POLYCARBONATE RESIN

Abstract

The present application provides a polycarbonate resin including structural units (A) represented by general formula (1) and structural units (B) represented by general formula (4).

##STR00001##

(In general formula (1), R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8 each independently represents a hydrogen atom, etc., and X represents —O—, etc.)

##STR00002##

(In general formula (4), R.sub.z and R.sub.x each independently represents a hydrogen atom or a C1-3 alkyl group, i represents an integer 3-10 and p represents an integer 5-600.)

Claims

1. A polycarbonate resin comprising a structural unit (A) represented by general formula (1) and a structural unit (B) represented by general formula (4): ##STR00021## wherein in general formula (1): R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms and an aralkyl group having 7 to 17 carbon atoms, and each of the alkyl group, the aryl group, the alkenyl group, the alkoxy group and the aralkyl group may have a substituent; and X represents —O—, —S—, —SO—, —SO.sub.2—, —CO—, a cycloalkylene group having 6 to 12 carbon atoms, or a divalent group represented by general formula (2) or general formula (3), and the cycloalkylene group may be substituted with 1 to 12 alkyl groups having 1 to 3 carbon atoms: ##STR00022## wherein in general formula (2): R.sub.9 and R.sub.10 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and an alkenyl group having 2 to 15 carbon atoms; each of the alkyl group, the alkoxy group, the aryl group, the aralkyl group and the alkenyl group of R.sub.9 and R.sub.10 may have a substituent; R.sub.9 and R.sub.10 may be bonded to each other so as to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and each of the carbocyclic ring and the heterocyclic ring may have a substituent; and n represents an integer of 0 to 20, ##STR00023## wherein in general formula (3): R.sub.11 and R.sub.12 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and an alkenyl group having 2 to 15 carbon atoms, and each of the alkyl group, the alkoxy group, the aryl group, the aralkyl group and the alkenyl group may have a substituent; and R.sub.11 and R.sub.12 may be bonded to each other so as to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and each of the carbocyclic ring and the heterocyclic ring may have a substituent, ##STR00024## wherein in general formula (4): 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 3 to 10; and p represents an integer of 5 to 600.

2. The polycarbonate resin according to claim 1, wherein the mass ratio between the structural unit (A) and the structural unit (B) (A/B) is 1/99 to 50/50.

3. A polycarbonate resin comprising only a structural unit (B) represented by general formula (4): ##STR00025## wherein: 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 3 to 10; and p represents an integer of 5 to 600.

4. The polycarbonate resin according to claim 1, wherein the concentration of a terminal hydroxyl group in the polycarbonate resin is 1 ppm to 3000 ppm.

5. The polycarbonate resin according to claim 1, wherein i in general formula (4) is an integer of 3 or 4.

6. The polycarbonate resin according to claim 1, wherein the polystyrene-equivalent weight average molecular weight (Mw) of the polycarbonate resin is 1,000 to 60,000.

7. The polycarbonate resin according to claim 1, wherein the glass transition temperature (Tg) of the polycarbonate resin is −100 to 140° C.

8. The polycarbonate resin according to claim 3, wherein the concentration of a terminal hydroxyl group in the polycarbonate resin is 1 ppm to 3000 ppm.

9. The polycarbonate resin according to claim 3, wherein i in general formula (4) is an integer of 3 or 4.

10. The polycarbonate resin according to claim 3, wherein the polystyrene-equivalent weight average molecular weight (Mw) of the polycarbonate resin is 1,000 to 60,000.

11. The polycarbonate resin according to claim 3, wherein the glass transition temperature (Tg) of the polycarbonate resin is −100 to 140° C.

Description

EXAMPLES

[0101] Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the below-described examples.

<Method for Measuring Concentration (Ppm) of Terminal Hydroxyl Group>

[0102] It was obtained by dissolving 0.05 g of a resin sample in 1 ml of deuterated chloroform (containing 0.05 w/v % TMS) and carrying out the .sup.1H-NMR measurement at 23° C. Specifically, the concentration of the terminal hydroxyl group (OH concentration) was calculated from the integration ratio between a peak related to the hydroxyl group and other peaks included in the resin skeleton.

