JP4593105B2 - Antistatic resin composition and molded article thereof - Google Patents

Description

  The present invention relates to a resin composition having permanent antistatic properties and a resin molded body thereof.

Conventionally, a method of adding a polymer having a polyoxyalkylene group is known as a method for imparting permanent antistatic properties to a thermoplastic resin. (For example, see Patent Documents 1 and 2)

Japanese Patent Laid-Open No. 03-255161 Japanese Patent Laid-Open No. 03-258850

However, the above method has a problem that the antistatic property may not be exhibited in the molded product depending on the type of the molding method.
An object of the present invention is to provide an antistatic resin composition capable of always obtaining a molded article having excellent antistatic properties regardless of the type of molding method.

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 block of polyether ester amide or polyolefin (a) derived from polyamide and an alkylene oxide adduct of a bisphenol compound, and a volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · The polymer (b) block having a polyoxyethylene chain of cm has a structure in which the block is repeatedly and alternately bonded through at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond and an imide bond. From a dispersed phase composed of an antistatic agent (A) having a polyoxyethylene chain, which is a block polymer, and one thermoplastic resin (B) selected from the group consisting of vinyl resins, polyamide resins, polyester resins and polycarbonate resins [Wherein (A) is a polyether ester amino acid] And (B) is a polypropylene resin.] The weight ratio of (A) and (B) is 10/90 to 30/70, and the number average particle diameter and the number average minor diameter of the dispersed phase are Alternatively, an antistatic resin composition that gives a molded article having a number average thickness of 0.01 to 1 μm; an antistatic resin molded article obtained by molding the resin composition; an alkylene oxide adduct of polyamide and a bisphenol compound; A block of a derived polyetheresteramide or polyolefin (a) and a block of a polymer (b) having a polyoxyethylene chain having a volume resistivity of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm, A block polymer having a structure in which the structure is repeatedly and alternately bonded through at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond and an imide bond A disperse phase comprising an antistatic agent (A) having a polyoxyethylene chain and a continuous phase comprising one thermoplastic resin (B) selected from the group consisting of vinyl resins, polyamide resins, polyester resins and polycarbonate resins [However, except that (A) is a polyether ester amide and (B) is a polypropylene resin] An antistatic resin composition is molded, or (A) and (B) are kneaded and molded A dispersed phase consisting of (A) and a continuous phase consisting of (B), wherein the weight ratio of (A) and (B) is 10/90 to 30/70, the number average particle diameter of the dispersed phase, An antistatic resin molded article having a number average minor diameter or a number average thickness of 0.01 to 1 μm; a molded article obtained by coating and / or printing the molded article; an alkylene oxide of polyamide and a bisphenol compound Polyetheresteramide derived from a Sid adduct, or polyolefin (a) of the block and a polymer volume resistivity having a polyoxyethylene chain of ^{1 × 10 5 ~1 × 10 11} Ω · cm (b) And a block polymer having a structure in which the block is repeatedly and alternately bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond and an imide bond It consists of a dispersed phase consisting of an inhibitor (A) and a continuous phase consisting of one type of thermoplastic resin (B) selected from the group consisting of vinyl resin, polyamide resin, polyester resin and polycarbonate resin [provided that (A) is in polyetheresteramide, and (B) excluding the case where the polypropylene resin antistatic properties From the disperse phase consisting of (A) and the continuous phase consisting of (B), characterized in that shearing is applied in the uniaxial or multiaxial direction during molding of the fat composition or (A) and (B). An antistatic resin in which the weight ratio of (A) and (B) is 10/90 to 30/70, and the number average particle diameter, number average minor diameter or number average thickness of the dispersed phase is 0.01 to 1 μm. It is a manufacturing method of a molded object.

The antistatic resin composition of the present invention is extremely useful because of the following effects.
(1) A molded product obtained by molding the composition has excellent permanent antistatic properties and excellent mechanical properties.
(2) The molded product of the composition does not depend on a molding method (injection molding method or compression molding method), and all have excellent permanent antistatic properties.
(3) Since the molded product of the composition has a small difference between the surface specific resistance value and the volume specific resistance value, it has excellent antistatic properties not only on the surface but also in the thickness direction.

Specifically, as the antistatic agent (A) having a polyoxyethylene chain of the present invention, a block of a polyether ester amide (A1) and a polyolefin (a), and a volume resistivity value of 1 × 10 ⁵ to 1 × A block polymer (A2), a polyetheramide imide (A3), an epihalohydrin / alkylene oxide (hereinafter referred to as a block polymer (b) having a structure in which a block of a polymer (b) having a polyoxyethylene chain of 10 ¹¹ Ω · cm is alternately and repeatedly bonded. Abbreviated as AO) copolymer (A4), polyether ester (A5), methoxypolyethylene glycol (meth) acrylate copolymer (A6), polyether group-containing ethylene / vinyl acetate copolymer (ethylene / vinyl alcohol copolymer) A combined ethylene oxide adduct) (A7) and a mixture of two or more thereof. It is.
Among these, (A1), (A2), (A3), (A4) and (A5) are preferable from the viewpoint of antistatic properties, and more preferable are polyetheresteramides (A1) and (A2) It is.

  Examples of (A1) include polyether ester amides described in JP-A-6-287547 and JP-B-4-5691. Among these, from the viewpoint of heat resistance, the number average molecular weight (hereinafter abbreviated as Mn, measured by GPC (gel permeation chromatography) method) 200 to 5,000 polyamide (a11) and Mn 300 to 5, Polyether ester amide derived from AO adduct (a12) of 000 bisphenol compounds.

Examples of (a11) include (1) a lactam ring-opening polymer, (2) a polycondensate of aminocarboxylic acid, and (3) a polycondensate of dicarboxylic acid and diamine.
Among the amide-forming monomers forming these polyamides, the lactam in (1) includes 6 to 12 carbon atoms, such as caprolactam, enantolactam, laurolactam, and undecanolactam.
The aminocarboxylic acid in (2) has 6 to 12 carbon atoms, such as ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid. , 12-aminododecanoic acid.
Examples of the dicarboxylic acid in (3) include aliphatic dicarboxylic acids, aromatic (aliphatic) dicarboxylic acids, alicyclic dicarboxylic acids, and amide-forming derivatives thereof [for example, acid anhydrides and lower (1 to 4 carbon atoms) alkyl esters. And a mixture of two or more thereof.

Examples of the aliphatic dicarboxylic acid include 4 to 20 carbon atoms such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid, and itacone. An acid etc. are mentioned.
Examples of the aromatic (aliphatic) dicarboxylic acid include 8 to 20 carbon atoms, such as ortho-, iso- and terephthalic acid, naphthalene-2,6- and -2,7-dicarboxylic acid, diphenyl-4,4'dicarboxylic acid, Examples include alkali metal (sodium, potassium, etc.) salts of diphenoxyethanedicarboxylic acid and 3-sulfoisophthalic acid.
Examples of the alicyclic dicarboxylic acid include those having 7 to 14 carbon atoms, such as cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid, and the like.
Among the amide-forming derivatives, examples of the acid anhydride include anhydrides of the above dicarboxylic acids, such as maleic anhydride, itaconic anhydride, phthalic anhydride, and the like. Lower alkyl esters of acids such as dimethyl adipate, ortho-, iso- and dimethyl terephthalate.
Examples of the diamine include 6 to 12 carbon atoms such as hexamethylene diamine, heptamethylene diamine, octamethylene diamine, and decamethylene diamine.

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 particularly preferable.

(A11) is obtained by using one or more dicarboxylic acids having 4 to 20 carbon atoms as a molecular weight modifier and subjecting the amide-forming monomer to ring-opening polymerization or polycondensation in the presence thereof in the usual manner.
Examples of the dicarboxylic acid having 4 to 20 carbon atoms include those exemplified in the above (3). Among these, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and 3-sulfones are preferable from the viewpoint of antistatic properties. Alkali metal isophthalates are more preferred, with 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% by weight and more preferably 4 to 75% by weight 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 (a11) is preferably 200 to 5,000, more preferably 500 to 3,000, from the viewpoint of reactivity and the heat resistance of (A1) obtained.

Examples of the bisphenol compound constituting the AO adduct (a12) of the bisphenol compound in the present invention include 13 to 20 carbon atoms, such as bisphenol A, bisphenol F, and bisphenol S. Among these, preferred from the viewpoint of dispersibility. Is bisphenol A.
The AO to be added to the bisphenol compound has 2 to 12 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 2,3- and 1,4. -Butylene oxide, epoxidized product of α-olefin having 5 to 12 carbon atoms, styrene oxide and epihalohydrin (such as epichlorohydrin and epibromohydrin), and a mixture of two or more thereof. Of these, EO is preferred from the viewpoint of antistatic properties.
Mn of (a12) is preferably 300 to 5,000, more preferably 500 to 4,000 from the viewpoint of antistatic properties.

  The proportion of (a12) based on the total weight of (a11) and (a12) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, from the viewpoint of antistatic properties and heat resistance of (A1). is there.

Specific examples of the production method of the polyetheresteramide (A1) include the following production methods (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 (a11), to which (a12) is added, at a high temperature (160 to 270 ° C.) under reduced pressure (0. 03 to 3 kPa).
Production method (2): An amide-forming monomer and a dicarboxylic acid (molecular weight modifier) and (a12) are simultaneously charged into a reaction vessel, and pressurized (0 to 160-270 ° C.) in the presence or absence of water (0 A method of producing an intermediate (a11) by reacting, and then performing a polymerization reaction with (a12) 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 (A1), in addition to the above, a method may be used in which the terminal hydroxyl group of (a12) 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.
As a method of substituting the terminal hydroxyl group of (a12) 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, (a12) and acrylonitrile And a method of hydrogenating the obtained cyanoethylated product].
Examples of the method of substituting the terminal hydroxyl group of (a12) with a carboxyl group include a method of oxidizing with an oxidizing agent [for example, a method of oxidizing the hydroxyl group of (a12) 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.), metal acetate catalysts (zinc acetate, And zirconyl acetate).
The amount of the catalyst used is preferably 0.1 to 5% by weight based on the total weight of (a11) and (a12), and more preferably 0.2 to 3% by weight from the viewpoint of reactivity and resin physical properties. .

Reduced viscosity of (A1) [η _SP / C, C = 0.5 wt% (m-cresol solution, 25 ° C.), value measured using an Ubbelohde 1A viscometer, unit is dl / g, and so on. ] Is preferably 0.5 to 4, more preferably 0.6 to 3, from the viewpoint of the heat resistance of (A1) and the moldability of the resin composition. In the following, the reduced viscosity is indicated only by numerical values.

As the block polymer (A2), block polymers described in the specification of WO00 / 47652 can be used.
As the block of the polyolefin (a), a polyolefin (a21) having a carbonyl group (preferably a carboxyl group), a hydroxyl group and an amino group at both ends of the polymer can be used.

As (a21), both polyolefins (a20) having a polyolefin whose both ends can be modified as a main component (content 50% by weight or more, more preferably 75% by weight or more, particularly preferably 80 to 100% by weight) are used. Examples thereof include those having a carbonyl group introduced at the terminal.
(A20) 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 terminal group that can be modified. Those are preferred.

  (A20) is a polyolefin obtained by (co) polymerization (meaning polymerization or copolymerization; the same applies hereinafter) of one or a mixture of two or more olefins having 2 to 30 carbon atoms [obtained by polymerization method. And low molecular weight polyolefins obtained by the thermal degradation method of high molecular weight polyolefins (polyolefins obtained by polymerization of olefins having 2 to 30 carbon atoms) can be used.

Examples of the olefin having 2 to 30 carbon atoms include ethylene, propylene, α-olefin having 4 to 30 carbon atoms (preferably 4 to 12 and more preferably 4 to 10), and 4 to 30 carbon atoms (preferably 4 to 18). More preferably, 4-8) dienes and the like can be mentioned.
Examples of the α-olefin having 4 to 30 carbon atoms include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene. Examples of the diene include butadiene, Examples include isoprene, cyclopentadiene and 1,11-dodecadiene.
Of these, preferred are olefins having 2 to 12 carbon atoms (ethylene, propylene, α-olefins having 4 to 12 carbon atoms, butadiene and / or isoprene, etc.), and more preferred are olefins having 2 to 10 carbon atoms (ethylene). , Propylene, α-olefins having 4 to 10 carbon atoms, and / or butadiene, etc.), particularly preferably ethylene, propylene and / or butadiene.

