JP2015131960A - Antistatic agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic agent that gives an excellent antistatic property to a thermoplastic resin molded article without impairing mechanical characteristics or a favorable appearance of the molded article.SOLUTION: The antistatic agent comprises a block polymer (A) and an anionic surfactant (B) represented by formula (1), the block polymer (A) having a structure where a block of a hydrophilic polymer (a) having a volume resistivity value of from 1×10to 1×10Ω cm, and a block of a hydrophobic polymer (b) are alternately bound repeatedly via at least one bond selected from an ester bond, amide bond, ether bond, urethane bond, and imide bond: (R-)nXZ(1). [In formula (1), R represents a monovalent hydrocarbon group having 8 to 30 carbon atoms; Xrepresents a sulfonate group, sulfinate group, sulfate group, carboxylate group, phosphate group, or phosphite group; and Zrepresents an amidinium, pyridinium, pyrazolium, or guanidium cation; and n is 1 or 2.

Description

  The present invention relates to an antistatic agent. More specifically, the present invention relates to an antistatic agent that imparts excellent antistatic properties to a molded article without impairing the mechanical properties and good appearance of the thermoplastic resin molded article.

  Conventionally, as a thermoplastic resin composition that gives a thermoplastic resin having antistatic properties, a resin containing a polyether chain-containing antistatic agent obtained by polymerization in the presence of an ionic surfactant in a thermoplastic resin Compositions (for example, see Patent Document 1), resin compositions (for example, see Patent Document 2) in which an antistatic agent composed of an ionic liquid and a block polymer having a polyether block structure is contained in a thermoplastic resin Are known.

JP 2002-146212 A JP 2004-217931 A

However, since the ionic surfactant as an antistatic agent is a solid at room temperature, when the amount used is increased for the purpose of improving the antistatic property, the mechanical property of the molded product is deteriorated. When moldings are made from antistatic resin compositions containing ionic liquids, many of them are low-viscosity liquids at room temperature, so ionic liquids can easily bleed out (exudate) ), The appearance deteriorated.
An object of the present invention is to provide an antistatic agent that imparts excellent antistatic properties to a molded article without impairing the mechanical properties and good appearance of the thermoplastic resin molded article.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the block of the hydrophilic polymer (a) having a volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm and the block of the hydrophobic polymer (b) are ester bonds, amide bonds, ether bonds, A block polymer (A) having a structure in which it is alternately and repeatedly bonded through at least one bond selected from the group consisting of a urethane bond and an imide bond, and an anion represented by the following general formula (1) An antistatic agent comprising a surfactant (B).

(R−) _n X ⁻ · Z ⁺ (1)

[Wherein R is a monovalent hydrocarbon group having 8 to 30 carbon atoms, X ⁻ is a group consisting of a sulfonic acid group, a sulfinic acid group, a sulfate ester group, a carboxyl group, a phosphate ester group, and a phosphite ester group. An anion obtained by removing a proton from at least one group selected from: Z ⁺ is a cation selected from the group consisting of amidinium, pyridinium, pyrazolium and guanidinium cations, n is 1 or 2, and when n is 2 A plurality of R may be the same or different. ]
An antistatic resin composition containing the antistatic agent in a thermoplastic resin; a molded article obtained by molding the composition; and a molded article obtained by coating and / or printing the molded article. is there.

  The antistatic resin composition containing the antistatic agent of the present invention exhibits the effect of the invention of giving a molded article excellent in permanent antistatic properties without impairing the mechanical properties and appearance of the thermoplastic resin.

[Hydrophilic polymer (a)]
The block polymer (A) in the present invention has a volume resistivity value (value measured by an after-mentioned method in an atmosphere of 23 ° C. and 50% RH) of 1 × 10 ⁵ to 1 × 10 ¹¹ (preferably 1 × 10 ⁶ to 1 × 10 ⁹ ) Ω · cm hydrophilic polymer (a) and hydrophobic polymer (b) block selected from the group consisting of ester bond, amide bond, ether bond, urethane bond and imide bond It is a block polymer characterized by having a structure in which it is alternately and alternately bonded through at least one kind of bond. If the volume specific resistance value of the hydrophilic polymer (a) is less than 1 × 10 ⁵ Ω · cm, the moldability of the resin composition described later deteriorates, and if it exceeds 1 × 10 ¹¹ Ω · cm, the antistatic property of the molded product described later is prevented. Sexuality gets worse.

  Examples of the hydrophilic polymer (a) include at least one selected from the group consisting of a polyether (a1), a cationic polymer (a2), and an anionic polymer (a3).

Examples of the polyether (a1) include polyether diol (a11), polyether diamine (a12), and modified products (a13) thereof.
Examples of the cationic polymer (a2) include a cationic polymer having 2 to 80, preferably 3 to 60, cationic groups (c2) separated by a nonionic molecular chain (c1) in the molecule. .
As the anionic polymer (a3), a dicarboxylic acid (e1) having a sulfonyl group and a diol (a0) or a polyether (a1) are essential structural units, and 2 to 80, preferably 3 to Examples include anionic polymers having 60 sulfonyl groups.

The polyether (a1) will be described.
Among (a1), the polyether diol (a11) has a structure obtained by addition reaction of alkylene oxide (hereinafter abbreviated as AO) to the diol (a0). The general formula: H- (OA ¹ ) those represented by ^{_{m -O-E 1 -O- (A}} 1 O) m '-H and the like.
In the formula, E ¹ is a residue obtained by removing a hydroxyl group from diol (a0), A ¹ is an alkylene group having 2 to 4 carbon atoms (hereinafter abbreviated as C), and m and m ′ are per hydroxyl group of diol (a0). Represents the AO addition number. m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form in the case where they are composed of two or more oxyalkylene groups is a block or Either random or a combination thereof may be used. m and m ′ are usually integers of 1 to 300, preferably 2 to 250, particularly preferably 10 to 100. M and m ′ may be the same or different.

Examples of the diol (a0) include dihydric alcohols (for example, C2-12 aliphatic, alicyclic or aromatic ring-containing dihydric alcohols), C6-18 dihydric phenols, and tertiary amino group-containing diols.
Examples of the aliphatic dihydric alcohol include alkylene glycol [ethylene glycol, propylene glycol (hereinafter abbreviated as EG and PG, respectively)], 1,4-butanediol, 1,6-hexanediol, neopentyl glycol (hereinafter 1 each). , 4-BD, 1,6-HD, abbreviated as NPG), and 1,12-dodecanediol.
Examples of the alicyclic dihydric alcohol include cyclohexanedimethanol, and examples of the aromatic ring-containing dihydric alcohol include xylylene diol.
Examples of the dihydric phenol include monocyclic dihydric phenol (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenol (bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane, Dihydroxybiphenyl and the like) and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol and the like).

Examples of the tertiary amino group-containing diol include C1-12 aliphatic or alicyclic primary monoamines (methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, amylamine, isoamylamine, hexylamine. 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-aminoheptane, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, dodecylamine, etc.) Examples thereof include bishydroxyalkylated products and bishydroxyalkylated products of C6-12 aromatic monocyclic monoamines (aniline, benzylamine, etc.).
Of these, preferred are aliphatic dihydric alcohols and bisphenols, particularly preferably EG and bisphenol A.

The polyether diol (a11) can be produced by adding AO to the diol (a0).
AO includes C2-4 AO [ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- and 1,3-butylene oxide (hereinafter abbreviated as EO, PO, BO, respectively), and Two or more of these combined systems are used, and if necessary, other AO or substituted AO (hereinafter collectively referred to as AO) such as C5-12 α-olefin, styrene oxide, epihalohydrin (epichlorohydrin). Etc.) can be used together in a small proportion (for example, 30% or less based on the weight of the total AO).
When two or more kinds of AO are used in combination, the coupling form may be random and / or block. Preferred as AO is EO alone or a combination of EO and another AO (random and / or block addition). The addition number of AO is an integer of usually 1 to 300, preferably 2 to 250, particularly preferably 10 to 100 per hydroxyl group of the diol (a0).

AO can be added by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst. The content of C2-4 oxyalkylene units in (a11) is usually from 5 to 99.8%, preferably from 8 to 99.6%, particularly preferably from 10 to 98%.
The content of oxyethylene units in the polyoxyalkylene chain is usually 5 to 100%, preferably 10 to 100%, more preferably 50 to 100%, and particularly preferably 60 to 100%.

The polyether diamine (a12) has the general formula: H ₂ N—A ² — (OA ¹ ) _m —O—E ¹ —O
-(A ¹ O) _{m '} -A ² -NH ₂ (in the formula, symbols E ¹ , A ¹ , m and m' are the same as above,
A ² is a C2-4 alkylene group. A ¹ and A ² may be the same or different. ) Can be used.
(A12) can be obtained by changing the hydroxyl group of (a11) to an amino group by a known method. For example, the terminal obtained by cyanoalkylating the hydroxyl group of (a11) is reduced to an amino group. Things can be used.
For example, it can be produced by reacting (a11) with acrylonitrile and hydrogenating the resulting cyanoethylated product.

Examples of the modified product (a13) include aminocarboxylic acid modified products (terminal amino groups), isocyanate modified products (terminal isocyanate groups) and epoxy modified products (terminal epoxy groups) of (a11) or (a12). It is done.
The aminocarboxylic acid-modified product can be obtained by reacting (a11) or (a12) with aminocarboxylic acid or lactam.
The isocyanate-modified product can be obtained by reacting (a11) or (a12) with a polyisocyanate as described below or reacting (a12) with phosgene.
The epoxy-modified product is obtained by reacting (a11) or H with (a12) and diepoxide (epoxy resins such as diglycidyl ether, diglycidyl ester, alicyclic diepoxide: epoxy equivalent 85 to 600), or (a11) And epihalohydrin (such as epichlorohydrin) can be reacted.

  Number average molecular weight of the polyether (a1) [hereinafter abbreviated as Mn. The measurement is performed by a gel permeation chromatography (GPC) method described later] is usually 150 to 20,000, and preferably 300 to 20,000 from the viewpoint of heat resistance and reactivity with the hydrophobic polymer (b) described later. It is 18,000, more preferably 500 to 15,000, particularly preferably 1,200 to 8,000.

The measurement conditions for Mn are as follows. Hereinafter, Mn is measured under the same conditions. Equipment: High temperature GPC
Solvent: Orthodichlorobenzene reference material: Polystyrene sample concentration: 3 mg / ml
Column temperature: 135 ° C

Next, the cationic polymer (a2) will be described. (A2) is a hydrophilic polymer having 2 to 80, preferably 3 to 60, cationic groups (c2) separated in the molecule by a nonionic molecular chain (c1).
Examples of the cationic group (c2) include a group having a quaternary ammonium salt or a phosphonium salt. Examples of the counter anion of (c2) include a super strong acid anion and other anions.
The super strong acid anion includes an anion of a super strong acid (tetrafluoroboric acid, hexafluorophosphoric acid, etc.) derived from a combination of a protonic acid (d1) and a Lewis acid (d2), a super strong acid anion such as trifluoromethanesulfonic acid, etc. Examples include strong acid anions.
Examples of other anions include halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ etc.), OH ⁻ , PO ₄ ⁻ , CH ₃ OSO ₄ ⁻ , C ₂ H ₅ OSO ₄ ⁻ , ClO ₄ ^{− and the} like. Can be mentioned.
Specific examples of the protonic acid (d1) that induces a super strong acid include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, and the like.
Specific examples of the Lewis acid (d2) include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, and tantalum pentafluoride.

The nonionic molecular chain (c1) includes a divalent hydrocarbon group, or an ether bond, a thioether bond, a carbonyl bond, an ester bond, an imino bond, an amide bond, an imide bond, a urethane bond, a urea bond, a carbonate bond, and / or Or a divalent organic group such as at least one divalent hydrocarbon group selected from the group consisting of a hydrocarbon group having a siloxy bond and a hydrocarbon group having a heterocyclic structure containing a nitrogen atom or an oxygen atom; and these These two or more types are used in combination.
Of these (c1), preferred are a divalent hydrocarbon group and a divalent hydrocarbon group having an ether bond.