Apparatus: 500 MHz nuclear magnetic resonance apparatus AVANCE III HD manufactured by BRUKER

<Method for Measuring Weight Average Molecular Weight (Mw)>

[0103] Using GPC with chloroform as a developing solvent, a calibration curve was produced using a standard polystyrene having an already-known molecular weight (molecular weight distribution=1) (“PStQuick MP-M” manufactured by Tosoh Corporation). The elution time and molecular weight value of each peak were plotted based on the measured standard polystyrene, and three-dimensional approximation was conducted to obtain a calibration curve. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were obtained as polystyrene equivalent values using the below-described calculation formula.

Mw=Σ(Wi×Mi)÷Σ(Wi)  [Calculation formula]

[0104] In this regard, “i” represents the “i”th dividing point when dividing the molecular weight M, “Wi” represents the “i”th weight, and “Mi” represents the “i”th molecular weight. The molecular weight M represents the value of the molecular weight of polystyrene at the corresponding elution time in the calibration curve.

[Measurement Conditions]

[0105] Apparatus: HLC-8320GPC manufactured by Tosoh Corporation

Columns:

[0106] Guard column: TSKguardcolumn SuperMPHZ-M×1

[0107] Analysis column: TSKgel SuperMultiporeHZ-M×3

Solvent: HPLC grade chloroform
Injection amount: 10 VL
Sample concentration: 0.2 w/v % HPLC grade chloroform solution
Flow rate of solvent: 0.35 ml/min
Measurement temperature: 40° C.

Detector: RI

<Measurement of Amount of Gas Generated>

[0108] The measurement was carried out using an apparatus for simultaneous thermogravimetry/differential thermal analysis (TG/TDA) (product name “TGDTA7300” manufactured by Hitachi High-Tech Science Corporation).

[0109] 5 mg of a sample was precisely weighed in a platinum pan (Pt open type sample container, cylindrical container having a diameter of 5.2 mm and a height of 5.0 mm) to prepare a measurement sample.

[0110] The measurement was carried out under nitrogen atmosphere (flow rate of nitrogen: 250 ml/min). For a reference cell, 5.52 mg of α-alumina was used as a reference substance. Further, the measurement sample was heated to measure the weight thereof as described later. Assuming that the whole decreased weight corresponds to the gasified sample, the amount of gas generated (%) “120° C..fwdarw.350° C.” was calculated as described below.

[0111] Amount of gas generated (%) “120° C..fwdarw.350° C.”=(weight at 350° C.-weight at 120° C.)/weight at 120° C.×100

[0112] The amount of gas generated (%) “120° C..fwdarw.320° C.” was calculated as described below.

[0113] Amount of gas generated (%) “120° C..fwdarw.320° C.”=(weight at 320° C.-weight at 120° C.)/weight at 120° C.×100

[0114] In this regard, the weight at 350° C. means a weight obtained when the temperature of the measurement sample was elevated from 120° C. at a rate of 10° C./min to reach 350° C. The weight at 120° C. means a weight obtained after the temperature of the measurement sample was elevated from room temperature to 120° C. at a rate of 10° C./min and then kept at 120° C. for 2 hours. The weight at 320° C. means a weight obtained when the temperature of the measurement sample was elevated from 120° C. at a rate of 10° C./min to reach 320° C.

<Measurement of Glass Transition Temperature (Tg)>

[0115] The measurement was carried out using a differential scanning calorimeter (DSC) (product name “DSC-7000” manufactured by Hitachi High-Tech Science Corporation).

[0116] 7 to 12 mg of a test piece was precisely weighed in a sample container for AI autosampler (RDC aluminum pan, cylindrical container having a diameter of 6.8 mm and a height of 2.5 mm), and the upper portion of the sample container was sealed using a cover for AI autosampler, thereby preparing a measurement sample.

[0117] The measurement was carried out under nitrogen atmosphere (flow rate of nitrogen: 50 ml/min). For a reference cell, 10.0 mg of alumina was used as a reference substance. Further, the temperature of the measurement sample was adjusted to −70° C. and then elevated to 200° C. at a rate of 10° C./min. After that, cooling was carried out at a rate of 10° C./min to decrease the temperature to −70° C. After that, the temperature was elevated again to 200° C. at a rate of 10° C./min, and the measurement was carried out.

<Measurement of YI Value>

[0118] The measurement was carried out using a spectroscopic colorimeter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. Specifically, 12 g of a resin sample was dissolved in 60 mL of dichloromethane, and the measurement was carried out using a quartz cell having an optical path length of 6 cm. As a blank, dichloromethane was used.

