JP5514396B2 - Antistatic resin composition - Google Patents

Description

  The present invention relates to an antistatic agent comprising a plasticizer and a hydrophilic group-containing polymer. More specifically, the present invention relates to an antistatic agent having a permanent antistatic effect, which is made of a hydrophilic group-containing polymer containing a plasticizer and having reduced crystallinity.

Conventionally, as a resin composition in which an antistatic agent is added to a thermoplastic resin to impart antistatic properties, a surfactant is directly contained in the thermoplastic resin as an antistatic agent (see, for example, Patent Document 1), A polyether chain-containing antistatic agent obtained by polymerization in the presence of a surfactant containing a thermoplastic resin (for example, see Patent Document 2), an ionic salt comprising a nitrogen onium cation and a fluorine-containing organic anion. What is contained in a thermoplastic resin as an antistatic agent (see, for example, Patent Document 3), and one made of a polymer solid electrolyte that contains an ionic liquid as an antistatic agent (see, for example, Non-Patent Document 1), etc. Was known.
Conventionally, a plasticizer is further added to the above resin composition obtained by adding an antistatic agent to a thermoplastic resin to impart antistatic properties for the purpose of improving moldability and imparting flexibility. (For example, see Patent Document 4)

JP-A-14-146212 (pages 33-42, FIG. 3) JP 2002-146212 A Special table 2003-511505 gazette "Chemistry and Industry", Vol. 54 (2001) No. 3, 281-285, The Chemical Society of Japan Publication Japanese Patent Laid-Open No. 2004-190028

However, in the above conventional method, when the amount of the antistatic agent used is increased for the purpose of further improving the antistatic property, the appearance of the molded product is deteriorated due to the moldability defect of the resin composition, or the machine of the molded product. There were problems such as deterioration of characteristics. Moreover, the effect that the plasticizer improves the antistatic property in the conventional method was not recognized.
An object of the present invention is to provide an antistatic agent excellent in antistatic property imparting effect, an antistatic resin composition excellent in moldability containing the antistatic agent, and a molded product excellent in permanent antistatic property and mechanical properties. Is to provide.

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 comprises a plasticizer (A) and a hydrophilic group-containing polymer (B) having a volume resistivity of 1 × 10 ⁶ to 1 × 10 ¹² Ω · cm. An antistatic agent; an antistatic resin composition containing the antistatic agent in a thermoplastic resin (C); a molded article formed by molding the composition; and coating and / or printing on the molded article. An antistatic agent comprising a plasticizer (A) and a hydrophilic group-containing polymer (B) having a volume resistivity of 1 × 10 ⁶ to 1 × 10 ¹² Ω · cm; It is a manufacturing method of the antistatic resin composition characterized by making it contain in a plastic resin (C).

The antistatic agent, antistatic resin composition and molded product of the present invention have the following effects.
(1) The antistatic agent of the present invention can impart excellent permanent antistatic properties to thermoplastic resins.
(2) An antistatic resin composition comprising the thermoplastic resin containing the antistatic agent is excellent in moldability.
(3) A molded product formed by molding the antistatic resin composition has excellent mechanical properties and high permanent antistatic properties.

As the plasticizer (A) in the present invention, mono- and diesters (A1) containing a polyoxyalkylene chain, polyester polyol (A2), polyether polyol (A3), aromatic carboxylic acid ester [carbon number (hereinafter referred to as C and Abbreviations) 10 to 28, such as phthalic acid esters (dioctyl phthalate, dibutyl phthalate, di2-ethylhexyl phthalate, etc.)], aliphatic monocarboxylic acid esters [C3-30, such as methylacetylricinoleate], aliphatic dicarboxylic acid esters [ C8 or more and number average molecular weight [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method. ] 2,000 or less, such as di (2-ethylhexyl) adipate, adipic acid-propylene glycol polyester (Mn 200 to 2,000)], aliphatic tricarboxylic acid ester [for example, citrate ester (triethyl citrate, etc.)], phosphorus Examples include acid triesters [for example, triphenyl phosphate] and petroleum resins.
Among these (A), (A1), (A2) and (A3) are preferable from the viewpoint of the effect of reducing the crystallinity of (B) and increasing the antistatic property.

The mono- and diester (A1) containing a polyoxyalkylene chain is obtained by reacting a polyether diol (b221) or a copolyether diol with a monocarboxylic acid, represented by any of the following formulas: Diesters are included.

R—CO— (OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _{m ′} —OC—R (A11)

R—CO— (OA ¹ ) _m —O—OC—R (A12)

R—CO— (OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _{m ′} —H (A13)

R—CO— (OA ¹ ) _m —O—H (A14)

Of (A1) represented by the above formula, (A11) and (A12) are preferable from the viewpoint of the effect of reducing the crystallinity of (B) and increasing the antistatic property.

In the formula, E ¹ represents a diol (b220) or a residue obtained by removing a hydroxyl group from a dihydric phenol, and A ¹ represents C 2 to 12 (preferably 2 to 8, more preferably a halogen atom). 2-4) represents an alkylene group. M and m ′ are integers of 1 to 300, preferably 2 to 250, and more preferably 8 to 150. M and m ′ may be the same or different. m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form in the case where they are composed of two or more oxyalkylene groups is a block or Either random or a combination thereof may be used.

Diols (b220) include C2-12 (preferably 2-10, more preferably 2-8) dihydric alcohols (eg, aliphatic, alicyclic or araliphatic dihydric alcohols), and tertiary amino Group-containing diols can be used.
Examples of the aliphatic dihydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 1,12-dodecanediol.
Examples of the alicyclic dihydric alcohol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-cyclooctanediol, and 1,3-cyclopentanediol.
Examples of the araliphatic dihydric alcohol include xylylenediol, 1-phenyl-1,2-ethanediol, and 1,4-bis (hydroxyethyl) benzene.

As the tertiary amino group-containing diol, for example, a bishydroxyalkyl (1-12, preferably 2-2) of an aliphatic or alicyclic primary monoamine (C1-12, preferably 2-10, more preferably 2-8). 10, more preferably 2-8) and bishydroxyalkyl (C1-12) compounds of aromatic (aliphatic) primary monoamines (C6-12).
The bishydroxyalkylated monoamine can be easily obtained by various methods, for example, by reacting monoamine with C2-4 or higher alkylene oxide (hereinafter abbreviated as AO) or C1-12. It can be obtained by reacting a monoamine with a C1-12 halogenated hydroxyalkyl (for example, 2-bromoethyl alcohol, 3-chloropropyl alcohol).

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

  Examples of the dihydric phenol include C6-18 (preferably 8-18, more preferably 10-15) such as monocyclic dihydric phenol (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenol (bisphenol A, -F). And -S, 4,4'-dihydroxydiphenyl-2,2-butane, etc.), dihydrokibiphenyl, and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol, etc.).

  In the above formula, R is a C1-24 monovalent hydrocarbon group, and specific examples include aliphatic, aromatic and alicyclic hydrocarbon groups.

  Aliphatic saturated hydrocarbon groups include C1-24 alkyl groups such as methyl, ethyl, n- and i-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl groups, dodecyl, tridecyl, tetradecyl. , Pentadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, 2-propyl-1-pentyl, 2-ethyl-1-hexyl, 4-methyl-3-heptyl and 6-methyl-2- Heptyl group; aliphatic unsaturated hydrocarbon group includes C2-24 alkenyl group or alkynyl group such as ethenyl, 1-, 2- and i-propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, decenyl, undecenyl, Dodecenyl, tri Cenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, henecocenyl, dococenyl, tricocenyl, tetracocenyl, ethynyl, 2-propynyl, pentynyl, hexynyl, 3-methyl-3-butenyl and 4-methyl-3-pentenyl groups Etc.

  Examples of the aromatic hydrocarbon group include C6-24, such as phenyl group, alkyl (C1-10) aryl group (o-, m- and p-methylphenyl, m, p-dimethylphenyl, 2,6-dimethylphenyl, o-, m- and p-ethylphenyl, pn-butylphenyl, p-octylphenyl and p-nonylphenyl groups), aralalkyl (C1-20 alkyl) groups (benzyl and phenethyl groups, etc.), substitution Aralalkyl (alkyl C1-20) group (o-, m- and p-methylbenzyl, pn-butylphenethyl group, etc.); as alicyclic hydrocarbon group, C4-20, such as cyclopentyl group, cyclohexyl Groups and the like.

Polyester polyol (A2) includes low molecular weight (usually C2 or more and Mn300 or less) polyol (2 to 8 or more) and polyvalent (2 to 3 or more) carboxylic acids or ester-forming derivatives thereof. And polycondensate polyol obtained by the ring-opening polymerization of lactone, polycarbonate polyol obtained by the reaction of ethylene carbonate and polyol (1,6-hexanediol, etc.), and the like. Both ends of (A2) may be either OH groups or COOH groups.
Of these (A2), preferred are condensed polyester polyols and polylactone polyols from the viewpoint of the effect of lowering the crystallinity of (B) and increasing antistatic properties.

The low molecular weight polyol constituting the condensed polyester polyol includes a dihydric to octahydric or higher polyhydric alcohol, and an AO low mole (1 to 8) of the polyhydric alcohol or a dihydric to octahydric or higher polyhydric phenol. 10) Additives are mentioned.
The polyhydric alcohol includes the following.
Dihydric alcohols (C2-20 or higher), for example C2-12 aliphatic dihydric alcohols [(di) alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,3 -, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentanediol (hereinafter abbreviated as EG, DEG, PG, DPG, BD, HD, NPG and MPD, respectively) ), Dodecanediol, etc.]; C6-10 alicyclic divalent alcohol [1,4-cyclohexanediol, cyclohexanedimethanol, etc.]; C8-20 aromatic ring-containing dihydric alcohol [xylylene glycol, bis (hydroxyethyl) Benzene etc.]; trivalent to octavalent or it The above polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol and dipentaerythritol (hereinafter referred to as GR, TMP, PE, SO and DPE respectively) Abbreviations), 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins, etc.], saccharides and their derivatives [eg sucrose, glucose, fructose, mannose, lactose, and glycosides (Methyl glucoside etc.)].

  The polyhydric phenol includes C6-18 dihydric phenol, such as monocyclic dihydric phenol (hydroquinone, catechol, resorcinol, urushiol, etc.), bisphenol (bisphenol A, -F, -C, -B, -AD and -S, dihydroxybiphenyl, 4,4'-dihydroxydiphenyl-2,2-butane, etc.), and condensed polycyclic dihydric phenols [dihydroxynaphthalene (eg, 1,5-dihydroxynaphthalene), binaphthol, etc.]; Octavalent or higher polyhydric phenols such as monocyclic polyphenols (pyrogallol, phloroglucinol, and mono- or dihydric phenols (phenol, cresol, xylenol, resorcinol, etc.) aldehydes or ketones (formaldehyde, glutaraldehyde) , Lyoxal, acetone) low condensates (eg phenol or cresol novolac resins, resole intermediates, polyphenols obtained by the condensation reaction of phenol and glyoxal or glutaraldehyde, and polyphenols obtained by the condensation reaction of resorcin and acetone) .

  Examples of polycarboxylic acids or ester-forming derivatives thereof include C2-20 dicarboxylic acids such as aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, etc.), and alicyclic dicarboxylic acids. Acids (1,3- and 1,4-cyclohexanedicarboxylic acid, dimer acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.); trivalent or higher polycarboxylic acids (trimellitic acid, Pyromellitic acid, etc.); anhydrides of these polycarboxylic acids (succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.); acid halides of these polycarboxylic acids (adipic acid dichloride, etc.) ); Lower alkyl (C1-4) esters of these polycarboxylic acids (dimethyl succinate, dimethyl phthalate, etc.) As well as mixtures of two or more of these.

  Specific examples of the condensed polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexa Methylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate Diol, Polyneopentyl terephthalate diol, Polyethylene Terephthalate diol, polyhexamethylene isophthalate diol.

