JP2010077422A - Antistatic agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic agent, which imparts excellent antistatic properties to a thermoplastic resin almost without impairing thermal stability and mechanical characteristics of the thermoplastic resin. <P>SOLUTION: The antistatic agent comprises a block polymer (A) having a structure where the following block polymer (a) and block polymer (b) are repeatedly bonded to each other via at least one type of bond selected from the group consisting of an ester bond, an amide bond, an ether bond, and an imide bond and has an acid number ranging from 0 to 2.0, wherein: the block polymer (a) is a polyamide (a1) or a polyolefin (a2); and the block polymer (b) is a polyether. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antistatic agent. More specifically, the present invention relates to an antistatic agent that hardly impairs the thermal stability and mechanical properties of a thermoplastic resin and imparts excellent antistatic properties to the thermoplastic resin.

  Conventionally, as a method for imparting permanent antistatic property to a thermoplastic resin, a method of adding an antistatic agent having a polyoxyalkylene chain to the thermoplastic resin is known. (For example, see Patent Documents 1 and 2)

Japanese Patent Laid-Open No. 03-255161 JP 2007-224247 A

However, when the amount of addition of the antistatic agent is increased for the purpose of improving the above prior art or antistatic properties, there is a problem that the thermal stability and mechanical properties of the thermoplastic resin are adversely affected.
An object of the present invention is to provide an antistatic agent that hardly impairs the thermal stability and mechanical properties of a thermoplastic resin and imparts excellent antistatic properties to the thermoplastic resin.

As a result of intensive studies to solve the above problems, the present inventor has reached the present invention. That is, in the present invention, the following block (a) and block (b) are alternately and repeatedly formed via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond and an imide bond. Antistatic agent (a): polyamide (a1) or polyolefin (a2) comprising block polymer (A) having a bonded structure and having an acid value of 0 to 2.0
(B): a polyether; an antistatic resin composition comprising the thermoplastic resin (B) containing the antistatic agent; a molded article obtained by molding the composition; Or it is a molded article formed by printing.

The antistatic agent of the present invention and a molded product containing the antistatic agent have the following effects.
(1) The antistatic agent can impart excellent antistatic properties to the thermoplastic resin.
(2) The molded article is excellent in permanent antistatic properties, and is excellent in thermal stability and mechanical properties.

In the block polymer (A) in the present invention, the following block (a) and block (b) are 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 has a structure that is alternately and alternately bonded.
(A): Polyamide (a1) or polyolefin (a2)
(B): Polyether

[(A) Polyamide (a1) or Polyolefin (a2)]
Examples of the polyamide (a1) include a lactam ring-opening polymer (a11), a polycondensation product of aminocarboxylic acid (a12), a polycondensation product of dicarboxylic acid and diamine (a13), and a copolymerized polyamide (a14) thereof. .
Among these amide-forming monomers constituting (a1), the lactam in (a11) includes 6 to 12 carbon atoms (hereinafter abbreviated as C), such as caprolactam, enantolactam, laurolactam, and undecanolactam. It is done.
Examples of the ring-opening polymer of lactam include nylon 4, -5, -6, -8 and -12.
The aminocarboxylic acid in (a12) is C2-12, such as glycine, alanine, valine, leucine, isoleucine, phenylalanine, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω. -Amino capric acid, 11-amino undecanoic acid, 12-amino dodecanoic acid are mentioned.
Examples of the polycondensate of aminocarboxylic acid include nylon 7 by polycondensation of aminoenanthic acid, nylon 11 by polycondensation of ω-aminoundecanoic acid, and nylon 12 by polycondensation of 12-aminododecanoic acid.
Examples of the dicarboxylic acid in (a13) include aliphatic dicarboxylic acids, aromatic (aliphatic) dicarboxylic acids, alicyclic dicarboxylic acids, amide-forming derivatives thereof [acid anhydrides, lower (C1-4) alkyl esters], and the like. Or a mixture of two or more thereof.

Aliphatic dicarboxylic acids include C2-20, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid, itaconic acid. Can be mentioned.
Aromatic (aliphatic) dicarboxylic acids include C8-20, such as ortho-, iso- and terephthalic acid, naphthalene-2,6- and -2,7-dicarboxylic acid, diphenyl-4,4'dicarboxylic acid, diphenoxy Examples include alkali metal (lithium, sodium, potassium, etc.) salts of ethanedicarboxylic acid and 3-sulfoisophthalic acid.
Alicyclic dicarboxylic acids include C5-20, such as cyclopropanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid, and dimer acid.
Among the amide-forming derivatives, examples of the acid anhydride include anhydrides of the above dicarboxylic acids, such as maleic anhydride, itaconic anhydride, and phthalic anhydride. Lower (C1-4) alkyl esters include those of the above dicarboxylic acids. Alkyl esters such as dimethyl adipate, ortho-, iso- and dimethyl terephthalate are mentioned.

Examples of the diamine in (a13) include aliphatic diamines, alicyclic diamines, aromatic (aliphatic) diamines, and mixtures thereof.
Aliphatic diamines include C2-20, such as ethylenediamine, propylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine and 1,20- Eicosanediamine is mentioned.
Alicyclic diamines include C5-20, such as 1,3- and 1,4-cyclohexanediamine, isophoronediamine, 4,4'-diaminocyclohexylmethane and 2,2-bis (4-aminocyclohexyl) propane. It is done.
Aromatic (aliphatic) diamines include C6-20, such as p-phenylenediamine, 2,4- and 2,6-toluylenediamine, 2,2-bis (4,4'-diaminophenyl) propane, 4- Examples include aminobenzylamine, xylylenediamine, bis (aminoethyl) benzene, bis (aminopropyl) benzene and bis (aminobutyl) benzene.

As the polycondensate of dicarboxylic acid and diamine, nylon 66, which is obtained by polycondensation of hexamethylenediamine and adipic acid, sebacic acid, azelaic acid or dodecanedioic acid, respectively,
-610, -69 or -612, and nylon 46 by polycondensation of tetramethylenediamine and adipic acid.
As the copolymerized polyamide (a14), nylon 6/66 [a copolymer of nylon 6 and nylon 66 [copolymerization ratio (weight ratio) = 5/95 to 95/5]] and nylon 6/12 [nylon 6 and nylon 12 copolymer [copolymerization ratio (polymerization ratio) = 5/95 to 95/5]] and the like.

  Among the above (a1), from the viewpoint of antistatic properties and heat resistance, a polycondensate of 12-aminododecanoic acid, a polycondensate of adipic acid and hexamethylenediamine, and a ring-opening polymer of caprolactam are more preferable. Is a ring-opening polymer of caprolactam.

Polyamide (a1) uses a C4-20 dicarboxylic acid and / or one or more of the above diamines as molecular weight regulators, and in the presence thereof the above amide-forming monomer is subjected to ring-opening polymerization or Obtained by condensation.
Among dicarboxylic acids as molecular weight modifiers, aliphatic and aromatic dicarboxylic acids and alkali metal 3-sulfoisophthalic acid (Li, Na, K, etc.) salts from the viewpoint of reactivity with amide-forming monomers and antistatic properties And adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate are more preferable.
Of the diamines as molecular weight modifiers, hexamethylene diamine and decamethylene diamine are preferred from the viewpoint of reactivity with the amide-forming monomer. When dicarboxylic acid is used, it becomes (a1) of both terminal carboxyl groups, and when diamine is used, it becomes (a1) of both terminal amino groups.

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

Number average molecular weight of the polyamide (a1) [hereinafter abbreviated as Mn. The measurement is based on GPC (gel permeation chromatography) method. ] Is preferably 200 to 5,000, more preferably 500 to 3,000 from the viewpoint of heat resistance.
The acid value of (a1) (mgKOH / g, the following is shown only by numerical values) is preferably 20 to 600, more preferably 30 to 250, from the viewpoints of reactivity with the later-described polyether (b) and molecular weight. is there.

  As the polyolefin (a2), carbonyl group-containing groups (carboxyl groups, aldehyde groups, carboxyalkyl groups, amide groups are included, and carboxyl groups are preferable from the viewpoint of easy formation of block polymers) are used at both ends of the polymer. Polyolefin (a21) having a hydroxyl group at both ends of the polymer, polyolefin (a23) having an amino group at both ends of the polymer, and further having a carbonyl group-containing group at one end of the polymer Polyolefin (a24), polyolefin (a25) having a hydroxyl group at one end of the polymer, and polyolefin (a26) having an amino group at one end of the polymer can be used. Of these, polyolefins (a21) and (a24) having a carbonyl group-containing group are preferred because of easy modification.

As (a21) to (a23), those in which a carbonyl group-containing group, a hydroxyl group, and an amino group are introduced at both ends of a polyolefin that can be modified at both ends are used.
As (a24) to (a26), those obtained by introducing a carbonyl group-containing group, a hydroxyl group, and an amino group into one end of a polyolefin that can be modified at least one end are used.
The polyolefin having a terminal-modifiable polyolefin includes a functional group (double bond, amino group, carboxyl group, allyl group, glycidyl group, etc., which can be modified at the end of the polyolefin chain. Is preferred).

Examples of the modifiable polyolefin include a polyolefin (a0) whose main component (preferably a content of 50% by weight or more, more preferably 75% by weight or more, particularly preferably 80 to 100% by weight) Can be used. (A0) 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, and when (a0) is modified, a functional group (carbonyl group) A mixture of a polyolefin having a containing group, a hydroxyl group or an amino group) introduced at both ends, a polyolefin having a functional group introduced at one end, and a polyolefin having no functional group introduced.

  As (a0), a polyolefin [polymerization method] obtained by (co) polymerization (meaning polymerization or copolymerization) of one or a mixture of two or more C2-30 olefins, and a high molecular weight A low molecular weight polyolefin [thermal degradation method] obtained by a thermal degradation method of polyolefin (polyolefin obtained by polymerization of C2-30 olefin) can be used.