Example 1

[0119] As raw materials, a poly-n-propylene glycol Velvetol H500 (Mw: 1700) manufactured by ALLESSA in an amount equivalent to 85% by mass, bisphenol A (hereinafter referred to as BPA) in an amount equivalent to 15% by mass, and diphenyl carbonate (hereinafter referred to as DPC) at a molar ratio relative to diol of 1.16 were put into a polymerization apparatus equipped with a three-necked flask. Further, as a catalyst, an aqueous solution of Cs.sub.2CO.sub.3 was added thereto in an amount of 11 μmol (as Cs) per 1 mol of diol.

[0120] Drying in the system was carried out for 1 hour, and then the pressure in the polymerization apparatus was recovered using nitrogen. The polymerization was initiated at the point when the polymerization apparatus in which the pressure was recovered was immersed in an oil bath, and the polymerization was carried out according to the temperature elevation/pressure reduction program shown in Table 1. Physical properties of the obtained polycarbonate resin are shown in Table 5. The concentration of OH in the polycarbonate resin obtained in Example 1 was 70 ppm.

TABLE-US-00001 TABLE 1 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 200  97 10 200 .fwdarw. 217 97 .fwdarw. 27 20 217 27 .fwdarw. 24 30 217 24 .fwdarw. 20 40 217 20 .fwdarw. 17 50 217 17 .fwdarw. 13 60 217 13 .fwdarw. 6  70 217 6 .fwdarw. 0.13 or less 80 217 0.13 or less 140 Finished 100

Examples 2 and 3

[0121] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 5. Physical properties of the obtained polycarbonate resin are shown in Table 5. The concentration of OH in the polycarbonate resin obtained in Example 2 was 240 ppm, and the concentration of OH in the polycarbonate resin obtained in Example 3 was 1100 ppm.

Example 4

[0122] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 5 and that the temperature elevation/pressure reduction program was changed to that shown in Table 2. Physical properties of the obtained polycarbonate resin are shown in Table 5.

TABLE-US-00002 TABLE 2 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 201  97 10 201 .fwdarw. 211 97 .fwdarw. 27 70 211 .fwdarw. 217  27 90 217 .fwdarw. 227 27 .fwdarw. 24 110 227 .fwdarw. 232 24 .fwdarw. 20 130 232 .fwdarw. 241 20 .fwdarw. 17 140 241 17 .fwdarw. 13 150 241 .fwdarw. 260 13 .fwdarw. 6  160 260 6 .fwdarw. 4 170 260 4 .fwdarw. 0.13 or less 230 260 0.13 or less 320 Finished 100

Example 5

[0123] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 5 and that the temperature elevation/pressure reduction program was changed to that shown in Table 3. Physical properties of the obtained polycarbonate resin are shown in Table 5. The concentration of OH in the polycarbonate resin obtained in Example 5 was 2200 ppm.

TABLE-US-00003 TABLE 3 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 200  99 10 200 99 .fwdarw. 27 40 200 .fwdarw. 211  27 70 211 27.fwdarw. 24 90 211 .fwdarw. 217  24 110 217 24.fwdarw. 20 130 217 .fwdarw. 227  20 150 227 20 .fwdarw. 17 170 222 .fwdarw. 232  17 180 232 17 .fwdarw. 13 200 232 13 .fwdarw. 6  220 232 6 .fwdarw. 0.13 or less 230 232 0.13 or less 290 Finished 100

Examples 6 and 7

[0124] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 5 and that the temperature elevation/pressure reduction program was changed to that shown in Table 4. Physical properties of the obtained polycarbonate resin are shown in Table 5.

TABLE-US-00004 TABLE 4 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 200  97 10 200 .fwdarw. 217 97 .fwdarw. 27 25 217 27 .fwdarw. 24 40 217 24 .fwdarw. 20 55 217 20 .fwdarw. 17 70 217 17 .fwdarw. 13 85 217 13 .fwdarw. 6  100 217 6 .fwdarw. 0.13 or less 110 217 0.13 or less 170 Finished 100

Comparative Example

[0125] The reaction was performed in a manner similar to that in Example 4, except that the raw materials were changed to those shown in Table 5. Physical properties of the obtained polycarbonate resin are shown in Table 5. The concentration of OH in the polycarbonate resin obtained in Comparative Example was 850 ppm.

