JP2008031461A - Antistatic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic resin composition giving a molded product of high moldability with excellent antistaticity and mechanical properties in view of the conventional problem that, for imparting a thermoplastic resin with electrical conductivity, there has been the need of using a resin composition compounded with much electrically conductive material, leading to impairing its moldability due to declining in its fluidity. <P>SOLUTION: An antistatic agent is provided, comprising a mixture of carbon nanotubes and a dispersant having a conjugated double bond and a hydrophilic group-containing polymer with a volume resistivity of 1×10<SP>6</SP>to 1×10<SP>12</SP>Ωcm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antistatic agent comprising carbon nanotubes. More specifically, the present invention relates to an antistatic agent excellent in dispersibility of carbon nanotubes, and an antistatic resin composition comprising the antistatic agent contained in a thermoplastic resin.

  Conventional elastomers (olefin elastomers, vinyl chloride elastomers, styrene elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, fluoroelastomers, syndiotactic-1,2-PB elastomers, chlorinated ethylene copolymer crosslinked alloys, chlorinated polyethylene and esters) As a method of imparting conductivity to a halogen polymer alloy or the like, a method of blending a conductive substance such as carbon, metal fiber, or metal powder (for example, see Patent Document 1) is known.

JP-A-7-216224

  However, in the above method, since it is necessary to add a large amount of a conductive substance, there is a problem that the moldability deteriorates due to a decrease in the fluidity of the resin composition, and the molded article becomes heavy. An object of the present invention is to provide an antistatic resin composition excellent in moldability and a molded article excellent in permanent antistatic property and mechanical properties.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to a mixture of a carbon nanotube (A) and a dispersant (B) having a conjugated double bond and a hydrophilic group-containing polymer (C) having a volume resistivity of 1 × 10 ⁶ to 1 × 10 ^12.
An antistatic agent comprising the thermoplastic resin (D) containing the antistatic agent; a molded product formed by molding the composition; and the molding A molded article obtained by painting and / or printing a product.

  The antistatic resin composition comprising the antistatic agent of the present invention contained in a thermoplastic resin is excellent in moldability, and a molded product formed by molding the composition is excellent in mechanical properties and has an unprecedented advanced level. There is an effect of having a permanent antistatic property.

The carbon nanotube (A) in the present invention has a structure in which a graphite layer in which carbon atoms are two-dimensionally arranged is closed in a cylindrical shape.
(A) has a single-walled structure (single-walled carbon nanotube), a multilayered structure in which a plurality of carbon nanotubes are nested (multi-walled carbon nanotube), and partially has a carbon nanotube structure. Carbon materials, and mixtures thereof are included.
The aspect ratio (length / diameter ratio) of (A) is preferably 10 to 1,000, more preferably 30 to 800, from the viewpoint of conductivity and moldability.
Further, the diameter of (A) is preferably 1 to 50 nm, more preferably 1 to 40 nm, from the viewpoint of industrial and electrical conductivity.

As a manufacturing method of (A), for example, a method of generating an arc discharge between carbon electrodes and growing it on the cathode surface of the discharge electrode, a method of heating and sublimating silicon carbide with a laser beam, a transition metal catalyst, And a method of carbonizing hydrocarbons in a gas phase under a reducing atmosphere.

The dispersant (B) having a conjugated double bond in the present invention is not particularly limited as long as it is an organic compound having 3 to 22 carbon atoms (hereinafter abbreviated as C) having a conjugated double bond in the molecule. The following are mentioned.
(1) Hydrocarbon (1-1) Aliphatic hydrocarbon C4-20, such as butadiene, 1,3-pentadiene, isoprene, 1,3- and 2,4-hexadiene, 1,3,5-hexatriene, 2 -, 3- and 4-methyl-1,3-pentadiene, 2-ethyl-1,3-butadiene, 1,3- and 2,4-heptadiene, 1,3,5-heptatriene, 2- and 3-methyl -1,3-hexadiene, 2- and 3-methyl-2,4-hexadiene, 2- and 3-methyl-1,3,5-hexatriene, 2-, 3- and 4-ethyl-1,3- Pentadiene and the like;
(1-2) Alicyclic ring-containing hydrocarbon C5-20, such as cyclopentadiene, cycloheptatriene and the like;
(1-3) Aromatic ring-containing hydrocarbons C6-22, such as monocyclic (C6-22, such as benzene, toluene, o-, m- and p-xylene, 1,2,3-trimethylbenzene, mesitylene, cumene, o-, m- and p-cymene, styrene, 1,4-divinylbenzene,) and polycyclic (C10-22, eg biphenyl, pentalene, indene, naphthalene, azulene, heptalene, as- and s-indacene, acenaphthylene. , Fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrene, aceanthrylene, triphenylene, pyrene, chrysene, naphthacene, pleiaden, picene, perylene, pentaphen, pentacene), among these, carbon nanotubes From the viewpoint of dispersibility Preferred are fluorene, anthracene and perylene;
(2) ether (2-1) linear or branched ether C7-20, such as anisole, ethyl phenyl ether, butyl phenyl ether, isobutyl phenyl ether, t-butyl phenyl ether, etc .;
(2-2) Cyclic (thio) ether furan, 2- and 3-methylfuran, 2- and 3-ethylfuran, 2- and 3-furanacetonitrile, 2- and 3-furanethylamine, thiophene, 2- and 3 -Methylthiophene, 2- and 3-ethylthiophene, 2- and 3-thiopheneacetonitrile, 2- and 3-thiopheneethylamine and the like;
(3) Ketone C7-20, such as methyl phenyl ketone, ethyl phenyl ketone, butyl phenyl ketone, isobutyl phenyl ketone, t-butyl phenyl ketone, benzophenone, etc .;
(4) Esters C7-20, such as methyl benzoate, ethyl benzoate, butyl benzoate, isobutyl benzoate, t-butyl benzoate and the like;
(5) Organic acid (salt)
C7-20, such as benzoic acid, o-, m- and p-hydroxybenzoic acid, o-, m- and p-methylbenzoic acid, phthalic acid, benzenesulfonic acid and their salts [alkali or alkaline earth metal salts , Ammonium salts, amines [provided that the amine of the following (5) is excluded], etc.], etc .;

(6) Amine (salt) [represents an amine, a salt thereof, and a quaternary ammonium salt. same as below. ]
(6-1) Aliphatic amine (salt)
C4-20, such as 1- and 2-amino-1,3-butadiene, 1-, 2-, 3-, 4- and 5-amino-1,3-pentadiene, 1-, 2-, 3--4 -, 5- and 6-amino 1,3-hexadiene, 1-, 2- and 3-amino-2,4-hexadiene, their salts and quaternary ammonium salts;
(6-2) Ring-containing amine (salt)
(6-2-1) Amine containing benzene ring (salt)
C6-20, such as aniline, tolylenediamine, xylylenediamine, their salts and quaternary ammonium salts;
(6-2-2) Heterocycle-containing amine (salt)
C3-20, such as imidazole compounds (imidazole, methylimidazole, ethylimidazole, 1,2,4-trimethylimidazole, 1,4-dimethyl-2-ethylimidazole, 1,2-dimethylimidazole, 2-diethylamino-1,4 -Dimethylimidazole, 2-diethylamino-1-ethyl-4-methylimidazole, 2-dimethylamino-4-ethyl-1-methylimidazole, 2-dimethylamino-1,4-dimethylimidazole, 2-diethylamino-1,4 -Dimethylimidazole, 2-diethylamino-4-ethyl-1-methylimidazole, 2-dimethylamino-4-ethyl-1-methylimidazolium, etc.), pyridine compounds (pyridine, 4-methylpyridine, etc.), pyrimidine compounds (pyrimidine) , 2-me Lupyrimidine etc.), pyrazine compounds (pyrazine, 2-methylpyrazine etc.), triazole compounds (1,2,4-triazole, 1H-1,2,3-triazole etc.), their salts and quaternary ammonium salts. In view of the dispersibility of the carbon nanotubes, imidazole compounds and quaternary ammonium salts thereof are preferable.

  Examples of the amine salt include inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salt of the amine, organic acid (C1-15 carboxylic acid, etc.) salt, etc .; Quaternized with an agent (methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate, etc.), and those quaternized with an acid exchange by the method described later (the quaternary ammonium salt Constituent cations and anions will be described later).

  Of the above (B), hydrocarbons and amines (salts) are preferred from the viewpoint of dispersibility of carbon nanotubes, more preferred are heterocyclic-containing amines (salts), and particularly preferred are imidazole compounds and quaternary ammonium salts thereof. It is.

Examples of the cation constituting the quaternary ammonium salt include an amidinium cation and a guanidinium cation.
Examples of the amidinium cation include an imidazolinium cation [1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium. 1,3-dimethyl-2,4-diethylimidazolinium, etc.], imidazolium cation [1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1, 2,3-trimethylimidazolium, etc.], pyrimidinium cation [1,3-dimethylpyrimidinium,
1,2,3-trimethylpyrimidinium, 1,2,3,4-tetramethylpyrimidinium, 1,2,3,5-tetramethylpyrimidinium, etc.];

  Examples of guanidinium cations include guanidinium cations having an imidazolium skeleton [2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino. -1,3-dimethyl-4-ethylimidazolium, 2-dimethylamino-1-methyl-3,4-diethylimidazolium, etc.].

The anion constituting the quaternary ammonium salt includes an anion of an organic acid or an inorganic acid. Examples of the organic acid include carboxylic acid, sulfate ester, higher alkyl ether sulfate ester, sulfonic acid and phosphate ester; inorganic Examples of the acid include super strong acids (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, and hexafluoroarsenic acid), phosphoric acid, and boric acid. . The organic acid and inorganic acid may be used alone or in combination of two or more.
Among the above organic acids and inorganic acids, from the viewpoint of the dispersibility of (A), it is preferable to form anions other than the super strong acid and the conjugate base of the super strong acid whose Hammett acidity function (-H0) is 12 to 100. Acid and mixtures thereof.

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

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

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

Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof.
The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

  As a method for producing the quaternary ammonium salt, for example, a dimethyl carbonate salt of an amidinium cation and / or a guanidinium cation obtained by quaternization with dimethyl carbonate or the like, an acid [forms an anion in the quaternary ammonium salt]. The above-mentioned organic acid or inorganic acid] is added to perform acid exchange, or the amidinium cation and / or guanidinium cation is once hydrolyzed to form a monoamidoamine, and then the monoamidoamine is converted into an acid (described above) And the same method).

The hydrophilic group-containing polymer (C) in the present invention is 1 × 10 ⁶ to 1 × 10 ¹² (preferably 5 × 10 ⁶ to 1 × 10 ¹¹ , more preferably 1 × 10 ⁷ to 1 × 10 ¹⁰ ) Ω · It is a hydrophilic group-containing polymer having a volume resistivity of cm. When the volume resistivity value of (C) is less than 1 × 10 ⁶ Ω · cm, the moldability of the composition is deteriorated, and when it exceeds 1 × 10 ¹² Ω · cm, the antistatic property is deteriorated.
(C) includes the following and mixtures of two or more thereof.
(C1): Number average molecular weight [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method. ] Is preferably a polyether ester derived from a polyamide (c11) having 200 to 5,000 and an alkylene oxide (hereinafter abbreviated as AO) adduct (c12) of a bisphenol compound having Mn preferably 300 to 5,000. Amide (C2): at least one selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond, and a urethane bond, in which the block of polyolefin (c21) and the polyoxyalkylene chain-containing compound ((c22) block) Block polymer (C3) having a structure that is alternately and repeatedly bonded via a bond: Polyetheramideimide (C4): Polyetherester Among these, (C1) to (C3) are preferable from the viewpoint of antistatic properties. More preferred are (C1) and (C2).

