JP4964806B2 - Conductive resin composition and antistatic resin composition - Google Patents

Description

  The present invention relates to a conductive resin composition and an antistatic resin composition. More specifically, the present invention relates to a conductive resin composition that gives a molded article having excellent conductivity without deteriorating water resistance and mechanical properties, and an antistatic resin composition containing the composition in a thermoplastic resin.

Conventionally, as a conductive resin composition, a resin composition in which a conductive filler is dispersed, a π-electron conjugated conductive polymer composition, an ionic salt composed of a nitrogen or phosphorus cation and a fluorine-containing anion is used as a thermoplastic resin. The resin composition (for example, refer patent document 1) contained, the conductive resin composition (for example, refer nonpatent literature 1) which consists of a polymer solid electrolyte containing an ionic liquid, etc. were used.
In addition, as an antistatic resin composition, a polymer type antistatic agent made of a polymer having a polyoxyalkylene chain has been conventionally used to give a molded article having good transparency, workability, bleedout resistance and water resistance A composition containing an agent is known (for example, see Patent Document 2).

JP 2006-193704 A “Chemistry and Industry”, Volume 54 (2001) No. 3, 281-285, published by the Japan Chemical Society JP 2002-321314 A

However, the conductive resin made of the resin composition in which the conductive filler is dispersed has a black or metallic color caused by the conductive filler, and the transparency is remarkably inhibited. It is afraid of applications where there is a fear that cleanliness is required.
A polymer composed of a π-electron conjugated conductive polymer composition is generally insoluble and infusible and therefore has poor processability, and further exhibits a black color due to the π-electron conjugated system and thus has low transparency.
In the case of a resin composition containing an ionic salt or ionic liquid composed of a nitrogen onium cation or a phosphorus onium cation and a fluorine-containing organic anion, the ionic salt or ionic liquid has a low molecular weight and an affinity for the resin. Due to the poor properties, ionic salts and ionic liquids easily bleed out on the surface of the molded product, and there was a problem that the conductivity was lowered or the water resistance was deteriorated by washing with water or wiping with cloth.

Further, since the antistatic resin composition has insufficient conductivity of the polymer antistatic agent, there is a problem that sufficient antistatic properties are not exhibited when it is kneaded into a thermoplastic resin. there were.
An object of the present invention is to provide a conductive resin composition that provides a molded article having excellent conductivity and water resistance, and an antistatic resin composition that provides a molded article having excellent antistatic properties and water resistance.

That is, the present invention provides a polymer type ionic liquid (A) comprising at least one onium cation group (a) and a polymer (b) having a counter anion group as a polyether ester, a polyether amide, a polyether ester. At least selected from the group consisting of amides and block polymers having a structure in which a polyolefin block and a hydrophilic polymer block having a volume resistivity of 1 × 10 ⁴ to 1 × 10 ¹¹ Ω · cm are alternately and repeatedly bonded. Conductive resin composition (X) characterized by being contained in one type of block polymer (B); antistatic resin composition comprising the conductive resin composition contained in thermoplastic resin (D) A molded article formed by molding the conductive resin composition or the antistatic resin composition; and coating and / or printing on the molded article Is a molded article.

The conductive resin composition or the antistatic resin composition of the present invention has the following effects.
(1) A molded product obtained by molding a conductive resin composition is excellent in conductivity and water resistance.
(2) A molded product formed by molding an antistatic resin composition is excellent in antistatic properties and water resistance.

  The polymer type ionic liquid (A) in the present invention comprises at least one onium cation group (a) and a polymer (b) having a counter anion group. Here and below, the ionic liquid means a molten salt having a melting point of 100 ° C. or lower or a glass transition point (hereinafter abbreviated as Tg) of room temperature or lower.

[Onium cation group (a)]
The onium cation group (a) includes an amidinium cation (a1) and a guanidinium cation (a2).
Examples of (a1) include the following.
[1] Imidazolinium cation 5 to 15 carbon atoms (hereinafter abbreviated as C), such as 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-triethylimidazole Linium, 1,2,3,4-tetraethylimidazolinium, 1,2,3-trimethylimidazolinium, 1,3-dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazole Linium, 1,2,3-triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium, 3-cyanomethyl-1,2-dimethylimidazole Zolinium, 2-cyanomethyl-1,3-dimethylimidazolinium, 4-acetyl-1,2,3-trimethylimidazolinium, 3-acetylmethyl-1,2-dimethylimidazolinium, 4-methylcarbooxymethyl -1,2,3-trimethylimidazolinium, 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, - dimethyl imidazolinium;

[2] Imidazolium cation C5-15, such as 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, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 1-benzyl-2,3-dimethyl-imidazolium, 4-cyano-1, 2,3-trimethylimidazolium, 3-cyanomethyl-1,2-dimethylimidazolium, 2-cyanomethyl-1,3 -Dimethyl-imidazolium, 4-acetyl-1,2,3-trimethylimidazolium, 3-acetylmethyl-1,2-dimethylimidazolium, 4-methylcarbooxymethyl-1,2,3-trimethylimidazolium, 3-methylcarbooxymethyl-1,2-dimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 3-methoxymethyl-1,2-dimethylimidazolium, 4-formyl-1,2, 3-trimethylimidazolium, 3-formylmethyl-1,2-dimethylimidazolium, 3-hydroxyethyl-1,2-dimethylimidazolium, 4-hydroxymethyl-1,2,3-trimethylimidazolium, 2-hydroxy Ethyl-1,3-dimethylimidazolium;

[3] Tetrahydropyrimidinium cation C6-15, such as 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyri Midinium, 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-tetrahydropyrimidinium, 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- , 2-dimethyl-1,4,5,6-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;

[4] Dihydropyrimidinium cation C6-20, such as 1,3-dimethyl-1,4- or -1,6-dihydropyrimidinium [these are 1,3-dimethyl-1,4 (6)- This is expressed as dihydropyrimidinium, and the same notation 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) - hydro pyrimidinium.

Examples of (a2) include the following.
[1] Guanidinium cation having imidazolinium skeleton C8-15, such as 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-methylimidazolinium, 2-diethylamino-1,3-diethylimidazole Linium, 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-Dimethylimidazolinium, 2-dimethylamino-3-acetylmethyl-1-methylimidazolinium, 2-dimethylamino-4-methylcarbooxymethyl 1,3-dimethylimidazolinium, 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;

[2] Guanidinium cation having imidazolium skeleton C8-15, such as 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-3-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;

[3] Guanidinium cation having tetrahydropyrimidinium skeleton C10-20, such as 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-dimethyl Amino-1-methyl-3,4-diethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1-methyl-3,4-diethyl-1,4,5,6-tetrahydropyrimidi Ni, 2-diethylamino-1,3,4-tetraethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-1,3-dimethyl Til-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-imide [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] pyrimidi , 2-dimethylamino-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-tetrahydropyrimidinium, 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;

[4] Guanidinium cation having dihydropyrimidinium skeleton C10-20, such as 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-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl-1,4 (6) -dihydropyrimidinium, -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-dimethyl Ruamino-3-cyanomethyl-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- -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 (6) -dihydro Pyrimidinium.

  Among these, (a1) is preferable from the viewpoint of conductivity, imidazolium cation is more preferable, and 1-ethyl-3-methylimidazolium cation is particularly preferable.

[Polymer having counter anion group (b)]
The polymer (b) in the present invention is a polymer selected from the group consisting of an addition polymer (b1), a polycondensation product (b2) and a polyaddition product (b3), and the counter anion group of the onium cation group (a). It is a polymer having
Examples of the anionic group constituting (b) include organic acid groups such as carboxylic acid groups, sulfuric acid ester groups, sulfonic acid groups, and phosphoric acid ester groups.

The addition polymer (b1) includes a (co) polymer of the ethylenically unsaturated group-containing monomer (b01) having at least one of the anionic groups.
The polycondensate (b2) includes a polycondensate (polyester, polyamide, polyesteramide, polyetherester, polyester comprising a polycarboxylic acid (b021) and a polyhydric alcohol (b022) and / or a polyamine (b023). Ether ester amide etc.) having at least one of the above anionic groups.
The polyadduct (b3) includes a polyurethane and / or polyurea composed of an active hydrogen atom-containing polyvalent compound (b031) and a polyisocyanate (b032) and having at least one of the above anionic groups.

  The addition polymerized product (b1) has the above-described anionic group-containing ethylenically unsaturated group-containing monomer (b011) as an essential component, and a copolymerizable ethylenically unsaturated group-containing monomer (b012) that does not contain the anionic group. Obtained by copolymerization.

Examples of (b011) include the following, and combinations thereof.
(1) Having a carboxylic acid group C3-30, such as (meth) acrylic acid, (iso) crotonic acid, cinnamic acid, vinylbenzoic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, mesaconic acid, and these And esterified products of polycarboxylic acids such as isophthalic acid, terephthalic acid, phthalic acid (anhydride) and trimellitic acid (anhydride) with a hydroxyl group-containing (meth) acrylate;
(2) Those having a sulfate ester group C5-20, for example, esterified product of hydroxyl group-containing (meth) acrylate and sulfuric acid (sulfate ester of 2-hydroxyethyl acrylate, sulfate ester of 3-hydroxypropyl acrylate, etc.);
(3) Those having a sulfonic acid group C6-30, such as (meth) acryloylmethylbenzenesulfonic acid, (meth) acryloyloxybenzenesulfonic acid, (meth) acryloyldecylbenzenesulfonic acid, styrenesulfonic acid, 2-acrylamide-2 -Methylpropanesulfonic acid and the like;
(4) Those having a phosphate ester group C6-30, such as 2- (meth) acryloyloxyethyl acid phosphate, (meth) acryloyloxypropyl acid phosphate, (meth) acryloyloxy-2- and 3-hydroxypropyl acid phosphate (Meth) acryloyloxy-3-chloro-2-hydroxypropyl acid phosphate, allyl alcohol acid phosphate, and the like.
Of these (b011), (1) and (3) are preferable from the viewpoint of conductivity.

Examples of the ethylenically unsaturated group-containing monomer (b012) include the following.
(1) Unsaturated hydrocarbon As the aliphatic hydrocarbon, C2-30, for example, olefin [ethylene, propylene, C4-30 α-olefin (1-butene, 4-methyl-1-pentene, 1-pentene, 1 -Octene, 1-decene, 1-dodecene, etc.)], C4-30 dienes [alkadienes (butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, etc.), etc.]; Examples of the aromatic ring-containing hydrocarbon include C8-30, such as styrene and derivatives thereof [o-, m- and p-alkyl (C1-10) styrene (α-methylstyrene, benzylstyrene, vinyltoluene, divinylbenzene, vinylnaphthalene]. ), Α-alkyl (C1-10) styrene (α-methylstyrene, etc.) and halogenated styrene (chloro Styrene, etc.), etc.]; the alicyclic ring-containing hydrocarbon, C4～30, for example (di) cycloalkenes, for example cyclohexene, (di) cyclopentadiene, pinene, limonene, indene, vinylcyclohexene and ethylidenebicycloheptene;

(2) (meth) acryloyl group-containing monomer C3-30, for example, (meth) acrylic acid derivatives [alkyl (C1-20) (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) Acrylate, etc.], mono- and dialkyl (C1-4) aminoalkyl (C2-4) (meth) acrylate [methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.], (meth) acrylamide, etc.] ;

(3) Carboxylic acid ester of unsaturated alcohol Carboxylic acid (C2-4, such as acetic acid, propionic acid) ester (vinyl acetate, etc.) of unsaturated alcohol [C2-6, such as vinyl alcohol, (meth) allyl alcohol];
(4) alkyl ether of unsaturated alcohol alkyl (C1-20) ether of the above unsaturated alcohol (methyl vinyl ether, ethyl vinyl ether, etc.);
(5) halogen-containing vinyl monomers C2-12, such as vinyl chloride, vinylidene chloride and chloroprene;
(6) Other vinyl monomers (meth) acrylonitrile and the like.
Among these (b012), preferred from the viewpoint of conductivity are a (meth) acryloyl group-containing monomer, an alkyl ether of an unsaturated alcohol, and (meth) acrylonitrile.

