JP2008031460A - Antistatic agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic agent imparting excellent permanent antistaticity to a thermoplastic resin with high productivity without impairing its appearance, in view of the problem involved in conventional antistatic agents that, after polymerization, when the resultant polymer is extruded from an extruder and cut into pellets, a cutting trouble occurs, leading to declining in the polymer's productivity. <P>SOLUTION: The antistatic agent comprises a hydrophilic block copolymer with a surface resistivity of 1×10<SP>6</SP>to 1×10<SP>13</SP>Ω and an ionic surfactant(B) having a heat of crystallization of 2-100 mJ/mg at the crystallization peak temperature as determined by differential scanning calorimetry. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antistatic agent. More specifically, the present invention relates to an antistatic agent excellent in productivity (cutting property).

  Conventionally, as a resin composition for imparting antistatic properties to a thermoplastic resin, a resin composition containing a polyether chain-containing antistatic agent obtained by polymerization in the presence of a surfactant in a thermoplastic resin (for example, And Patent Document 1) are known.

JP 2002-146212 A

However, the above-described antistatic agent has a problem in that when a polymer is extruded from an extruder after polymerization and is cut into pellets, many pellets become indefinite due to poor cutting, resulting in a significant reduction in productivity. .
The objective of this invention is providing the antistatic agent which is excellent in productivity (cutting property) and provides the permanent permanent antistatic property to a thermoplastic resin.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to a hydrophilic block polymer (A) having a surface resistivity of 1 × 10 ⁶ to 1 × 10 ¹³ Ω and a crystallization of 2 to 100 mJ / mg at a crystallization peak temperature by a differential scanning calorimeter. An antistatic agent comprising an ionic surfactant (B) having heat; an antistatic resin composition containing the antistatic agent in a thermoplastic resin (C); and molding the composition And a molded article obtained by painting and / or printing the molded article.

The antistatic agent and antistatic resin composition of the present invention have the following effects.
(1) The antistatic agent is excellent in productivity (cutting property).
(2) The antistatic agent has excellent dispersibility in a thermoplastic resin, and can impart excellent permanent antistatic properties to the thermoplastic resin.

[Hydrophilic block polymer (A)]
(A) in the present invention is a hydrophilic block polymer having a surface resistivity of 1 × 10 ⁶ to 1 × 10 ¹³ (preferably 1 × 10 ⁶ to 1 × 10 ¹² Ω). When the surface specific resistance value of (A) is less than 1 × 10 ⁶ Ω, the moldability of the resin composition described later is deteriorated, and when it exceeds 1 × 10 ¹³ Ω, the antistatic property of the molded product described later is deteriorated.
(A) includes the following and mixtures of two or more thereof.
(A1): Hydrophobic amide group-containing hydrophobic polymer (a1) composed of polyamide (a11) and / or polyamideimide (a12), polyether chain-containing hydrophilic composed of polyether diol (b11) and / or polyether diamine (b12) Block polymer (A2) composed of the functional polymer (b1) and the aromatic ring-containing polyester (c1): the block of the polyolefin (a21) and the block of the polyether chain-containing hydrophilic polymer (a22) are ester bonds, amide bonds, A block polymer (A3) having a structure in which the structure is repeatedly and alternately bonded through at least one bond selected from the group consisting of an ether bond, an imide bond, and a urethane bond, comprising a polyamide (a11) and / or a polyamideimide (a12) Amido group-containing hydrophobic Polymer (a1), and polyether diols (b11) and / or block polymer composed of polyether chains containing hydrophilic polymer (b1) consisting of polyether diamine (b12)

[Block polymer (A1)]
The amide group-containing hydrophobic polymer (a1) constituting the block polymer (A1) is composed of polyamide (a11) and / or polyamideimide (a12).
Here, the hydrophobic polymer means a polymer having a surface resistivity of 1 × 10 ¹⁴ to 1 × 10 ¹⁷ Ω.
Examples of the polyamide (a11) include those obtained by ring-opening polymerization or polycondensation of amide-forming monomers.
Amide-forming monomers include lactam (a011), aminocarboxylic acid (a012), and diamine (a013) / dicarboxylic acid (a014).
The lactam (a011) includes 6 to 12 carbon atoms (hereinafter abbreviated as C), such as caprolactam, enantolactam, laurolactam and undecanolactam.
Examples of the ring-opening polymer (a011) include nylon 4, -5, -6, -8 and -12.

As aminocarboxylic acid (a012), 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 (a012) 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 (a013) 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, isophoronediamine, 4,4'-diaminocyclohexylmethane and 2,2-bis (4-aminocyclohexyl) propane. It is done.
Examples of araliphatic diamines include C7-20, such as 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 (a014) 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 the 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, acid anhydrides include the above dicarboxylic acid anhydrides, such as maleic anhydride, itaconic anhydride and phthalic anhydride; lower (C1-4) alkyl esters include the lower alkyl esters of the above dicarboxylic acids, such as Mention may be 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 hexamethylene diamine with adipic acid, sebacic acid, azelaic acid or dodecanedioic acid. Nylon 46 by polycondensation of diamine and adipic acid is mentioned.
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). .

  Among the amide-forming monomers, caprolactam, 12-aminododecanoic acid and adipic acid / hexamethylenediamine are preferable from the viewpoint of antistatic properties, and caprolactam is more preferable.

The polyamide (a11) is produced by one or more of the dicarboxylic acid (a014) (C2-40, preferably 4-20) or the diamine (a013) (C2-40, preferably 4-20). Can be used as a molecular weight modifier, and in the presence thereof, the amide-forming monomer can be subjected to ring-opening polymerization or polycondensation.
Examples of the C2-40 diamine include those exemplified as the above (a013). 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 (a014). 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%.

  Number average molecular weight of polyamide (a11) [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method. ] Is preferably 200 to 5,000, more preferably 500 to 4,000 from the viewpoint of moldability and production of an antistatic agent.

Polyamideimide (a12) includes the above amide-forming monomer and a trivalent or tetravalent aromatic polycarboxylic acid or anhydride thereof capable of forming at least one imide ring with the amide-forming monomer [hereinafter referred to as fragrance. Abbreviated as group polycarboxylic acid (anhydride). (Hereinafter sometimes referred to as an amidoimide-forming monomer), and mixtures thereof. The diamine (a013) and dicarboxylic acid (a014) can also be used as a molecular weight adjusting agent 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 (a12), as in the case of the polyamide (a11), 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 above-mentioned amidoimide-forming monomer in the presence thereof. Preferred among the dicarboxylic acid and diamine are the same as in the case of (a11).
The amount of the molecular weight modifier used is preferably based on the total weight of the amide imide-forming monomer and the 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 (a12) 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 amide group-containing hydrophobic polymer (a1) is preferably from 200 to 5,000, more preferably from 500 to 4,000, particularly from the viewpoint of moldability, and the upper limit is from the viewpoint of production of the antistatic agent. Preferably it is 1,000-3,000.

The polyether chain-containing hydrophilic polymer (b1) constituting (A1) consists of a polyether diol (b11) and / or a polyether diamine (b12).
The polyether diol (b11) is usually at least 250 (preferably 250 to 3,000, more preferably 350 to 2,500, particularly preferably 400 to 2,000) of hydroxyl equivalent (based on hydroxyl value per hydroxyl group). (B11) is an active hydrogen atom-containing compound [low molecular diol (b011) having an OH equivalent of less than 250 and dihydric phenol (b012), alkylene oxide (described later). (Hereinafter abbreviated as AO)), and (b11) includes a low molecular diol or dihydric phenol AO adduct (b111) represented by the following general formula; and polyoxyalkylene (b112). included.

H- (OA ¹ ) _m -O-E ¹ -O- (A ¹ O) _{m '} -H

[In the formula, E ¹ is a residue obtained by removing a hydroxyl group from an active hydrogen-containing compound, A ¹ is a C2-4 alkylene group, and m and m ′ represent the number of AO additions per hydroxyl group of the active hydrogen-containing compound. M (OA ¹ ) and m ′ (A ¹ O) may be the same as or different from each other, and in the case where these are composed of two or more oxyalkylene groups, the bonding form is blocked. Or m or m ′ is usually an integer of 1 to 300, preferably 2 to 250, particularly preferably 10 to 100. m and m ′ may be the same. It may be different.]

The low molecular diol (b011) includes aliphatic dihydric alcohol [C2-12 (preferably 2-8, more preferably 2-6) alkylene glycol such as ethylene glycol, propylene glycol, 1,2-, 1, 3-, 2,3- and 1,4-butanediol, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 2,3-, 2,4-, 2,5- and 3,4-hexanediol, neopentyl glycol (hereinafter abbreviated as EG, PG, BD, HG and NPG, respectively), 2,2-, 2,3-, 2,4-, 2, 5-, 3,3- and 3,4-dimethyl-1,6-hexanediol and 1,12-dodecanediol]; alicyclic dihydric alcohol [C5-12 (preferably 5-10, more preferably 5 -8), for example cyclopen -1,2- and 1,3-diol, cyclohexane-1,2-, 1,3- and 1,4-diol, bis (hydroxymethyl) cyclohexane and hydrogenated bisphenol A]; aromatic ring-containing dihydric alcohol [C8-20, eg xylylene glycol, bis (hydroxymethyl) benzene and bis (hydroxyethyl) benzene]; and tertiary amino group-containing diols [eg C1-12 aliphatic or alicyclic primary monoamines [methyl Amine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, amylamine, isoamylamine, hexylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-aminoheptane, Cyclopentylamine, hexylami , Cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, dodecylamine, etc.] and bishydroxyalkylated products of C6-12 aromatic primary monoamines [aniline, benzylamine, etc.]. .
Of (b011), from the viewpoint of the dispersibility of (A) with respect to the thermoplastic resin (C) described later, an aliphatic dihydric alcohol is preferred, and EG is more preferred.

