Impact Strength Modifier for Chlorine-Containing Resin, Chlorine-Containing Resin Composition and Molded Body of Chlorine-Containing Resin Composition

Abstract

Disclosed is an impact strength modifier (α) for a chlorine-containing resin, comprising a powder of a graft copolymer (A) obtained by graft polymerizing one or more kinds of vinyl monomers (b1) onto a polyorganosiloxane rubber (A1) or a composite rubber (A2) containing a polyorganosiloxane rubber and a polyalkyl (meth)acrylate rubber, wherein the specific surface area of the powder of the graft copolymer (A) measured by a nitrogen gas adsorption method is from 0.6 to 30 m.sup.2/g, and the pH of water used for extraction under conditions, in which (1) in an oven at 180° C., 5.0 g of the powder of the graft copolymer (A) is left to stand still and heated for 15 minutes, and (2) after the heating, the powder is dispersed in 100 ml of heated pure water and extracted for 1 hour at 70° C. while stirring, is from 4 to 11.

Claims

1. An impact strength modifier (α) for a chlorine-containing resin, wherein the impact strength modifier comprises a powder of a graft copolymer (A) obtained by graft polymerizing one or more vinyl monomers (b1) onto a polyorganosiloxane rubber (A1) or a composite rubber (A2) containing a polyorganosiloxane rubber and a polyalkyl (meth)acrylate rubber, and wherein a specific surface area of the powder of the graft copolymer (A) measured by a nitrogen gas adsorption method is from 0.6 to 30 m.sup.2/g and water used for extraction under the following conditions (1) and (2) is at a pH of from 4 to 11: (1) in an oven at 180° C., 5.0 g of the powder of the graft copolymer (A) is left to stand still and heated for 15 minutes, and (2) after the heating, the powder is dispersed in 100 ml of water and extracted for 1 hour at 70° C. while stirring.

2. The impact strength modifier (α) for a chlorine-containing resin according to claim 1, wherein the powder of the graft copolymer (A) is obtained by spray drying latex of the graft copolymer (A).

3. The impact strength modifier (α) for a chlorine-containing resin according to claim 1, wherein a content of an emulsifier having a thermal decomposition temperature measured by a TG/DTA measuring device of less than 200° C. is 0.1 parts by mass or less with respect to 100 parts by mass of the modifier (α).

4. The impact strength modifier (α) for a chlorine-containing resin according to claim 1, wherein the impact strength modifier further comprises at least one kind of emulsifier selected from the group consisting of sodium dodecylbenzenesulfonate, sodium alkyl diphenyl ether disulfonate, sodium dialkylsulfosuccinate and a polyoxyethylene distyrenated phenyl ether.

5. The impact strength modifier (α) for a chlorine-containing resin according to claim 1, wherein an amount of an organosiloxane contained in the powder of the graft copolymer (A) is 0.4% by mass or less.

6. The impact strength modifier (α) for a chlorine-containing resin according to claim 1, wherein the vinyl monomer (b1) is at least one monomer selected from the group consisting of an aromatic alkenyl compound, an ester of (meth)acrylic acid and a vinyl cyanide compound.

7. (canceled)

8. A chlorine-containing resin composition, comprising the impact strength modifier (α) for a chlorine-containing resin according to claim 1 and a chlorine-containing resin (β).

9. The chlorine-containing resin composition according to claim 8, wherein the composition contains the impact strength modifier (α) for a chlorine-containing resin at from 0.1 to 30 parts by mass with respect to 100 parts by mass of the chlorine-containing resin (β).

10. A molded body obtained by molding the chlorine-containing resin composition according to claim 8.

11. A molded body obtained by molding the chlorine-containing resin composition according to claim 9.

Description

EXAMPLES

[0151] Hereinafter, the invention will be more specifically described with reference to Examples. In the following description, the terms “parts” and “%” each indicate “parts by mass” and “% by mass” unless particularly stated otherwise. The measurement metrics and judgment of each item were done as follows.