  The copolymerization ratio (weight ratio) of (b011) and (b012) is preferably 50/50 to 100/0, more preferably 70/30 to 100/0, from the viewpoint of conductivity and water resistance.

  The polycondensate (b2) includes a polycondensate (polyester, polyamide, polyesteramide, polyether formed from a polyvalent carboxylic acid (b021) and a polyhydric alcohol (b022) and / or a polyvalent amine (b023). Ester, polyether ester amide, etc.) having at least one anionic group.

The polyvalent carboxylic acid (b021) constituting the polycondensate (b2) includes the following divalent to tetravalent or higher polyvalent carboxylic acids, anhydrides of these acids, alkyl (C1-3) esters, Examples include sulfo group-containing polyvalent carboxylic acids, sulfate group-containing polyvalent carboxylic acids, sulfamic acid group-containing polyvalent carboxylic acids, phosphoric acid group-containing polyvalent carboxylic acids, and phosphonic acid group-containing polyvalent carboxylic acids.
Divalent carboxylic acids include aliphatic dicarboxylic acids (C2-20, such as oxalic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid. , Dodecenyl succinic acid, octyl succinic acid); aromatic ring-containing dicarboxylic acid (C8-15, such as phthalic acid, isophthalic acid, terephthalic acid); alicyclic dicarboxylic acid (C7-10, such as cyclohexanedicarboxylic acid); sulfo group-containing dicarboxylic acid Acid [C8-15, such as sulfoterephthalic acid, 5-sulfoisophthalic acid, dimethyl 5-sulfoisophthalate, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7dicarboxylic acid, 5 (4-sulfophenoxy) isophthalic acid] ;

Examples of the trivalent carboxylic acid include C6-20, such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid;
Tetravalent or higher carboxylic acids include C9-20, such as tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, and these acids. Anhydride, alkyl (C1-3) ester.

  Of these (b021), from the viewpoint of conductivity, preferred are sulfo group-containing dicarboxylic acids, and more preferred are sulfoterephthalic acid, 5-sulfoisophthalic acid, dimethyl 5-sulfoisophthalate, and 4-sulfophthalic acid. .

  As the polyhydric alcohol (b022), a low molecular polyol having two or more OH groups, an OH equivalent (molecular weight per OH based on OH value) of less than 250, a high molecular polyol having an OH equivalent of 250 or more, sulfo Examples include group-containing polyols and mixtures thereof.

As the low molecular weight polyhydric alcohol, dihydric alcohol (C2-20 or more), for example, aliphatic dihydric alcohol [C2-12, such as (di) alkylene glycol [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,3-, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentanediol (hereinafter EG, DEG, PG, DPG, BD, respectively) , HD, NPG and MPD), dodecanediol etc.]], alicyclic dihydric alcohol [C5-10, such as 1,3-cyclopentanediol, 1,3- and 1,4-cyclohexanediol, 1 , 4-cyclohexanedimethanol, etc.], aromatic aliphatic dihydric alcohols C8～20, for example, xylylene glycol, bis (hydroxyethyl) benzene];
Trihydric to octahydric or higher polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol and dipentaerythritol (hereinafter referred to as GR, TMP respectively) , PE, SO and DPE), 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins, etc.], sugars and derivatives thereof [sucrose, glucose, fructose Mannose, lactose, glucoside (methyl glucoside, etc.) etc.], etc .;
In addition, among the polyether polyol, polytetramethylene glycol (hereinafter abbreviated as PTMG), polyester polyol, polycaprolactone, polycarbonate, polybutadiene, hydrogenated polybutadiene, polyisoprene polyol and hydrogenated polyisoprene polyol described later, the OH equivalent is less than 250. Can be mentioned.

  The polymer polyol includes a polyether polyol {an alkylene oxide of the above dihydric alcohol or a trihydric to octahydric or higher polyhydric alcohol (hereinafter abbreviated as AO) [C2-4, such as ethylene oxide (hereinafter abbreviated as EO). ), Propylene oxide (hereinafter abbreviated as PO), 1,2- and 2,3-butylene oxide, tetrahydrofuran (hereinafter abbreviated as THF). same as below. ] Adduct [Number average molecular weight [hereinafter abbreviated as Mn. The measurement is performed by gel permeation chromatography (GPC). 500-20,000], for example, polyethylene glycol (hereinafter abbreviated as PEG) (Mn 500-10,000), for example, polypropylene glycol (hereinafter abbreviated as PPG) (Mn 500-10,000), polytetramethylene glycol (hereinafter abbreviated as PTMG). ) (Mn 500 to 10,000) etc.], polyester polyol (Mn 500 to 20,000), Mn 500 to 10,000, such as polycaprolactone, polycarbonate, polybutadiene, hydrogenated polybutadiene, polyisoprene polyol and hydrogenated polyisoprene polyol. included.

  Examples of the sulfo group-containing polyol include AO2 to 10 mol adducts of the sulfo group-containing dicarboxylic acid [5-sulfo-ortho-, iso- and EO2 mol adducts of terephthalic acid and the like].

  Examples of the polyvalent amine (b023) include C2-20 diamines such as aliphatic [ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, eicosanediamine, etc.], aromatic (aliphatic) [phenylene Diamine, naphthylenediamine, xylylenediamine, etc.] and alicyclic [cyclohexanediamine, etc.].

In the polyesterification reaction, the equivalent ratio of COOH group to OH group (COOH / OH) is preferably 1.2 / 1 to 2/1 from the viewpoint of the conductivity of the polymer type ionic liquid described later and the transparency of the molded product. More preferably, it is 1.5 / 1 to 2/1.
In the polyamidation reaction, the equivalent ratio of COOH groups to NH ₂ groups (COOH / NH ₂ ) is preferably 1.2 / 1 to 2/1, more preferably 1.5 / 1 to 2 from the same viewpoint as described above. / 1.
In the polyester amidation reaction, the equivalent ratio of COOH group, OH group and NH ₂ group (COOH / OH / NH ₂ ) is preferably 1.2 / 0.5 / 0.5 to 2 / from the same viewpoint as above. 0.5 / 0.5, more preferably 1.5 / 0.5 / 0.5 to 2.0 / 0.5 / 0.5.
In the polyether esterification reaction, the equivalent ratio of COOH group to OH group (COOH / OH) is preferably 1.1 / 1 to 2/1, more preferably 1.5 / 1 to 1, from the same viewpoint as described above. .9 / 1.
In the polyether ester amidation reaction, the equivalent ratio of COOH group, OH group and NH ₂ group (COOH / OH / NH ₂ ) is preferably 1.2 / 0.5 / 0.5 to 0.5 from the same viewpoint as above. It is 2 / 0.5 / 0.5, more preferably 1.5 / 0.5 / 0.5 to 2 / 0.5 / 0.5.

The polyadduct (b3) includes a polyhydric carboxylic acid (polyurethane and / or polyurea formed by urethanization and / or urea formation reaction of the active hydrogen atom-containing polyvalent compound (b031) and the polyisocyanate (b032). Formed by urethanization and / or urea formation reaction of polyisocyanate (b032) with an active hydrogen atom-containing polyvalent compound having the sulfo group-containing polyol as an essential component of (b031) and a reaction product of b021) Polyurethane and / or polyurea.
Among these, from the viewpoint of electrical conductivity, preferred are polyurethanes formed by urethanization and / or ureaization reaction of polyisocyanate (b032) with an active hydrogen atom-containing polyvalent compound having a sulfo group-containing polyol as an essential component, and / Or polyurea.
As the (b031), the polyhydric alcohol (b022) and / or the polyvalent amine (b023) can be used.

In the urethanization and / or urea formation reaction, the equivalent ratio [NCO / (OH + NR ⁰ H)] of the NCO group, the OH group, and / or the NR ⁰ H (R ⁰ is H or C 1-3 alkyl group) group is: Although not particularly limited, it is preferably 0.3 / 1 to 0.6 / 1, more preferably 0.4 / 1 to 0.5 / 1, from the viewpoint of the toughness of the molded product described later and the temporal stability of (b3). It is.
The carboxylic acid-terminated polycondensate (b2) may be added to the polyaddition product by esterification or amidation.

Examples of the polyisocyanate (b032) (hereinafter sometimes abbreviated as PI) include the following, and mixtures of two or more thereof.
(1) C (excluding C in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic PI
Diisocyanates (hereinafter abbreviated as DI), such as 1,3- and / or 1,4-phenylene DI, 2,4- and / or 2,6-tolylene DI (TDI), 4, 4′- and / or 2,4′-diphenylmethane DI (MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene DI, and m- and p-isocyanatophenylsulfonyl isocyanate; and trifunctional or higher functional PI (such as triisocyanate), such as crude TDI, crude MDI (polymethylene polyphenyl polyisocyanate) and 4,4 ′, 4 ″ -triphenyl meta Triisocyanate

(2) C2-18 aliphatic PI
DI, such as ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, nonamethylene DI, decamethylene DI, dodecamethylene DI, 2,2,4- and / or 2,4,4- Trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and Trimethylhexamethylene diisocyanate (TMDI); and trifunctional or higher functional PI (such as triisocyanate), such as 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexa Methyleneto Reisocyanates and lysine ester triisocyanates (phosgenates of reaction products of lysine and alkanolamines, such as 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl-2 , 6-Diisocyanatohexanoate)

(3) C4-45 alicyclic PI
DI, for example isophorone DI (IPDI), 2,4- and / or 2,6-methylcyclohexane DI (hydrogenated TDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexyl Silene DI, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- and / or 2,6-norbornane DI, dimer acid DI (DDI); PI (triisocyanate etc.), for example, bicycloheptane triisocyanate (4) C8-15 araliphatic PI
m- and / or p-xylylene DI (XDI), diethylbenzene DI and α, α, α ′, α′-tetramethylxylylene DI (TMXDI)
(5) Nurateated products of the above (1) to (4) Among these (b032), preferred from the viewpoint of light resistance are the aliphatic and alicyclic groups of (2), (3), and (5) It is a nurateated product of PI.

In the reaction of the polyurethane and / or polyurea with the polyvalent carboxylic acid (b021), the equivalent ratio (COOH / (OH + NR ⁰ H)) of the carboxyl group, the OH group, and / or the NR ⁰ H group is not particularly limited. From the viewpoint of the electric conductivity of the polymer type ionic liquid and the toughness of the molded product, it is preferably 1.2 / 1 to 2/1, more preferably 1.5 / 1 to 2/1.

[Block polymer (B)]
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. One or more selected block polymers (B1), and a structure in which a polyolefin block and a hydrophilic polymer block having a volume resistivity of 1 × 10 ⁴ to 1 × 10 ¹¹ Ω · cm are alternately and alternately bonded. The block polymer (B2) having

[Block polymer (B1)]
Examples of the block polymer (B1) include polyether esters, polyether amides and polyether ester amides described in JP-A No. 14-146212.
Specific examples of the bonding structure (B1) and the production method 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.
(B11) includes an alkylene oxide (hereinafter abbreviated as AO) adduct of a compound 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 C2-20 aliphatic glycol, C5-12 alicyclic glycol, C8-30 araliphatic glycol, and C5-10 alkanolamine.
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 divalent phenol (b112) include C6-30 phenols 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 their alkyl (C1-10) or halogen-substituted products.

