin of the present invention is preferably 24 or less, more preferably 22 or less, and still more preferably 21 or less. Abbe numbers can be calculated based on refractive indices of 486nm, 589nm, 656nm at 23℃using the following formulas.

ν＝(nD－1)/(nF－nC)

ND: refractive index at wavelength 589nm

NC: refractive index at 656nm

NF: refractive index at wavelength 486nm

The melt volume flow rate (MVR) of the polycarbonate resin of the present invention is preferably 10 to 100, more preferably 30 to 100, particularly preferably 30 to 50. In the present invention, MVR can be measured by the method described in examples described below.

The polycarbonate resin of the present invention preferably has a birefringence strength of-0.6 to +0.7, more preferably-0.5 to +0.5, and particularly preferably-0.3 to +0.3. In the present invention, the birefringence intensity can be measured by the method described in examples described below.

The in-plane birefringence of the polycarbonate resin of the present invention is preferably 0.1 to 15, more preferably 1 to 10, and particularly preferably 2 to 7. In the present invention, the in-plane birefringence of the lens can be measured by the method described in examples described below.

The haze of the polycarbonate resin of the present invention is preferably 0.05 to 3.00, more preferably 0.10 to 2.00. In the present invention, haze can be measured by the method described in examples described below.

The polycarbonate resin of the present invention can be blended with other resins for the production of molded articles. Examples of the other resin include polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, and the like.

The polycarbonate resin of the present invention may further contain an antioxidant, a mold release agent, an ultraviolet absorber, a fluidity improver, a crystallization nucleating agent, a reinforcing agent, a dye, an antistatic agent, an antibacterial agent, and the like.

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

When the polycarbonate resin of the present invention is used for injection molding, the glass transition temperature (Tg) is preferably 90 to 180 ℃, more preferably 95 to 175 ℃, still more preferably 100 to 170 ℃, still more preferably 130 to 170 ℃, particularly preferably 135 to 150 ℃. When Tg is lower than 90 ℃, the use temperature range becomes narrow, and thus is not preferable. When the temperature exceeds 180 ℃, the melting temperature of the resin increases, and cracking and coloring of the resin easily occur, so that it is not preferable. When the glass transition temperature of the resin is too high, in the general-purpose mold temperature controller, the difference between the mold temperature and the glass transition temperature of the resin increases. Therefore, in applications requiring strict surface accuracy for products, it is difficult to use a resin having an excessively high glass transition temperature, which is not preferable. In addition, from the viewpoint of molding fluidity and molding heat resistance, the lower limit value of Tg is preferably 130 ℃, more preferably 135 ℃, and the upper limit value of Tg is preferably 160 ℃, more preferably 150 ℃.

The amount of residual phenol contained in the polycarbonate resin of the present invention is preferably 500ppm or less, more preferably 300ppm or less, and still more preferably 50ppm or less.

The amount of residual diphenyl carbonate (DPC) contained in the polycarbonate resin of the present invention is preferably 200ppm or less, more preferably 100ppm or less, and still more preferably 50ppm or less.

< Method for producing polycarbonate resin >

The polycarbonate resin having the structural units represented by the general formulae (1B) to (3B) of the present invention can be produced by reacting a compound represented by the following general formulae (4B) to (6B) with a carbonate precursor such as a carbonic acid diester as a dihydroxy component. Specifically, the catalyst is produced by reacting a compound represented by the general formulae (4B) to (6B) with a carbonate precursor such as a carbonic acid diester in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst containing both, or by a melt polycondensation method in the absence of a catalyst.

In the general formula (4B), X represents an alkylene group having 1 to 4 carbon atoms, and a and B each independently represent an integer of 1 to 10;

In the general formula (5B), Y represents an alkylene group having 1 to 4 carbon atoms, and c and d each independently represent an integer of 1 to 10;

In the general formula (6B), Z represents an alkylene group having 1 to 4 carbon atoms, R ₁～R₆ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, and e and f each independently represent an integer of 0 to 5.