[0152] (1) Thermal Decomposition Temperature of Emulsifier (c)

[0153] An emulsifier of which the moisture content is adjusted to 1.0% or less by removing the moisture in a steam dryer at 70° C. was used as the specimen, and the mass decrease rate thereof was measured using the TG/DTA 6200 [Measuring device manufactured by Seiko Instruments Inc.]. The measurement condition was as follows. The emulsifier was kept for 5 minutes at 120° C. under an atmosphere of Air=200 ml/min and then measured at a temperature increasing speed of 15° C./min from 120° C. to 550° C. From the measurement results thus obtained, the temperature at which the mass of the emulsifier was decreased by 3% with respect to 100% of the mass of the emulsifier before measurement was adopted as the thermal decomposition temperature of the emulsifier.

[0154] (2) Mass Average Particle Size of Graft Copolymer (A)

[0155] The specimen was prepared by diluting the latex of the graft copolymer with deionized water so as to have a concentration of about 3%, and the mass average particle size thereof was measured using the CHDF 2000 model particle size distribution meter [Manufactured by Matec Applied Sciences, USA]. Measurement was conducted under the following standard conditions recommended by Matec Applied Sciences.

Cartridge: Dedicated capillary cartridge for particle separation [Trade name: C-202]
Carrier liquid: dedicated carrier liquid [Trade name: 2XGR500]
Acidity or alkalinity of carrier liquid: Neutral
Flow rate of carrier liquid: 1.4 ml/min
Pressure of carrier liquid: About 4,000 psi [2,600 kPa]
Measurement temperature: 35° C.
Amount of sample used: 0.1 ml

[0156] As the substance having a standard particle size, monodisperse polystyrenes with known particle sizes (Manufactured by Duke Scientific Corporation, USA) were used for 12 points in a particle size range of from 40 to 800 nm.

[0157] (3) Volume Average Particle Size of Powder of Graft Copolymer (A)

[0158] The powder of the graft copolymer (A) was diluted with deionized water containing a small amount of an emulsifier and subjected to the ultrasonic treatment for 15 minutes, and the volume average particle size thereof was then measured using the SALD-7100 of a laser diffraction/scattering type particle size distribution measuring device [Measuring device manufactured by Shimadzu Corporation]. The refractive index calculated from the composition of the monomer introduced was used as the refractive index, and the median size was used as the average size for each. The concentration of the sample was appropriately adjusted so as to be in a proper range on the scattered light intensity monitor provided to the device.

[0159] (4) Specific Surface Area of Powder of Graft Copolymer (A)

[0160] The value of the specific surface area was measured after the powder of the graft copolymer (A) (Volume: 0.6 cm.sup.3) was introduced into the sample tube for measurement and vacuum-dried for 12 hours at 70° C. using a specific surface area and pore distribution measuring device [Product name: Belsorp, manufactured by NIPPON BEL, Co.]. In this measurement, it is possible to adopt the value of the specific surface area calculated by the BET method of the following Equation (II).

P/[V(P.sub.0−P)]=[1/(VmC)]+[(C−1)/(VmC)][P/P.sub.0]  (II)

P: Adsorption equilibrium pressure
P.sub.0: Saturated vapor pressure
V: Adsorbed amount
Vm: Adsorbed amount of monomolecular layer, adsorbed amount when gaseous molecule forms monomolecular layer on fixed surface
C: Parameter of heat of adsorption>0

[0161] (5) pH of Water Used for Extraction of Powder of Graft Copolymer (A)

[0162] The method for measuring the pH was as follows. In a hot air circulation type dryer at 180° C., 5.0 g of the powder of the graft copolymer (A) was left to stand still and heated for 15 minutes and then dispersed in 100 ml of pure water and extracted for 1 hour at 70° C. while stirring. The water used for the extraction was filtered through a 0.2 μm membrane filter produced by cellulose mixed ester. The measurement was conducted using this filtrate as the specimen and the following measuring device, and the value measured was adopted.

[0163] Device: pH Meter, model F-52 [HORIBA, Ltd.]

[0164] Electrode: Model 9611 [HORIBA, Ltd.]

[0165] Internal solution of reference electrode: 3.33 mol/1 KC solution [HORIBA, Ltd.]

[0166] pH Standard solution: pH 4.00, pH 6.88, and pH 9.18 (25° C.)