  Mn of the cationic polymer (a2) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly from the viewpoint of antistatic properties and reactivity with the hydrophobic polymer (b) described later. Preferably, it is 1,200 to 8,000.

  Specific examples of the cationic polymer (a2) include cationic polymers described in JP-A No. 2001-278985.

Next, the polymer (a3) having an anionic group will be described. (A3) comprises dicarboxylic acid (e1) having a sulfonyl group and diol (a0) or polyether (a1) as essential structural units, and 2 to 80, preferably 3 to 60 sulfonyls in the molecule. An anionic polymer having a group.
As the dicarboxylic acid (e1), an aromatic dicarboxylic acid having a sulfonyl group, an aliphatic dicarboxylic acid having a sulfonyl group, or a salt of only these sulfonyl groups can be used.

Examples of the aromatic dicarboxylic acid having a sulfonyl group include 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid, and ester-forming derivatives thereof [lower Alkyl (C1-4) ester (methyl ester, ethyl ester, etc.), acid anhydride, etc.].
Examples of the aliphatic dicarboxylic acid having a sulfonyl group include sulfosuccinic acid and ester-forming derivatives thereof [lower alkyl (C1-4) ester (methyl ester, ethyl ester, etc.), acid anhydride, etc.].
Examples of the salts in which only these sulfonyl groups are converted include salts of alkali metals (lithium, sodium, potassium, etc.), salts of alkaline earth metals (magnesium, calcium, etc.), ammonium salts, hydroxyalkyl (C2-4). ) Amine salts such as mono-, di- or tri-amines having organic groups (organic amine salts such as mono-, di- or tri-ethylamine, mono-, di- or tri-ethanolamine, diethylethanolamine), etc. Examples include quaternary ammonium salts of amines and combinations of two or more of these.
Of these, preferred are aromatic dicarboxylic acids having a sulfonyl group, more preferred are 5-sulfoisophthalic acid salts, and particularly preferred are 5-sulfoisophthalic acid sodium salt and 5-sulfoisophthalic acid potassium salt.

Among (a0) and (a1) constituting (a3), C2-10 alkanediol, EG, polyethylene glycol (hereinafter abbreviated as PEG) (polymerization degree 2-20), bisphenol (bisphenol A, etc.) EO adduct (number of added moles 2 to 60) and a mixture of two or more thereof.
As a manufacturing method of (a3), a normal polyester manufacturing method can be applied as it is. The polyesterification reaction is usually performed in a temperature range of 150 to 240 ° C. under reduced pressure, and the reaction time is 0.5 to 20 hours. Moreover, in this esterification reaction, you may use the catalyst used for normal esterification reaction as needed.
Examples of esterification catalysts include antimony catalysts (such as antimony trioxide), tin catalysts (such as monobutyltin oxide and dibutyltin oxide), titanium catalysts (such as tetrabutyl titanate), zirconium catalysts (such as tetrabutylzirconate), and metal acetate. Examples thereof include salt catalysts (such as zinc acetate).

  Mn of (a3) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly preferably 1 from the viewpoint of antistatic properties and reactivity with the hydrophobic polymer (b) described later. , 200-8,000.

[Hydrophobic polymer (b)]
The hydrophobic polymer (b) in the present invention includes a hydrophobic polymer selected from the group consisting of polyolefin (b1), polyamide (b2) and polyamideimide (b3). Here, the hydrophobic polymer means a polymer having a surface resistivity of 1 × 10 ¹⁴ to 1 × 10 ¹⁷ Ω.

As the polyolefin (b1), a polyolefin (b11) having a carbonyl group (preferably a carboxyl group, the same shall apply hereinafter) at both ends of the polymer, a polyolefin (b12) having a hydroxyl group at both ends of the polymer, and an amino group as a polymer The polyolefin (b13) having both ends thereof and the polyolefin (b14) having isocyanate groups at both ends of the polymer can be used.
Further, a polyolefin (b15) having a carbonyl group at one end of the polymer, a polyolefin (b16) having a hydroxyl group at one end of the polymer, a polyolefin (b17) having an amino group at one end of the polymer, and an isocyanate group as a piece of polymer. Polyolefin (b18) having a terminal can be used.
Of these, polyolefins (b11) and (b15) having a carbonyl group are preferable because of easy modification.

As (b11), a carbonyl group is present at both ends of the polyolefin (b10) whose main component (preferably the content is 50% or more, more preferably 75% or more, particularly preferably 80 to 100%). A group into which a group is introduced is used.
As (b12), those having hydroxyl groups introduced at both ends of (b10) are used.
As (b13), those in which amino groups are introduced at both ends of (b10) are used.
As (b14), those obtained by introducing isocyanate groups at both ends of (b10) are used.

As (b15), one end of a polyolefin (b100) containing a polyolefin whose one end can be modified as a main component (preferably a content of 50% or more, more preferably 75% or more, particularly preferably 80 to 100%) A group into which a group is introduced is used.
As (b16), one obtained by introducing a hydroxyl group at one end of (b100) is used.
As (b17), one obtained by introducing an amino group at one end of (b100) is used.
As (b18), an isocyanate group introduced at one end of (b100) is used.

(B10) means (co) polymerization (polymerization or copolymerization) of one or a mixture of C2-30 (preferably 2-12, more preferably 2-10) olefins. )) And a degraded polyolefin [a product obtained by mechanically, thermally or chemically degrading a high molecular weight polyolefin (preferably Mn 50,000 to 150,000)] (reduced) Method).
From the viewpoint of easy modification and availability of introduction of a carbonyl group, a hydroxyl group, an amino group or an isocyanate group, a degraded polyolefin is preferred, and a thermally degraded polyolefin is particularly preferred. Is a low molecular weight polyolefin (such as polyethylene and / or polypropylene having a Mn of 1,200 to 6,000) by a thermal degradation method.
The heat-degraded polyolefin is not particularly limited, but is heat-degraded by heating a high molecular weight polyolefin in an inert gas (usually at 300 to 450 ° C. for 0.5 to 10 hours) (for example, JP-A-3 -62804).
Examples of the high molecular weight polyolefin used in the thermal degradation method include (co) polymers of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. Can be used. As the C2-30 olefin, the same as those used for the production of the polyolefin (polymerization method) described later can be used, and among these, ethylene, propylene and C4-12 α-olefin are preferred, and ethylene is more preferred. , Propylene and C4-10 alpha-olefins, particularly preferred are ethylene and propylene.

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

Mn of polyolefin (b10) mainly composed of polyolefin which can be modified at both ends is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000. is there. When Mn is within this range, the antistatic property is further improved.
The amount of double bonds in (b10) is preferably 1 to 40, more preferably 2 to 30, and particularly preferably 4 to 20 per 1,000 carbon atoms. When the amount of the double bond is within this range, the antistatic property is further improved.
The average number of double bonds per molecule is preferably 1.1 to 5.0, more preferably 1.3 to 3.0, particularly preferably 1.5 to 2.5, and most preferably 1.8. ~ 2.2. When the average number of double bonds is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.
According to the thermal degradation method, a low molecular weight polyolefin having an average terminal double bond amount per molecule of 1.5 to 2 can be easily obtained with Mn in the range of 800 to 6,000 [Katsuhide Murata, Tadahiko Makino. , Journal of Chemical Society of Japan, page 192 (1975)].

(B100) can be obtained in the same manner as (b10), and Mn of (b100) is usually 2,000 to 50,000, preferably 2,500 to 30,000, particularly preferably 3,000 to 20,000.
(B100) has 0.3 to 20, preferably 0.5 to 15, particularly preferably 0.7 to 10 double bonds per 1,000 carbon atoms.
From the viewpoint of easy modification, low molecular weight polyolefins (particularly polyethylene and / or polypropylene having Mn of 2,000 to 20,000) by thermal degradation are preferred.
In the low molecular weight polyolefin by the thermal degradation method, those having an average terminal double bond amount of 1 to 1.5 per molecule are obtained with Mn in the range of 5,000 to 30,000.

  In addition, (b10) and (b100) are usually obtained as a mixture of these, but these mixtures may be used as they are, or may be used after purification and separation. From the viewpoint of production cost and the like, it is preferably used as a mixture.

Hereinafter, (b11) to (b14) having a carbonyl group, a hydroxyl group, an amino group or an isocyanate group at both ends of the polyolefin (b10) will be described. About (b18), (b10
) Is replaced with (b100), and can be obtained in the same manner according to (b11) to (b14).

As the polyolefin (b11) having carbonyl groups at both ends of the polymer, the end of (b10) is α, β unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, C1-4 alkyl ester thereof) Or an anhydride thereof. The same applies hereinafter.) Polyolefin (b11-1) having a structure modified with (b11-1) and polyolefin (b11-2) having a structure obtained by secondary modification of (b11-1) with lactam or aminocarboxylic acid. ), (B10) is a polyolefin having a structure modified by oxidation or hydroformylation (b11-3), (b
A polyolefin (b11-4) having a structure obtained by secondary modification of 11-3) with a lactam or an aminocarboxylic acid and a mixture of two or more of these can be used.

(B11-1) can be obtained by modifying (b10) with an α, β-unsaturated carboxylic acid (anhydride).
As α, β-unsaturated carboxylic acid (anhydride) used for modification, monocarboxylic acid, dicarboxylic acid, alkyl (C1-4) ester thereof and anhydride thereof can be used, for example, (meth) acrylic acid (Means acrylic acid or methacrylic acid; the same shall apply hereinafter), methyl (meth) acrylate, butyl (meth) acrylate, maleic acid (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride) , Diethyl itaconate and citraconic acid (anhydride).
Among these, preferred are dicarboxylic acids, their alkyl esters and their anhydrides, more preferred are maleic acid (anhydride) and fumaric acid, and particularly preferred is maleic acid (anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used for modification is preferably 0.5 to 40%, more preferably 1 to 30%, particularly preferably 2 based on the weight of the polyolefin (b10). ~ 20%. When the amount of α, β-unsaturated carboxylic acid (anhydride) is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.
The modification with α, β-unsaturated carboxylic acid (anhydride) can be performed by various methods. For example, the terminal double bond of (b10) can be modified by either solution method or melt method. , Β-unsaturated carboxylic acid (anhydride) can be thermally added (ene reaction). The temperature at which (b10) is reacted with the α, β-unsaturated carboxylic acid (anhydride) is usually 170 to 230 ° C.

(B11-2) can be obtained by secondarily modifying (b11-1) with a lactam or an aminocarboxylic acid.
As the lactam used for the secondary modification, a C6-12 (preferably 6-8, more preferably 6) lactam or the like can be used, and examples thereof include caprolactam, enantolactam, laurolactam, and undecanolactam.
As the aminocarboxylic acid, C2-12 (preferably 4-12, more preferably 6-12) aminocarboxylic acid and the like can be used. For example, amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.) ), Ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Of these, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and caprolactam, laurolactam, ω-aminocaprylic acid, 11-amino are more preferred. Undecanoic acid and 12-aminododecanoic acid, particularly preferably caprolactam and 12-aminododecanoic acid.
The amount of lactam or aminocarboxylic acid used for secondary modification is α, β unsaturated carboxylic acid (
The number is preferably 0.1 to 50, more preferably 0.3 to 20, particularly preferably 0.5 to 10, and most preferably 1 to 2 per carboxyl group of (anhydride). When the amount is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.

(B11-3) can be obtained by introducing (b10) a carbonyl group by oxidation with oxygen and / or ozone or hydroformylation with an oxo method.
The introduction of the carbonyl group by the oxidation method can be performed by a known method, for example, the method described in US Pat. No. 3,692,877. Introduction of a carbonyl group by hydroformylation can be carried out by a known method, for example, see Macromolecules, Vol. 31, 5943 page.
(B11-4) can be obtained by secondarily modifying (b11-3) with a lactam or an aminocarboxylic acid.
The lactam and aminocarboxylic acid and preferred ranges thereof are the same as those which can be used in the production of (b11-2). The amount of lactam and aminocarboxylic acid used is the same.