As amine (b113), C1-20 aliphatic primary monoamine, C4-18 aliphatic secondary diamine, 4-13 heterocyclic primary monoamine and secondary diamine, 6-14 alicyclic 2 And secondary alkanolamines having 8 to 14 aromatic (aliphatic) secondary diamines and C3 to 22 secondary alkanolamines.
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 their alkyl (C1-10) or halogen-substituted products.

  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 alkyl (C1-10) 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 C2-20 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, icosandiic acid and the like.

  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.
Among 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.

  AO includes C2-4 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 of these], other AO or substituted AO, for example, C5-12 α-olefin, styrene oxide and epihalohydrin (such as epichlorohydrin) (hereinafter referred to as AO). Can be used together in a small proportion (for example, 30% or less based on the weight of the total AO).

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

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 (potassium hydroxide, etc.), amine catalyst (triethylamine, etc.), acidic catalyst (hydrochloric acid, etc.) )] (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 from 300 to 6,000, more preferably from 500 to 4,000, from the viewpoint of reactivity during production of the block polymer formed from (b11) and the condensation polymer (b13). Particularly preferred is 700 to 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 for 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) Although it will not specifically limit if it can superpose | polymerize, From a viewpoint of electroconductivity and polymeric property, the polyamide (imide) (b131) which has a carboxyl group in both ends, and polyester (b132) which has a carboxyl group in both ends are preferable. At least one dicarboxylic acid selected from the group consisting of: (b131).
Mn of (b131) and (b132) having a carboxyl group at both ends is preferably 300 to 7,000, more preferably from the viewpoints of conductivity, reactivity during polymer production, and ease of handling after polymer production. Is 500 to 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 C2-20 dicarboxylic acids such as those exemplified as the above (b114).

Amide-forming monomers include lactams, aminocarboxylic acids and diamine / dicarboxylic acids.
Examples of the lactam include C4-20 lactams such as γ-butyrolactam, γ-valerolactam, ε-caprolactam, γ-pimelolactam, γ-caprolactam, γ-decanolactam, enantolactam, laurolactam, undecanolactam, eicosano. Examples include lactam and 5-phenyl-2-piperidone.

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

Examples of the diamine include C2-20 diamines such as aliphatic [ethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, decamethylene diamine, eicosane diamine, etc.], aromatic (aliphatic) [phenylene diamine, naphthylene diamine. And xylylenediamine etc.] and alicyclic [cyclohexylenediamine etc.] and the like.
Examples of the dicarboxylic acid include C2-20 dicarboxylic acids such as those exemplified as the above (b114).

These amide-forming monomers may be used alone or in combination of two or more.
Of these, caprolactam, enantolactam, laurolactam, ω-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, adipic acid / hexamethylenediamine, and 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.

  As trivalent aromatic polycarboxylic acid, C9-20 polycarboxylic acid, for example, as trivalent polycarboxylic acid, 1,2,4-trimellitic acid, 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 tetravalent aromatic polycarboxylic acids include C10-20 polycarboxylic acids such as pyromellitic acid, diphenyl-2,2 ′, 3,3′-tetracarboxylic acid, benzophenone-2,2 ′, 3,3. Examples include '-tetracarboxylic acid, diphenylsulfone-2,2', 3,3'-tetracarboxylic acid, and diphenyl ether-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 regulator 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 C1-20 dicarboxylic acids 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 C1-20 dicarboxylic acids such as carbonic acid and those exemplified as the above (b114).
Examples of the dicarboxylic acid ester (C1-10 of the alcohol component constituting the ester) include carbonic acid or esters of the above dicarboxylic acid (C2-20), such as methyl ester, ethyl ester, butyl ester, and phenyl ester.
These may be used alone or in combination of two or more.
Of these, from the viewpoint of heat resistance, adipic acid, sebacic acid, icosanoic acid, ortho-, iso- and terephthalic acid, 1,4-cyclohexanedicarboxylic acid, sodium 3-sulfoisophthalate, dimethyl carbonate, carbonic acid are preferred. 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 C2-30 diols such as those exemplified as the glycol (b111) and diol (b11).
Examples of the dihydric phenol include C6-40 dihydric phenol, for example, those exemplified as the dihydric phenol (b112).
These may be used alone or in combination of two or more.
Among 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.

  Lactones include C4-20 lactones such as γ-butyrolactone, γ-valerolactone, ε-caprolactone, γ-pimerolactone, γ-caprolactone, γ-decanolactone, enanthlactone, laurolactone, undecanolactone and eico. And sanolactone.

  Examples of hydroxycarboxylic acids include C2-20 hydroxycarboxylic acids such as hydroxyacetic acid, lactic acid, ω-hydroxycaproic acid, ω-hydroxyenanthic acid, ω-hydroxycaprylic acid, ω-hydroxypergonic acid, ω-hydroxycaprin. Examples include acids, 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 thereto, and a polymerization reaction is carried out at a high temperature (220 to 245 ° C.) under reduced pressure (1 mmHg or less) to produce a block polymer (B1 )
The conductive resin composition of the present invention can be produced by melt-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 (phosphoric acid, etc.), metals [alkali metals (sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.), transition metals (nickel, iron, cobalt, etc.), IIB metals ( Organic acids (such as acetic acid), carbonates, sulfates, phosphates, oxides, chlorides, hydroxides and alkoxides of zinc, etc.), 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% based on the weight of the block polymer (B1), and preferably 0.1 to 1.0% from the viewpoint 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 90/110 from the viewpoint of conductivity and heat resistance. ~ 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 to 4, particularly preferably 1 to 3.

(B11) and / or (b) within the range of 30% (preferably 20%) based on the weight of (b11) and / or (b12) for the purpose of improving water resistance when producing (B1). A part of b12) may be used in place of the polyalkylenediol.
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 C4-20 α-olefins (1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, etc.) and C4-20. And diene (butadiene and the like).
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.

[Block polymer (B2)]
The block polymer (B2) has a structure in which a block of a polyolefin (b21) and a block of a hydrophilic polymer (b22) having a volume resistivity of 1 × 10 ⁴ to 1 × 10 ¹¹ Ω · cm are alternately and repeatedly bonded. (B2) includes the block polymer described in International Publication Pamphlet WO00 / 47652.
Specific examples of the polyolefin (b21), the hydrophilic polymer (b22), and their binding structures and production methods are as described in the pamphlet, and (B2) will be described below.

  The block polymer (B2) is at least one selected from the group consisting of an ester bond, an amide bond, an ether bond, a urethane bond and an imide bond, in which the block of the polyolefin (b21) and the block of the hydrophilic polymer (b22) It has a structure in which the bonds are alternately and alternately connected through bonds.

(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).
Of 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 polymerizing one or a mixture of two or more C2-30 olefins (preferably a C2-12 olefin, more preferably ethylene and / or propylene) and a high molecular weight [Mn30, 000 or more, preferably 50,000 to 200,000] polyolefins [preferably polyolefins obtained by polymerization of C2-30, more preferably C2-12 olefins, particularly preferably polyethylene and / or polypropylene] Examples thereof include low molecular weight polyolefins obtained by the synthesis method.
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 conductivity.
The amount of double bonds per 1,000 C in (b210) is preferably 1 to 40, more preferably 1 to 30, and particularly preferably 4 to 20 from the viewpoint of antistatic properties.
According to the above thermal degradation method, a low molecular weight polyolefin having an average terminal double bond amount per molecule of 1.5 to 2 can be easily obtained with Mn in the range of 800 to 6,000 [Katsuhide Murata, Makino Tadahiko, Journal of the Chemical Society of Japan, page 192 (1975)].
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 (content is 50% by weight or more, preferably 75 to 100% by weight) is a polyolefin whose one end can be modified. .
Examples of (b215) include those in which a hydroxyl group is introduced at one end of (b2100).
Examples of (b216) include those obtained by introducing an amino group 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 C in (b2100) is preferably 0.3 to 20, more preferably 0.5 to 15, and particularly preferably 0.7 to 10 from the viewpoint of conductivity. is there.
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. However, these mixtures may be used as they are or after being purified and separated.

As (b211), the terminal of (b210) is an α, β-unsaturated carboxylic acid and / or anhydride thereof [C3-15, such as monocarboxylic acid [(meth) acrylic acid etc.], dicarboxylic acid (maleic acid, Fumaric acid, itaconic acid, citraconic acid and the like), alkyl (C1-4) esters thereof [methyl (meth) acrylate, butyl (meth) acrylate, diethyl itaconate, etc.] and their anhydrides]. Modified polyolefins (b2111), (b2111) secondary modified with lactam (as described above such as caprolactam) or aminocarboxylic acid (as described above as 12 aminododecanoic acid) (b2112), (b210) as oxygen and / or Or polyolefin (b2113) and (b2113) modified by oxidation with ozone And polyolefin (b2114) secondarily modified with an amino acid (above) or aminocarboxylic acid (above) and a mixture of two or more thereof.
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 C2-10 hydroxylamine (such as 2-aminoethanol) and a mixture of two or more of these.
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), a polyolefin having an amino group at a terminal obtained by modifying (b211) with a C2-10 diamine (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 end of (b2100) is modified with an α, β-unsaturated carboxylic acid and / or an anhydride thereof [same as above], and (b2141) is a lactam (caprolactam or the like). ) Or an aminocarboxylic acid (12aminododecanoic acid or the like as described above), and a polyolefin (b2143) modified by oxidation with oxygen and / or ozone (b2143) and (b2143) a lactam (b2143). And polyolefins (b2144) secondarily modified with 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), polyolefin having a hydroxyl group at the terminal obtained by modifying (b214) with C2-10 hydroxylamine (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 C2-10 diamine (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.

In addition, (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 by an after-mentioned method in an atmosphere of 23 ° C. and 50% RH. The unit is Ω · cm) is 10 ⁴ to 10 ¹¹ , preferably 10 ^4. 10 is ^9. There is no volume resistivity of less than 10 ⁴ , and if it exceeds 10 ¹¹ , the conductivity deteriorates.

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 a C2-4 alkylene group.

-CHR-CHR'- (1)

—CH ₂ O (A ¹ O) _s R ″ (2)

Examples of the C2-4 alkylene group include 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 conductivity.
When the repeating unit is composed of an oxy-substituted alkylene group and / or one or more oxyalkylene groups, the bond 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, C1-20 alkyl group (methyl group, ethyl group, n- and i-propyl group, n-, sec-, i- and t-butyl group, 2-ethylhexyl group, etc.), aryl group (Phenyl group, etc.), alkylaryl group (nonylphenyl group, etc.), arylalkyl group (benzyl group, etc.), acyl group (acetyl group, benzoyl group, etc.) or chlorinated compounds thereof, etc. From this viewpoint, a C1 to C3 alkyl group is preferable.
A ¹ represents a C2-4 alkylene group such as an ethylene group, a propylene group, a 1,2-, 1,4-, 2,3- and 1,3-butylene group and two or more of these. Among these, an ethylene group is preferable from the viewpoint of conductivity.
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. Preferred examples of AO include EO alone and a combination of EO and other 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 two active hydrogen atoms.
Of these, from the viewpoint of electrical conductivity, 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 addition of bisphenol A are more preferred. It is a thing.

