JP4625255B2 - Antistatic agent and antistatic resin composition - Google Patents

Description

    The present invention relates to an antistatic agent and a resin composition containing this in a thermoplastic resin. More specifically, an antistatic agent that imparts an excellent antistatic property to the molded product without deteriorating the water resistance and mechanical properties of the thermoplastic resin molded product, and an antistatic property obtained by incorporating this into a thermoplastic resin. The present invention relates to a resin composition.

  Conventionally, as an antistatic resin composition, an antistatic thermoplastic resin composition containing a surfactant as an antistatic agent in a thermoplastic resin (see Patent Document 1), a nitrogen onium cation and a fluorine-containing organic anion. An antistatic composition containing an ionic salt made of a thermoplastic resin (see Patent Document 2), an antistatic resin composition made of a solid polymer electrolyte containing an ionic liquid (see Non-Patent Document 1), etc. Was used.

JP-A-14-146212 (pages 33-42, FIG. 3) Special table 2003-511505 gazette "Chemistry and Industry", Vol. 54 (2001) No. 3, 281-285, The Chemical Society of Japan Publication

However, since the ionic surfactant as an antistatic agent is solid at room temperature and is water-soluble, if the amount of use is increased for the purpose of improving antistatic properties, the mechanical properties of the molded product may be reduced. , Brings about deterioration of water resistance. In the case of a molded article of an antistatic resin composition containing an ionic salt or ionic liquid composed of a nitrogen onium cation and a fluorine-containing organic anion, the ionic salt or ionic liquid has a low molecular weight, Due to the poor affinity, ionic salts and ionic liquids easily bleed out on the surface of the molded product, and there was a problem that the antistatic property was lowered or the water resistance was deteriorated by washing with water or wiping with cloth.
An object of the present invention is to provide an antistatic agent that imparts excellent antistatic properties to a molded article without deteriorating the water resistance and mechanical properties of the thermoplastic resin molded article.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention contains an ionic liquid (A) having an initial conductivity of 1 to 200 ms / cm and a polyether block structure in an amount of 10 to 90% by weight and a water absorption of 10 to 150%. An antistatic agent comprising the block polymer (B); an antistatic resin composition comprising the antistatic agent contained in the thermoplastic resin (C); a molded article formed by molding the composition; And a molded article obtained by painting and / or printing the molded article.

The antistatic resin composition containing the antistatic agent of the present invention is extremely useful because of the following effects.
(1) A molded product obtained by molding the composition is excellent in permanent antistatic properties and mechanical properties.
(2) The molded product of the composition does not depend on the molding method (injection molding method or compression molding method), and all have excellent permanent antistatic properties.
(3) The molded body has excellent antistatic properties, and even when immersed in warm water for a long time, it does not cause deterioration of permanent antistatic properties, mechanical properties, or appearance deterioration of the molded product surface, and is extremely excellent in water resistance. Yes.

The ionic liquid (A) in the present invention has a melting point of room temperature or lower, and at least one of the cations or anions constituting (A) is an organic ion, preferably having an initial conductivity of 1 to 200 ms / cm, preferably Is a room temperature molten salt having 10 to 200 ms / cm, more preferably 20 to 200 ms / cm. Examples of the room temperature molten salt include those described in WO95 / 15572.
When the initial conductivity is less than 1 ms / cm, the antistatic property is deteriorated, and when it exceeds 200 ms / cm, synthesis is difficult. Here, the initial conductivity means the conductivity immediately after the start of measurement obtained at 30 ° C. using a specific conductivity measuring device.

  Examples of the cation constituting (A) include an amidinium cation (a11), a guanidinium cation (a12), and a tertiary ammonium cation (a13).

Examples of (a11) include the following.
[1] Imidazolinium cation 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium, 1,3-dimethyl -2,4-diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1-methyl-2,3,4-triethylimidazolinium, 1,2,3,4-tetraethylimidazole Linium, 1,2,3-trimethylimidazolinium, 1,3-dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium, 1,2,3-triethylimidazolinium 4-cyano-1,2,3-trimethylimidazolinium, 3-cyanomethyl-1,2-dimethylimidazolinium, 2-cyanomethyl-1,3- Dimethylimidazolinium, 4-acetyl-1,2,3-trimethylimidazolinium, 3-acetylmethyl-1,2-dimethylimidazolinium, 4-methylcarbooxymethyl-1,2,3-trimethylimidazoli Ni, 3-methylcarbooxymethyl-1,2-dimethylimidazolinium, 4-methoxy-1,2,3-trimethylimidazolinium, 3-methoxymethyl-1,2-dimethylimidazolinium, 4-formyl -1,2,3-trimethylimidazolinium, 3-formylmethyl-1,2-dimethylimidazolinium, 3-hydroxyethyl-1,2-dimethylimidazolinium, 4-hydroxymethyl-1,2,3 -Trimethylimidazolinium, 2-hydroxyethyl-1,3-dimethylimidazolinium and the like.

[2] Imidazolium cation 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1,2,3-trimethylimidazolium, 1,2,3,4- Tetramethylimidazolium, 1,3-dimethyl-2-ethylimidazolium, 1,2-dimethyl-3-ethyl-imidazolium, 1,2,3-triethylimidazolium, 1,2,3,4-tetraethylimidazolium Lithium, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 1-benzyl-2,3-dimethyl-imidazolium, 4-cyano-1,2,3-trimethyl Imidazolium, 3-cyanomethyl-1,2-dimethylimidazolium, 2-cyanomethyl-1,3-dimethyl-imidazole Zorium, 4-acetyl-1,2,3-trimethylimidazolium, 3-acetylmethyl-1,2-dimethylimidazolium, 4-methylcarbooxymethyl-1,2,3-trimethylimidazolium, 3-methylcarbo Oxymethyl-1,2-dimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 3-methoxymethyl-1,2-dimethylimidazolium, 4-formyl-1,2,3-trimethylimidazolium Rium, 3-formylmethyl-1,2-dimethylimidazolium, 3-hydroxyethyl-1,2-dimethylimidazolium, 4-hydroxymethyl-1,2,3-trimethylimidazolium, 2-hydroxyethyl-1, 3-dimethylimidazolium and the like.

[3] Tetrahydropyrimidinium cation 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1, 2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 8-methyl- 1,8-diazabicyclo [5,4,0] -7-undecenium, 5-methyl-1,5-diazabicyclo [4,3,0] -5-nonenium, 4-cyano-1,2,3-trimethyl- 1,4,5,6-tetrahydropyrimidinium, 3-cyanomethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-cyanomethyl-1,3-dimethyl-1,4 5,6- Tetrahydropyrimidinium, 4-acetyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-acetylmethyl-1,2-dimethyl-1,4,5,6-tetrahydro Pyrimidinium, 4-methylcarbooxymethyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-methylcarbooxymethyl-1,2-dimethyl-1,4,5 , 6-tetrahydropyrimidinium, 4-methoxy-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-methoxymethyl-1,2-dimethyl-1,4,5, 6-tetrahydropyrimidinium, 4-formyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-formylmethyl-1,2-dimethyl- , 4,5,6-tetrahydropyrimidinium, 3-hydroxyethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-hydroxymethyl-1,2,3-trimethyl-1 , 4,5,6-tetrahydropyrimidinium, 2-hydroxyethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium and the like.

[4] Dihydropyrimidinium cation 1,3-dimethyl-1,4- or -1,6-dihydropyrimidinium [these are referred to as 1,3-dimethyl-1,4 (6) -dihydropyrimidinium The same expression is used hereinafter. 1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4 (6) -dihydropyrimidinium, 1,2,3 5-tetramethyl-1,4 (6) -dihydropyrimidinium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,9 (10) -undecadienium, 5-methyl- 1,5-diazabicyclo [4,3,0] -5,7 (8) -nonadienium, 4-cyano-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3-cyanomethyl- 1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 2-cyanomethyl-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 4-acetyl-1,2,3- Trimethyl-1,4 (6) -dihydropyrimidinium, 3 Acetylmethyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-methylcarbooxymethyl-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3- Methylcarbooxymethyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-methoxy-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3-methoxy Methyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-formyl-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3-formylmethyl-1 , 2-Dimethyl-1,4 (6) -dihydropyrimidinium, 3-hydroxyethyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-hydroxymethyl-1,2,3 Trimethyl-1,4 (6) - dihydropyrimidinium, 1,3 2-hydroxyethyl dimethyl-1,4 (6) - such as hydro pyrimidinium.

Examples of (a12) include the following.
[1] Guanidinium cation having imidazolinium skeleton 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1, 3-dimethyl-4-ethylimidazolinium, 2-dimethylamino-1-methyl-3,4-diethylimidazolinium, 2-diethylamino-1-methyl-3,4-diethylimidazolinium, 2-diethylamino- 1,3,4-tetraethylimidazolinium, 2-dimethylamino-1,3-dimethylimidazolinium, 2-diethylamino-1,3-dimethylimidazolinium, 2-dimethylamino-1-ethyl-3-methyl Imidazolinium, 2-diethylamino-1,3-diethylimidazolinium, 1,5, 6,7-tetrahydro-1,2-dimethyl-2H-imide [1,2a] imidazolinium, 1,5-dihydro-1,2-dimethyl-2H-imide [1,2a] imidazolinium, 1, 5,6,7-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolinium, 1,5-dihydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolinium, 2-dimethylamino-4-cyano-1,3-dimethylimidazolinium, 2-dimethylamino-3-cyanomethyl-1-methylimidazolinium, 2-dimethylamino-4-acetyl-1,3-dimethylimidazoli Ni, 2-dimethylamino-3-acetylmethyl-1-methylimidazolinium, 2-dimethylamino-4-methylcarbooxymethyl-1,3-dimethyl Midazolinium, 2-dimethylamino-3-methylcarbooxymethyl-1-methylimidazolinium, 2-dimethylamino-4-methoxy-1,3-dimethylimidazolinium, 2-dimethylamino-3-methoxymethyl-1 -Methylimidazolinium, 2-dimethylamino-4-formyl-1,3-dimethylimidazolinium, 2-dimethylamino-3-formylmethyl-1-methylimidazolinium, 2-dimethylamino-3-hydroxyethyl -1-methylimidazolinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolinium, and the like.

[2] Guanidinium cation having imidazolium skeleton 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl -4-ethylimidazolium, 2-dimethylamino-1-methyl-3,4-diethylimidazolium, 2-diethylamino-1-methyl-3,4-diethylimidazolium, 2-diethylamino-1,3,4 Tetraethylimidazolium, 2-dimethylamino-1,3-dimethylimidazolium, 2-diethylamino-1,3-dimethylimidazolium, 2-dimethylamino-1-ethyl-3-methylimidazolium, 2-diethylamino-1, 3-diethylimidazolium, 1,5,6,7-tetrahydro- 1,2-dimethyl-2H-imide [1,2a] imidazolium, 1,5-dihydro-1,2-dimethyl-2H-imide [1,2a] imidazolium, 1,5,6,7-tetrahydro- 1,2-dimethyl-2H-pyrimido [1,2a] imidazolium, 1,5-dihydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolium, 2-dimethylamino-4-cyano-1 , 3-dimethylimidazolium, 2-dimethylamino-3-cyanomethyl-1-methylimidazolium, 2-dimethylamino-4-acetyl-1,3-dimethylimidazolinium, 2-dimethylamino-3-acetylmethyl- 1-methylimidazolium, 2-dimethylamino-4-methylcarbooxymethyl-1,3-dimethylimidazolium, 2-dimethylamino- -Methylcarbooxymethyl-1-methylimidazolium, 2-dimethylamino-4-methoxy-1,3-dimethylimidazolium, 2-dimethylamino-3-methoxymethyl-1-methylimidazolium, 2-dimethylamino- 4-formyl-1,3-dimethylimidazolium, 2-dimethylamino-3-formylmethyl-1-methylimidazolium, 2-dimethylamino-3-hydroxyethyl-1-methylimidazolium, 2-dimethylamino-4 -Hydroxymethyl-1,3-dimethylimidazolium and the like.

[3] Guanidinium cation having tetrahydropyrimidinium skeleton 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3,4 Trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-1-methyl -3,4-diethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1-methyl-3,4-diethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino -1,3,4-tetraethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-1,3-dimethyl-1,4,5,6 -Tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl-1,4,5,6- Tetrahydropyrimidinium, 2-diethylamino-1,3-diethyl-1,4,5,6-tetrahydropyrimidinium, 1,3,4,6,7,8-hexahydro-1,2-dimethyl-2H- Imido [1,2a] pyrimidinium, 1,3,4,6-tetrahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,3,4,6,7,8-hexahydro-1, 2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 1,3,4,6-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2-dimethyl Mino-4-cyano-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-cyanomethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium 2-dimethylamino-4-acetyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-acetylmethyl-1-methyl-1,4,5, 6-tetrahydropyrimidinium, 2-dimethylamino-4-methylcarbooxymethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-methylcarbooxymethyl- 1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-methoxy-1,3-dimethyl-1,4,5,6-tetrahydride Pyrimidinium, 2-dimethylamino-3-methoxymethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-formyl-1,3-dimethyl-1,4,5 6-tetrahydropyrimidinium, 2-dimethylamino-3-formylmethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-hydroxyethyl-1-methyl-1, 4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium and the like.

[4] Guanidinium cation having dihydropyrimidinium skeleton 2-dimethylamino-1,3,4-trimethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3,4-trimethyl -1,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-1-methyl-3, 4-diethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1-methyl-3,4-diethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3 4-tetraethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino No-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1 , 3-Diethyl-1,4 (6) -dihydropyrimidinium, 1,6,7,8-tetrahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,6-dihydro-1 , 2-Dimethyl-2H-imide [1,2a] pyrimidinium, 1,6,7,8-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 1,6-dihydro-1,2 -Dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2-dimethylamino-4-cyano-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-sia Methyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-acetyl-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino- 3-acetylmethyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-methylcarbooxymethyl-1,3-dimethyl-1,4 (6) -dihydropyrimidinium 2-dimethylamino-3-methylcarbooxymethyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-methoxy-1,3-dimethyl-1,4 (6) -Dihydropyrimidinium, 2-dimethylamino-3-methoxymethyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-formyl-1,3 Dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-formylmethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-hydroxy Ethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, and the like.
Of these, imidazoliniums are preferable, and 1,2,3,4-tetramethylimidazolinium, 1,2,3-trimethylimidazolinium, 1-ethyl-2,3 are particularly preferable. -Dimethylimidazolinium.