  As (C1), for example, polyether ester amides described in JP-A-6-287547 and JP-B-4-5691 can be used. Among these, from the viewpoint of heat resistance, the preferable lower limit of Mn is 200, more preferably 500, the preferable upper limit of Mn is 5,000, more preferably 3,000 polyamide (c11), and the preferable lower limit of Mn is 300, More preferred is a polyether ester amide derived from an AO adduct (c12) of a bisphenol compound having a preferred upper limit of 500 and Mn of 5,000, more preferably 4,000.

Examples of the polyamide (c11) include a lactam ring-opening polymer (c111), an aminocarboxylic acid polycondensate (c112), a dicarboxylic acid and diamine polycondensate (c113), and a copolymerized polyamide (c114) thereof. .
Among the amide-forming monomers forming these polyamides, the lactam in (c111) includes C6-12, such as caprolactam, enantolactam, laurolactam, and undecanolactam.
Examples of the ring-opening polymer of lactam include nylon 4, -5, -6, -8 and -12.
The aminocarboxylic acid in (c112) is C2-12, such as glycine, alanine, valine, leucine, isoleucine, phenylalanine, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω. -Amino capric acid, 11-amino undecanoic acid, 12-amino dodecanoic acid are mentioned.
Examples of the polycondensate of aminocarboxylic acid include nylon 7 by polycondensation of aminoenanthic acid, nylon 11 by polycondensation of ω-aminoundecanoic acid, and nylon 12 by polycondensation of 12-aminododecanoic acid.
Examples of the dicarboxylic acid in (c113) include aliphatic dicarboxylic acids, aromatic (aliphatic) dicarboxylic acids, alicyclic dicarboxylic acids, amide-forming derivatives thereof [acid anhydrides, lower (C1-4) alkyl esters], and the like. Or a mixture of two or more thereof.

Aliphatic dicarboxylic acids include C4-20, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid, itaconic acid. Can be mentioned.
Aromatic (aliphatic) dicarboxylic acids include C8-20, such as ortho-, iso- and terephthalic acid, naphthalene-2,6- and -2,7-dicarboxylic acid, diphenyl-4,4'dicarboxylic acid, diphenoxy Examples include alkali metal (lithium, sodium, potassium, etc.) salts of ethanedicarboxylic acid and 3-sulfoisophthalic acid.
Examples of the alicyclic dicarboxylic acid include C7 to 14 such as cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, and dicyclohexyl-4,4-dicarboxylic acid.
Among the amide-forming derivatives, examples of the acid anhydride include anhydrides of the above dicarboxylic acids, such as maleic anhydride, itaconic anhydride, and phthalic anhydride. Lower (C1-4) alkyl esters include those of the above dicarboxylic acids. Alkyl esters such as dimethyl adipate, ortho-, iso- and dimethyl terephthalate are mentioned.
Examples of the diamine include C6-12, such as hexamethylene diamine, heptamethylene diamine, octamethylene diamine, and decamethylene diamine.

Polycondensates of dicarboxylic acid and diamine (c113) include nylon 66, -610, -69, or -612, respectively, by polycondensation of hexamethylenediamine and adipic acid, sebacic acid, azelaic acid, or dodecanedioic acid, and tetra Nylon 46 by the polycondensation of methylenediamine and adipic acid is mentioned.
As the copolymerized polyamide (c114), nylon 6/66 [a copolymer of nylon 6 and nylon 66 [copolymerization ratio (weight ratio) = 5/95 to 95/5]] and nylon 6/12 [nylon 6 and nylon 12 copolymer [copolymerization ratio (polymerization ratio) = 5/95 to 95/5]] and the like.

  Two or more of those exemplified as the amide-forming monomer may be used in combination. Of these, caprolactam, 12-aminododecanoic acid and adipic acid / hexamethylenediamine are preferable from the viewpoint of antistatic properties, and caprolactam is more preferable.

The polyamide (c11) can be obtained by using one or more C4-20 dicarboxylic acids as molecular weight regulators and subjecting the amide-forming monomer to ring-opening polymerization or polycondensation in the presence thereof in the usual manner.
Examples of the C4-20 dicarboxylic acid include those exemplified in the above (c113). Among these, aliphatic dicarboxylic acid, aromatic dicarboxylic acid and 3-sulfoisophthalic acid are preferable from the viewpoint of antistatic properties. Alkali metal salts, more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate.

  The amount of the molecular weight modifier used is preferably 2 to 80%, more preferably 4 to 75%, from the viewpoint of antistatic properties and heat resistance, based on the total weight of the amide-forming monomer and the molecular weight modifier.

  Mn of the polyamide (c11) is preferably 200 to 5,000, more preferably 500 to 3, from the viewpoint of the reactivity with the AO adduct (c12) of the bisphenol compound described later and the heat resistance of the obtained (C1). 000.

  Examples of the bisphenol compound constituting the AO adduct (c12) of the bisphenol compound include C13-20, such as bisphenol A, -F, and -S. Among these, bisphenol A is preferred from the viewpoint of dispersibility. Examples of AO added to the bisphenol compound include C2-12, such as ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 2,3- and 1,4-butylene oxide, C5-12 alpha-olefin epoxids, styrene oxide and epihalohydrins (e.g. epichlorohydrin and epibromohydrin) and mixtures of two or more thereof. Of these, EO is preferable from the viewpoint of antistatic properties.

  Mn of (c12) is preferably 300 to 5,000, more preferably 500 to 4,000 from the viewpoint of antistatic properties.

  The ratio of (c12) based on the total weight of (c11) and (c12) is preferably 20 to 80%, more preferably 30 to 70%, from the viewpoint of the antistatic property and heat resistance of (C1).

Examples of the method for producing the polyetheresteramide (C1) include the following (1) and (2), but are not particularly limited.
Production Method (1) An amide-forming monomer and a dicarboxylic acid (molecular weight modifier) are reacted to form (c11), to which (c12) is added, at a high temperature (160 to 270 ° C.), under reduced pressure (0.03 -3 kPa).
Production Method (2) Amide Forming Monomer and Dicarboxylic Acid (Molecular Weight Modifier) and (c12)
A polyamide intermediate (c11) is produced by simultaneously charging a part of the reaction mixture into a reaction vessel and reacting under pressure (0.1 to 1 MPa) at a high temperature (160 to 270 ° C.) in the presence or absence of water. And then polymerizing with the remaining (c12) under reduced pressure (0.03 to 3 kPa). Of the above production methods, production method (1) is preferred from the viewpoint of reaction control.

As a production method of (C1), in addition to the above, a method in which the terminal hydroxyl group of (c12) is substituted with an amino group or a carboxyl group and reacted with a polyamide having a carboxyl group or an amino group at the terminal may be used.
As a method of substituting the terminal hydroxyl group of (c12) with an amino group, a known method, for example, a method of reducing a terminal cyanoalkyl group obtained by cyanoalkylating a hydroxyl group to form an amino group [for example, (c12) and acrylonitrile And a method of hydrogenating the resulting cyanoethylated product].
Examples of the method of substituting the terminal hydroxyl group of (c12) with a carboxyl group include a method of oxidizing with an oxidizing agent [for example, a method of oxidizing the hydroxyl group of (c12) with chromic acid] and the like.

In the above polymerization reaction, a commonly used known esterification catalyst is used. Examples of the catalyst include antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide, etc.), titanium catalysts (tetrabutyl titanate, etc.), zirconium catalysts (tetrabutyl zirconate, etc.), organic acid metal salts [zirconium organic acid Salts (such as zirconyl acetate) and zinc acetate].
The usage-amount of a catalyst is 0.1 to 5% normally based on the total weight of (c11) and (c12), Preferably it is 0.2 to 3% from a viewpoint of reactivity and a resin physical property.

The reduced viscosity [η _sp / C, C = 0.5 wt% (m-cresol solution, 25 ° C.)] of (C1) is preferably 0 from the viewpoint of the heat resistance of (C1) and the moldability of the resin composition. .5-4, more preferably 0.6-3.

As block polymer (C2), the block polymer described in the international publication WO00 / 47652 specification can be used.
(C2) is at least one selected from the group consisting of a block of the polyolefin (c21) and a block of the polyoxyalkylene chain-containing compound (c22) consisting of an ester bond, an amide bond, an ether bond, a urethane bond and an imide bond. It has a structure in which the bonds are alternately and alternately connected through the bonds.
The ratio of (c22) based on the total weight of (c21) and (c22) is preferably 20 to 80%, more preferably 30 to 70%, from the viewpoint of the antistatic property and heat resistance of (C2).
The block of (c21) constituting (C2) includes a polyolefin (c211) having carbonyl groups at both ends of the polymer, a polyolefin (c212) having hydroxyl groups at both ends of the polymer, and an amino group at both ends of the polymer. Polyolefin (c213) etc. can be used.

As (c211), those having a carbonyl group introduced at both ends of polyolefin (c210) mainly composed of a denatureable polyolefin at both ends are used.
As (c212), those having hydroxyl groups introduced at both ends of (c210) are used.
As (c213), those in which amino groups are introduced at both ends of (c210) are used.
(C210) is usually a mixture of a polyolefin that can be modified at both ends, a polyolefin that can be modified at one end, and a polyolefin that does not have a modifiable end group, but contains a polyolefin that can be modified at both ends as a main component. You can use it if you do.
The content of polyolefin that can be modified at both ends, which is the main component of (c210), is (c210
) Is preferably 50 to 100%, more preferably 75 to 100%, particularly preferably 80 to 100%.

(C210) means (co) polymerization (polymerization or copolymerization) of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. )) And a degraded polyolefin [made by mechanically, thermally and chemically degrading a high molecular weight polyolefin (preferably Mn 50,000 to 150,000)] ( (Degradation method). From the viewpoint of ease of modification and availability of introduction of a carbonyl group, hydroxyl group or amino group, a degraded polyolefin, particularly a thermally degraded polyolefin, is preferred.
The heat-degraded polyolefin is not particularly limited, but is heat-degraded by heating a high molecular weight polyolefin in an inert gas (usually at 300 to 450 ° C. for 0.5 to 10 hours) (for example, JP-A-3 -62804).
Examples of the high molecular weight polyolefin used in the thermal degradation method include (co) polymers of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. Can be used. As the C2-30 olefin, the same as those used for the production of the polyolefin (polymerization method) described later can be used, and among these, ethylene, propylene and C4-12 α-olefin are preferred, and ethylene is more preferred. , Propylene and C4-10 alpha-olefins, particularly preferred are ethylene and propylene.

Examples of the C2-30 olefin used for the production of the polyolefin (polymerization method) include ethylene, propylene, C4-30 (preferably 4-12, more preferably 4-10) α-olefin and C4-30. A diene of (preferably 4-18, more preferably 4-8) is used.
Examples of the α-olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene.
Examples of the diene include butadiene, isoprene, cyclopentadiene, 1,11-dodecadiene, and the like.
Of these, ethylene, propylene, C4-12 α-olefin, butadiene and isoprene are preferred, ethylene, propylene, C4-10 α-olefin and butadiene are more preferred, and ethylene, propylene and butadiene are particularly preferred. is there.

The polyolefin obtained by the polymerization method can be produced by various methods, and can be easily obtained, for example, by a (co) polymerization reaction in the presence of a radical catalyst, a metal oxide catalyst, a Ziegler catalyst or a Ziegler-Natta catalyst.
Various radical catalysts can be used, for example, organic peroxides (di-t-butyl peroxide, t-butyl peroxybenzoate, decanol peroxide, lauryl peroxide, peroxydicarbonate ester, etc.) , Azo compounds (azonitrile, azoamidine, azoamide compounds), and γ-alumina carriers having molybdenum oxide attached thereto.
Examples of the metal oxide catalyst include those obtained by attaching chromium oxide to a silica-alumina support. As the Ziegler catalyst or Ziegler-Natta catalyst, (C ₂
H ₅ ) ₃ Al—TiCl _{4 and the} like.

