JP2006265533A - Method for manufacturing electric equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an electric device being excellent in the protection of the electric parts and can be improved in a yield, because the conventional method has problems wherein a resin tray which is used for conveying the electric parts has a contamination of electric parts, troubles due to electrostatic discharge or drop of yield caused by the impermeablity of the tray in a process for manufacturing the electric equipment. <P>SOLUTION: The method for manufacturing the electric equipment comprising a process for conveying the electric equipment comprises using a conveying means prepared by molding an antistatic resin composition containing a thermoplastic resin (A) and an antistatic agent (B) having a hydrophilic chain and having a refractive index having a difference between itself and that of the thermoplastic resin (A) of ≤0.02. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an electrical device, wherein an electrical component is transported using a transport body formed by molding an antistatic resin composition.

  Conventionally, in the manufacturing process of electrical equipment, electrical components are carried in resin trays. At that time, the resin tray is required to have antistatic properties so that electric parts (liquid crystal display elements, devices, etc.) are not damaged by an electrical failure caused by electrostatic discharge, and the surface is prevented from being charged. In general, an agent is applied or an antistatic property is imparted by kneading carbon, a surfactant or a polymer type antistatic agent (see, for example, Patent Document 1).

JP-A-11-106665

However, in the above method, it is difficult to understand the contents because the antistatic component is peeled off due to contact between the tray and the component, the electrical component is destroyed due to the contamination of the component and the occurrence of electrostatic discharge, and the tray is opaque. There is a problem in that it results in a decrease in yield that occurs from.
An object of the present invention is to provide a method of manufacturing an electrical device that is excellent in yield improvement and component protection by using a translucent carrier having no deterioration in antistatic properties. Here, the transport body includes a transport container, a transport film, and a transport sheet formed by molding the antistatic resin composition according to the present invention, and so on. Moreover, in the following, a conveyance body may be called a molded article.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to an antistatic agent having a hydrophilic chain and having a refractive index difference of 0.02 or less from a thermoplastic resin (A) in a method for producing an electric device having a step of conveying an electric component. A method of manufacturing an electrical device, wherein an electrical component is transported using a transport body formed by molding an antistatic resin composition containing B) in (A).

The method for manufacturing an electrical device according to the present invention is extremely useful because of the following effects.
(1) Since a carrier having excellent antistatic properties and less contamination to electrical components is used, it is excellent in protecting electrical components from electrical failures.
(2) Since the conveyance body is excellent in transparency, the yield is not lowered, and the productivity of the electric device is excellent.

  As the thermoplastic resin (A) in the present invention, for example, vinyl resin (A1) [for example, polyolefin resin (A11), polyacrylic resin (A12) and polystyrene resin (A13)], polyester resin (A2), polyamide resin (A3) ), Polycarbonate resin (A4), polyacetal resin (A5), modified polyphenylene ether resin (A6), biodegradable resin (A7), and mixtures of two or more thereof.

  Of these, (A1) and (A3) are preferable from the viewpoint of ease of dispersion of the antistatic agent (B) described later in (A), and (A11) and (A13) are more preferable. .

  The vinyl resin (A1) is obtained by polymerization (homopolymerization or copolymerization) of one or more ethylenically unsaturated monomers. The ethylenically unsaturated monomers include the following (a1) to (a7). included.

(A1) Unsaturated hydrocarbon (hereinafter abbreviated as HC)
(A11) Aliphatic HC [carbon number (hereinafter abbreviated as C) 2-18 or more]
Alkenes such as ethylene, propylene, (iso) butene, pentene, 4-methyl-1-pentene, heptene, diisobutylene, octene, dodecene, octadecene and other α-olefins; dienes such as butadiene, isoprene, 1,4- Pentadiene, 1,6-hexadiene, 1,7-octadiene and 1,11-dodecadiene (a12) alicyclic HC (C4-18 or more)
(Di) cycloalkenes such as cyclohexene, (di) cyclopentadiene, pinene, limonene, indene, vinylcyclohexene and ethylidenebicycloheptene (a13) aromatic HC (C8-20 or more)
Styrene, its homologues such as α-methyl styrene, 2,4-dimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, vinyl toluene, crotyl benzene, polyvinyl aromatic HC (for example Divinylbenzene, divinyltoluene, divinylxylene and trivinylbenzene), vinylnaphthalene and halogenated styrene (eg chlorostyrene).

(A2) Alkyl (meth) acrylates having a C1-50 alkyl group, such as methyl, ethyl, propyl, butyl, 2-ethylhexyl, dodecyl, hexadecyl, heptadecyl and eicosyl (meth) acrylate.
(A3) Carboxyl group-containing vinyl monomer (a31) Unsaturated monocarboxylic acid C3-18 aliphatic, alicyclic and aromatic monocarboxylic acids such as (meth) acrylic, (iso) croton, cyclohexene monocarboxylic and Cinnamic acid (a32) unsaturated dicarboxylic acids and their anhydrides, such as aliphatic [C4-18, such as (anhydrous) malein, fumar, (anhydrous) itacone, (anhydrous) citracone, mesacone and allylmalonic acid] Alicyclic [C7-24, such as 4-cyclohexene-1,2-dicarboxylic acid] and aromatic ring-containing [C8-24, such as phenylmaleic acid]
(A33) dicarboxylic acid monoester monoalkyl (C1-8 or more) esters of the above dicarboxylic acid (a32), for example, monoalkyl esters of malee, fumarate, itacone and citraconic acid (a34) above (a31), (a32) And salts of (a33), such as alkali metal (eg lithium, sodium and potassium) salts, alkaline earth metal (eg calcium and magnesium) salts, ammonium salts, amine (C2-24) salts and quaternary ammonium (C4-24) )salt

(A4) carbonyl, ether and / or sulfur containing unsaturated monomers (a41) unsaturated esters (a411) unsaturated esters of carboxylic acids (eg aliphatic and aromatic mono- and polycarboxylic acids) [vinyl, isopropenyl, (Meth) allyl and vinyl phenyl ester]
Aliphatic unsaturated esters (C4-15) such as vinyl esters (eg acetate, propionate, butyrate, methoxyacetate and benzoate), isopropenyl esters (eg acetate) and (meth) allyl esters (eg diallyl adipate); and aromatics Unsaturated esters (C9-20) such as diallyl phthalate, methyl-4-vinylbenzoate and acetoxystyrene

(A412) Unsaturated carboxylic acid ester [other than (a2) above]
(A4121) Unsaturated monocarboxylic acid other than (meth) acrylic acid having a linear, branched or alicyclic C1-22 (cyclo) alkyl group [above (a31)] (cyclo) alkyl ester, cycloalkyl ( Di (cyclo) alkyl esters of (meth) acrylates and unsaturated dicarboxylic acids [above (a32)] such as alkyl (iso) crotonates, cyclohexyl (meth) acrylates, and dialkyl fumarate and maleate (a4122) (poly) oxyalkylene ( C2-4) Esters of unsaturated carboxylic acids having a group (degree of polymerization 1-30) [above (a31) and (a32)] eg mono- and di (meta) of dihydric alcohols [eg C2-12 alkylene glycol] ) Acrylate [eg hydroxyethyl (meth) acrylate Rate, polyether diol {polyalkylene glycol [molecular weight 106 to number average molecular weight [hereinafter, abbreviated as Mn. Unless otherwise specified, the measurement is based on GPC (gel permeation chromatography) method. GPC apparatus: HLC-8220, manufactured by Tosoh Corporation] 1,000], for example, polyethylene glycol (Mn300) and polypropylene glycol (Mn500), and aromatic ring-containing polyoxyalkylene diol, for example, ethylene oxide of bisphenol A (hereinafter referred to as EO) Abbreviation) and / or propylene oxide (hereinafter abbreviated as PO) adduct} mono- and di (meth) acrylates, polyether monools [for example, having one active hydrogen atom such as monohydric alcohol, monohydric phenol, etc. Polyoxyalkylene having a structure in which an alkylene oxide (hereinafter abbreviated as AO) (for example, C2-12, such as EO, PO, 1,2-, 2,3- and 1,4-butylene oxide) is added to an initiator Monools such as polyoxyalkylene alkyls (C1-18) ethers [such as methyl alcohol EO (10 moles) adduct and lauryl alcohol EO (30 moles) adduct] of] (meth) acrylate; and equivalent thereto (iso) crotonate, fumarate and maleate

(A42) unsaturated ether (a421) aliphatic alkenyl and alkadienyl ether (C3-20)
For example, vinyl ether (hereinafter abbreviated as VE), for example, alkyl (C1-10) VE (for example, methyl, ethyl, propyl, butyl and 2-ethylhexyl VE); (poly) oxyalkylene (C2-4) group (degree of polymerization of 1 30), such as (poly) alkoxy (C1-6) alkyl (C1-4) VE (eg 2-methoxyethyl VE, 2-butoxyethyl VE, 2-butoxy-2′-vinyl) Methoxybutadiene; and (meth) allyl ethers such as poly (2-4) (meth) allyloxyalkanes (C2-6) [eg di-, tri- and tetra ( (Meth) allyloxyethane, tetra (meth) allyloxypropane and tetra (meth) allyloxy Shibutan]
(A422) Aromatic unsaturated ether (C8-20)
Phenyl VE and phenoxystyrene (a423) heterocyclic unsaturated ethers such as 3,4-dihydro-1,2-pyran

(A43) Vinyl ketones, such as aliphatic vinyl ketones (C4-25) and aromatic vinyl ketones (C9-21), such as methyl vinyl, ethyl vinyl, divinyl and phenyl vinyl ketones (a44) monomers containing sulfide bonds (C4-20)
Sulfides corresponding to (a42), such as divinyl sulfide, p-vinyl diphenyl sulfide and vinyl ethyl sulfide

(A45) Sulfone group-containing monomer (C4-25)
(A451) Unsaturated sulfone and sulfoxide Vinylethyl sulfone, divinyl sulfone and divinyl sulfoxide (a452) Unsaturated sulfonic acid such as alkene sulfonic acid [eg vinyl sulfonic acid and (meth) allyl sulfonic acid], unsaturated aromatic sulfonic acid Alkenyl and alkyl (C1-18) alkenyl esters of sulfocarboxylic acids (eg α-sulfoalkanoic acids and sulfosuccinic acids) [eg methyl vinyl, propyl (meth) allyl and Stearyl (meth) allylsulfosuccinate, and (meth) allylsulfolaurate], sulfo (hydroxy) alkyl (meth) acrylates and corresponding (meth) acrylamides [e.g. sulfoe And sulfopropyl (meth) acrylate, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfone acid]

(A5) Phosphorus-containing unsaturated monomer (C5-30)
(A51) phosphate group-containing unsaturated monomers such as (meth) acryloyloxyalkyl (C1-24) mono- and diphosphates such as 2- (meth) acryloyloxyethyl phosphate and phenyl-2- (meth) acryl Leuoxyethyl phosphate (a52) phosphonic acid group-containing unsaturated monomers such as (meth) acryloyloxyalkanes (C1-24) phosphonic acids such as 2-acryloyloxyethylphosphonic acid (a53) above (a51) and (a52) [Salts similar to those in (a34) above]

(A6) Nitrogen-containing monomer (a61) Amide group-containing monomer For example, (meth) acrylamide monomer (C3-20), such as (meth) acrylamide [except for (a7) described later]; N-alkyl (C1-6) (Meth) acrylamide, such as N-methyl (meth) acrylamide, N-butyl (meth) acrylamide, diacetone acrylamide, N, N′-methylene-bis (meth) acrylamide; N, N-dialkyl (C1-6) or Diaralkyl (C7-15) (meth) acrylamide, such as N, N-dimethylacrylamide, N, N-dibenzylacrylamide; Amide group-containing vinyl monomer (C4-20) excluding the above (meth) acrylamide monomer, such as methacrylformamide N-methyl-N-vinylacetoa Cinnamates, cyclic amides (N-vinylpyrrolidone, etc.), quaternary ammonium group-containing vinyl monomers [for example, tertiary amino group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide 4 Graded product (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate)]

(A62) (Meth) acrylate monomer (C5-20)
For example, primary and secondary amino group-containing (meth) acrylates such as aminoalkyl (C1-6) (meth) acrylate [eg aminoethyl (meth) acrylate], alkyl (C1-6) aminoalkyl (C1-6) ( (Meth) acrylate [eg t-butylaminoethyl methacrylate]; tertiary amino group-containing (meth) acrylate, eg dialkyl (C1-4) aminoalkyl (C1-4) (meth) acrylate [eg dimethylaminoethyl (meth) Acrylate, diethylaminoethyl (meth) acrylate, di-t-butylaminoethyl methacrylate and morpholinoethyl (meth) acrylate]; quaternary ammonium group-containing (meth) acrylate such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl Tertiary amino group-containing, such as meth) acrylate (meth) quaternized product of acrylate (those quaternized with supra quaternizing agent)

(A63) Heterocycle-containing monomer such as pyridine compound (C7-14) such as 4-vinylpyridine, 2-vinylpyridine; imidazole compound (C5-12) such as N-vinylimidazole; pyrrole compound (C6-13), For example, N-vinylpyrrole (a64) nitrile group-containing monomer (C3-15)
For example (meth) acrylonitrile, cyanostyrene and cyanoalkyl (C1-4) acrylate (a65) and other nitrogen-containing monomers Nitro group-containing monomers (C8-16) such as nitrostyrene

(A7) Hydroxyl group-containing monomer (a71) Styrene monomer (C8-15), such as hydroxystyrene (a72) (meth) acrylamide monomer (C4-10), such as N-methylol (meth) acrylamide (a73) unsaturated carboxylic acid Acid ester (C5-12)
Hydroxyalkyl (C1-6) (meth) acrylate [for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate]; hydroxyl-containing monomer having a poly (n = 2-30) oxyalkylene (C2-4) chain [ For example, polyoxyalkylene mono (meth) acrylate [for example, poly (n = 10) oxyethylene mono (meth) acrylate]]; poly (n = 2-30) oxyalkylene (C2-4) unsaturated carboxylic acid (di) ester [Eg poly (n = 10) oxyethylenemaleic acid (di) ester]; poly (n = 2-30) oxyalkylene (C2-4) (meth) allyl ether, eg poly (n = 10) oxyethylene (meta) ) Allyl ether

(A74) Alcohol (C3-8)
For example, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol and 2-butene-1,4-diol (a75) hydroxyl group-containing ether (C5-20)
For example, hydroxyalkyl (C1-6) alkenyl (C3-6) ethers, such as 2-hydroxyethylpropenyl ether, polyhydric alcohols (divalent to octavalent or higher, C2-20, such as ethylene glycol, glycerin, glucose and sucrose ) Of allyl ethers such as sucrose allyl ether.