C2-30 olefins include ethylene, propylene, C4-30 (preferably 4-12, more preferably 4-10 from the viewpoint of antistatic properties), and C4-30 (antistatic properties). To preferably 4-18, more preferably 4-8).
Examples of the α-olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene, and the diene includes butadiene, isoprene, 1,4- Examples include pentadiene, 1,6-hexadiene, cyclopentadiene, and 1,11-dodecadiene.
Among these, C2-12 olefins (ethylene, propylene, C4-12 α-olefins, butadiene and / or isoprene, etc.) are preferable from the viewpoint of antistatic properties, and C2-10 (ethylene, propylene, C4-10 α-olefin and / or butadiene, etc.), particularly preferred are 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 various methods, 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 a radical catalyst, for example, di-t-butyl peroxide, t-butyl benzoate, decanol peroxide, lauryl peroxide, peroxy-dicarbonate ester, azo compound, etc., and molybdenum oxide are attached to a γ-alumina support. And the like. 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 .
Examples of the polymerization method include a method in which a catalyst and a monomer are added to a hydrocarbon solvent such as xylene and toluene cooled to −50 to −100 ° C. for polymerization.
From the viewpoint of easy introduction of a carbonyl group-containing group which is a modifying group and easy availability, a low molecular weight polyolefin by a thermal degradation method is preferred.

Mn of (a0) 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 double bonds in (a0) is preferably 1 to 40, more preferably 2 to 30, and particularly preferably 4 to 20 per C1,000 from the viewpoint of antistatic properties.
The average number of double bonds per molecule is preferably 1.1 to 5, more preferably 1.3 to 3, particularly preferably 1. from the viewpoints of repetitive structure formation and antistatic properties.
5-2.5, most preferably 1.8-2.2.
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 with an Mn in the range of 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)].

  As the polyolefin (a21) having a carbonyl group-containing group at both ends of the polymer, both ends of the polyolefin that can be modified at both ends are α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid). Means a C1-4 alkyl ester or an anhydride thereof. The same applies hereinafter.) Polyolefin (a211) having a structure modified with (211), a polyolefin having a structure obtained by secondary modification of (a211) with a lactam or aminocarboxylic acid (A212), a polyolefin (a213) having a structure obtained by oxidizing or hydroformylating a polyolefin capable of modifying both ends, a polyolefin (a214) having a structure obtained by secondary modification of (a213) with a lactam or an aminocarboxylic acid, (a213) ) Having a structure secondary modified with hydroxyamine Refin (a215) and a mixture of two or more thereof; polyolefin (a22) having hydroxyl groups at both ends of the polymer includes polyolefins (a221) and (a213) having a structure in which (a211) is modified with hydroxylamine Polyolefin (a222) having a structure modified with hydroxylamine, a mixture of two or more of these, etc .; as polyolefin (a23) having amino groups at both ends of the polymer, (a211) is secondarily modified with diamine Polyolefin (a231), polyolefin (a232) having a structure obtained by secondary modification of (a212) with diamine, polyolefin (a233) having a structure obtained by modifying (a212) with hydroxyamine, and (a213) secondary with diamine Has a modified structure Polyolefin (a234), polyolefin (a235) having a structure obtained by modifying (a213) with hydroxyamine, polyolefin (a236) having a structure obtained by secondary modification of (a214) with diamine, and a mixture of two or more of these It is done.

(A211) is obtained by modifying a polyolefin capable of modifying both ends with an α, β-unsaturated carboxylic acid (anhydride).
Examples of α, β-unsaturated carboxylic acids (anhydrides) include C3-12 carboxylic acids such as monocarboxylic acids [(meth) acrylic acid, etc.], dicarboxylic acids (maleic acid, fumaric acid, itaconic acid, citraconic acid, etc. ), These alkyl (C1-4) esters [methyl (meth) acrylate, butyl (meth) acrylate, diethyl itaconate, etc.], and anhydrides thereof.
Of these, dicarboxylic acids, their alkyl esters and their anhydrides are preferred, and maleic acid (anhydride) and fumaric acid are particularly preferred from the viewpoint of reactivity with polyolefins capable of modifying both ends. Is maleic acid (anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) to be used is preferably 0.5 to 40% based on the weight of the polyolefin that can be modified at both ends, from the viewpoint of the formation of a repeating structure and antistatic properties. %, More preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight.
The modification of the polyolefin capable of modifying both ends with an α, β-unsaturated carboxylic acid (anhydride) can be carried out in various ways, for example, by either the solution method or the melting method to the terminal double bond of the polyolefin capable of modifying both ends. This method can be carried out by thermally adding (ene reaction) an α, β-unsaturated carboxylic acid (anhydride).
As a solution method, an α, β-unsaturated carboxylic acid (anhydride) is added to a polyolefin that can be modified at both ends in the presence of a hydrocarbon solvent such as xylene and toluene, and the reaction is performed in an inert gas atmosphere such as nitrogen. The method of making it react at -230 degreeC etc. are mentioned.
As a melting method, there is a method in which a polyolefin capable of modifying both ends 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. Can be mentioned.
Among these methods, the solution method is preferable from the viewpoint of the uniformity of the reaction.

(A212) can be obtained by secondary modification of (a211) with lactam or aminocarboxylic acid.
As the lactam or aminocarboxylic acid, those described above can be used.
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.
The amount of lactam or aminocarboxylic acid used is preferably from the viewpoint of antistatic properties, and preferably 0.1 to 20 lactams or aminocarboxylic acids per residue obtained by removing the carboxyl group from the α, β-unsaturated carboxylic acid. More preferably, the number is 0.3 to 15, particularly preferably 0.5 to 10.

(A213) can be obtained by introducing a carbonyl group-containing group by oxidizing a polyolefin capable of modifying both ends with oxygen and / or ozone or hydroformylating it by an oxo method.
The introduction of the carbonyl group-containing group by oxidation can be performed by various methods, for example, the method described in US Pat. No. 3,692,877. Introduction of carbonyl group-containing groups by hydroformylation can be accomplished by various methods, for example, 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 mentioned above is mentioned, The usage-amount is also the same.

  (A215) can be obtained by secondary modification of (a213) with hydroxylamine. Hydroxylamine includes C2-10 hydroxylamines such as 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 3- Examples include aminomethyl-3,5,5-trimethylcyclohexanol. Of these, 2-aminoethanol is preferred. The modification with hydroxylamine can be carried out by directly reacting (a211) with hydroxylamine. The reaction temperature is usually 120 to 230 ° C. The amount of hydroxyl group of hydroxylamine used for modification is 0.1 to 2, preferably 0.3 to 1.5, per residue of α, β unsaturated carboxylic acid (anhydride) in (a211). The number is preferably 0.5 to 1.2, and most preferably 1.

  (A23) is obtained by secondarily modifying (a211) with diamine. Examples of the diamine include C2-18, preferably 2-12 diamines such as ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine and the like. Of these, ethylenediamine is preferred. The modification with diamine can be performed by directly reacting (a211) with diamine. The reaction temperature is usually 120 to 230 ° C. The amount of the amino group of the diamine used for modification is 0.1 to 2, preferably 0.3 to 1.5, per residue of α, β unsaturated carboxylic acid (anhydride) in (a211). The number is particularly preferably 0.5 to 1.2, and most preferably 1.

(A232) is obtained by secondary modification of (a212) with hydroxylamine.
Examples of hydroxylamine include those exemplified for (a215), and the amount used is also the same.

(A232) can be obtained by secondary modification of (a213) with diamine.
Examples of the diamine include those exemplified above, and the amount used is also the same.

  The polyolefins (a24) to (a26) whose one end is modified can be obtained by modifying a polyolefin whose one end can be modified by the same method as (a21) to (a23).

Mn of the polyolefin (a2) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2,500 to 2,000 from the viewpoint of heat resistance and reactivity with (b) described later. 10,000.
In addition, (a2) preferably contains a carboxyl group, in which case the acid value of (a2) (mgKOH / g, the following is indicated only by numerical values) is from the viewpoint of reactivity with (b). Preferably, it is 4-280, More preferably, it is 4-100, Most preferably, it is 5-50. In the case of containing a hydroxyl group, the hydroxyl value of (a2) (mgKOH / g, the following is shown only by numerical values) is preferably 4 to 280, more preferably 4 to 100, from the viewpoint of reactivity with (b). Especially preferably, it is 5-50. In the case of containing an amino group, the amine value of (a2) (mgKOH / g, the following is shown only by numerical values) is preferably 4 to 280, more preferably 4 to 280 from the viewpoint of reactivity with (b). 100, particularly preferably 5-50.

[(B) Polyether]
As the polyether (b), polyether diol (b1), polyether diamine (b2) and polyether dicarboxylic acid (b3) represented by the following general formula (1) can be used.

X-A- (OA) _{m-1 -OEO-} (AO) _{m'-1 -AX} (1)

In the formula, E is a residue obtained by removing a hydroxyl group from a diol or a divalent phenol, A is a C2-12 divalent hydrocarbon group which may be substituted with a halogen atom and / or a benzene ring, and m and m ′ are It represents an integer of 1 to 300, preferably 2 to 250, particularly preferably an integer of 10 to 100, and m and m ′ may be the same or different. In addition, m (OA) and m ′ (AO) may be the same or different, and when these are composed of two or more oxyalkylene groups, the bond form is block, random or Any of these combinations may be used. X represents a group selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group.

The upper limit of the volume resistivity of (b) is preferably 10 ¹¹ Ω · cm, more preferably 10 ¹⁰ Ω · cm, particularly preferably 10 ⁹ Ω · cm, from the viewpoint of antistatic properties, and from the viewpoint of the mechanical properties of the molded product. Therefore, the preferable lower limit is 10 ⁵ Ω · cm, more preferably 10 ⁶ Ω · cm, and particularly preferably 10 ⁷ Ω · cm.
Further, 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 (a). Most preferably, it is 1,200 to 8,000.

Examples of the polyether diol (b1) include those obtained by addition reaction of an alkylene oxide (hereinafter abbreviated as AO) (C2-12) to the diol (b01) or the dihydric phenol (b02).

Examples of the diol (b01) include C2-20 dihydric alcohols (aliphatic, alicyclic and araliphatic dihydric alcohols) (b011) and C1-12 tertiary amino group-containing diols.
Aliphatic dihydric alcohols include ethylene glycol, propylene glycol, 1,
Examples include 2-, 2,3-, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 3-methylpentanediol, and 1,12-dodecanediol.
Examples of the alicyclic dihydric alcohol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-cyclooctanediol, and 1,3-cyclopentanediol.
Examples of the araliphatic dihydric alcohol include xylylenediol, 1-phenyl-1,2-ethanediol and 1,4-bis (hydroxyethyl) benzene.