  Examples of (a13) include methyl dilauryl ammonium.

The above (a11) and (a12) may be used alone or in combination of two or more.
Among these, from the viewpoint of initial conductivity, (a11) is preferable, imidazolium cation is more preferable, and 1-ethyl-3-methylimidazolium cation is particularly preferable.

  In the ionic liquid (A), examples of the organic acid and / or inorganic acid constituting the anion include the following.

  Examples of the organic acid include carboxylic acid, sulfuric acid ester, higher alkyl ether sulfuric acid ester, sulfonic acid, and phosphoric acid ester.

  Examples of the carboxylic acid include aliphatic [monocarboxylic acid [C 1-30, for example, saturated carboxylic acid (formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, verargonic acid, Lauric acid, myristic acid, stearic acid, behenic acid, etc.) and unsaturated carboxylic acids (acrylic acid, methacrylic acid, oleic acid, etc.)], dicarboxylic acids [2-30 carbons such as oxalic acid, malonic acid, succinic acid, Fumaric acid, maleic acid, glutaric acid, adipic acid], trivalent or higher polyvalent carboxylic acid [having 6 to 30 carbon atoms such as citric acid], etc .; aromatic (aliphatic) [monocarboxylic acid (having 7 to 15 carbon atoms) For example, benzoic acid, cinnamic acid, naphthoic acid nicotinic acid, isonicotinic acid, 2-furic acid, benzylic acid, anthranilic acid, α-toluic acid, hydroatro Acid, atorvaic acid, hydrocinnamic acid, salicylic acid, anisic acid, orthopyrocatechuic acid, α-resorcylic acid, β-resorcylic acid, protocatechuic acid, vanillic acid, ortho-veratrumic acid, veratromic acid, biveronic acid, gallic acid, mandelic acid, Atrolactic acid, trovic acid, atroglyceric acid, homogentisic acid, umbelic acid, caffeic acid, ferulic acid, isoferulic acid, isatinic acid, isatoic acid, hippuric acid, phenylalanine, tyrosine, thyronine, doba, kynurenine), dicarboxylic acid [ 8 to 12 carbon atoms, such as ortho-, iso- and terephthalic acid, homophthalic acid, homoisophthalic acid, homoterephthalic acid, phthalonic acid, isophthalonic acid, terephthalonic acid], trivalent to hexavalent polyvalent carboxylic acid [carbon number 9-14, for example trimellitic acid, pyrome Tussic acid, hemimellitic acid, trimesic acid, merophanic acid, branitic acid, melittic acid, diphenic acid]]; Acid, cyclopropanecarboxylic acid, cyclohexanecarboxylic acid), dicarboxylic acid (C5-C10, such as camphoric acid, cyclopropanedicarboxylic acid, cyclohexane-1,4-dicarboxylic acid)], trivalent to tetravalent polyvalent Carboxylic acids (C6-C8, such as cholmuglaic acid, cyclopropanetricarboxylic acid) and the like.

As the sulfate ester, a sulfate ester of a higher alcohol having 8 to 30 carbon atoms and an ethylene oxide (hereinafter abbreviated as EO) 2 to 10 (preferably 2 to 4) mole adduct (higher alkyl) of a higher alcohol having 8 to 30 carbon atoms. Ether) sulfate and the like can be used.
Examples of the higher alcohol sulfate include octyl sulfate, lauryl sulfate, cetyl sulfate, stearyl sulfate, and eicosyl sulfate.
Examples of the higher alkyl ether sulfate include octyl ether sulfate, lauryl ether sulfate, dodecyl ether sulfate, stearyl ether sulfate, and eicosyl ether sulfate.

  As the sulfonic acid, alkylbenzene sulfonic acid having 1 to 30 carbon atoms in the alkyl group, alkane sulfonic acid having 1 to 30 carbon atoms, sulfosuccinic acid diester and number average molecular weight (hereinafter abbreviated as Mn, measurement is gel permeation) And 1,000 to 100,000 polyvinyl sulfonic acid (by chromatography).

Examples of the alkylbenzene sulfonic acid include P-toluenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, laurylbenzenesulfonic acid, octadecylbenzenesulfonic acid, and eicosylbenzenesulfonic acid.
Examples of the alkane sulfonic acid include methane sulfonic acid, octane sulfonic acid, dodecane sulfonic acid, eicosane sulfonic acid, and paraffin sulfonic acid.
Examples of the sulfosuccinic acid diester include sulfosuccinic acid-di-2-ethylhexyl ester.
Examples of polyvinyl sulfonic acid include polystyrene sulfonic acid.

  Examples of the phosphate ester include higher alcohol phosphate mono- and diesters having 8 to 30 carbon atoms, such as octyl phosphate monoester, octyl phosphate diester, lauryl phosphate monoester, lauryl phosphate diester, stearyl phosphate monoester. , Stearyl phosphate diester, eicosyl phosphate monoester, eicosyl phosphate diester and the like.

Examples of the inorganic acid include super strong acids (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid. It is done.
The organic acid and inorganic acid may be used alone or in combination of two or more.

Among the organic and inorganic acids, Hamett acidity function anions preferred from the viewpoint of the initial conductivity of the ionic liquids that make up the ionic liquid (A) (-H ₀₎ is 12 to 100, superacid A conjugated base, an anion other than a conjugated base of a super strong acid, and a mixture thereof.

  Examples of the anion other than the conjugate base of the super strong acid include halogen (fluorine, chlorine, bromine and the like) ions, alkyl (carbon number 1 to 12) benzenesulfonic acid (p-toluenesulfonic acid and the like) ions and poly (n = 1). -25) Fluoroalkanesulfonic acid (such as undecafluoropentanesulfonic acid) ions and the like.

Super strong acids include those derived from protonic acids and combinations of protonic acids and Lewis acids, and mixtures thereof.
Protonic acids as super strong acids include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane (carbon number) 1-30) sulfonic acid [e.g., methanesulfonic acid, dodecanesulfonic acid, etc.], poly (n = 1-30) fluoroalkane (C1-30) sulfonic acid (trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, Heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, and tridecafluorohexanesulfonic acid), borofluoric acid, tetrafluoroboric acid, and the like.
Of these, borofluoric acid, trifluoromethanesulfonic acid, and bis (pentafluoroethylsulfonyl) imidic acid are preferable from the viewpoint of ease of synthesis.

Protic acids used in combination with Lewis acids include hydrogen halides (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, Examples thereof include pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, and mixtures thereof.
Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of the ionic liquid.

Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, thallium pentafluoride, and mixtures thereof.
Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of the ionic liquid.
The combination of the protonic acid and the Lewis acid is arbitrary, but the super strong acid composed of these combinations includes tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorothalamic acid, hexafluoroantimonic acid, thallium hexafluorosulfone. Examples thereof include acids, tetrafluoroboric acid, hexafluorophosphoric acid, chlorotrifluoroboric acid, and mixtures thereof.

  Among the above-mentioned anions, a super strong acid conjugate base (a super strong acid consisting of a proton acid and a super strong acid consisting of a combination of a proton acid and a Lewis acid) is preferable from the viewpoint of the initial conductivity of the ionic liquid, and more preferably It is a conjugate base of a super strong acid consisting of a super strong acid consisting of a proton acid and a proton acid and boron trifluoride and / or phosphorus pentafluoride.

  The amount of the ionic liquid (A) used in the antistatic agent is selected from the viewpoints of the antistatic effect, (B) handling after production (blocking due to stickiness), appearance of the thermoplastic resin molded product and water resistance. To Preferably, it is 0.01-30 weight% based on the total weight of (A) and (B), More preferably, it is 0.1-20 weight%, Most preferably, it is 0.5-10 weight%.

As a manufacturing method of the ionic liquid (A) in this invention, the following are mentioned, for example.
<Production method of (A)>
An electrolyte salt is prepared by performing acid exchange by adding an acid to the dimethyl carbonate salt of amidinium cation and / or guanidinium cation obtained by quaternization with dimethyl carbonate or the like.
Alternatively, the amidinium cation and / or guanidinium cation is once hydrolyzed to form a monoamidoamine, and then the monoamidoamine is neutralized with an acid to prepare an electrolyte salt.

The block polymer (B) in the present invention contains a polyether block structure in the molecule in an amount of 10 to 90% by weight and has a water absorption rate of 10 to 150%. And one or more block polymers (B1) selected from the group consisting of polyetheresteramides, and polyolefin blocks and hydrophilic polymer blocks having a volume resistivity of 1 × 10 ⁴ to 1 × 10 ¹¹ Ω · cm However, a block polymer (B2) having a structure in which alternately and alternately bonded is included.

Here, the water absorption is a value obtained by the following method based on ASTM-D570 (hereinafter the same), and the weight of a test piece (100 × 100 × 2 mm) previously dried at 50 ° C. for 24 hours ( W1) and the test piece are immersed in ion-exchanged water at 23 ° C. for 24 hours, and then the weight (W2) after the water on the test piece is thoroughly wiped with a cloth is measured.

Water absorption (%) = [(W2) − (W1)] × 100 / (W1)

The test piece is usually produced using an injection molding machine [PS40E5ASE, manufactured by Nissei Plastic Industry Co., Ltd.] at a predetermined cylinder temperature [B1 is 180 ° C., B2 is 220 ° C.] and a mold temperature is 50 ° C.
The water absorption of (B) is 10 to 150%, preferably 20 to 100%, particularly preferably 30 to 90%. If the water absorption exceeds 150%, the surface becomes rough due to swelling and causes surface swelling. If the water absorption is less than 10%, the molded product described later is inferior in antistatic properties.

Examples of (B1) include one or more (co) polymers selected from the group consisting of polyether esters, polyether amides and polyether ester amides described in JP-A No. 14-146212.
Specific examples and preferred ranges of the bonding structure and production method of (B1) are as described in the above publication. Hereinafter, (B1) will be described.

(B1) is formed from a diol (b11) and / or diamine (b12) having a (poly) oxyalkylene group and a condensation polymer (b13) having at least two carboxyl groups in one molecule.
Examples of (b11) include alkylene oxide (hereinafter abbreviated as AO) adducts of compounds containing two active hydrogen atoms.
Examples of the compound containing two active hydrogen atoms include glycol (b111), divalent phenol (b112), amine (b113) and dicarboxylic acid (b114).

Examples of (b111) include an aliphatic glycol having 2 to 20 carbon atoms, an alicyclic glycol having 5 to 12 carbon atoms, an araliphatic glycol having 8 to 30 carbon atoms, and an alkanolamine having 5 to 10 carbon atoms. .
Aliphatic glycols include ethylene glycol, 1,2-propylene glycol, 1,2-, 1,3- and 1,4-butanediol, 1,3-, 1,4-, 1,6- and 2, Examples include 5-hexanediol, 1,2- and 1,8-octanediol, 1,10-decanediol, 1,18-octadecanediol, 1,20-eicosanediol, and the like.

Alicyclic glycols include 1-hydroxymethyl-1-cyclobutanol, 1,2-, 1,3- and 1,4-cyclohexanediol, 1-methyl-3,4-cyclohexanediol, 2- and 4- Examples thereof include hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol and 1,1′-dihydroxy-1,1′-dicyclohexyl.
Examples of the araliphatic glycol include dihydroxymethylbenzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, 2-benzyl-1,3-propanediol, and triphenylethylene glycol. , Tetraphenylethylene glycol, benzopinacol and the like.
Examples of the alkanolamine include N-methyldiethanolamine, N-methyldipropanolamine, N-octyldiethanolamine and N-stearyldiethanolamine.

  Examples of the bivalent phenol (b112) include phenols having 6 to 30 carbon atoms such as monocyclic phenols (catechol, resorcinol, hydroquinone, etc.), polycyclic phenols (dihydroxydiphenyl ether, dihydroxydiphenylthioether, binaphthol, etc.), bisphenol compounds ( Bisphenol A, bisphenol F, bisphenol S, etc.) and alkyls (1 to 10 carbon atoms) or halogen-substituted products thereof.

Examples of the amine (b113) include aliphatic primary monoamines having 1 to 20 carbon atoms, aliphatic secondary diamines having 4 to 18 carbon atoms, 4 to 13 heterocyclic primary monoamines and secondary diamines, and 6 to 14 Examples include alicyclic secondary diamines, aromatic (aliphatic) secondary diamines having 8 to 14 carbon atoms, and secondary alkanolamines having 3 to 22 carbon atoms.
Aliphatic primary monoamines include methylamine, ethylamine, n- and i-propylamine, n-, sec- and i-butylamine, methyl-n-propylamine, n- and i-amylamine, methyl-n-butylamine , Ethyl-n-propylamine, n-hexylamine, ethyl-n-butylamine, dimethyl-n-butylamine, n-heptylamine, n-octylamine, n-decylamine, n-octadecylamine and n-icosylamine It is done.

  Examples of the aliphatic secondary diamine include N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-dibutylethylenediamine, N, N′-dimethylpropylenediamine, and N, N′-diethylpropylenediamine. N, N′-dibutylpropylenediamine, N, N′-dimethyltetramethylenediamine, N, N′-diethyltetramethylenediamine, N, N′-dibutyltetramethylenediamine, N, N′-dimethylhexamethylenediamine, N, N′-diethylhexamethylenediamine, N, N′-dibutylhexamethylenediamine, N, N′-dimethyldecamethylenediamine, N, N′-diethyldecamethylenediamine, N, N′-dibutyldecamethylenediamine, etc. Is mentioned.

  Examples of the heterocyclic primary amine or secondary diamine include piperazine, 1-aminopiperidine, 1-aminohomopiperidine, 2-aminothiazole, 2-aminobenzothiazole, 3-aminotriazine, and 3-amino-9-methyl. Examples thereof include carbazole, 9-aminofluorene, and alkyls (having 1 to 10 carbon atoms) or halogen substituents thereof.

  Examples of the alicyclic secondary diamine include N, N′-dimethyl-, diethyl- and dibutyl-1,2-cyclobutanediamine, N, N′-dimethyl-, diethyl- and dibutyl-1,4-cyclohexanediamine, N , N′-dimethyl, diethyl- and dibutyl-1,3-cyclohexanediamine and their alkyls (1 to 10 carbon atoms) or halogen-substituted products.

