JP6602538B2 - Antistatic agent and antistatic resin composition - Google Patents

Description

  The present invention relates to an antistatic agent and an antistatic resin composition. More specifically, an antistatic agent that imparts excellent permanent antistatic properties to the molded product without impairing the mechanical properties and good appearance of the thermoplastic resin molded product, and an antistatic resin composition comprising the same Related to things.

Conventionally, the most common method for imparting antistatic properties to a highly insulating thermoplastic resin is a method in which a small amount of a surfactant is kneaded into the thermoplastic resin. However, the antistatic property of the molded product of the resin composition obtained by the addition of the surfactant is effective when the low molecular weight surfactant bleeds out on the surface of the molded product. For example, the antistatic effect is lost, and it is difficult to maintain permanent antistatic properties. On the other hand, methods for imparting permanent antistatic properties to thermoplastic resins include (1) a method of kneading a conductive filler such as carbon black, and (2) a method of kneading a polymer type antistatic agent. ing. In order to exhibit the antistatic effect by the method (1), it is generally necessary to add a large amount of conductive filler, the resin composition has a problem in workability, and the obtained molded product has an impact resistance. There was a problem that it was inferior to mechanical properties, such as property.
As the method (2), a small amount of a polymer type antistatic agent such as polyether ester amide (for example, see Patent Document 1) or polyether / polyolefin block polymer (for example, see Patent Document 2) is contained in the resin. A method of kneading is known.
However, even in the above-described method of kneading the polymer type antistatic agent, in order to impart sufficient antistatic properties to the thermoplastic resin, it is necessary to add more than 10% by weight. There has been a problem that the physical properties of molded articles such as the above deteriorate. Further, from an economical point of view, an antistatic agent capable of imparting permanent antistatic properties with a smaller amount of addition than conventional is desired.
In addition, as an antistatic resin composition containing an inorganic filler, one obtained by adding an inorganic filler to a polyether / polyolefin block polymer (for example, see Patent Document 3) is known.
However, the antistatic resin composition containing the above-described inorganic filler has a problem that the appearance of the molded product is impaired.

Japanese Patent Laid-Open No. 08-12755 JP 2001-278985 A JP 2002-097378 A

  An object of the present invention is to provide an antistatic agent that imparts sufficient permanent antistatic properties to the molded product without deteriorating the appearance and mechanical properties of the molded product, and with a small amount of addition, and an antistatic resin containing the same. It is to provide a composition.

  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 is an antistatic agent comprising a block polymer (A) and / or a hydrophilic polymer (B) and an inorganic filler (C) having a volume average particle diameter of 1 to 100 nm, Antistatic agent (Z), wherein (A) is a block polymer comprising a block of a hydrophobic polymer (D) and a block of a hydrophilic polymer (B); the antistatic agent (Z) and a thermoplastic resin ( An antistatic resin composition comprising E); a molded article formed by molding the antistatic resin composition; and a molded article obtained by coating and / or printing the molded article.

The antistatic agent of the present invention has the following effects.
(1) The antistatic agent can impart excellent permanent antistatic properties to a molded product even when added in a small amount.
(2) A molded product formed by molding the antistatic resin composition is excellent in appearance and mechanical properties.

The antistatic agent (Z) of the present invention comprises a block polymer (A) and / or a hydrophilic polymer (B) and an inorganic filler (C) having a volume average particle diameter of 1 to 100 nm.
The block polymer (A) is a block polymer having a hydrophobic polymer (D) block and a hydrophilic polymer (B) block as structural units.
The hydrophobic polymer (D) in the present invention means a polymer having a volume resistivity value exceeding 1 × 10 ¹¹ Ω · cm. Specifically, polyamide (D1), polyolefin (D2), polyamideimide (D3), etc. are mentioned, These may use 2 or more types together. Of (D), polyamide (D1) and polyolefin (D2) 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 (D1) 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 (D1) include nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, a copolymer of nylon 6 and nylon 66, and a copolymer of nylon 6 and nylon 12. , And copolymers of nylon 6, nylon 66, and nylon 12.

As the polyolefin (D2), a polyolefin (D2-1) having carboxyl groups at both ends of the polymer, a polyolefin (D2-2) having hydroxyl groups at both ends of the polymer, and a polyolefin (D2) having amino groups at both ends of the polymer -3) and a polyolefin having an isocyanate group at both ends of the polymer (D2-4), a polyolefin having a carboxyl group at one end of the polymer (D2-5), and a polyolefin having a hydroxyl group at one end of the polymer (D2-6) And polyolefin (D2-7) having an amino group at one end of the polymer and polyolefin (D2-8) having an isocyanate group at one end of the polymer. Among these, (D2-1) and (D2-5) having a carboxyl group at the terminal are preferable.
In addition, the terminal in this invention means the terminal part which the 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 of b in the main chain of the polymer, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol and the like. More preferred are 2-aminoethanol and 4-aminobutanol, and particularly preferred is 2-aminoethanol.

  (D2-1) is a polyolefin having a main component (preferably a content of 50% by weight or more, more preferably 75% by weight or more, particularly preferably 80 to 100% by weight) of a polyolefin that can be modified at both ends. -01) having carboxyl groups introduced at both ends; (D2-2) having (D2-01) having hydroxyl groups introduced; (D2-3) having (D2-01) As for (D2-4), those obtained by introducing isocyanate groups at both ends of (D2-01) can be used.

  As (D2-5) to (D2-8), instead of the polyolefin (D2-01), 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 the carboxyl group, the hydroxyl group, the amino group, or the isocyanate group to the one terminal of the polyolefin (D2-02) made into especially 80-80 weight%, respectively can be used.

In the polyolefin (D2-01) 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 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% by weight of orthodichlorobenzene 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 (1976). 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 (D2-01) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 200 from the viewpoint of antistatic properties of the molded product described later. 6,000.
The number of terminal double bonds in (D2-01) 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.

  (D2-01) 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, the average number of terminal double bonds per molecule is 1.5 to 2 (D2-01) in the range of Mn 800 to 6,000. [Katsuhide Murata, Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].

