Example 1
Polymerization of the polycarbonate resin was carried out using a continuous polymerization facility including three vertical stirring reactors, one horizontal stirring reactor, and a twin-screw extruder. ISB, CHDM, and DPC are each melted in a tank, and ISB, CHDM, and DPC were continuously supplied to the first vertical stirring reactor at flow rates of 29.8 kg/hr, 12.6 kg/hr, and 63.1 kg/hr, respectively (ISB/CHDM/DPC=0.700/0.300/1.010 in molar ratio). At the same time, an aqueous solution of calcium acetate monohydrate as a polymerization catalyst was supplied to the first vertical stirring reactor at an addition amount such that calcium acetate monohydrate was 1.5 μmol per 1 mol of all dihydroxy compounds. The internal temperature, internal pressure, and residence time of each reactor were set as follows: 190° C., 25 kPa, and 120 minutes for the first vertical stirring reactor, 195° C., 10 kPa, and 90 minutes for the second vertical stirring reactor, 205° C., 4 kPa, and 45 minutes for the third vertical stirring reactor, and 220° C., 0.1 to 1.0 kPa, and 120 minutes for the fourth horizontal stirring reactor. The operation was performed while finely adjusting the internal pressure of the fourth horizontal stirring reactor so that the reduced viscosity of the obtained polycarbonate resin was 0.42 dL/g to 0.44 dL/g. The polycarbonate resin extracted from the fourth horizontal stirring reactor was supplied in a molten state to a vent type twin-screw extruder TEX30α [manufactured by The Japan Steel Works, Ltd.]. The extruder has three vacuum vents, where residual low molecular weight components in the resin were removed by devolatilization, and 0.63 ppm by weight of phosphonic acid was added as a catalyst deactivator before the first vent to the polycarbonate resin, 1000 ppm by weight of Irganox 1010, 500 ppm by weight of AS2112, 3000 ppm by weight of E-275, and 200 ppm by weight of SEESORB709 were added to the polycarbonate resin before the third vent. The polycarbonate resin that passed through the extruder was continuously caused to pass through an Ultipleat candle filter (manufactured by PALL) with an opening of 10 μm in a molten state to filter foreign matters. Then, the polycarbonate resin was extruded in a strand form from the die, cooled with water, solidified, and then cut by a rotary cutter to be pelletized. The pelletized polycarbonate resin thus obtained is referred to as “PC-A1”.
After blending 700 parts by weight of pellets of the polycarbonate resin PC-A1 obtained in Production Example 1 and 300 parts by weight of pellets of the polycarbonate resin PC-B1 obtained in Production Example 4, a twin-screw extruder TEX30HSS equipped with a vacuum vent (manufactured by The Japan Steel Works, Ltd.) was used to perform extrusion kneading at a cylinder temperature of 240° C. and an extrusion rate of 18 kg/hr, thereby obtaining pellets of a polycarbonate resin composition. Next, the pellets of the resin composition were dried with a hot air dryer at a temperature of 90° C. for 5 hours, and then injection-molded using a 75-ton injection molding machine EC-75 [manufactured by Toshiba Machine Co., Ltd.]. The molding conditions were a mold temperature of 60° C. and a cylinder temperature of 240° C. Thus, a test piece composed of a plate-shaped molded article having a width of 100 mm, a length of 100 mm, and a thickness of 2 mm was obtained. Further, an ISO tensile test piece was obtained by performing molding in the same manner. From the ISO tensile test piece, a Charpy impact test piece with a notch of 0.25 mm was cut out to perform a Charpy impact test. The total light transmittance, YI, chemical resistance, and moist heat cycle resistance of the plate-shaped molded product were measured.
After blending 80 parts by weight of pellets of PC-A1 and 20 parts by weight of powder of PC-C1, a twin-screw extruder TEX30HSS equipped with a vacuum vent [manufactured by The Japan Steel Works, Ltd.] was used to perform extrusion-kneading at a cylinder temperature of 260° C. and an extrusion rate of 12 kg/hr to obtain a pellet of a polycarbonate resin composition (see Table 7). The obtained pellet was cloudy. As a result of measuring the glass transition temperature by dynamic viscoelasticity measurement using this pellet, two glass transition temperatures were detected. From this result, it can be judged that PC-A1 and PC-C1 are incompatible.
Example 2
The procedure of Production Example 1 was performed except that supply amounts of the raw materials were set as 21.3 kg/hr of ISB, 21.1 kg/hr of CHDM, and 62.9 kg/hr of DPC (ISB/CHDM/DPC=0.500/0.500/1.005 in molar ratio) and adjustment was performed so that the reduced viscosity of the obtained polycarbonate resin was 0.50 dL/g to 0.52 dL/g. The polycarbonate resin thus obtained is referred to as “PC-A2”.
