CHLORINATED VINYL CHLORIDE 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 having an average of a ratio (A/B) of a peak intensity A observed in a range of 300 to 340 cm-.sup.1 to a peak intensity B observed in a range of 1,450 to 1,550 cm.sup.-1 of 3.5 to 40.0 in Raman imaging measurement by Raman spectroscopy.

Claims

1. A chlorinated polyvinyl chloride resin having an average of a ratio (A/B) of a peak intensity A observed in a range of 300 to 340 cm.sup.-1 to a peak intensity B observed in a range of 1,450 to 1,550 cm.sup.-1 of 3.5 to 40 in Raman imaging measurement by Raman spectroscopy.

2. The chlorinated polyvinyl chloride resin according to claim 1, wherein a standard deviation of the ratio (A/B) of the peak intensity A to the peak intensity B is 0.01 to 10 in Raman imaging measurement by Raman spectroscopy.

3. The chlorinated polyvinyl chloride resin according to claim 1, which has a sulfur content of 10 mass ppm or more and 1,000 mass ppm or less.

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

[0139] 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

[0140] 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.

[0141] 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 and the chlorine consumption amount in the chlorination step were adjusted to 0.05 kg/PVC-kg.Math.5 min and 4.75 kg, respectively. 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.

[0142] 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. After dehydration, 0.05 kg of 2-ethylhexyl thioglycolate (produced by FUJIFILM Wako Pure Chemical Corporation) as a sulfur compound 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

[0143] 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.

[0144] 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 and the chlorine consumption amount in the chlorination step were adjusted to 0.05 kg/PVC-kg.Math.5 min and 4.75 kg, respectively. 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.

[0145] 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 7 and Comparative Examples 4 to 6

[0146] A powdery chlorinated polyvinyl chloride resin was obtained as in Example 1 except that the sulfur compound was added in the amount shown in Table 1, and that the chlorine consumption amount and the drying temperature and drying time in drying were as shown in Table 1.

Comparative Examples 2 and 3

[0147] A powdery chlorinated polyvinyl chloride resin was obtained as in Example 1 except that a polyvinyl chloride resin having the average degree of polymerization shown in Table 1 was used, and that the chlorine consumption amount in drying was as shown in Table 1.

Examples 8 and 9 and Comparative Examples 7 and 8

[0148] A powdery chlorinated polyvinyl chloride resin was obtained as in Example 1 except that a polyvinyl chloride resin having the average degree of polymerization shown in Table 1 was used, that the sulfur compound was added in the shown amount, and that the chlorine consumption amount and the drying temperature and drying time in drying were as shown in Table 1.

[0149] An amount of 4.0 parts by mass of an impact resistance modifier was then added to 100 parts by mass of the obtained chlorinated polyvinyl chloride resin. 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).

[0150] Further, 1.5 parts by mass of a polyethylene lubricant (produced by Mitsui Chemicals, Inc., Hiwax 220MP) 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.

[0151] The obtained chlorinated polyvinyl chloride resin composition was supplied to a conical counter-rotating twin screw extruder (produced by Osada Seisakusho, SLM-50) having a diameter of 50 mm and formed into pipes (molded articles) at a resin temperature of 200° C., each pipe having an outer diameter of 26.7 mm and a wall thickness of 2.4 mm.

Example 10

[0152] A powdery chlorinated polyvinyl chloride resin was obtained as in Example 1 except that a polyvinyl chloride resin having the average degree of polymerization shown in Table 1 was used and that the sulfur compound was used in the shown amount.

[0153] An amount of 5.0 parts by mass of an impact resistance modifier was then added to 100 parts by mass of the obtained chlorinated polyvinyl chloride resin. Further, 3.0 parts by mass of a thermal stabilizer was added and mixed. The impact resistance modifier used was Kane Ace M-511 (produced by Kaneka Corporation, methyl methacrylate-butadiene-styrene copolymer). The thermal stabilizer used was TVS#1380 (produced by Nitto Kasei Co., Ltd., organotin stabilizer).

[0154] Further, 2.0 parts by mass of a polyethylene lubricant (produced by Mitsui Chemicals, Inc., Hiwax 220MP) and 0.3 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.

