CHLORINATED VINYL CHLORIDE-BASED RESIN

Abstract

The present invention provides a chlorinated polyvinyl chloride resin that provides a molded article having excellent heat cycle characteristics and excellent weather resistance, as well as a resin composition for molding and a molded article each including the chlorinated polyvinyl chloride resin. Provided is a chlorinated polyvinyl chloride resin, containing two components including a A.sub.30 component and a B.sub.30 component, the A.sub.30 component and the B.sub.30 component being determined by measuring the resin by a solid echo method using pulse NMR at 30° C. to give a free induction decay curve of .sup.1H spin-spin relaxation, and subjecting the free induction decay curve to waveform separation into two curves derived from the A.sub.30 component and the B.sub.30 component in order of shorter relaxation time using the least square method, and having a ratio of T5.sub.B to T.sub.B [T5.sub.B/T.sub.B] of 96% or more and 120% or less, where T.sub.B is a relaxation time of the B.sub.30 component and T5.sub.B is a relaxation time of the B.sub.30 component after heating at 200° C. for five minutes.

Claims

1. A chlorinated polyvinyl chloride resin comprising two components including a A.sub.30 component and a B.sub.30 component, the A.sub.30 component and the B.sub.30 component being determined by measuring the resin by a solid echo method using pulse NMR at 30° C. to give a free induction decay curve of .sup.1H spin-spin relaxation, and subjecting the free induction decay curve to waveform separation into two curves derived from the A.sub.30 component and the B.sub.30 component in order of shorter relaxation time using the least square method, and having a ratio of T5.sub.B to T.sub.B [T5.sub.B/T.sub.B] of 96% or more and 120% or less, where T.sub.B is a relaxation time of the B.sub.30 component and T5.sub.B is a relaxation time of the B.sub.30 component after heating at 200° C. for five minutes.

2. The chlorinated polyvinyl chloride resin according to claim 1, having a ratio of T5.sub.B to T20.sub.B [T5.sub.B/T20.sub.B] of 96% or more and 120% or less, where T5.sub.B is the relaxation time of the B.sub.30 component after heating at 200° C. for 5 minutes and T20.sub.B is a relaxation time of the B.sub.30 component after heating at 200° C. for 20 minutes.

3. The chlorinated polyvinyl chloride resin according to claim 1, containing a structural unit having a sulfur-containing substituent.

4. A resin composition for molding, comprising the chlorinated polyvinyl chloride resin according to claim 1.

5. A molded article molded from the resin composition for molding according to claim 4.

Description

DESCRIPTION OF EMBODIMENTS

[0136] The present invention is hereinafter described in more detail with reference to examples; however, the present invention should not be limited to these examples.

Example 1

[0137] A glass-lined reaction vessel having an inner capacity of 300 L was charged with 130 kg of ion-exchanged water and 50 kg of a polyvinyl chloride resin having an average degree of polymerization of 1,000. They were stirred to disperse the polyvinyl chloride resin in water to prepare an aqueous suspension, and then the inside of the reaction vessel was heated to raise the temperature of the aqueous suspension to 140° C. Subsequently, the inside of the reaction vessel was depressurized to remove oxygen (oxygen content 100 ppm). Thereafter, with stirring, chlorine (oxygen content 50 ppm) was introduced at a partial pressure of chlorine of 0.40 MPa, thereby starting thermal chlorination.

[0138] Then, the chlorination temperature was kept at 140° C. and the partial pressure of chlorine was kept at 0.40 MPa. After the amount of added chlorine reached 4.4% by mass, addition of a 200 ppm hydrogen peroxide solution was started at 15 ppm/Hr in terms of hydrogen peroxide relative to the polyvinyl chloride resin, and the average chlorine consumption rate was adjusted to 0.05 kg/PVC-kg.Math.5 min. When the amount of added chlorine reached 9.5% by mass, the supply of the hydrogen peroxide solution and chlorine gas was terminated, whereby chlorination was terminated. The reaction time (time from the start to termination of chlorination) was eight hours.