Tertiary amino group-containing diols include aliphatic or alicyclic primary monoamines (C1-12, preferably 2-10, more preferably 2-8) bishydroxyalkyl (alkyl group C1-12, preferably 2-10, more preferably 2-8) and bishydroxyalkyl (alkyl group C1-12) compounds of aromatic (aliphatic) primary monoamines (C6-12).
The bishydroxyalkylated monoamine can be reacted with various methods, for example, by reacting monoamine with C2-4 AO [ethylene oxide (hereinafter abbreviated as EO) propylene oxide (hereinafter abbreviated as PO), butylene oxide, etc.] It can be easily obtained by reacting a monoamine with a C1-12 halogenated hydroxyalkyl (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 C6-18, such as monocyclic dihydric phenol (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenol (bisphenol A, -F, -C, -B, -AD and -S). , Dihydroxybiphenyl, 4,4′-dihydroxydiphenyl-2,2-butane, dihydrokibiphenyl, etc.) and condensed polycyclic divalent phenols (dihydroxynaphthalene, binaphthol, etc.).

  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 with diol (b01) or dihydric phenol (b02), C2-12 AO [EO, PO, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran (THF) And a mixture of two or more thereof], etc., other AO and substituted AO may be used in combination if necessary (in the present invention, these are also collectively referred to as AO).
Examples of other AO and substituted AO include epoxidized C5-12 α-olefin, styrene oxide and epihalohydrin (such as epichlorohydrin and epibromohydrin). The amount of each of other AO and substituted AO used is preferably 30% by weight or less, more preferably 0 to 25% by weight, particularly preferably 0 to 20% by weight based on the weight of the total AO from the viewpoint of antistatic properties. %.

When two or more kinds of AO are used in combination, the coupling form may be random and / or block.
Of AO, from the viewpoint of antistatic properties, EO alone and a combination of EO and AO other than EO (block and / or random addition) are more preferred, and EO alone and a combination of EO and PO are particularly preferred. Is EO alone.
The number of added moles of AO is preferably from the viewpoint of the volume resistivity value of (A), preferably 1 to 300 moles, more preferably 2 to 250 moles, particularly preferably 10 per hydroxyl group of (b01) or (b02). ~ 100 moles. When the added mole number of AO is within this range, the volume resistivity value of (b) tends to be more preferable.

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 the conditions of 100 to 200 ° C. and 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, more preferably 8 to 8% from the viewpoint of the volume resistivity value of (A) based on the weight of (b1). 99.6% by weight, particularly preferably 10 to 98% by weight.
Further, the content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100% by weight, more preferably 10 to 100% from the viewpoint of the volume resistivity value of (A) based on the weight of the polyoxyalkylene chain. % By weight, particularly preferably 50 to 100% by weight, most preferably 60 to 100% by weight. When the content of the oxyethylene unit is within this range, the volume resistivity value of (b) tends to be more preferable.

Examples of the polyether diamine (b2) include those obtained by modifying the hydroxyl group of the polyether diol (b1) to an amino group (primary or secondary amino group).
(B2) can be easily obtained by changing both terminal hydroxyl groups of (b1) to amino groups by various methods.
As a method for changing a hydroxyl group to an amino group, various methods, for example, a method of reducing a terminal cyanoalkyl group obtained by cyanoalkylating the hydroxyl group of (b1) to form an amino group [for example, (b1) and acrylonitrile And a method of hydrogenating the resulting cyanoethylated product], 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. .

Examples of the polyether dicarboxylic acid (b3) include those obtained by modifying the hydroxyl group of the polyether diol (b1) to a carbonyl group (preferably a carboxyl group).
(B3) can be easily obtained by changing both terminal hydroxyl groups of (b1) to carbonyl groups by various methods.
Examples of the method of changing the hydroxyl group to a carbonyl group include various methods, for example, a method of oxidizing the hydroxyl group of (b1) [for example, a method of oxidizing (b1) with chromium oxide] and the like.

[Block polymer (A)]
In the block polymer (A) in the present invention, the block (a) and the block (b) are 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 has a structure that is repeatedly and alternately connected, and includes (A1) composed of blocks (a1) and (b), and (A2) composed of blocks (a2) and (b).
When (A) has a plurality of blocks (a), the blocks (a) may be the same or different.
When (A) has a plurality of blocks (b), the blocks (b) may be the same or different.

  The proportion of (a) and (b) constituting (A) is preferably 10 to 80% based on the total weight of (a) and (b), from the viewpoint of heat resistance and antistatic properties. More preferably, it is 20 to 75%, particularly preferably 30 to 70%; (b) is preferably 20 to 90%, more preferably 25 to 80%, and particularly preferably 30 to 30% from the viewpoint of antistatic properties and heat resistance. 70%.

From the viewpoint of antistatic properties, the average number of repeating units (Nn) of the repeating units (A) and (b) constituting (A) is preferably 2 to 50, more preferably 2.3. 30, particularly preferably 2.7 to 20, most preferably 3 to 10.
Nn can be determined by Mn and 1H-NMR analysis of (A).
For example, when (A) has a structure in which (a1) blocks and (b1) blocks are repeatedly bonded alternately, in ¹ H-NMR analysis, 4.0 to 4.1 ppm of ester bonds {—C The signal attributed to the proton of (C═O) —OCH ₂ —}, and 3.2-3
. Since a signal attributed to 7 ppm polyalkylene glycol protons can be observed, the ratio of these proton integral values can be determined, and Nn can be determined from this ratio and Mn.

  The end of (A) is derived from the carboxyl group, amino group, hydroxyl group and / or unmodified polyolefin end derived from (a) (polyolefin end not modified at all, ie, alkyl group or alkenyl group), or derived from (b) Any one of hydroxyl group, carboxyl group and / or 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 carboxyl group and a hydroxyl group are more preferable.

The acid value of the block polymer (A) is 0 to 2.0, preferably 0 to 1.0, and more preferably 0 to 0.8. When the acid value exceeds 2.0, the thermal stability of the resin composition obtained by adding (A) to the thermoplastic resin (B) described later is deteriorated. Here, the method for measuring the acid value of (A) differs between the above (A1) and (A2) and follows the following method.
<Method for measuring acid value>
(A1): 2 g of sample is dissolved in 200 ml of benzyl alcohol by heating at 150 ° C., and titrated with a 0.1 mol / L potassium hydroxide / methyl alcohol titration solution using a phenolphthalein indicator.
(A2): 2 g of sample is dissolved by heating in 200 ml of xylene and titrated with a 0.1 mol / L potassium hydroxide / methyl alcohol titration solution using a phenolphthalein indicator.

  In the method of setting the acid value of (A) to 0 to 2.0, a method of increasing the reaction rate during the production of the block polymer (A), and an acid value inhibitor (C) described later are added to (A) For example, a method of adding (C) to an antistatic agent comprising the block polymer (A). Among these, the method of adding (C) is preferable from the viewpoint of efficiently reducing the acid value.

Mn of (A) is preferably from 2,000 to 60,000, more preferably from 5,000 to 40,000, and particularly preferably from 8,000 to 30 from the viewpoint of mechanical properties and antistatic properties of the molded article described later. , 000.
Among (A), the molecular size of (A1) can also be expressed by reduced viscosity [η _sp / C, C = 0.5 wt% (m-cresol solution, 25 ° C.)]. The reduced viscosity of is preferably from 0.5 to 4, more preferably from 0.6 to 3, from the viewpoint of the heat resistance of (A1) and the moldability of the resin composition described below.
Among (A), the molecular size of (A2) can also be expressed by melt flow rate (MFR), and the MFR of (A2) is preferably from the viewpoint of moldability and heat resistance of the resin composition described later. It is 0.5-150, More preferably, it is 1-100.

The volume specific resistance value (unit: Ω · cm) of (A) is preferably 1 × 10 ⁵ to 1 × 10 ¹² , more preferably 5 × 10 ⁶ from the viewpoint of the mechanical properties and antistatic properties of the molded product described later. ˜1 × 10 ¹¹ .
Note that the volume resistivity value is obtained by using an injection-molded test piece (100 × 100 × 2 mm) and a superinsulator [eg, model number “DSM-8103 (plate sample electrode SME-8310)”, Toa Denpa Kogyo Co., Ltd. ) Made] and measured under an atmosphere of 23 ° C. and 50% RH (according to ASTM D257).

Among (A), the production method of (A1) includes the following (1), (2) and (3), but is not particularly limited.
Production Method (1) A method in which a polyamide (a1) is formed by the above method, a polyether (b) is added thereto, and polymerized at a high temperature (160 to 270 ° C.) and under reduced pressure (0.03 to 3 kPa).
Production Method (2) The above-mentioned amide-forming monomer and dicarboxylic acid (molecular weight modifier) and a part of (b) are simultaneously charged into a reaction vessel at a high temperature (160 to 270 ° C.) in the presence or absence of water. A method of reacting under pressure (0.1 to 1 MPa) to form a polyamide intermediate and then polymerizing with the remaining (b) under reduced pressure (0.03 to 3 kPa).
Production Method (3) A method of polymerizing (a1) and (b) using a uniaxial or biaxial extruder, usually at 160 to 250 ° C. and a residence time of 0.1 to 20 minutes.
Of the above production methods, production method (1) is preferred from the viewpoint of reaction control.

Among (A), the production method (A2) includes the following (1) and (2), but is not particularly limited.
Production Method (1) A method in which the polyolefin (a2) is formed by the above-described method, and the polyether (b) is added thereto and polymerized at a constant temperature (200 to 250 ° C.) and under reduced pressure (0.03 to 2 kPa).
Production method (2) A method in which (a2) and (b) are polymerized using a uniaxial or biaxial extruder and usually at 160 to 250 ° C. and a residence time of 0.1 to 20 minutes.

