POLYCARBONATE RESIN, AND OPTICAL LENS AND OPTICAL FILM USING SAME

Abstract

A polycarbonate resin includes a constituent unit (a) given by general formula (1-IA); a constituent unit (b) given by general formula (1-1A), but different from the constituent unit (a); a constituent unit (c-1) given by general formula (1-2A) or a constituent unit (c-2) given by general formula (3-1); and a constituent unit (d) given by general formula (2), wherein the content of the constituent unit (a) is 1-50 mol %, the content of the constituent unit (b) is 1-70 mol %, the content of the constituent unit (c-1) or (c-2) is 1-50 mol %, and the content of the constituent unit (d) is 1-30 mol %, in each case with reference to the total amount of the constituent units (a) to (d).

Claims

1. A polycarbonate resin comprising: a structural unit (a) represented by general formula (1-1A); a structural unit (b) represented by general formula (1-1A), but different from the structural unit (a); a structural unit (c-1) represented by general formula (1-2A) or a structural unit (c-2) represented by general formula (3-1); and a structural unit (d) represented by general formula (2), wherein the content of the structural unit (a) is 1 to 50 mol %, the content of the structural unit (b) is 1 to 70 mol %, the content of the structural unit (c-1) or (c-2) is 1 to 50 mol %, and the content of the structural unit (d) is 1 to 30 mol %, in each case with reference to the total amount of the structural units (a) to (d): ##STR00020## wherein in formula (1-1A): R.sub.a and R.sub.b are each independently selected from a halogen atom; an alkyl group having 1 to 20 carbon atoms; an alkoxyl group having 1 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; a cycloalkoxyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heteroaryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, which contains at least one heterocyclic atom selected from O, N and S; and CCR.sub.h; R.sub.h represents an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 6 to 20 carbon atoms which contains at least one heterocyclic atom selected from O, N and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; and a and b each independently represent an integer of 0 to 10, ##STR00021## wherein in formula (1-2A): R.sub.a and R.sub.b are each independently selected from a hydrogen atom; a halogen atom; an alkyl group having 1 to 20 carbon atoms; an alkoxyl group having 1 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; a cycloalkoxyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heteroaryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, which contains at least one heterocyclic atom selected from O, N and S; and CCR; R.sub.h represents an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 6 to 20 carbon atoms which contains at least one heterocyclic atom selected from O, N and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; and a and b each independently represent an integer of 0 to 10, ##STR00022## wherein in formula (3-1): R.sub.a and R.sub.b are each independently selected from hydrogen, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms; Y represents a fluorene group; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 0 to 4; and a and b each independently represent an integer of 1 to 10, ##STR00023## wherein in formula (2): R.sub.z and R.sub.x each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; i represents an integer of 2 to 16; and p represents an integer of 1 to 600.

2. The polycarbonate resin according to claim 1, wherein the structural unit (a) is a structural unit derived from 2DNBINOL-2EO (6,6-di-(2-naphthyl)-2,2-bis-(2-hydroxyethoxy)-1,1-binaphthyl) represented by a structural formula below; the structural unit (b) is a structural unit derived from DPBHBNA (6,6-diphenyl-2,2-bis-(2-hydroxyethoxy)-1,1-binaphthyl) represented by a structural formula below; the structural unit (c-1) is a structural unit derived from BNEF (9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene) represented by a structural formula below; the structural unit (c-2) is a structural unit derived from BPPEF (9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene) represented by a structural formula below; and the structural unit (d) is a structural unit derived from a compound selected from the group consisting of diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol: ##STR00024##

3. The polycarbonate resin according to claim 1, which comprises an antioxidant and a catalyst deactivator.

4. The polycarbonate resin according to claim 3, wherein the antioxidant is pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; and the catalyst deactivator is dodecylbenzenesulfonic acid tetrabutylphosphonium salt.