[0139] Subsequently, unreacted chlorine was removed by nitrogen gas aeration, and the obtained chlorinated polyvinyl chloride resin slurry was neutralized with sodium hydroxide, washed with water, and dehydrated in a centrifuge (produced by Tanabe Tekkosho K.K., 0-15 model) for three minutes.

[0140] After dehydration, 0.05 kg of 2-ethylhexyl thioglycolate (produced by FUJIFILM Wako Pure Chemical Corporation) was added to 50 kg of the dehydrated chlorinated polyvinyl chloride resin at 200 g/min. This was followed by stationary drying at 90° C. for 12 hours. Thus, a powdery, thermally chlorinated polyvinyl chloride resin (amount of added chlorine: 9.5% by mass) was obtained.

Comparative Example 1

[0141] A glass-lined reaction vessel having an inner capacity of 300 L was charged with 130 kg of ion-exchanged water and 50 kg of a polyvinyl chloride resin having an average degree of polymerization of 1,000. They were stirred to disperse the polyvinyl chloride resin in water to prepare an aqueous suspension, and then the inside of the reaction vessel was heated to raise the temperature of the aqueous suspension to 140° C. Subsequently, the inside of the reaction vessel was depressurized to remove oxygen (oxygen content 100 ppm). Thereafter, with stirring, chlorine (oxygen content 50 ppm) was introduced at a partial pressure of chlorine of 0.40 MPa, thereby starting thermal chlorination.

[0142] Then, the chlorination temperature was kept at 140° C. and the partial pressure of chlorine was kept at 0.40 MPa. After the amount of added chlorine reached 4.4% by mass, addition of a 200 ppm hydrogen peroxide solution was started at 15 ppm/Hr in terms of hydrogen peroxide relative to the polyvinyl chloride resin, and the average chlorine consumption rate was adjusted to 0.05 kg/PVC-kg.Math.5 min. When the amount of added chlorine reached 9.5% by mass, the supply of hydrogen peroxide solution and chlorine gas was terminated, whereby chlorination was terminated. The reaction time (time from the start to termination of chlorination) was eight hours.

[0143] Subsequently, unreacted chlorine was removed by nitrogen gas aeration, and the obtained chlorinated polyvinyl chloride resin slurry was neutralized with sodium hydroxide, washed with water, and dehydrated in a centrifuge (produced by Tanabe Tekkosho K.K., 0-15 model) for three minutes. This was followed by stationary drying at a drying temperature of 90° C. for 12 hours. Thus, a powdery, thermally chlorinated polyvinyl chloride resin (amount of added chlorine: 9.5% by mass) was obtained.

Examples 2 to 8 and Comparative Examples 2 to 4

[0144] A powdery chlorinated polyvinyl chloride resin was obtained as in Example 1 except that the average degree of polymerization and the addition amount of the polyvinyl chloride resin, the amount of the sulfur compound added, the reaction time, the drying temperature, and the drying time were changed as shown in Table 1.

(Evaluation)

[0145] The chlorinated polyvinyl chloride resins obtained in the examples and the comparative examples were evaluated as follows. Table 1 shows the results.

(1) Pulse NMR Measurement

[0146] Each of the obtained powdery chlorinated polyvinyl chloride resins was placed in a glass sample tube having a diameter of 10 mm (produced by BRUKER, Product No. 1824511, 10 mm in diameter, 180 mm in length, flat bottom) so as to fall within the measurement range of a pulse NMR apparatus. The sample tube was set in the pulse NMR apparatus (produced by BRUKER, “the minispec mq20”) and subjected to measurement by the solid echo method at 30° C. under the conditions below, thereby obtaining a free induction decay curve of .sup.1H spin-spin relaxation. The measurement at 100° C. was performed in the same manner.

<Solid Echo Method>

[0147] Scans: 128 times
Recycle delay: 1 sec Acquisition scale: 0.5 ms

[0148] The free induction decay curve was subjected to waveform separation into two curves derived from the A.sub.30 component and the B.sub.30 component. The waveform separation was performed by fitting using both a Gaussian model and an exponential model. The percentages of the two components were determined from the curves derived from the components obtained in the measurement.