[0155] The obtained chlorinated polyvinyl chloride resin composition was supplied to a conical counter-rotating twin screw extruder (produced by Osada Seisakusho, OSC-30) having a diameter of 30 mm and formed into pellets at a resin temperature of 190° C. The obtained pellets were supplied to an injection molding machine (produced by JSW, J350ADS) and formed into a socket (molded article) having an outer diameter of 34.7 mm and an inner diameter of 26.9 mm.

Evaluation

[0156] The chlorinated polyvinyl chloride resins and molded articles obtained in the examples and the comparative examples were evaluated as follows. Table 1 shows the results.

Measurement of Amount of Added Chlorine

[0157] The amount of added chlorine was measured for each of the obtained chlorinated polyvinyl chloride resins in conformity with JIS K 7229.

Molecular Structure Analysis

[0158] 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 unit (b) relative to the total number of moles of the structural units (a), (b), and (c).

[0159] The NMR measurement conditions were as follows. [0160] Apparatus: FT-NMRJEOLJNM-AL-300 [0161] Measured nuclei: 13 C (proton complete decoupling) 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

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 (% by weight) 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 .Math.m (2 mm × 150 mm) [0179] Guard column: Dionex IonPac AG18-4 .Math.m (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 .Math.L

Raman Imaging Measurement

[0185] An amount of 300 parts by mass of THF was added to 10 parts by mass of each of the powdery chlorinated polyvinyl chloride resins obtained in Examples 1 to 7 and Comparative Examples 1 to 6, 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. The obtained resin was put in a vacuum drier (produced by Tokyo Rikakikai Co., Ltd., VOS-451SD) and dried at 80° C. for 24 hours to prepare a sample. The sample was heated in a gear oven (produced by Toyo Seiki Seisaku-Sho, Ltd., CO-O2) at 150° C. for 10 minutes, and the sample was subjected to Raman spectrum measurement using a Raman microscope (produced by inVia Qontor, Renishaw plc.).

[0186] In Examples 8 to 10 and Comparative Examples 7 and 8, 300 parts by mass of THF was added to 10 parts by mass of each of the molded articles of the 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. The obtained resin was put in a vacuum drier (produced by Tokyo Rikakikai Co., Ltd., VOS-451SD) and dried at 80° C. for 24 hours to prepare a sample. The sample was subjected to Raman spectrum measurement.

[0187] The Raman spectrum measurement was performed under the conditions of an objective lens magnification of 100× and an excitation wavelength of 532 nm in a region of 500 .Math.m × 500 .Math.m at 5-.Math.m intervals in the x direction and 5-.Math.m intervals in the y direction. Raman spectra of 10,201 points of the cross section of the resin sheet were thus obtained.

[0188] In the obtained Raman spectra, two peaks around 307 cm.sup.-1 and 357 cm.sup.-1 observed in the range of 245 to 420 cm.sup.-1 were subjected to peak separation using this range as the baseline. The peak height of the peak observed around 300 to 340 cm.sup.-1 from the baseline was determined as the peak intensity A. Two peaks around 1,495 cm.sup.-1 and 1,427 cm.sup.-1 observed in the range of 1,400 to 1,600 cm.sup.-1 were subjected to peak separation using this range as the baseline. The peak height of the peak observed around 1,450 to 1,550 cm.sup.-1 from the baseline was determined as the peak intensity B. The ratio (A/B) of the peak intensity A to the peak intensity B was then calculated, and the average of the A/B and the standard deviation were also calculated. For the calculation of the average of the A/B and the standard deviation, the region of an acrylic resin was excluded, and only the region of the chlorinated polyvinyl chloride resin was used.

Heat Cycle Test

Preparation of Chlorinated Polyvinyl Chloride Resin Composition

[0189] 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).

[0190] Further, 2.0 parts by mass of a polyethylene lubricant (produced by Mitsui Chemicals, Inc., Hiwax 220MP) 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]

[0191] 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 using 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

[0192] 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 rate of dimensional change from before to after the heat cycles was calculated.

Sag Test

[0193] 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.

[0194] 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.

