JP2023163293A - Antistatic resin composition and molding thereof - Google Patents

Abstract

To provide an antistatic resin composition that can provide a molding having superior wood-like texture as well as superior antistatic properties and its long-lasting nature.SOLUTION: An antistatic resin composition includes, based on synthetic resin of 100 pts.mass, the following (X) component of 1-200 pts.mass and the following (Y) component of 1-60 pts.mass. (X) component: wood flour. (Y) component: at least one polymer compound (E) which is a reaction product of polyester (a) resulting from a reaction between diol (a1) and dicarboxylic acid (a2), a compound (b) having one or more ethyleneoxy groups and hydroxy groups at both terminals, and an epoxy compound (D) having two or more epoxy groups.SELECTED DRAWING: None

Description

The present invention relates to an antistatic resin composition (hereinafter also simply referred to as a "resin composition"), specifically an antistatic resin that has a woody texture and can provide a molded article with excellent antistatic properties. The present invention relates to a composition and a molded article having a woody texture and excellent antistatic properties.

BACKGROUND ART In recent years, resin molded articles have been widely used, which are made by adding wood flour to synthetic resins such as thermoplastic resins to give them a woody feel, giving them a color tone and texture close to those of natural wood. This resin molded body having a wood texture is used, for example, in vehicle interior materials, side moldings, residential interior materials, building materials such as louvers and exterior building materials, flooring materials such as balconies, terraces, balconies, deck materials, fence materials, etc. It is used for handrail materials, bridges, civil engineering materials, wooden walkways across wetlands in natural parks, table frames, gaskets, etc.

Since these resin molded bodies have high electrical insulation properties of the synthetic resin itself, they are easily charged with electricity due to friction or the like. Once charged with static electricity, dust may adhere to it or it may discharge when a human body comes into contact with it, causing discomfort to the person.

In order to solve the above problem, an antistatic agent consisting of a surfactant has conventionally been blended into resin (Patent Document 1). When an antistatic agent consisting of a surfactant is kneaded into a compound, it bleeds onto the surface of the resin molding and exhibits its effect, but if used for many years, it disappears due to wind and rain and its effect persists. There was a problem with not doing so. Further, when applied to the surface, there is a problem that not only the antistatic property is not sufficient but also the antistatic property is lost due to surface abrasion or the like.
Furthermore, in order to improve the sustainability of antistatic properties, resin molded articles using polymeric antistatic agents have also been developed (Patent Document 2).

Japanese Patent Application Publication No. 2007-169350 Japanese Patent Application Publication No. 2014-105284

However, resin moldings using these conventional antistatic agents are not necessarily sufficient in terms of antistatic performance and durability, and at present, further improvements are desired. In addition, depending on the antistatic agent used, there is a problem that the woody feel of the molded product may be impaired, and even if a large amount of antistatic agent is used to achieve sufficient antistatic properties, the woody feel of the molded product may be impaired. There was a problem.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an antistatic resin composition that has an excellent wood texture and can provide a molded article with excellent antistatic properties and its durability, and an antistatic resin composition that has an excellent wood texture and has excellent antistatic properties and long-lasting properties. It is an object of the present invention to provide a molded article having excellent preventive properties and durability thereof.

As a result of intensive studies to solve the above-mentioned problems, the present inventors found that the above-mentioned problems could be solved by having the following configuration, and completed the present invention.

That is, the present invention provides an antistatic resin composition containing 1 to 200 parts by mass of the following component (X) and 1 to 60 parts by mass of the following component (Y) with respect to 100 parts by mass of the synthetic resin. It is something.
(X) Ingredient: Wood flour.
(Y) component: polyester (a) obtained by reacting diol (a1) and dicarboxylic acid (a2), compound (b) having hydroxyl groups at both ends and having one or more ethyleneoxy groups, and epoxy group. One or more kinds of polymer compounds (E) obtained by reacting an epoxy compound (D) having two or more of the following.

Further, in the present invention, the polymer compound (E) comprises a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the compound (b). formed by the reaction of the hydroxyl group or carboxyl group at the end of the polyester (a), the hydroxyl group at the end of the compound (b), and the epoxy group or epoxy group of the epoxy compound (D). The present invention provides the antistatic resin composition having a structure formed by a reaction with a hydroxyl group and bonded via an ester bond or an ether bond.

