JP6652830B2 - Antistatic resin composition - Google Patents

Description

  The present invention relates to an antistatic resin composition which is not only excellent in antistatic properties but also excellent in antibacterial properties against dust and propagation of fungi.

  Synthetic resins are widely used in various molded articles such as automotive materials, home appliances, household goods, films, sheets, and structural parts according to various advantages such as moldability, heat resistance, and low specific gravity. .

  Among them, the synthetic resin having the property of being insulative and easily charged has a problem that it attracts dust and dirt to deteriorate the product appearance. When the molded product is an electronic product, the circuit may not operate normally due to charging. Further, an electric shock may be generated from the charged resin member, and when the electric shock is received, not only a feeling of discomfort is felt, but also an explosion accident may be caused where there is a combustible gas or dust.

  In order to prevent such resin members from being charged, conventionally, measures such as adding an antistatic agent to the resin have been taken. Such antistatic agents include a coating type that is applied to the surface of the resin member and a kneading type that is used by kneading with the resin. There is a problem that the antistatic agent is wiped off when touched.

In addition, it is known that parts that come into contact with water, such as shower curtains and bath products, and parts that come into contact with the handle, such as a handgrip, change to black or brown after long-term use. The cause is propagation of bacteria such as mold.
In addition, agricultural greenhouses have a problem that their permeability is reduced due to adhesion of dust, soot, pollen, mold, moss, spores and the like, which affects harvesting of agricultural products. Furthermore, in a recent highly airtight house, lack of ventilation increases house dust such as dust and dust in the room, and dust adheres to the surface of the charged resin member, from which bacteria such as mold grow. There was a problem of damaging the living environment.

  A method of applying an antibacterial agent to a resin member in order to prevent the growth of bacteria such as mold is known, but there is a problem that the antibacterial property is lost by wiping. Further, when kneading and molding a resin and an antibacterial agent, a resin that can withstand the molding temperature of the synthetic resin is required. Normal antibacterial agents not only decompose due to the molding temperature and cannot exhibit antibacterial performance, but also have adverse effects such as coloring the resin member and deteriorating the physical properties of the molded article.

  From such a viewpoint, an antistatic resin composition capable of exhibiting a continuous antistatic property and a sufficient antibacterial effect is demanded. For example, Patent Literature 1 and Patent Literature 2 propose an antibacterial fungus composition in which an anti-moso bamboo extract is adsorbed on silica gel as an antibacterial agent, as an antistatic agent such as polyetheresteramide and conductive whiskers. In addition, the applicants of the present application have proposed, in Patent Documents 3 and 4, an antistatic resin composition containing a polyetherester-based polymer type antistatic agent.

JP-A-2002-322367 JP-A-2002-322368 International Publication No. WO 2014/115745 International Publication No. WO 2014/148454

  However, unless the antistatic agent composed of polyetheresteramide is added in a large amount to the resin, sufficient antistatic performance cannot be obtained. Further, although an antibacterial agent capable of preventing the propagation of microorganisms present in a washing machine is disclosed, no antibacterial property against Escherichia coli is described. Note that the antistatic agents disclosed in Patent Documents 3 and 4 do not contain an aromatic dicarboxylic acid, and thus have a different structure from the antistatic agent according to the present invention.

  Accordingly, an object of the present invention is to provide an antistatic resin composition which maintains excellent antistatic properties and a sustained effect, and also has excellent antibacterial properties.

The present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention.
That is, the antistatic resin composition of the present invention contains 3 to 60 parts by mass of the antistatic agent (A) and 0.1 to 20 parts by mass of the antibacterial agent (B) based on 100 parts by mass of the synthetic resin. A conductive resin composition,
The antistatic agent (A) is composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, and is represented by a block composed of a polyester (E) having a carboxyl group at both terminals and a general formula (1) shown below. Reaction with a block polymer (G) having carboxyl groups at both ends, wherein blocks composed of a compound (C) having at least one group and having hydroxyl groups at both ends are alternately and repeatedly bonded via ester bonds; A polymer compound having a structure in which the compound (D) having a functional group is bonded via an ester bond,
The number average molecular weight of the block composed of the polyester (E) is 800 to 8,000 in terms of polystyrene, and the number average molecular weight of the block composed of the compound (C) is 400 to 6,000 in terms of polystyrene. And the number average molecular weight of the block polymer (G) is 5,000 to 25,000 in terms of polystyrene,
The compound (C) is a polyethylene glycol, and the compound (D) having a reactive functional group is a polyvalent epoxy compound having two or more epoxy groups.

  The antistatic resin composition of the present invention preferably further contains 0.01 to 5 parts by mass of one or more alkali metal salts (F).

  In the antistatic resin composition of the present invention, the antibacterial agent (B) is preferably a compound of an inorganic metal salt.

  Furthermore, in the antistatic resin composition of the present invention, the synthetic resin is preferably a polyolefin-based resin or a styrene-based resin.

  The molded article of the present invention is obtained by molding the above antistatic resin composition.

  According to the present invention, an antistatic resin composition having antibacterial properties and excellent antistatic properties can be provided.

Hereinafter, the present invention will be described in detail.
First, the synthetic resin used in the present invention will be described.
Examples of the synthetic resin that can be used as the antistatic resin composition of the present invention include polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, cross-linked polyethylene, ultra-high-molecular-weight polyethylene, polybutene-1, and poly-3. Α-olefin polymers such as -methylpentene and poly-4-methylpentene, or polyolefin resins such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene copolymer, and copolymers thereof. Coalescence;
Polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, chloride Halogen-containing resins such as vinyl-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-cyclohexylmaleimide copolymer;
Vinyl group-containing aromatic hydrocarbon homopolymer, vinyl group-containing aromatic hydrocarbon, and other monomers (for example, maleic anhydride, phenylmaleimide, (meth) acrylate, butadiene, (meth) acrylonitrile (E.g., polystyrene (PS) resin, high impact polystyrene (HIPS), acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, methyl methacrylate-butadiene-styrene ( MBS) resin, heat-resistant ABS resin, acrylonitrile-acrylate-styrene (AAS) resin, styrene-maleic anhydride (SMA) resin, methacrylate-styrene (MS) resin, styrene-isoprene-styrene (SIS) resin, acrylonitrile-ethylene propylene Go Thermoplastic resins such as styrene (AES) resin, styrene-butadiene-butylene-styrene (SBBS) resin, and methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin, and hydrogen bonding between these butadiene and isoprene double bonds. Added styrene-ethylene-butylene-styrene (SEBS) resin, styrene-ethylene-propylene-styrene (SEPS) resin, styrene-ethylene-propylene (SEP) resin, styrene-ethylene-ethylene-propylene-styrene (SEEPS) resin, etc. Styrene-based resins such as hydrogenated styrene-based elastomer resins);
Petroleum resin, coumarone resin, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral;
Polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate and polycyclohexane dimethylene terephthalate;
Aromatic polyesters such as polyalkylene naphthalate such as polyethylene naphthalate and polybutylene naphthalate and linear polyesters such as polytetramethylene terephthalate;
Degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, poly (2-oxetanone);
Polyamide such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonate, polycarbonate / ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, fiber-based resin, polyimide resin, polysulfone, polyphenylene ether, polyether ketone, poly Ether ether ketone, liquid crystal polymer and the like can be mentioned.

  Further, these synthetic resins are isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluoro rubber, silicone rubber, olefin elastomer, styrene elastomer, polyester elastomer, nitrile elastomer, An elastomer such as a nylon-based elastomer, a vinyl chloride-based elastomer, a polyamide-based elastomer, or a polyurethane-based elastomer may be used, or may be used in combination. In the present invention, these synthetic resins may be used alone or in combination of two or more. Further, the synthetic resin may be alloyed.

  These synthetic resins have a molecular weight, a degree of polymerization, a density, a softening point, a proportion of an insoluble portion in a solvent, a degree of stereoregularity, presence or absence of a catalyst residue, a kind and a mixing ratio of a raw material monomer, a kind of a polymerization catalyst ( For example, it can be used regardless of Ziegler catalyst, metallocene catalyst and the like). Among these synthetic resins, those containing at least one of a polyolefin resin, a halogen-containing resin, a styrene resin, an aromatic polyester, a linear polyester, a polyamide, and a polycarbonate are preferable from the viewpoint of antistatic properties. Among them, polyolefin resins and styrene resins are preferred.

Next, the antistatic agent (A) will be described. The antistatic agent (A) is blended to impart antistatic properties to the resin composition.
The antistatic agent (A) used in the present invention has a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and one or more groups represented by the following general formula (1) and has hydroxyl groups at both ends. It can be produced by bonding the compound (C) and the compound (D) having a reactive functional group via an ester bond or via an ester bond and an amide bond.

  In the present invention, the antistatic agent (A) includes a polyester (E) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, the compound (C), and a compound having the reactive functional group. (D) preferably has a structure formed by bonding via an ester bond or an ester bond and an amide bond.

  The polyester (E) may be composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and the residue of the diol excluding the hydroxyl group and the residue of the aliphatic dicarboxylic acid excluding the carboxyl group may be used. Having a structure in which the residue excluding the hydroxyl group of the diol and the residue in which the carboxyl group of the aromatic dicarboxylic acid is removed through an ester bond. Are preferred.

  The polyester (E) preferably has a structure having carboxyl groups at both ends, and the degree of polymerization of the polyester (E) is preferably in the range of 2 to 50.