  Examples of the lactone constituting the polylactone polyol include C4 to 12, for example, ε-caprolactone, γ-butyrolactone, γ-valerolactone, and combinations of two or more thereof. Specific examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

  The polyether polyol (A3) includes an AO adduct having an active hydrogen atom-containing compound as an initiator, and examples of the initiator include polyvalent (divalent to octavalent or higher) alcohols, polyvalent (2 Valent to octavalent or higher) phenols and primary or secondary amino group-containing compounds.

Among the initiators, examples of the polyhydric alcohol include the divalent to octavalent polyhydric alcohols, and examples of the polyhydric phenol include the divalent to octavalent polyhydric phenols.
Examples of the primary or secondary amino group-containing compound include alkyl (C1-12) amine and (poly) alkylenepolyamine (alkylene group C2-6, alkylene group number 1-4, amino group number 2- 5) and the like.

  As AO, C2-4 or more AO, for example, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 2,3- and 1,3-butylene oxide , Tetrahydrofuran (THF), α-olefin oxide, styrene oxide, epihalohydrin (such as epichlorohydrin), and combinations of two or more thereof (random and / or block).

Among specific examples of the polyether polyol (A3), polyhydric alcohol AO adducts include, for example, polyethylene glycol (hereinafter abbreviated as PEG), polypropylene glycol (hereinafter abbreviated as PPG), polyoxyethylene / polyoxypropylene. , Polytetramethylene glycol (hereinafter abbreviated as PTMG), PO 2 mol adduct of GR and EO 6 mol adduct of sorbit; AO adduct of polyhydric phenol includes those having a bisphenol skeleton, such as EO or PO of bisphenol A Additives [EO2 mol adduct of bisphenol A, EO 20 mol adduct of bisphenol A, 2 mol adduct of bisphenol A, PO5 mol adduct of bisphenol A, etc.] and EO or PO adduct of resorcin [EO2 mol addition of resorcin object PO6 mol adduct] resorcinol; the AO adduct of primary or secondary amino group-containing compounds, for example EO2 mol adduct of monoethanolamine, PO2 mol adduct of diethanolamine.
Of these (A3), AO adducts of PEG, PPG, PTMG, and bisphenol A are preferred from the viewpoint of the effect of lowering the crystallinity of (B).

  Mn of the plasticizer (A) is preferably 150 to 8,000, more preferably 150 to 5,000, and particularly preferably 150 to 3,000, from the viewpoints of compatibility and antistatic properties.

  The absolute value of the difference in solubility parameter (hereinafter referred to as SP value) between the plasticizer (A) and the hydrophilic group-containing polymer (B) described later is preferably 0.01 to 1.5 from the viewpoint of antistatic properties. In view of the SP value, (A) is preferably a polyether ester (A1), a polyester polyol (A2), a polyether polyol (A3), an aromatic carboxylic acid ester, a phosphoric acid triester, and more preferably (A1), (A2), and (A3).

The hydrophilic group-containing polymer (B) in the present invention is a hydrophilic group-containing polymer having a volume resistivity of 1 × 10 ⁶ to 1 × 10 ¹² (preferably 1 × 10 ⁶ to 1 × 10 ¹⁰ ) Ω · cm. It is. When the volume resistivity value of (B) is less than 1 × 10 ⁶ Ω · cm, the moldability of the composition described later is deteriorated, and when it exceeds 1 × 10 ¹² Ω · cm, the antistatic property is deteriorated.
The hydrophilic group herein includes an oxyethylene group, a (meth) acryloyl group, a carboxylic acid (salt) group, and the like, and at least an oxyethylene group is preferable from the viewpoint of antistatic properties.
(B) includes the following (B1), (B2), (B3), (B4), (B5), (B6), (B7), (B8), (B9) and two or more of these A mixture is included.
(B1): Number average molecular weight [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method. Is preferably a polyamide derived from a polyamide (b11) having a molecular weight of 200 to 5,000 and an AO adduct (b12) and / or a polyalkylene glycol (b13) of a bisphenol compound having a Mn of preferably 300 to 5,000. Ether ester amide (B2): at least one selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond, and a urethane bond, in which the block of the polyolefin (b21) and the polyoxyalkylene chain-containing compound ((b22)) Block polymer (B3): polyetheramideimide (B4): polyetherester (B5): epihalohydrin / AO copolymer (B6): acrylamide copolymer B7): Ethylene / unsaturated carbo Acid (salt) or ethylene / (meth) acrylate / unsaturated carboxylic acid (salt) copolymer (B8): Methoxypolyethylene glycol (meth) acrylate copolymer (B9): Polyether group-containing ethylene / vinyl acetate copolymer Copolymer [EO adduct of ethylene / vinyl alcohol copolymer]

  Of these, (B1) to (B3) are preferable from the viewpoint of antistatic properties, and (B1) and (B2) are more preferable.

  As (B1), for example, polyether ester amides described in JP-A-6-287547 and JP-B-4-5691 can be used. Among these, from the viewpoint of heat resistance, the lower limit of Mn is 200, more preferably 500, the upper limit of Mn is 5,000, more preferably 3,000 polyamide (b11), and the lower limit of Mn is 300, More preferably, it is a polyether ester amide derived from an AO adduct (b12) and / or a polyalkylene glycol (b13) of a bisphenol compound having an upper limit of 500 and Mn of 5,000, more preferably 4,000.

Examples of the polyamide (b11) include a lactam ring-opening polymer (b111), an aminocarboxylic acid polycondensate (b112), and a dicarboxylic acid and diamine polycondensate (b113).
Among the amide-forming monomers that form these polyamides, the lactam in (b111) includes C6-12, such as caprolactam, enantolactam, laurolactam, and undecanolactam.
As the aminocarboxylic acid in (b112), C6-12, for example, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12 -Aminododecanoic acid.
Examples of the dicarboxylic acid in (b113) include aliphatic dicarboxylic acids, aromatic (aliphatic) dicarboxylic acids, alicyclic dicarboxylic acids, amide-forming derivatives thereof [acid anhydrides, lower (C1-4) alkyl esters], and the like. Or a mixture of two or more thereof.

Aliphatic dicarboxylic acids include C4-20, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid, itaconic acid. Can be mentioned.
Aromatic (aliphatic) dicarboxylic acids include C8-20, such as ortho-, iso- and terephthalic acid, naphthalene-2,6- and -2,7-dicarboxylic acid, diphenyl-4,4'dicarboxylic acid, diphenoxy Examples thereof include alkali metal (sodium, potassium, etc.) salts of ethanedicarboxylic acid and 3-sulfoisophthalic acid.
Examples of the alicyclic dicarboxylic acid include C7 to 14 such as cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, and dicyclohexyl-4,4-dicarboxylic acid.
Among the amide-forming derivatives, examples of the acid anhydride include anhydrides of the above dicarboxylic acids, such as maleic anhydride, itaconic anhydride, and phthalic anhydride. Lower (C1-4) alkyl esters include those of the above dicarboxylic acids. Alkyl esters such as dimethyl adipate, ortho-, iso- and dimethyl terephthalate are mentioned.
Examples of the diamine include C6-12, such as hexamethylene diamine, heptamethylene diamine, octamethylene diamine, and decamethylene diamine.

  Two or more of those exemplified as the amide-forming monomer may be used in combination. Of these, caprolactam, 12-aminododecanoic acid and adipic acid / hexamethylenediamine are preferable from the viewpoint of antistatic properties, and caprolactam is more preferable.

The polyamide (b11) can be obtained by using one or more C4-20 dicarboxylic acids as molecular weight regulators and subjecting the amide-forming monomer to ring-opening polymerization or polycondensation in the presence thereof in the usual manner.
Examples of the C4-20 dicarboxylic acid include those exemplified in the above (b113). Among these, aliphatic dicarboxylic acid, aromatic dicarboxylic acid and 3-sulfoisophthalic acid are preferable from the viewpoint of antistatic properties. Alkali metal salts, more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate.

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

  Mn of the polyamide (b11) is preferably from 200 to 200 from the viewpoint of heat resistance of the polyetheresteramide (B1) and reactivity with the AO adduct (b12) and / or polyalkylene glycol (b13) of a bisphenol compound described later. 5,000, more preferably 500 to 3,000.

Examples of the bisphenol compound constituting the AO adduct (b12) of the bisphenol compound include C13-20, such as bisphenol A, -F, and -S. Among these, the antistatic agent has a dispersibility in a thermoplastic resin. Bisphenol A is preferred from the viewpoint.
As the AO added to the bisphenol compound, C2-4 or more, for example, EO, PO, 1,2-, 2,3- and 1,4-butylene oxide, C5-12 α-olefin epoxidized product Styrene oxide and epihalohydrin (eg epichlorohydrin and epibromohydrin) and mixtures of two or more thereof (random and / or block). Of these, EO is preferable from the viewpoint of antistatic properties.

The volume specific resistance value (b12) (value measured in an atmosphere described below at 23 ° C. and 50% RH, the same shall apply hereinafter) is preferably 10 ¹¹ Ω · cm from the viewpoint of antistatic properties, More preferably 10 ¹⁰ Ω · cm, particularly preferably 10 ⁹ Ω · cm, and from the viewpoint of mechanical properties, the lower limit is preferably 10 ⁵ Ω · cm, more preferably 10 ⁶ Ω · cm, and particularly preferably 10 ⁷ Ω · cm. is there.
Further, Mn of (b12) is preferably 300 to 5,000, more preferably 500 to 4,000 from the viewpoint of antistatic properties and mechanical properties.

  The ratio of (b12) based on the total weight of (b11) and (b12) is preferably 20 to 80%, more preferably 30 to 70%, from the viewpoint of the antistatic property and heat resistance of (B1).

The volume specific resistance value of polyalkylene glycol (b13) (value measured by an after-mentioned method in an atmosphere of 23 ° C. and 50% RH) is preferably 10 ¹¹ Ω · cm from the viewpoint of antistatic properties, More preferably, it is 10 ¹⁰ Ω · cm, particularly preferably 10 ⁹ Ω · cm. From the viewpoint of mechanical properties, the lower limit is preferably 10 ⁵ Ω · cm, more preferably 10 ⁶ Ω · cm, and particularly preferably 10 ⁷ Ω · cm. is there.
Further, Mn of (b13) is preferably 150 to 20,000, more preferably 300 to 15,000, particularly preferably 1,000 to 8,000, most preferably 1 from the viewpoint of antistatic properties and mechanical properties. , 200 to 5,000.

  The ratio of (b13) based on the total weight of (b11) and (b13) is preferably 20 to 80%, more preferably 30 to 70%, from the viewpoint of the antistatic property and heat resistance of (B1).

Examples of the method for producing the polyetheresteramide (B1) 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 a polyamide (b11), and an AO adduct (b12) and / or a polyalkylene glycol (b13) of a bisphenol compound is added thereto. And polymerization at high temperature (160 to 270 ° C.) under reduced pressure (0.03 to 3 kPa).
Production Method (2) An amide-forming monomer and a dicarboxylic acid (molecular weight modifier) and a part of (b12) and / or (b13) are simultaneously charged into a reaction vessel, and heated at a high temperature (160 to 270 ° C.) under pressure (0.1 to 1 MPa) to form a polyamide intermediate (b11), and then the remaining (b12) and / or (b13) under reduced pressure (0.03 to 3 kPa) Polymerization method. Of the above production methods, production method (1) is preferred from the viewpoint of reaction control.

In addition to the above, (B1) is produced by replacing the terminal hydroxyl group of (b12) and / or (b13) with an amino group or a carboxyl group and reacting with a polyamide having a carboxyl group or an amino group at the terminal. It may be used.
As a method for substituting the terminal hydroxyl group of (b12) and / or (b13) with an amino group, a known method, for example, a method of reducing a terminal cyanoalkyl group obtained by cyanoalkylating a hydroxyl group to form an amino group [for example, , (B12) and / or (b13) and acrylonitrile are reacted, and the resulting cyanoethylated product is hydrogenated.
As a method of substituting the terminal hydroxyl group of (b12) and / or (b13) with a carboxyl group, a method of oxidizing with an oxidizing agent [for example, a method of oxidizing the hydroxyl group of (b12) and / or (b13) with chromic acid] Etc.