In the above polymerization reaction, various catalysts such as antimony catalyst (antimony trioxide, etc.), tin catalyst (monobutyltin oxide, etc.), titanium catalyst (tetrabutyl titanate, etc.), zirconate catalyst (tetrabutyl zirconate, etc.), organic acid Examples thereof include metal salt catalysts [zirconium organic acid salts (such as zirconyl acetate), zinc acetate, etc.], and mixtures of two or more thereof. Among these, a zirconate catalyst and a zirconium organic acid salt are preferable from the viewpoint of productivity, and zirconyl acetate is more preferable.
The usage-amount of a catalyst is 0.001 to 5% normally based on the total weight of (a) and (b), Preferably it is 0.01 to 3%.

[Thermoplastic resin (B)]
As the thermoplastic resin (B), polyacetal resin (B1); vinyl resin [polyolefin resin (B2) [for example, polypropylene, polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin]; Acrylic resin (B3) [for example, polymethyl methacrylate]; Polystyrene resin (B4) [Vinyl group-containing aromatic hydrocarbon alone or vinyl group-containing aromatic hydrocarbon, (meth) acrylic ester, (meth) acrylonitrile, and butadiene A copolymer having at least one selected from the group consisting of, for example, polystyrene, styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / Butadiene / Steel Copolymer (MBS resin), styrene / methyl methacrylate copolymer (MS resin), etc.]; polyester resin (B5) [for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate Polyamide resin (B6) [for example, nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12]; Polycarbonate resin (B7) [for example, polycarbonate, Polycarbonate / ABS alloy resin]; polyphenylene ether resin (B8); biodegradable resin (B9), and a mixture of two or more thereof.

  Among these, (B1), (B2), (B3), (B4), (B5) are preferable from the viewpoint of the mechanical properties of the molded product described later and the dispersibility of (A) in the present invention into (B). ), (B1), (B2), (B3), (B4), and (B1) are particularly preferable from the viewpoint of remarkable effects of the present invention.

Examples of the polyacetal resin (B1) include formaldehyde or trioxane homopolymer (polyoxymethylene homopolymer), and a copolymer of formaldehyde or trioxane and a cyclic ether [the above-mentioned AO (EO, PO, dioxolane, etc.)] (polyoxy). And methylene / polyoxyethylene copolymer [polyoxymethylene / polyoxyethylene (weight ratio) = 90/10 to 99/1 block copolymer, etc.].
The MFR of (B1) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR is measured according to JIS K7210 (1994) (in the case of polyacetal resin, 190 ° C., load 2.16 kgf).

  As the vinyl resins [(B2) to (B4)], those obtained by (co) polymerizing the following vinyl monomers by various polymerization methods (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.) Is mentioned.

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

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

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

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

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

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

Examples of the polyolefin resin (B2) include polypropylene, polyethylene, propylene-ethylene copolymer [copolymerization ratio (weight ratio) = 0.1 / 99.9 to 99.9 / 0.1], propylene and / or ethylene. And other α-olefin (C4-12) copolymers (random and / or block addition) [copolymerization ratio (weight ratio) = 99 / 1-5 / 95], ethylene / vinyl acetate Copolymer (EVA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40], ethylene / ethyl acrylate copolymer (EEA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40 ].
Among these, preferred are polypropylene, polyethylene, propylene-ethylene copolymer, propylene and / or a copolymer of ethylene and one or more of C4-12 α-olefin [copolymerization ratio (weight ratio) = 90. / 10 to 10/90, random and / or block addition].

The MFR of (B2) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of antistatic properties and resin physical properties. The MFR is measured according to JIS K6758 (in the case of polypropylene: 230 ° C., load 2.16 kgf, in the case of polyethylene: 190 ° C., load 2.16 kgf).
The crystallinity of (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).

  Examples of the polyacrylic resin (B3) include one or more (co) polymers [poly (meth) acrylic acid methyl ester, such as the above acrylic monomers [alkyl (C1-20) (meth) acrylate, (meth) acrylonitrile, etc.], Poly (meth) butyl acrylate, etc.] and copolymers with one or more of the above-mentioned vinyl monomers copolymerizable with one or more of these monomers [acrylic monomer / vinyl monomer copolymerization ratio (weight ratio) is a resin physical property In view of the above, preferably 5/95 to 95/5, more preferably 50/50 to 90/10] [however, those included in (B2) are excluded] are included.

The MFR of (B3) is preferably 0.5 to 15 from the viewpoint of antistatic properties and resin properties.
0, more preferably 1-100. The MFR is measured according to JIS K7210 (1994) (230 ° C in the case of polyacrylic resin, load 1.2 kgf).

As the polystyrene resin (B4), vinyl group-containing aromatic hydrocarbon alone or vinyl group-containing aromatic hydrocarbon, and at least one selected from the group consisting of (meth) acrylic acid ester, (meth) acrylonitrile and butadiene A copolymer as a structural unit is exemplified.
Examples of vinyl group-containing aromatic hydrocarbons include C8-30 styrene and its derivatives,
For example, o-, m-, and p-alkyl (C1-10) styrene (vinyl toluene, etc.), α-alkyl (C1-10) styrene (α-methylstyrene, etc.) and halogenated styrene (chlorostyrene, etc.) can be mentioned. .
Specific examples of (B4) include polystyrene, polyvinyltoluene, styrene / acrylonitrile copolymer (AS resin) [copolymerization ratio (weight ratio) = 70/30 to 80/20], styrene / methyl methacrylate copolymer. (MS resin) [copolymerization ratio (weight ratio) = 60/40 to 90/10], styrene / butadiene copolymer [copolymerization ratio (weight ratio) = 60/40 to 95/5], acrylonitrile / butadiene / Styrene copolymer (ABS resin) [copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)], methyl methacrylate / butadiene / styrene copolymer (MBS resin) [Copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)].

  The MFR of (B4) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of antistatic properties and resin physical properties. MFR is measured according to JIS K6871 (1994) (230 ° C. in the case of polystyrene resin, load 1.2 kgf).

  Examples of the polyester resin (B5) 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 (B5) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and antistatic properties. [Η] is measured with a Ubbelohde 1A viscometer at 25 ° C. for a 0.5 wt% orthochlorophenol solution of the polymer.

  The polyamide resin (B6) includes a lactam ring-opening polymer (B61), a dehydration polycondensation product of diamine and dicarboxylic acid (B62), a self-polycondensation product of aminocarboxylic acid (B63), and a poly (condensation) combination thereof. Examples thereof include copolymer nylon having two or more types of monomer units.

Examples of the lactam in (B61) include those exemplified in the above (a11), and examples of (B61) include nylon 4, nylon 5, nylon 6, nylon 8, nylon 12, and the like.
Examples of the diamine and dicarboxylic acid in (B62) include those exemplified in the above (a13). Examples of (B62) include nylon 66 obtained by polycondensation of hexanemethylenediamine and adipic acid, and the weight of hexamethylenediamine and sebacic acid. Examples thereof include nylon 610 by condensation.
Examples of the aminocarboxylic acid in (B63) include those exemplified in the above (a12). Examples of (B63) include nylon 7 by polycondensation of aminoenanthic acid, nylon 11 by polycondensation of ω-aminoundecanoic acid, Nylon 12 by polycondensation of 12-aminododecanoic acid and the like can be mentioned.

In the production of (B6), a molecular weight modifier may be used, and examples of the molecular weight modifier include the dicarboxylic acid and / or diamine exemplified in (a13).
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 (B6) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of antistatic properties and resin physical properties. The MFR is measured according to JIS K7210 (1994) (in the case of polyamide resin, 230 ° C., load 0.325 kgf).

Examples of the polycarbonate resin (B7) include bisphenols (C12-20, such as bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane) and dihydroxybiphenyl polycarbonates such as bisphenol and phosgene. Or the condensate with a carbonic acid diester is mentioned. Of the above bisphenols, bisphenol A is preferred from the viewpoint of dispersibility of (A).
The MFR of (B7) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of antistatic properties and resin physical properties. MFR is measured according to JIS K7210 (1994) (in the case of polycarbonate resin, 280 ° C., load 2.16 kgf).

  Examples of the polyphenylene ether resin (B8) include those represented by the following general formula (2).

In the general formula (2), p is an integer of 50 or more, R ¹ , R ² , R ³ and R ⁴ are H, a halogen atom, a C1-12 hydrocarbon group, a C2-12 substituted hydrocarbon group, and an alkoxy group. Represents a cyano group, a phenoxy group or a nitro group. R ¹ , R ² , R ³ and R ⁴ may be the same or different. Further, (B8) is a single polymer of the general formula (2), or a copolymer comprising two or more structural units or a blend of two or more polymers. Also good.

Specific examples of (B8) include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl). -1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6) -Propyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2,6-phenylene) Dibromo-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether, poly (2,6) Dibenzyl-1,4-phenylene) ether, poly (2,5-dimethyl-1,4-phenylene) ether.
Also, (B1) includes those (B1) grafted with the above styrene and / or its derivative monomer (modified polyphenylene ether).

  The intrinsic viscosity [η] of (B8) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and antistatic properties. [Η] is measured using a Ubbelohde 1A viscometer at 30 ° C. for a 0.5 wt% chloroform solution of the polymer.

  Examples of the biodegradable resin (B9) include polyhydroxybutyrate, polylactic acid, polycaprolactone, polybutylene succinate, adipate-modified polybutylene succinate, carbonate-modified polybutylene succinate, terephthalate-modified polybutylene succinate, polyethylene succinate And polyvinyl alcohol.

Among (B9), as polyhydroxybutyrate, for example, biogreen [manufactured by Mitsubishi Gas Chemical Co., Ltd.]; as polylactic acid, for example, Lacia [manufactured by Mitsui Chemicals, Inc.]; [Daicel Chemical Industries, Ltd.]; Polybutylene succinate, for example, Bionore [Showa High Polymer Co., Ltd.]; Polyethylene succinate, for example, Lunare SE [Nippon Shokubai Co., Ltd.]; Is, for example, Poval [manufactured by Kuraray Co., Ltd.].
Mn of (B9) is preferably 20,000 to 1,000,000, more preferably 50,000 to 500,000, from the viewpoint of resin physical properties and moldability of the molded product.

[Antistatic resin composition]
The antistatic resin composition of the present invention comprises an antistatic agent containing the block polymer (A) contained in a thermoplastic resin (B).
The weight ratio of (A) to (B) is preferably 1/99 to 40/60, more preferably 5/95 to 30/70, from the viewpoints of antistatic properties and mechanical properties of the molded product described later.