The content of C2-4 oxyalkylene units in (b2211) is preferably 8-99.6%, more preferably 10-98%, from the viewpoint of conductivity.
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 conductivity.

  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.
As organic diisocyanate, C (excluding carbon in NCO group, the same shall apply hereinafter) 6-20 aromatic diisocyanate, C2-18 aliphatic diisocyanate, C4-15 alicyclic diisocyanate, C8-15 araliphatic Examples thereof include 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.

The polyether ester amide (b2221) is composed of a polyamide (Q1) having a carboxyl group at the terminal and a polyether diol (b2211).
(Q1) includes a ring-opening polymer of C4-20 lactam (Q11) (described above); a polycondensate of C2-20 aminocarboxylic acid (Q12) (described above); diamine (Q13) ( The above) (C2-20 aliphatic diamine, C6-15 alicyclic diamine, C8-15 araliphatic diamine, C6-15 aromatic diamine, etc.) and C2-20 dicarboxylic acid (Q14) (The foregoing) Polyamide (Q15) with [aliphatic dicarboxylic acid, aromatic dicarboxylic acid, alicyclic dicarboxylic acid and their ester-forming derivatives [lower alkyl (C1-6) ester, anhydride, 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 polymer of caprolactam. It is.

The polyetheramide imide (b2222) is composed of a polyamideimide (Q2) having at least one imide ring and a polyether diol (b2211).
(Q2) includes a polymer comprising a C4-20 lactam (Q11) and a trivalent or tetravalent aromatic polycarboxylic acid (Q21) capable of forming at least one imide ring; a C2-20 amino Examples thereof include a polymer composed of carboxylic acid (Q12) and (Q21); a polymer composed of polyamide (Q15) and (Q21); and a mixture thereof.

The polyether ester (b2223) is composed of polyester (Q3) and polyether diol (b2211).
(Q3) is a polyester of C2-20 dicarboxylic acid (Q14) and glycol [as exemplified as (b111) above]; C6-12 lactone (above) or C2-20 hydroxycarboxylic acid Polyesters; 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, the polyether diol (b2211) or the polyether diamine (b2212) and, if necessary, the chain extender [glycol and diamine (Q31) etc. exemplified in the (b111)]. Is done.

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 the oxyethylene group 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.
Mn of (b222) is preferably 800, more preferably 1,000 from the viewpoint of heat resistance, and 50,000, more preferably 30,000, from the viewpoint of reactivity with polyolefin (b21). .

As the cationic polymer (b223), a cationic polymer having 2 to 80, preferably 3 to 60, cationic groups (b2232) separated by a nonionic molecular chain (b2231) in the molecule can be used. .
As the nonionic molecular chain (b2231), 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 And at least one divalent organic group selected from the group consisting of an organic group having a siloxy bond 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 C1-18 (preferably 2-8) linear or branched saturated or unsaturated aliphatic hydrocarbon group (such as an alkylene group and an alkenylene group), and a C6-20 aroma (fatty). ) Group hydrocarbon group and C4-15 alicyclic hydrocarbon group.
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.

Among these nonionic molecular chains (b2231), from the viewpoint of conductivity, a divalent hydrocarbon group and a divalent organic group having an ether bond are more preferable, and a C2-8 alkylene group (propylene) is more preferable. A divalent organic group having a phenylene group and a (poly) oxyalkylene group, particularly preferably a divalent organic group having a (poly) oxyethylene group, (poly) oxy It is a divalent organic group having a propylene group.
Mn of the nonionic molecular chain (b2231) is preferably 28 to 10,000, more preferably 300 to 5,000, from the viewpoint of conductivity.

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 conductivity.
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 And (C1-12) halide (methyl chloride, etc.), dialkyl (C1-12 of alkyl group) sulfuric acid (dimethylsulfuric acid, etc.) and the like].

Examples of the counter anion of (b2232) include a conjugate base of a super strong acid described later and other anions.
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.
Among these, from the viewpoint of initial conductivity, preferred are an anion other than the conjugate base of a super strong acid, a conjugate base of a super strong acid, and a mixture thereof, having an Hammett acidity function (−H ₀ ) of the anion of 12 to 100.

The terminal structure of the cationic polymer (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, and particularly preferably 1,200 to 8,8, from the viewpoint of conductivity and reactivity with polyolefin (b21). 000.

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

Examples of the sulfonic acid group-containing aromatic (aliphatic) dicarboxylic acid include C8-20, such as 2-, 5- and 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid, and ester-forming derivatives thereof [ Lower alkyl (C1-4) ester (methyl ester, ethyl ester, etc.), acid anhydride, etc.].
Examples of the sulfonic acid group-containing aliphatic dicarboxylic acid include C8-20, for example, sulfosuccinic acid and ester-forming derivatives thereof.
Examples of the salts of only these sulfonic acid groups include alkali metal salts, alkaline earth metal salts, ammonium salts, mono-, di- and trialkanols having a hydroxyalkyl (C2-4) group. Examples include amine salts such as amines, quaternary ammonium salts of these amines, and combinations of two or more of these.
Of these, aromatic (aliphatic) dicarboxylic acids having a sulfonic acid group are preferred from the viewpoint of antistatic properties.

Of the glycol (b111) or polyether (b221) constituting the anionic polymer (b224), preferred are C2-10 alkanediol, EG, PEG (degree of polymerization 2-20), bisphenol ( EO adduct (addition mole number 2 to 60) of bisphenol A and the like, and a mixture of two or more thereof.
Mn of (b224) is preferably from 500 to 20,000, more preferably from 1,000 to 15,000, particularly preferably from 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, preferably from the viewpoint of conductivity. It is 2.3-30, More preferably, it is 2.7-20, Most preferably, it is 3-10. 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 the hydrophilic polymer (b22) constituting (B2) is preferably 20 to 90% by weight, more preferably from the viewpoint of conductivity based on the total weight of the polyolefin (b21) and the hydrophilic polymer (b22). 30 to 70% by weight.

As a manufacturing method of (B2), the following are mentioned, for example.
<Production method of (B2)>
A known method, for example, polyether diol (b2211) is added to polyolefin (b211) having carbonyl groups at both ends of the polymer, and polymerization (polycondensation) reaction is carried out under reduced pressure (1 mmHg or less), usually at 200 to 250 ° C. It can be produced by a method or a polymerization method using a uniaxial or biaxial extruder, usually at 160 to 250 ° C. and a residence time of 0.1 to 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 (tetrabutyl zirconate, 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. Of these, preferred are zirconium catalyst and zirconium organic acid salt, and more preferred is zirconyl acetate.
The usage-amount of a catalyst is 0.001 to 5 weight% normally based on the total weight of polyolefin (b211) and polyether diol (b2211), Preferably it is 0.01 to 3 weight%.
The conductive resin composition of the present invention can be produced by kneading the obtained (B2) and the polymer type ionic liquid (A).

[Conductive resin composition]
The conductive resin composition of the present invention can be produced by adding the polymer type ionic liquid (A) to the block polymer (B) and melt-kneading.
The weight ratio of (A) to (B) is preferably from 1/99 to 50/50, more preferably from 5/95 to 40/60, particularly preferably from 10/90 to 30/70, from the viewpoints of conductivity and resin strength. It is.

  In the conductive resin composition of the present invention, an ionicity other than the alkali metal or alkaline earth metal salt (C1), surfactant (C2), or (A) is included as long as the effects of the present invention are not impaired. You may contain the at least 1 sort (s) of additive (C) chosen from the group which consists of a liquid (C3), a compatibilizing agent (C4), and the other additive (C5) for resin.

  (C1) include alkali metal (lithium, sodium, potassium, etc.) and / or alkaline earth metal (magnesium, calcium, etc.) organic acids (C1-12 mono- and dicarboxylic acids such as formic acid, acetic acid, Propionic acid, oxalic acid, succinic acid; salts of C1-20 sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid; thiocyanic acid, and inorganic acids (hydrohalic acids such as hydrochloric acid, hydrobromic acid; A salt of perchloric acid; sulfuric acid; nitric acid; phosphoric acid) can be used.

Specific examples of (C1) include halides [fluorides (lithium fluoride, -sodium, -potassium, -magnesium, -calcium, etc.), chlorides (lithium chloride, -sodium, -potassium, -magnesium, -calcium, etc.) ), Bromides (such as lithium bromide, -sodium, -potassium, -magnesium and -calcium) and iodides (such as lithium iodide, -sodium, -potassium, -magnesium and -calcium)], perchlorates ( Lithium perchlorate, -sodium, -potassium, -magnesium and -calcium), fluorinated sulfonates (lithium fluorosulfonate, -sodium, -potassium, -magnesium and -calcium), methanesulfonate (methane) Lithium sulfonate, -sodium, -ca Um, -magnesium and -calcium), trifluoromethanesulfonate (lithium trifluoromethanesulfonate, -sodium, -potassium, -magnesium and -calcium, etc.), pentafluoroethanesulfonate (lithium pentafluoroethanesulfonate, -Sodium, -potassium, -magnesium and -calcium), nonafluorobutane sulfonate (such as lithium nonafluorobutane sulfonate, -sodium, -potassium, -magnesium and -calcium), undecafluoropentane sulfonate ( Undecafluoropentanesulfonate lithium, -sodium, -potassium, -magnesium, -calcium, etc.), tridecafluorohexanesulfonate (tridecafluorohexanesulfone) Lithium acid, -sodium, -potassium, -magnesium and -calcium), acetate (lithium acetate, -sodium, -potassium, -magnesium and -calcium etc.), sulfate (sodium sulfate, -potassium, -magnesium and- Calcium, etc.), phosphates (sodium phosphate, -potassium, -magnesium, -calcium, etc.), thiocyanates (potassium thiocyanate, etc.) and the like.
Of these, halide, perchlorate, trifluoromethanesulfonate, and acetate are preferable from the viewpoint of conductivity, and lithium chloride, -potassium and -sodium, lithium perchlorate, -potassium and-are more preferable. Sodium, lithium trifluoromethanesulfonate, -potassium and -sodium, potassium acetate.

The amount of (C1) used is usually 10% or less based on the total weight of (A) and (B). From the viewpoint of the conductivity of the molded article and the viewpoint of giving a molded article having a good appearance without depositing on the surface of the molded article. Therefore, it is preferably 0.001 to 5%, more preferably 0.01 to 4%, particularly preferably 0.1 to 2%, and most preferably 0.15 to 1%.
The method for containing (C1) is not particularly limited, but it is preferable to disperse it in advance in the hydrophilic group-containing polymer (B) from the viewpoint of ease of effective dispersion in the composition.
Further, when (C) is dispersed in (B), it is particularly preferable that (C1) is contained and dispersed in advance during the production (polymerization) of (B). There is no particular limitation on the timing at which (C1) is contained during the production of (B), and any time before polymerization, during polymerization, or immediately after polymerization may be used.

(C2) includes nonionic, anionic, cationic and amphoteric surfactants, and mixtures thereof.
Nonionic surfactants include, for example, EO addition type nonionic surfactants [for example, higher alcohols (C8-18, the same shall apply hereinafter), higher fatty acids (C8-24, the same shall apply hereinafter) or higher alkylamines (C8-24). ) EO adduct (molecular weight 158 or more and Mn 200,000 or less); higher fatty acid ester of polyalkylene glycol (molecular weight 150 or more and Mn 6,000 or less) which is an EO adduct of glycol; polyhydric alcohol (C2-18-2) EO adduct of higher fatty acid ester (molecular weight of 250 or more and Mn of 30,000 or less); EO adduct of higher fatty acid amide (molecular weight 200) And Mn 30,000 or less); And polyhydric alcohol (as described above) EO adduct of alkyl (C3-60) ether (molecular weight of 120 or more and Mn of 30,000 or less)], and polyhydric alcohol (C3-60) type nonionic surfactant [For example, fatty acid (C3-60) ester of polyhydric alcohol, alkyl (C3-60) ether of polyhydric alcohol and fatty acid (C3-60) alkanolamide].

