Polyester carbonate resin and optical lens

Abstract

A polyester carbonate resin is provided and includes a constituent unit represented by the following general formula (1), a constituent unit represented by the following general formula (2), and a constituent unit represented by the following general formula (3): ##STR00001##
wherein R represents hydrogen or an alkyl group containing 1 to 4 carbon atoms, ##STR00002##
wherein Q represents the following: ##STR00003##
wherein n and m each independently represent an integer of 0 to 5, and ##STR00004##

Claims

1. A polyester carbonate resin comprising a constituent unit represented by the following general formula (1), a constituent unit represented by the following general formula (2), and a constituent unit represented by the following general formula (3): ##STR00029## wherein R represents hydrogen or an alkyl group containing 1 to 4 carbon atoms, ##STR00030## wherein Q represents the following: ##STR00031## wherein n and m each independently represent an integer of 0 to 5, and ##STR00032##

2. The polyester carbonate resin according to claim 1, further comprising a constituent unit represented by the following general formula (4): ##STR00033## wherein q represents the following, and R.sub.1 and R.sub.2 each independently represent hydrogen, a methyl group, or an aryl group, Z represents an alkylene group containing 1 to 8 carbon atoms, and e and f each independently represent an integer of 0 to 10, ##STR00034## wherein R.sub.3 and R.sub.4 each independently represent hydrogen, an optionally branched alkyl group containing 1 to 5 carbon atoms, or an aryl group, and q1 represents an integer of 1 to 12.

3. The polyester carbonate resin according to claim 1, further comprising a constituent unit represented by the following general formula (5): ##STR00035## wherein X represents an alkylene group containing 1 to 8 carbon atoms, and a and b each independently represent an integer of 0 to 10.

4. The polyester carbonate resin according to claim 1, further comprising a constituent unit represented by the following general formula (6): ##STR00036## wherein Y represents an alkylene group containing 1 to 8 carbon atoms, and c and d each independently represent an integer of 0 to 10.

5. An optical lens, in which the polyester carbonate resin according to claim 1 is used.

6. The polyester carbonate resin according to claim 2, further comprising a constituent unit represented by the following general formula (5): ##STR00037## wherein X represents an alkylene group containing 1 to 8 carbon atoms, and a and b each independently represent an integer of 0 to 10.

7. The polyester carbonate resin according to claim 2, further comprising a constituent unit represented by the following general formula (6): ##STR00038## wherein Y represents an alkylene group containing 1 to 8 carbon atoms, and c and d each independently represent an integer of 0 to 10.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described in the following examples. However, these examples are not intended to limit the scope of the present invention. It is to be noted that the measurement values described in the examples were obtained by applying the following methods or apparatuses.

(2) <Method of Measuring Weight Average Molecular Weight (Mw)>

(3) The weight average molecular weight relative to polystyrene standard was obtained from the calibration curve of previously produced standard polystyrene. That is to say, standard polystyrene (manufactured by Tosoh Corporation, “PStQuick MP-M”) whose molecular weight had been known (molecular weight distribution=1) was used to produce a standard curve. From the measured standard polystyrene, the elution time and the molecular weight value of each peak were plotted, and approximation was performed with a cubic equation to obtain a calibration curve. Mw was obtained according to the following equation:
Mw=Σ(Wi×Mi)/Σ(Wi).

(4) In this equation, i indicates an i.sup.th dividing point when the molecular weight M was divided; Wi indicates an i.sup.th weight; and Mi indicates an i.sup.th molecular weight. Moreover, the molecular weight M indicates the value of the molecular weight of polystyrene at the same elution time in the calibration curve. As a GPC apparatus, HLC-8320GPC manufactured by Tosoh Corporation was used. A single column of TSKguardcolumn SuperMPHZ-M was used as a guard column, and a TSKgel SuperMultiporeHZ-M column line consisting of three columns connected in series was used as an analysis column. Other conditions are as follows.

(5) Solvent: Tetrahydrofuran, HPLC grade

(6) Amount injected: 10 μL

(7) Sample concentration: 0.2 w/v % Chloroform solution, HPLC grade

(8) Solvent flow rate: 0.35 ml/min

(9) Measurement temperature: 40° C.