The low molecular weight polyolefin obtained by the thermal degradation method can be easily obtained by, for example, the method described in JP-A-3-62804.
The polyolefin obtained by the polymerization method can be produced by a known method, for example, easily obtained by (co) polymerizing the olefin in the presence of a radical catalyst, a metal oxide catalyst, a Ziegler catalyst, a Ziegler-Natta catalyst, or the like. be able to.

As the radical catalyst, known ones such as di-t-butyl peroxide, t-butyl benzoate, decanol peroxide, lauryl peroxide, peroxy-di-carbonate ester, azo compound, etc., and oxidized to γ-alumina carrier For example, molybdenum is attached.
Examples of the metal oxide catalyst include those obtained by attaching chromium oxide to a silica-alumina support.
Examples of Ziegler catalysts and Ziegler-Natta catalysts include (C ₂ H ₅ ) ₃ Al—TiCl ₄ .
A low molecular weight polyolefin by a thermal degradation method is preferable from the viewpoint of easy introduction of a carbonyl group as a modifying group and availability.

Mn in (a20) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000 from the viewpoint of antistatic properties.
The amount of the double bond in (a20) is preferably 1 to 40 per 1,000 carbon atoms, more preferably 2 to 30 and particularly preferably 4 to 20 from the viewpoint of antistatic properties. It is a piece.
The average number of double bonds per molecule is preferably from 1.1 to 5, more preferably from 1.3 to 3, particularly preferably from the viewpoints of repetitive structure formation and antistatic properties. Is 1.5 to 2.5, most preferably 1.8 to 2.2.
In the thermal degradation method, a low molecular weight polyolefin having an average number of terminal double bonds per molecule of 1.5 to 2 in the range of Mn from 800 to 6,000 can be easily obtained [for example, Katsuhide Murata, See Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].

The measurement conditions of Mn are as follows (in the above and below, Mn is measured under the same conditions).
Apparatus: High-temperature gel permeation chromatography solvent: Orthodichlorobenzene reference material: Polystyrene sample concentration: 3 mg / ml
Column stationary phase: PLgel MIXED-B
Column temperature: 135 ° C

  As polyolefin (a21) which has a carbonyl group at both ends of a polymer, both ends of (a20) are α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, its carbon number 1 to The polyolefin (a211) having a structure modified with an alkyl ester of 4 or an anhydride thereof (hereinafter the same)), the polyolefin (a212) having a structure obtained by secondary modification of (a211) with a lactam or an aminocarboxylic acid, Polyolefin (a213) having a structure obtained by oxidizing or hydroformylating (a20), polyolefin (a214) having a structure obtained by secondary modification of (a213) with lactam or aminocarboxylic acid, and a mixture of two or more of these It is done.

(A211) is obtained by modifying (a20) with an α, β-unsaturated carboxylic acid (anhydride).
Examples of the α, β-unsaturated carboxylic acid (anhydride) include carboxylic acids having 3 to 12 carbon atoms, such as monocarboxylic acids [(meth) acrylic acid and the like], dicarboxylic acids (maleic acid, fumaric acid, itaconic acid, citracone Acid etc.), these alkyl (C1-C4) ester [methyl (meth) acrylate, butyl (meth) acrylate, diethyl itaconate etc.], and these anhydrides are mentioned.
Of these, dicarboxylic acids, alkyl esters thereof, and anhydrides thereof are preferable from the viewpoint of reactivity with (a20), and maleic acid (anhydride) and fumaric acid are more preferable, and particularly preferable. Is maleic acid (anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used is preferably 0.5 to 40% by weight based on the weight of the polyolefin (a20), from the viewpoint of the formation of a repeating structure and antistatic properties. More preferably, it is 1-30 weight%, Most preferably, it is 2-20 weight%.
Modification of the polyolefin (a20) with an α, β-unsaturated carboxylic acid (anhydride) is carried out by a known method, for example, the terminal double bond of (a20) is subjected to α, It can be carried out by thermally adding (ene reaction) β-unsaturated carboxylic acid (anhydride).
As a solution method, α, β-unsaturated carboxylic acid (anhydride) is added to (a20) in the presence of a hydrocarbon solvent such as xylene and toluene, and the temperature is 170 to 230 ° C. in an inert gas atmosphere such as nitrogen. The method of making it react is mentioned.
Examples of the melting method include a method in which (a20) is heated and melted, and then α, β-unsaturated carboxylic acid (anhydride) is added and reacted at 170 to 230 ° C. in an inert gas atmosphere such as nitrogen.
Among these methods, the solution method is preferable from the viewpoint of reaction uniformity.

(A212) can be obtained by secondary modification of (a211) with lactam or aminocarboxylic acid.
Examples of the lactam include lactams having 6 to 12 carbon atoms (preferably 6 to 8, more preferably 6), such as caprolactam, enantolactam, laurolactam, and undecanolactam.
As the aminocarboxylic acid, an aminocarboxylic acid having 2 to 12 (preferably 4 to 12, more preferably 6 to 12) carbon atoms such as an amino acid (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.), ω- Examples include 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 from the viewpoint of reactivity of secondary modification, and caprolactam is more preferred. Laurolactam, ω-aminocaprylic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, particularly preferred are caprolactam and 12-aminododecanoic acid.

(A213) can be obtained by oxidizing (a20) with oxygen and / or ozone or hydroformylating with an oxo method to introduce a carbonyl group.
The introduction of the carbonyl group by oxidation can be carried out by a known method, for example, the method described in US Pat. No. 3,692,877. The introduction of the carbonyl group by hydroformylation can be carried out by a known method such as Macromolecules, Vol. 31, 5943 page.

(A214) can be obtained by secondary modification of (a213) with lactam or aminocarboxylic acid.
As lactam and aminocarboxylic acid, what was illustrated by (a12) is mentioned, The usage-amount is also the same.

Mn of the polyolefin (a21) having carbonyl groups at both ends of the polymer is preferably 800 to 25,000, more preferably 1 from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. 20,000 to 20,000, particularly preferably 2,500 to 10,000.
The acid value of (a21) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (b), and more preferably 4 to 100. Yes, particularly preferably 5-50.

  Polyether diol (b1) and polyether diamine (b2) can be used as the polymer (b) having a polyoxyethylene chain.

The polyether diol (b1) has a structure obtained by addition reaction of diol (b01) or dihydric phenol (b02) with AO (3 to 12 carbon atoms) containing EO as an essential component. Examples thereof include those represented by the formula: H (OA ¹ ) _m O—E ¹ —O (A ¹ O) _{m ′} H.
In the formula, E ¹ represents a residue obtained by removing a hydroxyl group from (b01) or (b02), and A ¹ represents an alkylene group having 2 carbon atoms which may contain a halogen atom as an essential component. 12 (preferably 2 to 8, more preferably 2 to 4) alkylene groups; m and m ′ represent an integer of 1 to 300, preferably 2 to 250, particularly preferably 10 to 100, and m and m ′ May be the same or different. Further, m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and these are composed of two or more oxyalkylene groups having EO as an essential component. In this case, the combination type may be block, random, or a combination thereof.

As the diol (b01), a dihydric alcohol (aliphatic, alicyclic and araliphatic dihydric alcohol) having 2 to 12 carbon atoms (preferably 2 to 10, more preferably 2 to 8 carbon atoms) and 1 to 1 carbon atoms are used. 12 tertiary amino group-containing diols and the like.
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, 1,4-bis (hydroxyethyl) benzene, and the like.

As the tertiary amino group-containing diol, an aliphatic or alicyclic primary monoamine (having 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms) bishydroxyalkyl (1 to 1 carbon atoms in the alkyl group). 12, preferably 2 to 10, more preferably 2 to 8) and aromatic (aliphatic) primary monoamines (6 to 12 carbon atoms) bishydroxyalkyl (alkyl group having 1 to 12 carbon atoms) compounds. It is done.
The bishydroxyalkylated product of monoamine can be obtained by a known method, for example, by reacting monoamine with C2-4 AO [EO, PO, butylene oxide, etc.], or monoamine and C1-12 halogenated hydroxyalkyl. It can be easily obtained by reacting with (2-bromoethyl alcohol, 3-chloropropyl alcohol, etc.).

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

  Examples of the dihydric phenol (b02) include 6 to 18 carbon atoms (preferably 8 to 18, more preferably 10 to 15), such as monocyclic dihydric phenol (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenol (bisphenol). A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyl and the like) and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol and the like).

  Of (b01) and (b02), from the viewpoint of antistatic properties, preferred are dihydric alcohols and dihydric phenols, more preferred are aliphatic dihydric alcohols and bisphenols, and particularly preferred are ethylene glycol and bisphenol A. .

As AO to be subjected to addition reaction to diol (b01) or dihydric phenol (b02), in addition to EO, AO having 3 to 12 carbon atoms (PO, 1,2-, 1,4-, 2,3- and 1, 3-butylene oxide and a mixture of two or more thereof), and other AOs and substituted AOs may be used in combination.
Examples of other AO and substituted AO include an epoxidized product of an α-olefin having 5 to 12 carbon atoms, styrene oxide, and epihalohydrin (such as epichlorohydrin and epibromohydrin). The amount of each of the other AO and substituted AO used is preferably 30% by weight or less, more preferably 0 or 25% by weight, particularly preferably based on the weight of the total AO from the viewpoint of antistatic properties. 0 or 20% by weight or less.

  The number of added moles of AO is preferably 1 to 300 moles per hydroxyl group of (b01) or (b02), more preferably 2 to 2 from the viewpoint of the volume resistivity of the polymer (b) having a polyoxyethylene chain. 250 mol, particularly preferably 10 to 100 mol. When two or more kinds of AO are used in combination, the coupling form may be random and / or block.

The addition reaction of AO can be performed by a known method, for example, in the presence of an alkali catalyst (potassium hydroxide, sodium hydroxide, etc.) under conditions of 100 to 200 ° C. and a pressure of 0 to 0.5 MPaG.
The content of the oxyalkylene unit in the polyether diol (b1) is preferably 5 to 99.8% by weight from the viewpoint of the volume resistivity value of the hydrophilic polymer (b) based on the weight of (b1). Preferably it is 8-99.6 weight%, Most preferably, it is 10-98 weight%. Further, the content of the oxyethylene unit in the polyoxyalkylene chain is preferably 5 to 100% by weight, more preferably 10 to 10% by weight from the viewpoint of the volume resistivity value of (b) based on the weight of the polyoxyalkylene chain. It is 100% by weight, particularly preferably 50 to 100% by weight, and most preferably 60 to 100% by weight.

The polyether diamine (b2) has a structure in which the hydroxyl group of the polyether diol (b1) is modified to an amino group (primary or secondary amino group), for example, a general formula: RNH-A ^2- (OA ¹ ) those represented by ^{_{m O-E 1 -O (A}} 1 O) m '-A 2 -NHR the like. Therefore, the content of oxyethylene units in the polyoxyalkylene chain is the same as in (b1), and the content of oxyalkylene units in (b2) is the same as the content of the corresponding oxyalkylene units in (b1). is there.
The symbol E ¹ in the formula represents a residue obtained by removing a hydroxyl group from (b01) or (b02), and A ¹ has 2 to 12 carbon atoms (preferably 2 to 8 carbon atoms) which may contain a halogen atom. Preferably 2-4) alkylene group; m and m ′ represent an integer of 1 to 300, preferably 2 to 250, particularly preferably 10 to 100, and m and m ′ may be the same or different. A ² represents an alkylene group having 2 to 12 carbon atoms (preferably 2 to 8, more preferably 2 to 4) which may contain a halogen atom, and A ¹ and A ² may be the same or different. One of them contains an alkylene group having 2 carbon atoms as an essential component. R represents H or an alkyl group having 1 to 4 carbon atoms (preferably 1 or 2).
(B2) can be easily obtained by changing both terminal hydroxyl groups of (b1) to amino groups by a known method.
As a method of changing a hydroxyl group to an amino group, a known method, for example, a method of reducing a terminal cyanoalkyl group obtained by cyanoalkylating a hydroxyl group of (b1) to form an amino group [for example, (b1) and acrylonitrile And a method of reacting (b1) with an aminocarboxylic acid or lactam, a method of reacting (b1) with a halogenated amine under alkaline conditions, and the like. .
As described above as (b), two or more kinds may be used in combination.