The polyolefin resin (A11) includes (co) polymers of the monomer (a11) among the ethylenically unsaturated monomers, such as polyethylene (PE resin), polypropylene [(transparent) PP resin], ethylene-propylene copolymer. [Copolymerization ratio (weight ratio) = 99.9 / 0.1 to 0.1 / 99.9], copolymerization of ethylene and / or propylene with one or more other α-olefins [C4-12] Copolymer [copolymerization ratio (weight ratio) = 99/1 to 5/95, random and / or block addition], copolymer of monomers of (a11) and (a411), for example, ethylene / vinyl acetate copolymer ( EVA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40], copolymer of monomers of (a11) and (a2), for example, ethylene / ethyl acrylate copolymer (EEA) [copolymerization The ratio (weight ratio) = 95 / 5-60 / 40], and mixtures thereof.
Among these, from the viewpoint of moldability of a resin composition described later (hereinafter simply referred to as a resin composition), a (co) polymer of the monomer (a11) is preferable, and polyethylene, polypropylene, and ethylene-propylene copolymer are more preferable. Polymer and copolymer of ethylene and / or propylene and one or more of C4-12 α-olefin [copolymerization ratio (weight ratio) = 90 /
10 to 10/90, random and / or block addition].

The melt flow rate (hereinafter abbreviated as MFR) of (A11) is preferably from 0.5 to 150, more preferably from 1 to 100, from the viewpoint of imparting resin physical properties and antistatic properties to the molded product described later. MFR of (A11) is JIS
It is measured according to K7210 (1976) (230 ° C. and load 2.16 kgf for polypropylene, 190 ° C. and load 2.16 kgf for polyethylene).

  The polyacrylic resin (A12) includes one or more (co) polymers of acrylic monomers [for example, the above monomers (a2) and (meth) acrylonitrile] [for example, polymethyl methacrylate (PMMA resin), polymethyl acrylate. (PMAA resin) and poly (meth) butyl acrylate] and one or more of the above-mentioned monomers (a11) and other vinyl monomers excluding (a13) copolymerizable with one or more of these monomers [Acrylic monomer / other vinyl monomer copolymerization ratio (weight ratio) is preferably from 5/95 to 95/5, more preferably from the viewpoint of moldability of the resin composition and resin physical properties of the molded article. 50 / 50-90 / 10].

  The MFR of (A12) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of the resin physical properties of the molded product. The MFR of (A12) is measured according to JIS K7210 (1976) [230 ° C., load 1.2 kgf for polyacrylic resin (A12)].

For the polystyrene resin (A13), the monomer (a13) alone or a copolymer having at least one selected from the group consisting of (a13) and (meth) acrylic acid ester, (meth) acrylonitrile and butadiene as a structural unit Is included.
Specific examples of (A13) include polystyrene (PS resin), polyvinyltoluene, styrene / acrylonitrile copolymer (AS resin) [copolymerization ratio (weight ratio) = 70/30 to 80/20], styrene / methacrylic acid. Methyl copolymer (MS resin) [copolymerization ratio (weight ratio) = 60/40 to 90/10], styrene / butadiene copolymer (HIPS resin) [copolymerization ratio (weight ratio) = 60/40 to 95 / 5], acrylonitrile / butadiene / styrene copolymer [(transparent) 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 (A13) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of the resin physical properties and antistatic properties of the molded product. The MFR of (A13) is measured according to JIS K7210 (1976) (in the case of polystyrene resin, 230 ° C., load 1.2 kgf).

  Polyester resins (A2) include condensed polyesters such as C2-40 dicarboxylic acids (eg aliphatic, alicyclic and aromatic ring-containing dicarboxylic acids) and / or their ester-forming derivatives (C1-4 alkyl esters and Anhydrides) and diol condensation products, and lactone ring-opening polymers.

Among the above dicarboxylic acids, aliphatic dicarboxylic acids include C2-40 (preferably 4-20, more preferably 6-12), such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Examples include sebacic acid, undecanedioic acid and dodecanedioic acid.
Alicyclic dicarboxylic acids include C5-20 (preferably 6-18, more preferably 8-14), such as 1,4-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid and camphoric acid. .
Examples of aromatic ring-containing dicarboxylic acids include C8-20 (preferably 8-16, more preferably 8-14), such as ortho-, iso- and terephthalic acid, naphthalene-2,6- and -2,7-dicarboxylic acid. , Diphenyl-4,4′dicarboxylic acid, diphenoxyethanedicarboxylic acid, tolylene dicarboxylic acid, xylylene dicarboxylic acid and alkali metal 5-sulfoisophthalic acid (for example, lithium, sodium and potassium) salts.

The diol includes a low molecular weight diol having a hydroxyl equivalent weight of less than 250 (based on hydroxyl value, molecular weight per hydroxyl group; hereinafter abbreviated as OH equivalent) and at least 250, preferably 250 to 3,000, more preferably 350 to 3,000. Polyether diols having an OH equivalent weight of 2,500, particularly preferably 400 to 2,000 are included.
Low molecular diols include aliphatic dihydric alcohols [C2-12 (preferably 2-8, more preferably 2-6) alkylene glycols such as ethylene glycol, propylene glycol, 1,3- and 2,3-butylene. Glycol, 1,4-butanediol, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 2,3-, 2,4-, 2,5- and 3 , 4-hexanediol, neopentyl glycol, 2,2-, 2,3-, 2,4-, 2,5-, 3,3- and 3,4-dimethyl-1,6-hexanediol and 1, 12-dodecanediol]; alicyclic dihydric alcohol [C5-12 (preferably 5-10, more preferably 5-8), such as cyclopentane-1,2- and 1,3-diol, cyclohexane-1, 2--1, 3- and 1,4-diol, bis (hydroxymethyl) cyclohexane and hydrogenated bisphenol A]; and aromatic ring-containing dihydric alcohols [C8-20, such as xylylene glycol, bis (hydroxymethyl) benzene and bis (hydroxyethyl) ) Benzene].

  Examples of the polyether diol include AO (C2-4, the same applies hereinafter) adducts of the above low molecular diols, and dihydric phenols (for example, monocyclic phenols (C6-16, such as hydroquinone, catechol, resorcin and urushiol), AO adducts of cyclic phenols (C10-30, such as dihydroxynaphthalene and binaphthol) and bisphenols (C12-18, such as bisphenol A, -F and -S)].

  Examples of the lactone include C6-12, such as caprolactone, enanthlactone, laurolactone, and undecanolactone.

  Among the condensed polyesters, examples of the aliphatic polyester include polybutylene adipate, polyethylene adipate and poly-ε-caprolactone, examples of the alicyclic polyester include polycyclohexanedimethylene terephthalate, and examples of the aromatic ring-containing polyester include polyethylene terephthalate. And polybutylene terephthalate.

  Examples of the ring-opening polymer of lactone include, for example, each ring-opening polymer of caprolactone using adipic acid, terephthalic acid, isophthalic acid or sebacic acid as a molecular weight regulator, and ring opening weight of enanthlactone using adipic acid as a molecular weight regulator. Examples include ring-opening polymers of undecanolactone using a combination and adipic acid as a molecular weight modifier.

  The intrinsic viscosity [η] of (A2) is preferably 0.1 to 4, more preferably 0.2 to 3.5, particularly preferably 0.3 to 3 from the viewpoint of the resin physical properties and antistatic properties of the molded product. It is. [Η] is measured with a Ubbelohde 1A viscometer at 25 ° C. for a 0.5 wt% orthochlorophenol solution of the polymer.

  The polyamide resin (A3) includes a lactam ring-opening polymer (A31), a self-polycondensation product of aminocarboxylic acid (A32), a dehydration polycondensation product of diamine and dicarboxylic acid (A33), and a poly (condensation) combination thereof. Copolymer nylon having two or more types of monomer units constituting is included.

Examples of the lactam constituting (A31) include C6-12, such as caprolactam, enantolactam, laurolactam, and undecanolactam.
(A31) includes nylon 4, nylon 5, nylon 6, nylon 8, and nylon 12.
As the aminocarboxylic acid constituting (A32), C6-12, for example, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecane And acid and 12-aminododecanoic acid.
Examples of (A32) include nylon 7 by polycondensation of aminoenanthic acid, nylon 11 by polycondensation of ω-aminoundecanoic acid, and nylon 12 by polycondensation of 12-aminododecanoic acid.

  Examples of the dicarboxylic acid constituting (A33) include aliphatic dicarboxylic acids, aromatic (aliphatic) dicarboxylic acids, alicyclic dicarboxylic acids, amide-forming derivatives thereof [for example, acid anhydrides and lower (C1-4) alkyl esters. And 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 and 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 Mention may be made of alkali metal (eg lithium, sodium and potassium) salts of ethanedicarboxylic acid and 3-sulfoisophthalic acid.
Alicyclic dicarboxylic acids include C5-20, 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 and ortho-, iso- and dimethyl terephthalate are mentioned.

Examples of the diamine constituting (A33) include aliphatic, alicyclic, and aromatic (aliphatic) diamines.
Aliphatic diamines include C2-20, such as ethylene diamine, propylene diamine, hexamethylene diamine, 1,12-dodecane diamine, 1,18-octadecane diamine, and 1,20-eicosane diamine.
Alicyclic diamines include C5-20, such as 1,4-cyclohexylenediamine, isophoronediamine, 4,4′-diaminocyclohexylmethane, and 2,2-bis (4-aminocyclohexyl) propane.
Examples of araliphatic diamines include C7-20, such as xylylenediamine, bis (aminoethyl) benzene, bis (aminopropyl) benzene and bis (aminobutyl) benzene.
Aromatic diamines include C6-20, such as p-phenylenediamine, 2,4- and 2,6-toluylenediamine and 2,2-bis (4,4'-diaminophenyl) propane.

(A33) includes nylon 66 by polycondensation of hexanemethylenediamine and adipic acid, nylon 610 by polycondensation of hexamethylenediamine and sebacic acid, nylon 69 by polycondensation of hexamethylenediamine and azelaic acid, hexamethylenediamine and dodecane Nylon 612 by polycondensation of diacid and nylon 46 by polycondensation of tetramethylenediamine and adipic acid.
Examples of the copolymer nylon include nylon 6/66 (a copolymer of nylon 6 and nylon 66) and nylon 6/12 (a copolymer of nylon 6 and nylon 12).

  Those exemplified as the monomer (amide-forming monomer) constituting the above (A3) may be used in combination of two or more. Of these, caprolactam, 12-aminododecanoic acid and adipic acid / hexamethylenediamine are preferable from the viewpoint of antistatic properties, and caprolactam is more preferable.

In the production of (A3), a molecular weight modifier may be used, and examples of the molecular weight modifier include the dicarboxylic acid or diamine.
Of the dicarboxylic acids as molecular weight modifiers, aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferred from the viewpoint of reactivity with diamines, and more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid, and 3-sulfo. Sodium isophthalate.
Of the diamines as molecular weight regulators, hexamethylenediamine and decamethylenediamine are preferred from the viewpoint of reactivity with dicarboxylic acid.
The amount used of the molecular weight modifier is preferably 2 to 80%, more preferably 4 to 75% from the viewpoint of the antistatic property and heat resistance of the molded product based on the total weight of the amide-forming monomer and the molecular weight modifier. .

The MFR of (A3) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of the resin physical properties and antistatic properties of the molded product. MFR of (A3) is JIS
It is measured according to K7210 (1976) (in the case of polyamide resin, 230 ° C., load 0.325 kgf).

Examples of the polycarbonate resin (A4) include bisphenol [C12-20, for example, bisphenol A, -F and -S. From the viewpoint of dispersibility of (B) with respect to (A4), bisphenol A] -based polycarbonate resin ( For example, a condensate of the above bisphenol and phosgene or diphenyl carbonate) and a polymer alloy [PC / ABS resin (PC / ABS weight ratio = 90/10 to 10/90)] of the polycarbonate resin and ABS resin are included.
The MFR of (A4) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of the resin physical properties and antistatic properties of the molded product. MFR of (A4) is JIS
Measured according to K7210 (1976) (280 ° C., load 2.16 kgf in the case of polycarbonate resin).

Examples of the polyacetal resin (A5) include formaldehyde or trioxane homopolymer (polyoxymethylene homopolymer), and copolymers of formaldehyde or trioxane and cyclic ethers [AO (EO, PO, etc.), dioxolane, etc.] (polyoxy). And methylene / polyoxyethylene copolymer [for example, polyoxymethylene / polyoxyethylene (weight ratio) = 90/10 to 99/1 block copolymer].
The MFR of (A5) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of the resin physical properties and antistatic properties of the molded product. MFR of (A5) is JIS K7210
According to (1994) (in the case of polyacetal resin, 190 ° C., load 2.16 kgf).
The intrinsic viscosity [η] of (A5) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3 from the viewpoint of the resin physical properties and antistatic properties of the molded product. It is.

The modified polyphenylene ether resin (A6) includes a polymer alloy of a polyphenylene ether resin and a resin selected from the group consisting of the polystyrene resin, polyamide resin and polyolefin resin.
Examples of polyphenylene ether resins include poly (2,6-dimethyl-, diethyl- and dipropyl-1,4-phenylene) ether and poly (2-methyl-6-methyl-, 2-methyl-6-propyl- and 2). -Ethyl-6-propyl-1,4-phenylene) ether.

Among (A6), as a polymer alloy of polyphenylene ether resin and polystyrene resin, for example, Noryl [manufactured by General Electric Co., Ltd.]; As a polymer alloy of polyphenylene ether resin and polyamide resin, for example, Noryl GTYX [General Electric ( As a polyphenylene ether resin and a polyolefin resin, for example, Noryl PPX [manufactured by General Electric Co., Ltd.] can be mentioned.
The MFR of (A6) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of the resin physical properties and antistatic properties of the molded product. MFR is JIS
According to K7210 (1994), [measured at 280 ° C., load 5.0 kgf in the case of (A6)].

Biodegradable resins (A7) 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 (A7), as polyhydroxybutyrate, for example, biogreen [manufactured by Mitsubishi Gas Chemical Co., Ltd.]]; as polylactic acid, for example, Laissia [manufactured by Mitsui Chemicals, Inc.]; as polycaprolactone, for example, cell Green [Daicel Chemical Industries, Ltd.]; Polybutylene succinate, for example, Bionore [Showa Polymer Co., Ltd.]; Polyethylene succinate, for example, Lunare SE [manufactured by Nippon Shokubai Co., Ltd.]; Polyvinyl alcohol For example, Poval [manufactured by Kuraray Co., Ltd.] can be mentioned.

The antistatic agent (B) having a refractive index difference with respect to (A) of 0.02 or less and having a hydrophilic chain has a block of polyetheresteramide (B1) and polyolefin (b21), and a volume resistivity value. 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm of the hydrophilic polymer (b22) block has 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. Block polymer (B2), polyether amide imide (B3), epihalohydrin / AO copolymer (B4), polyether ester (B5), polyether urethane (B6), methoxy polyethylene Glycol (meth) acrylate copolymer (B7), polyether group-containing ethylene / vinyl acetate copolymer (Eth EO adduct of a len / vinyl alcohol copolymer) (B8) and a mixture of two or more thereof.
Of these, (B1), (B2), (B3), (B4) and (B5) are preferable from the viewpoint of antistatic properties, and (B1) and (B2) are more preferable.
Here, the hydrophilic chain is usually 1 × 10 ⁴ to 1 × 10 ¹² Ω · cm, preferably 1 ×.
It means one having a volume resistivity of 10 ⁵ to 1 × 10 ¹¹ Ω · cm.