Examples of the dihydric phenol (b012) include monocyclic dihydric phenols (C6-18, such as hydroquinone, catechol, resorcin and urushiol), bisphenols (C12-20, such as bisphenol A, F and S, 4,4′-dihydroxy). Diphenyl-2,2-butane and dihydroxybiphenyl) and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol, etc.)] and the like.
Of (b012), from the viewpoint of the dispersibility of (A) with respect to the thermoplastic resin (C) described later, bisphenol and condensed polycyclic dihydric phenol are preferred, and bisphenol A is more preferred.

The low molecular diol or dihydric phenol AO adduct (b111) can be produced by addition reaction of the active hydrogen-containing compound with AO. AO includes C2-4 AO [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,4-, 2,3- or 1,3-butylene oxide. And a combination system of two or more of these], other AO or substituted AO (hereinafter collectively referred to as AO), for example, C5-12 α-olefin, styrene oxide, epihalohydrin if necessary. (Such as epichlorohydrin) can be used 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.
From the viewpoint of antistatic properties, AO is preferably EO alone or a combination of EO and another AO (block and / or random addition). The added number of AO is usually an integer of 1 to 300, preferably 2 to 250, more preferably 10 to 100 per hydroxyl group of the low molecular diol (b011) or dihydric phenol (b012).

The addition of AO can be performed at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst (potassium hydroxide or the like), for example. The content of C2-4 oxyalkylene units in (b111) is usually 5 to 99.8%, preferably 8 to 99.6%, and more preferably 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%.

(B111) may be used alone or in a mixture of two or more.
Of these, AO adducts of aliphatic dihydric alcohols, bisphenols or condensed polycyclic dihydric phenols are preferred from the viewpoint of antistatic properties, and more preferred are EG, diethylene glycol (hereinafter abbreviated as DEG), PG, BD. , Bisphenol A and -S, and dihydroxynaphthalene AO adducts, and particularly preferred are bisphenol A and -S and dihydroxynaphthalene AO adducts.

Examples of the polyoxyalkylene (b112) include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyhexamethylene, modified polyoxyalkylene, and mixtures thereof.
Examples of the modified polyoxyalkylene include at least two addition polymers of C2 to C10 alkylene oxide (addition may be random and / or block).
Among (b112), polyoxyethylene is preferable from the viewpoint of antistatic properties.

As the polyether diamine (b12) in the present invention, those obtained by modifying the terminal hydroxyl group of (b111) or (b112) to an amino group can be used.
Examples of the method for modifying the terminal hydroxyl group of (b111) or (b112) to an amino group include, for example, reducing the terminal cyanoalkyl group obtained by cyanoalkylating the terminal hydroxyl group of (b111) or (b112) to aminoalkylation And the like [for example, a method of reacting (b111) or (b112) with acrylonitrile and hydrogenating the resulting cyanoethyl compound].

  Mn of (b1) is preferably from 300 to 5,000, more preferably from 1,000 to 4,000, and particularly preferably from the viewpoint of the production of an antistatic agent, the lower limit from the viewpoint of antistatic properties. 600 to 3,000.

As the aromatic ring-containing polyester (c1) constituting (A1), the dicarboxylic acid (a014) or diol is used as a molecular weight modifier, and at least one ester-forming monomer containing an aromatic ring is polycondensed. The structure obtained by the above can be used.
Examples of the ester-forming monomer include a combination of a dicarboxylic acid (c011) and a diol (c012), a lactone (c013), a hydroxycarboxylic acid (c014), and a mixture thereof.

Examples of the dicarboxylic acid (c011) include C2-40 (preferably 4-20, more preferably 6-12) dicarboxylic acids. For example, those exemplified above as (a014) and mixtures of two or more of these Can be mentioned. These may be used alone or in combination of two or more.
Among these, the aliphatic dicarboxylic acid is preferably an adipic acid, sebacic acid, icosanoic acid, dimethyl adipate, an aromatic ring-containing dicarboxylic acid, from the viewpoint of dispersibility of the antistatic agent in the thermoplastic resin (C) described later. Terephthalic acid, isophthalic acid, phthalic acid, 2,6 and 2,7-naphthalenedicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, sodium 3-sulfoisophthalate, dimethyl sodium 3-sulfoisophthalate, 2, 6 and In dimethyl 2,7-naphthalenedicarboxylate and alicyclic dicarboxylic acid, they are 1,4-cyclohexanedicarboxylic acid and dimethyl 1,4-cyclohexanedicarboxylate.

Examples of the diol (c012) include C2-30 low molecular diols [for example, those exemplified as the low molecular diol (b011)] and polyether diols (for example, those exemplified as the polyether diol (b11)). These may be used alone or in combination of two or more.
Of these, EG, PG, BD, NPG, HG, 1,2-, 1,3- and 1,4- are preferable from the viewpoint of dispersibility of the antistatic agent in the thermoplastic resin (C) described later. Cyclohexanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, EO addition product of bisphenol A, PO addition product of bisphenol A, and EO addition product of bisphenol S.

  Examples of the lactone (c013) include C4-20 lactones such as γ-butyrolactone, γ-valerolactone, ε-caprolactone, γ-pimerolactone, γ-caprolactone, γ-decanolactone, enanthlactone, laurolactone, and undecanolactone. And eicosanolactone.

  Examples of the hydroxycarboxylic acid (c014) include C2-20 hydroxycarboxylic acids such as hydroxyacetic acid, lactic acid, ω-hydroxycaproic acid, ω-hydroxyenanthic acid, ω-hydroxycaprylic acid, ω-hydroxypelargonic acid, ω-hydroxycaprin. Examples include acids, 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid and 20-hydroxyeicosanoic acid.

  Among the ester-forming monomers, the combination of dicarboxylic acid (c011) / diol (c012) is preferable from the viewpoint of dispersibility of the antistatic agent in the thermoplastic resin (C) described later. / [EG and / or BD], [2,6- and / or -2,7-naphthalenedicarboxylic acid (dimethyl)] / [EG and / or BD], terephthalic acid (dimethyl) / [bisphenol A EO addition , EO adduct of bisphenol S and / or / dihydroxynaphthalene EO adduct], [2,6- and -2,7-naphthalenedicarboxylic acid (dimethyl)] / [EO adduct of bisphenol A, bisphenol S EO adduct and / or dihydroxynaphthalene EO adduct]; lactone (c013) and dical In the combination of acid (c011) / diol (c012), [ε-caprolactone and / or enanthlactone] / [dicarboxylic acid / diol combination above]; and hydroxycarboxylic acid (c014) and dicarboxylic acid (c011) / diol In the combination of (c012), [ω-hydroxycaproic acid and / or 11-hydroxyundecanoic acid] / [a combination of the above dicarboxylic acids / diol], more preferably a combination of dicarboxylic acid (c011) / diol (c012), Particularly preferred is terephthalic acid (dimethyl) / [EO addition of bisphenol A and / or EO addition of bisphenol S], [2,6 and 2,7-naphthalenedicarboxylic acid (dimethyl)] / [EO of bisphenol A]. Addenda and A / or EO adducts of bisphenol S].

Examples of the dicarboxylic acid as the molecular weight modifier include C2-40 (preferably 4-20) dicarboxylic acids such as those exemplified in the above (a014). Among these, the reactivity with the ester-forming monomer is included. From the viewpoint, aliphatic dicarboxylic acids and aromatic ring-containing dicarboxylic acids are preferred, and adipic acid, sebacic acid, terephthalic acid, isophthalic acid, sodium 3-sulfoisophthalate and 2,6-naphthalenedicarboxylic acid are more preferred.
Examples of the diol as the molecular weight modifier include those exemplified as the low molecular diol (b011). Among these, EG, PG, BD, 1, 2 are preferable from the viewpoint of reactivity with the ester-forming monomer. -, 1,3- and 1,4-cyclohexanediol,
Polyethylene glycol, polypropylene glycol, polytetramethylene glycol, EO addition product of bisphenol A, PO addition product of bisphenol A, EO addition product of bisphenol S, and EO addition product of dihydroxynaphthalene.
It is.
The amount of the molecular weight modifier used is based on the total weight of the ester-forming monomer and the molecular weight modifier. From a viewpoint of property, Preferably it is 2 to 80%, More preferably, it is 4 to 75%.

  Mn of (c1) is preferably from 300 to 6,000, the lower limit is from the viewpoint of dispersibility of the antistatic agent in the thermoplastic resin (C) described later, and the upper limit is preferably from 300 to 6,000, from the viewpoint of production of the antistatic agent. Preferably it is 1,000-5,000, Most preferably, it is 1,600-4,000.

