JP2015096595A - Antistatic agent and antistatic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic agent which has a light color and imparts excellent antistatic properties to a molded article, and to provide an antistatic resin composition containing the antistatic agent.SOLUTION: The antistatic agent contains: a block polymer having a hydrophobic polymer block and a hydrophilic polymer block as constituent units; an alkali inhibitor; and quaternary ammonium salt. The antistatic resin composition contains the antistatic agent and a thermoplastic resin. The molded article is obtained by molding the antistatic resin composition. Painted and/or printed matter is obtained by painting and/or printing the molded article.

Description

  The present invention relates to an antistatic agent and an antistatic resin composition. More specifically, the present invention relates to an antistatic agent that imparts excellent permanent antistatic properties to a molded product obtained by molding a thermoplastic resin composition, and an antistatic resin composition containing the same.

  Conventionally, as a method of imparting permanent antistatic property to a highly insulating thermoplastic resin, a method of kneading a polymer type antistatic agent such as polyether ester amide or polyether / polyolefin block polymer into the resin is known. (Patent Documents 1 and 2). Furthermore, in order to improve the antistatic performance, it has been proposed to use an ionic liquid or a specific surfactant (Patent Documents 3 and 4).

Japanese Patent Laid-Open No. 08-12755 JP 2001-278985 A JP 2004-217931 A JP 2010-196050 A

However, in Patent Documents 1 and 2, the antistatic performance is insufficient, and in Patent Documents 3 and 4, although the antistatic performance is high, the antistatic agent is affected by the ionic liquid and the specific surfactant used together. There is a problem that the product itself becomes yellow to brown, and further, the obtained molded product is yellowish, and improvement is demanded.
An object of the present invention is to provide an antistatic agent that is light in color and imparts an excellent antistatic property to a molded product, and an antistatic resin composition containing the same.

  The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention comprises a block polymer (A), an alkali inhibitor (B), and a quaternary ammonium salt (C) having a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as structural units. An antistatic agent (Z) containing; an antistatic resin composition containing (Z) and a thermoplastic resin (E); a molded article formed by molding the composition.

The antistatic agent and antistatic resin composition of the present invention have the following effects.
(1) The antistatic agent of the present invention is light in color and can impart excellent antistatic properties to a molded product.
(2) A molded product obtained by molding the antistatic resin composition of the present invention is excellent in appearance.

  The present invention contains a block polymer (A) having a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as structural units, an alkali adsorbent (B) and a quaternary ammonium salt (C). An antistatic agent (Z).

[Hydrophobic polymer (a)]
The hydrophobic polymer (a) in the present invention means a polymer having a volume resistivity value exceeding 1 × 10 ¹¹ Ω · cm. Specifically, polyamide (a1), polyolefin (a2), polyamideimide (a3), etc. are mentioned, These may use 2 or more types together. Among (a), polyamide (a1) and polyolefin (a2) are preferable from the viewpoint of antistatic properties.
In addition, the volume resistivity value in this invention is a numerical value obtained by measuring in 23 degreeC and 50% RH atmosphere based on ASTMD257 (2007).

  Examples of the polyamide (a1) include those obtained by ring-opening polymerization or polycondensation of an amide-forming monomer (α), and polycondensates of diamine (β) and dicarboxylic acid (γ).

Examples of the amide-forming monomer (α) include lactam (α1-1) and aminocarboxylic acid (α1-2).
Examples of the lactam (α1-1) include lactams having 4 to 20 carbon atoms (caprolactam, enantolactam, laurolactam, undecanolactam, and the like).
As the aminocarboxylic acid (α1-2), an aminocarboxylic acid having 2 to 20 carbon atoms (ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and a mixture thereof).

  Examples of the diamine (β) include aliphatic diamines having 2 to 20 carbon atoms (ethylenediamine, propylenediamine, hexamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, and 1,20-eicosane. Diamines, etc.), alicyclic diamines having 5 to 20 carbon atoms [1,3- or 1,4-cyclohexanediamine, isophoronediamine, 4,4′-diaminocyclohexylmethane and 2,2-bis (4-aminocyclohexyl) Propane and the like], aromatic diamines having 6 to 20 carbon atoms [p-phenylenediamine, 2,4- or 2,6-toluylenediamine and 2,2-bis (4,4′-diaminophenyl) propane, p- Or m-xylylenediamine, bis (aminoethyl) benzene, bis (aminopropyl) ben Emissions and bis (aminobutyl) benzene, etc.] and the like.

  Examples of the dicarboxylic acid (γ) include aliphatic dicarboxylic acids having 2 to 20 carbon atoms (succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid. , Fumaric acid and itaconic acid), aromatic dicarboxylic acids having 8 to 20 carbon atoms (phthalic acid, 2,6- or 2,7-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid) Acids, tolylene dicarboxylic acid, xylylene dicarboxylic acid and 5-sulfoisophthalic acid alkali metal salts, etc.), alicyclic dicarboxylic acids having 5 to 20 carbon atoms (cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid) Acid, dicyclohexyl-4,4′-dicarboxylic acid, camphoric acid, etc.) .

  Specific examples of the polyamide (a1) include nylon 6,6, nylon 6,9, nylon 6,12, nylon 6, nylon 11, nylon 12, nylon 4,6, and a copolymer of nylon 6 and nylon 6,6. , A copolymer of nylon 6 and nylon 12, and a copolymer of nylon 6 and nylon 6,6 and nylon 12.

Examples of the polyolefin (a2) include a polyolefin (a2-1) having carboxyl groups at both ends of the polymer, a polyolefin (a2-2) having hydroxyl groups at both ends of the polymer, and a polyolefin (a2) having amino groups at both ends of the polymer. -3) and polyolefin (a2-4) having an isocyanate group at both ends of the polymer, polyolefin (a2-5) having a carboxyl group at one end of the polymer, and polyolefin (a2-6) having a hydroxyl group at one end of the polymer And polyolefin (a2-7) having an amino group at one end of the polymer and polyolefin (a2-8) having an isocyanate group at one end of the polymer. Among these, (a2-1) and (a2-5) having a carboxyl group at the terminal are preferable.
In addition, the terminal in this invention means the terminal part which the longest repeating structure of the monomer unit which comprises a polymer interrupts. Moreover, both ends mean both ends in the main chain of the polymer, and one end means any one end in the main chain of the polymer.

  As (a2-1), a polyolefin (a2) whose main component (preferably the content is 50% by weight or more, more preferably 75% by weight or more, and particularly preferably 80 to 100% by weight) is a polyolefin that can be modified at both ends. -01) having carboxyl groups introduced at both ends thereof; (a2-2) having (a2-01) having hydroxyl groups introduced at both ends; (a2-3) having (a2-01) As for (a2-4), those obtained by introducing isocyanate groups at both ends of (a2-01) can be used.

  As (a2-5) to (a2-8), in place of the polyolefin (a2-01), a polyolefin whose one end can be modified is a main component (preferably a content of 50% by weight or more, more preferably 75% by weight). As mentioned above, what introduce | transduced respectively the carboxyl group, a hydroxyl group, an amino group, or an isocyanate group can be used for the one end of the polyolefin (a2-02) made into 80 weight% especially preferably.

In the polyolefin (a2-01) whose main component is a polyolefin whose both ends can be modified, one or two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10 carbon atoms) are used. (Co) polymerization of the mixture [(co) polymerization means polymerization or copolymerization. The same applies below. ] Obtained by (polymerization method) and degraded polyolefin {high molecular weight [preferably number average molecular weight (hereinafter abbreviated as Mn) 50,000 to 150,000] polyolefin, mechanical, thermal or chemical (Degraded method)} is included.
Of these, degraded polyolefin is preferable from the viewpoint of ease of modification and availability when introducing a carboxyl group, a hydroxyl group, an amino group, or an isocyanate group, and heat is more preferable. Degraded polyolefin. According to the thermal degradation, a low molecular weight polyolefin having an average number of terminal double bonds per molecule of 1.5 to 2 can be easily obtained as described later, and the low molecular weight polyolefin has a carboxyl group, a hydroxyl group, and an amino group. Alternatively, it is easy to modify by introducing an isocyanate group or the like.

Mn of the polymer in the present invention can be measured under the following conditions using gel permeation chromatography (GPC).
Apparatus (example): “HLC-8120” [manufactured by Tosoh Corporation]
Column (example): “TSKgelGMHXL” [manufactured by Tosoh Corporation] (two)
"TSKgelMultiporeHXL-M"
[Tosoh Co., Ltd.] (1)
Sample solution: 0.3 wt% orthodichlorobenzene solution Solution injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 135 ° C
Detection device: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE)
12 points (molecular weight: 500, 1,050, 2,800, 5,970,
9, 100, 18, 100, 37, 900, 96, 400,
190,000, 355,000, 1,090,000,
2,890,000) [manufactured by Tosoh Corporation]

  The heat-degraded polyolefin is not particularly limited, and is obtained by heating a high molecular weight polyolefin in an inert gas (at 300 to 450 ° C. for 0.5 to 10 hours, for example, JP-A-3-62804). And those obtained by heat degradation by heating in air.

The high molecular weight polyolefin used in the thermal degradation method is a (co) polymer of one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10). [Mn is preferably 12,000 to 100,000, more preferably 15,000 to 70,000. The melt flow rate (hereinafter abbreviated as MFR. The unit is g / 10 min) is preferably 0.5 to 150, more preferably 1 to 100. ] Etc. are mentioned. Here, MFR is a numerical value representing the melt viscosity of the resin, and the larger the numerical value, the lower the melt viscosity. For the measurement of MFR, an extrusion plastometer defined in JIS K6760 is used, and the measurement method conforms to the method defined in JIS K7210 (1999). For example, in the case of polypropylene, it is measured under conditions of 230 ° C. and a load of 2.16 kgf.
Examples of the olefin having 2 to 30 carbon atoms include α-olefins having 2 to 30 carbon atoms and dienes having 4 to 30 carbon atoms.
Examples of the α-olefin having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-icocene and 1-icosene. Tetracocene and the like can be mentioned.
Examples of the diene having 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene and 1,11-dodecadiene.
Among the olefins having 2 to 30 carbon atoms, ethylene, propylene, α-olefins having 4 to 12 carbon atoms, butadiene, isoprene and a mixture thereof are preferable from the viewpoint of molecular weight control, and ethylene, Propylene, C 4-10 α-olefin, butadiene and mixtures thereof, particularly preferred are ethylene, propylene, butadiene and mixtures thereof.

