Antistatic agent, antistatic agent composition, antistatic resin composition, and molded body

Abstract

Provided are: an antistatic agent which is capable of imparting excellent antistatic effect in a small amount and has sufficient persistence and wiping resistance; an antistatic agent composition; an antistatic resin composition; and a molded article. The antistatic agent comprises a polymer compound (E) having a structure in which a block polymer (C) and an epoxy compound (D) are bound via an ester bond formed by a carboxyl group of the block polymer (C) and an epoxy group of the epoxy compound (D), the block polymer (C) having a structure comprising carboxyl groups at both ends, in which structure a block constituted by a polyester (A) having carboxyl groups at both ends and a block constituted by a compound (B) having hydroxyl groups at both ends are repeatedly and alternately bound via ester bonds formed by the carboxyl groups and the hydroxyl groups, and the epoxy compound (D) comprising two or more epoxy groups.

Claims

1. An antistatic agent, comprising a polymer compound (E) having a structure in which a block polymer (C) and an epoxy compound (D) are bound via an ester bond formed by a carboxyl group of said block polymer (C) and an epoxy group of said epoxy compound (D), said block polymer (C) having a structure comprising carboxyl groups at both ends, in which structure a block constituted by a polyester (A) having carboxyl groups at both ends and a block constituted by a compound (B) having hydroxyl groups at both ends are repeatedly and alternately bound via ester bonds formed by the carboxyl group and the hydroxyl group, and said epoxy compound (D) comprising two or more epoxy groups, wherein compound (B) having hydroxyl groups at both ends is a polyethylene glycol, said block constituted by said polyester (A) has a number-average molecular weight of 800 to 8,000 in terms of polystyrene, said block constituted by said compound (B) having hydroxyl groups at both ends has a number-average molecular weight of 400 to 6,000 in terms of polystyrene, and said block polymer (C) has a number-average molecular weight of 5,000 to 25,000 in terms of polystyrene.

2. The antistatic agent according to claim 1, wherein said polymer compound (E) further comprises an ester bond formed by a carboxyl group of said polyester (A) having carboxyl groups at both ends and an epoxy group of said epoxy compound (D).

3. The antistatic agent according to claim 1, wherein said polyester (A) has a structure in which a residue obtained by removing a carboxyl group from an aliphatic dicarboxylic acid and a residue obtained by removing a hydroxyl group from a diol are repeatedly and alternately bound via ester bonds.

4. The antistatic agent according to claim 1, wherein said polyester (A) has a structure represented by Formula (2), ##STR00004## wherein, A1 represents a residue obtained by removing a carboxyl group from an aliphatic dicarboxylic acid, A2 represents a residue obtained by removing a hydroxyl group from a diol, and n represents a number of 1 to 50.

5. An antistatic agent composition, comprising an antistatic agent and at least one selected from the group consisting of alkali metal salts and Group II element salts, wherein said antistatic agent comprises a polymer compound (E) having a structure in which a block polymer (C) and an epoxy compound (D) are bound via an ester bond formed by a carboxyl group of said block polymer (C) and an epoxy group of said epoxy compound (D), said block polymer (C) having a structure comprising carboxyl groups at both ends, in which structure a block constituted by a polyester (A) having carboxyl groups at both ends and a block constituted by a compound (B) having hydroxyl groups at both ends are repeatedly and alternately bound via ester bonds formed by the carboxyl group and the hydroxyl group, and said epoxy compound (D) comprising two or more epoxy groups, wherein compound (B) having hydroxyl groups at both ends is a polyethylene glycol; said block constituted by said polyester (A) has a number-average molecular weight of 800 to 8,000 in terms of polystyrene, said block constituted by said compound (B) having hydroxyl groups at both ends has a number-average molecular weight of 400 to 6,000 in terms of polystyrene, and said block polymer (C) has a number-average molecular weight of 5,000 to 25.000 in terms of polystyrene.

6. An antistatic resin composition, comprising the antistatic agent composition according to claim 5 in a thermoplastic resin.