Polyolefin (D2-02) whose main component is a polyolefin whose one end can be modified can be obtained in the same manner as (D2-01), and Mn in (D2-02) 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 (D2-02) is preferably 0.3 to 20 from the viewpoint of the antistatic property of the molded product and the molecular weight control of the block polymer (A). More preferably, it is 0.5-15, Most preferably, it is 0.7-10.

(D2-02) 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.
Among (D2-02), 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 a thermal degradation method is more preferably 3. , 20,000 to 20,000 polyethylene and / or polypropylene.
When a method of 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 (D2−) 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, (D2-01) and (D2-02) 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, (D2-1) to (D2-4) having a carboxyl group, a hydroxyl group, an amino group or an isocyanate group at both ends of the polyolefin (D2-01) will be described, but at one end of the polyolefin (D2-02) (D2-5) to (D2-8) having these groups are the same as (D2-1) to (D2-4), except that (D2-01) is replaced with (D2-02). Can be obtained.

  Polyolefin (D2-1) having a carboxyl group at both ends of the polymer includes (D2-01) 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 (D2-1-1) and (D2-1-1) having a structure modified with a lactam or aminocarboxylic acid. Polyolefin (D2-1-2) having the following modified structure, polyolefin (D2-1-3), (D2-1-3) having a structure modified by oxidation or hydroformylation of (D2-01) or lactam or Polyolefin (D2-1-4) having a structure secondarily modified with aminocarboxylic acid and a mixture of two or more thereof can be used.

(D2-1-1) can be obtained by modifying (D2-01) 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, for example, the terminal double bond of (D2-01) by α, β-unsaturated carboxylic acid by either solution method or melt 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.

(D2-1-2) can be obtained by secondary modification of (D2-1-1) with lactam or aminocarboxylic acid.
Examples of the lactam used for the secondary modification include lactams having 6 to 12 carbon atoms (preferably 6 to 8 and more preferably 6). Specifically, caprolactam, enantolactam, laurolactam, undecanolactam and the like. Is mentioned.
Examples of the aminocarboxylic acid include aminocarboxylic acids having 2 to 12 carbon atoms (preferably 4 to 12 carbon atoms, more preferably 6 to 12 carbon atoms), 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 the secondary modification is based on the weight of the substance to be modified (D2-1), ease of repetitive structure in the molecule, antistatic property of the molded product and block polymer (A ) Is preferably 0.5 to 200% by weight, more preferably 1 to 150% by weight, and particularly preferably 2 to 100% by weight.

(D2-1-3) can be obtained by introducing a carboxyl group by a method of oxidizing (D2-01) 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 a carboxyl group by hydroformylation can be carried out by various methods including known methods such as Macromolecules, VOL. 31, 5943 page.

(D2-1-4) can be obtained by secondary modification of (D2-1-3) with a lactam or an 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 (D2-1-1), and preferred ranges and amounts used are also the same. .

Mn of (D2-1) 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 (D2-1) 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 (D2-2) having a hydroxyl group at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying the polyolefin (D2-1) having a carboxyl group at both ends of the polymer with an amine having a hydroxyl group, and these 2 Mixtures of more than one species 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 (D2-1), ease of repetitive structure in the molecule, antistatic property of the molded product, and antistatic resin composition described later. From the viewpoint of dispersibility of the block polymer (A) and 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 (D2-2) 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 (D2-2) 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 (D2-3) include polyolefins having amino groups obtained by modifying the polyolefin (D2-1) 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 (D2-1) 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, particularly preferably 2 to 30% by weight, based on the weight of (D2-1). is there. The modification of (D2-1) by (Q1) is preferably 0.5 to 1,000% by weight based on the weight of (D2-1) 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 (D2-3) 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 (D2-3) 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.

Polyolefin (D2-4) having an isocyanate group at both ends includes a polyolefin having an isocyanate group obtained by modifying (D2-2) 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.

  The alicyclic PI includes isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and 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 (D2-2) can be carried out in the same manner as a normal urethanization reaction.
The molar equivalent ratio (NCO / OH) of PI and (D2-2) is preferably 1.8 / 1 to 3/1, 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 (D2-2).

  Mn of (D2-4) 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 (D3) include the amide-forming monomer (α), 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 (D3), as in the case of the polyamide (D1), 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 of (D3) is preferably 200 to 5,000, more preferably 500 to 4,000, from the viewpoint of moldability and production of an antistatic agent.

  The Mn of the hydrophobic polymer (D) is preferably 200 to 25,000, more preferably 500 to 20,000, particularly preferably from the viewpoint of dispersibility of the block polymer (A) and mechanical properties of the molded product. 1,000 to 15,000.

[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, 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, polyether (B1), polyether-containing hydrophilic polymer (B2), and cationic polymer (B3). And an anionic polymer (B4). Polyethers (B1) and (B2) are desirable from the viewpoint of antistatic properties and resin properties.

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 the 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 ) _a —O—E ¹ —O— (R ² O) _b —H (1)

E ¹ in the general formula (1) is a residue obtained by removing all hydroxyl groups from the diol (B0).
Diols (B0) include aliphatic dihydric alcohols having 2 to 12 carbon atoms, alicyclic dihydric alcohols having 5 to 12 carbon atoms, aromatic dihydric alcohols having 6 to 18 carbon atoms, and tertiary amino group-containing diols. Etc.
Examples of the aliphatic dihydric alcohol having 2 to 12 carbon atoms include ethylene glycol (hereinafter abbreviated as EG), 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,12-dodecanediol is mentioned.
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 the aromatic dihydric alcohol 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, dihydroxybiphenyl, dihydroxynaphthalene, 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.
A and b 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 a and b are each 2 or more, R ¹ and R ² may be the same or different, and the (OR ¹ ) _a and (R ² O) _b moieties may be 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, 1,2-, 1,3-, 1,4- or 2,3-butylene oxide and a combination system of two or more of these are used, but other AO [alpha-olefin oxide having 5 to 12 carbon atoms, styrene oxide, epihalohydrin (such as epichlorohydrin), etc.] may be used as necessary. (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 ) _a and (R ² O) _b 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 ) _a and (R ² O) _{b 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%.