As (B1), for example, polyether ester amides described in JP-A-6-287547 and JP-B-4-5691 can be used. Of these, from the viewpoint of heat resistance, the preferred lower limit of Mn is 200, more preferably 500, the preferred upper limit of Mn is 5,000, more preferably 3,000, and the preferred lower limit of Mn. Is a polyether ester amide derived from an AO adduct (b12) of bisphenol having a preferable upper limit of 5,000, more preferably 4,000.
Examples of (b11) include those exemplified as the above (A3).
) May be used in combination of two or more.
Of these monomers, caprolactam, 12-aminododecanoic acid and adipic acid / hexamethylenediamine are preferable from the viewpoint of antistatic properties, and caprolactam is more preferable.

(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 (A3). Among these, aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferable from the viewpoint of antistatic properties, and adipine is more preferable. Acids, 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 4 from the viewpoint of the antistatic property and heat resistance of the resin of the molded product based on the total weight of the amide-forming monomer and the molecular weight modifier. 75%.

Examples of the bisphenol constituting (b12) include those exemplified in the above (A4). Among these, bisphenol A is preferred from the viewpoint of dispersibility of (B) with respect to (A).
As AO to be added to bisphenol, C2-12, for example, EO, PO, 1,2-, 2,3- and 1,4-butylene oxide, epoxidized product of C5-12 α-olefin, styrene oxide and And epihalohydrins (eg, epichlorohydrin and epibromohydrin) and mixtures of two or more thereof. Of these, EO is preferable from the viewpoint of the antistatic property of the resin of the molded product.

  The proportion of (b12) based on the total weight of (b11) and (b12) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, from the viewpoint of antistatic properties and heat resistance of the resin of the molded product. It is.

Specific examples of the production method of the polyetheresteramide (B1) include the following production methods [1], [2] and [3], but are not particularly limited.
Production method [1]: An amide-forming monomer and a dicarboxylic acid (molecular weight modifier) are reacted to form (b11), to which (b12) is added, at a high temperature (160 to 270 ° C.) under reduced pressure (0. 03 to 3 kPa).
Production method [2]: An amide-forming monomer and dicarboxylic acid (molecular weight modifier) and a part of (b12) are simultaneously charged into a reaction vessel, and heated at a high temperature (160 to 270 ° C.) in the presence or absence of water. A method in which an intermediate is formed by reacting under pressure (0.1 to 1 MPa), and then the remaining (b12) is subjected to a polymerization reaction under reduced pressure (0.03 to 3 kPa).
Production method [3]: A method in which the terminal hydroxyl group of (b12) is substituted with an amino group or a carboxyl group and reacted with a polyamide (b11) having a carboxyl group or an amino group at the terminal.
Of the above production methods, production method [1] is preferable from the viewpoint of reaction control.

In the production method [3], as a method for substituting the terminal hydroxyl group of (b12) with an amino group, various methods, for example, a method of reducing a terminal cyanoalkyl group obtained by cyanoalkylating a hydroxyl group to form an amino group [ For example, there is a method of reacting (b12) with acrylonitrile and hydrogenating the resulting cyanoethylated product.
Examples of the method for substituting the terminal hydroxyl group of (b12) with a carboxyl group include a method of oxidizing with an oxidizing agent [for example, a method of oxidizing the hydroxyl group of (b12) with chromic acid].

In the polymerization reaction in the production methods [1] to [3], an esterification catalyst can be used. Examples of the catalyst include an antimony catalyst (for example, antimony trioxide), a tin catalyst (for example, monobutyltin oxide), a titanium catalyst (for example, tetrabutyl titanate), a zirconium catalyst (for example, tetrabutylzirconate), and a metal acetate catalyst (for example, acetic acid). Zinc and zirconyl acetate).
The amount of the catalyst used is preferably 0.1 to 5%, more preferably 0.2 to 3 based on the total weight of (b11) and (b12) from the viewpoints of reactivity and resin physical properties of the molded product. %.

The reduced viscosity [η _SP / C, C = 0.5 wt% (m-cresol solution, 25 ° C.)] of (B1) is preferably 0 from the viewpoint of the heat resistance of (B1) and the moldability of the resin composition. .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.
The block of the polyolefin (b21) constituting (B2) includes a polyolefin (b211) having a carbonyl group (preferably a carboxyl group) at both ends of the polymer, a polyolefin (b212) having a hydroxyl group, and a polyolefin having an amino group (b213). ), And a polyolefin (b214) having a carbonyl group (preferably a carboxyl group) at one end of the polymer, a polyolefin (b215) having a hydroxyl group, and a polyolefin (b216) having an amino group.

As (b211), both polyolefins (b210) having a polyolefin which can be modified at both ends as a main component (content 50% by weight or more, more preferably 75% by weight or more, particularly preferably 80 to 100% by weight) are used. Examples thereof include those having a carbonyl group introduced at the terminal.
(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 terminal group that can be modified, but the main component is a polyolefin that can be modified at both ends. Those are preferred.

  (B210) includes a low molecular weight polyolefin [polymerized polyolefin] obtained by (co) polymerization of one or a mixture of two or more C2-30 olefins and a high molecular weight polyolefin [(co) olefin of C2-30 olefins]. Low molecular weight polyolefins obtained by thermal degradation of high molecular weight polyolefins obtained by polymerization] are included.

Examples of the C2-30 olefin include those exemplified as the above (a11), for example, ethylene, propylene, C4-30 (preferably 4-12, more preferably 4-10) α-olefin, and C4-30 (preferably). Is a diene of 4 to 18, more preferably 4 to 8).
Of these, from the viewpoint of miscibility with the resin of (B), preferred are C2-12 olefins and / or C4-8 dienes, and more preferred are C2-10 olefins and / or butadienes. Is ethylene, propylene and / or butadiene.

[Polymerized polyolefin] can be easily obtained by a method of (co) polymerizing the olefin in the presence of, for example, a radical catalyst, a metal oxide catalyst or a Ziegler-Natta catalyst.
Examples of the radical catalyst include di-t-butyl peroxide, t-butyl benzoate, decanol peroxide, lauryl peroxide, peroxy-dicarbonate ester, azo compound, and molybdenum oxide attached to a γ-alumina carrier. Is mentioned.
As the metal oxide catalyst, for example, a silica-alumina support having chromium oxide attached thereto can be mentioned.
Ziegler-Natta catalysts include (C ₂ H ₅ ) ₃ Al—TiCl ₄ and (C ₂ H ₅ ) ₃ A
1-TiCl ₃ may be mentioned.
[Thermal degradation polyolefin] can be easily obtained, for example, by the method described in JP-A-3-62804.
Of the above polyolefins, [thermally degraded polyolefin] is preferable from the viewpoint of easy introduction of a carbonyl group as a modifying group and availability.

Mn of (b210) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000 from the viewpoint of the antistatic property of the resin of the molded product.
The amount of double bonds in (b210) is preferably 1 to 40, more preferably 2 to 30, particularly preferably 4 to 1,000 per C1,000 from the viewpoint of the antistatic property and appearance of the resin of the molded product. There are 20 pieces.
The average number of double bonds per molecule is preferably from 1.1 to 5, more preferably from 1.3 to 3, particularly preferably from 1.5 to 2, from the viewpoints of repetitive structure formation and antistatic properties. .5, most preferably 1.8-2.2.
According to the thermal degradation method, a low-molecular-weight polyolefin having an average number of terminal double bonds per molecule of 1.5 to 2 can be easily obtained in a range of 800 to 6,000 [for example, Katsuhide Murata, See Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].

The measurement conditions of Mn in (b210) are as follows: Apparatus: High-temperature gel permeation chromatography solvent: Orthodichlorobenzene reference material: Polystyrene sample concentration: 3 mg / ml
Column stationary phase: PLgel MIXED-B
Column temperature: 135 ° C

  The polyolefin (b211) having a carbonyl group at both ends of the polymer has an α, β-unsaturated carboxylic acid (anhydride) [α, β-unsaturated carboxylic acid, alkyl of the carboxylic acid at both ends of (b210). (C1-4) means an ester or an anhydride thereof. The same applies below. ] (B2111), a polyolefin (b2112) having a structure obtained by secondary modification of (b2111) with a lactam or an aminocarboxylic acid, and a polyolefin (b2113) having a structure obtained by oxidizing or hydroformylating (b210) ), Polyolefin (b2114) having a structure obtained by secondary modification of (b2113) with lactam or aminocarboxylic acid, and a mixture of two or more thereof.

(B2111) is obtained by modifying both ends of (b210) with α, β-unsaturated carboxylic acid (anhydride).
α, β-unsaturated carboxylic acids (anhydrides) include C3-12 carboxylic acids such as monocarboxylic acids [eg (meth) acrylic acid], dicarboxylic acids (eg maleic acid, fumaric acid, itaconic acid and citraconic acid) ), Their alkyl (C1-4) esters [eg methyl (meth) acrylate, butyl (meth) acrylate and diethyl itaconate] and anhydrides.
Of these, from the viewpoint of reactivity with (b210), dicarboxylic acids, their alkyl esters and anhydrides are preferred, maleic acid (anhydride) and fumaric acid are more preferred, and maleic acid (anhydride is particularly preferred). Thing).

  The amount of α, β-unsaturated carboxylic acid (anhydride) used is preferably from 0.5 to 40%, more preferably from the viewpoint of the formation of a repeating structure and antistatic properties, based on the weight of the polyolefin (b210). Is 1 to 30%, particularly preferably 2 to 20%.

The modification of the polyolefin (b210) with an α, β-unsaturated carboxylic acid (anhydride) can be carried out by, for example, converting the terminal double bond of (b210) to α, β-unsaturated by either a solution method or a melting method. It can be carried out by thermally adding (ene reaction) a saturated carboxylic acid (anhydride).
As the solution method, for example, an α, β-unsaturated carboxylic acid (anhydride) is added to (b210) in the presence of a hydrocarbon (eg, xylene and toluene) solvent, and an inert gas (eg, nitrogen, the same applies hereinafter) atmosphere. The method of making it react at 170-230 degreeC inside is mentioned.
Examples of the melting method include a method in which (b210) is heated and melted, and then α, β-unsaturated carboxylic acid (anhydride) is added and reacted at 170 to 230 ° C. in an inert gas atmosphere.
Among these methods, the solution method is preferable from the viewpoint of reaction uniformity.

(B2112) can be obtained by secondary modification of (b2111) with lactam or aminocarboxylic acid.
Lactams include C6-12 (preferably 6-8, more preferably 6) lactams such as caprolactam, enantolactam, laurolactam and undecanolactam.
As aminocarboxylic acids, C2-12 (preferably 4-12, more preferably 6-12) aminocarboxylic acids such as amino acids (eg glycine, alanine, valine, leucine, isoleucine and phenylalanine), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Of these, glycine, leucine, and more preferable caprolactam, laurolactam, ω-aminocaprylic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid are particularly preferable from the viewpoint of reactivity of secondary modification. Are caprolactam and 12-aminododecanoic acid.

  The amount of lactam or aminocarboxylic acid to be used is preferably 0.5 to 40%, more preferably 1 to 30%, particularly preferably based on the weight of the polyolefin (b2111) from the viewpoint of the formation of a repeating structure and antistatic properties. Is 2 to 20%.

As a method for secondary modification of (b2111) with a lactam, for example, after heating and melting (b2111), a lactam is added and reacted at 170 to 230 ° C. in an inert gas atmosphere.
Moreover, as a method of carrying out secondary modification | denaturation by aminocarboxylic acid, after heating (b2111), for example, aminocarboxylic acid is added and the method of making it react at 170-230 degreeC in inert gas atmosphere is mentioned.

  (B2113) can be obtained by oxidizing (b210) with oxygen and / or ozone or hydroformylating with an oxo method to introduce a carbonyl group. The introduction of the carbonyl group by oxidation can be performed, for example, by the method described in US Pat. No. 3,692,877. The introduction of a carbonyl group by hydroformylation is described in, for example, Macromolecules, Vol. 31, 5, 943 page.

(B2114) can be obtained by secondary modification of (b2113) with lactam or aminocarboxylic acid.
Examples of the lactam and aminocarboxylic acid include those exemplified in the description of the above (b2112), and the use amount thereof based on the weight of (b2113) is also the same.

The Mn of the polyolefin (b211) having a carbonyl group at both ends of the polymer is preferably 800, more preferably 1,000, particularly preferably 1,000 from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b22) described later. Is 2,500, and the preferable upper limit is 25,000, more preferably 20,000, and particularly preferably 10,000.
The acid value of (b211) is preferably 4 to 280 (unit is mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (b22), more preferably 4 to 100, particularly. Preferably it is 5-50.

As the hydrophilic polymer (b22) having a volume specific resistance value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm constituting (B2), polyether (b221), polyether-containing hydrophilic polymer (b222), Cationic polymer (b223) and anionic polymer (b224) can be used.
As (b221), polyether diol (b221-1), polyether diamine (b221-2), and modified products thereof (b221-3) can be used. As (b222), polyether ester amide (b222-1) having a segment of polyether diol (b221-1) as a polyether segment forming component, polyetheramide imide having a segment of (b221-1) (b222- 2), polyether ester (b222-3) having a segment of (b2211-1); polyetheramide (b222-4) having a segment of (b2211-2), and (b2211-1) or (b221-2) Polyether urethane (b222-5) having a segment of) can be used.
As (b223), a cationic polymer having 2 to 80, preferably 3 to 60, cationic groups (c2) separated by a nonionic molecular chain (c1) in the molecule can be used.
As (b224), dicarboxylic acid (e1) having a sulfo group and diol (b2201) or polyether (b221) are essential structural units, and 2 to 80, preferably 3 to 60 in the molecule. An anionic polymer having a sulfo group can be used.

Of the polyether (b221), the polyether diol (b221-1) is obtained by addition reaction of AO (C2-12) containing EO as an essential component in the diol (b2201) or dihydric phenol (b2202). For example, the structure shown by the following general formula is mentioned.

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

In the formula, E ¹ represents a residue obtained by removing a hydroxyl group from (b2201) or (b2202), A ¹ is a C2-4 alkylene group; m and m ′ are 1 to 300, preferably 2 to 250, and more preferably. Represents an integer of 10 to 100, and m and m ′ may be the same or different. Further, m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form when these are composed of two or more oxyalkylene groups is random. And / or blocks.

Examples of the diol (b2201) include C2-12 (preferably 2-10, more preferably 2-8) dihydric alcohols (for example, aliphatic, alicyclic and araliphatic dihydric alcohols) and C1-12. A tertiary amino group-containing diol may be mentioned.
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 xylylene diol, 1-phenyl-1,2-ethanediol, and 1,4-bis (hydroxyethyl) benzene.

Tertiary amino group-containing diols include aliphatic or alicyclic primary monoamines (C1-12, preferably 2-10, more preferably 2-8) bishydroxyalkyl (alkyl group C1-12, preferably 2-10, more preferably 2-8) and aromatic (aliphatic) primary monoamines (C6-12) bishydroxyalkyl (alkyl group C1-12) compounds.
Monoamine bishydroxyalkylates are obtained by reacting, for example, monoamines with C2-4 AO [eg EO, PO and butylene oxide] or monoamines with C1-12 halogenated hydroxyalkyl (eg 2-bromoethyl alcohol and 3 It can be easily obtained by reacting with (chloropropyl alcohol).