Mn of the polyolefin (a2-01) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 200 from the viewpoint of the antistatic property of the molded product described later. 6,000.
The number of terminal double bonds in (a2-01) is preferably 1-40 per 1,000 carbon atoms, more preferably 2-30, particularly preferably from the viewpoint of antistatic properties of the molded product. Is 4-20.

  (A2-01) The average number of terminal double bonds per molecule is preferably from the viewpoint of the ease of taking a repeating structure in the molecule, the antistatic property of the molded product, and the thermoplasticity of the block polymer (A) described later. Is 1.1 to 5, more preferably 1.3 to 3, particularly preferably 1.5 to 2.5, and most preferably 1.8 to 2.2.

  When a method for obtaining a low molecular weight polyolefin by a thermal degradation method is used, (a2-01) in which the average number of terminal double bonds per molecule is 1.5 to 2 (a2-01) in the range of 800 to 6,000 Mn. [Katsuhide Murata, Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].

Polyolefin (a2-02) whose main component is a polyolefin whose one end can be modified can be obtained in the same manner as (a2-01), and Mn in (a2-02) is an antistatic property of a molded product to be described later. From the viewpoint of properties, it is preferably 2,000 to 50,000, more preferably 2,500 to 30,000, and particularly preferably 3,000 to 20,000.
The number of double bonds per 1,000 carbon atoms in (a2-02) is preferably 0.3 to 20 from the viewpoint of antistatic properties of the molded product and molecular weight control of the block polymer (A). More preferably, it is 0.5-15, Most preferably, it is 0.7-10.

(A2-02) The average number of double bonds per molecule is preferably from the viewpoint of the ease of taking a repeating structure in the molecule, the antistatic property of the molded product, and the thermoplasticity of the block polymer (A) described later. It is 0.5 to 1.4, more preferably 0.6 to 1.3, particularly preferably 0.7 to 1.2, and most preferably 0.8 to 1.1.
Of the (a2-02), from the viewpoint of ease of modification, a low molecular weight polyolefin obtained by a thermal degradation method is preferred, and a Mn obtained by the thermal degradation method is more preferably 3. , 20,000 to 20,000 polyethylene and / or polypropylene.
When a method for obtaining a low molecular weight polyolefin by a thermal degradation method is used, the average number of terminal double bonds per molecule is 1 to 1.5 (a2−) with Mn in the range of 6,000 to 30,000. 02) is obtained.
Since the low molecular weight polyolefin obtained by the thermal degradation method has the average number of the terminal double bonds, it can be easily modified by introducing a carboxyl group, a hydroxyl group, an amino group or an isocyanate group.

  In addition, (a2-01) and (a2-02) are usually obtained as a mixture thereof, but the mixture may be used as it is, or may be used after purification and separation. Among these, a mixture is preferable from the viewpoint of production cost and the like.

  Hereinafter, (a2-1) to (a2-4) having a carboxyl group, a hydroxyl group, an amino group or an isocyanate group at both ends of the polyolefin (a2-01) will be described, but at one end of the polyolefin (a2-02) (A2-5) to (a2-8) having these groups are the same as (a2-1) to (a2-4), except that (a2-01) is replaced with (a2-02). Can be obtained.

  The polyolefin (a2-1) having a carboxyl group at both ends of the polymer includes (a2-01) having an α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, its alkyl) (C1-C4) means an ester or its anhydride. The same shall apply hereinafter.) Polyolefins (a2-1-1) and (a2-1-1) having a structure modified with lactam or aminocarboxylic acid Polyolefin (a2-1-2) having a modified structure (a2-1-2), polyolefin (a2-1-3) having a structure modified by oxidation or hydroformylation (a2-1-01), and lactam or (a2-1-3) Polyolefin (a2-1-4) having a structure secondarily modified with aminocarboxylic acid and a mixture of two or more of these can be used.

(A2-1-1) can be obtained by modifying (a2-01) with an α, β-unsaturated carboxylic acid (anhydride).
Examples of α, β-unsaturated carboxylic acids (anhydrides) used for modification include monocarboxylic acids, dicarboxylic acids, mono- or dicarboxylic acid alkyl (C 1-4) esters, and mono- or dicarboxylic acid anhydrides. Specifically, (meth) acrylic acid [(meth) acrylic acid means acrylic acid or methacrylic acid. The same applies below. ], Methyl (meth) acrylate, butyl (meth) acrylate, maleic acid (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride), diethyl itaconate and citraconic acid (anhydride) It is done.
Of these, dicarboxylic acid, mono- or dicarboxylic acid alkyl ester, and mono- or dicarboxylic acid anhydride are preferable from the viewpoint of ease of modification, and maleic acid (anhydride) and fumaric acid are more preferable. Particularly preferred is maleic acid (anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used for modification is based on the weight of the polyolefin (a2-01), ease of repetitive structure in the molecule, antistatic property of the molded product, and later described. From the viewpoint of dispersibility of the block polymer (A) in the antistatic resin composition, it is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight. is there.
The modification with α, β-unsaturated carboxylic acid (anhydride) is carried out by, for example, converting the terminal double bond of (a2-01) to α, β-unsaturated carboxylic acid by either the solution method or the melting method. The reaction can be carried out by subjecting (anhydride) to an addition reaction (ene reaction), and the reaction temperature is preferably 170 to 230 ° C.

(A2-1-2) can be obtained by secondary modification of (a2-1-1) with lactam or aminocarboxylic acid.
Examples of the lactam used for the secondary modification include a lactam having 6 to 12 carbon atoms (preferably 6 to 8 and more preferably 6). Is mentioned.
Examples of the aminocarboxylic acid include aminocarboxylic acids having 2 to 12 carbon atoms (preferably 4 to 12 and more preferably 6 to 12), and specifically include amino acids (glycine, alanine, valine, leucine, isoleucine). And phenylalanine), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Of the lactams and aminocarboxylic acids, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and caprolactam, laurolactam, Omega-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, particularly preferred are caprolactam and 12-aminododecanoic acid.

  The amount of lactam or aminocarboxylic acid used for secondary modification is based on the weight of the substance to be modified (a2-1-1), ease of repetitive structure in the molecule, antistatic property of the molded product and block polymer From the viewpoint of the thermoplasticity of (A), it is preferably 0.5 to 200% by weight, more preferably 1 to 150% by weight, and particularly preferably 2 to 100% by weight.

(A2-1-3) can be obtained by introducing a carboxyl group by a method of oxidizing (a2-01) with oxygen and / or ozone (oxidation method) or hydroformylation by an oxo method.
The introduction of the carboxyl group by the oxidation method can be performed by a known method, for example, the method described in US Pat. No. 3,692,877. Introduction of the carbonyl group by hydroformylation can be carried out by various methods including known methods such as Macromolecules, Vol. 31, 5943 page.
(A2-1-4) can be obtained by secondary modification of (a2-1-3) with lactam or aminocarboxylic acid.
Examples of the lactam and aminocarboxylic acid include those exemplified as the lactam and aminocarboxylic acid used for the secondary modification of the above (a2-1-1), and preferred ranges and use amounts thereof are also the same. .

Mn of (a2-1) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. Preferably it is 2,500-10,000.
The acid value of (a2-1) is preferably 4 to 280 mgKOH / g, more preferably 4 to 100 mgK, from the viewpoint of reactivity with (b) and the thermoplasticity of the block polymer (A).
OH / g, particularly preferably 5 to 50 mg KOH / g.

As the polyolefin (a2-2) having a hydroxyl group at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying the polyolefin (a2-1) having the carboxyl group at both ends of the polymer with an amine having a hydroxyl group, and these A mixture of two or more can be used.
Examples of the amine having a hydroxyl group that can be used for modification include amines having a hydroxyl group having 2 to 10 carbon atoms, and specifically include 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-amino. Examples include butanol, 5-aminopentanol, 6-aminohexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol.
Of these, amines having a hydroxyl group having 2 to 6 carbon atoms (2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-amino are preferable from the viewpoint of ease of modification. Hexanol and the like), 2-aminoethanol and 4-aminobutanol are more preferable, and 2-aminoethanol is particularly preferable.

The amount of the amine having a hydroxyl group used for modification is based on the weight of the object to be modified (a2-1), easy to take a repeating structure in the molecule, antistatic property of the molded product, and an antistatic resin composition described later. From the viewpoint of the dispersibility of the block polymer (A) and the mechanical properties of the molded product, it is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, particularly preferably 2 to 30% by weight. It is.
Mn of (a2-2) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. Preferably it is 2,500-10,000.
The hydroxyl value of (a2-2) is preferably 4 to 280 mgKOH / g, more preferably 4 to 100 mgKOH / g, particularly from the viewpoint of the reactivity with (b) and the thermoplasticity of the block polymer (A). Preferably it is 5-50 mgKOH / g.

Polyolefins having amino groups at both ends of the polymer (a2-3) include polyolefins having amino groups obtained by modifying the polyolefin (a2-1) having carboxyl groups at both ends of the polymer with diamine (Q1) and these A mixture of two or more of these can be used.
As diamine (Q1), C2-C12 diamine etc. can be used, Specifically, ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, etc. are mentioned.
Among these, diamines having 2 to 8 carbon atoms (ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, etc.) are preferable from the viewpoint of ease of modification, and ethylenediamine and hexamethylenediamine are more preferable. Particularly preferred is ethylenediamine.

The amount of (Q1) used for modification of (a2-1) is the ease of taking a repeating structure in the molecule, the antistatic property of the molded product, and the dispersibility of the block polymer (A) in the antistatic resin composition, From the viewpoint of mechanical properties of the molded product, it is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, and particularly preferably 2 to 30% by weight based on the weight of (a2-1). is there.
The modification of (a2-1) by (Q1) is preferably 0.5 to 1,000% by weight based on the weight of (a2-1) from the viewpoint of preventing polyamide (imide) formation, It is preferable to use 1 to 500% by weight, particularly preferably 2 to 300% by weight of (Q1), and then remove unreacted (Q1) at 120 to 230 ° C. under reduced pressure.