[0167] (6) Amount of Organosiloxane Contained in Powder of Graft Copolymer (A)

[0168] The method for measuring the content of the organosiloxane was employed as follows. Into a 50 ml sample tube, 0.3 g of the powder of the graft copolymer (A) was weighed and 20 ml of acetone and 5 μl of butyl acetate were weighed and put in to the sample tube. The measurement was conducted using this as the specimen and the following measuring device, and the value measured is adopted.

[0169] Device: Gas chromatograph (GC) [HP6890 manufactured by Agilent Technologies Japan, Lit.]

[0170] Capillary column: DB-WAX

[0171] Column oven: 40° C./5 min, raising at 10° C./min, 140° C./0 min, raising at 20° C./min, 220° C./1 min, post-run=230° C./2 min, column flow rate (He)=2.3 ml/min, average linear velocity=36 cm/sec

[0172] Inlet: Temperature=200° C.

[0173] Detector: Temperature=200°, hydrogen flow rate=40 ml/min, air flow rate=450 ml/min, make-up flow rate (He)=45 ml/min

[0174] Injection amount: 1 μl

[0175] (7) Charpy Impact Strength

[0176] The Charpy impact strength was measured under a temperature condition of −10° C. in conformity with JIS K 7111. The test piece was fabricated as follows. The materials were kneaded at the blending proportions presented in Table 3 and Table 4 for 3 minutes using a dielectric heating type 8 inch test roll [Kneader manufactured by KANSAI ROLL Co., Ltd.] heated to 180° C., then heated for 10 minutes in a press molding machine set to 180° C., and then cooled for 5 minutes to mold a press plate, and the press plate was cut to have the following sizes and notched.

Test piece: Length 80.0 mm×width 10.0 mm×thickness 4.0 mm, notch depth: 2.0 mm

[0177] The test piece was conditioned in a low temperature incubator at −10° C. for 48 hours or longer before the start of the measurement.

[0178] (8) Gelation Time

[0179] The measurement of gelation time of the formulation was conducted under the following conditions.

[0180] <Preparation Condition of Formulation>

[0181] (a) 6.0 parts of the graft copolymer (A),

[0182] (b) 100 parts of a vinyl chloride resin, TK-1000 [Trade name, manufactured by Shin-Etsu Chemical Co., Ltd., average polymerization degree of 1050, average particle size of 150 μm],

[0183] (c) 3.0 parts of a CaZn-based stabilizer [Manufactured by SUN ACE CORPORATION],

[0184] (d) 5.0 parts of calcium carbonate, HAKUENKA CCR [Trade name, manufactured by SHIRAISHI CALCIUM KAISHA, LTD., primary particle size of 50 nm, surface treatment agent: fatty acid], and

[0185] (e) 5.0 parts of titanium dioxide, R-830 [Trade name, manufactured by ISHIHARA SANGYO KAISHA, LTD., TiO.sub.2 of 93%, average particle size of 0.25 μm, oil absorption of 21].

[0186] The materials of (a) to (e) above were blended, and after a Z blade and a flat blade were mounted to a 20 L Henschel mixer, FM20C/I [Product number, manufactured by NIPPON COKE & ENGINEERING CO., LTD.] heated to 40° C., the mixture was hot blended at a frequency of 65 Hz until the internal temperature thereof reached 110° C. to obtain a formulation.

[0187] <Measurement Condition of Gelation Time>

[0188] A batch type mixer attachment [Heating type: electric heater, use temperature range of from 0 to 350° C.] was mounted to the Brabender Plasti-Corder [Measuring device manufactured by Brabender GmbH & Co. KG] and heated to 180° C., 77.55 cc of the formulation prepared in the above conditions was introduced into the measuring device, kept for 5 minutes, and kneaded at a rotation number of rotor of 30 rpm, and the time required from the start of kneading to the point at which the maximum torque was exhibited was adopted as the gelation time.

[0189] (9) Bleedout Resistance

[0190] The dirt of the roll when 50 g of the formulation was introduced into the roll bank portion of a dielectric heating type 8 inch test roll [Kneader manufactured by KANSAI ROLL Co., Ltd.] and kneaded for 30 minutes at 180° C. was visually judged according to the following criteria.

[0191] ◯: There is no dirt on roll after kneading for 30 minutes.

[0192] x: There is dirt on roll after kneading for 30 minutes.

