JP2008133469A - Antistatic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic resin composition being excellent in moldability and giving a molded product that excels in permanent antistatic property, water resistance and mechanical characteristics, whereas a conventional method for providing an antistatic property for a highly insulative thermoplastic resin heretofore has not produced a molded product that satisfies all of a permanent antistatic property, water resistance, mechanical characteristics and the like. <P>SOLUTION: The antistatic agent for use in the resin composition of the present invention comprises a block polymer (A) having a structure in which a block of a polyamide (a1) or a polyolefin (a2) and a block of a specific polyether (b) consisting at least of two kinds of polyethers, a polyether having a solubility parameter of ≥9.1 obtained by excluding the functional groups on both terminals and another polyether having one of <9.1, are repeatedly alternately linked through at least one bond selected from ester bond, amide bond, ether bond and imide bond, and having a water absorption of 0.3-60%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antistatic agent, an antistatic agent composition, and an antistatic resin composition. More specifically, the present invention relates to an antistatic agent, an antistatic agent composition, and an antistatic resin composition that are excellent in moldability and give a molded article having excellent permanent antistatic properties, water resistance and mechanical properties.

  Conventionally, methods for imparting antistatic properties to thermoplastic resins having high insulation properties include (1) a method of kneading a low molecular weight surfactant and (2) a method of kneading a metal filler or conductive carbon black. However, since the molded product formed by molding the resin composition obtained by the method (1) exhibits an effect by bleed-out of the low molecular weight surfactant, the antistatic effect is lost by wiping the surface or the like. In addition, there is a problem that surface roughness occurs with the passage of time, and the molded product by the method (2) is excellent in the durability of the antistatic effect, but a large amount of addition of a metal filler or the like is required. There was a problem that the impact property was lowered. Therefore, as a method for solving these problems, (3) a method of kneading a water-insoluble hydrophilic polymer has been proposed (see, for example, Patent Document 1).

JP 2003-183529 A

  However, in the method (3), since the hydrophilic polymer has high water absorption, there are problems such as surface roughness due to water absorption, surface blistering, and poor dimensional stability in applications that require water resistance. There is. An object of the present invention is to provide an antistatic agent, an antistatic agent composition and an antistatic resin composition which give a molded article having excellent permanent antistatic properties, water resistance and mechanical properties.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, at least 2 of a polyamide (a1) or polyolefin (a2) block and a polyether represented by the following general formula (1) and having a solubility parameter excluding X of 9.1 or more and a polyether of less than 9.1 The block of the polyether (b) composed of the seed has a structure in which the block is repeatedly and alternately bonded through at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond and an imide bond. An antistatic agent comprising a block polymer (A) having an amount of 0.3 to 60%; an antistatic agent composition obtained by adding an additive to the antistatic agent; and adding the antistatic agent to the thermoplastic resin (B). A resin composition to be contained; a molded article formed by molding the antistatic agent, the antistatic agent composition or the resin composition; and the molded article is coated and / or printed. A molded article comprising Te.

X-A- (OA) _{m-1 -OE-} O- (AO) _{m′-1 -AX} (1)

(Wherein E is a residue obtained by removing a hydroxyl group from a diol or divalent phenol, A is a divalent hydrocarbon group having 2 to 12 carbon atoms which may be substituted with a halogen atom and / or a benzene ring, m and m ′ is an integer of 1 to 300, and X is a group selected from the group consisting of a hydroxyl group, an amino group and a carboxyl group.)

The antistatic agent, antistatic agent composition and antistatic resin composition of the present invention have the following effects.
(1) A molded product obtained by molding the antistatic agent, the antistatic agent composition or the resin composition is excellent in permanent antistatic properties and mechanical properties.
(2) The molded article is excellent in water resistance.

In the block polymer (A) in the present invention, the block of polyamide (a1) or polyolefin (a2) and the block of polyether (b) are at least selected from the group consisting of an ester bond, an amide bond, an ether bond and an imide bond. It has a structure in which they are alternately and alternately bonded through one type of bond.
As the polyamide (a1), a polyamide (a11) having carboxyl groups at both ends of the polymer and a polyamide (a12) having amino groups at both ends of the polymer can be used. (A1) includes a lactam ring-opening polymer, a self-polycondensate of aminocarboxylic acid, a polycondensate of diamine and dicarboxylic acid, and a mixture thereof.

Examples of the lactam include 6 to 12 carbon atoms (hereinafter abbreviated as C), such as caprolactam, enantolactam, laurolactam, and undecanolactam.
Examples of the ring-opening polymer of lactam include nylon 4, -5, -6, -8 and -12.

Examples of aminocarboxylic acids include C2-12, such as glycine, alanine, valine, leucine, isoleucine, phenylalanine, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocaprin. Examples include acids, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Examples of the self-polycondensate of aminocarboxylic acid include nylon 7 by polycondensation of aminoenanthate, nylon 11 by polycondensation of ω-aminoundecanoic acid, and nylon 12 by polycondensation of 12-aminododecanoic acid.

Diamines include aliphatic, alicyclic, aromatic (aliphatic) diamines and mixtures thereof.
Aliphatic diamines include C2-20, such as ethylene diamine, propylene diamine, hexamethylene diamine, 1,12-dodecane diamine, 1,18-octadecane diamine and 1,20-eicosane diamine.
Alicyclic diamines include C5-20, such as 1,3- and 1,4-cyclohexanediamine, isophorone diamine, 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.

  Examples of the dicarboxylic acid include aliphatic dicarboxylic acids, aromatic ring-containing dicarboxylic acids, alicyclic dicarboxylic acids, amide-forming derivatives thereof [for example, acid anhydrides and lower (C1-4) alkyl esters], and two or more kinds thereof. A mixture is mentioned.

Examples of the aliphatic dicarboxylic acid include C2-40 (preferably 4-20, more preferably 6-12), such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid. , Dodecanedioic acid, maleic acid, fumaric acid and itaconic acid.
Examples of aromatic ring-containing dicarboxylic acids include C8-20 (preferably 8-16, more preferably 8-14), such as ortho-, iso- and terephthalic acid, naphthalene-2,6- and -2,7-dicarboxylic acid. , Diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, tolylene dicarboxylic acid, xylylene dicarboxylic acid and 5-sulfoisophthalic acid alkali metal (eg lithium, sodium and potassium) salts.
Examples of the alicyclic dicarboxylic acid include C5-20 (preferably 6-18, more preferably 8-14), such as cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, dicyclohexyl-4,4 ′. -Dicarboxylic acid and camphoric acid are mentioned.
Among the amide-forming derivatives, as the acid anhydride, anhydrides of the above dicarboxylic acids, such as maleic anhydride, itaconic anhydride and phthalic anhydride; as lower (C1-4) alkyl esters, lower alkyl esters of the above dicarboxylic acids, Examples include dimethyl adipate and ortho-, iso- and dimethyl terephthalate.

Polycondensates of diamines and dicarboxylic acids include nylon 66, -610, -69 or -612, respectively, and tetramethylene diamine by polycondensation of hexamethylene diamine and adipic acid, sebacic acid, azelaic acid or dodecanedioic acid, respectively. And nylon 46 by polycondensation of adipic acid.
As the copolymer nylon, nylon 6/66 [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 copolymers [copolymerization ratio (polymerization ratio) = 5/95 to 95/5]] and the like.

  Of the above (a1), from the standpoint of antistatic properties, a self-polycondensate of 12-aminododecanoic acid, a polycondensate of adipic acid and hexamethylenediamine, and more preferably a ring-opening polymer of caprolactam It is.

(A1) can be obtained by using, for example, the above-mentioned dicarboxylic acid having 4 to 20 carbon atoms and / or the above-mentioned diamine as a molecular weight regulator, and in the presence thereof, the polyamide-forming monomer is subjected to ring-opening polymerization, self-polycondensation or polycondensation. It is done. Of the dicarboxylic acids as molecular weight modifiers, aliphatic and aromatic dicarboxylic acids are preferred from the viewpoint of reactivity with diamines, and more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and 3-sulfoisophthalic acid. Sodium. Of the diamines as molecular weight regulators, hexamethylenediamine and decamethylenediamine are preferred from the viewpoint of reactivity with dicarboxylic acid. If dicarboxylic acid is used, it will become (a11) of both terminal carboxyl groups, and if diamine is used, it will be (a12) 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 polyamide-forming monomer and the molecular weight modifier, from the viewpoint of the antistatic property and heat resistance of the molded product described later. %.

  Number average molecular weight of (a1) [hereinafter abbreviated as Mn. The measurement is based on GPC (gel permeation chromatography) method. ] Is preferably 200 from the viewpoint of heat resistance of the block polymer (A), more preferably 500, and from the viewpoint of production of (A), the upper limit is preferably 5,000, more preferably 3,000.

  Examples of the polyolefin (a2) include a polyolefin (a21) having carbonyl groups (preferably carboxyl groups, the same shall apply hereinafter) groups at both ends of the polymer, a polyolefin (a22) having hydroxyl groups at both ends of the polymer, and amino groups having both ends of the polymer. A polyolefin having a terminal (a23), a polyolefin having a carbonyl group at one end of the polymer (a24), a polyolefin having a hydroxyl group at one end of the polymer (a25), and a polyolefin having an amino group at one end of the polymer (A26) can be used. Of these, polyolefins (a21) and (a24) having a carbonyl group are preferable because of easy modification.

(A21) is preferably a polyolefin which can be modified at both ends, as a main component (content 5).
And those having carbonyl groups introduced at both ends of the polyolefin (a0) having a weight of 0% by weight or more, more preferably 75% by weight or more, and particularly preferably 80 to 100% by weight.
As (a22), those obtained by introducing hydroxyl groups at both ends of (a0) are used.
As (a23), an amino group introduced at both ends of (a0) is 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. Those are preferred.

  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 to 18, more preferably 4 to 8) dienes.
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 alpha-olefins 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.
A low molecular weight polyolefin by a thermal degradation method is preferable from the viewpoint of easy introduction of a carbonyl group as a modifying group and availability.