  In order to further improve the effect of the present invention, the resin composition of the present invention may contain an acid value inhibitor (C).

The acid value inhibitor (C) is a compound having one or more functional groups in the molecule that react with the carboxyl group in the block polymer (A). Examples of the functional group that reacts with the carboxyl group include a carbodiimide group, an oxazoline group, an epoxy group, a cyclocarbonate group, an aziridine group, and two or more of these. Among (C), a compound having a carbodiimide group and / or an oxazoline group is preferable from the viewpoint of the thermal stability of the antistatic resin composition.
Examples of (C) having a carbodiimide group include polyvalent carbodiimide, and specific examples of commercially available products thereof include, for example, “Carbodilite HMV-8CA”, “Carbodilite LA-1” [trade names, both of which are Nisshinbo ( Co., Ltd.].
Examples of (C) having an oxazoline group include a styrene-2-isopropenyl-2-oxazoline copolymer, and specific examples of commercially available products thereof include, for example, “Epocross RPS-1005” and “Epocross RAS-1005”. [Trade name, both manufactured by Nippon Shokubai Co., Ltd.].

The amount of (C) used based on the weight of (A) is preferably 0.01 to 10%, more preferably 0.1 to 5%, particularly preferably from the viewpoint of the thermal stability and appearance of the molded product described later. The amount of (C) is 0.1 to 1%, and (A) and (C) react to form an antistatic agent having an acid value of 0 to 0.2.
There is no particular limitation on the method of containing (C), and it can be contained in a method of containing it in an antistatic agent containing (A) in advance, a method of containing it in the production of an antistatic resin composition, or both. Although a method etc. are mentioned, The method of making it contain in an antistatic agent beforehand from a viewpoint of the thermal stability of a molded article is preferable.
When (C) is contained in the antistatic agent in advance, it is more preferable to contain (C) during the production of (A), and the timing of incorporating (C) during the production of (A) is not particularly limited. Although it may be any before production, during production, or immediately after production, it is particularly preferred to disperse immediately after production of (A).

  The antistatic resin composition may be selected from the group consisting of an antistatic property improver (D), a compatibilizer (E), and other resin additives (F) as necessary as long as the effects of the present invention are not impaired. At least one selected additive may be included.

The antistatic property improver (D) comprises other than the antistatic agent of the present invention, for example, an alkali metal or alkaline earth metal salt (D1), a surfactant (D2) and an ionic liquid (D3). One type or two or more types selected from the group are included.
(D1) includes alkali metal (lithium, sodium, potassium, etc.) and / or alkaline earth metal (magnesium, calcium, etc.) organic acids (C1-12 mono- and di-carboxylic acids such as formic acid, acetic acid, Propionic acid, oxalic acid, succinic acid; salts of C1-20 sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid; thiocyanic acid, and inorganic acids (hydrohalic acids such as hydrochloric acid, hydrobromic acid, Perchloric acid, sulfuric acid, nitric acid, phosphoric acid) salts can be used.

Specific examples of (D1) include halides [fluorides (lithium fluoride, -sodium, -potassium, -magnesium, -calcium, etc.), chlorides (lithium chloride, -sodium, -potassium, -magnesium, and -calcium). Etc.), bromides (such as lithium bromide, -sodium, -potassium, -magnesium and -calcium) and iodides (such as lithium iodide, -sodium, -potassium, -magnesium and -calcium) etc.], perchlorates (Such as lithium perchlorate, -sodium, -potassium, -magnesium and -calcium), fluorinated sulfonates (such as lithium fluorosulfonate, -sodium, -potassium, -magnesium and -calcium), methanesulfonate ( Lithium methanesulfonate, -sodium, Potassium, -magnesium and -calcium), trifluoromethanesulfonate (lithium trifluoromethanesulfonate, -sodium, -potassium, -magnesium and -calcium), pentafluoroethanesulfonate (lithium pentafluoroethanesulfonate, -Sodium, -potassium, -magnesium and -calcium), nonafluorobutane sulfonate (such as lithium nonafluorobutane sulfonate, -sodium, -potassium, -magnesium and -calcium), undecafluoropentane sulfonate ( Undecafluoropentanesulfonate lithium, -sodium, -potassium, -magnesium and -calcium, etc.), tridecafluorohexanesulfonate (tridecafluorohexanes) Lithium fonate, -sodium, -potassium, -magnesium and -calcium), acetates (lithium acetate, -sodium, -potassium, -magnesium and -calcium etc.), sulfates (sodium sulfate, -potassium, -magnesium and -Calcium etc.), phosphate (sodium phosphate, -potassium, -magnesium, -calcium etc.), thiocyanate (potassium thiocyanate etc.), etc. are mentioned.
Of these, from the viewpoint of antistatic properties, preferred are halides, perchlorates, trifluoromethanesulfonates, acetates, and more preferred are lithium chloride, -potassium and -sodium, lithium perchlorate, -potassium. And -sodium, lithium trifluoromethanesulfonate, -potassium and -sodium, potassium acetate.

The amount of (D1) used is preferably based on the total weight of (A) and (B) from the viewpoint of an antistatic improvement effect and from the viewpoint of giving a resin molded article having a good appearance without being deposited on the resin surface. 0.001 to 3%, more preferably 0.01 to 2.5%, particularly preferably 0.1 to 2%, and most preferably 0.15 to 1%.
Although there is no limitation in particular about the method of containing (D1), it is preferable to make it disperse | distribute beforehand in (A) from a viewpoint of effective dispersion | distribution in a resin composition.
In addition, when (D1) is dispersed in (A), it is particularly preferable that (D1) is contained and dispersed in advance during the production (polymerization) of (A). There is no particular limitation on the timing at which (D1) is contained during the production of (A), and any of the timing before production, during production, and immediately after production may be used.

(D2) includes nonionic, anionic, cationic and amphoteric surfactants, and mixtures thereof.
Nonionic surfactants include, for example, EO addition type nonionic surfactants [for example, higher alcohol (C8-18, the same hereinafter), higher fatty acid (C8-24, same hereinafter) or higher alkylamine (C8-24). ) EO adduct (molecular weight 158 or more and Mn 200,000 or less); higher fatty acid ester of polyalkylene glycol (molecular weight 150 or more and Mn 6,000 or less) which is an EO adduct of glycol; polyhydric alcohol (C2-18) EO adduct of higher fatty acid ester (molecular weight of 250 or more and Mn of 30,000 or less); EO adduct of higher fatty acid amide (molecular weight 200) Above and Mn 30,000 or less); And polyhydric alcohol (as described above) EO adduct of alkyl (C3-60) ether (molecular weight of 120 or more and Mn30,000 or less)], and polyhydric alcohol (C3-60) type nonionic surfactant [For example, fatty acid (C3-60) ester of polyhydric alcohol, alkyl (C3-60) ether of polyhydric alcohol and fatty acid (C3-60) alkanolamide].

  As the anionic surfactant, compounds other than the above (D1) can be used, for example, carboxylates such as higher fatty acid salts; sulfates such as higher alcohol sulfates and higher alkyl ether sulfates; alkylbenzene sulfones. Examples thereof include sulfonates such as acid salts, alkyl sulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphate salts.

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

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

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

The amount of (D2) used is preferably 0.001 to 5%, based on the total weight of (A) and (B), from the viewpoint of antistatic properties and giving a molded article having a good appearance without depositing on the resin surface. More preferably, the content is 0.01 to 3%, and particularly preferably 0.1 to 2.5%.
The method of containing (D2) is also not particularly limited, but it is preferable to disperse in (A) in advance from the viewpoint of effective dispersion in the resin composition. Further, the timing when (D2) is dispersed in (A) is the same as in (D1).

  (D3) is a compound other than the above (D1) and (D2), has a melting point of room temperature or lower, and at least one of cations or anions constituting (D3) is an organic ion, and has an initial conductivity of 1 to 1. A room temperature molten salt of 200 ms / cm (preferably 10 to 200 ms / cm), for example, a room temperature molten salt described in WO95 / 15572. Examples of the cation constituting (D3) include an amidinium cation, a guanidinium cation, and a tertiary ammonium cation.

Examples of the amidinium cation include an imidazolinium cation [1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium. 1,3-dimethyl-2,4-diethylimidazolinium, etc.], imidazolium cation [1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1, 2,3-trimethylimidazolium etc.], tetrahydropyrimidinium cation [1,3-dimethyl-1,4
, 5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetramethyl-1,4,5,6- Tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium, etc.], and dihydropyrimidinium cation [1,3-dimethyl-1,4- or- 1,6-dihydropyrimidinium, 1,2,3-trimethyl-1,4- or -1,6-dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4- or -1 , 6-dihydropyrimidinium and the like].

Examples of the guanidinium cation include a guanidinium cation having an imidazolinium skeleton [2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolinium, 2-dimethylamino-1-methyl-3,4-diethylimidazolinium, etc.], guanidinium cation having an imidazolium skeleton [2-dimethyl Amino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-dimethylamino-1-methyl -3,4-diethylimidazolium etc.], tetrahydropyrimidiniu Guanidinium cation having a skeleton [2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4 , 5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium, etc.], and guanidinium having a dihydropyrimidinium skeleton Cation [2-dimethylamino-1,3,4-trimethyl-1,4- or -1,6-dihydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4- or -1, 6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4- or -1,6-dihydropyrimidinium, etc.] And the like.

  Examples of the tertiary ammonium cation include methyl dilauryl ammonium.

The amidinium cation, guanidinium cation and tertiary ammonium cation may be used alone or in combination of two or more.
Of these, from the viewpoint of initial conductivity, an amidinium cation is preferable, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

In (D3), examples of the organic acid or inorganic acid constituting the anion include the following.
Examples of the organic acid include carboxylic acid, sulfate ester, higher alkyl ether sulfate ester, sulfonic acid and phosphate ester.
Examples of the inorganic acid include super strong acids (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid. It is done.
The organic acid and inorganic acid may be used alone or in combination of two or more.
Among the organic and inorganic acids, Hamett acidity function initial conductivity standpoint preferred from of the anion constituting the (D3) of (D3) (-H ₀₎ is 12 to 100, the superacid conjugate base , Acids that form anions other than the conjugate bases of super strong acids, and mixtures thereof.