TABLE-US-00005 TABLE 5 Ex- Ex- Ex- Ex- Ex- Ex- Ex- Com- ample ample ample ample ample ample ample parative 1 2 3 4 5 6 7 Example Raw materials Mass ratio of diol [00018] Rz = H, Rx = H i = 3, p = 9   Rz = H, Rx = H manufactured by ALLESSA poly-n-propylene glycol Velvetol H500 manufactured by Mitsubishi 85         0 85         0 0         85 0         0 0         0 100         0 0         100 0         0 i = 4, p = Chemical 9 Corporation polytetramethylene glycol PTMG 650 Rz = H, manufactured 0 0 0 7 0 0 0 0 Rx = H by BASF i = 4, p = polytetramethylene 9 glycol PTMG 650 Rz = H, manufactured 0 0 0 0 85 0 0 0 Rx = H by Mitsubishi i = 4, Chemical p = 21 Corporation polytetramethylene glycol PTMG 1500 manufactured by Mitsubishi Chemical Corporation 15 15 15 93 15 0 0 100 bisphenol A Amount of Cs per 1 mol of diol (unit: μmol/diol) 11 10 10 1 10 10 10 10 Molar ratio of diphenyl carbonate (DPC) relative to diol 1.16 1.07 1.10 1.12 1.07 1.07 1.07 1.07 Physical Polystyrene-equivalent molecular weight (Mw) 15000 38000 26000 28000 25000 32000 14000 38000 properties Glass transition temperature Tg (° C.) <35 <35 <35 105 <35 <35 <35 148

Example 8

[0126] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 6. Physical properties of the obtained polycarbonate resin are shown in Table 17.

TABLE-US-00006 TABLE 6 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 200  97 10 200 .fwdarw. 217 97 .fwdarw. 27 20 217 27 .fwdarw. 24 30 217 24 .fwdarw. 20 40 217 20 .fwdarw. 17 50 217 17 .fwdarw. 13 60 217 13 .fwdarw. 6  70 217 6 .fwdarw. 0.13 or less 80 217 0.13 or less 140 Finished (217° C.) 100

Example 9

[0127] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 7. Physical properties of the obtained polycarbonate resin are shown in Table 17.

TABLE-US-00007 TABLE 7 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 200  97 10 200 .fwdarw. 217 97 .fwdarw. 27 80 217 27 .fwdarw. 24 170 217 24 .fwdarw. 20 210 217 20 .fwdarw. 17 230 217 17 .fwdarw. 13 260 217 13 .fwdarw. 6  280 217 6 .fwdarw. 0.13 or less 290 217 0.13 or less 350 Finished (217° C.) 100

Example 10

[0128] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 8. Physical properties of the obtained polycarbonate resin are shown in Table 17.

TABLE-US-00008 TABLE 8 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 200  97 30 200 97 .fwdarw. 27 70 200 .fwdarw. 217  27 90 217 27 .fwdarw. 24 110 217 24 .fwdarw. 20 130 217 20 .fwdarw. 17 140 217 .fwdarw. 227  17 150 227 17 .fwdarw. 13 160 227 13 .fwdarw. 6  170 227 6 .fwdarw. 0.13 or less 180 227 0.13 or less 240 Finished (227° C.) 100

Example 11

[0129] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 9. Physical properties of the obtained polycarbonate resin are shown in Table 17.

TABLE-US-00009 TABLE 9 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 120 97 10 120 .fwdarw. 150 97 20 150 .fwdarw. 180 97 30 180 .fwdarw. 200 27 50 200 .fwdarw. 217 97 .fwdarw. 27 65 217 27 .fwdarw. 24 80 217 24 .fwdarw. 20 95 217 20 .fwdarw. 17 110 217 17 .fwdarw. 13 125 217 13 .fwdarw. 6  140 217 6 .fwdarw. 0.13 or less 150 217 0.13 or less 210 Finished (217° C.) 0.13 or less

Example 12

[0130] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 10. Physical properties of the obtained polycarbonate resin are shown in Table 17.

TABLE-US-00010 TABLE 10 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 200  97 10 200 97 .fwdarw. 27 40 200 .fwdarw. 217  27 60 217 27 .fwdarw. 24 80 217 24 .fwdarw. 20 110 217 20 .fwdarw. 17 120 217 .fwdarw. 227 17 .fwdarw. 13 130 227 17 .fwdarw. 13 140 227 13 .fwdarw. 6  150 227 6 .fwdarw. 0.13 or less 160 227 0.13 or less 220 Finished (227° C.) 100

Example 13

[0131] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 11. Physical properties of the obtained polycarbonate resin are shown in Table 17.