  The proportion of (a1) based on the total weight of (a1), (b1) and (c1) constituting the block polymer (A1) is the lower limit of the dispersibility of the antistatic agent in the thermoplastic resin (C) described later. From the viewpoint, the upper limit is preferably 10 to 80% from the viewpoint of antistatic properties, more preferably 25 to 65%; the proportion of (b1) is the lower limit from the viewpoint of antistatic properties, and the upper limit is the thermoplastic resin (C). From the viewpoint of transparency, the proportion of (c1) is preferably 10 to 80%, more preferably 20 to 60%; and the lower limit is the thermoplastic resin (C) from the viewpoint of transparency of the thermoplastic resin (C). From the viewpoint of dispersibility of the antistatic agent in C), it is preferably 5 to 60%, more preferably 10 to 45%.

Specific examples of the production method of the block polymer (A1) include the following production methods [1], [2] and [3], but are not particularly limited.
Production Method [1] An amide-forming monomer and a dicarboxylic acid (molecular weight modifier) are reacted at a high temperature (160 to 270 ° C.) and under a pressure (0.1 to 1 MPa) to produce an amide group-containing hydrophobic polymer (a1). Let it form. On the other hand, an ester-forming monomer and a dicarboxylic acid or diol (molecular weight modifier) are reacted at high temperature (160 to 270 ° C.) under reduced pressure (0.03 to 3 kPa) to form an aromatic ring-containing polyester (c1). (A1) and a polyether chain-containing hydrophilic polymer (b1) are added, and a polymerization reaction is performed at a high temperature (160 to 270 ° C.) under reduced pressure (0.03 to 3 kPa).
Production method [2] An ester-forming monomer and a dicarboxylic acid or diol (molecular weight modifier) are reacted at high temperature (160 to 270 ° C.) under reduced pressure (0.03 to 3 kPa) to form (c1). An amide-forming monomer, a dicarboxylic acid (molecular weight modifier), and a part of (b1) are charged into a reaction vessel at the same time, in the presence or absence of water, at a high temperature (160 to 270 ° C.) and pressure (0.1 ~ 1 MPa) reaction to form a polyamide intermediate, followed by a polymerization reaction with the remaining (b1) under reduced pressure (0.03 to 3 kPa).
Production Method [3] An amide-forming monomer and a dicarboxylic acid (molecular weight modifier) are reacted at high temperature (160 to 270 ° C.) and under pressure (0.1 to 1 MPa) to form (a1), which is an ester. A method in which a forming monomer, a dicarboxylic acid or diol (molecular weight modifier) and (b1) are simultaneously charged in a reaction vessel, and a polymerization reaction is performed at a high temperature (160 to 270 ° C.) under reduced pressure (0.03 to 3 kPa).
Of the above production methods, production method [1] is preferable from the viewpoint of reaction control.

Among the polymerization reactions in the above production method, an esterification catalyst can be used for the polyesterification reaction. Examples of the catalyst include an antimony compound (for example, antimony trioxide), a tin compound (for example, monobutyltin oxide), a titanium compound (for example, tetrabutyltitanate), a zirconium compound (for example, tetrabutylzirconate), an organic acid metal salt [zirconium organic acid Salt (such as zirconyl acetate), zinc acetate, etc.], and a mixture of two or more thereof.
The amount of the catalyst used is preferably 0.1 to 5%, more preferably 0 based on the total weight of (a1), (b1) and (c1) from the viewpoint of reactivity and resin physical properties of the molded product. .2 to 3%.

  Mn in (A1) is preferably from 2,000 to 100,000, more preferably from 5,000 to 80,000, from the viewpoint of moldability and production of an antistatic agent.

[Block polymer (A2)]
The block polymer (A2) is selected from the group in which the block of the polyolefin (a21) and the block of the polyether chain-containing hydrophilic polymer (a22) are composed of an ester bond, an amide bond, an ether bond, an imide bond, and a urethane bond. It is a block polymer having a structure in which it is alternately and repeatedly bonded through at least one bond.
The proportion of (a22) based on the total weight of (a21) and (a22) is preferably 20 to 80%, more preferably 30 to 70%, from the viewpoint of the antistatic property and heat resistance of (A2).
The block of (a21) constituting (A2) includes a polyolefin (a211) having a carbonyl group at both ends of the polymer, a polyolefin (a212) having a hydroxyl group at both ends of the polymer, and an amino group at both ends of the polymer. Polyolefin (a213) and polyolefin (a214) having isocyanate groups at both ends of the polymer can be used.

As (a211), what introduce | transduced the carbonyl group into the both terminal of the polyolefin (a210) which has the polyolefin which can modify | denature at both terminals as a main component is used.
As (a212), those in which hydroxyl groups are introduced at both ends of (a210) are used.
As (a213), those in which amino groups are introduced at both ends of (a210) are used.
As (a214), those obtained by introducing isocyanate groups at both ends of (a212) are used.
(A210) is usually a mixture of a polyolefin that can be modified at both ends, a polyolefin that can be modified at one end, and a polyolefin that does not have a modifiable end group, but contains a polyolefin that can be modified at both ends as a main component. You can use it if you do.
The content of the polyolefin which can be modified at both ends as the main component of (a210) is preferably 50 to 100%, more preferably 75 to 100%, particularly preferably 80 to 100% based on the weight of (a210). It is.

(A210) means (co) polymerization (polymerization or copolymerization) of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. )) And a degraded polyolefin [a product obtained by mechanically, thermally and chemically degrading a high molecular weight polyolefin (preferably Mn 50,000 to 150,000)] (reduced) Method). From the viewpoint of ease of modification and availability of introduction of a carbonyl group, hydroxyl group or amino group, a degraded polyolefin, particularly a thermally degraded polyolefin, is preferred.
The heat-degraded polyolefin is not particularly limited, but is heat-degraded by heating a high molecular weight polyolefin in an inert gas (usually at 300 to 450 ° C. for 0.5 to 10 hours) (for example, JP-A-3 -62804).
Examples of the high molecular weight polyolefin used in the thermal degradation method include (co) polymers of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. Can be used. As the C2-30 olefin, the same as those used for the production of the polyolefin (polymerization method) described later can be used, and among these, ethylene, propylene and C4-12 α-olefin are preferred, and ethylene is more preferred. , Propylene and C4-10 alpha-olefins, particularly preferred are ethylene and propylene.

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

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

Mn of the polyolefin (a210) whose main component is a polyolefin that 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 number of double bonds in (a210) is preferably 1 to 40 per 1,000 carbons, more preferably 2 to 30, and particularly preferably 4 to 20. 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 of 1.5 to 2 per molecule in the range of 800 to 6,000 can be easily obtained [Katsuhide Murata, Tadahiko Makino. , Journal of Chemical Society of Japan, page 192 (1975)].

The polyolefin having a carbonyl group at both ends of the polymer (a211) is as follows. Or an anhydride thereof. The same applies hereinafter.) Polyolefin (a211-1) having a structure modified with (a211-2) and polyolefin (a211-2) having a structure obtained by secondary modification of (a211-1) with lactam or aminocarboxylic acid. ), A polyolefin having a structure obtained by modifying (a210) by oxidation or hydroformylation (a211
-3), polyolefin (a211-4) having a structure obtained by secondary modification of (a211-3) with lactam or aminocarboxylic acid, and a mixture of two or more thereof.

(A211-1) can be obtained by modifying (a210) 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 (a210). ~ 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 carried out by various methods. For example, the terminal double bond of (a210) can be subjected to α or β by a solution method or a melt method. , Β-unsaturated carboxylic acid (anhydride) can be thermally added (ene reaction). The temperature at which (a210) is reacted with the α, β-unsaturated carboxylic acid (anhydride) is usually 170 to 230 ° C.

(A211-2) can be obtained by secondary modification of (a211-1) with lactam or aminocarboxylic acid.
As the lactam used for the secondary modification, C6-12 (preferably 6-8, more preferably 6) lactam and the like can be used, and examples thereof include caprolactam, enantolactam, laurolactam and undecanolactam.
As the aminocarboxylic acid, C2-12 (preferably 4-12, more preferably 6-12) aminocarboxylic acid and the like can be used. For example, amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.) ), Ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Of these, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and caprolactam, laurolactam, ω-aminocaprylic acid, 11-amino are more preferred. Undecanoic acid and 12-aminododecanoic acid, particularly preferably caprolactam and 12-aminododecanoic acid.
The amount of lactam or aminocarboxylic acid used for secondary modification is preferably 0.1 to 50, more preferably 0.3 to 20 per carboxyl group of α, β unsaturated carboxylic acid (anhydride). The number is particularly preferably 0.5 to 10, most preferably 1 to 2. When this amount is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.

(A211-3) can be obtained by introducing (a210) 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.
(A211-4) can be obtained by secondary modification of (a211-3) with lactam or aminocarboxylic acid.
The lactam and aminocarboxylic acid and preferred ranges thereof are the same as those which can be used in the production of (a211-2). The amount of lactam and aminocarboxylic acid used is the same.

Mn of (a211) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably from the viewpoint of heat resistance and reactivity with the polyether chain-containing hydrophilic polymer (a22). 2,500 to 10,000.
The acid value of (a211) 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 (a22). Preferably it is 5-50.