Mn in (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 per C1,000, more preferably 2 to 30, and particularly preferably 4 to 20 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 polyolefin (a21) which has a carbonyl group at both ends of a polymer, both ends of (a0) are α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, its C1-4 Means an alkyl ester or an anhydride thereof. The same applies hereinafter.) Polyolefin (a211) having a structure modified with (a211), Polyolefin (a211) having a structure obtained by secondary modification of (a211) with lactam or aminocarboxylic acid (a0) ), A polyolefin (a213) having a structure obtained by oxidation or hydroformylation modification, a polyolefin (a214) having a structure obtained by secondary modification of (a213) with lactam or aminocarboxylic acid, and a structure obtained by secondary modification of (a213) with hydroxyamine Having polyolefin (a215) and a mixture of two or more thereof As the polyolefin (a22) having hydroxyl groups at both ends of the polymer, a polyolefin (a221) having a structure obtained by modifying (a211) with hydroxylamine, a polyolefin (a222) having a structure obtained by modifying (a213) with hydroxylamine, and Mixtures of two or more of these; polyolefin (a23) having amino groups at both ends of the polymer, polyolefin (a231) having a structure obtained by secondary modification of (a211) with diamine, and (a212) Polyolefin (a232) having a secondary modified structure, polyolefin (a233) having a structure in which (a212) is modified with hydroxyamine, polyolefin (a234) having a structure in which (a213) is secondarily modified with diamine (a213) Hydroxya Examples thereof include polyolefin (a235) having a structure modified with min, polyolefin (a236) having a structure obtained by secondary modification of (a214) with diamine, and a mixture of two or more thereof.

(A211) is obtained by modifying (a0) with an α, β-unsaturated carboxylic acid (anhydride).
As α, β-unsaturated carboxylic acid (anhydride), C3-12 carboxylic acid such as monocarboxylic acid [(meth) acrylic acid, etc.], dicarboxylic acid (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, from the viewpoint of reactivity with (a0), dicarboxylic acids, their alkyl esters and their anhydrides are preferred, maleic acid (anhydride) and fumaric acid are more preferred, and maleic acid is particularly preferred. (Anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used is preferably from 0.5 to 40% by weight based on the weight of the polyolefin (a0), from the viewpoint of the formation of a repeating structure and antistatic properties, Preferably it is 1-30 weight%, Most preferably, it is 2-20 weight%.
The modification of the polyolefin (a0) with α, β-unsaturated carboxylic acid (anhydride) can be carried out in various ways, for example, the terminal double bond of (a0) can be converted into α, It can be carried out by thermally adding (ene reaction) β-unsaturated carboxylic acid (anhydride).
As a solution method, α, β-unsaturated carboxylic acid (anhydride) is added to (a0) in the presence of a hydrocarbon solvent such as xylene and toluene, and the temperature is 170 to 230 ° C. in an inert gas atmosphere such as nitrogen. The method of making it react is mentioned.
Examples of the melting method include a method in which (a0) is heated and melted, and then α, β-unsaturated carboxylic acid (anhydride) is added and reacted at 170 to 230 ° C. in an inert gas atmosphere such as nitrogen.
Among these methods, the solution method is preferable from the viewpoint of reaction uniformity.

(A212) can be obtained by secondary modification of (a211) with lactam or aminocarboxylic acid.
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 preferable from the viewpoint of reactivity of secondary modification, and caprolactam is more preferable. Laurolactam, ω-aminocaprylic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, particularly preferred are caprolactam and 12-aminododecanoic acid.
The amount of the 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 oxidizing (a0) with oxygen and / or ozone or hydroformylating with an oxo method to introduce a carbonyl group.
The introduction of the carbonyl group by oxidation can be performed by various methods, for example, the method described in US Pat. No. 3,692,877. Introduction of a carbonyl group 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.

Mn of the polyolefin (a2) having carboxyl groups at both ends of the polymer is preferably from 800 to 25,000, more preferably from 1,000, from the viewpoint of heat resistance and reactivity with the polyether (b) described later. 20,000, particularly preferably 2,500 to 10,000.
The acid value of (a2) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (b), more preferably 4 to 100, particularly preferably. Is 5-50.

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 -OE-} O- (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.

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

Diol (b01) includes C2-12 (preferably 2-10, more preferably 2-8) dihydric alcohol (aliphatic, alicyclic and araliphatic dihydric alcohol) and C1-12 tertiary. Examples thereof include amino group-containing diols.
Examples of the aliphatic dihydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 1,12-dodecanediol.
Examples of the alicyclic dihydric alcohol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-cyclooctanediol, and 1,3-cyclopentanediol.
Examples of the araliphatic dihydric alcohol include xylylenediol, 1-phenyl-1,2-ethanediol and 1,4-bis (hydroxyethyl) benzene.

As the tertiary amino group-containing diol, aliphatic or alicyclic primary monoamine (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, and cyclohexylamine.
Examples of the aromatic (aliphatic) primary monoamine include aniline and benzylamine.

  As the dihydric phenol (b02), C6-18 (preferably 8-18, more preferably 10-15), for example, monocyclic dihydric phenol (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenol (bisphenol A, Bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane, dihydrokibiphenyl, etc.) and condensed polycyclic dihydric 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. .

AO to be subjected to addition reaction with diol (b01) or dihydric phenol (b02) includes C2-12 AO (EO, PO, 1,2-, 1,4-, 2,3- and 1,3-butylene oxide. And a mixture of two or more thereof), and other AOs and substituted AOs may be used in combination.
Examples of other AO and substituted AO include epoxidized products of C5-12 α-olefin, styrene oxide and epihalohydrin (such as epichlorohydrin and epibromohydrin). The amount of each of the other AO and substituted AO used is preferably 30% by weight or less, more preferably 0 or 25% by weight, particularly preferably 0 or 20% from the viewpoint of antistatic properties based on the weight of the total AO. % By weight or less.

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 moles of AO added is preferably 1 to 300 moles, more preferably 2 to 250 moles per hydroxyl group of (b01) or (b02), from the viewpoint of the volume resistivity value of the hydrophilic polymer (b). Preferably it is 10-100 mol.

The addition reaction of AO can be carried out in various ways, 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 oxyalkylene units in the polyether diol (b1) is preferably 5 to 99.8% by weight, more preferably from the viewpoint of the volume resistivity value of the hydrophilic polymer (b) based on the weight of (b1). Is 8 to 99.6% by weight, particularly preferably 10 to 98% by weight. Further, the content of the oxyethylene unit in the polyoxyalkylene chain is preferably 5 to 100% by weight from the viewpoint of the volume resistivity value of (b) based on the weight of the polyoxyalkylene chain.
More preferably, it is 10 to 100% by weight, particularly preferably 50 to 100% by weight, and most preferably 60 to 100% by weight.

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 the hydroxyl group to an amino group, various methods, for example, a method in which a terminal cyanoalkyl group obtained by cyanoalkylating the hydroxyl group of (b1) is reduced to 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 for changing the hydroxyl group to a carbonyl group include various methods such as a method of oxidizing the hydroxyl group of (b1) [for example, a method of oxidizing (b1) with chromium oxide] and the like.

(B) is a polymer having a solubility parameter (hereinafter abbreviated as SP value) excluding a terminal functional group of 9.1 or more (preferably 9.1 to 12.4, more preferably 9.3 to 10.0). Ether and at least two kinds of polyethers less than 9.1 (preferably 8.6 or more and less than 9.1, more preferably 8.7 to 9.0) are arbitrarily used in combination, and (b) For example, in each of (b1), (b2) and (b3), a combination of at least two different A and / or E in the formula (1), and (b1), (b2) and (b3) At least two types of combinations [for example, each combination of (b1) / (b2), (b2) / (b3), (b1) / (b3)] are included.
Among the above, preferred from the viewpoint of water resistance is the combined use of two kinds of polyethers having an SP value of 9.1 or more and less than 9.1, and the ratio (weight ratio) is preferably 1. / 99 to 97/3, more preferably 4/96 to 89/11.
The SP value is obtained, for example, according to the method of Fedors (A Method for Estimating both the Solidity Parameters and Polar Volumes of Liquids', POLYMER ENGINEERING AND SCIENCE, 14

  The block polymer (A) in the present invention is selected from the group consisting of a polyamide (a1) or polyolefin (a2) block and a polyether (b) block consisting of an ester bond, an amide bond, an ether bond and an imide bond. (A) includes (A1) and (a2) and (b) each consisting of blocks (a1) and (b). (A2) consisting of each block is included.

(A1) is obtained by polymerizing the polyamide (a11) having the carboxyl group at both ends of the polymer and the polyether diol (b1) and / or the polyether diamine (b2) (A11), (A12) obtained by polymerizing a polyamide (a12) having an amino group at both ends of the polymer and a polyether dicarboxylic acid (b3).
(A11) includes (A111) in which (a11) and (b1) are combined, (A112) in which (a11) and (b2) are combined, and a mixture of (A111) and (A112).

(A1) is a variety of methods, for example, a method in which (b1) is added to (a11) and a polymerization (polycondensation) reaction is usually performed at 200 to 250 ° C. under reduced pressure, or a single-screw or twin-screw extruder is used. In general, it can be produced by a method of polymerization 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.); zirconium catalyst (tetrabutyl zirconate, etc.); Metal salt catalysts [zirconium organic acid salts (such as zirconyl acetate), zinc acetate, etc.]; and mixtures of two or more of these. Among these, a zirconium catalyst and a zirconium organic acid salt are preferable, and zirconyl acetate is more preferable.
The usage-amount of a catalyst is 0.001 to 5% normally based on the total weight of (a11) and (b1), Preferably it is 0.01 to 3%.

  In addition, (A2) as another form of (A) is subjected to a polymerization reaction of (a211), (a212), (a213) and / or (a214) and (b1) and / or (b2). (A21) obtained by the polymerization reaction of (a221), (a232), (a233) and / or (a234) and (b3) (A22); (a231), (a232) and / or Alternatively, (A23) obtained by polymerizing (a235) and (b3) is included.

  (A21) is a combination of (a211) and (b1) (A211), a combination of (a211) and (b2) (A212); a combination of (a212) and (b1) (A213); (A214) combining (a212) and (b2); (A215) combining (a213) and (b1); (A216) combining (a213) and (b2) (A214); (A217) combined with (b1); (A218) combined with (a214) and (b2); and at least two mixtures selected from (A211) to (A218).

(A22) is a combination of (a221) and (b3) (A221), a combination of (a232) and (b3) (A222), a combination of (a233) and (b3) (A223), (A224) in which (a234) and (b3) are combined, and a mixture of at least two selected from (A221) to (A224).
(A23) is a combination of (a231) and (b3) (A231), (a232) and (b3) are combined (A232), (a235) and (b3) are combined (A233), And a mixture of at least two selected from (A231) to (A233).
(A21), (A22) and (A23) can be produced by the same method as (A11) and (A12).

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

  Mn in (A) is preferably from 2,000 to 60,000, more preferably from 5,000 to 40,000, and particularly preferably from 8,000 to 30,000, from the viewpoint of resin physical properties and antistatic properties.