TABLE-US-00011 TABLE 11 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 200  97 10 200 97 .fwdarw. 27 30 200 .fwdarw. 211  27 70 211 27 .fwdarw. 24 80 211 .fwdarw. 217  24 100 217 24 .fwdarw. 20 110 217 .fwdarw. 227  20 130 227 20 .fwdarw. 17 140 227 .fwdarw. 237  17 150 237 17 .fwdarw. 13 170 237 13 .fwdarw. 6  190 237 6 .fwdarw. 0.13 or less 200 237 0.13 or less 260 237 100

Examples 14 and 15

[0132] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 12. Physical properties of the obtained polycarbonate resin are shown in Table 17.

TABLE-US-00012 TABLE 12 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 200  97 10 200 .fwdarw. 217 97 .fwdarw. 27 25 217 27 .fwdarw. 24 40 217 24 .fwdarw. 20 55 217 20 .fwdarw. 17 70 217 17 .fwdarw. 13 85 217 13 .fwdarw. 6  100 217 6 .fwdarw. 0.13 or less 110 217 0.13 or less 170 Finished (217° C.) 100

Example 16

[0133] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 13. Physical properties of the obtained polycarbonate resin are shown in Table 17.

TABLE-US-00013 TABLE 13 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 200  97 10 200 .fwdarw. 217 97 .fwdarw. 27 100 217 27 .fwdarw. 24 130 217 .fwdarw. 227  24 170 227 24 .fwdarw. 20 190 227 20 .fwdarw. 17 210 227 17 .fwdarw. 13 230 227 13 .fwdarw. 6  250 227 .fwdarw. 232   6 270 232 6 .fwdarw. 0.13 or less 280 232 0.13 or less 340 Finished (232° C.) 100

Example 17

[0134] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 14. Physical properties of the obtained polycarbonate resin are shown in Table 17.

TABLE-US-00014 TABLE 14 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 200  97 10 200 .fwdarw. 217 97 .fwdarw. 27 40 217 27 .fwdarw. 24 60 217 24 .fwdarw. 20 80 217 20 .fwdarw. 17 90 217 17 .fwdarw. 13 110 217 13 .fwdarw. 6  130 217 6 .fwdarw. 0.13 or less 140 217 0.13 or less 200 Finished (217° C.) 100

Example 18

[0135] The reaction was performed in a manner similar to that in Example 1, except that the raw materials were changed to those shown in Table 16 and that the temperature elevation/pressure reduction program was changed to that shown in Table 15. Physical properties of the obtained polycarbonate resin are shown in Table 17.

TABLE-US-00015 TABLE 15 Time Set temperature Set pressure (min) (° C.) (kPaA) 0 200  97 10 200 .fwdarw. 217 97 .fwdarw. 27 70 217 .fwdarw. 222  27 90 217 27 .fwdarw. 24 120 217 24 .fwdarw. 20 150 222 .fwdarw. 227  20 160 227 20 .fwdarw. 17 180 227 17 .fwdarw. 13 200 227 13 .fwdarw. 6  220 227 6 .fwdarw. 0.13 or less 230 227 0.13 or less 290 Finished (227° C.) 100