  Examples of aromatic (aliphatic) diamines include N, N′-dimethyl-phenylenediamine, N, N′-dimethyl-xylylenediamine, N, N′-dimethyl-diphenylmethanediamine, and N, N′-dimethyl-diphenylamine. Terdiamine, N, N′-dimethyl-benzidine, N, N′-dimethyl-1,4-naphthalenediamine and the like can be mentioned.

  Secondary alkanolamines include N-methylmonoethanolamine, N-methylmonopropanolamine, N-methylmonobutanolamine, N-octylmonoethanolamine, N-dodecylmonoethanolamine, N-stearylmono Ethanolamine and the like can be mentioned.

Examples of the dicarboxylic acid (b114) include C2-C20 aliphatic dicarboxylic acid, aromatic (aliphatic) dicarboxylic acid, and alicyclic dicarboxylic acid.
Aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, methyl succinic acid, dimethyl malonic acid, β-methyl glutaric acid, ethyl succinic acid, isopropyl malonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid , Sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and icosandiic acid.

  Aromatic (aliphatic) dicarboxylic acids include ortho-, iso- and terephthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α- and β-phenyladipic acid, biphenyl-2,2 Examples include '-and 4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate, and potassium 3-sulfoisophthalate.

  Alicyclic dicarboxylic acids include 1,3- and 1,2-cyclopentanedicarboxylic acid, 1,2-, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,2-, 1,3- and Examples thereof include 1,4-cyclohexanediacetic acid and dicyclohexyl-4,4′-dicarboxylic acid.

These active hydrogen atom-containing compounds may be used alone or in combination of two or more.
Of these, from the viewpoint of heat resistance, preferred are glycol (b111), divalent phenol (b112) and dicarboxylic acid (b114), more preferred are aliphatic glycol, (b112) and aliphatic dicarboxylic acid, Preferred are ethylene glycol, propylene glycol, butanediol, hydroquinone, bisphenol A, bisphenol S and adipic acid, most preferred are ethylene glycol, propylene glycol and bisphenol A, and most preferred is bisphenol A.

  As AO, C2-C4 AO [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,4-, 2,3- and 1,3- Butylene oxide and a combination system of two or more thereof] are used, but other AO or substituted AO, for example, an α-olefin having 5 to 12 carbon atoms, styrene oxide, and epihalohydrin (such as epichlorohydrin) (hereinafter also these) Including AO) may be used in a small proportion (for example, 30% or less based on the weight of all AO).

AO may be used alone or in combination of two or more, and the addition type in the latter case may be either block addition (chip type, balance type, active secondary type, etc.), random addition, or a mixed system thereof.
Among these AOs, from the viewpoint of antistatic properties, EO alone, a combination of PO and EO (weight ratio 1/99 to 99/1), a combination of PO and / or EO and THF (weight) 1/99 to 99/1), more preferably EO alone.

The addition reaction of AO to the active hydrogen atom-containing compound can be carried out in the usual manner, without a catalyst, or with a catalyst [alkali catalyst (such as potassium hydroxide), amine catalyst (such as triethylamine), acidic catalyst (such as hydrochloric acid). )] (Especially in the latter half of the AO addition) in one or more stages under normal pressure or pressure.
Mn of diol (b11) is preferably 300, more preferably 500, particularly preferably 600, most preferably from the viewpoint of reactivity during production of the block polymer formed from (b11) and the condensation polymer (b13). Is 700, preferably 6,000, more preferably 4,000, particularly preferably 3,000, most preferably 2,000.

The degree of unsaturation of (b11) is preferably smaller from the viewpoint of side reactions, and is usually 0.1 meq / g or less, preferably 0 to 0.05 meq / g, more preferably 0 to 0.02 meq / g.
The primary hydroxyl group content [(number of primary hydroxyl groups) × 100 / (total number of hydroxyl groups) (%)] of (b11) is preferably 30 to 100%, more preferably 50 to 50% from the viewpoint of polymerizability. 100%, particularly preferably 70 to 100%.

As the diamine (b12) having a polyoxyalkylene group, one obtained by modifying the terminal hydroxyl group of the diol (b11) to an amino group can be used.
As a method of modifying the terminal hydroxyl group of (b11) to an amino group, a known method, for example, a method of reducing the terminal cyanoalkyl group obtained by cyanoalkylating the terminal hydroxyl group of (b11) to aminoalkylate [(b11 ) And acrylonitrile are reacted, and the resulting cyanoethylated product is hydrogenated, etc.].
Mn of (b12) is preferably from 300 to 8,000, more preferably from 500 to 6,000, particularly from the viewpoint of reactivity during production of the block polymer formed from (b12) and the condensation polymer (b13). Preferably it is 700-4,000.

The condensation polymer (b13) having at least two carboxyl groups in one molecule has at least two (preferably two) carboxyl groups in one molecule, and (b11) and / or (b12) The polymer is not particularly limited as long as it can be polymerized, but from the viewpoint of antistatic properties and polymerizability, polyamides (imide) (b131) having carboxyl groups at both ends and polyesters having carboxyl groups at both ends ( at least one dicarboxylic acid selected from the group consisting of b132), more preferably (b131).
Mn of (b131) and (b132) having a carboxyl group at both ends is preferably 300, more preferably 500 from the viewpoints of antistatic properties, reactivity during production of the polymer and ease of handling after production of the polymer. The upper limit is preferably 7,000, and more preferably 5,000.

Of polyamides (imide) (b131) having carboxyl groups at both ends, polyamide (b1311) is obtained by ring-opening polymerization or polycondensation of an amide-forming monomer using dicarboxylic acid as a molecular weight regulator. Is mentioned.
Examples of the dicarboxylic acid used as the molecular weight modifier include dicarboxylic acids having 2 to 20 carbon atoms, such as those exemplified as the above (b114).

Amide-forming monomers include lactams, aminocarboxylic acids and diamine / dicarboxylic acids.
As the lactam, a lactam having 4 to 20 carbon atoms such as γ-butyrolactam, γ-valerolactam, ε-caprolactam, γ-pimelolactam, γ-caprolactam, γ-decanolactam, enantolactam, laurolactam, undecanolactam, Examples include eicosanolactam and 5-phenyl-2-piperidone.

  Examples of aminocarboxylic acids include C2-C20 aminocarboxylic acids such as glycine, alanine, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, Examples include 11-aminoundecanoic acid, 12-aminododecanoic acid, and 20-aminoeicosanoic acid.

Examples of the diamine include diamines having 2 to 20 carbon atoms, such as aliphatic [ethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, decamethylene diamine, eicosane diamine, etc.], aromatic (aliphatic) [phenylene diamine, naphthy Range amine, xylylenediamine, etc.] and alicyclic [cyclohexylenediamine, etc.] and the like.
Examples of the dicarboxylic acid include dicarboxylic acids having 2 to 20 carbon atoms, such as those exemplified as the above (b114).

These amide-forming monomers may be used alone or in combination of two or more.
Among these, caprolactam, enantolactam, laurolactam, ω-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, adipic acid / hexamethylenediamine and the like are preferable from the viewpoint of reactivity during production of the block polymer. Adipic acid / xylylenediamine, more preferred are caprolactam, laurolactam, ω-aminocaproic acid and 12-aminododecanoic acid, particularly preferred are caprolactam and laurolactam, most preferred caprolactam.
Polyamide (b1311) among (b131) can be easily produced by a known method, for example, a method described in JP-B-4-72855.

  As the polyamide-imide (b1312) having carboxyl groups at both ends of (b131), all or part of the molecular weight modifier in the production of (b131) may be a trivalent or tetravalent aromatic polycarboxylic acid, or these The acid anhydride is replaced with the amide-forming monomer, or all or part of the dicarboxylic acid in the amide-forming monomer is converted into a trivalent or tetravalent aromatic polycarboxylic acid or an acid anhydride thereof. Those obtained by substitution and ring-opening polymerization or polycondensation in combination with the above-mentioned amide-forming monomers can be mentioned.

  Examples of the trivalent aromatic polycarboxylic acid include those having 9 to 20 carbon atoms, such as 1,2,4-trimellitic acid and 1,2,5-naphthalenetricarboxylic acid. 2,6,7-naphthalenetricarboxylic acid, 3,3 ′, 4-diphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tricarboxylic acid, diphenylsulfone-3,3 ′, 4-tricarboxylic acid and diphenylether-3 , 3 ', 4-tricarboxylic acid and the like.

  Examples of the tetravalent aromatic polycarboxylic acid include polycarboxylic acids having 10 to 20 carbon atoms such as pyromellitic acid, diphenyl-2,2 ′, 3,3′-tetracarboxylic acid, and benzophenone-2,2 ′, 3. , 3′-tetracarboxylic acid, diphenylsulfone-2,2 ′, 3,3′-tetracarboxylic acid and diphenylether-2,2 ′, 3,3′-tetracarboxylic acid.

These may be used alone or in combination of two or more. Among these, from the viewpoint of reactivity during production of the block polymer, 1,2,4-trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, 2,6,7-naphthalenetricarboxylic acid, 3 ′, 4-diphenyltricarboxylic acid, pyromellitic acid, diphenyl-2,2 ′, 3,3′-tetracarboxylic acid and benzophenone-2,2 ′, 3,3′-tetracarboxylic acid, more preferably 1 2,4-trimellitic acid and pyromellitic acid.
Of polyamide (b131), polyamideimide (b1312) can be easily produced by a known method, for example, the method described in Japanese Patent Publication No. 7-119342.

Examples of the polyester (b132) having carboxyl groups at both ends include those obtained by using a dicarboxylic acid as a molecular weight modifier and subjecting an ester-forming monomer to polycondensation or transesterification by a conventional method.
Examples of the dicarboxylic acid used as the molecular weight modifier include dicarboxylic acids having 1 to 20 carbon atoms, such as carbonic acid and those exemplified as the above (b114).
Examples of ester-forming monomers include combinations of dicarboxylic acids and / or dicarboxylic acid lower alkyl esters with dihydric alcohols and / or dihydric phenols, lactones, hydroxycarboxylic acids, and mixtures thereof.

Examples of the dicarboxylic acid include dicarboxylic acids having 1 to 20 carbon atoms such as carbonic acid and those exemplified as the above (b114).
Examples of the dicarboxylic acid ester (carbon number 1 to 10 of the alcohol component constituting the ester) include carbonic acid or esters of the above dicarboxylic acid (carbon number 2 to 20), such as methyl ester, ethyl ester, butyl ester, and phenyl ester. Can be mentioned.
These may be used alone or in combination of two or more.
Of these, from the viewpoint of heat resistance, preferred are adipic acid, sebacic acid, icosanoic acid, ortho-, iso- and terephthalic acid, 1,4-cyclohexanedicarboxylic acid, sodium 3-sulfoisophthalate, dimethyl carbonate, carbonic acid. Diphenyl, dimethyl adipate, dimethyl iso- and terephthalate, dimethyl 1,4-cyclohexanedicarboxylate, dimethyl sodium 3-sulfoisophthalate and diethyl sodium 3-sulfoisophthalate.

Examples of the dihydric alcohol include diols having 2 to 30 carbon atoms, such as those exemplified as the glycol (b111) and diol (b11).
Examples of the divalent phenol include divalent phenols having 6 to 40 carbon atoms, for example, those exemplified as the divalent phenol (b112).
These may be used alone or in combination of two or more.
Of these, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanediol, bisphenol A, polyethylene glycol (Mn 300 to 6) are preferable from the viewpoint of reactivity during the production of the block polymer. , 000), polypropylene glycol (Mn 300-6,000), polytetramethylene glycol (Mn 300-6,000), EO (EO 2-110 mol) addition product of bisphenol A, PO (PO 2-110 mol) addition of bisphenol A It is a thing.

  Examples of the lactone include lactones having 4 to 20 carbon atoms, such as γ-butyrolactone, γ-valerolactone, ε-caprolactone, γ-pimerolactone, γ-caprolactone, γ-decanolactone, enanthlactone, laurolactone, and undecanolactone. And eicosanolactone.

  Examples of the hydroxycarboxylic acid include hydroxycarboxylic acids having 2 to 20 carbon atoms such as hydroxyacetic acid, lactic acid, ω-hydroxycaproic acid, ω-hydroxyenanthic acid, ω-hydroxycaprylic acid, ω-hydroxypergonic acid, ω- Examples include hydroxycapric acid, 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid and 20-hydroxyeicosanoic acid, tropic acid, benzylic acid and the like.

Of these, terephthalic acid (dimethyl) -ethylene glycol, terephthalic acid (dimethyl) -butanediol, terephthalic acid (dimethyl) -cyclohexanediol, and isophthalic acid (dimethyl) are preferred from the viewpoint of reactivity during production of the block polymer. / Ethylene glycol, isophthalic acid (dimethyl) / butanediol, adipic acid (dimethyl) / 1,6-hexanediol, caprolactone, enanthlactone, laurolactone, ω-hydroxycaproic acid, 11-hydroxyundecanoic acid, 12-hydroxydodecane Acids, more preferably terephthalic acid (dimethyl) / ethylene glycol, terephthalic acid (dimethyl) / butanediol, terephthalic (dimethyl) acid / cyclohexanediol, isophthalic acid (dimethyl) / ethyl Glycol and isophthalic acid (dimethyl) / butanediol, particularly preferred is terephthalic acid (dimethyl) / ethylene glycol and terephthalic acid (dimethyl) / butanediol.
The polyester (b132) having a carboxyl group at both ends can be easily produced by a known method, for example, a method described in JP-B-58-19696.

As a manufacturing method of the block polymer (B1) in this invention, the following are mentioned, for example.
<Production method of (B1)>
A polyamide (b1311) having a carboxyl group at both ends by reacting a dicarboxylic acid and / or a trivalent or tetravalent polycarboxylic acid as a molecular weight modifier with an amide-forming monomer and / or an ester-forming monomer. An imide (b1312) and / or a polyester (b132) is formed.
A diol (b11) and / or a diamine (b12) having a (poly) oxyalkylene group is added to these, and a polymerization reaction is performed at a high temperature (220 to 245 ° C.) under reduced pressure (1 mmHg or less) to produce a block polymer (B1 )
The antistatic agent of the present invention can be produced by kneading the obtained (B1) and (A).