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

  Examples of the dihydric phenol (b2202) include C6-18 (preferably 8-18, more preferably 10-15), such as monocyclic dihydric phenol (for example, hydroquinone, catechol, resorcin and urushiol), bisphenol (for example, bisphenol A). And -F) and condensed polycyclic dihydric phenols such as dihydroxynaphthalene and binaphthol.

  Of (b2201) and (b2202), from the viewpoint of antistatic properties, preferred are dihydric alcohols and dihydric phenols, more preferred are aliphatic dihydric alcohols and bisphenols, and particularly preferred are ethylene glycol and bisphenol A. .

As AO to be subjected to addition reaction with diol (b2201) or dihydric phenol (b2202), in addition to EO, for example, C3-12 AO (for example, PO, 1,2-, 1,4-, 2,3- and 1, 3-butylene oxide and a mixture of two or more thereof), but other AOs and substituted AOs may be used in combination if necessary.
Examples of other AO and substituted AO include epoxidized C5-12 α-olefin, styrene oxide and epihalohydrin (for example, epichlorohydrin and epibromohydrin). The amount of each of other AO and substituted AO used is preferably 30% or less, more preferably 0 or 25%, particularly preferably 0 or 20% or less from the viewpoint of antistatic properties based on the weight of the total AO. is there.

  The number of added moles of AO is preferably 1 to 300 moles, more preferably 2 to 250 moles per hydroxyl group of (b2201) or (b2202), from the viewpoint of the volume resistivity value of the hydrophilic polymer (b22). Preferably it is 10-100 mol. When two or more kinds of AO are used in combination, the coupling form may be random and / or block.

The addition reaction of AO can be performed, for example, in the presence of an alkali catalyst (for example, potassium hydroxide and sodium hydroxide) at 100 to 200 ° C. and a pressure of 0 to 0.5 MPaG.
The content of the oxyalkylene unit in the polyether diol (b221-1) is determined based on the weight specific resistance value of the hydrophilic polymer (b22) and the dispersibility of (B) in (A) based on the weight of (b2211-1). From this viewpoint, it is preferably 5 to 99.8%, more preferably 8 to 99.6%, and particularly preferably 10 to 98%. The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 from the viewpoint of the volume resistivity value of (b22) and the dispersibility of (B) in (A) based on the weight of the polyoxyalkylene chain. -100%, more preferably 10-100%, particularly preferably 50-100%, most preferably 60-100%.

The polyether diamine (b221-2) has a structure in which the hydroxyl group of the polyether diol (b221-1) is modified to an amino group (primary or secondary amino group), for example, the general formula: RNH-A ² — Examples include (OA ¹ ) _m O—E ¹ —O (A ¹ O) _{m ′} —A ² —NHR. Therefore, the content of the oxyethylene unit in the polyoxyalkylene chain is the same as in the case of (b2211-1), and the content of the oxyalkylene unit in (b2211-2) is the corresponding oxyalkylene in (b2211-1) Same as unit content.
Symbols E ¹ , A ¹ , m and m ′ in the above formula are the same as described above, A ² represents a C2-4 alkylene group, 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.
(B221-2) can be easily obtained by changing both terminal hydroxyl groups of (b2211-1) to amino groups by various methods.
As a method of changing the hydroxyl group to an amino group, for example, a method of reducing a terminal cyanoalkyl group obtained by cyanoalkylating the hydroxyl group of (b221-1) to an amino group [for example, (b2211-1) and acrylonitrile A method of reacting and hydrogenating the resulting cyanoethylated product], a method of reacting (b221-1) with an aminocarboxylic acid or lactam, and a method of reacting (b221-1) with a halogenated amine under alkaline conditions. Can be mentioned.

  Examples of the modified product (b221-1) of (b2211-1) or (b221-2) include, for example, an aminocarboxylic acid modified product (terminal amino group) and an isocyanate modified product of (b221-1) or (b2211-2) (Terminal isocyanate group) and the same epoxy modified product (terminal epoxy group).

  Mn of the polyether (b221) is preferably 150 to 20,000, more preferably 300 to 18,000, and particularly preferably 1,000 to 15 from the viewpoint of heat resistance and reactivity with the block of the polyolefin (b21). 1,000, most preferably 1,200 to 8,000.

  Examples of the polyether-containing hydrophilic polymer (b222) include the polyether-containing hydrophilic polymer (b2) described in WO 00/47652.

The cationic polymer (b223) has 2 to 80, preferably 3 to 60, cationic groups (c2) in the molecule separated by a nonionic molecular chain (c1).
Examples of (c2) include groups having a quaternary ammonium salt and a phosphonium salt.

As the counter anion of (c2), Hammett acidity function (-H ₀₎ super strong acid anions 12-20, and other anions. Examples of super strong acids include (1) super strong acids (tetrafluoroboric acid, hexafluorophosphoric acid, etc.) derived from a combination of protonic acid (d1) and Lewis acid (d2), and (2) protonic acid (peroxygen). Chloric acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, etc.).
Examples of other anions include halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ^−, etc.), OH ⁻ , PO ₄ ⁻ , CH ₃ OSO ₄ ⁻ , C ₂ H ₅ OSO ₄ ⁻ , and ClO ₄ ^−. It is done.

Specific examples of (d1) include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide and the like. Specific examples of (d2) include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, and tantalum pentafluoride.
The combination of (d1) and (d2) is arbitrary, but preferred examples of superacid anions derived from these combinations include BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , TaF ₆ ^−. , BF ₃ Cl ⁻ , PF ₅ Cl ⁻ , SbF ₅ Cl ⁻ , AsF ₅ Cl ⁻ , TaF ₅ Cl ⁻ , BF ₃ Br ⁻ , PF ₅ Br ⁻ , SbF ₅ Br ⁻ , AsF ₅ Br ⁻ , TaF ₅ Br ⁻ BF ₃ I ⁻ , PF ₅ I ⁻ , SbF ₅ I ⁻ , AsF ₅ I ^−, TaF ₅ I ^{− and the} like, and a combination of two or more of these may be used. Among these counter anions, from the viewpoint of heat resistance, an anion of a super strong acid is preferable, BF ₄ ⁻ , PF ₆ ⁻ , BF ₃ Cl ⁻ and PF ₅ Cl ⁻ are particularly preferable, and BF ₄ ⁻ and are particularly preferable. PF ₆ ^- is.

  The nonionic molecular chain (c1) includes a divalent hydrocarbon group, or an ether bond, a thioether bond, a carbonyl bond, an ester bond, an imino bond, an amide bond, an imide bond, a urethane bond, a urea bond, a carbonate bond, and / or Or at least one divalent organic group selected from the group consisting of a hydrocarbon group having a siloxy bond and a hydrocarbon group having a heterocyclic structure containing a nitrogen atom or an oxygen atom; and combinations of two or more thereof. It is done.

  Examples of the divalent hydrocarbon group include C1-18 (preferably 2-8) linear or branched aliphatic hydrocarbon groups (alkylene group, alkenylene group, etc.), such as ethylene, propylene, tetramethylene, hexamethylene, Decamethylene, dodecamethylene, 2,2,4-trimethylhexamethylene, etc .; C6-20 aromatic hydrocarbon groups such as 1,3- and 1,4-phenylene, 2,4- and 2,6-tolylene, 4 , 4′- and 2,4′-methylenebisphenylene, m- and p-xylylene, α, α, α ′, α′-tetramethylxylylene, naphthylene, etc .; C4-15 alicyclic hydrocarbon group, Examples include cyclohexylene, methylcyclohexylene, 4,4′-methylenebiscyclohexylene, 2,5- and / or 2,6-norbornylene. That.

The divalent hydrocarbon group having an ether bond, thioether bond, carbonyl bond, ester bond, imino bond, amide bond, imide bond, urethane bond, urea bond, carbonate bond and / or siloxy bond includes (poly) oxyalkylene group, for example, residues [e.g. the polyether diol ^{(b22-1) - (OA 1)} m -E 1 - (a 1 O) m '- ( wherein, E ^1, a ^1, m and m' The same as above), and the residue of a monoether diol represented by the general formula -A ¹ -O-E ^1- (wherein E ¹ and A ¹ are the same as above); Residues of polythioethers (replaced by sulfur atoms); residues of polyesters and / or polyamides, eg groups of the following general formulas (1) to (4); polyurethanes and / or polyureas A group such as a group represented by the following general formula (5); a residue of polycarbonate [derived from the diol (b2201) and phosgene]; a residue of polysiloxane (polyorganosiloxane such as polydimethylsiloxane) Can be mentioned.

In the general formulas (1) to (5), D is an oxygen atom or imino group, R ¹ is a C 1-11 hydrocarbon group, R ² is a divalent organic group bonded to a cationic group, and E ² is a diol. (if D is an imino group) residue (when D is an oxygen atom) or a diamine residue, E3 residues of dicarboxylic acids, residue of an organic diisocyanate E ⁴ will be described later, u and v are 0 or 1, k represents an integer of 1-20.
R ¹ includes a lactam residue (when D is an imino group) and a lactone residue (when D is an oxygen atom), the lactam as described above, and the lactone as a lactone corresponding to the lactam. (Such as caprolactone).
The R2, divalent hydrocarbon group of C2-12, such as an alkylene group, and the (poly) oxyalkylene group ^{[-A 1 -O-E 1 -} , - (A 1 O) m -E 1 - ( OA ¹⁾ _{m '-]} and the like.

Among E ² , diol residues include dihydric alcohols (for example, C2-12 aliphatic, alicyclic and aromatic dihydric alcohols as described above), and AO (C2-4) adducts (additions). 1 to 20 or more moles), AO (C2-4) adducts (2 to 20 or more moles added) of dihydric phenols (eg, C6-18 dihydric phenols as described above), and these And a residue obtained by removing a hydroxyl group from a diol, such as a mixture of two or more thereof.

Among E ² , the diamine residue is a low molecular weight diamine, for example, a diamine corresponding to the diisocyanate: C2-20 aliphatic diamine (ethylenediamine, propylenediamine, hexamethylenediamine, 1,12-dodecanediamine, etc.), C6 -15 alicyclic diamine (1,4-cyclohexylenediamine, isophorone diamine, 4,4'-diaminocyclohexylmethane, etc.), C8-15 araliphatic diamine (xylylenediamine, etc.), C6-15 fragrance Group diamine [p-phenylenediamine, 2,4- and 2,6-toluenediamine, 2,2-bis (4,4′-diaminophenyl) propane, etc.], the polyether diamine (b221-2), and these A residue obtained by removing an amino group from a diamine, such as a mixture of two or more of The

E ³ may be a dicarboxylic acid [C4-12 aliphatic dicarboxylic acid (for example, succinic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc.) Dicarboxylic acid), C8-15 aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, etc.), and residues obtained by removing the carboxyl group from dicarboxylic acid such as a mixture of two or more thereof.
E ⁴ is a residue obtained by removing an isocyanate group from an organic diisocyanate (for example, aromatic, aliphatic, alicyclic and araliphatic diisocyanates as described above, modified products thereof, and mixtures of two or more thereof). Can be mentioned.

Examples of the organic diisocyanate include C (excluding carbon in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic diisocyanate, C2 to 18 aliphatic diisocyanate, C4 to 15 alicyclic diisocyanate, and C8 to 15 aromatic fat. Group diisocyanates, modified products of these diisocyanates, and mixtures of two or more thereof.
Specific examples of the aromatic diisocyanate include 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and 4,4. '-Diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanato Examples thereof include diphenylmethane and 1,5-naphthylene diisocyanate.
Specific 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-diisocyanatomethyl carbonate. Examples include proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Specific examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2- And isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate.
Specific examples of the araliphatic diisocyanate include m- or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.
Examples of the modified diisocyanate include urethane-modified, urea-modified, carbodiimide-modified, and uretdione-modified.
Of these, TDI, MDI and HDI are preferred, and HDI is particularly preferred.

  The molecular weight of the nonionic molecular chain (c1) is usually a molecular weight of 28 to Mn 10,000, preferably 300 to 5,000. Among these nonionic molecular chains (c1), a divalent hydrocarbon group and a divalent hydrocarbon group having an ether bond are preferable, and a C1-8 alkylene group (such as a hexamethylene group) is more preferable. , Phenylene groups; and (poly) oxyalkylene groups, particularly preferred are (poly) oxyethylene groups and (poly) oxypropylene groups.

  Examples of the cationic polymer (b223) include those having a repeating unit represented by the following general formula (6).

In the formula, M is a nitrogen atom or phosphorus atom, J ⁻ is a counter anion, d is an integer of 2 to 60, L ¹ is a nonionic molecular chain (c1), R ³ and R ⁴ are monovalent nonionic organic compounds It is a group. Further, (b223) is a divalent nonionic organic compound in which adjacent R ³ and / or R ⁴ in the general formula (6) are bonded to each other as shown in the following general formula (7) or (8). It may become a group (L ³ , L ⁵ ) and may form a ring together with M ⁺ .

In the formula, M is a nitrogen atom or phosphorus atom, L ² , L ³ , L ⁴ and L ⁵ are divalent nonionic molecular chains, R ⁴ and R ^{4 ′} are monovalent nonionic organic groups, J ⁻ Is a counter anion, and e is an integer of 1-30.

R ³ , R ⁴ and R ^{4 ′ in the} general formulas (6) and (7) may have an ether bond or an ester bond, and may be an aliphatic, cycloaliphatic or aromatic group of C1-20. Monovalent hydrocarbon group [eg, alkyl group (methyl group, ethyl group, octyl group, dodecyl group, etc.), alkenyl group (allyl group, 1-butenyl group, oleyl group, etc.), (substituted) aralkyl group (benzyl group, 4-methylbenzyl group, etc.), alicyclic hydrocarbon group (cyclohexyl group, etc.), alkoxy (C1-12) alkyl (C1-20) group (methoxyethyl group, etc.), acyloxy (C1-12) alkyl (C1- 20) group (acetoxy group and the like)] and the like.
d is an integer of usually 2 to 60 or more, preferably 3 to 50, more preferably an integer of 5 to 30 from the viewpoint of antistatic properties and reactivity with the terminal-modified polyolefins (b211) to (b216). is there.

Examples of L ^{1 to} L ⁵ include the nonionic molecular chain (c1) as described above.

Preferable examples of the cationic polymer (b223) are those having a repeating unit of the general formula (6) or (8). More preferable examples include those in the general formula (6), wherein R ³ and R ⁴ are C1-8 alkyl groups, and L ¹ is a polyester residue [particular preference is given to R ^{2 in the} general formula (2) being C2-4. An alkylene group, a polyester in which D is an oxygen atom, and k is 1], and in general formula (8), L ² , L ³ and L ⁵ are C2-8 alkylene groups, and L ⁴ is C2-20. It is an alkylene group. Specific examples thereof include those having a repeating unit represented by the following formulas (9) and (10).