5. The polycarbonate resin according to claim 1, which has a refractive index (nD) of 1.685 to 1.800.

6. The polycarbonate resin according to claim 1, which has an Abbe number () of 14.0 to 18.0.

7. The polycarbonate resin according to claim 1, which has a glass transition temperature of 130 to 160 C.

8. The polycarbonate resin according to claim 1, which has a melt volume-flow rate (MVR) of 30 to 100 cm.sup.3/10 min.

9. The polycarbonate resin according to claim 1, which has a water absorption rate of less than 0.11%.

10. An optical lens comprising the polycarbonate resin according to claim 1.

11. An optical film comprising the polycarbonate resin according to claim 1.

Description

EXAMPLES

[0122] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. Note that measurement values in the Examples were measured using the below-described methods and apparatuses.

1) Glass transition temperature (Tg): The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC). The specified conditions are as described below. [0123] Apparatus: DSC7000X manufactured by Hitachi High-Tech Science Corporation [0124] Amount of sample: 5 mg [0125] Atmosphere: under nitrogen gas atmosphere [0126] Temperature raising condition: 10 C./min
2) Refractive index (nD): The refractive index of a film having a thickness of 0.1 mm made of the polycarbonate resin produced in the Examples described below was measured according to the method of JIS-K-7142 using an Abbe's refractometer.
3) Abbe number (d): Refractive indexes of a film having a thickness of 0.1 mm made of the polycarbonate resin produced in the Examples described below were measured at 23 C. and at wavelengths of 486 nm, 589 nm and 656 nm according to the method of JIS-K-7142 using an Abbe's refractometer, and the Abbe number was calculated using the below-described formula:

d=(nD1)/(nFnC) [0127] nD: refractive index at a wavelength of 589 nm [0128] nC: refractive index at a wavelength of 656 nm [0129] nF: refractive index at a wavelength of 486 nm

4) Weight-Average Molecular Weight (Mw)

[0130] The weight-average molecular weight of resin was measured according to the gel permeation chromatography (GPC) method and calculated based on standard polystyrene conversion. The apparatuses and columns used and measurement conditions are as described below. [0131] GPC apparatus: HLC-8420GPC manufactured by Tosoh Corporation [0132] Columns: [0133] TSKgel SuperHM-M3, manufactured by Tosoh Corporation [0134] TSKgel guardcolumn SuperH-H1, manufactured by Tosoh Corporation [0135] TSKgel SuperH-RC1, manufactured by Tosoh Corporation [0136] Detector: RI detector [0137] Standard polystyrene: standard polystyrene kit PStQuick C manufactured by Tosoh Corporation [0138] Sample solution: 0.2% by mass solution of tetrahydrofuran [0139] Eluent: tetrahydrofuran [0140] Flow rate of eluent: 0.6 mL/min [0141] Column temperature: 40 C.

5) Melt Volume-Flow Rate: MVR (Cm.SUP.3./10 Min)

[0142] The measurement was carried out at 260 C. with a load of 2.16 kg in accordance with ISO1133.

[0143] Measurement apparatus: Melt Indexer T-111 (manufactured by Toyo Seiki Seisaku-sho, Ltd.)

6) Water Absorption Rate (%)

[0144] The measurement was carried out according to the method of JIS K7209. Specifically, a test piece having a diameter of 50 mm and a thickness of 3 mm obtained by injection molding was dried at 50 C. for 24 hours using a hot air dryer. After that, the mass of the test piece was measured and defined as M0. Next, the test piece was immersed in water whose temperature was controlled to 23 C.2 C. (21 C. to 25 C.). After 24 hours, the test piece was taken out, and water adhering to the surface was wiped off. Then the mass was measured and defined as Mt. The water absorption rate (%) was calculated according to the formula below.

Water absorption rate (%)=(MtM0)/M0100

[0145] Note that the mass measurement was carried out in an environment in which the temperature was controlled to 23 C.2 C. (21 C. to 25 C.).

Example 1

[0146] As raw materials, 5342.4 g (8.52 mol) of 2DNBINOL-2EO (molecular weight: 626.8) represented by a structural formula below, 4629.2 g (8.79 mol) of DPBHBNA (molecular weight: 526.6) represented by a structural formula below, 3300.0 g (6.13 mol) of BNEF (molecular weight: 538.6) represented by a structural formula below, and 646.8 g (3.20 mol) of 1,12-dodecanediol (molecular weight: 202.3) were put into a 50 L reactor equipped with a stirrer and a distillation apparatus, and subsequently 5877.4 g (27.4 mol) of diphenyl carbonate (DPC) and 2.2410.sup.2 g (2.6610.sup.4 mol) of sodium hydrogen carbonate were added thereto. After that, substitution with nitrogen in the reaction system was carried out, and the mixture was heated to 180 C. over 30 minutes under nitrogen atmosphere (760 Torr) and stirred.

