JP2017114927A - Antistatic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic resin composition in which an excellent antistatic property and a sustained effect are maintained, and the antibacterial property is also excellent.SOLUTION: There is provided an antistatic resin composition containing 3 to 60 pts.mass of an antistatic agent (A) and 0.1 to 20 pts.mass of an antimicrobial agent (B) per 100 pts.mass of a synthetic resin; and said antistatic agent (A) is a polymer compound having a structure in which a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a compound (C) having one or more groups represented by the following general formula (1) and hydroxyl groups at both terminals, and a compound (D) having a reactive functional group are bonded via an ester bond or via an ester bond and an amide bond.SELECTED DRAWING: None

Description

  The present invention relates to an antistatic resin composition that is not only excellent in antistatic properties but also excellent in antibacterial properties against dust and fungal growth.

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

  Among these, a synthetic resin having an insulating property and a property of being easily charged has a problem of attracting dust and dust and deteriorating the appearance of the product. In addition, when the molded product is an electronic product, the circuit may not operate normally due to charging. Furthermore, an electric shock may be generated from the charged resin member, and not only does the user feel uncomfortable when the electric shock is received, but there is a possibility of causing an explosion accident in the presence of flammable gas or dust.

  In order to prevent the resin member from being charged, conventionally, an antistatic agent is added to the resin. 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 together with the resin. There was a problem that the antistatic agent was 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 hand grips, etc., change to black or brown with long-term use. The cause is propagation of bacteria such as mold.
Furthermore, agricultural greenhouses have a problem in that the permeability is reduced due to adhesion of dust, soot, pollen, soot, moss, spores and the like, which affects the harvest of crops. Furthermore, in recent highly airtight houses, house dust such as dust and dust in the room increases due to insufficient ventilation, and dust adheres to the surface of the charged resin member, from which bacteria such as mold propagate. There was a problem that damaged the living environment.

  In order to prevent the growth of bacteria such as mold, a method of applying an antibacterial agent to the resin member is known, but there is a problem that the antibacterial property is lost by wiping. Moreover, when knead | mixing and shape | molding resin and an antibacterial agent, what can endure the molding temperature of a synthetic resin is required. Normal antibacterial agents not only decompose due to molding temperature and cannot exhibit antibacterial performance, but also have adverse effects such as coloring resin members and lowering physical properties of molded products.

  From such a viewpoint, there is a demand for an antistatic resin composition that can exhibit sustained antistatic properties and sufficient antibacterial effects. For example, Patent Document 1 and Patent Document 2 propose an antibacterial soot composition in which anti-soot bamboo extract is adsorbed on silica gel as an antibacterial agent such as polyether ester amide or conductive whisker as an antistatic agent. In addition, in the patent documents 3 and 4, the present applicant has proposed an antistatic resin composition containing a polyether ester polymer type antistatic agent.

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

  However, an antistatic agent comprising a polyether ester amide cannot obtain a sufficient antistatic performance unless it is added in a large amount to the resin. Moreover, although the antibacterial agent which can prevent the proliferation of the microorganisms which exist in a washing machine is shown, the antimicrobial property with respect to colon_bacillus | E._coli is not described. In addition, since the antistatic agent disclosed by patent document 3, 4 does not contain aromatic dicarboxylic acid, a structure differs from the antistatic agent which concerns on this invention.

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

As a result of intensive studies to solve the above problems, the present inventors have 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) with respect to 100 parts by mass of the synthetic resin. A functional resin composition comprising:
The antistatic agent (A) is a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a compound (C) having one or more groups represented by the following general formula (1) and having hydroxyl groups at both ends; and The compound (D) having a reactive functional group is a polymer compound having a structure formed by bonding via an ester bond or via an ester bond and an amide bond.

  In the antistatic resin composition of the present invention, the antistatic agent (A) is a polyester (E) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, the compound (C) and the reaction. The compound (D) having a functional functional group is preferably bonded via an ester bond or via an ester bond and an amide bond.

  In the antistatic resin composition of the present invention, the antistatic agent (A) is composed of a block composed of the polyester (E) and a block composed of the compound (C) repeated via an ester bond. The block polymer (G) having a carboxyl group at both ends formed by alternately bonding and the compound (D) having the reactive functional group are bonded via an ester bond or via an ester bond and an amide bond. It preferably has a structure formed by bonding.

  Furthermore, in the antistatic resin composition of the present invention, the polyester (E) preferably has a structure having carboxyl groups at both ends.

  Furthermore, in the antistatic resin composition of the present invention, the number average molecular weight of the block composed of the polyester (E) is 800 to 8,000 in terms of polystyrene, and is composed of the compound (C). The number average molecular weight of the block is preferably 400 to 6,000 in terms of polystyrene, and the number average molecular weight of the block polymer (G) is preferably 5,000 to 25,000 in terms of polystyrene.

  Furthermore, in the antistatic resin composition of the present invention, the compound (C) is more preferably polyethylene glycol.

  Furthermore, in the antistatic resin composition of the present invention, the compound (D) having a reactive functional group is a polyvalent epoxy compound having two or more epoxy groups, and a polyhydric alcohol having three or more hydroxyl groups. Preferably, the compound is selected from a compound and a polyvalent amine compound having two or more amino groups.

  Furthermore, 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).

  Furthermore, 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 resin or a styrene resin.

  The molded article of the present invention is formed by molding the 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 synthetic resins 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, crosslinked polyethylene, ultrahigh 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, chlorinated 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-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexyl maleimide copolymer;
Vinyl group-containing aromatic hydrocarbon homopolymer, vinyl group-containing aromatic hydrocarbon and other monomers (for example, maleic anhydride, phenylmaleimide, (meth) acrylic acid ester, butadiene, (meth) acrylonitrile) Etc.) (for example, 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-ethylenepropylene Go -Thermoplastic resins such as styrene (AES) resin, styrene-butadiene-butylene-styrene (SBBS) resin, methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin, and double bonds of these butadienes or isoprenes to hydrogen 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 resins such as hydrogenated styrene 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, polycyclohexanedimethylene terephthalate;
Aromatic polyesters such as polyalkylene naphthalates 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);
Polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonate, polycarbonate / ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, fiber resin, polyimide resin, polysulfone, polyphenylene ether, polyether ketone, poly Examples include ether ether ketone and liquid crystal polymer.