The diol used in the present invention includes an aliphatic diol and an aromatic group-containing diol. The diol may be a mixture of two or more. Examples of the aliphatic diol include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, and 1,3-butanediol. , 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl- 1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentane Diol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol 1,2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,2 -, 1,3- or 1,4-cyclohexanediol, cyclododecanediol, dimer diol, hydrogenated dimer diol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol and the like.
Among these aliphatic diols, 1,4-cyclohexane dimethanol and hydrogenated bisphenol A are preferable from the viewpoint of durability of antistatic performance, and 1,4-cyclohexane dimethanol is more preferable.

  In addition, since the aliphatic diol preferably has hydrophobicity, it is necessary to avoid using hydrophilic polyethylene glycol alone among the aliphatic diols. However, when it is used together with a hydrophobic diol, this is not always the case.

  As the aromatic group-containing diol, for example, bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, ethylene oxide adduct of bisphenol A, Examples include a propylene oxide adduct of bisphenol A, a polyhydroxyethyl adduct of a mononuclear dihydric phenol compound such as 1,4-bis (2-hydroxyethoxy) benzene, resorcinol, and pyrocatechol. Among these diols having an aromatic group, an ethylene oxide adduct of bisphenol A and 1,4-bis (β-hydroxyethoxy) benzene are preferable from the viewpoint of durability of antistatic performance.

Next, the aliphatic dicarboxylic acid used in the present invention will be described.
The aliphatic dicarboxylic acid may be a derivative of the aliphatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, or the like). When the derivative is used to produce a polyester (E), Finally, the reaction may proceed to obtain a block polymer (G) having a structure having carboxyl groups at both ends. Further, the aliphatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

  The aliphatic dicarboxylic acid in the present invention is preferably an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid Examples include acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, maleic acid, fumaric acid, and the like. Among these aliphatic dicarboxylic acids, from the viewpoint of melting point and heat resistance, aliphatic dicarboxylic acids having 4 to 16 carbon atoms are preferable, and aliphatic dicarboxylic acids having 6 to 12 carbon atoms are more preferable.

Next, the aromatic dicarboxylic acid used in the present invention will be described.
The aromatic dicarboxylic acid may be a derivative of the aromatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, or the like). When the derivative is used to produce a polyester (E), Finally, the reaction may proceed to obtain a block polymer (G) having a structure having carboxyl groups at both ends. Further, the aromatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

  The aromatic dicarboxylic acid in the present invention is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms, for example, terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β- Phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate and 3-sulfo And potassium isophthalate.

上記一般式（２）中、ｍは５〜２５０の整数を表す。ｍは、耐熱性や相溶性の点から、好ましくは２０〜１５０である。 Next, the compound (C) having at least one group represented by the general formula (1) and having hydroxyl groups at both ends, which is used in the present invention, will be described.
The compound (C) is preferably a compound having hydrophilicity, and particularly preferably a polyethylene glycol represented by the following general formula (2).

In the general formula (2), m represents an integer of 5 to 250. m is preferably from 20 to 150 from the viewpoint of heat resistance and compatibility.

  As the compound (C), in addition to polyethylene glycol obtained by subjecting the group represented by the general formula (1) to an addition reaction, ethylene oxide and another alkylene oxide (for example, propylene oxide, 1,2-, Polyether obtained by addition reaction with one or more of 1,4-, 2,3- or 1,3-butylene oxide. The polyether may be random or block.

  Further examples of compound (C) include compounds having a structure in which ethylene oxide is added to a compound containing an active hydrogen atom, and ethylene oxide and other alkylene oxides (for example, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide). These may be either random addition or block addition.

  Examples of the active hydrogen atom-containing compound include glycol, dihydric phenol, primary monoamine, secondary diamine, and dicarboxylic acid.

  As the glycol, an aliphatic glycol having 2 to 20 carbon atoms, an alicyclic glycol having 5 to 12 carbon atoms and an aromatic glycol having 8 to 26 carbon atoms can be used.

  As the aliphatic glycol, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3- Hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecane Diol, 1,20-eicosanediol, diethylene glycol, triethylene glycol, thiodiethylene glycol and the like.

  Examples of the alicyclic glycol include 1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 1-methyl-3,4-cyclohexanediol. , 2-hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol, 1,1'-dihydroxy-1,1'-dicyclohexyl, and the like.

  Examples of the aromatic glycol include dihydroxymethylbenzene, 1,4-bis (β-hydroxyethoxy) benzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, and 2-benzyl -1,3-propanediol, triphenylethylene glycol, tetraphenylethylene glycol, benzopinacol and the like.

  As the dihydric phenol, phenols having 6 to 30 carbon atoms can be used. For example, catechol, resorcinol, 1,4-dihydroxybenzene, hydroquinone, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenylether, dihydroxydiphenylthioether, binaphthol And alkyl (1 to 10 carbon atoms) or halogen-substituted products thereof.

  Examples of the primary monoamine include an aliphatic primary monoamine having 1 to 20 carbon atoms, and examples thereof include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, s-butylamine, isobutylamine, and n-butylamine. Examples include amylamine, isoamylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-octadecylamine, and n-icosylamine.

  Examples of the secondary diamine include an aliphatic secondary diamine having 4 to 18 carbon atoms, a heterocyclic secondary diamine having 4 to 13 carbon atoms, an alicyclic secondary diamine having 6 to 14 carbon atoms, and 8 carbon atoms. -14 aromatic secondary diamines and secondary alkanol diamines having 3 to 22 carbon atoms can be used.

  Examples of the aliphatic secondary diamine include N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-dibutylethylenediamine, N, N′-dimethylpropylenediamine, and N, N′-diethylpropylene. Diamine, N, N'-dibutylpropylenediamine, N, N'-dimethyltetramethylenediamine, N, N'-diethyltetramethylenediamine, N, N'-dibutyltetramethylenediamine, N, N'-dimethylhexamethylenediamine N, N'-diethylhexamethylenediamine, N, N'-dibutylhexamethylenediamine, N, N'-dimethyldecamethylenediamine, N, N'-diethyldecamethylenediamine and N, N'-dibutyldecamethylenediamine And the like.

  Examples of the heterocyclic secondary diamine include piperazine and 1-aminopiperidine.

  Examples of the alicyclic secondary diamine include N, N′-dimethyl-1,2-cyclobutanediamine, N, N′-diethyl-1,2-cyclobutanediamine, and N, N′-dibutyl-1,2-diamine. Cyclobutanediamine, N, N'-dimethyl-1,4-cyclohexanediamine, N, N'-diethyl-1,4-cyclohexanediamine, N, N'-dibutyl-1,4-cyclohexanediamine, N, N'- Dimethyl-1,3-cyclohexanediamine, N, N'-diethyl-1,3-cyclohexanediamine, N, N'-dibutyl-1,3-cyclohexanediamine, and the like.

  As the aromatic secondary diamine, for example, N, N′-dimethyl-phenylenediamine, N, N′-dimethyl-xylylenediamine, N, N′-dimethyl-diphenylmethanediamine, N, N′-dimethyl-diphenyletherdiamine , N, N'-dimethyl-benzidine and N, N'-dimethyl-1,4-naphthalenediamine.

  Examples of the secondary alkanoldiamine include N-methyldiethanolamine, N-octyldiethanolamine, N-stearyldiethanolamine, N-methyldipropanolamine, and the like.

  As the dicarboxylic acid, a dicarboxylic acid having 2 to 20 carbon atoms can be used, and for example, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid and the like are used.

  As the aliphatic dicarboxylic acid, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, methyl succinic acid, dimethyl malonic acid, β-methyl glutaric acid, ethyl succinic acid, isopropyl malonic acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecandioic acid, tetradecandioic acid, hexadecandioic acid, octadecandioic acid and icosandioic acid.

  As the aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2 , 2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate and potassium 3-sulfoisophthalate.

  Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid Acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, dicyclohexyl-4,4′-dicarboxylic acid and the like.

  These active hydrogen atom-containing compounds can be used alone or as a mixture of two or more.

Next, the compound (D) having a reactive functional group will be described.
In the present invention, the compound (D) having a reactive functional group has a structure in which the polyester (E) and the compound (C) are bonded via an ester bond and the compound (D) having a reactive functional group. , An ester bond or an amide bond, or a combination of a block composed of the polyester (E) and a block composed of the compound (C) repeatedly and alternately bonded through an ester bond. It is only necessary that the block polymer (G) having a carboxyl group at the terminal and the compound (D) having a reactive functional group be bonded via an ester bond or an amide bond.

  The compound (D) having a reactive functional group may be any of those which bind to a carboxyl group via an ester bond or those which bind via an amide bond. Epoxy compounds, polyhydric alcohol compounds, and polyamine compounds.

The polyhydric epoxy compound used in the present invention is not particularly limited as long as it is a compound having two or more epoxy groups, and examples thereof include mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds: dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3 -Bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as 4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, and terpene phenol Polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-ethylene oxide adducts; ; Maleic acid, fumaric acid, itaconic acid, Citric acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydro Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as phthalic acid and endomethylenetetrahydrophthalic acid and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- Epoxy compounds having a glycidylamino group such as (N-methyl-N-glycidylamino) phenyl) methane and diglycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4 -Epoxy Epoxidized products of cyclic olefin compounds such as chlorohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidation Examples include epoxidized conjugated diene polymers such as polybutadiene and epoxidized styrene-butadiene copolymer, heterocyclic compounds such as triglycidyl isocyanurate, and epoxidized soybean oil.
These polyepoxy compounds can be prepared by internally cross-linking with a prepolymer of terminal isocyanate or using a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). It may have a reduced molecular weight. Two or more polyepoxy compounds may be used.