Of the polymerization reactions in the above production method, an esterification catalyst is usually used in the polyesterification reaction.
Examples of esterification catalysts include proton acids (such as phosphoric acid), metals [alkali metals (such as sodium and potassium), alkaline earth metals (such as calcium and magnesium), transition metals (such as nickel, iron, and cobalt), IIB metals (such as Organic acids (such as acetic acid), carbonates, sulfates, phosphates, oxides, chlorides, hydroxides, and alkoxides of zinc (such as zinc), IVB metals (such as titanium, zirconium) and VB metals (such as vanadium)] Etc.
Of these, antimony trioxide, monobutyltin oxide, tetrabutyl titanate, tetrabutyl zirconate, zirconyl acetate, and zinc acetate are preferred from the viewpoint of the color of the product.
The amount of the esterification catalyst used is usually 0.005 to 5% by weight based on the weight of the block polymer (B1), and preferably 0.1 to 1.0% by weight from the viewpoints of reactivity and color tone.

The equivalent ratio in the reaction between (b11) and / or (b12) and (b131) and / or (b132) is usually 80/120 to 120/80, preferably 90/120 from the viewpoint of antistatic properties and heat resistance. 110-110 / 90.
The reduced viscosity (0.5 wt% m-cresol solution, 25 ° C.) of the block polymer (B1) is preferably 0.5 to 5 from the viewpoint of handling of the polymer and compatibility with the thermoplastic resin described later. More preferably, it is 0.5-4, and particularly preferably 1-3.

In the production of (B1), for the purpose of improving water resistance, (b11) and / or within the range of 30% by weight (preferably 20% by weight) based on the weight of (b11) and / or (b12). Alternatively, a part of (b12) may be used in place of the polyalkylene diol.
Examples of the polyalkylene diol include those obtained by polymerizing olefins and hydroxylating the terminals and those obtained by further hydrogenating the double bonds contained therein.
Examples of olefins include ethylene, propylene, and α-olefins having 4 to 20 carbon atoms (1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, etc.) and carbon. Examples thereof include diene having a number of 4 to 20 (such as butadiene).
The Mn of the polyalkylene diol is preferably 500 to 10,000, more preferably 1,000 to 5,000, from the viewpoint of improving water resistance.

Examples of the block polymer (B2) include block polymers described in International Publication Pamphlet WO00 / 47652.
Specific examples, preferred ranges and the like of the polyolefin (b21), the hydrophilic polymer (b22) constituting the (B2), and their bonding structure and production method are as described in the pamphlet, and the following (B2) Will be described.

  The block polymer (B2) having a structure in which a block of the polyolefin (b21) and a block of the hydrophilic polymer (b22) are alternately bonded to each other has an ester bond between the block (b21) and the block (b22). It has a structure in which they are alternately and repeatedly bonded via at least one bond selected from the group consisting of an amide bond, an ether bond, a urethane bond and an imide bond.

(B21) includes a polyolefin (b211) having a carbonyl group (preferably a carboxyl group, the same shall apply hereinafter) at both ends of the polymer, a polyolefin (b212) having a hydroxyl group at both ends of the polymer, and an amino group at both ends of the polymer. Polyolefin (b213) having a carbonyl group at one end of the polymer, polyolefin (b215) having a hydroxyl group at one end of the polymer, and polyolefin having an amino group at one end of the polymer. (B216).
Among these, polyolefins (b211) and (b214) having a carbonyl group at the end of the polymer are preferable from the viewpoint of easy modification.

Examples of (b211) include those in which a carbonyl group is introduced at both ends of a polyolefin (b210) whose main component (content is 50% by weight or more, preferably 75 to 100% by weight) is a polyolefin that can be modified at both ends. .
Examples of (b212) include those in which hydroxyl groups are introduced at both ends of (b210).
Examples of (b213) include those in which amino groups are introduced at both ends of (b210).

(B210) includes a polyolefin obtained by polymerization of one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably olefins having 2 to 12 carbon atoms, more preferably ethylene and / or propylene) and high Polyolefin having a molecular weight [Mn 30,000 or more, preferably 50,000 to 200,000] [preferably a polyolefin having 2 to 30 carbon atoms, more preferably a polyolefin obtained by polymerization of an olefin having 2 to 12 carbon atoms, particularly preferred Is a low molecular weight polyolefin obtained by a thermal degradation method of polyethylene and / or polypropylene].
Mn of (b210) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000 from the viewpoint of antistatic properties.
The amount of double bonds per 1,000 carbon atoms in (b210) is preferably 1 to 40, more preferably 1 to 30, particularly preferably 4 to 20 from the viewpoint of antistatic properties.
From the viewpoint of ease of modification, (b210) is preferably a low molecular weight polyolefin (especially polyethylene and polypropylene having Mn of 1,200 to 6,000) by a thermal degradation method.

Examples of (b214) include those in which a carbonyl group is introduced at one end of a polyolefin (b2100) whose main component is a polyolefin that can be modified at one end (content is 50 wt% or more, preferably 75 to 100 wt%). .
Examples of (b215) include those obtained by introducing a hydroxyl group at one end of (b2100).
Examples of (b216) include those in which an amino group is introduced at one end of (b2100).

(B2100) can be obtained in the same manner as (b210), and Mn of (b2100) is preferably 2,000 to 50,000, more preferably 2,500 to 30,000, particularly from the viewpoint of antistatic properties. Preferably it is 3,000-20,000.
The amount of double bonds per 1,000 carbon atoms in (b2100) is preferably 0.3 to 20, more preferably 0.5 to 15, particularly preferably 0.7 to 1,000 from the viewpoint of antistatic properties. 10 pieces.
From the viewpoint of ease of modification, (b2100) is preferably a low molecular weight polyolefin (especially polyethylene and polypropylene having Mn of 2,000 to 20,000) by a thermal degradation method.
In addition, (b210) and (b2100) are usually obtained as a mixture thereof, but these mixtures may be used as they are or after being purified and separated.

As (b211), the end of (b210) is an α, β-unsaturated carboxylic acid and / or anhydride thereof [having 3 to 15 carbon atoms, for example, a monocarboxylic acid [(meth) acrylic acid or the like], dicarboxylic acid (maleic acid) Acid, fumaric acid, itaconic acid, citraconic acid, etc.), alkyl (1 to 4 carbon atoms) esters thereof (methyl (meth) acrylate, butyl (meth) acrylate, diethyl itaconate, etc.) and their anhydrides Modified polyolefin (b2111), (b2111) secondary modified with lactam (caprolactam or the like) or aminocarboxylic acid (12 aminododecanoic acid or the like) or (b2112) or (b210) Modified by oxidation with oxygen and / or ozone (b2113), (b21 And polyolefin (b2114) obtained by secondary modification of 13) with lactam (as described above) or aminocarboxylic acid (as described above) and a mixture of two or more of these.
The acid value of (b211) is preferably 4 to 280, more preferably 4 to 100, and particularly preferably 5 to 50 from the viewpoint of reactivity with the hydrophilic polymer (b22) described later.

Examples of (b212) include a polyolefin having a hydroxyl group at the terminal obtained by modifying (b210) with a hydroxylamine having 2 to 10 carbon atoms (such as 2-aminoethanol) and a mixture of two or more thereof.
The hydroxyl value of (b212) is preferably 4 to 280, more preferably 4 to 100, and particularly preferably 5 to 50, from the viewpoint of reactivity with the hydrophilic polymer (b22) described later.
As (b213), polyolefin having an amino group at the terminal obtained by modifying (b211) with a diamine having 2 to 10 carbon atoms (ethylenediamine or the like) and a mixture of two or more of these can be used.
The amine value of (b213) is preferably 4 to 280, more preferably 4 to 100, and particularly preferably 5 to 50 from the viewpoint of reactivity with the hydrophilic polymer (b22) described later.

(B214) is a polyolefin (b2141) in which the terminal of (b2100) is modified with an α, β-unsaturated carboxylic acid and / or its anhydride [same as above], and (b2141) is a lactam (caprolactam or the like). ) Or an aminocarboxylic acid (12 aminododecanoic acid or the like as described above) and a polyolefin (b2142), (b210) modified by oxidation with oxygen and / or ozone (b2143), and (b2143) a lactam ( Examples thereof include polyolefins (b2144) secondary-modified with the above) or aminocarboxylic acids (above) and mixtures of two or more thereof.
The acid value of (b214) is preferably 1 to 70, more preferably 2 to 50, from the viewpoint of reactivity with the hydrophilic polymer (b22) described later.

As (b215), a polyolefin having a hydroxyl group at the terminal obtained by modifying (b214) with a hydroxylamine having 2 to 10 carbon atoms (such as 2-aminoethanol) and a mixture of two or more of these can be used.
The hydroxyl value of (b215) is preferably 1 to 70, more preferably 2 to 50, from the viewpoint of reactivity with the hydrophilic polymer (b22) described later.
Examples of (b216) include polyolefins having an amino group at the terminal obtained by modifying (b214) with a diamine having 2 to 10 carbon atoms (the above-mentioned ones such as ethylenediamine) and mixtures of two or more thereof.
The amine value of (b216) is preferably 1 to 70, more preferably 2 to 50, from the viewpoint of reactivity with the hydrophilic polymer (b22) described later.

(B211) and (b214) are usually obtained as a mixture thereof, but these mixtures may be used as they are, or may be used after being purified and separated. From the viewpoint of production cost and the like, it is preferably used as a mixture.
Further, (b212) and (b215) and (b213) and (b216) may be used after being purified and separated in the same manner, but are preferably used as a mixture from the viewpoint of production cost and the like.
From the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b22) described later, Mn of (b211), (b212) and (b213) is preferably 800 to 25,000, and more preferably 1,000 to 20 , Particularly preferably 2,500 to 10,000, Mn of (b214), (b215) and (b216) is preferably 800 to 50,000, more preferably 1,000 to 30,000, particularly preferably Is 2,000 to 20,000.

Examples of the hydrophilic polymer (b22) include polyether (b221), polyether-containing hydrophilic polymer (b222), cationic polymer (b223), and anionic polymer (b224).
Examples of (b221) include polyether diol (b2211), polyether diamine (b2212), and modified products thereof (b2213).

The volume resistivity value of the hydrophilic polymer (b22) (value measured in an atmosphere of 23 ° C. and 50% RH by the method described later) is preferably 10 ⁴ to 10 ¹¹ Ω · from the viewpoint of antistatic properties. cm, more preferably 10 ⁴ to 10 ⁹ Ω · cm.

The alkylene group in the polyoxyalkylene group in the block of the hydrophilic polymer (b22) constituting the block polymer (B2) is an alkylene group in which at least a part of the repeating unit is represented by the following general formula (1). The remainder may be an alkylene group having 2 to 4 carbon atoms.

-CHR-CHR'- (1)

—CH ₂ O (A ¹ O) _s R ″ (2)

Examples of the alkylene group having 2 to 4 carbon atoms include ethylene group, propylene group, 1,2-, 1,4-, 2,3- and 1,3-butylene groups, and two or more kinds thereof. Among these, an ethylene group is preferable from the viewpoint of antistatic properties.
When the repeating unit is composed of an oxy-substituted alkylene group and / or one or more oxyalkylene groups, the bonding form may be any of block, random, or a combination thereof.
In the above repeating unit, the proportion of the oxy-substituted alkylene group is preferably 90 mol% or less, more preferably 0 to 0% from the viewpoint of antistatic properties based on the total number of moles of the oxy-substituted alkylene group and the (unsubstituted) oxyalkylene group. 60 mol%.
In the formula (1), R and R ′ are both H, or one of them is H and the other is a group represented by the general formula (2). In general formula (2), s represents an integer of 0 to 10, preferably 2 to 4.
R ″ is H, an alkyl group having 1 to 20 carbon atoms (methyl group, ethyl group, n- and i-propyl group, n-, sec-, i- and t-butyl group, 2-ethylhexyl group, etc.), Represents an aryl group (such as a phenyl group), an alkylaryl group (such as a nonylphenyl group), an arylalkyl group (such as a benzyl group), an acyl group (such as an acetyl group and a benzoyl group), or a chlorinated product thereof. From the viewpoint of prevention, an alkyl group having 1 to 3 carbon atoms is preferred.
A ¹ represents an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a propylene group, 1,2-, 1,4-, 2,3- and 1,3-butylene groups, and two or more thereof. Among these, an ethylene group is preferable from the viewpoint of antistatic properties.
When A ¹ is composed of two or more alkylene groups, the bond form of the oxyalkylene group may be block, random, or a combination thereof.

  Examples of the polyether-containing hydrophilic polymer (b222) include polyetheresteramide (b2221) having a segment of polyetherdiol (b2211) as a polyether segment-forming component, and polyetheramideimide (b2222) having a segment of (b2211). ), Polyether ester (b2223) having the same segment (b2211), polyether amide (b2224) having the same segment of polyether diamine (b2212), and polyether urethane having the same segment (b2211) or (b2212) (B2225).

The polyether diol (b2211) is obtained by subjecting a compound having two active hydrogen atoms to addition reaction with AO, and examples thereof include those exemplified as the (b11).
Examples of AO include those described above, and preferred AO is EO alone or a combination of EO and another AO (block and / or radam addition). The added mole number of AO is usually 1 to 300, preferably 2 to 250, more preferably 10 to 100 per active hydrogen atom of the compound having 2 active hydrogen atoms.
Of these, from the viewpoint of antistatic properties, an AO adduct of an aliphatic dihydric alcohol and an AO adduct of bisphenol are preferred, and an AO 10-100 mol adduct of ethylene glycol and an AO 10-100 mol of bisphenol A are more preferred. It is an adjunct.

The content of oxyalkylene units having 2 to 4 carbon atoms in (b2211) is preferably 8 to 99.6%, more preferably 10 to 98% from the viewpoint of antistatic properties.
The content of oxyethylene units in the polyoxyalkylene chain is preferably 10 to 100% by weight, more preferably 50 to 100% by weight, and particularly preferably 60 to 100% by weight from the viewpoint of antistatic properties.

  The polyether diamine (b2212) is obtained by changing the hydroxyl group of (b2211) to an amino group by a known method. For example, the end group obtained by cyanoalkylating the hydroxyl group of (b2211) is reduced to form an amino group. The thing which was done is mentioned.