7. An antistatic resin composition comprising a thermoplastic resin and an antistatic agent, wherein the antistatic agent comprises a polymer compound (E) having a structure in which a block polymer (C) and an epoxy compound (D) are bound via an ester bond formed by a carboxyl group of said block polymer (C) and an epoxy group of said epoxy compound (D), said block polymer (C) having a structure comprising carboxyl groups at both ends, in which structure a block constituted by a polyester (A) having carboxyl groups at both ends and a block constituted by a compound (B) having hydroxyl groups at both ends are repeatedly and alternately bound via ester bonds formed by the carboxyl group and the hydroxyl group, and said epoxy compound (D) comprising two or more epoxy groups, wherein compound (B) having hydroxyl groups at both ends is a polyethylene glycol; and wherein said thermoplastic resin is at least one selected from the group consisting of polyolefin-based resins and polystyrene-based resins, said block constituted by said polyester (A) has a number-average molecular weight of 800 to 8,000 in terms of polystyrene, said block constituted by said compound (B) having hydroxyl groups at both ends has a number-average molecular weight of 400 to 6,000 in terms of polystyrene, and said block polymer (C) has a number-average molecular weight of 5,000 to 25.000 in terms of polystyrene.

8. The antistatic resin composition according to claim 7, wherein the mass ratio of said thermoplastic resin and said antistatic agent is in a range of 99/1 to 40/60.

9. The antistatic resin composition according to claim 7, wherein the mass ratio of said thermoplastic resin and said antistatic agent composition is in a range of 99/1 to 40/60.

10. A molded article, characterized by being composed of the antistatic resin composition according to claim 7.

Description

EXAMPLES

(1) The present invention will now be described more concretely by way of examples thereof. It is noted here that, in the below-described working examples and the like, % and ppm are all based on mass unless otherwise specified.

(2) Antistatic agents were produced in accordance with the below-described Production Examples. Further, in the Production Examples, the number-average molecular weight was determined by the below-described method of measuring the molecular weight.

(3) <Method of Measuring Molecular Weight>

(4) The number-average molecular weight (hereinafter, referred to as Mn) was measured by gel permeation chromatography (GPC). The conditions of the Mn measurement were as follows.

(5) Apparatus: GPC apparatus, manufactured by JASCO Corporation

(6) Solvent: tetrahydrofuran

(7) Standard substance: polystyrene

(8) Detector: differential refractometer (RI detector)

(9) Column stationary phase: SHODEX KF-804L, manufactured by Showa Denko K.K.

(10) Column temperature: 40 C.

(11) Sample concentration: 1 mg/1 mL

(12) Flow rate: 0.8 mL/min

(13) Injection volume: 100 L

Production Example 1

(14) To a separable flask, 420 g of 1,4-cyclohexane dimethanol, 485 g of adipic acid, 0.5 g of an antioxidant (tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane: ADK STAB AO-60, manufactured by ADEKA Corporation) and 0.5 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 4 hours under normal pressure with the temperature being slowly increased from 160 C. to 200 C. and then for 3 hours at 200 C. under reduced pressure, thereby obtaining a polyester (A)-1. This polyester (A)-1 had an acid value of 56 and a number-average molecular weight (Mn) of 3,200 in terms of polystyrene.

(15) Next, 600 g of the thus obtained polyester (A)-1, 400 g of polyethylene glycol having a number-average molecular weight of 2,000 as a compound (B)-1 having hydroxyl groups at both ends, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded and allowed to polymerize at 200 C. for 7 hours under reduced pressure, thereby obtaining a block polymer (C)-1 having a structure comprising carboxyl groups at both ends. This block polymer (C)-1 had an acid value of 11 and a number-average molecular weight (Mn) of 10,000 in terms of polystyrene.

(16) Then, 300 g of the thus obtained block polymer (C)-1 and 8.5 g of epoxidized soybean oil as an epoxy compound (D)-1 were loaded and allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining an antistatic agent (E)-1 according to the present invention.

Production Example 2

(17) To a separable flask, 360 g of 1,4-bis(-hydroxyethoxy)benzene, 310 g of adipic acid, 0.4 g of an antioxidant (ADK STAB AO-60) and 0.4 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 4 hours under normal pressure with the temperature being slowly increased from 160 C. to 220 C. and then for 3 hours at 220 C. under reduced pressure, thereby obtaining a polyester (A)-2. This polyester (A)-2 had an acid value of 56 and a number-average molecular weight (Mn) of 2,500 in terms of polystyrene.

(18) Next, 300 g of the thus obtained polyester (A)-2, 150 g of polyethylene glycol having a number-average molecular weight of 2,000 as a compound (B)-1 having hydroxyl groups at both ends, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded and allowed to polymerize at 200 C. for 9 hours under reduced pressure, thereby obtaining a block polymer (C)-2 having a structure comprising carboxyl groups at both ends. This block polymer (C)-2 had an acid value of 11 and a number-average molecular weight (Mn) of 10,000 in terms of polystyrene.