The compound of the general formula (4B) may be 9, 9-bis (hydroxy (poly) alkoxynaphthyl) fluorene. Examples of the compound of the general formula (4) include 9, 9-bis [6- (1-hydroxy methoxy) naphthalen-2-yl ] fluorene, 9-bis [6- (2-hydroxy ethoxy) naphthalen-2-yl ] fluorene, 9-bis [6- (3-hydroxy propoxy) naphthalen-2-yl ] fluorene, and 9, 9-bis [6- (4-hydroxy butoxy) naphthalen-2-yl ] fluorene. Of these, 9-bis [6- (2-hydroxyethoxy) naphthalen-2-yl ] fluorene is preferable. These compounds may be used alone or in combination of two or more.

In the production of the compound of the general formula (4B), a compound having either one of a and B as an impurity of 0 may be produced as an impurity. The content of such impurities in the monomer containing the compound of the general formula (4B) as a main component is preferably 1000ppm or less, more preferably 500ppm or less, further preferably 200ppm or less, particularly preferably 100ppm or less in total. Besides these impurities, fluorenone, which is one of the raw materials, may be contained as an impurity. The fluorenone content in the monomer containing the compound of the general formula (4B) as a main component is preferably 1000ppm or less, more preferably 100ppm or less, further preferably 50ppm or less, particularly preferably 10ppm or less. Fluorenone contained in a monomer containing a compound of the general formula (4B) as a main component may remain in the resin after polymerization. The smaller the fluorenone content, the better the hue of the resin, and thus is preferable. Further, although not an impurity, the total of the compounds having a and B different from each other (i.e., a+.b) in the general formula (4B) in the monomer containing the compound of the general formula (4B) as a main component is preferably 50ppm or less, more preferably 20ppm or less.

The compound of the general formula (4B) can be produced by various synthetic methods. For example, as described in Japanese patent No. 5442800, 9-bis (hydroxynaphthalene) fluorene is produced by a method of reacting fluorenones with hydroxynaphthalene in the presence of hydrogen chloride gas and mercapto carboxylic acid, (b) a method of reacting 9-fluorenones with hydroxynaphthalene in the presence of an acid catalyst (and alkyl mercaptan), (c) a method of reacting fluorenones with hydroxynaphthalene in the presence of hydrochloric acid and mercaptans (mercapto carboxylic acid, etc.), and (d) a method of reacting fluorenones with hydroxynaphthalene in the presence of sulfuric acid and mercaptans (mercapto carboxylic acid, etc.), and crystallizing by a crystallization solvent composed of hydrocarbons and polar solvents. For example, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene can be obtained by reacting 9, 9-bis [ 6-hydroxynaphthyl ] fluorene with 2-chloroethanol under alkaline conditions.

Examples of the dihydroxy compound represented by general formula (5B) include 2,2 '-bis (1-hydroxymethyl) -1,1' -binaphthyl, 2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl, 2 '-bis (3-hydroxypropoxy) -1,1' -binaphthyl, 2 '-bis (4-hydroxybutoxy) -1,1' -binaphthyl and the like. Among them, 2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl (hereinafter sometimes abbreviated as "BHEBN") is preferable. These compounds may be used alone or in combination of two or more.

When the compound of the general formula (5B) is produced, a compound having either one of c and d of 0 may be produced as an impurity. The content of such impurities in the monomer containing the compound of the general formula (5B) as a main component is preferably 1000ppm or less, more preferably 500ppm or less, further preferably 200ppm or less, particularly preferably 100ppm or less in total. Further, although not an impurity, the compounds of the general formula (5B) in which c and d are different (i.e., c+.d) are preferably 50ppm or less, more preferably 20ppm or less in total, in the monomer containing the compound of the general formula (5B) as a main component.