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

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

Examples of the protonic acid used in combination with the Lewis acid include hydrogen halide (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid. , Pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof.
Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of (D3).
Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof. Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of (D3).
The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

  Among the above anions, (D3) from the viewpoint of the initial conductivity, a super strong acid conjugate base (a super strong acid consisting of a proton acid and a super strong acid consisting of a combination of a proton acid and a Lewis acid), more preferably It is a conjugate base of a super strong acid consisting of a super strong acid consisting of a proton acid and a proton acid and boron trifluoride and / or phosphorus pentafluoride.

The amount of (D3) used is usually 10% or less based on the total weight of (A) and (B). 5%, more preferably 0.01 to 3%.
The method for adding (D3) is also not particularly limited, but it is preferable to disperse in (A) in advance from the viewpoint of effective dispersion in the resin composition. Further, the timing when (D3) is dispersed in (A) is the same as in (D1).

  The production method of (D3) includes, for example, an amidinium cation and / or guanidinium cation dimethyl carbonate salt obtained by quaternization with dimethyl carbonate, etc. Acid or inorganic acid] for acid exchange, or once the amidinium cation and / or guanidinium cation is hydrolyzed to form a monoamidoamine, then the monoamidoamine is converted to an acid (same as above) The method of neutralizing with is mentioned.

As the compatibilizer (E), a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group is used. Examples thereof include polymers described in JP-A-3-258850. Further, for example, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, a block polymer having a polyolefin portion and an aromatic vinyl polymer portion, and the like can be used.
The amount of (E) used is preferably from 0.1 to 15%, more preferably from 1 to 10%, particularly from the viewpoint of the mechanical properties of the resin molded product, based on the total weight of (A) and (B). Preferably it is 1.5 to 8%.
The method of containing (E) is not particularly limited, but it is preferable to disperse in (A) in advance from the viewpoint of effective dispersion or dissolution in the resin composition.
The timing when (E) is dispersed or dissolved in (A) is the same as in (D) above.

  Other resin additives (F) include nucleating agent (F1), lubricant (F2), pigment (F3), dye (F4), mold release agent (F5), antioxidant (F6), flame retardant ( F7), an ultraviolet absorber (F8), an antibacterial agent (F9), a dispersant (F10), a plasticizer (F11), a conductive substance (F12), and a filler (F13). Can be mentioned.

Examples of the nucleating agent (F1) include organic nucleating agents [for example, 1,3,2,4-di-benzylidene-sorbitol, aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium-bis (4-t -Butylphenyl) phosphate and sodium benzoate] and inorganic nucleating agents (eg graphite, carbon black, magnesium oxide, calcium silicate, magnesium silicate, talc, kaolin, calcium carbonate, magnesium carbonate, sodium carbonate, potassium carbonate, zinc oxide, Alumina, barium sulfate and calcium sulfate).
Lubricants (F2) include waxes (eg carnauba wax, paraffin wax and polyolefin wax), higher fatty acids (C8-24, eg stearic acid, oleic acid, linoleic acid and linolenic acid), higher alcohols (C8-18, eg stearyl). Alcohols, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetostearyl alcohol and behenyl alcohol) and higher fatty acid amides (C8-24, such as stearic acid amide, oleic acid amide, linoleic acid amide and linolenic acid amide).

Examples of the pigment (F3) include inorganic pigments [white pigments (titanium oxide, lithopone, lead white, zinc white, etc.), cobalt compounds (aureolin, cobalt green, etc.), iron compounds (iron oxide, bitumen, etc.), chromium compounds (oxidation). Chromium, lead chromate, etc.) and sulfides (cadmium sulfide, ultramarine, etc.)], organic pigments [azo pigments (azo lakes, monoazos, disazos, chelate azos, etc.), polycyclic pigments (benzoimidazolones) Phthalocyanine, isoindolinone, anthraquinone, etc.).
Examples of the dye (F4) include azo, indigoid, sulfide, alizarin, acridine, thiazole, nitro, and aniline.
As the release agent (F5), lower fatty acid (C1-4) alcohol ester (for example, butyl stearate) of higher fatty acid (above), polyvalent (divalent to tetravalent or higher) of fatty acid (C2-18) ) Alcohol esters (such as hydrogenated castor oil), glycol (C2-8) esters of fatty acids (C2-18) (such as ethylene glycol monostearate) and liquid paraffin.

Antioxidants (F6) include phenolic {eg monocyclic phenols [eg 2,6-di-t-butyl-p-cresol and butylated hydroxyanisole], bisphenols [eg 2,2′-methylenebis (4- Methyl-6-tert-butylphenol), 4,4
'-Butylidenebis (3-methyl) -6-t-butylphenol and 4,4'-thiobis (3-methyl) -6-t-butylphenol] and polycyclic phenols [eg 1,3,5-trimethyl-2,4 , 6-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tetrakis [methylene -3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane]}; sulfur-based [eg dilauryl 3,3'-thiodipropionate, distearyl 3,3'- Thiodipropionate, lauryl stearyl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl β, β′-thiodibutyrate and Dilauryl sulfide]; phosphorous [for example, triphenyl phosphite, triisodecyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, 2,2 -Methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4'-butylidene-bis (3-methyl-6-t-butylphenylditridecyl) phosphite, cyclic neopentanetetraylbis (Octadecyl phosphite), cyclic neopentanetetrayl bis (2,6-di-t-butyl-4-methylphenyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl) ) Phosphite and diisodecyl pentaerythritol And diamines such as octylated diphenylamine, Nn-butyl-p-aminophenol, N, N-diisopropyl-p-phenylenediamine, N, N-bis (1-ethyl-3-methylpentyl); ) -P-phenylenediamine, N, N-diphenyl-p-phenylenediamine, N-phenyl-α-naphthylamine, phenyl-β-naphthylamine and phenothiazine].

  The flame retardant (F7) includes a halogen-containing flame retardant (F71), a nitrogen-containing flame retardant (F72), a sulfur-containing flame retardant (F73), a silicon-containing flame retardant (F74), and a phosphorus-containing flame retardant (F75). 1 type or 2 types or more of flame retardants chosen from these are included.

  Examples of the halogen-containing flame retardant (F71) include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, tetrabromobisphenol A, tetromophthalimide, hexabromobutene, Hexabromocyclododecane, etc .;

Examples of the nitrogen-containing flame retardant (F72) include a salt of urea compound, guanidine compound or triazine compound (melamine, guanamine, etc.) and cyanuric acid or isocyanuric acid;
Examples of the sulfur-containing flame retardant (F73) include sulfuric acid ester, organic sulfonic acid, sulfamic acid, organic sulfamic acid, and salts, esters and amides thereof;
Examples of the silicon-containing flame retardant (F74) include polyorganosiloxane;

  Examples of the phosphorus-containing flame retardant (F75) include phosphorus-containing acids and esters thereof (C2-20) such as phosphoric acid, phosphate, halogen-containing phosphate, phosphorous acid, phosphonate, and ammonium phosphate.

Examples of the phosphate include phosphate [trialkyl (alkyl group is C1-12) phosphate and the like], condensed phosphate [trialkyl (alkyl group is C1-12) poly (n = 2 to 30) phosphate and the like];
Examples of the halogen-containing phosphate include tris alkyl halide (alkyl group is C2-4) phosphate and the like;
Examples of the phosphonate include phosphonate [trialkyl (alkyl group is C1-12) phosphonate, etc.], condensed phosphonate [trialkyl (alkyl group is C1-12) poly (n = 2-30) phosphonate, etc.];
As the ammonium phosphate, those usually marketed for flame retardants can be used. These may be used in combination with a melamine compound (for example, melamine alone), a pentaerythritol compound (for example, pentaerythritol, dipentaerythritol), an amide (for example, nylon 6, nylon 66), or the like as necessary.

The flame retardant may be used in combination with a flame retardant aid [anti-drip agent (for example, polytetrafluoroethylene), metal oxide (for example, zinc oxide), etc.] as necessary.
Of the above flame retardants, (F72) is preferred from the viewpoint of flame retardancy and the absence of environmental pollution such as dioxin generation during incineration.

  Examples of the ultraviolet absorber (F8) include benzotriazoles [for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole], Benzophenone series [eg 2-hydroxy-4-methoxybenzophenone and 2,2′-dihydroxy-4-methoxybenzophenone], salicylate series [eg phenyl salicylate and ethylene glycol monosalicylate] and acrylate series [eg 2-ethylhexyl 2-cyano-3,3′1-diphenyl acrylate].

  Examples of the antibacterial agent (F9) include benzoic acid, paraoxybenzoic acid ester, sorbic acid, halogenated phenol (for example, 2,4,6-tribromophenol sodium salt), organic iodine (for example, 4-chlorophenyl-3-iodopropargyl). Formal), nitrile (eg, 2,4,5,6-tetrachloroisophthalonitrile), thiocyano (eg, methylene bisthianocyanate), N-haloalkylthioimide (eg, N-tetrachloroethyl-thio-tetrahydrophthalimide), copper agent (Eg 8-oxyquinoline copper), benzimidazole (eg 2-4-thiazolylbenzimidazole), benzothiazole (eg 2-thiocyanomethylthiobenzothiazole), trihaloallyl (eg 3-bromo-2,3-diiodo- 2-propenyl Til carbonate), triazoles (eg azaconazole), organic nitrogen sulfur compounds (eg Suraoff 39), quaternary ammonium compounds (eg trimethoxysilyl-propyloctadecylammonium chloride) and pyridine compounds [eg 2,3,5,6- Cytochloro-4- (methylsulfonyl) -pyridine].

  As the dispersant (F10), a dispersant of Mn 1,000 to 100,000, for example, naphthalene sulfonic acid formalin condensate (Mn 1,000 to 10,000), polystyrene sulfonate metal [for example, alkali metals (for example, sodium and potassium) ] Salt (Mn 1,000-100,000), polyacrylic acid metal [for example, alkali metal (same as above)] salt (Mn 2,000-50,000), carboxymethyl cellulose and polyvinyl alcohol.