Examples of the modified product (b2213) include the aminocarboxylic acid modified product (terminal amino group), the isocyanate modified product (terminal isocyanate group) and the epoxy modified product (terminal epoxy group) of (b2211) or (b2212). It is done.
The aminocarboxylic acid-modified product can be obtained by reacting (b2211) or (b2212) with aminocarboxylic acid (above) or lactam (above).
The isocyanate-modified product can be obtained by reacting (b2211) or (b2212) with an organic diisocyanate or reacting (b2212) with phosgene.
Examples of organic diisocyanates include aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, and carbon numbers. Examples thereof include 8 to 15 araliphatic diisocyanates, modified products of these diisocyanates, and mixtures of two or more thereof.

  Epoxy modified products include (b2211) or (b2212), diepoxide [epoxy equivalent 85-600, such as diglycidyl ether, diglycidyl ester, alicyclic diepoxide (1,2,5,6-diepoxy crooctane), etc. ] Or a reaction between (b2211) and epihalohydrin (such as epichlorohydrin).

  Mn of (b221) is preferably 150 to 20,000, more preferably 300 to 20,000, particularly preferably 1,000 to 15,000, most preferably from the viewpoint of heat resistance and reactivity with (b21). Is 1,200 to 8,000.

(B2221) is composed of polyamide (Q1) having a carboxyl group at the terminal and (b2211).
(Q1) is a ring-opened polymer of lactam (Q11) (above) having 4 to 20 carbon atoms; a polycondensate of aminocarboxylic acid (Q12) (above) having 2 to 20 carbon atoms; diamine (Q13) (as described above) (C2-C20 aliphatic diamine, C6-C15 alicyclic diamine, C8-C15 araliphatic diamine, and C6-C15 aromatic diamine) Etc.) and a dicarboxylic acid having 2 to 20 carbon atoms (Q14) (as described above) [aliphatic dicarboxylic acid, aromatic dicarboxylic acid, alicyclic dicarboxylic acid and ester-forming derivatives thereof [lower alkyl (having 1 to 6) Esters, anhydrides, etc.], etc.], and mixtures thereof.
(Q1) is preferably a ring-opening polymer of caprolactam, a polycondensate of 12-aminododecanoic acid and a polyamide of adipic acid and hexamethylenediamine, and more preferably a ring-opening weight of caprolactam. It is a coalescence.

(B2222) is composed of polyamideimide (Q2) having at least one imide ring and (b2211).
(Q2) is a polymer comprising (Q11) and a trivalent or tetravalent aromatic polycarboxylic acid (Q21) capable of forming at least one imide ring; and (Q12) and (Q21). A polymer; a polymer comprising (Q15) and (Q21); and a mixture thereof.

The polyether ester (b2223) is composed of polyester (Q3) and (b2211).
(Q3) is a polyester of (Q14) and glycol [as exemplified as the above (b111)]; a lactone having 6 to 12 carbon atoms (described above) or a polyester having a hydroxycarboxylic acid having 2 to 20 carbon atoms; And mixtures thereof.
The polyether amide (b2224) is composed of polyamide (Q1) and polyether diamine (b2212).
The polyether urethane (b2225) is composed of the organic diisocyanate, (b2211) or (b2212), and, if necessary, a chain extender [glycol and diamine (Q31) etc. exemplified in the (b111)].

The content of the polyether (b221) segment in the polyether-containing hydrophilic polymer (b222) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight based on the weight of (b222), from the viewpoint of moldability. %.
The content of oxyethylene groups in (b222) is 30 to 80% by weight, more preferably 40 to 70% by weight, based on the weight of (b222), from the viewpoints of conductivity and moldability.
The lower limit of Mn in (b222) is preferably 800 from the viewpoint of heat resistance, more preferably 1,000, and the upper limit is preferably 50,000 from the viewpoint of reactivity with (b21), more preferably 30,000.

As (b223), a cationic polymer having 2 to 80, preferably 3 to 60, cationic groups (b2232) separated by a nonionic molecular chain (b2231) can be used.
(B2231) is an organic compound having a divalent hydrocarbon group; ether bond, thioether bond, carbonyl bond, ester bond, imino bond, amide bond, imide bond, urethane bond, urea bond, carbonate bond and / or siloxy bond And at least one divalent organic group selected from the group consisting of a group and an organic group having a heterocyclic structure containing a nitrogen atom or an oxygen atom; and combinations of two or more thereof.

Examples of the divalent hydrocarbon group include a linear or branched saturated or unsaturated aliphatic hydrocarbon group (such as an alkylene group and an alkenylene group) having 1 to 18 (preferably 2 to 8) carbon atoms, and 6 to 20 carbon atoms. Aromatic (aliphatic) hydrocarbon groups and alicyclic hydrocarbon groups having 4 to 15 carbon atoms.
As the divalent organic group having an ether bond, thioether bond, carbonyl bond, ester bond, imino bond, amide bond, imide bond, urethane bond, urea bond, carbonate bond and / or siloxy bond, (poly) oxyalkylene group For example, a residue obtained by removing a hydroxyl group from the polyether diol (b2211) or monoether diol; a residue obtained by removing SH from a polythioether corresponding to the above (in which an oxygen atom is replaced by a sulfur atom); Or a residue obtained by removing a carboxyl group or an amino group from polyamide; a residue obtained by removing a hydroxyl group, an amino group or an isocyanate group from polyurethane and / or polyurea; a polycarbonate [derived from the glycol (b111) and phosgene] Hydroxyl group Except residues; residues such as by removing a hydroxyl group from polyorganosiloxanes are exemplified.

Of these (b2231), from the viewpoint of antistatic properties, a divalent hydrocarbon group and a divalent organic group having an ether bond are more preferable, and an alkylene group having 2 to 8 carbon atoms (propylene group, A divalent organic group having a butylene group, a hexamethylene group, etc.), a phenylene group and a (poly) oxyalkylene group, particularly preferably a divalent organic group having a (poly) oxyethylene group, a (poly) oxypropylene group Is a divalent organic group.
Mn of (b2231) is preferably 28 to 10,000, more preferably 300 to 5,000, from the viewpoint of antistatic properties.

Examples of the cationic group (b2232) include a group having a quaternary ammonium salt or a phosphonium salt. The group having a quaternary ammonium salt is preferably a divalent quaternary ammonium salt-containing heterocyclic group from the viewpoint of antistatic properties.
As the divalent quaternary ammonium base-containing heterocyclic group, a divalent tertiary amino group-containing heterocyclic group [divalent imidazole ring group (1,4-imidazolene group and 2-phenyl-1,4-imidazolene group] Etc.) Divalent piperidine ring groups (2,3-, 3,4- and 2,6-piperidylene groups etc.) and divalent aromatic heterocyclic groups (2,3-, 2,4-, 2,5) -, 2,6-, 3,4- and 3,5-pyridylene groups, 2,5-pyrimidinylene groups, 3,6-pyridazinylene groups and 2,5-pyrazinylene groups, etc.)] are quaternizing agents [alkyl (C1-C12) halide (methyl chloride, etc.), dialkyl (C1-C12 of alkyl group) sulfuric acid (dimethylsulfate, etc.), etc.] group of structure quaternized.

Hamett acidity function anions (-H ₀₎ is 12 to 100, conjugate base of the superacid is an anion, and mixtures thereof other than the conjugate base of a superacid.
Examples of the counter anion of (b2232) include a conjugate base of a super strong acid and other anions.
Examples of the super strong acid conjugate base include the super strong acid conjugate bases exemplified as the anion constituting the ionic liquid (A).
Other anions include halogen ions (F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ ), OH ⁻ , PO ₄ ³⁻ , CH ₃ OSO ₃ ⁻ , C ₂ H ₅ OSO ₃ ⁻ , bis (trifluoromethylsulfonyl). ) Imido ion and ClO _4- ^{and the} like.

The terminal structure of (b223) is preferably a group containing a carbonyl group, a hydroxyl group and an amino group from the viewpoint of reactivity with the polyolefin (b21).
Mn of (b223) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly preferably 1,200 to 8,8, from the viewpoints of conductivity and reactivity with polyolefin (b21). 000.

As the anionic polymer (b224), dicarboxylic acid having a sulfone group and glycol (b111) or polyether (b221) are essential constituent units, and preferably 2 to 80 from the viewpoint of antistatic properties in the molecule. More preferable examples include anionic polymers having 3 to 60 sulfone groups.
Examples of the dicarboxylic acid having a sulfone group include a sulfone group-containing aromatic (aliphatic) dicarboxylic acid, a sulfone group-containing aliphatic dicarboxylic acid, and those in which only these sulfone groups are converted into salts.

Examples of the sulfo group-containing aromatic (aliphatic) dicarboxylic acid include 8 to 20 carbon atoms, such as 2-, 5- and 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid, and ester-forming derivatives thereof. [Lower alkyl (1 to 4 carbon atoms) ester (methyl ester, ethyl ester, etc.), acid anhydride, etc.].
Examples of the sulfone group-containing aliphatic dicarboxylic acid include those having 8 to 20 carbon atoms, such as sulfosuccinic acid and ester-forming derivatives thereof.
Examples of salts of only these sulfone groups include alkali metal salts, alkaline earth metal salts, ammonium salts, and mono-, di- and tri-alkyls having a hydroxyalkyl (2 to 4 carbon atoms) group. Examples include amine salts such as alkanolamines, quaternary ammonium salts of these amines, and combinations of two or more of these.
Of these, aromatic (aliphatic) dicarboxylic acids having a sulfone group are preferred from the viewpoint of antistatic properties.

Of glycol (b111) or polyether (b221) constituting (b224), from the viewpoint of antistatic properties, alkanediol having 2 to 10 carbon atoms, ethylene glycol, polyethylene glycol (degree of polymerization 2 to 20), An EO adduct of bisphenol (such as bisphenol A) (addition mole number: 2 to 60) and a mixture of two or more of these.
Mn of (b224) is preferably 500 to 20,000, more preferably 1,000 to 15,000, and particularly preferably 1,200 to 8,8, from the viewpoints of conductivity and reactivity with polyolefin (b21). 000.

In the structure of the block polymer (B2), the average repeating number (Nn) of repeating units of the polyolefin (b21) block and the hydrophilic polymer (b22) block is usually 2 to 50, which is preferable from the viewpoint of antistatic properties. Is 2.3 to 30, more preferably 2.7 to 20, and particularly preferably 3 to 10. Nn is preferably in this range.
Nn can be determined by the method described in International Publication Pamphlet WO00 / 47652 from the Mn and ¹ H-NMR analysis of (B2).

The Mn of the block polymer (B2) is preferably 2,000 to 60,000, more preferably 5,000 to 40,000, and particularly preferably 8,000 to 30,000 from the viewpoint of conductivity.
The proportion of (b22) constituting (B2) is preferably 20 to 90 wt%, more preferably 30 to 70 wt%, from the viewpoint of conductivity based on the total weight of (b21) and (b22). .

As a manufacturing method of (B2), the following are mentioned, for example.
<Production method of (B2)>
Using a known method, for example, a method of performing polymerization (polycondensation) reaction at 200 to 250 ° C. under reduced pressure (1 mmHg or less) by adding (b2111) to (b211), or using a single or twin screw extruder Usually, it can manufacture by the method of superposing | polymerizing with 160-250 degreeC and residence time 0.1-20 minutes.
In the above polymerization reaction, known catalysts such as antimony catalyst (antimony trioxide, etc.); tin catalyst (monobutyltin oxide, etc.); titanium catalyst (tetrabutyl titanate, etc.); zirconium catalyst (tetrabutylzirconate, etc.); organic acid Metal salt catalysts [zirconium organic acid salts (such as zirconyl acetate), zinc acetate, etc.]; and mixtures of two or more of these. Among these, a zirconium catalyst and a zirconium organic acid salt are preferable, and zirconyl acetate is more preferable.
The usage-amount of a catalyst is 0.001 to 5 weight% normally based on the total weight of (b211) and (b2211), Preferably it is 0.01 to 3 weight%.
The antistatic agent of the present invention can be produced by kneading the obtained (B2) and the ionic liquid (A).

  The weight ratio of (A) to (B) is preferably 0.1 / 99.9 to 30/70, more preferably 0.5 / 99.5 to 20/80, particularly preferably 1 from the viewpoint of antistatic properties. / 99 to 5/95.

The antistatic resin composition of the present invention comprises the thermoplastic resin (C) containing the antistatic agent of the present invention.
As (C), polyester resin (C1), polyamide resin (C2), polyacetal resin (C3), polyolefin resin (C4), polystyrene resin (C5), polycarbonate resin (C6), polycarbonate / ABS resin (C7), Examples thereof include modified polyphenylene ether resin (C8), acrylic resin (C9), and other thermoplastic resins (C10). These (C) may be used alone or in combination of two or more.

  Examples of the polyester resin (C1) include aromatic ring-containing polyesters (polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, etc.) and aliphatic polyesters (polybutylene adipate, polyethylene adipate, poly-ε-caprolactone, etc.).

  The intrinsic viscosity [η] of (C1) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and antistatic properties. [Η] is measured with a Ubbelohde 1A viscometer at 25 ° C. for a 0.5 wt% orthochlorophenol solution of the polymer.

  As the polyamide resin (C2), a lactam ring-opening polymer (C21), a dehydration polycondensation product of diamine and dicarboxylic acid (C22), a self-polycondensation product of aminocarboxylic acid (C23), and a poly (condensation) combination thereof. Examples thereof include copolymer nylon having two or more types of monomer units.

Examples of the lactam in (C21) include those exemplified in the above (b1311), and examples of (C21) include nylon 4, nylon 5, nylon 6, nylon 8, nylon 12, and the like.
Examples of the diamine and dicarboxylic acid in (C22) include those exemplified in the above (b1311). Examples of (C22) include nylon 66 obtained by polycondensation of hexanemethylenediamine and adipic acid, and a combination of hexamethylenediamine and sebacic acid. Examples thereof include nylon 610 by condensation.
Examples of the aminocarboxylic acid in (C23) include those exemplified in the above (b1311). Examples of (C23) include nylon 7 by polycondensation of aminoenanthate, nylon 11 by polycondensation of ω-aminoundecanoic acid, Examples thereof include nylon 12 by polycondensation of 12-aminododecanoic acid.

In the production of (C2), a molecular weight modifier may be used, and examples of the molecular weight modifier include the dicarboxylic acid and / or diamine exemplified in (b1311).
Of the dicarboxylic acids as molecular weight modifiers, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and It is sodium 3-sulfoisophthalate.
Of the diamines as molecular weight regulators, hexamethylene diamine and decamethylene diamine are preferable.