  These synthetic resins include isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluorine rubber, silicone rubber, olefin elastomer, styrene elastomer, polyester elastomer, nitrile elastomer, It may be an elastomer such as nylon elastomer, vinyl chloride elastomer, polyamide elastomer, polyurethane elastomer or the like, and may be used in combination. In the present invention, these synthetic resins may be used alone or in combination of two or more. The synthetic resin may be alloyed.

  These synthetic resins include molecular weight, degree of polymerization, density, softening point, proportion of insoluble matter in the solvent, degree of stereoregularity, presence or absence of catalyst residues, types and blending ratios of raw materials, and types of polymerization catalyst ( For example, it can be used regardless of Ziegler catalyst, metallocene catalyst, etc.). Among these synthetic resins, those containing one or more of polyolefin resins, halogen-containing resins, styrene resins, aromatic polyesters, linear polyesters, polyamides, and polycarbonates are preferable from the viewpoint of antistatic properties. Among these, polyolefin resins and styrene resins are preferable.

Next, the antistatic agent (A) will be described. The antistatic agent (A) is blended in order 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, one or more groups represented by the following general formula (1), and has hydroxyl groups at both ends. The compound (C) and the compound (D) having a reactive functional group can be produced by bonding 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 via an ester bond and an amide bond.

  The polyester (E) is only required to be composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and includes a residue obtained by removing the hydroxyl group of the diol and a residue obtained by removing the carboxyl group of the aliphatic dicarboxylic acid. , Having a structure bonded through an ester bond, and having a structure in which a residue excluding a hydroxyl group of a diol and a residue excluding a carboxyl group of an aromatic dicarboxylic acid are bonded through an ester bond Those 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 2-50.

Examples of the diol used in the present invention include aliphatic diols and aromatic group-containing diols. 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-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentane Diol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanedio 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-cyclohexanedimethanol and hydrogenated bisphenol A are preferable from the viewpoint of sustaining antistatic performance, and 1,4-cyclohexanedimethanol is more preferable.

  Moreover, since it is preferable that an aliphatic diol has hydrophobicity, you should avoid using polyethylene glycol which has hydrophilicity alone among aliphatic diols. However, this is not the case when used with a hydrophobic diol.

  Examples of the aromatic group-containing diol include bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, ethylene oxide adduct of bisphenol A, Examples include propylene oxide adducts of bisphenol A, polyhydroxyethyl adducts of mononuclear dihydric phenol compounds such as 1,4-bis (2-hydroxyethoxy) benzene, resorcin, 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 an aliphatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.). When the polyester (E) is produced using the derivative, The reaction may finally proceed to obtain a block polymer (G) having a structure having carboxyl groups at both ends. The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more.

  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, azelain 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, aliphatic dicarboxylic acids having 4 to 16 carbon atoms are preferable, and aliphatic dicarboxylic acids having 6 to 12 carbon atoms are more preferable from the viewpoint of melting point and heat resistance.

Next, the aromatic dicarboxylic acid used in the present invention will be described.
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, etc.). When the polyester (E) is produced using the derivative, The reaction may finally proceed to obtain a block polymer (G) having a structure having carboxyl groups at both ends. Moreover, 2 or more types of mixtures may be sufficient as aromatic dicarboxylic acid and its derivative (s).

  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 Examples include 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 one or more groups represented by the above general formula (1) and having hydroxyl groups at both ends used in the present invention will be described.
The compound (C) is preferably a hydrophilic compound, and particularly preferably 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 20 to 150 from the viewpoint of heat resistance and compatibility.

  As the compound (C), in addition to polyethylene glycol obtained by addition reaction of the group represented by the general formula (1), ethylene oxide and other alkylene oxides (for example, propylene oxide, 1,2-, 1, 4-, 2,3- or 1,3-butylene oxide and the like, and polyether obtained by addition reaction. This polyether may be either random or block.

  Further examples of the compound (C) include compounds having a structure in which ethylene oxide is added to an active hydrogen atom-containing compound, ethylene oxide and other alkylene oxides (for example, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and the like). 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 glycol, C2-C20 aliphatic glycol, C5-C12 alicyclic glycol, C8-C26 aromatic glycol, etc. can be used.

  Examples of the aliphatic glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-butanediol, Hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecane Examples include diol, 1,20-eicosanediol, diethylene glycol, triethylene glycol, and thiodiethylene glycol.

  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. Examples include -1,3-propanediol, triphenylethylene glycol, tetraphenylethylene glycol, and benzopinacol.

  As the dihydric phenol, phenol having 6 to 30 carbon atoms can be used, for example, catechol, resorcinol, 1,4-dihydroxybenzene, hydroquinone, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxydiphenylthioether, binaphthol. And these alkyls (having 1 to 10 carbon atoms) or halogen substituents.

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

  Secondary diamines include aliphatic secondary diamines having 4 to 18 carbon atoms, heterocyclic secondary diamines having 4 to 13 carbon atoms, alicyclic secondary diamines 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 Etc.

  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, N, N′-dibutyl-1,2- Cyclobutanediamine, N, N'-dimethyl-1,4-cyclohexanediamine, N, N'-diethyl-1,4-cyclohexanediamine, N, N'-dibutyl-1,4-cyclohexanediamine, N, N'- Examples include dimethyl-1,3-cyclohexanediamine, N, N′-diethyl-1,3-cyclohexanediamine, and N, N′-dibutyl-1,3-cyclohexanediamine.

  Examples of the aromatic secondary diamine include N, N′-dimethyl-phenylenediamine, N, N′-dimethyl-xylylenediamine, N, N′-dimethyl-diphenylmethanediamine, and 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, and N-methyldipropanolamine.