[0149] Using analysis software “TD-NMRA (Version 4.3, Rev. 0.8)” produced by BRUKER, a Gaussian-model fitting was applied to the A.sub.30 component and B.sub.30 component in conformity with the product manual.

[0150] The following equation was used in the fitting.

[00001]$\begin{array}{cc}Y=A\times \exp \left(-\frac{1}{2}\times {\left(\frac{t}{T_A}\right)}^2\right)+B\times \exp \left(-\frac{1}{2}\times {\left(\frac{t}{T_B}\right)}^2\right)+C\times \exp \left(-\frac{t}{T_C}\right)& \left[\mathrm{Math}.1\right]\end{array}$

[0151] In the formula, A represents the percentage of the A.sub.30 component, B represents the percentage of the B.sub.30 component, T.sub.A represents the relaxation time of the A.sub.30 component, T.sub.B represents the relaxation time of the B.sub.30 component, and t represents time.

[0152] The A.sub.30 component and the B.sub.30 component are components defined in order of shorter relaxation time in pulse NMR measurement.

(Measurement after Heating at 200° C. for Five Minutes)

[0153] Each of the obtained powdery chlorinated polyvinyl chloride resins in an amount of 300 g was uniformly levelled using an aluminum tray, and heated in a gear oven produced by Toyo Seiki Seisaku-Sho, Ltd., (model: CO-02) at 200° C. for five minutes. Thereafter, the percentages of the two components (A.sub.30 component and B.sub.30 component), the relaxation time T5.sub.A of the A.sub.30 component, and the relaxation time T5.sub.B of the B.sub.30 component were determined by the same method as above.

(Measurement after Heating at 200° C. for 20 Minutes)

[0154] Each of the obtained powdery chlorinated polyvinyl chloride resins in an amount of 300 g was uniformly levelled using an aluminum tray, and then heated in a gear oven produced by Toyo Seiki Seisaku-Sho, Ltd., (model: CO—O2) at 200° C. for 20 minutes. Thereafter, the percentages of the two components (A.sub.30 component and B.sub.30 component), the relaxation time T20.sub.A of the A.sub.30 component, and the relaxation time T20.sub.B of the B.sub.30 component were determined by the same method as above.

[0155] The T5.sub.B/T.sub.B and the T5.sub.B/T20.sub.B were calculated from the obtained T.sub.B, T5.sub.B, and T20.sub.B.

(2) Measurement of Amount of Added Chlorine

[0156] The amount of added chlorine was measured for each of the obtained chlorinated polyvinyl chloride resins in conformity with JIS K 7229.

(3) Molecular Structure Analysis

[0157] The molecular structure of each of the obtained chlorinated polyvinyl chloride resins was analyzed in conformity with the NMR measurement method described in R. A. Komoroski, R. G. Parker, J. P. Shocker, Macromolecules, 1985, 18, 1257-1265 so as to determine the amount of the structural units (a) and (b) relative to the total number of moles of the structural units (a), (b), and (c).

[0158] The NMR measurement conditions were as follows.

[0159] Apparatus: FT-NMRJEOLJNM-AL-300

[0160] Measured nuclei: 13C (proton complete decoupling)

[0161] Pulse width: 90°

[0162] PD: 2.4 sec

[0163] Solvent: o-dichlorobenzene:deuterated benzene (C5D5)=3:1

[0164] Sample concentration: about 20%

[0165] Temperature: 110° C.