In formulas (9) and (10), J ⁻ represents a counter anion, and f represents an integer of 2 to 12.

  Other examples of the cationic polymer (b3) include those having a repeating unit represented by the following general formula (11).

In formula (11), A is a trivalent hydrocarbon group, M, J ⁻ , R ³ , R ⁴ , R ^{4 ′} and d are the same as described above.
The trivalent hydrocarbon group A is a C2-20 trivalent aliphatic hydrocarbon group, for example, a group represented by —CH ₂ (CH ₂ ) _g CH <(g is 0 or an integer of 1 to 18). , C6-12 trivalent aromatic hydrocarbon group, for example, a benzene ring in which the bonding position is 1,3,5-, 1,2,4- or 1,2,3-.
Examples of the cationic group (c2) include a group having a quaternary ammonium salt or a phosphonium salt. The group having a quaternary ammonium salt is preferably a divalent quaternary ammonium salt-containing heterocyclic group.
Examples of the divalent quaternary ammonium base-containing heterocyclic group include a divalent tertiary amino group-containing heterocyclic group [for example, a divalent imidazole ring group (1,4-imidazolene group, 2-phenyl-1,4-imidazolene). Group), divalent piperidine ring group (2,3-, 3,4- or 2,6-piperidylene group), divalent aromatic heterocyclic group (2,3-, 2,4-, 2,5). -, 2,6-, 3,4- or 3,5-pyridylene group, 2,5-pyrimidinylene group, 3,6-pyridazinylene group, 2,5-pyrazinylene group, etc.)] Groups.

The terminal structure of the cationic polymer (b223) is preferably a carbonyl group, a hydroxyl group or an amino group from the viewpoint of reactivity with the block of the polyolefin (b21).
Mn of (b223) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly from the viewpoint of antistatic properties and reactivity with the terminal-modified polyolefins (b211) to (b216). Preferably, it is 1,200 to 8,000.

  The anionic polymer (b224) has a dicarboxylic acid (e1) having a sulfo group and a diol (b2201) or a polyether (b221) as essential structural units, and 2 to 80, preferably 3 to 60 in the molecule. Having one sulfo group.

(E1) is an aromatic dicarboxylic acid having a sulfo group, such as 5-sulfo-, 2-sulfo- and 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid, and ester forming properties thereof. Derivatives [lower alkyl (C1-4) esters (methyl esters, ethyl esters, etc.), acid anhydrides, etc.]; aliphatic dicarboxylic acids having a sulfo group, such as sulfosuccinic acid, ester-forming derivatives thereof [lower alkyl (C1-4 ) Esters (methyl esters, ethyl esters, etc.), acid anhydrides, etc.]; and salts of these sulfo groups only [alkali metal (lithium, sodium, potassium, etc.) salts, alkaline earth metal (magnesium, calcium, etc.) salts, Ammonium salts, organic amine salts [mono-, di- and tri-alkyl (C1-4) amines -, Di- and triethylamine etc.), or amines having hydroxyalkyl (C2-4) groups (mono-, di- and triethanolamine, diethylethanolamine etc.) and the like, and quaternary ammonium salts of these amines etc.]; And a combination of two or more of these.
Of these, preferred are aromatic dicarboxylic acids (salts) having a sulfo group, and more preferred are 5-sulfoisophthalates (especially 5-sulfoisophthalic acid-sodium and -potassium).

Of the diol (b2201) or polyether (b221) constituting the anionic polymer (b224), C2-10 alkanediol, ethylene glycol, polyethylene glycol (degree of polymerization 2-20), bisphenol (bisphenol A, etc.) ) EO adduct (addition mole number 2 to 60) and a mixture of two or more thereof.
Mn of (b224) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly from the viewpoint of antistatic properties and reactivity with the terminal-modified polyolefins (b211) to (b216). Preferably, it is 1,200 to 8,000.
As the hydrophilic polymer (b22), two or more kinds may be arbitrarily used in combination.

The volume resistivity value of (b22) (value measured in an atmosphere described later at 23 ° C. and 50% RH. Unit Ω · cm) is preferably 10 ⁵ from the viewpoint of the mechanical properties of the resin of the molded product. More preferably, it is 10 ⁶ , particularly preferably 10 ⁷ , and the upper limit is preferably 10 ¹¹ , more preferably 10 ¹⁰ , and particularly preferably 10 ⁹ from the viewpoint of the antistatic property of the resin of the molded product.
Mn of (b22) is preferably 150 from the viewpoint of heat resistance and reactivity with the block of polyolefin (b21), more preferably 300, particularly preferably 1,000, most preferably 1,200, and preferred upper limit is 20,000, more preferably 18,000, particularly preferably 15,000, most preferably 8,000.

  The block polymer (B2) is 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 polyolefin (b21) block and the hydrophilic polymer (b22) block are included. The block polymer (B21) in which (b22) is a polyether (b221) is preferable from the viewpoint of antistatic properties and transparency. (B22) is a block polymer (B23) which is a cationic polymer (b223), and (b22) is a block polymer (B24) which is an anionic polymer (b224).

  The block polymer (B21) has a repeating unit represented by the following general formula (12).

In the formula (12), n is an integer of 2 to 50 (preferably 3 to 40, more preferably 4 to 30, particularly preferably 4 to 30); one of R ⁵ and R ⁶ is H and the other is H or methyl A group; 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 described above; (13), (14) and a corresponding group selected from (13 ′), (14 ′), that is, when X is a group represented by the general formula (13), X ′ is represented by the general formula (13 ′) It is a group shown, and the same relations apply to the general formulas (14) and (14 ′).

In the general formulas (13) and (14) and the corresponding formulas (13 ′) and (14 ′), R is the same as described in the above (b222) and H or C1-4 (preferably 1 or 2); R ⁷ is a C 2-22 (preferably 3-16, more preferably 5-11) divalent hydrocarbon group, R ⁸ is H or C 1-10 (preferably 1-8, more preferably 1-6) alkyl group; r is an integer of 1-20 (preferably 1-15, more preferably 1-10), u is 0 or 1; Q, Q ′, T and T ′ are represented by the following formulae: Group represented by

In the above general formulas (15) and (16) and the corresponding (15 ′) and (16 ′) formulas, R 9 is H or C 1-10 (preferably 1-8, more preferably 1-6) A group, R ¹⁰ is H or a methyl group, t is 1 when R ¹⁰ is a methyl group, and 0 when H is H.

Polyether segment {in {} in the repeating unit represented by the general formula (12) {(O
A ¹ ) _m O—E ¹ —O (A ¹ O) _{m ′} } is a structure derived from the polyether diol (b221-1) or the polyether diamine (b221-2), and E ^{1 in} the formula , A ¹ , m and m ′ are the same as described above.

In the general formula (12), the terminal-modified polyolefin (b2111) and / or the block polymer in which X is a group represented by the general formula (13) and X ′ is a group represented by the general formula (13 ′) (B2112) obtained by polymerizing (b2112) and (b2211-1) and (b2111) and / or (b2112) and (b221-2) obtained by polymerizing (B212) And are included.
(B211) is a combination of (b2111) and (b221-1) (B21-1), (b2112) is a combination of (b21-1) (B2111-2), and (B21-1) A mixture of (B211-2) is included. Similarly, (B212) is a combination of (B212-1), (b2112) and (b221-2) is combined with (B212-2), and (B212) is combined with (B212). -1) and a mixture of (B212-2).

(B211) is, for example, a method in which (b2211-1) is added to (b2111) and / or (b2112) and a polymerization (polycondensation) reaction is usually performed at 200 to 250 ° C. under reduced pressure, or uniaxial or biaxial In general, it can be produced by a method of polymerizing at 160 to 250 ° C. and a residence time of 0.1 to 20 minutes.
In the above polymerization reaction, various catalysts such as antimony catalysts (eg antimony trioxide); tin catalysts (eg monobutyltin oxide); titanium catalysts (eg tetrabutyl titanate); zirconium catalysts (eg tetrabutylzirconate); organic acids Metal salt catalysts [eg zirconium organic acid salts (eg zirconyl acetate) and zinc acetate]; and mixtures of two or more thereof. Of these, preferred are zirconium catalyst and zirconium organic acid salt, and more preferred is zirconyl acetate.
The amount of the catalyst used is preferably 0.001 to 5%, more preferably 0.01 to 3%, based on the total weight of (b2111) and / or (b2112) and (b2211-1).

  Among (B211), (B2111) may be reacted with (b2111) after the secondary modification of (b2111) with the lactam or aminocarboxylic acid, or (b2111) and the lactam or An aminocarboxylic acid may be reacted in the presence of (b2211-1) and subsequently reacted with (b2211-1).

(B212) is different from (B2111) except that the combination of (b2111) and / or (b2112) and (b221-1) is replaced with the combination of (b2111) and / or (b2112) and (b221-2) ( B211).
Moreover, (B212-2) among (B212) may be produced by reacting (b2111) with (b2111) after secondary modification of (b2111) with the lactam or aminocarboxylic acid.

In the general formula (12), the block polymer in which X is a group represented by the general formula (14) and X ′ is a group represented by the general formula (14 ′) includes (b2113) (when r = 1) And / or (b2114) (in the case of r ≧ 2) and (b221-1) and (B213), (b2113) and / or (b2114) and (b2211-2) obtained by polymerization reaction (B214) obtained by a polymerization reaction.
(B213) is a combination of (B2113) and (b221-1), (B213-1), (b2114) and (b221-1) are combined (B213-2), and (B213-1) A mixture of (B213-2) is included. Similarly, (B214) is a combination of (B214-1) in which (b2113) and (b221-2) are combined with (B214-1), (B214-2) in which (b2114) is combined with (b221-2), and (B214). -1) and a mixture of (B214-2).
(B213) and (B214) can be produced in the same manner as (B211) and (B212).

The block polymer (B23) has a block of the cationic polymer (b223) and has a structure in which the polyolefins (b21) and (b223) are repeatedly and alternately bonded. (B23) can be obtained by the polymerization reaction of (b211) to (b213) and (b223), and the polymerization reaction of (b2111) and / or (b2112) and (b221) in (B21) above It can be manufactured by a similar method. Moreover, (b223) and (b221) can be used together in arbitrary ratios (for example, weight ratio of 1: 9-9: 1) as needed.
The content of the cationic group (c2) in (B23) is preferably 2 to 500, more preferably 10 to 300, and particularly preferably 15 to 250 per molecule from the viewpoint of antistatic properties (B23). is there. Further, the Mn of (B23) per (c2) is preferably 120 to 30,000, more preferably 200 to 6,000, and particularly preferably 300 to 4,000 from the viewpoint of antistatic properties.

The block polymer (B24) has a block of the anionic polymer (b224), and has a structure in which the polyolefins (b21) and (b224) are repeatedly and alternately bonded. (B24) can be obtained by the polymerization reaction of (b211) to (b213) and (b224), and can be produced by the same method as (B21) above. Moreover, you may use together (b224) and (b221) by arbitrary ratios (for example, weight ratio of 1: 9-9: 1) as needed.
The content of the sulfo group in (B24) is preferably 2 to 500, more preferably 10 to 300, and particularly preferably 15 to 250 per molecule of (B24) from the viewpoint of antistatic properties. The Mn of (B24) per sulfo group is preferably 120 to 30,000, more preferably 200 to 6,000, and particularly preferably 300 to 4,000 from the viewpoint of antistatic properties.

  The amount of (b22) constituting the block polymer (B2) is preferably 20 to 90%, more preferably 25 to 80% based on the total weight of (b21) and (b22), from the viewpoint of antistatic properties. Especially preferably, it is 30 to 70%.

  Mn of the block polymer (B2) is preferably from 2,000 to 60,000, more preferably from 5,000 to 40,000, particularly preferably from the viewpoint of antistatic properties and dispersibility of (B2) in (A). Is 8,000-30,000.

In the structure of (B2), the average repeating number (Nn) of the repeating units of the block (b21) and the block (b22) is from the viewpoint of antistatic properties and dispersibility of (B2) in (A). Preferably it is 2-50, More preferably, it is 2.3-30, Most preferably, it is 2.7-20, Most preferably, it is 3-10.
Nn can be determined by Mn and ¹ H-NMR analysis of (B2).
For example, in the case of (B211) having a structure in which the blocks of (b2111) and the blocks of (b2211-1) are repeatedly bonded alternately, in ¹ H-NMR analysis, 4.0 to 4.1 ppm ester bond { Since 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 Nn can be obtained from this ratio and Mn.

  The end of (B2) is a carbonyl group derived from (b21), an amino group and / or an unmodified polyolefin end (polyolefin end not modified at all, ie, an alkyl group or an alkenyl group), or a hydroxyl group derived from (b22) And / or any amino group. Among these, an amino group is preferable as a terminal from the viewpoint of reactivity, and a carbonyl group and a hydroxyl group are more preferable.

  Examples of the polyether amide imide (B3) include polyether amide imides having a polyoxyethylene chain among those described in JP-B-7-119342 and JP-A-06-172609. Of these, caprolactam (b31), trivalent or tetravalent aromatic polycarboxylic acid (b32) capable of forming at least one imide ring by reacting with an amino group, and polyethylene glycol are preferable from the viewpoint of heat resistance. Alternatively, it is derived from a mixture (b33) of at least 50% by weight of polyethylene glycol and a polyalkylene glycol other than polyethylene glycol, the content of (b33) is 30 to 85% by weight, and the reduced viscosity at 30 ° C. is 1.5 to 4 is a polyetheramide imide.

(B32) includes aromatic polycarboxylic acids and acid anhydrides thereof.
Examples of the trivalent aromatic polycarboxylic acid (anhydride) include C9-18, such as 1,2,4-trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, 2,6,7-naphthalenetricarboxylic acid, 3,3 ′, 4-diphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tricarboxylic acid, diphenylsulfone-3,3 ′, 4-tricarboxylic acid, diphenylether-3,3 ′, 4-tricarboxylic acid, and these Of the acid anhydride.
Examples of the tetravalent aromatic polycarboxylic acid (anhydride) include C10-20, such as pyromellitic acid, diphenyl-2,2 ′, 3,3′-tetracarboxylic acid, benzophenone-2,2 ′,
3,3′-tetracarboxylic acid, diphenylsulfone-2,2 ′, 3,3′-tetracarboxylic acid, diphenyl ether-2,2 ′, 3,3′-tetracarboxylic acid, and acid anhydrides thereof It is done.

  Among (b33), Mn of polyethylene glycol is not particularly limited, but is preferably 500 to 5,000, more preferably 800 to 3,000, from the viewpoint of imparting antistatic property to (B3) and production.

Examples of the polyalkylene (alkylene C3-18) glycol other than polyethylene glycol include polypropylene glycol, polytetramethylene glycol and modified polyalkylene glycol having a Mn of 500 to 5,000. Examples of the modified polyalkylene glycol include at least two addition polymers of C2-10 AO (addition form may be random and / or block).
Among the AOs, EO, PO, 1,3-propylene oxide, 2-methyl-1,3-propylene oxide, 2,2-dimethyl-1,3-propylene oxide, are preferable from the viewpoint of imparting antistatic properties. 1,5-pentamethylene oxide and 1,6-hexamethylene oxide.