In the above polymerization reaction, a commonly used known esterification catalyst is used. Examples of the catalyst include antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide, etc.), titanium catalysts (tetrabutyl titanate, etc.), zirconium catalysts (tetrabutyl zirconate, etc.), organic acid metal salts [zirconium organic acid Salts (such as zirconyl acetate) and zinc acetate].
The amount of the catalyst used is usually 0.1 to 5% based on the total weight of (b11) and (b12) and / or (b13), preferably 0.2 to 3% from the viewpoint of reactivity and resin properties. It is.

The reduced viscosity [η _sp / C, C = 0.5 wt% (m-cresol solution, 25 ° C.)] of (B1) is preferable from the viewpoint of the heat resistance of (B1) and the moldability of the resin composition described later. Is 0.5-4, more preferably 0.6-3.

As the block polymer (B2), a block polymer described in the specification of International Publication WO00 / 47652 can be used.
(B2) is at least one selected from the group consisting of an ester bond, an amide bond, an ether bond, a urethane bond and an imide bond, in which the block of the polyolefin (b21) and the block of the polyoxyalkylene chain-containing compound (b22) It has a structure in which they are alternately and alternately connected through the bonds.
The ratio of (b22) based on the total weight of (b21) and (b22) is preferably 20 to 80%, more preferably 30 to 70%, from the viewpoint of the antistatic property and heat resistance of (B2).
The block of (b21) constituting (B2) includes a polyolefin (b211) having carbonyl groups at both ends of the polymer, a polyolefin (b212) having hydroxyl groups at both ends of the polymer, and an amino group at both ends of the polymer. Polyolefin (b213) or the like can be used.

As (b211), those having carbonyl groups introduced at both ends of polyolefin (b210) mainly composed of a denatureable polyolefin at both ends are used.
As (b212), those having hydroxyl groups introduced at both ends of (b210) are used.
As (b213), those in which amino groups are introduced at both ends of (b210) are used.
(B210) 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 (b210) is preferably 50 to 100%, more preferably 75 to 100%, particularly preferably 80 to 100% based on the weight of (b210). It is.

(B210) 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. )) Obtained by (polymerization method) and 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). According to the thermal degradation, a low molecular weight polyolefin having an average terminal double bond amount per molecule of 1.5 to 2 can be easily obtained as described later.
Examples of the high molecular weight polyolefin used in the thermal degradation method include (co) polymers of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. Can be used. As the C2-30 olefin, the same as those used for the production of the polyolefin (polymerization method) described later can be used, and among these, ethylene, propylene and C4-12 α-olefin are preferred, and ethylene is more preferred. , Propylene and C4-10 alpha-olefins, particularly preferred are ethylene and propylene.

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

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 with molybdenum oxide attached thereto.
Examples of the metal oxide catalyst include those obtained by attaching chromium oxide to a silica-alumina support. Examples of the Ziegler catalyst or Ziegler-Natta catalyst include (C ₂ H ₅ ) ₃ Al—TiCl ₄ .

Mn of (b210) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000. When Mn is within this range, the antistatic property is further improved.
The amount of double bonds in (b210) is preferably 1 to 40 per 1,000 C, 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 (b211) having a carbonyl group at both ends of the polymer is as follows: (b210) is terminated with α, β unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, C1-4 alkyl ester thereof Or the anhydride thereof (hereinafter the same shall apply)) polyolefin (b211-1) having a structure modified with (b211-1), polyolefin having a structure obtained by secondary modification of (b211-1) with lactam or aminocarboxylic acid (b211-2) ), Polyolefin (b211-3) having a structure obtained by modifying (b210) by oxidation or hydroformylation, polyolefin (b211-4) having a structure obtained by secondary modification of (b211-3) with lactam or aminocarboxylic acid, and A mixture of two or more of these can be used.

(B211-1) can be obtained by modifying (b210) 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 (b210). ~ 20%. When the amount of α, β-unsaturated carboxylic acid (anhydride) is within this range, it becomes easier to take a repeating structure, and filler dispersibility and antistatic properties are 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 (b210) can be modified by either solution method or melt method. , Β-unsaturated carboxylic acid (anhydride) can be thermally added (ene reaction). The temperature at which (b210) is reacted with the α, β-unsaturated carboxylic acid (anhydride) is usually 170 to 230 ° C.

(B211-2) can be obtained by secondary modification of (b211-1) with lactam or aminocarboxylic acid.
As the lactam used for the secondary modification, a C6-12 (preferably 6-8, more preferably 6) lactam or the like can be used, and examples thereof include caprolactam, enantolactam, laurolactam, and undecanolactam.
As the aminocarboxylic acid, C2-12 (preferably 4-12, more preferably 6-12) aminocarboxylic acid and the like can be used. For example, amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.) ), Ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Of these, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and caprolactam, laurolactam, ω-aminocaprylic acid, 11-amino are more preferred. Undecanoic acid and 12-aminododecanoic acid, particularly preferably caprolactam, laurolactam and 12-aminododecanoic acid.
The amount of lactam or aminocarboxylic acid used for secondary modification is preferably 0.1-50, more preferably 0.3-20, 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 filler dispersibility and antistatic properties are further improved.

(B211-3) can be obtained by introducing (b210) a carbonyl group by oxidation with oxygen and / or ozone or hydroformylation by the 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.
(B211-4) can be obtained by secondarily modifying (b211-3) with a lactam or an aminocarboxylic acid.
The lactam and aminocarboxylic acid and preferred ranges thereof are the same as those which can be used in the production of (b211-2). The amount of lactam and aminocarboxylic acid used is the same.

Mn of the polyolefin (b211) having carbonyl groups at both ends of the polymer is preferably 800 to 25,000, more preferably from the viewpoint of heat resistance and reactivity with the polyoxyalkylene chain-containing compound (b22) described later. 1,000 to 20,000, particularly preferably 2,500 to 10,000.
The acid value of (b211) is preferably 4 to 280 (mg KOH / g. In the following, only numerical values will be described), more preferably 4 to 100, particularly from the viewpoint of reactivity with (b22). Preferably it is 5-50.

As the polyolefin (b212) having hydroxyl groups at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying (b211) 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 (b211) 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 (b212) 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 polyoxyalkylene chain-containing compound (b22) described later. Is 2,500 to 10,000.
The hydroxyl value of (b212) 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 (b22). Preferably it is 5-50.

As the polyolefin (b213) having an amino group at both ends of the polymer, a polyolefin having an amino group obtained by modifying (b211) 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.
Among 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 performed by a known method, for example, by reacting (b211) 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 filler dispersibility and antistatic properties are further improved.
In actual production, in order to prevent polyamide (imide) formation, 2 to 1,000, more preferably 5 to 800, per residue of α, β unsaturated carboxylic acid (anhydride). Particularly preferably, 10 to 500 diamines are used, and it is preferable to remove unreacted excess diamine under reduced pressure (usually 120 ° C. to 230 ° C.).

Mn of (b213) 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 polyoxyalkylene chain-containing compound (b22) described later. Is 2,500 to 10,000.
In addition, the amine value of (b213) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (b22), more preferably 4 to 100, and particularly preferably. Is 5-50.

As the polyoxyalkylene chain-containing compound (b22) constituting the block polymer (B2), polyether diol (b221), polyether diamine (b222), and modified products thereof (b223) can be used.
The upper limit of the volume resistivity of (b22) is preferably 10 ¹¹ Ω · cm, more preferably 10 ¹⁰ Ω · cm, particularly preferably 10 ⁹ Ω · cm, from the viewpoint of antistatic properties, and the lower limit preferable from the viewpoint of mechanical properties. Is 10 ⁵ Ω · cm, more preferably 10 ⁶ Ω · cm, and particularly preferably 10 ⁷ Ω · cm.
Further, Mn of (b22) is preferably 150 to 20,000, more preferably 300 to 20,000, and particularly preferably 1,000 to 15,000, from the viewpoint of heat resistance and reactivity with (b21). Most preferably, it is 1,200 to 8,000.

As the polyether diol (b221), one having a structure obtained by addition reaction of diol (b220) or dihydric phenol with AO can be used.

H— (OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _{m ′} —H

The thing shown by is mentioned.
In the formula, A ¹ , E ¹ , m and m ′ are the same as described above, and the diol (b220) or dihydric phenol is the same as described above.

  Of these diols (b220) and dihydric phenols, dihydric alcohols and dihydric phenols are preferable from the viewpoint of reactivity, aliphatic dihydric alcohols and bisphenols are more preferable, and ethylene glycol and bisphenol A are particularly preferable. It is.

The polyether diol (b221) can be produced, for example, by subjecting the diol (b220) or dihydric phenol to AO addition reaction.
As AO, C2-4 AO (EO, PO, 1,2-, 1,4-, 2,3- and 1,3-butylene oxide and a mixture of two or more thereof) and the like are used. If necessary, other AO or substituted AO may be used in combination (in the present invention, these are collectively referred to as AO). Examples of other AO or substituted AO include epoxidized C5-12 α-olefin, styrene oxide and epihalohydrin (such as epichlorohydrin and epibromohydrin). The amount of other AO or substituted AO is preferably 30% or less, more preferably 0 to 25%, and particularly preferably 0 to 20% based on the weight of the total AO.

When two or more kinds of AO are used in combination, the binding form may be either block and / or random.
Preferred as AO is EO alone and a combination of EO and other AO (block and / or random addition), more preferred is a combination of EO and EO / PO, and particularly preferred is EO alone.
The number of moles of AO added is preferably 1 to 300 moles, more preferably 2 to 250 moles, and particularly preferably 10 to 100 moles per hydroxyl group of (b220) or dihydric phenol. When the added mole number of AO is within this range, the volume resistivity value of (b22) tends to be more preferable.

AO can be added by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst.
The content of the C2-4 oxyalkylene unit in the polyether diol (b221) is preferably 5 to 99.8%, more preferably 8 to 99.6%, particularly preferably based on the weight of (b221). 10 to 98%.
The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100%, more preferably 10 to 100%, particularly preferably 50 to 100%, most preferably 60, based on the weight of the polyoxyalkylene chain. ~ 100%. When the content of the oxyethylene unit is within this range, the volume resistivity value of (b22) tends to be more preferable.

The polyether diamine (b222) having a structure in which the hydroxyl group of (b221) is modified to an amino group can be used.

R ″ NH—A ² — (OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _{m ′} —A ² —NHR ”

The thing shown by is mentioned.
Symbols E ¹ , A ¹ , m and m ′ in the formula are the same as those in the formula (b221), and A ² may contain a halogen atom, C 2-12 (preferably 2-8, more preferably Represents an alkylene group of 2 to 4), and A ¹ and A ² may be the same or different. R ″ represents H or a C1-4 (preferably 1 or 2) alkyl group.
(B222) can be easily obtained by changing the hydroxyl group of (b221) to an amino group by a known method.
Various methods can be used as a method for changing the hydroxyl group to an amino group. For example, a method in which the terminal cyanoalkyl group obtained by cyanoalkylating the hydroxyl group of (b221) is reduced to an amino group [for example, (b221) And a method of reacting acrylonitrile and hydrogenating the resulting cyanoethylated product], a method of reacting (b221) with an aminocarboxylic acid or lactam, and a method of reacting a halogenated amine under alkaline conditions.

Examples of the modified product (b223) of (b221) or (b222) include the isocyanate-modified product (terminal isocyanate group) and the epoxy-modified product (terminal epoxy group) of (b221) or (b222).
The isocyanate-modified product can be obtained by reacting (b221) or (b222) with an organic diisocyanate or reacting (b222) with phosgene.
The epoxy-modified product is obtained by reacting (b221) or (b222) with a diepoxide (epoxy resin such as diglycidyl ether, diglycidyl ester, alicyclic diepoxide: epoxy equivalent 85 to 600), or (b221) and epihalohydrin. It can be obtained by reacting with (e.g. epichlorohydrin).