  The polyhydric alcohol compound used in the present invention is not particularly limited as long as it has three or more hydroxyl groups. For example, glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, -Methyl-1,2,3-propanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,3,5-pentanetriol, 2,3,4-pentanetriol, 2- Methyl-2,3,4-butanetriol, trimethylolethane, 2,3,4-hexanetriol, 2-ethyl-1,2,3-butanetriol, trimethylolpropane, 4-propyl-3,4,5 -Heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, triethanolamine, triisopropanolamine, 1,3, Trihydric alcohols such as tris (2-hydroxyethyl) isocyanurate; pentaerythritol, 1,2,3,4-pentane tetrol, 2,3,4,5-hexane tetrol, 1,2,4,5 -Pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, ditrimethylolpropane, sorbitan, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N Tetrahydric alcohols such as', N'-tetrakis (2-hydroxyethyl) ethylenediamine; pentahydric alcohols such as adonitol, arabitol, xylitol, triglycerin; dipentaerythritol, sorbitol, mannitol, iditol, inositol, darcitol, talose, allose Hexahydric alcohols, such as; Tripentaerythritol, and the like. The molecular weight of the polyhydric alcohol compound is not particularly limited, and high molecular weight polyhydric alcohols such as polypentaerythritol and polyvinyl alcohol can be used, and polyester polyhydric alcohols can also be used. Two or more polyhydric alcohol compounds may be used.

  The polyvalent amine compound used in the present invention is not particularly limited as long as it has two or more primary amino groups and / or secondary amino groups. For example, ethylenediamine, trimethylenediamine, hexamethylenediamine Alkylene diamines having 2 to 12 carbon atoms such as heptamethylene diamine, octamethylene diamine, decamethylene diamine; aliphatic amines such as 2,2 ', 2 "-triaminotriethylamine and bis (hexamethylene) triamine; diethylene triamine A polyalkylene polyamine having an alkylene group having 2 to 6 carbon atoms and a degree of polymerization of 2 to 5; 1,6,11-undecanetriamine, 1,8-diamino-4-aminomethyloctane, 1,3,6-hexamethylene Alkanetriamines such as triamine; melamine, piperazine; N N-aminoalkylpiperazines having 2 to 6 carbon atoms in the alkylene group, such as aminoethylpiperazine; heterocyclic polyamines such as heterocyclic polyamines described in JP-B-55-21044; dicyclohexylmethanediamine, isophoronediamine, bicycloheptane Alicyclic polyamines having 4 to 20 carbon atoms such as triamine; carbon atoms such as phenyldiamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine and triphenylmethanetriamine Examples thereof include aromatic polyamines of the formulas 6 to 20. Such polyamine compounds may be used in combination of two or more.

  The antistatic agent (A) has a polyester (E) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, the compound (C), and the reactive functional group from the viewpoint of antistatic properties. It is preferable that the compound (D) has a structure formed by bonding via an ester bond or via an ester bond and an amide bond.

  Further, from the viewpoint of antistatic properties, the antistatic agent (A) comprises a block composed of a polyester (E) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and the compound (C). An ester bond or an amide bond is formed between the block polymer (G) having a carboxyl group at both terminals formed by alternately bonding the configured blocks via an ester bond and the compound (D) having the reactive functional group. It is preferable to have a structure formed by bonding via

  The polyester (E) having a carboxyl group at both ends can be obtained, for example, by subjecting the aliphatic diol and the aromatic dicarboxylic acid to a polycondensation reaction with the diol.

  The aliphatic dicarboxylic acid may be a derivative of an aliphatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, or the like). When the derivative is used to obtain a polyester (E), Finally, both ends may be treated to form a carboxyl group, and the reaction may proceed as it is to obtain a block polymer (G) having a structure having a carboxyl group at both ends. Further, the aliphatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

  The aromatic dicarboxylic acid may be a derivative of an aromatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, or the like). When the derivative is used to obtain a polyester (E), Finally, both ends may be treated to form a carboxyl group, and the reaction may proceed as it is to obtain a block polymer (G) having a structure having a carboxyl group at both ends. Further, the aromatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

  In the polyester (E), the molar ratio of the residue excluding the carboxyl group of the aliphatic dicarboxylic acid to the residue excluding the carboxyl group of the aromatic dicarboxylic acid was 90:10 to 99.9: 0. 1 is preferable, and 93: 7 to 99.9: 0.1 is more preferable.

  The polyester (E) can be obtained by subjecting the above-mentioned aliphatic dicarboxylic acid or derivative thereof and the above-mentioned aromatic dicarboxylic acid or derivative thereof to polycondensation reaction with the above-mentioned diol.

  The reaction ratio between the aliphatic dicarboxylic acid or derivative thereof and the aromatic dicarboxylic acid or derivative thereof and the diol is such that the aliphatic dicarboxylic acid or the derivative thereof and the aromatic dicarboxylic acid or the derivative thereof are carboxyl groups at both ends. It is preferable to use it in excess, and it is preferable to use it in a molar ratio of 1 mole excess with respect to the diol.

  The mixing ratio of the aliphatic dicarboxylic acid or its derivative to the aromatic dicarboxylic acid or its derivative during the polycondensation reaction is preferably 90:10 to 99.9: 0.1, and 93: 7 to 99.9 in molar ratio. : 0.1 is more preferable.

  Further, depending on the mixing ratio and the reaction conditions, a polyester composed only of a diol and an aliphatic dicarboxylic acid or a polyester composed only of a diol and an aromatic dicarboxylic acid may be produced. E) may be mixed with them, or they may be reacted with the compound (C) to obtain a block polymer (G).

  In the polycondensation reaction, a catalyst that promotes the esterification reaction may be used. As the catalyst, conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used.

  In the case where a derivative such as a carboxylic acid ester, a carboxylic acid metal salt, or a carboxylic acid halide is used instead of the dicarboxylic acid, the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid are both reacted after the reaction with the diol. The terminal may be treated to be a dicarboxylic acid, or the reaction may proceed as it is to obtain a block polymer (G) having a structure having carboxyl groups at both terminals.

  A suitable polyester (E) comprising a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid and having a carboxyl group at both terminals is formed by reacting with the compound (C) to form an ester bond, thereby forming a block polymer (G). As long as it forms a structure, the carboxyl groups at both ends may be protected, modified, or in the form of a precursor. Further, an antioxidant such as a phenolic antioxidant may be added to the reaction system in order to suppress oxidation of the product during the reaction.

  The compound (C) may be any compound as long as it reacts with the polyester (E) to form an ester bond to form the structure of the block polymer (G), and the hydroxyl groups at both terminals may be protected. And may be in the form of a precursor.

上記一般式（３）中、（Ｅ）は、上記両末端にカルボキシル基を有するポリエステル（Ｅ）から構成されたブロックを表し、（Ｃ）は、上記エチレンオキサイド基を一つ以上有し両末端に水酸基を有する化合物（Ｃ）から構成されたブロックを表し、ｔは繰り返し単位の繰り返しの数であり、好ましくは１〜１０の数を表す。ｔは、より好ましくは１〜７の数であり、最も好ましくは１〜５の数である。 The block polymer (G) having a carboxyl group at both ends according to the present invention has a block composed of the polyester (E) and a block composed of the compound (C). Has a structure in which they are alternately and repeatedly bonded via an ester bond formed by a carboxyl group and a hydroxyl group. As an example of such a block polymer (G), for example, a polymer having a structure represented by the following general formula (3) may be mentioned.

In the above general formula (3), (E) represents a block composed of the polyester (E) having a carboxyl group at both ends, and (C) has at least one ethylene oxide group at both ends. Represents a block composed of a compound (C) having a hydroxyl group, and t represents the number of repeating units, and preferably represents the number of 1 to 10. t is more preferably a number from 1 to 7, and most preferably a number from 1 to 5.

  Part of the block composed of polyester (E) in the block polymer (G) is composed of a block composed of polyester composed only of diol and aliphatic dicarboxylic acid, or composed of only diol and aromatic dicarboxylic acid. May be replaced by a block made of polyester.

  The block polymer (G) having a structure having carboxyl groups at both ends is obtained by subjecting the polyester (E) having carboxyl groups at both ends and the compound (C) having hydroxyl groups at both ends to a polycondensation reaction. A structure equivalent to that having a structure in which the polyester (E) and the compound (C) are alternately and repeatedly bonded via an ester bond formed by a carboxyl group and a hydroxyl group. Is not necessarily required to be synthesized from the polyester (E) and the compound (C).

  The reaction ratio between the polyester (E) and the compound (C) is adjusted such that the polyester (E) becomes X + 1 moles with respect to the X moles of the compound (C). A block polymer (G) having the following formula:

  In the reaction, after the completion of the synthesis reaction of the polyester (E), the compound (C) may be added to the reaction system without isolating the polyester (E), and the reaction may be performed as it is.

  In the polycondensation reaction, a catalyst that promotes the esterification reaction may be used. As the catalyst, conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used. Further, an antioxidant such as a phenolic antioxidant may be added to the reaction system in order to suppress oxidation of the product during the reaction.

  Further, the polyester (E) may be mixed with a polyester composed only of a diol and an aliphatic dicarboxylic acid or a polyester composed only of a diol and an aromatic dicarboxylic acid. ) To obtain a block polymer (G).

  The block polymer (G) includes, in addition to the block composed of the polyester (E) and the block composed of the compound (C), a block composed of a polyester composed only of a diol and an aliphatic dicarboxylic acid, And a block composed of a polyester composed only of an aromatic dicarboxylic acid may be included in the structure.

  The antistatic agent (A) according to the present invention comprises a block polymer (G) having a structure having carboxyl groups at both ends, a terminal carboxyl group, a polyepoxy compound having two or more epoxy groups, and a hydroxyl group. And a polyamine compound having two or more amino groups, a terminal carboxyl group of the block polymer (G) and an epoxy group of the polyhydric epoxy compound, a hydroxyl group of the polyhydric alcohol compound or It is preferable to have a structure formed by bonding via an ester bond or an amide bond formed by the amino group of the multivalent amine compound. Further, the antistatic agent (A) further comprises an ester bond formed from a carboxyl group of the polyester (E) and an epoxy group of a polyhydric epoxy compound, a hydroxyl group of a polyhydric alcohol compound or an amino group of a polyamine, or It may contain an amide bond.