The volume resistivity of the polymer (b) having a polyoxyethylene chain (value measured in an atmosphere of 23 ° C. and 50% RH by the method described later) is 10 ⁵ to 10 ¹¹ Ω · cm. From the viewpoint of antistatic properties, it is preferably 10 ⁶ to 10 ¹⁰ Ω · cm, more preferably 10 ⁷ to 10 ⁹ Ω · cm.
Mn of (b) is preferably 150 to 20,000, more preferably 300 to 18,000, particularly preferably 1,000 to 15,000, from the viewpoint of heat resistance and reactivity with polyolefin (a). Most preferably, it is 1,200 to 8,000.

  The block polymer (A2) is at least one selected from the group consisting of an ester bond, an amide bond, an ether bond, and an imide bond, wherein the block of the polyolefin (a) and the block of the polymer (b) having a polyoxyethylene chain are included. Of these, a polymer having a repeating unit represented by the following general formula (1) is preferred from the viewpoint of antistatic properties and transparency.

In the formula (1), n is an integer of 2 to 50 (preferably 3 to 40, more preferably 4 to 30, particularly preferably 5 to 25); ^one of R ¹ and R ² is H and the other is H or methyl group; y is from 15 to 800 (preferably 20 to 500, more preferably 30 to 400) an integer; E ¹ is the residue minus the hydroxyl groups from diol (b01) or the dihydric phenol (bO2); a ¹ is An ethylene group, or an alkylene group having 2 to 4 carbon atoms which essentially contains an ethylene group; m and m ′ are integers of 1 to 300 (preferably 5 to 200, more preferably 8 to 150); X and X ′ are When a group selected from the following general formulas (2) and (3) and the corresponding (2 ′) and (3 ′), that is, X is a group represented by the general formula (2), X ′ represents the general formula (2 It is a group represented by '), and the same relationship applies to general formulas (3) and (3') A.

In the general formulas (2) and (3) and the corresponding formulas (2 ′) and (3 ′), R is the same as described in the above (b2) and is H or 1 to 4 carbon atoms (preferably 1 or 2) an alkyl group, R ³ is a divalent hydrocarbon group having 1 to 11 carbon atoms (preferably 2 to 11 and more preferably 5 to 11), and R ⁴ is H or 1 to 10 carbon atoms (preferably 1). -8, more preferably 1-6) alkyl group; r is an integer of 1-20 (preferably 1-15, more preferably 1-10), u is 0 or 1; Q, Q ', T And T ′ is a group represented by the following formula:

In the above general formulas (4) and (5) and the corresponding (4 ′) and (5 ′) formulas, R ⁵ is H or a carbon number of 1 to 10 (preferably 1 to 8, more preferably 1 to 6). ), R ⁶ is H or a methyl group, t is 1 when R ⁶ is a methyl group, and 0 when H is 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) is the polyether diol (b1) or poly This is a structure derived from ether diamine (b2), 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 in which X is a group represented by the general formula (2) and X ′ is a group represented by the general formula (2 ′) includes (a211) and / or (a212) (A21) obtained by polymerizing (b1) and (A22) obtained by polymerizing (a211) and / or (a212) and (b2) are included.
(A21) includes (A211) in which (a211) and (b1) are combined, (A212) in which (a212) and (b1) are combined, and a mixture of (A211) and (A212). Similarly, (A22) includes (A221) in which (a211) and (b2) are combined, (A222) in which (a212) and (b2) are combined, and a mixture of (A221) and (A222). included.

(A21) is a known method, for example, a method in which (b1) is added to (a211) and / or (a212) and a polymerization (polycondensation) reaction is carried out under reduced pressure, preferably at 200 to 250 ° C., or uniaxial Or it can manufacture by the method of superposing | polymerizing using a twin-screw extruder, Preferably it is 160-250 degreeC and residence time 0.1-20 minutes.
In the above polymerization reaction, known catalysts such as antimony catalyst (antimony trioxide, etc.); tin catalyst (monobutyltin oxide, etc.); titanium catalyst (tetrabutyl titanate, etc.); zirconium catalyst (tetrabutylzirconate, etc.); organic acid And metal salt catalysts [zirconium organic acid salts (such as zirconyl acetate), zinc acetate, etc.]; and mixtures of two or more of these. Of these, preferred are a zirconium catalyst and a zirconium organic acid salt, and more preferred is zirconyl acetate.
The amount of the catalyst used is preferably 0.001 to 5%, more preferably 0.01 to 3%, based on the total weight of (a211) and / or (a212) and (b1).

  Among (A21), (A212) may be reacted by adding (b1) after secondary modification of (a211) with the lactam or aminocarboxylic acid, or reacting (a211) with the lactam or aminocarboxylic acid. The reaction may be carried out in the presence of (b1) followed by reaction with (b1).

(A22) is the same as (A21) except that the combination of (a211) and / or (a212) and (b1) in (A21) is replaced with the combination of (a211) and / or (a212) and (b2) It can be manufactured by the method.
Of (A22), (A222) may be produced by secondarily modifying (b2) with the lactam or aminocarboxylic acid and then reacting it with (a211).

In the general formula (1), the block polymer in which X is a group represented by the general formula (3) and X ′ is a group represented by the general formula (3 ′) includes (a213) (when r = 1) And / or (a214) (when r ≧ 2) and (b1) are subjected to a polymerization reaction (A23) and (a213) and / or (a214) and (b2) are subjected to a polymerization reaction (A24) obtained by the above.
(A23) includes (A231) in which (a213) and (b1) are combined, (A232) in which (a214) and (b1) are combined, and a mixture of (A231) and (A232). Similarly, (A24) includes (A241) in which (a213) and (b2) are combined, (A242) in which (a214) and (b2) are combined, and a mixture of (A241) and (A242). included.
(A23) and (A24) can be produced by the same method as (A21) and (A22).

  The amount of (b) constituting the block polymer (A2) is preferably 20 to 90% by weight, more preferably 25 to 80% based on the total weight of (a) and (b) from the viewpoint of antistatic properties. % By weight, particularly preferably 30 to 70% by weight.

  The Mn of the block polymer (A2) is preferably from 2,000 to 60,000, more preferably from 5,000 to 40,000, particularly preferably from 8,000 to 30,000, from the viewpoint of antistatic properties.

In the structure (A2), the average number of repeating units (Nn) of the block of the polyolefin (a) and the block of the polymer (b) having a polyoxyethylene chain is preferably 2 from the viewpoint of antistatic properties. 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 of (A2) and ¹ H-NMR analysis.
For example, in the case of (A21) having a structure in which blocks (a211) and (b1) are alternately and repeatedly bonded, 4.0-4.1 ppm ester bond {-C in ¹ H-NMR analysis Since the signal attributed to the proton of (C═O) —OCH ₂ —} and the 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 was determined. Thus, Nn can be obtained from this ratio and Mn.

  The terminal of (A2) is a carbonyl group, amino group and / or unmodified polyolefin terminal derived from (a) (polyolefin terminal without any modification, ie, alkyl group or alkenyl group), or hydroxyl group derived from (b) And / or any amino group. Among these, a carbonyl group, an amino group, and a hydroxyl group are preferable as a terminal from the viewpoint of reactivity, and a carbonyl group and a hydroxyl group are more preferable.

  Examples of (A3) include polyetheramide imides having a polyoxyethylene chain, as described in JP-B-7-119342 and JP-A-06-172609. Of these, caprolactam (a31), trivalent or tetravalent aromatic polycarboxylic acid (a32) capable of forming at least one imide ring by reacting with an amino group, and polyethylene glycol are preferable from the viewpoint of heat resistance. Alternatively, it is derived from a mixture (a33) of at least 50% by weight of polyethylene glycol and a polyalkylene glycol other than polyethylene glycol, the content of (a33) is 30 to 85% by weight, and the reduced viscosity at 30 ° C. is 1.5 to 4 is a polyether amide imide.

(A32) includes a trivalent or tetravalent aromatic polycarboxylic acid that can react with an amino group to form at least one imide ring, and an acid anhydride thereof.
Examples of the trivalent aromatic polycarboxylic acid include 9 to 18 carbon atoms such as 1,2,4-trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, 2,6,7-naphthalenetricarboxylic acid, 3, 3 ′, 4-diphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tricarboxylic acid, diphenylsulfone-3,3 ′, 4-tricarboxylic acid, diphenylether-3,3 ′, 4-tricarboxylic acid, and the like An acid anhydride is mentioned.
Examples of the tetravalent aromatic polycarboxylic acid include 10 to 20 carbon atoms such as pyromellitic acid, diphenyl-2,2 ′, 3,3′-tetracarboxylic acid, benzophenone-2,2 ′, 3,3′-. Examples thereof include tetracarboxylic acid, diphenylsulfone-2,2 ′, 3,3′-tetracarboxylic acid, diphenyl ether-2,2 ′, 3,3′-tetracarboxylic acid, and acid anhydrides thereof.

  (A33) includes polyethylene glycol or a mixture of at least 50% by weight of polyethylene glycol and a polyalkylene glycol other than polyethylene glycol.

  The Mn of polyethylene glycol is not particularly limited, but is preferably 500 to 5,000, more preferably 800 to 3,000, from the viewpoint of imparting antistatic properties to (A3) and production.

Examples of the polyalkylene (alkylene having 3 to 18 carbon atoms) glycol other than polyethylene glycol include Mn of 500 to 5,000, such as polypropylene glycol, polytetramethylene glycol, and modified polyalkylene glycol.
Examples of the modified polyalkylene glycol include at least two types of addition polymers of AO having 2 to 10 carbon atoms (addition form may be random or block).
Among the AOs, EO, PO, 1,3-propylene oxide, 2-methyl-1,3-propylene oxide, 2,2-dimethyl-1,3-propylene oxide, are preferable from the viewpoint of imparting antistatic properties. 1,5-pentamethylene oxide and 1,6-hexamethylene oxide.

The equivalent ratio in the reaction of (a32) and glycol (a33) is preferably 0.9 / 1 to 1.1 / 1, more preferably 0.95 / 1 to 1.05 / 1 mol from the viewpoint of resin physical properties. is there.

The content of polyamideimide constituting (A3) is preferably 15 to 70% by weight, more preferably 30 to 65% by weight, from the viewpoint of imparting antistatic properties to (A3) and the water resistance of the molded article described later.
Moreover, Mn of the polyamide-imide part in (A3) is preferably 500 to 3,000, more preferably 800 to 2,000 from the viewpoint of the heat resistance of (A3) and the mechanical strength of the molded product described later. .

Although the following method is mentioned as a manufacturing method of (A3), It does not specifically limit. That is, (a31), (a32) and (a33) are ratios in which the equivalent ratio of (a32) and (a33) is preferably 0.9 to 1.1 (more preferably 0.95 to 1.05). From the viewpoint of antistatic properties, (a33) is preferably 30 to 85% by weight, more preferably 35 to 70% by weight with respect to the total weight of (a31), (a32) and (a33). This is a method of polycondensation at 150 to 300 ° C., more preferably 180 to 280 ° C. while keeping the water content of the polymer to be mixed and maintained at 0.1 to 1 wt%.
In the polycondensation, the reaction temperature can be raised stepwise. At this time, some caprolactam remains unreacted, but it is desirable to remove it from the reaction mixture by distilling it off under reduced pressure from the viewpoint of the resin physical properties of the molded product described later. The reaction mixture after removing unreacted caprolactam is further polymerized by polymerizing at 200 to 300 ° C. (more preferably 230 to 280 ° C.) under reduced pressure (0.03 to 3 kPa) as necessary. It can be made into a polymer.

  The reduced viscosity of (A3) is preferably 1.5 to 4, more preferably 1.7 to 3.5 from the viewpoint of moldability of the resin composition.