The same procedure as in Reference Example 1 was performed except that 80 parts by weight of pellets of PC-A1 and 20 parts by weight of powder of PA-C1 were used and the cylinder temperature of the extruder was set to 240° C. (see Table 7). The obtained pellet was cloudy and two glass transition temperatures were detected, and thus it can be judged that PC-A1 and PA-C1 are incompatible.
After blending 90 parts by weight of pellets of PC-A1, 9.76 parts by weight of pellets of PC-B1, and 0.24 parts by weight of powder of PC-C1, a twin-screw extruder TEX30HSS equipped with a vacuum vent [The Japan Steel Works, Ltd.] was used to perform extrusion-kneading at a cylinder temperature of 240° C. and an extrusion rate of 12 kg/hr to obtain a pellet of a polycarbonate resin composition. Next, the pellets of the resin composition were dried with a hot air dryer at a temperature of 90° C. for 5 hours, and then injection-molded using a 75-ton injection molding machine EC-75 [manufactured by Toshiba Machine Co., Ltd.]. The molding conditions were a mold temperature of 60° C. and a cylinder temperature of 240° C. Thus, a test piece composed of a plate-shaped molded article having a width of 100 mm, a length of 100 mm, and a thickness of 2 mm was obtained. Further, an ISO tensile test piece was obtained by performing molding in the same manner. From the ISO tensile test piece, a Charpy impact test piece with a notch of 0.25 mm was cut out to perform a Charpy impact test. The total light transmittance, haze, YI, chemical resistance, and moist heat cycle resistance of the plate-shaped molded article were measured. The results are shown in Table 8.
Example 3
The procedure of Production Example 1 was performed except that supply amounts of the raw materials were set as 27.3 kg/hr of ISB, 15.7 kg/hr of TCDDM, and 57.6 kg/hr DPC (ISB/TCDDM/DPC=0.700/0.300/1.007 in molar ratio), the addition amount of calcium acetate monohydrate was set to 1.5 μmol per 1 mol of all dihydroxy compounds, adjustment was performed so that the reduced viscosity of the obtained polycarbonate resin was 0.38 dL/g to 0.40 dL/g, and the addition amount of phosphonic acid was set to 1.3 ppm by weight with respect to the polycarbonate resin. The polycarbonate resin thus obtained is referred to as “PC-A3”. The content of ISB structural unit in PC-A3 is 53.9° by weight, and the content of TCDDM structural unit is 31.1% by weight.
The same procedure as in Reference Example 1 was performed except that 80 parts by weight of pellets of PC-B3 and 20 parts by weight of powder of PC-C1 were used (see Table 7). The obtained pellet was transparent, and one glass transition temperature was detected between the glass transition temperatures of PC-B3 and PC-C1, and thus it can be judged that PC-B3 and PC-C1 are compatible.
After blending 90 parts by weight of pellets of PC-A1 and 10 parts by weight of pellets of PC-B5, a twin-screw extruder TEX30HSS equipped with a vacuum vent [manufactured by The Japan Steel Works, Ltd.] was used to perform extrusion-kneading at a cylinder temperature of 240° C. and an extrusion rate of 12 kg/hr to obtain a pellet of the polycarbonate resin composition. Various properties of the polycarbonate resin composition were evaluated according to the methods described above. The results are shown in Table 10.
The same operation as in Example 3-1 was performed, except that the composition was changed to those shown in Table 10. Further, for Example 3-2, Example 3-3, and Comparative Examples 3-1 to 3-3, various properties of the polycarbonate resin compositions were evaluated by the methods described above. The results are shown in Table 10.
As known from Table 10, the resin compositions of Examples 3-1 to 3-3 are excellent in a plurality of properties such as transparency, heat resistance, color tone, moldability, chemical resistance, mechanical properties, weather resistance, and optical properties in good balance. In addition, in the multilayer bodies including the resin layers containing the resin compositions of Examples 3-1 to 3-3, warpage generated under use environment or storage environment was suppressed.
On the other hand, in Comparative Example 3-1 and Comparative Example 3-2, the resin compositions contained the first polycarbonate resin, but did not contain the second polycarbonate resin. In this case, the warpage of the multilayer body was large. In Comparative Example 3-3, the resin composition contained the second polycarbonate resin, but did not contain the first polycarbonate resin. Also, in this case, the warpage of the multilayer body was large.
Example 4
The procedure of Production Example 1 was performed except that supply amounts of the raw materials were set as 17.1 kg/hr of ISB, 25.3 kg/hr of CHDM, and 62.6 kg/hr of DPC (ISB/CHDM/DPC=0.400/0.600/1.000 in molar ratio), the addition amount of calcium acetate monohydrate was set to 3 μmol per 1 mol of all dihydroxy compounds, adjustment was performed so that the reduced viscosity of the obtained polycarbonate resin was 0.66 dL/g to 0.68 dL/g, and the addition amount of phosphonic acid was set to 1.3 ppm by weight with respect to the polycarbonate resin. The polycarbonate resin thus obtained is referred to as “PC-B1”.
