CHLORINATED VINYL CHLORIDE-BASED RESIN

Abstract

The present invention provides a chlorinated polyvinyl chloride resin that has resistance to thermal decomposition, provides excellent continuous productivity in molding, and imparts both processability and unevenness-preventing properties to a molded article. The present invention relates to a chlorinated polyvinyl chloride resin, containing three components including a A.sub.150 component, a B.sub.150 component, and a C.sub.150 component, and having a percentage of the C.sub.150 component (C.sub.150 component/(A.sub.150 component+B.sub.150 component+C.sub.150 component)) of less than 8.0%, the three components being identified by measuring the chlorinated polyvinyl chloride resin by a solid echo method using pulse NMR at 150° 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 three curves derived from the A.sub.150 component, the B.sub.150 component, and the C.sub.150 component in order of shorter relaxation time using the least square method.

Claims

1. A chlorinated polyvinyl chloride resin, comprising three components including a A.sub.150 component, a B.sub.150 component, and a C.sub.150 component, and having a percentage of the C.sub.150 component (C.sub.150 component/(A.sub.150 component+B.sub.150 component+C.sub.150 component)) of less than 8.0%, the three components being identified by measuring the chlorinated polyvinyl chloride resin by a solid echo method using pulse NMR at 150° 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 three curves derived from the A.sub.150 component, the B.sub.150 component, and the C.sub.150 component in order of shorter relaxation time using the least square method.

2. The chlorinated polyvinyl chloride resin according to claim 1, wherein the chlorinated polyvinyl chloride resin comprises two components including a A.sub.100 component and a B.sub.100 component, and has a percentage of the B.sub.100 component (B.sub.100 component/(A.sub.100 component+B.sub.100 component)) of less than 9.0%, and the two components are identified by measuring the chlorinated polyvinyl chloride resin by a solid echo method using pulse NMR at 100° 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.100 component and the B.sub.100 component in order of shorter relaxation time using the least square method.

3. The chlorinated polyvinyl chloride resin according to claim 2, wherein a product of a relaxation time of the A.sub.100 component and the percentage of the B.sub.100 component (Relaxation time (ms) of A.sub.100 component×Percentage (%) of B.sub.100 component) is 0.12 (ms %) or less.

4. The chlorinated polyvinyl chloride resin according to claim 1, having a degree of polymerization of 100 to 2,000.

5. The chlorinated polyvinyl chloride resin according to claim 1, having an amount of added chlorine of 1.0 to 16.0% by mass.

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

7. The resin composition for molding according to claim 6, comprising 1 to 30% by mass of an impact resistance modifier.

8. A molded article molded from the resin composition for molding according to claim 7.

9. The molded article according to claim 8, further comprising a glass fiber or a carbon fiber.

10. The molded article according to claim 8, which is a member for use in transportation machinery.

11. The molded article according to claim 8, which is a member for use in battery systems.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0138] FIG. 1 shows a perspective view of recession and projection dies and an evaluation sheet used for moldability evaluation.

[0139] FIG. 2 shows a cross-sectional view illustrating moldability evaluation.

DESCRIPTION OF EMBODIMENTS

[0140] The present invention is hereinafter described in more detail with reference to examples; however, the present invention should not be limited to the examples.

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 having an average degree of polymerization of 1,000. They were stirred to disperse the polyvinyl chloride 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 100° C. Subsequently, the inside of the reaction vessel was depressurized to remove oxygen (oxygen content 100 ppm). Thereafter, while stirring was performed such that the vortex formed at the liquid-gas interface by stirring had a vortex volume of 8.2 L, 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 100° C. and the partial pressure of chlorine was kept at 0.40 MPa. After the amount of added chlorine reached 4.0% 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, and the average chlorine consumption rate was adjusted to 0.02 kg/PVC-kg.Math.5 min. When the amount of added chlorine reached 10.4% by mass, the supply of hydrogen peroxide solution and chlorine gas was terminated, whereby chlorination was terminated.

[0143] Next, unreacted chlorine was removed by nitrogen gas aeration, and the obtained chlorinated polyvinyl chloride resin slurry was neutralized with sodium hydroxide, washed with water, dehydrated, and then dried. Accordingly, a powdery, thermally chlorinated polyvinyl chloride resin (amount of added chlorine: 10.4% by mass) was obtained.