Examples of the epihalohydrin / AO copolymer (A4) include an epihalohydrin / AO copolymer having a polyoxyethylene chain in JP-B-7-84564.
Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, and epifluorohydrin, and epichlorohydrin is preferable from the viewpoint of reactivity and cost.
As AO, C2-C4, for example, EO, PO, and tetrahydrofuran are mentioned.
(A4) includes an epihalohydrin and a comonomer composed of one or more selected from 1,2-epoxide monomers [especially alkyl (carbon number 2 to 4) glycidyl ether] and AO (especially EO and PO). Copolymers are also included.
The weight ratio of epihalohydrin to AO is usually 5/95 to 95/5, and preferably 10/90 to 60/40 from the viewpoint of antistatic property. The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100% by weight, more preferably 10 to 100% by weight.
Among (A4), a copolymer of epichlorohydrin / EO (weight ratio 50/50) is more preferable from the viewpoint of imparting resin physical properties and antistatic properties.

In the production of (A4), a known catalyst, for example, an organoaluminum compound [triethylaluminum, etc.], or a catalyst obtained by reacting water with an organoaluminum compound to improve the polymerizability is used for bulk polymerization or solution polymerization. Easy to manufacture. The molar ratio of water to the organoaluminum compound (water / organoaluminum compound) is usually 0.1 / 1 to 1/1, preferably 0.3 / 1 to 0.7 / 1, from the viewpoint of polymerizability. .
Mn of (A4) is preferably from 30,000 to 100,000, more preferably from 60,000 to 90,000, from the viewpoints of resin physical properties and moldability.

Examples of the polyether ester (A5) include polyether esters having a polyoxyethylene chain in JP-B-58-19696.
(A5) is a polyester having a segment composed of polyether diol or copolyether diol, and examples thereof are (a12) and (a33) exemplified as the constituents of the polyetheresteramide (A1) or polyetheramideimide (A3). ) And one or more dicarboxylic acids exemplified as a constituent of (A1) or their ester-forming derivatives [lower (carbon number 1 to 4) alkyl ester, acid anhydride, etc.] It can be obtained by a reaction or a transesterification reaction between the diol component and polyethylene terephthalate, polybutylene terephthalate or the like.
The polyether segment content of (A5) is preferably 30 to 70% by weight, more preferably 40 to 60% by weight from the viewpoint of imparting antistatic properties to (A5) and moldability of the resin composition, and (A5) The melting point of [measurement 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. The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100% by weight, more preferably 10 to 100% by weight.

Specifically, the thermoplastic resin (B) in the present invention is a vinyl resin [polyolefin resin (B1) [for example, polypropylene, polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin, etc.] , Polyacrylic resin (B2) [for example, polymethyl methacrylate, etc.], polystyrene resin (B3) [vinyl group-containing aromatic hydrocarbon alone or vinyl group-containing aromatic hydrocarbon, (meth) acrylic acid ester, (meth) Copolymers having at least one selected from the group consisting of acrylonitrile and butadiene as structural units, such as polystyrene, styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methacryl Both methyl acid / butadiene / styrene Polymer (MBS resin), styrene / methyl methacrylate copolymer (MS resin), etc.]]; Polyester resin (B4) [for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate ] Polyamide resin (B5) [eg nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12 etc.]; Polycarbonate resin (B6) [eg polycarbonate , Polycarbonate / ABS resin alloy, etc.] And mixtures of two or more thereof.

  Of these, vinyl resins [(B1) to (B3)] and polyamide resin (B5) are preferable from the viewpoint of ease of dispersion of (A) into (B), and (B1) and more preferable. (B3).

  The vinyl resins [(B1) to (B3)] are obtained by (co) polymerizing the following vinyl monomers by a known polymerization method (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.).

  Examples of vinyl monomers include unsaturated hydrocarbons (aliphatic hydrocarbons, aromatic ring-containing hydrocarbons, alicyclic hydrocarbons, etc.), acrylic monomers, other unsaturated mono- or 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 olefins having 2 to 30 carbon atoms [ethylene, propylene, α-olefins having 4 to 30 carbon atoms (1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1 -Decene, 1-dodecene, etc.)], and C4-30 diene [alkadiene (butadiene, isoprene, etc.), cycloalkadiene (cyclopentadiene, etc.)] and the like.

  Examples of the aromatic ring-containing hydrocarbon include styrene and derivatives thereof having 8 to 30 carbon atoms, such as o-, m- and p-alkyl (1 to 10 carbon atoms) styrene (vinyl toluene, etc.), α-alkyl (carbon number). 1-10) Styrene (α-methylstyrene and the like) and halogenated styrene (chlorostyrene and the like).

As an acrylic monomer, a C3-C30 thing, for example, (meth) acrylic acid and its derivative (s) are mentioned.
Examples of (meth) acrylic acid derivatives include alkyl (C1-20) (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.], mono- and di- Alkyl (1 to 4 carbon atoms) aminoalkyl (2 to 4 carbon atoms) (meth) acrylate [methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.], (meth) acrylonitrile and (meth) acrylamide Can be mentioned.

  Other unsaturated mono- and dicarboxylic acids include C2-C30 (preferably 3-20, more preferably 4-15) unsaturated mono- and dicarboxylic acids such as crotonic acid, maleic acid, and fumaric acid. The derivatives thereof include 5 to 30 carbon atoms, such as mono- and dialkyl (1 to 20 carbon atoms) esters, acid anhydrides (maleic anhydride, etc.) and acid imides (maleic acid imide, etc.). ) And the like.

As carboxylic acid ester of unsaturated alcohol, carboxylic acid (carbon number 2-4, for example, acetic acid, propionic acid) ester (vinyl acetate) of unsaturated alcohol [2-6 carbon atoms, for example, vinyl alcohol, (meth) allyl alcohol]. Etc.).
Examples of the alkyl ether of the unsaturated alcohol include alkyl (carbon number 1 to 20) ethers (methyl vinyl ether, ethyl vinyl ether, etc.) of the unsaturated alcohol.
Examples of the halogen-containing vinyl monomer include 2 to 12 carbon atoms such as vinyl chloride, vinylidene chloride and chloroprene.

Examples of the polyolefin resin (B1) 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 (4 to 12 carbon atoms) copolymer (random and / or block addition) [copolymerization ratio (weight ratio) = 99/1 to 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] and the like.
Among these, polypropylene, polyethylene, propylene-ethylene copolymer, propylene and / or a copolymer of ethylene and one or more α-olefins having 4 to 12 carbon atoms [copolymerization ratio (weight ratio)] = 90/10 to 10/90, random and / or block addition].

  The melt flow rate (hereinafter abbreviated as MFR) of (B1) is preferably 0.5 to 150, more preferably 1 to 100 from the viewpoint of imparting resin physical properties and antistatic properties. The MFR of (B1) 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).

  Examples of the polyacrylic resin (B2) include one or more (co) polymers [poly (meth) acrylic acid] of the above acrylic monomers [alkyl (carbon number 1 to 20) (meth) acrylate, (meth) acrylonitrile, etc.]. Methyl, poly (meth) butyl acrylate, etc.] and copolymers with one or more of these vinyl monomers copolymerizable with one or more of these monomers [acrylic monomer / vinyl monomer copolymerization ratio (weight ratio) is From the viewpoint of the physical properties of the resin, 5/95 to 95/5, more preferably 50/50 to 90/10] [however, those included in (B1) are excluded] are included.

The MFR of (B2) is preferably 0.5 to 150, more preferably 1 to 100 from the viewpoint of resin physical properties. The MFR of (B2) is measured according to JIS K7210 (1994) [230 ° C., load 1.2 kgf for polyacrylic resin (B3)].
The crystallinity of (B2) 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—Human Laboratory for Polymer Experiments 2” (Hatsugoro Nanshino), page 42, published by Kyoritsu Shuppan 1958).

As the polystyrene resin (B3), vinyl group-containing aromatic hydrocarbons alone or vinyl group-containing aromatic hydrocarbons and at least one selected from the group consisting of (meth) acrylic acid esters, (meth) acrylonitrile and butadiene A copolymer as a structural unit is exemplified.
Examples of the vinyl group-containing aromatic hydrocarbon include styrene and derivatives thereof having 8 to 30 carbon atoms such as o-, m- and p-alkyl (1 to 10 carbon atoms) styrene (vinyl toluene, etc.), α-alkyl ( C1-C10) styrene ((alpha) -methylstyrene etc.) and halogenated styrene (chlorostyrene etc.) are mentioned.
Specific examples of (B3) 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)], methyl methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS resin) [Copolymerization ratio (weight ratio) = (48-70) / (0-5) / (2-20) / (25-50)], and the like.

  The MFR of (B3) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR of (B3) is measured according to JIS K6871 (1994) (in the case of polystyrene resin, 230 ° C., load 1.2 kgf).

  Examples of the polyester resin (B4) 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 (B4) 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. Here, [η] is a value (unit: dl / g) measured with an Ubbelohde 1A viscometer at 25 ° C. with respect to a 0.5 wt% orthochlorophenol solution of the polymer, and so on. Note that [η] is indicated only by a numerical value in the following.

  As the polyamide resin (B5), a lactam ring-opening polymer (B51), a dehydration polycondensation product of diamine and dicarboxylic acid (B52), a self-polycondensation product of aminocarboxylic acid (B53), and a polycondensation (condensation) of these. Examples thereof include copolymer nylon having two or more types of monomer units.

Examples of the lactam in (B51) include those exemplified in the above (a11), and examples of (B51) include nylon 4, nylon 5, nylon 6, nylon 8, nylon 12, and the like.
Examples of the diamine and dicarboxylic acid in (B52) include those exemplified in the above (a11). Examples of (B52) include nylon 66 by condensation polymerization of hexanemethylenediamine and adipic acid, Examples thereof include nylon 610 by condensation.
Examples of the aminocarboxylic acid in (B53) include those exemplified in the above (a11). Examples of (B53) include nylon 7 by polycondensation of aminoenanthate, nylon 11 by polycondensation of ω-aminoundecanoic acid, Nylon 12 and the like by polycondensation of 12-aminododecanoic acid.

In the production of (B5), a molecular weight modifier may be used, and examples of the molecular weight modifier include the dicarboxylic acid and / or diamine exemplified in (a11).
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 (B5) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR of (B5) is measured according to JIS K7210 (1994) (in the case of polyamide resin, 230 ° C., load 0.325 kgf).

As the polycarbonate resin (B6), bisphenol (carbon number 12 to 20, for example, bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane, etc.) type polycarbonate, for example, the above bisphenol and phosgene or A condensate with a carbonic acid diester is mentioned.
Examples of the bisphenol include 12 to 20 carbon atoms, such as bisphenol A, bisphenol F, bisphenol S, and 4,4′-dihydroxydiphenyl-2,2-butane. Among these, bisphenol is more preferable from the viewpoint of dispersibility. A.
The MFR of (B6) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR of (B6) is measured according to JIS K7210 (1994) (in the case of polycarbonate resin, 280 ° C., load 2.16 kgf).

  The antistatic resin composition of the present invention is produced by melt-mixing (A) and (B) so that (A) is contained in (B), and the dispersed phase comprising (A) and (B) The number average particle diameter, the number average minor diameter, or the number average thickness of the dispersed phase is 0.01 to 1 μm. The method of melt mixing will be described later. The content of (A) in (B) can be variously changed according to the required performance, but from the viewpoint of providing sufficient antistatic properties and mechanical properties, the total of (A) and (B) is preferred. Based on weight, it is preferably 1 to 50% by weight, more preferably 1.5 to 30%.