[0193] (10) Time Until to Twine

[0194] Into the roll bank portion of a dielectric heating type 8 inch test roll [Kneader manufactured by KANSAI ROLL Co., Ltd.], 50 g of the formulation was introduced and kneaded by taking the time point at which the introduction was finished as the starting time, and the time until the formulation melted and twined around the roll was measured. The temperature of the front and back rolls was set to 190° C., the rotation number of the roll was 14 rpm for the front roll and 16 rpm for the back roll, and kneading was conducted at an interspace between the front and back rolls of 0.3 mm to measure the time.

(Production Example 1) Production of Polyorganosiloxane Rubber Latex (S-1)

[0195] By mixing 2 parts of tetraethoxysilane, 0.5 parts of γ-methacryloyloxypropyldimethoxymethylsilane, and 97.5 parts of octamethylcyclotetrasiloxane, 100 parts of siloxane-based mixture was obtained. To this, a solution prepared by dissolving 0.67 parts of sodium dodecylbenzenesulfonate and 0.67 parts of dodecylbenzenesulfonic acid in 233 parts of deionized water was added and stirred for 5 minutes at 10000 rpm using a homomixer. Subsequently, the mixture was passed through a homogenizer at a pressure of 20 MPa two times, thereby obtaining a stable premixed organosiloxane emulsion.

[0196] This emulsion was introduced into a separable flask equipped with a cooling condenser and heated for 5 hours at 80° C. while stirring. Thereafter, the flask was cooled and kept for 6 hours at 50° C. to polymerize the organosiloxane. Subsequently, the resultant was neutralized to pH=7.0 using 5% aqueous solution of sodium hydroxide, thereby obtaining the polyorganosiloxane rubber latex (S-1).

[0197] This polyorganosiloxane rubber latex (S-1) was dried for 30 minutes at 180° C., and the solid content thereof was determined to obtain a result of 29.8%.

(Production Example 2) Production of Polyalkyl (Meth)Acrylate Rubber Latex (A-1)

[0198] Into a separable flask equipped with a cooling condenser, 4.95 parts of butyl acrylate, 0.025 parts of allyl methacrylate, 0.025 parts of 1,3-butylene glycol dimethacrylate, 0.2 parts of sodium dialkylsulfosuccinate, and 107.5 parts of deionized water were introduced and stirred for 2 hours in a nitrogen gas stream, and the internal temperature was then raised to 70° C. Subsequently, 0.01 parts of potassium persulfate and 2.5 parts of deionized water were added thereto to start the polymerization. The internal temperature was kept at 70° C. for 90 minutes to complete the polymerization, thereby obtaining the polyalkyl (meth)acrylate rubber latex (A-1).

[0199] This polyalkyl (meth)acrylate rubber latex (A-1) was dried for 30 minutes at 180° C., and the solid content thereof was determined to obtain a result of 4.3%.

(Production Example 3) Production of Graft Copolymer (G-1)

[0200] Into a separable flask, 33.22 parts (9.9 parts as solid content) of the polyorganosiloxane rubber latex (S-1) obtained in Production Example 1 was introduced, and 200 parts of distilled water was added thereto and mixed together. Thereafter, a mixture of 77.5 parts of butyl acrylate, 1.6 parts of allyl methacrylate, 0.3 part of t-butyl hydroperoxide and 0.5 parts of sodium dodecylbenzenesulfonate was added thereto.

[0201] Subsequently, a nitrogen gas stream was allowed to pass through this separable flask to purge the internal atmosphere of the flask with nitrogen gas, and the temperature was raised to 60° C. At the time point at which the liquid temperature reached 60° C., an aqueous solution prepared by dissolving 0.001 parts of ferrous sulfate, 0.003 parts of ethylenediaminetetraacetic acid disodium salt, and 0.24 parts of Rongalite in 10 parts of distilled water was added thereto to conduct the radical polymerization. This state was maintained for another one hour in order to complete the polymerization, thereby obtaining a latex of a composite rubber containing a polyorganosiloxane rubber and a polyalkyl (meth)acrylate rubber.