Examples of the dihydroxy compound represented by general formula (6B) include 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (hereinafter, abbreviated as "BPEF" in some cases), 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, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene (hereinafter, abbreviated as "BPPEF" in some cases), and the like. Among them, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene and 9, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene are preferable. These compounds may be used alone or in combination of two or more.

When the compound of the general formula (6B) is produced, a compound having either one of e and f of 0 may be produced as an impurity. The content of such impurities in the monomer containing the compound of the general formula (6B) as a main component is preferably 1000ppm or less, more preferably 500ppm or less, further preferably 200ppm or less, particularly preferably 100ppm or less in total. Further, although not an impurity, the compounds having e and f different from each other (that is, e.noteq.f) in the general formula (6B) are preferably 50ppm or less, more preferably 20ppm or less in total in the monomer containing the compound of the general formula (6B) as a main component.

Examples of the aromatic dihydroxy compound which may be used in combination other than the above 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, bisphenol Z, and the like.

Examples of the carbonic acid diester used in the present invention include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-tolyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. Among them, diphenyl carbonate is particularly preferable. The diphenyl carbonate is preferably used in a proportion of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, based on 1 mol of the total of the dihydroxy compounds.

Among the transesterification catalysts, alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and the like are particularly exemplified as the basic compound catalyst.

Examples of the alkali metal compound used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, and the like of alkali metals. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogencarbonate, 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 benzoborate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium salt, dipotassium salt, cesium salt or dilithium salt of bisphenol a, sodium salt, potassium salt, cesium salt or 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 bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, 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, salts thereof, amines, and the like. Specific examples thereof include quaternary ammonium hydroxides having an alkyl group, an aryl group, and the like, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine; secondary amines such as diethylamine and dibutylamine; primary amines such as propylamine and butylamine; imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; or an alkali or basic salt such as ammonia, tetramethylammonium borohydride, tetrabutylammonium tetraphenylborate, or tetraphenylammonium tetraphenylborate.

As the transesterification catalyst, salts of zinc, tin, zirconium, lead, etc. are preferably used, and these compounds may be used alone or in combination.

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

These catalysts may be used in a proportion of 1X 10 ^-9～1×10^-3 mol, preferably 1X 10 ^-7～1×10^-4 mol, based on 1 mol of the total dihydroxy compounds.

The melt polycondensation method is a method of performing melt polycondensation while removing by-products by transesterification under normal pressure or reduced pressure using the above raw materials and a catalyst.

In the melt polycondensation of the component system of the present invention, it is desirable that the compounds represented by the general formulae (4B) to (6B) and the carbonic acid diester are melted in a reaction vessel and then reacted in a state where the by-product monohydroxy compound is retained. In order to achieve the retention, the reaction device may be closed, or pressure control such as pressure reduction or pressure increase may be performed. 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 distilled off immediately after the formation of the by-product monohydroxy compound, the content of the high molecular weight product of the finally obtained polycarbonate resin is reduced. However, if the by-product monohydroxy compound is allowed to remain in the reaction vessel for a certain period of time, the content of the high molecular weight product of the finally obtained polycarbonate resin is large.

The melt polycondensation reaction may be carried out continuously or batchwise. The reaction apparatus used in the reaction may be a vertical apparatus including an anchor type stirring blade, MAXBLEND stirring blade, ribbon type stirring blade, or the like, a horizontal apparatus including a paddle blade, a lattice blade, a spectacle type blade, or the like, or an extruder type apparatus including a screw. In addition, 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 polycarbonate resin used in the present invention, after the polymerization reaction is completed, the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolytic stability. A method of inactivating the catalyst by adding a known acidic substance can be preferably performed. Specific examples of the acidic substance include esters such as butyl benzoate and aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonates 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; phosphate esters such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, and the like; phosphonates such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearoyl chloride, benzoyl chloride and p-toluenesulfonyl chloride; alkyl sulfuric acid such as dimethyl sulfuric acid; organic halides such as benzyl chloride, and the like. Among them, butyl p-toluenesulfonate and tetrabutylphosphonium dodecylbenzenesulfonate are particularly preferably used. These deactivators are used in an amount of 0.01 to 50 mol per mol of the catalyst, preferably 0.3 to 20 mol per mol of the catalyst. When the amount is less than 0.01 times by mole, the deactivation effect may be insufficient, which is not preferable. In addition, when the amount of the catalyst is more than 50 times by mol, the heat resistance of the resin tends to be low, and the molded article tends to be colored, which is not preferable.