As the polyolefin (a212) having a hydroxyl group at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying (a211) with hydroxylamine and a mixture of two or more of these can be used.
Examples of hydroxylamine that can be used for the modification include C2-10 (preferably 2-6, more preferably 2-4) hydroxylamine, and the like. For example, 2-aminoethanol, 3-aminopropanol, 1-amino- Examples include 2-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol.
Of these, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-aminohexanol are more preferable, 2-aminoethanol and 4-aminobutanol are particularly preferable. Is 2-aminoethanol.
The modification with hydroxylamine can be performed by various methods, for example, by directly reacting (a211) with hydroxylamine. The reaction temperature is usually 120 ° C to 230 ° C.

The amount of hydroxylamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, particularly preferably per residue of α, β unsaturated carboxylic acid (anhydride). Is 0.5 to 1.2, most preferably 1. When the amount of hydroxylamine is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.
Mn of (a212) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably from the viewpoint of heat resistance and reactivity with the polyether chain-containing hydrophilic polymer (a22). 2,500 to 10,000.
The hydroxyl value of (a212) 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 (a22). Preferably it is 5-50.

As the polyolefin (a213) having an amino group at both ends of the polymer, a polyolefin having an amino group obtained by modifying (a211) with a diamine (Q1) and a mixture of two or more of these can be used.
As the diamine (Q1) used for this modification, C2-12 (preferably 2-8, more preferably 2-6) diamines can be used, for example, ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine. And decamethylenediamine.
Of these, ethylenediamine, hexamethylenediamine, heptamethylenediamine and octamethylenediamine are preferable, ethylenediamine and hexamethylenediamine are more preferable, and ethylenediamine is particularly preferable.
The modification with diamine can be carried out by a known method, for example, by reacting (a211) and diamine (Q1) directly. The reaction temperature is usually 120 ° C to 230 ° C.

The amount of diamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, and still more preferably, per residue of α, β unsaturated carboxylic acid (anhydride). 0.5 to 1.2, particularly preferably 1. When the amount of diamine is within this range, it becomes easier to take a repeating structure, and 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 to 230 ° C.).

Mn of (a213) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly from the viewpoint of heat resistance and reactivity with the polyether chain-containing hydrophilic polymer (a22) described later. Preferably it is 2,500-10,000.
Further, the amine value of (a213) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (a22), more preferably 4 to 100, and particularly preferably. Is 5-50.

  Examples of the polyolefin having an isocyanate group at both ends (a214) include the polyolefin having a hydroxyl group at both ends of the polymer (a212) modified with diisocyanate and having an isocyanate group at both ends and a mixture of two or more of these. Can be used. As the diisocyanate, C (excluding carbon in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic diisocyanate, C2 to 18 aliphatic diisocyanate, C4 to 15 alicyclic diisocyanate, and C8 to 15 araliphatic diisocyanate , Modified products of these diisocyanates and mixtures of two or more thereof.

  Specific examples of the aromatic diisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, and 2,4′-. And / or 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4, 4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, etc. are mentioned.

Specific examples of the aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI).
, Dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, Examples include 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

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

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

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

The reaction between (a212) and diisocyanate can be carried out in the same manner as in a normal urethanization reaction.
The equivalent ratio (NCO / OH ratio) of diisocyanate and (a212) 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 in the urethanization reaction may be used if necessary. Such catalysts include metal catalysts such as tin catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate, etc.); lead catalyst (Lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.); other metal catalysts [naphthalic acid metal salts such as cobalt naphthenate, phenylmercuric propionate, etc.]; and amine catalysts such as Triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diazabicycloalkene {1,8-diazabicyclo [5,4,0] undecene-7 [DBU (manufactured by San Apro Co., Ltd., registered trademark)]]]; dialkyl (C1-3) aminoalkyl C2-8) amine [dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropylaminopropylamine, etc.] or heterocyclic aminoalkyl (C1-3) amine [2- (1-aziridinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine etc.] carbonates and organic acids (formic acid etc.) salts, etc .; N-alkyl (C1-3, eg methyl, ethyl) morpholine, tri Examples include alkyl (C1-3, such as ethyl, propyl) amine, dialkyl (C1-3) alkanol (C2-4) amine (dimethylethanolamine, diethylethanolamine, etc.); and combinations of two or more of these.
The amount of the catalyst used is usually 3% or less, preferably 0.001 to 2%, based on the total weight of diisocyanate and (a212).

  Mn of (a214) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably from the viewpoint of heat resistance and reactivity with the polyether chain-containing hydrophilic polymer (a22). 2,500 to 10,000.

  Examples of the polyether chain-containing hydrophilic polymer (a22) constituting (A2) include the modified polyether chain-containing hydrophilic polymers (b1) and (b1) and mixtures thereof. Hereinafter, the polyether diol (b11) and the polyether diamine (b12) may be referred to as a polyether diol (a221) and a polyether diamine (a222), respectively.

Examples of the modified product include the aminocarboxylic acid modified product (terminal amino group), the isocyanate modified product (terminal isocyanate group) and the epoxy modified product (terminal epoxy group) of (a221) or (a222).
The aminocarboxylic acid-modified product can be obtained by reacting (a221) or (a222) with aminocarboxylic acid or lactam.
The isocyanate-modified product can be obtained by reacting (a221) or (a222) with the diisocyanate or reacting (a222) with phosgene.
The epoxy modified product is obtained by reacting (a221) or (a222) with a diepoxide (epoxy equivalent of 85 to 600, for example, diglycidyl ether, diglycidyl ester, alicyclic diepoxide), or (a221) and an epihalohydrin (epichlorohydrin, etc.) ).

The block polymer (A2) can be produced by various methods. For example, a polyether diol (a221) is added to a polyolefin (a211) having carbonyl groups at both ends of the polymer, and polymerization is usually performed at 200 to 250 ° C. under reduced pressure ( It can be produced by a method of performing a (polycondensation) reaction. Or it can manufacture by the method of superposing | polymerizing by 160-250 degreeC and residence time 0.1-20 minutes normally under reduced pressure using a uniaxial or biaxial extruder. Among the polymerization reaction in the said manufacturing method, polyester In the esterification reaction, the same esterification catalyst as in (A1) can be used.
The usage-amount of a catalyst is 0.001 to 5% normally with respect to the total weight of (a211) and (a221).

[Block polymer (A3)]
The amide group-containing hydrophobic polymer (a1) and the polyether chain-containing hydrophilic polymer (b1) constituting the block polymer (A3) are the same as those in the above (A1).
Examples of the method for producing the block polymer (A3) include the following [1] and [2], but are not particularly limited.
Production Method [1] An amide-forming monomer and a dicarboxylic acid (molecular weight modifier) are reacted to form (a1), to which a polyether chain-containing hydrophilic polymer (b1) is added, and a high temperature (160 to 270 ° C.) is added. ), Polymerization under reduced pressure (0.03 to 3 kPa).
Production Method [2] An amide-forming monomer and a dicarboxylic acid (molecular weight modifier) and a part of (b1) are simultaneously charged into a reaction vessel and added at high temperature (160 to 270 ° C.) in the presence or absence of water. A method in which a polyamide intermediate (a1) is produced by a pressure (0.1 to 1 MPa) reaction and then polymerized with the remaining (b1) under reduced pressure (0.03 to 3 kPa).
Of the above production methods, production method [1] is preferable from the viewpoint of reaction control.

Of the polymerization reactions in the above production method, the same esterification catalyst as in (A1) and (A2) can be used for the polyesterification reaction.
The amount of the catalyst used is preferably 0.1 to 5%, more preferably 0.2 to 3 based on the total weight of (a1) and (b1) from the viewpoints of reactivity and resin physical properties of the molded product. %.

[Surfactant (B)]
(B) in the present invention is 2 to 100 (preferably 2 to 50, more preferably 2 to 25, particularly preferably 2 to 20, most preferably 2 to 10) mJ at the crystallization peak temperature by a differential scanning calorimeter. A surfactant having a heat of crystallization of / mg.
The heat of crystallization herein refers to only the heat of crystallization at that temperature when the crystallization peak temperature is one point, and refers to the sum of the heat of crystallization at each temperature when there are a plurality of crystallization peak temperatures.
When the crystallization heat is less than 2 mJ / mg, the cutting property is deteriorated, and when it exceeds 100 mJ / mg, the antistatic property is deteriorated.
From the viewpoint of cutting (productivity), the crystallization peak temperature is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, preferably 230 ° C. or lower, more preferably 200 ° C. or lower.
Examples of the differential scanning calorimeter (DSC) used in the measurement include DSC2910 [trade name, manufactured by T.A. Instruments Co., Ltd.], and the crystallization heat in the present invention is the differential scanning calorimeter. Is a value obtained by measuring under the following conditions according to the transition heat measurement method described in JIS K7122.
[Measurement condition]
After the sample was conditioned for 24 hours or more in the standard temperature state grade 2 and standard humidity state grade 2 described in JIS K 7100, about 5 mg was weighed, heated to 250 ° C. at a heating rate of 10 ° C. per minute, and held for 10 minutes. Cool to −50 ° C. at 10 ° C. per minute From the obtained DSC curve, the transition heat (crystallization heat) by cooling is determined.