Mn of (c210) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000. When Mn is within this range, the dispersibility and antistatic property of the carbon nanotubes are further improved.
The amount of double bonds in (c210) is preferably 1-40 per 1,000 C, more preferably 2-30, and particularly preferably 4-20. When the amount of double bonds is within this range, the carbon nanotube dispersibility and antistatic properties are further improved.
The average number of double bonds per molecule is preferably 1.1 to 5.0, more preferably 1.3 to 3.0, particularly preferably 1.5 to 2.5, and most preferably 1.8. ~ 2.2. When the average number of double bonds is within this range, it becomes easier to take a repeating structure, and the carbon nanotube dispersibility and antistatic property are further improved.
According to the thermal degradation method, a low-molecular-weight polyolefin having an average terminal double bond amount of 1.5 to 2 per molecule in the range of 800 to 6,000 can be easily obtained [Katsuhide Murata, Tadahiko Makino. , Journal of Chemical Society of Japan, page 192 (1975)].

  As (c211), the terminal of (c210) is an α, β unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, a C1-4 alkyl ester thereof or an anhydride thereof. The same as above.) Polyolefin (c211-1) having a structure modified with (c211-1), polyolefin (c211-2) having a structure secondarily modified with lactam or aminocarboxylic acid (c211-2), and (c210) oxidized or hydroformylated Polyolefin (c211-3) having a structure modified by the above, polyolefin (c211-4) having a structure obtained by secondary modification of (c211-3) with lactam or aminocarboxylic acid, and a mixture of two or more of these it can.

(C211-1) can be obtained by modifying (c210) with an α, β-unsaturated carboxylic acid (anhydride).
As α, β-unsaturated carboxylic acid (anhydride) used for modification, monocarboxylic acid, dicarboxylic acid, alkyl (C1-4) ester thereof and anhydride thereof can be used, for example, (meth) acrylic acid (Means acrylic acid or methacrylic acid; the same shall apply hereinafter), methyl (meth) acrylate, butyl (meth) acrylate, maleic acid (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride) , Diethyl itaconate and citraconic acid (anhydride).
Among these, preferred are dicarboxylic acids, their alkyl esters and their anhydrides, more preferred are maleic acid (anhydride) and fumaric acid, and particularly preferred is maleic acid (anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used for modification is preferably 0.5 to 40%, more preferably 1 to 30%, particularly preferably 2 based on the weight of the polyolefin (c210). ~ 20%. When the amount of α, β-unsaturated carboxylic acid (anhydride) is within this range, it becomes easier to take a repeating structure, and filler dispersibility and antistatic properties are further improved.
The modification with α, β-unsaturated carboxylic acid (anhydride) can be carried out by various methods. For example, the terminal double bond of (c210) can be modified by either solution method or melt method. , Β-unsaturated carboxylic acid (anhydride) can be thermally added (ene reaction). The temperature at which (c210) is reacted with the α, β-unsaturated carboxylic acid (anhydride) is usually 170 to 230 ° C.

(C211-2) can be obtained by secondary modification of (c211-1) with lactam or aminocarboxylic acid.
As the lactam used for the secondary modification, C6-12 (preferably 6-8, more preferably 6) lactam and the like can be used, and examples thereof include caprolactam, enantolactam, laurolactam and undecanolactam.
As the aminocarboxylic acid, C2-12 (preferably 4-12, more preferably 6-12) aminocarboxylic acid and the like can be used. For example, amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.) ), Ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Of these, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and caprolactam, laurolactam, ω-aminocaprylic acid, 11-amino are more preferred. Undecanoic acid and 12-aminododecanoic acid, particularly preferably caprolactam and 12-aminododecanoic acid.
The amount of lactam or aminocarboxylic acid used for secondary modification is preferably 0.1 to 50, more preferably 0.3 to 20 per carboxyl group of α, β unsaturated carboxylic acid (anhydride). The number is particularly preferably 0.5 to 10, most preferably 1 to 2. When this amount is within this range, it becomes easier to take a repeating structure, and filler dispersibility and antistatic properties are further improved.

(C211-3) can be obtained by introducing (c210) a carbonyl group by oxidation with oxygen and / or ozone or hydroformylation with an oxo method.
The introduction of the carbonyl 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 carbonyl group by hydroformylation can be carried out by a known method, for example, see Macromolecules, Vol. 31, 5943 page.
(C211-4) can be obtained by secondary modification of (c211-3) with lactam or aminocarboxylic acid.
The lactam and aminocarboxylic acid and preferred ranges thereof are the same as those that can be used in the production of (c211-2). The amount of lactam and aminocarboxylic acid used is the same.

Mn of (c211) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably from the viewpoint of heat resistance and reactivity with the polyoxyalkylene chain-containing compound (c22) described later. Is 2,500 to 10,000.
The acid value of (c211) is preferably 4 to 280 (mg KOH / g. In the following, only numerical values are described), more preferably 4 to 100, particularly from the viewpoint of reactivity with (c22). Preferably it is 5-50.

As the polyolefin (c212) having a hydroxyl group at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying (c211) with hydroxylamine and a mixture of two or more of these can be used.
Examples of hydroxylamine that can be used for the modification include C2-10 (preferably 2-6, more preferably 2-4) hydroxylamine, and the like. For example, 2-aminoethanol, 3-aminopropanol, 1-amino- Examples include 2-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol.
Of these, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-aminohexanol are more preferable, 2-aminoethanol and 4-aminobutanol are particularly preferable. Is 2-aminoethanol.
The modification with hydroxylamine can be performed by various methods, for example, by directly reacting (c211) with hydroxylamine. The reaction temperature is usually 120 ° C to 230 ° C.

The amount of hydroxylamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, particularly preferably per residue of α, β unsaturated carboxylic acid (anhydride). Is 0.5 to 1.2, most preferably 1. When the amount of hydroxylamine is within this range, it becomes easier to take a repeating structure, and the carbon nanotube dispersibility and antistatic property are further improved.
Mn of (c212) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably from the viewpoint of heat resistance and reactivity with the polyoxyalkylene chain-containing compound (c22) described later. Is 2,500 to 10,000.
The hydroxyl value of (c212) is preferably 4 to 280 (mg KOH / g. In the following, only numerical values are described), more preferably 4 to 100, particularly from the viewpoint of reactivity with (c22). Preferably it is 5-50.

As (c213), polyolefin having an amino group obtained by modifying (c211) with diamine (Q1) and a mixture of two or more of these can be used.
As the diamine (Q1) used for this modification, C2-12 (preferably 2-8, more preferably 2-6) diamines can be used, for example, ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine. And decamethylenediamine.
Of these, ethylenediamine, hexamethylenediamine, heptamethylenediamine and octamethylenediamine are preferable, ethylenediamine and hexamethylenediamine are more preferable, and ethylenediamine is particularly preferable.
The modification with diamine can be performed by a known method, for example, by reacting (c211) and diamine (Q1) directly. The reaction temperature is usually 120 ° C to 230 ° C.

The amount of diamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, and still more preferably, per residue of α, β unsaturated carboxylic acid (anhydride). 0.5 to 1.2, particularly preferably 1. When the amount of diamine is within this range, it becomes easier to take a repeating structure, and filler dispersibility and antistatic properties are further improved.
In actual production, in order to prevent polyamide (imide) formation, 2 to 1,000, more preferably 5 to 800, per residue of α, β unsaturated carboxylic acid (anhydride). Particularly preferably, 10 to 500 diamines are used, and it is preferable to remove unreacted excess diamine under reduced pressure (usually 120 to 230 ° C.).

Mn of (c213) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably from the viewpoint of heat resistance and reactivity with the polyoxyalkylene chain-containing compound (c22) described later. Is 2,500 to 10,000.
Further, the amine value of (c213) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (c22), more preferably 4 to 100, and particularly preferably. Is 5-50.

As the polyoxyalkylene chain-containing compound (c22) constituting the block polymer (C2), polyether diol (c221), polyether diamine (c222), and modified products thereof (c223) can be used.
From the viewpoint of antistatic properties, the upper limit of the specific volume resistance value of (c22) (value measured in an atmosphere of 23 ° C. and 50% RH by the method described later) is preferably 10 ¹¹ Ω · cm, more preferably 10 ¹⁰ Ω · cm, particularly preferably 10 ⁹ Ω · cm, and from the viewpoint of mechanical properties, the lower limit is preferably 10 ⁵ Ω · cm, more preferably 10 ⁶ Ω · cm, and particularly preferably 10 ⁷ Ω · cm.
Further, Mn of (c22) is preferably 150 to 20,000, more preferably 300 to 20,000, and particularly preferably 1.0 from the viewpoint of heat resistance and reactivity with (c21).
It is 00 to 15,000, most preferably 1,200 to 8,000.

As the polyether diol (c221), a diol (c220) or a structure obtained by adding AO to a dihydric phenol can be used. For example, a general formula:

H— (OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _{m ′} —H

The thing shown by is mentioned.
In the formula, E ¹ represents a diol (c220) or a residue obtained by removing a hydroxyl group from a dihydric phenol, and A ¹ represents C 2 to 12 (preferably 2 to 8, more preferably a halogen atom). 2-4) represents an alkylene group. M and m ′ are integers of 1 to 300, preferably 2 to 250, and more preferably 8 to 150. M and m ′ may be the same or different. m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form in the case where they are composed of two or more oxyalkylene groups is a block or Either random or a combination thereof may be used.

As the diol (c220), a C2-12 (preferably 2-10, more preferably 2-8) dihydric alcohol (for example, an aliphatic, alicyclic or araliphatic dihydric alcohol), C6-18 ( Preferably, the dihydric phenol and tertiary amino group-containing diol of 8 to 18, more preferably 10 to 15) can be used.
Examples of the aliphatic dihydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 1,12-dodecanediol.
Examples of the alicyclic dihydric alcohol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-cyclooctanediol, and 1,3-cyclopentanediol.
Examples of the araliphatic dihydric alcohol include xylylenediol, 1-phenyl-1,2-ethanediol, and 1,4-bis (hydroxyethyl) benzene.

Examples of the tertiary amino group-containing diol include bishydroxyalkyls (C1-12, preferably 2 to 8) of aliphatic or alicyclic primary monoamines (C1-12, preferably 2-10, more preferably 2-8). 10, more preferably 2-8) and bishydroxyalkyl (C1-12) compounds of aromatic (aliphatic) primary monoamines (C6-12).
The bishydroxyalkylated product of monoamine can be easily obtained by various methods. For example, monoamine and C2-4 AO (for example, EO, PO, butylene oxide) are reacted, or C1-12 It can be obtained by reacting a monoamine with a C1-12 halogenated hydroxyalkyl (for example, 2-bromoethyl alcohol, 3-chloropropyl alcohol).

Examples of the aliphatic or alicyclic primary monoamine include methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, amylamine, isoamylamine, hexylamine, 1,3-dimethylbutylamine, 3,3 -Dimethylbutylamine, 2-aminoheptane, 3-aminoheptane, cyclopentylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine and dodecylamine.
Examples of the aromatic (aliphatic) primary monoamine include aniline and benzylamine.

Examples of the dihydric phenol include monocyclic dihydric phenol (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenol (bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane, etc. ), Dihydrokibiphenyl and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol, etc.).

  Of these diols (c220) and dihydric phenols, dihydric alcohols and dihydric phenols are preferable from the viewpoint of reactivity, aliphatic dihydric alcohols and bisphenols are more preferable, and ethylene glycol and bisphenol A are particularly preferable. is there.

The polyether diol (c221) can be produced, for example, by subjecting the diol (c220) or dihydric phenol to addition reaction with AO.
As AO, C2-4 AO (EO, PO, 1,2-, 1,4-, 2,3- and 1,3-butylene oxide and a mixture of two or more thereof) and the like are used. If necessary, other AO or substituted AO may be used in combination (in the present invention, these are also collectively referred to as AO). Examples of other AO or substituted AO include epoxidized C5-12 α-olefin, styrene oxide and epihalohydrin (such as epichlorohydrin and epibromohydrin). The amount of other AO or substituted AO is preferably 30% or less, more preferably 0 to 25%, and particularly preferably 0 to 20% based on the weight of the total AO.