  Examples of the plasticizer (F11) include mono- and diesters containing polyoxyalkylene chains, polyester polyols, polyether polyols, aromatic carboxylic acid esters [C10-28, such as phthalic acid esters (for example, dioctyl phthalate and dibutyl phthalate, di-2). -Ethyl hexyl phthalate, etc.)], aliphatic monocarboxylic acid esters [C3-30, such as methylacetylricinoleate and triethylene glycol dibenzoate], aliphatic dicarboxylic acid esters [C8 or more and Mn 2,000 or less, such as di (2- Ethylhexyl) adipate and adipic acid-propylene glycol-based polyester (Mn 200 to 2,000)], aliphatic tricarboxylic acid ester [eg citrate ester (eg triethyl citrate)] Phosphoric acid triester [e.g. triphenyl phosphate] and petroleum resins.

  Examples of the conductive substance (F12) are compounds other than the above (D1) and (D3), and examples thereof include carbon nanotubes, carbon black, and white carbon.

  Examples of the filler (F13) include inorganic fillers (eg, calcium carbonate, talc, clay, silicic acid, silicate, asbestos, mica, glass fiber, glass balloon, carbon fiber, metal fiber, ceramic whisker and titanium whisker). And organic fillers [for example, urea, calcium stearate and organic crosslinked fine particles (for example, epoxy-based and urethane-based)].

The total amount of (F) used is usually 45% or less based on the total weight of (A) and (B), preferably 0.001 to 40 from the viewpoint of the effect of each additive and the mechanical properties of the molded product. %, More preferably 0.01 to 35%, particularly preferably 0.05 to 30%.
Of (F), (F9), (F10), (F11) and (F13) are each usually 10% or less, preferably 1 to 5%; (F7) is usually 20% or less, preferably 1 to 10%. (F3), (F4) and (F12) are usually 5% or less, preferably 0.1 to 3%; (F1), (F2), (F5), (F6) and (F8) are usually 3% Hereinafter, it is preferably 0.05 to 1%.

The antistatic resin composition of the present invention is obtained by melt-mixing (A), (B), and (C), (D), (E) and / or (F) as necessary in the present invention. can get. As a method of melt mixing, generally, a method in which pellet or powdery components are mixed with an appropriate mixer such as a Henschel mixer and then melt mixed with an extruder to be pelletized can be applied.
There is no particular limitation on the melt mixing method of each component, for example,
(1) A method in which (A), (B), and if necessary, (C), (D), (E) and / or (F) are melt-mixed together,
(2) (A) and, if necessary, (C) are melt-mixed in advance, (B) is added to this and melt-mixed, and (D), (E) and / or (F) are further melt-mixed if necessary how to,
(3) A part of (A) and (B) is previously melt-mixed to prepare a high-concentration composition (master batch resin composition) of (A), and then the remaining (B) and as necessary (C), (
D), (E) and / or a method of melt-mixing (F),
(4) (A) and, if necessary, (C) are melt-mixed in advance, and a part of (B) is added thereto and melt-mixed to obtain a high-concentration composition of (A) or (A) and (C) (Masterbatch resin composition)
And then the remaining (B) and, if necessary, (D), (E) and / or (F) are melt-mixed.
The concentration of the antistatic agent of the present invention in the masterbatch resin composition in the methods (3) and (4) is preferably 40 to 80% by weight, more preferably 50 to 70% by weight.
Among the above methods, the methods (3) and (4) are methods called a master batch method or a master pellet method, and are preferable methods from the viewpoint of efficient dispersion of the antistatic agent of the present invention in a thermoplastic resin. .

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

The molded article made of the antistatic resin composition of the present invention has excellent mechanical strength and permanent antistatic properties, and also has good paintability and printability, and the molded article is coated and / or printed. Thus, a molded article is obtained.
Examples of methods for coating the molded product include air spray coating, airless spray coating,
Examples include, but are not limited to, electrostatic spray coating, dip coating, roller coating, and brush coating.
Examples of the paint include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint.
The coating film thickness (film thickness after drying) can be appropriately selected according to the purpose, but is usually 10 to 50 μm.

In addition, as a method of printing after coating the molded product or the molded product, any printing method generally used for plastic printing can be used. For example, gravure printing, flexographic printing , Screen printing, pad printing, dry offset printing, offset printing, and the like.
As the printing ink, those usually used for printing plastics, for example, gravure ink, flexographic ink, screen ink, pad ink, dry offset ink and offset ink can be used.

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

Example 1
In a stainless steel autoclave, 21.5 parts of ε-caprolactam, 26.5 parts of isophthalic acid, an antioxidant [trade name “Irganox 1010”, manufactured by Ciba Specialty Chemicals Co., Ltd., tetrakis [methylene-3- (3 ′ 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, and so on. ] 0.2 parts and 3 parts of water were charged, and the inside of the autoclave was replaced with nitrogen, and then heated and stirred for 4 hours under pressure (0.3 to 0.5 MPa) sealed at 220 ° C. Thereafter, water and unreacted substances were distilled off under reduced pressure at 220 ° C. and 1.3 kPa or less to obtain 45 parts of polyamide (a1-1) having an acid value of 370 and Mn300 having carboxyl groups at both ends. Next, 400 parts of EO product of bisphenol A (Mn2,700) (b1-1), 7 parts of lithium chloride and 0.5 part of zinc acetate were added, and polymerization was performed at 245 ° C. under reduced pressure of 0.13 kPa or less for 5 hours. To obtain a viscous polymer.
99 parts of the polymer obtained and an acid value inhibitor [trade name “Epocross RPS-1005”, manufactured by Nippon Shokubai Co., Ltd., and the same shall apply hereinafter. An antistatic agent (X1-1) containing the block polymer (A1-1) was melted and kneaded with 1 part using a twin screw extruder at a temperature of 220 ° C. and a residence time of 10 minutes and pelletized. Obtained. Mn of (A1-1) was 12,000, the reduced viscosity was 1.2, the volume resistivity value was 5 × 10 ⁷ Ω · cm, and the acid value of (X1-1) was 0.7.

Example 2
A stainless steel autoclave was charged with 87 parts of 12-aminododecanoic acid, 13 parts of adipic acid, 0.3 part of antioxidant and 4 parts of water, and the inside of the autoclave was purged with nitrogen and pressurized at 220 ° C. (0.3 to 0). .5 MPa) Stir for 4 hours under sealing. Thereafter, water and unreacted substances were distilled off under reduced pressure at 220 ° C. and 1.3 kPa or less to obtain 96 parts of polyamide (a1-2) having an acid value of 102 and Mn1,100 having carboxyl groups at both ends.
Next, 185 parts of EO / THF random copolymer [EO / THF weight ratio = 40/60] (Mn2,000) (b1-2) and 0.5 part of tetrabutyl titanate were added, and 240 ° C., 0.13 kPa. Polymerization was performed under the following reduced pressure for 8 hours to obtain a viscous polymer.
The obtained polymer was taken out in a strand form on a belt and pelletized to obtain an antistatic agent (X1-2) containing a block polymer (A1-2). Mn of (A1-2) was 20,000, the reduced viscosity was 1.5, the volume resistivity value was 7 × 10 ⁹ Ω · cm, and the acid value of (X1-2) was 1.0.

Example 3
Low molecular weight polypropylene obtained by a thermal degradation method (Mn 2,500, density 0.89, 10.5 double bonds per 1,000 C, average of double bonds per molecule) 1.9 parts, content of polypropylene which can be modified at both ends (95%) and 85 parts of maleic anhydride are charged, melted at 200 ° C. under nitrogen gas atmosphere (sealed), and reacted at 200 ° C. for 20 hours. I let you.
Then, excess maleic anhydride was distilled off under reduced pressure at 200 ° C. for 3 hours to obtain a modified polypropylene (a2-1). (A2-1) had an acid value of 39.8 and Mn of 2,800.
Next, 70 parts of (a2-1) and 40 parts of bis (2-aminoethyl) ether were melted at 200 ° C. with stirring under a nitrogen gas atmosphere and reacted at 200 ° C. for 2 hours. Thereafter, excess bis (2-aminoethyl) ether was distilled off under reduced pressure at 200 ° C. for 2 hours to obtain a modified polypropylene (a2-2) having amino groups at both ends. (A2-2) had an amine value of 36 and Mn 3,000.
Next, in a stainless steel autoclave, (a2-2) 31 parts, polyethylene glycol (hereinafter abbreviated as PEG) (Mn5,000) (b1-3) 50 parts, dodecanedioic acid 4 parts, lithium chloride 1 part, antioxidant 0.3 parts of an agent and 0.5 parts of zinc acetate were charged and polymerized at 230 ° C. under a reduced pressure of 0.13 kPa or less for 8 hours to obtain a viscous polymer.
99 parts of the polymer obtained and an acid value inhibitor [trade name “Carbodilite LA-1”, manufactured by Nisshinbo Co., Ltd., and the same shall apply hereinafter. An antistatic agent (X2-1) containing the block polymer (A2-1) was prepared by melt-kneading 1 part using a twin-screw extruder at a temperature of 200 ° C. and a residence time of 5 minutes and pelletizing. Obtained. Mn of (A2-1) was 32,000, MFR was 18, the volume resistivity value was 5 × 10 ⁷ Ω · cm, and the acid value of (X2-1) was 0.1.

Example 4
A stainless steel autoclave was charged with 36 parts of (a2-1), 90 parts of PEG (Mn5,000) (b1-3), 0.3 part of an antioxidant and 0.5 part of antimony trioxide. Polymerization was performed for 14 hours under a reduced pressure of 13 kPa or less to obtain a viscous polymer.
The obtained polymer was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X2-2) containing a block polymer (A2-2). Mn of (A2-2) was 35,800, MFR was 12, volume specific resistance value was 2 × 10 ⁷ Ω · cm, and acid value of (X2-2) was 1.4.