##STR00017##

[0147] After the raw materials were completely dissolved, the temperature was increased to 190 C. over 20 minutes and then the pressure reducing degree was adjusted to 200 Ion Conditions were kept at 190 C. and 200 Torr for 20 minutes to perform a transesterification reaction. Further, the temperature was increased to 220 C. at a rate of 30 C./hr, and the pressure reducing degree was adjusted to 150 Torr. After that, the temperature was increased to 240 C. at a rate of 60 C./hr, and the pressure reducing degree was adjusted to 100 Torr. Further, the pressure reducing degree was adjusted to 1 Torr or less over 40 minutes, and stirring was performed under conditions of 240 C. and 1 Torr for 30 minutes to perform a polymerization reaction. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and a polycarbonate resin produced was taken out therefrom while being pelletized by a pelletizer.

[0148] The obtained pellet of the polycarbonate resin was dried at 100C for 3 hours, and

pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate](ADK STAB AO-60 manufactured by ADEKA Corporation) (1000 ppm relative to the polycarbonate resin);
3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (ADK STAB PEP-36 manufactured by ADEKA Corporation) (300 ppm relative to the polycarbonate resin);
dodecylbenzenesulfonic acid tetrabutylphosphonium salt (MGA-614 manufactured by TAKEMOTO OIL & FAT CO., LTD.) (15 ppm relative to the polycarbonate resin); and glycerin monostearate (monoglyceride stearate, S-100 manufactured by Riken Vitamin Co., Ltd.) (1500 ppm relative to the polycarbonate resin)
were added thereto, and the mixture was kneaded by a twin screw extruder. Details regarding extrusion are as described below. Physical properties of the obtained polycarbonate resin are shown in Table 1. [0149] Twin screw extruder: TEM-18SS manufactured by SHIBAURA MACHINE CO., LTD. [0150] Resin temperature: 260 C. [0151] Screw rotation speed: 200 rpm

Example 2

[0152] A polycarbonate resin was obtained in a manner similar to that in Example 1, except that 663.1 g (1.06 mol) of 2DNBINOL-2EO, 6017.7 g (11.4 mol) of DPBHBNA, 3500.0 g (5.92 mol) of BPPEF (molecular weight: 590.7) represented by a structural formula below, 556.6 g (2.75 mol) of 1,12-dodecanediol, and 4669.1 g (21.8 mol) of DPC were used as raw materials. Physical properties of the obtained polycarbonate resin are shown in Table 1.

##STR00018##

Comparative Example 1

[0153] A polycarbonate resin was obtained in a manner similar to that in Example 1, except that 5000.0 g (13.4 mol) of BNE (molecular weight: 374.4) represented by a structural formula below, 2344.1 g (4.45 mol) of DPBHBNA, 6393.4 g (11.9 mol) of BNEF, and 6547.5 g (30.6 mol) of DPC were used as raw materials. Physical properties of the obtained polycarbonate resin are shown in Table 1.

##STR00019##

TABLE-US-00001 TABLE 1 Physical properties Aromatic compound glycol Water Structural Structural Structural Structural Structural absorption unit unit unit unit unit Tg (cm.sup.3/10 rate (a)/mol % (b)/mol % (c-1)/mol % (c-2)/mol % (d)/mol % ( C.) min) (%, ) Exam- 2DNBINOL- 32 DPBHBNA BNEF 1,12- 12 1.7 1 151 0.0 ple 1 2EO dodecanediol Exam- 2DNBINOL- 5 DPBHBNA BPPEF 28 1,12- 13 1.7 15.2 138 90 0.08 ple 2 2EO dodecanediol Compar- DPBHBNA 15 BNEF 1.081 18.1 147 4 0. ative Exam- ple 1 indicates data missing or illegible when filed