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

  Examples of the aliphatic dicarboxylic acid include 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, undecanedioic acid, dodecanedioic acid, tridecanediic acid, tetradecanediic acid, hexadecanediic acid, octadecanediic acid and icosandiic acid.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, and biphenyl-2. 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. Examples include acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid and dicyclohexyl-4,4′-dicarboxylic acid.

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

Next, the compound (D) having a reactive functional group will be described.
Regarding the compound (D) having a reactive functional group in the present invention, the 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 are: , An ester bond or an amide bond, or a block composed of the polyester (E) and a block composed of the compound (C), which are alternately and repeatedly bonded via an ester bond. Any block polymer (G) having a carboxyl group at the terminal and a compound (D) having a reactive functional group may be bonded via an ester bond or an amide bond.

  The compound (D) having a reactive functional group may be any compound that binds to a carboxyl group via an ester bond, or any compound that binds via an amide bond. Examples thereof include polyvalent epoxy compounds, polyhydric alcohol compounds, and polyvalent amine compounds.

The polyvalent 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, resorcin, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (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 4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, polyglycidyl ether compounds of polynuclear polyphenols such as terpene phenol Polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct Maleic acid, fumaric acid, itaconic acid, co Succinic 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 Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as phthalic acid and endomethylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) epoxy compounds having a glycidylamino group such as methane and diglycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4 -Epoxy Epoxidized products of cyclic olefin compounds such as chlorohexane carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; Examples thereof include epoxidized conjugated diene polymers such as polybutadiene and epoxidized styrene-butadiene copolymer, heterocyclic compounds such as triglycidyl isocyanurate, and epoxidized soybean oil.
In addition, these polyvalent epoxy compounds can be obtained by using those internally crosslinked by terminal isocyanate prepolymers or polyvalent active hydrogen compounds (polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphate esters, etc.). The molecular weight may be used. Two or more kinds of such polyvalent epoxy 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, 2 -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-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5 -Pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, ditrimethylolpropane, sorbitan, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N Tetravalent alcohols such as', N'-tetrakis (2-hydroxyethyl) ethylenediamine; pentavalent alcohols such as adonitol, arabitol, xylitol, triglycerin; dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, allose A hexahydric alcohol such as Tripentaerythritol, and the like. Moreover, there is no restriction | limiting in particular in the molecular weight of a polyhydric alcohol compound, High molecular weight polyhydric alcohols, such as polypentaerythritol and polyvinyl alcohol, can be used, Polyester polyhydric alcohol etc. can also be used. Two or more kinds of such 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 heptamethylenediamine, octamethylenediamine, decamethylenediamine, etc .; aliphatic amines such as 2,2 ′, 2 ″ -triaminotriethylamine and bis (hexamethylene) triamine, diethylenetriamine, etc. A polyalkylene polyamine having an alkylene group of 2 to 6 carbon atoms and a polymerization degree of 2 to 5; 1,6,11-undecantriamine, 1,8-diamino-4-aminomethyloctane, 1,3,6-hexamethylene Alkanetriamines such as triamine; melamine, piperazine; N N-aminoalkylpiperazine having 2 to 6 carbon atoms in the alkylene group, such as aminoethylpiperazine; heterocyclic polyamines such as heterocyclic polyamine described in JP-B No. 55-21044, isophoronediamine, bicycloheptane C4-C20 alicyclic polyamine such as triamine; carbon atoms such as phenyldiamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine, triphenylmethanetriamine Examples include aromatic polyamines of formula 6 to 20. Two or more kinds of such polyvalent amine compounds may be used.

  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. The compound (D) preferably 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) includes a block composed of a polyester (E) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and the compound (C). A block polymer (G) having carboxyl groups at both ends, in which the constituted block is repeatedly and alternately bonded via an ester bond, and the compound (D) having the reactive functional group are an ester bond or an amide bond. It is preferable to have a structure formed by bonding via the.

  The polyester (E) having carboxyl groups at both ends can be obtained, for example, by subjecting the aliphatic dicarboxylic acid 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, etc.). When the polyester (E) is obtained using the derivative, It is sufficient that the both ends are finally treated to form carboxyl groups, and the reaction for proceeding to the next block polymer (G) having a structure having carboxyl groups at both ends may be proceeded as it is. The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more.

  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, etc.). When the polyester (E) is obtained using the derivative, It is sufficient that the both ends are finally treated to form carboxyl groups, and the reaction for proceeding to the next block polymer (G) having a structure having carboxyl groups at both ends may be proceeded as it is. Moreover, 2 or more types of mixtures may be sufficient as aromatic dicarboxylic acid and its derivative (s).

  In the polyester (E), the 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 is 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 polycondensation reaction of the aliphatic dicarboxylic acid or derivative thereof and the aromatic dicarboxylic acid or derivative thereof with the diol.

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

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

  Further, depending on the blending ratio and reaction conditions, there are cases where 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. They may be mixed in E), or they may be reacted with the compound (C) as they are to obtain the block polymer (G).

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

  In addition, aliphatic dicarboxylic acids and aromatic dicarboxylic acids can be obtained by reacting them with a diol when 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 terminal may be treated to form a dicarboxylic acid, and the reaction may proceed to the next reaction for obtaining a block polymer (G) having a structure having carboxyl groups at both ends in the same state.

  A suitable polyester (E) comprising a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid and having a carboxyl group at both ends forms an ester bond by reacting with the compound (C), and the block polymer (G) Any structure may be used, and the carboxyl groups at both ends may be protected, modified, or in the form of a precursor. Moreover, in order to suppress the oxidation of a product at the time of reaction, you may add antioxidants, such as a phenolic antioxidant, to a reaction system.

  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 ends may be protected. It may also 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). Have a structure in which they are repeatedly and alternately bonded through ester bonds formed by carboxyl groups and hydroxyl groups. An example of such a block polymer (G) is, for example, one having a structure represented by the following general formula (3).

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

  A part of the block composed of the polyester (E) in the block polymer (G) is composed of a polyester composed only of a diol and an aliphatic dicarboxylic acid, or composed only of a diol and an aromatic dicarboxylic acid. It may be replaced with a block made of polyester.