  As the organic diisocyanate, C (excluding carbon in the NCO group, the same shall apply hereinafter) 6-20 (preferably 6-18, more preferably 8-14) aromatic diisocyanate, C2-18 (preferably 4-16, More preferably 6-14) aliphatic diisocyanate, C4-15 (preferably 4-13, more preferably 6-11) alicyclic diisocyanate, C8-15 (preferably 8-13, more preferably 9- 11) Aro-aliphatic diisocyanates, modified products of these diisocyanates, and mixtures of two or more thereof can be used.

  Examples of the aromatic diisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 2,4′- or 4,4′-diphenylmethane diisocyanate ( MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane and 1,5 -Naphthylene diisocyanate.

  Examples of the aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethylcaproate. Bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and the like.

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

Examples of the araliphatic diisocyanate include m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).
Examples of modified diisocyanates include urethane-modified products, urea-modified products, carbodiimide-modified products, and uretdione-modified products.
Of these organic diisocyanates, aromatic and aliphatic diisocyanates are preferable from the viewpoint of reactivity, TDI, MDI and HDI are more preferable, and HDI is particularly preferable.

In order to accelerate the polyurethane-forming reaction, a commonly used catalyst may be used if necessary. As such a catalyst, a metal catalyst, an amine catalyst and a mixture of two or more thereof can be used.
Examples of metal catalysts include tin catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate, etc.); lead catalysts (lead oleate) , Lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.); other metal catalysts (naphthalic acid metal salts such as cobalt naphthenate, phenylmercuric propionate, etc.).

  Examples of the amine catalyst include triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diazabicycloalkene {1,8-diazabicyclo [5,4,0] undecene-7 [manufactured by San Apro Co., Ltd., registered trademark DBU]. Etc.}, dialkylaminoalkylamines (dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropylaminopropylamine, etc.) and heterocyclic aminoalkylamines {2- (1- Aziridinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine, etc.} carbonates and organic acid salts (formate, etc.), etc. In addition, N-methylmorpholine, N-ethylmorpholine, Ethylamine, diethylethanolamine, dimethylethanolamine and the like can be used.

In the present invention, (B2) includes a polymer having a repeating unit represented by the general formula (1).

In general formula (1), n is an integer of 2-50, preferably 3-40, more preferably 4-30. One of R ¹ and R ² is H, and the other is H or an alkyl group of C1-10 (preferably 1-8, more preferably 1-6). Moreover, y is an integer of 15 to 800, preferably 20 to 500, more preferably 30 to 400.
E ¹ , A ¹ , m and m ′ are the same as above, and X and X ′ are groups selected from the groups represented by the general formulas (2) to (8) and the corresponding (2 ′) to (8 A group selected from the group represented by '), that is, when X is a group represented by the general formula (2), X' is a group represented by the general formula (2 '), and the general formulas (3) to (3) to ( The same relationship applies to 8) and (3 ′) to (8 ′).

In the general formulas (2) to (8) and (2 ′) to (8 ′), R ³ and R ^{3 ′} represent a C2-3 trivalent hydrocarbon group, and R ⁴ represents C1-11 ( Preferably, it represents a divalent hydrocarbon group of 1 to 8, more preferably 1 to 6, and R ⁵ represents H or an alkyl group of C1 to 10 (preferably 1 to 8, more preferably 1 to 6). R ⁶ represents a C 2-22 (preferably 4-18, more preferably 6-12) hydrocarbon group, E ² represents an organic diisocyanate residue, and r is 1-10 (preferably 1 to 8, more preferably 1 to 6), u and v each represents 0 or 1, and A ² and R are the same as defined above. Q, Q ′, T and T ′ are groups represented by the following formula.

However, R ⁵ is H or C1-10 (preferably 1 to 8, more preferably 1 to 6) represents an alkyl group, R ⁷ represents H or a methyl group, t is, R ⁷ is a methyl group 1 for H, 0 or 1 for H.
The polyether segment {(OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _{m ′} } in {} in the repeating unit represented by the general formula (1) depends on the polyether diol (b221). It is a structure to be constructed, and E ¹ , A ¹ , m and m ′ in the formula are the same as described above.

  In the general formula (1), the block polymer (B21) in which X is a group represented by the general formula (2) and X ′ is a group represented by the general formula (2 ′) is a polyolefin having the carbonyl group (b211 -1) and polyether diol (b221) can be obtained. R3 and R3 'in the general formulas (2) and (2') are formulas formed from unsaturated dicarboxylic acids.

（Ｒ’はＨまたはメチル基、ｔはＲ’がＨのとき１または０、Ｒ’がメチル基のとき１である。）
で示される基であり、例えば、ポリオレフィンのカルボニル変性に、マレイン酸またはフマル酸を用いた場合は、Ｒ³は−ＣＨ₂−ＣＨ＜であり、Ｒ^3'は＞ＣＨ−ＣＨ₂−である。

(R ′ is H or a methyl group, t is 1 or 0 when R ′ is H, and 1 when R ′ is a methyl group.)
For example, when maleic acid or fumaric acid is used for carbonyl modification of polyolefin, R ³ is —CH ₂ —CH <and R ^{3 ′} is> CH—CH ₂ —. .

(B21) can be produced by various methods. For example, polyether diol (b221) is added to polyolefin (b211-1) having a carbonyl group, and polymerization (polycondensation) reaction is usually performed at 200 to 250 ° C. under reduced pressure. It can be manufactured by the method to be performed. It can also be produced using a single or twin screw extruder. Usually, it can manufacture by the method of superposing | polymerizing with 160-250 degreeC and residence time 0.1-20 minutes. Various catalysts can be used for the above polymerization reaction.
Catalysts include antimony catalysts (such as antimony trioxide), tin catalysts (such as monobutyltin oxide), titanium catalysts (such as tetrabutyl titanate), zirconium catalysts (such as tetrabutylzirconate), organic acid metal salts [zirconium organic acid salts (Zirconyl acetate and the like), zinc acetate and the like], and a mixture of two or more thereof.
Of these, preferred are a zirconium catalyst and an organic acid metal salt, and more preferred is zirconyl acetate.
The usage-amount of a catalyst is 0.001 to 5% normally with respect to the total weight of (b211-1) and (b221).

  In the general formula (1), a block polymer (B22) in which X is a group represented by the general formula (3) and X ′ is a group represented by the general formula (3 ′) is a polyolefin having a carbonyl group (b211-1 ) And polyether diamine (b222). The polymerization reaction of (b211-1) and (b222) can be performed by the same method as the polymerization reaction of (b211-1) and (b221).

  In the general formula (1), the block polymer (B23) in which X is a group represented by the general formula (4) and X ′ is a group represented by the general formula (4 ′) is represented by (b211-2) and (b221 ). The polymerization reaction of (b211-2) and (b221) can be performed by the same method as the polymerization reaction of (b211-1) and (b221).

  In the general formula (1), the block polymer (B24) in which X is a group represented by the general formula (5) and X ′ is a group represented by the general formula (5 ′) is represented by (b211-2) and (b222). ). Alternatively, (b222) may be secondarily modified with the lactam or aminocarboxylic acid and then reacted with (b211-1) for production. These polymerization reactions can be performed in the same manner as the polymerization reaction of (b211-1) and (b221).

  In the general formula (1), the block polymer (B25) in which X is a group represented by the general formula (6) and X ′ is a group represented by the general formula (6 ′) is (b211-3) (r = 1) or (b211-4) (when r ≧ 2) and (b221) (when u = 0) or polyetherdiamine (b222) (when u = 1). be able to. The polymerization reaction of (b211-3) or (b211-4) and (b221) or (b222) can be carried out in the same manner as the polymerization reaction of (b21-1) and (b221).

  In the general formula (1), the block polymer (B26) in which X is a group represented by the general formula (7) and X ′ is a group represented by the general formula (7 ′) has hydroxyl groups at both ends of the polymer. Polyolefin (b212) and polyether diol (b221) (when u = 0) or polyether diamine (b222) (when u = 1) are bonded via an organic diisocyanate. It can be obtained by reacting simultaneously or sequentially. For example, (b212) and an organic diisocyanate are reacted to obtain an isocyanate-modified polyolefin, and then this is reacted with (b221) or (b222).

In the general formula (1), the block polymer (B26) in which X is a group represented by the general formula (8) and X ′ is a group represented by the general formula (8 ′) is (b211-3) (v = 0) or (b212) (when v = 1) and (b221) or (b222) are bonded via an organic diisocyanate, and these are reacted simultaneously or sequentially. Can be obtained. For example, (b211-3) or (b212) is reacted with an organic diisocyanate to obtain an isocyanate-modified polyolefin, and then reacted with (b221) or (b222). it can.
The reaction between (b212) and organic diisocyanate, the reaction between (b221) or (b222) and organic diisocyanate, and the reaction between isocyanate-modified polyolefin and (b221) or (b222) are the same as the usual urethanization or urealation reaction. Can be done by the method.

  The equivalent ratio (NCO / OH ratio) of the organic diisocyanate and (b212) and the equivalent ratio of the isocyanate-modified polyolefin and (b221) or (b222) (NCO / OH ratio) in forming the isocyanate-modified polyolefin are: The ratio is preferably 1.8 / 1 to 3/1, more preferably 1.9 / 1 to 2.5 / 1, and particularly preferably 2/1. When the equivalent ratio is within this range, it becomes easier to take a repeating structure, and filler dispersibility and antistatic properties are further improved. As the organic diisocyanate and the catalyst for promoting the reaction, those described above can be used.

Among the block polymers (B2) having a repeating unit represented by the general formula (1), (B21), (B22), (B23), (B24) are preferable, and (B21) and (B23 are more preferable. Particularly preferred is (B23).
The amount of the polyoxyalkylene chain-containing compound (b22) constituting the block polymer (B2) is preferably 20 to 90% based on the total weight of (b21) and (b22) from the viewpoint of antistatic properties. More preferably, it is 25 to 90%, and particularly preferably 30 to 70%. Moreover, Mn of (B2) is preferably 2,000 to 60,000, more preferably 5,000 to 40,000, and particularly preferably 8,000 to 30,000, from the viewpoint of antistatic properties.

In the structure of the block polymer (B2), the average number of repeating units (Nn) of the block of the polyolefin (b21) and the block of the polyoxyalkylene chain-containing compound (b22) is preferably from the viewpoint of antistatic properties. It is 2 to 50, more preferably 2.3 to 30, particularly preferably 2.7 to 20, and most preferably 3 to 10.
Nn can be determined by Mn and ¹ H-NMR analysis of (B2). For example, the case of (B21) having a structure in which blocks (b211) and (b221) are alternately and repeatedly bonded will be described. In ¹ H-NMR analysis, 4.0 to 4.1 ppm ester bond { A signal attributed to protons of —C (C═O) —OCH ₂ —} and a signal attributed to protons of polyethylene glycol of 3.2 to 3.7 ppm can be observed. The ratio of these proton integral values is obtained, and Nn can be obtained from this ratio and Mn.

  Both ends of (B2) have a carbonyl group, amino group, hydroxyl group and / or unmodified polyolefin end derived from (b21), and a hydroxyl group, amino group, isocyanate group and / or epoxy group derived from (b22). The unmodified polyolefin means a polyolefin terminal that is not modified at all, that is, an alkyl group or an alkenyl group.

Examples of the polyether amide imide (B3) include polyether amide imides described in JP-B-7-119342 and JP-A-6-172609.
Of these, from the viewpoint of heat resistance, caprolactam, trivalent or tetravalent aromatic polycarboxylic acid capable of reacting with an amino group to form at least one imide ring and polyethylene glycol or at least 50% by weight are preferred. Polyether amide imide derived from a mixture of polyethylene glycol and a polyalkylene glycol other than polyethylene glycol, wherein the content of the mixture is 30 to 85% by weight and the reduced viscosity at 30 ° C. is 1.5 to 4. .
The reduced viscosity of (B3) is preferably 1.5 to 4, more preferably 1.7 to 3.5 from the viewpoint of moldability of the resin composition.