[0166] Reference material: central signal for benzene set to 128 ppm

[0167] Number of scans: 20,000

(4) Measurement of Sulfur Content of Chlorinated Polyvinyl Chloride Resin

[0168] An amount of 300 parts by mass of THF was added to 10 parts by mass of each of the obtained chlorinated polyvinyl chloride resins, stirred for 24 hours for dissolution, followed by further stirring in a centrifuge (produced by Kokusan Co., Ltd., H-200NR) at 14,000 rpm for 1 hour to precipitate insoluble components. The insoluble components were filtered out, and to the filtrate was added 1,000 parts by mass of methanol to reprecipitate the resin. While the resin was washed with methanol, suction filtration was performed using an aspirator (produced by AS ONE Corporation, GAS-1N) to separate the resin from the filtrate. In this manner, a sulfur-bound resin was obtained. The resin was put in a vacuum drier (produced by Tokyo Rikakikai Co., Ltd., VOS-451SD) and dried at 80° C. for 24 hours. Combustion IC was performed to detect CS bonds. The obtained sample was weighed in a ceramic boat, and then burned in an automatic sample combustion device. The generated gas was captured in 10 mL of an absorber liquid. This absorber liquid was adjusted to 15 mL with ultrapure water, and subjected to IC quantitative analysis. After a linear approximation of a SO.sub.4.sup.2− anion calibration curve by measurement of a reference substance, the sample was measured to quantify the sulfur content (mass ppm) of the chlorinated polyvinyl chloride resin.

[0169] The measurement conditions for the automatic combustion device are as follows.

[0170] Device: AQF-2100H, produced by Mitsubishi Chemical Analytech

[0171] Inlet temperature: 1,000° C.

[0172] Outlet temperature: 1,100° C.

[0173] Gas flow rate O.sub.2: 400 mL/min

[0174] Gas flow rate Ar: 200 mL/min

[0175] Ar water supply unit: 100 mL/min

[0176] The conditions for IC are as follows.

[0177] Device: ICS-5000, produced by Thermo Fisher Scientific

[0178] Separation column: Dionex IonPac AS18-4 μm (2 mm×150 mm)

[0179] Guard column: Dionex IonPac AG18-4 μm (2 mm×30 mm)

[0180] Suppressor system: Dionex AERS-500 (external mode)

[0181] Detector: conductivity detector

[0182] Eluent: aqueous KOH solution (eluent generator EGC500)

[0183] Eluent flow rate: 0.25 mL/min

[0184] Sample injection volume: 100 μL

(5) Acidification Time

[0185] An amount of 1 g of each of the obtained chlorinated polyvinyl chloride resins was put in a 10-ml glass test tube and heated in an oil bath at 190° C. under nitrogen flow. The gas generated from the chlorinated polyvinyl chloride resin was trapped in water (pH: 6.0), and the pH of the water was measured. The time taken for the pH to reach 3.4 was measured.

(6) Heat Cycle Test

(Preparation of Chlorinated Polyvinyl Chloride Resin Composition)

[0186] An amount of 6.0 parts by mass of an impact resistance modifier was added to 100 parts by mass of each of the obtained chlorinated polyvinyl chloride resins. Then, 0.5 parts by mass of a thermal stabilizer was added and mixed. The impact resistance modifier used was Kane Ace B-564 (produced by Kaneka Corporation, methyl methacrylate-butadiene-styrene copolymer). The thermal stabilizer used was TVS*1380 (produced by Nitto Kasei Co., Ltd., organotin stabilizer).

[0187] Further, 2.0 parts by mass of a polyethylene lubricant (produced by Mitsui Chemicals, Inc., Hiwax 220 MP) and 0.2 parts by mass of a fatty acid ester lubricant (produced by Emery Oleochemicals Japan Ltd., LOXIOL G-32) were added. They were then uniformly mixed in a super mixer to prepare a chlorinated polyvinyl chloride resin composition.

(Preparation of Specimen [Roll Press Machine])

[0188] The obtained chlorinated polyvinyl chloride resin composition was kneaded in a roll mill with 8-inch rolls (produced by Yasuda Seiki Seisakusho, Ltd.: NO. 191-TM) at a temperature of 200° C. for three minutes. The obtained rolled sheet was pressed in a heating and cooling press machine (produced by Kodaira Seisakusho Co., Ltd., PA-40E/40C) at a temperature of 200° C. and a pressure of 20 MPa (preheating: three minutes, pressing: four minutes), whereby a plate having a thickness of 3.2 mm was prepared. The plate was cut using an automatic cutting machine, whereby a specimen having a width of 13 mm, a length of 127 mm, and a thickness of 3.2 mm was prepared.