  The block polymer (G) having a structure having carboxyl groups at both ends is a polycondensation reaction between the polyester (E) having carboxyl groups at both ends and the compound (C) having hydroxyl groups at both ends. A structure equivalent to that having a structure in which the polyester (E) and the compound (C) are alternately and repeatedly bonded through ester bonds formed by carboxyl groups and hydroxyl groups. It is not always necessary to synthesize from the polyester (E) and the compound (C).

  The reaction ratio between the polyester (E) and the compound (C) is adjusted so that the compound (C) is X mol and the polyester (E) is X + 1 mol with respect to X mol. A block polymer (G) having the following can be preferably obtained.

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

  For the polycondensation reaction, a catalyst that promotes the esterification reaction may be used. As the catalyst, conventionally known ones such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used. Moreover, in order to suppress the oxidation of a product at the time of reaction, you may add antioxidants, such as a phenolic antioxidant, to a reaction system.

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

  The antistatic agent (A) according to the present invention comprises a carboxyl group at the end of a block polymer (G) having a structure having a carboxyl group at both ends, a polyvalent epoxy compound having two or more epoxy groups, a hydroxyl group of 3 The polyhydric alcohol compound having two or more, or the polyamine compound having two or more amino groups is a carboxyl group at the terminal of the block polymer (G), an epoxy group of the polyhydric epoxy compound, a hydroxyl group or a polyhydric group of the polyhydric alcohol compound. It preferably has a structure formed by bonding via an ester bond or an amide bond formed by an amino group of a polyvalent amine compound. The antistatic agent (A) further includes an ester bond formed from a carboxyl group of the polyester (E) and an epoxy group of a polyvalent epoxy compound, a hydroxyl group of a polyhydric alcohol compound, or an amino group of a polyvalent amine. An amide bond may be included.

  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 What is necessary is just to make it react with the amino group of a polyvalent amine compound.

  In the case where the component (D) is a polyvalent epoxy compound having two or more epoxy groups, the number of epoxy groups in the polyvalent epoxy compound is 0.5 to 5 which is the number of carboxyl groups in the block polymer (G) to be reacted. The equivalent is preferable, and 0.5 to 1.5 equivalent is more preferable.

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

  In the case where the component (D) is a polyhydric alcohol compound having 3 or more hydroxyl groups, the number of hydroxyl groups in the polyhydric alcohol compound is 0.5 to 5 equivalents of the number of carboxyl groups in the block polymer (G) to be reacted. Preferably, 0.5 to 1.5 equivalents are more preferable.

  The polyhydric alcohol compound (D) having three or more hydroxyl groups to be reacted is preferably 0.1 to 2.0 equivalents, 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 polyvalent amine compound having two or more amino groups, the number of amino groups of the polyvalent amine compound is 0.5 to 5 which is the number of carboxyl groups of the block polymer (G) to be reacted. The equivalent is preferable, and 0.5 to 1.5 equivalent is more preferable.

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

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

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

  In the present invention, the number average molecular weight of the block composed of the polyester (E) in the antistatic agent (A) is preferably 800 to 8,000 in terms of polystyrene, more preferably 1,000 to 6,000. More preferably, it is 2,000 to 4,000. In addition, 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, more preferably 1,000 in terms of polystyrene. It is -5,000, More preferably, it is 2,000-4,000.

  Furthermore, 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, it is 7,000-17,000, More preferably, it is 9,000-13,000.

  In addition, 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 without isolating the polyester (E). And / or reaction with the compound (D) having a reactive functional group.

  When mix | blending antistatic agent (A) with a synthetic resin, it is 3-60 mass parts with respect to 100 mass parts of synthetic resins, and 5-18 mass parts from a viewpoint of antistatic property and ion elution suppression. 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 product 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 that exhibit 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 capable of withstanding the molding processing temperature of the synthetic resin are preferable, and it is particularly desirable to use a compound of an inorganic metal salt.
The blending amount of the antibacterial agent needs to be 0.1 to 20 parts by mass with respect to 100 parts by mass of the synthetic resin, and is preferably in the range of 0.2 to 10 parts by mass. If the blending amount of the antibacterial agent is less than 0.1 parts by mass, antibacterial properties cannot be obtained, and if it 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 sustainability and 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 acid, acetic acid, propionic acid, butyric acid, lactic acid, pentanoic acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid C 1-18 aliphatic monocarboxylic acids such as stearic acid, 12-hydroxystearic acid; C 1-12 carbon atoms such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid Aliphatic dicarboxylic acids; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; carbon atoms such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethanesulfonic acid 1 -20 sulfonic acids and the like. Examples of inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like. Among these, lithium, sodium, and potassium are more preferable from the viewpoint of antistatic properties, and lithium and sodium are most preferable. From the viewpoint of antistatic properties, acetic acid salts, perchloric acid salts, p-toluenesulfonic acid salts, and dodecylbenzenesulfonic acid salts 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 preferable.

  The blending 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 with respect to 100 parts by mass of the synthetic resin from the viewpoint of durability of antistatic performance and crystallinity. The amount can be 5.0 parts by mass, preferably 0.3 to 2.0 parts by mass, and more preferably 0.4 to 1.0 parts by mass. If the amount of the alkali metal salt (F) is less than 0.01 parts by mass, the effect of adding the alkali metal salt (F) may not be sufficient, and if it exceeds 5.0 parts by mass, the physical properties of the resin are affected. May affect.

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

  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, nonionic, anionic, cationic or amphoteric surfactants 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; polyethylene oxide, fatty acid esters of glycerin And polyvalent alcohol type nonionic surfactants such as fatty acid esters of pentaerythritol, fatty acid esters of sorbit or sorbitan, alkyl ethers of polyhydric alcohols, aliphatic amides of alkanolamines, and the like.