  As the anionic surfactant, compounds other than the above (C1) can be used, for example, carboxylates such as higher fatty acid salts; sulfates such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfones. Examples thereof include sulfonates such as acid salts, alkyl sulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphate salts.

  Cationic surfactants include quaternary ammonium salt types [eg, tetraalkyl (C4-100) ammonium salts (eg, lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide and stearyltrimethylammonium bromide), Alkyl (C3-80) benzylammonium salts (eg lauryldimethylbenzylammonium chloride (benzalkonium chloride), alkyl (C2-60) pyridinium salts (eg cetylpyridinium chloride), polyoxyalkylene (C2-4) trialkylammonium salts (Eg, polyoxyethylenetrimethylammonium chloride) and sapamine type quaternary ammonium salts (eg, stearamide ester) Rudiethylmethyl ammonium methosulfate)]; and amine salt forms [eg higher aliphatic amines (C12-60, eg laurylamine, stearylamine, cetylamine, hardened tallow amine and rosinamine) inorganic acids (eg hydrochloric acid, sulfuric acid, nitric acid and Phosphoric acid) salts or organic acids (C2-22, eg acetic acid, propionic acid, lauric acid, oleic acid, benzoic acid, succinic acid, adipic acid and azelaic acid) salts, ethylene oxide adducts of aliphatic amines (C1-30) Inorganic acids (above) or organic acids (above) salts and tertiary amines (C3-30, eg triethanolamine monostearate and stearamide ethyl diethyl methylethanolamine) Thing) salt or organic acid (above thing) salt] It is.

Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine.
Examples of amphoteric surfactants include amino acid type amphoteric surfactants [for example, propionates of higher alkylamines (C8-24)], betaine type amphoteric surfactants [for example, higher alkyl (C12-18) dimethylbetaines, higher alkyldihydroxys. Ethyl betaine], sulfate ester type amphoteric surfactants [for example, sulfate esters of higher alkylamines (C8-24) and hydroxyethylimidazoline sulfate esters], sulfonate type amphoteric surfactants (eg, pentadecyl sulfotaurine salts) And imidazoline sulfonate) and phosphate ester type amphoteric surfactants [for example, phosphate ester salts of glycerin higher fatty acid (C8-24) esterified products].

These may be used alone or in combination of two or more.
Salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and group IIB metals (zinc, etc.); And ammonium salts [alkylamine (C1-20) and alkanolamine (C2-12, such as mono-, di- and triethanolamine) salts] and quaternary ammonium salts.
Of these, anionic surfactants are preferred from the viewpoint of conductivity, sulfonates are more preferred, alkylbenzene sulfonates (such as sodium dodecylbenzene sulfonate), alkyl sulfonates and paraffin sulfones are particularly preferred. Acid salt.

The amount of (C2) used is usually 10% or less based on the total weight of (A) and (B), preferably from 0.001 to 5%, more preferably 0 from the viewpoint of the conductivity and water resistance of the molded product. 0.01 to 3%, particularly preferably 0.1 to 2.5%.
The method for containing (C2) is not particularly limited, but in order to effectively disperse it in the resin composition, it is preferable to disperse it in (B) in advance. Further, when (C2) is dispersed in (B), it is particularly preferable that (C2) is previously contained and dispersed during the production (polymerization) of (B). There is no particular limitation on the timing at which (C2) is contained during the production of (B), and any time before polymerization, during polymerization, or immediately after polymerization may be used.

  (C3) is an ionic liquid other than (A) and is a compound other than the above (C1) and (C2), and has a melting point of 100 ° C. or lower or a Tg of room temperature or lower, and constitutes (C3) Alternatively, at least one of the anions is an organic ion. Examples of the cation constituting (C3) include the above (a1) and (a2).

  The above (a1) and (a2) may be used alone or in combination of two or more. Of these, (a1) is preferable from the viewpoint of conductivity, imidazolium cation is more preferable, and 1-ethyl-3-methylimidazolium cation is particularly preferable.

In (C3), examples of the organic acid or inorganic acid constituting the anion include the following.
Examples of the organic acid include carboxylic acid, sulfuric acid ester, sulfonic acid and phosphoric acid ester.
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, are preferred from the viewpoint of conductivity of the (C3) is anionic Hamett acidity function constituting the (C3) (-H ₀₎ is 12 to 100, the superacid conjugate base, Acids that form anions other than conjugate bases of super strong acids and mixtures thereof.

  Examples of the anion other than the conjugate base of the super strong acid include halogen (for example, fluorine, chlorine and bromine) ions, alkyl (C1-12) benzenesulfonic acid (for example, p-toluenesulfonic acid and dodecylbenzenesulfonic acid) ions and poly (n = 1-25) Fluoroalkanesulfonic acid (for example, undecafluoropentanesulfonic acid) ion.

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

Examples of the protonic acid used in combination with the Lewis acid include hydrogen halide (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid. , 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 (C3).

Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof. Among these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of (DC3).
The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

  Of the above anions, (C3) from the viewpoint of conductivity, a super strong acid conjugate base (a super strong acid comprising a proton acid and a super strong acid comprising a combination of a proton acid and a Lewis acid), and more preferably a proton. It is a conjugate base of a super strong acid consisting of a super strong acid and a proton acid consisting of an acid and boron trifluoride and / or phosphorus pentafluoride.

The amount of (C3) used is usually 10% or less based on the total weight of (A) and (B), preferably 0.001 to 5%, more preferably 0 from the viewpoint of the conductivity and mechanical properties of the molded product. 0.01 to 3%.
The method of adding (C3) is not particularly limited, but it is preferable to disperse in (B) in advance from the viewpoint of effective dispersion in the resin. Further, when (C3) is dispersed in (B), it is particularly preferable that (C3) is contained and dispersed in advance during the production (polymerization) of (B). There is no particular limitation on the timing at which (C3) is contained during the production of (B), and any time before polymerization, during polymerization, or immediately after polymerization may be used.

  The production method of (C3) includes, for example, the above-mentioned organic compound constituting an anion in an acid [(C3) and an amidinium cation and / or a guanidinium cation dimethyl carbonate salt obtained by quaternization with dimethyl carbonate or the like. Acid or inorganic acid] to perform acid exchange, or a method of once hydrolyzing the amidinium cation and / or guanidinium cation to produce a monoamidoamine, and then neutralizing the monoamidoamine with an acid Is mentioned.

As the compatibilizing agent (C4), a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group is used. Examples thereof include polymers described in JP-A-3-258850. Further, for example, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, a block polymer having a polyolefin portion and an aromatic vinyl polymer portion, and the like can be used.
The amount of (C4) used is usually 20% or less based on the total weight of (A) and (B), preferably from 0.01 to 15%, more preferably from the viewpoint of the conductivity and mechanical properties of the molded product. It is 0.1 to 10%, particularly preferably 1 to 8%.
The method for containing (C4) is not particularly limited, but it is preferable to disperse it in advance in the hydrophilic group-containing polymer (B) from the standpoint of effective dispersion or dissolution in the composition. . In addition, when (C4) is dispersed or dissolved in (B), it is particularly preferable to contain (C4) in advance during the production (polymerization) of (B). There is no particular limitation on the timing at which (C4) is contained during the production of (B), and any time before polymerization, during polymerization, or immediately after polymerization may be used.

Moreover, according to various uses, the other resin additive (C5) can be arbitrarily added to the resin composition of this invention in the range which does not inhibit the effect of this invention.
(C5) includes nucleating agent (C51), lubricant (C52), pigment (C53), dye (C54), mold release agent (C55), antioxidant (C56), flame retardant (C57), ultraviolet absorber Examples thereof include at least one selected from the group consisting of (C5), an antibacterial agent (C59), a dispersant (C510), a conductive substance (C511), and a filler (C512).

Examples of the nucleating agent (C51) include organic nucleating agents [for example, 1,3,2,4-di-benzylidene-sorbitol, aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium bis (4-t- Butylphenyl) phosphate and sodium benzoate] and inorganic nucleating agents (eg graphite, carbon black, magnesium oxide, calcium silicate, magnesium silicate, talc, kaolin, calcium carbonate, magnesium carbonate, sodium carbonate, potassium carbonate, zinc oxide, alumina, Barium sulfate and calcium sulfate).
Lubricants (C52) include waxes (eg carnauba wax, paraffin wax and polyolefin wax), higher fatty acids (C8-24, eg stearic acid, oleic acid, linoleic acid and linolenic acid), higher alcohols (C8-18, eg stearyl). Alcohols, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetostearyl alcohol and behenyl alcohol) and higher fatty acid amides (C8-24, such as stearic acid amide, oleic acid amide, linoleic acid amide and linolenic acid amide).

Examples of the pigment (C53) include inorganic pigments [white pigments (titanium oxide, lithopone, lead white, zinc white, etc.), cobalt compounds (aureolin, cobalt green, etc.), iron compounds (iron oxide, bitumen, etc.), chromium compounds (oxidation). Chromium, lead chromate, etc.) and sulfides (cadmium sulfide, ultramarine, etc.)], organic pigments [azo pigments (azo lakes, monoazos, disazos, chelate azos, etc.), polycyclic pigments (benzoimidazolones) Phthalocyanine, isoindolinone, anthraquinone, etc.).
Examples of the dye (C54) include azo, indigoid, sulfide, alizarin, acridine, thiazole, nitro, and aniline.
As the release agent (C55), lower fatty acid (C1-4) alcohol ester (for example, butyl stearate) of higher fatty acid (above), polyvalent (divalent to tetravalent or higher) of fatty acid (C2-18) ) Alcohol esters (eg hydrogenated castor oil), glycol (C2-8) esters of fatty acids (C2-18) (eg ethylene glycol monostearate) and liquid paraffin.

  Antioxidants (C56) include phenolic {eg monocyclic phenols [eg 2,6-di-t-butyl-p-cresol and butylated hydroxyanisole], bisphenols [eg 2,2′-methylenebis (4- Methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl) -6-tert-butylphenol and 4,4′-thiobis (3-methyl) -6-tert-butylphenol] and polycyclic phenols [ For example, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-) 5-t-butylphenyl) butane, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propione Methane]}; sulfur-based [eg, dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, lauryl stearyl 3,3′-thiodipropionate, dimyristyl 3,3 ′ -Thiodipropionate, distearyl β, β'-thiodibutyrate and dilauryl sulfide]; phosphorus systems (eg triphenyl phosphite, triisodecyl phosphite, diphenylisodecyl 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 neopentanetetra Rubis (octadecyl phosphite), cyclic neopentanetetrayl bis (2,6-di-t-butyl-4-methylphenyl) phosphite, cyclic neopentane tetrayl bis (2,4-di-t-butyl) Phenyl) phosphite and diisodecylpentaerythritol diphosphite]; and amine systems such as 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 and phenothiazine.

  The flame retardant (C57) includes a halogen-containing flame retardant (C571), a nitrogen-containing flame retardant (C572), a sulfur-containing flame retardant (C573), a silicon-containing flame retardant (C574), and a phosphorus-containing flame retardant (C575). 1 type or 2 types or more of flame retardants chosen from these are included.