Examples of the polyether ester (B4) include polyesters obtained by reacting a polyether diol or copolyether diol with a divalent or higher polyvalent carboxylic acid, for example, a polyether ester described in Japanese Patent Publication No. 58-19696. Can be mentioned.
The melting point of (B4) [measurement is by differential scanning calorimetry (hereinafter abbreviated as DSC method)] is preferably 100 ° C. or higher, more preferably 120 to 210 ° C. from the viewpoint of heat resistance.

Examples of the epihalohydrin / AO copolymer (B5) include an epihalohydrin / AO copolymer described in JP-B-7-84564.
Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, and epifluorohydrin, and epichlorohydrin is preferable from the viewpoint of reactivity and cost. AO includes C2-4, such as EO, PO, and THF.
(B5) includes co-polymerization of epihalohydrin with a comonomer composed of one or more selected from 1,2-epoxide monomers [especially alkyl (C2-4) glycidyl ether] and AO (especially EO and PO). Mergers are also included.
The weight ratio of epihalohydrin to AO is usually 5/95 to 95/5, and preferably 10/90 to 60/40 from the viewpoint of antistatic property.
Among (B5), a copolymer of epichlorohydrin / EO (weight ratio 50/50) is preferable from the viewpoint of imparting resin physical properties and antistatic properties.
Mn of (B5) is preferably from 30,000 to 100,000, more preferably from 60,000 to 90,000, from the viewpoints of resin physical properties and moldability.

Examples of the acrylamide copolymer (B6) include an acrylamide copolymer comprising 65 to 99 mol% of ethylene units, 0 to 15 mol% of acrylate units, and 1 to 35 mol% of acrylamide units described in JP-A-4-198308. Coalescence is mentioned.
Mn of (B6) is preferably 1,000 to 150,000, more preferably 3,000 to 100,000, from the viewpoint of the balance between the heat resistance of (B6) and the moldability of the resin composition.

Examples of the ethylene / unsaturated carboxylic acid (salt) or ethylene / (meth) acrylate / unsaturated carboxylic acid (salt) copolymer (B7) include ethylene / unsaturated carboxylic acid described in JP-A-8-269276. Or the ionomer by which the one part or all part of the carboxyl group of the random copolymer of ethylene / (meth) acrylate / unsaturated carboxylic acid was neutralized with the alkali metal is mentioned.
The melt flow rate (hereinafter abbreviated as MFR, measurement conditions are 190 ° C., 2.16 kg) of (B7) is preferably 1 to 20, more preferably 1.5 to 15 from the viewpoint of moldability of the resin composition. .

As the methoxypolyethylene glycol (meth) acrylate copolymer (B8), methoxypolyethylene glycol (Mn is preferably 250 to 4,950, more preferably 750 to 2,950) (meth) acrylate and a vinyl monomer described later. A copolymer may be mentioned.
Mn of methoxypolyethylene glycol (meth) acrylate is preferably 300 to 5,000, more preferably 800 to 3,000, from the viewpoint of antistatic properties. Preferred as the monomer to be copolymerized are (meth) acrylic acid, alkyl (C1-20) (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.].
Mn of (B8) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000 from the viewpoint of physical properties of the resin. The methoxypolyethylene glycol (meth) acrylate unit and vinyl monomer in (B8) The weight ratio of the units is preferably 20/80 to 80/20, more preferably 30/70 to 60/40 from the viewpoint of antistatic properties.

Examples of the polyether group-containing ethylene / vinyl acetate copolymer (B9) include those obtained by hydrolyzing an ethylene / vinyl acetate copolymer to give an ethylene / vinyl alcohol copolymer with EO addition.
In the ethylene / vinyl acetate copolymer, the weight ratio of ethylene units to vinyl acetate units is preferably 20/80 to 80/20, more preferably 30/70 to 60/40, from the viewpoint of antistatic properties. The hydrolysis rate of vinyl units [vinyl acetate unit before hydrolysis / vinyl alcohol unit after hydrolysis] (mol%) is preferably 30 to 100 mol%, more preferably 40 to 80 mol, from the viewpoint of antistatic properties. %. The number of moles of EO added per vinyl alcohol unit is preferably 5 to 30, more preferably 10 to 20, from the viewpoint of antistatic properties.
Mn of (B9) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000 from the viewpoint of resin physical properties.

The antistatic agent of the present invention comprises a mixture of (A) and (B) containing the plasticizer (A) and the hydrophilic group-containing polymer (B), and the crystallinity of (B) is lowered. As a result, the antistatic effect further superior to the antistatic effect of (B) alone is obtained.
In particular, when the hydrophilic group in (B) is an oxyethylene group, the crystallinity of (B) [that is, the oxyethylene group portion in (B)] in the antistatic agent of the present invention is Using the differential scanning calorimetry (DSC) method, the crystallinity of the oxyethylene group portion in (B) can be evaluated, and the crystallinity is determined by the mechanical properties of the molded article described later. From the viewpoint of antistatic properties, it is preferably 35 to 50%, more preferably 35 to 40%.
Regarding the crystallinity of (B) [that is, the oxyethylene group portion in (B)] in the antistatic resin composition of the present invention described later, the antistatic resin composition is the same as in the case of the antistatic agent. It can be evaluated by the crystallinity obtained by measuring with a DSC method using the product, and the preferred range and further preferred range of the crystallinity are the same as in the case of the antistatic agent.

The degree of crystallinity can be obtained from the following equation [New Journal of
Chemistry, 2005, vol. 29, p. 1454].

Crystallinity (%) = [ΔHm / [Oxyethylene in antistatic agent or antistatic resin composition]
Group content (%)]] × 10,000 / ΔHm *

In the formula, ΔHm is the melting enthalpy derived from the oxyethylene group in the antistatic agent or antistatic resin composition (unit: J / g, the same applies hereinafter), ΔHm * is the melting enthalpy of PEG [literature value 213.7 J / G (New Journal of Chemistry,
2005, vol. 29, p. 1454)].
Here, the melting enthalpy indicates only the melting enthalpy at that temperature when the melting peak temperature is one point, and indicates the sum of the melting enthalpies at each temperature when there are a plurality of melting peak temperatures.

As a differential scanning calorimeter (DSC) used for the measurement, for example, DSC2910 [trade name, manufactured by T.A. Instruments Co., Ltd.] can be mentioned. According to the measurement method, it can be determined based on the melting enthalpy measured under the following conditions.
[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 a cooling rate of 10 ° C. per minute. From the obtained DSC curve, the heat of transition (melting enthalpy) by heating is determined.

  The weight ratio [(A) / (B)] of (A) and (B) in the antistatic agent of the present invention is preferably 1/99 to 30/70 from the viewpoint of antistatic properties and mechanical properties of the molded product. More preferably, it is 5/95 to 20/80.

  As a method for producing the antistatic agent of the present invention, (1) a method in which (A) and (B) are heated in a reaction vessel such as an autoclave, melt mixed and pelletized, and (2) (A) and ( B) is mixed with an appropriate mixer, such as a Henschel mixer, and then melt-mixed with a closed kneader (Banbury mixer, plast mill, etc.), single screw extruder, twin screw extruder, etc., and pelletized. (3) A method of dispersing (A) in advance during the production (polymerization) of (B). Among these, the methods (1) and (2) are preferable from the viewpoint of dispersibility of (A) into (B).

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 vinyl group-containing aromatic hydrocarbon alone or vinyl group-containing aromatic hydrocarbon, (meth) acrylic acid 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); biodegradable resin (C9), and a mixture of two or more thereof.

  Among these, (C1), (C2), (C3), (C4) and (C7) are preferable from the viewpoint of the mechanical properties of the molded product described later and the dispersibility of the antistatic agent of the present invention in (C). More preferred are (C2), (C4) and (C7).

  The content of the antistatic agent based on the total weight of the antistatic agent of the present invention and (C) is preferably 1 to 30%, more preferably 5 to 15% from the viewpoint of antistatic properties and mechanical properties.

  Examples of the polyphenylene ether resin (C1) include those represented by the following general formula (9).

In the general formula (9), p is an integer of 50 or more, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are H, a halogen atom, a C1-12 hydrocarbon group, a C2-12 substituted hydrocarbon group, and an alkoxy group. Represents a cyano group, a phenoxy group or a nitro group. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be the same or different. Further, (C1) is a single polymer of the general formula (9) or a copolymer of two or more structural units or a blend of two or more polymers. Also good.

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

The intrinsic viscosity [η] of (C1) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and antistatic properties. [Η] is measured using a Ubbelohde 1A viscometer at 30 ° C. for a 0.5 wt% chloroform solution of the polymer.
The glass transition temperature (hereinafter abbreviated as Tg) of (C1) is preferably 190 to 240 ° C., more preferably 210 to 230 ° C. from the viewpoint of moldability. Tg is measured by a differential scanning calorimetry (DSC) method.

  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 thereof include acid esters, alkyl ethers of unsaturated alcohols, halogen-containing vinyl monomers, and combinations of two or more thereof (random and / or block).

  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.), etc.], C4-30 dienes [alkadiene (butadiene, isoprene etc.), cycloalkadiene (cyclopentadiene etc.) etc.] and the like.

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

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

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

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

Examples of the polyolefin resin (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 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—Human Laboratory for Polymer Experiments 2” (Hatsugoro Nanshino), 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. MFR is measured according to JIS K7210 (1994) (230 ° C. and load 1.2 kgf in the case of polyacrylic resin).

As the polystyrene resin (C4), a vinyl group-containing aromatic hydrocarbon alone or a vinyl group-containing aromatic hydrocarbon, and at least one selected from the group consisting of (meth) acrylic acid ester, (meth) acrylonitrile and butadiene Examples thereof include a copolymer as a structural unit.
Examples of vinyl group-containing aromatic hydrocarbons include C8-30 styrene and its derivatives, such as o-, m- and p-alkyl (C1-10) styrene (vinyltoluene etc.), α-alkyl (C1-10). Examples include styrene (α-methylstyrene and the like) and halogenated styrene (chlorostyrene and the like).
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.

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

Examples of the lactam in (C61) include those exemplified in the above (b111), and examples of (C61) include nylon 4, nylon 5, nylon 6, nylon 8, nylon 12, and the like.
Examples of the diamine and dicarboxylic acid in (C62) include those exemplified in the above (b113). Examples of (C62) include nylon 66 obtained by polycondensation of hexanemethylenediamine and adipic acid, and the weight of hexamethylenediamine and sebacic acid. Examples thereof include nylon 610 by condensation.
Examples of the aminocarboxylic acid in (C63) include those exemplified in the above (b112). Examples of (C63) include nylon 7 by polycondensation of aminoenanthic acid, nylon 11 by polycondensation of ω-aminoundecanoic acid, Nylon 12 and the like by polycondensation of 12-aminododecanoic acid.

In the production of (C6), a molecular weight modifier may be used, and examples of the molecular weight modifier include the dicarboxylic acid and / or diamine exemplified in (b113).
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 dispersibility of (A).
The MFR of (C7) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoints of resin physical properties and antistatic properties. The 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 and the like].
The MFR of (C8) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. The MFR is measured according to JIS K7210 (1994) (in the case of polyacetal resin, 190 ° C., load 2.16 kgf).
Intrinsic viscosity [η] of (C8) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, and particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and antistatic properties.

  Examples of the biodegradable resin (C9) include polyhydroxybutyrate, polylactic acid, polycaprolactone, polybutylene succinate, adipate-modified polybutylene succinate, carbonate-modified polybutylene succinate, terephthalate-modified polybutylene succinate, polyethylene succinate And polyvinyl alcohol.

  Among (C9), as polyhydroxybutyrate, for example, biogreen [manufactured by Mitsubishi Gas Chemical Co., Ltd.]]; as polylactic acid, for example, Lacia [manufactured by Mitsui Chemicals, Inc.]]; as polycaprolactone, for example, Cell Green [manufactured by Daicel Chemical Industries, Ltd.]; Polybutylene succinate, for example, Bionore [manufactured by Showa Polymer Co., Ltd.]; Polyethylene succinate, for example, Lunare SE [manufactured by Nippon Shokubai Co., Ltd.] Examples of polyvinyl alcohol include Poval [manufactured by Kuraray Co., Ltd.].