  Examples of the anionic surfactant include carboxylates such as alkali metal salts of higher fatty acids; sulfates such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfonates, alkyl sulfonates, Examples thereof include sulfonates such as paraffin sulfonates; phosphate esters such as higher alcohol phosphates.

  Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts.

  Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, betaine-type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkyldihydroxyethylbetaines, and these are used alone or Two or more types can be used in combination.

  0.1-5 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending surfactant, 0.5-2 mass parts is more preferable.

  Furthermore, the antistatic resin composition of the present invention may be blended with a polymer type antistatic agent 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 polyether ester amide can be used, and examples of the known polyether ester amide include those described in JP-A-7-10989. And polyether ester amides comprising the polyoxyalkylene adducts of bisphenol A described. Moreover, the block polymer which has a repeating structure whose coupling unit of a polyolefin block and a hydrophilic polymer block is 2-50 can be used, For example, the block polymer of US Patent 6552131 can be mentioned.

  0.1-10 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending a polymer type antistatic agent, 0.5-5 mass parts is more preferable.

  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 are those having a melting point of room temperature or lower and at least one of 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 following are mentioned as an amidinium cation.
(1) Imidazolinium cation Examples include those having 5 to 15 carbon atoms, such as 1,2,3,4-tetramethylimidazolinium and 1,3-dimethylimidazolinium;
(2) Imidazolium cation Examples include those having 5 to 15 carbon atoms, such as 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium;
(3) Tetrahydropyrimidinium cation One having 6 to 15 carbon atoms is exemplified, for example, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetra Methyl-1,4,5,6-tetrahydropyrimidinium;
(4) Dihydropyrimidinium cation A thing with 6-20 carbon atoms is mentioned, for example, 1,3-dimethyl-1,4-dihydropyrimidinium, 1,3-dimethyl-1,6-dihydropyrimidi Ni, 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.

The following are mentioned as a guanidinium cation.
(1) Guanidinium cation having an imidazolinium skeleton One having 8 to 15 carbon atoms is exemplified, for example, 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3 , 4-trimethylimidazolinium;
(2) Guanidinium cation having an imidazolium skeleton, those having 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4 -Trimethylimidazolium;
(3) A 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, such as 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 cation may be used alone or in combination of two or more. Among these, from the viewpoint of antistatic properties, an amidinium cation is preferable, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

  In the ionic liquid, examples of the organic acid or inorganic acid constituting the anion include the following. Examples of the organic acid include carboxylic acid, sulfuric acid ester, sulfonic acid and phosphoric acid ester; examples of the inorganic acid include super strong acid (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, phosphorus hexafluoride). Acid, hexafluoroantimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid. The organic acid and inorganic acid may be used singly or in combination of two or more.

Among the above organic acids and inorganic acids, from the viewpoint of antistatic properties of the ionic liquid, a super strong acid conjugate in which the Hammett acidity function (−H _o ) of the anion constituting the ionic liquid is 12 to 100 is preferable. Bases, acids that form anions other than conjugate bases of super strong acids, and mixtures thereof.

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

  Examples of super strong acids include those derived from proton acids, combinations of proton acids and Lewis acids, and mixtures thereof. Examples of the protonic acid as the super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane ( 1 to 30 carbon atoms) sulfonic acid (for example, methanesulfonic acid, dodecanesulfonic acid, etc.), poly (n = 1 to 30) fluoroalkane (1 to 30 carbon atoms) sulfonic acid (for example, trifluoromethanesulfonic acid, Pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboric acid. Of these, borofluoric acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imidic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferable from the viewpoint of ease of synthesis.

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

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

  The combination of the protonic acid and the Lewis acid is arbitrary, but examples of the super strong acid composed of these combinations include tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, hexafluoride. Tantalum sulfonate, tetrafluoroboronic acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride and mixtures thereof.

  Of the above anions, preferred from the viewpoint of antistatic properties of the ionic liquid is a conjugate base of a super strong acid (a super strong acid comprising a proton acid and a super strong acid comprising a combination of a proton acid and a Lewis acid), and more preferred. Is a conjugate base of a super strong acid composed of a proton acid and a super strong acid composed of a proton acid and boron trifluoride and / or phosphorus pentafluoride.

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

  0.01-5 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending an ionic liquid, 0.1-3 mass parts is more preferable.

  Furthermore, the antistatic resin composition of the present invention may contain a compatibilizing agent as long as the effects of the present invention are not impaired. By mix | blending a compatibilizing agent, the compatibility with an antistatic component, another component, and a 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. And the polymer described in JP-A-258850, the modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, or the block polymer having a polyolefin portion and an aromatic vinyl polymer portion. .

  0.01-5 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending a compatibilizing agent, 0.1-3 mass parts is more preferable.

  In addition, the antistatic resin composition of the present invention may be any known resin additive (for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based 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 included. The known resin additive may be added to the synthetic resin after being mixed with the antistatic agent (A) and the antibacterial agent (B), or separately added to the synthetic resin for molding. Also good.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 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′-oxamido-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 -Di-tert-butyl-4-hydroxy-benzenepropanoic acid and C13-15 alkyl ester, 2,5-di-tert-amylhydroquinone, hindered phenol polymer (trade name AO.OH manufactured by Adeka Palmalol) .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, hexamethylene bis [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- 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) butyric 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) ) Propionic acid amide, palmityl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide Myristyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, etc. And 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives.
0.001-5 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending a phenolic antioxidant, 0.03-3 mass parts is more preferable.

Examples of the phosphorus antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, Diphenyl tridecyl 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, dinonylpheny 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, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite, a mixture of distearyl pentaerythritol 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 Nord 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) hexatridecyl phosphite, 2,2′-methylenebis ( 4,6-di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methyle Bis (4,6-di-tert-butylphenyl) -octadecyl phosphite, 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] dioxaphosphine Pin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphesspiro [5,5] undecane, 2 , 4,6-Tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4′-isopropylidenediphenol 12-15 alcohol phosphite, and the like.
0.001-10 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending phosphorus antioxidant, 0.01-0.5 mass part is more preferable.