  Examples of the halogen-containing flame retardant (C571) include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, tetrabromobisphenol A, tetromophthalimide, hexabromobutene, Hexabromocyclododecane, etc .;

Examples of the nitrogen-containing flame retardant (C572) include a salt of urea compound, guanidine compound or triazine compound (melamine, guanamine, etc.) and cyanuric acid or isocyanuric acid, etc .; Sulfonic acid, sulfamic acid, organic sulfamic acid, and their salts, esters and amides;
Examples of the silicon-containing flame retardant (C574) include polyorganosiloxane;

  Phosphorus-containing flame retardants (C575) include phosphorus-containing acids and esters thereof (C2-20) such as phosphoric acid, phosphates, halogen-containing phosphates, phosphorous acid, phosphonates, halogen-containing phosphonates, and ammonium phosphate salts. Can be mentioned.

Examples of the phosphate include phosphates and condensed phosphates (di- and polyphosphates).
Examples of the phosphate include trialkyl (alkyl group is C1-12) phosphate [trimethyl-, triethyl-, tributyl-, and trioctylphosphate, etc.], trialkoxy (alkoxy group is C1-6) phosphate [triethoxy-, tributoxyphosphate, etc. ], Triaryl phosphate [triphenyl phosphate and the like], alkyl (alkyl group is C1-10) aryl phosphate [tricresyl-, cresyldiphenyl-, octyldiphenyl-, diisopropylphenyl- and resorcinol-bis (di-2,6- Dimethylphenyl) phosphate, etc.].

  Examples of the condensed phosphate include trialkyl (alkyl group is C1-12) poly (n = 2-30) phosphate, phenyl resorcinol poly (n = 2-30) phosphate, resorcinol poly (n = 2-30) phosphate [resorcin bis. Phosphate, cresyl resorcinol polyphosphate, etc.], hydroquinone poly (n = 2-30) phosphate [hydroquinone bisphosphate, hydroquinone polyphosphate, etc.], bisphenol A bisphosphate, trioxybenzene triphosphate and the like.

  Examples of the halogen-containing phosphate include tris halogenated alkyl (alkyl group is C2-4) phosphate [trischloroethyl phosphate, trisdichloropropyl phosphate, tris-β-chloropropyl phosphate, tris (tribromoneopentyl) phosphate, etc.], And tris-halogenated aryl phosphate [tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, etc.].

Examples of the phosphonate include phosphonates and condensed phosphonates.
As phosphonates, trialkyl (alkyl group is C1-12) phosphonate [trimethylphosphonate, triethylphosphonate, tributylphosphonate, trioctylphosphonate, etc.], trialkoxy (alkoxy group is C1-6) phosphonate [triethoxyphosphonate, tributoxyphosphonate Etc.], triaryl phosphonate [triphenyl phosphonate etc.], alkyl (alkyl group is C1-10) aryl phosphonate [tricresyl phosphonate, cresyl diphenyl phosphonate, octyl diphenyl phosphonate, diisopropyl phenyl phosphonate, resorcinol bis (di-2) , 6-dimethylphenyl) phosphonate and the like.

  As the condensed phosphonate, trialkyl (alkyl group is C1-12) poly (n = 2 to 30) phosphonate, phenyl resorcinol poly (n = 2 to 30) phosphonate, resorcinol poly (n = 2 to 30) phosphonate [resorcinbis Phosphate, cresyl resorcinol polyphosphonate, etc.], hydroquinone poly (n = 2-30) phosphonate [hydroquinone bisphosphonate, hydroquinone polyphosphonate, etc.], bisphenol A bisphosphonate, trioxybenzene triphosphonate and the like.

  Examples of the halogen-containing phosphonate include tris halogenated alkyl (alkyl group is C2-4) phosphonate [trischloroethyl phosphonate, tris dichloropropyl phosphonate, tris-β-chloropropyl phosphonate, tris (tribromoneopentyl) phosphonate, etc.], And tris-halogenated aryl phosphonate [tris (tribromophenyl) phosphonate, tris (dibromophenyl) phosphonate, etc.].

  As said ammonium phosphate, what is marketed normally for flame retardants can be used. These may be used in combination with a melamine compound (for example, melamine alone), a pentaerythritol compound (for example, pentaerythritol, dipentaerythritol), an amide (for example, nylon 6, nylon 66) or the like, if necessary.

  These flame retardants may be used in combination with a flame retardant aid [anti-drip agent (for example, polytetrafluoroethylene), metal oxide (for example, zinc oxide), etc.] as necessary.

  Of these flame retardants, a nitrogen-containing flame retardant (C572) is preferable from the viewpoint of flame retardancy and the absence of environmental pollution such as dioxin generation during incineration.

  Examples of the ultraviolet absorber (C58) include benzotriazoles [for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole], Benzophenone series [eg 2-hydroxy-4-methoxybenzophenone and 2,2′-dihydroxy-4-methoxybenzophenone], salicylate series [eg phenyl salicylate and ethylene glycol monosalicylate] and acrylate series [eg 2-ethylhexyl 2-cyano-3,3′1-diphenyl acrylate].

  Examples of the antibacterial agent (C59) include benzoic acid, paraoxybenzoic acid ester, sorbic acid, halogenated phenol (for example, 2,4,6-tribromophenol sodium salt), organic iodine (for example, 4-chlorophenyl-3-iodopropargyl). Formal), nitrile (eg, 2,4,5,6-tetrachloroisophthalonitrile), thiocyano (eg, methylene bisthianocyanate), N-haloalkylthioimide (eg, N-tetrachloroethyl-thio-tetrahydrophthalimide), copper agent (Eg 8-oxyquinoline copper), benzimidazole (eg 2-4-thiazolylbenzimidazole), benzothiazole (eg 2-thiocyanomethylthiobenzothiazole), trihaloallyl (eg 3-bromo-2,3-diiodo- 2-propenis Ethyl carbonate), triazoles (eg azaconazole), organic nitrogen sulfur compounds (eg Suraoff 39), quaternary ammonium compounds (eg trimethoxysilyl-propyloctadecylammonium chloride) and pyridine-based compounds [eg 2,3,5,6- Cytochloro-4- (methylsulfonyl) -pyridine].

  As the dispersant (C510), a dispersant having Mn of 1,000 to 100,000, such as naphthalene sulfonic acid formalin condensate (Mn 1,000 to 10,000), polystyrene sulfonate metal [for example, alkali metals (for example, sodium and potassium) ] Salt (Mn 1,000-100,000), polyacrylic acid metal [for example, alkali metal (same as above)] salt (Mn 2,000-50,000), carboxymethyl cellulose and polyvinyl alcohol.

  The conductive substance (C511) is a compound other than the above (C1) and (C3), and examples thereof include carbon nanotubes, carbon black, and white carbon.

  Examples of the filler (C512) include inorganic fillers (eg, calcium carbonate, talc, clay, silicic acid, silicate, asbestos, mica, glass fiber, glass balloon, carbon fiber, metal fiber, ceramic whisker and titanium whisker). And organic fillers [for example, urea, calcium stearate and organic crosslinked fine particles (for example, epoxy-based and urethane-based)].

The total amount used of (C5) is usually 45% or less based on the total weight of (A) and (B), preferably 0.001 to 0.005 in view of the additive effect of each additive and the mechanical properties of the molded product. It is 40%, more preferably 0.01 to 35%, particularly preferably 0.05 to 30%.
Of (C5), (C51), (C52), (C53), (C54), (C55), (C510) and (C512) are each usually 10% or less, preferably 1 to 5%; (C57) Is usually 20% or less, preferably 1 to 10%; (C56), (C58) and (C511) are usually 5% or less, preferably 0.1 to 3%; (C59) is usually 3% or less, preferably 0.05 to 1%.

The conductive resin composition of the present invention is obtained by melt-kneading (A) and (B) and, if necessary, (C).
As a method of melt-kneading, a normal method is used, and generally, a pellet-like or powder-like polymer is mixed with an appropriate mixer such as a Henschel mixer and then melt-kneaded with an extruder. A pelletizing method can be applied.

[Antistatic resin composition]
The antistatic resin composition of the present invention comprises the thermoplastic resin (D) containing the conductive resin composition (X).

  (D) includes polyphenylene ether resin (D1); vinyl resin [polyolefin resin (D2) [for example, polypropylene, polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin], polyacrylic resin (D3) [for example, polymethyl methacrylate], polystyrene resin (D4) [comprising vinyl group-containing aromatic hydrocarbon alone or vinyl group-containing aromatic hydrocarbon, (meth) acrylic ester, (meth) acrylonitrile and butadiene Copolymers having at least one selected from the group as structural units, such as polystyrene, styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / Styrene Polyester resin (D5) [for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate]; Polyamide resin (D6) [for example, nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12]; polycarbonate resin (D7) [for example, polycarbonate, polycarbonate / ABS alloy resin]; polyacetal resin (D8); biodegradable resin (D9), and a mixture of two or more thereof.

  Among these, (D1), (D2), (D3), (D4) and (D7) are preferable from the viewpoint of the mechanical properties of the molded product described later and the dispersibility of the antistatic agent of the present invention in (D). More preferred are (D2), (D4) and (D7).

  Examples of the polyphenylene ether resin (D1) include those represented by the following general formula (93).

In general formula (3), p is an integer of 50 or more, R ¹ , R ² , R ³ , and R ⁴ are H, a halogen atom, a C1-12 hydrocarbon group, a C2-12 substituted hydrocarbon group, and an alkoxy group. Represents a cyano group, a phenoxy group or a nitro group. R ¹ , R ² , R ³ and R ⁴ may be the same or different. Further, (D1) is a single polymer of the general formula (3) or a copolymer of two or more structural units or a blend of two or more polymers. Also good.

Specific examples of (D1) include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl). -1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6) -Propyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2,6-phenylene) Dibromo-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether, poly (2,6) Dibenzyl-1,4-phenylene) ether, poly (2,5-dimethyl-1,4-phenylene) ether.
Further, (D1) includes those obtained by grafting the above styrene and / or its derivative monomer (modified polyphenylene ether) to (D1).

The intrinsic viscosity [η] of (D1) 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 using a Ubbelohde 1A viscometer at 30 ° C. for a 0.5 wt% chloroform solution of the polymer.
Tg of (D1) is preferably 190 to 240 ° C., more preferably 210 to 230 ° C. from the viewpoint of moldability. Tg is measured by a differential scanning calorimetry (DSC) method.

  As the vinyl resins [(D2) to (D4)], those obtained by (co) polymerizing the following vinyl monomers by various polymerization methods (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.) Is mentioned.

  Examples of vinyl monomers include unsaturated hydrocarbons (aliphatic hydrocarbons, aromatic ring-containing hydrocarbons, alicyclic hydrocarbons, etc.), acrylic monomers, other unsaturated mono- and dicarboxylic acids and their derivatives, and carboxylic acids of unsaturated alcohols. Examples thereof include acid esters, alkyl ethers of unsaturated alcohols, halogen-containing vinyl monomers, and combinations of two or more thereof (random and / or block).

  Aliphatic hydrocarbons include C2-30 olefins [ethylene, propylene, C4-30 α-olefins (1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1 -Dodecene etc.), etc.], C4-30 dienes [alkadiene (butadiene, isoprene etc.), cycloalkadiene (cyclopentadiene etc.) etc.] and the like.

  Examples of the aromatic ring-containing hydrocarbon include C8-30 styrene and derivatives thereof, such as o-, m- and p-alkyl (C1-10) styrene (vinyltoluene, etc.), α-alkyl (C1-10) styrene ( α-methylstyrene and the like) and halogenated styrene (chlorostyrene and the like).