When two or more kinds of AO are used in combination, the binding form may be either block and / or random.
Preferred as AO is EO alone or a combination of EO and another AO (block and / or random addition), more preferred is a combination of EO and EO / PO, and particularly preferred is EO alone.
The number of moles of AO added is preferably 1 to 300 moles, more preferably 2 to 250 moles, and particularly preferably 10 to 100 moles per hydroxyl group of (c220) or dihydric phenol. When the added mole number of AO is within this range, the volume resistivity value of (c22) tends to be more preferable.

AO can be added by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst.
The content of the C2-4 oxyalkylene unit in the polyether diol (c221) is preferably 5 to 99.8%, more preferably 8 to 99.6%, particularly preferably based on the weight of (c221). 10 to 98%.
The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100%, more preferably 10 to 100%, particularly preferably 50 to 100%, most preferably 60, based on the weight of the polyoxyalkylene chain. ~ 100%. When the content of the oxyethylene unit is within this range, the volume resistivity value of (c22) tends to be a more preferable range.

As the polyether diamine (c222), one having a structure in which the hydroxyl group of (c221) is modified to an amino group can be used.

^{RNH-A 2 - (OA 1} ) m -O-E 1 -O- (A 1 O) m '-A 2 -NHR

The thing shown by is mentioned.
The symbols E ¹ , A ¹ , m and m ′ in the formula are the same as those in the formula (c221), and A ² may be a C 2-12 (preferably 2-8, more preferably a halogen atom). Represents an alkylene group of 2 to 4), and A ¹ and A ² may be the same or different. R represents H or a C1-4 (preferably 1 or 2) alkyl group.
(C222) can be easily obtained by changing the hydroxyl group of (c221) to an amino group by a known method.
Various methods can be used as a method for changing a hydroxyl group to an amino group. For example, a method in which a terminal cyanoalkyl group obtained by cyanoalkylating a hydroxyl group in (c221) is reduced to an amino group [for example, (c221) And a method of reacting acrylonitrile and hydrogenating the resulting cyanoethylated product], a method of reacting (c221) with an aminocarboxylic acid or lactam, and a method of reacting a halogenated amine under alkaline conditions.

Examples of the modified product (c223) of (c221) or (c222) include the isocyanate-modified product (terminal isocyanate group) and the epoxy-modified product (terminal epoxy group) of (c221) or (c222).
The isocyanate-modified product can be obtained by reacting (c221) or (c222) with an organic diisocyanate or reacting (c222) with phosgene.
The epoxy-modified product is obtained by reacting (c221) or (c222) with diepoxide (epoxy resin such as diglycidyl ether, diglycidyl ester, alicyclic diepoxide: epoxy equivalent 85 to 600), or (c221) and epihalohydrin. It can be obtained by reacting with (e.g. epichlorohydrin).

  As the organic diisocyanate, C (excluding carbon in the NCO group, the same shall apply hereinafter) 6-20 (preferably 6-18, more preferably 8-14) aromatic diisocyanate, C2-18 (preferably 4-16, More preferably 6-14) aliphatic diisocyanate, C4-15 (preferably 4-13, more preferably 6-11) alicyclic diisocyanate, C8-15 (preferably 8-13, more preferably 9- 11) Aro-aliphatic diisocyanates, modified products of these diisocyanates, and mixtures of two or more thereof can be used.

  Examples of the aromatic diisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (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 1,5 -Naphthylene diisocyanate.

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

  Examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanato). And ethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

Examples of the araliphatic diisocyanate include m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).
Examples of the modified diisocyanate include urethane-modified products, urea-modified products, carbodiimide-modified products, and uretdione-modified products.
Of these organic diisocyanates, aromatic and aliphatic diisocyanates are preferable from the viewpoint of reactivity, TDI, MDI and HDI are more preferable, and HDI is particularly preferable.

In order to accelerate the polyurethane formation reaction, a commonly used catalyst may be used if necessary. As such a catalyst, a metal catalyst, an amine catalyst, and a mixture of two or more thereof can be used.
Examples of metal catalysts include tin catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate, etc.); lead catalysts (lead oleate) , Lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.); other metal catalysts (metal naphthenate such as cobalt naphthenate, phenylmercuric propionate, etc.).

  Examples of the amine catalyst include triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diazabicycloalkene {1,8-diazabicyclo [5,4,0] undecene-7 [manufactured by San Apro Co., Ltd., registered trademark DBU]. Etc.}, dialkylaminoalkylamines (dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropylaminopropylamine, etc.) and heterocyclic aminoalkylamines {2- (1- Aziridinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine, etc.} carbonates and organic acid salts (formate, etc.), etc. In addition, N-methylmorpholine, N-ethylmorpholine, Ethylamine, diethylethanolamine, dimethylethanolamine and the like can be used.

In the present invention, (C2) includes a polymer having a repeating unit represented by the general formula (1).

In general formula (1), n is an integer of 2 to 50, preferably 3 to 40, and more preferably 4 to 30. One of R ¹ and R ² is H, and the other is H or an alkyl group of C1-10 (preferably 1-8, more preferably 1-6). Moreover, y is an integer of 15 to 800, preferably 20 to 500, more preferably 30 to 400.
E ¹ , A ¹ , m and m ′ are the same as above, and X and X ′ are groups selected from the groups represented by the general formulas (2) to (8) and the corresponding (2 ′) to (8 A group selected from the group represented by '), that is, when X is a group represented by the general formula (2), X' is a group represented by the general formula (2 '), and the general formulas (3) to (3) to ( The same relationship applies to 8) and (3 ′) to (8 ′).

In the general formulas (2) to (8) and (2 ′) to (8 ′), R ³ and R ^{3 ′} represent a C2-3 trivalent hydrocarbon group, and R ⁴ represents C1-11 ( Preferably, it represents a divalent hydrocarbon group of 1-8, more preferably 1-6, and R ⁵ is H or C1-10 (preferably 1-8).
, More preferably 1-6), and R ⁶ is C 2-22 (preferably 4-4).
18 and more preferably 6-12), E ² represents an organic diisocyanate residue, r is an integer of 1 to 10 (preferably 1 to 8, more preferably 1 to 6), u and v represent 0 or 1, and A ² and R are the same as defined above.
Q, Q ′, T and T ′ are groups represented by the following formula.

However, R ⁵ is H or C1-10 (preferably 1 to 8, more preferably 1 to 6) represents an alkyl group, R ⁷ represents H or a methyl group, t is, R ⁷ is a methyl group 1 for H, 0 or 1 for H.
The polyether segment {(OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _{m ′} } in {} in the repeating unit represented by the general formula (1) depends on the polyether diol (c221). It is a structure to be constructed, and E ¹ , A ¹ , m and m ′ in the formula are the same as described above.

In the general formula (1), the block polymer (C21) in which X is a group represented by the general formula (2) and X ′ is a group represented by the general formula (2 ′) is a polyolefin having a carbonyl group (c211 -1) and polyether diol (c221) can be obtained. R ³ and R ^{3 ′} in general formulas (2) and (2 ′) are formulas formed from unsaturated dicarboxylic acids.

（Ｒ’はＨまたはメチル基、ｔはＲ’がＨのとき１または０、Ｒ’がメチル基のとき１である。）
で示される基であり、例えば、ポリオレフィンのカルボニル変性に、マレイン酸またはフマル酸を用いた場合は、Ｒ³は−ＣＨ²−ＣＨ＜であり、Ｒ^3'は＞ＣＨ−ＣＨ²−である。

(R ′ is H or a methyl group, t is 1 or 0 when R ′ is H, and 1 when R ′ is a methyl group.)
For example, when maleic acid or fumaric acid is used for carbonyl modification of polyolefin, R ³ is —CH ² —CH <and R ^{3 ′} is> CH—CH ² —. .

(C21) can be produced by various methods. For example, polyether diol (c221) is added to polyolefin (c211-1) having a carbonyl group, and polymerization (polycondensation) reaction is usually performed at 200 to 250 ° C. under reduced pressure. It can be manufactured by the method to be performed. It can also be produced using a single or twin screw extruder. Usually, it can manufacture by the method of superposing | polymerizing with 160-250 degreeC and residence time 0.1-20 minutes. Various catalysts can be used for the above polymerization reaction.
Catalysts include antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide, etc.), titanium catalysts (tetrabutyl titanate, etc.), zirconium catalysts (tetrabutyl zirconate, etc.), organic acid metal salts [zirconium organic acid salts (Such as zirconyl acetate) and zinc acetate], and mixtures of two or more thereof.
Of these, preferred are a zirconium catalyst and an organic acid metal salt, and more preferred is zirconyl acetate.
The usage-amount of a catalyst is 0.001 to 5% normally with respect to the total weight of (c211-1) and (c221).

  In the general formula (1), the block polymer (C22) in which X is a group represented by the general formula (3) and X ′ is a group represented by the general formula (3 ′) is a polyolefin having a carbonyl group (c211-1 ) And polyether diamine (c222). The polymerization reaction of (c211-1) and (c222) can be carried out in the same manner as the polymerization reaction of (c211-1) and (c221).

  In the general formula (1), the block polymer (C23) in which X is a group represented by the general formula (4) and X ′ is a group represented by the general formula (4 ′) is represented by (c211-2) and (c221). ). The polymerization reaction of (c211-2) and (c221) can be performed in the same manner as the polymerization reaction of (c211-1) and (c221).

  In the general formula (1), the block polymer (C24) in which X is a group represented by the general formula (5) and X ′ is a group represented by the general formula (5 ′) includes (c211-2) and (c222 ). Alternatively, (c222) may be secondarily modified with the lactam or aminocarboxylic acid and then reacted with (c211-1) to produce the product. These polymerization reactions can be carried out in the same manner as the polymerization reaction of (c211-1) and (c221).

  In the general formula (1), the block polymer (C25) in which X is a group represented by the general formula (6) and X ′ is a group represented by the general formula (6 ′) is (c211-3) (r = 1) or (c211-4) (when r ≧ 2) and (c221) (when u = 0) or polyetherdiamine (c222) (when u = 1). be able to. The polymerization reaction of (c211-3) or (c211-4) and (c221) or (c222) can be carried out in the same manner as the polymerization reaction of (c21-1) and (c221).

  In the general formula (1), the block polymer (C26) in which X is a group represented by the general formula (7) and X ′ is a group represented by the general formula (7 ′) has hydroxyl groups at both ends of the polymer. Polyolefin (c212) and polyether diol (c221) (when u = 0) or polyether diamine (c222) (when u = 1) are bonded via an organic diisocyanate. It can be obtained by reacting simultaneously or sequentially. As a method of sequentially reacting, for example, (c212) and an organic diisocyanate are reacted to obtain an isocyanate-modified polyolefin, and then this is reacted with (c221) or (c222).

In the general formula (1), the block polymer (C26) in which X is a group represented by the general formula (8) and X ′ is a group represented by the general formula (8 ′) is (c211-3) (v = 0) or (c212) (when v = 1) and (c221) or (c222) are bonded via an organic diisocyanate, and these are reacted simultaneously or sequentially. Obtainable. For example, (c211-3) or (c212) is reacted with an organic diisocyanate to obtain an isocyanate-modified polyolefin, and then reacted with (c221) or (c222). it can.
The reaction between (c212) and an organic diisocyanate, the reaction between (c221) or (c222) and an organic diisocyanate, and the reaction between an isocyanate-modified polyolefin and (c221) or (c222) are the same as the usual urethanization or urea formation reaction. Can be done in a way.