Examples of the thioether-based antioxidant include tetrakis [methylene-3- (laurylthio) propionate] methane, 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 / stearyl thiodipropionate, 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-thiobis (6-tert-butyl-p-cresol), distearyl- Disulfide is mentioned.
0.001-10 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending a thioether type | system | group antioxidant, 0.01-0.5 mass part is more preferable.

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, 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, 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-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts; Alternatively, metal chelates, particularly nickel, chromium salts, chelates and the like can be mentioned.
0.001-10 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending the said ultraviolet absorber, 0.01-0.5 mass part is more preferable.

Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 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, 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-pi 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} decanedionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate, TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals It is done.
0.001-5 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending the said hindered amine compound, 0.005-0.5 mass part is more preferable.

Examples of the nucleating agent include sodium-2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, lithium-2,2′-methylenebis (4,6-di-tert-butylphenyl). ) Phosphate, aluminum hydroxybis [2,2′methylenebis (4,6-di-tert-butylphenyl) phosphate], sodium benzoate, 4-tert-butyl aluminum benzoate, sodium adipate and disodium bicyclo [2 2.1] Carboxylic acid metal salts 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 silylidene) 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, 1,3,5-tri (dimethylisopropoylamino) benzene, and the like.
0.001-5 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending the said nucleating agent, 0.005-0.5 mass part is more preferable.

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-phenylenetetraphenyl diphosphate, 1,3-phenylenetetrakis (2,6-dimethylphenyl) phosphate, trade name ADEKA STAB FP-500 manufactured by ADEKA Corporation, trade name ADEKA STAB FP-600 manufactured by ADEKA Corporation, ADEKA Co., Ltd. product name Adeka Stub FP-800 and other aromatic phosphates, phenylphosphonic acid divinyl, phenylphosphonic acid diallyl, phenylphosphonic acid (1-butenyl) and other phosphonic acid esters Phosphinic acid esters such as phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, bis (2-allylphenoxy) phosphazene, dicresyl phosphazene, etc. Phosphazene compounds, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus, Metal hydroxide such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylene vinyl (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, tribromophenyl maleimide, 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 anti-drip agents such as fluororesins, and flame retardant aids such as polyhydric alcohols and hydrotalcite.
1-50 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending the said flame retardant, 10-30 mass parts is more preferable.

The lubricant is added for the purpose of imparting lubricity to the surface of the molded body and enhancing the effect of preventing damage. Examples of the lubricant include 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, Examples include sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearic acid amide, oleic acid amide, ethylene bis stearic acid amide and the like. These may be used alone or in combination of two or more.
0.01-2 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending the said lubricant, 0.03-0.5 mass part is more preferable.

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, Examples thereof include dolomite, mica, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate, etc., and the particle diameter (in the fibrous form, the fiber diameter, fiber length, and aspect ratio) is appropriately selected and used. be able to. Moreover, what was surface-treated as needed can be used for a filler.
0.01-80 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending the said filler, 1-50 mass parts is more preferable.

Examples of the metal soap include 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.
0.001-10 mass parts of metal soap is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending the said metal soap, 0.01-5 mass parts is more preferable.

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。 The hydrotalcite is a complex salt compound composed of magnesium, aluminum, hydroxyl group, carbonate group and any crystal water known as a natural product or synthetic product, and part of magnesium or aluminum may be alkali metal, zinc, etc. And those obtained by substituting hydroxyl groups and carbonate groups with other anionic groups. Specifically, for example, the hydrotalcite metal represented by the following general formula (4) is used as an alkali metal. Substituted ones are mentioned. In addition, as the Al—Li hydrotalcites, compounds represented by the following general formula (5) can also be used.

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

Here, in general formula (5), A ^q− represents a q-valent anion, and p represents 0 or a positive number.
The carbonate anion in the hydrotalcite may be partially substituted with another anion.

  The hydrotalcites may be those obtained by dehydrating crystal water, 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 dodecylbenzenesulfonate. It may be coated with a metal salt, higher fatty acid amide, higher fatty acid ester or wax.

The hydrotalcites may be natural products or synthetic products. As methods for synthesizing the compounds, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, Japanese Patent Publication No. 61-174270, Known methods described in, for example, Kaihei No. 5-179052. Further, the hydrotalcites can be used without being limited by their crystal structure, crystal particles and the like.
0.001-5 mass parts is preferable with respect to 100 mass parts of synthetic resins, and, as for the compounding quantity in the case of mix | blending the said hydrotalcite, 0.05-3 mass parts is more preferable.

  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.

  Examples of the dye include 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 Examples thereof include dyes and dyes such as cyanine dyes, and a plurality of these may be used in combination.

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

Further, the antistatic agent (A) may be added as it is, but if necessary, it may be added after impregnating the carrier. In order to impregnate the carrier, it may be heated and mixed as it is, or if necessary, it may be diluted with an organic solvent, impregnated into the carrier, and then the solvent is removed.
As such a carrier, those known as fillers and fillers of synthetic resins, or flame retardants and light stabilizers that are solid at room temperature can be used. For example, calcium silicate powder, silica powder, talc powder, alumina powder In addition, titanium oxide powder, those obtained by chemically modifying the surface of these carriers, solid ones among the flame retardants and antioxidants listed below, and the like can be mentioned. Among these carriers, those obtained by chemically modifying the surface of the carrier are preferred, and those obtained by chemically modifying the surface of the silica powder are more preferred. These carriers preferably have an average particle size of 0.1 to 100 μm, and more preferably 0.5 to 50 μm.

Furthermore, 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 blended separately. May be.
The antistatic agent (A) may be blended by synthesizing the antistatic agent (A) while kneading the block polymer (G) and the compound (D) having a reactive functional group into a synthetic resin. At that time, the antibacterial agent (B) may be kneaded at the same time, and the antistatic agent (A), the antibacterial agent (B) and a synthetic resin are mixed at the time of molding such as injection molding to obtain a molded product. Further, a master batch of an antistatic agent (A) and / or an antibacterial agent (B) and a synthetic resin may be produced in advance, and this master batch may be blended.