(19) Then, 300 g of the thus obtained block polymer (C)-2 and 8.5 g of epoxidized soybean oil as an epoxy compound (D)-1 were loaded and allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining an antistatic agent (E)-2 according to the present invention.

Production Example 3

(20) To a separable flask, 413 g of an ethylene oxide adduct of bisphenol A, 235 g of adipic acid, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 4 hours under normal pressure with the temperature being slowly increased from 160 C. to 200 C. and then for 5 hours at 200 C. under reduced pressure, thereby obtaining a polyester (A)-3. This polyester (A)-3 had an acid value of 56 and a number-average molecular weight (Mn) of 2,100 in terms of polystyrene.

(21) Next, 300 g of the thus obtained polyester (A)-3, 150 g of polyethylene glycol having a number-average molecular weight of 2,000 as a compound (B)-1 having hydroxyl groups at both ends, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded and allowed to polymerize at 200 C. for 7 hours under reduced pressure, thereby obtaining a block polymer (C)-3 having a structure comprising carboxyl groups at both ends. This block polymer (C)-3 had an acid value of 11 and a number-average molecular weight (Mn) of 10,500 in terms of polystyrene.

(22) Then, 300 g of the thus obtained block polymer (C)-3 and 8.5 g of epoxidized soybean oil as an epoxy compound (D)-1 were loaded and allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining an antistatic agent (E)-3 according to the present invention.

Production Example 4

(23) To a separable flask, 382 g of hydrogenated bisphenol A, 276 g of adipic acid, 0.4 g of an antioxidant (ADK STAB AO-60) and 0.4 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 4 hours under normal pressure with the temperature being slowly increased from 160 C. to 200 C. and then for 4 hours at 200 C. under reduced pressure, thereby obtaining a polyester (A)-4. This polyester (A)-4 had an acid value of 56 and a number-average molecular weight (Mn) of 2,900 in terms of polystyrene.

(24) Next, 300 g of the thus obtained polyester (A)-4, 150 g of polyethylene glycol having a number-average molecular weight of 2,000 as a compound (B)-1 having hydroxyl groups at both ends, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded and allowed to polymerize at 200 C. for 5 hours under reduced pressure, thereby obtaining a block polymer (C)-4 having a structure comprising carboxyl groups at both ends. This block polymer (C)-4 had an acid value of 11 and a number-average molecular weight (Mn) of 9,300 in terms of polystyrene.

(25) Then, 300 g of the thus obtained block polymer (C)-4 and 8.5 g of epoxidized soybean oil as an epoxy compound (D)-1 were loaded and allowed to polymerize at 240 C. for 2 hours under reduced pressure, thereby obtaining an antistatic agent (E)-4 according to the present invention.

Production Example 5

(26) To a separable flask, 300 g of the block polymer (C)-1 obtained by the method described in Production Example 1 and 12 g of an o-cresol novolac-type epoxy resin as an epoxy compound (D)-2 were loaded, and these loaded materials were allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining an antistatic agent (E)-5 according to the present invention.

Production Example 6

(27) To a separable flask, 300 g of the block polymer (C)-1 obtained by the method described in Production Example 1 and 12 g of a partially epoxidized polybutadiene as an epoxy compound (D)-3 were loaded, and these loaded materials were allowed to polymerize at 200 C. for 6 hours under reduced pressure, thereby obtaining an antistatic agent (E)-6 according to the present invention.

Production Example 7

(28) To a separable flask, 188 g of 1,4-cyclohexane dimethanol, 259 g of 1,4-cyclohexanedicarboxylic acid, 0.3 g of an antioxidant (ADK STAB AO-60) and 0.3 g of zinc acetate were loaded. The loaded materials were allowed to polymerize for 4 hours under normal pressure with the temperature being slowly increased from 160 C. to 200 C. and then for 5 hours at 200 C. under reduced pressure, thereby obtaining a polyester (A)-5. This polyester (A)-5 had an acid value of 56 and a number-average molecular weight (Mn) of 3,200 in terms of polystyrene.

(29) Next, 300 g of the thus obtained polyester (A)-5, 150 g of polyethylene glycol having a number-average molecular weight of 2,000 as a compound (B)-1 having hydroxyl groups at both ends, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zinc acetate were loaded and allowed to polymerize at 200 C. for 7 hours under reduced pressure, thereby obtaining a block polymer (C)-5 having a structure comprising carboxyl groups at both ends. This block polymer (C)-5 had an acid value of 11 and a number-average molecular weight (Mn) of 11,000 in terms of polystyrene.