  The equivalent ratio (NCO / OH ratio) between the organic diisocyanate and (c212) and the equivalent ratio between the isocyanate-modified polyolefin and (c221) or (c222) (NCO / OH ratio) in forming the isocyanate-modified polyolefin are: The ratio is preferably 1.8 / 1 to 3/1, more preferably 1.9 / 1 to 2.5 / 1, and particularly preferably 2/1. When the equivalent ratio is within this range, it becomes easier to take a repeating structure, and filler dispersibility and antistatic properties are further improved. As the organic diisocyanate and the catalyst for promoting the reaction, those described above can be used.

Among the block polymers (C2) having the repeating unit represented by the general formula (1), (C21), (C22), (C23), (C24) are preferable, and (C21) and (C23 are more preferable. Particularly preferred is (C23).
The amount of the polyoxyalkylene chain-containing compound (c22) constituting the block polymer (C2) is preferably 20 to 90% based on the total weight of (c21) and (c22) from the viewpoint of antistatic properties. More preferably, it is 25 to 90%, and particularly preferably 30 to 70%. Further, Mn of (C2) is preferably from 2,000 to 60,000, more preferably from 5,000 to 40,000, particularly preferably from 8,000 to 30 from the viewpoint of carbon nanotube dispersibility and antistatic performance. , 000.

In the structure of the block polymer (C2), the average number of repeating units (Nn) of the block of the polyolefin (c21) and the block of the polyoxyalkylene chain-containing compound (c22) is the carbon nanotube dispersibility and antistatic property. From the viewpoint, it is preferably 2 to 50, more preferably 2.3 to 30, particularly preferably 2.7 to 20, and most preferably 3 to 10.
Nn can be determined by Mn and ¹ H-NMR analysis of (C2). For example, the case of (C21) having a structure in which blocks (c211) and (c221) are alternately and repeatedly bonded will be described. In ¹ H-NMR analysis, 4.0 to 4.
A signal attributed to the proton of 1 ppm ester bond {—C (C═O) —OCH ₂ —} and a signal attributed to the proton of polyethylene glycol of 3.2 to 3.7 ppm can be observed. The ratio of these proton integral values is obtained, and Nn can be obtained from this ratio and Mn.

  Both ends of (C2) have a carbonyl group, amino group, hydroxyl group and / or unmodified polyolefin end derived from (c21), and a hydroxyl group, amino group, isocyanate group and / or epoxy group derived from (c22). The unmodified polyolefin means a polyolefin terminal that is not modified at all, that is, an alkyl group or an alkenyl group.

Examples of the polyether amide imide (C3) include polyether amide imides described in JP-B-7-119342 and JP-A-06-172609.
Of these, from the viewpoint of heat resistance, caprolactam, trivalent or tetravalent aromatic polycarboxylic acid capable of reacting with an amino group to form at least one imide ring and polyethylene glycol or at least 50% by weight are preferred. Polyether amide imide derived from a mixture of polyethylene glycol and a polyalkylene glycol other than polyethylene glycol, wherein the content of the mixture is 30 to 85% by weight and the reduced viscosity at 30 ° C. is 1.5 to 4. .
The reduced viscosity of (C3) is preferably 1.5 to 4, more preferably 1.7 to 3.5 from the viewpoint of antistatic properties and moldability of the resin composition.

Examples of the polyether ester (C4) include polyesters having a segment made of polyether diol or copolyether diol, for example, polyether esters described in JP-B No. 58-19696.
The melting point of [C4] [measurement is by differential scanning calorimetry (hereinafter abbreviated as DSC method)] is preferably 100 ° C. or higher, more preferably 120 to 210 ° C. from the viewpoint of heat resistance.
Mn of (C4) is preferably from 2,000 to 60,000, more preferably from 5,000 to 40,000, from the viewpoint of carbon nanotube dispersibility and antistatic performance.

The antistatic agent of the present invention comprises a mixture of a carbon nanotube (A) and a dispersant (B) having a conjugated double bond, and the above (C).
The proportion based on the total weight of (A), (B), and (C) in the antistatic agent can be variously changed according to the required performance. (A) is an antistatic property and a resin composition. From the viewpoint of moldability of the resin, preferably 1 to 20%, more preferably 2 to 15%; (B) is 1 to 40%, more preferably 2 from the viewpoint of the dispersibility of the carbon nanotubes and the moldability of the resin composition. -35%; (C) is preferably 40-98%, more preferably 50-96%, from the viewpoint of the dispersibility and antistatic properties of the carbon nanotubes.

The antistatic agent of the present invention is produced by previously mixing the carbon nanotube (A) and the dispersant (B) having a conjugated double bond, and then adding this to (C).
The mixing method of (A) and (B) is not particularly limited, but may be ground and mixed with a mortar, or a ball mill, a roller mill, or the like may be used. The mixing time is preferably 1 minute to 3 hours, more preferably 5 minutes to 2 hours from the dispersibility of carbon nanotubes and from an industrial viewpoint; more preferably 5 minutes to 2 hours; the mixing temperature is preferably 0 to 150 ° C. from the dispersibility of carbon nanotubes and an industrial viewpoint. More preferably, it is 20-100 degreeC; The end point of mixing can be judged by confirming visually that the mixture of (A) and (B) became paste-form.
Further, the method of incorporating the mixture of (A) and (B) into (C) is not particularly limited, but from the viewpoint of effective dispersion of the mixture into (C), a hydrophilic group-containing polymer ( It is preferable to disperse in C) in advance, and in this case, it is particularly preferable to disperse the mixture in advance during the production (polymerization) of (C). There is no particular limitation on the timing of containing and dispersing the mixture during the production of (C), and it may be any before, during or immediately after polymerization.

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

  Among these, (D1) and (D) are preferable from the viewpoint of the mechanical properties of the molded product described later and the dispersibility of the antistatic agent comprising (C) in (D). (D2), (D3), (D4) and (D7), more preferably (D2), (D4) and (D7).

  The amount of (D) used is the weight ratio of the mixture of (A) and (B) and the antistatic agent comprising (C) to (D) from the viewpoint of antistatic properties and mechanical properties of the molded product [antistatic Agent / (D)] is preferably 1/99 to 30/70, more preferably 5/95 to 20/80.

  Examples of the polyphenylene ether resin (D1) include those represented by the following general formula (9).

In general formula (9), p is an integer of 50 or more, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are H, a halogen atom, a C1-12 hydrocarbon group, a C2-12 substituted hydrocarbon group, and an alkoxy group. Represents a cyano group, a phenoxy group or a nitro group. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be the same or different. Further, (D1) is a single polymer of the general formula (9) or a copolymer of two or more structural units or a blend of two or more polymers. Also good.

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

The intrinsic viscosity [η] of (D1) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and antistatic properties. [Η] is measured using a Ubbelohde 1A viscometer at 30 ° C. for a 0.5 wt% chloroform solution of the polymer.
The glass transition temperature (hereinafter abbreviated as Tg) of (D1) is preferably 190 to 240 ° C., more preferably 210 to 230 ° C. from the viewpoint of moldability. Tg is measured by a differential scanning calorimetry (DSC) method.

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

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

Aliphatic hydrocarbons include C2-30 olefins [ethylene, propylene, C4 ~
30 α-olefins (1-butene, 4-methyl-1-pentene, 1-pentene, 1-
Octene, 1-decene, 1-dodecene, etc.)], C4-30 dienes [alkadienes (butadiene, isoprene, etc.), cycloalkadienes (cyclopentadiene, etc.), etc.].

Examples of the aromatic ring-containing hydrocarbon include C8-30 styrene and its derivatives, such as o.
-, M- and p-alkyl (C1-10) styrene (vinyl toluene, etc.), α-alkyl (C1-10) styrene (α-methylstyrene, etc.) and halogenated styrene (chlorostyrene, etc.).

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

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

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

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

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

  As the polyacrylic resin (D3), for example, one or more (co) polymers [poly (meth) acrylic acid methyl ester, such as acrylic monomers [alkyl (C1-20) (meth) acrylate, (meth) acrylonitrile, etc.], Poly (meth) butyl acrylate, etc.] and copolymers with one or more of the above-mentioned vinyl monomers copolymerizable with one or more of these monomers [acrylic monomer / vinyl monomer copolymerization ratio (weight ratio) is a resin physical property From the viewpoint of the above, preferably 5/95 to 95/5, more preferably 50/50 to 90/10] [however, those included in (D2) are excluded] are included.

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

As the polystyrene resin (D4), a vinyl group-containing aromatic hydrocarbon alone or a vinyl group-containing aromatic hydrocarbon, and at least one selected from the group consisting of (meth) acrylic acid ester, (meth) acrylonitrile and butadiene A copolymer as a structural unit is exemplified.
Examples of vinyl group-containing aromatic hydrocarbons include C8-30 styrene and its derivatives,
For example, o-, m-, and p-alkyl (C1-10) styrene (vinyl toluene, etc.), α-alkyl (C1-10) styrene (α-methylstyrene, etc.) and halogenated styrene (chlorostyrene, etc.) can be mentioned. .
Specific examples of (D4) include polystyrene, polyvinyltoluene, styrene / acrylonitrile copolymer (AS resin) [copolymerization ratio (weight ratio) = 70/30 to 80/20], styrene / methyl methacrylate copolymer. (MS resin) [copolymerization ratio (weight ratio) = 60/40 to 90/10], styrene / butadiene copolymer [copolymerization ratio (weight ratio) = 60/40 to 95/5], acrylonitrile / butadiene / Styrene copolymer (ABS resin) [copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)], methyl methacrylate / butadiene / styrene copolymer (MBS resin) [Copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)].

  The MFR of (D4) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. MFR is measured according to JIS K6871 (1994) (230 ° C. in the case of polystyrene resin, load 1.2 kgf).

  Examples of the polyester resin (D5) include aromatic ring-containing polyesters (polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, etc.) and aliphatic polyesters (polybutylene adipate, polyethylene adipate, poly-ε-caprolactone, etc.).

  The intrinsic viscosity [η] of (D5) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and antistatic properties. [Η] is measured with a Ubbelohde 1A viscometer at 25 ° C. for a 0.5 wt% orthochlorophenol solution of the polymer.

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

Examples of the lactam in (D61) include those exemplified in the above (c111), and examples of (D61) include nylon 4, nylon 5, nylon 6, nylon 8, nylon 12, and the like.
Examples of the diamine and dicarboxylic acid in (D62) include those exemplified in the above (c113). Examples of (D62) include nylon 66 obtained by condensation polymerization of hexanemethylenediamine and adipic acid, and a combination of hexamethylenediamine and sebacic acid. Examples thereof include nylon 610 by condensation.
Examples of the aminocarboxylic acid in (D63) include those exemplified in the above (c112). Examples of (D63) include nylon 7 by polycondensation of aminoenanthate, nylon 11 by polycondensation of ω-aminoundecanoic acid, Nylon 12 by polycondensation of 12-aminododecanoic acid and the like can be mentioned.

In the production of (D6), a molecular weight modifier may be used, and examples of the molecular weight modifier include the dicarboxylic acid and / or diamine exemplified in (c113).
Of the dicarboxylic acids as molecular weight modifiers, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and It is sodium 3-sulfoisophthalate. Of the diamines as molecular weight regulators, hexamethylene diamine and decamethylene diamine are preferable.

The MFR of (D6) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR is measured according to JIS K7210 (1994) (in the case of polyamide resin, 230 ° C., load 0.325 kgf).

Examples of the polycarbonate resin (D7) include bisphenols (C12-20, such as bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane) and dihydroxybiphenyl polycarbonates such as bisphenol and phosgene. Or the condensate with a carbonic acid diester is mentioned. Of the above bisphenols, bisphenol A is preferred from the viewpoint of the dispersibility of (A).
The MFR of (D7) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. MFR is measured according to JIS K7210 (1994) (in the case of polycarbonate resin, 280 ° C., load 2.16 kgf).