Mn of (a2-3) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. Preferably it is 2,500-10,000.
The amine value of (a2-3) is preferably 4 to 280 mgKOH / g, more preferably 4 to 100 mgKOH / g, particularly from the viewpoint of the reactivity with (b) and the thermoplasticity of the block polymer (A). Preferably it is 5-50 mgKOH / g.

As the polyolefin (a2-4) having an isocyanate group at both ends, a polyolefin having an isocyanate group obtained by modifying (a2-2) with poly (2-3 or more) isocyanate (hereinafter abbreviated as PI) and these The mixture of 2 or more types of these is mentioned.
PI includes aromatic PI having 6 to 20 carbon atoms (excluding carbon atoms in the NCO group; the same applies hereinafter), aliphatic PI having 2 to 18 carbon atoms, alicyclic PI having 4 to 15 carbon atoms, carbon Included are araliphatic PIs of several 8-15, modified products of these PIs, and mixtures of two or more thereof.

  As aromatic PI, 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane and 1, Examples include 5-naphthylene diisocyanate.

  Aliphatic PIs include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and the like.

  Alicyclic PI includes isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) Examples include -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the araliphatic PI include m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).

Examples of modified PI include urethane-modified, urea-modified, carbodiimide-modified, and uretdione-modified.
Among PIs, TDI, MDI and HDI are preferable, and HDI is more preferable.

The reaction between PI and (a2-2) can be carried out in the same manner as in a normal urethanization reaction.
The equivalent ratio (NCO / OH) of PI and (a2-2) is preferably 1.8 / 1 to 3/1, and more preferably 2/1.
In order to accelerate the urethanization reaction, a catalyst usually used in the urethanization reaction may be used if necessary. Catalysts include metal catalysts {tin catalysts [dibutyltin dilaurate and stannous octoate, etc.], lead catalysts [lead 2-ethylhexanoate, lead octenoate, etc.], other metal catalysts [metal naphthenate (cobalt naphthenate) Etc.) and phenylmercurypropionate etc.}; amine catalysts {triethylenediamine, diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7 etc.], dialkylaminoalkylamines (dimethylaminoethylamine and Dimethylaminooctylamine etc.), heterocyclic aminoalkylamine [2- (1-aziridinyl) ethylamine and 4- (1-piperidinyl) -2-hexylamine etc.] carbonate or organic acid (formic acid etc.) salt, N Methyl or ethylmorpholine, triethylamine and diethyl or dimethyl Ethanolamine}; and use of two or more types of system thereof.
The amount of the catalyst used is preferably 3% by weight or less, preferably 0.001 to 2% by weight, based on the total weight of PI and (a2-2).

  Mn of (a2-4) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. Preferably it is 2,500-10,000.

  Examples of the polyamideimide (a3) include the amide-forming monomer (α), and a trivalent or tetravalent aromatic polycarboxylic acid that can form at least one imide ring with (α) or an anhydride thereof (δ). Are included as a constituent monomer, and mixtures thereof.

  (Δ) is a trivalent carboxylic acid [monocyclic trivalent carboxylic acid (such as trimellitic acid), polycyclic trivalent carboxylic acid (1,2,5- or 2,6,7-naphthalene tricarboxylic acid, 3, 3 ′, 4-biphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tricarboxylic acid, diphenylsulfone-3,3 ′, 4-tricarboxylic acid and diphenylether-3,3 ′, 4-tricarboxylic acid) and the like Anhydrides] and tetravalent carboxylic acids [monocyclic tetravalent carboxylic acids (pyromellitic acid, etc.), polycyclic tetravalent carboxylic acids (biphenyl-2,2 ', 3,3'-tetracarboxylic acid, benzophenone-2,2 ', 3,3'-tetracarboxylic acid, diphenylsulfone-2,2', 3,3'-tetracarboxylic acid and diphenyl ether-2,2 ', 3,3'-tetracarboxylic acid, etc.), and These anhydrides] and the like.

As a method for producing the polyamideimide (a3), as in the case of the polyamide (a1), one or more selected from the diamine (β) and the dicarboxylic acid (γ) are used as molecular weight regulators. And a method of ring-opening polymerization or polycondensation of the amidimide-forming monomer in the presence thereof.
The amount used of the molecular weight modifier is preferably 2 to 80% by weight, more preferably 4%, from the viewpoint of antistatic properties and heat resistance of the molded product, based on the total weight of the amidoimide-forming monomer and the molecular weight modifier. ~ 75 wt%.

  Mn in (a3) is preferably 200 to 5,000, more preferably 500 to 4,000, from the viewpoint of moldability and production of an antistatic agent.

[Hydrophilic polymer (b)]
The hydrophilic polymer (b) in the present invention means a polymer having a volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm.
The volume resistivity value of (b) is preferably 1 × 10 ⁶ to 1 × 10 ⁹ Ω · cm, and more preferably 1 × 10 ⁶ to 1 × 10 ⁸ Ω · cm. Those having a volume resistivity of less than 1 × 10 ⁵ Ω · cm are substantially difficult to obtain, and if it exceeds 1 × 10 ¹¹ Ω · cm, the antistatic property of the molded product described later decreases.

  Examples of the hydrophilic polymer (b) include hydrophilic polymers described in Japanese Patent No. 3488163. Specifically, the polyether (b1), the polyether-containing hydrophilic polymer (b2), and the cationic polymer (b3). And an anionic polymer (b4).

Examples of the polyether (b1) include polyether diol (b1-1), polyether diamine (b1-2), and modified products (b1-3) thereof.
Examples of the polyether diol (b1-1) include those obtained by addition reaction of alkylene oxide (hereinafter abbreviated as AO) to the diol (b0). Specifically, the polyether diol (b1-1) is represented by the general formula (1). What is done.

H— (OR ¹ ) _m —O—E ¹ —O— (R ² O) _n —H (1)

E ¹ in the general formula (1) is a residue obtained by removing all hydroxyl groups from the diol (b0).
The diol (b0) includes an aliphatic dihydric alcohol having 2 to 12 carbon atoms, an alicyclic dihydric alcohol having 5 to 12 carbon atoms, an aromatic dihydric alcohol having 6 to 18 carbon atoms, and a tertiary amino group-containing diol. Etc.
Examples of the aliphatic dihydric alcohol having 2 to 12 carbon atoms include ethylene glycol (hereinafter abbreviated as EG), 1,2-propylene glycol (hereinafter abbreviated as PG), 1,4-butanediol (hereinafter referred to as 1, 4-BD), 1,6-hexanediol (hereinafter abbreviated as 1,6-HD), neopentyl glycol (hereinafter abbreviated as NPG), and 1,12-dodecanediol.
Examples of the alicyclic dihydric alcohol having 5 to 12 carbon atoms include 1,4-di (hydroxymethyl) cyclohexane and 1,5-di (hydroxymethyl) cycloheptane.
Examples of aromatic dihydric alcohols having 6 to 18 carbon atoms include monocyclic aromatic dihydric alcohols (xylylene diol, hydroquinone, catechol, resorcin, urushiol, etc.) and polycyclic aromatic dihydric alcohols (bisphenol A, bisphenol F). Bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyldihydroxynaphthalene, binaphthol, and the like).
The tertiary amino group-containing diol includes aliphatic or alicyclic primary amines having 1 to 12 carbon atoms (methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, pentylamine, isopentylamine. Bishydroxyalkylated products such as cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine and dodecylamine) and aromatic primary amines having 6 to 12 carbon atoms (such as aniline and benzylamine) Bishydroxyalkylated products can be mentioned.
Of these, preferred are aliphatic dihydric alcohols having 2 to 12 carbon atoms and aromatic dihydric alcohols having 6 to 18 carbon atoms, and more preferred is EG from the viewpoint of reactivity with bishydroxyalkylated products. And bisphenol A.

R ¹ and R ² in the general formula (1) are each independently an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include ethylene group, 1,2- or 1,3-propylene group and 1,2-, 1,3-, 1,4- or 2,3-butylene group. It is done.
M and n in General formula (1) are the numbers of 1-300 each independently, Preferably it is 2-250, More preferably, it is 10-100.
In the general formula (1), when m and n are each 2 or more, R ¹ and R ² may be the same or different, and the (OR ¹ ) _m and (R ² O) _n portions are random bonds or block bonds. But you can.

The polyether diol (b1-1) can be produced by adding AO to the diol (b0).
As AO, C2-C4 AO [ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide (hereinafter abbreviated as PO), 1,2-, 1, 3-, 1,4- or 2,3-butylene oxide (hereinafter abbreviated as BO) and a combination system of two or more of these may be used. -Olefin oxide, styrene oxide and epihalohydrin (such as epichlorohydrin) can be used in a small proportion (30 wt% or less based on the total weight of AO).
When two or more kinds of AO are used in combination, the bond form may be either random bond or block bond. Preferred as AO is EO alone or a combination of EO and another AO.

The addition reaction of AO can be performed by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst.
The content of (OR ¹ ) _m and (R ² O) _n based on the weight of the polyether diol (b1-1) represented by the general formula (1) is preferably 5 to 99.8% by weight. More preferably, it is 8 to 99.6% by weight, particularly preferably 10 to 98% by weight.
The content of the oxyethylene group based on the weight of (OR ¹ ) _m and (R ² O) _{n in} the general formula (1) is preferably 5 to 100% by weight, more preferably 10 to 100% by weight, particularly Preferably it is 50-100 weight%, Most preferably, it is 60-100 weight%.

Examples of the polyether diamine (b1-2) include those represented by the general formula (2).

H ₂ N—R ³ — (OR ⁴ ) _p —O—E ² —O— (R ⁵ O) _q —R ⁶ —NH ₂ (2)

E ² in the general formula (2) is a residue obtained by removing all hydroxyl groups from the diol (b0). Examples of the diol (b0) are the same as those described above.
R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula (2) are each independently an alkylene group having 2 to 4 carbon atoms. The alkylene group having 2 to 4 carbon atoms, the general formula (1) the same as those exemplified as R ¹ and R ² can be mentioned in the preferred range is also the same.
P and q in General formula (2) are the numbers of 1-300 each independently, Preferably it is 2-250, More preferably, it is 10-100.
R ⁴ and R ⁵ in the general formula (2) when p and q are each 2 or more may be the same or different, and the (OR ⁴ ) _p and (R ⁵ O) _q moieties are random bonds or block bonds. But you can.