Examples 2 to 8, Comparative Examples 1 to 6

[0144] Chlorinated polyvinyl chloride resins were obtained as in Example 1, except that the average degree of polymerization of the raw material PVC, the reaction temperature, the vortex volume in stirring, the average chlorine consumption rate, and the amount of added chlorine were changed as indicated in Tables 1 and 2.

(Evaluation)

[0145] The chlorinated polyvinyl chloride resins obtained in the examples and the comparative examples were evaluated as follows. Tables 1 and 2 show the results.

(1) Pulse NMR Measurement

[0146] The powdery chlorinated polyvinyl chloride resin 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 heating while the temperature was stepwise raised from 30° C. (for 10 minutes), 100° C. (for 30 minutes), and 150° C. (for 30 minutes).

[0147] Measurements by the solid echo method were performed at 30° C., 100° C., and 150° C. under the conditions below, thereby obtaining free induction decay curves of .sup.1H spin-spin relaxation.

<Solid Echo Method>

[0148] Scans: 128 times
Recycle delay: 1 sec
Acquisition scale: 0.5 ms

(Measurement at 150° C.)

[0149] The free induction decay curve obtained in the measurement at 150° C. was subjected to waveform separation into three curves derived from the A.sub.150 component, the B.sub.150 component, and the C.sub.150 component. The waveform separation was performed by fitting to both a Gaussian model and an exponential model. The percentages of the three components were determined from the curves derived from the components obtained in the measurements.

[0150] Using analytical software “TD-NMRA (Version 4.3, Rev. 0.8)” produced by BRUKER, the A.sub.150 component and the B.sub.150 component were fitted to a Gaussian model, and the C.sub.150 component was fitted to an exponential model in conformity with the product manual.

[0151] The following equation was used in the fitting.

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

[0152] In the formula, A represents the percentage of the A.sub.150 component, B represents the percentage of the B.sub.150 component, C represents the percentage of the C.sub.150 component, T.sub.A represents the relaxation time of the A.sub.150 component, T.sub.B represents the relaxation time of the B.sub.150 component, Tc represents the relaxation time of the C.sub.150 component, and t represents time.

[0153] The A.sub.150 component, the B.sub.150 component, and the C.sub.150 component are components defined in order of shorter relaxation time in pulse NMR measurement. The value of the relaxation time of each component is not limited. Usually, the relaxation time of the A.sub.150 component is less than 0.020 ms; the relaxation time of the B.sub.150 component is from 0.020 ms to less than 0.090 ms; and the relaxation time of the C.sub.150 component is 0.090 ms or more.

(Measurements at 30° C. and 100° C.)

[0154] The free induction decay curves obtained in the measurements at 30° C. and 100° C. were each subjected to waveform separation into two curves derived from the A.sub.30 component and the B.sub.30 component or two curves derived from the A.sub.100 component and the B.sub.100 component. The waveform separation was performed by fitting to 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 measurements.

[0155] Using analytical software “TD-NMRA (Version 4.3, Rev. 0.8)” produced by BRUKER, the A.sub.30 component and the A.sub.100 component were fitted to a Gaussian model, and the B.sub.30 component and the B.sub.100 component were fitted to an exponential model in conformity with the product manual.

[0156] The following equation was used in the fitting.

[00002]$\begin{array}{cc}Y=A\times \exp \left(-\frac{1}{2}\times {\left(\frac{t}{T_A}\right)}^2\right)+B\times \exp \left(-\frac{t}{T_B}\right)& \left[\mathrm{Math}.2\right]\end{array}$

[0157] In the formula, A represents the percentage of the A.sub.30 component or the A.sub.100 component, B represents the percentage of the B.sub.30 component or the B.sub.100 component, T.sub.A represents the relaxation time of the A.sub.30 component or the A.sub.100 component, T.sub.B represents the relaxation time of the B.sub.30 component or the B.sub.100 component, and t represents time.

[0158] The A.sub.30 component and the B.sub.30 component, or the A.sub.100 component and the B.sub.100 component are components defined in order of shorter relaxation time in pulse NMR measurement. The value of the relaxation time of each component is not limited. Usually, the relaxation time of the A component is less than 0.020 ms; and the relaxation time of the B component is 0.020 ms or more.

(2) Measurement of Amount of Added Chlorine

[0159] 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

[0160] 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), (b), and (c).

