CHLORINATED VINYL CHLORIDE RESIN COMPOSITION AND CHLORINATED VINYL CHLORIDE RESIN MOLDED BODY

Abstract

The present invention provides a chlorinated polyvinyl chloride resin composition that is excellent in low-volatility in molding, processability after molding, thermal stability, and heat resistance and that enables the production of a molded body with high surface smoothness, and also provides a chlorinated polyvinyl chloride resin molded body. Provided is a chlorinated polyvinyl chloride resin composition containing: a chlorinated polyvinyl chloride resin; chlorinated polyethylene; and a thermal stabilizer, the chlorinated polyvinyl chloride resin containing a vinylidene unit in an amount of 3 to 32% by mass, the chlorinated polyvinyl chloride resin composition having a mass ratio of the chlorinated polyethylene to the thermal stabilizer (chlorinated polyethylene/thermal stabilizer) of 1.0 to 7.0, the chlorinated polyvinyl chloride resin composition having a loss on heating at 200? C. of less than 3% by mass.

Claims

1. A chlorinated polyvinyl chloride resin composition comprising: a chlorinated polyvinyl chloride resin; chlorinated polyethylene; and a thermal stabilizer, the chlorinated polyvinyl chloride resin containing a vinylidene unit in an amount of 3 to 32% by mass, the chlorinated polyvinyl chloride resin composition having a mass ratio of the chlorinated polyethylene to the thermal stabilizer (chlorinated polyethylene/thermal stabilizer) of 1.0 to 7.0, the chlorinated polyvinyl chloride resin composition having a loss on heating at 200? C. of less than 3% by mass.

2. A chlorinated polyvinyl chloride resin molded body comprising the chlorinated polyvinyl chloride resin composition according to claim 1.

Description

DESCRIPTION OF EMBODIMENTS

[0158] The present invention is more specifically described in the following with reference to, but not limited to, examples.

Example 1

[0159] (Preparation of Chlorinated Polyvinyl Chloride Resin Composition)

[0160] To 100 parts by mass of a chlorinated polyvinyl chloride resin [degree of chlorination: 67.0% by mass, amount of added chlorine: 10.2% by mass, degree of polymerization: 1,000] were added 1.5 parts by mass of the butyltin mercaptan compound below as a thermal stabilizer (primary stabilizer) and 1.6 parts by mass of the sodium adipate below as a thermal stabilizer (co-stabilizer).

[0161] Further, 10 parts by mass of chlorinated polyethylene (chlorine content 34% by mass, density 1.19 g/cm.sup.3, Mooney viscosity 81), 1.0 parts by mass of the polyethylene wax below as a lubricant, and 0.5 parts by mass of the partly saponified montanic acid ester below were added and mixed uniformly using a super mixer, whereby a chlorinated polyvinyl chloride resin composition was obtained. [0162] Butyltin mercaptan compound (available from Nitto Kasei Co., Ltd., TVS*1380, dibutyltin mercaptide) [0163] Sodium adipate (available from Tokyo Chemical Industry Co., Ltd.) [0164] Polyethylene wax (available from Mitsui Chemicals, Inc., Hi-WAX 220MP) [0165] Partly saponified montanic acid ester (available from Clariant (Japan) K.K., Licowax OP)

[0166] The obtained chlorinated polyvinyl chloride resin was subjected to measurement of the amounts (% by mass) of the vinylidene unit, the structural unit (b), and the different structural unit using FT-NMRJEOLJNM-AL-300. The NMR analysis can be performed by the method described in R. A. Komoroski, R. G. Parker, J. P. Shocker, Macromolecules, 1985, 18, 1257-1265.

[0167] (Preparation of Chlorinated Polyvinyl Chloride Resin Molded Body)

[0168] The obtained chlorinated polyvinyl chloride resin composition was supplied to a 65-mm single-screw extruder (available from Ikegai Corporation, FS65) equipped with a mold for a solid molded body. The composition was molded at a resin temperature of 165? C. and an extrusion amount of 15 kg/hr into a solid, rectangular plate-shaped chlorinated polyvinyl chloride resin molded body with a width of 45 mm and a height of 15 mm.

Examples 2 to 11 and Comparative Examples 1 to 3 and 6 to 8

[0169] A chlorinated polyvinyl chloride resin composition and a chlorinated polyvinyl chloride resin molded body were prepared as in Example 1 except that the type of the chlorinated polyvinyl chloride resin (molecular structure and amount of added chlorine), the amount of chlorinated polyethylene added, and the amounts of thermal stabilizers (primary stabilizer and co-stabilizer) added were as shown in Table 1.