As polyether diamine (B1-2), what is represented by General formula (2) is mentioned.

H ₂ N—R ³ — (OR ⁴ ) _c —O—E ² —O— (R ⁵ O) _d —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) include the same ones as described above, and preferred ranges thereof are also the same.
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 in (1) the same as those exemplified as R ¹ and R ² can be mentioned.
C and d 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 c and d are each 2 or more may be the same or different, and the (OR ⁴ ) _c and (R ⁵ O) _d portions may be 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 modified aminocarboxylic acid 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).

When the polyether (B1) is used as a structural unit of the block polymer (A), Mn of (B1) is preferably 150 to 20,000 from the viewpoint of heat resistance and reactivity with the hydrophobic polymer (D). More preferably 300 to 18,000, particularly preferably 1,000 to 15,000, and most preferably 1,200 to 8,000.
When the antistatic agent (Z) of the present invention contains (B1), the Mn of (B1) is preferably 1,000 to 10,000,000 from the viewpoint of antistatic properties and mechanical properties. More preferably, it is 5,000 to 5,000,000, particularly preferably 50,000 to 1,000,000.

  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) and (B1-1) or (B1) having a segment of polyetherdiamine (B1-2) -2) polyether urethane (B2-5) having a segment.

The polyether ester amide (B2-1) is composed of a polyamide (D1 ′) having carboxyl groups at both ends of the polyamide (D1) and a polyether diol (B1-1).
Examples of (D1 ′) 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.
Among (D1 ′), 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 polyether amide imide (B2-2) is composed of a polyamide imide (D3) having at least one imide ring and a polyether diol (B1-1).
(D3) includes a polymer composed of lactam (α1-1) and a trivalent or tetravalent aromatic polycarboxylic acid (δ) capable of forming at least one imide ring, an aminocarboxylic acid ( Examples thereof include a polymer composed of α1-2) and (δ), a polymer composed of polyamide (D1 ′) 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 (D1) and polyether diamine (D212).
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 (D).

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 ^{− and the} like), OH ⁻ , PO ₄ ⁻ , 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 (D). , 200-8,000.

The anionic polymer (B4) contains dicarboxylic acid (γ ′) having a sulfonyl group and diol (B0) or 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.) 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, diethylethanolamine, etc.), etc. Examples include amine salts and quaternary ammonium salts of the above amines.
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. .

Of (B0) or (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), a normal manufacturing method of polyester 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, bistriethanolamine titanate, and potassium oxalate titanate), zirconium catalysts (Tetrabutyl zirconate, zirconyl acetate, etc.) and zinc catalyst (zinc acetate, etc.).

  Mn of (B4) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly preferably 1 from the viewpoint of antistatic properties and reactivity with the hydrophobic polymer (D). , 200-8,000.

[Block polymer (A)]
The block polymer (A) in the present invention includes a hydrophobic polymer (D) 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): (D) is a polyamide (D1), (B) is a polyether (B1) or a polyether-containing hydrophilic polymer (B2), and (D1), (B1) and / or ( Polyether ester amide obtained by reacting B2).
(A2): (D) is polyolefin (D2), and the block of (D2) and the block of 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.

  From the viewpoint of antistatic properties and water resistance, the weight ratio of the block (D) constituting (A) to the block (B) is preferably 10/90 to 80/20, more preferably 20 / 80-75 / 25.

(D)-(B) type, (D)-(B)-(D) type, (B )-(D)-(B) type and [(D)-(B)] e type (n represents the average number of repetitions).
The structure of the block polymer (A) is preferably a [(D)-(B)] e type in which (D) and (B) are repeatedly and alternately bonded from the viewpoint of antistatic properties.
[(D)-(B)] e in the e-type structure is preferably 2 to 50, more preferably 2.3 to 30, particularly preferably from the viewpoint of antistatic properties and mechanical properties of the molded product. 2.7 to 20, most preferably 3 to 10. e 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 (D) and the block of (B) are bonded via an ester bond, an amide bond, an ether bond or an imide bond, the following method is used. Can do.
(D) 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 (D) 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 an esterification reaction, it is preferable to use 0.05 to 0.5% by weight of a catalyst based on the weight of (D) 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), antimony catalysts (such as antimony trioxide), and tin catalysts (monobutyltin). Oxide and dibutyltin oxide), titanium catalyst (tetrabutyl titanate, bistriethanolamine titanate, potassium oxalate titanate, etc.), zirconium catalyst (tetrabutyl zirconate, zirconyl acetate, etc.) and zinc catalyst (zinc acetate, etc.) Can be mentioned. 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 the produced water from the reaction system by azeotropically boiling the organic solvent and the produced 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 (D) and the block of (B) are bonded via a urethane bond or a urea bond, it can be produced by the following method.
There is a method in which (D) is charged into a reaction vessel, heated to 30 to 100 ° C. with stirring, and then (B) is charged and reacted at the same temperature for 1 to 20 hours. The weight ratio of (D) 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 accelerate the reaction, it is preferable to use 0.001 to 5% by weight of catalyst based on the weight of (D) and (B). Catalysts include organometallic compounds (dibutyltin dilaurate, dioctyltin dilaurate, lead octoate, bismuth octoate, etc.), tertiary amines {triethylenediamine, trialkylamines having 1-8 carbon atoms (trimethylamine, tributylamine). And trioctylamine etc.), diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7] etc.]; and combinations of two or more thereof.

[Antistatic agent (Z)]
The antistatic agent (Z) of this invention contains the said block polymer (A) and / or hydrophilic polymer (B), and the inorganic filler (C) mentioned later. That is, (Z) includes (Z1), (A), (B), and (C) containing (A) and (C) (Z2), (B) And (C3) containing (C3).
Of the above (Z1) to (Z3), (Z1) is preferable from the viewpoint of antistatic properties and mechanical properties.
In addition, when (Z) contains (B), among (B1) to (B4) exemplified as (B), from the viewpoint of antistatic properties and mechanical properties, (B1) and (B2) are preferable. ).