[0195] 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 (mm)] was calculated. The dimensions of the specimen and the amount of sag were measured using a micrometer having a least count of 0.001 mm.

Color Tone Retention (Rate of Color Tone Change)

[0196] 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* values were measured using a color difference meter (produced by KONICA MINOLTA, CM-26dG). Using the sample before heating as a reference, ΔE*ab was calculated.

[00007]$\text{ΔE*ab=((ΔL}*{)}^2+{(\text{Δa}*)}^2+{(\text{Δb}*)}^2{)}^{1/2}$

TABLE-US-00001 Example Comparative Example 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 Production method PVC Average degree of polymerization 1000 1000 1000 1000 1000 1000 1000 1000 1400 700 1000 1730 340 1000 1000 1000 1000 1000 Chlorination Chlorine consumption amount kg 4.75 4.75 4.75 4.75 4.75 4.75 4.75 2.9 6.75 4.75 4.75 4.75 3.4 4.75 7.4 6.6 2.7 4.75 Sulfur additive Amount of ethyl 2-ethylhexyl thioglycolate added parts by mass 0.1 5 10 - - 5 5 0.05 0.05 0.05 - - - 0.001 - - 0.01 0.01 Amount of isooctyl thioglycolate added parts by mass - - - 10 - - - - - - - - - - 40 - - - Amount of butanediol bisthioglycolate added parts by mass - - - 5 - - - - - - - - - - 30 - - Drying temperature °C 90 90 90 90 90 65 110 90 90 90 90 90 90 90 120 120 150 100 Drying time h 12 12 12 12 12 36 8 12 12 12 12 12 12 12 24 24 12 12 Amount of added chlorine mass% 9.5 9.5 9.5 9.5 9.5 9.5 9.5 5.8 13.5 9.5 9.5 9.5 6.8 9.5 14.8 13.2 5.4 9.5 Structure Structural unit (b) —CH.sub.2—CCl.sub.2— mol% 19.0 17.3 15.6 13.6 18.1 19.1 16.5 9.3 33.7 18.4 19.2 18.9 10.6 19.2 20.5 24.3 21.7 19.4 Raman imaging spectroscopy Peak intensity A/B Average 32.1 33.9 36.8 39.4 20.6 32.8 33.6 4.2 17.6 3.6 3.2 3.4 0.82 3.3 45.3 44.8 0.95 0.13 Standard deviation 5.63 5.94 6.32 8.27 3.59 5.43 6.04 2.56 2.57 0.87 1.00 1.23 0.009 0.98 33.1 26.7 0.008 0.07 (Average of A/B) + (Standard deviation).sup.½ 34.47 36.34 39.31 42.28 22.49 35.13 36.06 5.80 19.20 4.55 4.20 4.51 0.91 4.29 51.05 49.97 1.04 0.39 (Amount of added chlorine)/(Average of A/B) 0.30 0.28 0.26 0.24 0.46 0.29 0.28 1.38 0.77 2.62 2.97 2.79 829 2.88 0.33 0.29 5.68 73.08 (Average of A/B)/((Amount of added chlorine) × (Structural unit b)) 0.1778 0.2063 02483 0.3050 0.1198 0.1808 0.2144 0.0779 0.0387 0.0207 0.0175 0.0189 0.0114 0.0181 0.1493 0.1397 0.0081 0.0007 Sulfur content of resin (mass ppm) 33 48 105 109 39 15 29 12 15 13 0 0 0 4 592 521 14 8 Molded article Amount of sag (mm) 0.50 0.05 0.04 0.05 0.13 0.97 0.13 0.32 0.12 0.49 2.00 1.98 2.25 1.82 2.780 2.850 2.73 1.84 Heat cycle test (%) 0.10 0.10 0.08 0.07 0.12 1.48 0.18 1.65 0.07 0.68 3.00 2.79 3.78 3.25 3.59 3.06 2.65 2.17 Color tone retention 11.50 10.32 8.30 4.2 6.6 11.3 9.25 23.3 10.60 11.80 32.70 25.6 38.7 29.8 3.8 5.0 36.5 28.5

INDUSTRIAL APPLICABILITY

[0197] 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.