The number average particle diameter, number average minor diameter or number average thickness of the dispersed phase in the resin composition of the present invention is essential to be 0.01 to 1 μm, preferably 0.05 to 0.8 μm. When the number average particle diameter, number average minor diameter or number average thickness is less than 0.01 μm, the antistatic property of the molded product is insufficient, and when it exceeds 1 μm, the antistatic property and the resin physical properties are deteriorated depending on the type of molding method. In some cases, the purpose of this application is not achieved. Here, the number average particle diameter is a value for the granular material, the number average minor diameter is a value for the minor axis of the rod-shaped article (corresponds to the number average particle diameter in a cross section perpendicular to the major axis of the rod-like article), and the number. The average thickness refers to the value for the thickness of a layered (thin plate) object.
The number average particle diameter, number average minor diameter or number average thickness of the dispersed phase is measured as follows.
The temperature of the resin composition comprising (A) and (B) is controlled at −100 to −50 ° C. (If no shear is applied as described below, the direction is not particularly determined, but if shear is applied, shear is applied. It is carried out by observing a surface cut out by a general technique using a microtome (in a direction perpendicular to a given direction) with a scanning electron microscope or a section with a transmission electron microscope.
At that time, the dispersed phase may be dyed for easy observation. As the staining agent, phosphotungstic acid, osmium oxide, ruthenium oxide and the like can be used. As a dyeing method, a method of immersing a slice of the resin composition in an aqueous solution of 1 to 5% by weight of these dyeing agents for about 1 hour, and an aqueous solution of the dyeing agent are put to about one third of a sealed container, Examples thereof include a method in which a section of the resin composition is placed on a filter paper on a shelf provided in the upper part and left in a gas phase for about 12 to 24 hours to stain the dispersed phase.
The dispersed phase particle size (number average particle size) can be determined visually or by an image analysis device with respect to the photograph taken. When the particle diameter d _L is determined for N particles within an appropriate range (for example, 10 μm × 10 μm), the number average particle diameter D of the dispersed particles is calculated by D = Σd _L / N.

The antistatic resin molded product of the present invention is formed by (1) molding the above-described resin composition of the present invention and (2) molding a resin composition containing (A) and (B), or (A ) And (B) are kneaded and molded, and consist of a dispersed phase consisting of (A) and a continuous phase consisting of (B), and the dispersed phase has a number average particle diameter, number average minor diameter or number average thickness of 0.00. What is 01-1 micrometer is contained.
In the resin molded body of the present invention, it is preferable that the dispersed phase is in the form of particles, rods and / or layers.
In a non-stretched sheet or a non-stretched film, the dispersed phase exists as fine particles (granular). However, when shear is applied in the uniaxial direction, the dispersed phase is stretched in the stretching direction to form a rod, and when shear is applied in the multiaxial direction. It is stretched in the multiaxial direction to form a layer (a thin plate). Among the manufacturing methods of the molded body, the manufacturing method is preferable from the viewpoint of the antistatic property of the molded body, in which shearing is applied in a uniaxial or multiaxial direction.

When formed with almost no shear, such as an unstretched sheet, unstretched film, and rotationally molded product, the number average particle size of the dispersed phase is 0.01 to 1 μm, preferably 0.05 from the viewpoint of antistatic properties. It is -1 micrometer, Preferably it is 0.06-0.8 micrometer.
When molded by shearing in the uniaxial direction such as injection molded products, extrusion molded products (plates, sheets), uniaxially stretched films, etc., the number average particle diameter of the dispersed phase in the cross section perpendicular to the stretching direction [bar-shaped Corresponds to the number average minor axis of the dispersed phase] is 0.01 to 1 μm, and preferably 0.02 to 0.8 μm from the viewpoint of antistatic properties. When shear is applied in a uniaxial direction, the number average particle diameter of the dispersed phase is preferably 1/3 to 1/50 compared to when shear is not applied.

  When shearing is applied in a multiaxial direction such as a biaxially stretched film or an inflation film, the number average thickness of the layers of the dispersed phase in a cross section perpendicular to the stretched direction is 0.01 to 1 μm, antistatic From the viewpoint of property, it is preferably 0.005 to 0.5 μm, more preferably 0.005 to 0.3 μm. The number average thickness of the dispersed phase layer when shear is applied in the multiaxial direction is preferably 1/10 to 1/100 of the number average particle diameter of the dispersed phase when shear is not applied. .

When shear is applied in the multiaxial direction, the number average thickness of the layers of the dispersed phase is measured as follows.
Under temperature control at −100 to −50 ° C., using a microtome, cut out to be perpendicular to the plane including the sheared direction, and photograph in the same manner as above. The number average thickness is obtained for a photograph taken by visual observation or by an image analysis device. When the thickness t _N is determined for _N layers within an appropriate range (for example, 10 μm × 10 μm), the number average thickness T of the dispersed phase layers is calculated by T = Σt _N / N.

In the case of applying shear, the magnitude of shear is preferably 10 sec ⁻¹ or more from the viewpoint of antistatic properties.

The method for setting the number average particle diameter, number average minor diameter or number average thickness of the dispersed phase in the resin composition of the present invention to 0.01 to 1 μm is not particularly limited, but specifically, the following method is used. It can be carried out.
(i) The SP value (Solubility Parameter) of (A) is made close to the SP value of (B). The difference in SP value between (A) and (B) is preferably 2 or less, and more preferably 1 or less. The SP value can be obtained by the Fedors method. (Polymer Engineering Science, vol. 14, p. 152)
(ii) Close the melt viscosities of (A) and (B) at the molding temperature. The difference in melt viscosity between (A) and (B) is preferably 20 Pa · s or less, and more preferably 10 Pa · s or less.
(iii) A mechanically strong kneading action is imparted. A strong kneading action can be imparted by changing the type of kneading apparatus, the rotational speed, and the like. For example, a twin screw extruder is preferable to a single screw extruder.
(iv) A compatibilizing agent is used so that (A) and (B) are easily compatible. A known compatibilizing agent can be used, but in the present invention, the following modified vinyl copolymer (C) is preferably used.
By combining two or more of the above methods, the number average particle diameter, number average minor diameter, or number average thickness of the dispersed phase in the resin composition can be easily adjusted to 0.01 to 1 μm.

  In the present invention, in order to improve the compatibility between (A) and (B), at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and a polyoxyalkylene group. You may contain the modified vinyl copolymer (C) which has. When (C) is used, the amount of (C) used is preferably 0.1 to 15% by weight based on the total weight of (A) and (B), more preferably from the viewpoint of resin physical properties. 1 to 10% by weight.

  Examples of the vinyl monomer (c1) constituting the above (C) include vinyl monomers having a functional group reactive or compatible with the carboxyl group, hydroxyl group and / or amide group present in (A). For example, a vinyl monomer having at least one functional group selected from a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a polyoxyalkylene group and derivatives thereof described in JP-A-3-258850 is exemplified. be able to.

Examples of vinyl monomers having a carboxyl group (including an anhydride group) include monocarboxylic acids [3 to 15 carbon atoms, such as (meth) acrylic acid, 4-vinyl-benzoic acid], dicarboxylic acids [4 to 4 carbon atoms]. 15, for example, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, citraconic acid], dicarboxylic acid monoester [monoalkyl of the above dicarboxylic acid (C1-C8 or more, such as methyl, ethyl, butyl, Octyl) esters such as maleic acid monoalkyl esters, fumaric acid monoalkyl esters, itaconic acid monoalkyl esters, citraconic acid monoalkyl esters, and the like.
Specific examples of the vinyl monomer having an epoxy group include 5 to 12 carbon atoms such as glycidyl (meth) acrylate and glycidyl itaconate.
Specific examples of the vinyl monomer having an amino group include those having 5 to 16 carbon atoms, such as alkyl ester derivatives of (meth) acrylic acid [aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, (Meth) acrylic acid methylaminoethyl, (meth) acrylic acid ethylaminopropyl, (meth) acrylic acid phenylaminoethyl, (meth) acrylic acid cyclohexylaminoethyl, etc.], vinylamine derivatives [N-vinyldiethylamine and N-acetylvinyl Amine etc.], aminostyrene [p-aminostyrene etc.] and the like.
Examples of vinyl monomers having a polyoxyalkylene group include (meth) acrylates [polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polytetramethylene glycol (meth)] of polyalkylene glycol (Mn 150 to 3,000). Acrylate etc.] and the like.
Among these vinyl monomers, a vinyl monomer having a carboxyl group, an epoxy group, an amino group, a hydroxyl group and / or a polyoxyalkylene group is preferable from the viewpoint of reactivity or affinity with (A), A vinyl monomer having a carboxyl group, an epoxy group and / or an amino group is more preferable, and a vinyl monomer having an epoxy group is particularly preferable.

(C) is obtained by using the vinyl monomer (c1) as an essential constituent unit and, if necessary, copolymerizing with another vinyl monomer. There is no restriction | limiting in particular as another vinyl monomer (c2), A thing other than (c1) is mentioned.
As (c2), aromatic vinyl monomer [carbon number 8 to 20, for example, styrene], vinyl cyanide [carbon number 3 to 6, for example, (meth) acrylonitrile], (meth) acrylic acid ester [carbon number 4 -30, for example methyl methacrylate, maleimide [5-30 carbons, for example N-methylmaleimide], olefins [2-12 carbons, for example ethylene, propylene] and halogen-containing vinyl monomers (2-2 carbons). 12, for example, vinyl chloride).
In addition, (C) includes those obtained by post-modifying the above-mentioned (c1) by addition reaction with heat-degraded polyolefin.

  (C2) can be selected according to the type of the thermoplastic resin (B) in the present invention. For example, when (B) is a polystyrene resin (B3), the compatibility between (A) and (B3) is improved. For the purpose of illustration, it is preferable to copolymerize a vinyl monomer (such as styrene) as a component of (B3), and when (B) is an acrylonitrile / butadiene / styrene copolymer (ABS), It is preferable to copolymerize vinyl cyanide such as (meth) acrylonitrile and / or aromatic vinyl monomers such as styrene.

The method for producing (C) is a commonly used method, and examples thereof include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method in the presence of a known polymerization initiator. A solution polymerization method is preferable from the viewpoint of ease of process.
Mn in (C) is not particularly limited, but is preferably from 1,000 to 200,000, more preferably from 5,000 to 100,000, from the viewpoints of dispersibility in the resin composition and physical properties of the resin.

  The method of adding (C) is not particularly limited, but from the viewpoint of effective dispersion in the resin composition of (C), a method of dispersing in (A) in advance is preferable. Further preferred is a method in which (C) is previously added and dispersed during the production of (A) [in the raw material of (A), during the production of (A) and / or after the production of (A)].

In addition, the antistatic resin composition of the present invention may contain an antistatic agent (D) other than (A) if necessary for the purpose of further improving the antistatic property.
(D) includes surfactant (D1) [anionic surfactant (D11), cationic surfactant (D12), nonionic surfactant (D13), amphoteric surfactant (D14), etc.] and (D1) Examples include salts (D2) other than the salt in them.

Examples of the anionic surfactant (D11) include carboxylate, sulfate ester salt, sulfonate salt and phosphate ester salt.
The cation constituting (D11) is not particularly limited as long as it forms a salt, and usually includes alkali metal, alkaline earth metal, ammonium and the like.

  Examples of the carboxylate include salts of higher fatty acids having 8 to 20 carbon atoms (octanoic acid, lauric acid, stearic acid, oleic acid, eicosanoic acid, etc.).

  Examples of the sulfate ester salts include sulfate ester salts of higher alcohols having 8 to 20 carbon atoms (octyl alcohol, cetyl alcohol, lauryl alcohol, stearyl alcohol, eicosyl alcohol, etc.) and higher alkyl ethers [EO (1 to 50 mol) adducts] sulfate salt, funnel oil, castor oil, sulfated oil (sulfated cow oil, sulfated peanut oil, sulfated macaw whale oil, etc.), sulfated fatty acid ester ( And a salt of a sulfated olefin having 8 to 20 carbon atoms, and the like.

Examples of the sulfonate include alkylbenzene sulfonates having an alkyl group having 8 to 20 carbon atoms (octyl, lauryl, octadecyl, eicosyl, etc.), alkyl sulfonates having 8 to 20 carbon atoms (above), sulfonate having 10 carbon atoms, and the like. To 20 (alkyl) naphthalene (di) sulfonates (1-naphthalenesulfonate, 1,4-naphthalenedisulfonate, 2-methyl-1-naphthalenesulfonate, 2-methyl-1,4-naphthalene Disulfonate, etc.), α-olefin sulfonate having 8 to 20 carbon atoms, Igepon T-type sulfonate, and sulfosuccinate dialkyl ester having an alkyl group having 8 to 20 carbon atoms (sulfosuccinic acid di-2-ethylhexyl ester) Sodium), polyvinyl sulfonate (polystyrene sulfonate, etc.) That.
Examples of phosphoric acid ester salts include mono- and di-ester salts of higher alcohols having 8 to 20 carbon atoms (as described above).