  The melt flow rate (hereinafter abbreviated as MFR) of (C2) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR is measured according to JIS K7210 (1994) (in the case of polyamide resin, 230 ° C., load 0.325 kgf).

Examples of the polyacetal resin (C3) include formaldehyde or trioxane homopolymer (polyoxymethylene homopolymer, etc.), a copolymer of formaldehyde or trioxane and a cyclic ether (AO, such as EO, PO, dioxolane, etc.) (polyoxymethylene). / Polyoxyethylene copolymer (block copolymer, weight ratio 90 to 99/1 to 10) and the like.
The MFR of (C3) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR is measured according to JIS K7210 (1994) (in the case of polyacetal resin, 190 ° C., load 2.16 kgf).

  The polyolefin resin (C4) includes one or more (co) polymers of aliphatic hydrocarbon vinyl monomers and one or more vinyl monomers copolymerizable with one or more aliphatic hydrocarbon vinyl monomers (weight ratio is In general, a copolymer with 5/95 to 95/5, preferably 50/50 to 90/10) is included. Examples of the copolymerizable vinyl monomer include the vinyl monomers other than the aliphatic hydrocarbon vinyl monomer.

Specific examples of (C4) include polyethylene, polypropylene, ethylene / propylene copolymer (weight ratio 0.1 / 99.9 to 99.9 / 0.1), ethylene and / or propylene, and 4 to 12 carbon atoms. Copolymers (random or block) with one or more of α-olefins, ethylene / vinyl acetate copolymers (EVA, weight ratio 95 / 5-60 / 40), ethylene / ethyl acrylate copolymers (EEA, Weight ratio 95/5 to 60/40).
Of these, polyethylene, polypropylene, ethylene / propylene copolymer, ethylene and / or propylene and the co-polymerization of one or more α-olefins having 4 to 12 carbon atoms are preferred from the viewpoints of transparency and antistatic properties. It is a coalescence (random or block, weight ratio of ethylene and / or propylene to α-olefin 9: 1 to 1: 9).

The MFR of (C4) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoints of resin physical properties and antistatic properties. The MFR is measured according to JIS K7210 (1976) (for example, in the case of polypropylene, the temperature is 230 ° C. and the load is 2.16 kgf; in the case of polyethylene, the temperature is 190 ° C. and the load is 2.16 kgf).
The crystallinity of (C4) is preferably 0 to 80%, more preferably 0 to 70%, and particularly preferably 0 to 60% from the viewpoint of transparency. The degree of crystallinity is measured by methods such as X-ray diffraction and infrared absorption spectrum ["Polymer solid structure-Polymer Experimental Laboratory 2", Hatsugoro Nanshino, page 42, Kyoritsu Shuppan (1958)].

As the polystyrene resin (C5), vinyl group-containing aromatic hydrocarbons alone or vinyl group-containing aromatic hydrocarbons and at least one selected from the group consisting of (meth) acrylic acid esters, (meth) acrylonitrile and butadiene are used. A copolymer as a structural unit is exemplified.
Examples of the vinyl group-containing aromatic hydrocarbon include styrene and derivatives thereof having 8 to 30 carbon atoms such as o-, m- and p-alkyl (1 to 10 carbon atoms) styrene (vinyl toluene, etc.), α-alkyl ( C1-C10) styrene ((alpha) -methylstyrene etc.) and halogenated styrene (chlorostyrene etc.) are mentioned.
Specific examples of (C5) include polystyrene, polyvinyl toluene, styrene / acrylonitrile copolymer (AS resin) [copolymerization ratio (weight ratio) = 70/30 to 80/20], styrene / methyl methacrylate copolymer. (MS resin) [copolymerization ratio (weight ratio) = 60/40 to 90/10], styrene / butadiene copolymer [copolymerization ratio (weight ratio) = 60/40 to 95/5], acrylonitrile / butadiene / Styrene copolymer (ABS resin) [copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)], methyl methacrylate / butadiene / styrene copolymer (MBS resin) [Copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)].

  The MFR of (C5) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. MFR is measured according to JIS K6871 (1994) (230 ° C. in the case of polystyrene resin, load 1.2 kgf). As the polystyrene resin (C5), one or more (co) polymers of styrenic vinyl monomers and one or more vinyl monomers copolymerizable with one or more of these monomers (weight ratio: usually 5/95 to 95/5, preferably 50/50 to 90/10).

Examples of the polycarbonate resin (C6) include bisphenol [C13-20, such as bisphenol A, bisphenol F, bisphenol S and 4,4′-dihydroxydiphenyl-2,2-butane, dispersibility of (A) in (B). From this viewpoint, preferred are bisphenol A] -based and biphenyl (C12-20, for example, 4,4′-dihydroxybiphenyl) -based polycarbonates, for example, condensates of the above bisphenol or biphenyl with phosgene or carbonic acid diester.
The MFR of (C6) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of mechanical properties and antistatic properties of the molded body. MFR is measured according to JIS K7210 (1994) (in the case of polycarbonate resin, 280 ° C., load 2.16 kgf).

As the polycarbonate / ABS resin (C7), for example, an alloy resin (weight ratio; usually 95/5 to 60/40, preferably 90/10 to 70) of the ABS resin exemplified above and the polycarbonate resin exemplified in (C6). / 30).
The MFR of (C7) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of mechanical properties and antistatic properties of the molded body. MFR is measured according to JIS K7210 (1994) (in the case of polycarbonate / ABS resin, 250 ° C., load 2.16 kgf).

The modified polyphenylene ether resin (C8) includes a polymer alloy of a polyphenylene ether resin and a resin selected from the group consisting of a styrene resin, a polyamide resin, and a polyolefin resin.
Examples of polyphenylene ether resins include poly (2,6-dimethyl-, diethyl- and dipropyl-1,4-phenylene) ether and poly (2-methyl-6-methyl-, 2-methyl-6-propyl- and 2). -Ethyl-6-propyl-1,4-phenylene) ether.

Among (C8), as a polymer alloy of polyphenylene ether resin and styrene resin, for example, Noryl [manufactured by Generalel Electric Co., Ltd.]; As a polymer alloy of polyphenylene ether resin and polyamide resin, for example, Noryl GTYX [General As an example of the polyphenylene ether resin and the polyolefin resin, Noryl PPX [manufactured by General Electric Co., Ltd.] can be given.
The MFR of (C8) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of mechanical properties and antistatic properties of the molded body. The MFR is measured according to JIS K7210 (1994) (in the case of a modified polyphenylene ether resin, 280 ° C., load 5.0 kgf).

As the acrylic resin (C9), one or more (co) polymers of acrylic monomers [alkyl (C1-20) (meth) acrylate, acrylonitrile, etc.] (for example, polymethyl methacrylate, polybutyl acrylate, etc.) And copolymers with one or more vinyl monomers copolymerizable with one or more of these monomers (weight ratio is usually 5/95 to 95/5, preferably 50/50 to 90/10). Examples of the copolymerizable vinyl monomer include the monomers other than the acrylic monomer, such as vinyl esters, dienes, and halogen-containing vinyl monomers.
The MFR of (C9) is preferably from 0.5 to 150, more preferably from 1 to 100, particularly preferably from 2 to 80, from the viewpoints of resin physical properties and antistatic properties. The melt flow rate is measured according to JIS K7210 (1976) (for example, temperature 230 ° C., load 1.2 kgf).

  Other thermoplastic resins (C10) other than the above include thermoplastic polyurethane resins, polyvinyl chloride resins, silicone resins, and fluororesins.

  Of the above (C), from the viewpoint of antistatic properties, (C1), (C2), (C3), (C4), (C5), (C6), (C7) and (C8) are more preferable. Are (C4), (C5), (C6), (C7) and (C8).

  The weight ratio of (B) to (C) in the antistatic resin composition of the present invention is preferably (3-35) / (97-65), more preferably from the viewpoint of antistatic properties and resin physical properties. (5-15) / (95-85).

  The proportion based on the total weight of (A), (B) and (C) in the antistatic resin composition of the present invention is preferably (A) from 0.003 to 10% by weight from the viewpoint of antistatic properties, Preferably they are 0.03 to 3 weight%, (B) is 3 to 35 weight%, More preferably, it is 5 to 15 weight%, (C) is 55 to 97 weight%, More preferably, it is 80 to 95 weight%.

The antistatic resin composition of the present invention may further contain a compatibilizer (D) having a polar group for the purpose of further improving the compatibility between (B) and (C).
The polar group possessed by (D) is selected from the group consisting of carboxylic acid (salt) groups, epoxy groups, amino groups, hydroxyl groups, ester groups, amide groups, sulfonic acid (salt) groups and (poly) oxyalkylene groups. A polar group is mentioned.

Examples of the (poly) oxyalkylene group include segments of Mn 500 to 10,000 having a structural unit of AO having 2 to 8 carbon atoms (as exemplified above). Specific examples of polyoxyalkylene groups include polyoxyethylene groups, polyoxypropylene groups, polyoxybutylene groups, polyoxystyrene groups, polyoxyethylene / polyoxypropylene groups, polyoxyethylene / polyoxybutylene groups and polyoxyethylene groups. Examples include ethylene / polyoxystyrene groups.
The addition form in the case where two or more oxyalkylene groups are included may be either block and / or random.

Specific examples of (D) include carboxylic acid (salt) groups, epoxy groups, amino groups, hydroxyl groups, sulfonic acid (salt) groups and / or polyoxyalkylene groups described in JP-A-3-258850. And a modified low molecular weight polyolefin (D2) described in JP-A No. 5-125111. These may be used alone or in combination of two or more.
The amount of (D) used is usually 20% by weight or less based on the total weight of (B) and (C), preferably 0.1 to 15% by weight, more preferably 1 to 10% by weight from the viewpoint of resin physical properties. It is.

The antistatic resin composition of the present invention may contain another antistatic agent (E) other than the antistatic agent of the present invention for the purpose of further improving the antistatic effect.
(E) includes (1) a surfactant and (2) a conductive substance. (E) may be used alone or in combination of two or more. (E) includes the following.

(1) Surfactant (carboxylate)
Lithium octoate, sodium octoate, potassium octoate, magnesium octoate, calcium octoate, lithium laurate, potassium laurate, sodium laurate, magnesium laurate, calcium laurate, lithium stearate, sodium stearate, potassium stearate Magnesium stearate, calcium stearate, lithium oleate, sodium oleate, potassium oleate, magnesium oleate, calcium oleate, lithium eicosanoate, sodium eicosanoate, magnesium eicosanoate, calcium eicosanoate;

(Sulfate ester salt)
・ Higher alcohol sulfate ester lithium octyl sulfate ester, sodium octyl sulfate ester, potassium octyl sulfate ester, magnesium octyl sulfate ester, calcium octyl sulfate ester, lithium lauryl sulfate ester, sodium lauryl sulfate ester, potassium lauryl sulfate ester, magnesium lauryl sulfate ester , Calcium lauryl sulfate, lithium cetyl sulfate, sodium cetyl sulfate, potassium cetyl sulfate, magnesium cetyl sulfate, calcium cetyl sulfate, lithium stearyl sulfate, sodium stearyl sulfate, potassium stearyl sulfate, magnesium stearyl sulfate , Calcium stearyl sulfate, ray Cosyl sulfate lithium, eicosyl sulfate sodium, eicosyl sulfate potassium, eicosyl sulfate magnesium, eicosyl sulfate calcium,

・ Higher alkyl ether sulfates: octyl ether sulfate lithium, octyl ether sulfate sodium, octyl ether sulfate potassium, octyl ether sulfate magnesium, octyl ether sulfate calcium, lauryl ether sulfate lithium, lauryl ether sulfate sodium, lauryl Potassium ether sulfate, magnesium lauryl ether sulfate, calcium lauryl ether sulfate, lithium dodecyl ether sulfate, sodium dodecyl ether sulfate, potassium dodecyl ether sulfate, magnesium dodecyl ether sulfate, calcium dodecyl ether sulfate, lithium stearyl ether sulfate, stearyl ether sulfate Sodium, stearyl Potassium ether sulfate, magnesium stearyl ether sulfate, calcium stearyl ether sulfate, lithium eicosyl ether sulfate, sodium eicosyl ether sulfate, potassium eicosyl ether sulfate, magnesium eicosyl ether sulfate, calcium eicosyl ether sulfate;

(Sulfonate)
・ Alkylbenzene sulfonate Lithium octylbenzenesulfonate, sodium octylbenzenesulfonate, potassium octylbenzenesulfonate, magnesium octylbenzenesulfonate, potassium octylbenzenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, dodecylbenzenesulfone Potassium acid, magnesium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, lithium laurylbenzenesulfonate, sodium laurylbenzenesulfonate, potassium laurylbenzenesulfonate, magnesium laurylbenzenesulfonate, calcium laurylbenzenesulfonate, lithium octadecylbenzenesulfonate , Octadecylbenzene sulfonate sodium Lithium, potassium octadecylbenzenesulfonate, magnesium octadecylbenzenesulfonate, calcium octadecylbenzenesulfonate, lithium eicosylbenzenesulfonate, sodium eicosylbenzenesulfonate, potassium eicosylbenzenesulfonate, magnesium eicosylbenzenesulfonate, eicosyl Calcium benzenesulfonate,

・ Alkyl sulfonate Lithium octyl sulfonate, sodium octyl sulfonate, potassium octyl sulfonate, magnesium octyl sulfonate, calcium octyl sulfonate, lithium lauryl sulfonate, sodium lauryl sulfonate, potassium lauryl sulfonate, magnesium lauryl sulfonate, Calcium lauryl sulfonate, lithium eicosyl sulfonate, sodium eicosyl sulfonate, potassium eicosyl sulfonate, magnesium eicosyl sulfonate, calcium eicosyl sulfonate,

・ Sulfosuccinic acid diester type lithium sulfosuccinic acid di-2-ethylhexyl ester lithium, sulfosuccinic acid di-2-ethylhexyl ester sodium, sulfosuccinic acid di-2-ethylhexyl ester potassium, sulfosuccinic acid di-2-ethylhexyl ester magnesium, sulfosuccinic acid di-2 -Ethylhexyl ester calcium,