[0202] After the liquid temperature of the latex dropped to 65° C., a liquid mixture of 10 parts of methyl methacrylate, 1 part of butyl acrylate, and 0.06 parts of cumene hydroperoxide was added to the latex dropwise over 30 minutes to conduct the polymerization. After finishing the dropwise addition, the state having a temperature of 60° C. or higher was maintained for 1 hour and then cooled, thereby obtaining a latex of the graft copolymer (G-1) in which a methyl methacrylate-butyl acrylate copolymer was grafted onto the composite rubber. The mass average particle size of this graft copolymer (G-1) is presented in Table 1.

[0203] (Production Example 4 to 6) Production of Graft Copolymers (G-2) to (G-4)

[0204] The graft polymers were obtained in the same manner as in Production Example 3 except that the kind of the additional emulsifiers was changed as presented in Table 1. The mass average particle size of the graft copolymers (G-2) to (G-4) is presented in Table 1.

(Production Example 7) Production of Graft Copolymer (G-5)

[0205] To the polyalkyl (meth)acrylate rubber latex (A-1) latex obtained in Preparation Example 2, an aqueous solution prepared by dissolving 0.0003 parts of ferrous sulfate, 0.0009 parts of ethylenediaminetetraacetic acid disodium salt, and 0.03 parts of Rongalite in 2.5 parts of deionized water was added.

[0206] Subsequently, a liquid mixture of 69.3 parts of butyl acrylate, 0.7 parts of allyl methacrylate, 0.35 parts of 1,3-butylene glycol dimethacrylate, 0.35 parts of t-butyl hydroperoxide, 0.6 parts of sodium dialkylsulfosuccinate, and 35 parts of deionized water was added thereto dropwise over 2 hours, and the internal temperature was kept at 70° C. for 90 minutes to complete the polymerization, thereby obtaining a latex of an acrylic rubber. The solid content of this latex of the acrylic rubber was 33.5%.

[0207] To this acrylic rubber latex, 0.1 parts of sodium dialkylsulfosuccinate, 0.03 parts of Rongalite, and 2.5 parts of deionized water were added. Subsequently, 20 parts of methyl methacrylate, 5 parts of isobutyl methacrylate, 0.25 parts of t-butyl hydroperoxide were added thereto dropwise over 1 hour, the internal temperature was kept at 70° C. for 90 minutes to complete the polymerization, thereby obtaining a latex (solid content of 39.8%) of the graft copolymer (G-5). The mass average particle size of this graft copolymer (G-5) is presented in Table 1.

TABLE-US-00001 TABLE 1 Production Production Production Production Production Example 3 Example 4 Example 5 Example 6 Example 7 Kind of graft copolymer (A) G-1 G-2 G-3 G-4 G-5 Rubber latex Kind S-1 S-1 S-1 S-1 A-1 Parts 9.9 9.9 9.9 9.9 5.0 Emulsifier NEOPELEX G15 Parts 0.1 0.1 0.1 0.1 — PELEX OTP Parts — — — — 0.2 Thermal ° C. 275 275 275 275 224 decomposition temperature Composite Composition BA Parts 77.5 77.5 77.5 77.5 69.3 rubber Emulsifier AMA Parts 1.6 1.6 1.6 1.6 0.7 moiety NEOPELEX G15 Parts 0.5 — — — — PELEX SSL Parts — 0.5 — — — EMULGEN A90 Parts — — 0.5 — — EMAL 20C Parts — — — 0.5 — PELEX OTP Parts — — — — 0.6 Thermal ° C. 275 250 268 176 224 decomposition temperature Graft moiety Composition MMA Parts 10 10 10 10 20 BA Parts 1 1 1 1 — i-BMA Parts — — — — 5 Emulsifier PELEX OTP Parts — — — — 0.1 Thermal ° C. — — — — 224 decomposition temperature Mass average Graft copolymer (A) nm 243 238 249 210 240 particle size

[0208] The abbreviations in Table 1 denote the following compounds.