Mn in (b11) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2,500 from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (a). -10,000.
The acid value of (b11) is preferably 4 to 280 (mg KOH / g. In the following, only numerical values are described), more preferably 4 to 100, particularly from the viewpoint of reactivity with (a). Preferably it is 5-50.

As the polyolefin (b12) having a hydroxyl group at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying the polyolefin (b11) having a carbonyl group at both ends of the polymer with hydroxylamine and a mixture of two or more of these are used. it can.
Hydroxylamines that can be used for modification include C2-10 hydroxylamines such as 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-aminobutanol, 5-aminopentanol, 6-amino. Examples include hexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol.
Of these, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-aminohexanol are more preferable, 2-aminoethanol and 4-aminobutanol are particularly preferable. Is 2-aminoethanol.

The amount of hydroxylamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, particularly preferably per residue of α, β unsaturated carboxylic acid (anhydride). Is 0.5 to 1.2, most preferably 1. When the amount of hydroxylamine is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.
Mn of (b12) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably 2,500, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (a). -10,000.
The hydroxyl value of (b12) is preferably 4 to 280 (mg KOH / g. In the following, only numerical values are described), more preferably 4 to 100, particularly from the viewpoint of reactivity with (a). Preferably it is 5-50.

As the polyolefin (b13) having amino groups at both ends of the polymer, a polyolefin having an amino group obtained by modifying the polyolefin (b11) having the carbonyl group at both ends of the polymer with a diamine (Q1), and two or more of these Mixtures can be used.
As diamine (Q1) used for this modification | denaturation, C2-12 diamine etc. can be used, For example, ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, etc. are mentioned.
Among these, ethylenediamine, hexamethylenediamine, heptamethylenediamine and octamethylenediamine are preferable, ethylenediamine and hexamethylenediamine are more preferable, and ethylenediamine is particularly preferable.

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

Mn of (b13) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2,500, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (a). -10,000.
In addition, the amine value of (b13) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (a), more preferably 4 to 100, and particularly preferably. Is 5-50.

  As the polyolefin (b14) having isocyanate groups at both ends, a polyolefin having an isocyanate group obtained by modifying (b12) with poly (2 to 3 or more) isocyanate (hereinafter abbreviated as PI), and a mixture of two or more of these. Can be used. As PI, C (excluding C in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic PI, C2 to 18 aliphatic PI, C4 to 15 alicyclic PI, and C8 to 15 araliphatic PI , Modified products of these PIs, and mixtures of two or more thereof.

  Specific examples of the aromatic PI include 1,3- and / or 1,4-phenylene diisocyanate (diisocyanate is hereinafter abbreviated as DI), 2,4- and / or 2,6-tolylene DI (TDI), crude TDI, 2,4′- and / or 4,4′-diphenylmethane DI (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene DI and the like can be mentioned.

  Specific examples of the aliphatic PI include ethylene DI, tetramethylene DI, hexamethylene DI (HDI), dodecamethylene DI, 2,2,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethyl carbonate. Examples include proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

  Specific examples of the alicyclic PI include isophorone DI (IPDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI (hydrogenated TDI), bis (2- And isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane DI.

  Specific examples of the araliphatic PI include m- and / or p-xylylene DI (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

Examples of the modified PI include urethane-modified, urea-modified, carbodiimide-modified, uretdione-modified, and the like.
Of these, TDI, MDI and HDI are preferred, and HDI is more preferred.

The reaction between (b12) and PI can be carried out in the same manner as a normal urethanization reaction.
The equivalent ratio (NCO / OH ratio) between PI and (b12) in forming the isocyanate-modified polyolefin is usually 1.8 / 1 to 3/1, preferably 2/1.
In order to accelerate the reaction, a catalyst usually used for polyurethane may be used if necessary. Examples of such catalysts include metal catalysts such as tin catalysts [dibutyltin dilaurate, stannous octoate, etc.], lead catalysts [lead 2-ethylhexanoate, lead octenoate, etc.], other metal catalysts [metal naphthenates] (Cobalt naphthenate, etc.), phenylmercuric propionate, etc.]; amine catalysts such as triethylenediamine, diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7 [DBU (San Apro Corporation) Manufactured, registered trademark)], etc.], dialkylaminoalkylamine [dimethylaminoethylamine, dimethylaminooctylamine, etc.], heterocyclic aminoalkylamine [2- (1-aziridinyl) ethylamine, 4- (1-piperidinyl) -2 -Hexylamine etc.] carbonates and organic acid salts (eg formate), N-methyl Beauty - ethylmorpholine, triethylamine, diethyl - and dimethylethanolamine; and use of two or more types of system thereof.
The amount of these catalysts used is usually 3% or less, preferably 0.001 to 2%, based on the total weight of PI and (b12).

  Mn in (b14) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2,500 from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (a). -10,000.

Among the hydrophobic polymers (b), examples of the polyamide (b2) include those obtained by ring-opening polymerization or polycondensation of amide-forming monomers.
Examples of amide forming monomers include lactam (b21), aminocarboxylic acid (b22), and diamine (b23) / dicarboxylic acid (b24).
Examples of the lactam (b21) include C6-12, such as caprolactam, enantolactam, laurolactam, and undecanolactam.
Examples of the ring-opening polymer (b21) include nylon 4, -5, -6, -8 and -12.

As aminocarboxylic acid (b22), C6-12, for example, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12 -Aminododecanoic acid and mixtures thereof.
Examples of the self-polycondensate of (b22) include nylon 7 by polycondensation of ω-aminoenanthic acid, nylon 11 by polycondensation of ω-aminoundecanoic acid, and nylon 12 by polycondensation of 12-aminododecanoic acid. .

Diamine (b23) includes C2-40, such as aliphatic, alicyclic and aromatic (aliphatic) diamines, and mixtures thereof.
Aliphatic diamines include C2-40, such as ethylene diamine, propylene diamine, hexamethylene diamine, decamethylene diamine, 1,12-dodecane diamine, 1,18-octadecane diamine and 1,20-eicosane diamine.
Alicyclic diamines include C5-40, such as 1,3- and 1,4-cyclohexanediamine, isophorone diamine, 4,4'-diaminocyclohexylmethane and 2,2-bis (4-aminocyclohexyl) propane. It is done.
Examples of araliphatic diamines include C7-20, such as (para or meta) xylylenediamine, bis (aminoethyl) benzene, bis (aminopropyl) benzene and bis (aminobutyl) benzene.
Aromatic diamines include C6-40, such as p-phenylenediamine, 2,4- and 2,6-toluylenediamine and 2,2-bis (4,4'-diaminophenyl) propane.

  Examples of the dicarboxylic acid (b24) include C2-40 dicarboxylic acids such as aliphatic dicarboxylic acids, aromatic ring-containing dicarboxylic acids, alicyclic dicarboxylic acids, derivatives of these dicarboxylic acids [for example, acid anhydrides, lower (C1-4 ) Alkyl esters and dicarboxylates [alkali metal (eg, lithium, sodium and potassium) salts]] and mixtures of two or more thereof.

Examples of the aliphatic dicarboxylic acid include C2-40 (preferably 4 to 20, more preferably 6-12 from the viewpoint of antistatic properties), such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Examples include sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid and itaconic acid.
Examples of the aromatic ring-containing dicarboxylic acid include C8-40 (preferably 8 to 16, more preferably 8-14 from the viewpoint of antistatic properties), such as ortho-, iso- and terephthalic acid, 2,6- and -2, Examples include 7-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, tolylene dicarboxylic acid, xylylene dicarboxylic acid and 5-sulfoisophthalic acid alkali metal (same as above) salts.
As alicyclic dicarboxylic acid, C5-40 (preferably 6-18, more preferably 8-14 from the viewpoint of antistatic properties), for example, cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, Examples include dicyclohexyl-4,4'-dicarboxylic acid and camphoric acid. Of these, aliphatic dicarboxylic acids and aromatic ring-containing dicarboxylic acids are preferable from the viewpoint of antistatic properties, and adipic acid, sebacic acid, terephthalic acid, isophthalic acid, and sodium 3-sulfoisophthalate are more preferable.
Among the dicarboxylic acid derivatives, examples of the acid anhydride include anhydrides of the above dicarboxylic acids, such as maleic anhydride, itaconic anhydride and phthalic anhydride; examples of lower (C1-4) alkyl esters include lower alkyl esters of the above dicarboxylic acids, such as Mention is made of dimethyl adipate and ortho-, iso- and dimethyl terephthalate.

Polycondensates of diamines and dicarboxylic acids include nylon 66, -610, -69 or -612, respectively, and tetramethylene by polycondensation of hexamethylenediamine and adipic acid, sebacic acid, azelaic acid or dodecanedioic acid. Mention may be made of nylon 46 or MXD6 by polycondensation of diamine or metaxylylenediamine and adipic acid.
Examples of the copolymer nylon include nylon 6/66 (adipic acid / hexamethylenediamine nylon salt and caprolactam copolymer) and nylon 6/12 (12-aminododecanoic acid and caprolactam copolymer). .

Of the amide-forming monomers, caprolactam, 12-aminododecanoic acid, adipic acid / metaxylylenediamine and adipic acid /
Hexamethylenediamine, more preferably caprolactam.

The production method of the polyamide (b2) is one or more of the dicarboxylic acid (b24) (C2-40, preferably 4-20) or the diamine (b23) (C2-40, preferably 4-20). May be used as a molecular weight modifier, and in the presence thereof, the amide-forming monomer may be subjected to ring-opening polymerization or polycondensation.
Examples of the C2-40 diamine include those exemplified as the above (b23). Of these, aliphatic diamines are preferable from the viewpoint of reactivity with other amide-forming monomers, and hexamethylenediamine is more preferable. And decamethylenediamine.
Examples of the C2-40 dicarboxylic acid include those exemplified as the above (b24). Among these, aliphatic dicarboxylic acids and aromatic ring-containing dicarboxylic acids are preferable from the viewpoint of reactivity with other amide-forming monomers. Acids, more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate.

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

  Mn of the polyamide (b2) is preferably 200 to 5,000, more preferably 500 to 4,000 from the viewpoint of moldability and production of an antistatic antistatic agent.

  Of the hydrophobic polymer (b), the polyamideimide (b3) includes the amide-forming monomer, and a trivalent or tetravalent aromatic polymer that can form at least one imide ring with the amide-forming monomer. Carboxylic acid or its anhydride [hereinafter abbreviated as aromatic polycarboxylic acid (anhydride). (Hereinafter sometimes referred to as an amidoimide-forming monomer), and mixtures thereof. The diamine (b23) and the dicarboxylic acid (b24) can also be used as a molecular weight modifier during polymerization.

  Examples of the aromatic polycarboxylic acid (anhydride) include monocyclic (C9-12) and polycyclic (C13-20) carboxylic acids such as trivalent [monocyclic (trimellitic acid, etc.), polycyclic (1,2 , 5- and 2,6,7-naphthalenetricarboxylic acid, 3,3 ′, 4-biphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tricarboxylic acid, diphenylsulfone-3,3 ′, 4-tricarboxylic acid, Diphenyl ether-3,3 ′, 4-tricarboxylic acid and the like, and their anhydrides] carboxylic acid; and tetravalent [monocyclic (pyromellitic acid etc.), polycyclic (biphenyl-2,2 ′, 3,3 ′] -Tetracarboxylic acid, benzophenone-2,2 ', 3,3'-tetracarboxylic acid, diphenylsulfone-2,2', 3,3'-tetracarboxylic acid, diphenylether-2,2 ', 3,3 - tetracarboxylic acid, etc.), and these anhydrides], and carboxylic acids.