  In order to obtain the antistatic agent (A), the carboxyl group of the block polymer (G), the epoxy group of the polyvalent epoxy compound of the compound (D) having a reactive functional group, the hydroxyl group of the polyhydric alcohol compound or What is necessary is just to react with the amino group of a valent amine compound.

  In the case where the component (D) is a polyepoxy compound having two or more epoxy groups, the number of epoxy groups in the polyepoxy compound is 0.5 to 5 times the number of carboxyl groups in the block polymer (G) to be reacted. Equivalents are preferred, and 0.5 to 1.5 equivalents are more preferred.

  The polyepoxy compound (D) having two or more epoxy groups to be reacted is preferably 0.1 to 2.0 equivalents, more preferably 0.2 to 1.5 equivalents, of the carboxyl group of the block polymer (G) to be reacted. Is more preferred.

  When the component (D) is a polyhydric alcohol compound having three or more hydroxyl groups, the number of hydroxyl groups of the polyhydric alcohol compound is 0.5 to 5 equivalents of the number of carboxyl groups of the block polymer (G) to be reacted. Preferably, 0.5 to 1.5 equivalents are more preferred.

  The polyhydric alcohol compound (D) having three or more hydroxyl groups to be reacted preferably has 0.1 to 2.0 equivalents, more preferably 0.2 to 1.5 equivalents, of the carboxyl group of the block polymer (G) to be reacted. More preferred.

  In the case where the component (D) is a polyamine compound having two or more amino groups, the number of amino groups of the polyamine compound is 0.5 to 5 times the number of carboxyl groups of the block polymer (G) to be reacted. Equivalents are preferred, and 0.5 to 1.5 equivalents are more preferred.

  The polyvalent amine compound (D) having two or more amino groups to be reacted is preferably 0.1 to 2.0 equivalents, more preferably 0.2 to 1.5 equivalents, of the carboxyl group of the block polymer (G) to be reacted. Is more preferred.

  In the reaction, after the completion of the synthesis reaction of the block polymer (G), the compound (D) having a reactive functional group is added to the reaction system without isolating the block polymer (G), and the reaction is allowed to proceed as it is. Good. In that case, one of the carboxyl groups of the unreacted polyester (E) used excessively when synthesizing the block polymer (G) and the epoxy group of the polyvalent epoxy compound as the compound (D) having a reactive functional group is used. Part, part of the hydroxyl group of the polyhydric alcohol compound, or part of the amino group of the polyhydric amine compound may react to form an ester bond or an amide bond.

  The preferred antistatic agent (A) of the present invention has a structure in which a block polymer (G) having a structure having carboxyl groups at both terminals and the compound (D) are bonded via an ester bond or an amide bond. The block polymer (G) is not necessarily limited to the compound (D) having a reactive functional group as long as it has a structure equivalent to the above.

  In the present invention, the number average molecular weight of the block composed of the polyester (E) in the antistatic agent (A) is preferably from 800 to 8,000 in terms of polystyrene, more preferably from 1,000 to 6,000. And more preferably 2,000 to 4,000. The number average molecular weight of the block composed of the compound (C) having a hydroxyl group at both ends in the antistatic agent (A) is preferably 400 to 6,000 in terms of polystyrene, more preferably 1,000. 5,000, more preferably 2,000-4,000.

  Further, the number average molecular weight of the block composed of the block polymer (G) having a structure having carboxyl groups at both ends in the antistatic agent (A) is preferably 5,000 to 25,000 in terms of polystyrene. , More preferably from 7,000 to 17,000, and more preferably from 9,000 to 13,000.

  The antistatic agent (A) according to the present invention is obtained by obtaining the polyester (E) from a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and then isolating the polyester (E) without isolating the polyester (E). And / or the compound (D) having a reactive functional group.

  When the antistatic agent (A) is mixed with the synthetic resin, the amount is 3 to 60 parts by mass with respect to 100 parts by mass of the synthetic resin, and 5 to 18 parts by mass from the viewpoint of antistatic property and suppression of ion elution. Is preferable, and 7 to 15 parts by mass is more preferable. If the amount is less than 3 parts by mass, sufficient antistatic properties may not be obtained, and if it exceeds 60 parts by mass, the physical properties of the molded article may be adversely affected.

Next, in the present invention, the antibacterial agent (B) can be used without being limited to a known compound as long as it can exhibit an antibacterial effect or an antifungal effect. Examples of compounds exhibiting antibacterial and antifungal effects include, for example, nitrile compounds, pyridine compounds, haloalkylthio compounds, organic iodine compounds, thiazole compounds, benzimidazole compounds, wasabi components (allyl isothiocyanate), silver Examples include inorganic compounds such as zinc and copper.
In the present invention, those which can withstand the molding temperature of the synthetic resin are preferable, and it is particularly preferable to use a compound of an inorganic metal salt.
The compounding amount of the antibacterial agent needs to be 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass, per 100 parts by mass of the synthetic resin. When the amount of the antibacterial agent is less than 0.1 part by mass, antibacterial properties cannot be obtained, and when the amount exceeds 20 parts by mass, the physical properties of the resin are adversely affected.

  The antistatic resin composition of the present invention preferably further contains one or more alkali metal salts (F) from the viewpoint of improving the antistatic property, its durability, and the crystallinity.

Examples of the alkali metal salt (F) include salts of organic acids or inorganic acids.
Examples of the alkali metal include lithium, sodium, potassium, cesium, rubidium and the like. Examples of organic acids include formic, acetic, propionic, butyric, lactic, pentanoic, caproic, heptanoic, caprylic, pelargonic, capric, lauric, myristic, pentadecyl, palmitic, margaric , Stearic acid, aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as 12-hydroxystearic acid; having 1 to 12 carbon atoms such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid and adipic acid; Aliphatic dicarboxylic acid; aromatic carboxylic acid such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; and 1 carbon atom such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethanesulfonic acid To 20 sulfonic acids. Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like. Among them, lithium, sodium and potassium are more preferable, and lithium and sodium are most preferable from the viewpoint of antistatic property. In addition, from the viewpoint of antistatic properties, salts of acetic acid, salts of perchloric acid, salts of p-toluenesulfonic acid, and salts of dodecylbenzenesulfonic acid are preferred.

  Specific examples of the alkali metal salt (F) include, for example, lithium acetate, sodium acetate, potassium acetate, lithium butyrate, sodium butyrate, potassium butyrate, lithium laurate, sodium laurate, potassium laurate, lithium myristate, myristic acid Sodium, potassium myristate, lithium palmitate, sodium palmitate, potassium palmitate, lithium stearate, sodium stearate, potassium stearate, lithium 12-hydroxystearate, sodium 12-hydroxystearate, potassium 12-hydroxystearate , Lithium chloride, sodium chloride, potassium chloride, lithium phosphate, sodium phosphate, potassium phosphate, lithium sulfate, sodium sulfate, lithium perchlorate, perchloric acid Thorium, potassium perchlorate, lithium p- toluenesulfonic acid, sodium p- toluenesulfonic acid, potassium p- toluenesulfonic acid, lithium dodecylbenzenesulfonate, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate and the like. Among these, lithium acetate, potassium acetate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, lithium chloride and the like are preferred.

  The compounding amount of the alkali metal salt (F) in the antistatic resin composition of the present invention is from 0.01 to 100 parts by mass of the synthetic resin from the viewpoint of durability of antistatic performance and crystallization. It can be 5.0 parts by mass, preferably 0.3 to 2.0 parts by mass, more preferably 0.4 to 1.0 part by mass. If the amount of the alkali metal salt (F) is less than 0.01 part by mass, the effect of adding the alkali metal salt (F) may be insufficient, and if the amount exceeds 5.0 parts by mass, the physical properties of the resin may be affected. May be exerted.

  The antistatic resin composition of the present invention may further contain a salt of a Group 2 element as long as the effects of the present invention are not impaired.

Examples of the salt of the Group 2 element include salts of an organic acid or an inorganic acid, and examples of the Group 2 element include beryllium, magnesium, calcium, strontium, barium, and the like.
Examples of the organic acid include aliphatic monocarboxylic acids having 1 to 18 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, and adipic acid Aliphatic carboxylic acids having 1 to 12 carbon atoms; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethane Examples thereof include sulfonic acids having 1 to 20 carbon atoms such as sulfonic acids.
Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like.

  Further, the antistatic resin composition of the present invention may contain a surfactant as long as the effects of the present invention are not impaired. As the surfactant, a nonionic, anionic, cationic or amphoteric surfactant can be used.

  Nonionic surfactants include polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; fatty acid esters of polyethylene oxide and glycerin And fatty acid esters of pentaerythritol, fatty acid esters of sorbit or sorbitan, alkyl ethers of polyhydric alcohols, and polyhydric alcohol-type nonionic surfactants such as aliphatic amides of alkanolamines.

  Examples of the anionic surfactant include a carboxylate such as an alkali metal salt of a higher fatty acid; a sulfate such as a higher alcohol sulfate or a higher alkyl ether sulfate; an alkylbenzene sulfonate; an alkyl sulfonate; Sulfonates such as paraffin sulfonates; phosphate esters such as higher alcohol phosphates; and the like.

  Examples of the cationic surfactant include a quaternary ammonium salt such as an alkyltrimethylammonium salt.