[0209] “NEOPELEX G15”: Sodium dodecylbenzenesulfonate (Manufactured by Kao Corporation, trade name: NEOPELEX G15)

[0210] “PELEX SSL”: Sodium alkyl diphenyl ether disulfonate (Manufactured by Kao Corporation, trade name: PELEX SSL)

[0211] “EMULGEN A90”: Polyoxyethylene distyrenated phenyl ether (Manufactured by Kao Corporation, trade name: EMULGEN A90)

[0212] “EMAL 20C”: Sodium polyoxyethylene alkyl ether sulfate (Manufactured by Kao Corporation, trade name: EMAL 20C)

[0213] “PELEX OTP”: Sodium dialkyl sulfosuccinate (Manufactured by Kao Corporation, trade name: PELEX OTP)

[0214] “BA”: n-Butyl acrylate

[0215] “MMA”: Methyl methacrylate

[0216] “AMA”: Allyl methacrylate

[0217] “i-BMA”: isobutyl methacrylate

(Production Example 8) Production of Powder of Graft Copolymer (B-1)

[0218] The latex of the graft copolymer (G-1) obtained in Production Example 3 was subjected to the spray drying treatment under the following conditions using an atomizer type spray dryer (Manufactured by OHKAWARA KAKOKI CO., LTD., L8 spray dryer) to obtain the powder (B-1) of the graft copolymer.

[0219] <Condition of Spray Drying Treatment>

Spray method: Rotating disc type
Disk rotation number: 25000 rpm
Hot air temperature: Inlet temperature=150° C., outlet temperature=65° C.

[0220] The volume average particle size and specific surface area of the powder (B-1) of the graft copolymer thus obtained, pH of water used for the extraction thereof, and the amount of the organosiloxane contained therein are presented in Table 2.

(Production Examples 9, 10, 11 and 13) Production of Powders (B-2), (B-3), (B-4) and (B-6) of Graft Copolymer

[0221] The powders (B-2), (B-3), (B-4) and (B-6) of the graft copolymer were obtained by conducting the same spray drying treatment as in Production Example 8 except that the kind of the graft copolymers was changed as presented in Table 2. The volume average particle sizes and specific surface areas of the powders thus obtained, pH's of water used for the extraction thereof, and the amounts of the organosiloxane contained therein are presented in Table 2.

(Production Example 12) Production of Powder (B-5) of Graft Copolymer

[0222] The latex (G-1) of the graft copolymer obtained in Production Example 3 was gradually added to 500 parts of an aqueous solution prepared by dissolving aluminum sulfate at a proportion of 2.5% dropwise while heating at 35° C. to coagulate. After finishing the dropwise addition, the resultant was completely solidified by further heating up to 80° C. This is separated, washed with water, and dried, thereby obtaining the powder (B-5) of the graft copolymer.

[0223] The volume average particle size and specific surface area of the powder (B-5) of the graft copolymer thus obtained, pH of water used for the extraction thereof, and the amount of the organosiloxane contained therein are presented in Table 2. As well, the respective measuring methods of these are as previously described.

TABLE-US-00002 TABLE 2 Production Production Production Production Production Production Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Kind of powder of graft copolymer(A) B-1 B-2 B-3 B-4 B-5 B-6 Graft copolymer (A) Kind G-1 G-2 G-3 G-4 G-1 G-5 Recovery method — SD SD SD SD Coagulation SD Volume average particle size μm 56 58 68 51 201 68 Specific surface area m.sup.2/g 2.7 3.2 2.9 2.0 0.3 2.9 pH of water used for extraction pH 4.6 4.1 5.4 3.6 3.6 4.5 Amount of organosiloxane contained % 0.13 0.15 0.16 0.18 0.19 0.00

[0224] The abbreviations in Table 2 denote the following methods.

[0225] “SD”: Spray drying (Spray drying method)

[0226] “Coagulation”: Coagulation method

Examples 1 to 3 and Comparative Examples 1 to 3

[0227] The formulations 1 to 6 were produced using the powder particles (B-1) to (B-6) of the graft copolymer obtained in Production Examples 8 to 13 and at the blending proportions presented in Table 3 as following conditions.

[0228] <Preparation Conditions of Formulations 1 to 6>

[0229] (a) 6.0 parts of the graft copolymer (A),

[0230] (b) 100 parts of a vinyl chloride resin, TK-1000 [Trade name, manufactured by Shin-Etsu Chemical Co., Ltd., average polymerization degree of 1050, average particle size of 150 μm],

[0231] (c) 3.0 parts of a CaZn-based stabilizer [Manufactured by SUN ACE CORPORATION],

[0232] (d) 5.0 parts of calcium carbonate, HAKUENKA CCR [Trade name, manufactured by SHIRAISHI CALCIUM KAISHA, LTD., primary particle size of 50 nm, surface treatment agent: fatty acid], and

[0233] (e) 5.0 parts of titanium dioxide, R-830 [Trade name, manufactured by ISHIHARA SANGYO KAISHA, LTD., TiO.sub.2 of 93%, average particle size of 0.25 μm, oil absorption of 21].