(B) includes (B1) anionic, (B2) cationic, (B3) amphoteric surfactants, and mixtures thereof.
The anionic surfactant (B1) includes a carboxylic acid (for example, a C8-24 saturated or unsaturated fatty acid and ether carboxylic acid) and a salt thereof having a linear hydrophobic group, and a sulfate ester salt (for example, a higher alcohol sulfate ester). Salts (eg sulfate salts of C8-18 aliphatic alcohols) and higher alkyl ether sulfate salts [eg sulfate esters of EO (1-10 mol) adducts of C8-18 aliphatic alcohols]]; sulfonic acids Salts [C10-20, such as alkyl benzene sulfonates (eg sodium dodecylbenzene sulfonate), alkyl sulfonates, alkyl naphthalene sulfonates, dialkyl ester sulfosuccinates, hydrocarbons (eg alkanes, α-olefins) sulfonates And Igepon T type]; and Phosphate ester salts [e.g. higher alcohol (C8~60) EO adduct phosphoric acid ester salts and alkyl (C4~60) phenol EO adduct phosphoric acid ester salts] and the like.

  The cationic surfactant (B2) has a quaternary ammonium salt type [for example, tetraalkyl (C11-100) ammonium salt (for example, lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyl) having a linear hydrophobic group portion. Dimethylammonium bromide and stearyltrimethylammonium bromide), trialkyl (C10-80) benzylammonium salts [eg lauryldimethylbenzylammonium chloride (benzalkonium chloride)], alkyl (C8-60) pyridinium salts (eg cetylpyridinium chloride) and Sapamine type quaternary ammonium salts (eg stearamide ethyl diethyl methyl ammonium methosulfate)]; and amine salt types [eg higher aliphatic amino acids] Inorganic acids (eg, hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid) salts or organic acids (C2-22, eg, acetic acid, propionic acid, lauryl) of C12-60 (eg, laurylamine, stearylamine, cetylamine, hardened tallowamine and rosinamine) Inorganic acids (above) or organic acids (above) such as EO ethylene oxide adducts of acids, oleic acid, benzoic acid, succinic acid, adipic acid and azelaic acid) salts, higher aliphatic amines (C12-30) ) Salt].

Examples of the amphoteric surfactant (B3) include amino acid-type amphoteric surfactants [for example, higher alkyl (C8-24) amine propionate], betaine-type amphoteric surfactants, which have a linear hydrophobic group.
For example, higher alkyl (C8-24) dimethyl betaine, higher alkyl (C8-24) dihydroxyethyl betaine], sulfate ester type amphoteric surfactants [for example, higher alkyl (C8-24) amine sulfate and hydroxyethyl imidazoline sulfate Ester salts], sulfonate type amphoteric surfactants (for example, pentadecyl sulfotaurine salt and imidazoline sulfonate salt) and phosphate ester type amphoteric surfactants [for example, glycerin higher fatty acid (C8-24) esterified phosphoric acid Ester salt].

  Examples of the salts of (B1) and (B3) include alkali metal (lithium, sodium, potassium, etc.) salts, alkaline earth metal (calcium, magnesium, etc.) salts, Group IIB metal (zinc, etc.) salts, ammonium salts, and the like. , Alkylamine (C1-20) salts and alkanolamine (C2-12, such as mono-, di- and triethanolamine) salts.

These (B) may be used alone or in combination of two or more.
Of these, anionic surfactants are preferred from the viewpoint of cutting properties and antistatic properties, more preferred are sulfonates, and particularly preferred are alkylbenzene (C12-24) sulfonates (sodium linear dodecylbenzenesulfonate). Etc.), alkyl (C8-24) sulfonates and hydrocarbon (eg alkane, α-olefin) sulfonates.

[Antistatic agent]
The antistatic agent of the present invention comprises the hydrophilic block polymer (A) and the surfactant (B).
The weight ratio of (A) to (B) is preferably 99.9 / 0.1 to 80/20, more preferably 99.5 / 0.5 to 90/10 from the viewpoint of antistatic properties and cutting properties. is there.
The production method of the antistatic agent of the present invention includes a method of producing (A) in the presence of (B), and a method of post-adding (B) to (A). From the viewpoint of dispersibility of (B) into (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 for incorporating (B) during the production of (A) is not particularly limited, and may be any before 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 thermoplastic resin (C) containing the antistatic agent.
(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], polyacrylic resin (C3) [for example, polymethyl methacrylate], polystyrene resin (C4) [consisting of a vinyl group-containing aromatic hydrocarbon alone or a vinyl group-containing aromatic hydrocarbon, (meth) acrylic ester, (meth) acrylonitrile, and butadiene Copolymers having at least one selected from the group as structural units, such as polystyrene, styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / Styrene Polyester resin (C5) [for example, 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 15/85, 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-
Octene, 1-decene, 1-dodecene, etc.)], C4-30 dienes [alkadienes (butadiene, isoprene, etc.), cycloalkadienes (cyclopentadiene, etc.), etc.].

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

Acrylic monomers include C3-30, such as (meth) acrylic acid and its derivatives.
Examples of derivatives of (meth) acrylic acid include alkyl (C1-20) (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)
Acrylates, etc.], mono- and di-alkyl (C1-4) aminoalkyl (C2-4)
(Meth) acrylate [methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.], (meth) acrylonitrile and (meth) acrylamide may be 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 (such as methyl vinyl ether and ethyl vinyl ether). Halogen-containing vinyl monomers include C2-12, such as vinyl chloride, vinylidene chloride and chloroprene.

Examples of the polyolefin resin (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, preferred are polypropylene, polyethylene, propylene-ethylene copolymer, propylene and / or a copolymer of ethylene and one or more of C4-12 α-olefin [copolymerization ratio (weight ratio) = 90. / 10 to 10/90, random and / or block addition].

The melt flow rate (hereinafter abbreviated as MFR) of (C2) is preferably 0.5 to 150, more preferably 1 to 100 from the viewpoint of imparting resin physical properties and antistatic properties. The MFR is measured according to JIS K6758 (in the case of polypropylene: 230 ° C., load 2.16 kgf, in the case of polyethylene: 190 ° C., load 2.16 kgf).
The crystallinity of (C2) is preferably 0 to 98%, more preferably 0 to 80%, particularly preferably 0 to 70% from the viewpoint of antistatic properties.
The crystallinity is measured by a method such as X-ray diffraction, infrared absorption spectrum, etc. [Refer to “Solid Structure of Polymers—Lecture of Polymer Experiments 2” (Hatsugoro Minamishino), page 42, published by Kyoritsu Shuppan 1958).

  Examples of the polyacrylic resin (C3) include one or more (co) polymers [poly (meth) acrylic acid methyl ester, such as the above-mentioned acrylic monomers [alkyl (C1-20) (meth) acrylate, (meth) acrylonitrile, etc.], Poly (meth) butyl acrylate, etc.] and copolymers with one or more of the above-mentioned vinyl monomers copolymerizable with one or more of these monomers [acrylic monomer / vinyl monomer copolymerization ratio (weight ratio) is a resin physical property In view of the above, preferably 5/95 to 95/5, more preferably 50/50 to 90/10] [however, those included in (C2) are excluded] are included.

The MFR of (C3) is preferably 0.5 to 150, more preferably 1 to 100 from the viewpoint of resin physical properties. The MFR is measured according to JIS K7210 (1994) (230 ° C in the case of polyacrylic resin, load 1.2 kgf).

As the polystyrene resin (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 vinyl group-containing aromatic hydrocarbons include C8-30 styrene and its derivatives,
For example, o-, m-, and p-alkyl (C1-10) styrene (vinyl toluene, etc.), α-alkyl (C1-10) styrene (α-methylstyrene, etc.) and halogenated styrene (chlorostyrene, etc.) can be mentioned. .
Specific examples of (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. MFR is measured according to JIS K6871 (1994) (230 ° C. in the case of polystyrene resin, load 1.2 kgf).

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

  The polyamide resin (C6) includes 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 in the above (a011), and examples of (C61) include nylon 4, -5, -6, -8, -12 and the like.
Examples of the diamine and dicarboxylic acid in (C62) include those exemplified in the above (a013) and (a014), and (C62) includes nylon 66, hexamethylenediamine obtained by condensation polymerization of hexanemethylenediamine and adipic acid, and Examples thereof include nylon 610 by polycondensation of sebacic acid.
Examples of the aminocarboxylic acid in (C63) include those exemplified in the above (a012). 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.
Examples thereof include the diamine and / or dicarboxylic acid exemplified in the above (a013) and (a014).
Of the dicarboxylic acids as molecular weight modifiers, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and It is sodium 3-sulfoisophthalate. Of the diamines as molecular weight regulators, hexamethylene diamine and decamethylene diamine are preferable.

The MFR of (C6) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR is measured according to JIS K7210 (1994) (in the case of polyamide resin, 230 ° C., load 0.325 kgf).

Polycarbonate resins (C7) include bisphenols (C12-20, such as bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane) and dihydroxybiphenyl polycarbonates such as bisphenol and phosgene. Or the condensate with a carbonic acid diester is mentioned. Of the above bisphenols, bisphenol A is preferred from the viewpoint of the dispersibility of (A).
The MFR of (C7) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. MFR is measured according to JIS K7210 (1994) (in the case of polycarbonate resin, 280 ° C., load 2.16 kgf).

Examples of the polyacetal resin (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, etc.].
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. The MFR is measured according to JIS K7210 (1994) (in the case of polyacetal resin, 190 ° C., load 2.16 kgf).
The intrinsic viscosity [η] of (C8) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and antistatic properties.