  Furthermore, the antistatic agent (A) and the antibacterial agent (B) may be mixed in advance and then blended into the synthetic resin. The antistatic agent synthesized by adding the antibacterial agent (B) during the reaction. You may mix | blend (A) with a synthetic resin.

Next, the molded product of the present invention will be described.
The molded article of the present invention is formed by molding the antistatic resin composition of the present invention. By molding the antistatic resin composition of the present invention, a molded product 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, such as resin plates, sheets, films, bottles, fibers, and irregular shaped products. Various shaped articles can be produced.

  Usually, when an antistatic agent is blended, the physical properties are often lowered. However, the molded article of the present invention is excellent in antistatic properties and durability of antibacterial effect, and has few physical properties. In particular, it has antistatic resistance against wiping of the surface of the molded body.

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

  More specifically, the antistatic resin composition of the present invention and the molded product thereof are printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic money registers). Machine), calculator, electronic notebook, card, holder, stationery, office equipment, OA equipment, washing machine, refrigerator, vacuum cleaner, microwave oven, lighting equipment, game machine, iron, kotatsu and other household appliances, TV, VTR, video Cameras, radio cassettes, tape recorders, mini-discs, CD players, speakers, liquid crystal displays and other AV equipment, connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor sealing materials, LED sealing materials, electric wires, cables, transformers , Deflection yokes, distribution boards, electrical and electronic parts such as watches 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.

  Further, the antistatic resin composition of the present invention and the molded product thereof are a seat (filling, outer material, etc.), belt, ceiling, compatible top, armrest, door trim, rear package tray, carpet, mat, sun visor, foil cover. , Mattress cover, air bag, insulation material, suspension hand, suspension band, electric wire coating material, electrical insulation material, paint, coating material, upholstery material, flooring, corner wall, carpet, wallpaper, wall covering material, exterior material , Interior materials, roofing materials, deck materials, wall materials, pillar materials, floorboards, fence materials, frames and repetitive shapes, window and door shapes, slabs, siding, terraces, balconies, soundproofing plates, heat insulating plates, windows Automobiles such as materials, vehicles, ships, aircraft, buildings, housing and building materials and civil engineering materials, clothing, curtains, sheets, nonwoven fabrics, plywood, synthetic fiber boards, 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 specifically described by way of examples.
An antistatic agent (A) was produced according to the following production example. 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 a gel permeation chromatography (GPC) method under the following measurement conditions.
Apparatus: GPC apparatus manufactured by JASCO Corporation Solvent: Tetrahydrofuran Reference material: Polystyrene Detector: Differential refractometer (RI detector)
Column stationary phase: Shodex KF-804L manufactured by Showa Denko KK
Column concentration: 40 ° C
Sample concentration: 1 mg / 1 mL
Flow rate: 0.8mL / 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), 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 added, and the temperature was gradually raised from 160 ° C. to 210 ° C. while polymerizing at normal pressure for 5 hours and then 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, a polyethylene glycol having a number average molecular weight of 4,000 as a compound having 600 g of the obtained polyester (E) -1 and having one or more groups represented by the general formula (1) and having hydroxyl groups at both ends. (C) -1 (300 g), antioxidant (Adeka Stub AO-60) 0.5 g, and zirconium octylate 0.8 g were charged and polymerized under reduced pressure at 210 ° C. for 7 hours to form carboxyl groups at both ends. A block polymer (G) -1 was obtained. The acid value of this block polymer (G) -1 was 9, and the number average molecular weight Mn was 12,000 in terms of polystyrene.

  360 g of the obtained block polymer (G) -1 having a carboxyl group at both ends is charged with 6 g of bisphenol F diglycidyl ether (D) -1 as a compound (D) having a reactive functional group of a polyvalent epoxy compound. Polymerization was performed 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, aromatic dicarboxylic acid As an example, 8 g (0.05 mol) of isophthalic acid and 0.5 g of an antioxidant (ADK STAB AO-60) were charged, and polymerization was performed at normal pressure for 5 hours while gradually raising the temperature from 180 ° C to 220 ° C. Thereafter, 0.5 g of tetraisopropoxy titanate was charged and polymerized at 220 ° C. under reduced pressure for 5 hours to obtain 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.

  Polyethylene glycol (C) having a number average molecular weight of 4,000 as a compound having 300 g of the obtained polyester (E) -2, one or more groups represented by the general formula (1) and having hydroxyl groups at both ends. -1 is charged with 150 g, antioxidant (ADK STAB AO-60) 0.5 g and zirconium acetate 0.5 g are charged, polymerized at 220 ° C. for 7 hours under reduced pressure, and a block polymer having carboxyl at both ends (G ) -2 was obtained. This block polymer (G) -2 had an acid value of 11, and a number average molecular weight Mn of 12,300 in terms of polystyrene.

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

[Production Example 3]
(Production of antistatic agent (A) -3)
In a separable flask, 591 g of an 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 one or more groups represented by the general formula (1) and having hydroxyl groups at both ends, an antioxidant (ADK STAB) AO-60) was charged in an amount of 0.8 g, and polymerization was performed at normal pressure for 5 hours while gradually increasing the temperature from 180 ° C to 220 ° C. Thereafter, 0.6 g of tetraisopropoxy titanate 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. This block polymer (G) -3 had an acid value of 10, and a number average molecular weight Mn of 10,100 in terms of polystyrene.

  300 g of the resulting block polymer (G) -3 is charged with 7 g of epoxidized soybean oil (D) -3 and 0.5 g of zirconium acetate as the compound (D) having a reactive functional group of a polyvalent epoxy compound. Was polymerized 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 phenol-based antioxidant (trade name “Adeka Stub AO-60” manufactured by ADEKA Corporation), 0.05 part by weight of a phosphorus-based antioxidant (trade name “Adeka Stub 2112” manufactured by ADEKA Corporation), calcium stearate A resin composition blended based on 0.05 parts by mass and the components and blending amounts (parts by mass) shown in Tables 1 to 4 below is a twin screw extruder (product name: PCM30, 60 manufactured by Ikegai Co., Ltd.). 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 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 made.