  The polyether diamine (b1-2) can be obtained by converting all the hydroxyl groups of the polyether diol (b1-1) into alkylamino groups. For example, it can be produced by reacting (b1-1) with acrylonitrile and hydrogenating the obtained cyanoethylated product.

Modified products (b1-3) include (b1-1) or (b1-2) aminocarboxylic acid modified products (terminal amino groups), isocyanate modified products (terminal isocyanate groups) and epoxy modified products (terminal epoxy groups). Etc.
The aminocarboxylic acid-modified product can be obtained by reacting (b1-1) or (b1-2) with aminocarboxylic acid or lactam.
The isocyanate-modified product can be obtained by reacting (b1-1) or (b1-2) with polyisocyanate or reacting (b1-2) with phosgene.
The epoxy-modified product is obtained by reacting (b1-1) or (b1-2) with diepoxide (epoxy resins such as diglycidyl ether, diglycidyl ester and alicyclic diepoxide: epoxy equivalents 85 to 600). It can be obtained by reacting b1-1) with epihalohydrin (such as epichlorohydrin).

  Mn of the polyether (b1) is preferably 150 to 20,000, more preferably 300 to 18,000, particularly preferably 1, from the viewpoint of heat resistance and reactivity with the hydrophobic polymer (a). 000 to 15,000, most preferably 1,200 to 8,000.

  As the polyether-containing hydrophilic polymer (b2), polyether ester amide (b2-1) having a segment of polyether diol (b1-1), polyether amide imide having a segment of (b1-1) (b2- 2), polyether ester (b2-3) having a segment of (b1-1), polyether amide (b2-4) having a segment of polyetherdiamine (b1-2) and (b1-1) or (b1 -2) polyether urethane (b2-5).

The polyether ester amide (b2-1) is composed of a polyamide (a1 ′) having a carboxyl group at both ends of the polyamide (a1) and a polyether diol (b1-1).
Examples of (a1 ′) include a ring-opening polymer of the lactam (α1-1), a polycondensate of the aminocarboxylic acid (α1-2), and a polyamide of the diamine (β) and a dicarboxylic acid (γ). Is mentioned.
Of (a1 ′), from the viewpoint of antistatic properties, a ring-opening polymer of caprolactam, a polycondensate of 12-aminododecanoic acid, and a polyamide of adipic acid and hexamethylenediamine are more preferable. Is a ring-opening polymer of caprolactam.

The polyetheramide imide (b2-2) is composed of a polyamideimide (a3) having at least one imide ring and a polyether diol (b1-1).
As (a3), a polymer composed of lactam (α1-1) and the above trivalent or tetravalent aromatic polycarboxylic acid (δ) capable of forming at least one imide ring, aminocarboxylic acid ( Examples thereof include a polymer composed of α1-2) and (δ), a polymer composed of polyamide (a1 ′) and (δ), and a mixture thereof.

Examples of the polyether ester (b2-3) include those composed of polyester (Q) and polyether diol (b1-1).
Examples of (Q) include polyesters of dicarboxylic acid (γ) and diol (b0).
Examples of the polyether amide (b2-4) include those composed of polyamide (a1) and polyether diamine (a212).
As polyether urethane (b2-5), diisocyanate in the PI, polyether diol (b1-1) or polyether diamine (b1-2) and, if necessary, chain extender [the diol (b0) and diamine (Β) etc.].

From the viewpoint of moldability, the content of the polyether (b1) segment in the polyether-containing hydrophilic polymer (b2) is preferably 30 to 80% by weight, more preferably 40 to 40%, based on the weight of (b2). 70% by weight.
The content of the oxyethylene group in (b2) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight, based on the weight of (b2), from the viewpoint of antistatic properties and moldability. .
The lower limit of Mn in (b2) is preferably 800 from the viewpoint of heat resistance, and more preferably 1,000. The upper limit of Mn in (b2) is preferably 50,000, more preferably 30,000, from the viewpoint of reactivity with the hydrophobic polymer (a).

Examples of the cationic polymer (b3) include a polymer having a cationic group separated by a nonionic molecular chain in the molecule.
The nonionic molecular chain includes 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 siloxy bond. And a divalent hydrocarbon group having one or more groups selected from the above, and a hydrocarbon group having a heterocyclic structure having a nitrogen atom or an oxygen atom.
Among the nonionic molecular chains, a divalent hydrocarbon group and a divalent hydrocarbon group having an ether bond are preferable.
Examples of the cationic group include a group having a quaternary ammonium salt or a phosphonium salt. Examples of counter anions that form quaternary ammonium salts or phosphonium salts include super strong acid anions and other anions.
Examples of the super strong acid anion include an anion of a super strong acid (such as tetrafluoroboric acid and hexafluorophosphoric acid) derived from a combination of a protonic acid and a Lewis acid, and an anion such as trifluoromethanesulfonic acid.
Other anions include halogen ions (F ⁻ , Cl ⁻ , Br ⁻ and I ^−, etc.), OH ⁻ , PO ₃ ⁻ , CH ₃ OSO ₄ ⁻ , C ₂ H ₅ OSO ₄ ⁻ , ClO ₄ ^{− and the} like. Can be mentioned.
Examples of the protonic acid that induces a super strong acid include hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide.
Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, and tantalum pentafluoride.
(B3) The number of cationic groups in one molecule is preferably 2 to 80, and more preferably 3 to 60.

  Specific examples of (b3) include cationic polymers described in JP-A No. 2001-278985.

  Mn of (b3) is preferably 500 to 20,000, more preferably 1,000 to 15,000, and particularly preferably 1 from the viewpoint of antistatic properties and reactivity with the hydrophobic polymer (a). , 200-8,000.

The anionic polymer (b4) comprises a dicarboxylic acid (γ ′) having a sulfonyl group and a diol (b0) or a polyether (b1) as essential constituent units, and 2 to 80, preferably 3 to A polymer having 60 sulfonyl groups.
Examples of (γ ′) include those obtained by introducing a sulfonyl group into the dicarboxylic acid (γ), and only an aromatic dicarboxylic acid having a sulfonyl group, an aliphatic dicarboxylic acid having a sulfonyl group, and a sulfonyl group become a salt. And aromatic dicarboxylic acids or aliphatic dicarboxylic acids having a sulfonyl group.

Examples of the aromatic dicarboxylic acid having a sulfonyl group include 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid, and ester-forming derivatives thereof [alkyl (C1-C4) esters (such as methyl ester and ethyl ester) and acid anhydrides].
Examples of the aliphatic dicarboxylic acid having a sulfonyl group include sulfosuccinic acid and ester-forming derivatives thereof [alkyl (carbon number 1 to 4) ester (such as methyl ester and ethyl ester) and acid anhydrides].
Examples of the salt that forms an aromatic dicarboxylic acid or aliphatic dicarboxylic acid having a sulfonyl group in which only the sulfonyl group is converted to a salt include alkali metal (lithium, sodium, potassium, etc.) salts, alkaline earth metals (magnesium, calcium, etc.) Amines of salts, ammonium salts, amines having alkyl (2-4 carbon atoms) or hydroxyalkyl (2-4 carbon atoms) groups (mono, di or triethylamine, mono, di or triethanolamine and diethylethanolamine, etc.) And a quaternary ammonium salt of the amine.
Among these, preferred are aromatic dicarboxylic acids having a sulfonyl group, more preferred are 5-sulfoisophthalate, and particularly preferred are sodium 5-sulfoisophthalate and potassium 5-sulfoisophthalate. .

Among (b0) and (b1) constituting (b4), alkanediol having 2 to 10 carbon atoms, EG, polyethylene glycol (hereinafter abbreviated as PEG) (degree of polymerization 2 to 20), bisphenol ( EO adduct (addition mole number: 2 to 60 mol) of bisphenol A and the like, and a mixture of two or more thereof.
As a manufacturing method of (b4), the normal polyester manufacturing method can be applied as it is. The polyesterification reaction is performed in a temperature range of 150 to 240 ° C. under reduced pressure, and the reaction time is preferably 0.5 to 20 hours. Moreover, you may use the catalyst used for normal esterification reaction as needed. Examples of esterification catalysts include antimony catalysts (such as antimony trioxide), tin catalysts (such as monobutyltin oxide and dibutyltin oxide), titanium catalysts (such as tetrabutyl titanate), zirconium catalysts (such as tetrabutylzirconate), and metal acetates Examples include catalysts (such as zinc acetate).

  Mn of (b4) is preferably 500 to 20,000, more preferably 1,000 to 15,000, and particularly preferably 1 from the viewpoint of antistatic properties and reactivity with the hydrophobic polymer (a). , 200-8,000.

[Block polymer (A)]
The block polymer (A) in the present invention includes a hydrophobic polymer (a) block and a hydrophilic polymer (b) block as structural units.
Among (A), the following (A1) and / or (A2) are preferable from the viewpoint of antistatic properties.
(A1): (a) is a polyamide (a1), (b) is a polyether (b1) or a polyether-containing hydrophilic polymer (b2), and (a1), (b1) and / or ( Polyether ester amide obtained by reacting b2).
(A2): (a) is a polyolefin (a2), and the block of (a2) and the block of the hydrophilic polymer (b) are an ester bond, an amide bond, an ether bond, an imide bond, a urethane bond and a urea. A block polymer having a structure bonded through at least one bond selected from the group consisting of bonds.

  The weight ratio of the block (a) and the block (b) [(a) block / (b) block] constituting (A) is preferably 10 / from the viewpoint of antistatic properties and water resistance. It is 90-80 / 20, More preferably, it is 20 / 80-75 / 25.

The structure in which the block (a) and the block (b) constituting (A) are combined includes (a)-(b) type, (a)-(b)-(a) type, (b )-(A)-(b) type and [(a)-(b)] n type (n represents the average number of repetitions).
The structure of the block polymer (A) is preferably an [(a)-(b)] n type in which (a) and (b) are repeatedly and alternately bonded from the viewpoint of conductivity.
[(A)-(b)] n in the n-type structure is preferably 2 to 50, more preferably 2.3 to 30, particularly preferably 2 from the viewpoints of electrical conductivity and mechanical properties of the molded product. .7-20, most preferably 3-10. n can be determined by Mn and ¹ H-NMR analysis of the block polymer (A).