[0234] The materials of (a) to (e) above were blended, a Z blade and a flat blade were mounted to a 20 L Henschel mixer, FM20C/I [product number, manufactured by NIPPON COKE & ENGINEERING CO., LTD.] heated to 40° C., and the mixture was hot blended at a frequency of 65 Hz until the internal temperature thereof reached 110° C. to obtain the formulations 1 to 7.

[0235] These were kneaded for 3 minutes using a dielectric heating type 8 inch test roll [Kneader manufactured by KANSAI ROLL Co., Ltd.] heated to 180° C., then heated for 10 minutes in a press molding machine set to 180° C., and then cooled for 5 minutes to obtain plate-shaped test pieces having dimensions of length 200 mm×width 200 mm×thickness 4.0 mm. This test piece was cut according to the evaluation method and subjected to the evaluation. The results are presented in Table 3.

TABLE-US-00003 TABLE 3 Comparative Comparative Comparative Example 1 Example 1 Example 3 Example 1 Example 2 Example 3 Formulation 1 Formulation 2 Formulation 3 Formulation 4 Formulation 5 Formulation 6 (parts) (parts) (parts) (parts) parts) (parts) Vinyl chloride resin 100 100 100 100 100 100 CaZn-based stabilizer 3.0 3.0 3.0 3.0 3.0 3.0 Calcium carbonate 5.0 5.0 5.0 5.0 5.0 5.0 Titanium dioxide 5.0 5.0 5.0 5.0 5.0 5.0 Graft copolymer (B-1) 6.0 powder (B-2) 6.0 particles (B-3) 6.0 (B-4) 6.0 (B-5) 6.0 6.0 Charpy impact strength: 5.4 5.1 5.1 4.0 4.5 2.6 −10° C. (kJ/m.sup.2) Gelation time (sec) 186.0 208.0 204.0 224.0 220.0 200.5 Bleedout resistance ∘ ∘ ∘ x ∘ ∘

Examples 4 to 6 and Comparative Examples 4 to 6

[0236] The formulations 7 to 12 were produced using the powder particles (B-1) to (B-6) of the graft copolymer obtained in Production Examples 8 to 13 and at the blending proportions presented in Table 4 as following conditions.

[0237] <Preparation Condition of Formulations 7 to 12>

[0238] (a) 6.0 parts of the graft copolymer (A),

[0239] (b) 100 parts of a chlorinated vinyl chloride resin, HA-17F [Trade name manufactured by SEKISUI CHEMICAL CO., LTD., chlorine content of 64% by weight],

[0240] (c) 4.0 parts of dibutyl tin bisthioglycolate [Manufactured by NITTO KASEI CO., LTD.],

[0241] (d) 1.5 parts of partially oxidized polyethylene wax, PE-220 [Trade name, manufactured by Mitsui Chemicals Inc.], and

[0242] (e) 5.0 parts of titanium dioxide, R-830 [trade name, manufactured by ISHIHARA SANGYO KAISHA, LTD., TiO.sub.2 of 93%, average particle size of 0.25 μm, oil absorption of 21].

[0243] The materials of (a) to (e) above were blended, a Z blade and a flat blade were mounted to a 20 L Henschel mixer, FM20C/I [Product number, manufactured by NIPPON COKE & ENGINEERING CO., LTD.] heated to 40° C., and the mixture was hot blended at a frequency of 65 Hz until the internal temperature thereof reached 110° C. to obtain the formulations 7 to 12.

[0244] These were kneaded for 3 minutes using a dielectric heating type 8 inch test roll [Kneader manufactured by KANSAI ROLL Co., Ltd.] heated to 190° C., then heated for 10 minutes in a press molding machine set to 190° C., and then cooled for 5 minutes to obtain plate-shaped test pieces having dimensions of length 200 mm×width 200 mm×thickness 4.0 mm. This test piece was cut according to the evaluation method and subjected to the evaluation. The results are presented in Table 4.