The same procedure as in Reference Example 1 was performed except that 80 parts by weight of pellets of PC-B3 and 20 parts by weight of powder of PA-C1 were used and the cylinder temperature of the extruder was set to 240° C. (see Table 7). The obtained pellet was transparent, and one glass transition temperature was detected between the glass transition temperatures of PC-B3 and PA-C1, and thus it can be judged that PC-B3 and PA-C1 are compatible.
Example 5
The Procedure of Production Example 1 was Performed except that supply amounts of the raw materials were set as 15.0 kg/hr of ISB, 27.4 kg/hr of CHDM, and 62.7 kg/hr of DPC (ISB/CHDM/DPC=0.350/0.650/1.000 in molar ratio), the addition amount of calcium acetate monohydrate was set to 3 μmol per 1 mol of all dihydroxy compounds, adjustment was performed so that the reduced viscosity of the obtained carbonate resin was 0.73 dL/g to 0.75 dL/g, and the addition amount of phosphonic acid was 1.3 ppm by weight with respect to the polycarbonate resin. The polycarbonate resin thus obtained is described as “PC-B2”.
Example 6
The procedure of Production Example 1 was performed except that supply amounts of the raw materials were set as 12.8 kg/hr of ISB, 29.6 kg/hr of CHDM, and 62.7 kg/hr of DPC (ISB/CHDM/DPC=0.300/0.700/1.000 in molar ratio), the addition amount of calcium acetate monohydrate was set to 3 μmol per 1 mol of all dihydroxy compounds, adjustment was performed so that the reduced viscosity of the obtained polycarbonate resin was 0.75 dL/g to 0.77 dL/g, and the addition amount of phosphonic acid was set to 1.3 ppm by weight with respect to the polycarbonate resin. The polycarbonate resin thus obtained is described as “PC-B3”.
Example 7
The procedure of Production Example 1 was performed except that supply amounts of the raw materials were set as 15.0 kg/hr of ISB, 27.4 kg/hr of CHDM, and 63.3 kg/hr of DPC (ISB/CHDM/DPC=0.350/0.650/1.010), the addition amount of calcium acetate monohydrate was set to 3 μmol per 1 mol of all dihydroxy compounds, adjustment was performed so that the reduced viscosity of the obtained polycarbonate resin was 0.44 dL/g to 0.46 dL/g, and the addition amount of phosphonic acid was 1.3 ppm by weight with respect to the polycarbonate resin. The obtained polycarbonate resin is described as “PC-B4”.
Example 8
The procedure of Production Example 1 was performed except that supply amounts of the raw materials were set as 12.8 kg/hr of ISB, 29.6 kg/hr of CHDM, and 63.3 kg/hr of DPC (ISB/CHDM/DPC=0.300/0.700/1.010 in molar ratio), the addition amount of calcium acetate monohydrate was set to 3 μmol per 1 mol of all dihydroxy compounds, adjustment was performed so that the reduced viscosity of the obtained polycarbonate resin was 0.44 dL/g to 0.46 dL/g, and the addition amount of phosphonic acid was set to 1.3 ppm by weight with respect to the polycarbonate resin. The polycarbonate resin thus obtained is referred to as “PC-B5”.
Example 9
The procedure of Production Example 1 was performed except that supply amounts of the raw materials were set as 12.8 kg/hr of ISB, 29.6 kg/hr of CHDM, and 63.7 kg/hr of DPC (ISB/CHDM/DPC=0.300/0.700/1.015 in molar ratio), the addition amount of calcium acetate monohydrate was set to 3 μmol per 1 mol of all dihydroxy compounds, adjustment was performed so that the reduced viscosity of the obtained polycarbonate resin was 0.38 dL/g to 0.40 dL/g, and the addition amount of phosphonic acid was set to 1.3 ppm by weight with respect to the polycarbonate resin. The polycarbonate resin thus obtained is referred to as “PC-B6”.
Tables 1, 6, and 9 show structural units and physical properties of the first polycarbonate resin and the second polycarbonate resin obtained in the above-mentioned Production Examples. Note that, of the components constituting the first polycarbonate resin and the second polycarbonate resin, components other than the structural units shown in Tables 1, 6, and 9 are linking groups such as a carbonyl group. In addition, Table 6 shows the physical properties of the resin C (that is, PC-C1 and PA-C1). Table 1 shows structural units and physical properties of the resins used in Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-3 below. Table 6 shows structural units and physical properties of the resins used in Reference Examples 1 to 4, Examples 2-1 to 2-8, and Comparative Examples 2-1 to 2-3 below. Table 9 shows structural units and physical properties of the resins used in Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-3 below.