Acrylic monomers include C3-30, such as (meth) acrylic acid and its derivatives.
Examples of (meth) acrylic acid derivatives include alkyl (C1-20) (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.], mono- and di-alkyl ( C1-4) aminoalkyl (C2-4) (meth) acrylate [methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.], (meth) acrylonitrile and (meth) acrylamide.

  Other unsaturated mono- and dicarboxylic acids include C2-30 (preferably 3-20, more preferably 4-15) unsaturated mono- and dicarboxylic acids such as crotonic acid, maleic acid, fumaric acid and itacon. Examples thereof include C5-30, such as mono- and dialkyl (C1-20) esters, acid anhydrides (maleic anhydride, etc.) and acid imides (maleic imide, etc.).

Examples of carboxylic acid esters of unsaturated alcohols include carboxylic acids (C2-4, such as acetic acid and propionic acid) esters (such as vinyl acetate) of unsaturated alcohols [C2-6, such as vinyl alcohol, (meth) allyl alcohol]. It is done.
Examples of the alkyl ether of the unsaturated alcohol include alkyl (C1-20) ethers of the above unsaturated alcohol (methyl vinyl ether, ethyl vinyl ether, etc.). Halogen-containing vinyl monomers include C2-12, such as vinyl chloride, vinylidene chloride and chloroprene.

Examples of the polyolefin resin (D2) include polypropylene, polyethylene, propylene-ethylene copolymer [copolymerization ratio (weight ratio) = 0.1 / 99.9 to 99.9 / 0.1], propylene and / or ethylene. And other α-olefin (C4-12) copolymers (random and / or block addition) [copolymerization ratio (weight ratio) = 99 / 1-5 / 95], ethylene / vinyl acetate Copolymer (EVA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40], ethylene / ethyl acrylate copolymer (EEA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40 ].
Among these, preferred are polypropylene, polyethylene, propylene-ethylene copolymer, propylene and / or a copolymer of ethylene and one or more of C4-12 α-olefin [copolymerization ratio (weight ratio) = 90. / 10 to 10/90, random and / or block addition].

The melt flow rate (hereinafter abbreviated as MFR) of (D2) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of imparting resin physical properties and antistatic properties. The MFR here is measured according to JIS K6758 (in the case of polypropylene: 230 ° C., load 2.16 kgf, in the case of polyethylene: 190 ° C., load 2.16 kgf).
The crystallinity of (D2) is preferably 0 to 98%, more preferably 0 to 80%, and particularly preferably 0 to 70% from the viewpoint of antistatic properties.
The crystallinity here is measured by a method such as X-ray diffraction, infrared absorption spectrum, etc. [Refer to “Solid Structure of Polymers—Human Goro Laboratory 2” (Hatsugoro Minamishino), page 42, published by Kyoritsu Shuppan 1958. ].

  As the polyacrylic resin (D3), for example, one or more (co) polymers [poly (meth) acrylic acid methyl ester, such as acrylic monomers [alkyl (C1-20) (meth) acrylate, (meth) acrylonitrile, etc.], Poly (meth) butyl acrylate, etc.] and copolymers with one or more of the above-mentioned vinyl monomers copolymerizable with one or more of these monomers [acrylic monomer / vinyl monomer copolymerization ratio (weight ratio) is a resin physical property In view of the above, preferably 5/95 to 95/5, more preferably 50/50 to 90/10] [however, those included in (C2) are excluded] are included.

  The MFR of (D3) is preferably 0.5 to 150, more preferably 1 to 100 from the viewpoint of resin physical properties. MFR is measured according to JIS K7210 (1994) (230 ° C. and load 1.2 kgf in the case of polyacrylic resin).

As the polystyrene resin (D4), a vinyl group-containing aromatic hydrocarbon alone or a vinyl group-containing aromatic hydrocarbon, and at least one selected from the group consisting of (meth) acrylic acid ester, (meth) acrylonitrile and butadiene Examples thereof include a copolymer as a structural unit.
Examples of vinyl group-containing aromatic hydrocarbons include C8-30 styrene and its derivatives, such as o-, m- and p-alkyl (C1-10) styrene (vinyltoluene etc.), α-alkyl (C1-10). Examples include styrene (α-methylstyrene and the like) and halogenated styrene (chlorostyrene and the like).
Specific examples of (D4) include polystyrene, polyvinyltoluene, 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 (D4) 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).

  Examples of the polyester resin (D5) 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 (D5) 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.

  The polyamide resin (D6) includes a lactam ring-opening polymer (D61), a dehydration polycondensation product of diamine and dicarboxylic acid (D62), a self-polycondensation product of aminocarboxylic acid (D63), and a poly (condensation) combination thereof. Examples thereof include copolymer nylon having two or more types of monomer units.

Examples of the lactam in (D61) include C4-20 lactams such as γ-butyrolactam, γ-valerolactam, ε-caprolactam, γ-pimelolactam, γ-caprololactam, γ-decanolactam, enantolactam, laurolactam, undecano Examples include lactam, eicosanolactam, and 5-phenyl-2-piperidone. Examples of (D61) include nylon 4, nylon 5, nylon 6, nylon 8, nylon 12, and the like.
Examples of the diamine in (D62) include C2-20 diamines such as aliphatic [ethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, decamethylene diamine, eicosane diamine, etc.], aromatic (aliphatic) [phenylene diamine. , Naphthylenediamine, xylylenediamine, etc.] and alicyclic [cyclohexylenediamine, etc.].
Examples of the dicarboxylic acid include C2-20 dicarboxylic acids such as those exemplified as the dicarboxylic acid (b114).
Examples of (D62) include nylon 66 by condensation polymerization of hexanemethylenediamine and adipic acid, nylon 610 by polycondensation of hexamethylenediamine and sebacic acid, and the like.
Examples of the aminocarboxylic acid in (D63) include C2-20 aminocarboxylic acids such as glycine, alanine, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, and ω-aminocaprin. Acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 20-aminoeicosanoic acid, etc., and (D63) is nylon 7 by polycondensation of aminoenanthic acid, by polycondensation of ω-aminoundecanoic acid Nylon 11, 12-aminododecanoic acid nylon 12 by polycondensation and the like.

In the production of (D6), a molecular weight modifier may be used, and examples of the molecular weight modifier include the dicarboxylic acid and / or diamine shown above.
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 MFR of (D6) 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 polycarbonate resin (D7) include bisphenols (C12-20, such as bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane) and dihydroxybiphenyl polycarbonates such as bisphenol and phosgene. Or the condensate with a carbonic acid diester is mentioned. Of the above bisphenols, bisphenol A is preferred from the viewpoint of dispersibility of (A).
The MFR of (D7) 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 K7210 (1994) (in the case of polycarbonate resin, 280 ° C., load 2.16 kgf).

Examples of the polyacetal resin (D8) include formaldehyde or trioxane homopolymer (polyoxymethylene homopolymer), and a copolymer of formaldehyde or trioxane and a cyclic ether [the above-mentioned AO (EO, PO, dioxolane, etc.)] (polyoxy). And methylene / polyoxyethylene copolymer [polyoxymethylene / polyoxyethylene (weight ratio) = 90/10 to 99/1 block copolymer and the like].
The MFR of (D8) 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).
Intrinsic viscosity [η] of (C8) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, and particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and antistatic properties.

  Examples of the biodegradable resin (D9) include polyhydroxybutyrate, polylactic acid, polycaprolactone, polybutylene succinate, adipate-modified polybutylene succinate, carbonate-modified polybutylene succinate, terephthalate-modified polybutylene succinate, polyethylene succinate And polyvinyl alcohol.

  Among (D9), as polyhydroxybutyrate, for example, biogreen [manufactured by Mitsubishi Gas Chemical Co., Ltd.]]; as polylactic acid, for example, Lacia [manufactured by Mitsui Chemicals, Inc.]]; Cell Green [manufactured by Daicel Chemical Industries, Ltd.]; Polybutylene succinate, for example, Bionore [manufactured by Showa Polymer Co., Ltd.]; Polyethylene succinate, for example, Lunare SE (manufactured by Nippon Shokubai Co., Ltd.)] Examples of polyvinyl alcohol include Poval [manufactured by Kuraray Co., Ltd.].

  The antistatic resin composition of the present invention contains at least one additive (C) selected from the group consisting of the additives (C1) to (C5) as necessary, as long as the effects of the present invention are not impaired. You may make it contain.

  The amount of the alkali metal or alkaline earth metal salt (C1) used is usually 10% or less based on the total weight of the thermoplastic resin (D) and the conductive resin composition (X). And preferably from 0.001 to 5%, more preferably from 0.01 to 4%, particularly preferably from 0.1 to 2%, most preferably from the viewpoint of giving a molded article having a good appearance without depositing on the surface of the molded article. Is 0.15 to 1%.

  The amount of the surfactant (C2) used is usually 10% or less based on the total weight of (D) and (X), preferably 0.001 to 5% from the viewpoint of the conductivity and water resistance of the molded product, Preferably it is 0.01 to 3%, Most preferably, it is 0.1 to 2.5%.

  The amount of the ionic liquid (C3) other than (A) is usually 10% or less based on the total weight of (D) and (X), preferably 0.001 from the viewpoint of the conductivity and mechanical properties of the molded product. -5%, more preferably 0.01-3%.

  The amount of the compatibilizing agent (C4) used is usually 20% or less based on the total weight of (D) and (X), preferably 0.01 to from the viewpoint of the conductivity of the molded product and the mechanical properties of the molded product 15%, more preferably 0.1 to 10%, particularly preferably 1 to 8%.

The total amount of other additives for resin (C5) used is usually 45% or less based on the total weight of (D) and (X), from the viewpoint of the additive effect of each additive and the mechanical properties of the molded product. Preferably it is 0.001 to 40%, more preferably 0.01 to 35%, particularly preferably 0.05 to 30%.
The amount of each additive used in (C5) is based on the total weight of (D) and (X) (C51), (C52), (C53), (C54), (C55), (C510) And (C512) is usually 10% or less, preferably 1 to 5%; (C57) is usually 20% or less, preferably 1 to 10%; (C56), (C58) and (C511) are usually 5% or less. , Preferably 0.1 to 3%; (C59) is usually 3% or less, preferably 0.05 to 1%.

The antistatic resin composition for molding according to the present invention is obtained by melt-kneading the conductive resin composition (X) and, if necessary, the additive (C) in the thermoplastic resin (D).
As a method of melt-kneading, a usual method is used. Generally, pellets or powdery polymers are mixed (blended) with an appropriate mixer such as a Henschel mixer and then melted with an extruder. The method of kneading (150-250 degreeC) and pelletizing is applicable.
There is no particular limitation on the order of addition of each component during kneading, for example,
(1) A method of melt-kneading (X) and (D) and, if necessary, (C) all together;
(2) A high concentration resin composition of the polymer type ionic liquid (A) and the block polymer (B) by melt-kneading a part of (X), part of (D), and part of (C) if necessary A method of preparing a product (masterbatch antistatic resin composition) and then adding the remaining (D) and, if necessary, the remaining (C) and melt-kneading. In the masterbatch antistatic resin composition in the method (2), the total content of (A) and (B) is preferably 50 to 90%, more preferably 55 to 80, based on the weight of (D). %.
Among these, the method (2) is a method called a master batch method or a master pellet method, and is preferable from the viewpoint of efficient dispersion of the (A) and (B) in the thermoplastic resin (D) in the present invention. Is the method.