In the structure of (A), the average number of repeating units (Nn) of the repeating units of the block (a) and the block (b) is preferably 2 to 50, more preferably 2. It is 3-30, Most preferably, it is 2.7-20, Most preferably, it is 3-10.
Nn can be determined by Mn and ¹ H-NMR analysis of (A).
For example, in the case of (A111) having a structure in which the blocks of (a11) and (b1) are alternately and repeatedly bonded, in ¹ H-NMR analysis, 4.0 to 4.1 ppm of ester bond {—C The signal attributed to the proton of (C═O) —OCH ₂ —}, and 3
. Since signals attributed to protons of 2 to 3.7 ppm of polyalkylene glycol 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 water absorption of (A) is 0.3 to 60%, preferably 0.5 to 40%, and more preferably 1 to 30%. When the water absorption is less than 0.3%, the antistatic property of (A) is deteriorated, and when it exceeds 60%, the water resistance of the molded product described later is deteriorated.
As the polyether (b) constituting (A), by using at least two of a polyether having an SP value of 9.1 or more excluding the terminal functional group and a polyether having a viscosity of less than 9.1, (A ) In the above preferred range. For example, by using together 50% or more of a polyether having an SP value less than 9.1 excluding a terminal functional group and 50% or less of a polyether having an SP value of 9.1 or more excluding a terminal functional group, (A) having a lower water absorption rate, 20% or less of polyether having an SP value of less than 9.1 excluding the terminal functional group, and an SP value of 9.1 excluding the terminal functional group. By using together 80% or more of the above polyether, (A) having a higher water absorption rate can be obtained. This is because the polyether has an SP value of 9.1 as a boundary.
This is thought to be due to the change in water-insoluble / water-soluble properties.
Here, the water absorption is a value (hereinafter the same) measured by the following method.
<Water absorption measurement method>
Conforms to ASTM-D570. Specifically, a 50 × 50 × 3 mm test piece is dried at 50 ° C. for 24 hours, allowed to cool in a desiccator, and the weight (M1) is measured. This is immersed for 24 hours in a glass 300 ml beaker containing 250 ml of ion-exchanged water in a room at 23 ° C. and 50% RH. The weight (M2) of the test piece after immersion is measured, and the water absorption is obtained by the following formula.
Water absorption (%) = (M2−M1) × 100 / M1

In the antistatic agent comprising the block polymer (A) of the present invention, the alkali metal or alkaline earth metal salt (C), surfactant (D), An antistatic agent composition may be prepared by adding at least one additive selected from the group consisting of an ionic liquid (E) and other additives (G) for resins. Specific examples of (C) to (G) include those described below.
The total amount of the additive based on the weight of (A) is usually 170% or less, and preferably 0.001 to 100% from the viewpoint of the additive effect and the mechanical properties of the molded product described later. Among these, (C), (D) and (E) are added for the purpose of further improving the antistatic property.

  The amount of (C) used is preferably 5% or less based on the weight of (A), preferably from the viewpoint of improving the antistatic property and giving a molded article having a good appearance without depositing on the resin surface. 001 to 5%, more preferably 0.01 to 3%, particularly preferably 0.1 to 2.5%, most preferably 0.15 to 1.5%.

  The amount of (D) used is usually 15% or less based on the weight of (A), preferably from 0.001 from the viewpoint of antistatic improvement effect and ion elution (reduction of elution of metal ions, etc .; the same applies hereinafter). It is 10%, more preferably 0.01 to 8%, particularly preferably 0.1 to 5%.

  The amount of (E) used is usually 10% or less based on the weight of (A), preferably 0.001 to 5%, more preferably 0.01 to 3% from the viewpoint of antistatic improvement effect and ion elution. is there.

The total amount used of (G) is usually 170% or less based on the weight of (A), and preferably 0.1 to 100% from the viewpoint of the effect of addition and the mechanical properties of the molded product.
The amount of each (G) used is based on the weight of (A), (G1) is usually 5% or less, preferably 0.1 to 3%; (G2) is usually 150% or less, preferably 5 to 100. %; (G3) is usually 20% or less, preferably 1 to 10%; (G4) is usually 20% or less, preferably 1 to 10%; (G5) is usually 20% or less, preferably 1 to 10%; (G6) is usually 10% or less, preferably 0.1-5%; (G7) is usually 5% or less, preferably 0.1-3%; (G8) is usually 20% or less, preferably 1-10. %; (G9) is usually 5% or less, preferably 0.1 to 3%; (G10) is usually 3% or less, preferably 0.05 to 1%.
When the additive is the same and overlaps between (G1) to (G10) above, the amount of each additive effect is not used regardless of other effects, but the amount used is adjusted according to the purpose of use. It shall be.

The antistatic resin composition of the present invention contains the antistatic agent in the thermoplastic resin (B).
Specific examples of the thermoplastic resin (B) include a vinyl resin [polyolefin resin (B1) [for example, polypropylene, polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin, etc.], polyacrylic resin, and the like. Resin (B2) [for example, polymethyl methacrylate, etc.], Polystyrene resin (B3) [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 / styrene copolymer (M S resin), styrene / methyl methacrylate copolymer (MS resin), etc.]; polyester resin (B4) [for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate, polylactic acid Etc.]; Polyamide resin (B5) [eg nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12 etc.]; Polycarbonate resin (B6) [eg Polycarbonate, polycarbonate / ABS resin alloy, etc.]; polyacetal resin (B7) and mixtures of two or more thereof.

  Of these, vinyl resin [(B1) to (B3)] and polyester resin (B4) are preferable from the viewpoint of ease of dispersion of (A) into (B), and (B1) is more preferable. (B3) and (B4).

  The proportion of (A) based on the total weight of (A) and (B) is preferably from 2 to 50%, more preferably from 3 to 40%, particularly from the viewpoint of antistatic properties and mechanical properties of the molded product described later. Preferably it is 5 to 30%.

  Vinyl resins [(B1) to (B3)] can be obtained by (co) polymerizing the following vinyl monomers by various polymerization methods (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.).

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

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

  Examples of the aromatic ring-containing hydrocarbon include C8-30 styrene and 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 those having 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.], hydroxyalkyl (C2-20) ( Meth) acrylate [hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc.], mono- and di-alkyl (C1-4) aminoalkyl (C2-4) (meth) acrylate [methylaminoethyl (meth) ) Acrylate, dimethylaminoethyl (meth) acrylate, etc.], cyano group-containing monomer [(meth) acrylonitrile, α-chloroacrylonitrile, etc.], unsaturated carboxylic acid amide [(meth) acrylamide, N-methylolacrylamide, etc.) and epoxy group Contains Mer [(meth) glycidyl acrylic acid, etc.] and the like.

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

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

Examples of the polyolefin resin (B1) include polypropylene, polyethylene, propylene-ethylene copolymer [copolymerization ratio (weight ratio) = 0.1 / 99.9 to 99.9 / 0.1], propylene and / or ethylene. And other α-olefin (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 ] Etc. are mentioned.
Among these, preferred are polypropylene, polyethylene, propylene-ethylene copolymer, propylene and / or a copolymer of ethylene and one or more of C4-12 α-olefin [copolymerization ratio (weight ratio) = 90. / 10 to 10/90, random and / or block addition].

The melt flow rate (hereinafter abbreviated as MFR) of (B1) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of imparting resin physical properties and antistatic properties. The MFR of (B1) is in accordance with JIS K6758 (in the case of polypropylene; 230 ° C., load 2.16 k).
gf, in the case of polyethylene; 190 ° C., load 2.16 kgf)).

  Examples of the polyacrylic resin (B2) include one or more (co) polymers [poly (meth) acrylic acid methyl ester, such as acrylic monomers [alkyl (C1-20) (meth) acrylate, (meth) acrylonitrile, etc.]). Poly (meth) butyl acrylate, etc.] and copolymers with one or more of the above-mentioned vinyl monomers copolymerizable with one or more of these monomers [acrylic monomer / vinyl monomer copolymerization ratio (weight ratio) is a resin physical property In view of the above, preferably 5/95 to 95/5, more preferably 50/50 to 90/10] [however, those included in (B1) are excluded] are included.

The MFR of (B2) is preferably 0.5 to 150, more preferably 1 to 100 from the viewpoint of resin physical properties. The MFR of (B2) is measured in accordance with JIS K7210 (1994) [230 ° C., load 1.2 kgf for polyacrylic resin (B3)].
The crystallinity of (B2) is preferably 0 to 98%, more preferably 0 to 80%, and particularly preferably 0 to 70% from the viewpoint of antistatic properties.
The crystallinity is measured by a method such as X-ray diffraction, infrared absorption spectrum, etc. [Refer to “Solid Structure of Polymers—Lecture of Polymer Experiments 2” (Hatsugoro Minamishino), page 42, published by Kyoritsu Shuppan 1958).

As the polystyrene resin (B3), 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 (B3) include polystyrene, polyvinyltoluene, styrene / acrylonitrile copolymer (AS resin) [copolymerization ratio (weight ratio) = 70/30 to 80/20], styrene / methyl methacrylate copolymer. (MS resin) [copolymerization ratio (weight ratio) = 60 / 40-9
0/10], styrene / butadiene copolymer [copolymerization ratio (weight ratio) = 60/40 to 95/5], acrylonitrile / butadiene / styrene copolymer (ABS resin) [copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)], methyl methacrylate / butadiene / styrene copolymer (MBS resin) [copolymerization ratio (weight ratio) = (20-30) / (5 -40) / (40-70)], methyl methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS resin) [copolymerization ratio (weight ratio) = (48-70) / (0-5) / (2 ~ 20) / (25-50)] and the like.

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

  Examples of the polyester resin (B4) include aromatic ring-containing polyesters (polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, etc.) and aliphatic polyesters (polybutylene adipate, polyethylene adipate, poly-ε-caprolactone, polylactic acid, etc.). Can be mentioned.

  The intrinsic viscosity [η] of (B4) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and antistatic properties. Here, [η] is a value (unit: dl / g) measured with an Ubbelohde 1A viscometer at 25 ° C. with respect to a 0.5 wt% orthochlorophenol solution of the polymer, and so on. Note that [η] is indicated only by a numerical value in the following.

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

Examples of the lactam in (B51) include those exemplified in the above (a1), and examples of (B51) include nylon 4, nylon 5, nylon 6, nylon 8, nylon 12, and the like.
Examples of the diamine and dicarboxylic acid in (B52) include those exemplified in the above (a1). Examples of (B52) include nylon 66 obtained by polycondensation of hexanemethylenediamine and adipic acid, hexamethylenediamine and sebacic acid Examples thereof include nylon 610 by condensation.
Examples of the aminocarboxylic acid in (B53) include those exemplified in the above (a1). As (B53), 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 (B5), a molecular weight modifier may be used, and examples of the molecular weight modifier include the dicarboxylic acid and / or diamine exemplified in (a1).
Of the dicarboxylic acids as molecular weight modifiers, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and It is sodium 3-sulfoisophthalate.
Of the diamines as molecular weight regulators, hexamethylene diamine and decamethylene diamine are preferable.

The MFR of (B5) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR of (B5) is JIS K7210 (1994).
(In the case of polyamide resin, 230 ° C., load 0.325 kgf).