After the deactivation of the catalyst, a step of devolatilizing and removing the low boiling point compounds in the polymer at a pressure of 0.1 to 1mmHg and a temperature of 200 to 350 ℃ may be provided. In this step, a horizontal type apparatus or a thin film evaporator having stirring paddles excellent in surface renewal such as paddle blades, lattice blades, and spectacle blades can be preferably used.

The polycarbonate resin of the present invention preferably contains as little foreign matter as possible, and is preferably obtained by filtering a molten raw material, filtering a catalyst liquid, or the like. The mesh size of the filter is preferably 5 μm or less, more preferably 1 μm or less. The resin produced is preferably filtered by a polymer filter. The mesh size 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 a low-dust environment, and is preferably 6 or less, more preferably 5 or less.

In another embodiment of the present invention, in the case of producing a polycarbonate resin containing structural units represented by the general formulae (1B) to (3B), a copolymer containing structural units represented by the general formulae (1B) to (3B) may be produced using compounds represented by the general formulae (4B) to (6B), or a ternary resin containing homopolymers of the respective structural units may be produced by polymerizing the compounds represented by the general formulae (4B) to (6B). Alternatively, the copolymer containing the structural units represented by the general formulae (1B) and (2B) may be blended after polymerization with the homopolymer containing the structural unit represented by the general formula (3B), or the copolymer containing the structural units represented by the general formulae (1B) and (2B) may be blended after polymerization with the copolymer containing the structural units represented by the general formulae (1B) and (3B).

< Optical molded body >

The polycarbonate resin of the present invention can be used to produce an optical molded article. The molding can be performed by any method such as injection molding, compression molding, extrusion molding, or solution casting. The polycarbonate 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. In molding, the polycarbonate resin of the present invention may be used by mixing with other resins such as other polycarbonate resins and polyester resins. In addition, additives such as antioxidants, processing stabilizers, light stabilizers, polymeric metal deactivators, flame retardants, slip agents, antistatic agents, surfactants, antibacterial agents, mold release agents, ultraviolet absorbers, plasticizers, and compatibilizers may be blended.

Examples of the antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3, 5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3, 9-bis {1, 1-dimethyl-2- [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl } -2,4,8, 10-tetraoxaspiro (5.5) undecane, 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) -3H-benzofuran-2-one, 3, 9-bis (2, 6-di-tert-butyl-4-methylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphospho spiro [5.5] undecane, and the like. Of these, pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) -3H-benzofuran-2-one and 3, 9-bis (2, 6-di-tert-butyl-4-methylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane are particularly preferably used. The content of the antioxidant in the polycarbonate resin is preferably 0.001 to 0.3 parts by weight, more preferably 0.05 to 0.2 parts by weight, relative to 100 parts by weight of the polycarbonate 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, phosphonic acid, and esters thereof. Specific examples thereof include 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, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl 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-diphenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, tetrakis (2, 4-di-tert-butylphenyl) -4,4' -biphenylene diphosphonate, tetrakis (2, 4-di-tert-butylphenyl) -4,3' -biphenylene diphosphonate, tetrakis (2, 4-di-tert-butylphenyl) -3,3' -biphenylene diphosphonate, bis (2, 4-di-t-butylphenyl) -4-phenyl-phenylphosphonate, bis (2, 4-di-t-butylphenyl) -3-phenyl-phenylphosphonate, and the like. The content of the phosphorus-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by weight based on 100 parts by weight of the polycarbonate resin.