TABLE-US-00004 TABLE 4 Comparative Comparative Comparative Example 4 Example 5 Example 6 Example 4 Example 5 Example 6 Formulation 7 Formulation 8 Formulation 9 Formulation 10 Formulation 11 Formulation 12 (parts) (parts) (parts) (parts) (parts) (parts) Chlorinated vinyl chloride resin 100 100 100 100 100 100 Dibutyl tin bisthioglycolate 4.0 4.0 4.0 4.0 4.0 4.0 Partially oxidized polyethylene wax 1.5 1.5 1.5 1.5 1.5 1.5 Titanium dioxide 5.0 5.0 5.0 5.0 5.0 5.0 Graft copolymer (B-1) 6.0 powder (B-2) 6.0 particles (B-3) 6.0 (B-4) 6.0 (B-5) 6.0 6.0 Charpy impact strength: 2.5 2.4 22 1.9 2.1 1.7 −10° C. (kJ/m.sup.2) Time until to twine (sec) 58.0 57.0 52.0 108.0 69.0 58.0

[0245] (Evaluation)

[0246] As evidenced by the results in Table 3, it has been confirmed that Examples 1 to 3 in which the graft copolymers (B-1) to (B-3) have been blended with a vinyl chloride resin maintain a practically sufficient low temperature impact strength, have a short gelation time, that is, exhibit excellent processability, and exhibit bleedout resistance.

[0247] On the other hand, it has been confirmed that Comparative Example 1 in which the graft copolymer (B-4) having a pH of water used for extraction of less than 4 has been blended has a lower low temperature impact strength and a longer gelation time, that is, exhibits inferior processability, and exhibits inferior bleedout resistance as compared to Examples. In addition, Comparative Example 2 in which the graft copolymer (B-5) having a specific surface area of less than 0.6 m.sup.2/g and a pH of water used for extraction of less than 4 has been blended has a practically sufficient low temperature impact strength but a long gelation time, that is, exhibits inferior processability. Comparative Example 3 in which the graft copolymer (B-6) not containing a polyorganosiloxane rubber or a composite rubber thereof has been blended has a short gel time, that is, exhibits favorable processability, but has an insufficient low temperature impact strength.

[0248] Furthermore, as evidenced by the results in Table 4, it has been confirmed that Examples 4 to 6 in which the graft copolymers (B-1) to (B-3) have been blended with a chlorinated vinyl chloride resin also maintain a practically sufficient low temperature impact strength, have a short time until to twine, that is, exhibit excellent processability.

[0249] On the other hand, it has been confirmed that Comparative Example 4 in which the graft copolymer (B-4) having a pH of water used for extraction of 4 or less has been blended has a lower low temperature impact strength and a longer time until to twine, that is, exhibits inferior processability as compared to Examples. In addition, Comparative Example 5 in which the graft copolymer (B-5) having a specific surface area of less than 0.6 m.sup.2/g and a pH of water used for extraction of less than 4 has been blended has a practically sufficient low temperature impact strength but a long time until to twine, that is, exhibits inferior processability. Comparative Example 6 in which the graft copolymer (B-6) not containing a polyorganosiloxane rubber or a composite rubber thereof has been blended has a short time until to twine, that is, exhibits favorable processability but has an insufficient low temperature impact strength.

[0250] As described above, it has been confirmed that the impact strength modifier for a chlorine-containing resin of the invention can improve the low temperature impact strength without deteriorating the processability in case of being blended and kneaded with a chlorine-containing resin.

INDUSTRIAL APPLICABILITY

[0251] It is possible to improve the low temperature impact strength without deteriorating the processability when the impact strength modifier (α) for a chlorine-containing resin of the invention is blended into and kneaded with the chlorine-containing resin (β). Hence, the chlorine-containing resin composition of the invention is useful for a variety of molded articles as various kinds of industrial materials. For example, it can be suitably used for applications such as a film, a bottle, a tray, a plate, a package, a pipe and a sheet. In addition to these, it can also be used, for example, in building materials such as a wall material, a flooring material, a window frame, a wall material, a corrugated plate, and a rain gutter; interior and exterior materials for motor vehicle; fish food packaging materials; and general goods such as packing, a gasket, a hose, a joint and a toy.