Examples of the polyacetal resin (D8) include formaldehyde or trioxane homopolymer (polyoxymethylene homopolymer), and a copolymer of formaldehyde or trioxane and a cyclic ether [the above-mentioned AO (EO, PO, dioxolane, etc.)] (polyoxy). And methylene / polyoxyethylene copolymer [polyoxymethylene / polyoxyethylene (weight ratio) = 90/10 to 99/1 block copolymer and the like].
The MFR of (D8) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR is measured according to JIS K7210 (1994) (in the case of polyacetal resin, 190 ° C., load 2.16 kgf).
The intrinsic viscosity [η] of (D8) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and antistatic properties.

  The resin composition of the present invention is a group comprising an antistatic property improver (E), a compatibilizing agent (F), and other additives for resin (G) as necessary, as long as the effects of the present invention are not impaired. You may contain the at least 1 sort (s) of additive chosen from these.

(E) includes one or more selected from the group consisting of an alkali metal or alkaline earth metal salt (E1) and a surfactant (E2).
(E1) include alkali metal (lithium, sodium, potassium, etc.) and / or alkaline earth metal (magnesium, calcium, etc.) organic acids (C1-12 mono- and di-carboxylic acids such as formic acid, acetic acid, Propionic acid, oxalic acid, succinic acid; salts of C1-20 sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid; thiocyanic acid, and inorganic acids (hydrohalic acids such as hydrochloric acid, hydrobromic acid; A salt of perchloric acid; sulfuric acid; nitric acid; phosphoric acid) can be used.

Specific examples of (E1) include halides [fluorides (lithium fluoride, -sodium, -potassium, -magnesium, -calcium, etc.), chlorides (lithium chloride, -sodium, -potassium, -magnesium, -calcium, etc.) ), Bromides (such as lithium bromide, -sodium, -potassium, -magnesium and -calcium) and iodides (such as lithium iodide, -sodium, -potassium, -magnesium and -calcium)], perchlorates ( Lithium perchlorate, -sodium, -potassium, -magnesium and -calcium), fluorinated sulfonates (lithium fluorosulfonate, -sodium, -potassium, -magnesium and -calcium), methanesulfonate (methane) Lithium sulfonate, -sodium, -ca Um, -magnesium and -calcium), trifluoromethanesulfonate (lithium trifluoromethanesulfonate, -sodium, -potassium, -magnesium and -calcium), pentafluoroethanesulfonate (lithium pentafluoroethanesulfonate, -Sodium, -potassium, -magnesium and -calcium), nonafluorobutane sulfonate (such as lithium nonafluorobutane sulfonate, -sodium, -potassium, -magnesium and -calcium), undecafluoropentane sulfonate ( Undecafluoropentanesulfonate lithium, -sodium, -potassium, -magnesium, -calcium, etc.), tridecafluorohexanesulfonate (tridecafluorohexanesulfone) Lithium acid, -sodium, -potassium, -magnesium and -calcium), acetate (lithium acetate, -sodium, -potassium, -magnesium and -calcium etc.), sulfate (sodium sulfate, -potassium, -magnesium and- Calcium, etc.), phosphates (sodium phosphate, -potassium, -magnesium, -calcium, etc.), thiocyanates (potassium thiocyanate, etc.) and the like.
Of these, halide, perchlorate, trifluoromethanesulfonate, and acetate are preferable from the viewpoint of antistatic properties, and lithium chloride, -potassium, and-are more preferable.
Sodium, lithium perchlorate, -potassium and -sodium, lithium trifluoromethanesulfonate, -potassium and -sodium, potassium acetate.

The amount of (E1) used is preferably based on the total weight of (A), (B), (C), and (D) from the viewpoint of giving a resin molded article having a good appearance without being deposited on the resin surface. 0.001 to 3%, more preferably 0.01 to 2.5%, particularly preferably 0.1 to 2%, and most preferably 0.15 to 1%.
The method of containing (E1) is not particularly limited, but it is preferable to disperse it in advance in the hydrophilic group-containing polymer (C) because it is easy to effectively disperse it in the composition.
Further, when (E1) is dispersed in (C), it is particularly preferable that (E1) is contained and dispersed in advance during the production (polymerization) of (C). There is no particular limitation on the timing at which (E1) is contained during the production of (C), and any of the timing before polymerization, during polymerization, and immediately after polymerization may be used.

  Among (E2), as the nonionic surfactant, higher alcohol (C8-18) EO adduct, fatty acid (C8-24) EO adduct, higher alkylamine (C8-24) EO adduct, polypropylene glycol Polyethylene glycol type nonionic surfactants such as EO adducts; polyethylene oxide, fatty acid ester of glycerin, fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, etc. And polyhydric alcohol type nonionic surfactants.

  As the anionic surfactant, compounds other than the above (E1) can be used, for example, carboxylates such as higher fatty acid salts; sulfates such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfones. Examples thereof include sulfonates such as acid salts, alkyl sulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphate salts.

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

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

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

The amount of (E2) used is preferably 0.001 to 5%, more preferably 0.01 to 3%, especially based on the total weight of (A), (B), (C) and (D). Preferably it is 0.1 to 2.5%.
The method of containing (E2) is not particularly limited, but it is preferable to disperse in (C) in advance in order to effectively disperse it in the resin composition. Further, when (E2) is dispersed in (C), it is particularly preferable that (E2) is previously contained and dispersed during the production (polymerization) of (C). There is no particular limitation on the timing at which (E2) is contained during the production of (C), and any time before polymerization, during polymerization, or immediately after polymerization may be used.

As the compatibilizer (F), a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group is used. Examples thereof include polymers described in JP-A-3-258850. Further, for example, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, a block polymer having a polyolefin portion and an aromatic vinyl polymer portion, and the like can be used.
The amount of (F) used is preferably 0.1 to 15%, more preferably 1 to 15% based on the total weight of (A), (B), (C), and (D) from the viewpoint of resin physical properties. 10%, particularly preferably 1.5 to 8%.
The method of containing (F) is not particularly limited, but it is preferable to disperse it in advance in the hydrophilic group-containing polymer (C) from the viewpoint of ease of effective dispersion or dissolution in the composition. .
In addition, when (F) is dispersed or dissolved in (C), it is particularly preferable to contain (F) in advance during the production (polymerization) of (C). There is no particular limitation on the timing at which (F) is contained during the production of (C), and any of the timing before polymerization, during polymerization, and immediately after polymerization may be used.

  (G) includes nucleating agent (G1), lubricant (G2), plasticizer (G3), mold release agent (G4), antioxidant (G5), flame retardant (G6), ultraviolet absorber (G7) and The at least 1 sort (s) chosen from the group which consists of an antibacterial agent (G8) is mentioned.

(G1) includes organic nucleating agents [for example, 1,3,2,4-di-benzylidene-sorbitol, aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium-bis (4-tert-butyl Phenyl) phosphate and sodium benzoate] and inorganic nucleating agents (eg, graphite, carbon black, magnesium oxide, calcium silicate, magnesium silicate, talc, kaolin, calcium carbonate, magnesium carbonate, sodium carbonate, potassium carbonate, zinc oxide, alumina, Barium sulfate and calcium sulfate).
(G2) include waxes (eg carnauba wax, paraffin wax and polyolefin wax), higher fatty acids (C8-24, eg stearic acid, oleic acid, linoleic acid and linolenic acid), higher alcohols (C8-18, eg stearyl alcohol). , Lauryl alcohol, myristyl alcohol, cetyl alcohol, cetostearyl alcohol and behenyl alcohol) and higher fatty acid amides (C8-24, such as stearic acid amide, oleic acid amide, linoleic acid amide and linolenic acid amide).

(G3) includes aromatic carboxylic acid esters [for example, phthalic acid esters (for example, dioctyl phthalate and dibutyl phthalate)], aliphatic monocarboxylic acid esters [for example, methyl acetyl ricinoleate and triethylene glycol dibenzoate], aliphatic dicarboxylic acids Esters [eg di (2-ethylhexyl) adipate and adipic acid-propylene glycol based polyesters (Mn 200-2000)], aliphatic tricarboxylic esters [eg citrate esters (eg triethyl citrate)], phosphate triesters [eg tri Phenyl phosphate] and petroleum resins.
(G4) includes lower (C1-4) alcohol esters of higher fatty acids (above) (for example, butyl stearate), polyvalent (divalent to tetravalent or higher) alcohol esters of fatty acids (C2-18) (E.g. hydrogenated castor oil), glycol (C2-8) esters of fatty acids (C2-18) (e.g. ethylene glycol monostearate) and liquid paraffin.

  (G5) may be phenol-based [eg monocyclic phenol [eg 2,6-di-t-butyl-p-cresol and butylated hydroxyanisole], bisphenol [eg 2,2′-methylenebis (4-methyl-6 -T-butylphenol), 4,4'-butylidenebis (3-methyl) -6-t-butylphenol and 4,4'-thiobis (3-methyl) -6-t-butylphenol] and polycyclic phenols [eg 1, 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and 1,1,3-tris (2-methyl-4-hydroxy-5-t -Butylphenyl) butane]]; sulfur-based [eg dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate Lauryl stearyl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl β, β′-thiodibutyrate and dilauryl sulfide]; phosphorus systems [eg triphenyl phosphite, tri Isodecyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl Phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), cyclic neopentanetetrayl bis (2 , 6-Di-tert-butyl-4-methylphenol Nyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite and diisodecylpentaerythritol diphosphite]; and amine systems [eg octylated diphenylamine, Nn-butyl- p-aminophenol, N, N-diisopropyl-p-phenylenediamine, N, N-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N-diphenyl-p-phenylenediamine, N- Phenyl-α-naphthylamine, phenyl-β-naphthylamine and phenothiazine].

(G6) includes organic flame retardants [for example, nitrogen-containing [for example, urea compounds, guanidine compounds, and triazine compounds (for example, melamine and guanamine) salts (for example, inorganic acid (the foregoing) salts), cyanurate and isocyanuric acid] Salt)], sulfur-containing systems [for example, sulfates, organic sulfonic acids, sulfamic acids, organic sulfamic acids, and salts, esters and amides thereof], silicon-containing systems (for example, polyorganosiloxane) and phosphorus-containing systems [for example, phosphoric acid Esters (for example tricresyl phosphate)]] and inorganic flame retardants [for example antimony trioxide, magnesium hydroxide, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus and ammonium polyphosphate].

  (G7) includes benzotriazole-based [eg, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole], benzophenone-based [ For example 2-hydroxy-4-methoxybenzophenone and 2,2′-dihydroxy-4-methoxybenzophenone], salicylate systems [eg phenyl salicylate and ethylene glycol monosalicylate] and acrylate systems [eg 2-ethylhexyl-2- Cyano-3,3′1-diphenyl acrylate].

  (G8) includes benzoic acid, paraoxybenzoic acid ester, sorbic acid, halogenated phenol (for example, 2,4,6-tribromophenol sodium salt), organic iodine (for example, 4-chlorophenyl-3-iodopropargyl formal) , Nitriles (eg 2,4,5,6-tetrachloroisophthalonitrile), thiocyano (eg methylene bisthianocyanate), N-haloalkylthioimides (eg N-tetrachloroethyl-thio-tetrahydrophthalimide), copper agents (eg 8-oxyquinoline copper), benzimidazole (eg 2-4-thiazolylbenzimidazole), benzothiazole (eg 2-thiocyanomethylthiobenzothiazole), trihaloallyl (eg 3-bromo-2,3-diiodo-2-yl) Propenyl ethyl Sulfonates), triazoles (eg azaconazole), organic nitrogen sulfur compounds (eg Suraoff 39), quaternary ammonium compounds (eg trimethoxysilyl-propyloctadecyl ammonium chloride) and pyridine-based compounds [eg 2,3,5,6-cytochloro- 4- (methylsulfonyl) -pyridine].

  The amount of (G) used is usually 10% or less for each of (G1), (G2) and (G4) based on the total weight of (A), (B), (C) and (D), preferably 1 to 10%; (G3) and (G6) are each usually 20% or less, preferably 1 to 10%; (G5) and (G7) are usually 5% or less, preferably 0.1 to 3%; (G8 ) Is usually 3% or less, preferably 0.05 to 1%.