  Mn in (A) is preferably from 2,000 to 1,000,000, more preferably from 4,000 to 500,000, and particularly preferably from the viewpoint of mechanical properties and antistatic properties of the molded product described later. 6,000 to 100,000.

When (A) has a structure in which the block of (a) and the block of (b) are bonded via an ester bond, an amide bond, an ether bond, or an imide bond, it is produced by the following method. Can do.
(A) and (b) are charged into a reaction vessel, and water produced by amidation reaction, esterification reaction or imidization reaction at a reaction temperature of 100 to 250 ° C. and a pressure of 0.003 to 0.1 MPa with stirring ( Hereinafter, it is abbreviated as generated water.), And a method of reacting for 1 to 50 hours while removing from the reaction system. The weight ratio of (a) and (b) is from 10/90 to 80/20, more preferably from 20/80 to 75/25, from the viewpoint of antistatic properties and water resistance.
In the case of the esterification reaction, it is preferable to use 0.05 to 0.5% by weight of catalyst based on the weight of (a) and (b) in order to accelerate the reaction. Catalysts include inorganic acids (such as sulfuric acid and hydrochloric acid), organic sulfonic acids (such as methanesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, and naphthalenesulfonic acid), and organic metal compounds (dibutyltin oxide, tetraisopropoxytitanate, Ethanolamine titanate and potassium oxalate titanate). When a catalyst is used, the catalyst can be neutralized as necessary after completion of the esterification reaction and treated with an adsorbent to remove and purify the catalyst. Examples of the method for removing the produced water from the reaction system include the following methods.
(1) A method of removing only generated water from the reaction system by azeotropically boiling the organic solvent and generated water under reflux using an organic solvent incompatible with water (for example, toluene, xylene, cyclohexane, etc.) .
(2) A method in which a carrier gas (for example, air, nitrogen, helium, argon, carbon dioxide, etc.) is blown into the reaction system, and the generated water is removed from the reaction system together with the carrier gas.
(3) A method of removing the generated water from the reaction system by reducing the pressure in the reaction system.

When (A) has a structure in which the block of (a) and the block of (b) are bonded via a urethane bond or a urea bond, the production method of (A) includes: A method may be mentioned in which the mixture is put into a reaction vessel and heated to 30 to 100 ° C. with stirring, and then (b) is added and reacted at the same temperature for 1 to 20 hours. The weight ratio of (a) and (b) is from 10/90 to 80/20, more preferably from 20/80 to 75/25, from the viewpoint of antistatic properties and water resistance.
In order to promote the reaction, it is preferable to use 0.001 to 5% by weight of catalyst based on the weight of (a) and (b). Catalysts include organometallic compounds (dibutyltin dilaurate, dioctyltin dilaurate, lead octoate, bismuth octoate, etc.), tertiary amines {triethylenediamine, trialkylamines having an alkyl group of 1 to 8 carbon atoms (trimethylamine, tributylamine) , And trioctylamine), diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7] and the like}; and combinations of two or more thereof.

[Alkali inhibitor (B)]
Examples of the alkali inhibitor in the present invention include the following alkali adsorbent (B1), phosphorus oxo acid (salt) (B2), and organic phosphorus compound (B3). These may be used alone or in combination of two or more.
Of the above (B), (B1) and (B2) are preferred, and (B1) is more preferred from the viewpoint of the appearance color of the antistatic agent (Z) described later.

Examples of the alkali adsorbent (B1) include silicates such as aluminum silicate and magnesium silicate, activated clay, acidic clay and silica gel. Examples of commercially available adsorbents include KYOWARD 600, 700 (manufactured by Kyowa Chemical Co., Ltd.), Mizuka Life P-1, P-1S, P-1G, F-1G (manufactured by Mizusawa Chemical Co., Ltd.), Tomita-AD600, 700. Examples thereof include silicates such as Tomita Pharmaceutical Co., Ltd., activated clay such as Galeon Earth (manufactured by Mizusawa Chemical Co., Ltd.), and acid clay such as Mizuka Ace (Mizusawa Chemical Co., Ltd.). In addition, (B) may be used alone or in combination of two or more.
Among these, from the viewpoint of the color of the appearance of the antistatic agent (Z), silicate and acid clay are preferable, and silicate is more preferable.

  The shape of (B1) is preferably granular, and the average particle size of (B1) is preferably 0.1 to 10 μm, more preferably from the viewpoint of dispersibility in the antistatic resin composition described later. Is 0.2-5 μm.

Examples of the phosphorus oxo acid (salt) (B2) include phosphorus oxo acid and salts thereof (sodium salt, potassium salt, calcium salt, ammonium salt, etc.). Examples of the phosphorus oxo acid include phosphoric acid, phosphorous acid, hypophosphorous acid and the like.
Of these, phosphorous acid, hypophosphorous acid, sodium hypophosphite are preferred, and hypophosphorous acid is more preferred from the viewpoint of the appearance color of the antistatic agent (Z).

Examples of the organic phosphorus compound (B3) include phosphoric acid monoesters such as methyl phosphate and phenyl phosphate; phosphoric acid diesters such as dimethyl phosphate and diphenyl phosphate; phosphoric acid triesters such as triethyl phosphate and triphenyl phosphate Phosphorous acid monoesters such as methyl phosphite and phenyl phosphite; phosphorous acid diesters such as diphenyl phosphite; phosphorous acid triesters such as triphenyl phosphite; arylphosphonic acids such as phenylphosphonic acid Alkylphosphonic acids such as methylphosphonic acid; alkylphosphonic acids such as methylphosphonic acid; arylphosphonic acids such as phenylphosphonic acid; alkylphosphinic acids such as dimethylphosphinic acid; diphenylphosphinic acid, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, etc. Alkylphosphinic acids such as phenylmethylphosphinic acid; alkylphosphinic acids such as dimethylphosphinic acid; arylphosphinic acids such as diphenylphosphinic acid; alkylarylphosphinic acids such as phenylmethylphosphinic acid; Examples thereof include acidic phosphate esters such as lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate.
Among these, from the viewpoint of the appearance color of the antistatic agent (Z), preferred are phosphorous acid triesters, alkylphosphonous acid, arylphosphonous acid, arylphosphinic acid, alkylarylphosphinic acid, and particularly preferred. Is a phosphorous acid triester.

[Quaternary ammonium salt (C)]
The quaternary ammonium salt (C) in the present invention is represented by the following general formula (3).

(R ⁷ −) _r X ⁻ · Z ⁺ (3)

In general formula (3), R ⁷ represents a monovalent hydrocarbon group having 8 to 30 carbon atoms (hereinafter sometimes abbreviated as C) (preferably C10 to 24, more preferably C12 to 21). . When R ⁷ is less than C8, the appearance of the molded product described later is deteriorated, and when it exceeds 30, the antistatic property is deteriorated.
Examples of R ⁷ include an alkyl group, an alkenyl group, an alkylaryl group, and an arylalkyl group.
Examples of alkyl groups include octyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl and triacontyl groups; examples of alkenyl groups include octenyl, decenyl, dodecenyl, pentadecenyl, octadecenyl, eicosenyl and triacontenyl groups; Ethylphenyl, pentylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, pentadecylphenyl, octadecylphenyl, eicosylphenyl and tetracosylphenyl groups; arylalkyl groups include phenylethyl, phenylpentyl, phenyldecyl, phenylnonyl , Phenyldodecyl, phenylpentadecyl, phenyloctadecyl, phenyleicosyl and phenyltetracosyl groups.
Of the above R ⁷ , an alkyl group and an alkylaryl group are preferable from the viewpoint of antistatic properties, a C12-21 alkylaryl group is more preferable, and a dodecylphenyl group and a pentadecylphenyl group are particularly preferable.

In general formula (3), r represents 1 or 2. When r is 1, the case where X ⁻ described later is an anion obtained by removing a proton from a sulfonic acid group, a sulfinic acid group, a sulfate ester group, a carboxyl group and / or a phosphite ester group can be mentioned. In some cases, X ⁻ is an anion obtained by removing a proton from a phosphate group. When r is 2, the plurality of R ⁷ may be the same or different.

In the general formula (3), X ⁻ represents a proton from at least one group selected from the group consisting of a sulfonic acid group, a sulfinic acid group, a sulfate ester group, a carboxyl group, a phosphate ester group, and a phosphite ester group. Represents the removed anion. Of these groups, sulfonic acid groups, sulfinic acid groups and sulfate ester groups are preferred from the viewpoint of antistatic properties, sulfonic acid groups and sulfate ester groups are more preferred, and sulfonic acid groups are particularly preferred.

In the general formula (3), Z ⁺ represents a cation selected from the group consisting of ammonium, amidinium, pyridinium, pyrazolium and guanidinium cations.

The following are mentioned as an ammonium cation.
[1] Aliphatic quaternary ammonium having an alkyl and / or alkenyl group having 4 to 30 or more carbon atoms Tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, trimethylethylammonium, tetraethylammonium, trimethyl Propylammonium, dimethyldipropylammonium, ethylmethyldipropylammonium, butyltrimethylammonium, dimethyldibutylammonium, tetrabutylammonium, tetrahexylammonium, trimethyldecylammonium, dimethyldidecylammonium, etc .;
[2] Aromatic quaternary ammonium having 6 to 30 or more carbon atoms Trimethylphenylammonium, dimethylethylphenylammonium, triethylphenylammonium and the like;
[3] C3-C30 or higher alicyclic quaternary ammonium N, N-dimethylpyrrinium, N-ethyl-N-methylpyrrolidinium, N, N-diethylpyrrolidinium, N, N -Dimethylmorpholinium, N-ethyl-N-methylmorpholinium, N, N-diethylmorpholinium, N, N-dimethylpiperidinium, N, N-diethylpiperidinium, etc .;

The following are mentioned as an amidinium cation.
[1] Imidazolinium cation C5-15, for example 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium, 1,3-dimethyl-2,4-diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1-methyl-2,3,4-triethylimidazolinium, 1,2,3 , 4-tetraethylimidazolinium, 1,2,3-trimethylimidazolinium, 1,3-dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium, 1,2,3 -Triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium, 3-cyanomethyl-1,2-dimethylimidazolinium, 2-sia Nomethyl-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-dimethylimidazole Linium, 4-formyl-1,2,3-trimethylimidazolinium, 3-formylmethyl-1,2-dimethylimidazolinium, 3-hydroxyethyl-1,2-dimethylimidazolinium, 4-hydroxymethyl -1,2,3-trimethylimidazolinium, 2-hydroxyethyl-1,3-dimethylimidazole Bromide;

[2] Imidazolium cation C5-15, such as 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1,2 , 3-trimethylimidazolium, 1,2,3,4-tetramethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 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-benzyl Imidazolium, 1-benzyl-2,3-dimethyl-imidazolium, 4-cyano-1,2,3-trimethylimidazole Lithium, 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-dimethyl Imidazolium, 4-hydroxymethyl-1,2,3-trimethylimidazolium, - hydroxyethyl-1,3-dimethyl imidazolium;

[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 1,8-diazabicyclo [5,4,0] -7-undecenium, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium, 1,5-diazabicyclo [4,3,0 ] -5-nonenium, 5-methyl-1,5-diazabicyclo [4,3,0] -5-nonenium, 4-cyano-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidi Ni, 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-tetrahydropyrimidi 4-formyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-formylmethyl-1,2-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 the pyridinium cation include C6-20, such as 3-methyl-1-propylpyridinium, 1-propyl-3-methylpyridinium, 1-butyl-3-methylpyridinium, 1-butyl-4-methylpyridinium, 1-butyl- Examples include 3,4-dimethylpyridinium and 1-butyl-3,5-dimethylpyridinium.