  The resin composition of the present invention includes a group consisting of an antistatic property improver (D), a compatibilizer (E), and other additives for resin (F) as necessary, as long as the effects of the present invention are not impaired. You may contain the at least 1 sort (s) of additive chosen from these.

(D) includes one or more selected from the group consisting of an alkali metal or alkaline earth metal salt (D1), a surfactant (D2) and an ionic liquid (D3).
(D1) includes alkali acids (lithium, sodium, potassium, etc.) and / or alkaline earth metals (magnesium, calcium, etc.) organic acids (C1-12 mono- and di-carboxylic acids such as formic acid, acetic acid, Propionic acid, oxalic acid, succinic acid; salts of C1-20 sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid; thiocyanic acid, and inorganic acids (hydrohalic acids such as hydrochloric acid, hydrobromic acid; A salt of perchloric acid; sulfuric acid; nitric acid; phosphoric acid) can be used.

Specific examples of (D1) include halide [fluoride (lithium fluoride, -sodium, -potassium, -magnesium, -calcium, etc.), chloride (lithium chloride, -sodium, -potassium, -magnesium, -calcium, etc.) ), Bromides (such as lithium bromide, -sodium, -potassium, -magnesium and -calcium) and iodides (such as lithium iodide, -sodium, -potassium, -magnesium and -calcium)], perchlorates ( Lithium perchlorate, -sodium, -potassium, -magnesium and -calcium), fluorinated sulfonates (lithium fluorosulfonate, -sodium, -potassium, -magnesium and -calcium), methanesulfonate (methane) Lithium sulfonate, -sodium, -ca Um, -magnesium and -calcium), trifluoromethanesulfonate (lithium trifluoromethanesulfonate, -sodium, -potassium, -magnesium and -calcium), pentafluoroethanesulfonate (lithium pentafluoroethanesulfonate, -Sodium, -potassium, -magnesium and -calcium), nonafluorobutane sulfonate (such as lithium nonafluorobutane sulfonate, -sodium, -potassium, -magnesium and -calcium), undecafluoropentane sulfonate ( Undecafluoropentanesulfonate lithium, -sodium, -potassium, -magnesium, -calcium, etc.), tridecafluorohexanesulfonate (tridecafluorohexanesulfone) Lithium acid, -sodium, -potassium, -magnesium and -calcium), acetate (lithium acetate, -sodium, -potassium, -magnesium and -calcium etc.), sulfate (sodium sulfate, -potassium, -magnesium and- Calcium, etc.), phosphates (sodium phosphate, -potassium, -magnesium, -calcium, etc.), thiocyanates (potassium thiocyanate, etc.) and the like.
Of these, from the viewpoint of antistatic properties, preferred are halides, perchlorates, trifluoromethanesulfonates, acetates, and more preferred are lithium chloride, -potassium and -sodium, lithium perchlorate, -potassium and -Sodium, lithium trifluoromethanesulfonate,-potassium and-sodium, potassium acetate.

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

(D2) includes nonionic, anionic, cationic and amphoteric surfactants, and mixtures thereof.
Nonionic surfactants include, for example, EO addition type nonionic surfactants [for example, higher alcohols (C8-18, the same shall apply hereinafter), higher fatty acids (C8-24, the same shall apply hereinafter) or higher alkylamines (C8-24). ) EO adduct (molecular weight 158 or more and Mn 200,000 or less); higher fatty acid ester of polyalkylene glycol (molecular weight 150 or more and Mn 6,000 or less) which is an EO adduct of glycol; polyhydric alcohol (C2-18-2) EO adduct of higher fatty acid ester (molecular weight of 250 or more and Mn of 30,000 or less); EO adduct of higher fatty acid amide (molecular weight 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 Mn of 30,000 or less)], and polyhydric alcohol (C3-60) type nonionic surfactant [For example, fatty acid (C3-60) ester of polyhydric alcohol, alkyl (C3-60) ether of polyhydric alcohol and fatty acid (C3-60) alkanolamide].

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

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

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

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

The amount of (D2) 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 containing (D2) is also not particularly limited, but it is preferable to disperse in (B) in advance in order to effectively disperse it in the resin composition. Further, when (D2) is dispersed in (B), it is particularly preferable that (D2) is previously contained and dispersed during the production (polymerization) of (B). There is no particular limitation on the timing at which (D2) is contained during the production of (B), and any time before polymerization, during polymerization, or immediately after polymerization may be used.

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

Examples of the amidinium cation include 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 etc.].

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

  Examples of the tertiary ammonium cation include methyl dilauryl ammonium.

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

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

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

Super strong acids include those derived from protonic acids and combinations of protonic acids and Lewis acids, and mixtures thereof.
Examples of the protonic acid as the super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane (C1 -30) sulfonic acid [for example, methanesulfonic acid, dodecanesulfonic acid, etc.], poly (n = 1-30) fluoroalkane (C1-30) sulfonic acid (for example, trifluoromethanesulfonic acid, pentafluoroethanesulfonic 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 halide (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid. , Pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof.
Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of (D3).

Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof. Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of (D3).
The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

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

The amount of (D3) used is usually 10% or less based on the total weight of (A), (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 of adding (D3) is also not particularly limited, but it is preferable to disperse in (B) in advance from the viewpoint of effective dispersion in the resin. Further, when (D3) is dispersed in (B), it is particularly preferable that (D3) is contained and dispersed in advance during the production (polymerization) of (B). There is no particular limitation on the timing at which (D3) is contained during the production of (B), and any time before polymerization, during polymerization, or immediately after polymerization may be used.

  The production method of (D3) includes, for example, an amidinium cation and / or guanidinium cation dimethyl carbonate salt obtained by quaternization with dimethyl carbonate, etc. Acid or inorganic acid] 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 compatibilizer (E), a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group is used. Examples thereof include polymers described in JP-A-3-258850. Further, for example, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, a block polymer having a polyolefin portion and an aromatic vinyl polymer portion, and the like can be used.
The use amount of (E) is preferably 0.1 to 15%, more preferably 1 to 10%, particularly preferably 1 to 10%, based on the total weight of (A), (B) and (C), from the viewpoint of resin physical properties. Preferably it is 1.5 to 8%.
The method of containing (E) is not particularly limited, but it is preferable to disperse in the hydrophilic group-containing polymer (B) in advance from the standpoint of effective dispersion or dissolution in the composition. .
In addition, when (E) is dispersed or dissolved in (B), it is particularly preferable to contain (E) in advance during the production (polymerization) of (B). There is no particular limitation on the timing of incorporating (E) during the production of (B), and any of the timing before polymerization, during polymerization, and immediately after polymerization may be used.

Moreover, according to various uses, the other resin additive (F) can be arbitrarily added to the resin composition of this invention in the range which does not inhibit the effect of this invention.
(F) includes nucleating agent (F1), lubricant (F2), pigment (F3), dye (F4), mold release agent (F5), antioxidant (F6), flame retardant (F7), ultraviolet absorber Examples thereof include at least one selected from the group consisting of (F8), antibacterial agent (F9), dispersant (F10), conductive substance (F11), and filler (F12).

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

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

  Antioxidants (F6) include phenolic {eg monocyclic phenols [eg 2,6-di-t-butyl-p-cresol and butylated hydroxyanisole], bisphenols [eg 2,2′-methylenebis (4- Methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl) -6-tert-butylphenol and 4,4′-thiobis (3-methyl) -6-tert-butylphenol] and polycyclic phenols [ For example, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-) 5-t-butylphenyl) butane, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate ] Methane]}; sulfur-based [eg, dilauryl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, dimyristyl 3,3'- Thiodipropionate, distearyl β, β′-thiodibutyrate and dilauryl sulfide]; phosphorus systems [eg triphenyl phosphite, triisodecyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-t) -Butylphenylditridecyl) phosphite, cyclic neopentanetetri Bis (octadecyl phosphite), cyclic neopentanetetrayl bis (2,6-di-t-butyl-4-methylphenyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butyl) Phenyl) phosphite and diisodecylpentaerythritol diphosphite]; and amine systems such as octylated diphenylamine, Nn-butyl-p-aminophenol, N, N-diisopropyl-p-phenylenediamine, N, N-bis ( 1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N-diphenyl-p-phenylenediamine, N-phenyl-α-naphthylamine, phenyl-β-naphthylamine and phenothiazine.

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

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

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

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

Examples of the phosphate include 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-, 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, (F72) is preferred from the viewpoint of flame retardancy and the absence of environmental pollution such as dioxin generation during incineration.

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

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

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

  The conductive substance (F11) is a compound other than the above (D1) and (D3), and examples thereof include carbon nanotubes, carbon black, and white carbon.

  Examples of the filler (F12) include inorganic fillers (eg, calcium carbonate, talc, clay, silicic acid, silicate, asbestos, mica, glass fiber, glass balloon, carbon fiber, metal fiber, ceramic whisker and titanium whisker). And organic fillers [for example, urea, calcium stearate and organic crosslinked fine particles (for example, epoxy-based and urethane-based)].

The total amount of (F) used is usually 45% or less based on the total weight of (A), (B), and (C), and is preferably 0 from the viewpoint of the effect of each additive and the mechanical properties of the molded product. 0.001 to 40%, more preferably 0.01 to 35%, particularly preferably 0.05 to 30%.
Of (F), (F1), (F2), (F3), (F4), (F5), (F10) and (F12) are each usually 10% or less, preferably 1 to 5%; (F7) Is usually 20% or less, preferably 1 to 10%; (F6), (F8) and (F11) are usually 5% or less, preferably 0.1 to 3%; (F9) is usually 3% or less, preferably 0.05 to 1%.

The resin composition of the present invention can be obtained by melt-mixing the antistatic agent of the present invention, (C), and (D), (E) and / or (F) as necessary. 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.
The order of addition of each component during melt mixing is not particularly limited. For example, (1) after the antistatic agent of the present invention is melt mixed, (C), and (D), (E) and / or Or (F) batch melting and mixing, (2) the antistatic agent of the present invention is melt mixed, and then a part of (C) is melted and mixed in advance to obtain a high concentration of the antistatic agent of the present invention. A method of preparing a composition (masterbatch resin composition) and then melt-mixing the remaining (C) and (D), (E) and / or (F) as required is mentioned.
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, film molding (casting method, tenter method, inflation method, etc.) and the like. Molding can be performed by any method that incorporates means such as layer molding, multilayer molding, and foam molding.

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

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

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

Example 1
In a stainless steel autoclave, 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, antioxidant [trade name “Irganox 1010”, manufactured by Ciba Specialty Chemicals Co., Ltd., tetrakis [methylene-3- (3 ′ 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, and so on. ] 0.3 parts and 6 parts of water were charged, the inside of the autoclave was purged with nitrogen, then heated and stirred at 220 ° C. under pressure (0.3 to 0.5 MPa) for 4 hours, and an acid having carboxyl groups at both ends. 96 parts of polyamide having a value of 112 and Mn of 1,000 were obtained.
Next, 192 parts of EO product of bisphenol A (b12-1) (Mn2,000) and 0.5 part of zirconyl acetate were added and polymerized at 245 ° C. under reduced pressure of 0.13 kPa or less for 5 hours to obtain a polyether ester. An amide (B1-1) was obtained. The volume resistivity value of (B1-1) was 2 × 10 ⁸ Ω · cm, and the SP value was 10.1.
A stainless steel autoclave was charged with 90 parts of (B1-1), and the atmosphere in the autoclave was replaced with nitrogen, followed by heating and stirring at 230 ° C. 10 parts of polyethylene glycol dibenzoate (A1-1) (Mn640, SP value 10.2) was added and mixed, and after melting and stirring at 230 ° C. for 1 hour, the resulting mixture was taken out as a strand on a belt and pelletized To obtain an antistatic agent (X1). The crystallinity of the oxyethylene group part in (B1-1) in (X1) was 40%. The crystallinity was obtained in accordance with the above method (hereinafter the same).