  Examples of the amphoteric surfactant include an amino acid-type amphoteric surfactant such as a higher alkylaminopropionate, a betaine-type amphoteric surfactant such as a higher alkyldimethylbetaine and a higher alkyldihydroxyethylbetaine, and the like. Two or more kinds can be used in combination.

  When the surfactant is compounded, the amount is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the synthetic resin.

  Furthermore, a polymer type antistatic agent may be added to the antistatic resin composition of the present invention as long as the effects of the present invention are not impaired. As the polymer antistatic agent, for example, a polymer type antistatic agent such as a known polyetheresteramide can be used, and as the known polyetheresteramide, for example, JP-A-7-10989 And polyetheresteramides comprising the above-mentioned bisphenol A polyoxyalkylene adducts. Further, a block polymer having a repeating structure in which a bonding unit between a polyolefin block and a hydrophilic polymer block has 2 to 50 can be used, and examples thereof include a block polymer described in US Pat. No. 6,552,131.

  When the polymer type antistatic agent is compounded, the compounding amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin.

  Furthermore, the antistatic resin composition of the present invention may contain an ionic liquid as long as the effects of the present invention are not impaired. Examples of the ionic liquid have a melting point below room temperature, at least one of the cations or anions constituting the ionic liquid is an organic ion, and the initial conductivity is preferably 1 to 200 ms / cm, more preferably A room-temperature molten salt of 10 to 200 ms / cm, for example, a room-temperature molten salt described in International Publication No. 95/15572.

  Examples of the cation constituting the ionic liquid include a cation selected from the group consisting of amidinium, pyridinium, pyrazolium and guanidinium cations.

The amidinium cations include the following.
(1) imidazolinium cations having 5 to 15 carbon atoms, for example, 1,2,3,4-tetramethylimidazolinium, 1,3-dimethylimidazolinium;
(2) imidazolium cations having 5 to 15 carbon atoms, for example, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium;
(3) Tetrahydropyrimidinium cation The one having 6 to 15 carbon atoms, for example, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetra Methyl-1,4,5,6-tetrahydropyrimidinium;
(4) Dihydropyrimidinium cation Examples thereof include those having 6 to 20 carbon atoms, such as 1,3-dimethyl-1,4-dihydropyrimidinium and 1,3-dimethyl-1,6-dihydropyrimidi. , 8-Methyl-1,8-diazabicyclo [5,4,0] -7,9-undecadienium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,10-un Decadienium.

  Examples of the pyridinium cation include those having 6 to 20 carbon atoms, such as 3-methyl-1-propylpyridinium and 1-butyl-3,4-dimethylpyridinium.

  Examples of the pyrazolium cation include those having 5 to 15 carbon atoms, such as 1,2-dimethylpyrazolium and 1-n-butyl-2-methylpyrazolium.

Examples of the guanidinium cation include the following.
(1) Guanidinium cation having an imidazolinium skeleton having 8 to 15 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3 , 4-trimethylimidazolinium;
(2) Guanidinium cation having an imidazolium skeleton having 8 to 15 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4 -Trimethylimidazolium;
(3) Guanidinium cation having a tetrahydropyrimidinium skeleton having 10 to 20 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydro Pyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium;
(4) A guanidinium cation having a dihydropyrimidinium skeleton having 10 to 20 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethyl-1,4-dihydropyrimidinium, 2-dimethylamino-1,3,4-trimethyl-1,6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4-dihydropyrimidinium, 2-diethylamino-1 , 3-Dimethyl-4-ethyl-1,6-dihydropyrimidinium.

  The above cations may be used alone or in combination of two or more. Among these, an amidinium cation, more preferably an imidazolium cation, and particularly preferably a 1-ethyl-3-methylimidazolium cation from the viewpoint of antistatic properties.

  In the ionic liquid, examples of the organic acid or inorganic acid constituting the anion include the following. Organic acids include, for example, carboxylic acids, sulfates, sulfonic acids and phosphates; inorganic acids include, for example, superacids (eg, borofluoric acid, tetrafluoroboric acid, perchloric acid, phosphorus hexafluoride) Acids, antimony hexafluoride and arsenate hexafluoride), phosphoric acid and boric acid. The above organic acids and inorganic acids may be used alone or in combination of two or more.

Among the organic and inorganic acids, are preferred from the viewpoint of antistatic properties of the ionic liquids, Hammett acidity function anion constituting the ionic liquid (-H _o) is 12 to 100, the superacid conjugate Bases, acids that form anions other than the conjugate base of super-strong acids, and mixtures thereof.

  Examples of anions other than the conjugate base of the super strong acid include halogen (eg, fluorine, chlorine and bromine) ions, alkyl (C 1 to C 12) benzenesulfonic acid (eg, p-toluenesulfonic acid and dodecylbenzenesulfonic acid) ) Ions and poly (n = 1-25) fluoroalkanesulfonic acid (e.g., undecafluoropentanesulfonic acid) ions.

  In addition, examples of the super strong acid include those derived from a protic acid and a combination of a protic acid and a Lewis acid, and a mixture thereof. Examples of the protic acid as a super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, and alkane ( C1-30 sulfonic acid (e.g., methanesulfonic acid, dodecanesulfonic acid, etc.), poly (n = 1-30) fluoroalkane (C1-30) sulfonic acid (e.g., trifluoromethanesulfonic acid, Pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and boron tetrafluoride. Of these, preferred from the viewpoint of ease of synthesis are borofluoric acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imidic acid, and bis (pentafluoroethylsulfonyl) imidic acid.

  Protic acids used in combination with Lewis acids include, for example, hydrogen halides (eg, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethane Sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof. Among these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of the ionic liquid.

  Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and a mixture thereof. Among these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of the ionic liquid.

  The combination of a protonic acid and a Lewis acid is optional, but examples of the super strong acid comprising these combinations include tetrafluoroboric acid, hexafluorophosphoric acid, tantalum hexafluoride, antimony hexafluoride, and hexafluoro acid. Tantalum sulfonic acid, boron tetrafluoride, hexafluorophosphoric acid, boron trifluoride, arsenic hexafluoride, and mixtures thereof.

  Among the above anions, preferred from the viewpoint of the antistatic property of the ionic liquid are conjugate bases of a superacid (a superacid composed of a protic acid and a superacid composed of a combination of a proton acid and a Lewis acid), and more preferred. Is a conjugate base of a super-strong acid consisting of a protic acid and a pro-acid and a super-strong acid consisting of boron trifluoride and / or phosphorus pentafluoride.

  Among the ionic liquids, preferred from the viewpoint of antistatic properties are ionic liquids having an amidinium cation, more preferred are ionic liquids having a 1-ethyl-3-methylimidazolium cation, and particularly preferred are 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide.

  When the ionic liquid is compounded, the compounding amount is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the synthetic resin.

  Furthermore, the antistatic resin composition of the present invention may contain a compatibilizer within a range not to impair the effects of the present invention. By blending the compatibilizer, the compatibility between the antistatic component and other components or the resin component can be improved. Examples of the compatibilizer include a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and a polyoxyalkylene group. -258850, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, or a block polymer having a polyolefin portion and an aromatic vinyl polymer portion. .

  The amount of the compatibilizer to be added is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the synthetic resin.

  In addition, the antistatic resin composition of the present invention may optionally contain any of known resin additives (for example, phenolic antioxidant, phosphorus antioxidant, thioether antioxidant) as long as the effects of the present invention are not impaired. , UV absorbers, hindered amine compounds, nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, antistatic agents different from the antistatic agent (A) of the present invention, pigments, dyes, etc. ) May be contained. Known resin additives may be added to the synthetic resin after being mixed with the antistatic agent (A) and the antibacterial agent (B), or may be separately added to the synthetic resin and molded. Is also good.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, and 2,2′-methylenebis ( 4-ethyl-6-tert-butylphenol), 2,2′-thiobis- (6-tert-butyl-4-methylphenol), 2,2′-thiodiethylenebis [3- (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2′-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, 2,2′-oxamide-bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , 2-ethylhexyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2,2'-ethylenebis (4,6-di-tert-butylphenol), 3,5 Polymer of di-tert-butyl-4-hydroxy-benzenepropanoic acid and an ester of C13-15 alkyl, 2,5-di-tert-amylhydroquinone, and a hindered phenol (trade name AO.OH manufactured by Adeka Palmarol Co.) .998), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2-tert-butyl -6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl]- 4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butylbenz [d , F] [1,3,2] -dioxaphosphobin, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [monoethyl (3,5-di -Tert-butyl-4-hydroxybenzyl) phosphonate] calcium salt, 5,7-bis (1,1-dimethylethyl) -3-hydroxy-2 (3H)- Reaction product of nzofuranone and o-xylene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, DL-a -Tocophenol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3,3-bis- (4′-hydroxy-3′-tert-butyl-phenyl) butanoic acid Glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, Distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-tert-butyl-4-h Roxybenzylthioacetate, thiodiethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-m-cresol), 2-octylthio- 4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3- Bis (4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, 4,4′-butylidenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -3-methylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl- 5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di -Tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3 5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- ( ', 5'-tert-Tributyl-4'-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol , 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 .5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], stearyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionamide, palmityl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide , Myristyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, lauryl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, etc. 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives and the like.
The amount of the phenolic antioxidant to be added is preferably 0.001 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, per 100 parts by mass of the synthetic resin.