As the polycarbonate resin (B6), bisphenol (C12-20, for example, bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane, etc.) type polycarbonate, for example, the above bisphenol and phosgene or carbonic acid diester And a condensate thereof.
Examples of the bisphenol include C12-20, such as bisphenol A, bisphenol F, bisphenol S, and 4,4′-dihydroxydiphenyl-2,2-butane. Among these, bisphenol A is more preferable from the viewpoint of dispersibility. is there.
The MFR of (B6) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR of (B6) is JIS K7210 (1994).
(In the case of polycarbonate resin, 280 ° C., load 2.16 kgf).

Examples of the polyacetal resin (B7) include formaldehyde or trioxane homopolymer (polyoxymethylene homopolymer), and a copolymer of formaldehyde or trioxane and a cyclic ether [said AO (EO, PO, dioxolane, etc.) (polyoxymethylene / Polyoxyethylene copolymer [polyoxymethylene / polyoxyethylene (weight ratio) = 90/10 to 99/1 block copolymer, etc.] and the like.
The MFR of (B7) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR of (B7) is measured according to JIS K7210 (1994) (in the case of polyacetal resin, 190 ° C., load 2.16 kgf).
The intrinsic viscosity [η] of (B7) is preferably 0.1 to 4, more preferably 0.2 to 3.5, and particularly preferably 0.3 to 3 from the viewpoints of resin physical properties and antistatic properties.

In the antistatic resin composition of the present invention, an alkali metal or alkaline earth metal salt (C), a surfactant (D), an ionic liquid (E), if necessary, as long as the effects of the present invention are not impaired. In addition, at least one additive selected from the group consisting of a compatibilizing agent (F) and other additive for resin (G) may be contained. The total amount of the additive used based on the total weight of (A) and (B) is usually 170% or less, preferably 0.001 to 100% from the viewpoint of the additive effect and the mechanical properties of the molded product described later. It is.
Among these, (C), (D) and (E) are added for the purpose of further improving the antistatic property.

  (C) includes organic acids of alkali metals (lithium, sodium, potassium, etc.) and / or alkaline earth metals (magnesium, calcium, etc.) [C1-12 mono- and dicarboxylic acids (formic acid, acetic acid, propion) Acid, oxalic acid, succinic acid, etc.), salts of C1-20 sulfonic acids (methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc.), thiocyanic acid etc., and inorganic acids [hydrohalic acid ( Hydrochloric acid, hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.].

Specific examples of (C1) include halides [fluorides (lithium fluoride, -sodium, -potassium, -magnesium, -calcium, etc.), chlorides (lithium chloride, -sodium, -potassium, -magnesium, -calcium, etc.) ), Bromides (such as lithium bromide, -sodium, -potassium, -magnesium and -calcium) and iodides (such as lithium iodide, -sodium, -potassium, -magnesium and -calcium)], perchlorates ( Lithium perchlorate, -sodium, -potassium, -magnesium and -calcium), fluorinated sulfonates (lithium fluorosulfonate, -sodium, -potassium, -magnesium and -calcium), methanesulfonate (methane) Lithium sulfonate, -sodium, -ca Um, -magnesium and -calcium), trifluoromethanesulfonate (lithium trifluoromethanesulfonate, -sodium, -potassium, -magnesium and -calcium, etc.), pentafluoroethanesulfonate (lithium pentafluoroethanesulfonate, -Sodium, -potassium, -magnesium and -calcium, etc.), bis (trifluoromethylsulfonyl) imidoate [lithium bis (trifluoromethylsulfonyl) imidate, -sodium, -potassium, -magnesium and -calcium etc.], Bis (pentafluoroethylsulfonyl) imido acid salt [such as lithium bis (pentafluoroethylsulfonyl) imidate, -sodium, -potassium, -magnesium and -calcium], nonaflu Lobutane sulfonate (such as lithium nonafluorobutane sulfonate, -sodium, -potassium, -magnesium and -calcium), undecafluoropentane sulfonate (lithium undecafluoropentane sulfonate, -sodium, -potassium,- Magnesium and -calcium), tridecafluorohexanesulfonate (lithium tridecafluorohexanesulfonate, -sodium, -potassium, -magnesium and -calcium, etc.), acetate (lithium acetate, -sodium, -potassium,- Magnesium and -calcium, etc.), sulfates (sodium sulfate, -potassium, -magnesium and -calcium etc.), phosphates (sodium phosphate, -potassium, -magnesium and -calcium etc.), thiocyanates (such as And potassium thiocyanate).
Of these, from the viewpoint of antistatic properties, preferred are chloride, perchlorate, trifluoromethanesulfonate, bis (trifluoromethylsulfonyl) imidoate, acetate, and more preferred are lithium chloride and -potassium. And -sodium, lithium perchlorate, -potassium and -sodium, lithium trifluoromethanesulfonate, -potassium and -sodium, lithium bis (trifluoromethylsulfonyl) imidate, -sodium and -potassium, potassium acetate.

The amount of (C) used is usually 5% or less based on the total weight of (A) and (B), from the viewpoint of providing an antistatic improvement effect and a resin having a good appearance without being deposited on the resin surface. Preferably it is 0.001 to 5%, more preferably 0.01 to 3%, particularly preferably 0.1 to 2.5%, and most preferably 0.15 to 1.5%.
The method of containing (C) is preferably a method of dispersing in (A) in advance, and more preferably a method of containing (C) and dispersing and dissolving in the production of (A). There is no particular limitation on the timing of incorporating (C) during the production of (A), and it may be before, during or after polymerization of the polyolefin block and the hydrophilic polymer block.

Examples of the surfactant (D) include nonionic, anionic, cationic or amphoteric surfactants.
Nonionic surfactants include polyethylene glycol type [higher alcohols (C8-18, such as stearyl alcohol, lauryl alcohol and myristyl alcohol, the same shall apply hereinafter) EO (2-50 mol) adducts, higher fatty acids (C8-24). , E.g. stearic acid, lauric acid and myristic acid, hereafter the same) EO (2-50 mol) adduct, higher alkylamine (C8-24, e.g. stearylamine, laurylamine and myristylamine, hereafter the same) EO (2 -50 mol) adduct, polypropylene glycol (Mn 800-4,000) EO (2-50 mol) adduct, etc.], and polyhydric alcohol type [polyoxyethylene (Mn 200-3,000), higher fatty acid ester of glycerin , Pentaeri slit high fatty acid beauty treatment salon , Higher fatty acid esters of sorbit or sorbitan, alkyl (C3-60) ethers of polyhydric (divalent to pentavalent or higher) alcohols (C3-60, such as glycerin, pentaerythritol, sorbit and glucose), alkanolamines ( C2-24) higher fatty acid amides, etc.].

Examples of the anionic surfactant include compounds other than the above (C), such as carboxylates [alkali metal salts of higher fatty acids (described above)], sulfate esters [higher alcohol sulfate esters, higher alkyl ethers (C8-24). ) Sulfate ester salt, etc.], sulfonate [alkyl (C8-24) benzenesulfonate, alkyl (C8-18) sulfonate, paraffin (C25-60) sulfonate, etc.], phosphate ester salt [higher grade Alcohol phosphate ester salts, etc.).
Examples of the cationic surfactant include quaternary ammonium salts [alkyl (C8-24) trimethylammonium salts and the like].
Examples of amphoteric surfactants include amino acid types (such as higher alkylaminopropionates), betaine types [higher alkyl (C8-24) dimethylbetaine, higher alkyl (C8-24) dihydroxyethyl betaine, etc.] and the like.
These surfactants may be used alone or in combination of two or more. Of these, anionic surfactants are preferable from the viewpoint of heat resistance and antistatic properties, sulfonates are more preferable, and alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates are particularly preferable. .

The amount of (D) used is usually 15% or less based on the total weight of (A) and (B), preferably from 0.001 to 10%, more preferably from the viewpoint of an antistatic improvement effect and ion elution described later. Is 0.01 to 8%, particularly preferably 0.1 to 5%.
The method for containing (D) is not particularly limited, but in order to effectively disperse in the sheet-like substrate, it is preferable to disperse in (A) in advance. When (D) is dispersed in (A) in advance, it is particularly preferable to contain (D) in advance during the production (polymerization) of (A). There is no particular limitation on the timing at which (D) is contained during the production of (A), and it may be before, during or after polymerization of the polyolefin block and the hydrophilic polymer block.

  The ionic liquid (E) is a compound other than the above (C) and (D), has a melting point of room temperature or lower, and at least one of cations or anions constituting (E) is an organic ion, and has an initial conductivity. Is a room temperature molten salt of 1 to 200 ms / cm (preferably 10 to 200 ms / cm), for example, a room temperature molten salt described in WO95 / 15572.

  Examples of the cation constituting (E) include an amidinium cation, a guanidinium cation, and a tertiary ammonium cation.

Examples of the amidinium cation include 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 and the like]; 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-dimethylamino-1,3,4- Trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-dimethylamino-1-methyl-3,4-diethylimidazolium Etc.]; Guanidinium cation having a tetrahydropyrimidinium 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 and the like]; and a guanidinium cation having a dihydropyrimidinium skeleton [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.].

  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 (E), examples of the organic acid and / 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 above organic acids and inorganic acids, from the viewpoint of the initial conductivity of (E), a super strong acid or a super strong acid in which the Hammett acidity function (-H ₀ ) of the anion constituting (E) is 12 to 100 is preferable. These are acids that form anions other than the conjugated base, 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) ions and poly (n = 1 to 25). ) Fluoroalkanesulfonic acid (for example, undecafluoropentanesulfonic acid) ion.

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

Examples of the protonic acid used in combination with the Lewis acid include hydrogen halides (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, and 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 (E).

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 (E).
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, (E) 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 (E) used is usually 10% or less based on the total weight of (A) and (B), preferably from 0.001 to 5%, more preferably from the viewpoint of antistatic improvement effect and ion elution. 01-3%.
The method of adding (E) is not particularly limited, but from the viewpoint of effective dispersion in the resin, it is preferably preliminarily dispersed in (A), and after the production of (A) (E) More preferably, it is added and dispersed in advance.

Among the above additives, the compatibilizer (F) is added for the purpose of further improving the compatibility of (A) and (B).
(F) includes a modified vinyl polymer having at least one polar group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group (for example, in JP-A-3-258850) And a modified vinyl polymer having a sulfonyl group (for example, those described in JP-A-6-345927) and a block copolymer having a polyolefin portion and an aromatic vinyl polymer portion.
These (F) s may be used alone or in combination of two or more.
The amount of (F) used is usually 20% or less based on the total weight of (A) and (B), preferably 0.1 to 15%, more preferably 1 from the viewpoints of compatibility and mechanical properties of the molded product. -10%, particularly preferably 1.5-8%.