As a method for producing the polyamideimide (b3), as in the case of the polyamide (b2), one or more of the dicarboxylic acid (C2-40) or the diamine (C2-40) is used as a molecular weight modifier, Examples thereof include a method of ring-opening polymerization or polycondensation of the amidoimide-forming monomer in the presence thereof. Preferred among the dicarboxylic acid and diamine are the same as in the case of (b2).
The amount of the molecular weight modifier used is preferably based on the weight of the amide imide-forming monomer and the total molecular weight modifier, the lower limit is from the viewpoint of antistatic properties of the molded product described later, and the upper limit is from the viewpoint of heat resistance of the molded product. Is from 2 to 80%, more preferably from 4 to 75%.

  Mn of (b3) is preferably 200 to 5,000, more preferably 500 to 4,000 from the viewpoint of moldability and production of an antistatic agent.

  The Mn of the hydrophobic polymer (b) is preferably 200 to 25,000, more preferably 500 to 20,000, and particularly preferably 1,000 to 15,000.

[Block polymer (A)]
In the block polymer (A) in the present invention, the hydrophilic polymer (a) block and the hydrophobic polymer (b) block are composed of an ester bond, an amide bond, an ether bond, a urethane bond and an imide bond. It has a structure in which they are alternately and repeatedly bonded through at least one selected bond.
The proportion of the block (a) based on the weight of (A) is preferably 20 to 80%, more preferably 30 to 70% from the viewpoint of antistatic properties and moldability of the antistatic resin composition described later. is there.

  Of the bonds between the blocks (a) and (b), an ester bond, an amide bond and an imide bond are formed, for example, by a reaction between the polyether (a1) and the hydrophobic polymer (b). For example, the epoxy-modified product obtained by reacting a polyether diol (a11) with an epihalohydrin and a polyolefin (b12) having hydroxyl groups at both ends of the polymer are formed. It is formed by reaction with a polyolefin (b14) having isocyanate groups at both ends.

  The Mn of the block polymer (A) is preferably 2,000 to 100,000, more preferably 5,000 to 60,000, and particularly preferably 10,000 to 40,000.

[Anionic surfactant (B)]
(B) in the present invention is represented by the following general formula (1).

(R−) _n X ⁻ · Z ⁺ (1)

In the formula, R represents a C8-30 (preferably C10-24, more preferably C12-21) monovalent hydrocarbon group. When R is less than C8, the appearance of the molded product described later is deteriorated, and when it exceeds 30, the antistatic property is deteriorated.
Examples of R include an alkyl group, an alkenyl group, an alkylaryl group, and an arylalkyl group.
Examples of the alkyl group include octyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl and triacontyl groups;
Examples of the alkenyl group include octenyl, decenyl, dodecenyl, pentadecenyl, octadecenyl, eicocenyl and triacontenyl groups;
Examples of the alkylaryl group include ethylphenyl, pentylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, pentadecylphenyl, octadecylphenyl, eicosylphenyl and tetracosylphenyl groups;
Examples of the arylalkyl group include phenylethyl, phenylpentyl, phenyldecyl, phenylnonyl, phenyldodecyl, phenylpentadecyl, phenyloctadecyl, phenyleicosyl and phenyltetracosyl groups.
Of the above R, from the viewpoint of antistatic properties, alkyl groups and alkylaryl groups are preferred, C12-21 alkylaryl groups are more preferred, and dodecylphenyl and pentadecylphenyl groups are particularly preferred.

In the formula, n represents 1 or 2. When n is 1, the case where X ⁻ described later is an anion obtained by removing a proton from a sulfonic acid group, a sulfinic acid group, a sulfuric ester group, a carboxyl group and / or a phosphite group is mentioned. In some cases, X ⁻ is an anion obtained by removing a proton from a phosphate group. Further, when n is 2, the plurality of R may be the same or different.

In the formula, X ⁻ represents an anion obtained by removing a proton from at least one group selected from the group consisting of a sulfonic acid group, a sulfinic acid group, a sulfate ester group, a carboxyl group, a phosphate ester group, and a phosphite ester group. Represent. Of these groups, sulfonic acid groups, sulfinic acid groups and sulfate ester groups are preferred from the viewpoint of antistatic properties, sulfonic acid groups and sulfate ester groups are more preferred, and sulfonic acid groups are particularly preferred.

In the formula, Z ⁺ represents a cation selected from the group consisting of amidinium, pyridinium, pyrazolium and guanidinium cations.
The following are mentioned as an amidinium cation.
[1] Imidazolinium cation C5-15, for example 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium, 1,3-dimethyl-2,4-diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1-methyl-2,3,4-triethylimidazolinium, 1,2,3 , 4-tetraethylimidazolinium, 1,2,3-trimethylimidazolinium, 1,3-dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium, 1,2,3 -Triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium, 3-cyanomethyl-1,2-dimethylimidazolinium, 2-sia Nomethyl-1,3-dimethylimidazolinium, 4-acetyl-1,2,3-trimethylimidazolinium, 3-acetylmethyl-1,2-dimethylimidazolinium, 4-methylcarbooxymethyl-1,2 , 3-trimethylimidazolinium, 3-methylcarbooxymethyl-1,2-dimethylimidazolinium, 4-methoxy-1,2,3-trimethylimidazolinium, 3-methoxymethyl-1,2-dimethylimidazole Linium, 4-formyl-1,2,3-trimethylimidazolinium, 3-formylmethyl-1,2-dimethylimidazolinium, 3-hydroxyethyl-1,2-dimethylimidazolinium, 4-hydroxymethyl -1,2,3-trimethylimidazolinium, 2-hydroxyethyl-1,3-dimethylimidazole Bromide;

[2] Imidazolium cation C5-15, such as 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1,2 , 3-trimethylimidazolium, 1,2,3,4-tetramethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1,3-dimethyl-2-ethylimidazolium, 1,2-dimethyl- 3-ethyl-imidazolium, 1,2,3-triethylimidazolium, 1,2,3,4-tetraethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzyl Imidazolium, 1-benzyl-2,3-dimethyl-imidazolium, 4-cyano-1,2,3-trimethylimidazole Lithium, 3-cyanomethyl-1,2-dimethylimidazolium, 2-cyanomethyl-1,3-dimethyl-imidazolium, 4-acetyl-1,2,3-trimethylimidazolium, 3-acetylmethyl-1,2- Dimethylimidazolium, 4-methylcarbooxymethyl-1,2,3-trimethylimidazolium, 3-methylcarbooxymethyl-1,2-dimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 3-methoxymethyl-1,2-dimethylimidazolium, 4-formyl-1,2,3-trimethylimidazolium, 3-formylmethyl-1,2-dimethylimidazolium, 3-hydroxyethyl-1,2-dimethyl Imidazolium, 4-hydroxymethyl-1,2,3-
Trimethylimidazolium, 2-hydroxyethyl-1,3-dimethylimidazolium;

[3] Tetrahydropyrimidinium cation C6-15, such as 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyri Midinium, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium 1,8-diazabicyclo [5,4,0] -7-undecenium, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium, 1,5-diazabicyclo [4,3,0 ] -5-nonenium, 5-methyl-1,5-diazabicyclo [4,3,0] -5-nonenium, 4-cyano-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidi Ni, 3 -Cyanomethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-cyanomethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-acetyl-1 , 2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-acetylmethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-methylcarbooxymethyl -1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-methylcarbooxymethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4- Methoxy-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-methoxymethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidi 4-formyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-formylmethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium 3-hydroxyethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-hydroxymethyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium 2-hydroxyethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium;

[4] Dihydropyrimidinium cation C6-20, such as 1,3-dimethyl-1,4- or -1,6-dihydropyrimidinium [these are 1,3-dimethyl-1,4 (6)- This is expressed as dihydropyrimidinium, and the same notation is used hereinafter. 1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4 (6) -dihydropyrimidinium, 1,2,3 5-tetramethyl-1,4 (6) -dihydropyrimidinium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,9 (10) -undecadienium, 5-methyl- 1,5-diazabicyclo [4,3,0] -5,7 (8) -nonadienium, 4-cyano-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3-cyanomethyl- 1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 2-cyanomethyl-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 4-acetyl-1,2,3- Trimethyl-1,4 (6) -dihydropyrimidinium, 3 Acetylmethyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-methylcarbooxymethyl-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3- Methylcarbooxymethyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-methoxy-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3-methoxy Methyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-formyl-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3-formylmethyl-1 , 2-Dimethyl-1,4 (6) -dihydropyrimidinium, 3-hydroxyethyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-hydroxymethyl-1,2,3 Trimethyl-1,4 (6) - dihydropyrimidinium, 1,3 2-hydroxyethyl dimethyl-1,4 (6) - hydro pyrimidinium.

Examples of the pyridinium cation include C6-20, such as 3-methyl-1-propylpyridinium, 1-propyl-3-methylpyridinium, 1-butyl-3-methylpyridinium, 1-butyl-4-methylpyridinium, 1-butyl- Examples include 3,4-dimethylpyridinium and 1-butyl-3,5-dimethylpyridinium.

  Examples of the pyrazolium cation include C5-15, such as 1,2-dimethylpyrazolium, 1-methyl-2-propylpyrazolium, 1-n-butyl-2-methylpyrazolium, 1-n-butyl. -2-Ethylpyrazolium.

The following are mentioned as a guanidinium cation.
[1] Guanidinium cation having imidazolinium skeleton C8-15, such as 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, 2-diethylamino-1-methyl-3,4-diethylimidazolinium 2-diethylamino-1,3,4-tetraethylimidazolinium, 2-dimethylamino-1,3-dimethylimidazolinium, 2-diethylamino-1,3-dimethylimidazolinium, 2-dimethylamino-1- Ethyl-3-methylimidazolinium, 2-diethylamino-1,3-diethylimidazole Linium, 1,5,6,7-tetrahydro-1,2-dimethyl-2H-imide [1,2a] imidazolinium, 1,5-dihydro-1,2-dimethyl-2H-imide [1,2a] Imidazolinium, 1,5,6,7-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolinium, 1,5-dihydro-1,2-dimethyl-2H-pyrimido [1, 2a] imidazolinium, 2-dimethylamino-4-cyano-1,3-dimethylimidazolinium, 2-dimethylamino-3-cyanomethyl-1-methylimidazolinium, 2-dimethylamino-4-acetyl-1 , 3-Dimethylimidazolinium, 2-dimethylamino-3-acetylmethyl-1-methylimidazolinium, 2-dimethylamino-4-methylcarbooxymethyl 1,3-dimethylimidazolinium, 2-dimethylamino-3-methylcarbooxymethyl-1-methylimidazolinium, 2-dimethylamino-4-methoxy-1,3-dimethylimidazolinium, 2-dimethylamino -3-methoxymethyl-1-methylimidazolinium, 2-dimethylamino-4-formyl-1,3-dimethylimidazolinium, 2-dimethylamino-3-formylmethyl-1-methylimidazolinium, 2- Dimethylamino-3-hydroxyethyl-1-methylimidazolinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolinium;

[2] Guanidinium cation having imidazolium skeleton C8-15, such as 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, 2-diethylamino-1-methyl-3,4-diethylimidazolium, 2-diethylamino-1 , 3,4-tetraethylimidazolium, 2-dimethylamino-1,3-dimethylimidazolium, 2-diethylamino-1,3-dimethylimidazolium, 2-dimethylamino-1-ethyl-3-methylimidazolium, 2 -Diethylamino-1,3-diethylimidazolium, 1,5,6, 7-tetrahydro-1,2-dimethyl-2H-imide [1,2a] imidazolium, 1,5-dihydro-1,2-dimethyl-2H-imide [1,2a] imidazolium, 1,5,6, 7-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolium, 1,5-dihydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolium, 2-dimethylamino-4 -Cyano-1,3-dimethylimidazolium, 2-dimethylamino-3-cyanomethyl-1-methylimidazolium, 2-dimethylamino-4-acetyl-1,3-dimethylimidazolinium, 2-dimethylamino-3 -Acetylmethyl-1-methylimidazolium, 2-
Dimethylamino-4-methylcarbooxymethyl-1,3-dimethylimidazolium, 2-dimethylamino-3-methylcarbooxymethyl-1-methylimidazolium, 2-dimethylamino-4-methoxy-1,3-dimethyl Imidazolium, 2-dimethylamino-3-methoxymethyl-1-methylimidazolium, 2-dimethylamino-4-formyl-1,3-dimethylimidazolium, 2-dimethylamino-3-formylmethyl-1-methylimidazole Lithium, 2-dimethylamino-3-hydroxyethyl-1-methylimidazolium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolium;