[0161] The NMR measurement conditions were as follows.

Apparatus: FT-NMRJEOLJNM-AL-300

[0162] Measured nuclei: 13C (proton complete decoupling)
Pulse width: 90°

PD: 2.4 sec

[0163] Solvent: o-dichlorobenzene:deuterated benzene (C5D5)=3:1
Sample concentration: about 20%

Temperature: 110° C.

[0164] Reference material: central signal for benzene set to 128 ppm
Number of scans: 20,000

(4) Developed Interfacial Area Ratio (Sdr)

(Production of Chlorinated Polyvinyl Chloride Resin Composition)

[0165] 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).

[0166] 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 uniformly mixed in a super mixer, whereby a chlorinated polyvinyl chloride resin composition was obtained.

(Production of Extrusion-Molded Article)

[0167] The obtained chlorinated polyvinyl chloride resin composition was fed into a twin-screw counter-rotating conical extruder with a diameter of 50 mm (produced by Osada Seisakusho, SLM-50) to prepare a sheet-shaped molded article with a thickness of 2 mm and a width of 80 mm at a resin temperature of 205° C., a back pressure of 120 to 140 kg/cm.sup.2, and an extrusion amount of 38 kg/hr.

(Sdr Measurement)

[0168] The Sdr value of a surface of the obtained molded article was measured using a 3D measurement system (produced by Keyence Corporation, VR-3100). Each Sdr value shown in Tables 1 and 2 is the average of five measurement regions.

[0169] Sdr is a ratio representing the degree of increase in the surface area of the measured region compared to the area of the measured region. A completely level surface has an Sdr of 0. A molded article having a low Sdr has excellent flatness. For example, the use of the molded article as a pipe-shaped molded article for plumbing or the like can reduce noise when water is running.

(5) Surface Shape (Unevenness)

[0170] The surface shape of the molded article was examined visually and by touch, and evaluated in accordance with the following criteria.

∘(Good): Neither the visual examination nor the touch examination found surface irregularities.
Δ (Fair): The visual examination found no surface irregularities but the touch examination found surface irregularities.
x (Poor): The visual examination found surface irregularities.

(6) Continuous Productivity

[0171] The obtained chlorinated polyvinyl chloride resin composition was fed into a twin-screw counter-rotating conical extruder with a diameter of 50 mm (produced by Osada Seisakusho, “SLM-50”) to prepare a sheet-shaped molded article with a thickness of 2 mm and a width of 80 mm at a resin temperature of 205° C., a back pressure of 120 to 140 kg/cm.sup.2, and an extrusion amount of 38 kg/hr. The time from the start of the molding to the occurrence of a scorch mark (discoloration) in the obtained molded article was measured, and the continuous productivity was evaluated.

[0172] A longer time before the occurrence of a scorch mark (discoloration) in the molded article indicates that the chlorinated polyvinyl chloride resin has higher resistance to thermal decomposition and is less likely to contaminate the die surface, and therefore enables excellent continuous productivity when products are continuously produced by repeating similar operations for a long time.

(7) Thermal Moldability

[0173] A solution was prepared by mixing 20% by mass of the obtained chlorinated polyvinyl chloride resin, 79% by mass of tetrahydrofuran (THF, FUJIFILM Wako Pure Chemical Corporation), and 1% by mass of a thermal stabilizer (organotin thermal stabilizer, TVS #1380, Nitto Kasei Co., Ltd.).

[0174] A glass fiber was immersed in the solution by the hand lay-up technique. By repeating this operation for five times, a five-layer solution-immersed glass fiber was obtained.

[0175] The solution-immersed glass fiber was molded into a shape of 15 cm×15 cm×2.5 mm in thickness, and then THF was dried, thereby preparing a resin-immersed glass fiber sheet. The resulting sheet was placed between Teflon (®) sheets, and the workpiece was subjected to hot pressing at 200° C. at a pressure of 0.2 MPa for three minutes and at a pressure of 10 MPa for three minutes using a hot press machine, thereby preparing a 2 mm-thick evaluation sheet.

[0176] Next, recession and projection dies (assumed as a cover for batteries) shown in FIG. 1 were preliminary heated to 200° C. by a hot press machine. Then, the evaluation sheet was sandwiched between the dies and maintained at 200° C. and at 2 MPa for five minutes as shown in FIG. 2 and further maintained at 10 MPa for five minutes. Subsequently, the dies were cooled by cold pressing, and then the evaluation sheet was recovered from the dies. Edges of the sheet were visually observed and evaluated in accordance with the following criteria.