  Among the above additives, as other resin additives (G), a colorant (G1), a filler (G2), a nucleating agent (G3), a lubricant (G4), a plasticizer (G5), a release agent ( G6), antioxidant (G7), flame retardant (G8), ultraviolet absorber (G9) and at least one selected from the group consisting of antibacterial agent (G10).

Examples of the colorant (G1) include pigments and dyes.
Pigments include inorganic pigments [alumina white, graphite, titanium oxide (such as ultrafine titanium oxide), zinc white, black iron oxide, mica-like iron oxide, lead white, white carbon, molybdenum white, carbon black, fullerene, single wall Carbon nanotube, double wall carbon nanotube, multiwall carbon nanotube, carbon nanohorn, carbon nanofiber, graphite nanotube, carbon aerogel, risurge, lithopone, barite, cadmium red, cadmium mercury red, molybdenum red, bengara, red lead, yellow lead, Barium yellow, cadmium yellow, strontium yellow, titanium yellow, aureolin, titanium black, chromium oxide green, cobalt oxide, cobalt green, cobalt chrome green, ultramarine, bitumen, cobalt blue Cerulean blue, manganese violet, cobalt violet, etc., and organic pigments (shellac, insoluble azo pigments, soluble azo pigments, condensed azo pigments, phthalocyanine blue, color lakes, etc.).
Examples of dyes include azo, anthraquinone, indigoid, sulfide, triphenylmethane,
Examples include pyrazolone, stilbene, diphenylmethane, xanthene, alizarin, acridine, quinoneimine, thiazole, methine, nitro, nitroso and aniline dyes.

Examples of the filler (G2) include fibrous, granular, and plate-like fillers.
Examples of the fibrous filler include glass fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, aramid fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, and the like. Of these, glass fibers and carbon fibers are preferable from the viewpoint of mechanical properties of the molded product.
As granular fillers, carbon black, silica, quartz powder, glass beads, silicates (calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silica powder, etc.), metal oxides (iron oxide, titanium oxide, Zinc oxide, alumina, etc.), metal carbonates (calcium carbonate, magnesium carbonate, etc.), metal (sulfur) sulfates (calcium sulfate, barium sulfate, aluminum sulfate, calcium sulfite, etc.), metal sulfides (molybdenum disulfide) Etc.), silicon carbide, silicon nitride, boron nitride and various metal (magnesium, silicon, aluminum, titanium, copper, silver, gold, etc.) powders.
Examples of the plate-like filler include mica, glass flakes, and various metal (aluminum, copper, silver, gold, etc.) foils.
These fillers may be used alone or in combination of two or more.
Of the above fillers, a fibrous filler is preferable from the viewpoint of mechanical properties of a molded product, and a glass fiber is more preferable.

    Examples of the nucleating agent (G3) include polyvalent organic acids and / or metal salts thereof, aryl phosphate compounds, cyclic polyvalent metal aryl phosphate compounds, and dibenzylidene sorbitol compounds.

  Examples of polyvalent organic acids and / or metal salts thereof include malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid, sebacic acid, dodecanedioic acid, citric acid, butanetricarboxylic acid, butanetetracarboxylic acid, naphthenic acid, Cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid Acid, 4-butylcyclohexanecarboxylic acid, 4-octylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid, xylic acid, ethylbenzoic acid, 4-t-butyl Carboxylic acids such as benzoic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid (excluding aliphatic monocarboxylic acids) or alkali metals such as lithium, sodium, potassium, magnesium, calcium, strontium, barium And alkaline earth metal, zinc or aluminum salts.

Examples of the aryl phosphate compound include metal salts of the following compounds.
Bis (4-t-butylphenyl) phosphate, bis (4-cumylphenyl) phosphate, 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, 2,2′-methylene-bis ( 4-cumyl-6-tert-butylphenyl) phosphate, 2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate, 2,2′-methylene-bis (4-ethyl-6- t-butylphenyl) phosphate, 2,2′-methylene-bis (4,6-di-methylphenyl) phosphate, 2,2′-methylene-bis (4,6-di-ethylphenyl) phosphate, 2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, 2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate 2,2′-ethylidene-bis (4-s-butyl-6-tert-butylphenyl) phosphate, 2,2′-butylidene-bis (4,6-di-methylphenyl) phosphate, 2,2′-butylidene -Bis (4,6-di-t-butylphenyl) phosphate, 2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, 2,2'-t-octylmethylene-bis Alkali metals such as (4,6-di-t-butylphenyl) phosphate, 4,4′-dimethyl-6,6′-di-t-butyl-2,2′-biphenyl) phosphate (eg, lithium, sodium) , Potassium), mono- and bis- (4-tert-butylphenyl) phosphate, dihydrooxy- (4-tert-butylphenyl) phosphate, dihydroxy-bis (4-t Butylphenyl) phosphate, tris (4-t- butylphenyl) aluminum such as phosphates, salts of calcium and zinc.

  Examples of the cyclic polyvalent metal aryl phosphate compound include bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], bis [2,2′-methylene-bis (4-methyl-). 6-t-butylphenyl) phosphate], bis [2,2′-thiobis (4-methyl-6-t-butylphenyl) phosphate], bis [2,2′-thiobis (4-ethyl-6-t-) Butylphenyl) phosphate], bis [2,2′-thiobis (4,6-di-t-butylphenyl) phosphate], bis [2,2′-thiobis (4-t-octylphenyl) phosphate], bis [ 2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], bis [(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl ) Phosphate], bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) Phosphate], tris [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], dihydroxy-2,2′-methylene-bis (4,6-di-t-butyl) Phenyl) phosphate, dihydrooxy-2,2′-methylene-bis (4-cumyl-6-tert-butylphenyl) phosphate, dihydrooxy-bis [2,2′-methylene-bis (4,6-di-t) -Butylphenyl) phosphate], dihydrooxy-2,2'-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate, dihydrooxy-2,2'-ethyl Den-bis (4,6-di-t-butylphenyl) phosphate, hydroxy-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], hydroxy-bis [2, 2′-methylene-bis (4-cumyl-6-tert-butylphenyl) phosphate], bis [2,2′-methylene-bis (4,6-di-tert-butylphenyl) phosphate], hydroxy-bis [2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate], hydroxy-bis [2,2′-ethylidene-bis (4,6-di-tert-butylphenyl) phosphate] And alkaline earth metals (for example, calcium and barium), aluminum, titanium, magnesium, zinc, oxyzirconium salts, and the like.

Examples of the dibenzylidene sorbitol compound include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, and 1.3.
-Benzylidene-2 • 4-p-ethylbenzylidenesorbitol, 1,3-p-methylbenzylidene-2 • 4-benzylidenesorbitol, 1,3-p-ethylbenzylidene-2 • 4-benzylidenesorbitol, 1,3-p -Methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-bis (p-methylbenzylidene) sorbitol, 1,3,2,4-bis (p-ethylbenzylidene) sorbitol, 1,3,2,4-bis (pn-propylbenzylidene) sorbitol, 1,3,2,4-bis (pi) Propylbenzylidene) sorbitol, 1,3,2,4-bis (pn-butylbenzylidene) sorbitol, 1.3 2,4-bis (ps-butylbenzylidene) sorbitol, 1,3,2,4-bis (pt-butylbenzylidene) sorbitol, 1,3- (2 ′, 4′-dimethylbenzylidene) -2 4-benzylidene sorbitol, 1,3-benzylidene-2, 4- (2 ′, 4′-dimethylbenzylidene) sorbitol, 1,3,2,4-bis (2 ′, 4′-dimethylbenzylidene) sorbitol, 3,2,4-bis (3 ′, 4′-dimethylbenzylidene) sorbitol, 1,3,2,4-bis (p-methoxybenzylidene) sorbitol, 1,3,2,4-bis (p-ethoxy) Benzylidene) sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4 -P-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3,2,4-bis (p-chlorobenzylidene) sorbitol and the like can be mentioned.

  Examples of the lubricant (G4) include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), higher fatty acid amides (such as stearic acid amide), and the like.

As the plasticizer (G5), aromatic carboxylic acid ester type [phthalic acid ester (diethyl phthalate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, dilauryl phthalate, distearyl phthalate, diisononyl phthalate, etc.)], aliphatic monoester Carboxylic acid ester type [methyl acetyl ricinoleate, triethylene glycol dibenzoate, etc.], aliphatic dicarboxylic acid ester type [di (2-ethylhexyl) adipate, dioctyl adipate, dioctyl sebacate, adipic acid-propylene glycol type polyester, etc.], Aliphatic tricarboxylic acid esters (such as citrate esters (such as triethyl citrate)), phosphoric acid triesters (such as triphenyl phosphate), hydrocarbons (process oil, -Like polybutadiene, liquid polyisobutylene, liquid polyisoprene, liquid paraffin, paraffin wax, copolymer of ethylene and α-olefin (C3-20) (weight ratio 99.9 / 0.1-0.1 / 99.9) oligomer (Mn 5,000-100,000), α-olefin (C4-20) excluding ethylene and propylene copolymer (weight ratio 99.9 / 0.1-0.1 / 99.9) oligomer (Mn 5,000) ˜100,000), etc.], petroleum resins, chlorinated paraffins and the like.
Examples of the release agent (G6) include lower alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters of fatty acids (such as hardened castor oil), glycol esters of fatty acids (such as ethylene glycol monostearate), and liquid paraffin. And hydrogenated substances having unsaturated double bonds that can be hydrogenated, and the like. One plasticizer may be used, or two or more plasticizers may be used in combination.

Examples of the antioxidant (G7) include phenolic [monocyclic phenol [2,6-di-t-butyl-p-cresol, butylated hydroxyanisole and the like], bisphenol [2,2′-methylenebis (4-methyl- 6-t-butylphenol), 4,4′-butylidenebis (3-methyl) -6-t-butylphenol, 4,4′-thiobis (3-methyl) -6-t-butylphenol], polycyclic phenol [1 , 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5- t-butylphenyl) butane, etc.]; sulfur-based [dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, lauryl stearyl 3,3′-thio Dipropionate, dimyristyl 3,3′-thiodipropionate, distearyl β, β′-thiodibutyrate, dilauryl sulfide, etc.]; phosphorus system [triphenyl phosphite, triisodecyl phosphite, diphenylisodecyl phosphite, Phenyldiisodecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), cyclic neopentanetetrayl bis (2,6-di-tert-butyl-4- Methylphenyl) phosphite, cyclic neopenta Tetraylbis (2,4-di-t-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, etc.]; amine-based [octylated diphenylamine, Nn-butyl-p-aminophenol, N, N-diisopropyl-p -Phenylenediamine, N, N-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N-diphenyl-p-phenylenediamine, N-phenyl-α-naphthylamine, phenyl-β-naphthylamine, Phenothiazine and the like].