  Examples of the pyrazolium cation include C5-15, such as 1,2-dimethylpyrazolium, 1-methyl-2-propylpyrazolium, 1-n-butyl-2-methylpyrazolium, 1-n-butyl. -2-Ethylpyrazolium.

The following are mentioned as a guanidinium cation.
[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-methyl Carboxymethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-methoxy-1,3-dimethyl-1,4 , 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.

  Of these, an amidinium cation is preferable from the viewpoint of antistatic properties, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

Among the quaternary ammonium salts (C), specific examples of the sulfonates include imidazolium salts of alkanesulfonic acid (1-ethyl-3-methylimidazolium salt of dodecanesulfonic acid and pentadecanesulfonic acid and 1,3 -Dimethyl-2-ethylimidazolium salt, etc.), alkene sulfonic acid imidazolium salt (dodecenesulfonic acid and pentadecenesulfonic acid 1-ethyl-3-methylimidazolium salt and 1,3-dimethyl-2-ethyl salt) Imidazolium salts, etc.), imidazolium salts of alkylarene sulfonic acids (1-ethyl-3-methylimidazolium salt and 1,3-dimethyl-2-ethylimidazolium salt of dodecylbenzenesulfonic acid and pentadecylbenzenesulfonic acid, respectively) Etc.), imidazo of arylalkanesulfonic acid Umushio (phenyl each 1-ethyl-3-methylimidazolium salt of dodecanoic acid and phenyl pentadecane sulfonic acid and 1,3-dimethyl-2-ethyl imidazolium salt, etc.) and the like.
Of these, from the viewpoint of antistatic properties and appearance of the molded product, imidazolium salts of alkylarene (C8-30) sulfonic acid are preferable, and 1-ethyl-3-methylimidazole of dodecylbenzenesulfonic acid is more preferable. The 1-ethyl-3-methylimidazolium salt and the 1,3-dimethyl-2-ethylimidazolium salt of the lithium salt and 1,3-dimethyl-2-ethylimidazolium salt, pentadecanebenzenesulfonic acid.
The quaternary ammonium salt (C) may be used alone or in combination of two or more.

[Antistatic agent (Z)]
The antistatic agent (Z) of the present invention comprises the block polymer (A), an alkali inhibitor (B) and a quaternary ammonium salt (C).
With respect to each content based on the total weight of (A) to (C) in (Z), (A) is preferably 80 to 99.94% by weight, more preferably 88 from the viewpoint of antistatic properties of the molded product. To 99.85% by weight, particularly preferably 92 to 99.4% by weight; (B) is preferably 0.01 to 10% by weight from the viewpoint of the antistatic agent, the color of the appearance of the molded article and the antistatic property, More preferably 0.05 to 5% by weight, particularly preferably 0.1 to 3% by weight; (C) is preferably 0.05 to 10% by weight from the viewpoint of antistatic properties and antistatic agent handling properties. More preferably, it is 0.1-7 weight%, Most preferably, it is 0.5-5 weight%.
The lower limit of the weight ratio of (B) to (C) [(B) / (C)] is preferably 0.3 from the viewpoint of the balance between the antistatic agent and the color of the appearance of the molded product and the antistatic property. /99.7, more preferably 1/99, particularly preferably 10/90, and the upper limit is preferably 70/30, more preferably 60/40, particularly preferably 50/50.

The antistatic agent (Z) can be produced by mixing (A), (B) and (C) by a known method. Before the production of (A), (B) and (C) can be mixed or dispersed in advance in the raw material of (A), the additive (E) described later, and the like. It is preferable from the viewpoint of uniform mixing.
The timing of mixing (B) and (C) is not particularly limited, but it is preferable to mix (B) and (C) at the same time or after (C) from the viewpoint of antistatic properties and appearance color. .

[Antistatic resin composition]
The antistatic resin composition of the present invention comprises the antistatic agent (Z) and the thermoplastic resin (D).
(D) includes polyphenylene ether resin (PPE) (D1); polyolefin resin (D2) [polypropylene (PP), polyethylene (PE), ethylene-vinyl acetate copolymer resin (EVA), and ethylene-ethyl acrylate copolymer resin. Etc.]; poly (meth) acrylic resin (D3) [polymethyl methacrylate and the like]; polystyrene resin (D4) [vinyl group-containing aromatic hydrocarbons alone and vinyl group-containing aromatic hydrocarbons, and (meth) acrylic acid] Copolymers comprising at least one selected from the group consisting of esters, (meth) acrylonitrile and butadiene; for example, polystyrene (PS), styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer Polymer (ABS resin), methyl methacrylate / butadi Polystyrene resin (D5) [polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polybutylene adipate and polyethylene] Adipate]; polyamide resin (D6) [nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12, etc.]; polycarbonate resin (D7) [polycarbonate and Polycarbonate / ABS alloy resin (PC / ABS) and the like]; polyacetal resin (D8), 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 (Z) into (D). is there.

  The content of (Z) in the antistatic resin composition is preferably 1 to 50% by weight, more preferably 2 based on the weight of (D), from the viewpoint of antistatic properties and mechanical properties of the molded product. -40% by weight, particularly preferably 3-15% by weight.

  If necessary, the antistatic resin composition of the present invention can contain an additive (E) as long as the effects of the present invention are not impaired. (E) includes a colorant (E1), a release agent (E2), an antioxidant (E3), a flame retardant (E4), an ultraviolet absorber (E5), an antibacterial agent (E6), and a compatibilizer (E7). ), A filler (E8), a stabilizer (E9), and the like. (E) may use 2 or more types together.

  Examples of the colorant (E1) include inorganic pigments (white pigments, cobalt compounds, iron compounds, sulfides, etc.), organic pigments (azo pigments, polycyclic pigments, etc.), and dyes (azo, indigoid, sulfide, alizarin). System, acridine system, thiazole system, nitro system, aniline system, etc.).

  As a mold release agent (E2), C12-18 fatty acid alkyl (C1-4) ester (butyl stearate etc.), C2-18 fatty acid glycol (C2-8) ester (Ethylene glycol monostearate, etc.), polyhydric (trivalent or higher) alcohol esters (hardened castor oil, etc.) of fatty acids having 2 to 18 carbon atoms, liquid paraffin and the like.

  Antioxidants (E3) include phenolic compounds [monocyclic phenols (2,6-di-t-butyl-p-cresol, etc.), bisphenols [2,2′-methylenebis (4-methyl-6-t-butylphenol). And the like] and polycyclic phenols [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc.]], sulfur compounds (dilauryl- 3,3′-thiodipropionate and the like) and amine compounds (octylated diphenylamine and the like).

Examples of the flame retardant (E4) include halogen-containing flame retardants, nitrogen-containing flame retardants, sulfur-containing flame retardants, and silicon-containing flame retardants.

  Examples of the ultraviolet absorber (E5) include benzotriazole [2- (2′-hydroxy-5′-methylphenyl) benzotriazole and the like], benzophenone (2-hydroxy-4-methoxybenzophenone and the like), salicylate (phenyl salicylate). Etc.) and acrylates (2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate etc.) and the like.

  Antibacterial agents (E6) include benzoic acid, sorbic acid, halogenated phenol, organic iodine, nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyanate (methylenebisthiocyanate, etc.), N-halo. Examples include alkylthioimides, copper agents (such as 8-oxyquinoline copper), benzimidazoles, benzothiazoles, trihaloallyls, triazoles, organic nitrogen sulfur compounds (such as Suraoff 39), and the like.

  As the compatibilizer (E7), 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 (for example, A polymer described in JP-A-3-258850, a modified vinyl polymer having a sulfonic acid group described in JP-A-6-345927, and a block polymer having a polyolefin part and an aromatic vinyl polymer part) Etc.

  Examples of the filler (E8) include inorganic fillers (such as calcium carbonate, talc, and clay) and organic fillers (such as urea and calcium stearate).

  Examples of the stabilizer (E9) include hindered phenol compounds, thioether compounds, vitamin compounds, triazole compounds, polyvalent amine compounds, hydrazine derivative compounds, and phosphorus compounds.

The total content of (E) based on the weight of the thermoplastic resin (D) is preferably 45% by weight or less, more preferably 0.001 to 40% by weight, particularly preferably from the viewpoint of mechanical properties of the molded product. Is 0.01 to 35% by weight.
The content of (E1) based on the weight of the thermoplastic resin (D) is preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, from the viewpoint of mechanical properties of the molded product. is there.
The content of each of (E2), (E3), and (E5) based on the weight of the thermoplastic resin (D) is preferably 0.01 to 3% by weight, more preferably from the viewpoint of mechanical properties of the molded product. Is 0.05 to 1% by weight.
Each content of (E4) and (E6) based on the weight of the thermoplastic resin (D) is preferably 0.5 to 20% by weight, and more preferably 1 to 10%, from the viewpoint of mechanical properties of the molded product. % By weight.
Each content of (E7) and (E8) based on the weight of the thermoplastic resin (D) is preferably 0.5 to 10% by weight, more preferably 1 to 5%, from the viewpoint of mechanical properties of the molded product. % By weight.