Examples of the phosphorus antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctyl phenyl phosphite, Diphenyltridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, Bis (tridecyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecylphosphite, dinonylphenyl Bis (nonylphenyl) phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyldipropylene glycol diphosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,4-di-tert-butyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methyl Phenyl] phosphite, tri (decyl) phosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, distearylpentaerythritol diphosphite, a mixture of distearylpentaerythritol and calcium stearate, alkyl C10) Bisphenol A phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) ) Pentaerythritol diphosphite, tetraphenyl-tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidene diphe Nol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4 -Hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide, (1-methyl-1-propenyl-3-ylidene) tris (1,1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecylphosphite, 2,2′-methylenebis ( 4,6-di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methyl Bis (4,6-di-tert-butylphenyl) -octadecylphosphite, 2,2′-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphite, 4,4′-butylidenebis (3- Methyl-6-tert-butylphenylditridecyl) phosphite, tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphospho Pin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphesspiro [5,5] undecane, , 4,6-Tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4'-isopropylidene diphenol 12-15 alcohol phosphite, and the like.
When the phosphorus-based antioxidant is compounded, the amount is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 part by mass, per 100 parts by mass of the synthetic resin.

Examples of the thioether-based antioxidant include tetrakis [methylene-3- (laurylthio) propionate] methane and bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butyl. Phenyl) sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipro Pionate, lauryl / stearylthiodipropionate, 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-thiobis (6-tert-butyl-p-cresol), distearyl- Disulfide.
The amount of the thioether-based antioxidant to be added is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 part by mass, per 100 parts by mass of the synthetic resin.

Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methyl) Phenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- ( 2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tert -Octyl-6-benzotriazolylphenol), 2- (2-hydroxy Polyethylene glycol ester of -3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy -3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3- tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2- Hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [ 2- (2-hydroxy) such as 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole and 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole Phenyl) benzotriazoles Phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate , Dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl-4) Benzoates such as -hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate and behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2 '-Ethoxyoxanilide, 2-ethoxy-4'-dodecyl Substituted oxanilides such as oxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts; Alternatively, metal chelates, particularly salts of nickel and chromium, chelates and the like can be mentioned.
The amount of the ultraviolet absorber to be added is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 part by mass, per 100 parts by mass of the synthetic resin.

Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, and 2,2,6,6 -Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,2 3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6 -Tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Lysyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5 -Di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6 -Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6 6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N- Butyl-N- 2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2 , 4-Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraaza Dodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] amino Undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] Aminoundecane, bis {4- (1-octyloxy-2,2,6, (6-tetramethyl) piperidyl} decandionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate, TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals, and the like. Can be
When the hindered amine compound is compounded, the amount is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 part by mass, per 100 parts by mass of the synthetic resin.

Examples of the nucleating agent include sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate and lithium-2,2'-methylenebis (4,6-di-tert-butylphenyl). ) Phosphate, aluminum hydroxybis [2,2'methylenebis (4,6-di-tert-butylphenyl) phosphate], sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate and disodium bicyclo [2 2.2.1] Metal salts of carboxylic acids such as heptane-2,3-dicarboxylate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, bis (p-ethylbenzylidene) Sorbitol and bis (dimethylbenzene) Polyhydric alcohol derivatives such as dilidene) sorbitol, N, N ', N "-tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N', N" -tricyclohexyl-1,3 Amide compounds such as 1,5-benzenetricarboxamide, N, N'-dicyclohexylnaphthalenedicarboxamide and 1,3,5-tri (dimethylisopropoylamino) benzene.
The compounding amount when the nucleating agent is compounded is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass, based on 100 parts by mass of the synthetic resin.

Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis (diphenyl phosphate), (1-methylethylidene) ) -4,1-phenylenetetraphenyldiphosphate, 1,3-phenylenetetrakis (2,6-dimethylphenyl) phosphate, trade name ADK STAB FP-500 manufactured by ADEKA Corporation, trade name ADK STAB FP-600 manufactured by ADEKA Corporation Aromatic phosphate esters such as ADK STAB FP-800 (trade name, manufactured by ADEKA Corporation), and phosphonate esters such as divinyl phenylphosphonate, diallyl phenylphosphonate, and phenylphosphonic acid (1-butenyl). Phosphinic acid esters such as phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, bis (2-allylphenoxy) phosphazene, dicresylphosphazene, etc. Phosphazene compounds, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing flame retardants such as vinylbenzyl compounds containing phosphorus and red phosphorus, Metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolak type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebi (Pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, bromination Polyphenylene ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A-type dimethacrylate Pentabromobenzyl acrylate, and brominated flame retardants such as brominated styrene. These flame retardants are preferably used in combination with an anti-drip agent such as a fluororesin or a flame retardant aid such as a polyhydric alcohol or hydrotalcite.
When the flame retardant is compounded, the compounding amount is preferably 1 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the synthetic resin.

The lubricant is added for the purpose of imparting lubricity to the surface of the molded article and enhancing the effect of preventing damage. As the lubricant, for example, unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, stearic acid monoglyceride, sorbitan monopalmititate, Sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearic acid amide, oleic acid amide, ethylenebisstearic acid amide and the like can be mentioned. These may be used alone or in combination of two or more.
When blending the lubricant, the blending amount is preferably 0.01 to 2 parts by mass, more preferably 0.03 to 0.5 part by mass, based on 100 parts by mass of the synthetic resin.

Examples of the filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, Dolomite, mica, silica, alumina, potassium titanate whiskers, wollastenite, fibrous magnesium oxysulfate, and the like can be mentioned, and the particle diameter (the fiber diameter, fiber length, and aspect ratio in fibrous form) is appropriately selected and used. be able to. In addition, a filler that has been subjected to a surface treatment as necessary can be used.
The amount of the filler to be added is preferably 0.01 to 80 parts by mass, more preferably 1 to 50 parts by mass, based on 100 parts by mass of the synthetic resin.

Examples of the metal soap include salts of metals such as magnesium, calcium, aluminum, and zinc, and salts of saturated or unsaturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid.
The amount of the metal soap is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the synthetic resin.

ここで、一般式（４）中、ｘ１及びｘ２はそれぞれ下記式、
０≦ｘ２／ｘ１＜１０，２≦ｘ１＋ｘ２≦２０
で表される条件を満たす数を表し、ｐは０または正の数を表す。

ここで、一般式（５）中、Ａ^q-は、ｑ価のアニオンを表し、ｐは０または正の数を表す。
また、前記ハイドロタルサイト類における炭酸アニオンは、一部を他のアニオンで置換したものでもよい。 Examples of the hydrotalcites are complex salts of magnesium, aluminum, hydroxyl groups, carbonate groups and any water of crystallization known as natural products and synthetic products. And those in which a hydroxyl group or a carbonate group is substituted with another anion group. Specifically, for example, a metal of hydrotalcite represented by the following general formula (4) is converted into an alkali metal. And substituted ones. Further, as the Al—Li-based hydrotalcites, a compound represented by the following general formula (5) can also be used.

Here, in the general formula (4), x1 and x2 are the following formulas, respectively.
0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 ≦ 20
And p represents 0 or a positive number.

Here, in the general formula (5), A ^q- represents a q-valent anion, and p represents 0 or a positive number.
Further, the carbonate anion in the hydrotalcites may be one in which a part is substituted with another anion.

  The hydrotalcites may be those obtained by dehydrating water of crystallization, higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, and organic sulfonic acids such as alkali metal dodecylbenzenesulfonic acid. It may be coated with a metal salt, a higher fatty acid amide, a higher fatty acid ester or a wax.

The hydrotalcites may be natural products or synthetic products. Examples of the method for synthesizing the compound include JP-B-46-2280, JP-B-50-30039, JP-B-51-29129, JP-B-3-36839, JP-A-61-174270, and JP-A-61-174270. Known methods described in, for example, JP-A-5-179052 can be used. Further, the hydrotalcites can be used without being limited by the crystal structure, crystal particles and the like.
When the hydrotalcites are compounded, the amount is preferably 0.001 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the synthetic resin.

  As the pigment, commercially available pigments can also be used, for example, Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

  As the dye, azo dye, anthraquinone dye, indigoid dye, triarylmethane dye, xanthene dye, alizarin dye, acridine dye, stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamine dye, oxazine dye, phthalocyanine Dyes such as dyes and cyanine dyes, etc., may be mentioned, and these may be used as a mixture of two or more.

  The method for producing the antistatic resin composition of the present invention is not particularly limited, and the synthetic resin may contain an antistatic agent (A), an antibacterial agent (B), an alkali metal salt (F) if necessary, and other optional components. And any method commonly used can be used. For example, they may be mixed by kneading with a roll, kneading with a bumper, an extruder, a kneader, or the like, and mixing.

The antistatic agent (A) may be added as it is, or may be added after impregnating the carrier, if necessary. In order to impregnate the carrier, the mixture may be heated and mixed as it is, or if necessary, may be diluted with an organic solvent, then impregnated into the carrier, and then the solvent may be removed.
As such a carrier, those known as synthetic resin fillers and fillers, or flame retardants and light stabilizers which are solid at ordinary temperature can be used, for example, calcium silicate powder, silica powder, talc powder, alumina powder , Titanium oxide powder, or those obtained by chemically modifying the surface of these carriers, and the following flame retardants and antioxidants which are solid. Among these carriers, those obtained by chemically modifying the surface of the carrier are preferable, and those obtained by chemically modifying the surface of the silica powder are more preferable. These carriers preferably have an average particle size of 0.1 to 100 μm, more preferably 0.5 to 50 μm.

Further, as a method of blending the antistatic agent (A) into the synthetic resin, the block polymer (G), the antistatic agent (A) and the antibacterial agent (B) may be blended together or separately. May be.
Further, the antistatic agent (A) may be compounded by kneading the block polymer (G) and the compound (D) having a reactive functional group into the synthetic resin to synthesize the antistatic agent (A). At this time, the antibacterial agent (B) may be kneaded at the same time, or a method of obtaining a molded product by mixing the antistatic agent (A), the antibacterial agent (B), and the synthetic resin during molding such as injection molding. The masterbatch of the antistatic agent (A) and / or the antibacterial agent (B) and the synthetic resin may be manufactured in advance, and the masterbatch may be blended.