The resin composition of the present invention is obtained by melt-mixing (A), (B), (C), (D) and, if necessary, (E), (F) and / or (G). . As a method of melt mixing, generally, a method in which pellets or powdery components are mixed with an appropriate mixer such as a Henschel mixer, and then melt mixed with an extruder to be pelletized can be applied.
The order of addition of each component during melt mixing is not particularly limited. For example, (1) (A) and (B) are mixed, (C) is then melt mixed, and then (D) and (E ), (F) and / or (G), and (2) (A) and (B) are mixed, then (C) is melt-mixed and then (D) is mixed. Parts are melt-mixed in advance to prepare a high concentration composition (masterbatch resin composition) of (A), (B), (C), and then the remaining (D) as well as (E) as necessary, A method of melt-mixing (F) and / or (G).
The concentration of (C) in the masterbatch resin composition in the method (2) is preferably 40 to 80% by weight, more preferably 50 to 70% by weight.
Among these, the method (2) is a method called a master batch method or a master pellet method, and is a preferable method from the viewpoint of efficient dispersion of (A), (B), and (C) into (D). .

  The molded product of the present invention can be obtained by molding the antistatic resin composition. Examples of the molding method include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (cast method, tenter method, inflation method, etc.), foam molding, etc. Depending on the method, it can be formed by any method.

The volume resistivity (Ω · cm) of the molded product of the present invention is preferably 1 × 10 ² to 1 × 10 ⁹ , more preferably 1 × 10 ³ to 1 from the viewpoint of mechanical properties and antistatic properties of the molded product. × 10 ⁷ , particularly preferably 1 × 10 ⁴ to 1 × 10 ⁶ .

The molded article has excellent mechanical properties, heat resistance, and permanent antistatic properties, as well as good paintability and printability.
Examples of the method for coating the molded product include, but are not limited to, an air spray method, an airless spray method, an electrostatic spray method, a dipping method, a roller method, and a brush coating method. Examples of the paint include various paints such as polyester melamine, epoxy melamine, acrylic melamine, and acrylic urethane resin paint.
The coating film thickness (film thickness after drying) can be appropriately selected according to the purpose, but is preferably 10 to 50 μm, more preferably 15 to 40 μm from the viewpoint of physical properties of the coating film.
Examples of the method for printing on the molded product include various printing methods such as gravure printing, flexographic printing, screen printing, and offset printing.
Examples of the printing ink include those usually used for plastic printing.

  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.

Example 1
Single-walled carbon nanotube (A-1) [trade name “S-SWNT”, NTP (Shent
en Nanotech Port Co. ) Manufactured by Co., Ltd., diameter 10 nm, aspect ratio 500] 10 parts and 1-ethyl-3-methylimidazolium tetrafluoroborate (B-1)
90 parts were blended and mixed in a mortar for 30 minutes at 25 ° C. It was confirmed that the mixture of (A-1) and (B-1) became a paste.
Next, in a stainless steel autoclave, 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, an antioxidant [trade name “Irganox 1010”, manufactured by Ciba Specialty Chemicals Co., Ltd., and so on. ] 0.3 parts and 6 parts of water were charged, the inside of the autoclave was purged with nitrogen, then heated and stirred at 220 ° C. under pressure (0.3 to 0.5 MPa) for 4 hours, and an acid having carboxyl groups at both ends. 96 parts of polyamide having a value of 112 and Mn of 1,000 were obtained.
Next, 192 parts of an EO adduct of bisphenol A with Mn of 2,000 and 0.5 part of zirconyl acetate were added and polymerized at 245 ° C. under reduced pressure of 0.13 kPa or less for 5 hours to obtain a polyether ester amide (C1-1). Got. The volume resistivity value of (C1-1) is 2 × 10 ⁸ Ω ·
cm.
A stainless steel autoclave was charged with 80 parts of (C1-1), and the interior of the autoclave was purged with nitrogen, and then heated and stirred at 230 ° C. 20 parts of the mixture of (A-1) and (B-1) was added and mixed, and after melting and stirring at 230 ° C. for 1 hour, the resulting mixture was taken out as a strand on a belt and pelletized to prevent charging. Agent (X1) was obtained.

Example 2
50 parts of (A-1) and 50 parts of (B-1) were blended and mixed at 25 ° C. for 30 minutes in a mortar. It was confirmed that the mixture of (A-1) and (B-1) became a paste.
Next, 67 parts of ε-caprolactam, 33 parts of terephthalic acid, 0.3 part of antioxidant and 6 parts of water were charged into a stainless steel autoclave, and the interior of the autoclave was purged with nitrogen and then pressurized at 220 ° C. (0.3 to 0.5 MPa) Under sealing, the mixture was heated and stirred for 4 hours to obtain 96 parts of polyamide having an acid value of 224 and Mn500 having carboxyl groups at both ends.
Next, 96 parts of an EO adduct of bisphenol A of Mn500 and 0.5 part of zirconyl acetate were added and polymerized at 245 ° C. under reduced pressure of 0.13 kPa or less for 5 hours to obtain a polyether ester amide (C1-2). It was. The volume resistivity value of (C1-2) was 1 × 10 ¹² Ω · cm.
A stainless steel autoclave was charged with 98 parts of (C1-2), and the atmosphere in the autoclave was replaced with nitrogen, followed by heating and stirring at 230 ° C. 2 parts of the mixture of (A-1) and (B-1) was added and mixed, and after melting and stirring at 230 ° C. for 1 hour, the resulting mixture was taken out as a strand on a belt and pelletized. Agent (X2) was obtained.

Example 3
20 parts of (A-1) and 40 parts of (B-1) were blended and mixed at 25 ° C. for 30 minutes in a mortar. It was confirmed that the mixture of (A-1) and (B-1) became a paste.
Next, 50 parts of ε-caprolactam, 50 parts of terephthalic acid, 0.3 part of an antioxidant and 6 parts of water were charged into a stainless steel autoclave, and the autoclave was purged with nitrogen and pressurized at 220 ° C. (0.3 to 0.5 MPa) Under sealing, the mixture was heated and stirred for 4 hours to obtain 96 parts of polyamide having an acid value of 560 and Mn200 having carboxyl groups at both ends.
Next, 64 parts of an EO adduct of bisphenol A of Mn300 and 0.5 part of zirconyl acetate were added and polymerized at 245 ° C. under reduced pressure of 0.13 kPa or less for 5 hours to obtain a polyether ester amide (C1-3). It was. The volume resistivity value of (C1-3) was 1 × 10 ¹¹ Ω · cm.
A stainless steel autoclave was charged with 40 parts of (C1-3), the inside of the autoclave was purged with nitrogen, and then heated and stirred at 230 ° C. 60 parts of the mixture of (A-1) and (B-1) was added and mixed, and after melting and stirring at 230 ° C. for 1 hour, the resulting mixture was taken out as a strand on a belt and pelletized to prevent charging. Agent (X3) was obtained.

Example 4
15 parts of (A-1) and 35 parts of (B-1) were blended and mixed at 25 ° C. for 30 minutes in a mortar. It was confirmed that the mixture of (A-1) and (B-1) became a paste.
Next, 94 parts of ε-caprolactam, 6 parts of terephthalic acid, 0.3 part of antioxidant and 6 parts of water were charged into a stainless steel autoclave, and the inside of the autoclave was purged with nitrogen, and then pressurized at 220 ° C. (0.3 to 0.5 MPa) Under sealing, the mixture was heated and stirred for 4 hours to obtain 96 parts of polyamide having an acid value of 37 and Mn of 3,000 having carboxyl groups at both ends.
Next, 72 parts of EO adduct of bisphenol A of Mn 4,000 and 0.5 part of zirconyl acetate were added and polymerized at 245 ° C. under reduced pressure of 0.13 kPa or less for 5 hours to obtain polyetheresteramide (C1-4). Got. The volume resistivity value of (C1-4) was 5 × 10 ⁶ Ω · cm.
A stainless steel autoclave was charged with 50 parts of (C1-4), and the interior of the autoclave was purged with nitrogen, and then heated and stirred at 230 ° C. Add 50 parts of the mixture of (A-1) and (B-1), mix and stir at 230 ° C. for 1 hour, take out the resulting mixture in the form of a strand on a belt and pelletize it to prevent charging Agent (X4) was obtained.

Example 5
10 parts of (A-1) and 90 parts of (B-1) were blended and mixed at 25 ° C. for 30 minutes in a mortar. It was confirmed that the mixture of (A-1) and (B-1) became a paste.
Next, 96 parts of ε-caprolactam, 4 parts of terephthalic acid, 0.3 part of antioxidant and 6 parts of water were charged into a stainless steel autoclave, and the inside of the autoclave was purged with nitrogen, and then pressurized at 220 ° C. (0.3 to 0.5 MPa) Under sealing, the mixture was heated and stirred for 4 hours to obtain 96 parts of polyamide having an acid value of 22 and Mn of 5,000 having carboxyl groups at both ends.
Next, 96 parts of an EO adduct of bisphenol A of Mn 5,000 and 0.5 part of zirconyl acetate were added and polymerized at 245 ° C. under reduced pressure of 0.13 kPa or less for 5 hours to obtain a polyether ester amide (C1-5). Got. The volume resistivity value of (C1-5) was 1 × 10 ⁶ Ω · cm.
A stainless steel autoclave was charged with 80 parts of (C1-5), and the interior of the autoclave was purged with nitrogen, and then heated and stirred at 230 ° C. 20 parts of the mixture of (A-1) and (B-1) was added and mixed. After melting and stirring at 230 ° C. for 1 hour, the resulting mixture was taken out as a strand on a belt and pelletized. Agent (X5) was obtained.

Example 6
In Example 1, instead of (A-1), a multi-walled carbon nanotube (A-2) [trade name “MWNT-AP”, manufactured by Sun Nanotech Co., Ltd.], diameter 1 nm, aspect ratio 500] was used. Except that, an antistatic agent (X6) was obtained in the same manner as in Example 1.

Example 7
Example 1 except that 50 parts of (A-1) and 50 parts of (B-1) were blended instead of blending 10 parts of (A-1) and 90 parts of (B-1) in Example 1. In the same manner as above, an antistatic agent (X7) was obtained.

Example 8
An antistatic agent (X8) was obtained in the same manner as in Example 1 except that imidazole trifluoromethanesulfonate (B-2) was used instead of (B-1) in Example 1.

Example 9
10 parts of (A-1) and 90 parts of (B-1) were mixed and mixed at 50 ° C. for 30 minutes in a mortar. It was confirmed that the mixture of (A-1) and (B-1) became a paste.
Low molecular weight polypropylene (Mn 2,500, density 0.89, 10.5 double bonds per 1,000 C, average double bonds per molecule) obtained by a stainless steel autoclave 1.9 parts, content of polyolefin which can be modified at both ends (95%) and 85 parts of maleic anhydride and 15 parts of maleic anhydride were melted at 200 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 200 ° C. for 20 hours. I let you.
Thereafter, excess maleic anhydride was distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polypropylene (c21-1). (C21-1) had an acid value of 39.8 and Mn of 2,800.
Next, in a stainless steel autoclave, 50 parts of (c21-1), 50 parts of polyethylene glycol (c22-1) (Mn2,800, volume resistivity 1 × 10 ⁷ Ω · cm), 0.3 parts of antioxidant Then, 0.5 part of zirconyl acetate was charged and polymerized at 230 ° C. under a reduced pressure of 0.13 kPa or less for 3 hours to obtain a viscous polymer (C2-1). Mn of (C2-1) was 22,000, and the average number of repetitions (Nn) determined from the Mn and ¹ H-NMR analysis was 3.9. The volume resistivity value of (C2-1) was 5 × 10 ⁸ Ω · cm.
80 parts of (C2-1) was charged into a stainless steel autoclave, the inside of the autoclave was purged with nitrogen, and heated and stirred at 200 ° C., and 20 parts of the mixture of (A-1) and (B-1) was added and mixed. After melting and stirring at 200 ° C. for 1 hour, the obtained polymer was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X9).