Further, the present invention provides that the polymer compound (E) has a carboxyl group at both ends formed by repeatedly and alternately bonding the polyester block (A) and the polyether block (B) via ester bonds. The present invention provides the antistatic resin composition having a structure in which a block polymer (C) having a group and the epoxy compound (D) are bonded via an ester bond.

Further, the present invention further provides the antistatic resin composition containing 0.01 to 15.0 parts by mass of one or more selected from the group consisting of an alkali metal salt (F) and an ionic liquid (G). It provides:

The present invention also provides a molded article obtained from the antistatic resin composition.

According to the present invention, there is provided an antistatic resin composition capable of providing a molded article having an excellent wood texture and excellent antistatic properties and its sustainability, and an antistatic resin composition having an excellent wood texture and antistatic properties. A molded article having excellent durability can be provided.

Embodiments of the present invention will be described in detail below.
The antistatic resin composition of the present invention contains 1 to 200 parts by mass of the following component (X) and 1 to 60 parts by mass of the following component (Y) per 100 parts by mass of the synthetic resin.
(X) Ingredient: Wood flour.
(Y) component: polyester (a) obtained by reacting diol (a1) and dicarboxylic acid (a2), compound (b) having hydroxyl groups at both ends and having one or more ethyleneoxy groups, and epoxy group. One or more kinds of polymer compounds (E) obtained by reacting an epoxy compound (D) having two or more of the following.

First, the synthetic resin used in the present invention will be explained. The resin that can be used in the antistatic resin composition of the present invention is not particularly limited as long as it is a synthetic resin, but from the viewpoint of moldability, thermoplastic resins are preferable, and among them, thermoplastic resins are preferred, especially due to their antistatic properties, durability, and moldability. From the viewpoint of the woody feel of the body, polyolefin resins, polystyrene resins, polycarbonate resins, polyester resins, polyether resins, polyamide resins, and halogen-containing resins are more preferred; Resins are particularly preferred.

Examples of polyolefin resins include polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, crosslinked polyethylene, ultra-high molecular weight polyethylene, polypropylene, homopolypropylene, impact copolymer polypropylene, random copolymer polypropylene, block copolymer polypropylene, Isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, polybutene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4- α-olefin polymers such as methyl-1-pentene, ethylene-propylene block or random copolymers, ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene- Examples include butyl acrylate copolymers, α-olefin copolymers such as ethylene-vinyl acetate copolymers, polyfluoroolefins, and polyolefin thermoplastic elastomers, and copolymers of two or more of these may also be used.

Examples of polystyrene resins include vinyl group-containing aromatic hydrocarbons alone, vinyl group-containing aromatic hydrocarbons, and other monomers (for example, maleic anhydride, phenylmaleimide, (meth)acrylic esters, butadiene, (meth)acrylonitrile, etc.), such as 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, acrylate-styrene-acrylonitrile (ASA) resin, styrene-maleic anhydride (SMA) resin, methacrylate-styrene (MS) resin, styrene-isoprene-styrene (SIS) resin, acrylonitrile-ethylene propylene rubber-styrene (AES) resin, styrene-butadiene-butylene-styrene (SBBS) resin, methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin, and other thermoplastic resins; Styrene-ethylene-butylene-styrene (SEBS) resin, styrene-ethylene-propylene-styrene (SEPS) resin, styrene-ethylene-propylene (SEP) resin, styrene-ethylene-styrene-styrene (SEBS) resin, styrene-ethylene-propylene-styrene (SEPS) resin, which is obtained by hydrogenating the double bonds of butadiene or isoprene. Examples include hydrogenated styrenic elastomer resins such as ethylene-propylene-styrene (SEEPS) resins.

Examples of the polycarbonate resin include polycarbonate, polycarbonate/ABS resin, polycarbonate/ASA resin, and branched polycarbonate.
Examples of polyester resins include polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, and polycyclohexane dimethylene terephthalate; aromatic polyesters such as polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate; and polytetramethylene terephthalate. Linear polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, poly(2-oxetanone) and other degradable aliphatic polyesters, etc. can be mentioned.