(10) Detector: RI

(11) <Glass Transition Temperature (Tg)>

(12) The glass transition temperature (Tg) was measured in accordance with JIS K7121-1987, using a differential scanning calorimeter (DSC). As the analyzer, Hitachi High-Tech Science X-DSC7000 was used.

(13) <Oriented Refractive Index>

(14) The obtained polyester carbonate resin was heated to the Tg of the resin +65° C., and the resulting resin was then pressed using a pressing machine (100 kgf/cm.sup.2, 2 minutes) to produce a sheet. The produced sheet was subjected to uniaxial extension to an extension magnification of 1.5 times at the Tg of the resin +20° C., and the phase difference at 600 nm was then measured using M-220 manufactured by JASCO Corporation.

(15) <Photoelastic Coefficient>

(16) The obtained polyester carbonate resin was heated to the Tg of the resin +65° C., and the resulting resin was then pressed using a pressing machine (100 kgf/cm.sup.2, 2 minutes) to produce a sheet. The produced sheet was subjected to uniaxial extension to an extension magnification of 1.5 times at the Tg of the resin +20° C., and the measurement was then carried out using M-220 manufactured by JASCO Corporation.

(17) <Refractive Index>

(18) The obtained polyester carbonate resin was press-molded into a disk having 40 φ and a thickness of 3 mm according to press molding (molding conditions: 200° C., 100 kgf/cm.sup.2, and 2 minutes), and was then cut at a right angle, which was then measured using KPR-200 manufactured by Kalnew.

Example 1

(19) D-NDM represented by the following structural formula (200.00 g; 0.900 moles), 9,9-fluorene-methyl dipropionate (FDPM) represented by the following structural formula (66.67 g; 0.197 moles), diphenyl carbonate (155.00 g; 0.724 moles), and titanium tetrabutoxide (29.1 mg; 8.6×10.sup.−5 moles), which were used as raw materials, were placed in a 500 mL reactor equipped with a stirrer and a distillation apparatus. Thereafter, the obtained mixture was heated to 180° C. in a nitrogen atmosphere at a pressure of 101.3 kPa over 1 hour, and was stirred. After the temperature had reached 180° C., the pressure was reduced to 40 kPa over 30 minutes. After initiation of the pressure reduction, the temperature was increased to 255° C. over 2 hours. When the distilled methanol and the distilled phenol became 60%, the pressure was further reduced to 0.133 kPa or less over 1 hour. The reaction mixture was retained at a pressure of 0.133 kPa or less for 30 minutes to obtain a polyester carbonate resin.

(20) The physical properties of the obtained polyester carbonate resin are shown in Table 1.

(21) ##STR00024##

Example 2

(22) A polyester carbonate resin was obtained by performing the same operations as those in Example 1, with the exception that the aforementioned D-NDM (185.11 g; 0.833 moles), 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) represented by the following structural formula (26.45 g; 0.060 moles), the aforementioned FDPM (52.90 g; 0.156 moles), diphenyl carbonate (163.40 g; 0.763 moles), and titanium tetrabutoxide (19.4 mg; 5.8×10.sup.−5 moles) were used as raw materials.

(23) ##STR00025##

Example 2-1

(24) A polyester carbonate resin was obtained by performing the same operations as those in Example 1, with the exception that the aforementioned D-NDM (135.00 g; 0.607 moles), the aforementioned BPEF (110.00 g; 0.251 moles), the aforementioned FDPM (52.90 g; 0.156 moles), diphenyl carbonate (163.40 g; 0.763 moles), and titanium tetrabutoxide (19.4 mg; 5.8×10.sup.−5 moles) were used as raw materials.

Example 2-2

(25) A polyester carbonate resin was obtained by performing the same operations as those in Example 1, with the exception that the aforementioned D-NDM (140.00 g; 0.630 moles), the aforementioned BPEF (20.00 g; 0.046 moles), the aforementioned FDPM (100.00 g; 0.296 moles), diphenyl carbonate (163.40 g; 0.763 moles), and titanium tetrabutoxide (19.4 mg; 5.8×10.sup.−5 moles) were used as raw materials.