  The equivalent ratio in the reaction of (b32) and (b33) is usually 0.9 / 1 to 1.1 / 1, preferably 0.95 / 1 to 1.05 / 1 from the viewpoint of the mechanical properties of the resin of the molded product. It is.

The content of polyamideimide constituting (B3) is preferably 15 to 70% by weight, more preferably 30 to 65% by weight, from the viewpoint of imparting antistatic properties to (B3) and water resistance of the resin of the molded product.
In addition, Mn of the polyamideimide moiety in (B3) is preferably 500, more preferably 800, and preferably 3000 in terms of the heat resistance of (B3) and the mechanical strength of the resin of the molded product. Preferably it is 2,000.

Although the following method is mentioned as a manufacturing method of (B3), It does not specifically limit.
That is, (b31), (b32) and (b33) have an equivalent ratio of (b32) and (b33) of usually 0.9 / 1 to 1.1 / 1 (preferably 0.95 / 1 to 1.05). / B) is preferably 30 to 85%, more preferably 35 to 70 from the viewpoint of antistatic properties with respect to the total weight of (b31), (b32) and (b33). %, And the resulting polymer is polycondensed at 150 to 300 ° C., preferably 180 to 280 ° C. while maintaining the water content of the polymer at 0.1 to 1% by weight.
In the polycondensation, the reaction temperature can be raised stepwise. At this time, some caprolactam remains unreacted, but it is desirable to remove it from the reaction mixture by distillation under reduced pressure from the viewpoint of the mechanical properties of the resin of the molded product. The reaction mixture after removing unreacted caprolactam is further polymerized under a reduced pressure (0.03 to 3 kPa), usually at 200 to 300 ° C. (preferably 230 to 280 ° C.) as necessary, thereby further increasing the weight of the polymer. Can be combined.

The reduced viscosity [η _SP / C, C = 0.5 wt% (m-cresol solution, 30 ° C.) of (B3) is preferably 1.5 to 4, more preferably from the viewpoint of moldability of the resin composition. 1.7-3.5.

Examples of the epihalohydrin / AO copolymer (B4) include an epihalohydrin / AO copolymer having a polyoxyethylene chain in JP-B-7-84564.
Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, and epifluorohydrin. Epichlorohydrin is preferable from the viewpoint of reactivity and cost.
AO includes C2-4, such as EO, PO, and tetrahydrofuran.
(B4) includes an epihalohydrin and a co-polymer of 1,2-epoxide monomer [especially alkyl (C2-4) glycidyl ether] and a comonomer composed of one or more selected from AO (especially EO and PO) Mergers are also included.
The weight ratio of epihalohydrin to AO is preferably 5/95 to 95/5, preferably 10/90 to 60/40 from the viewpoint of imparting antistatic properties and dispersibility of (B4) in (A). The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100% by weight, more preferably 10 to 100% by weight.
Among (B4), a copolymer of epichlorohydrin / EO (weight ratio 50/50) is more preferable from the viewpoint of imparting antistatic properties and mechanical properties of the resin of the molded product.

In the production of (B4), various catalysts, for example, organoaluminum compounds [for example, triethylaluminum], or bulk polymerization or solution polymerization using a catalyst obtained by reacting water with an organoaluminum compound to improve polymerizability. Easy to manufacture. The molar ratio of water to the organoaluminum compound is usually 0.1 / 1 to 1/1, preferably 0.3 / 1 to 0.7 / 1, from the viewpoint of polymerizability.
The lower limit of Mn in (B4) is preferably 30,000, more preferably 60,00, and the upper limit is preferably 100,000, more preferably 90,000 from the viewpoints of moldability and mechanical properties of the resin of the molded product.

Examples of the polyether ester (B5) include polyether esters having a polyoxyalkylene chain described in JP-B No. 58-19696.
(B5) is a polyester having a segment composed of a polyether diol or a copolyether diol. For example, (b12) and (b33) exemplified as the constituent components of the polyether ester amide (B1) or the polyether amide imide (B3). And a polycondensation reaction of one or more of the dicarboxylic acids exemplified as the constituent of (B1) or their ester-forming derivatives [for example, lower (C1-4) alkyl esters and acid anhydrides], Alternatively, it can be obtained by an ester exchange reaction between the diol component and polyethylene terephthalate, polybutylene terephthalate, or the like.
The polyether segment content of (B5) is preferably 30 to 70% by weight, more preferably 40 to 60% by weight from the viewpoint of imparting antistatic properties to (B5) and moldability of the resin composition, and (B5) The melting point of [measurement 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. The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100% by weight, more preferably 10 to 100% by weight.

The polyether urethane (B6) is composed of an organic diisocyanate, a polyether diol (b221-1) or a polyether diamine (b221-2) and, if necessary, a chain extender.
Specific examples of (B6) include those described in JP-B-47-35300, JP-A-62-236854, and JP-B-3-296565.
The polyether segment content of (B6) is preferably 30 to 70% by weight, more preferably 40 to 60% by weight from the viewpoint of imparting antistatic properties to (B6) and moldability of the resin composition, (B6) The melting point of [measured by DSC method] is preferably 100 ° C. or higher, more preferably 120 to 210 ° C. from the viewpoint of heat resistance. The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100% by weight, more preferably 10 to 100% by weight.

The difference in refractive index between the thermoplastic resin (A) and the antistatic agent (B) having a hydrophilic chain is 0.02 or less, preferably 0.01 or less, more preferably 0 to 0.005, particularly preferably. 0 to 0.003. When the difference in refractive index between (A) and (B) exceeds 0.02, transparency of a molded product (including a film) described later is deteriorated.
As long as (B1) to (B8) satisfy the relationship between (A) and (B) for the refractive index, each may be used alone or in combination of two or more. In the present invention, the difference in refractive index between (A) and (B) means the absolute value of the difference in refractive index between (A) and (B), and so on.

  The refractive index of (A) and (B) is calculated from the theoretical formula or the refractive index of the resin obtained by polymerizing the monomer constituting (A) or (B) in advance is in accordance with JIS K7105 (1981). It is obtained by measuring. The refractive index in the present invention is a value measured with an Abbe refractometer.

The refractive index of (A) is preferably 1.480 to 1.550 from the viewpoint of the difference from the refractive index of (B), and is preferable from the same viewpoint among (A) having a refractive index in this range. Is one or more thermoplastic resins selected from the group consisting of (A1), (A2), (A3) and (A4).
Moreover, the refractive index of (B1) among (B) is preferably 1.520 to 1.540 from the viewpoint of the difference from the refractive index of (A), and the refractive index of (B2) is preferably from the same viewpoint. Is 1.498 to 1.515.
Of the combinations of (A) and (B) in which the difference in refractive index is 0.02 or less, (B) and the above refraction are preferable from the viewpoint of the difference in refractive index between (B) and (A). In combination with (A) having a refractive index and (B1) and / or (B2) having the above-mentioned refractive index, and (B2) and / or (B2) having the above-mentioned refractive index. ) And (A) having the above refractive index.

In order to make the refractive index difference between (A) and (B) 0.02 or less, it is necessary to adjust the refractive index of (B) corresponding to the refractive index of (A). In this case, it is necessary to consider the balance with antistatic properties. Usually, the antistatic property and the refractive index are in a contradictory relationship, and it is not easy to obtain a desired refractive index while maintaining the antistatic property of (B).
The method for adjusting the antistatic property and refractive index of (B) in the present invention includes the following methods.
(1) Method of applying (B) to (A) having a high refractive index (1.510 to 1.550 or more) (B1) having a relatively high refractive index among (B) is used. When adjusting the refractive index of (B1) to be higher, the ratio of (b12) which is a hydrophilic part in (B1) is reduced within a range not impairing the antistatic property of (B1), and conversely (B1 ) Can be adjusted by increasing the proportion of (b12) within a range not impairing the water resistance of the molded product.
Moreover, when adjusting the refractive index of (B1) low, it can also adjust by using together (B2) which has a comparatively low refractive index.
(2) Method of applying (B) to (A) having a low refractive index (1.480 or less to less than 1.510) (B2) having a relatively low refractive index among (B) is used. When adjusting the refractive index of (B2) to be high, the ratio of (b22) which is a hydrophilic part in (B2) is reduced within a range that does not impair the antistatic property of (B2), or (B2) It can be adjusted by using a highly hydrophilic cationic polymer (b223) or anionic polymer (b224) in a small proportion as the hydrophilic part (b22) in the inside.
Moreover, when adjusting the refractive index of (B2) high, it can also adjust by using (B1) which has a comparatively high refractive index together.

  The antistatic resin composition forming the carrier in the present invention comprises the above (A) and (B). Although the ratio of (B) based on the total weight of (A) and (B) can be variously changed according to the required performance, the preferable lower limit is 1%, more preferably 1 from the viewpoint of sufficient antistatic properties. From the viewpoint of the mechanical properties of the resin of the molded product, 0.5%, the upper limit is preferably 50%, more preferably 30%.

The number average particle diameter of (B) obtained by observing the surface of the antistatic resin composition in the present invention extruded from the capillary at a shear rate of 10 ³ s ⁻¹ with a scanning electron microscope is (B) ( From the viewpoint of dispersibility in A) and antistatic properties, it is preferably 0.05 to 1 μm, more preferably 0.1 to 0.5 μm. The number average particle diameter is determined as follows.
200-280 ° C. [Measurement temperature varies depending on the type of (A), for example, 200 ° C. for PE resin, 230 ° C. for PP resin and ABS resin, 220 ° C. for PMMA resin, and 280 for polycarbonate (PC) resin. After the temperature is adjusted to [° C.], the properties of the molten polymer (for example, melt viscosity, melt elasticity and melt tension) when the heated polymer flows out from the barrel through the capillary (caliber 1 mm, length 10 mm) are measured. Using a device such as Model 1B manufactured by Toyo Seiki Seisakusho, the resin composition extruded from the capillary at a shear rate of 10 ³ s ⁻¹ is taken out, rapidly cooled to room temperature, and (B) on the surface of the resin composition The dispersion state is observed with a scanning electron microscope.
The number average particle diameter of the dispersed (B) is obtained visually or by an image analyzer with respect to the photograph taken. When the particle diameter dL is obtained from the following calculation formula for N particles in an appropriate range (for example, 10 μm × 10 μm), the number average particle diameter D of the dispersed (B) is D = (ΣdL) / N is calculated.

Particle diameter dL = (maximum major axis + minimum minor axis) × (1/2)

The smaller the value of D, the better the dispersibility of (B) in (A) or the compatibility of (A) and (B).

In the resin composition forming the carrier in the present invention, an alkali metal or alkaline earth metal salt is used as long as it does not impair the effects of the present invention if necessary for the purpose of further improving the antistatic property of the resin of the molded product. An additive (C) selected from the group consisting of (C1), surfactant (C2), ionic liquid (C3), compatibilizer (C4) and other additives for resin (C5) may be contained. Good.
The total content of (C) is usually 40% or less based on the total weight of (A) and (B), preferably from 0.001 to 30%, more preferably 0 from the viewpoint of the mechanical properties of the resin of the molded product. 0.01 to 25%, particularly preferably 0.2 to 20%, and most preferably 0.5 to 10%. ]

  (C1) may be an organic acid of an alkali metal (for example, lithium, sodium and potassium, the same shall apply hereinafter) or an alkaline earth metal (for example, magnesium and calcium; , Acetic acid, propionic acid, oxalic acid and succinic acid), C1-20 sulfonic acids (eg methanesulfonic acid and p-toluenesulfonic acid, trifluoromethanesulfonic acid and thiocyanic acid) salts and inorganic acids [eg hydrohalic acid ( For example, hydrochloric acid and hydrobromic acid), perchloric acid, sulfuric acid, nitric acid and phosphoric acid] salts.

Specific examples of (C1) include, for example, halides (for example, lithium chloride, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, lithium bromide, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, perchlorine). Lithium acetate, sodium perchlorate and potassium perchlorate), lithium acetate, potassium sulfate, potassium phosphate and potassium thiocyanate.
Of the above (C1), preferred from the viewpoint of antistatic properties are halide (more preferably lithium chloride, sodium chloride, potassium chloride and potassium perchlorate) and acetate (more preferably potassium acetate).
The amount of (C1) used is usually 5% or less, based on the total weight of (A) and (B), from the viewpoint of giving good appearance and antistatic properties to the molded product without precipitating on the resin surface. Preferably it is 0.001 to 3%, More preferably, it is 0.01 to 2.5%, Especially preferably, it is 0.1 to 2%, Most preferably, it is 0.15 to 1%.
As a method of containing (C1), in order not to impair the transparency of the molded product, it is preferable to disperse in (B) in advance, and a method of containing (C1) during the production of (B). Further preferred. There is no particular limitation on the timing at which (C1) is contained during the production of (B), and it may be any before, during or after polymerization, but is preferably contained in the raw material before polymerization.

(C2) includes nonionic, anionic, cationic and amphoteric surfactants.
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 to Mn 200,000); higher fatty acid ester of polyalkylene glycol (molecular weight 150 to Mn 6,000) which is an EO adduct of glycol; polyhydric alcohol (C2-18 divalent to octavalent) Or higher, eg, ethylene glycol, propylene glycol, glycerin, pentaerythritol and sorbitan) EO adducts of higher fatty acid esters (molecular weight 250-Mn 30,000); EO adducts of higher fatty acid amides (molecular weight 200-Mn 30,000); And polyhydric alcohols (as above) alkyl EO adduct of C3-60) ether (molecular weight 120-Mn30,000)], and polyhydric alcohol (C3-60) type nonionic surfactant [for example, fatty acid (C3-60) ester of polyhydric alcohol , Alkyl (C3-60) ethers and fatty acids (C3-60) alkanolamides of polyhydric alcohols].

Examples of the anionic surfactant include compounds other than the above (C1), such as carboxylic acids (for example, C8-22 saturated or unsaturated fatty acids and ether carboxylic acids) or salts thereof; sulfate salts [for example, higher alcohol sulfate salts ( For example, sulfate esters of C8-18 aliphatic alcohols) and higher alkyl ether sulfate esters [eg sulfate esters of EO (1-10 mol) adducts of C8-18 aliphatic alcohols]]; sulfonates [ C10-20, such as alkyl benzene sulfonates (eg sodium dodecylbenzene sulfonate), alkyl sulfonates, alkyl naphthalene sulfonates, dialkyl ester sulfosuccinates, hydrocarbon (eg alkane, α-olefin) sulfonates and Igepon T type] And phosphoric acid ester salts [e.g. higher alcohol (C8~60) EO adduct phosphoric acid ester salts and alkyl (C4~60) phenol EO adduct phosphoric acid ester salts], and.
Examples of the salts include alkali metal salts, alkaline earth metal salts, ammonium salts, alkylamine (C1-20) salts, and alkanolamine (C2-12, such as mono-, di-, and triethanolamine) salts. It is done.

  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, EO adducts of aliphatic amines (C1-30) Inorganic acids (above) or organic acids (above) and tertiary amines (C3-30, eg triethanolamine monostearate and stearamide ethyl diethyl methylethanolamine) Or salt of organic acid (above)].