[3] Guanidinium cation having tetrahydropyrimidinium skeleton C10-20, such as 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, 2-dimethyl Amino-1-methyl-3,4-diethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1-methyl-3,4-diethyl-1,4,5,6-tetrahydropyrimidi Ni, 2-diethylamino-1,3,4-tetraethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-1,3-dimethyl Til-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl -1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-diethyl-1,4,5,6-tetrahydropyrimidinium, 1,3,4,6,7,8-hexahydro -1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,3,4,6-tetrahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,3,4,6 , 7,8-Hexahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 1,3,4,6-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidi , 2-dimethylamino-4-cyano-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-cyanomethyl-1-methyl-1,4,5,6 -Tetrahydropyrimidinium, 2-dimethylamino-4-acetyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-acetylmethyl-1-methyl-1 , 4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-methylcarbooxymethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3- Methylcarbooxymethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-methoxy-1,3-dimethyl-1,4 5,6-tetrahydropyrimidinium, 2-dimethylamino-3-methoxymethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-formyl-1,3-dimethyl -1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-formylmethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-hydroxyethyl -1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium;

[4] Guanidinium cation having dihydropyrimidinium skeleton C10-20, such as 2-dimethylamino-1,3,4-trimethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1, 3,4-trimethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-1 -Methyl-3,4-diethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1-methyl-3,4-diethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino -1,3,4-tetraethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-1,3-dimethyl-1,4 (6) -dihydropyrimidinium 2-diethylamino-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl-1,4 (6) -dihydropyrimidinium, -Diethylamino-1,3-diethyl-1,4 (6) -dihydropyrimidinium, 1,6,7,8-tetrahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,6 -Dihydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,6,7,8-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 1,6-dihydro -1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2-dimethylamino-4-cyano-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-dimethyl Ruamino-3-cyanomethyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-acetyl-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2 -Dimethylamino-3-acetylmethyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-methylcarbooxymethyl-1,3-dimethyl-1,4 (6)- Dihydropyrimidinium, 2-dimethylamino-3-methylcarbooxymethyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-methoxy-1,3-dimethyl-1, 4 (6) -dihydropyrimidinium, 2-dimethylamino-3-methoxymethyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino- -Formyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-formylmethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2 -Dimethylamino-3-hydroxyethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-1,4 (6) -dihydro Pyrimidinium.

  Of these, an amidinium cation is preferable from the viewpoint of antistatic properties, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

The melting point of the anionic surfactant (B) in the present invention by a differential scanning calorimeter (DSC) is preferably 30 to 180 ° C., more preferably 50 to 150 ° C. from the viewpoint of the appearance of the molded product and antistatic properties. .
Here, the melting point refers to the melting peak temperature measured using DSC according to JIS K7122 (transition heat measurement method). Examples of the DSC include DSC2910 [trade name, manufactured by T.A. Instruments Co., Ltd.].

Among the anionic surfactants (B), specific examples of sulfonates include imidazolium salts of alkane sulfonic acids (1-ethyl-3-methylimidazolium salts of dodecane sulfonic acid and pentadecane sulfonic acid and 1,3 -Dimethyl-2-ethylimidazolium salt, etc.), alkene sulfonic acid imidazolium salt (dodecenesulfonic acid and pentadecenesulfonic acid 1-ethyl-3-methylimidazolium salt and 1,3-dimethyl-2-ethyl salt) Imidazolium salts, etc.), imidazolium salts of alkylarene sulfonic acids (1-ethyl-3-methylimidazolium salt and 1,3-dimethyl-2-ethylimidazolium salt of dodecylbenzenesulfonic acid and pentadecylbenzenesulfonic acid, respectively) Etc.), imidazo of arylalkanesulfonic acid Umushio (phenyl each 1-ethyl-3-methylimidazolium salt of dodecanoic acid and phenyl pentadecane sulfonic acid and 1,3-dimethyl-2-ethyl imidazolium salt, etc.) and the like.
Of these, from the viewpoint of antistatic properties and appearance of the molded product, imidazolium salts of alkylarene (C8-30) sulfonic acid are preferable, and 1-ethyl-3-methylimidazole of dodecylbenzenesulfonic acid is more preferable. The 1-ethyl-3-methylimidazolium salt and the 1,3-dimethyl-2-ethylimidazolium salt of the lithium salt and 1,3-dimethyl-2-ethylimidazolium salt, pentadecanebenzenesulfonic acid.

[Antistatic agent]
The antistatic agent of the present invention comprises the block polymer (A) and an anionic surfactant (B).
The weight ratio of (A) to (B) is preferably 80/20 to 99/1, more preferably 85/15 to 95/5, from the viewpoint of the appearance and antistatic property of the molded product described later.
The method for producing the antistatic agent of the present invention includes a method for producing (A) in the presence of (B), and a method for post-adding (B) to (A). From the viewpoint of dispersibility of (B) in (A), a method for producing (A) in the presence of (B) is preferred.
In the method for producing (A) in the presence of (B), the timing of incorporating (B) during the production of (A) is not particularly limited, and may be any before polymerization and / or during polymerization, but before polymerization. It is preferable to make it contain in a raw material.

[Antistatic resin composition]
The antistatic resin composition of the present invention comprises the above-described antistatic agent in the thermoplastic resin (C). The antistatic agent of the present invention in the composition may be prepared by mixing (A) and (B) in advance and containing this in (C), or separately (A) and (B) in (C). Either may be included. Of these, the former is preferable from the viewpoint of imparting antistatic properties.
(C) includes polyphenylene ether resin (C1); vinyl resin [polyolefin resin (C2) [for example, polypropylene, polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin], poly (meta ) Acrylic resin (C3) [eg polymethyl methacrylate], polystyrene resin (C4) [vinyl group-containing aromatic hydrocarbon alone or vinyl group-containing aromatic hydrocarbon, (meth) acrylic acid ester, (meth) acrylonitrile and Copolymers having at least one selected from the group consisting of butadiene as structural units, such as polystyrene, styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / Butadiene / su Lene copolymer (MBS resin), styrene / methyl methacrylate copolymer (MS resin)], etc.]; Polyester resin (C5) [eg, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene Adipate]; polyamide resin (C6) [for example, nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12]; polycarbonate resin (C7) [for example, polycarbonate , Polycarbonate / ABS alloy resin]; polyacetal resin (C8), and a mixture of two or more thereof.

  Of these, (C1), (C2), (C3), (C4), (C), (C1), (C2), (C4), (C7) and more preferred are (C2), (C4) and (C7).

  The weight ratio of the antistatic agent of the present invention to (C) is preferably 1/99 to 30/70, more preferably 5/95 to 20/80, from the viewpoint of antistatic properties and mechanical properties of the molded product. .

Examples of the polyphenylene ether resin (C1) include poly (1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene). ) Ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4) -Phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1, 4-phenylene) ether, poly (2,6-dibromo-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly 2,6-dichloro-1,4-phenylene) ether, poly (2,6-dibenzyl-1,4-phenylene) ether, poly (2,5-dimethyl-1,4-phenylene) ether.
Also, (C1) includes those obtained by grafting the above styrene and / or its derivative monomer (modified polyphenylene ether) to (C1).

  As the vinyl resins [(C2) to (C4)], those obtained by (co) polymerizing the following vinyl monomers by various polymerization methods (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.) Is mentioned.

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

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

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

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

  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 (methyl vinyl ether, ethyl vinyl ether, etc.). Halogen-containing vinyl monomers include C2-12, such as vinyl chloride, vinylidene chloride and chloroprene.

Examples of the polyolefin resin (C2) include polypropylene, polyethylene, propylene-ethylene copolymer [copolymerization ratio (weight ratio) = 0.1 / 99.9 to 99.9 / 0.1], propylene and / or ethylene. And other α-olefin (C4-12) copolymers (random and / or block addition) [copolymerization ratio (weight ratio) = 99 / 1-5 / 95], ethylene / vinyl acetate Copolymer (EVA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40], ethylene / ethyl acrylate copolymer (EEA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40 ].
Among these, from the viewpoint of imparting antistatic properties, polypropylene, polyethylene, propylene-ethylene copolymer, propylene and / or 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 (C2) is preferably 0.5 to 150, more preferably 1 to 100 from the viewpoint of imparting resin physical properties and antistatic properties. Here, MFR is according to JISK7210 (1994) (in the case of polypropylene: 230).
° C, load 2.16 kgf, polyethylene: 190 ° C, load 2.16 kgf).
The crystallinity of (C2) is preferably 0 to 98%, more preferably 0 to 80%, and particularly preferably 0 to 70% from the viewpoint of antistatic properties.
Here, the degree of crystallinity is measured by methods such as X-ray diffraction and infrared absorption spectrum [Refer to “Solid Structure of Polymers—Lecture of Polymer Experiments 2” (Hatsugoro Nanshino), page 42, published by Kyoritsu Shuppan 1958. ].

  Examples of the poly (meth) acrylic resin (C3) include one or two or more (co) polymers [methyl poly (meth) acrylate, poly (meth) butyl butyl, etc.] of the acrylic monomers and the like. Copolymer with one or more of the above-mentioned vinyl monomers copolymerizable with one or more of the monomers [copolymerization ratio (weight ratio) is preferably 5/95 to 95/5, more preferably 50 from the viewpoint of resin physical properties. / 50 to 90/10] [however, those included in (C2) are excluded].

  The MFR of (C3) is preferably 0.5 to 150, more preferably 1 to 100 from the viewpoint of resin physical properties. Here, the MFR is measured according to JIS K7210 (1994) [230 ° C., load 1.2 kgf for poly (meth) acrylic resin].

As the polystyrene resin (C4), a vinyl group-containing aromatic hydrocarbon alone or a vinyl group-containing aromatic hydrocarbon, and at least one selected from the group consisting of (meth) acrylic acid ester, (meth) acrylonitrile and butadiene Examples thereof include a copolymer as a structural unit.
Examples of the vinyl group-containing aromatic hydrocarbon 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 (C4) include polystyrene, polyvinyltoluene, styrene / acrylonitrile copolymer (AS resin) [copolymerization ratio (weight ratio) = 70/30 to 80/20], styrene / methyl methacrylate copolymer. (MS resin) [copolymerization ratio (weight ratio) = 60/40 to 90/10], styrene / butadiene copolymer [copolymerization ratio (weight ratio) = 60/40 to 95/5], acrylonitrile / butadiene / Styrene copolymer (ABS resin) [copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)], methyl methacrylate / butadiene / styrene copolymer (MBS resin) [Copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)].

  The MFR of (C4) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoints of resin physical properties and antistatic properties. Here, the MFR is measured in accordance with JIS K7210 (1994) (in the case of polystyrene resin, 230 ° C., load 1.2 kgf).

  Examples of the polyester resin (C5) include aromatic ring-containing polyesters (polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, etc.) and aliphatic polyesters (polybutylene adipate, polyethylene adipate, poly-ε-caprolactone, etc.).

  The intrinsic viscosity [η] of (C5) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, and particularly preferably from 0.3 to 3 from the viewpoints of resin physical properties and antistatic properties. [Η] is measured with a Ubbelohde 1A viscometer at 25 ° C. for a 0.5 wt% orthochlorophenol solution of the polymer.