TABLE-US-00016 TABLE 16 Exam- Exam- Exam- Exam- ple 8 ple 9 ple 10 Example 11 ple 12 Mass ratio of diol [00019] Rz = H, Rx = H i = 3, p = 9   Rz = H, Rx = H i = 4, manufactured by ALLESSA poly-n-progylene glycol Velvetol H500 manufactured by Mitsabishi Chemical  0         85 85          0  0         85  0         85  0         85 p = 9 Corporation polytetramethylene glycol PTMG 650 Raw Rz = H, manufactured by  0  0  0  0  0 materials Rx = H BASF i = 4, polytetramethylene p = 9 glycol PTMG 650 Rz = H, manufactured by  0  0  0  0  0 Rx = H Mitsubishi Chemical i = 4, Corporation p = 21 polytetramethylene glycol PTMG 1500 manufactured by Mitsubishi Chemical Corporation 15 15  0  0  0 bisphenol A manufactured by Tokyo Chemical Industry Co., Ltd. 15  0  0 bisphenol S manufactured by Tokyo Chemical Industry Co., Ltd.  0 15  0 4,4′-oxydiphenol manufactured by Tokyo Chemical Industry Co., Ltd.  0  0 15 4,4′-biphenol manufactured by Tokyo Chemical Industry Co., Ltd.  0  0  0 4,4′-thiodiphenol Amount of Cs per 1 mol of diol (unit: μmol/diol) 10  5 10 10 10 Molar ratio of diphenyl carbonate (DPC) relative to diol    1.15    1.10    1.07    1.07    1.07 Exam- Exam- Exam- Exam- Exam- Exam- ple 13 ple 14 ple 15 ple 16 ple 17 ple 18 Raw materials Mass ratio of diol [00020] Rz = H, Rx = H i = 3, p = 9   Rz = H, Rx = H i = 4, manufactured by ALLESSA poly-n-progylene glycol Velvetol H500 manufactured by Mitsabishi Chemical  0         85  0         85  0         85 85          0 85          0 85          0 p = 9 Corporation polytetramethylene glycol PTMG 650 Rz = H, manufactured by  0  0  0  0 0  0 Rx = H BASF i = 4, polytetramethylene p = 9 glycol PTMG 650 Rz = H, manufactured by  0  0  0  0 0  0 Rx = H Mitsubishi Chemical i = 4, Corporation p = 21 polytetramethylene glycol PTMG 1500 manufactured by Mitsubishi Chemical Corporation  0  0  0  0 0  0 bisphenol A manufactured by Tokyo Chemical Industry Co., Ltd.  0  0  0 15 0  0 bisphenol S manufactured by Tokyo Chemical Industry Co., Ltd.  0  0  0  0 0  0 4,4′-oxydiphenol manufactured by Tokyo Chemical Industry Co., Ltd. 15 15  0  0 15  0 4,4′-biphenol manufactured by Tokyo Chemical Industry Co., Ltd.  0  0 15  0  0 15 4,4′-thiodiphenol Amount of Cs per 1 mol of diol (unit: μmol/diol) 10 10 10  5  5  5 Molar ratio of diphenyl carbonate (DPC) relative to diol    1.07    1.07    1.07    1.07   1.1   1.1

TABLE-US-00017 TABLE 17 Amount of gas generated (%) GPC (PSt-equivalent) 120° C. .fwdarw. 120° C. .fwdarw. YI of Diol monomer/% by mass Mw Mn Mw/Mn 350° C. 320° C. solution Example 8 BPA 15 PTMG 85 22800 10200 2.24  9.8 4.1  0.61 Example 9 BPA 15 P3MG 85 22800  9680 2.35  8.1 1.8  3.31 Example 10 BPS 15 PTMG 85 21100  9060 2.33  2.9 1.0  2.28 Example 11 BPO 15 PTMG 85 17600  7380 2.38  9.0 3.6  2.51 Example 12 BF 15 PTMG 85 14100  5390 2.62  6.5 2.7  2.27 Example 13 BF 15 PTMG 85 10800  3880 2.78  6.0 2.0  1.82 Example 14 BF 15 PTMG 85 22100  8450 2.62  7.7 3.5  0.97 Example 15 TDP 15 PTMG 85 23200  9350 2.49 11.0 4.0  2.14 Example 16 BPS 15 P3MG 85 21200  6300 3.37  7.6 2.4 16.98 Example 17 BF 15 P3MG 85 22600  9770 2.31  7.8 1.8  9.76 Example 18 TDP 15 P3MG 85 23500  9920 2.37 12.7 2.1  8.26 BPA: bisphenol A BPS: bisphenol S BPO: 4,4′-oxydiphenol BF: 4,4′-biphenol TDP: 4,4′-thiodiphenol PTMG: polytetramethylene ether glycol P3MG: poly-n-propylene glycol

INDUSTRIAL APPLICABILITY

[0136] When using the polycarbonate resin of the present invention, the amount of gas generated is very small, and therefore it can be suitably utilized for various molded products.

[0137] In general, a polycarbonate resin has a high Tg, and for this reason, at the time of melt molding, it is required to be heated to a high temperature (180° C. or higher) and melted. For reduction of the cost for molding, molding at lower temperatures has been desired. Further, as a material for various industrial products, a polycarbonate having a low Tg has been desired. For example, though Tg of a widely-known bisphenol A-type polycarbonate resin is generally about 150° C., a material having a Tg lower than that has been desired. In the present invention, the copolymerized polycarbonate of polytetramethylene glycol and bisphenol A, and in particular, the copolymerized polycarbonate of poly-n-propylene glycol and bisphenol A have a low Tg and can be widely and usefully used as materials for industrial products.