∘ (Good): No fracture was observed.
Δ (Fair): Small fractures were observed.
x (Poor): Fractures were observed.

TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 7 8 Production Raw material Average degree of polymerization 1000 1000 1000 1000 350 450 1900 1000 method PVC Charge amount kg 50 50 50 50 50 50 50 50 Water Ion-exchanged water kg 130 130 130 130 130 130 130 130 Chlorination Reaction temperature ° C. 100 100 100 100 100 100 100 100 conditions Reaction pressure Mpa 0.40 0.40 0.4 0.4 0.4 0.4 0.4 0.4 PVC + water kg 180 180 180 180 180 180 180 180 Vortex volume in stirring L 8.2 2.0 7.6 7.5 7.4 7.5 7.5 25.2 Vortex volume/(PVC + water) L/kg 0.0456 0.0111 0.0422 0.0417 0.0411 0.0417 0.0417 0.1400 Average chlorine consumption rate kg/pvc-kg .Math. 0.020 0.010 0.010 0.006 0.008 0.009 0.008 0.014 5 min 200 ppm hydrogen peroxide ppm/hr 15 15 15 15 15 15 15 15 Chlorinated Amount of added chlorine mass % 10.4 10.4 6.7 15 10.3 10.5 12 10.6 polyvinyl Structure Structural unit (a) —CH.sub.2—CHCl— mol % 36.0 36.2 58.9 5.2 36.9 35.8 27 35.3 chloride Structural unit (b) —CH.sub.2—CCl.sub.2— mol % 25.6 32.3 17.3 39.9 33 24 24.2 24 resin Structural unit (c) —CHCl—CHCl— mol % 38.4 31.5 23.8 54.9 30.1 40.2 48.8 40.7 Pulse NMR  30° C. Percentage A.sub.30 % 99.2 99.1 99.1 99.1 99.1 99.1 99.1 99.1 B.sub.30 % 0.8 0.9 0.9 0.9 0.9 0.9 0.9 0.9 Relaxation A.sub.30 ms 0.011 0.011 0.011 0.011 0.011 0.011 0.011 0.011 time B.sub.30 ms — — — — — — — — 100° C. Percentage A.sub.100 % 91.2 90.1 91.6 90.7 85.4 86.3 99.3 91.4 B.sub.100 % 8.8 9.9 8.4 9.3 14.7 13.8 0.7 8.6 Relaxation A.sub.100 ms 0.0120 0.0120 0.0111 0.0128 0.0118 0.0118 0.0123 0.0120 time B.sub.100 ms 0.0262 0.0244 0.0236 0.0286 0.0204 0.0213 0.0343 0.0248 150° C. Percentage A.sub.150 % 65.5 65.5 64.3 63.7 65.9 66.4 65.8 66.1 B.sub.150 % 28.0 26.8 27.8 29.5 26.4 26.2 28.4 27.8 C.sub.150 % 6.5 7.7 7.9 6.8 7.7 7.4 5.8 6.1 Relaxation A.sub.150 ms 0.0125 0.0127 0.0128 0.0124 0.0124 0.0124 0.0126 0.0125 time B.sub.150 ms 0.0274 0.0277 0.0324 0.0208 0.0290 0.0288 0.0259 0.0273 C.sub.150 ms 0.1127 0.1346 0.1182 0.1057 0.1022 0.1032 0.1177 0.1101 Molded Sdr 0.0011 0.0080 0.0015 0.0028 0.0019 0.002 0.0029 0.0026 article Surface shape (unevenness) ○ ○ ○ ○ ○ ○ ○ ○ Continuous productivity (hr) 8.1 5.3 4.8 5.1 4 4.4 4.5 7.6 Thermal moldability ○ ○ ○ ○ ○ ○ ○ ○