(30) Then, 300 g of the thus obtained block polymer (C)-5 and 11 g of bisphenol F diglycidyl ether as an epoxy compound (D)-4 were loaded and allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining an antistatic agent (E)-7 according to the present invention.

Production Example 8

(31) To a separable flask, 300 g of the block polymer (C)-5 obtained by the method described in Production Example 7 and 11 g of dicyclopentadiene methanol diglycidyl ether as an epoxy compound (D)-5 were loaded, and these loaded materials were allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining an antistatic agent (E)-8 according to the present invention.

Production Example 9

(32) To a separable flask, 394 g of 1,4-cyclohexane dimethanol, 405 g of succinic acid, 0.6 g of an antioxidant (ADK STAB AO-60) and 0.6 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 4 hours under normal pressure with the temperature being slowly increased from 160 C. to 200 C. and then for 6 hours at 200 C. under reduced pressure, thereby obtaining a polyester (A)-6. This polyester (A)-6 had an acid value of 112 and a number-average molecular weight (Mn) of 1,600 in terms of polystyrene.

(33) Next, 300 g of the thus obtained polyester (A)-6, 200 g of polyethylene glycol having a number-average molecular weight of 1,000 as a compound (B)-2 having hydroxyl groups at both ends, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded and allowed to polymerize at 200 C. for 7 hours under reduced pressure, thereby obtaining a block polymer (C)-6 having a structure comprising carboxyl groups at both ends. This block polymer (C)-6 had an acid value of 22 and a number-average molecular weight (Mn) of 5,200 in terms of polystyrene.

(34) Then, 300 g of the thus obtained block polymer (C)-6 and 19 g of hydrogenated bisphenol A diglycidyl ether as an epoxy compound (D)-6 were loaded and allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining an antistatic agent (E)-9 according to the present invention.

Production Example 10

(35) To a separable flask, 461 g of hydrogenated bisphenol A, 309 g of succinic acid, 0.4 g of an antioxidant (ADK STAB AO-60) and 0.4 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 4 hours under normal pressure with the temperature being slowly increased from 160 C. to 200 C. and then for 4 hours at 200 C. under reduced pressure, thereby obtaining a polyester (A)-7. This polyester (A)-7 had an acid value of 112 and a number-average molecular weight (Mn) of 1,700 in terms of polystyrene.

(36) Next, 300 g of the thus obtained polyester (A)-7, 240 g of polyethylene glycol having a number-average molecular weight of 1,000 as a compound (B)-2 having hydroxyl groups at both ends, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded and allowed to polymerize at 200 C. for 6 hours under reduced pressure, thereby obtaining a block polymer (C)-7 having a structure comprising carboxyl groups at both ends. This block polymer (C)-7 had an acid value of 13 and a number-average molecular weight (Mn) of 8,200 in terms of polystyrene.

(37) Then, 300 g of the thus obtained block polymer (C)-7 and 16 g of epoxidized soybean oil as an epoxy compound (D)-1 were loaded and allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining an antistatic agent (E)-10 according to the present invention.

Production Example 11

(38) To a separable flask, 479 g of 1,4-cyclohexane dimethanol, 439 g of succinic acid, 0.6 g of an antioxidant (ADK STAB AO-60) and 0.6 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 4 hours under normal pressure with the temperature being slowly increased from 160 C. to 200 C. and then for 4 hours at 200 C. under reduced pressure, thereby obtaining a polyester (A)-8. This polyester (A)-8 had an acid value of 56 and a number-average molecular weight (Mn) of 3,100 in terms of polystyrene.

(39) Next, 300 g of the thus obtained polyester (A)-8, 150 g of polyethylene glycol having a number-average molecular weight of 2,000 as a compound (B)-1 having hydroxyl groups at both ends, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded and allowed to polymerize at 200 C. for 5 hours under reduced pressure, thereby obtaining a block polymer (C)-8 having a structure comprising carboxyl groups at both ends. This block polymer (C)-8 had an acid value of 19 and a number-average molecular weight (Mn) of 7,300 in terms of polystyrene.

(40) Then, 300 g of the thus obtained block polymer (C)-8 and 24 g of epoxidized soybean oil as an epoxy compound (D)-1 were loaded and allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining an antistatic agent (E)-11 according to the present invention.