Paraffin sulfonate lithium paraffin sulfonate, sodium paraffin sulfonate, potassium paraffin sulfonate, magnesium paraffin sulfonate, calcium paraffin sulfonate, lithium polystyrene sulfonate, sodium polystyrene sulfonate, potassium polystyrene sulfonate, polystyrene sulfonate, Polystyrene sulfonate calcium;

(Phosphate salt)
・ Higher alcohol phosphate ester salt Octyl phosphate monoester dilithium, octyl phosphate monoester disodium, octyl phosphate monoester dipotassium, octyl phosphate monoester magnesium, octyl phosphate monoester calcium, octyl phosphate diester lithium, Octyl phosphate sodium diester, octyl phosphate potassium, lauryl phosphate monoester dilithium, lauryl phosphate monoester disodium, lauryl phosphate monoester dipotassium, lauryl phosphate monoester magnesium, lauryl phosphate monoester calcium, lauryl Lithium diester lithium, sodium lauryl phosphate diester, potassium lauryl phosphate diester, lithium stearyl phosphate diester, Sodium stearyl phosphate, potassium stearyl phosphate, dilithium eicosyl phosphate monoester, eicosyl phosphate monoester disodium, eicosyl phosphate monoester dipotassium, eicosyl phosphate monoester magnesium, eicosyl phosphate monoester calcium, eicosyl phosphate diester lithium, eicosyl phosphate Sodium diester, potassium eicosyl phosphate diester;

(Imidate)
Lithium bis (trifluoromethylsulfone) imidate, potassium bis (trifluoromethylsulfone) imidate, sodium bis (trifluoromethylsulfone) imidate, magnesium bis (trifluoromethylsulfone) imidate;
(Perchlorate)
Lithium perchlorate, potassium perchlorate, sodium perchlorate, magnesium perchlorate;
(Fluorosulfonate)
Lithium fluorosulfonate, sodium fluorosulfonate, magnesium fluorosulfonate;

(Fluoroalkanesulfonate)
Lithium methanesulfonate, potassium methanesulfonate, sodium methanesulfonate, magnesium methanesulfonate, lithium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, lithium pentafluoroethanesulfonate , Potassium pentafluoroethanesulfonate, sodium pentafluoroethanesulfonate, magnesium pentafluoroethanesulfonate, lithium nonafluorobutanesulfonate, potassium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, magnesium nonafluorobutanesulfonate, Lithium tridecafluorohexanesulfonate, tridecafluorohexanesulfone Potassium, sodium tridecafluoro hexane sulfonic acid, magnesium tridecafluoro hexane sulfonic acid;

(Borate)
Lithium borate, potassium borate, sodium borate, magnesium borate, lithium borofluoride, potassium borofluoride, sodium borofluoride, magnesium borofluoride, lithium tetrafluoroborate, potassium tetrafluoroborate, Sodium tetrafluoroborate, magnesium tetrafluoroborate;

(Inorganic acid salt)
Lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, potassium iodide, sodium thiocyanate, potassium thiocyanate, sodium sulfate, magnesium sulfate, sodium nitrate, potassium nitrate, Lithium carbonate, sodium carbonate, potassium carbonate, sodium borate, potassium borate;
(Organic acid salt)
Examples thereof include lithium acetate, sodium acetate, potassium acetate, calcium acetate, lithium succinate, and sodium succinate.

Of these, from the viewpoint of antistatic properties, imidoates, perchlorates, fluorosulfonates, fluoroalkanesulfonates, borates and fluoroborates are preferred, and bis ( Trifluoromethylsulfone) lithium imidoate, potassium bis (trifluoromethylsulfone) imidate, sodium bis (trifluoromethylsulfone) imidate, lithium perchlorate, potassium perchlorate, sodium perchlorate, lithium fluorosulfonate , Sodium fluorosulfonate, lithium methanesulfonate, potassium methanesulfonate, sodium methanesulfonate, lithium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, pentafluoroethanesulfur Lithium phosphate, potassium pentafluoroethanesulfonate, sodium pentafluoroethanesulfonate, lithium nonafluorobutanesulfonate, potassium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, lithium tridecafluorohexanesulfonate, tridecafluoro Potassium hexanesulfonate, sodium tridecafluorohexanesulfonate, lithium borate, potassium borate, sodium borate, lithium borofluoride, potassium borofluoride, sodium borofluoride, lithium tetrafluoroborate, tetrafluoride Potassium borate and sodium tetrafluoroborate.
(2) Conductive substances Carbon nanotubes, carbon black, white carbon, etc.

The amount of (E) used is preferably 0.01 to 20% by weight, more preferably 1 to 15% by weight, particularly preferably 2 based on the weight of (C) from the viewpoint of antistatic properties and water resistance. -10% by weight.
The method of adding (E) is not particularly limited, but it is preferable to disperse in the polymer (B) or (C) in advance in order to effectively disperse it in the composition. In the case of dispersing in (B), the method of adding and dispersing during the polymerization of (B) is particularly preferred.

For the purpose of further improving the antistatic effect, an antistatic auxiliary agent (F) may be used in combination. Examples of (F) include at least one resin selected from the group consisting of (C1), (C2) and (C3) and / or oligomers thereof.
Among these, preferred are oligomers of (C2) and / or (C2), and more preferred are polyamide polymers selected from nylon 6, nylon 66, nylon 12 and nylon 612, and oligomers thereof, particularly molded articles. From the viewpoint of the mechanical properties, polyamide polymers are preferred.
Mn of (F) is usually 700 to 100,000, preferably 1,000 to 50,000, from the viewpoint of antistatic properties and resin physical properties.
By containing (F) in the thermoplastic resin composition of the present invention, the antistatic property of the molded article of the composition can be further supplementarily improved.
From the viewpoint of antistatic properties and physical properties of the resin, the amount of (F) used is the other (C) when (C1), (C2) and / or (C3) is not used as (C). Preferably it is 1-20 weight% based on the total weight of (F), More preferably, it is 1-15 weight%, (C1), (C2) and / or (C3) are partially used as (C) When these ratios are less than the above, it is preferable to add the ratio as (F) to the above ratio.
In particular, when applied to a resin composition when (C) is a resin mainly composed of polyolefin (C4) or (C4), by combining (F) having a crystallization temperature higher than (C4), Addition of a smaller amount of antistatic agent can significantly improve the antistatic property.

The resin composition of the present invention can contain other resin additives (G) in a range that does not impair the effects of the present invention, depending on various applications.
(G) includes nucleating agent (G1), lubricant (G2), plasticizer (G3), mold release agent (G4), antioxidant (G5), flame retardant (G6), ultraviolet absorber (G7), Examples include at least one selected from the group consisting of an antibacterial agent (G8) and a filler (G9).

As the nucleating agent (G1), 1,3,2,4-di-benzylidene-sorbitol, aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium-bis (4-tert-butylphenyl) phosphate And sodium benzoate.
Examples of the lubricant (E2) include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), higher fatty acid amides (such as stearic acid amide), and the like.

As the plasticizer (G3), aromatic carboxylic acid ester type [phthalic acid ester (dioctyl phthalate, dibutyl phthalate, etc.)], aliphatic monocarboxylic acid ester type [methyl acetyl ricinolate, triethylene glycol dibenzoate, etc.], Aliphatic dicarboxylic acid ester type [di (2-ethylhexyl) adipate, adipic acid-propylene glycol type polyester, etc.], aliphatic tricarboxylic acid ester type [citric acid esters (such as triethyl citrate), etc.], phosphoric acid triester type [Triphenyl phosphate etc.], petroleum resin and the like.
Examples of the release agent (G4) include lower alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters of fatty acids (such as hardened castor oil), glycol esters of fatty acids (such as ethylene glycol monostearate), and liquid paraffin. Etc.

  Examples of the antioxidant (G5) include phenolic [monocyclic phenol [2,6-di-t-butyl-p-cresol, butylated hydroxyanisole and the like], bisphenol [2,2′-methylenebis (4-methyl- 6-t-butylphenol), 4,4′-butylidenebis (3-methyl) -6-t-butylphenol, 4,4′-thiobis (3-methyl) -6-t-butylphenol, etc.], polycyclic phenol [1 , 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5- t-butylphenyl) butane and the like]; sulfur-based [dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, lauryl stearyl 3, '-Thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl β, β'-thiodibutyrate, dilauryl sulfide, etc.]; phosphorous [triphenyl phosphite, triisodecyl phosphite, diphenyl Isodecyl phosphite, phenyl diisodecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4 '-Butylidene-bis (3-methyl-6-t-butylphenylditridecyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), cyclic neopentanetetrayl bis (2,6-di-t -Butyl-4-methylphenyl) phosphite, cyclic Neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, etc.]; amine-based [octylated diphenylamine, Nn-butyl-p-aminophenol, N, N -Diisopropyl-p-phenylenediamine, N, N-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N-diphenyl-p-phenylenediamine, N-phenyl-α-naphthylamine, phenyl- β-naphthylamine, phenothiazine, etc.].

  Examples of the flame retardant (G6) include organic flame retardants (such as nitrogen-containing [urea compounds, guanidine compounds, triazine compounds (melamine, guanamine, etc.) salts (inorganic acid salts, cyanuric acid salts, isocyanuric acid salts, etc.), etc.) ], Sulfur-containing [sulfuric acid ester, organic sulfonic acid, sulfamic acid, organic sulfamic acid and their salts, esters, amides, etc.], silicon-containing (polyorganosiloxane, etc.), phosphorus-containing [phosphoric acid ester (tri Inorganic flame retardants (such as antimony trioxide, magnesium hydroxide, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus, ammonium polyphosphate) and the like.

  Examples of the ultraviolet absorber (G7) include benzotriazole series [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, etc.], Benzophenone [2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, etc.], salicylate [phenyl salicylate, ethylene glycol monosalicylate, etc.], acrylate [2-ethylhexyl- 2-cyano-3,3′1-diphenyl acrylate, etc.].

  Antibacterial agents (G8) include benzoic acid, paraoxybenzoic acid ester, sorbic acid, halogenated phenol (2,4,6-tribromophenol sodium salt, etc.), organic iodine (4-chlorophenyl-3-iodopropargyl formal) ), Nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylene bisthocyanocyanate, etc.), N-haloalkylthioimide (N-tetrachloroethyl-thio-tetrahydrophthalimide, etc.), copper agent (Such as 8-oxyquinoline copper), benzimidazole (such as 2-4-thiazolylbenzimidazole), benzothiazole (such as 2-thiocyanomethylthiobenzothiazole), trihaloallyl (3-bromo-2,3-diiodo-2 -Propenyl ethyl carbonate, etc. , Triazole (such as azaconazole), organic nitrogen sulfur compound (such as Suraoff 39), quaternary ammonium compound (such as trimethoxysilyl-propyloctadecyl ammonium chloride), pyridine compound (2,3,5,6-cytochloro-4- ( Methylsulfonyl) -pyridine) and the like.

Examples of the filler (G9) include fillers usually used for resins, such as metal oxides, metal hydroxides, metal carbonates, metal sulfates, metal silicates, metal nitrides, carbon and other fillers. Can be mentioned.
Examples of the metal oxide include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, and antimony oxide.
Examples of the metal hydroxide include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and basic magnesium carbonate.
Examples of the metal carbonate include calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, and hydrotalcite.

Examples of the metal sulfate salt include calcium sulfate, barium sulfate and gypsum fiber.
Examples of the metal silicate include calcium silicate, talc, kaolin, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, and shirasu balloon.
Examples of the metal nitride include aluminum nitride, boron nitride, and silicon nitride.
Examples of carbon include carbon black, graphite, carbon fiber, charcoal powder, fullerene, and carbon nanotube.

Other fillers include, for example, metal powder (gold, silver, copper, tin, etc.), potassium titanate, lead zirconate titanate, zinc borate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, slag fiber , Aramid fiber, Teflon [registered trademark of DuPont Co., Ltd.] powder, wood powder, pulp and rubber powder.
(G9) may be used alone or in combination of two or more.
Of these, preferred are metal sulfates, and more preferred are metal oxides, metal hydroxides, metal carbonates and metal silicates, particularly preferred are silica, titanium oxide, zinc oxide, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, talc, clay, most preferred are titanium oxide, magnesium hydroxide, calcium carbonate, talc and clay.

  The amount of (G) used is based on the weight of (C), (G1) is usually 20% by weight or less, preferably 1 to 10% by weight; (G2) is usually 20% by weight or less, preferably 1 to 10% by weight. (G3) is usually 20% by weight or less, preferably 1 to 10% by weight; (G4) is usually 10% by weight or less, preferably 0.1 to 5% by weight; (G5) is usually 5% by weight or less, (G6) is usually 20% by weight or less, preferably 1 to 10% by weight; (G7) is usually 5% by weight or less, preferably 0.1 to 3% by weight; (G8) ) Is usually 3% by weight or less, preferably 0.05 to 1% by weight; (G9) is usually 10% by weight or less, preferably 0.05 to 7% by weight.

The resin composition of the present invention is obtained by melt-mixing an antistatic agent containing (A) and (B1) and / or (B2), (C) and, if necessary, (D) to (G). can get.
As a method of melt-mixing, a normal method is used. Generally, a pellet-shaped or powder-shaped polymer is mixed with an appropriate mixer such as a Henschel mixer, and then melt-mixed with an extruder. A pelletizing method can be applied.
The order of addition of each component during kneading is not particularly limited. For example, (I) (A) and (B1) and / or (B2), (C) and optionally (D) to (G) are added. Blending and melt-kneading (150 to 250 ° C.), (II) (B1) and / or (B2), a composition obtained by melt-kneading a small amount of (C), and blending (A) and (D) Thereafter, the method of blending and melt-kneading the remaining (C) and, if necessary, (E) to (G), and charging comprising (III) (A), (B1) and / or (B2) Examples thereof include a method of blending and melt-kneading the inhibitor, a small amount of (C) and (D), and then blending and melt-kneading the remaining (C) and, if necessary, (E) to (G).
Among these, the methods (II) and (III) are methods called a master batch method or a master pellet method.

Examples of the molding method of the resin composition of the present invention include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.) and the like. Depending on the purpose, it can be molded by any method.
The molded product comprising the resin composition of the present invention has excellent mechanical strength and permanent antistatic properties, and also has good paintability and printability, and is molded by coating and / or printing the molded product. An article is obtained.

Examples of the method for coating the molded product include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating.
Examples of the paint include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm.