Examples of the heat stabilizer for the sulfur-based processing 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 polycarbonate resin is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the polycarbonate resin.

The release agent is preferably composed of 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 ester or a 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 polyol and a fatty acid is preferably a partial or full ester of a polyol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

Specifically, examples of esters of monohydric alcohols and saturated fatty acids include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Examples of the partial or full ester of a polyhydric alcohol and a saturated fatty acid include a partial or full ester of dipentaerythritol such as glyceryl monostearate, diglyceryl stearate, glyceryl tristearate, sorbitan monostearate, glyceryl behenate, glyceryl caprate, glyceryl laurate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrasonanoate, propylene glycol monostearate, diphenyl diphenoate, sorbitol monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, and the like. 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 even more preferably in the range of 0.02 to 0.5 parts by weight, relative to 100 parts by weight of the polycarbonate resin.

The ultraviolet absorber is preferably at least one ultraviolet absorber selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic imido ester-based ultraviolet absorbers and cyanoacrylate-based ultraviolet absorbers. That is, any one of the ultraviolet absorbers described below may be used alone, or two or more may be used in combination.

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-di-tert-pentylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2 '-methylenebis [4- (1, 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-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octyloxy) benzotriazole, 2' -bis- [2, 5-di-tert-butylphenyl ] benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) benzotriazole, and 2- (2-hydroxy-3, 5-di-tert-butylphenyl) benzotriazole.

Examples of the benzophenone-based ultraviolet light absorber include 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxy-benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-5-sulfoacid trihydrate benzophenone, 2 '-dihydroxy-4-methoxybenzophenone, 2',4 '-tetrahydroxybenzophenone, 2' -dihydroxy-4, 4 '-dimethoxybenzophenone, 2' -dihydroxy-4, 4 '-dimethoxy-5-sulfosodium benzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecoxybenzophenone, and 2-hydroxy-4-methoxy-2' -carboxybenzophenone.

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

As the cyclic iminoester-based ultraviolet absorber, examples thereof include 2,2 '-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) 2,2'- (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), 2' - (2-chloro-p-phenylene) bis (3, 1-benzoxazin-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 parts by weight, and still more preferably 0.05 to 0.8 parts by weight, based on 100 parts by weight of the polycarbonate resin. When the amount is within the above range, sufficient weather resistance can be imparted to the polycarbonate resin for the intended use.

The polycarbonate resin of the present invention has a high refractive index and a low abbe number. In addition to the optical lens, the optical lens can be advantageously used as a molding for optical use as a structural material or a functional material for optical components such as transparent conductive substrates, optical disks, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor deposited plastic mirrors, and displays, which are used for liquid crystal displays, organic EL displays, solar cells, and the like.

The surface of the optical molded body may be provided with a coating such as an antireflection layer or a hard coat layer, if necessary. The antireflection layer may be a single layer or a plurality of layers, and may be organic or inorganic, but 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.

< Optical lens >

The optical lens produced using the polycarbonate resin of the present invention has a high refractive index, a low abbe number, a small absolute value of birefringence strength, and a small in-plane birefringence, and therefore can be used in the field of conventional expensive high refractive index glass lenses such as telescopes, binoculars, and television projectors, and is therefore extremely useful. If necessary, it is preferable to use an aspherical lens. Since the aspherical lens can realize substantially zero spherical aberration by 1 lens, there is no need to eliminate spherical aberration by combining a plurality of spherical lenses, and the weight and production cost can be reduced. Therefore, an aspherical lens is useful as an optical lens, particularly as a camera lens.

The optical lens may be molded by any method such as injection molding, compression molding, injection compression molding, or the like. According to the present invention, an aspherical lens having a high refractive index and low birefringence, which is technically difficult to process in terms of glass lenses, can be more easily obtained.

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

(Optical film)

The optical film produced using the polycarbonate resin of the present invention is excellent in transparency and heat resistance, and therefore is suitable for use as a film for a liquid crystal substrate, an optical memory card, or the like.