Production Example 12

(41) To a separable flask, 297 g of 1,4-bis(-hydroxyethoxy)benzene, 364 g of sebacic acid, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 5 hours under normal pressure with the temperature being slowly increased from 160 C. to 200 C. and then for 4 hours at 220 C. under reduced pressure, thereby obtaining a polyester (A)-9. This polyester (A)-9 had an acid value of 56 and a number-average molecular weight (Mn) of 2,100 in terms of polystyrene.

(42) Next, 400 g of the thus obtained polyester (A)-9, 300 g of polyethylene glycol having a number-average molecular weight of 2,000 as a compound (B)-1 having hydroxyl groups at both ends, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded and allowed to polymerize at 200 C. for 8 hours under reduced pressure, thereby obtaining a block polymer (C)-9 having a structure comprising carboxyl groups at both ends. This block polymer (C)-9 had an acid value of 8 and a number-average molecular weight (Mn) of 14,000 in terms of polystyrene.

(43) Then, 300 g of the thus obtained block polymer (C)-9 and 11 g of epoxidized soybean oil as an epoxy compound (D)-1 were loaded and allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining an antistatic agent (E)-12 according to the present invention.

Production Example 13

(44) To a separable flask, 354 g of 1,4-cyclohexane dimethanol, 538 g of sebacic acid, 0.6 g of an antioxidant (ADK STAB AO-60) and 0.6 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 4 hours under normal pressure with the temperature being slowly increased from 160 C. to 200 C. and then for 4 hours at 200 C. under reduced pressure, thereby obtaining a polyester (A)-10. This polyester (A)-10 had an acid value of 28 and a number-average molecular weight (Mn) of 5,200 in terms of polystyrene.

(45) Next, 400 g of the thus obtained polyester (A)-10, 200 g of polyethylene glycol having a number-average molecular weight of 4,000 as a compound (B)-3 having hydroxyl groups at both ends, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded and allowed to polymerize at 200 C. for 8 hours under reduced pressure, thereby obtaining a block polymer (C)-10 having a structure comprising carboxyl groups at both ends. This block polymer (C)-10 had an acid value of 9 and a number-average molecular weight (Mn) of 13,000 in terms of polystyrene.

(46) Then, 300 g of the thus obtained block polymer (C)-10 and 12 g of epoxidized soybean oil as an epoxy compound (D)-1 were loaded and allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining an antistatic agent (E)-13 according to the present invention.

Production Example 14

(47) To a separable flask, 300 g of the polyester (A)-10 obtained by the method described in Production Example 13, 200 g of polyethylene glycol having a number-average molecular weight of 4,000 as a compound (B)-3 having hydroxyl groups at both ends, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 6 hours at 220 C. under reduced pressure, thereby obtaining a block polymer (C)-11 having a structure comprising carboxyl groups at both ends. This block polymer (C)-11 had an acid value of 5.6 and a number-average molecular weight (Mn) of 18,000 in terms of polystyrene.

(48) Then, 300 g of the thus obtained block polymer (C)-11 and 7 g of epoxidized soybean oil as an epoxy compound (D)-1 were loaded and allowed to polymerize at 240 C. for 2 hours under reduced pressure, thereby obtaining an antistatic agent (E)-14 according to the present invention.

Production Example 15

(49) To a separable flask, 323 g of 1,4-cyclohexane dimethanol, 478 g of sebacic acid, 0.6 g of an antioxidant (ADK STAB AO-60) and 0.6 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 4 hours under normal pressure with the temperature being slowly increased from 160 C. to 200 C. and then for 4 hours at 200 C. under reduced pressure, thereby obtaining a polyester (A)-11. This polyester (A)-11 had an acid value of 19 and a number-average molecular weight (Mn) of 6,900 in terms of polystyrene.

(50) Next, 400 g of the thus obtained polyester (A)-11, 200 g of polyethylene glycol having a number-average molecular weight of 6,000 as a compound (B)-4 having hydroxyl groups at both ends, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded and allowed to polymerize at 200 C. for 8 hours under reduced pressure, thereby obtaining a block polymer (C)-12 having a structure comprising carboxyl groups at both ends. This block polymer (C)-12 had an acid value of 6.2 and a number-average molecular weight (Mn) of 17,500 in terms of polystyrene.

(51) Then, 300 g of the thus obtained block polymer (C)-12 and 6 g of bisphenol A diglycidyl ether as an epoxy compound (D)-7 were loaded and allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining an antistatic agent (E)-15 according to the present invention.

Comparative Production Example 1

(52) The block polymer (C)-1 having a structure comprising carboxyl groups at both ends was synthesized by the method described in Production Example 1. The thus obtained block polymer (C)-1 was used as a comparative antistatic agent (1) in a Comparative Example.