  In the antistatic resin composition for molding of the present invention, the total content of (A) and (B) is preferably 1 to 50% from the viewpoint of antistatic properties and mechanical properties based on the weight of (D). More preferably, it is 5 to 40%.

Examples of the molding method of the resin composition of the present invention (conductive resin composition and antistatic resin composition for molding, the same shall apply hereinafter) include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, Examples thereof include blow molding, film molding (casting method, tenter method, inflation method, etc.), and the like can be molded by any method depending on the purpose.
The molded article comprising the resin composition of the present invention has excellent mechanical properties and permanent antistatic properties, and also has good paintability and printability, and is formed by applying and / or printing the molded 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 resin composition of the present invention can be added to a known paint or 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 resin composition of the present invention [conductive resin composition and antistatic resin composition (including master batch and molding)], and the same applies to known paints. The total ratio of (A) and (B) is preferably 5 to 60%, more preferably 5 to 60% from the viewpoint of antistatic properties and water resistance based on the solid content weight of a known paint. 50%, particularly preferably 5 to 40%.
The total ratio of (A) and (B) when a solvent is added to the resin composition of the present invention to form a paint is preferably from the viewpoint of antistatic properties and water resistance based on the solid content weight of the paint. It is 5 to 60%, more preferably 5 to 50%, particularly preferably 5 to 40%.

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 polymer type ionic liquid (A-1)>
Production Example 1
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 2700 parts of ion exchange water and 300 parts of 2-acrylimido-2-methylpropanesulfonic acid were charged and then heated to 100 ° C. under normal pressure. 3.5 parts of valeric acid was dropped in about 1 minute, polymerized for 3 hours, and further aged for 3 hours. Next, dehydration was performed, and after drying, poly-2-acrylamido-2-methylpropanesulfonic acid was obtained. The yield was 98% and Mn was 130,000.
Next, 250 parts of the obtained poly-2-acrylamido-2-methylpropanesulfonic acid was dissolved in 1644 parts of ion-exchanged water at room temperature, and 1-ethyl-3-methylimidazolium monomethyl carbonate (the synthesis method was disclosed in JP-A-2001-2001). 427 parts of a methanol solution (concentration 48%) in accordance with the method described in -316372. The reaction is carried out while generating carbon dioxide by the reaction, and after the generation of carbon dioxide is stopped, the solvent is removed at a temperature of 60 to 80 ° C. under a reduced pressure for about 5 hours. A certain poly (1-ethyl-3-methylimidazolium) 2-acrylamido-2-methylpropanesulfonate (A-1) was obtained. The yield was 95%.

<Production of polymer type ionic liquid (A-2)>
Production Example 2
300 parts of 5-sulfoisophthalic acid was dissolved in 500 parts of methanol, and 674 parts of methanol solution (concentration 48%) of 1-ethyl-3-methylimidazolium monomethyl carbonate was mixed. After completion of the reaction, 1-ethyl-3-methylimidazolium 5-sulfoisophthalate was obtained by removing all of the solvent and the like at a temperature of 60 to 80 ° C. under reduced pressure for about 5 hours. The yield was 95%.
Next, 200 parts of the obtained 1-ethyl-3-methylimidazolium 5-sulfoisophthalate, 59 parts of hexamethylenediamine, an antioxidant [trade name “Irganox 1010”, Ciba Geigy Co., Ltd.] Manufactured, the same applies hereinafter) 0.1 parts were charged, and after substitution with nitrogen, the mixture was heated and stirred at 220 ° C. for 4 hours under pressure and hermetically sealed, and both ends of Mn 1,400, acid value 80, which are polymer type ionic liquids, were carboxylated. A polyamide (A-2) having a group was obtained.

<Production of polymer type ionic liquid (A-3)>
Production Example 3
In a reaction vessel, 52.7 parts of EO2 molar adduct of 5-sulfoisophthalic acid, 31.5 parts of IPDI, and 0.1 part of a bismuth tri (2-ethylhexanoate) solution (2-ethylhexanoic acid 50% solution) were added. Charged and reacted at 80 ° C. for 6 hours. After allowing to cool, 27.7 parts of 1-ethyl-3-methylimidazolium monomethyl carbonate are mixed and reacted, and after completion of the reaction, all of the solvent and the like are removed at a temperature of 60 to 80 ° C. under reduced pressure for about 5 hours. As a result, 1-ethyl-3-methylimidazolium polyurethane (A-3), which is a polymer type ionic liquid, was obtained.

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

<Production of block polymer (B2-1)>
Production Example 5
In a stainless steel autoclave, polypropylene obtained by the thermal degradation method (Mn 2,500, density 0.89, 10.5 double bonds per 1,000 C, average number of double bonds per molecule 1) .90) 85 parts and maleic anhydride 15 parts 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 (b211-1). The acid value of (b211-1) was 39.8, and Mn was 2,800.

Production Example 6
In a stainless steel autoclave, 87 parts of (b211-1) and 13 parts of 12-aminododecanoic acid are charged, melted at 200 ° C., reacted at 200 ° C. for 2 hours and 10 mmHg or less, and acid-modified polypropylene (b2112-1 ) The acid value of (b2112-1) was 32.1, and Mn was 3,100.

Production Example 7
In a stainless steel autoclave, 51 parts of (b2112-1), 49 parts of polyethylene glycol (b2211-1) of Mn 3,300 (volume resistivity 1 × 10 ⁷ Ω · cm), 0.3 part of antioxidant and zinc acetate 0.5 parts was charged and polymerized for 4 hours at 230 ° C. under reduced pressure of 1 mmHg or less to obtain a viscous polymer. Thereafter, the same operation as in Production Example 4 was performed to obtain a block polymer (B2-1). The Mn of (B2-1) was 26,000.

Examples 1-24, Comparative Examples 1-14
In accordance with the formulation (parts) shown in Tables 1 and 2, A to C for the conductive resin composition, C, D and X for the antistatic resin were blended for 3 minutes with a Henschel mixer, and then a twin screw extruder with a vent. The resin composition was obtained by melt kneading at 240 ° C., 100 rpm, and a residence time of 5 minutes.

(Note) The symbols in the table are as follows.
C5-1: Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxy
Ciphenyl) propionate] methane C3-1: 1-ethyl-3-methylimidazolium tetrafluoroborate C3-2: 1-ethyl-3-methylimidazolium trifluoromethanesulfonylimide C2-1: sodium dodecylbenzenesulfonate C4-1 : Epoxidized polystyrene elastomer [trade name “Epofriend AT501”, manufactured by Daicel Chemical Industries, Ltd.]
D-1: Polypropylene [trade name “NOVATEC MA3H”, manufactured by Nippon Polypro Co., Ltd.]
D-2: Modified polyphenylene ether resin [trade name “Noryl V095”, manufactured by Nippon GE Plastics Co., Ltd.]

<Performance evaluation>
Using the injection molding machine [model number “PS40E5ASE”, manufactured by Nissei Plastic Industry Co., Ltd.], the resin composition obtained above was used at a predetermined cylinder temperature [(D-1) containing resin composition was 220 ° C., (D-2 ) Containing resin composition is 270 ° C.] and mold temperature [(D-1) containing resin composition is 50 ° C., (D-2) containing resin composition is 80 ° C.] to create a test piece, It was used for evaluation of tensile strength, tensile elongation at break, flexural modulus, surface resistivity, and surface resistivity after washing with water.
For these specimens, mechanical strength (tensile strength, tensile fracture elongation, flexural modulus), conductivity or antistatic properties (surface resistivity) and water resistance (surface resistivity after washing) based on the following test methods Value). The results are shown in Table 3.

(1) Tensile strength, tensile elongation at break compliant with JIS K7113.
(2) Flexural modulus Conforms to ASTM D790. Test piece (10 × 4 × 100 mm), distance between fulcrums 60 mm.

(3) Surface resistivity (Examples 1-12 and Comparative Examples 1-6)
Using a test piece (injection molding: 100 × 100 × 2 mm), using a resistivity meter [model number “Loresta GP, MCP-T600”, manufactured by Dia Instruments Co., Ltd.], in an atmosphere of 23 ° C. and humidity 50% RH Measured with
(4) Surface resistivity (Examples 13 to 24 and Comparative Examples 7 to 14)
Conforms to ASTM D257 (1984). Using a test piece (injection molding: 100 × 100 × 2 mm), measurement was performed in an atmosphere of 23 ° C. and humidity 50% RH with a super insulation meter [model number “DSM-8103”, manufactured by Toa Denpa Co., Ltd.].

(5) Surface resistivity after washing with water (Examples 1 to 12 and Comparative Examples 1 to 6)
Ion exchange water is poured to a depth of 3 cm in a polypropylene lidded container 30 cm long, 40 cm wide, and 5 cm high, and the temperature is adjusted to 25 ° C., and a test piece (100 × 100 × 2 mm) is submerged horizontally. After being kept for 24 hours, it is taken out and washed with 100 ml of deionized water and dried at 80 ° C. for 5 hours in a circulating air dryer. About the test piece after drying, it measured similarly to (3).
(6) Surface resistivity after washing with water (Examples 13 to 24 and Comparative Examples 7 to 14)
The test piece was washed and dried in the same manner as in (5) above, and the measurement was carried out in the same manner as in (4).

Since the conductive resin composition of the present invention has excellent conductivity, and a molded product formed by molding the composition has excellent conductivity and mechanical properties, various compositions for solid electrolytes for secondary batteries. It is extremely useful as a composition for various molding materials such as products, electronic components that require high antistatic properties, electronic component transport members, process control labels, floor materials for clean rooms, static elimination sheets, static elimination mats and wristbands. It is.
In addition, the antistatic resin composition of the present invention includes various types 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.). Charging of household appliances / OA equipment, housing equipment for office equipment, office equipment, various plastic containers such as IC trays, various packaging films, flooring sheets, artificial grass, mats, automobile parts, etc. It is extremely useful because it can be widely used as a composition for various molding materials that require prevention.

Claims (9)

Polymeric ionic liquid (A) comprising at least one onium cation group (a) and a polymer (b) having a counter anion group is converted into a polyether ester, a polyether amide, a polyether ester amide, and a polyolefin block. And at least one block polymer selected from the group consisting of block polymers having a structure in which hydrophilic polymer blocks having a volume resistivity of 1 × 10 ⁴ to 1 × 10 ¹¹ Ω · cm are alternately and repeatedly bonded ( A conductive resin composition (X), which is contained in B). The composition according to claim 1, wherein (b) is a polymer selected from the group consisting of an addition polymer, a polycondensate and a polyaddition. The composition according to claim 1 or 2, wherein the weight ratio of (A) to (B) is from 1/99 to 50/50. Further, at least one additive (C) selected from the group consisting of an alkali metal or alkaline earth metal salt, a surfactant, an ionic liquid other than (A), a compatibilizing agent, and other additives for resins. The composition according to any one of claims 1 to 3, which is contained. The composition (X) containing (A) and (B) according to any one of claims 1 to 4 is contained in a thermoplastic resin (D), and the total content of (A) and (B) is ( A master batch antistatic resin composition which is 50 to 90% based on the weight of D). The thermoplastic resin (D) is further added to the composition according to claim 5, and the total content of (A) and (B) is 1 to 50% based on the total weight of (D). Antistatic resin composition. Further, at least one additive (C) selected from the group consisting of an alkali metal or alkaline earth metal salt, a surfactant, an ionic liquid other than (A), a compatibilizing agent, and other additives for resins. The composition according to claim 6, which comprises A molded article formed by molding the composition according to any one of claims 1 to 4 or claims 6 to 7. A molded article obtained by coating and / or printing the molded article according to claim 8.