In the resin composition of the present invention, an antistatic property improver (D1), a compatibilizing agent (D2), a flame retardant (D3), and others other than (B) as necessary, as long as the effects of the present invention are not impaired. One or two or more additives (D) selected from the group consisting of the additive for resin (D4) 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.) ), Bromide (lithium bromide, −
Sodium, -potassium, -magnesium and -calcium, etc.) and iodide (lithium iodide, -sodium, -potassium, -magnesium and -calcium etc.), etc.], perchlorates (lithium perchlorate, -sodium,- Potassium, -magnesium and -calcium, etc.), fluorinated sulfonic acid salts (lithium fluorosulfonate, -sodium, -potassium, -magnesium and -calcium etc.), methanesulfonate (lithium methanesulfonate, -sodium, -potassium) , -Magnesium and -calcium), trifluoromethanesulfonate (lithium trifluoromethanesulfonate, -sodium, -potassium, -magnesium and -calcium etc.), pentafluoroethanesulfonate (pentafluoroethane) Lithium fonate, -sodium, -potassium, -magnesium and -calcium), nonafluorobutanesulfonate (lithium nonafluorobutanesulfonate, -sodium, -potassium, -magnesium and -calcium), undecafluoropentane Sulfonates (lithium undecafluoropentanesulfonate, -sodium, -potassium, -magnesium, -calcium, etc.), tridecafluorohexanesulfonate (lithium tridecafluorohexanesulfonate, -sodium, -potassium, -magnesium) And -calcium, etc.), acetates (lithium acetate, -sodium, -potassium, -magnesium, -calcium, etc.), sulfates (sodium sulfate, -potassium, -magnesium, -calcium, etc.) Phosphate (sodium phosphate, - potassium - magnesium and - calcium, etc.), and the like thiocyanates (potassium thiocyanate, etc.).
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%.
The method of adding (D11) is not particularly limited, but it is preferable to disperse it in advance in the hydrophilic polymer (A) because it is easy to effectively disperse it 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 alcohol (C8-18, the same hereinafter), higher fatty acid (C8-24, same hereinafter) or higher alkylamine (C8-24). ) EO adduct (molecular weight 158 or more and Mn 200,000 or less); higher fatty acid ester of polyalkylene glycol (molecular weight 150 or more and Mn 6,000 or less) which is an EO adduct of glycol; polyhydric alcohol (C2-18) EO adduct of higher fatty acid ester (molecular weight of 250 or more and Mn of 30,000 or less); EO adduct of higher fatty acid amide (molecular weight 200) And Mn 30,000 or less); And polyhydric alcohol (as described above) EO adduct of alkyl (C3-60) ether (molecular weight of 120 or more and Mn30,000 or less)], and polyhydric alcohol (C3-60) type nonionic surfactant [For example, fatty acid (C3-60) ester of polyhydric alcohol, alkyl (C3-60) ether of polyhydric alcohol and fatty acid (C3-60) alkanolamide].

  Examples of the anionic surfactant are those excluding the (B1) and (D11), and among the (B1), those in which the hydrophobic group portion is not linear are exemplified. For example, branched sodium dodecylbenzenesulfonate, Examples include branched sodium dodecyl sulfonate.

  Examples of the cationic surfactant include those excluding the above (B2), and among the above (B2), those in which the hydrophobic group portion is not linear.

  Examples of the amphoteric surfactant are those excluding the above (B3), and among the above (B3), those in which the hydrophobic group portion is not linear are exemplified.

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

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 (D11) and (D12), has a melting point of room temperature or lower, and at least one of cations or anions constituting (D13) is an organic ion, and has an initial conductivity. Is a room temperature molten salt of 1 to 200 ms / cm (preferably 10 to 200 ms / cm), for example, a room temperature molten salt described in WO95 / 15572. Examples of the cation constituting (D13) include an amidinium cation, a guanidinium cation, and a tertiary ammonium cation.

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

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

  Examples of the tertiary ammonium cation include methyl dilauryl ammonium.

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

In the ionic liquid (D13), examples of the organic acid or inorganic acid constituting the anion include the following.
Examples of the organic acid include carboxylic acid, sulfate ester, higher alkyl ether sulfate ester, sulfonic acid and phosphate ester.
Examples of the inorganic acid include super strong acids (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid. It is done.
The organic acid and inorganic acid may be used alone or in combination of two or more.
Among the organic and inorganic acids, Hamett acidity function initial conductivity standpoint preferred from of the anion constituting the (D13) of (D13) (-H ₀₎ is 12 to 100, the superacid conjugate base , Acids that form anions other than the conjugate bases of super strong acids, and mixtures thereof.

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

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

Examples of the protonic acid used in combination with the Lewis acid include hydrogen halides (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. , Pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof.
Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of (F3).

Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof. Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of (D13).
The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

  Of the above anions, (D13) from the viewpoint of the initial conductivity, a super strong acid conjugate base (a super strong acid comprising a proton acid and a super strong acid comprising a combination of a proton acid and a Lewis acid), more preferably It is a conjugate base of a super strong acid consisting of a super strong acid consisting of a proton acid and a proton acid and boron trifluoride and / or phosphorus pentafluoride.

The amount of (D13) used is usually 10% or less based on the total weight of (A), (B) and (C), preferably from the viewpoint of good appearance and antistatic effect of the molded product, and mechanical properties. 0.001 to 5%, more preferably 0.01 to 3%.
The method for adding (D13) is not particularly limited, but from the viewpoint of effective dispersion in the resin, it is preferably preliminarily dispersed in (A), and after the production (polymerization) of (A). More preferably, (D13) is added and dispersed in advance.

  The production method of (D13) is, for example, an amidatenium cation and / or a dimethyl carbonate salt of a guanidinium cation obtained by quaternization with dimethyl carbonate or the like, and an acid [(D13) above, which constitutes an anion. Acid or inorganic acid] to perform acid exchange, or after amidinium cation and / or guanidinium cation is hydrolyzed to form monoamidoamine, the monoamidoamine is converted to acid (same as above) The method of neutralizing with is mentioned.

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 sulfonyl group described in JP-A-6-345927, a block polymer having a polyolefin portion and an aromatic vinyl polymer portion, and the like can be used.
The amount of (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 for adding (D2) is not particularly limited, but it is preferable to disperse it in advance in the hydrophilic 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 for 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 salts, esters and amides thereof;
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.

Examples of the phosphate include phosphates and condensed phosphates (di- and polyphosphates).
Examples of the phosphate include trialkyl (alkyl group is C1-12) phosphate [trimethyl-, triethyl-, tributyl- and trioctylphosphate etc.], trialkoxy (alkoxy group is C1-6) phosphate [triethoxy- and tributoxyphosphate etc. ], Triaryl phosphate [triphenyl phosphate and the like], alkyl (alkyl group is C1-10) aryl phosphate [tricresyl-, cresyldiphenyl-, octyldiphenyl-, diisopropylphenyl- and resorcinol-bis (di-2,6- Dimethylphenyl) phosphate, etc.].

  Examples of the condensed phosphate include trialkyl (alkyl group is C1-12) poly (n = 2-30) phosphate, phenyl resorcinol poly (n = 2-30) phosphate, resorcinol poly (n = 2-30) phosphate [resorcin bis. Phosphate, cresyl resorcinol polyphosphate, etc.], hydroquinone poly (n = 2-30) phosphate [hydroquinone bisphosphate, hydroquinone polyphosphate, etc.], bisphenol A bisphosphate, trioxybenzene triphosphate and the like.

  Examples of the halogen-containing phosphate include tris halogenated alkyl (alkyl group is C2-4) phosphate [trischloroethyl phosphate, trisdichloropropyl phosphate, tris-β-chloropropyl phosphate, tris (tribromoneopentyl) phosphate, etc.], And tris-halogenated aryl phosphate [tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, etc.].

Examples of the phosphonate include phosphonates and condensed phosphonates.
As phosphonates, trialkyl (alkyl group is C1-12) phosphonate [trimethylphosphonate, triethylphosphonate, tributylphosphonate, trioctylphosphonate, etc.], trialkoxy (alkoxy group is C1-6) phosphonate [triethoxyphosphonate, tributoxyphosphonate Etc.], triaryl phosphonate [triphenyl phosphonate etc.], alkyl (alkyl group is C1-10) aryl phosphonate [tricresyl phosphonate, cresyl diphenyl phosphonate, octyl diphenyl phosphonate, diisopropyl phenyl phosphonate, resorcinol-bis (di-2) , 6-dimethylphenyl) phosphonate and the like.

  As the condensed phosphonate, trialkyl (alkyl group is C1-12) poly (n = 2 to 30) phosphonate, phenyl resorcinol poly (n = 2 to 30) phosphonate, resorcinol poly (n = 2 to 30) phosphonate [resorcinbis Phosphate, cresyl resorcinol polyphosphonate, etc.], hydroquinone poly (n = 2-30) phosphonate [hydroquinone bisphosphonate, hydroquinone polyphosphonate, etc.], bisphenol A bisphosphonate, trioxybenzene triphosphonate and the like.

  Examples of the halogen-containing phosphonate include tris halogenated alkyl (alkyl group is C2-4) phosphonate [trischloroethyl phosphonate, tris dichloropropyl phosphonate, tris-β-chloropropyl phosphonate, tris (tribromoneopentyl) phosphonate, etc.], And tris-halogenated aryl phosphonate [tris (tribromophenyl) phosphonate, tris (dibromophenyl) phosphonate, etc.].