Comparative Production Example 2

(53) To a separable flask, 328 g of 1,4-cyclohexane dimethanol, 354 g of adipic acid, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 4 hours under normal pressure with the temperature being slowly increased from 160 C. to 200 C. and then for 3 hours at 200 C. under reduced pressure, thereby obtaining a comparative polyester-1. This comparative polyester-1 had an acid value of 28 and a number-average molecular weight (Mn) of 5,300 in terms of polystyrene.

(54) Then, 400 g of the comparative polyester-1, 200 g of polyethylene glycol having a number-average molecular weight of 4,000, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded and allowed to polymerize at 200 C. for 7 hours under reduced pressure, thereby obtaining a comparative polyether ester-1 comprising carboxyl groups at both ends. The thus obtained comparative polyether ester-1 had an acid value of 9 and a number-average molecular weight (Mn) of 12,200 in terms of polystyrene. This comparative polyether ester-1 was used as a comparative antistatic agent (2) in a Comparative Example.

Comparative Production Example 3

(55) To a separable flask, 300 g of the polyester (A)-1 obtained by the method described in Production Example 1, 300 g of polyethylene glycol having a number-average molecular weight of 2,000, 0.5 g of an antioxidant (ADK STAB AO-60) and 0.5 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 8 hours at 200 C. under reduced pressure, thereby obtaining a comparative polyether ester-2 comprising a hydroxyl group at one end. The thus obtained comparative polyether ester-2 had an acid value of 5.6 and a number-average molecular weight (Mn) of 10,200 in terms of polystyrene. This comparative polyether ester-2 was used as a comparative antistatic agent (3) in a Comparative Example.

Comparative Production Example 4

(56) To a separable flask, 300 g of the comparative polyether ester-2 comprising a hydroxyl group at one end, which was obtained by the method described in Comparative Production Example 3, and 7 g of epoxidized soybean oil were loaded, and these materials were allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining a comparative antistatic agent (4). The thus obtained comparative antistatic agent (4) was used in a Comparative Example.

Comparative Production Example 5

(57) To a separable flask, 400 g of the polyester (A)-1 obtained by the method described in Production Example 1, 600 g of polyethylene glycol having a number-average molecular weight of 2,000, 0.6 g of an antioxidant (ADK STAB AO-60) and 0.6 g of zirconium acetate were loaded. The loaded materials were allowed to polymerize for 5 hours at 200 C. under reduced pressure, thereby obtaining a comparative polyether ester-3 comprising hydroxyl groups at both ends. The thus obtained comparative polyether ester-3 had a hydroxyl value of 11 and a number-average molecular weight (Mn) of 10,000 in terms of polystyrene.

(58) Then, 300 g of the comparative polyether ester-3 and 14 g of epoxidized soybean oil were loaded and allowed to polymerize at 240 C. for 3 hours under reduced pressure, thereby obtaining a comparative antistatic agent (5). The thus obtained comparative antistatic agent (5) was used in a Comparative Example.

Comparative Production Example 6

(59) To a separable flask, 300 g of the polyester (A)-1 obtained by the method described in Production Example 1, 16 g of 2-hexadecyloxirane were loaded, and these materials were allowed to polymerize at 200 C. for 6 hours under reduced pressure, thereby obtaining a comparative antistatic agent (6). This comparative antistatic agent (6), which had a hydroxyl value of 11 and a number-average molecular weight (Mn) of 10,500 in terms of polystyrene, was used in a Comparative Example.

Examples 1 to 27, Comparative Examples 1 to 8

(60) Using antistatic resin compositions that were blended based on the respective amounts shown in Tables 1 to 4 below, test pieces thereof were obtained in accordance with the below-described conditions of test piece preparation. For each of the thus obtained test pieces, the surface specific resistance (SR value) was measured and a test for evaluation of resistance to wiping with water was conducted. In the same manner, the resin compositions of Comparative Examples were prepared in accordance with the respective formulations shown in Table 5 below and each subjected to the evaluations.

(61) <Conditions for Preparing Test Pieces of Impact Copolymer Polypropylene Resin Compositions>

(62) Using a biaxial extruder manufactured by Ikegai Corp. (PCM30, equipped with a 60-mesh screen), antistatic resin compositions that were blended based on the respective amounts shown in Tables below were each granulated under the conditions of 200 C. and 6 kg/hr to obtain a pellet. Then, using a horizontal injection molding machine (NEX80, manufactured by Nissei Plastic Industrial Co., Ltd.), the thus obtained pellet was molded at a resin temperature of 200 C. and a die temperature of 40 C. to obtain a test piece of 100 mm100 mm3 mm in size.