Example 2
In Example 1, in place of (A1-1), polyhexamethylene adipate diol (A2-1) (Mn 3,000, SP value 10.4) was used in the same manner as in Example 1 to prevent antistatic. Agent (X2) was obtained. The crystallinity of the oxyethylene group portion in (B1-1) in (X2) was 40%.

Example 3
A stainless steel autoclave was charged with 72 parts of 12-aminododecanoic acid, 28 parts of terephthalic acid, 0.3 part of an antioxidant and 6 parts of water, and the inside of the autoclave was purged with nitrogen and pressurized at 220 ° C. (0.3 to 0). 0.5 MPa) The mixture was heated and stirred for 4 hours in a sealed state to obtain 96 parts of polyamide having an acid value of 224 and Mn500 having carboxyl groups at both ends.
Next, 96 parts of EO product of bisphenol A (b12-2) (Mn500) and 0.5 part of tetrabutyl titanate were added and polymerized at 245 ° C. under a reduced pressure of 0.13 kPa or less for 5 hours to obtain a polyether ester amide. (B1-2) was obtained. The volume resistivity value of (B1-2) was 1 × 10 ¹² Ω · cm, and the SP value was 11.0.
A stainless steel autoclave was charged with 91 parts of (B1-2), and the interior of the autoclave was purged with nitrogen and then heated and stirred at 230 ° C. (A2-1) 9 parts were added and mixed, and after melting and stirring at 230 ° C. for 1 hour, the obtained mixture was taken out in a strand form on a belt and pelletized to obtain an antistatic agent (X3). The crystallinity of the oxyethylene group portion in (B1-2) in (X3) was 50%.

Example 4
A stainless steel autoclave was charged with 53 parts of ε-caprolactam, 47 parts of adipic acid, 0.3 part of an antioxidant and 6 parts of water, and the inside of the autoclave was purged with nitrogen and pressurized at 220 ° C. (0.3 to 0.5 MPa) ) Under sealing, the mixture was heated and stirred for 4 hours to obtain 96 parts of polyamide having an acid value of 560 and Mn200 having carboxyl groups at both ends.
Next, 64 parts of polyethylene glycol (b13-1) (Mn300, volume resistivity 1 × 10 ⁷ Ω · cm) and 0.5 part of antimony trioxide were added, and 5 parts under reduced pressure at 245 ° C. and 0.13 kPa or less. Polymerization was performed for a time to obtain polyetheresteramide (B1-3). The volume resistivity value of (B1-3) was 1 × 10 ¹¹ Ω · cm, and the SP value was 11.4.
A stainless steel autoclave was charged with 80 parts of (B1-3), the inside of the autoclave was purged with nitrogen, and then heated and stirred at 230 ° C. (A2-1) 20 parts was added and mixed, and after melting and stirring at 230 ° C. for 1 hour, the obtained mixture was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X4). The crystallinity of the oxyethylene group portion in (B1-3) in (X4) was 47%.

Example 5
A stainless steel autoclave was charged with 94 parts of ε-caprolactam, 6 parts of terephthalic acid, 0.3 part of an antioxidant and 6 parts of water, and the inside of the autoclave was purged with nitrogen and pressurized at 220 ° C. (0.3 to 0.5 MPa ) Under sealing, the mixture was heated and stirred for 4 hours to obtain 96 parts of polyamide having an acid value of 37 and Mn of 3,000 having carboxyl groups at both ends.
Next, 72 parts of EO product of bisphenol A (b12-3) (Mn 4,000) and 0.5 part of zinc acetate were added and polymerized at 245 ° C. under reduced pressure of 0.13 kPa or less for 5 hours to obtain a polyether ester. The amide (B1-4) was obtained. The volume resistivity value of (B1-4) was 5 × 10 ⁶ Ω · cm, and the SP value was 10.2.
A stainless steel autoclave was charged with 83 parts of (B1-4), the inside of the autoclave was purged with nitrogen, and then heated and stirred at 230 ° C. 17 parts of (A1-1) was added and mixed, and after melting and stirring at 230 ° C. for 1 hour, the resulting mixture was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X5). The crystallinity of the oxyethylene group portion in (B1-4) in (X5) was 35%.

Example 6
A stainless steel autoclave was charged with 97 parts of 12-aminododecanoic acid, 3 parts of terephthalic acid, 0.3 part of an antioxidant and 6 parts of water, and the inside of the autoclave was purged with nitrogen and pressurized at 220 ° C. (0.3 to 0). 0.5 MPa) The mixture was heated and stirred under sealing for 4 hours to obtain 96 parts of polyamide having an acid value of 22 and Mn of 5,000 having carboxyl groups at both ends.
Next, 96 parts of polyethylene glycol (b13-2) (Mn 5,000, volume resistivity 1 × 10 ⁷ Ω · cm) and 0.5 part of zirconyl acetate were added, and 245 ° C. under a reduced pressure of 0.13 kPa or less. Polymerization was performed for 5 hours to obtain a polyether ester amide (B1-5). The volume resistivity value of (B1-5) was 1 × 10 ⁶ Ω · cm, and the SP value was 10.1.
90 parts of (B1-5) was charged in a stainless steel autoclave, and the interior of the autoclave was purged with nitrogen, followed by heating and stirring at 230 ° C. (A1-1) 10 parts were added and mixed, and after melting and stirring at 230 ° C. for 1 hour, the obtained mixture was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X6). The crystallinity of the oxyethylene group portion in (B1-5) in (X6) was 35%.

Example 7
In Example 4, polyether ester amide (B1-6) was used in the same manner as in Example 4 except that EO addition product of bisphenol A (b12-4) (Mn300) was used instead of (b13-1). Got. The volume resistivity value of (B1-6) was 1 × 10 ¹¹ Ω · cm, and the SP value was 11.5.
95 parts of (B1-6) was charged into a stainless steel autoclave, and the interior of the autoclave was purged with nitrogen, and then heated and stirred at 230 ° C. 5 parts of (A2-1) was added and mixed, and after melting and stirring at 230 ° C. for 1 hour, the resulting mixture was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X7). The crystallinity of the oxyethylene group portion in (B1-6) in (X7) was 49%.

Example 8
In Example 7, an antistatic agent (X8) was added in the same manner as in Example 7 except that polyethylene glycol (A3-1) (Mn150, SP value 13.0) was used instead of (A2-1). Obtained. The crystallinity of the oxyethylene group portion in (B1-6) in (X8) was 50%.

Example 9
In Example 6, a polyether ester amide (B1-) was used in the same manner as in Example 6 except that the EO adduct of bisphenol A (b12-5) (Mn 5,000) was used instead of (b13-2). 7) was obtained. The volume resistivity value of (B1-7) was 2 × 10 ⁶ Ω · cm, and the SP value was 10.3.
70 parts of (B1-7) was charged in a stainless steel autoclave, and the interior of the autoclave was purged with nitrogen, and then heated and stirred at 230 ° C. 30 parts of (A1-1) was added and mixed, and after melting and stirring at 230 ° C. for 1 hour, the resulting mixture was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X9). The crystallinity of the oxyethylene group portion in (B1-7) in (X9) was 35%.

Example 10
In Example 9, the same procedure as in Example 9 was followed except that 70 parts of (B1-7) were replaced with 99 parts of the same and 30 parts of (A1-1) were replaced with the same part of 1, thereby obtaining an antistatic agent (X10). It was. The crystallinity of the oxyethylene group portion in (B1-7) in (X10) was 37%.

Example 11
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 which can be modified at both ends (95%) and 85 parts of maleic anhydride and 15 parts of maleic anhydride are melted at 200 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 200 ° C. for 20 hours. I let you.
Then, excess maleic anhydride was distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polypropylene (b21-1). (B21-1) had an acid value of 39.8 and Mn of 2,800.
Next, in a stainless steel autoclave, 50 parts of (b21-1), 50 parts of polyethylene glycol (b22-1) (Mn2,800, volume resistivity 1 × 10 ⁷ Ω · cm), 0.3 part of antioxidant And 0.5 part of zirconyl acetate were charged and polymerized at 230 ° C. under a reduced pressure of 0.13 kPa or less for 3 hours to obtain a viscous polymer (B2-1). Mn of (B2-1) was 22,000, and the average number of repetitions (Nn) determined from the Mn and ¹ H-NMR analysis was 3.9. The volume resistivity value of (B2-1) was 1 × 10 ⁸ Ω · cm, and the SP value was 8.8.
90 parts of the (B2-1) was charged into a stainless steel autoclave, the inside of the autoclave was purged with nitrogen, and then heated and stirred at 200 ° C. to obtain 10 parts of polyethylene glycol diacetate (A1-2) (Mn520, SP value 9.5). After adding and mixing and melting and stirring at 200 ° C. for 1 hour, the obtained polymer was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X11). The crystallinity of the oxyethylene group portion in (B2-1) in (X11) was 40%.

Example 12
In Example 11, an antistatic agent was used in the same manner as in Example 11 except that polytetramethylene glycol (A3-2) (Mn2,000, SP value 9.9) was used instead of (A1-2). (X12) was obtained. The crystallinity of the oxyethylene group portion in (B2-1) in (X12) was 45%.

Example 13
In Example 11, an antistatic agent (X13) was obtained in the same manner as in Example 11 except that di-2-ethylhexyl phthalate (SP value 9.5) was used instead of (A1-2). The crystallinity of the oxyethylene group portion in (B2-1) in (X13) was 40%.

Example 14
Low molecular weight polypropylene obtained by a thermal degradation method (Mn 3,400, density 0.89, 7.0 double bonds per 1,000 C, average of double bonds per molecule, and stainless steel autoclave) 1.8 parts, 90 parts of polyolefin capable of modifying both ends) and 10 parts of maleic anhydride were melted at 200 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 200 ° C. for 20 hours. I let you. Then, excess maleic anhydride was distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polypropylene (b21-2). (B21-2) had an acid value of 27.5 and Mn3,600.
Next, 97 parts of (b21-2) and 5 parts of ethanolamine were melted at 180 ° C. in a nitrogen gas atmosphere in a stainless steel autoclave and reacted at 180 ° C. for 2 hours. Then, excess ethanolamine was distilled off under reduced pressure at 180 ° C. for 2 hours to obtain a modified polypropylene (b21-3) having a hydroxyl group. (B21-3) had a hydroxyl value of 26.7, an amine value of 0.01, and Mn of 3,700.
Next, an isocyanate-modified polyethylene glycol (b22-3) obtained by reacting polyethylene glycol (b22-2) (Mn3,200, volume resistivity 1 × 10 ⁷ Ω · cm) with MDI in a stainless steel autoclave. 43 parts (NCO content 3.0%, volume resistivity 1 × 10 ⁷ Ω · cm) and 57 parts of modified polypropylene (b21-3) having a hydroxyl group at 200 ° C., residence time The viscous polymer (B2-2) was obtained by kneading in 30 seconds, taking it out into a strand, and pelletizing it. The volume resistivity value of (B2-2) was 4 × 10 ⁸ Ω · cm, and the SP value was 9.0.
90 parts of (B2-2) was charged into a stainless steel autoclave, the inside of the autoclave was purged with nitrogen, and heated and stirred at 200 ° C., 10 parts of (A1-2) was added and mixed, and after 1 hour melting and stirring at 200 ° C. The obtained polymer was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X14). The crystallinity of the oxyethylene group portion in (B2-2) in (X14) was 45%.

Example 15
In Example 11, the same procedure as in Example 7 was used except that polyether diamine (b22-4) (Mn 2,800, volume resistivity 2 × 10 ⁷ Ω · cm) was used instead of (b22-1). Thus, a viscous polymer (B2-3) was obtained. Mn of (B2-3) was 20,000, and the average number of repetitions (Nn) determined from the Mn and 1H-NMR analysis was 3.6. The volume resistivity value of (B2-3) was 8 × 10 ⁷ Ω · cm, and the SP value was 8.8. Further, in the same manner as in Example 7, an antistatic agent (X15) was obtained. The crystallinity of the oxyethylene group portion in (B2-3) in (X15) was 40%.