  Examples of amphoteric surfactants include amino acid type amphoteric surfactants [for example, higher alkylamine (C8-24) sodium propionate], betaine type amphoteric surfactants [for example, alkyl (C12-18) dimethylbetaine], sulfate ester salts Type amphoteric surfactants [e.g. sulfate sodium salt of higher alkylamine (C8-24) and hydroxyethyl imidazoline sulfate sodium salt], sulfonate type amphoteric surfactants (e.g. pentadecyl sulfotaurine and imidazoline sulfonic acid) and Examples thereof include phosphate ester type amphoteric surfactants [for example, phosphate ester amine salts of glycerin higher fatty acid (C8-24) esterified products].

These (C2) may be used alone or in combination of two or more.
Of these, anionic surfactants are preferred from the viewpoint of heat resistance and antistatic properties of the resin of the molded article, more preferred are sulfonates, and particularly preferred are alkylbenzene sulfonates, alkyl sulfonates and paraffins. Sulfonate.

The amount of (C2) used is usually 15% or less, based on the total weight of (A) and (B), from the viewpoint of giving good appearance and antistatic properties to the molded product without depositing on the film surface, Preferably it is 0.001 to 12%, more preferably 0.01 to 10%, particularly preferably 0.1 to 8%.
The method for containing (C2) is not particularly limited, but it is preferably contained in advance in (B) for effective dispersion in the resin composition. When (C2) is preliminarily contained in (B), it is preferably contained during the production (polymerization) of (B), and the timing of inclusion is not particularly limited, and may be any before, during or after polymerization. Although it is good, it is preferable to make it contain in the raw material before superposition | polymerization.

  The ionic liquid (C3) is a compound excluding the above (C1) and (C2), has a melting point of room temperature or lower, and at least one of cations or anions constituting (C3) is an organic ion, and has an initial conductivity. Is a room temperature molten salt of 1 to 200 ms / cm (preferably 10 to 200 ms / cm), for example, a room temperature molten salt described in WO95 / 15572. Examples of the cation constituting (C3) include an amidinium cation, a guanidinium cation, and a tertiary ammonium cation.

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

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

  Examples of the tertiary ammonium cation include methyl dilauryl ammonium.

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

In the ionic liquid (C3), 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, are preferred from the viewpoint of the initial conductivity of the (C3) is anionic Hamett acidity function constituting the (C3) (-H ₀₎ is 12 to 100, the superacid conjugate base , Acids that form anions other than the conjugate bases of super strong acids and mixtures thereof.

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

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

Examples of the protonic acid used in combination with the Lewis acid include hydrogen halide (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid. , Pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof.
Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of (C3).

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 (C3).
The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

  Of the above anions, (C3) from the viewpoint of the initial conductivity, a super strong acid conjugate base (a super strong acid composed of a proton acid and a super strong acid composed 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 (C3) used is usually 10% or less based on the total weight of (A) and (B). 5%, more preferably 0.01 to 3%.
The method for adding (C3) is not particularly limited, but from the viewpoint of effective dispersion in the resin, it is preferable to disperse in (A) in advance, and after the production (polymerization) of (A). More preferably, (C3) is added and dispersed in advance.

  The production method of (C3) includes, for example, the above-mentioned organic compound constituting an anion in an acid [(C3) and an amidinium cation and / or a guanidinium cation dimethyl carbonate salt obtained by quaternization with dimethyl carbonate or the like. Acid or inorganic acid] to perform acid exchange, or once the amidinium cation and / or guanidinium cation is hydrolyzed to form a monoamidoamine, then the monoamidoamine is converted to an acid (same as above) The method of neutralizing with is mentioned.

Examples of (C4) include a modified vinyl (co) polymer having at least one polar group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group (for example, JP-A-3- 258850), modified vinyl (co) polymers having sulfo groups (for example, those described in JP-A-6-345927), and blocks having polyolefin moieties and aromatic vinyl polymer moieties (copolymers). ) Polymers (for example, those described in JP-A-6-345927).
These (C4) may be used alone or in combination of two or more, but from the viewpoint of transparency of the molded product, the difference in refractive index from (A) and (B) is preferably 0.01 or less, more preferably 0.008 or less, particularly preferably 0.005 or less.
The amount of (C4) used is usually 15% or less based on the total weight of (A) and (B), preferably from the viewpoint of the compatibility of (A) and (B) and the mechanical properties of the molded product. It is 1 to 12%, more preferably 1 to 10%, particularly preferably 1.5 to 8%.

  (C5) includes nucleating agent (C51), lubricant (C52), plasticizer (C53), mold release agent (C54), antioxidant (C55), flame retardant (C56), ultraviolet absorber (C57) and The at least 1 sort (s) chosen from the group which consists of an antibacterial agent (C58) is mentioned.

(C51) includes organic nucleating agents [for example, 1,3,2,4-di-benzylidene-sorbitol, aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium-bis (4-tert-butyl Phenyl) 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).
(C52) 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 alcohol). , 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).

(C53) includes aromatic carboxylic acid esters [for example, phthalic acid esters (for example, dioctyl phthalate and dibutyl phthalate)], aliphatic monocarboxylic acid esters [for example, methyl acetyl ricinoleate and triethylene glycol dibenzoate], aliphatic dicarboxylic acids Esters [eg di (2-ethylhexyl) adipate and adipic acid-propylene glycol-based polyesters (Mn 200-2000)], aliphatic tricarboxylic esters [eg citrate esters (eg triethyl citrate)], phosphate triesters [eg tri Phenyl phosphate] and petroleum resins.
(C54) includes lower (C1-4) alcohol esters of higher fatty acids (above) (for example, butyl stearate), polyvalent (divalent to tetravalent or higher) alcohol esters of fatty acids (C2-18) (E.g. hydrogenated castor oil), glycol (C2-8) esters of fatty acids (C2-18) (e.g. ethylene glycol monostearate) and liquid paraffin.

  (C55) includes phenolic [eg monocyclic phenol [eg 2,6-di-t-butyl-p-cresol and butylated hydroxyanisole], bisphenol [eg 2,2′-methylenebis (4-methyl-6 -T-butylphenol), 4,4'-butylidenebis (3-methyl) -6-t-butylphenol and 4,4'-thiobis (3-methyl) -6-t-butylphenol] and polycyclic phenols [eg 1, 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and 1,1,3-tris (2-methyl-4-hydroxy-5-t -Butylphenyl) butane]]; 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-tert-butylphenylditridecyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), cyclic neopentane tetrayl bis ( 2,6-di-tert-butyl-4-methyl Phenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite and diisodecylpentaerythritol diphosphite]; and amine systems [eg 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].

  (C56) includes organic flame retardants [for example, nitrogen-containing [for example, urea compounds, guanidine compounds and triazine compounds (for example, melamine and guanamine) salts (for example, inorganic acid (the foregoing) salts), cyanurate and isocyanuric acid] Salt)], sulfur-containing systems [for example, sulfates, organic sulfonic acids, sulfamic acids, organic sulfamic acids, and salts, esters, and amides thereof], silicon-containing systems (for example, polyorganosiloxane) and phosphorus-containing systems [for example, phosphoric acid Esters (eg tricresyl phosphate)]] and inorganic flame retardants [eg antimony trioxide, magnesium hydroxide, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus and ammonium polyphosphate].

  (C57) includes benzotriazole-based [for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole], benzophenone-based [ For example 2-hydroxy-4-methoxybenzophenone and 2,2′-dihydroxy-4-methoxybenzophenone], salicylate systems [eg phenyl salicylate and ethylene glycol monosalicylate] and acrylate systems [eg 2-ethylhexyl-2- Cyano-3,3′1-diphenyl acrylate].

  (C58) includes 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) , Nitriles (eg 2,4,5,6-tetrachloroisophthalonitrile), thiocyano (eg methylene bisthianocyanate), N-haloalkylthioimides (eg N-tetrachloroethyl-thio-tetrahydrophthalimide), copper agents (eg 8-oxyquinoline copper), benzimidazole (eg 2-4-thiazolylbenzimidazole), benzothiazole (eg 2-thiocyanomethylthiobenzothiazole), trihaloallyl (eg 3-bromo-2,3-diiodo-2-yl) Propenyl ethyl Carbonates), triazoles (eg azaconazole), organic nitrogen sulfur compounds (eg Suraoff 39), quaternary ammonium compounds (eg trimethoxysilyl-propyloctadecyl ammonium chloride) and pyridine-based compounds [eg 2,3,5,6-cytochloro- 4- (methylsulfonyl) -pyridine].

  The amount of (C5) used is based on the total weight of (A) and (B), (C51), (C52) and (C54) are each usually 10% or less, preferably 1 to 10%; (C53) And (C56) is usually 20% or less, preferably 1 to 10%; (C55) and (C57) are usually 5% or less, preferably 0.1 to 3%; (C58) is usually 3% or less, preferably Is 0.05 to 1%.

The molded article in the present invention can be obtained by molding the above resin composition, for example, according to the following steps. Here, the molded product includes a film having a thickness of 100 μm or less and a molded product having a thickness exceeding 100 μm, and the film includes a multilayer film described later.
1. Production of film <1> Mixing step of (A), (B) and (C) optionally added;
<2> Film forming step;
<3> Cooling step using rolls or the like;
<4> Stretching step (performed as necessary)
Moreover, it can also be set as the multilayer film formed by laminating | stacking the film which consists of a film which consists of a thermoplastic resin and / or the resin composition in this invention as a base layer, and the film which consists of the resin composition in this invention as a surface layer.

When laminating, the surface film may be laminated on one side or both sides of the base layer, and the type of surface layer resin when laminating on both sides may be the same or different, and the type of resin on each of the front and back sides of the base layer Different films may be laminated in multiple layers (2-6 layers or more). The base layer may be a multilayer film in which units of a film made of a resin composition containing thermoplastic resin films (A) and (B) are repeated.
Further, either or both of the surface layer and the base layer may be a foamed layer or a multilayer film composed of a foamed layer and a non-foamed layer, or a multilayer film in which at least one of the surface layer and the base layer is stretched uniaxially or multiaxially.

The film production process will be described in more detail below.
<1> Mixing step The mixing method of the resin composition is not particularly limited. For example, (1) (A), (B) and, if necessary, (C) are dry-blended with a tumble mixer, ribbon blender, Henschel mixer or the like. A method of mixing, (2) a method of dry blending each of the above components by the above method, and then melt-mixing with an extruder (usually 200 to 280 ° C.) to pelletize, (3) (A) and (B) The master batch resin composition is prepared in advance by melt mixing (200 to 280 ° C.) using an extruder [the content of (B) in the master batch resin composition is preferably 30 to 70% by weight], A method of dry blending the master batch, (A), and if necessary (C) with the above mixer is mentioned.
Among these methods, the methods (2) and (3) are preferable from the viewpoint of dispersibility of (B) into (A), and the method (2) is particularly preferable. In the resin composition which forms the conveyance body in the present invention, (A) and (B) are excellent in compatibility, so that a good film can also be obtained by the method (1).

<2> Film-forming step The film-forming method is not particularly limited, and various film-forming methods (for example, an extrusion molding method, an inflation method, and a tubular method) can be used.
In either method, the resin composition is laminated from a die that can be co-extruded to form a film, or a surface layer is laminated to the base layer, or the surface layer and the base layer are bonded together using an adhesive or an adhesive layer. It is good also as a multilayer film.
A foaming layer can also be formed in the film by adding a foaming agent (for example, methyl chloride, butane, carbon dioxide and azobisisobutyronitrile) during film formation.

In coextrusion, for example, the temperature of the resin composition is preferably 85 to 280 ° C., and the die temperature is preferably 180 to 280 ° C.
In the case of laminating the surface layer on the base layer, for example, the layers may be laminated and then thermocompression bonded, or the respective bonding surfaces may be preliminarily heated with a heating device and then bonded and pressure bonded.
The adhesive used in the laminating method is not particularly limited. For example, ethylene-vinyl acetate copolymer and methyl methacrylate polymer elastomer [for example, trade names: Tuffprene and Tuftec [both manufactured by Asahi Kasei Kogyo Co., Ltd.] ] Is preferred.

<3> Cooling step by rolls etc. As for the cooling method, for example, a method of cooling by contact with a roll (for example, extrusion method) and a method of cooling by blowing air (for example, an inflation method and a tubular method) are used. Can be used.

<4> Stretching step As a stretching method, for example, after forming an unstretched film in advance, a method of stretching in a separate step (for example, a method of stretching using a difference in peripheral speed of rolls and a tenter method) and a film Examples of the production process include a stretching process (for example, an inflation method and a tubular method).

  In any stretching method, the stretching ratio is preferably 2 to 20 times in the case of uniaxial stretching, and preferably 2 to 15 times in each direction in the case of biaxial stretching, from the viewpoint of antistatic properties. The antistatic resin film in the present invention can exhibit further excellent antistatic properties through a stretching process.

In addition, the antistatic resin film in the present invention can be used depending on the purpose (for example, printing on a film and adhesion of the film to another object) and purpose (for example, improvement of fixing property of printing ink or film adhesion). Surface treatment such as corona treatment and flame treatment can also be performed.
The surface to be surface-treated may be the surface of the antistatic surface layer or the back surface side (base layer surface) where the antistatic surface layer is not laminated (in the case of one-side lamination).

2-1. Manufacture of molded products (for example, injection molding)
<1> A mixing step of (A), (B) and, if necessary, an additive (C);
<2> Injection molding process The manufacturing process of an injection molded product will be described in more detail below.
<1> Mixing step The method of (1)-(3) is mentioned similarly to the <1> mixing process in manufacture of a film, A preferable method is also the same among these methods. In the resin composition forming the carrier in the present invention, (A) and (B) are excellent in compatibility, so that a good film can be obtained even by the method (1).
<2> Injection molding process The injection molding method is not particularly limited, and a molten resin is pressed into a gap between molds formed of a male mold and a female mold, and the molded product is obtained by cooling and solidifying. Various injection molding methods (for example, injection molding, gas assist molding, injection compression molding, and injection blow molding) can be used.
By adding a foaming agent (same as above) at the time of injection molding, a foamed layer can be formed in the molded product.
2-2. Manufacture of molded products (for example, vacuum forming)
<1> Mixing step of (A), (B) and (C) added as necessary;
<2> Sheet forming step;
<3> Cooling step using rolls or the like;
<4> Vacuum forming process

  In the case of laminating, it may be a multilayer sheet, may contain a foamed layer, or may be stretched, as in the production of the film.

The manufacturing process of the vacuum formed product will be described in more detail below.
<1> Mixing step The method of (1)-(3) is mentioned similarly to the <1> mixing process in manufacture of a film, A preferable method is also the same among these methods. In the resin composition which forms the conveyance body in the present invention, since (A) and (B) are excellent in compatibility, a good sheet can also be obtained by the method (1).

<2> Sheet Forming Step There are no particular limitations on the sheet forming method, and various sheet forming methods (for example, extrusion molding methods) can be used.
In either method, the resin composition is laminated from a die that can be co-extruded to form a sheet, or a surface layer is laminated to the base layer, or the surface layer and the base layer are bonded together using an adhesive or an adhesive layer. It is good also as a multilayer sheet.
A foaming layer can be formed in the sheet by adding a foaming agent (the same as above) at the time of forming the sheet.