These anionic surfactants (D11) may be one kind or a mixture of two or more kinds.
Of these, higher fatty acid salts, alkylbenzene sulfonates, alkyl sulfonates and mixtures thereof are preferable from the viewpoint of antistatic properties, and stearates, dodecylbenzene sulfonates, lauryl sulfonates are more preferable. And mixtures thereof, particularly preferred are sodium stearate, sodium dodecylbenzene sulfonate, sodium lauryl sulfonate and mixtures thereof.

  Examples of the cationic surfactant (D12) include quaternary ammonium salts and / or phosphonium salts such as compounds represented by the following general formula (6).

In the formula, J is a nitrogen atom or phosphorus atom (preferably a nitrogen atom); R ⁷ and R ¹⁰ are alkyl groups having 1 to 20 carbon atoms or (substituted) phenyl groups having 6 to 20 carbon atoms; R ⁸ and R ⁹ may have an amide bond, an imide bond, an ester bond, an ether bond or a urea bond, and R ⁸ and R ⁹ may be bonded to each other to form a ring. An alkylene group or a (substituted) phenylene group; M ⁻ is an anion; v is an integer of 1 to 10 (preferably 1 to 6).

As the anion constituting (D12), the heat loss start temperature in the air of (D12) [The heat loss start temperature is that of JIS K7120 (1987) 8. Are values] can be used those to be 200 ° C. or higher measured according to the analysis method of the TG curve of Item, conjugate base and rest of superacid [Hammett acidity function (-H ₀₎ of at least 12 Of the anion.
When R ⁷ , R ⁸ , R ⁹ and R ¹⁰ do not have β hydrogen (for example, tetramethylammonium, trimethylbenzylammonium), Hofmann decomposition cannot occur. However, when R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have β hydrogen (for example, trimethylethylammonium, didecyldimethylammonium), a conjugate base of a super strong acid is preferable.

  Examples of anions other than the conjugate base of super strong acid include halogen (fluorine, chlorine, bromine, etc.) ions, p-toluenesulfonic acid ions, undecafluoropentanesulfonic acid ions, and the like.

Super strong acids include those derived from protonic acids and combinations of protonic acids and Lewis acids.
Examples of the protonic acid as the super strong acid include perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, and tridecafluorohexanesulfonic acid.

  Examples of the protonic acid used in combination with Lewis acid include hydrogen halide (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfone. Examples include acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, and tridecafluorohexanesulfonic acid. Of these, hydrogen fluoride is preferred from the viewpoint of antistatic properties.

Examples of Lewis acids include fluorides of group IIIA elements (boron, thallium, etc.) (boron trifluoride, thallium pentafluoride, etc.) and fluorides of group VA elements (phosphorus, antimony, arsenic, etc.) (phosphorus pentafluoride). , Antimony pentafluoride, arsenic pentafluoride, etc.). Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of antistatic properties.
The combination of a protonic acid and a Lewis acid is arbitrary, but as a super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorothalamic acid, hexafluoroantimonic acid, hexafluorothallium sulfone Examples thereof include acids, tetrafluoroboric acid, hexafluorophosphoric acid, and chlorotrifluoroboric acid. These may be used alone or as a mixture of two or more.

  Among the anions constituting (D12), preferred from the viewpoint of antistatic properties is a super strong acid conjugate base (a super strong acid comprising a proton acid and a super strong acid conjugate base comprising a combination of a proton acid and a Lewis acid), More preferred is a super strong acid composed of a proton acid and a conjugate base of a super strong acid composed of a proton acid and boron trifluoride and / or phosphorus pentafluoride among Lewis acids.

Of (D12), a specific example of a quaternary ammonium salt is (1) a salt of an anion other than a conjugate base of a super strong acid, and (2) a super strong acid (a combination of a proton acid, a proton acid and a Lewis acid). Examples are divided into salts with conjugate bases.
(1) A salt of a super strong acid with an anion other than a conjugated base. Examples include salts in combination with anions other than the conjugate bases of strong acids, such as fluoride, chloride, bromide, p-toluenesulfonic acid, undecafluoropentanesulfonic acid, and the like.

(2-1) Salt of super strong acid (protonic acid) with conjugate base Above quaternary ammonium and super strong acid (protonic acid) conjugate base, such as methanesulfonic acid, perchloric acid, fluorosulfonic acid, trifluoromethane Examples thereof include salts obtained by combining sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid and tridecafluorohexanesulfonic acid.

(2-2) Salt of super strong acid (combination of proton acid and Lewis acid) with conjugate base Conjugate base of quaternary ammonium and super strong acid (combination of proton acid and Lewis acid), for example, tetrafluoroboric acid , Salts obtained by combining hexafluorophosphoric acid, hexafluorothalamic acid, hexafluoroantimonic acid, thallium hexafluorosulfonic acid, and the like.

Specific examples of phosphonium salts in (D12): (3) a salt of an anion other than a conjugate base of a super strong acid and (4) a conjugate base of a super strong acid (a combination of a proton acid, a proton acid and a Lewis acid) Examples are divided into salts.
(3) Super strong acid salts with anions other than conjugated bases Conjugation of super strong acids with phosphonium, such as tetramethylphosphonium, tetraethylphosphonium, trimethylbenzylphosphonium, trimethyldodecylphosphonium, didecyldimethylphosphonium, trimethyl-2-ethylhexylphosphonium, etc. Examples include salts in combination with anions other than bases, such as fluoride, chloride, bromide, p-toluenesulfonic acid, undecafluoropentanesulfonic acid, and the like.

(4-1) Salt of super strong acid (protonic acid) with conjugate base The above phosphonium and super strong acid (protonic acid) conjugate base, such as methanesulfonic acid, perchloric acid, fluorosulfonic acid, trifluoromethanesulfonic acid, Examples thereof include salts combined with pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, tridecafluorohexanesulfonic acid and the like.

(4-2) A salt of a super strong acid (a combination of a proton acid and a Lewis acid) with a conjugate base. A conjugate base of the above phosphonium and a super strong acid (a combination of a proton acid and a Lewis acid) such as tetrafluoroboric acid or hexafluoro. Examples thereof include salts obtained by combining phosphoric acid, hexafluorothalamic acid, hexafluoroantimonic acid, and hexafluorothallium sulfonic acid.

Among the above (1) to (4), from the viewpoint of antistatic properties, a super strong acid conjugate base (a super strong acid comprising a proton acid and a super strong acid conjugate base comprising a combination of a proton acid and a Lewis acid) is preferred. It is preferable to have a super strong acid composed of a proton acid and a conjugate base of a super strong acid composed of boron trifluoride and / or phosphorus pentafluoride among proton acids and Lewis acids.
These may be used alone or as a mixture of two or more kinds, or may be a mixture of an anion other than a conjugate base of a super strong acid and a conjugate base of a super strong acid. In the case of a mixture of an anion other than a conjugate base of a super strong acid and a conjugate base of a super strong acid, the ratio (weight ratio) is preferably 95/5 to 5/95, more preferably 70/30 to from the viewpoint of antistatic properties. 30/70.

  Nonionic surfactants (D13) include polyethylene glycol type [EO (1-50 mol) adduct of higher alcohol (same as above), EO (1-30 mol of higher fatty acid (same as above)). ) Adduct, EO (1 to 50 mol) adduct of higher alkylamine (8 to 18 carbon atoms such as 1-octylamine, 1-dodecylamine, etc.), EO of polypropylene glycol (Mn 1,000 to 3,000) (5-150 mol) adducts, etc.]; polyhydric alcohol type [polyethylene oxide (degree of polymerization n = 3 to 300), fatty acid of glycerol (carbon number 4 to 30, for example, caproic acid, octylic acid, lauric acid, stearic acid) , Oleic acid, etc.) ester, pentaerythritol fatty acid (above) ester, sorbitol or sorbitan fatty acid (above) Thing) ester, polyhydric alcohol (C3-C12, for example, glycerol, sorbitan, etc.) alkyl (C1-C30) ether, alkanolamine (C2-C20) fatty acid (above-mentioned) amide, etc. ] Etc. are mentioned.

Examples of the amphoteric surfactant (D14) include amino acid type [higher alkyl (carbon number 8 to 18) aminopropionate, etc.], betaine type [higher alkyl (carbon number 8 to 18) dimethylbetaine, higher alkyl (carbon number 8). -18) dihydroxyethyl betaine etc.] etc. are mentioned.
These may be used alone or in combination of two or more.

Examples of the other salt (D2) include a salt of an alkali metal (lithium, sodium, potassium, etc.) or an alkaline earth metal (magnesium, calcium, etc.) and a protonic acid.
Examples of the protonic acid include those exemplified as those used in combination with the Lewis acid.

Specific examples of (D2) include fluoride (lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, etc.), chloride (lithium chloride, sodium chloride, potassium chloride, magnesium chloride, chloride). Calcium), bromide (lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, etc.), iodide (lithium iodide, sodium iodide, potassium iodide, magnesium iodide, calcium iodide) Etc.), perchlorates (lithium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate, calcium perchlorate, etc.), fluorinated sulfonates (lithium fluorosulfonate, sodium fluorosulfonate) , Potassium fluorosulfonate, magnesium fluorosulfonate, full Calcium sulfonate), methanesulfonate (lithium methanesulfonate, sodium methanesulfonate, potassium methanesulfonate, magnesium methanesulfonate, calcium methanesulfonate, etc.), trifluoromethanesulfonate (lithium trifluoromethanesulfonate, Sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, etc.), pentafluoroethanesulfonate (lithium pentafluoroethanesulfonate, sodium pentafluoroethanesulfonate, pentafluoroethane) Potassium sulfonate, magnesium pentafluoroethanesulfonate, calcium pentafluoroethanesulfonate ), Nonafluorobutanesulfonate (lithium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, potassium nonafluorobutanesulfonate, magnesium nonafluorobutanesulfonate, calcium nonafluorobutanesulfonate, etc.), undecafluoropentane Sulfonates (lithium undecafluoropentanesulfonate, sodium undecafluoropentanesulfonate, potassium undecafluoropentanesulfonate, magnesium undecafluoropentanesulfonate, calcium undecafluoropentanesulfonate), tridecafluorohexane Sulfonates (lithium tridecafluorohexanesulfonate, sodium tridecafluorohexanesulfonate, tridecafluorohexanesulfone Potassium carbonate, magnesium tridecafluorohexanesulfonate, calcium tridecafluorohexanesulfonate, etc.).
Of these, chlorides and perchlorates are preferable from the viewpoint of antistatic properties, and lithium chloride, potassium chloride, lithium perchlorate, potassium perchlorate, and sodium perchlorate are more preferable.

The use amount of the other antistatic agent (D) is preferably 0.001 to 5% by weight, more preferably 0.01 to 5% based on the total weight of (A) and (B) from the viewpoint of the physical properties of the resin. 3% by weight.
The method for adding (D) is not particularly limited, but from the viewpoint of effective dispersion in the resin composition of (D), a method of dispersing in (A) in advance is preferable. More preferred is a method in which (D) is previously added and dispersed during the production of (A) [in the raw material of (A), during the production of (A) and / or after the production of (A)].

To the antistatic resin composition of the present invention, other resin additives (E) can be added as necessary within a range not impairing the effects of the present invention.
The (E) may be added after the resin composition comprising (A) and (B) is mixed, or may be previously contained in (A).
(E) includes colorant (E1), filler (E2), nucleating agent (E3), lubricant (E4), plasticizer (E5), mold release agent (E6), antioxidant (E7), difficulty A flame retardant (E8), a ultraviolet absorber (E9), an antibacterial agent (E10), etc. are mentioned.

Examples of the colorant (E1) include pigments and dyes.
Examples of pigments include inorganic pigments (titanium oxide, aureolin, iron oxide, chromium oxide, cadmium sulfide, etc.); organic pigments (azo lake, monoazo, disazo, chelate azo, benzimidazolone, phthalocyanine, quinacridone, dioxazine Type, isoindolinone type, thioindigo type, perylene type, quinophthalone type, anthraquinone type, etc.).