Examples of the polyether resin include polyacetal, polyphenylene ether, polyether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone, polyether sulfone, and polyether imide.

Examples of polyamide resins include ε-caprolactam (nylon 6), undecanelactam (nylon 11), lauryl lactam (nylon 12), aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9- Polymers such as aminononanoic acid, α-pyrrolidone, α-piperidone; diamines such as hexamethylenediamine, nonanediamine, nonanemethylenediamine, methylpentadiamine, undecanemethylenediamine, dodecanemethylenediamine, metaxylenediamine, and adibic acid, sebacic acid. , a copolymer obtained by copolymerizing carboxylic acid compounds such as dicarboxylic acids such as terephthalic acid, isophthalic acid, dodecanedicarboxylic acid, and glutaric acid, or a mixture of these polymers or copolymers. . Other examples include aramid resins such as "Kevlar" (trade name) manufactured by DuPont, "Nomex" (trade name) manufactured by DuPont, and "Twaron" (registered trademark) and "Conex" manufactured by Teijin Corporation.

Examples of halogen-containing resins include polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, and vinyl chloride-chloride. Vinylidene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexylmaleimide copolymer, etc. It will be done.

Further examples of thermoplastic resins include petroleum resin, coumaron resin, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyphenylene sulfide, polyurethane, cellulose resin, and polyimide resin. Thermoplastic resins such as , polysulfone, liquid crystal polymers, and blends thereof can be used.

In addition, thermoplastic resins include isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, polyester elastomer, nitrile elastomer, nylon elastomer, vinyl chloride elastomer, Elastomers such as polyamide elastomers and polyurethane elastomers may be used, and they may be used in combination.

These thermoplastic resins may be used alone or in combination of two or more. Further, it may be alloyed. These thermoplastic resins are characterized by their molecular weight, degree of polymerization, density, softening point, proportion of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and blending ratio of monomers used as raw materials, and polymerization catalyst. It can be used regardless of the type (for example, Ziegler catalyst, metallocene catalyst, etc.).

Next, the wood flour of component (X) of the present invention will be explained.
In the antistatic resin composition of the present invention, wood flour is used as the component (X). The average particle size of the wood flour is preferably 30 to 500 μm, more preferably 100 to 200 μm. When the average particle size is less than 30 μm, the bulk specific gravity of the wood flour tends to be small and the miscibility with synthetic resins and other compounds tends to deteriorate, and when it exceeds 500 μm, the surface condition of the molded product tends to deteriorate. This is not desirable.

The types of trees used for the wood powder are not particularly limited, but include coniferous trees such as cedar, lauan, toga, cypress, pine, fir, beech, birch, zelkova, boxwood, wig, chestnut, cherry, etc. Wood flour obtained from hardwoods such as oak can be used. Further, finely pulverized materials such as sawdust, rice husks, and particle board surface polishing powder can also be used. The method for turning wood flour into fine powder is not particularly limited, and includes, for example, a method of finely pulverizing chipped wood using a dry grinder.

In the resin composition, the content of component (X) is 1 to 200 parts by mass based on 100 parts by mass of the synthetic resin, and is preferably from the viewpoint of antistatic property, its sustainability, and the woody texture of the molded product. The amount is 5 to 150 parts by weight, more preferably 10 to 100 parts by weight. If it is less than 1 part by mass, the woody feel will be poor, and if it exceeds 200 parts by mass, the uniformity and surface condition will tend to deteriorate.

Next, the polymer compound (E) as component (Y) of the present invention will be explained.
Component (Y) of the present invention is one or more types of polymer compounds (E).
This polymer compound (E) is a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2), and a compound (b) having a hydroxyl group at both ends and having one or more ethyleneoxy groups. and an epoxy compound (D) having two or more epoxy groups. Here, the ethyleneoxy group is a group represented by the following general formula (1).