(Heat Cycle Test)

[0189] The obtained specimen was placed in a bath at 23° C., and the dimensions (dimensions before heat cycles) were measured. The specimen was left to stand at 100° C. for 30 minutes, then the inside of the bath was cooled to 23° C., and the specimen was left to stand for 30 minutes. This cycle was repeated five times. The dimensions after the standing at 23° C. for 30 minutes in the fifth cycle (dimensions after heat cycles) were measured, and the amount of dimensional change from before to after the heat cycles was calculated.

(7) Sag Test

[0190] The amount of sag before and after heating was measured by a method in conformity with JIS K7195 except for the heating temperature and the heating time. Specifically, the following method was used.

[0191] One end of the specimen was held from above and below with a specimen holder so as to secure the specimen in a cantilever manner.

[0192] Subsequently, the specimen holder was put in a gear oven (produced by Toyo Seiki Seisaku-Sho, Ltd., CO—O2) and left to stand at 90° C. for 30 minutes for heating. After standing, the specimen was further left to stand at a temperature of 23° C. for 30 minutes. The amount of sag of the specimen before and after heating was measured, and the change in the amount of sag before and after heating [before heating−after heating] was calculated.

(8) Color Retention (Rate of Color Change)

[0193] The obtained specimen was put in a gear oven (produced by Toyo Seiki Seisaku-Sho, Ltd., CO—O2) and left to stand at 100° C. for 72 hours. L*, a*, b*, and GU were measured using a color difference meter (produced by KONICA MINOLTA, CM-26dG) (light source D65, viewing angle 2°). Using the sample before heating as a reference, ΔE*ab and the change in GU were calculated.