Example 3

(26) A polyester carbonate resin was obtained by performing the same operations as those in Example 1, with the exception that the aforementioned D-NDM (185.11 g; 0.833 moles), 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF) represented by the following structural formula (35.63 g; 0.060 moles), the aforementioned FDPM (52.90 g; 0.156 moles), diphenyl carbonate (163.40 g; 0.763 moles), and titanium tetrabutoxide (19.4 mg; 5.8×10.sup.−5 moles) were used as raw materials.

(27) ##STR00026##

Example 4

(28) A polyester carbonate resin was obtained by performing the same operations as those in Example 1, with the exception that the aforementioned D-NDM (185.11 g; 0.833 moles), 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene (BNE) represented by the following structural formula (22.60 g; 0.060 moles), the aforementioned FDPM (52.90 g; 0.156 moles), diphenyl carbonate (163.40 g; 0.763 moles), and titanium tetrabutoxide (19.4 mg; 5.8×10.sup.−5 moles) were used as raw materials.

(29) ##STR00027##

Example 5

(30) A polyester carbonate resin was obtained by performing the same operations as those in Example 1, with the exception that the aforementioned D-NDM (200.00 g; 0.900 moles), dimethyl terephthalate (DMT) represented by the following structural formula (38.26 g; 0.197 moles), diphenyl carbonate (155.00 g; 0.724 moles), and titanium tetrabutoxide (19.4 mg; 5.8×10.sup.−5 moles) were used as raw materials.

(31) ##STR00028##

Comparative Example 1

(32) The same operations as those in Example 1 were performed, with the exception that the aforementioned D-NDM (200.00 g; 0.900 moles), diphenyl carbonate (220.00 g; 1.027 moles), and sodium hydrogen carbonate (1.3 mg; 15.0 μmoles) were used as raw materials.

Comparative Example 2

(33) The same operations as those in Example 1 were performed, with the exception that the aforementioned D-NDM (170.00 g; 0.765 moles), the aforementioned BPEF (60.00 g; 0.137 moles), diphenyl carbonate (220.00 g; 1.027 moles), and sodium hydrogen carbonate (1.3 mg; 15.0 μmoles) were used as raw materials.

(34) TABLE-US-00001 TABLE 1 Ex. 1 Ex. 2 Ex. 2-1 Ex. 2-2 Ex. 3 Composition D-NDM mol % 82 79 60 65 79 ratio of raw BPEF mol % 0 6 25 5 0 materials BPPEF mol % 0 0 0 0 6 BNE mol % 0 0 0 0 0 FDPM mol % 18 15 15 30 15 DMT mol % 0 0 0 0 0 Physical Orientation nm 13 8 2 2 8 properties birefringence Photoelastic ×10.sup.−12 .Math. 12 14 18 15 16 coefficient Pa.sup.−1 Tg ° C. 132 135 138 131 137 Mw — 38000 45000 40000 42000 42000 Refractive nd 1.550 1.555 1.583 1.566 1.558 index Comp. Comp. Ex. 4 Ex. 5 Ex. 1 Ex. 2 Composition D-NDM mol % 79 82 100 85 ratio of raw BPEF mol % 0 0 0 15 materials BPPEF mol % 0 0 0 0 BNE mol % 6 0 0 0 FDPM mol % 15 0 0 0 DMT mol % 0 18 0 0 Physical Orientation nm 9 150 120 55 properties birefringence Photoelastic ×10.sup.−12 .Math. 17 25 8 15 coefficient Pa.sup.−1 Tg ° C. 131 138 135 136 Mw — 40000 39000 37000 37000 Refractive nd 1.559 1.540 1.531 1.558 index

(35) When the results of Example 1 were compared with the results of Example 5, the oriented refractive index and the photoelastic coefficient became higher values in Example 5 using dimethyl terephthalate (DMT), than in Example 1 using fluorene dimethyl dipropionate (FDPM). However, dimethyl terephthalate (DMT) is advantageous in that it is more expensive than fluorene dimethyl dipropionate (FDPM). Hence, the polyester carbonate resin obtained in Example 5 may be mixed into the polyester carbonate resin obtained in Example 1, and the thus mixed resin may be used. Naturally, the polyester carbonate resin obtained in Example 5 may also be used alone.