  As said ammonium phosphate, what is marketed normally for flame retardants can be used. These may be used in combination with a melamine compound (for example, melamine alone), a pentaerythritol compound (for example, pentaerythritol, dipentaerythritol), an amide (for example, nylon 6, nylon 66) or the like, if necessary.

  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%.

Moreover, according to various uses, the other resin additive (D4) can be arbitrarily added to the resin composition of this invention in the range which does not inhibit the effect of this invention.
(D4) includes one or more additives selected from the group consisting of pigments, dyes, nucleating agents, lubricants, plasticizers, mold release agents, antioxidants, ultraviolet absorbers and antibacterial agents. .

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 lakes, monoazos, disazos, chelate azos, etc.), polycyclic pigments (benzoimidazolones, phthalocyanines) Examples of the dye include azo, indigoid, sulfide, alizarin, acridine, thiazole, nitro, and aniline.
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 polyhydric (divalent to tetravalent or higher) alcohol esters of fatty acids (C2-18). (Hardened castor oil etc.), glycol (C2-8) ester of fatty acid (C2-18) (ethylene glycol monostearate etc.) and liquid paraffin etc .;

Antioxidants include phenolic [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.), bisphenol [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;
Antibacterial agents include benzoic acid, sorbic acid, halogenated phenol, organic iodine, nitriles (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, and pyridine compounds.

  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 comprising (A) and (B), (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 are no particular limitations on the order of addition of each component during melt mixing. For example, (1) a method in which (1) an antistatic agent, (C) and, if necessary, (D) are melt mixed together, (2) An antistatic agent 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) and if necessary (D) And a method of melt mixing.
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 or a master pellet 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 mechanical properties, heat resistance, and permanent antistatic properties, as well as good paintability and printability.
Examples of the method for coating the molded product include, but are not limited to, an air spray method, an airless spray method, an electrostatic spray method, a dipping method, a roller method, and a brush coating method. Examples of the paint include various paints such as polyester melamine, epoxy melamine, acrylic melamine, and acrylic urethane resin paint.
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
In a stainless steel autoclave, 103 parts of ε-caprolactam, 21.8 parts of terephthalic acid, an antioxidant [trade name “Irganox 1010”, manufactured by Ciba Specialty Chemicals Co., Ltd., and so on. ] 0.4 parts and 7 parts of water were charged, the inside of the autoclave was purged with nitrogen, and then heated and stirred at 220 ° C. under pressure (0.3 to 0.5 MPa) for 4 hours under sealed conditions. Acid value having carboxyl groups at both ends 120 parts of 118 polyamide (a-1) were obtained.
Next, 119 parts of an EO adduct of bisphenol A (Mn1,600), 16 parts of an EO adduct of bisphenol A (Mn310) and 0.5 part of zirconyl acetate were added, and the mixture was heated at 240 ° C. under a reduced pressure of 0.13 kPa or less for 6 hours. A viscous block polymer (A-1) was obtained by polymerization. The surface specific resistance value of (A-1) was 4 × 10 ⁹ Ω, and Mn was 22,000.
Next, 16.1 parts of linear dodecylbenzenesulfonate lithium (B-1) [crystallization heat at crystallization peak temperature (98 ° C.) is 3 mJ / mg] is added to 245 parts of (A-1). The mixture was stirred for 1 hour to obtain an antistatic agent (X-1) composed of (A-1) and (B-1). (X-1) was taken out, formed into a sheet shape with a cooling roll, and pelletized. The surface specific resistance value of (X-1) was 1 × 10 ⁸ Ω. Further, the cutting property evaluated by the method described later is (X
In the case of -1), the proportion of pellets having a good shape was 82%.

Example 2
In the production of the polyamide of Example 1, in the same manner as in Example 1 except that 103 parts of ε-caprolactam and 21.8 parts of terephthalic acid were used, 104 parts of 12-aminododecanoic acid and 21 parts of adipic acid were used. 120 parts of polyamide (a-2) having an acid value of 126 having carboxyl groups at both ends were obtained.
In another stainless steel autoclave, 87.3 parts of dimethyl terephthalate, 37 parts of EG, and 0.2 part of zinc acetate were charged, and the temperature was raised to 210 ° C. while distilling a predetermined amount of methanol. After cooling to room temperature, 128 parts of polyethylene glycol (Mn 3,000), 106 parts of (a-2) and 0.3 part of zirconyl acetate were added and polymerized at 240 ° C. under reduced pressure of 0.13 kPa or less for 6 hours. A block polymer (A-2) was obtained. The surface resistivity of (A-2) was 1 × 10 ¹¹ Ω, and Mn was 15,000.
Next, with respect to 314 parts of (A-2), linear sodium stearate [total crystallization heat at crystallization peak temperatures (101, 122 and 183 ° C.) is 49 mJ / mg] (B-2) 17.5 Part was added and stirred for 1 hour to obtain an antistatic agent (X-2) composed of (A-2) and (B-2). Thereafter, (X-2) was pelletized in the same manner as in Example 1. The surface specific resistance value of (X-2) was 8 × 10 ⁸ Ω, and the cutting property was 93% in the proportion of well-shaped pellets.

Example 3
A stainless steel autoclave was charged with 56.8 parts of EO product of bisphenol A (Mn310), 23.5 parts of terephthalic acid, and 0.4 parts of dibutyltin oxide, and heated and stirred at 235 ° C. under a reduced pressure of 3 kPa or less for 12 hours. 75 parts of a polyester having hydroxyl groups at both ends (hydroxyl value 53) (c-1) was obtained.
Next, 140 parts of EO product of bisphenol A (Mn1,600), 116 parts of (a-1) and 0.4 part of zirconyl acetate were added and polymerized at 240 ° C. under reduced pressure of 0.13 kPa or less for 6 hours. A thick block polymer (A-3) was obtained. The surface specific resistance value of (A-3) was 4 × 10 ¹⁰ Ω, and Mn was 28,000.
Next, linear sodium lauryl alcohol sulfate ester (total sum of crystallization heat at crystallization peak temperatures (6 and 180 ° C.) is 25 mJ / mg) with respect to 320 parts of (A-3) (B-3) 11.7 Part was added and stirred for 1 hour to obtain an antistatic agent (X-3) composed of (A-3) and (B-3). Thereafter, (X-3) was pelletized in the same manner as in Example 1. The surface specific resistance value of (X-3) was 7 × 10 ⁸ Ω, and the cutting property was 87% in a well-shaped pellet.

Example 4
Low molecular weight polypropylene obtained by a thermal degradation method (Mn 2,500, density 0.89, 10.5 double bonds per 1,000 C, average of double bonds per molecule) 1.9 parts, content of polyolefin that can be modified at both ends (95%) 170 parts and 30 parts of maleic anhydride are charged, melted at 200 ° C. in a nitrogen gas atmosphere (sealed), and reacted at 200 ° C. for 20 hours. I let you.
Thereafter, unreacted maleic anhydride was distilled off under reduced pressure of 0.67 kPa or less at 200 ° C. for 3 hours to obtain acid-modified polypropylene (a-3). (A-3) had an acid value of 41.
Next, another stainless steel autoclave was charged with 120 parts of (a-3), 130 parts of polyethylene glycol (Mn3,000), 0.6 part of antioxidant and 1 part of zirconyl acetate, and 230 ° C. and 0.13 kPa or less. The mixture was polymerized for 3 hours under reduced pressure to obtain a viscous polymer (A-4). The surface resistivity of (A-4) was 5 × 10 ⁹ Ω, and Mn was 10,000.
Next, linear cetyltrimethylammonium chloride [total crystallization heat at crystallization peak temperatures (11 and 43 ° C.) is 12 mJ / mg] (B-4) 20.8 parts relative to 238 parts (A-4) And stirred for 1 hour to obtain an antistatic agent (X-4) composed of (A-4) and (B-4). Thereafter, (X-4) was pelletized in the same manner as in Example 1. The surface specific resistance value of (X-4) was 5 × 10 ⁸ Ω, and the cutting property was 80% of a well-shaped pellet.

Example 5
In Example 1, instead of post-adding (B-1) to the block polymer (A-1), 16.1 parts of (B-1) was charged during the production of (A-1), (B- The antistatic agent (X-5) comprising (A-1) and (B-1) was obtained in the same manner as in Example 1 except that (A-1) was produced in the presence of 1), and pellets were obtained. Turned into. The surface specific resistance value of (X-5) was 8 × 10 ⁷ Ω. Further, regarding the cutting property of (X-5), the proportion of pellets having a good shape was 91%.

Example 6
In the production of the polyamide of Example 1, in place of 103 parts of ε-caprolactam and 21.8 parts of terephthalic acid, 207 parts of 12-aminododecanoic acid and 16.2 parts of trimellitic acid were used. Thus, 204 parts of polyamideimide (a-6) having an acid value of 41 having carboxyl groups at both ends were obtained.
Next, 5.6 parts of polyoxyethylenedipropylamine (Mn10,000), 22 parts of EO adduct of bisphenol A (Mn310) and 0.5 part of zirconyl acetate were added, and the mixture was subjected to reduced pressure at 240 ° C. and 0.13 kPa or less. For 6 hours to obtain a viscous block polymer (A-6). The surface resistivity of (A-6) was 1 × 10 ¹³ Ω, and Mn was 17,000.
Next, 0.2 part of (B-1) is added to 180 parts of (A-6), and the mixture is stirred for 1 hour, and the antistatic agent (X-6) comprising (A-6) and (B-1) is added. ) Thereafter, (X-6) was pelletized in the same manner as in Example 1. The surface specific resistance value of (X-6) was 1 × 10 ¹² Ω, and the cutting property was 90% of a well-shaped pellet.