(63) <Conditions for Preparing Test Pieces of Homopolypropylene Resin Compositions>

(64) Using a biaxial extruder manufactured by Ikegai Corp. (PCM30, equipped with a 60-mesh screen), antistatic resin compositions that were blended based on the respective amounts shown in Tables below were each granulated under the conditions of 230 C. and 6 kg/hr to obtain a pellet. Then, using a horizontal injection molding machine (NEX80, manufactured by Nissei Plastic Industrial Co., Ltd.), the thus obtained pellet was molded at a resin temperature of 230 C. and a die temperature of 40 C. to obtain a test piece of 100 mm100 mm3 mm in size.

(65) <Conditions for Preparing Test Pieces of ABS Resin Compositions>

(66) Using a biaxial extruder manufactured by Ikegai Corp. (PCM30, equipped with a 60-mesh screen), antistatic resin compositions that were blended based on the respective amounts shown in Tables below were each granulated under the conditions of 230 C. and 6 kg/hr to obtain a pellet. Then, using a horizontal injection molding machine (NEX80, manufactured by Nissei Plastic Industrial Co., Ltd.), the thus obtained pellet was molded at a resin temperature of 230 C. and a die temperature of 50 C. to obtain a test piece of 100 mm100 mm3 mm in size.

(67) <Method of Measuring Surface Specific Resistance (SR Value)>

(68) The thus obtained test pieces were each molded and, immediately thereafter, stored under the conditions of a temperature of 25 C. and a humidity of 60% RH. After 1 day and 30 days of storage, under the same atmosphere, the surface specific resistance (/) of each molded test piece was measured using an R8340 resistance meter manufactured by Advantest Corporation under the conditions of an applied voltage of 100 V and an application time of 1 minute. The measurement was performed at five spots and an average thereof was determined.

(69) <Test for Evaluation of Resistance to Wiping with Water>

(70) The surface of each of the thus obtained test pieces was wiped with a waste cloth 50 times in running water and subsequently stored for 2 hours under the conditions of a temperature of 25 C. and a humidity of 60%. Thereafter, under the same atmosphere, the surface specific resistance (/) was measured using an R8340 resistance meter manufactured by Advantest Corporation under the conditions of an applied voltage of 100 V and an application time of 1 minute. The measurement was performed at five spots and an average thereof was determined.

(71) TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 7 Antistatic agent (E)-1 10 10 10 10 10 (E)-2 10 (E)-3 10 Alkali metal salt KOAc*.sup.1 0.5 NaDBS*.sup.2 0.5 LiOTs*.sup.3 0.5 0.5 0.5 Ionic liquid IBTFS*.sup.4 0.5 Thermoplastic resin ICP*.sup.5 100 100 100 100 100 100 100 hPP*.sup.6 ABS*.sup.7 Surface specific After 1 day 5 10.sup.12 1 10.sup.11 9 10.sup.11 2 10.sup.11 3 10.sup.10 4 10.sup.11 5 10.sup.11 resistance (/ ) After 30 days 5 10.sup.12 1 10.sup.11 9 10.sup.11 3 10.sup.11 1 10.sup.10 3 10.sup.11 3 10.sup.11 Evaluation of resistance 4 10.sup.12 9 10.sup.10 9 10.sup.11 2 10.sup.11 2 10.sup.10 3 10.sup.11 4 10.sup.11 to wiping with water *1: potassium acetate *2: sodium dodecylbenzenesulfonate *3: lithium p-toluenesulfonate *4: l-ethyl-3-methylimidazolium-bis(trifiuoromethanesulfonyl)imide *5: impact copolymer polypropylene; trade name BC03B, manufactured by Japan Polypropylene Corporation *6: homopolypropylene; trade name MA3, manufactured by Japan Polypropylene Corporation *7: ABS resin; trade name TECHNO ABS110, manufactured by Techno Polymer Co., Ltd.