The polymer compound (E) is a polyester block (A) composed of polyester (a) and a polyether block composed of a compound (b) having one or more ethyleneoxy groups and a hydroxyl group at both ends. (B), and is formed by the reaction of the hydroxyl group or carboxyl group at the end of the polyester (a), the hydroxyl group at the end of the compound (b), and the epoxy group or epoxy group of the epoxy compound (D). It is preferable to have a structure formed by the reaction of hydroxyl groups, which are bonded via ester bonds or ether bonds, from the viewpoint of antistatic properties and durability thereof, and the woody feel of the molded product.

The polyester block (A) of the polymer compound (E) is composed of a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2). Note that the polyester (a) can be obtained by subjecting a diol and a dicarboxylic acid to an esterification reaction.

Examples of the diol (a1) used in the polymer compound (E) according to the present invention include aliphatic diols and aromatic group-containing diols. The diol (a1) may be a mixture of two or more.

Examples of aliphatic diols include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, and 1,3-butanediol. , 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl- 1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentane Diol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 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 and the like. However, it is preferable that the aliphatic diol has hydrophobicity from the viewpoint of antistatic property, durability thereof, and woody feel of the molded product, and therefore, it is not preferable to use polyethylene glycol that has hydrophilicity.

Examples of aromatic group-containing diols 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, resorcinol, and pyrocatechol.

Among these diols, 1,4-cyclohexanedimethanol, 1,4-butanediol, and ethylene glycol are preferred from the viewpoint of antistatic properties, durability thereof, and woody feel of the molded product.

The dicarboxylic acid (a2) used in the polymer compound (E) according to the present invention includes aliphatic dicarboxylic acids and aromatic dicarboxylic acids. The dicarboxylic acid (a2) may be a mixture of two or more.

The aliphatic dicarboxylic acid used in the polymer compound (E) according to the present invention may be an aliphatic dicarboxylic acid derivative (eg, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.). A mixture of two or more types of aliphatic dicarboxylic acids and derivatives thereof may be used.

The aliphatic dicarboxylic acids preferably include aliphatic dicarboxylic acids having 2 to 20 carbon atoms, such as oxalic acid, malonic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid, 3-methylglutaric acid, Ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid (1,10-decanedicarboxylic acid), tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid , octadecanedioic acid, eicosanedioic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid , 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, 1,1-cyclohexanediacetic acid, dimer acid, maleic acid, fumaric acid and the like. Among these aliphatic dicarboxylic acids, succinic acid and adipic acid are preferred from the viewpoint of antistatic properties, durability thereof, and wood texture of the molded product.

The aromatic dicarboxylic acid used in the polymer compound (E) according to the present invention may be a derivative of aromatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.). Moreover, a mixture of two or more types of aromatic dicarboxylic acids and derivatives thereof may be used.

The aromatic dicarboxylic acid preferably includes aromatic dicarboxylic acids having 8 to 20 carbon atoms, such as terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, and β-phenylglutaric acid. acids, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalene dicarboxylic acid, sodium 3-sulfoisophthalate and 3-sulfoisophthalic acid. Examples include potassium. Among these aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, and phthalic acid (including phthalic anhydride) are preferred from the viewpoint of antistatic properties, durability, and wood texture of the molded product; ) is more preferred.

As the dicarboxylic acid (a2), it is preferable to use both an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid in combination, from the viewpoint of antistatic properties, durability thereof, and wood texture of the molded product, and adipic acid and phthalic acid (phthalic anhydride). It is more preferable to use both (including acids) in combination.

The dicarboxylic acid (a2) is preferably succinic acid or a mixture of dicarboxylic acids containing succinic acid, more preferably succinic acid, from the viewpoint of antistatic properties, durability thereof, and wood texture of the molded article.

Examples of dicarboxylic acids that can be used as a mixture with succinic acid include the aforementioned aliphatic dicarboxylic acids and aromatic dicarboxylic acids, which may be used alone or in combination of two or more.

The dicarboxylic acid used in the mixture with succinic acid is preferably an aliphatic dicarboxylic acid, more preferably adipic acid or sebacic acid, and most preferably adipic acid, from the viewpoint of antistatic properties, durability, and wood texture of the molded product. .