  Examples of the flame retardant (G8) include organic flame retardants [nitrogen-containing [urea compounds, guanidine compounds, triazine compounds (melamine, guanamine, etc.) salts (inorganic acid salts, cyanurates, isocyanurates, etc.), etc.] ], Sulfur-containing [sulfuric acid ester, organic sulfonic acid, sulfamic acid, organic sulfamic acid and their salts, esters, amides, etc.], silicon-containing (polyorganosiloxane, etc.), phosphorus-containing [phosphoric acid ester (tri Inorganic flame retardants (such as antimony trioxide, magnesium hydroxide, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus, ammonium polyphosphate) and the like.

  Examples of the ultraviolet absorber (G9) include benzotriazole series [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, etc.], Benzophenone [2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, etc.], salicylate [phenyl salicylate, ethylene glycol monosalicylate, etc.], acrylate [2-ethylhexyl- 2-cyano-3,3′1-diphenyl acrylate, etc.].

  Antibacterial agents (G10) include benzoic acid, paraoxybenzoic acid ester, sorbic acid, halogenated phenols (2,4,6-tribromophenol sodium salt, etc.), organic iodine (4-chlorophenyl-3-iodopropargyl formal) ), Nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylene bisthocyanocyanate, etc.), N-haloalkylthioimide (N-tetrachloroethyl-thio-tetrahydrophthalimide, etc.), copper agent (Such as 8-oxyquinoline copper), benzimidazole (such as 2-4-thiazolylbenzimidazole), benzothiazole (such as 2-thiocyanomethylthiobenzothiazole), trihaloallyl (3-bromo-2,3-diiodo-2 -Propenyl ethyl carbonate ), Triazole (such as azaconazole), organic nitrogen sulfur compound (such as Suraoff 39), quaternary ammonium compound (such as trimethoxysilyl-propyloctadecyl ammonium chloride), pyridine-based compound (2,3,5,6-cytochloro-4-) (Methylsulfonyl) -pyridine) and the like.

The total amount of (G) used is usually 170% or less based on the total weight of (A) and (B), preferably 0.1 to 100% from the viewpoint of the effect of addition and the mechanical properties of the molded product. . The amount of each (G) used is based on the total weight of (A) and (B), (G1) is usually 5% or less, preferably 0.1 to 3%; (G2) is usually 150% or less, Preferably 5 to 100%; (G3) is usually 20% or less, preferably 1 to 10%; (G4) is usually 20% or less, preferably 1 to 10%; (G5) is usually 20% or less, preferably 1 to 10%; (G6) is usually 10% or less, preferably 0.1 to 5%; (G7) is usually 5% or less, preferably 0.1 to 3%; (G8) is usually 20% or less, Preferably, it is 1 to 10%; (G9) is usually 5% or less, preferably 0.1 to 3%; (G10) is usually 3% or less, preferably 0.05 to 1%.
When the additive is the same and overlaps between (G1) to (G10) above, the amount of each additive effect is not used regardless of other effects, but the amount used is adjusted according to the purpose of use. It shall be.

As the method for producing the antistatic resin composition of the present invention, (A) and (B), or (C), (D), (E), (F) and / or (G) as required ) [(C), (D) and (E) may be previously contained in (A) from the viewpoint of effective dispersion as described above. It is manufactured by melt mixing.
As a method of melt-mixing, a usual method, for example, pellets or powdery components are mixed with an appropriate mixer (Henschel mixer, etc.) and then melt-mixed with an extruder (temperature 150 to 260 ° C.) to form pellets. The method of making it.
There are no particular restrictions on the order of addition of each component during mixing, but for example, (1) (A) and (B), or (C), (D), (E), (F) as necessary. ) And / or (G) and blending and kneading, (2) (A), a part of (B), or (C), (D), (E), if necessary, (F) and / or (G) is blended and kneaded, and then the remaining (B) is blended and kneaded, (3) (A) and (C) and part of (B) if necessary, Furthermore, after blending and kneading (D), (E), (F) and / or (G), the remaining (B) is blended and kneaded.
Among these methods, the methods (2) and (3) are called a master batch method or a master pellet method, and a small amount of (C), (D), (E), (F) and / or (G) is uniformly distributed. This is a preferable method from the viewpoint of dispersing in a resin.

  The antistatic agent, antistatic agent composition or antistatic resin composition of the present invention may be molded by injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting). Method, tenter method, inflation method, etc.), depending on the purpose, single layer molding, multilayer molding (antistatic agent, antistatic agent composition or antistatic resin composition may be either a surface layer portion or a core layer) Or may be molded by any method that incorporates means such as foam molding.

Molded articles obtained from the antistatic agent, antistatic agent composition or antistatic resin composition of the present invention have excellent mechanical properties, water resistance and permanent antistatic properties, as well as good paintability and printability. Have.
Examples of the method for coating the molded product include, but are not limited to, an air spray method, an airless spray method, an electrostatic spray method, a dipping method, a roller method, and a brush coating method.
Examples of the paint include 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.
Although a coating film thickness (film thickness after drying) can be appropriately selected according to the purpose, it is preferably 10 to 50 μm, more preferably 15 to 40 μm from the viewpoint of coating film properties and drying efficiency.
In addition, examples of the method of printing after coating the molded product or the molded product include printing methods generally used for plastic printing, such as gravure printing, flexographic printing, screen printing, and offset printing. . Examples of the printing ink include those usually used for plastic printing.

Furthermore, the antistatic agent of the present invention can be added to a paint or used as an antistatic paint by adding a solvent (for example, xylene and toluene).
Examples of the paint include the paints described above.
When the antistatic agent is added to the paint, the proportion of the block polymer (A) is preferably 5 to 60% from the viewpoint of antistatic properties and film-forming properties of the coating film based on the solid content weight of the paint. More preferably, it is 10 to 50%, and particularly preferably 15 to 40%.
In addition, the concentration of the antistatic agent when a solvent is further added to the coating material containing the antistatic agent is preferably 5 to 60 weights as a proportion of (A) from the viewpoint of antistatic properties and film-forming properties of the coating film. %, More preferably 10 to 55% by weight, particularly preferably 15 to 50% by weight.

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

Example 1
In a stainless steel autoclave, 83.5 parts of ε-caprolactam, 16.5 parts of adipic acid, antioxidant [trade name: Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd., and so on. 0.3 parts and 6 parts of water were charged, and the inside of the autoclave was purged with nitrogen. Thereafter, the pressure was gradually reduced at the same temperature, and unreacted ε-caprolactam was distilled off at 0.13 kPa or less for 3 hours to obtain 96 parts of polyamide having an acid value of 112 having carboxyl groups at both ends.
Next, bisphenol A EO adduct (Mn 2,000, SP value 9.6 excluding terminal hydroxyl group) 77 parts, polytetramethylene glycol (hereinafter abbreviated as PTMG) (Mn 1,000, SP excluding terminal hydroxyl group) (Value 9.0) 58 parts and 0.5 parts of zirconyl acetate were added and polymerized at 245 ° C. under a reduced pressure of 0.13 kPa or less for 5 hours to obtain a viscous polymer. The polymer was taken out in a strand form on a belt and pelletized to obtain an antistatic agent (X1-1) comprising a block polymer (A1-1) having a water absorption of 50%. The water absorption was in accordance with the method described above.

Example 2
In the production of the polyamide of Example 1, 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, and 6 parts of water were used, and 89.7 parts of 12-aminododecanoic acid and 10.3 parts of adipic acid were used. The reaction was carried out in the same manner as in Example 1 except that. Thereafter, the pressure was gradually reduced at the same temperature, and unreacted 12-aminododecanoic acid was distilled off at 0.13 kPa or less for 2 hours to obtain 98 parts of polyamide having an acid value of 79 having carboxyl groups at both ends.
Next, instead of 77 parts EO adduct of bisphenol A of Mn 2,000, 58 parts of PTMG of Mn 1,000 and 0.5 part of zirconyl acetate in Example 1, PEG of Mn 4,000 (SP excluding the terminal hydroxyl group) Value 9.4) Water absorption 35 as in Example 1 except that 60 parts, 42 parts PPG of Mn 1,500 (SP value 8.7 excluding terminal hydroxyl group) and 0.3 parts zirconyl acetate were used. % Of an antistatic agent (X1-2) comprising a block polymer (A1-2).

Example 3
Example 1 was the same as Example 1 except that 1 part was used instead of 77 parts of EO product of bisphenol A (Mn2,000) and 96 parts were used instead of 58 parts of PTMG (Mn1,000). Thus, an antistatic agent (X1-3) comprising a block polymer (A1-3) having a water absorption rate of 0.3% was obtained.

Example 4
Example 1 Except for using 77 parts of EO adduct of bisphenol A (Mn 2,000) in Example 1 and using 15 parts of EO adduct of bisphenol S (Mn 400, SP value 12.4 excluding terminal hydroxyl groups). In the same manner as in Example 1, an antistatic agent (X1-4) comprising a block polymer (A1-4) having a water absorption of 7% was obtained.

Production Example 1
Stainless steel autoclave, thermal degradation method [density 0.90 at 23 ° C. (unit is g / cm ³ , below only shows numerical values), MFR 6 (unit is g / 10 min, below shows only numerical values) Low-molecular-weight ethylene / propylene random copolymer (Mn 3,400, density 0) obtained by thermal degradation of ethylene / propylene random copolymer (ethylene content 2%) at 410 ± 0.1 ° C. for 16 minutes] .89, 7.0 double bonds per 1,000 C, average number of double bonds per molecule 1.8, content of polyolefin capable of modification at both ends 90%) 90 parts maleic anhydride After mixing 10 parts and 30 parts of xylene, the mixture was melted at 200 ° C. with stirring in a nitrogen gas atmosphere (sealed) and reacted at 200 ° C. with stirring for 20 hours.
Thereafter, excess maleic anhydride and xylene were distilled off under reduced pressure at 200 ° C. for 3 hours to obtain 95 parts of acid-modified polyolefin (a2-1). The acid value of (a2-1) was 27.5, and Mn was 3,600.

Production Example 2
Low molecular weight polypropylene (Mn10, Mn10, obtained by heat degradation in a stainless steel autoclave with a thermal degradation method of polypropylene having a density of 0.90 at 23 ° C and a MFR of 10 at 410 ± 0.1 ° C for 14 minutes) 000, density 0.89, 1.2 C double bonds per 1,000, average number of double bonds per molecule 1.7, content of both ends modified polyolefin 90%) 94 parts After mixing 6 parts of maleic anhydride and 30 parts of xylene, 98 parts of acid-modified polyolefin (a2-2) was obtained in the same manner as in Production Example 1. The acid value of (a2-2) was 5.1, and Mn was 10,000.