ΔE*ab=((ΔL*).sup.2+(Δa*).sup.2+(Δb*).sup.2).sup.1/2

TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 Pro- Raw Average degree of polymerization 1000 1000 1000 700 1000 1000 duc- mate- Addition amount kg   50   60 40  50   50 50 tion rial method PVC Water Ion-exchanged water kg  130  130 130 130  130 130 Chlo- Reaction temperature ° C.  140  140 140 140  140 140 rination Reaction pressure Mpa    0.40    0.40 0.40   0.04    0.04 0.04 con- PVC + water kg  180  190 170 180  180 180 ditions Resin concentration (PVC/ mass %   28   32 24  28   28 28 (PVC + water))*100 Average chlorine kg/pvc-    0.05    0.05 0.05   0.05    0.05 0.05 consumption rate kg-5 min Reaction time hr    8    9.5 8   8    7.5 8 200 ppm hydrogen peroxide ppm/hr   15   15 15  15   15 15 Amount of 2-ethylhexyl parts by    0.1    0.1 0.1   0.1    0.1 0.05 thioglycolate added mass Drying temperature ° C.   90   90 90  90   90 90 Drying time hr   12   12 12  12   12 12 Chlo- Amount of added chlorine mass %    9.5   11.5 9.5   9.5    7.3 9.5 rinated Sulfur content in resin mass   13   12 13  13   12 11 poly- ppm vinyl Struc- Structural unit (a) mol %   42.0   20.9 38.8  40.8   48.2 42.0 chlo- ture —CH.sub.2—CHCl— ride Structural unit (b) mol %   19.1   26.5 28.1  17.1   22.3 19.1 resin —CH.sub.2—CCl.sub.2— Acidification time ms 3.0E+05 3.2E+05 2.8E+05 3.0E+05 3.4E+05 2.6E+05 Pulse Not Relaxa- T.sub.A ms    0.0114    0.0114 0.0114   0.0114    0.0114 0.0114 NMR heated tion T.sub.B ms    0.1662    0.1678 0.1659   0.1444    0.1941 0.2111 [30° C. time meas- Per- A.sub.30 %   98.2   98.2 98.2  98.4   98.0 98.7 ure- centage B.sub.30 %    1.8    1.8 1.8   1.6    2.0 1.3 ment] After Relaxa- T5.sub.A ms    0.0114    0.0114 0.0114   0.0114    0.0114 0.0114 heating at tion T5.sub.B ms    0.1672    0.1980 0.1603   0.1451    0.1967 0.2223 200° C. time for Per- A.sub.30 %   97.8   97.8 97.8  98.4   98.1 98.7 5 minutes centage B.sub.30 %    2.2    2.2 2.2   1.6    1.9 1.3 After Relax- T20.sub.A ms    0.0114    0.0114 0.0114   0.0116    0.0114 0.0114 heating at ation T20.sub.B ms    0.1654    0.1707 0.1652   0.1475    0.1894 0.2178 200° C. time for 20 Per- A.sub.30 %   98.0   98.0 98.0  98.5   98.1 98.9 minutes centage B.sub.30 %    2.0    2.0 2.0   1.5    1.9 1.1 Relaxation time ratio T5.sub.B/T.sub.B %  101  118 97 101  101 105 Relaxation time ratio T5.sub.B/ %  101  116 97  98  104 102 T20.sub.B Acidification time/T5.sub.B 1.79E+06 1.62E+06 1.75E+06 2.07E+06 1.73E+06 1.17E+06 Acidification time/T.sub.B 1.81E+06 1.91E+06 1.69E+06 2.08E+06 1.75E+06 1.23E+06 Pulse Not Relaxa- T.sub.A ms    0.012    0.012 0.012 — — — NMR heated tion T.sub.B ms    0.144    0.144 0.144 — — — [100° time C. Per- A.sub.100 %   97.4   97.2 97.4 — — — meas- centage B.sub.30 %    2.6    2.8 2.6 — — — ure- After Relaxa- T5.sub.A ms    0.012    0.012 0.012 — — — ment] heating at tion T5.sub.B ms    0.180    0.213 0.168 — — — 200° C. time for Per- A.sub.100 %   97.4   97.5 97.5 — — — 5 minutes centage B.sub.100 %    2.6    2.5 2.5 — — — After Relaxa T20.sub.A ms    0.012    0.012 0.012 — — — heating at tion T20.sub.B ms    0.151    0.153 0.150 — — — 200° C. time for 20 Per- A.sub.100 %   97.3   97.3 97.1 — — — minutes centage B.sub.100 %    2.7    2.7 2.9 — — — Relaxation time ratio T5.sub.B/T.sub.B %  125  148 117 — — — Relaxation time ratio T5.sub.B/ %  119  139 112 — — — T20.sub.B Mol- Sag Amount of sag mm    0.50    0.3 0.61   0.91    0.69 0.57 ded test Appearance change  E —    7.7   16.9 9.2   8.6    7.4 14.9 article after test GU —   −2.7  −19.1 −8.8  −4.3   −3.9 −29.2 change Heat Amount of change %    0.1    1.9 0.16   0.6    1.6 0.15 cycle test Example Comparative Example 7 8 1 2 3 4 Pro- Raw Average degree of polymerization 