Comparative Examples 4 and 5

[0170] A chlorinated polyvinyl chloride resin composition and a chlorinated polyvinyl chloride resin molded body were prepared as in Example 1 except that instead of sodium adipate, zeolite (available from Mizusawa Industrial Chemicals, Ltd., Mizukalizer SAP) in an amount shown in Table 1 was added as a thermal stabilizer (co-stabilizer).

<Evaluation>

[0171] The chlorinated polyvinyl chloride resin compositions and chlorinated polyvinyl chloride resin molded bodies obtained in the examples and the comparative examples were evaluated as follows. Table 1 shows the results.

[Evaluation of Composition]

<Loss on Heating>

[0172] The loss on heating of the obtained chlorinated polyvinyl chloride resin composition was measured with a thermogravimetry (TG) device (available from Seiko Instruments Inc., TG/DTA6200). The measurement was performed from 30 to 300? C. at a rate of temperature rise of 5? C./min.

[0173] Based on the measurement results, the loss on heating at 200? C. was determined by substituting the values in the following formula.

Loss on heating (% by mass)=(Mass before measurement?Mass at 200? C.)/(Mass before measurement)?100

<Heat Distortion Temperature>

[0174] The obtained chlorinated polyvinyl chloride resin composition was supplied to two 8-inch rolls, kneaded at 205? C. for three minutes, and formed into sheets each having a thickness of 1.0 mm. The obtained sheets were placed on top of each other, preheated with a press at 205? C. for three minutes, and then pressed for four minutes. This produced a pressed plate having a thickness of 3 mm. The obtained pressed plate was cut by machining to prepare a specimen. This specimen was used to measure the heat distortion temperature in conformity with ASTM D648 at a load of 186 N/cm.sup.2. The heat distortion temperature was measured after the obtained pressed plate was annealed for 24 hours in a gear oven at 100? C..

<Flow Evaluation (Fluidity)>

[0175] Flow evaluation was performed using Shimadzu Flow Tester (CFT-500D/100D, available from Shimadzu Corporation). Specifically, a rolled sheet prepared in <Heat distortion temperature>was cut to an about 5-mm square piece, supplied to a barrel heated to 160? C., preheated for 10 minutes, and then extruded through a capillary with a die diameter of 1 mm and a die length of 10 mm at a load of 205 kgf. The measurement was started when 3 mm of molten resin was discharged from the capillary. The number of seconds it took per mm was measured.

[Evaluation of Molded Body]

<Surface Roughness (Molded Body Appearance)>

[0176] The surface roughness (Sa) was measured using a surface roughness tester (available from Tokyo Seimitsu Co., Ltd., SURFCOM 480A) by a method in conformity with JIS B 0601. The measurement conditions were as follows: evaluation length: 0.3 mm; measurement speed: 0.3 mm/sec; and cut-off: 0.08 mm.

<Cross-Sectional Observation of Molded Body>

[0177] The obtained solid, rectangular plate-shaped molded body was cut with a saw for vinyl chloride, and the cross section was smoothed with sandpaper. The state of the cross section was then visually observed to evaluate the presence or absence of bubbles (foaming).

<Processability after Molding (Cutting Test with Diamond Cutter)>

[0178] The obtained solid, rectangular plate-shaped molded body was left to stand in a freezer at ?10? C. for 24 hours and cut with a diamond cutter. The molded body was then visually observed for the presence or absence of chips or cracks.

TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 7 8 9 10 Composition CPVC Amount of % by mass 10.2 10.2 13.3 10.4 10.2 10.2 10.2 6.1 8.1 10.3 (parts by added chlorine mass) Degree of 1000 1000 1000 1000 1000 1000 1000 1000 1000 700 polymerization Molecular CCl.sub.2 10.1 10.1 31.8 13.8 10.1 10.1 10.1 5.6 3.4 10.2 structure CHCl 65.2 65.2 29.3 58.4 65.2 65.2 65.2 61.9 72.8 65.3 (% by mass) Others 24.7 24.7 38.9 27.8 24.7 24.7 24.7 32.5 23.8 24.5 Addition amount 100 100 100 100 100 100 100 100 100 100 (parts by weight) CPE Chlorinated polyethylene 10 10 10 10 15 10 10 11 10 10 (CPE) Thermal Primary stabilizer 1.5 1.5 1.5 2.5 1.5 1.5 1.0 1.5 1.5 1.5 stabilizer (dibutyltin mercaptide) Co-stabilizer (sodium 1.6 2.8 1.6 1.6 1.6 6.2 0.5 1.6 1.6 1.6 adipate) Co-stabilizer (zeolite) 0 0 0 0 0 0 0 0 0 0 Additive Polyethylene lubricant 1 1 1 1 1 1 1 1 1 1 Ester lubricant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 CPE/thermal stabilizer 3.2 2.3 3.2 2.4 4.8 1.3 6.7 3.5 3.2 3.2 Total amount of CPE + (CCl.sub.2) (% by mass) 18.8 18.7 40.5 22.5 22.6 18.5 18.9 15.1 12.1 18.9 CHCl content (% by mass) in total amount of 68.6 68.6 32.7 61.8 68.6 68.6 68.6 65.3 76.2 68.7 (CPE + CPVC) Co-stabilizer/primary stabilizer 1.1 1.9 1.1 0.6 1.1 4.1 0.5 1.1 1.1 1.1 Evaluation Volatility (loss on heating % by mass 1.1 1.2 1.2 2.8 1.7 1.7 0.9 1.0 0.9 1.1 (resin 200? C.) composition) Fluidity (flow tester 160? C.) mm.sup.3/sec 40 43 28 48 53 51 24 57 50 54 Heat distortion temperature ? C. 106 104 121 103 100 106 108 101 104 109 (HDT) Evaluation Molded body appearance ?m 19 21 26 18 12 27 26 11 13 11 (molded (surface roughness meter body) Sa) Molded body cross section None None None None None None None None None None (visual observation, presence or absence of void) Cutting test with diamond None None None None None None None None None None cutter (presence or absence of chip) Example Comparative Example 11 1 2 3 4 5 6 7 8 Composition CPVC Amount of % by mass 10.1 10.2 10.2 10.2 10.2 10.2 13.8 4.7 10.2 (parts by added chlorine mass) Degree of 1300 1000 1000 1000 1000 1000 1000 1000 1000 polymerization Molecular CCl.sub.2 10.1 10.1 10.1 10.1 10.1 10.1 37.3 2.7 10.1 structure CHCl 65.0 65.2 65.2 65.2 65.2 65.2 19.7 63.1 65.2 (% by mass) Others 24.9 24.7 24.7 24.7 24.7 24.7 43.1 34.2 24.7 Addition amount 100 100 100 100 100 100 100 100 100 (parts by weight) CPE Chlorinated polyethylene 10 5 10 9 10 10 10 10 10 (CPE) Thermal Primary stabilizer 1.5 1.5 1.5 0.9 1.5 1.5 1.5 1.5 3 stabilizer (dibutyltin mercaptide) Co-stabilizer (sodium 1.6 5 11 0.3 0 0 1.6 1.6 1 adipate) Co-stabilizer (zeolite) 0 0 0 0 2.8 2 0 0 0 Additive Polyethylene lubricant 1 1 1 1 1 1 1 1 1 Ester lubricant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 CPE/thermal stabilizer 3.2 0.8 0.8 7.5 2.3 2.9 3.2 3.2 2.5 Total amount of CPE + (CCl.sub.2) (% by mass) 18.8 14.5 18.2 18.2 18.7 18.8 46.0 11.4 18.8 CHCl content (% by mass) in total amount of 68.4 68.6 68.6 68.6 68.6 68.6 23.1 66.5 68.6 (CPE + CPVC) Co-stabilizer/primary stabilizer 1.1 3.3 7.3 0.3 1.9 1.3 1.1 1.1 0.3 Evaluation Volatility (loss on heating % by mass 1.1 1.2 1.2 0.8 3.8 3.1 3.3 1.1 3.2 (resin 200? C.) composition) Fluidity (flow tester 160? C.) mm.sup.3/sec 26 13 17 22 41 40 7 62 28 Heat distortion temperature ? C. 108 110 110 109 103 104 123 92 97 (HDT) Evaluation Molded body appearance ?m 28 33 46 30 32 36 56 10 25 (molded (surface roughness meter body) Sa) Molded body cross section None None None Present Present Present Present None Present (visual observation, presence or absence of void) Cutting test with diamond None Chip Chip None Chip Chip Chip None Chip cutter (presence or absence of chip)

INDUSTRIAL APPLICABILITY

[0179] The present invention can provide a chlorinated polyvinyl chloride resin composition that is excellent in low-volatility in molding, processability after molding, thermal stability, and heat resistance and that enables the production of a molded body with high surface smoothness, and can also provide a chlorinated polyvinyl chloride resin molded body.