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

Examples

The following examples and comparative examples of the present invention are shown together to explain the summary of the invention in detail, but the present invention is not limited to these examples. The measurement values in the examples were measured by the following methods and apparatuses.

1) Refractive index (nD):

According to JIS B7071-2: 2018, molding a polycarbonate resin to obtain a V-shaped block as a test piece. The refractive index was measured at 23℃by a refractive index meter (KPR-3000 manufactured by Shimadzu corporation).

2) Abbe number (v)

The refractive indices of 486nm, 589nm and 656nm at 23℃were measured using a refractive index meter using the same test piece (V-block) as that used for the refractive index measurement, and Abbe numbers were calculated using the following formulas.

Refractive index meter: KPR-3000 manufactured by Shimadzu corporation

ν＝(nD－1)/(nF－nC)

ND: refractive index at wavelength 589nm

NC: refractive index at 656nm

NF: refractive index at wavelength 486nm

3) Intensity of birefringence

Test piece molding

The obtained resin was extrusion molded to obtain a film test piece having a thickness of 100. Mu.m.

And (3) a forming machine: PULAENG-EXTRUDER

The molding conditions are as follows: barrel temperature 260 ℃, roller temperature Tg+10deg.C

Determination of the birefringence:

the film test piece was stretched to measure the birefringence at 450 nm.

Measurement device: JASCO ellipsometer (Spectroellipsometer) M-220

Measurement conditions: measurement was performed using a film stretched 1.5 times

The birefringence strength is the ratio of the birefringence of the resulting resin at 450nm to the birefringence of the polycarbonate (homopolymer) derived from BPEF at 450 nm.

4) Glass transition temperature (Tg)

The measurement was performed according to JIS K7121-1987 by using a differential scanning calorimeter with a temperature-raising program of 10℃per minute.

Differential thermal scanning calorimeter: X-DSC7000 manufactured by Hitachi technology science, kagao, co., ltd

5) Weight average molecular weight

The weight average molecular weight of the obtained resin was measured by Gel Permeation Chromatography (GPC), and calculated by conversion with standard polystyrene. The apparatus, column and measurement conditions are shown below.

GPC apparatus: tosoh Co., ltd., HLC-8420GPC

Column: tosoh co., ltd. TSKgel SuperHM-mx3 roots

Tosoh co., ltd. TSKgel guardcolumn SuperH-h×1 root

Tosoh Co., ltd. TSKgel SuperH-RC. Times.1 root

A detector: RI detector

Standard polystyrene: tosoh Co., ltd., standard polystyrene kit PStQuick C

Sample solution: 0.2% by mass tetrahydrofuran solution

Eluent: tetrahydrofuran (THF)

Eluent flow rate: 0.6mL/min

Column temperature: 40 DEG C

6) Melt volume flow Rate (MVR)

The obtained resin was dried under vacuum at 120℃for 4 hours and measured in accordance with JIS K7210.

Measurement device: melt index instrument T-111 manufactured by Toyo refiner of Kagaku Co., ltd

Measurement conditions: the measurement was performed under a load of 2160g at a temperature of 260 ℃.

The operation is as follows: MVR (unit: cm ³/10 min) was calculated based on the amount of resin extruded every 10 minutes from a standard die set at the bottom of the barrel.

7) Internal birefringence of lens face

Test piece molding

The obtained resin was injection molded to obtain a concave lens test piece having a diameter of 4.5mm and a center thickness of 0.2 mm.

And (3) a forming machine: SUMITOMO SHIDEMAG SE EV

The molding conditions are as follows: barrel temperature 280 ℃, die temperature Tg-15 ℃, injection speed 40mm/s, VP pressure 70MPa (position 2.3 mm), pressure maintaining 65MPa×1s+55MPa×1.5s

Determination of the birefringence in a lens face

The retardation of the concave lens test piece obtained as described above was measured.