1000 1000 1000 1000 1000 1000 duc- mate- Addition amount kg   50 50 50   35   70   50 tion rial method PVC Water Ion-exchanged water kg  130 130 130  130  130  130 Chlo- Reaction temperature ° C.  140 140 140  140  140  140 rination Reaction pressure Mpa    0.04 0.04 0.40    0.4    0.4    0.4 con- PVC + water kg  180 180 180  165  190  180 ditions Resin concentration (PVC/ mass %   28 28 28   21   37   28 (PVC + water))*100 Average chlorine kg/pvc-    0.05 0.05 0.05    0.05    0.05    0.05 consumption rate kg-5 min Reaction time hr    8 8 8    8   10.5    8 200 ppm hydrogen peroxide ppm/hr   15 15 15   15   15   15 Amount of 2-ethylhexyl parts by    5 0.1 0    0    0.1    0.1 thioglycolate added mass Drying temperature ° C.   90 120 90   90   90   50 Drying time hr   12 6 12   12   12   72 Chlo- Amount of added chlorine mass %    9.5 9.5 9.5    9.5   14.2    9.5 rinated Sulfur content in resin mass   18 13 0    0    2    1 poly- ppm vinyl Struc- Structural unit (a) mol %   42.0 42.0 42.0   40.4   12.9   42 chlo- ture —CH.sub.2—CHCl— ride Structural unit (b) mol %   19.1 19.1 19.2   38.1   31.3   19.1 resin —CH.sub.2—CCl.sub.2— Acidification time ms 3.5E+05 2.9E+05 1.5E+05 1.20E+05 2.00E+05 1.60E+05 Pulse Not Relaxa- T.sub.A ms    0.0114 0.0114 0.0115    0.01137    0.0114    0.0114 NMR heated tion T.sub.B ms    0.1279 0.1543 0.1676    0.1666    0.1688    0.1612 [30° C. time meas- Per- A.sub.30 %   98.2 98.2 97.7   98.2    98.4   98.3 ure- centage B.sub.30 %    1.8 1.8 2.3    1.8    1.6    1.7 ment] After Relaxa- T5.sub.A ms    0.0114 0.0114 0.0114    0.01143    0.0115    0.0144 heating at tion T5.sub.B ms    0.1398 0.1517 0.1577    0.1349    0.2042    0.1535 200° C. time for 5 minutes Per- A.sub.30 %   97.8 97.9 97.9   97.8   98.4   98.4 centage B.sub.30 %    2.2 2.1 2.1    2.2    1.6    1.6 After Relaxa- T20.sub.A ms    0.0114 0.0113 0.0114 Un-    0.0114    0.0114 heating at tion T20.sub.B ms    0.1302 0.1520 0.1653 measurable    0.1661    0.1552 200° C. time due to for 20 Perc- A.sub.30 %   98.1 98.2 97.9 pyrolysis   98.5   98.4 minutes entage B.sub.30 %    1.9 1.8 2.1    1.5    1.6 Relaxation time ratio T5.sub.B/T.sub.B %  109 98 94   81  121   95.2 Relaxation time ratio T5.sub.B/ %  107 100 95 Un-  123   98.9 T20.sub.B measurable Acidification time/T5.sub.B 2.50E+06 1.91E+06 9.51E+05 8.89E+05 9.79E+05 1.04E+06 Acidification time/T.sub.B 2.74E+06 1.88E+06 8.95E+05 7.20E+05 1.18E+06 9.93E+05 Pulse Not Relaxa- T.sub.A ms — — 0.013 — — — NMR heated tion T.sub.B ms — — 0.167 — — — [100° time C. Per- A.sub.100 % — — 97.3 — — — meas- centage B.sub.30 % — — 2.7 — — — ure- After Relaxa- T5.sub.A ms — — 0.012 — — — ment] heating at tion T5.sub.B ms — — 0.161 — — — 200° C. for time 5 minutes Per- A.sub.100 % — — 97.5 — — — centage B.sub.100 % — — 2.5 — — — After Relaxa T20.sub.A ms — — Unmeasurable — — — heating at tion T20.sub.B ms — — due — — — 200° C. time to pyrolysis for 20 minutes Per- A.sub.100 % — — — — — centage B.sub.100 % — — — — — Relaxation time ratio T5.sub.B/T.sub.B % — — 96 — — — Relaxation time ratio T5.sub.B/ % — — Unmeasurable — — — T20.sub.B Mol- Sag Amount of sag mm    0.47 0.79 2.0    2.41    0.21    0.6 ded test Appearance change  E —    3.2 16.6 18.7   23.1   24.8   20.1 article after test GU —   −2.6 −17.3 −48  −74  −39  −21.3 change Heat Amount of change %    0.1 0.8 3.0    3.4    4.3    0.3 cycle test

INDUSTRIAL APPLICABILITY

[0194] The present invention can provide a chlorinated polyvinyl chloride resin that provides a molded article having excellent heat cycle characteristics and excellent weather resistance, as well as a resin composition for molding and a molded article each including the chlorinated polyvinyl chloride resin.