In addition, as a method of printing after coating the molded product or the molded product, any printing method generally used for plastic printing can be used. For example, gravure printing, flexographic printing , Screen printing, pad printing, dry offset printing, offset printing, and the like.
As the printing ink, those usually used for printing plastics, for example, gravure ink, flexographic ink, screen ink, pad ink, dry offset ink and offset ink can be used.

Furthermore, the antistatic agent of the present invention can be added to a known paint, or can be used as an antistatic paint by adding a solvent (for example, xylene or toluene).
Examples of the known paint include the paints described above.
The proportion in the case of adding an antistatic agent to a known paint is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, particularly preferably from the viewpoint of antistatic properties based on the solid content weight of the known paint. Is from 15 to 40% by weight.
Further, the concentration of the antistatic agent when a solvent is added to the antistatic agent to form a paint is preferably 20 to 60% by weight, more preferably 25 to 55% by weight, and particularly preferably 30 to 30% from the viewpoint of antistatic properties. 50% by weight.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In the examples, “parts” represents parts by weight, and “%” represents% by weight.

<Production of ionic liquid (A)>
Production Example 1
A reaction vessel made of Teflon [registered trademark of DuPont Co., Ltd.] was charged with 128 parts of methanol, and then 20 parts by weight of anhydrous HF was blown and absorbed at a temperature of 20 to 30 ° C. under normal pressure in about 30 minutes. Next, 131.9 parts of BF ₃ 2 methanol complex (BF ₃ content 51.4%) was added dropwise at 30 to 40 ° C. in about 30 minutes, and then a methanol solution of 1-ethyl-3-methylimidazolium methyl carbonate. (Concentration 50%) 372 parts were dropped over about 30 minutes. The reaction was carried out while generating carbon dioxide gas from the reaction. After the generation of carbon dioxide gas was stopped, the solvent and the like were all removed at a temperature of 60 to 70 ° C. under reduced pressure for about 1 hour. A colorless and transparent liquid was obtained in the reaction vessel. As a result of NMR analysis, the obtained liquid was 1-ethyl-3-methylimidazolium tetrafluoroborate (A1). The yield was 99%. Moreover, it was 200 ppm as a result of measuring the water | moisture content of a liquid.

<Manufacture of block polymer (B1)>
Production Example 2
In a pressure resistant reaction vessel, 105 parts of ε-caprolactam, 19.4 parts of terephthalic acid, 0.3 parts of antioxidant [trade name: “Irganox 1010”, manufactured by Ciba Geigy Co., Ltd., the same shall apply hereinafter], and 6 parts of water After charging and replacing with nitrogen, the mixture was heated and stirred at 220 ° C. under pressure and sealing for 4 hours to obtain 115 parts of a polyamide oligomer having carboxyl groups at both ends of Mn 1,000 and acid value 110. Next, 230 parts of an EO adduct of bisphenol A with Mn of 2,000 and 0.5 part of zirconyl acetate were added and polymerized for 5 hours under a reduced pressure of 245 ° C. and 1 mmHg or less to obtain a viscous polymer. This polymer was taken out in a strand form on a belt and pelletized to obtain an antistatic agent (B11) of the present invention.
The reduced viscosity of this product was 2.05 (0.5% m-cresol solution, 25 ° C.), and the water absorption was 70%.

<Manufacture of block polymer (B2)>
Production Example 3
Polypropylene obtained by a thermal degradation method (Mn: 2,500, density 0.89, amount of double bonds per 1,000 carbon atoms, 10.5 double bonds per molecule, and stainless steel autoclave) The average number 1.90) of 85 parts and 15 parts of maleic anhydride were charged, melted at 200 ° C. in a nitrogen gas atmosphere, and reacted at 200 ° C. for 20 hours.
Thereafter, unreacted maleic anhydride was distilled off under reduced pressure to obtain acid-modified polypropylene (b1-1).
The acid value of (b1-1) was 39.8, and Mn was 2,800.

Production Example 4
A stainless steel autoclave was charged with 87 parts of (b1-1) and 13 parts of 12-aminododecanoic acid, melted at 200 ° C., and reacted at 200 ° C. for 2 hours at 10 mmHg or less. 2) was obtained.
The acid value of (b1-2) was 32.1, and Mn was 3,100.

Production Example 5
A stainless steel autoclave was charged with 51 parts of (b1-2), 49 parts of polyethylene glycol (b2-1) of Mn 3,300, 0.3 part of an antioxidant and 0.5 part of zinc acetate, at 230 ° C. and 1 mmHg or less. Polymerization was performed for 4 hours under reduced pressure to obtain a viscous polymer.
Thereafter, the same operation as in Production Example 3 was performed to obtain a block polymer (B21).
Mn of (B21) was 26,000, Nn was 4.1, and the water absorption was 60%.

Production Example 6
80 parts of low molecular weight polypropylene obtained by thermal degradation with Mn of 2,500 and density of 0.89 are melted at 160 ° C., 7 parts of maleic anhydride and 14 parts of 12-aminododecanoic acid are added, and nitrogen is added. The reaction was carried out for 1 hour.
Then, reaction was performed at 200 degreeC for 20 hours, and the acid-modified polypropylene (b1-3) was obtained.
The acid value of (b1-3) was 32.1, and Mn was 2,800.

Production Example 7
Epichlorohydrin and diethylene glycol monomethyl ether were reacted in the presence of sodium hydroxide to synthesize methyl diethylene glycol glycidyl ether. 20 parts of ethylene glycol and 80 parts of methyldiethylene glycol glycidyl ether were reacted at 100 ° C. in the presence of potassium hydroxide to obtain a polyether diol (b2-2). The hydroxyl value of (b2-2) was 57.0, Mn was 2,000, and the volume resistivity value was 1 × 10 ⁷ Ω · cm.

Production Example 8
In a stainless steel autoclave, 64 parts of acid-modified polypropylene (b1-3) obtained in Production Example 6, 36 parts of polyether diol (b2-2) obtained in Production Example 7, 0.3 part of antioxidant and acetic acid Zirconyl (0.5 part) was added, and polymerization was performed at 230 ° C. under reduced pressure of 1 mmHg or less for 4 hours to obtain a viscous polymer.
The polymer was taken out as a strand on a belt and pelletized to obtain a block polymer (B22) in the present invention.
Mn of (B22) was 22,000, and the water absorption was 70%.
Production Example 9
95 parts of a low molecular weight polypropylene having a Mn of 12,000 and a density of 0.89 and 5 parts of maleic anhydride were dissolved at 180 ° C. in a nitrogen atmosphere, and then 1.5 parts of dicumyl peroxide was added thereto. A dissolved 50% solution of xylene was added dropwise over 15 minutes, and after 1 hour of reaction, the solvent was distilled off to obtain acid-modified low molecular weight polypropylene (D1). The acid value of this product was 25.7, and Mn was 15,000.

Examples 1-10, Comparative Examples 1-12
According to the formulations (parts) shown in Tables 1 and 2, A to F were blended for 3 minutes with a Henschel mixer, optionally with a solid ionic surfactant at room temperature, and then at 240 ° C. in a twin screw extruder with a vent. The resin compositions (Examples 1 to 10) of the present invention and comparative resin compositions (Comparative Examples 1 to 12) were obtained by melt-kneading under conditions of 100 rpm and a residence time of 5 minutes.

(Note 1)
C1: ABS resin {Brand name: ABS10, manufactured by Technopolymer Co., Ltd.}
C2: Polypropylene {Product name: Ubepoly Pro J609, manufactured by Ube Industries, Ltd.}
C3: Polycarbonate resin {Brand name: NOVAREX 7025A, manufactured by Mitsubishi Engineering Plastics Co., Ltd.}
C4: Polycarbonate / ABS resin {Brand name: Psycholoy C1100HF, manufactured by Nippon GE Plastics Co., Ltd.}
C5 modified polyphenylene ether resin {Brand name: Noryl GTX, manufactured by Nippon GE Plastics Co., Ltd.}
E1: sodium dodecylbenzenesulfonate E2: sodium trifluoromethanesulfonate F1: 6-nylon {trade name: UBE nylon 6 1013B, manufactured by Ube Industries, Ltd.}

Performance Test The resin composition of the present invention and the comparative resin composition were used with an injection molding machine [PS40E5ASE, manufactured by Nissei Plastic Industry Co., Ltd.], and a predetermined cylinder temperature [C1-containing resin composition was 240 ° C., C2-containing resin composition]. 220 ° C., C3 and C5 resin composition is 280 ° C., C4 containing resin composition is 260 ° C.] and mold temperature [C1 and C2 containing resin composition is 50 ° C., C3 and C5 containing resin composition is 110 C., C4 containing resin composition is molded at 80.degree. C.] to produce a test piece, impact strength, flexural modulus, compatibility, surface resistivity, volume resistivity, surface resistivity after washing, primary Used for evaluation of adhesion and water resistance.
In addition, the surface specific resistance value is determined using a compression molding machine [TABLE TYPE TEST PRESS SA-302, manufactured by Tester Sangyo Co., Ltd.] at a predetermined temperature [220 ° C. for C1-containing resin composition, C2-containing resin composition]. Was 200 ° C., the C3 and C5-containing resin composition was 260 ° C., the C4 containing resin composition was 240 ° C.], a pressure of 20 kg / cm ² , and a time of 30 seconds, a test piece was prepared and used for evaluation.
These test pieces are mechanical strength (impact strength, flexural modulus, compatibility), antistatic properties (surface resistivity, volume resistivity, surface resistivity after washing) and water resistance based on the following test methods The property (surface state) was evaluated. The results are shown in Table 3.

(1) Impact strength: ASTM D256 (1984) (notched, 3.2 mm thick)
Conforms to Method A.
(2) Flexural modulus: compliant with ASTM D790 (1984).
Test piece (10 x 4 x 100 mm), distance between fulcrums 60 mm
(3) Compatibility: Bend the test piece (100 x 100 x 2 mm) and observe its fracture surface
Was evaluated by
Evaluation criteria ○: Uniform and no delamination.
X: Poor compatibility, delamination

(4) Surface resistivity: Conforms to ASTM D257 (1984).
Test piece (injection molding: 100 × 100 × 2 mm, compression molding: diameter 10
Super insulation meter [manufactured by Toa Denpa Co., Ltd.]
DSM-8103] measured at 23 ° C and humidity of 50% RH
Set.
(5) Volume resistivity: Conforms to ASTM D257 (1984).
Using a test piece (100 x 100 x 2 mm), a super insulation meter [Toa Radio (
Co., Ltd. DSM-8103] at 23 ° C. and humidity 50% RH
Measured below.
(6) Surface resistivity after washing with water: Conforms to ASTM D257.
The surface of a test piece (100 × 100 × 2 mm) leaning diagonally
Wash with 100 ml of ion exchange water (23 ° C.) in an amount of 100 ml / min,
Then, it is dried for 3 hours at 80 ° C. in a circulating dryer. Washing and drying operation
For the test piece that was repeated 10 times, as with (4),
Measured in an atmosphere of 23 ° C. and humidity 50% RH.

(7) Primary adhesion: Test piece (100 x 100 x 2 mm) is grounded, and air flow combined electrostatic
Atomizing electrostatic coating machine [Nippon Landsburg Co., Ltd. Turbonia G Minibe
Electrostatic coating was performed using the “Lu type automatic electrostatic coating device” (applied voltage = −90K).
V, discharge rate = 100 cc / min, rotation speed = 24,000 rpm, atomization
Head diameter = 70mm, 2-component urethane paint is made by Nippon Oil & Fats Co., Ltd.
# 5000). The painted plate is baked at 80 ° C for 2 hours.
JIS K5400 (1990)
The adhesion test was performed by the cross-cut tape method.
[In addition, the test created using the resin composition containing resin other than C1
All specimens are corona treatment devices [HFS-20 manufactured by Kasuga Denki Co., Ltd.
2] using a corona discharge treatment (30 V × 10 A = 300 W, 1 second
After the treatment, electrostatic coating was performed. ]

(8) Water resistance: deep in a polypropylene lidded container with a diameter of 15 cm and a height of 20 cm
Tap water up to 15cm and adjust the temperature to 50 ° C.
100x100x2mm) is submerged horizontally about 5cm below the surface of the water.
Hold for 240 hours and visually observe the surface condition to
Appearance is evaluated by JIS K5400.
The adhesion test was performed by the cross-cut tape method of (1990).
Evaluation criteria ○ No change before and after evaluation
× Ward-shaped blisters or rough surface

  The antistatic resin composition of the present invention is produced by various molding methods such as injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding and film molding (casting method, tenter method, inflation method, etc.). Antistatic properties of home appliances / OA equipment, housing equipment for office equipment, various plastic containers such as IC trays, films for packaging materials, sheets for flooring materials, artificial grass, mats, automobile parts, etc. It can be widely used as a composition for various molding materials that require the above.

Claims (9)

From an ionic liquid (A) having an initial conductivity of 1 to 200 ms / cm and a block polymer (B) having a polyether block structure in the molecule of 10 to 90% by weight and a water absorption of 10 to 150%. An antistatic agent characterized by comprising: The antistatic agent according to claim 1, wherein the weight ratio of (A) to (B) is 0.1 / 99.9 to 30/70. The antistatic agent according to claim 1 or 2, wherein (B) is one or more block polymers (B1) selected from the group consisting of polyether esters, polyether amides and polyether ester amides. (B) is a block polymer having a structure in which a block of polyolefin (b21) and a block of hydrophilic polymer (b22) having a volume resistivity value of 1 × 10 ⁴ to 1 × 10 ¹¹ Ω · cm are repeatedly and alternately bonded. The antistatic agent according to any one of claims 1 to 3, which is (B2). An antistatic resin composition comprising the thermoplastic resin (C) containing the antistatic agent according to claim 1. The ratio based on the total weight of (A), (B) and (C) is (A) 0.003 to 10%, (B) 3 to 35%, and (C) 55 to 97%. Composition. Further, a compatibilizing agent having a polar group selected from the group consisting of carboxylic acid (salt) group, epoxy group, amino group, hydroxyl group, ester group, amide group, sulfonic acid (salt) group and (poly) oxyalkylene group ( The composition according to claim 5 or 6, comprising D). A molded article formed by molding the composition according to claim 5. A molded article obtained by coating and / or printing the molded article according to claim 8.