  When the antistatic agent (Z) of the present invention contains (A) and (B), the weight ratio ((A) / (B)) of (A) and (B) is an antistatic property and a mechanical property. From the viewpoint, it is preferably 50/50 to 99/1, and more preferably 60/40 to 99/1.

[Inorganic filler (C)]
The inorganic filler (C) in the present invention has a volume average particle diameter of 1 to 100 nm, preferably 5 to 50 nm. When the volume average particle diameter of (C) is less than 1 nm, the particles tend to aggregate due to van der Waals attractive force, and it is difficult to disperse in a particle state. Moreover, when the volume average particle diameter of (C) exceeds 100 nm, the effect of lowering the surface specific resistance value cannot be obtained, and the transparency in the visible light region is deteriorated.
The volume average particle diameter refers to the average value of the equivalent sphere diameters of the inorganic filler, and examples of the measuring method include a direct observation method using an electron microscope, a light or X-ray scattering method, and a dynamic light scattering method. In the present invention, it is measured by a dynamic light scattering method. Further, the shape of the filler (C) may be any of particles, fibers, and plates.

Examples of (C) used in the present invention include metal oxides such as silica, titanium oxide, barium titanate, zirconium oxide, and aluminum oxide; clay minerals such as montmorillonite, saponite, and clay. From the viewpoint of antistatic performance and dispersibility, silica fine particles are preferable.
Furthermore, it is preferable to use the water-dispersed sol of (C) or the organic solvent sol of (C) from the viewpoint of dispersibility. That is, it is a sol in which (C) is dispersed in water or an organic solvent. As the dispersion medium of (C), water or a general-purpose organic solvent can be used. Examples thereof include water, methyl ethyl ketone, methanol, ethanol, isopropyl alcohol, ethyl acetate, toluene, and a mixture of two or more thereof. It is done. From the viewpoint of dispersibility with respect to (A) and / or (B), water, methanol, ethanol and isopropyl alcohol are preferred.

  Examples of a method for stably dispersing (C) in (A) and / or (B) include addition of a dispersant and introduction of a functional group by surface modification in (C). Examples of such a dispersant include an anionic surfactant, a cationic surfactant, a polycarboxylic acid polymer dispersant, a polyimine polymer dispersant, and the like. By adsorbing these dispersants on the surface of (C), an interparticle repulsion effect by surface potential and a steric hindrance effect by molecular chains can be obtained, and the dispersibility of (C) can be improved. Moreover, as a general method of surface modification of (C), introduction of a functional group such as a carboxyl group, a nitro group, and a sulfone group by a strong acid treatment, introduction of a hydrocarbon chain by a silane coupling agent, and the like can be given.

  The weight ratio {[(A) + (B)] / (C)} of the total weight of (A) and (B) and (C) contained in the antistatic agent (Z) of the present invention is the antistatic property and From the viewpoint of moldability, it is preferably 90/10 to 99.9 / 0.1, and more preferably 95/5 to 99.5 / 0.5.

  Although there is no restriction | limiting in particular as a manufacturing method of antistatic agent (Z), From a viewpoint of disperse | distributing (C) uniformly in (Z), [1] (C) is made into (A) and / or polymer ( A method of dispersing in advance in B) and a method of containing (C) in the production of [2] (A) and / or polymer (B) are preferred. In addition, there is no limitation in particular in the timing which (C) is contained at the time of manufacture of (A) and / or polymer (B), and it may be any before polymerization, during polymerization, and after polymerization, but it is contained in the raw material before polymerization. preferable. The dispersion medium (C) is preferably not contained in (Z).

The upper limit of the volume specific resistance value of the antistatic agent (Z) of the present invention (value measured by an after-mentioned method in an atmosphere of 23 ° C. and 50% RH) is preferably 10 ¹¹ from the viewpoint of antistatic properties. Ω · cm, more preferably 10 ¹⁰ Ω · cm, and particularly preferably 10 ⁹ Ω · cm. From the viewpoint of mechanical properties, the lower limit is preferably 10 ⁴ Ω · cm, and more preferably 10 ⁵ Ω · cm.
In addition, the antistatic agent (Z) is a permanent antistatic property excellent in the molded product described later by improving the ion conductivity of the (Z) by nanodispersing (C) in (Z). It is considered that mechanical properties and appearance can be imparted.

The antistatic agent (Z) of the present invention can further contain an antistatic property improver (F) if necessary, as long as the effects of the present invention are not impaired.
Examples of the antistatic property improver (F) include alkali metal or alkaline earth metal salt (F1), quaternary ammonium salt (F2), surfactant (F3), ionic liquid (F4), and the like. In addition, (F1)-(F4) may use 2 or more types together.

  Examples of the alkali metal or alkaline earth metal salt (F1) include an alkali metal (lithium, sodium, potassium, etc.) or an alkaline earth metal (magnesium, calcium, etc.), an organic acid [mono-or C1-C7 or Di-carboxylic acids (formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), sulfonic acids having 1 to 7 carbon atoms (methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc.) and thiocyanic acid] And salts of the organic acid and inorganic acid [(hydrohalic acid (for example, hydrochloric acid, hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.]).

  As the quaternary ammonium salt (F2), amidinium (1-ethyl-3-methylimidazolium or the like) or guanidinium (2-dimethylamino-1,3,4-trimethylimidazolinium or the like), the organic acid or the inorganic Examples include salts with acids.

  Examples of the surfactant (F3) include known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. In addition, (E3) may use 2 or more types together.

  The ionic liquid (F4) is a compound other than the above (F1) to (F3), has a melting point of 25 ° C. or lower, and at least one of the constituent cations or anions is an organic ion, and has an initial conductivity. Is a room temperature molten salt of 1 to 200 ms / cm (preferably 10 to 200 ms / cm). Specifically, the room temperature molten salt exemplified in WO95 / 15572 is exemplified.

  The content of each of (F1) to (F4) based on the weight of the antistatic agent (Z) is preferably 10% by weight from the viewpoint of antistatic properties and a resin molded product having a good appearance without being deposited on the resin surface. Or less, more preferably 0.01 to 8% by weight, and particularly preferably 0.1 to 6% by weight.