(72) TABLE-US-00002 TABLE 2 Example 8 9 10 11 12 13 14 Antistatic agent (E)-4 10 (E)-5 10 (E)-6 10 (E)-7 10 10 10 (E)-8 10 Alkali metal salt KOAc*.sup.1 NaDBS*.sup.2 LiOTs*.sup.3 0.5 0.5 0.5 0.5 0.5 0.5 Ionic liquid IBTFS*.sup.4 Thermoplastic resin ICP*.sup.5 100 100 100 100 100 hPP*.sup.6 100 ABS*.sup.7 100 Surface specific After 1 day 4 10.sup.11 7 10.sup.11 5 10.sup.11 2 10.sup.11 7 10.sup.11 7 10.sup.11 6 10.sup.12 resistance (/ ) After 30 days 3 10.sup.11 7 10.sup.11 6 10.sup.11 2 10.sup.11 6 10.sup.11 7 10.sup.11 5 10.sup.12 Evaluation of resistance 4 10.sup.11 5 10.sup.11 5 10.sup.11 2 10.sup.11 5 10.sup.11 5 10.sup.11 5 10.sup.12 to wiping with water

(73) TABLE-US-00003 TABLE 3 Example 15 16 17 18 19 20 21 Antistatic agent (E)-8 10 (E)-9 10 (E)-10 10 (E)-11 10 (E)-12 10 (E)-13 10 10 Alkali metal salt KOAc*.sup.1 0.5 0.5 NaDBS*.sup.2 LiOTs*.sup.3 0.5 0.5 0.5 0.5 Ionic liquid IBTFS*.sup.4 Thermoplastic resin ICP*.sup.5 100 100 100 100 100 100 hPP*.sup.6 100 ABS*.sup.7 Surface specific After 1 day 4 10.sup.11 8 10.sup.11 6 10.sup.11 6 10.sup.11 1 10.sup.11 2 10.sup.11 7 10.sup.12 resistance (/ ) After 30 days 3 10.sup.11 7 10.sup.11 6 10.sup.11 6 10.sup.11 9 10.sup.10 2 10.sup.11 6 10.sup.12 Evaluation of resistance 2 10.sup.11 8 10.sup.11 6 10.sup.11 5 10.sup.11 1 10.sup.11 2 10.sup.11 7 10.sup.12 to wiping with water

(74) TABLE-US-00004 TABLE 4 Example 22 23 24 25 26 27 Antistatic agent (E)-1 7 7 15 15 (E)-14 10 (E)-15 10 Alkali metal salt KOAc*.sup.1 NaDBS*.sup.2 LiOTs*.sup.3 0.5 0.5 0.5 0.5 Ionic liquid IBTFS*.sup.4 Thermoplastic resin ICP*.sup.5 100 100 100 100 100 100 hPP*.sup.6 ABS*.sup.7 Surface specific After 1 day 5 10.sup.11 9 10.sup.11 9 10.sup.12 7 10.sup.11 9 10.sup.11 8 10.sup.9 resistance (/ ) After 30 days 4 10.sup.11 9 10.sup.11 9 10.sup.12 5 10.sup.11 8 10.sup.11 8 10.sup.9 Evaluation of resistance 4 10.sup.11 8 10.sup.11 8 10.sup.12 6 10.sup.11 8 10.sup.11 7 10.sup.9 to wiping with water

(75) TABLE-US-00005 TABLE 5 Comparative Example 1 2 3 4 5 6 7 8 Comparative antistatic agent (1) 10 10 (2) 10 (3) 10 (4) 10 (5) 10 (6) 10 (7)*.sup.8 10 Alkali metal salt KOAc*.sup.1 0.5 NaDBS*.sup.2 LiOTs*.sup.3 Ionic liquid IBTFS*.sup.4 Thermoplastic resin ICP*.sup.5 100 100 100 100 100 100 100 100 hPP*.sup.6 ABS*.sup.7 Surface specific After 1 day 5 10.sup.14 4 10.sup.14 8 10.sup.14 1 10.sup.15 1 10.sup.15 3 10.sup.15 1 10.sup.15 3 10.sup.14 resistance (/ ) After 30 days 5 10.sup.14 2 10.sup.14 1 10.sup.15 1 10.sup.15 8 10.sup.14 2 10.sup.15 1 10.sup.15 3 10.sup.14 Evaluation of resistance to 4 10.sup.14 4 10.sup.14 8 10.sup.14 1 10.sup.15 9 10.sup.14 1 10.sup.15 1 10.sup.15 3 10.sup.14 wiping with water *.sup.8polyether ester amide-based antistatic agent; trade name IRGASTAT P-22, manufactured by BASF Japan Ltd.

(76) As shown in Tables above, according to the results of the antistatic resin compositions of Examples, excellent antistatic effect was attained with an addition of a small amount of an antistatic agent or antistatic agent composition, and it was confirmed that the antistatic effect was not reduced with time or by wiping with water.