  As the polyamide resin (C6), a lactam ring-opening polymer (C61), a dehydration polycondensation product of diamine and dicarboxylic acid (C62), a self-polycondensation product of aminocarboxylic acid (C63), and a poly (condensation) combination thereof. Examples thereof include copolymer nylon having two or more types of monomer units.

Examples of the lactam in (C61) include those exemplified as the above (b21), and examples of (C61) include nylon 4, -5, -6, -8 and -12.
Examples of the diamine and dicarboxylic acid in (C62) include those exemplified as the above (b23) and (b24). Examples of (C62) include nylon 66 and hexamethylenediamine obtained by condensation polymerization of hexanemethylenediamine and adipic acid. Examples thereof include nylon 610 by polycondensation of sebacic acid.
Examples of the aminocarboxylic acid in (C63) include those exemplified as the above (b22). Examples of (C63) include nylon 7 by polycondensation of aminoenanthic acid, nylon 11 by polycondensation of ω-aminoundecanoic acid, Nylon 12 and the like by polycondensation of 12-aminododecanoic acid.

In the production of (C6), a molecular weight modifier may be used, and examples of the molecular weight modifier include the diamines and / or dicarboxylic acids exemplified as the above (b23) and (b24).
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 3- Sodium sulfoisophthalate. Of the diamines as molecular weight regulators, hexamethylene diamine and decamethylene diamine are preferable.

The MFR of (C6) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. Here, MFR is JISK7210 (199
4 years) (in the case of polyamide resin, 230 ° C., load 0.325 kgf).

Polycarbonate resins (C7) include bisphenol compounds (C12-20, such as bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane) and dihydroxybiphenyl polycarbonates such as bisphenol and phosgene or A condensate with a carbonic acid diester is mentioned. Of the bisphenol compounds, bisphenol A is preferable from the viewpoint of dispersibility of the block polymer (A).
The MFR of (C7) is preferably 0.5 to 150 from the viewpoint of resin physical properties and antistatic properties.
More preferably, it is 1-100. Here, MFR is JISK7210 (1
994) (in the case of polycarbonate resin, 280 ° C., load 2.16 kgf).

Examples of the polyacetal resin (C8) include formaldehyde or trioxane homopolymer (polyoxymethylene homopolymer), and a copolymer of formaldehyde or trioxane and a cyclic ether [the above-mentioned AO (EO, PO, dioxolane, etc.)] (polyoxy). And methylene / polyoxyethylene copolymer [polyoxymethylene / polyoxyethylene (weight ratio) = 90/10 to 99/1 block copolymer and the like].
The MFR of (C8) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. Here, MFR is JISK7210 (1
994) (in the case of polyacetal resin, 190 ° C., load 2.16 kgf).
Intrinsic viscosity [η] of (C8) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, and particularly preferably from 0.3 to 3, from the viewpoint of resin physical properties and antistatic properties.

In the antistatic resin composition of the present invention, an antistatic property improver (D1), a compatibilizer (D2), a flame retardant (D3) other than the above (B) is necessary as long as the effects of the present invention are not impaired. ) And other additives for resin (D4), one or more additives (D) selected from the group consisting of additives may be contained.
The antistatic property improver (D1) includes one or two selected from the group consisting of an alkali metal or alkaline earth metal salt (D11), a surfactant (D12) and / or an ionic liquid (D13). The above is included.

  As (D11), organic acids (C1-7 mono- and di-carboxylic acids) of alkali metals (lithium, sodium, potassium, etc.) and / or alkaline earth metals (magnesium, calcium, etc.) excluding (B) above Salts of acids such as formic acid, acetic acid, propionic acid, oxalic acid, succinic acid; C1-7 sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid; thiocyanic acid, and inorganic acids (hydrohalic acid, For example, salts of hydrochloric acid, hydrobromic acid; perchloric acid; sulfuric acid; nitric acid; phosphoric acid) can be used.

Specific examples of (D11) 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,- Such as lithium, -magnesium and -calcium), trifluoromethanesulfonate (such as lithium trifluoromethanesulfonate, -sodium, -potassium, -magnesium and -calcium), pentafluoroethanesulfonate (lithium pentafluoroethanesulfonate, -Sodium, -potassium, -magnesium and -calcium), nonafluorobutane sulfonate (such as lithium nonafluorobutane sulfonate, -sodium, -potassium, -magnesium and -calcium), undecafluoropentane sulfonate ( Undecafluoropentanesulfonate lithium, -sodium, -potassium, -magnesium and -calcium, etc.), tridecafluorohexanesulfonate (tridecafluorohexanesulfate) Lithium acetate, -sodium, -potassium, -magnesium and -calcium), acetates (lithium acetate, -sodium, -potassium, -magnesium and -calcium etc.), sulfates (sodium sulfate, -potassium, -magnesium and -Calcium etc.), phosphate (sodium phosphate, -potassium, -magnesium, -calcium etc.), thiocyanate (potassium thiocyanate etc.), etc. are mentioned.
Of these, from the viewpoint of antistatic properties, preferred are halides, perchlorates, trifluoromethanesulfonates, acetates, and more preferred are lithium chloride, -potassium and -sodium, lithium perchlorate, -potassium and -Sodium, lithium trifluoromethanesulfonate,-potassium and-sodium, potassium acetate.

The use amount of (D11) is preferably 0.001 to 0.001 based on the total weight of (A), (B), and (C) from the viewpoint of giving a resin molded article having a good appearance without precipitating on the resin surface. It is 3%, more preferably 0.01 to 2.5%, particularly preferably 0.1 to 2%, and most preferably 0.15 to 1%.
Although there is no particular limitation on the method of adding (D11), it is preferable to disperse in the block polymer (A) in advance from the viewpoint of ease of effective dispersion in the composition.
When (D11) is dispersed in (A), it is particularly preferable to add (D11) in advance during the production (polymerization) of (A). The timing for adding (D11) during the production of (A) is not particularly limited, and may be any before, during or after polymerization.

Examples of the surfactant (D12) include nonionic, anionic, cationic and amphoteric surfactants excluding (B), and mixtures thereof.
Nonionic surfactants include, for example, EO addition type nonionic surfactants [for example, higher alcohols (C8-18, the same shall apply hereinafter), higher fatty acids (C8-24, the same shall apply hereinafter) or higher alkylamines (C8-24). ) EO adduct (molecular weight 158 or more and Mn 200,000 or less); higher fatty acid ester of polyalkylene glycol (molecular weight 150 or more and Mn 6,000 or less) which is an EO adduct of glycol; polyhydric alcohol (C2-18-2) EO adduct of higher fatty acid ester (molecular weight of 250 or more and Mn of 30,000 or less); EO adduct of higher fatty acid amide (molecular weight of 200 or more and Mn 30,000 or less); and polyhydric alcohols (as described above) EO adduct of alkyl (C3-60) ether (molecular weight of 120 or more and Mn of 30,000 or less)], and polyhydric alcohol (the above) (C3-60) type nonionic surfactant [for example, polyvalent Fatty acid (C3-60) ester of alcohol, alkyl (C3-60) ether of polyhydric alcohol and fatty acid (C3-60) alkanolamide].

Examples of the anionic surfactant are those excluding (B) and (D11), and examples thereof include sodium dodecylbenzenesulfonate.
Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts.
Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine.
These surfactants may be used alone or in combination of two or more.

  Salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and group IIB metals (zinc, etc.); Ammonium salts; and amine salts [alkylamine (C1-720) salts and alkanolamine (C2-12, such as mono-, di- and triethanolamine) salts, etc.] and quaternary ammonium salts [except (B) ] Is included.

The amount of (D12) used is preferably 0.001 to 5%, more preferably 0.01 to 3%, and particularly preferably 0.001% based on the total weight of (A), (B) and (C). 1 to 2.5%.
The method of adding (D12) is also not particularly limited, but it is preferable to disperse in (A) in advance in order to effectively disperse it in the resin composition. Further, when (D12) is dispersed in (A), it is particularly preferable to add (D12) in advance during the production (polymerization) of (A). The timing for adding (D12) during the production of (A) is not particularly limited, and may be any before, during or after polymerization.

  The ionic liquid (D13) is a compound other than the above (B), the above (D11) and (D12), and has a melting point of room temperature or lower, and at least one of cations or anions constituting (D13). One is an organic ion, and a normal temperature molten salt having an initial conductivity of 1 to 200 ms / cm (preferably 10 to 200 ms / cm), for example, a normal temperature molten salt described in WO95 / 15572.

The amount of (D13) used is preferably 0.001 to 5%, more preferably 0.01 to 3%, and particularly preferably 0.001% based on the total weight of (A), (B) and (C). 1 to 2.5%.
The method of adding (D13) is also not particularly limited, but it is preferable to disperse in (A) in advance in order to effectively disperse it in the resin composition. Further, when (D13) is dispersed in (A), it is particularly preferable to add (D13) in advance during the production (polymerization) of (A). The timing for adding (D13) during the production of (A) is not particularly limited, and may be any before, during or after polymerization.

As the compatibilizing agent (D2), a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group is used. Examples thereof include polymers described in JP-A-3-258850. Further, for example, a modified vinyl polymer having a sulfonic acid group described in JP-A-6-345927, a block polymer having a polyolefin portion and an aromatic vinyl polymer portion, and the like can be used.
The amount of (D2) used is usually 20% or less based on the total weight of (A), (B) and (C), preferably from 0.1 to 15 from the viewpoint of the compatibilizing effect and the mechanical properties of the molded product. %, More preferably 1 to 10%, particularly preferably 1.5 to 8%.
The method of adding (D2) is not particularly limited, but it is preferable to disperse it in advance in the block polymer (A) from the viewpoint of ease of effective dispersion or dissolution in the composition.
When (D2) is dispersed or dissolved in (A), it is particularly preferable to add (D2) in advance during the production (polymerization) of (A). The timing of adding (D2) during the production of (A) is not particularly limited, and may be any before, during or after polymerization.

  The flame retardant (D3) includes a halogen-containing flame retardant (D31), a nitrogen-containing flame retardant (D32), a sulfur-containing flame retardant (D33), a silicon-containing flame retardant (D34), and a phosphorus-containing flame retardant (D35). 1 type or 2 types or more of flame retardants chosen from these are included.

  Examples of the halogen-containing flame retardant (D31) include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, tetrabromobisphenol A, tetromophthalimide, hexabromobutene, Hexabromocyclododecane, etc .;

Examples of the nitrogen-containing flame retardant (D32) include a salt of urea compound, guanidine compound or triazine compound (melamine, guanamine, etc.) and cyanuric acid or isocyanuric acid;
Examples of the sulfur-containing flame retardant (D33) include sulfate ester, organic sulfonic acid, sulfamic acid, organic sulfamic acid, and their salts, esters, amides, and the like;
Examples of the silicon-containing flame retardant (D34) include polyorganosiloxane;

Examples of the phosphorus-containing flame retardant (D35) include phosphorus-containing acids and esters thereof (C2-20) such as phosphoric acid, phosphate, halogen-containing phosphate, phosphorous acid, phosphonate, and ammonium phosphate.

  These flame retardants may be used in combination with a flame retardant aid [anti-drip agent (for example, polytetrafluoroethylene), metal oxide (for example, zinc oxide), etc.] as necessary.

  Of these flame retardants, (D32) is preferable from the viewpoint of flame retardancy and the absence of environmental pollution such as dioxin generation during incineration.

  The total amount of (D3) used is usually 30% or less based on the total weight of (A), (B) and (C), preferably from 0.1 to 20 from the viewpoint of flame retardancy and mechanical properties of the molded product. %, More preferably 1 to 10%.

  As other resin additives (D4), one or more selected from the group consisting of pigments, dyes, nucleating agents, lubricants, plasticizers, mold release agents, antioxidants, ultraviolet absorbers and antibacterial agents These additives may be mentioned.