Example 7
A stainless steel autoclave was charged with 78 parts of adipic acid, 75 parts of xylylene glycol and 0.2 part of dibutyltin oxide, and polymerized at 230 ° C. under reduced pressure of 0.13 kPa or less for 2 hours. After cooling to room temperature, 140 parts of (a-6), 24 parts of polyoxypolyethylenepropylamine (Mn10,000) and 0.5 part of zirconyl acetate are added and polymerized for 6 hours at 240 ° C. under reduced pressure of 0.13 kPa or less. A viscous block polymer (A-7) was obtained. The surface resistivity of (A-7) was 7 × 10 ¹¹ Ω, and Mn was 44,000.
Next, 27 parts of (B-2) is added to 240 parts of (A-7), and the mixture is stirred for 1 hour, and an antistatic agent (X-7) comprising (A-7) and (B-2) is added. Obtained. Thereafter, (X-7) was pelletized in the same manner as in Example 1. The surface specific resistance value of (X-7) was 8 × 10 ⁹ Ω, and the cutting property was 89% of the pellets having a good shape.

Example 8
In a stainless steel autoclave, 110 parts of (a-3), 35 parts of 12-aminododecanoic acid, and 0.6 part of an antioxidant were charged and polymerized at 210 ° C. under reduced pressure of 0.13 kPa or less for 1 hour. After cooling to room temperature, 62 parts of polyoxypolyethylenepropylamine (Mn10,000), 102 parts of polyethylene glycol (Mn3,000), 1 part of sodium sulfate and 1 part of dibutyltin oxide were charged, and the pressure was reduced to 230 ° C. and 0.13 kPa or less. For 6 hours to obtain a viscous polymer (A-8). The surface resistivity of (A-8) was 1 × 10 ⁶ Ω, and Mn was 26,000.
Next, 70 parts of (B-4) is added to 280 parts of (A-8), and the mixture is stirred for 1 hour, and antistatic agent (X-8) comprising (A-8) and (B-4) is added. Obtained. Thereafter, (X-8) was pelletized in the same manner as in Example 1. The surface specific resistance value of (X-8) was 7 × 10 ⁵ Ω, and the cutting property was 79% of the pellets having a good shape.

Example 9
A stainless steel autoclave was charged with 135 parts of (a-3) and 3.1 parts of 2-aminoethanol, and reacted at 210 ° C. under reduced pressure of 0.13 kPa or less for 1 hour. After normal pressure with nitrogen, 17 parts of hexamethylene diisocyanate (HDI) and 0.1 part of dibutyltin dilaurate were added and reacted at 180 ° C. for 1 hour. Furthermore, 148 parts of polyethylene glycol (Mn3,000) and 1 part of dibutyltin oxide were added and polymerized at 230 ° C. under reduced pressure of 0.13 kPa or less for 3 hours to obtain a viscous polymer (A-9). The surface resistivity of (A-9) was 3 × 10 ⁹ Ω, and Mn was 19,000.
Next, 1.2 parts of (B-4) is added to 240 parts of (A-9), and the mixture is stirred for 1 hour. The antistatic agent (X-9) comprising (A-9) and (B-4) ) Thereafter, (X-9) was pelletized in the same manner as in Example 1. The surface specific resistance value of (X-9) was 5 × 10 ⁸ Ω, and the cutting property was 87% in a well-shaped pellet.

Comparative Example 1
In Example 1, instead of 16.1 parts of linear lithium dodecylbenzenesulfonate (B-1), branched lithium dodecylbenzenesulfonate [crystallization heat at crystallization peak temperature (85 ° C.) is 1 mJ / mg] ( Comparative B-1) Except that 16.1 parts were used, the same procedure as in Example 1 was performed to obtain an antistatic agent (Ratio X-1) consisting of (A-1) and (Ratio B-1). Turned into. The surface specific resistance value of (Ratio X-1) was 1 × 10 ⁸ Ω, and the cutting property was 61% in a well-shaped pellet.

The cutting property and the surface resistivity (antistatic property) in the above were evaluated by the following methods. The results are shown in Table 1 together with the cutting properties.
[Cutting properties]
After producing the antistatic agent, it is taken out, formed into a sheet of about 3 mm thickness with a cooling roll, cooled to a resin temperature of about 50 ° C., and then with a square pelletizer [trade name “SGG-220”, manufactured by Horai Co., Ltd.] Cutting into 4 mm square pellets, sampling 50 g (about 1,000 pellets), good shape (4 mm square shape) pellets and defective shape (indefinite shape and several pellets connected without being cut completely) Are also included). The ratio (%) of the selected well-shaped pellets was calculated.

[Surface specific resistance]
Each of the above-mentioned antistatic agent pellets was molded with a pressure press (200 ° C.) to prepare a test piece having a thickness of 1 mm and a diameter of about 100 mm. (However, the molded article to be described later was used as a test piece as it was.) About the test piece, 23 ° C. was measured by a superinsulator [DSM-8103 (plate sample electrode SME-8310), manufactured by Toa Denpa Kogyo Co., Ltd.]. The surface specific resistance value (antistatic property) was evaluated in accordance with ASTM D257 under an atmosphere with a humidity of 50% RH.

Examples 10-22, Comparative Example 2
According to the formulation (parts) shown in Table 1, the antistatic agent and the thermoplastic resin (C) [described later (C-1) or (C-2)] are optionally combined with the additive (D) in a Henschel mixer. And then blended for 3 minutes in a twin screw extruder with a vent at 230 ° C., 100 rpm, residence time 5 minutes to obtain a resin composition (Examples 10-22, Comparative Example 2). .

  Using the injection molding machine [PS40E5ASE, manufactured by Nissei Plastic Industry Co., Ltd.], a molded product (test piece) (100 × 100 × 2 mm) was prepared at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. These were used to measure the surface resistivity. The results are shown in Table 1.

(C-1): ABS resin [trade name “Cebian-V320”, manufactured by Daicel Polymer Co., Ltd.]
(C-2): PP resin “trade name“ Chisso Polypro K1008 ”, manufactured by Chisso Corporation]
(D-1): Octyl alcohol EO adduct (Mn400)
(D-2): Compatibilizer [trade name “Yumex 1001”, manufactured by Sanyo Chemical Industries, Ltd.]
(D-3): Flame retardant [trade name “ADK STAB FP-2200”, manufactured by ADEKA Corporation]

  From the results of Table 1, it can be seen that the antistatic agents (X-1) to (X-9) of the present invention are all excellent in cutting property, that is, productivity, as compared with the comparative (ratio X-1).

  The antistatic agent of the present invention is excellent in productivity (cutting properties) and permanent antistatic properties, and a molded product obtained by molding a resin composition containing the antistatic agent in a thermoplastic resin, It has excellent permanent antistatic properties and excellent paintability and printing characteristics. Therefore, the antistatic resin composition of the present invention is produced by injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding and film molding (for example, casting method, tenter method and inflation method). ), Etc., housing products such as home appliances / OA equipment, game machines and office equipment, various plastic container materials such as trays and containers used in clean rooms such as IC trays, various cushioning materials, etc. It can be widely used as a material for various moldings such as coating materials for packaging materials, protective films, etc., flooring sheets, artificial turf, mats, tape base materials for semiconductor manufacturing processes, and automobile parts.

Claims (7)

Hydrophilic block polymer (A) having a surface resistivity of 1 × 10 ⁶ to 1 × 10 ¹³ Ω and an ionic interface having a crystallization heat of 2 to 100 mJ / mg at the crystallization peak temperature measured by a differential scanning calorimeter An antistatic agent comprising the activator (B). The antistatic agent according to claim 1, wherein (A) is at least one selected from the group consisting of the following (A1), (A2) and (A3).
(A1): Hydrophobic amide group-containing hydrophobic polymer (a1) composed of polyamide (a11) and / or polyamideimide (a12), polyether chain-containing hydrophilic composed of polyether diol (b11) and / or polyether diamine (b12) Block polymer (A2) composed of the functional polymer (b1) and the aromatic ring-containing polyester (c1): the polyolefin (a21) block and the polyether chain-containing hydrophilic polymer (a22) block are ester bonds, amide bonds, A block polymer having a structure in which the structure is repeatedly and alternately bonded through at least one bond selected from the group consisting of an ether bond, an imide bond and a urethane bond (A3): composed of polyamide (a11) and / or polyamideimide (a12) Amide group containing sparse Sex polymer (a1), and polyether diols (b11) and / or block polymer composed of polyether chains containing hydrophilic polymer (b1) consisting of polyether diamine (b12) The antistatic agent according to claim 1 or 2, wherein the weight ratio of (A) to (B) is 99.9 / 0.1 to 80/20. The antistatic resin composition which makes the thermoplastic resin (C) contain the antistatic agent in any one of Claims 1-3. Further, at least one additive (D) selected from the group consisting of an antistatic improver, a compatibilizer, a flame retardant, and other additives for resin other than (B) is contained. The composition as described. An antistatic resin molded product obtained by molding the composition according to claim 4 or 5. A molded article obtained by coating and / or printing the molded article according to claim 6.