The antistatic resin composition of the present invention can be obtained by melt-mixing the antistatic agent (Z) of the present invention, the thermoplastic resin (D), and, if necessary, (E). As a method of melt-mixing, there is generally a method of mixing each component in pellet form or powder form with an appropriate mixer (such as Henschel mixer), and then melt-mixing with an extruder to pelletize. Applicable.
There is no particular limitation on the order of addition of each component during melt mixing, for example,
[1] A method in which (Z) is melted and mixed, and then (D), and (E) is batch-added if necessary, and melt mixed.
[2] After (Z) is melt-mixed, a part of (D) is melt-mixed in advance to prepare a high-concentration composition (masterbatch resin composition) of (Z), and then the remaining (D) and A method of melting and mixing (E) as necessary (master batch method or master pellet method).
Etc.
The concentration of (Z) in the masterbatch resin composition in the method [2] is preferably 40 to 80% by weight, more preferably 50 to 70% by weight.
Of the methods [1] and [2], the method [2] is preferable from the viewpoint that (Z) can be efficiently dispersed in (D).

[Antistatic resin molded product]
The antistatic resin molded product of the present invention is obtained by molding the antistatic resin composition of the present invention. Examples of molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), etc., depending on the purpose. Molding, multilayer molding or foam molding can be used for any molding method.

[Antistatic resin molded article]
The molded article of the present invention has excellent mechanical properties and permanent antistatic properties, as well as good paintability and printability, and a molded article can be obtained by coating and / or printing the molded article.
Examples of the method for coating a molded product include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, dip coating, roller coating, and brush coating.
As the paint, paints generally used for plastic coating can be used, and specific examples include 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.

As a method for printing on a molded product or a surface on which a molded product has been coated, any printing method generally used for plastic printing can be used. Gravure printing, flexographic printing, screen printing, pad printing And dry offset printing and offset printing.
As the printing ink, those usually used for plastic printing can be used, and examples include gravure ink, flexo ink, screen ink, pad ink, dry offset ink, and offset ink.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example is a weight part. % Represents% by weight.

<Production Example 1> [Production of polyamide (a1-1)]
In a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introduction tube and a decompression device, 173 parts of ε-caprolactam, 33.2 parts of terephthalic acid, an antioxidant [“Irganox 1010”, BASF [Production] 0.4 parts and 10 parts of water were added, and after nitrogen substitution, the temperature was raised to 220 ° C. with stirring in a sealed state, and the mixture was stirred at the same temperature (pressure: 0.2 to 0.3 MPa) for 4 hours. A polyamide (a1-1) having carboxyl groups at both ends was obtained. The acid value of (a1-1) was 111, and Mn was 1,000.

<Production Example 2> [Production of polyolefin having carboxyl groups at both ends (a2-1-1)]
In the same pressure resistant reactor as in Production Example 1, low molecular weight polypropylene obtained by the thermal degradation method [polypropylene (MFR: 10 g / 10 min) is 410 ± 0.1 ° C. under nitrogen aeration (80 mL / min) for 16 minutes. Obtained by heat degradation. Mn: 3,400, number of double bonds per 1,000 carbon atoms: 7.0, average number of double bonds per molecule: 1.8, content of polyolefin that can be modified at both ends: 90 weight %] 90 parts, 10 parts of maleic anhydride and 30 parts of xylene were added, mixed uniformly, purged with nitrogen, melted by heating to 200 ° C. with stirring and sealed, and reacted at the same temperature for 10 hours. I let you. Next, excess maleic anhydride and xylene are distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 3 hours to obtain a polyolefin (a2-1-1α) 95 having carboxyl groups at both ends of the polymer. Got a part. The acid value of (a2-1-1α) was 27.5, and Mn was 3,600.

<Production Example 3> [Production of polyolefin (a2-1-2) obtained by secondary modification of (a2-1-1α)]
88 parts of (a2-1-1α) and 12 parts of 12-aminododecanoic acid are introduced into a pressure-resistant reaction vessel similar to Production Example 1, mixed uniformly, and then heated to 200 ° C. with stirring in a nitrogen gas atmosphere. The mixture was reacted at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours to obtain 96 parts of polyolefin (a2-1-2α) obtained by secondary modification of (a2-1-1α). The acid value of (a2-1-2α) was 24.8, and Mn was 4,000.

<Production Example 4> [Production of polyolefin having hydroxyl groups at both ends (a2-2)]
In Production Example 2, 90 parts of low molecular weight polypropylene and 10 parts of maleic anhydride obtained by the thermal degradation method were replaced with 94 parts of low molecular weight ethylene / propylene random copolymer obtained by the thermal degradation method and 6 parts of maleic anhydride. Except having changed into the part, it carried out similarly to manufacture example 2, and obtained 98 parts of polyolefin (a2-1-1β) which has a carboxyl group in the both ends of a polymer. The acid value of (a2-1-1β) was 9.9, and Mn was 10,200. The low molecular weight ethylene / propylene random copolymer obtained by the above thermal degradation method (Mn: 10,000, number of double bonds per 1,000 carbon atoms: 2.5, double per molecule) The average number of bonds: 1.8, the content of polyolefin that can be modified at both ends: 90% by weight) is an ethylene / propylene random copolymer (ethylene content: 2% by weight, MFR: 10 g / 10 min) of 410 ±. It was obtained by thermal degradation for 14 minutes at 0.1 ° C. under nitrogen flow (80 mL / min).
Next, 97 parts of (a2-1-1β) and 5 parts of ethanolamine were put into a pressure-resistant reaction vessel similar to Production Example 1, and the temperature was raised to 180 ° C. with stirring in a nitrogen gas atmosphere. Reacted for hours. Excess ethanolamine was distilled off under reduced pressure (0.013 MPa or less) at 180 ° C. over 2 hours to obtain a polyolefin (a2-2α) having hydroxyl groups at both ends of the polymer. The hydroxyl value of (a2-2α) was 9.9, the amine value was 0.01, and Mn was 10,200.

<Production Example 5> [Production of modified polyolefin having amino groups at both ends (a2-4)]
In Production Example 2, except that 90 parts of low molecular weight polypropylene and 10 parts of maleic anhydride obtained by the thermal degradation method were changed to 80 parts of low molecular weight polypropylene obtained by the thermal degradation method and 20 parts of maleic anhydride. In the same manner as in Production Example 2, 92 parts of polyolefin (a2-1-1γ) having carboxyl groups at both ends of the polymer was obtained. The acid value of (a2-1-1γ) was 64.0, and Mn was 1,700. The low molecular weight polypropylene obtained by the above thermal degradation method (Mn: 1,500, the number of double bonds per 1,000 carbon atoms: 17.8, the average number of double bonds per molecule: 1.94, the content of polyolefin that can be modified at both ends: 98% by weight) is an ethylene / propylene random copolymer (ethylene content: 3% by weight, MFR: 7 g / 10 min) of 410 ± 0.1 ° C., It was obtained by heat degradation for 18 minutes.
Next, 90 parts of (a2-1-1γ) and 10 parts of bis (2-aminoethyl) ether are put into a pressure resistant reactor similar to Production Example 1, and the temperature is raised to 200 ° C. with stirring in a nitrogen gas atmosphere. And reacted at the same temperature for 2 hours. Excess bis (2-aminoethyl) ether was distilled off under reduced pressure (0.013 MPa or less) at 200 ° C. over 2 hours to obtain a modified polyolefin (a2-4α) having amino groups at both ends. The amine value of (a2-4α) was 64.0, and Mn was 1,700.

<Production Example 6> [Production of cationic polymer (b3)]
In a pressure-resistant reaction vessel similar to Production Example 1, 41 parts of N-methyldiethanolamine, 49 parts of adipic acid and 0.3 part of zirconyl acetate were added, and the temperature was raised to 220 ° C. over 2 hours, followed by 1 hour. The pressure was reduced to 0.013 MPa over a polyester reaction. After completion of the reaction, the reaction mixture was cooled to 50 ° C. and dissolved by adding 100 parts of methanol. While stirring, the temperature in the reaction vessel was kept at 120 ° C., 31 parts of dimethyl carbonate was added dropwise over 3 hours, and the mixture was aged at the same temperature for 6 hours. After cooling to room temperature, 100 parts of a 60 wt% hexafluorophosphoric acid aqueous solution was added and stirred at room temperature for 1 hour. Subsequently, methanol was distilled off under reduced pressure, and a cationic polymer (b3α) having an average of 12 quaternary ammonium groups (hydroxyl value: 30.1, acid value: 0.5, volume resistivity: 1 × 10 ⁵ Ω · cm )

<Production Example 7> [Production of anionic polymer (b4α)]
In a pressure-resistant reaction vessel similar to Production Example 1, 114 parts of diethylene glycol, 268 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 part of dibutyltin oxide were added, and the temperature was increased to 190 ° C. under a reduced pressure of 0.067 MPa. An anionic polymer (b4α) having an average of 6 sodium sulfonate bases in one molecule (hydroxyl value is 49, acid value is 0.6 The volume resistivity value was 3 × 10 ⁸ Ω · cm).

<Production Example 8> [Production of anionic polymer (b4β)]
67 parts of PEG (Mn: 300), 49 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 part of dibutyltin oxide were put into a pressure-resistant reaction vessel similar to Production Example 1, and the pressure was reduced to 0.067 MPa. The temperature was raised to 190 ° C., and the ester exchange reaction was carried out at the same temperature for 6 hours while distilling off methanol. Acid value: 0.4, volume resistivity: 2 × 10 ⁶ Ω · cm).

<Production Example 9> [Production of block polymer (A1-1)]
In a reaction vessel equipped with a stirrer, a thermometer and a heating / cooling device, 199 parts of (a1-1) and bisphenol A EO adduct (Mn: 4,000, volume resistivity: 2 × 10 ⁷ Ω · cm) 780 parts and 0.6 parts of zirconyl acetate were added, the temperature was raised to 240 ° C. with stirring, and the mixture was polymerized at the same temperature under reduced pressure (0.013 MPa or less) for 6 hours to form a viscous block polymer (A1-1). Got. The Mn of (A1-1) was 24,000.