TABLE-US-00002 TABLE 2 Comparative Example 1 2 3 Production Raw material Average degree of polymerization 1000 1000 1000 method PVC Charge amount kg 50 50 50 Water Ion-exchanged water kg 130 130 130 Chlorination Reaction temperature ° C. 140 100 100 conditions Reaction pressure Mpa 0.40 0.40 0.4 PVC + water kg 180 180 180 Vortex volume in stirring L 30 1.0 30.6 Vortex volume/(PVC + water) L/kg 0.1667 0.0056 0.1700 Average chlorine consumption rate kg/pvc-kg .Math. 0.050 0.010 0.025 5 min 200 ppm hydrogen peroxide ppm/hr 15 15 15 Chlorinated Amount of added chlorine mass % 10.4 10.4 6.3 polyvinyl Structure Structural unit (a) —CH.sub.2—CHCl— mol % 35.9 36.0 58.2 chloride Structural unit (b) —CH.sub.2—CCl.sub.2— mol % 41.7 44.8 17.1 resin Structural unit (c) —CHCl—CHCl— mol % 22.4 19.2 24.7 Pulse NMR  30° C. Percentage A.sub.30 % 99.1 99.1 99.1 B.sub.30 % 0.9 0.9 0.9 Relaxation A.sub.30 ms 0.011 0.011 0.011 time B.sub.30 ms — — — 100° C. Percentage A.sub.100 % 88.6 86.9 91.7 B.sub.100 % 11.4 13.1 8.3 Relaxation A.sub.100 ms 0.0119 0.0120 0.0103 time B.sub.100 ms 0.0254 0.0259 0.0223 150° C. Percentage A.sub.150 % 64.7 63.1 65.8 B.sub.150 % 25.3 25.1 25.9 C.sub.150 % 10.0 11.8 8.3 Relaxation A.sub.150 ms 0.0128 0.0125 0.0128 time B.sub.150 ms 0.0294 0.0281 0.0330 C.sub.150 ms 0.1515 0.1671 0.1188 Molded Sdr 0.083 0.069 0.004 article Surface shape (unevenness) x x ○ Continuous productivity (hr) 1.2 1.1 2.1 Thermal moldability Δ Δ Δ Comparative Example 4 5 6 Production Raw material Average degree of polymerization 2100 1000 1000 method PVC Charge amount kg 50 50 50 Water Ion-exchanged water kg 130 130 130 Chlorination Reaction temperature ° C. 100 100 100 conditions Reaction pressure Mpa 0.4 0.4 0.4 PVC + water kg 180 180 180 Vortex volume in stirring L 28.8 1.5 27.2 Vortex volume/(PVC + water) L/kg 0.1600 0.0083 0.1511 Average chlorine consumption rate kg/pvc-kg .Math. 0.020 0.004 0.016 5 min 200 ppm hydrogen peroxide ppm/hr 15 15 15 Chlorinated Amount of added chlorine mass % 12.2 10.6 10.5 polyvinyl Structure Structural unit (a) —CH.sub.2—CHCl— mol % 25.4 35.4 35 chloride Structural unit (b) —CH.sub.2—CCl.sub.2— mol % 35 44 28 resin Structural unit (c) —CHCl—CHCl— mol % 39.6 20.6 37 Pulse NMR  30° C. Percentage A.sub.30 % 99.1 99.1 99.1 B.sub.30 % 0.9 0.9 0.9 Relaxation A.sub.30 ms 0.011 0.011 0.011 time B.sub.30 ms — — — 100° C. Percentage A.sub.100 % 99.4 90.8 91.8 B.sub.100 % 0.6 9.2 8.2 Relaxation A.sub.100 ms 0.0128 0.1200 0.1200 time B.sub.100 ms 0.0352 0.0283 0.0241 150° C. Percentage A.sub.150 % 64.7 64.6 64.2 B.sub.150 % 27.1 27.2 27.5 C.sub.150 % 8.2 8.2 8.3 Relaxation A.sub.150 ms 0.0126 0.0127 0.0125 time B.sub.150 ms 0.0251 0.0289 0.0289 C.sub.150 ms 0.1151 0.1482 0.1081 Molded Sdr 0.005 0.003 0.003 article Surface shape (unevenness) x ○ Δ Continuous productivity (hr) 2 2 2.5 Thermal moldability x Δ Δ

INDUSTRIAL APPLICABILITY

[0177] The present invention can provide a chlorinated polyvinyl chloride resin that has resistance to thermal decomposition, provides excellent continuous productivity in molding, and imparts both processability and unevenness-preventing properties to a molded article.

REFERENCE SIGNS LIST

[0178] 1 recession and projection dies [0179] 2 evaluation sheet