As dyes, azo, anthraquinone, indigoid, sulfide, triphenylmethane, pyrazolone, stilbene, diphenylmethane, xanthene, alizarin, acridine, quinoneimine, thiazole, methine, nitro , Nitroso, aniline and the like.
The amount of (E1) used is preferably 5% by weight or less, more preferably 0.1 to 3% by weight, based on the total weight of (A) and (B).

Examples of the filler (E2) include fibrous, granular, and plate-like fillers.
Examples of the fibrous filler include glass fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, aramid fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, and the like. Of these, glass fibers and carbon fibers are preferable from the viewpoint of the mechanical strength of the molded product.
As granular fillers, carbon black, silica, quartz powder, glass beads, silicates (calcium silicate, aluminum silicate, kaolin, talc, clay, etc.), metal oxides (iron oxide, titanium oxide, zinc oxide, alumina, etc.) , Metal carbonates (calcium carbonate, magnesium carbonate, etc.), metal sulfates (calcium sulfate, barium sulfate, etc.), silicon carbide, silicon nitride, boron nitride and various metals (magnesium, silicon, aluminum, titanium, copper, silver) , Gold, etc.) and the like.
Examples of the plate-like filler include mica, glass flakes and various metal (aluminum, copper, silver, gold, etc.) foils.
These fillers may be used alone or in combination of two or more.
Of the above fillers, a fibrous filler is preferable from the viewpoint of the mechanical strength of the molded product, and a glass fiber is more preferable.
The amount of the filler used is preferably 150% by weight or less, more preferably 5 to 100% by weight, based on the total weight of (A) and (B).

As the nucleating agent (E3), 1,3,2,4-di-benzylidene-sorbitol, aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium-bis (4-tert-butylphenyl) phosphate, Examples thereof include sodium benzoate.
The amount of (E3) used is preferably 20% by weight or less, more preferably 1 to 10% by weight, based on the total weight of (A) and (B).

Examples of the lubricant (E4) include waxes (such as carnauba wax), higher fatty acids (as described above, such as stearic acid), higher alcohols (as described above, such as stearyl alcohol), and higher fatty acid amides (such as stearic acid amide). Is mentioned.
The amount of (E4) used is preferably 20% by weight or less, more preferably 1 to 10% by weight, based on the total weight of (A) and (B).

Examples of the plasticizer (E5) include aromatic carboxylic acid esters [phthalic acid esters (dioctyl phthalate, dibutyl phthalate, etc.)], aliphatic monocarboxylic acid esters [methyl acetylricinolate, triethylene glycol dibenzoate, etc.], aliphatic Dicarboxylic acid esters [di (2-ethylhexyl) adipate, adipic acid-propylene glycol-based polyester, etc.], aliphatic tricarboxylic acid esters [citric acid esters (triethyl citrate, etc.), etc.], phosphoric acid triesters [triphenyl phosphate, etc. ], Epoxide [epoxidized oil, epoxy fatty acid ester (epoxybutyl stearate, epoxyoctyl stearate, etc.), etc.], petroleum resin and the like.
The amount of (E5) used is preferably 20% by weight or less, more preferably 1 to 10% by weight, based on the total weight of (A) and (B).

As the release agent (E6), lower fatty acid (1 to 4 carbon atoms) alcohol ester (such as butyl stearate) of higher fatty acid (as described above), polyhydric alcohol ester (cured castor) of fatty acid (4 to 30 carbon atoms) Oil), glycol esters of fatty acids (the above) (ethylene glycol monostearate, etc.), liquid paraffin, and the like.
The amount of (E6) used is preferably 10% by weight or less, more preferably 0.1 to 5% by weight, based on the total weight of (A) and (B).

Antioxidants (E7) include phenolic [monocyclic phenol [2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, etc.], polycyclic phenol [1,3,5-trimethyl-2 , 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, tetrakis [Methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane [trade name “Irganox 1010”, manufactured by Ciba Geigy Co., Ltd.], etc.], bisphenol [2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl) 6-t-butylphenol) etc.]; Sulfur [dilauryl-3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate , Dimyristyl-3,3′-thiodipropionate, distearyl-β, β′-thiodibutyrate, dilauryl sulfide, etc.]; Phosphorus [triphenyl phosphite, triisodecyl phosphite, diphenylisodecyl phosphite] , Phenyl diisodecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene- Bis (3-methyl-6-tert-butylphenylditridecyl) phosphite, cyclic neopentane Trilebis (octadecylphosphite), cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite], cyclic neopentanetetraylbis (2,4-di-t-) Butylphenyl) phosphite, diisodecylpentaerythritol diphosphite]; amine-based [octylated diphenylamine, Nn-butyl-p-aminophenol, N, N-diisopropyl-p-phenylenediamine, N, N-bis (1 -Ethyl-3-methylpentyl) -p-phenylenediamine, N, N-diphenyl-p-phenylenediamine, N-phenyl-α-naphthylamine, phenyl-β-naphthylamine, phenothiazine and the like.
The amount of (E7) used is preferably 5% by weight or less, more preferably 0.1 to 3% by weight, based on the total weight of (A) and (B).

Examples of the flame retardant (E8) include organic flame retardants [nitrogen-containing [urea compounds, guanidine compounds, triazine compounds (melamine, guanamine, etc.) and other salts (inorganic acid salts, cyanuric acid salts, isocyanuric acid salts, etc.), etc.] ], Sulfur-containing [sulfuric acid ester, organic sulfonic acid, sulfamic acid, organic sulfamic acid, and their salts, esters, amides, etc.], silicon-containing (polyorganosiloxane, etc.), phosphorus-containing [phosphoric acid ester (triester Etc.], etc.], inorganic flame retardants [antimony trioxide, magnesium hydroxide, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus, ammonium polyphosphate, etc.].
The amount of (E8) used is preferably 20% by weight or less, more preferably 3 to 15% by weight, based on the total weight of (A) and (B).

Examples of the ultraviolet absorber (E9) include benzotriazole-based [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxyphenyl) benzotriazole, etc.], benzophenone-based (2-hydroxy Benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, etc.), salicylic acid type (phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, etc.), acrylate type (2-ethylhexyl-2-cyano-3,3 ′, 1-diphenyl acrylate and the like).
The amount of (E9) used is preferably 5% by weight or less, more preferably 0.1 to 3% by weight, based on the total weight of (A) and (B).

Antibacterial agents (E10) include quaternary ammonium salts [trimethoxysilyl-propyloctadecylammonium chloride, etc.], pyridine compounds [2,3,5,6-cytochloro-4- (methylsulfonyl) -pyridine, etc.], organic Acid (ester) [benzoic acid, sorbic acid, paraoxybenzoic acid ester, etc.], halogenated phenol [2,4,6-tribromophenol sodium salt, 2,4,6-trichlorophenol sodium salt, parachlorometaxylenol, etc. ], Organic iodine [4-chlorophenyl-3-iodopropargyl formal, 5-chloro-2-methyl-4-isothiazolin-3-one, etc.].
The amount of (E10) used is preferably 3% by weight or less, more preferably 0.05 to 1% by weight, based on the total weight of (A) and (B).

The antistatic resin composition of the present invention is produced by melt-mixing (A) and (B), and if necessary, (C), (D), and (E).
As a method of melt-mixing, a normal method, for example, pellets or powdery polymers are mixed with an appropriate mixer such as a Henschel mixer and then melt-kneaded (temperature 160 to 280 ° C.) with an extruder. The method of pelletizing after that is mentioned.
The kneading time is preferably 0.1 to 10 minutes, more preferably 1 to 7 minutes. If it is 0.1 minutes or longer, kneading is sufficient, and if it is 10 minutes or less, resin deterioration is less likely to occur. The kneading temperature is preferably not lower than the melting point of (B) and not higher than 280 ° C. When the temperature is 280 ° C. or lower, resin deterioration hardly occurs. The size of the pelletized pellet is not particularly limited, but is preferably a cylindrical shape having a diameter of 1 to 5 mm and a height of 1 to 5 mm from the viewpoint of ease of handling during molding.
There are no particular limitations on the order of addition of each component during kneading, for example, (1) (A) and (B), and, if necessary, (C) to (E) are blended together and kneaded, and (2) a small amount (B), (A), and (C) to (E), if necessary, after blending / kneading, and then blending / kneading the remaining (B), and (3) (A), (C ), (D) and (E) are blended / kneaded and then (B) is blended / kneaded.
Among these, the method (2) is a method called a master batch method or a master pellet method.

Methods for molding the antistatic resin composition of the present invention include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.) Depending on the purpose, it can be molded by any method incorporating means such as single layer molding, multilayer molding or foam molding.
The molded product obtained from the resin composition of the present invention has excellent mechanical properties and permanent antistatic properties, as well as good paintability and printability.
Examples of the method for coating the molded body 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 paints generally used for painting plastic such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is preferably 10 to 50 μm, more preferably 15 to 40 μm from the viewpoint of physical properties of the coating film.
In addition, examples of the method of printing after applying the coating to the molded body or the molded body include printing methods generally used for plastic printing, such as gravure printing, flexographic printing, screen printing, and offset printing. .
Examples of the printing ink include those usually used for printing plastics.

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

[Production of antistatic agent (A) having polyoxyethylene chain]
Production Example 1
In a 3 L stainless steel autoclave, 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, antioxidant “Irganox 1010” [manufactured by Ciba Specialty Chemicals Co., Ltd., and the same shall apply hereinafter. ] 0.3 parts and 6 parts of water were charged, the interior of the autoclave was purged with nitrogen, and then heated and stirred at 220 ° C. under pressure (0.3 to 0.5 MPa) for 4 hours under sealed conditions. Acid value having carboxyl groups at both ends 96 parts of polyamide 112 were obtained.
Next, 192 parts of an EO adduct of bisphenol A of Mn 2,000 and 0.5 part of zirconyl acetate were added and polymerized at 245 ° C. under a reduced pressure of 0.13 kPa or less for 5 hours to obtain a viscous polymer.
The polymer was taken out in a strand form on a belt and pelletized to obtain polyether ester amide [A-1]. The reduced viscosity of [A-1] is 2.10, and the heat loss starting temperature is the same as described below by TG-DTA measurement according to the method of thermogravimetry of plastics described in [JIS K7120 (1987)]. ] 285 ° C.

Production Example 2
In Production Example 1, the amounts used of ε-caprolactam and terephthalic acid were changed to 93.1 parts and 6.9 parts in place of 83.5 parts and 16.5 parts, respectively. Then, 96 parts of polyamide having an acid value of 23 having carboxyl groups at both ends were obtained.
Next, in place of 192 parts of the EO adduct of bisphenol A with Mn 2,000, 27 parts of the EO adduct of bisphenol A with Mn 1,400 was used, and the same procedure as in Production Example 1 was carried out. 2] was obtained. [A-2] had a reduced viscosity of 2.98 and a heat loss starting temperature of 290 ° C.

Production Example 3
Thermal degradation method [Thermal degradation of ethylene / propylene copolymer (ethylene content 2%) at a density of 0.90 at 23 ° C. and a melt flow rate of 6.0 g / 10 min at 410 ± 0.1 ° C.] The resulting low molecular weight ethylene / propylene random copolymer (Mn 3,500, density 0.89, 7.1 double bonds per 1,000 carbon atoms, average number of double bonds per molecule 1) .8, 95% by weight of polyolefin capable of modification at both ends), 10 parts of maleic anhydride and 30 parts of xylene were melted at 200 ° C. in a nitrogen gas atmosphere (sealed). Time reaction was performed.
Then, excess maleic anhydride and xylene were distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polypropylene (a31). The acid value of (a31) was 27.2, and Mn was 3,700.
66 parts of the obtained (a31) and 34 parts of 12-aminododecanoic acid were melted at 200 ° C. in a nitrogen gas atmosphere, and reacted at 200 ° C. for 3 hours under reduced pressure of 10 mmHg or less to produce acid-modified polypropylene (a32). Got. The acid value of (a32) was 17.7, and Mn was 5,700.
In a stainless steel autoclave, 60 parts of the obtained (a32), 33 parts of polyethylene glycol (b1) (Mn 3,200, volume resistivity 3 × 10 ⁸ Ω · cm), 7 parts of sodium dodecylbenzenesulfonate, antioxidant 0.3 parts of the agent “Irganox 1010” and 0.5 parts of zirconyl acetate were added, and polymerization was performed at 230 ° C. under reduced pressure of 1 mmHg or less for 4 hours to obtain a viscous polymer.
The polymer was taken out as a strand on a belt and pelletized to obtain a block polymer [A-3].
Mn of [A-3] was 28,000. Moreover, from this Mn and ¹ H-NMR analysis, the average number of repetitions Nn of [A-3] was 3.4.