Examples of pigments include inorganic pigments [white pigments (titanium oxide, lithopone, lead white, zinc white, etc.), cobalt compounds (aureolin, cobalt green, etc.), iron compounds (iron oxide, bitumen, etc.), chromium compounds (chromium oxide, chromium, etc.) Lead acid, etc.) and sulfides (cadmium sulfide, ultramarine, etc.)], organic pigments [azo pigments (azo lake, monoazo, disazo, chelate azo, etc.), polycyclic pigments (benzimidazolone, phthalocyanine] Examples of dyes include azo, indigoid, sulfide, alizarin, acridine, thiazole, nitro, aniline, and the like;
Examples of nucleating agents include organic nucleating agents [1,3,2,4-di-benzylidene-sorbitol, aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium benzoate, etc.] and inorganic nucleating agents [graphite, Carbon black, magnesium oxide, talc, kaolin, calcium carbonate, alumina, calcium sulfate, etc.];
Examples of lubricants include waxes (carnauba wax, paraffin wax, polyolefin wax, etc.), higher fatty acids (C8-24, such as stearic acid, oleic acid), higher alcohols (C8-18, such as stearyl alcohol, lauryl alcohol) and higher fatty acid amides. (C8-24, such as stearamide, oleamide) and the like;

Examples of plasticizers include aromatic carboxylic acid esters [phthalic acid esters (dioctyl phthalate, dibutyl phthalate, etc.)], aliphatic monocarboxylic acid esters [methyl acetyl ricinolate, triethylene glycol dibenzoate, etc.], aliphatic dicarboxylic acid esters. [Di (2-ethylhexyl) adipate, adipic acid-propylene glycol-based polyester (Mn 200 to 2,000), etc.], aliphatic tricarboxylic acid ester [citrate ester (triethyl citrate, etc.)], phosphoric acid triester [triphenyl Phosphate etc.] and petroleum resin etc .;
Release agents include lower fatty acid (C1-4) alcohol esters (such as butyl stearate) of higher fatty acids (above) and polyvalent (divalent to tetravalent or higher) alcohol esters of fatty acids (C2-18). (Hardened castor oil, etc.), glycol (C2-8) esters of fatty acids (C2-18) (ethylene glycol monostearate, etc.) and liquid paraffin, etc .;

Antioxidants include phenols [monocyclic phenols (2,6-di-t-butyl-p-cresol, etc.), bisphenols [2,2′-methylenebis (4-methyl-6-t-butylphenol), etc.] Polycyclic phenol [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene etc.], etc.], sulfur-based (dilauryl 3,3 ′ -Thiodipropionate etc.), phosphorus (triphenyl phosphite etc.), amine (octylated diphenylamine etc.), etc .;
Examples of ultraviolet absorbers include benzotriazole [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, etc.], benzophenone [2-hydroxy-4-methoxybenzophenone, etc.], salicylate [phenyl salicylate]. Etc.], acrylate-based [2-ethylhexyl-2-cyano-3,3′1-diphenyl acrylate etc.] and the like;
As an antibacterial agent, benzoic acid, sorbic acid, halogenated phenol, organic iodine, nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylene bisthianocyanate), N-haloalkylthioimide, Examples thereof include copper agents (such as 8-oxyquinoline copper), benzimidazole, benzothiazole, trihaloallyl, triazole, organic nitrogen sulfur compounds (such as Suraoff 39), quaternary ammonium compounds, pyridine compounds, and the like.

  The total amount of (D4) used is usually 45% or less based on the total weight of (A), (B) and (C), and preferably 0.001 from the viewpoint of the effect of each additive and the mechanical properties of the molded product. -40%, more preferably 0.01-35%, particularly preferably 0.05-30%.

The antistatic resin composition of the present invention can be obtained by melt-mixing the antistatic agent of the present invention, the thermoplastic resin (C) and, if necessary, (D).
As a method of melt mixing, generally, a method in which pellets or powdery components are mixed with an appropriate mixer such as a Henschel mixer, and then melt mixed with an extruder to be pelletized can be applied.
There is no particular limitation on the order of addition of each component during melt mixing, for example,
(1) A method of melt-mixing the antistatic agent, (C) and, if necessary, (D) all together,
(2) The antistatic agent of the present invention and a part of (C) are previously melt-mixed to prepare a high-concentration resin composition (masterbatch resin composition) of the antistatic agent, and then the remaining (C) In addition, there is a method of melt-mixing (D) if necessary.
The concentration of the antistatic agent of the present invention in the masterbatch resin composition in the method (2) is preferably 40 to 80% by weight, more preferably 50 to 70% by weight.
Among these, the method (2) is a method called a master batch method, which is a preferable method from the viewpoint of efficient dispersion of the antistatic agent of the present invention in (C).

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

The molded article has excellent permanent antistatic properties, mechanical properties, and heat resistance, as well as good paintability and printability.
Examples of the method for coating the molded product include, but are not limited to, an air spray method, an airless spray method, an electrostatic spray method, a dipping method, a roller method, and a brush coating method. Examples of the paint include various paints such as polyester melamine, epoxy melamine, acrylic melamine, and acrylic urethane resin paint.
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 physical properties of the coating film.
Examples of the method for printing on the molded product include various printing methods such as gravure printing, flexographic printing, screen printing, and offset printing. Examples of the printing ink include those usually used for printing plastics.

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

Example 1
Low molecular weight polypropylene obtained by a thermal degradation method (Mn 3,500, 7.1 double bonds per 1,000 carbon atoms, average number of double bonds per molecule 1.8, 210 parts (polypropylene content 90% which can be modified at both ends) and 30 parts of maleic anhydride were charged, uniformly melted at 200 ° C. in a nitrogen gas atmosphere, and reacted for 20 hours. Thereafter, excess maleic anhydride was distilled off under reduced pressure for 3 hours to obtain acid-modified polypropylene (b1-1). The acid value of (b1-1) was 30, and Mn was 3,800.

Next, for 224 parts of (b1-1), 352 parts of PEG (a1-1) (Mn 6,000, volume resistivity 1 × 10 ⁵ Ω · cm), antioxidant [trade name “Irganox 1010
"Ciba-Gaiky Co., Ltd.," and so on. 0.4 parts and 0.5 parts of zirconyl acetate were added and polymerized at 230 ° C. under reduced pressure of 0.13 kPa or less for 3 hours to obtain a viscous block polymer (A-1). The Mn of (A-1) was 32,000.
Next, 2 parts of 1-ethyl-2,3-dimethylimidazolium pentadecylbenzenesulfonate (melting point: 143 ° C.) (B-1) is added to 198 parts of (A-1), and the mixture is heated at 220 ° C. for 1 hour. Mixing and stirring were performed to obtain an antistatic agent (T-1) containing (A-1) and (B-1). (T-1) was taken out as a strand on the belt and pelletized.

Example 2
A stainless steel autoclave was charged with 173 parts of ε-caprolactam, 33.2 parts of terephthalic acid, 0.4 part of an antioxidant and 10 parts of water, and the inside of the autoclave was purged with nitrogen and pressurized at 220 ° C. (0.3 to 0). 4 MPa, the same applies hereinafter.) Under sealing, the mixture was heated and stirred for 4 hours to obtain a polyamide (b2-1) having an acid value of 111 having carboxyl groups at both ends. Mn of (b2-1) was 1,000.

Next, 199 parts of (b2-1) EO adduct of bisphenol A (Mn 4,000, volume resistivity 2 × 10 ⁷ Ω · cm) (a1-2) 780 parts and zirconyl acetate 0
. 6 parts was added and polymerized under reduced pressure of 240 ° C. and 0.13 kPa or less for 6 hours to obtain a viscous block polymer (A-2). Mn of (A-2) was 24,000.
Next, 40 parts of 1-ethyl-3-methylimidazolium dodecylbenzenesulfonate (B-2) (melting point 117 ° C.) is added to 160 parts of (A-2), and the mixture is stirred at 230 ° C. for 1 hour. Thus, an antistatic agent (T-2) containing (A-2) and (B-2) was obtained. (T-2) was taken out as a strand on the belt and pelletized.

Example 3
A stainless steel autoclave was charged with 107 parts of N-methyldiethanolamine, 162 parts of sebacic acid, 0.2 part of antioxidant and 0.2 part of dibutyltin oxide, and after nitrogen substitution, the temperature was raised to 220 ° C. over 3 hours. The pressure was reduced to 0.13 kPa over 1 hour to conduct the polyesterification reaction. After completion of the reaction, the mixture was cooled to 50 ° C., and 250 parts of methanol was added and dissolved. While stirring, the temperature in the reaction vessel was kept at 120 ° C., 75 parts of dimethyl carbonate was gradually added dropwise over 3 hours, and aged at the same temperature for 6 hours. After cooling to room temperature, 261 parts of a 60% hexafluorophosphoric acid aqueous solution was added and stirred at room temperature for 1 hour. Subsequently, the solvent was distilled off under reduced pressure to obtain a cationic polymer (a2-1) having an average of 9 quaternary ammonium bases in the molecule and having hydroxyl groups at both ends. The hydroxyl value of (a2-1) was 43, the acid value was 0.5, and the volume resistivity value was 1 × 10 ⁷ Ω · cm.

Next, to 241 parts of (a2-1), 322 parts of acid-modified polypropylene (b1-1) is added and polymerized at 230 ° C. under reduced pressure of 0.13 kPa or less for 4 hours to obtain a viscous block polymer (A -3) was obtained. Mn of (A-3) was 26,000.
Next, 20 parts of 1-ethyl-3-methylimidazolium dodecylbenzenesulfonate (B-2) is added to 180 parts of (A-3), and the mixture is stirred at 230 ° C. for 1 hour, (A-3) And an antistatic agent (T-3) containing (B-3). (T-3) was taken out as a strand on the belt and pelletized.

Example 4
A stainless steel autoclave was charged with 114 parts of diethylene glycol, 268 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 part of dibutyltin oxide, and the temperature was raised to 190 ° C. under a reduced pressure of 0.65 kPa, and methanol was distilled off. Then, the ester exchange reaction was carried out for 6 hours to obtain an anionic polymer (a3-1) having an average of 6 sodium sulfonate bases in one molecule. The hydroxyl value of (a3-1) was 49, the acid value was 0.6, and the volume resistivity value was 3 × 10 ⁸ Ω · cm.

Next, 143 parts of polyamide (b2-1) and 0.3 part of antioxidant are added to 320 parts of (a3-1) and polymerized at 240 ° C. under a reduced pressure of 0.13 kPa or less for 5 hours. A thick block polymer (A-4) was obtained. Mn of (A-4) was 21,000.
Next, 10 parts of ethylbenzenesulfonate 1-ethyl-3-methylimidazolium (B-3) (melting point 35 ° C.) is added to 190 parts of (A-4), and the mixture is stirred at 230 ° C. for 1 hour. , (A-4) and (B-3) were obtained to obtain an antistatic agent (T-4). (T-4) was taken out as a strand on the belt and pelletized.

Example 5
A stainless steel autoclave was charged with 597 parts of 12-aminododecanoic acid, 30 parts of trimellitic acid and 0.5 part of antioxidant, and replaced with nitrogen gas. Thus, polyamideimide (b3-1) having an acid value of 29 having carboxyl groups at both ends was obtained.
Next, with respect to 570 parts of (b3-1), 146 parts of PEG (a1-3) (Mn 1,000, volume resistivity 1 × 10 ⁹ Ω · cm), 0.4 part of antioxidant and zirconyl acetate 0.
8 parts were added, and polymerization was performed at 230 ° C. under reduced pressure of 0.13 kPa or less for 3 hours to obtain a viscous block polymer (A-5). Mn of (A-5) was 35,000.
Next, 30 parts of 3-methyl-1-propylpyridinium dodecylbenzenesulfonate (B-4) (melting point: 125 ° C.) is added to 170 parts of (A-5), mixed and stirred at 230 ° C. for 1 hour, An antistatic agent (T-5) comprising (A-5) and (B-4) was obtained. (T-5) was taken out as a strand on the belt and pelletized.