<Method for measuring surface resistivity (SR value)>
The obtained test piece (100 mm × 100 mm × 3 mm) was stored immediately after molding under conditions of a temperature of 25 ° C. and a humidity of 60% RH, and after storage for 1 day and 30 days in the same atmosphere, Using a R8340 resistance meter manufactured by Advantest Corporation, the surface specific resistance value (Ω / □) was measured under the conditions of an applied voltage of 500 V and an applied time of 1 minute. The measurement was performed for 5 points, and the average value was obtained. These results are shown in Tables 1 to 4, respectively.

<Antimicrobial test method>
From the obtained test piece (100 mm × 100 mm × 3 mm), it was cut out to 50 mm × 50 mm × 1 mm to obtain a test piece. Drop 0.4 ml of the bacterial solution containing E. coli on the surface of the test piece, cover the top of the test piece with a polyethylene film, store at 34-36 ° C, RH 90% or more for 24 hours, and then measure the number of viable bacteria did.
These 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. × 2.16 kg) = 8 g / 10 min)
(B) -1: manufactured by Sinanen Zeomic Co., Ltd., trade name “Zeomic AJ10D” (A-type zeolite containing 2.5% silver)
(B) -2: manufactured by Toa Gosei Co., Ltd., trade name “NOVALON AG300” (3.5% silver-containing zirconium phosphate)
(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. × 2.16 kg) = 8 g / 10 min)
ABS resin: manufactured by Techno Polymer Co., Ltd. Trade name “Techno ABS 110” (melt flow rate (ISO 1133, 220 ° C. × 10 kg) = 23 g / 10 min)
(B) -1: manufactured by Sinanen Zeomic Co., Ltd., trade name “Zeomic AJ10D” (A-type zeolite containing 2.5% silver)
(B) -2: manufactured by Toa Gosei Co., Ltd., trade name “NOVALON AG300” (3.5% silver-containing zirconium phosphate)
(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. × 2.16 kg) = 8 g / 10 min)
(B) -1: manufactured by Sinanen Zeomic Co., Ltd., trade name “Zeomic AJ10D” (A-type zeolite containing 2.5% silver)
(B) -2: manufactured by Toa Gosei Co., Ltd., trade name “NOVALON AG300” (3.5% silver-containing zirconium phosphate)
(F) -1: Sodium dodecylbenzenesulfonate (F) -2: Lithium p-toluenesulfonate Comparative compound 1: Polyetheresteramide type antistatic agent, manufactured by BASF, trade name “Irgastat 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: manufactured by Techno Polymer Co., Ltd. Trade name “Techno ABS 110” (melt flow rate (ISO 1133, 220 ° C. × 10 kg) = 23 g / 10 min)
(B) -1: manufactured by Sinanen Zeomic Co., Ltd., trade name “Zeomic AJ10D” (A-type zeolite containing 2.5% silver)
(B) -2: manufactured by Toa Gosei Co., Ltd., trade name “NOVALON AG300” (3.5% silver-containing zirconium phosphate)
(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 is used, the antistatic property is poor. Further, from the comparison between Comparative Example 4 and Comparative Example 7 and Comparative Example 12 and Comparative Example 15, when an antistatic agent different from the antistatic agent (A) according to the present invention is used, the antibacterial property is slightly reduced. On the other hand, from the 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 blended. However, no decrease in antibacterial properties was observed.

Further, from Comparative Example 2 and Comparative Example 10, it is not possible to improve the antistatic property only with the alkali metal salt (F), but from the comparison between Example 2 and Example 5, the antistatic agent (A) according to the present invention and When the alkali metal salt (F) was blended, the antistatic property was improved. Furthermore, from Example 11 and Example 12, it was confirmed that the antistatic agent (A) according to the present invention can achieve the desired effect even with respect to 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 has been confirmed that the antistatic resin composition of the present invention has both continuous antistatic properties and excellent antibacterial properties.

Claims (11)

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) with respect to 100 parts by mass of a synthetic resin,
The antistatic agent (A) is a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a compound (C) having one or more groups represented by the following general formula (1) and having hydroxyl groups at both ends; and An antistatic resin, wherein the compound (D) having a reactive functional group is a polymer compound having a structure formed by bonding via an ester bond or via an ester bond and an amide bond Composition.

  The antistatic agent (A) is a polyester (E) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, the compound (C) and the compound (D) having a reactive functional group are esters. The antistatic resin composition according to claim 1, wherein the antistatic resin composition is bonded via a bond or via an ester bond and an amide bond.   The antistatic agent (A) has a carboxyl group at both ends formed by alternately and alternately connecting a block composed of the polyester (E) and a block composed of the compound (C) via an ester bond. The charge according to claim 2, wherein the block polymer (G) and the compound (D) having a reactive functional group have a structure formed by bonding via an ester bond or via an ester bond and an amide bond. Preventive resin composition.   The antistatic resin composition according to claim 2 or 3, wherein the polyester (E) has a structure having carboxyl groups at both ends.   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. The antistatic resin composition according to claim 3, wherein the block polymer (G) has a number average molecular weight of 5,000 to 25,000 in terms of polystyrene.   The said compound (C) is polyethyleneglycol, The antistatic resin composition as described in any one of Claims 1-5.   The compound (D) having a reactive functional group is a polyvalent epoxy compound having two or more epoxy groups, a polyhydric alcohol compound having three or more hydroxyl groups, and a polyvalent amine having two or more amino groups The antistatic resin composition according to any one of claims 1 to 6, which is selected from compounds.   Furthermore, the antistatic resin composition as described in any one of Claims 1-7 containing 0.01-5 mass parts of 1 or more types of alkali metal salt (F).   The antistatic resin composition according to any one of claims 1 to 8, 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 9, wherein the synthetic resin is a polyolefin resin or a styrene resin. A molded article obtained by molding the antistatic resin composition according to any one of claims 1 to 10.