Production Example 3
A low molecular weight polypropylene (Mn1, Mn1, obtained by heat degradation of a polypropylene having a density of 0.90 at 23 ° C. and a MFR of 10 at 410 ± 0.1 ° C. for 18 minutes) in a stainless steel autoclave. 500, density 0.89, C3.8 double bond amount per 1,000, average number of double bonds per molecule 1.94, content of polyolefin which can be modified at both ends 98%) 80 parts After mixing 20 parts of maleic anhydride and 30 parts of xylene, 92 parts of acid-modified polyolefin (a2-3) was obtained in the same manner as in Production Example 1. The acid value of (a2-3) was 55.4, and Mn was 1,700.

Production Example 4
In a stainless steel autoclave, 66 parts of acid-modified polyolefin (a2-1) and 34 parts of 12-aminododecanoic acid are melted at 200 ° C. under stirring in a nitrogen gas atmosphere, and at 200 ° C. for 3 hours under reduced pressure of 10 mmHg or less. To obtain 96 parts of acid-modified polypropylene (a2-4). The acid value of (a2-4) was 17.7, and Mn was 5,700.

Production Example 5
90 parts of low molecular weight polypropylene and 0.5 part of cobalt hydroxide used in Production Example 2 are placed in a pressure resistant reactor, melted at 150 ° C. with stirring, and a mixed gas of hydrogen and carbon monoxide 1: 1 (volume ratio). Was allowed to react at 150 ° C. for 5 hours with stirring. Thereafter, the pressure was returned to normal pressure, Tollens reagent (silver nitrate-ammonia aqueous solution) was added, and the mixture was reacted at 150 ° C. for 3 hours to obtain 89 parts of acid-modified polyolefin (a2-5). The acid value of (a2-5) was 41.5, and Mn was 2,600.

Production Example 6
In a nitrogen gas atmosphere, 250 parts of toluene was charged into a stainless steel autoclave, cooled to -78 ° C, and at the same temperature, 12.1 parts of a 15% n-heptane solution of diethylaluminum chloride and 15 parts of triacetylacetonatovanadium were added. 3.1 parts of a% toluene solution was added.
Subsequently, the system was evacuated, 106 parts of a mixed gas of ethylene and propylene (2.8 / 97.2 weight ratio) was continuously supplied, and polymerization was carried out at −78 ° C. for 3 hours. Subsequently, 2.2 parts of methacrylic acid was added at the same temperature. Further, polymerization is performed at −60 ° C. for 3 hours, and the contents are added to 500 parts of methanol to precipitate a reaction product. After filtration, washing is performed 5 times with methanol, and drying is performed at 50 ° C. and 10 mmHg for 5 hours. 76 parts of acid-modified polyolefin (a2-6) were obtained. The acid value of (a2-6) was 13.0, and Mn was 8,500.

Production Example 7
97 parts of acid-modified polyolefin (a2-1) and 5 parts of ethanolamine were 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 polyolefin (a2-7) having hydroxyl groups at both ends. The hydroxyl value of (a2-7) was 26.7, the amine value was 0.01, and Mn was 3,700.

Production Example 8
95 parts of acid-modified polyolefin (a2-1) and 40 parts of bis (2-aminoethyl) ether were melted at 180 ° C. in a nitrogen gas atmosphere and reacted at the same temperature for 2 hours. Thereafter, excess bis (2-aminoethyl) ether was distilled off under reduced pressure at 180 ° C. for 2 hours to obtain a modified polyolefin (a2-8) having amino groups at both ends. The amine value of (a2-8) was 26.2, and Mn was 3,800.

Example 5
In a stainless steel autoclave, 60 parts of acid-modified polyolefin (a2-4), 18 parts of PEG (Mn 3,200, SP value 9.4 excluding terminal hydroxyl group), PTMG (Mn 4,000, SP excluding terminal hydroxyl group) (Value 9.0) 15 parts, 5 parts of sodium dodecylbenzenesulfonate, 0.3 part of antioxidant and 0.5 part of zinc acetate were added and polymerized for 8 hours under stirring and under reduced pressure at 230 ° C. and 1 mmHg or less. To obtain a viscous polymer. The polymer was taken out in the form of a strand on the belt and pelletized to obtain an antistatic agent (X2-1) comprising a block polymer (A2-1) having a water absorption of 20%.

Example 6
In a stainless steel autoclave, 71 parts of acid-modified polyolefin (a2-2), 2 parts of 12-aminododecanoic acid, α, ω-diaminoPEG (Mn 8,000, SP value 9.4 excluding terminal amino group) 15 parts , Α, ω-diaminoPPG (Mn 8,000, SP value 8.7 excluding terminal amino group), 0.5 part of lithium trifluoromethanesulfonate, 0.3 part of antioxidant, and 0.2% of zirconyl acetate. 5 parts were added and polymerized for 5 hours under stirring at 230 ° C. under reduced pressure of 1 mmHg or less to obtain a viscous polymer. Thereafter, an antistatic agent (X2-2) comprising a block polymer (A2-2) having a water absorption of 15% was obtained in the same manner as in Example 5.

Example 7
In a stainless steel autoclave, 45 parts of acid-modified polyolefin (a2-5), 25 parts of PEG (Mn 3,000, SP value 9.4 excluding terminal hydroxyl group), EO / tetrahydrofuran-random copolymer (EO / tetrahydrofuran = (Weight ratio 20/80, Mn 3,000, SP value 9.0 excluding terminal hydroxyl group, potassium hydroxide used as catalyst) 20 parts, potassium acetate 0.5 part, antioxidant 0.3 part and zinc acetate 0.5 parts was added, and polymerization was performed for 8 hours under stirring at 230 ° C. under reduced pressure of 1 mmHg or less to obtain a viscous polymer. Thereafter, an antistatic agent (X2-3) comprising a block polymer (A2-3) having a water absorption of 20% was obtained in the same manner as in Example 5.

Example 8
In a stainless steel autoclave, 59 parts of acid-modified polyolefin (a2-6), 27 parts of PEG (Mn 8,000, SP value 9.4 excluding terminal hydroxyl groups), PPG (Mn 4,000, excluding hydroxyl groups at both ends) SP value 8.7) 14 parts, 3.0 parts of ethyl methylimidazolium trifluoromethanesulfonate, 0.3 parts of antioxidant, 0.5 parts of antimony trioxide, and with stirring, at 230 ° C., 1 mmHg or less Polymerization was performed for 6 hours under reduced pressure to obtain a viscous polymer. Thereafter, an antistatic agent (X2-4) comprising a block polymer (A2-4) having a water absorption rate of 35% was obtained in the same manner as in Example 5.

Example 9
In stainless steel autoclave, modified polyolefin (a2-7) 60 parts, dodecanedioic acid 5 parts, bisphenol A EO adduct (Mn 3,000, SP value 9.5 excluding terminal hydroxyl group) 19 parts, PPG (Mn 2 , 1,000, SP value 8.7) excluding terminal hydroxyl group, 0.5 part of lithium trifluoromethanesulfonate, 0.3 part of antioxidant and 0.5 part of zinc acetate were added and stirred at 230 ° C. Polymerization was performed for 7 hours under a reduced pressure of 1 mmHg or less to obtain a viscous polymer. Thereafter, an antistatic agent (X2-5) comprising a block polymer (A2-5) having a water absorption of 16% was obtained in the same manner as in Example 5.

Example 10
Stainless steel autoclave, modified polyolefin (a2-8) 48 parts, terephthalic acid 12 parts, PEG (Mn 4,000, SP value 9.4 excluding terminal hydroxyl group) 24 parts, PTMG (Mn 3,000, terminal hydroxyl group (SP value of 9.0) 12 parts, 0.5 part of sodium trifluoromethanesulfonate, 0.3 part of antioxidant and 0.5 part of p-toluenesulfonic acid were added, and, under stirring, 230 ° C., 1 mmHg or less The polymer was polymerized for 7 hours under the reduced pressure condition to obtain a viscous polymer. Thereafter, in the same manner as in Example 5, an antistatic agent (X2-6) comprising a block polymer (A2-6) having a water absorption rate of 25% was obtained.

Example 11
60% water absorption in the same manner as in Example 5 except that 29 parts were used instead of 18 parts PEG (Mn3,200) and 1 part was used instead of 15 parts PTMG (Mn4,000) in Example 5. An antistatic agent (X2-7) comprising the block polymer (A2-7) was obtained.

Example 12
In Example 6, instead of 15 parts of α, ω-diaminoPEG (Mn8,000), 31 parts of α, ω-diaminoPEG (Mn8,800, SP value 9.4 excluding terminal amino group), α, ω -Implemented except using 1 part of α, ω-diaminopolyoctamethylene glycol (Mn 8,000, SP value 8.8 excluding terminal amino group) instead of 14 parts of diamino PPG (Mn 8,000) In the same manner as in Example 6, an antistatic agent (X2-8) comprising a block polymer (A2-8) having a water absorption rate of 40% was obtained.

Example 13
In Example 7, 40 parts instead of 25 parts PEG (Mn3,000), 20 parts EO / tetrahydrofuran-random copolymer (Mn3,000), polydodecamethylene glycol (Mn3,000, terminal hydroxyl group) An antistatic agent (X2-9) composed of a block polymer (A2-9) having a water absorption rate of 30% was obtained in the same manner as in Example 7 except that 5 parts of the SP value except 8.7) was used.

Example 14
In Example 8, in place of 27 parts of PEG (Mn 8,000) and 14 parts of PPG (Mn 4,000), α, ω-dicarboxy PEG (Mn 26,400, SP value 9.4 excluding terminal carboxyl group) An antistatic agent (X2-10) comprising a block polymer (A2-10) having a water absorption of 0.5% was obtained in the same manner as in Example 8 except that 1 part and 27 parts of PPG (Mn4,000) were used. It was.

Example 15
In Example 9, instead of 19 parts of EO product of bisphenol A (Mn 3,000), 2 parts of EO product of bisphenol A (Mn 300, SP value 10.0 excluding terminal hydroxyl groups), PPG (Mn 2,000) Instead of 16 parts, an antistatic agent (X2-11) comprising a block polymer (A2-11) having a water absorption of 1% was obtained in the same manner as in Example 9 except that 15 parts were used.

Example 16
In a stainless steel autoclave, 60 parts of modified polyolefin (a2-7), 20 parts of α, ω-dicarboxy PEG (Mn 22,000, SP value 9.4 excluding terminal carboxyl group), α, ω-dicarboxy PTMG (Mn 1,500, SP value of 9.0 excluding the carboxyl group at the end) 20 parts, 0.3 parts of antioxidant and 0.5 parts of zinc acetate were added, and the mixture was stirred under conditions of 230 ° C. and 1 mmHg or less. Polymerization was performed for a time to obtain a viscous polymer. Thereafter, an antistatic agent (X2-12) comprising a block polymer (A2-12) having a water absorption rate of 35% was obtained in the same manner as in Example 5.