Measurement device: photonic Lattice Co., ltd. WPA-100

The data processing method comprises the following steps: the value of the birefringence in the lens surface was determined from the retardation average using software "PA/WPA View" manufactured by Photonic Lattice co., ltd.

8) Haze degree

The obtained resin was molded to a thickness of 3mm, and measured in accordance with JIS K-7136.

Measuring instrument: spectral haze meter SH7000 manufactured by Nippon electric color industry Co., ltd

Example 1A

As a raw material, 9391.9g (15.9 mol) of 9, 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene (hereinafter sometimes abbreviated as "OPPFL") represented by the following structural formula, 1457.7g (2.7 mol) of 9, 9-bis [6- (2-hydroxyethoxy) -2-naphthyl ] fluorene (hereinafter sometimes abbreviated as "NOLE") represented by the following structural formula, 5700.0g (15.2 mol) of 2,2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl (hereinafter sometimes abbreviated as "BNE") represented by the following structural formula, 7450g (hereinafter sometimes abbreviated as "DPC") and 12 ml (3.0X10 ^-4 mol) of an aqueous sodium bicarbonate solution (2.5X10 ^-2 mol, namely 10X 10 ^﹣6 mol relative to 1 mol of the total dihydroxy compound) were charged into a 50 liter reactor equipped with a stirrer and a distillation apparatus, and after the nitrogen gas was replaced with nitrogen gas, the nitrogen gas was stirred at 700℃under a temperature of 200℃under a heating atmosphere. After confirming that the raw material was completely dissolved 20 minutes after the start of heating, the mixture was stirred under this condition for 80 minutes. Then, the degree of decompression was adjusted to 200Torr for 20 minutes, and the reaction was kept at 200℃for 10 minutes under 200Torr to carry out transesterification. The temperature was raised to 215℃for 30 minutes, and the pressure was reduced to 180Torr. Then adjusted to 230℃and 150Torr in 40 minutes. Then adjusted to 120Torr for another 10 minutes. And then adjusted to 100Torr, 240℃for 10 minutes. Then, the polymerization was carried out at 240℃for 30 minutes under 1Torr with a temperature of 1Torr being adjusted to 1Torr for 50 minutes. After the completion of the reaction, nitrogen was introduced into the reaction system in the reactor to pressurize the reaction system, and the produced polycarbonate resin was pelletized and extracted to obtain a polycarbonate resin. Physical properties of the obtained resin are shown in table 2.

Examples 2A to 4A and comparative examples 1A to 8A

A polycarbonate resin was obtained in the same manner as in example 1A, except that the raw materials shown in table 1 were used. Physical properties of the obtained resin are shown in table 2.

TABLE 1

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TABLE 2

The 3mmt can be molded, but the strength of the molded thin-wall lens is insufficient

Example 1B

As a raw material, 1690g (3.14 mol) of 9, 9-bis (6- (2-hydroxyethoxy) naphthalen-2-yl ] fluorene (BNEF), 6170g (16.5 mol) of 2,2 '-bis (2-hydroxyethoxy) -1,1' -Binaphthyl (BNE), 4760g (10.9 mol) of 9, 9-bis (4- (2-hydroxyethoxy) phenyl ] fluorene (BPEF), 8390g (14.2 mol) of 9, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene (BPPEF), 10000g (46.7 mol) of diphenyl carbonate (DPC) and 16ml (4.0X10 ^-4 mol) of an aqueous sodium bicarbonate solution of 2.5X10 ^-2 mol/liter, i.e., 8.9X10 ^-6 mol relative to the total 1 mol of dihydroxyl compound were charged into a 50L reactor equipped with a stirrer and a distillation device under nitrogen atmosphere of 760mmHg, heating to 180deg.C for 30min, stirring for 120 min, regulating vacuum to 200mmHg, heating to 200deg.C at 60deg.C/hr, maintaining at 200deg.C for 20min, reacting, heating to 230deg.C at 75deg.C/hr for 10min, maintaining at the temperature, regulating pressure reduction to below 1mmHg, heating to 245 deg.C at 60deg.C/hr, stirring for 30min, introducing nitrogen into the reaction system, pressurizing, granulating, and extracting, a polycarbonate resin was obtained. The physical properties of the obtained resin are shown in Table 3.