Example 10
15 parts of (A-1) and 35 parts of (B-1) were blended and mixed at 25 ° C. for 30 minutes in a mortar. It was confirmed that the mixture of (A-1) and (B-1) became a paste.
Low molecular weight polypropylene obtained by a thermal degradation method (Mn 3,400, density 0.89, 7.0 double bonds per 1,000 C, average of double bonds per molecule, and stainless steel autoclave) 1.8 parts, 90 parts of polyolefin capable of modifying both ends) and 10 parts of maleic anhydride were melted at 200 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 200 ° C. for 20 hours. I let you.
Then, excess maleic anhydride was distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polypropylene (c21-2). (C21-2) had an acid value of 27.5 and Mn3,600.
Next, 97 parts of (c21-2) and 5 parts of ethanolamine were melted at 180 ° C. in a nitrogen gas atmosphere in a stainless steel autoclave and reacted at 180 ° C. for 2 hours. Then, excess ethanolamine was distilled off under reduced pressure at 180 ° C. for 2 hours to obtain a modified polypropylene (b21-3) having a hydroxyl group. (B21-3) had a hydroxyl value of 26.7, an amine value of 0.01, and Mn of 3,700.
Next, an isocyanate-modified polyethylene glycol (c22-3) obtained by reacting polyethylene glycol (c22-2) (Mn3,200, volume resistivity 1 × 10 ⁷ Ω · cm) with MDI in a stainless steel autoclave. 43 parts (NCO content 3.0%, volume resistivity 1 × 10 ⁷ Ω · cm) and modified polypropylene (c21-3) having a hydroxyl group
57 parts were kneaded with a twin-screw extruder at 200 ° C. for a residence time of 30 seconds, taken out into a strand shape, and pelletized to obtain a viscous polymer (C2-2). The volume resistivity value of (C2-2) was 4 × 10 ⁸ Ω · cm.
80 parts of the (C2-1) was charged into a stainless steel autoclave, the inside of the autoclave was purged with nitrogen, heated and stirred at 200 ° C., and 20 parts of the mixture of the above (A-1) and (B-1) was added and mixed. After melting and stirring at 200 ° C. for 1 hour, the obtained polymer was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X10).

Example 11
In Example 9, the same procedure as in Example 9 was used except that polyether diamine (c22-4) (Mn 2,800, volume resistivity 2 × 10 ⁷ Ω · cm) was used instead of (c22-1). Thus, a viscous polymer (C2-3) was obtained. Mn of (C2-3) was 20,000, and the average number of repetitions (Nn) obtained from the Mn and ¹ H-NMR analysis was 3.6. The volume resistivity value of (C2-3) was 1 × 10 ⁷ Ω · cm. Further, in the same manner as in Example 9, an antistatic agent (X11) was obtained.

Example 12
50 parts of (A-1) and 50 parts of (B-1) were blended and mixed at 25 ° C. for 30 minutes in a mortar. It was confirmed that the mixture of (A-1) and (B-1) became a paste.
Low molecular weight polypropylene (Mn 19,000, density 0.89, average number of double bonds per 1,000 C, 1,000 double bonds per molecule) obtained by a stainless steel autoclave 1.7 parts, content of polyolefin which can be modified at both ends (90%) 250 parts and maleic anhydride 10 parts were melted at 220 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 220 ° C. for 29 hours. I let you.
Thereafter, excess maleic anhydride was distilled off under reduced pressure at 220 ° C. for 3 hours to obtain acid-modified polypropylene (c21-4). (C21-4) had an acid value of 5.5 and Mn of 19,200.
Next, 135 parts of acid-modified polypropylene (c21-4) and 10 parts of bis (2-aminoethyl) ether were melted at 200 ° C. under stirring in a nitrogen gas atmosphere and reacted at 200 ° C. for 2 hours. Thereafter, excess bis (2-aminoethyl) ether was distilled off under reduced pressure at 200 ° C. for 2 hours to obtain a modified polypropylene (c21-5) having amino groups at both ends. The amine value of (c21-5) was 5.8, and Mn was 19,400.
Next, in a stainless steel autoclave, 50 parts of (c21-5), 40 parts of polyethylene glycol (c22-5) (Mn 20,000, volume resistivity 1 × 10 ⁸ Ω · cm), 5.2 parts of dodecanedioic acid Then, 0.3 part of an antioxidant and 0.5 part of zinc acetate were charged and polymerized at 230 ° C. under a reduced pressure of 0.13 kPa or less for 15 hours to obtain a viscous polymer (C2-4). The volume resistivity value of (C2-4) was 1 × 10 ¹⁰ Ω · cm.
96 parts of the (C2-4) were charged into a stainless steel autoclave, the inside of the autoclave was purged with nitrogen, heated and stirred at 200 ° C., and 4 parts of the mixture of the above (A-1) and (B-1) were added and mixed. After melting and stirring at 200 ° C. for 1 hour, the obtained polymer was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X12).

Example 13
10 parts of (A-1) and 90 parts of (B-1) were mixed and mixed at 50 ° C. for 30 minutes in a mortar. It was confirmed that the mixture of (A-1) and (B-1) became a paste.
Next, 40 parts of polyetheresteramide (C1-1) and 40 parts of a viscous polymer (C2-1) were charged into a stainless steel autoclave, and the interior of the autoclave was purged with nitrogen, followed by heating and stirring at 200 ° C. -1) and 20 parts of a mixture of (B-1) were added and mixed, and after melting and stirring at 200 ° C. for 1 hour, the resulting polymer was taken out in a strand form on a belt and pelletized to give an antistatic agent (X13 )

Comparative Example 1
In Example 1, in place of (A-1), Ketjen Black (ratio A-1) [trade name “EC300J”, manufactured by Lion Corporation, aspect ratio 1], which is a carbon material different from carbon nanotubes, is used. An antistatic agent (ratio X1) was obtained in the same manner as in Example 1 except that it was used.

Comparative Example 2
In Example 1, an antistatic agent (ratio X2) was obtained in the same manner as in Example 1 except that (A-1) was not used.

Comparative Example 3
In Example 1, an antistatic agent (ratio X3) was obtained in the same manner as in Example 1 except that 1-heptane-sulfonic acid (ratio B-1) was used instead of (B-1).

Comparative Example 4
In Example 1, an antistatic agent (ratio X4) was obtained in the same manner as in Example 1 except that (B-1) was not used.

Comparative Example 5
10 parts of carbon nanotubes (A-1) and 90 parts of (B-1) were mixed and mixed in a mortar for 30 minutes to obtain a paste-like mixture (antistatic agent) (ratio X5).

Comparative Example 6
In Example 9, an antistatic agent (Ratio X6) was obtained in the same manner as in Example 5 except that (Ratio A-1) was used instead of (A-1).

Comparative Example 7
In Example 9, an antistatic agent (ratio X7) was obtained in the same manner as in Example 9 except that (A-1) was not used.

Examples 14 to 28, Comparative Examples 8 to 15
According to the blending composition shown in Table 1, (X1) to (X13) or (Ratio X1) to (Ratio X7) and the thermoplastic resin (D-1) or (D-2) are optionally added to an antistatic property improving agent. (E-1) After blending for 3 minutes with a Henschel mixer together with the compatibilizer (F-1), the mixture is melt-kneaded in a twin-screw extruder with a vent at 220 ° C., 100 rpm, and a residence time of 5 minutes. Resin compositions (Examples 14 to 28 and Comparative Examples 8 to 15) were obtained.

（Ｄ−１）：ＡＢＳ樹脂[商品名「セビアン−Ｖ３２０」、ダイセルポリマー（株）製]
（Ｄ−２）：ポリプロピレン樹脂[商品名「サンアロマーＰＭ７７１Ｍ」、サンアロマー
（株）製]
（Ｅ−１）：ドデシルベンゼンスルホン酸ナトリウム
（Ｆ−１）：相溶化剤[商品名「エポフレンド」、ダイセル化学（株）製、変性ビニル重
合体]

(D-1): ABS resin [trade name “Cebian-V320”, manufactured by Daicel Polymer Co., Ltd.]
(D-2): Polypropylene resin [Brand name "Sun Allomer PM771M", Sun Allomer
Manufactured by]
(E-1): Sodium dodecylbenzenesulfonate (F-1): Compatibilizer [trade name “Epofriend”, manufactured by Daicel Chemical Industries, Ltd., modified vinyl heavy
Combined]

<Performance evaluation>
Using the above resin composition, injection molding machines [PS40E5ASE, Nissei Plastic Industry (
The product was molded at a mold temperature of 50 ° C. to produce test pieces, and the impact strength, antistatic property and moldability were evaluated. The results are shown in Table 2.

[1] Mechanical properties (1) Impact strength Conforms to ASTM D256 (with notch, 3.2 mm thickness) Method A.
[2] Antistatic property (1) Volume specific resistance value For a test piece (100 × 100 × 2 mm), a superinsulator [DSM-8103 (plate sample electrode SME-8310), Toa Denpa Kogyo Co., Ltd., and so on . ] At 23 ° C
, And measured under an atmosphere of humidity 50% RH (according to ASTM D257).
(2) Volume specific resistance value after washing with water The surface of a test piece (100 × 100 × 2 mm) leaning diagonally is set at a flow rate of 100 ml.
Wash with 100 ml of ion-exchanged water (23 ° C.) per minute, and then dry for 3 hours in a circulating dryer at 80 ° C. About the test piece which repeated this washing-drying operation 10 times, (1
) And measured in the same manner.
[3] Moldability 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 that of 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 Table 2, the resin compositions of the present invention (Examples 14 to 28) were compared with the comparative resin compositions (Comparative Examples 8 to 15) in mechanical properties, permanent antistatic properties and molding of the molded products. It turns out that it is excellent in property.

Since the antistatic resin composition of the present invention is excellent in moldability and gives a molded product having excellent permanent antistatic properties and mechanical properties, various molding methods [injection molding, compression molding, calendar molding, slush molding, rotation Molding, extrusion molding, blow molding, foam molding, film molding (casting method, tenter method, inflation method, etc.)] and housings for home appliances / OA equipment, game machines and office equipment that require antistatic properties It is extremely useful as various molding materials for products, various plastic containers such as IC trays, various packaging films, flooring sheets, artificial turf, mats, and automobile parts.

Claims (7)

A mixture of a carbon nanotube (A) and a dispersant (B) having a conjugated double bond and a hydrophilic group-containing polymer (C) having a volume resistivity of 1 × 10 ⁶ to 1 × 10 ¹² Ω · cm An antistatic agent characterized by that. The antistatic agent according to claim 1, wherein (C) is at least one selected from the group consisting of the following (C1) and (C2).
(C1): polyamide (c11) having a number average molecular weight of 200 to 5,000 and a number average molecular weight of 30
0 to 5,000 alkylene oxide adducts of bisphenol compounds (c12)
Polyether ester amide (C2) derived from: The block of the polyolefin (c21) and the block of the polyoxyalkylene chain-containing compound (c22) are composed of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond. A block polymer having a structure in which they are repeatedly bonded alternately via at least one bond selected from the group consisting of The proportion based on the total weight of (A), (B), and (C) is 1 to 20% for (A), 1 to 40% for (B), and 40 to 98% for (C). Or the antistatic agent according to 2. The antistatic resin composition which makes the thermoplastic resin (D) contain the antistatic agent in any one of Claims 1-3. 5. The composition according to claim 4, further comprising at least one additive selected from the group consisting of an antistatic property improver, a compatibilizing agent and other additives for resins. A molded article formed by molding the composition according to claim 4 or 5. A molded article obtained by coating and / or printing the molded article according to claim 6.