Production Example 9
Low molecular weight polypropylene (Mn 12,000, Mn 12,000, obtained by heat degradation of a stainless steel autoclave with a density of 0.90 at 23 ° C. and MFR10 polypropylene at 410 ± 0.1 ° C. for 13 minutes). Density 0.89, 1.2 C double bonds per 1,000 units, 0.97 average number of double bonds per molecule, 3% content of both end-modifiable polyolefins) 95 parts and anhydrous 5 parts of maleic acid was melted at 180 ° C. under stirring in a nitrogen atmosphere, and then a 50% solution of xylene containing 1.5 parts of dicumyl peroxide was added dropwise over 15 minutes, followed by reaction for 1 hour. It was. Thereafter, the solvent was distilled off to obtain 99 parts of a modified vinyl polymer (F1) as a compatibilizer. The acid value of (F1) was 25.7, and Mn was 15,000.

Comparative Example 1
A stainless steel autoclave was charged with 83.5 parts of ε-caprolactam, 16.5 parts of adipic acid, 0.3 part of an antioxidant and 6 parts of water, and the interior of the autoclave was purged with nitrogen and pressurized at 220 ° C. (0.3 The reaction was carried out by heating and stirring for 4 hours in a sealed state. Thereafter, the pressure was gradually reduced at the same temperature, and unreacted ε-caprolactam was distilled off at 1 mmHg or less for 3 hours to obtain 96 parts of polyamide having an acid value of 112 having carboxyl groups at both ends.
Next, 144 parts of an EO adduct of bisphenol A of Mn 2,000 and 0.5 part of zirconyl acetate were added and polymerized at 245 ° C. under reduced pressure of 0.13 kPa or less for 5 hours to obtain a viscous polymer. Thereafter, in the same manner as in Example 1, an antistatic agent (X′1-1) comprising a block polymer (A′1-1) having a water absorption rate of 80% was obtained.

Comparative Example 2
To a stainless steel autoclave, add 74 parts of acid-modified polyolefin (a2-2), 25 parts of PEG (Mn1,500), 0.5 part of potassium acetate, 0.3 part of antioxidant and 0.5 part of zinc acetate. Polymerization was performed for 8 hours under the reduced pressure of 1 mmHg or less at 1 ° C. to obtain a viscous polymer. Thereafter, an antistatic agent (X′2-1) comprising a block polymer (A′2-1) having a water absorption of 65% was obtained in the same manner as in Example 5.

Comparative Example 3
To a stainless steel autoclave, add 26 parts of acid-modified polyolefin (a2-3), 74 parts of PEG (Mn6,000), 0.5 part of lithium chloride, 0.3 part of antioxidant and 0.5 part of zirconyl acetate, and 230 Polymerization was carried out for 8 hours under the conditions of reduced pressure of 1 mmHg or less, and a viscous polymer was obtained. Thereafter, an antistatic agent (X′2-2) comprising a block polymer (A′2-2) having a water absorption rate of 70% was obtained in the same manner as in Example 5.

Examples 17 to 34, Comparative Examples 4 to 9
According to the formulation (parts) shown in Table 1, the antistatic agent and the thermoplastic resin obtained above (B1, B2, B3, B4 described below) were mixed with a Henschel mixer, optionally with a compatibilizing agent (F1). After blending for 1 minute, charge and knead in a twin screw extruder with a vent at 100 rpm and a residence time of 3 minutes under conditions of 230 ° C when using B1 and B4, and 200 ° C when using B2 and B3. Preventive resin compositions (Examples 17 to 32 and Comparative Examples 4 to 7) were obtained. Further, some of the antistatic agents obtained above were used as molding antistatic agents (Examples 33 to 34 and Comparative Examples 8 to 9) for performance evaluation described later.

B1: ABS [Brand name: ABS10, manufactured by Technopolymer Co., Ltd.]
B2: Polypropylene [trade name: Sun Allomer PM771M, manufactured by Sun Allomer Co., Ltd.] B3: Polyethylene [Product Name: ULT XEX 25100J, manufactured by Sumitomo Mitsui Polyolefin Co., Ltd.]
B4: High impact polystyrene [trade name: PSJ polystyrene H0103, manufactured by PS Japan Ltd.]

Performance Test About the resin composition and the antistatic agent obtained above, respectively, using an injection molding machine [PS40E5ASE, manufactured by Nissei Plastic Industry Co., Ltd.], cylinder temperature 230 ° C. (when using B1 and B4) or 200 ° C. ( B2 and B3, and antistatic agent), each molding test piece was prepared at a mold temperature of 50 ° C., and using these, mechanical properties (Charpy impact strength, flexural modulus and compatibility) Evaluation of water resistance, antistatic property (surface specific resistance value and surface specific resistance value after washing with water), and paintability (primary adhesion, water resistance and coating efficiency) of the resin were performed according to the following methods. . The results are shown in Table 2.

(1) Mechanical properties 1) Charpy impact strength Measured according to JIS K7111 (1984) (No. 1 E / A test piece).
2) Flexural modulus Using a test piece (10 × 4 × 100 mm), ASTM D790 (distance between fulcrums 60)
mm).
3) Compatibility The test piece (100 x 100 x 2 mm) is bent at 23 ± 5 ° C (if it does not break once, the bending operation is repeated until it breaks), and the following criteria are obtained by observing the fracture surface. It was evaluated with.
Evaluation criteria ○ Good
X Defect [layer peeling with poor compatibility between (A) and (B)]

(2) Antistatic property 1) Surface specific resistance value Using a test piece (100 × 100 × 2 mm), a super insulation meter [manufactured by Advantest Corporation,
same as below. ] In an atmosphere of 23 ° C. and 50% RH (ASTM D2
57, the same shall apply hereinafter. ).
2) Surface resistivity after washing with water A test piece (100 × 100 × 2 mm) leaning diagonally was placed at 23 ° C. and a flow rate of 100 ml /
The water was washed with 100 ml of ion-exchanged water (23 ° C.) for one minute, and dried at 80 ° C. for 3 hours with a circulating dryer. The washing and drying operation is repeated 10 times, using a super insulation meter at 23 ° C and humidity 50
It was measured under an atmosphere of% RH.

(3) Water resistance of the resin Tap water is adjusted to a temperature of 40 ° C. up to a depth of 15 cm in a polypropylene lidded container with a diameter of 15 cm and a height of 20 cm.
Evaluation was performed according to the following criteria by immersing for 120 hours in a state of being sunk horizontally at cm and observing the surface state.
Evaluation criteria ○ No change before and after evaluation
× Ward-shaped blisters or rough surface

(4) Paintability A test piece (100 × 100 × 2 mm) was subjected to corona discharge treatment (30 V × 10 A = 300 W, 1 second treatment) using a corona treatment device [HFS-202, manufactured by Kasuga Denki Co., Ltd.]. It was. Ground the corona-treated specimen and electrostatically coat the specimen using an electrostatic atomizing electrostatic coating machine combined with air flow [Turbonea G minibell type automatic electrostatic coating equipment, manufactured by Nippon Landsburg Co., Ltd.] (Applied voltage −90 KV, discharge rate 100 cc / min, rotation speed 24,000
0 rpm, atomization head diameter 70 mm, 2-component urethane paint is Nippon Oil & Fats High Urethane #
5000 used). After the painted plate was baked at 80 ° C. for 2 hours, the following test was performed.
1) Primary adhesion The coating surface of the coated plate was subjected to an adhesion test in accordance with the JIS K5400 (1990) 8.5.2 cross-cut tape method.
2) Water resistance of the coating film A state of 15cm in diameter and 20cm in height with a polypropylene lid with tap water up to a depth of 15cm. After 240 hours, the adhesion (primary adhesion) test was conducted as in 1).
3) Coating efficiency It calculated | required according to the following formula | equation.
Coating efficiency = (weight after painting of test piece−weight before painting of test piece) × 100
/ (Absolute dry weight of discharged paint)

The absolute dry weight of the discharged paint was determined by the following method.
10 g of the paint was placed in a petri dish having a diameter of 15 cm and a depth of 1 cm, dried at 80 ° C. for 2 hours with a circulating dryer, the weight (W1) of the paint after drying was measured, and calculated according to the following formula.

Absolute dry weight of discharged paint = weight of paint discharged in coating test × (W1) / 10

  As is apparent from Table 2, the molded product formed by molding the antistatic resin composition and the antistatic agent of the present invention is compared with the molded product formed by molding the resin composition and the antistatic agent of Comparative Example. Thus, it can be seen that it has excellent water resistance, permanent antistatic properties and mechanical properties.

  Molded articles formed by molding the antistatic agent, antistatic agent composition and antistatic resin composition of the present invention have excellent permanent antistatic properties, mechanical properties, moldability and water resistance, as well as paintability and Excellent printability. Accordingly, the antistatic agent, antistatic agent composition and antistatic resin composition of the present invention are injection molded, compression molded, calendar molded, slush molded, rotational molded, extruded molded, blow molded, film molded (casted) Method, tenter method, inflation method, etc.), home appliances / OA equipment, game machines and office work that are molded by any of various molding methods that incorporate means such as single layer molding, multilayer molding or foam molding depending on the purpose. For various molded products such as housing products such as equipment, various plastic containers such as IC trays, various packaging films, electronic / electrical process materials, protective films, flooring sheets, artificial turf, mats, and automotive parts Widely used as a material.

Claims (7)

A block of polyamide (a1) or polyolefin (a2) and at least two types of polyethers having a solubility parameter excluding X of 9.1 or more and less than 9.1 represented by the following general formula (1) And a block of polyether (b) consisting of repeating bonds alternately and 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 which consists of block polymer (A) which is 0.3 to 60%.

X-A- (OA) _{m-1 -OE-} O- (AO) _{m′-1 -AX} (1)

(Wherein E is a residue obtained by removing a hydroxyl group from a diol or divalent phenol, A is a divalent hydrocarbon group having 2 to 12 carbon atoms which may be substituted with a halogen atom and / or a benzene ring, m and m ′ represents an integer of 1 to 300, and X represents a group selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group. The antistatic agent according to claim 1, wherein at least one additive selected from the group consisting of an alkali metal or alkaline earth metal salt, a surfactant, an ionic liquid, a compatibilizing agent and other additives for resins. An antistatic agent composition comprising An antistatic resin composition comprising the thermoplastic resin (B) containing the antistatic agent according to claim 1. The composition according to claim 3, wherein the ratio of (A) based on the total weight of (A) and (B) is 2 to 50%. Furthermore, at least one additive selected from the group consisting of an alkali metal or alkaline earth metal salt, a surfactant, an ionic liquid, a compatibilizing agent and other additives for resin is contained. Or the composition of 4. A molded article formed by molding the antistatic agent according to claim 1 or the composition according to any one of claims 2 to 5. A molded article obtained by coating and / or printing the molded article according to claim 6.