Example 16
Low molecular weight polypropylene obtained by the thermal degradation method (Mn 19,000, density 0.89, 1.2 double bonds per 1,000 C, average double bond per molecule) on stainless steel autoclave 1.6 parts, content of polyolefin which can be modified at both ends (90%) 250 parts and maleic anhydride 10 parts were melted at 220 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 220 ° C. for 29 hours. I let you. Then, excess maleic anhydride was distilled off under reduced pressure at 220 ° C. for 3 hours to obtain acid-modified polypropylene (b21-4). (B21-4) had an acid value of 5.5 and Mn of 19,200.
Next, 135 parts of acid-modified polypropylene (b21-4) and 10 parts of bis (2-aminoethyl) ether were melted at 200 ° C. under stirring in a nitrogen gas atmosphere and reacted at 200 ° C. for 2 hours. Thereafter, excess bis (2-aminoethyl) ether was distilled off under reduced pressure at 200 ° C. for 2 hours to obtain a modified polypropylene (b21-5) having amino groups at both ends. The amine value of (b21-5) was 5.8, and Mn was 19,400.
Next, in a stainless steel autoclave, 50 parts of (b21-5), 40 parts of polyethylene glycol (b22-5) (Mn 20,000, volume resistivity 1 × 10 ⁸ Ω · cm), 5.2 parts of dodecanedioic acid Then, 0.3 part of an antioxidant and 0.5 part of zinc acetate were charged and polymerized at 230 ° C. under a reduced pressure of 0.13 kPa or less for 15 hours to obtain a viscous polymer (B2-4). The volume resistivity value of (B2-4) was 1 × 10 ¹⁰ Ω · cm, and the SP value was 8.8.
91 parts of the (B2-4) was charged into a stainless steel autoclave, the inside of the autoclave was purged with nitrogen, and heated and stirred at 200 ° C., 10 parts of (A1-2) was added and mixed, and after 1 hour melting and stirring at 200 ° C. The obtained polymer was taken out in a strand form on a belt and pelletized to obtain an antistatic agent (X16). The crystallinity of the oxyethylene group portion in (B2-4) in (X16) was 50%.

Example 17
In a stainless steel autoclave, 66 parts of acid-modified polypropylene (b21-2) and 34 parts of 12-aminododecanoic acid were melted at 200 ° C. under stirring in a nitrogen gas atmosphere, at 200 ° C. for 3 hours, 1.3 kPa or less. The reaction was carried out under reduced pressure to obtain 96 parts of acid-modified polypropylene (b21-6). (B21-6) had an acid value of 17.7 and Mn of 5,700.
Next, in a stainless steel autoclave, 63 parts of (b21-6), 50 parts of polyethylene glycol (b22-6) (Mn 5,000, volume resistivity 1 × 10 ⁷ Ω · cm), 6 parts of sodium dodecylbenzenesulfonate Then, 0.3 part of an antioxidant and 0.5 part of tetrabutyl titanate were charged and polymerized at 230 ° C. under a reduced pressure of 0.13 kPa or less for 8 hours to obtain a viscous polymer (B2-5). The volume resistivity value of (B2-5) was 1 × 10 ⁸ Ω · cm, and the SP value was 9.4.
91 parts of (B2-5) were charged into a stainless steel autoclave, the inside of the autoclave was purged with nitrogen, heated and stirred at 200 ° C., 10 parts of (A1-2) was added and mixed, and melted and stirred at 200 ° C. for 1 hour. The obtained polymer was taken out as a strand on a belt and pelletized to obtain an antistatic agent (X17). The crystallinity of the oxyethylene group portion in (B2-5) in (X17) was 37%.

Example 18
In Example 17, an antistatic agent (X18) was used in the same manner as in Example 17 except that polyethylene glycol (A3-3) (Mn 8,000, SP value 9.5) was used instead of (A1-2). ) The crystallinity of the oxyethylene group portion in (B2-5) in (X18) was 40%.

Comparative Example 1
In Example 1, an antistatic agent (ratio X1) was obtained in the same manner as in Example 1 except that (A1-1) was not used. The crystallinity of the oxyethylene group portion in (B1-1) in (Ratio X1) was 64%.

Comparative Example 2
In Example 3, an antistatic agent (ratio X2) was obtained in the same manner as in Example 3 except that (A2-1) was not used. The crystallinity of the oxyethylene group portion in (B1-2) in (Ratio X2) was 66%.

Comparative Example 3
In Example 6, an antistatic agent (ratio X3) was obtained in the same manner as in Example 6 except that (A1-1) was not used. The crystallinity of the oxyethylene group portion in (B1-5) in (Ratio X3) was 62%.

Comparative Example 4
In Example 11, an antistatic agent (ratio X4) was obtained in the same manner as in Example 11 except that (A1-2) was not used. The crystallinity of the oxyethylene group portion in (B2-1) in (Ratio X4) was 64%.

Comparative Example 5
(A1-1) in Example 1 was used as an antistatic agent (ratio X5).

Examples 19 to 41, Comparative Examples 6 to 12
According to the blending composition shown in Table 1, (X1) to (X18) or (Ratio X1) to (Ratio X5) and the thermoplastic resin (C-1) or (C-2) are optionally antistatic improvers After blending with (D-1) or (D-2) and compatibilizer (E-1) for 3 minutes with a Henschel mixer, using a twin screw extruder with a vent, 220 ° C., 100 rpm, residence time 5 minutes It melt-kneaded on conditions, and obtained the resin composition (Examples 19-41 and Comparative Examples 6-12), respectively.

Comparative Example 13
After blending 9 parts of (Ratio X1) and 88 parts of (C-1) together with 1 part of (A1-1) and 2 parts of (D-1) with a Henschel mixer for 3 minutes, The mixture was melt-kneaded under the conditions of 220 ° C., 100 rpm, and a residence time of 5 minutes to obtain a resin composition (Comparative Example 13).

（Ｃ−１）：ＡＢＳ樹脂[商品名「セビアン−Ｖ３２０」、ダイセルポリマー（株）製]
（Ｃ−２）：ポリプロピレン樹脂[商品名「サンアロマーＰＭ７７１Ｍ」、サンアロマー
（株）製]
（Ｄ−１）：ドデシルベンゼンスルホン酸ナトリウム
（Ｄ−２）：塩化リチウム
（Ｅ−１）：相溶化剤[商品名「エポフレンド」、ダイセル化学（株）製、変性ビニル重
合体]

(C-1): ABS resin [trade name “Cebian-V320”, manufactured by Daicel Polymer Co., Ltd.]
(C-2): Polypropylene resin [trade name “Sun Aroma PM771M”, Sun Aroma
Made by]
(D-1): Sodium dodecylbenzenesulfonate (D-2): Lithium chloride (E-1): Compatibilizer [trade name “Epofriend”, manufactured by Daicel Chemical Industries, Ltd., modified vinyl heavy
Combined]

<Performance evaluation>
Using the above resin composition, the cylinder temperature [240 ° C. in the case of (C-1), 220 ° C. in the case of (C-2)] by an injection molding machine [PS40E5ASE, manufactured by Nissei Plastic Industry Co., Ltd.] Then, molding was performed at a mold temperature of 50 ° C. to prepare test pieces, and the impact strength, antistatic property and moldability were evaluated. The results are shown in Table 2.

[1] Mechanical properties (1) Impact strength Conforms to ASTM D256 (with notch, 3.2 mm thickness) Method A.
[2] Antistatic property (1) Volume specific resistance value With respect to a test piece (100 × 100 × 2 mm), a superinsulator [DSM-8103 (electrode SME-8310 for flat plate sample), Toa Denpa Kogyo Co., Ltd., and so on. . ] In an atmosphere of 23 ° C. and humidity 50% RH (according to ASTM D257).
(2) Volume resistivity value after washing with water The surface of a test piece (100 × 100 × 2 mm) leaning diagonally was washed with 100 ml of ion exchange water (23 ° C.) at a flow rate of 100 ml / min, and then circulating at 80 ° C. Dry in a dryer for 3 hours. The test piece obtained by repeating the washing-drying operation 10 times was measured in the same manner as (1).
[3] Moldability Molding was performed under the same conditions as molding with a single thermoplastic resin, and the surface condition of the molded product was compared with that of a single thermoplastic resin according to the following criteria.
○: The surface of the molded product is equivalent to a molded product of a single thermoplastic resin.
X: The surface of the molded product is uneven as compared with a molded product of a single thermoplastic resin.
[4] Crystallinity of oxyethylene group portion in hydrophilic group-containing polymer (B) in antistatic agent The method described above was followed.

  As is apparent from Table 2, the resin compositions of the present invention (Examples 19 to 41) were compared with the comparative resin compositions (Comparative Examples 6 to 13) in terms of mechanical properties, permanent antistatic properties and molding. It turns out that it is excellent in property.

  Since the antistatic resin composition of the present invention is excellent in moldability and gives a molded product having excellent permanent antistatic properties and mechanical properties, various molding methods [injection molding, compression molding, calendar molding, slush molding, rotation Molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.)], and any various molding methods that incorporate means such as single layer molding, multilayer molding or foam molding depending on the purpose. Molded and required antistatic properties, housing products for home appliances / OA equipment, game equipment and office equipment, various plastic containers such as IC trays, various packaging films, flooring sheets, artificial grass, mats, and It is extremely useful as various molding materials for automobile parts.

Claims (10)

An antistatic agent comprising a plasticizer (A) and a hydrophilic group-containing polymer (B) having a volume resistivity of 1 × 10 ⁶ to 1 × 10 ¹² Ω · cm. (A) is a polyether polyol (A3), and (B) is at least one selected from the group consisting of the following (B1) and (B2) .
(B1): derived from a polyamide (b11) having a number average molecular weight of 200 to 5,000 and an alkylene oxide adduct (b12) and / or a polyalkylene glycol (b13) of a bisphenol compound having a number average molecular weight of 300 to 5,000. Polyether ester amide
(B2): At least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond, in which the block of the polyolefin (b21) and the block of the polyoxyalkylene chain-containing compound (b22) Block polymer having a structure in which it is alternately and alternately bonded through The hydrophilic group in (B) comprises an oxyethylene group. The antistatic agent as described. The antistatic agent according to claim 1 or 2 , wherein the weight ratio of (A) to (B) is from 1/99 to 30/70. The antistatic resin composition which makes the thermoplastic resin (C) contain the antistatic agent in any one of Claims 1-3 . The composition according to claim 4 , wherein the degree of crystallinity of the oxyethylene group moiety in (B) measured by a differential scanning calorimetry (DSC) method is 35 to 50%. The composition according to claim 4 or 5 , wherein the content of the antistatic agent is 1 to 30% based on the total weight of the antistatic agent and (C). The composition according to any one of claims 4 to 6 , further comprising at least one additive selected from the group consisting of an antistatic property improver, a compatibilizing agent, and other additives for resins. A molded article formed by molding the composition according to any one of claims 4 to 7 . A molded article obtained by coating and / or printing the molded article according to claim 8 . An antistatic agent comprising a plasticizer (A) and a hydrophilic group-containing polymer (B) having a volume resistivity of 1 × 10 ⁶ to 1 × 10 ¹² Ω · cm is added to the thermoplastic resin (C). A method for producing an antistatic resin composition, characterized in that (A) is a polyether polyol (A3), and (B) is a group consisting of the following (B1) and (B2): The manufacturing method of the antistatic resin composition which is at least 1 sort (s) chosen from .
(B1): derived from a polyamide (b11) having a number average molecular weight of 200 to 5,000 and an alkylene oxide adduct (b12) and / or a polyalkylene glycol (b13) of a bisphenol compound having a number average molecular weight of 300 to 5,000. Polyether ester amide
(B2): At least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond, in which the block of the polyolefin (b21) and the block of the polyoxyalkylene chain-containing compound (b22) Block polymer having a structure in which it is alternately and alternately bonded through