Example 5
Low molecular weight polypropylene (Mn 3500, density 0.89, 7.1 double bonds per 1,000 C, average number of double bonds per molecule 1) obtained by heat degradation method on stainless steel autoclave 8 parts, content of polypropylene which can be modified at both ends 90%), 5 parts of maleic anhydride and 30 parts of xylene were charged, melted at 200 ° C. in a nitrogen gas atmosphere (sealed), 200 ° C., 20 Reacted for hours.
Then, excess maleic anhydride and xylene were distilled off under reduced pressure at 200 ° C. for 3 hours to obtain a modified polypropylene (a2-3). (A2-3) had an acid value of 27.2 and Mn3,700.
Next, 66 parts of (a2-3) and 34 parts of 12-aminododecanoic acid were melted at 200 ° C. under stirring in a nitrogen gas atmosphere, and reacted at 200 ° C. for 3 hours under reduced pressure of 1.3 kPa or less to modify. Polypropylene (a2-4) was obtained. (A2-4) had an acid value of 17.7 and Mn 6,300.
Next, in a stainless steel autoclave, 78 parts (a2-4), 20 parts α, ω-diaminoPEG (Mn2,000) (b2-1), 2 parts dodecanedioic acid, 1 part lithium chloride, antioxidant 0 .3 parts and 0.5 parts of zinc acetate were charged and polymerized at 230 ° C. under a reduced pressure of 0.13 kPa or less for 20 hours to obtain a viscous polymer.
The obtained polymer was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X2-3) containing a block polymer (A2-3). In (A2-3), Mn was 28,000, MFR was 40, the volume resistivity value was 5 × 10 ¹¹ Ω · cm, and the acid value of (X2-3) was 1.9.

Example 6
In a stainless steel autoclave, 97 parts of (a2-3) and 5 parts of ethanolamine were charged, melted at 180 ° C. in a nitrogen gas atmosphere, and reacted at 180 ° C. for 2 hours. Thereafter, excess ethanolamine was distilled off under reduced pressure at 180 ° C. for 2 hours to obtain a modified polypropylene (a2-5) having a hydroxyl group. The hydroxyl value of (a2-5) was 26.7, the amine value was 0.01, and Mn was 3,700.
Next, (a2-5) 60 parts, dodecanedioic acid 5 parts, bisphenol A EO adduct (Mn3,000) (b1-4) 19 parts, polypropylene glycol (hereinafter abbreviated as PPG) (Mn2,000) ( 16 parts of b1-5), 0.5 part of lithium trifluoromethanesulfonate, 0.3 part of antioxidant and 0.5 part of zinc acetate were added, and the mixture was stirred under reduced pressure at 230 ° C. and 0.13 kPa or less. Polymerization was performed for a time to obtain a viscous polymer.
99 parts of the obtained polymer and 1 part of an acid value inhibitor [trade name “Epocross RAS-1005”] were melt-kneaded at a temperature of 220 ° C. and a residence time of 10 minutes using a twin-screw extruder, and blocked by pelletization. An antistatic agent (X2-4) containing the polymer (A2-4) was obtained. In (A2-4), Mn is 33,000, MFR is 17, and volume resistivity is 8 × 10 ⁸ Ω · c.
m, the acid value of (X2-4) was 1.2.

Comparative Example 1
In Example 1, the same procedure as in Example 1 was used except that 600 parts of PEG (Mn 4,000) (b1-6) was used instead of 400 parts of EO product of bisphenol A (Mn 2,700) (b1-1). A viscous polymer was obtained.
The obtained polymer was taken out as a strand on the belt and pelletized to obtain an antistatic agent (ratio X1-1) containing a block polymer (ratio A1-1). Mn of (ratio A1-1) is 32,000, the reduced viscosity is 1.8, and the volume resistivity is 5 × 10 ⁷ Ω ·
The acid value of cm, (ratio X1-1) was 2.5.

Comparative Example 2
In Example 3, it replaced with 50 parts of PEG (Mn5,000) (b1-3), and it replaced with EO adduct (Mn8,000) (b1-7) 72 parts of bisphenol A, and was carried out similarly to Example 3. A viscous polymer was obtained.
The obtained polymer was taken out in a strand form on a belt and pelletized to obtain an antistatic agent (ratio X2-1) containing a block polymer (ratio A2-1). Mn of (ratio A2-1) is 16,500, MFR is 80, volume resistivity is 3 × 10 ⁷ Ω · cm,
The acid value of (Ratio X2-1) was 3.2.

Examples 7-20, Comparative Examples 3-14
According to the composition shown in Table 1, the antistatic agent and the thermoplastic resin obtained above ((B-1) to (B-4) to be described later) were optionally combined with an acid value inhibitor (C-1, C- 2) together with a Henschel mixer for 3 minutes, and then melt-kneaded in a twin-screw extruder with a vent at 100 rpm, a residence time of 5 minutes, and a molding temperature of 210 ° C. to obtain an antistatic resin composition (Examples 7 to 7). 20 and Comparative Examples 3 to 10) were obtained. In addition, only the thermoplastic resin was made into Comparative Examples 11-14.

<Performance test>
Using only the resin composition or thermoplastic resin obtained above, the injection molding machine [PS
40E5ASE, manufactured by Nissei Plastic Industry Co., Ltd. same as below. ] In the case of (B-1), the cylinder temperature is 210 ° C, the mold temperature is 70 ° C, and in the case of (B-2) Molding at cylinder temperature 250 ° C, mold temperature 80 ° C, (B-3) cylinder temperature 230 ° C, mold temperature 80 ° C, (B-4) at cylinder temperature 220 ° C, mold temperature 50 ° C Articles (test pieces) were prepared, and the performance evaluation of the following items was performed. The results are shown in Table 1.

[1] Thermal stability <Method for measuring heat loss time>
Thermal stability is evaluated by measuring a 20% weight loss time (heat weight loss time) of the initial weight of the antistatic resin composition pellets. As an apparatus used for the measurement, for example, a thermogravimetric measurement apparatus [model number “TG / DTA6200”, manufactured by Seiko Instruments Inc.] can be cited.
The heat loss time was measured by weighing about 10 mg of a sample into an aluminum pan sample container, with a temperature increase rate of 30 ° C. to 10 ° C./min under air flow of 200 ml / min, and in the case of (B-1), 230 ° C. Thermogravimetric (TG) curve when held for 60 minutes after raising the temperature, and in the case of (B-2), (B-3), and (B-4), when heated to 300 ° C. and held for 60 minutes It is obtained by analyzing the TG curve.
[2] Antistatic property (1) Volume specific resistance value Using a test piece (100 × 100 × 2 mm), a superinsulator [model number “DSM-8103” (plate sample electrode SME-8310), Toa Denki Kogyo ( The same shall apply hereinafter. ] In an atmosphere of 23 ° C. and humidity 50% RH (according to ASTM D257).
(2) Volume resistivity value after washing with water The surface of a test piece (100 × 100 × 2 mm) leaning diagonally was washed with 100 ml of ion-exchanged water (23 ° C.) at a flow rate of 100 ml / min, and then circulating drying at 80 ° C. Dry on machine for 3 hours. The test piece obtained by repeating the washing-drying operation 10 times was measured in the same manner as (1). [3] Mechanical properties (1) Impact strength Conforms to ASTM D256 (with notch, 3.2 mm thickness) Method A.
[4] Moldability Using the above injection molding machine, molded products were prepared for the resin compositions obtained above. The molding conditions are as described above. About each molded article, the surface condition was evaluated visually according to the following criteria.

○: Appearance is the same as the molded product of the thermoplastic resin alone, and there is no appearance defect (irregularities, dullness, etc.). There are unevenness and dullness

(note)
(B-1): Polyacetal resin [trade name “Duracon M90S”, polyplastics
Manufactured by MFR = 9]
(B-2): High-density polyethylene (HDPE) resin [trade name “Novatech HY331”,
Nippon Polyethylene Co., Ltd., MFR = 1]
(B-3): Polyacrylic resin [trade name “Acrypet VH”, manufactured by Mitsubishi Rayon Co., Ltd.,
MFR = 2]
(B-4): Polystyrene resin [trade name “PSJ-polystyrene H0103”, PS
Bread, MFR = 3]
(C-1): Acid value inhibitor [trade name “Epocross RPS-1005”, Nippon Shokubai Co., Ltd.].
The reaction product of block polymer (ratio X1-1) and (C-1) (weight ratio =
The acid value of 20/1) was 0.06.
(C-2): Acid value inhibitor [trade name “Carbodilite LA-1”, manufactured by Nisshinbo Co., Ltd.].
The reaction product of the block polymer (ratio X2-1) and (C-2) (weight ratio =
The acid value of 20/1) was 0.04.

  As is clear from Table 1, the resin compositions (Examples 7 to 20) of the present invention were compared with the comparative resin compositions (Comparative Examples 3 to 10) in the case of the thermoplastic resin alone (Comparative Examples 11 to 11). It can be seen that the molded article having excellent antistatic properties is obtained with little deterioration in the thermal stability and moldability of 14).

  Molded articles formed by molding the antistatic resin composition of the present invention have excellent thermal stability, permanent antistatic properties, mechanical properties and moldability, and therefore various molding methods [injection molding, compression molding, calendaring] Molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding and film molding (casting method, tenter method, inflation method, etc.)], which are required to have antistatic properties, home appliances / OA equipment, game machines, and the like It is extremely useful as various molding materials for various housing products for office equipment, various plastic containers such as IC trays, various films for packaging materials, sheets for flooring materials, artificial grass, mats, and automobile parts.

Claims (9)

A block having a structure in which the following block (a) and block (b) are alternately and repeatedly 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 An antistatic agent comprising a polymer (A) and having an acid value of 0 to 2.0.
(A): Polyamide (a1) or polyolefin (a2)
(B): Polyether The antistatic agent according to claim 1, wherein the content of (b) is 20 to 90% based on the total weight of (a) and (b). The antistatic agent according to claim 1 or 2, further comprising an acid value inhibitor (C). The antistatic resin composition which makes the thermoplastic resin (B) contain the antistatic agent in any one of Claims 1-3. A block having a structure in which the following blocks (a) and (b) are alternately and repeatedly 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. Antistatic resin comprising polymer (A) and thermoplastic resin (B) containing acid value inhibitor (C) that reacts with (A) to form an antistatic agent having an acid value of 0 to 2.0 Composition.
(A): Polyamide (a1) or polyolefin (a2)
(B): Polyether The resin composition according to claim 4 or 5, wherein the weight ratio of (A) to (B) is from 1/99 to 40/60. The resin composition according to any one of claims 4 to 6, further comprising at least one additive selected from the group consisting of an antistatic improver, a compatibilizer, a flame retardant, and other additives for resins. object. A molded article formed by molding the resin composition according to claim 4. A molded article obtained by coating and / or printing the molded article according to claim 8.