  Furthermore, the antistatic agent (A) and the antibacterial agent (B) may be mixed in advance and then mixed with the synthetic resin, and the antistatic agent synthesized by adding the antibacterial agent (B) during the reaction. (A) may be blended with the synthetic resin.

Next, the molded article of the present invention will be described.
The molded article of the present invention is obtained by molding the antistatic resin composition of the present invention. By molding the antistatic resin composition of the present invention, a molded article having excellent antistatic properties and antibacterial properties can be produced. The molding method is not particularly limited, and examples include extrusion, calendering, injection molding, roll, compression molding, blow molding, rotational molding, and the like. Resin plates, sheets, films, bottles, fibers, deformed products, and the like Moldings of various shapes can be manufactured.

  In general, when an antistatic agent is added, the physical properties often decrease. However, the molded article of the present invention has excellent antistatic properties and excellent persistence of the antibacterial effect, and has little decrease in physical properties. In particular, it has resistance to antistatic properties against wiping the surface of the molded product.

  The antistatic resin composition of the present invention and a molded article thereof are used for electric / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical care, coal, petroleum, rubber, leather, automobile, precision equipment, and wood. It can be used in a wide range of industrial fields such as building materials, civil engineering, furniture, printing, musical instruments, etc.

  More specifically, the antistatic resin composition of the present invention and a molded article thereof include a printer, a personal computer, a word processor, a keyboard, a PDA (small information terminal), a telephone, a copying machine, a facsimile, and an ECR (electronic cash register). Office), office equipment such as calculators, electronic organizers, cards, holders, stationery, etc., OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, home appliances such as lighting equipment, game machines, irons, kotatsu, TVs, VTRs, videos Cameras, boomboxes, tape recorders, minidiscs, CD players, speakers, AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, wires, cables, transformers , Deflection yoke, distribution board, clock and other electric and electronic parts and communication equipment, automotive interior and exterior , Plate making film, adhesive film, bottles, food containers, food packaging films, pharmaceutical and pharmaceutical wrap film, product packaging film, agricultural film, agricultural sheeting, used in applications such as greenhouse films.

  Furthermore, the antistatic resin composition of the present invention and a molded article thereof include a seat (filling, dress material, etc.), a belt, ceiling covering, a compatible top, an armrest, a door trim, a rear package tray, a carpet, a mat, a sun visor, and a foil cover. , Mattress covers, airbags, insulating materials, hanging hands, hanging bands, wire covering materials, electrical insulating materials, paints, coating materials, overlays, flooring, corner walls, carpets, wallpaper, wall coverings, exterior materials , Interior materials, roof materials, deck materials, wall materials, pillar materials, floor boards, fence materials, frames and profiles, windows and door profiles, shingles, panels, terraces, balconies, soundproofing boards, heat insulating boards, windows Materials, such as automobiles, vehicles, ships, aircraft, buildings, housing and construction materials, civil engineering materials, clothing, curtains, sheets, non-woven fabrics, plywood, plywood, carpets, doormats, sheets, buckets, Over vinegar, container, glasses, bags, cases, goggles, skis, it is possible to use racket, tents, household goods of musical instruments, etc., in various applications such as sporting goods.

Hereinafter, the present invention will be described specifically with reference to Examples.
An antistatic agent (A) was produced according to the following production examples. In the following Production Examples, the number average molecular weight was measured by the following method.

<Molecular weight measurement>
The number average molecular weight (hereinafter sometimes abbreviated as “Mn”) was measured by gel permeation chromatography (GPC) under the following measurement conditions.
Apparatus: GPC apparatus manufactured by JASCO Corporation Solvent: tetrahydrofuran Reference substance: polystyrene Detector: Differential refractometer (RI detector)
Column stationary phase: Shodex KF-804L manufactured by Showa Denko KK
Column concentration: 40 ° C
Sample concentration: 1mg / 1mL
Flow rate: 0.8 mL / min
Injection volume: 100 μL

[Production Example 1]
(Production of antistatic agent (A) -1)
In a separable flask, 656 g (4.55 mol) of 1,4-cyclohexanedimethanol as a diol, 708 g (4.84 mol) of adipic acid as an aliphatic dicarboxylic acid, and phthalic anhydride as an aromatic dicarboxylic acid 0.7 g (4.73 × 10 ⁻³ mol) of an antioxidant (tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane; trade name of ADEKA Corporation) 0.7 g of “ADK STAB AO-60”) was charged and polymerized at normal pressure for 5 hours while gradually raising the temperature from 160 ° C. to 210 ° C., and then polymerized at 210 ° C. under reduced pressure for 3 hours to obtain polyester (E) -1. Obtained. Polyester (E) -1 had an acid value of 28 and a number average molecular weight Mn of 5,400 in terms of polystyrene.

  Next, 600 g of the obtained polyester (E) -1 was used as a compound having at least one group represented by the general formula (1) and having hydroxyl groups at both ends, and a polyethylene glycol having a number average molecular weight of 4,000. 300 g of (C) -1, 0.5 g of an antioxidant (Adecastab AO-60) and 0.8 g of zirconium octylate were charged, and polymerized at 210 ° C. for 7 hours under reduced pressure to form carboxyl groups at both ends. The obtained block polymer (G) -1 was obtained. The acid value of the block polymer (G) -1 was 9, and the number average molecular weight Mn was 12,000 in terms of polystyrene.

  6 g of bisphenol F diglycidyl ether (D) -1 as a compound (D) having a reactive functional group of a polyepoxy compound was charged into 360 g of the obtained block polymer (G) -1 having a carboxyl group at both ends. Polymerization under reduced pressure at 240 ° C. for 3 hours to obtain an antistatic agent (A) -1.

[Production Example 2]
(Production of antistatic agent (A) -2)
In a separable flask, 289 g (1.87 mol) of 1,4-bis (β-hydroxyethoxy) benzene as a diol, 289 g (1.98 mol) of adipic acid as an aliphatic dicarboxylic acid, and aromatic dicarboxylic acid Then, 8 g (0.05 mol) of isophthalic acid and 0.5 g of an antioxidant (ADEKA STAB AO-60) were charged, and polymerized at normal pressure for 5 hours while gradually raising the temperature from 180 ° C. to 220 ° C. Thereafter, 0.5 g of tetraisopropoxytitanate was charged and polymerized at 220 ° C. under reduced pressure for 5 hours to obtain a polyester (E) -2. Polyester (E) -2 had an acid value of 56 and a number average molecular weight Mn of 4,900 in terms of polystyrene.

  300 g of the obtained polyester (E) -2, polyethylene glycol (C) having a number average molecular weight of 4,000 as a compound having at least one group represented by the general formula (1) and having hydroxyl groups at both ends. -1, 150 g of antioxidant (ADEKA STAB AO-60) and 0.5 g of zirconium acetate were charged, and polymerized under reduced pressure at 220 ° C. for 7 hours to obtain a block polymer having carboxyl at both terminals (G ) -2. The acid value of this block polymer (G) -2 was 11, and the number average molecular weight Mn was 12,300 in terms of polystyrene.

  To 300 g of the obtained block polymer (G) -2, 11 g of dicyclopentadienemethanol diglycidyl ether was charged as a compound (D) having a reactive functional group of a polyvalent epoxy compound, and the mixture was heated at 240 ° C. for 4 hours under reduced pressure. To obtain an antistatic agent (A) -2.

[Production Example 3]
(Production of antistatic agent (A) -3)
In a separable flask, 591 g of ethylene oxide adduct of bisphenol A as a diol, 235 g (1.16 mol) of sebacic acid as an aliphatic dicarboxylic acid, and 8 g (0.05 mol of isophthalic acid as an aromatic dicarboxylic acid) ), 300 g of polyethylene glycol (C) -2 having a number average molecular weight of 2,000 as a compound having at least one group represented by the general formula (1) and having hydroxyl groups at both ends, and an antioxidant (ADK STAB) AO-60) was charged in an amount of 0.8 g and polymerized at normal pressure for 5 hours while gradually raising the temperature from 180 ° C to 220 ° C. Thereafter, 0.6 g of tetraisopropoxytitanate was charged and polymerized at 220 ° C. under reduced pressure for 7 hours to obtain a block polymer (G) -3 having carboxyl at both ends. The acid value of the block polymer (G) -3 was 10, and the number average molecular weight Mn was 10,100 in terms of polystyrene.

  300 g of the obtained block polymer (G) -3 was charged with 7 g of epoxidized soybean oil (D) -3 and 0.5 g of zirconium acetate as a compound (D) having a reactive functional group of a polyvalent epoxy compound. Polymerization under reduced pressure at 240 ° C. for 5 hours to obtain an antistatic agent (A) -3.

  Using the antistatic agents (A) -1 to (A) -3 obtained by the above production method, test pieces were prepared by the following method and evaluated.

<Test specimen preparation conditions>
0.1 parts by mass of a phenolic antioxidant (trade name “ADK STAB AO-60” manufactured by ADEKA Corporation), 0.05 parts by mass of a phosphorus antioxidant (trade name “ADK STAB 2112” manufactured by ADEKA CORPORATION), calcium stearate A twin-screw extruder (product name: PCM30, 60) manufactured by Ikegai Co., Ltd. was obtained by blending 0.05 parts by mass and a resin composition blended based on the components and the amounts (parts by mass) shown in Tables 1 to 4 below. Using a mesh screen), granulation was performed at 230 ° C. and 9 kg / hour to obtain pellets.
The obtained pellets were molded using a horizontal injection molding machine (product name: NEX80) manufactured by Nissei Plastic Industry Co., Ltd. under the processing conditions of a resin temperature of 230 ° C. and a mold temperature of 50 ° C., and a test piece (100 mm × 100 mm × 3 mm) Was prepared.