In coextrusion, for example, the temperature of the resin composition is preferably 85 to 280 ° C., and the die temperature is preferably 180 to 280 ° C.
In the case of laminating the surface layer on the base layer, for example, the layers may be laminated and then thermocompression bonded, or the respective bonding surfaces may be preliminarily heated with a heating device and then bonded and pressure bonded.
The adhesive used in the laminating method is not particularly limited, but the same adhesive as in the production of the film is preferable.

<3> Cooling step with roll or the like As the cooling method, for example, a method of cooling by contact with a roll (for example, an extrusion method) can be used.

<4> Vacuum forming process The vacuum forming method is not particularly limited, and a heated and softened sheet is placed on the concave mold, the gap between the sheet and the mold is vacuum sucked, molded, cooled and solidified, and molded. Get the goods.

The haze (index indicating transparency) of the molded product in the present invention is preferably 20% or less, more preferably 0 to 10%, and particularly preferably 0 to 5% or less from the viewpoint of transparency.
Haze can be measured by the method of JIS K7105-1981. As an apparatus used for this measurement, Nippon Denshoku Industries Co., Ltd. ND-300A is mentioned, for example.

The molded article in the present invention has excellent mechanical properties and permanent antistatic properties, and also has good paintability and printability.
Examples of the method for coating the molded product include, but are not limited to, an air spray method, an airless spray method, an electrostatic spray method, a dipping method, a roller method, and a brush coating method.
Examples of the paint include various paints such as polyester melamine, epoxy melamine, acrylic melamine, and acrylic urethane resin paint.
Although a coating film thickness (film thickness after drying) can be appropriately selected according to the purpose, it is preferably 10 to 50 μm, more preferably 15 to 40 μm from the viewpoint of physical properties of the coating film.
Examples of the method for printing on the molded product include various printing methods such as gravure printing, flexographic printing, screen printing, and offset printing.
Examples of the printing ink include those usually used for plastic printing.

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

Production Example 1 [Production of polyetheresteramide (B1-1)]
In a 3L 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., hereinafter the same] 0.3 part and water 6 parts were charged, and the inside of the autoclave was purged with nitrogen, and then heated and stirred at 220 ° C. under pressure (0.3 to 0.5 MPa) for 4 hours to obtain 96 parts of polyamide having an acid value of 112 having carboxyl groups at both ends. It was.
Next, 144 parts of an EO adduct of bisphenol A of Mn 1,500 and 0.5 part of zirconyl acetate were added and polymerized at 245 ° C. under reduced pressure of 0.13 kPa or less for 5 hours to obtain a viscous polymer.
The polymer was taken out as a strand on a belt and pelletized to obtain a polyether ester amide (B1-1). The refractive index of (B1-1) was 1.512.

Production Example 2 [Production of polyetheresteramide (B1-2)]
Production Example 1 Production Example 1 except that 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, and 6 parts of water were replaced with 89.7 parts of 12-aminododecanoic acid and 10.3 parts of adipic acid. The reaction was carried out in the same manner as in 1. Thereafter, the pressure was gradually reduced at the same temperature, and unreacted 12-aminododecanoic acid was distilled off at 0.13 kPa or less for 2 hours to obtain 98 parts of polyamide having an acid value of 79 having carboxyl groups at both ends.
Next, 144 parts of EO addition product of bisphenol A of Mn 1,500 in Production Example 1 and 35 parts of EO addition product of bisphenol A of Mn 500 and 0.3 part of zirconyl acetate were used instead of 0.5 part of zirconyl acetate. Obtained the antistatic agent which consists of polyetheresteramide (B1-2) like manufacture example 1. The refractive index of (B1-2) was 1.537.

Production Example 3 [Production of acid-modified polypropylene (b21-1)]
Thermal degradation method [Thermal degradation of ethylene / propylene (random addition) copolymer (ethylene content 2%) at a density of 0.90 g / cm ^{3 at} 23 ° C. and MFR 6.0 g / 10 min at 410 ± 0.1 ° C. Low molecular weight ethylene / propylene random copolymer (Mn 3,500, density 0.89 g / cm ³ , 7.1 double bond amount per 1,000 C, average double bond per molecule) (Number 1.8, content of polyolefin which can be modified at both ends 90%) 95 parts, maleic anhydride 10 parts and xylene 30 parts were melted at 200 ° C. in a nitrogen gas atmosphere (sealed), Time reaction was performed.
Then, excess maleic anhydride and xylene were distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polypropylene (b21-1). The acid value of (b21-1) was 27.2, and Mn was 3,700.

Production Example 4 [Production of secondary modified polypropylene (b21-2)]
(B21-1) 66 parts and 34 parts of 12-aminododecanoic acid were melted at 200 ° C. under a nitrogen gas atmosphere, reacted at 200 ° C. for 3 hours under reduced pressure of 1.3 kPa or less, and secondary modified polypropylene ( b21-2) was obtained. The acid value of (b21-2) was 17.7, and Mn was 5,700.

Production Example 5 [Production of block polymer (B2-1)]
In a stainless steel autoclave, 76.0 parts of (b21-2), Mn 2,000, 24.0 parts of polyethylene glycol having a volume resistivity of 1 × 10 ⁷ Ω · cm, 0.3 part of an antioxidant and 0. 5 parts were charged and polymerized for 4 hours under the conditions of 230 ° C. and reduced pressure of 0.13 kPa or less to obtain a viscous polymer. The polymer was taken out as a strand on the belt and pelletized to obtain a block polymer (B2-1). The refractive index of (B2-1) was 1.492.

Production Example 6 [Production of block polymer (B2-2)]
In Production Example 5, instead of 74.0 parts of (b21-2), Mn2,000, and 24.0 parts of polyethylene glycol having a volume resistivity of 1 × 10 ⁷ Ω · cm, 86.0 parts of (b21-2) A block polymer (B2-2) was obtained in the same manner as in Production Example 5 except that 33.5 parts of an EO adduct of bisphenol A having a volume resistivity of 2 × 10 ⁸ Ω · cm was used. It was. The refractive index of (B2-2) was 1.495.

Production Example 7 [Production of block polymer (B2-3)]
A terminal cyanoalkyl group obtained by cyanoalkylating hydroxyl groups at both ends of polyethylene glycol having (b21-2) 75.8 parts, Mn 2,000, volume resistivity 1 × 10 ⁷ Ω · cm, on a stainless steel autoclave Reduced to primary amino group modified hydrophilic polymer (volume resistivity 2 × 10 ⁸ Ω · cm) 24.2 parts, antioxidant 0.3 part, 220 ° C., 0.13 kPa or less Polymerization was performed for 6 hours under reduced pressure to obtain a viscous polymer. The polymer was taken out as a strand on a belt and pelletized to obtain a block polymer (B2-3). The refractive index of (B2-3) was 1.497.

Production Example 8 [Production of block polymer (B2-4)]
In a stainless steel autoclave, 73.3 parts of (b21-1), the terminal cyanoalkyl group obtained by cyanoalkylating the hydroxyl groups at both ends of the EO adduct of Bisphenol A (Mn1,500) is reduced to a primary amino group 26.7 parts of a modified hydrophilic polymer (volume resistivity 2 × 10 ⁸ Ω · cm) and polymerized for 3 hours at 200 ° C. under reduced pressure of 1.3 kPa or less to obtain a viscous polymer It was. The polymer was taken out as a strand on the belt and pelletized to obtain a block polymer (B2-4). The refractive index of (B2-4) was 1.488.

Production Example 9 [Production of Modified Vinyl Copolymer (C4-1)]
Low molecular weight polypropylene (Mn 12,000, density 0.89 g / cm) obtained by a thermal degradation method [thermal degradation conditions: heat treatment at 350 ° C. for 2 hours under a nitrogen gas flow with PP resin (A-3) described later] ³ ) 95 parts and 5 parts of maleic anhydride were melted at 180 ° C. in a nitrogen atmosphere, and then a 50% xylene solution containing 1.5 parts of dicumyl peroxide was added dropwise over 15 minutes. Time reaction was performed. Thereafter, the solvent was distilled off under reduced pressure to obtain a modified vinyl copolymer (C4-1) as a compatibilizing agent. The acid value of (C4-1) was 25.7, and Mn was 15,000.

Examples 1-11, Comparative Examples 1-6
In accordance with the formulation shown in Table 1, after blending each component for 3 minutes with a Henschel mixer, using a vented twin screw extruder, 240 ° C. when using A-5, 230 ° C. when using A-2, use A-3 The resin composition (Examples 1 to 11 and Comparative Examples 1 to 6) was obtained by melt kneading at 220 ° C. when using A-1 and A-4 and 200 ° C. when using A-1 and A-4 at 100 rpm and a residence time of 5 minutes. It was.

(note)
A-1: PMMA resin [Product name: Acrypet VH, manufactured by Mitsubishi Rayon Co., Ltd., refractive index is
1.490]
A-2: Transparent ABS resin [trade name: Techno ABS 810, manufactured by Techno Polymer Co., Ltd.,
Refractive index is 1.518]
A-3: Transparent PP resin [Brand name: Sun Allomer PM863V, manufactured by Sun Allomer Co., Ltd.,
Refractive index is 1.500]
A-4: MS resin [Brand name: Estyrene MS600, manufactured by Nippon Steel Chemical Co., Ltd., refractive index is
1.533]
A-5: Polyester resin (cyclohexanedimethanol / ethylene glycol / terephthalic acid copolymer) [trade name: EASTER PETG6763, manufactured by Eastman Chemical Japan Co., Ltd., refractive index is 1.554]
B-3: Glycerol monostearate [refractive index is 1.491]
C1-1: Lithium chloride C1-2: Lithium trifluoromethanesulfonate C2-1: Sodium dodecylbenzenesulfonate C1-1, C1-2, C2-1 are bisphenol A in the production of the antistatic agent (B). When the AO adduct or polyethylene glycol was used, it was added and used simultaneously.

[Molding]
About the resin composition obtained above, injection molding, extrusion sheet molding, and biaxially stretched film molding were performed under the following conditions, respectively.
(1) Injection molding Using an injection molding machine [PS40E5ASE, manufactured by Nissei Plastic Industry Co., Ltd.], cylinder temperature 240 ° C (when A-5 is used), 230 ° C (when A-2 is used), 220 ° C (A-3) Test pieces were prepared at the time of use) or at 200 ° C. (when using A-1 and A-4) and at a mold temperature of 50 ° C.
(2) Extruded film, extruded sheet molding Using an extrusion molding machine equipped with a T-die [Lab plast mill 2D20C type, manufactured by Toyo Seiki Seisakusho Co., Ltd.], melt-extruded under the same cylinder temperature conditions as in (1), 20 ° C Were cooled with a chill roll to obtain an extruded film having a thickness of 100 μm and an extruded sheet having a thickness of 1 mm.
(3) Biaxially stretched film molding For Examples 4 to 7 and Comparative Example 4, the 100 μm extruded film obtained in (2) above was stretched with a batch-type stretching apparatus heated to 155 ° C., and the thickness was 10 μm. An axially stretched film was obtained.

[performance test]
Parts damage and yield due to electrical failure in the manufacturing process of electrical equipment were replaced by evaluating the antistatic property and transparency of the molded product. The evaluation items and criteria were as follows, and performance evaluation was performed on the obtained molded product or film. The results are shown in Table 2.
[1] Antistatic property [Conforms to ASTM D257 (1984)]
(1) Saturation voltage A test piece (50 × 50 mm) cut out from an injection molded product, an extruded film, an extruded sheet and a biaxially stretched film was used, and the test piece was subjected to conditions of 23 ° C. and humidity 50% RH for 48 hours. After standing, in accordance with JIS L1094 (1988), a static one meter [TYPE H0110, manufactured by Sicid Electrostatic Co., Ltd., and so on. The saturation voltage (unit: V) was evaluated under the condition of an applied voltage of 10,000 V. Since an electrical failure to an electrical component occurs at 500 V or higher, the evaluation criteria for the presence or absence of an electrical failure as a carrier were as follows.

Saturation voltage 500V or less ○ No failure
Over 500V x Failure may occur

(2) Saturation voltage after washing After washing a test piece similar to that in (1) with 100 ml of ion exchange water at 23 ° C. at a flow rate of 100 ml / min, the test piece was washed in an air circulation dryer. Dry at 3 ° C. for 3 hours. After the operation of washing with water and drying was repeated 10 times, the test piece was allowed to stand for 48 hours under the conditions of 23 ° C. and humidity 50% RH, and then measured with a static Honest meter under the same conditions. The fact that there was no change in the saturation voltage before and after washing with water was used as an evaluation criterion for the presence or absence of contamination of electrical components due to peeling of the antistatic agent component or powder falling.

Difference in saturation voltage between before and after washing is less than ± 50V ○
More than ± 50V ×

[2] Transparency [conforms to JIS K7105-1981]
Haze is measured about the injection molded products of Examples 1 to 11 and Comparative Examples 1 to 6, extruded films, and extruded sheets, and the transparency is evaluated. Haze 10 indicating the transparency with which the contents can be seen from the outside of the carrier is used as the evaluation criterion for transparency.
Molded product haze is 10% or less ○
Over 10% ×

  As is apparent from Table 2, the molded articles (Examples 1 to 11) in the present invention are superior in antistatic properties and transparency as compared with the comparative molded articles (Comparative Examples 1 to 6). As a result, it can be seen that the carrier is excellent in evaluation of electrical obstruction and electrical component contamination and transparency. By using such a carrier, it is possible to provide a method for manufacturing an electrical device that is excellent in protecting electrical components and that does not reduce yield.

  The manufacturing method of the electric equipment which has the process of conveying an electric component of this invention has an antistatic agent (B) which has a hydrophilic chain and a refractive index difference with a thermoplastic resin (A) is 0.02 or less. By using a transport body formed by molding an antistatic resin composition containing (A) in the form of (A), it is possible to prevent failures due to electrostatic discharge (device destruction, etc.) and yield reduction. For this reason, in the manufacture of a wide range of electrical equipment such as home appliances (liquid crystal televisions, digital televisions, etc.), OA equipment and game equipment, it is possible to protect electrical components and improve productivity.

Claims (2)

In the manufacturing method of the electric equipment which has the process of conveying an electrical component, the antistatic agent (B) which has a hydrophilic chain and a refractive index difference with a thermoplastic resin (A) is 0.02 or less (A) A method for producing an electrical device, comprising transporting an electrical component using a transport body formed by molding an antistatic resin composition contained in the composition. The production method according to claim 1, wherein (B) is at least one selected from the group consisting of the following (B1) and (B2).
(B1): Polyether ester amide derived from polyamide (b11) having a number average molecular weight of 200 to 5,000 and an alkylene oxide adduct (b12) of bisphenol having a number average molecular weight of 300 to 5,000 (B2): Polyolefin The block of (b21) and the volume specific resistance value are 1 × 10 ⁵ to 1
A block of × 10 ¹¹ Ω · cm hydrophilic polymer (b22) was repeatedly bonded alternately through 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. Block polymer with structure