<Production Example 10> [Production of block polymer (A1-2)]
In a pressure resistant reactor similar to Production Example 9, 143 parts of (a1-1), 320 parts of (b4α) and 0.3 part of the antioxidant “Irganox 1010” were added, and the temperature was raised to 240 ° C. while stirring. The mixture was polymerized at the same temperature under reduced pressure (0.013 MPa or less) for 5 hours to obtain a viscous block polymer (A1-2). Mn of (A1-2) was 21,000.

<Production Example 11> [Production of block polymer (A2-1)]
In a pressure resistant reactor similar to Production Example 9, 67.1 parts of (a2-1-1α), polyether diamine (b1-2α) [α, ω-diaminoPEG (Mn: 2,000, volume resistivity: 1 × 10 ⁷ Ω · cm)] 32.9 parts, 0.3 parts of the antioxidant “Irganox 1010” and 0.5 parts of zirconyl acetate were added, the temperature was raised to 220 ° C. with stirring, and the pressure was reduced ( 0.013 MPa or less) The mixture was polymerized at the same temperature for 3 hours to obtain a viscous block polymer (A2-1). The Mn of (A2-1) was 50,000.

<Production Example 12> [Production of block polymer (A2-2)]
In Production Example 11, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2α), 60.1 parts of (a2-1-2α) and polyether diol (b1-1α) [PEG (Mn: 3,000, volume resistivity: 1 × 10 ⁷ Ω · cm)] A block polymer (A2-2) was obtained in the same manner as in Production Example 11 except that the content was changed to 39.9 parts. Mn of (A2-2) was 30,000.

<Production Example 13> [Production of block polymer (A2-3)]
In Production Example 11, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2α), 48.0 parts of (a2-2α), 48.0 parts of (b3α) and dodecanedioic acid 4 A block polymer (A2-3) was obtained in the same manner as in Production Example 11 except for changing to the part. The Mn of (A2-3) was 100,000.

<Production Example 14> [Production of block polymer (A2-4)]
In Production Example 11, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2α), 31.6 parts of (a2-4α), 68.4 parts of (b4β) and dodecanedioic acid 8 Except having changed into the part, it carried out similarly to manufacture example 11, and obtained the block polymer (A2-4). The Mn of (A2-4) was 10,000.

<Production Example 15> [Production of block polymer (A2-5)]
In Production Example 11, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2α), 71.5 parts of (a2-1-2α) and polyether diol (b1-1β) [poly A block polymer (A2-5) was obtained in the same manner as in Production Example 11 except that tetramethylene glycol (Mn: 1,800, volume resistivity: 1 × 10 ¹¹ Ω · cm) was changed to 28.5 parts. . The Mn of (A2-5) was 40,000.

<Production Example 16> [Production of block polymer (A2-6)]
In Production Example 11, 67.1 parts of (a2-1-1α) and 32.9 parts of (b1-2α) were converted to 48.0 parts of (a2-2α), 48.0 parts of (b3α) and hexamethylene diisocyanate ( (HDI) A block polymer (A2-6) was obtained in the same manner as in Production Example 11 except that the content was changed to 3 parts. The Mn of (A2-6) was 100,000.

<Examples 1-9, Comparative Examples 1-9>
According to the blending composition (parts by weight) shown in Table 1, the blending components were mixed with a Henschel mixer for 3 minutes, and then melt-mixed with a vented twin-screw extruder at 100 rpm, 230 ° C., and a residence time of 1 hour. The antistatic agents (Z-1) to (Z-9) and (Z′-1) to (Z′-9) of Examples 1 to 9 and Comparative Examples 1 to 9 were obtained. The obtained antistatic agent was evaluated by the performance test described below. The results are shown in Table 1.

The contents of the symbols in Table 1 are as follows.
(B1-1):
Magnesium silicate "KYOWARD 600" [manufactured by Kyowa Chemical Industry Co., Ltd.]
(B1-2):
Aluminum silicate "KYOWARD 700" [Kyowa Chemical Industry Co., Ltd.]
(B2-1):
Hypophosphorous acid [manufactured by Taihei Chemical Industry Co., Ltd.]
(B2-2):
Sodium hypophosphite [manufactured by Taihei Chemical Industry Co., Ltd.]
(B3-1):
Tris phosphite (2,4-di-t-butylphenyl) "Irgafos 168"
[BASF made]
(C-1):
1-ethyl-3-methylimidazolium dodecylbenzene sulfonate (C-2):
2-Dimethylamino-1,3,4-trimethylimidazolinium dodecylbenzenesulfonate (C-3):
1,3-dimethylimidazolinium pentadecylphenyl sulfate (C-4):
1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium pentadecylphenylsulfinate (C-5):
Tetrabutylammonium dodecane sulfonate

<Performance test>
(1) Appearance yellowness of antistatic agent (Z) (unit:%)
The obtained antistatic agent (Z) and the block polymer (A) for comparison were each injected at a cylinder temperature of 210 ° C. and a mold temperature of 50 ° C. using an injection molding machine “PS40E5ASE” [manufactured by Nissei Plastic Industry Co., Ltd.] A test piece (100 × 100 × 2 mm) was produced by molding. Each produced test piece (100 × 100 × 2 mm) was measured according to JIS K7373 using a colorimetric color difference meter [ND-300A, manufactured by Nippon Denshoku Industries Co., Ltd.] (hereinafter abbreviated as YI). ) And was calculated using the following formula.

Appearance yellowness (%) = [YI of test piece of (Z)] × 100 / [YI of test piece of (A)]

<Examples 10 to 18 and Comparative Examples 10 to 18>
According to the blending composition (parts by weight) shown in Table 2, the blending components were mixed for 3 minutes with a Henschel mixer and then melt-kneaded using a vented twin-screw extruder at 100 rpm, 220 ° C., and a residence time of 5 minutes. The antistatic resin compositions of Examples 10 to 18 and Comparative Examples 10 to 18 were obtained.
The obtained antistatic resin composition was used with an injection molding machine “PS40E5ASE” [manufactured by Nissei Plastic Industry Co., Ltd.] and a cylinder temperature of 220 ° C. [when (D-1) was used] or 230 ° C. [(D− 2, 3) When used], a test piece (100 × 100 × 2 mm) was produced by molding at a mold temperature of 50 ° C. The produced test piece was evaluated by the performance test described later. The results are shown in Table 2.

The contents of the symbols in Table 2 are as follows.
(D-1): Impact resistant PS resin “HIPS 433” [manufactured by PS Japan Ltd.]
(D-2): PP resin “PM771M” [manufactured by Sun Allomer Co., Ltd.]
(D-3): ABS resin “Cebian V 320F” [manufactured by Daicel Polymer Ltd.]

<Performance test>
(1) Surface resistivity (unit: Ω)
In accordance with ASTM D257, a test piece (100 × 100 × 2 mm) was measured using a super insulation meter “DSM-8103” [manufactured by Toa DKK Co., Ltd.] in an atmosphere of 23 ° C. and humidity 50% RH.
(2) Appearance yellowness of molded product of antistatic resin composition (unit:%)
Based on JIS K7373, YI [YIZ] was measured for the test piece (100 × 100 × 2 mm) using a colorimetric color difference meter [ND-300A, manufactured by Nippon Denshoku Industries Co., Ltd.].
Separately, for control, an antistatic resin composition comprising a block polymer (A) and a thermoplastic resin (D) was produced, and a test piece (100 × 100 × 2 mm) was produced in the same manner as described above. About the produced test piece, YI [YIA] was measured using the said colorimetric color difference meter. The appearance yellowness of the molded article of the antistatic resin composition was calculated using the following formula.

Appearance Yellowness (%) = [YIZ] × 100 / [YIA]

  As is clear from the results in Tables 1 and 2, the antistatic agent of the present invention is light in color and can impart excellent antistatic properties to the molded product. Moreover, it turns out that the antistatic resin composition of this invention gives the molded article excellent in the antistatic property and the external appearance.

  Since the antistatic agent of the present invention can impart excellent permanent antistatic properties and appearance to molded products, various molding methods [injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, foaming, etc. Molding and film molding (cast method, tenter method, inflation method, etc.)] Housing products (for home appliances / OA equipment, game machines, office equipment, etc.), plastic container materials [Trays used in clean rooms (IC trays) Etc.) and other containers, etc.], various cushioning materials, covering materials (films for packaging materials, protective films, etc.), sheets for flooring, artificial turf, mats, tape base materials (for semiconductor manufacturing processes, etc.) and various molded products ( It can be widely used as a material for automobile parts, etc., and is particularly suitable for containers that can be seen by consumers who want an excellent appearance. That.

Claims (8)

  An antistatic material comprising a block polymer (A) comprising a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b) as structural units, an alkali inhibitor (B) and a quaternary ammonium salt (C). Agent (Z). The antistatic agent according to claim 1, wherein (A) is the following (A1) and / or (A2).
(A1): (a) is a polyamide (a1), (b) is a polyether (b1) and / or a polyether-containing hydrophilic polymer (b2), and (a1), (b1) and / or Or polyether ester amide (A2) obtained by reacting (b2): (a) is polyolefin (a2), and the block of (a2) and the block of the hydrophilic polymer (b) are ester bonds , A block polymer having a structure bonded via one or more bonds selected from the group consisting of amide bond, ether bond, imide bond, urethane bond and urea bond   The weight ratio of the block (a) and the block (b) [(a) block / (b) block] constituting (A) is 10/90 to 80/20. The antistatic agent as described.   (B2) constituting (A2) is at least one selected from the group consisting of polyether (b1), polyether-containing hydrophilic polymer (b2), cationic polymer (b3) and anionic polymer (b4) The antistatic agent according to claim 2 or 3.   The antistatic material according to any one of claims 1 to 4, wherein (B) is at least one selected from the group consisting of an alkali adsorbent (B1), a phosphorus oxo acid (salt) (B2), and an organophosphorus compound (B3). Agent.   An antistatic resin composition comprising the antistatic agent (Z) according to any one of claims 1 to 5 and a thermoplastic resin (E).   A molded product formed by molding the antistatic resin composition according to claim 6.   A molded article obtained by coating and / or printing the molded article according to claim 7.