TABLE 3

Example 2B, comparative examples 1B to 3B

A polycarbonate resin was obtained in the same manner as in example 1B, except that the raw materials shown in table 4 were used. Physical properties of the obtained polycarbonate resin are shown in table 3.

TABLE 4

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Claims

1. A thermoplastic resin characterized in that:

The resin contains, relative to 100 mol% of the total amount of structural units in the resin, 22 to 49 mol% of structural units (A) derived from a diol represented by the following general formula (1A), 40 to 75 mol% of structural units (B) derived from a diol represented by the following general formula (2A), and 0 to 15 mol% of structural units (C) derived from a diol represented by the following general formula (3A),

A and b each independently represent an integer of 0 to 10,

C and d each independently represent an integer of 0 to 10,

E and f each independently represent an integer of 0 to 10.

2. The thermoplastic resin of claim 1 wherein:

The proportion of the structural unit (A) derived from the diol represented by the general formula (1A) is 24 to 47 mol%, the proportion of the structural unit (B) derived from the diol represented by the general formula (2A) is 45 to 70 mol%, and the proportion of the structural unit (C) derived from the diol represented by the general formula (3A) is 0 to 8 mol%, based on 100 mol% of the total amount of the structural units in the resin.

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

the dihydric alcohol shown in the general formula (1A) comprises dihydric alcohol shown in the following structural formula,

4. A thermoplastic resin according to any one of claims 1 to 3, wherein:

The diol represented by the general formula (2A) contains at least one of the diols represented by the following structural formulas,

5. The thermoplastic resin according to any one of claims 1 to 4, wherein:

the diol represented by the general formula (3A) comprises a diol represented by the following structural formula,

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

The thermoplastic resin is a polycarbonate resin.

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

The thermoplastic resin further comprises structural units derived from at least one monomer selected from the group of monomers,

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

the thermoplastic resin has a birefringence of 1 to 21 in the lens surface.

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

The weight average molecular weight (Mw) of the thermoplastic resin in terms of polystyrene is 10,000 ～ 100,000.

10. The thermoplastic resin according to any one of claims 1 to 9, characterized in that:

the refractive index (nD) of the thermoplastic resin is 1.650-1.695.

11. The thermoplastic resin according to any one of claims 1 to 10, characterized in that:

the Abbe number (v) of the thermoplastic resin is 16.0 to 21.0.

12. The thermoplastic resin according to any one of claims 1 to 11, characterized in that:

The glass transition temperature of the thermoplastic resin is 130-190 ℃.

13. The thermoplastic resin according to any one of claims 1 to 12, characterized in that:

The thermoplastic resin has a melt volume flow rate (MVR) of 20 to 55.

14. The thermoplastic resin according to any one of claims 1 to 13, characterized in that:

the thermoplastic resin has a haze of 0.01 to 1.00.

15. An optical component, characterized by:

A thermoplastic resin according to any one of claims 1 to 14.

16. An optical lens, characterized by:

A thermoplastic resin according to any one of claims 1 to 14.

17. An optical film, characterized in that:

A thermoplastic resin according to any one of claims 1 to 14.

18. A polycarbonate resin characterized in that:

Comprising a structural unit represented by the following general formula (1B), a structural unit represented by the following general formula (2B) and a structural unit represented by the following general formula (3B),

in the general formula (3B),

Z represents an alkylene group having 1 to 4 carbon atoms,

E and f each independently represent an integer of 0 to 5.

19. The polycarbonate resin of claim 18, wherein:

the proportion of the structural unit represented by the general formula (1B) is 2 to 9 mol%,

20. An optical lens, characterized by:

A polycarbonate resin according to claim 18 or 19.