  The total content of (F1) to (F4) based on the weight of the antistatic agent (Z) is preferably from the viewpoint of antistatic properties and a resin molded product having a good appearance without being deposited on the resin surface. It is 01-10 weight%, More preferably, it is 0.1-8 weight%.

  As a method of adding (F) to the antistatic agent (Z) of the present invention, a method of dispersing in advance in the antistatic agent (Z) is preferable in order not to impair the appearance of a molded product described later. A method in which (F) is contained during the production of A) and / or polymer (B) is more preferred. There is no particular limitation on the timing of containing (F) during the production of (A), and it may be before polymerization, at the time of polymerization, or after polymerization, but is preferably contained in the raw material before polymerization. Moreover, (F) can also be contained at the time of manufacture of the below-mentioned antistatic resin composition.

[Antistatic resin composition]
The antistatic resin composition of the present invention comprises the antistatic agent (Z) and the thermoplastic resin (E).

(E) includes polyphenylene ether resin (PPE) (E1); vinyl resin {polyolefin resin (E2) [for example, polypropylene (PP), polyethylene, ethylene-vinyl acetate copolymer resin (EVA), and ethylene-ethyl acrylate copolymer Resin, etc.], polyacrylic resin (E3) [for example, polymethyl methacrylate, etc.], polystyrene resin (E4) [vinyl group-containing aromatic hydrocarbon alone, vinyl group-containing aromatic hydrocarbon, and (meth) acrylic acid ester , A copolymer having at least one selected from the group consisting of (meth) acrylonitrile and butadiene; for example, polystyrene (PS), styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer Combined (ABS resin), methacrylic acid Chill / butadiene / styrene copolymer (MBS resin) and styrene / methyl methacrylate copolymer (MS resin), etc.]]; polyester resin (E5) [for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, Polybutylene adipate and polyethylene adipate, etc.]; polyamide resin (E6) (for example, nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12, etc.); polycarbonate Examples thereof include resin (E7) (for example, polycarbonate and polycarbonate / ABS alloy resin); polyacetal resin (E8); biodegradable resin (E9), and a mixture of two or more thereof.
Among these, (E1), (E2), (E3), and (E4) are preferable from the viewpoint of the mechanical properties of the molded product described later and the dispersibility of the antistatic agent (Z) of the present invention in (E). (E5) and (E7), and (E2), (E4) and (E7) are more preferable.

  The content of (Z) based on the total weight of the antistatic agents (Z) and (E) of the present invention is preferably 1 to 15% by weight, more preferably 2 from the viewpoint of antistatic properties and mechanical properties. -10% by weight.

  If necessary, the antistatic resin composition of the present invention may further contain other additives (G) other than (F) as long as the effects of the present invention are not impaired. (G) includes a colorant (G1), a release agent (G2), an antioxidant (G3), a flame retardant (G4), an ultraviolet absorber (G5), an antibacterial agent (G6), and a compatibilizer (G7). ) And a filler (G8) having a volume average particle diameter of more than 100 nm. In addition, (G) may use 2 or more types together.

  Examples of the colorant (G1) 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 (G2), C12-18 fatty acid alkyl (carbon number 1-4) ester (butyl stearate, etc.), C2-18 fatty acid glycol (carbon number 2-8) 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.

  Examples of the antioxidant (G3) include phenol compounds [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.), bisphenol [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 etc.), phosphorus compounds (triphenyl phosphite etc.), amine compounds (octylated diphenylamine etc.) and the like.

  Examples of the flame retardant (G4) include halogen-containing flame retardants, nitrogen-containing flame retardants, sulfur-containing flame retardants, silicon-containing flame retardants and phosphorus-containing flame retardants.

  Examples of the ultraviolet absorber (G5) 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 (G6) 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), quaternary ammonium compounds, and pyridine compounds.

  As the compatibilizing agent (G7), a modified vinyl polymer having one or more functional groups (polar groups) 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 special vinyl polymer) Polymers described in Kaihei 3-258850, modified vinyl polymers having a sulfonic acid group described in JP-A-6-345927, and block polymers having a polyolefin portion and an aromatic vinyl polymer portion, etc.) Is mentioned.

  Examples of the filler (G8) include inorganic fillers (such as calcium carbonate, talc, and clay) other than the above (C), organic fillers (such as urea and calcium stearate), and the like.

  The total content of (G) based on the weight of the thermoplastic resin (E) is usually 45% or less, preferably 0.001 to 40%, more preferably from the viewpoint of the effect of each additive and the mechanical properties of the molded product. 0.01 to 35%; The content of each (E) is preferably 0.1 to 3%, more preferably 0.2 to 2%, and (G2) is preferably 0 from the same viewpoint. 0.01-3%, more preferably 0.05-1%; (G3) is preferably 0.01-3%, more preferably 0.05-1%; (G4) is preferably 0.5-20. %, More preferably 1-10%; (G5) is preferably 0.01-3%, more preferably 0.05-1%; (G6) is preferably 0.5-20%, more preferably 1. -10%; (G7) is preferably 0.5 to 10%, more preferably 1 to %; (G8) is preferably from 0.5 to 10%, more preferably 1-5%.

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 (E), and, if necessary, other additives (G).
As a method of melting and mixing, generally, a method of mixing each component in pellet form or powder form with an appropriate mixer (Henschel mixer etc.) and then melt mixing and pelletizing with an extruder is applied. it can.
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 melt-mixed, and then (E), and (G) is batch-added as necessary to melt-mix;
[2] After (Z) is melt-mixed, a part of (E) is melt-mixed in advance to prepare a high-concentration composition (masterbatch resin composition) of (Z), and then the remaining (E) and A method of melt-mixing (F) 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 (E).

[Molded products, molded articles]
The molded article 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.

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 of the present invention will be described below, but the present invention is not limited thereto. Below, a part shows a weight part. In the following, Examples 9 to 11 are referred to as Reference Examples 1 to 3, respectively.