<Method of measuring surface resistivity (SR value)>
The obtained test piece (100 mm × 100 mm × 3 mm) was stored immediately after the molding under the conditions of a temperature of 25 ° C. and a humidity of 60% RH. The surface resistivity (Ω / □) was measured using an R8340 resistance meter manufactured by Advantest Co., Ltd. under the conditions of an applied voltage of 500 V and an applied time of 1 minute. The measurement was performed for five points, and the average value was obtained. The results are shown in Tables 1 to 4, respectively.

<Antibacterial test method>
From the obtained test piece (100 mm x 100 mm x 3 mm), it was cut into 50 mm x 50 mm x 1 mm to obtain a test piece. 0.4 ml of a bacterial solution containing Escherichia coli is dropped on the surface of the test piece, a polyethylene film is put on the test piece, and stored at 34 to 36 ° C. and RH 90% or more for 24 hours. did.
The results are shown in Tables 1 to 4, respectively.

ポリプロピレン：ホモポリプロピレン（メルトフローレート（ＩＳＯ１１３３，２３０℃×２．１６ｋｇ）＝８ｇ／１０ｍｉｎ）
（Ｂ）−１：シナネンゼオミック社製、商品名「ゼオミックＡＪ１０Ｄ」（銀２．５％含有Ａ型ゼオライト）
（Ｂ）−２：東亜合成株式会社製、商品名「ノバロンＡＧ３００」（銀３．５％含有リン酸ジルコニウム）
（Ｆ）−１：ドデシルベンゼンスルホン酸ナトリウム
（Ｆ）−２：ｐ−トルエンスルホン酸リチウム

Polypropylene: homopolypropylene (melt flow rate (ISO 1133, 230 ° C x 2.16 kg) = 8 g / 10 min)
(B) -1: “Zeomic AJ10D” (trade name, manufactured by Sinanen Zeomic) (A type zeolite containing 2.5% silver)
(B) -2: "NOVALON AG300" (trade name, manufactured by Toa Gosei Co., Ltd. (zirconium phosphate containing 3.5% silver))
(F) -1: sodium dodecylbenzenesulfonate (F) -2: lithium p-toluenesulfonate

ポリプロピレン：ホモポリプロピレン（メルトフローレート（ＩＳＯ１１３３，２３０℃×２．１６ｋｇ）＝８ｇ／１０ｍｉｎ）
ＡＢＳ樹脂：テクノポリマー株式会社製 商品名「テクノＡＢＳ１１０」（メルトフローレート（ＩＳＯ１１３３、２２０℃×１０ｋｇ）＝２３ｇ／１０ｍｉｎ）
（Ｂ）−１：シナネンゼオミック社製、商品名「ゼオミックＡＪ１０Ｄ」（銀２．５％含有Ａ型ゼオライト）
（Ｂ）−２：東亜合成株式会社製、商品名「ノバロンＡＧ３００」（銀３．５％含有リン酸ジルコニウム）
（Ｆ）−１：ドデシルベンゼンスルホン酸ナトリウム
（Ｆ）−２：ｐ−トルエンスルホン酸リチウム

Polypropylene: homopolypropylene (melt flow rate (ISO 1133, 230 ° C x 2.16 kg) = 8 g / 10 min)
ABS resin: Techno Techno Co., Ltd. product name “Techno ABS110” (melt flow rate (ISO1133, 220 ° C. × 10 kg) = 23 g / 10 min)
(B) -1: “Zeomic AJ10D” (trade name, manufactured by Sinanen Zeomic) (A type zeolite containing 2.5% silver)
(B) -2: "NOVALON AG300" (trade name, manufactured by Toa Gosei Co., Ltd. (zirconium phosphate containing 3.5% silver))
(F) -1: sodium dodecylbenzenesulfonate (F) -2: lithium p-toluenesulfonate

ポリプロピレン：ホモポリプロピレン（メルトフローレート（ＩＳＯ１１３３，２３０℃×２．１６ｋｇ）＝８ｇ／１０ｍｉｎ）
（Ｂ）−１：シナネンゼオミック社製、商品名「ゼオミックＡＪ１０Ｄ」（銀２．５％含有Ａ型ゼオライト）
（Ｂ）−２：東亜合成株式会社製、商品名「ノバロンＡＧ３００」（銀３．５％含有リン酸ジルコニウム）
（Ｆ）−１：ドデシルベンゼンスルホン酸ナトリウム
（Ｆ）−２：ｐ−トルエンスルホン酸リチウム
比較化合物１：ポリエーテルエステルアミド型帯電防止剤、ＢＡＳＦ社製、商品名「イルガスタットＰ−１８」

Polypropylene: homopolypropylene (melt flow rate (ISO 1133, 230 ° C x 2.16 kg) = 8 g / 10 min)
(B) -1: “Zeomic AJ10D” (trade name, manufactured by Sinanen Zeomic) (A type zeolite containing 2.5% silver)
(B) -2: "NOVALON AG300" (trade name, manufactured by Toa Gosei Co., Ltd. (zirconium phosphate containing 3.5% silver))
(F) -1: Sodium dodecylbenzenesulfonate (F) -2: Lithium p-toluenesulfonate Comparative compound 1: Polyetheresteramide type antistatic agent, manufactured by BASF, trade name "Ilgastat P-18"

ＡＢＳ樹脂：テクノポリマー株式会社製 商品名「テクノＡＢＳ１１０」（メルトフローレート（ＩＳＯ１１３３、２２０℃×１０ｋｇ）＝２３ｇ／１０ｍｉｎ）
（Ｂ）−１：シナネンゼオミック社製、商品名「ゼオミックＡＪ１０Ｄ」（銀２．５％含有Ａ型ゼオライト）
（Ｂ）−２：東亜合成株式会社製、商品名「ノバロンＡＧ３００」（銀３．５％含有リン酸ジルコニウム）
（Ｆ）−１：ドデシルベンゼンスルホン酸ナトリウム
（Ｆ）−２：ｐ−トルエンスルホン酸リチウム
比較化合物２：ポリエーテルエステルアミド型帯電防止剤、ＢＡＳＦ社製、商品名「イルガスタットＰ−２０」

ABS resin: Techno Techno Co., Ltd. product name “Techno ABS110” (melt flow rate (ISO1133, 220 ° C. × 10 kg) = 23 g / 10 min)
(B) -1: “Zeomic AJ10D” (trade name, manufactured by Sinanen Zeomic) (A type zeolite containing 2.5% silver)
(B) -2: "NOVALON AG300" (trade name, manufactured by Toa Gosei Co., Ltd. (zirconium phosphate containing 3.5% silver))
(F) -1: Sodium dodecylbenzenesulfonate (F) -2: Lithium p-toluenesulfonate Comparative compound 2: Polyetheresteramide type antistatic agent, manufactured by BASF, trade name "IRGASTAT P-20"

  As shown in the above table, from Comparative Examples 6 to 8 and Comparative Examples 14 to 16, when an antistatic agent different from the antistatic agent (A) of the present invention was used, the antistatic properties were poor. Also, from the comparison between Comparative Examples 4 and 7, and between Comparative Examples 12 and 15, when an antistatic agent different from the antistatic agent (A) according to the present invention was used, the antibacterial properties were slightly reduced. On the other hand, from a comparison between Comparative Example 4 and Example 5 and Comparative Example 13 and Comparative Example 11, when the antistatic agent (A) according to the present invention was used, the antistatic agent (A) was added. No decrease in antibacterial activity was observed.

Further, from Comparative Examples 2 and 10, although the antistatic property cannot be improved only by the alkali metal salt (F), the comparison between Example 2 and Example 5 shows that the antistatic agent (A) and When the alkali metal salt (F) was added, the antistatic property was improved. Further, from Example 9 and Example 10, it was confirmed that the antistatic agent (A) according to the present invention can obtain the expected effect on the ABS resin. Furthermore, it was confirmed that the antistatic effect of the antistatic resin composition of the present invention was maintained after 30 days.
From the above, it was confirmed that the antistatic resin composition of the present invention has both continuous antistatic properties and excellent antibacterial properties.

Claims (5)

An antistatic resin composition containing 3 to 60 parts by mass of an antistatic agent (A) and 0.1 to 20 parts by mass of an antibacterial agent (B) based on 100 parts by mass of a synthetic resin,
The antistatic agent (A) is composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, and is represented by a block composed of a polyester (E) having a carboxyl group at both terminals and a general formula (1) shown below. Reaction with a block polymer (G) having carboxyl groups at both ends, wherein blocks composed of a compound (C) having at least one group and having hydroxyl groups at both ends are alternately and repeatedly bonded via ester bonds; compounds having a sexual functional group and (D) but state, and are polymer compounds having a binding combined comprising structure via an ester bond,
The number average molecular weight of the block composed of the polyester (E) is 800 to 8,000 in terms of polystyrene, and the number average molecular weight of the block composed of the compound (C) is 400 to 6,000 in terms of polystyrene. And the number average molecular weight of the block polymer (G) is 5,000 to 25,000 in terms of polystyrene,
The compound (C) is a polyethylene glycol, and the compound (D) having a reactive functional group is a polyvalent epoxy compound having two or more epoxy groups .

Further, antistatic resin composition according to claim 1 containing 0.01 to 5 parts by weight of one or more alkali metal salts (F). 3. The antistatic resin composition according to claim 1, wherein the antibacterial agent (B) is a compound of an inorganic metal salt. The antistatic resin composition according to any one of claims 1 to 3 , wherein the synthetic resin is a polyolefin-based resin or a styrene-based resin. A molded article obtained by molding the antistatic resin composition according to any one of claims 1 to 4 .