Example 6
In Example 2, instead of post-adding (B-2) to the block polymer (A-2), (a1-2) and (b2-1) which are raw materials during the production of (A-2) And (B-2) was prepared, and (A-2) was produced in the presence of (B-2) [(A-2) / (B-2) weight ratio = 80/20]. In the same manner as in Example 2, an antistatic agent (T-6) containing (A-2) and (B-2) was obtained and pelletized.

Example 7
In Example 1, instead of using 352 parts of PEG (a1-1), 352 parts of polytetramethylene glycol (a1-4) (Mn 6,000, volume resistivity 1 × 10 ¹¹ Ω · cm) were used. Was obtained in the same manner as in Example 1 to obtain a viscous block polymer (A-6) (Mn 30,000). Further, in the same manner as in Example 1, the weight ratio of (A-6) and (B-1) was 198. An antistatic agent (T-7) contained at 2 was obtained and pelletized.

Example 8
In a stainless steel autoclave, 103 parts of acid-modified polypropylene (b1-1) and 6 parts of ethanolamine were reacted at 180 ° C. for 2 hours in a nitrogen gas atmosphere. Thereafter, excess ethanolamine was decompressed to 0.13 kPa and distilled off at 180 ° C. for 2 hours to obtain a modified polypropylene (b1-2) having a hydroxyl group. (B1-2) had a hydroxyl value of 29, an amine value of 0.01, and Mn of 3,900.
Next, isocyanate-modified PEG (a1-5) obtained by reacting PEG (a1-1) with 4,4′-MDI (86% of (b1-2)) (NCO content 2.0%, 94 parts by volume resistivity 1 × 10 ⁷ Ω · cm) and 1-ethyl-3-dodecylbenzenesulfonate
Add 20 parts of methylimidazolium (B-2), knead in a twin-screw extruder at 200 ° C. for a residence time of 30 seconds, and block polymers (A-7) (Mn40,000) and (B-2) Was obtained at a weight ratio of 180/20 to obtain an antistatic agent (T-8), which was taken out into a strand and pelletized.

Example 9
In Example 8, instead of 86 parts of the modified polypropylene (b1-2) having a hydroxyl group, 117 parts of the same, and 94 parts of the isocyanate-modified PEG (a1-5), α, ω-diepoxy PEG (a1-6) ( Mn2,100, except for using volume resistivity ^{2 × 10 7 Ω · cm)} 63 parts in the same manner as in example 8, a block polymer and (a-8 (Mn27,000) the (B-2) An antistatic agent (T-9) contained at a weight ratio of 180/20 was obtained and pelletized.

Example 10
In a stainless steel autoclave, 105 parts of acid-modified polypropylene (b1-1) and 15 parts of 12-aminododecanoic acid are charged and reacted in a nitrogen gas atmosphere at 210 ° C. for 2 hours to have a carboxyl group-modified polypropylene (b1-3). Got. The acid value of (b1-3) was 26, and Mn was 4,300.
Next, with respect to 92 parts of (b1-3), 90 parts of isocyanate-modified PEG (a1-5), 0.2 part of dibutyltin oxide and 0.4 part of antioxidant were charged and stirred at 210 ° C., 0 parts. The pressure was reduced to 13 kPa or less and polymerization was performed for 4 hours to obtain a block polymer (A-9) (Mn 23,000).
Next, 20 parts of 1-ethyl-3-methylimidazolium dodecylbenzenesulfonate (B-2) is mixed with 180 parts of (A-9) for 1 hour at 210 ° C., and (A-9) An antistatic agent (T-10) containing (B-2) was obtained, taken out into a strand, and pelletized.

Example 11
A three-necked flask was charged with 27 parts of lauryl sulfuric acid, 8 parts of 1,8-diazabicyclo (5,4,0) -7-undecenium and 40 parts of methanol, stirred and reacted at room temperature for 1 hour, and then a nitrogen gas atmosphere Then, it was dried under reduced pressure at 60 ° C. to obtain a salt (B-5) (melting point: 176 ° C.) of dodecylbenzenesulfonic acid and 1,8-diazabicyclo (5,4,0) -7-undecenium.
Next, in Example 1, (A-1) and (B-5) were performed in the same manner as in Example 1 except that (B-5) 2 parts were used instead of (B-1) 2 parts. The antistatic agent (T-11) containing this was obtained, took out in the shape of a strand, and pelletized.

Example 12
A three-necked flask was charged with 23 parts of triacontanoic acid, 11 parts of 1,5-diazabicyclo (4,3,0) -5-nonenium and 130 parts of isopropyl alcohol, and stirred and reacted at 80 ° C. for 1 hour. Drying under reduced pressure at 100 ° C. under a nitrogen gas atmosphere gave triacontanoic acid and 1,5-diazabicyclo (4,3,0) -5-nonenium salt (B-6) (melting point 154 ° C.).
Next, in Example 5, (A-5) and (B-6) were performed in the same manner as in Example 5 except that 30 parts of (B-6) were used instead of 30 parts of (B-4). The antistatic agent (T-12) containing this was obtained, took out in the shape of a strand, and pelletized.

Example 13
In Example 1, it replaced with 2 parts of (B-1), and it was the same as that of Example 1 except having used 2 parts of 1-butyl-3-methylimidazolium (B-7) (melting point 30 degreeC) of octyl sulfate. Thus, an antistatic agent (T-13) containing (A-1) and (B-7) was obtained and pelletized.

Example 14
In Example 1, instead of 2 parts of (B-1), Example 1 was used except that 2 parts of 1-butyl-3-methylimidazolium dioctylphosphate (B-8) (melting point: 66 ° C.) was used. Similarly, an antistatic agent (T-14) containing (A-1) and (B-8) was obtained and pelletized.

Example 15
In Example 1, instead of 352 parts of (a1-1), Example 1 is used except that 350 parts of polyoxypolyethylenepropylamine (Mn 6,000, volume resistivity 2 × 10 ⁵ Ω · cm) is used. Similarly, an antistatic agent (T-15) containing viscous block polymers (A-10) and (B-1) was obtained, taken out into a strand shape, and pelletized. The Mn of (A-10) was 29,000.

Comparative Example 1
In Example 2, instead of 40 parts of (B-2), Example 2 was used except that 40 parts of 1-ethyl-3-methylimidazolium methanesulfonate (ratio B-1) (melting point: 29 ° C.) was used. In the same manner as above, an antistatic agent (ratio T-1) containing (A-2) and (ratio B-1) was obtained and pelletized.

Comparative Example 2
In Example 3, instead of 20 parts of (B-2), 20 parts of lithium dodecylbenzenesulfonate (ratio B-2) (melting point: 84 ° C.) was used in the same manner as in Example 3 (A-3 ) And (Ratio B-2) to obtain an antistatic agent (Ratio T-2) and pelletized.

Examples 16-32, Comparative Examples 3-7
According to the composition shown in Tables 1 and 2, after blending the antistatic agent (T-1 to T-15, ratio T-1 to ratio T-2) and the thermoplastic resin, into a twin screw extruder with a vent. The mixture was melt-kneaded at 240 ° C., 100 rpm, and a residence time of 5 minutes to obtain antistatic resin compositions (Examples 16 to 32, Comparative Examples 3 to 7).

  Using the injection molding machine [model number “PS40E5ASE”, manufactured by Nissei Plastic Industry Co., Ltd.], the above resin composition was molded at a cylinder temperature of 240 ° C. and a mold temperature of 50 ° C., respectively, and test pieces cut out from the molded product were as follows. The performance test was evaluated. The results are shown in Tables 1 and 2.

熱可塑性樹脂（Ｃ−１）：ポリプロピレン樹脂［商品名「サンアロマーＰＭ７７１Ｍ」、
サンアロマー（株）製］
熱可塑性樹脂（Ｃ−２）：ＡＢＳ樹脂［商品名「セビアン−Ｖ３２０」、ダイセルポリマ
ー（株）製］

Thermoplastic resin (C-1): Polypropylene resin [trade name “Sun Allomer PM771M”,
Sun Allomer Co., Ltd.]
Thermoplastic resin (C-2): ABS resin [trade name “Cebian-V320”, Daicel Polymer
-Made by Co., Ltd.]

<Performance test>
(1) Appearance of molded product The surface of the molded product was visually observed and evaluated according to the following criteria.

○ Good (no bleeding out)
△ Slightly bad (There are some bleed-out items)
× Defect (Many bleed-out items)

(2) Volume resistivity value In accordance with ASTM D257, using a test piece (80 × 80 × 2 mm), a super insulation meter [model number “DSM-8103” (plate sample electrode SME-8310), Toa Denpa Kogyo ( Measured in an atmosphere of 23 ° C. and humidity 50% RH.

(3) Impact strength (mechanical properties)
Conforms to ASTM D256 (notched, 3.2 mm thick) Method A.

  As is apparent from Tables 1 and 2, it can be seen that the thermoplastic resin composition containing the antistatic agent of the present invention is excellent in permanent antistatic properties and in appearance and mechanical properties of the molded product.

  Since the antistatic agent of the present invention can impart excellent antistatic properties to the molded product without impairing the mechanical properties and good appearance of the thermoplastic resin molded product, various molding methods [injection molding, compression molding, calendering] Housing products that are molded by molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding and film molding (for example, casting method, tenter method and inflation method) [for home appliances / OA equipment, game machines and office equipment] Etc.], plastic container materials [tray used in clean rooms (IC trays, etc.), other containers, etc.], various cushioning materials, coating materials (wrapping film, protective film, etc.), flooring sheet, artificial grass, mat It can be widely used as a material for tape base materials (for semiconductor manufacturing processes, etc.) and various molded products (automobile parts, etc.). It is.

Claims (11)

A block of hydrophilic polymer (a) having a volume resistivity of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm and a block of hydrophobic polymer (b) are ester bonds, amide bonds, ether bonds, urethane bonds. And a block polymer (A) characterized in that it has a structure in which it is repeatedly and alternately bonded via at least one bond selected from the group consisting of imide bonds, and an anionic interface represented by the following general formula (1) An antistatic agent comprising an activator (B).

(R−) _n X ⁻ · Z ⁺ (1)

[Wherein R is a monovalent hydrocarbon group having 8 to 30 carbon atoms, X ⁻ is a group consisting of a sulfonic acid group, a sulfinic acid group, a sulfate ester group, a carboxyl group, a phosphate ester group, and a phosphite ester group. An anion obtained by removing a proton from at least one group selected from: Z ⁺ is a cation selected from the group consisting of amidinium, pyridinium, pyrazolium and guanidinium cations, n is 1 or 2, and when n is 2 A plurality of R may be the same or different. ] The antistatic agent according to claim 1, wherein (a) is at least one selected from the group consisting of polyethers, cationic polymers and anionic polymers. The antistatic agent according to claim 1, wherein (b) is a hydrophobic polymer selected from the group consisting of polyolefin, polyamide and polyamideimide. The antistatic agent according to any one of claims 1 to 3, wherein the proportion of the block (a) is 20 to 80% based on the weight of (A). The antistatic agent according to any one of claims 1 to 4, wherein (B) has a melting point of 30 to 180 ° C as measured by a differential scanning calorimeter. The antistatic agent according to any one of claims 1 to 5, wherein (B) is an imidazolium salt of an alkylarene sulfonic acid having 8 to 30 carbon atoms. The antistatic agent according to any one of claims 1 to 6, wherein the weight ratio of (A) to (B) is 99/1 to 80/20. An antistatic resin composition comprising the thermoplastic resin (C) containing the antistatic agent according to any one of claims 1 to 7. The antistatic property improver other than (B), a compatibilizer, a flame retardant, and at least one additive (D) selected from the group consisting of other additives for resin is further contained. Composition. An antistatic resin molded article obtained by molding the composition according to claim 8 or 9. A molded article obtained by coating and / or printing the molded article according to claim 10.