<Production Example 1>
[Production of polyamide (D1-1)]
In a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen introducing tube and a decompression device, 173 parts by weight of ε-caprolactam, 33.2 parts by weight of terephthalic acid, an antioxidant [“Irganox 1010” , Manufactured by Ciba Specialty Chemicals Co., Ltd.] 0.4 parts by weight and 10 parts by weight of water were added. After purging with nitrogen, the temperature was raised to 220 ° C. with stirring and the same temperature (pressure: 0.2 to 0.3 MPa) for 4 hours to obtain a polyamide (D1-1) having carboxyl groups at both ends. The acid value of (D1-1) was 111, and Mn was 1,000.

<Production Example 2>
[Production of polyolefin having carboxyl groups at both ends (D2-1-1α)]
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 by weight, 10 parts by weight of maleic anhydride and 30 parts by weight of xylene were added, mixed uniformly, then purged with nitrogen, heated to 200 ° C. with stirring under stirring, and melted at the same temperature. The reaction was allowed for 10 hours. 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 (D2-1-1α) 95 having carboxyl groups at both ends of the polymer. Part by weight was obtained. The acid value of (D2-1-1α) was 27.5, and Mn was 3,600.

<Production Example 3>
[Production of polyolefin (D2-1-2α) obtained by secondary modification of (D2-1-1α)]
In a pressure resistant reactor similar to Production Example 1, 88 parts by weight of (D2-1-1α) and 12 parts by weight of 12-aminododecanoic acid were added and mixed uniformly, and then stirred up to 200 ° C. in a nitrogen gas atmosphere. The temperature was raised and the mixture was reacted at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours to obtain 96 parts by weight of polyolefin (D2-1-2α) obtained by secondary modification of (D2-1-1α). . The acid value of (D2-1-2α) was 24.8, and Mn was 4,000.

<Production Example 4>
[Production of polyolefin having hydroxyl groups at both ends (D2-2α)]
In Production Example 2, 90 parts by weight of low molecular weight polypropylene obtained by the thermal degradation method and 10 parts by weight of maleic anhydride were combined with 94 parts by weight of a low molecular weight ethylene / propylene random copolymer obtained by the thermal degradation method and anhydrous. 98 parts by weight of polyolefin (a2-1-1β) having carboxyl groups at both ends of the polymer was obtained in the same manner as in Production Example 2 except that the amount was changed to 6 parts by weight of maleic acid. The acid value of (D2-1-1β) 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, two per molecule) The average number of heavy bonds: 1.8, the content of polyolefin that can be modified at both ends: 90% by weight) is 410 ethylene / propylene random copolymer (ethylene content: 2% by weight, MFR: 10 g / 10 min). It was obtained by thermal degradation for 14 minutes at ± 0.1 ° C. under nitrogen aeration (80 mL / min).
Next, 97 parts by weight of (D2-1-1β) and 5 parts by weight of ethanolamine were put into a pressure resistant reactor similar to Production Example 1, and the temperature was raised to 180 ° C. with stirring in a nitrogen gas atmosphere. For 2 hours. Excess ethanolamine was distilled off under reduced pressure (0.013 MPa or less) at 180 ° C. over 2 hours to obtain polyolefin (D2-2α) having hydroxyl groups at both ends of the polymer. (D2-2α) had a hydroxyl value of 9.9, an amine value of 0.01, and Mn of 10,200.

<Production Example 5>
[Production of modified polyolefin having amino groups at both ends (D2-4α)]
In Production Example 2, 90 parts by weight of low molecular weight polypropylene obtained by the thermal degradation method and 10 parts by weight of maleic anhydride were changed to 80 parts by weight of low molecular weight polypropylene obtained by the thermal degradation method and 20 parts by weight of maleic anhydride. Except having changed, it carried out similarly to manufacture example 2, and obtained 92 weight part of polyolefin (D2-1-1 (gamma)) which has a carboxyl group in the both terminal of a polymer. The acid value of (D2-1-1γ) 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 by weight of (D2-1-1γ) and 10 parts by weight of bis (2-aminoethyl) ether are charged into a pressure-resistant reaction vessel similar to Production Example 1, and the mixture is stirred at 200 ° C. in a nitrogen gas atmosphere. The temperature was raised and the reaction was carried out 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 (D2-4α) having amino groups at both ends. The amine value of (D2-4α) was 64.0, and Mn was 1,700.

<Production Example 6>
[Production of Cationic Polymer (B3α)]
In a pressure resistant reactor similar to Production Example 1, 41 parts by weight of N-methyldiethanolamine, 49 parts by weight of adipic acid and 0.3 parts by weight of zirconyl acetate were added, and after nitrogen substitution, the temperature was raised to 220 ° C. over 2 hours. The pressure was reduced to 0.013 MPa over 1 hour for the polyesterification reaction. After completion of the reaction, the mixture was cooled to 50 ° C. and dissolved by adding 100 parts by weight of methanol. While stirring, the temperature in the reaction vessel was kept at 120 ° C., 31 parts by weight of dimethyl carbonate was added dropwise over 3 hours, and aged at the same temperature for 6 hours. After cooling to room temperature, 100 parts by weight of a 60% by weight 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 by weight of diethylene glycol, 268 parts by weight of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 parts by weight of dibutyltin oxide were added, and 190 ° C. under a reduced pressure of 0.067 MPa. The temperature was raised to 0 ° C., and the ester exchange reaction was carried out at the same temperature for 6 hours while distilling off methanol. An anionic polymer (B4α) having an average of 6 sodium sulfonate groups in one molecule (hydroxyl value was 49, acid value was 0.6, and the volume resistivity was 3 × 10 ⁸ Ω · cm).

<Production Example 8>
[Production of anionic polymer (B4β)]
In a pressure-resistant reaction vessel similar to Production Example 1, 67 parts by weight of PEG (Mn: 300), 49 parts by weight of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 parts by weight of dibutyltin oxide were charged, and 0.067 MPa of The temperature was raised to 190 ° C. under reduced pressure, transesterification was carried out at the same temperature for 6 hours while distilling off methanol, and an anionic polymer (B4β) having an average of 5 sodium sulfonate groups in one molecule (hydroxyl value: 29 .6, acid value: 0.4, volume resistivity: 2 × 10 ⁶ Ω · cm).