[Production of modified vinyl (co) polymer (C)]
Production Example 4
To a flask equipped with a stirrer, reflux condenser, two dropping funnels, a thermometer, and a nitrogen gas inlet, 235 parts of dimethylformamide (hereinafter abbreviated as DMF) was charged. The dropping funnel 1 was charged with 16 parts of acrylonitrile, 81 parts of styrene, 4 parts of glycidyl methacrylate, and the dropping funnel 2 was charged with 1 part of azobisisobutyronitrile and 6 parts of DMF. The liquid temperature in the flask was agitated to 80 ° C., and the contents were dropped from the dropping funnels 1 and 2 over 2 hours while maintaining the liquid temperature at 80 ° C. in a nitrogen stream. After completion of dropping all the contents, the temperature was maintained at 80 ° C. for 5 hours. The solvent and unreacted monomer were distilled off to obtain a styrene-acrylonitrile-glycidyl methacrylate copolymer [modified vinyl copolymer [C-1]]. The Mn of [C-1] was 39,000, and the glass transition point (hereinafter abbreviated as Tg) was 110 ° C.

Production Example 5
95 parts of a low molecular weight polypropylene obtained by a thermal degradation method having a Mn of 12,000 and a density of 0.89 and 5 parts of maleic anhydride are melted at 180 ° C. in a nitrogen atmosphere, and then dicumyl par A 50% xylene solution in which 1.5 parts of oxide had been dissolved was added dropwise over 15 minutes, followed by reaction for 1 hour. Thereafter, the solvent was distilled off to obtain a modified vinyl polymer [C-2] as a compatibilizing agent. [C-2] had an acid value of 25.7 and Mn of 15,000.

Example 1-8, Comparative Examples 1-6
In accordance with the prescription (parts) shown in Table 1, antistatic agents [A-1] to [A-3] and thermoplastic resins [B-1] to [B-5] are optionally modified vinyl copolymer [C -1], [C-2] and / or salt (other antistatic agent) [D-1], [D-2] and blended for 3 minutes in a Henschel mixer, then in a twin screw extruder with a vent , 230 ° C. (at B-1 used) or 220 ° C. (B-2 when used), 100 rpm, and melt-kneaded under conditions of a residence time of 5 minutes, the resin composition of the present invention (example 1-8) and comparative Resin compositions (Comparative Examples 1 to 6) were obtained.

(Note 1)
B-1: ABS resin [Brand name: Ceviane-V 320, manufactured by Daicel Polymer Ltd.]
B-2: PP resin [Brand name: Chisso Polypro K1008, manufactured by Chisso Corporation]
B-3: PE resin [Brand name: JEREX E780, manufactured by Nippon Polyolefin Co., Ltd.]
B-4: Polyamide resin [trade name: Ube Nylon 1013B, manufactured by Ube Industries, Ltd.]
B-5: Polyacetal resin [Brand name: Duracon M90S, manufactured by Polyplastics Co., Ltd.]
B-6: Transparent ABS resin [trade name: Techno ABS810, manufactured by Technopolymer Co., Ltd.]
D-1: Lithium chloride D-2: Sodium dodecylbenzenesulfonate D-1 and D-2 were added simultaneously with the addition of bisphenol A EO adduct or polyethylene glycol during the production of the antistatic agent (A). .

Performance Test For the resin compositions of the present invention obtained in Examples 1 to 8 and the comparative resin compositions obtained in Comparative Examples 1 to 6, compression molding, extrusion sheet molding, injection molding, and biaxial stretching molding were performed, respectively. .
(1) Compression molding Using a compression molding machine, temperatures 230 ° C. (when using B-1, B-4), 220 ° C. (when using B-2), 200 ° C. (when using B-3, B-5), Test pieces were prepared at a pressure of 20 kg / cm ² and a time of 30 seconds. It used for evaluation of the surface specific resistance value and the surface specific resistance value after washing with water.
(2) Extrusion sheet molding Extruder equipped with a T-shaped die (cylinder temperature 230 ° C (when using B-1, B-4), 220 ° C (when using B-2), 200 ° C (B-3, B-) 5))) and melt-extruded using a cooling roll at 20 ° C. to obtain an extruded sheet having a thickness of 70 μm. It used for evaluation of the surface specific resistance value and the surface specific resistance value after washing with water.
(3) Injection molding Using an injection molding machine, cylinder temperature 230 ° C (when using B-1, B-4), 220 ° C (when using B-2), 200 ° C (when using B-3, B-5) A test piece was prepared at a mold temperature of 50 ° C. It was used for evaluation of impact strength, flexural modulus, compatibility, surface resistivity, surface resistivity after washing with water, and volume resistivity.
(4) Biaxial stretch molding The extruded sheet of (2) was stretched by a batch-type stretching apparatus heated to 155 ° C. (when B-2 was used) and 200 ° C. (when B-4 was used), and the thickness was 14 μm. An axially stretched film was obtained. It used for evaluation of the surface specific resistance value and the surface specific resistance value after washing with water.
These test pieces were subjected to mechanical strength (impact strength, flexural modulus, compatibility) and antistatic properties (surface resistivity, surface resistivity after washing, based on the following test methods (2) to (7), And volume resistivity). The number average particle size of the dispersed phase in the resin composition was evaluated based on the following test method (1). The results are shown in Table 2.

(1) Number average particle diameter of dispersed phase: For the resin composition pellets, the number average particle diameter of the dispersed phase is measured by the above method (method using a transmission electron microscope).
(2) Compatibility: The test piece (100 × 100 × 2 mm) is bent at 23 ± 5 ° C. (If the sample is not broken once, the bending operation is repeated until it breaks), and the fracture surface is observed as follows. Evaluated by criteria.
Evaluation criteria ○: Good ×: Poor [Antistatic agent (A) and thermoplastic resin (B) are poorly compatible with each other and layered]
(3) Impact strength: ASTM D256 (1984) (notched, 3.2 mm thickness) measured by Method A (4) Flexural modulus: ASTM D790 (1984)
Test piece (10 x 4 x 100 mm), distance between fulcrums 60 mm
(5) Surface resistivity: Using a test piece (100 × 100 × 2 mm), a super insulation meter [manufactured by Advantest Corporation, the same shall apply hereinafter. ] In an atmosphere of 23 ° C. and 50% RH [conforms to ASTM D257].
(6) Surface specific resistance value after washing with water: A test piece (100 × 100 × 2 mm) leaning diagonally was washed with running water of 100 ml of ion-exchanged water at 23 ° C. (flow rate 100 ml / min), and a circulating dryer And dried at 80 ° C. for 3 hours. This operation was repeated 10 times, and measured with a superinsulator in an atmosphere of 23 ° C. and a humidity of 50% RH [according to ASTM D257].
(7) Volume resistivity: measured using a test piece (100 × 100 mm) with a superinsulator in an atmosphere of 23 ° C. and humidity of 50% RH [according to ASTM D257].

As is apparent from Table 2, the performance of the molded bodies of Examples 1 to 8 obtained by molding the composition of the present invention is higher than that of the molded bodies of Comparative Examples 1 to 6, in terms of impact strength, flexural modulus, Excellent in all compatibility.
Moreover, even if the composition of the present invention was molded by different molding methods (injection molding method and compression molding method), each exhibited a surface specific resistance value that exhibited good antistatic properties.
In addition, it can be seen that the antistatic property of the molded product formed by molding the composition of the present invention has almost no change in the surface resistivity even when washed with water, and the effect is maintained semipermanently.
In addition, it can be seen that the molded body formed by molding the composition of the present invention is excellent in both surface resistivity and volume resistivity, and exhibits good antistatic properties not only on the surface of the molded product but also inside. .
Furthermore, it turns out that the molded object obtained when an alkali metal salt or surfactant is added to the composition of this invention exhibits the especially outstanding performance.

  Since the molded product obtained by molding the antistatic resin composition of the present invention is excellent in antistatic properties and mechanical strength, housing products for home appliances (TVs, etc.), OA equipment, game equipment, office equipment, etc., IC Various plastic containers such as trays, tape substrates for semiconductor manufacturing processes, films for packaging materials, sheets for flooring, artificial turf, mats, automotive parts, etc. It can be used and is extremely useful.

Claims (8)

Polyether ester amide derived from polyamide and an alkylene oxide adduct of a bisphenol compound, or a block of polyolefin (a), and a polyoxyethylene chain having a volume resistivity of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm A block polymer having a structure in which the block of the polymer (b) having a repeating structure is alternately and alternately bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond and an imide bond. It consists of a dispersed phase composed of an antistatic agent (A) having an oxyethylene chain and a continuous phase composed of one kind of thermoplastic resin (B) selected from the group consisting of vinyl resin, polyamide resin, polyester resin and polycarbonate resin [ However, (A) is a polyetheresteramide and (B) is Except for the case of a propylene resin] , the weight ratio of (A) and (B) is 10/90 to 30/70, and the number average particle diameter, number average minor diameter or number average thickness of the dispersed phase is 0.00. An antistatic resin composition which gives a molded product having a size of 01 to 1 μm. An antistatic resin molded article obtained by molding the resin composition according to claim 1. Polyether ester amide derived from polyamide and an alkylene oxide adduct of a bisphenol compound, or a block of polyolefin (a), and a polyoxyethylene chain having a volume resistivity of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm A block polymer having a structure in which the block of the polymer (b) having a repeating structure is alternately and alternately bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond and an imide bond. It consists of a dispersed phase composed of an antistatic agent (A) having an oxyethylene chain and a continuous phase composed of one kind of thermoplastic resin (B) selected from the group consisting of vinyl resin, polyamide resin, polyester resin and polycarbonate resin [ However, (A) is a polyetheresteramide and (B) is Except in the case of a propylene resin] An antistatic resin composition is molded, or (A) and (B) are kneaded and molded, and a dispersed phase composed of (A) and a continuous phase composed of (B) And (A) and (B) have a weight ratio of 10/90 to 30/70, and the dispersed phase has a number average particle diameter, number average minor diameter or number average thickness of 0.01 to 1 μm. Resin molded body. The molded article according to claim 2 or 3, wherein the molded article is formed by applying shear in a uniaxial direction during molding, and the number average particle diameter of the dispersed phase in a cross section perpendicular to the applied shear direction is 0.01 to 1 µm. . The molded product according to claim 2 or 3, wherein the molded product is formed by applying shear in a multiaxial direction at the time of molding, and the number average thickness of the dispersed phase in a cross section perpendicular to the applied direction is 0.01 to 1 µm. . The molded body according to any one of claims 2 to 5, wherein the dispersed phase has a granular, rod-like and / or layered shape. A molded article obtained by coating and / or printing the molded body according to claim 2. Polyether ester amide derived from polyamide and an alkylene oxide adduct of a bisphenol compound, or a block of polyolefin (a), and a polyoxyethylene chain having a volume resistivity of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm A block polymer having a structure in which the block of the polymer (b) having a repeating structure is alternately and alternately bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond and an imide bond. It consists of a dispersed phase composed of an antistatic agent (A) having an oxyethylene chain and a continuous phase composed of one kind of thermoplastic resin (B) selected from the group consisting of vinyl resin, polyamide resin, polyester resin and polycarbonate resin [ However, (A) is a polyetheresteramide and (B) is Except for the case of a propylene resin] characterized in that shearing is applied in the uniaxial or multiaxial directions during molding of the antistatic resin composition or during kneading and molding of (A) and (B), (A) And a continuous phase consisting of (B), wherein the weight ratio of (A) and (B) is 10/90 to 30/70, and the number average particle diameter, number average minor axis or number average of the dispersed phase The manufacturing method of the antistatic resin molding which thickness is 0.01-1 micrometer.