<Production Example 9>
[Production of block polymer mixture (A1-1C)]
In a reaction vessel equipped with a stirrer, a thermometer and a heating / cooling device, 199 parts by weight of (D1-1), bisphenol A EO adduct (Mn: 4,000, volume resistivity: 2 × 10 ⁷ Ω · cm 780 parts by weight, zirconyl acetate 0.6 parts by weight, and water-dispersed titanium oxide sol [trade name: Nanotitania NTB-1, manufactured by Showa Denko KK, volume average particle size 10 nm, solid content 15 wt%] (C-2) 6 .7 parts by weight, heated to 240 ° C. with stirring, polymerized for 6 hours at the same temperature under reduced pressure (0.013 MPa or less), and the viscous block polymer (A1-1) and inorganic filler (C) A block polymer mixture (A1-1C) was obtained. The Mn of (A1-1) was 24,000.

<Production Example 10>
[Production of block polymer mixture (A1-2C)]
In a pressure-resistant reaction vessel similar to Production Example 9, (D1-1) 143 parts by weight, (B4α) 320 parts by weight, antioxidant “Irganox 1010” 0.3 part by weight and water-dispersed zirconium oxide sol [trade name: Nano-use ZR-20AS, manufactured by Nissan Chemical Industries, Ltd., volume average particle size 50 nm, solid content 20 wt%] (C-3) 25 parts by weight were added, and the temperature was raised to 240 ° C. with stirring, The block polymer mixture (A1-2C) containing the viscous block polymer (A1-2) and the inorganic filler (C) was obtained by polymerization at the same temperature for 5 hours. Mn of (A1-2) was 21,000.

<Production Example 11>
[Production of block polymer mixture (A2-1C)]
In a pressure resistant reactor similar to Production Example 9, 67.1 parts by weight of (D2-1-1α), polyetherdiamine (B1-2α) [α, ω-diaminoPEG (Mn: 2,000, volume resistivity) 1 × 10 ⁷ Ω · cm)] 32.9 parts by weight, 0.3 parts by weight of the antioxidant “Irganox 1010”, 0.5 parts by weight of zirconyl acetate and methanol-dispersed silica sol [trade name: MA-ST-M , Manufactured by Nissan Chemical Industries, Ltd., volume average particle diameter 20 nm, solid content 40 wt%] (C-1) 51 parts by weight were added, the temperature was raised to 220 ° C. with stirring, and the pressure was reduced (0.013 MPa or less) Polymerization was performed at the same temperature for 3 hours to obtain a block polymer mixture (A2-1C) containing a viscous block polymer (A2-1) and an inorganic filler (C). The Mn of (A2-1) was 50,000.

<Production Example 12>
[Production of block polymer mixture (A2-2C)]
In Production Example 11, 67.1 parts by weight of (D2-1-1α) and 32.9 parts by weight of (B1-2α) were added to 60.1 parts by weight of (D2-1-2α) and polyether diol (B1-1α). ) [PEG (Mn: 3,000, volume resistivity: 1 × 10 ⁷ Ω · cm)] The block polymer (A2-2) was prepared in the same manner as in Production Example 11 except that the content was changed to 39.9 parts by weight. And a block polymer mixture (A2-2C) containing inorganic filler (C). Mn of (A2-2) was 30,000.

<Production Example 13>
[Production of block polymer mixture (A2-3C)]
In Production Example 11, 67.1 parts by weight of (D2-1-1α) and 32.9 parts by weight of (B1-2α), 48.0 parts by weight of (D2-2α), 48.0 parts by weight of (B3α) and A block polymer mixture (A2-3C) containing a block polymer (A2-3) and an inorganic filler (C) was obtained in the same manner as in Production Example 11 except that the amount was changed to 4 parts by weight of dodecanedioic acid. The Mn of (A2-3) was 100,000.

<Production Example 14>
[Production of block polymer mixture (A2-4C)]
In Production Example 11, 67.1 parts by weight of (D2-1-1α) and 32.9 parts by weight of (B1-2α), 31.6 parts by weight of (D2-4α), 68.4 parts by weight of (B4β) and A block polymer mixture (A2-4C) containing a block polymer (A2-4) and an inorganic filler (C) was obtained in the same manner as in Production Example 11 except that the amount was changed to 8 parts by weight of dodecanedioic acid. The Mn of (A2-4) was 10,000.

<Production Example 15>
[Production of block polymer mixture (A2-5C)]
In Production Example 11, 67.1 parts by weight of (D2-1-1α) and 32.9 parts by weight of (B1-2α), 71.5 parts by weight of (D2-1-2α) and polyether diol (B1-1β ) [Polytetramethylene glycol (Mn: 1,800, volume resistivity: 1 × 10 ¹¹ Ω · cm)] The block polymer (A2-5) was prepared in the same manner as in Production Example 11 except that the amount was changed to 28.5 parts by weight. ) And an inorganic filler (C) to obtain a block polymer mixture (A2-5C). The Mn of (A2-5) was 40,000.

<Production Example 16>
[Production of block polymer mixture (A2-6C)]
In Production Example 11, 67.1 parts by weight of (D2-1-1α) and 32.9 parts by weight of (B1-2α), 48.0 parts by weight of (D2-2α), 48.0 parts by weight of (B3α) and A block polymer mixture (A2-6C) containing a block polymer (A2-6) and an inorganic filler (C) was prepared in the same manner as in Production Example 11 except that the amount was changed to 3 parts by weight of hexamethylene diisocyanate (HDI). Obtained. The Mn of (A2-6) was 100,000.

<Production Example 17>
[Production of block polymer (A2-4)]
In a pressure resistant reaction vessel similar to Production Example 9, 31.6 parts by weight of (D2-4α), 68.4 parts by weight of (B4β), 8 parts by weight of dodecanedioic acid, 0.3 weight of the antioxidant “Irganox 1010” Part and 0.5 parts by weight of zirconyl acetate were added, the temperature was raised to 220 ° C. with stirring, and the mixture was polymerized at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours to obtain a block polymer (A2-4). . The Mn of (A2-4) was 10,000.

<Production Example 18>
[Production of block polymer (A2-5)]
In Production Example 17, (D2-4α) 31.6 parts by weight, (B4β) 68.4 parts by weight, dodecanedioic acid 8 parts by weight, (D2-1-2α) 71.5 parts by weight and (B1-1β ) A block polymer (A2-5) was obtained in the same manner as in Production Example 17 except that the amount was changed to 28.5 parts by weight. The Mn of (A2-5) was 40,000.

<Examples 1-12, Comparative Examples 1-4>
According to the composition shown in Table 1 (parts by weight), the blended components were blended for 3 minutes with a Henschel mixer, and then melt-kneaded in a vented twin-screw extruder at 100 rpm, 200 ° C. and a residence time of 5 minutes, The antistatic agents (Z-1) to (Z-12) and (Z′-1) to (Z′-4) of Examples 1 to 12 and Comparative Examples 1 to 4 were obtained. The results are shown in Table 1.

The contents of the symbols in Table 1 are as follows.
(B1-1γ): Polyethylene oxide [“PEO-1Z”, manufactured by Sumitomo Seika Co., Ltd.]
(B2-5α): Polyether urethane [“Melpol HA-2200”,
Sanyo Chemical Industries, Ltd.]
(C-1): Methanol-dispersed silica sol
["MA-ST-M", manufactured by Nissan Chemical Industries, Ltd.
Volume average particle diameter 20 nm, solid content 40 wt%]
(C-2): Water-dispersed silica sol [“Snowtex O-40”, manufactured by Nissan Chemical Industries, Ltd.
Volume average particle diameter 25 nm, solid content 40 wt%]
(Ratio C-1): Talc ["Microace P-6", manufactured by Nippon Talc Co., Ltd.,
Volume average particle diameter 4μm]
(F1-1): lithium trifluoromethanesulfonate (F3-1): sodium dodecylbenzenesulfonate

<Examples 13 to 28, Comparative Examples 5 to 13>
In accordance with the blending composition (parts by weight) shown in Tables 2 and 3, the blending components were mixed for 3 minutes with a Henschel mixer, then, with a twin screw extruder with a vent, 100 rpm, residence time 5 minutes, cylinder temperature 220 ° C. [(E-1 ) When used] Melt-kneaded under the conditions of 230 ° C. [when (E-2), (E-3), (E-5) is used]] or 280 ° C. [when (E-4) is used]. Thus, antistatic resin compositions of Examples 13 to 28 and Comparative Examples 5 to 13 were obtained.

The contents of symbols in Tables 2 and 3 are as follows.
(E-1): Impact resistant PS resin
["HIPS 433", manufactured by PS Japan Ltd.]
(E-2): ABS resin
["Cebian 680SF" manufactured by Daicel Polymer Ltd.]
(E-3): PC / ABS resin
["Psycholoy C6600",
SABIC Innovative Plastics Japan GK]
(E-4): Modified PPE resin
“Noryl PPO534”,
SABIC Innovative Plastics Japan GK]
(E-5): PP resin ["PM771M", manufactured by Sun Allomer Co., Ltd.]
(G3-1): Antioxidant [“Irganox 1010”,
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-
Hydroxyphenyl) propionate] methane,
Ciba Specialty Chemicals Co., Ltd.]
(G7-1): Compatibilizer
["Epofriend AT501", epoxidized polystyrene elastomer,
Daicel Chemical Industries, Ltd.]

  The obtained antistatic resin composition was used with an injection molding machine “PS40E5ASE” [manufactured by Nissei Plastic Industry Co., Ltd.], cylinder temperature 220 ° C. [when (E-1) was used], 230 ° C. [(E- 2) When using (E-3), (E-5)], or 280 ° C. [When using (E-4)] Molding specimens at a mold temperature of 50 ° C. evaluated. The results are shown in Tables 2 and 3.

<Performance test>
(1) Surface resistivity (unit: Ω)
In accordance with ASTM D257, a test piece (100 × 100 × 2 mm) was measured using a superinsulator “DSM-8103” [manufactured by Toa Denpa Co., Ltd.] in an atmosphere of 23 ° C. and humidity 50% RH.
(2) Izod impact strength (Unit: J / m)
Measured according to ASTM D256 Method A (notched, 3.2 mm thickness).
(3) Appearance Molding was performed under the same conditions as molding with a single thermoplastic resin, and the surface condition of the molded product was compared with a molded product with a single thermoplastic resin according to the following criteria.
○: The surface of the molded product is equivalent to a molded product of a single thermoplastic resin.
X: The surface of the molded product is uneven as compared with a molded product of a single thermoplastic resin.

  As is apparent from Tables 2 and 3, the antistatic agent (Z) of the present invention imparts excellent permanent antistatic properties to the molded product even when added in a small amount, compared to the comparative product. It turns out that it is excellent in mechanical strength and appearance.

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

Claims (6)

An antistatic agent comprising a block polymer (A) and silica fine particles (C) having a volume average particle diameter of 5 to 50 nm , wherein the weight ratio of (A) to (C) [(A) / (C)] is 90/10 to 99.9 / 0.1, and (A) is a block polymer comprising a block of a hydrophobic polymer (D) and a block of a hydrophilic polymer (B) as structural units An antistatic agent (Z) in which (A) is the following (A1) and / or (A2).
(A1): Polyether ester amide derived from a polyamide and a polyether composed of an alkylene oxide adduct (number average molecular weight 300 to 5,000) and / or polyalkylene glycol of a bisphenol compound (A2): Block of polyolefin And a block polymer having a structure in which a polyether block is repeatedly bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond   The antistatic agent according to claim 1, wherein (B) is a polyether (B1) or a polyether-containing hydrophilic polymer (B2).   Further, at least one antistatic property selected from the group consisting of an alkali metal or alkaline earth metal salt (F1), a quaternary ammonium salt (F2), a surfactant (F3), and an ionic liquid (F4). The antistatic agent according to claim 1 or 2, comprising an agent (F).   An antistatic resin composition comprising the antistatic agent (Z) according to any one of claims 1 to 3 and a thermoplastic resin (E).   A molded product obtained by molding the antistatic resin composition according to claim 4. A molded article obtained by coating and / or printing the molded article according to claim 5.