When the dicarboxylic acid (a2) is a mixture of dicarboxylic acids containing succinic acid, from the viewpoint of antistatic properties, durability, and wood texture of the molded product, it is preferable to use succinic acid and other dicarboxylic acids (e.g., adipic acid). The molar ratio is preferably 100:0 to 50:50. The ratio is more preferably 100:0 to 70:30, even more preferably 100:0 to 80:20, and even more preferably 100:0 to 90:10.

Next, the compound (b) and the polyether (B) block of the polymer compound (E) will be explained. The polyether (B) block is composed of a compound (b) having one or more ethyleneoxy groups and a hydroxyl group at both ends, represented by the following general formula (1).

As the compound (b) having one or more ethyleneoxy groups represented by the general formula (1) and hydroxyl groups at both ends, a hydrophilic compound is preferable. In terms of antistatic property, durability thereof, and woody feel of the molded article, polyethylene glycol is even more preferred, and polyethylene glycol represented by the following general formula (2) is particularly preferred.

In general formula (2), m represents a number from 5 to 250. m is preferably 20 to 200, more preferably 40 to 180, from the viewpoint of antistatic properties, durability thereof, and woody texture of the molded product.

In addition to polyethylene glycol obtained by addition reaction of ethylene oxide, the compound (b) may include ethylene oxide and other alkylene oxides (for example, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, etc.), and this polyether may be either random or block.

Further examples of compound (b) include compounds with 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, etc.). These may be either random addition or block addition.

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

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

Examples of aliphatic glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3- Hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecane Examples include diol, 1,20-eicosandiol, 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, 1-methyl-3,4-cyclohexanediol , 2-hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol and 1,1'-dihydroxy-1,1'-dicyclohexyl.

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

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

Examples of primary monoamines 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.

Examples of 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 alicyclic secondary diamines having 6 to 14 carbon atoms. Aromatic secondary diamines having 8 to 14 carbon atoms and secondary alkanol diamines having 3 to 22 carbon atoms can be used.

Examples of aliphatic secondary diamines 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, and 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 aromatic secondary diamines include N,N'-dimethyl-phenylenediamine, N,N'-dimethyl-xylylenediamine, N,N'-dimethyl-diphenylmethanediamine, and N,N'-dimethyl-diphenyl ether diamine. , N,N'-dimethyl-benzidine and N,N'-dimethyl-1,4-naphthalenediamine.

Examples of the secondary alkanol diamine include N-methyldiethanolamine, N-octyldiethanolamine, N-stearyldiethanolamine, and N-methyldipropanolamine.

As the dicarboxylic acid, dicarboxylic acids having 2 to 20 carbon atoms can be used, such as aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.

Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid, β-methylglutaric acid, ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelic acid, suberic acid, Mention may be made of azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid and icosandioic acid.

Examples of aromatic dicarboxylic acids include 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, naphthalene dicarboxylic acid, sodium 3-sulfoisophthalate and potassium 3-sulfoisophthalate.

Examples of alicyclic dicarboxylic acids include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid. acid, 1,4-cyclohexane diacetic acid, 1,3-cyclohexane diacetic acid, 1,2-cyclohexane diacetic acid, and dicyclohexyl-4,4'-dicarboxylic acid.

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

Next, the epoxy compound (D) having two or more epoxy groups constituting the polymer compound (E) will be explained. The epoxy compound (D) used in the present invention is not particularly limited as long as it has two or more epoxy groups, and examples include mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromo bisphenol A, 1,3 -bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra( Polyglydyl ethers of polynuclear polyhydric phenol compounds such as 4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, and terpene phenol. Compounds; ethylene glycol, propylene glycol, butylene glycol, hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct , polyglycidyl ethers of polyhydric alcohols such as dicyclopentadiene dimethanol; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, Glycidyl aliphatic, aromatic or alicyclic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, etc. Homopolymers or copolymers of esters and glycidyl methacrylate; glycidylamino groups such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, diglycidyl orthotoluidine, etc. Epoxy compounds with; vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate , epoxidized products of cyclic olefin compounds such as bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, triglycidyl isocyanurate and epoxidized soybean oil. In addition, these epoxy compounds are internally crosslinked with a prepolymer of terminal isocyanates, or are made to have a high molecular weight using polyvalent active hydrogen compounds (polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphate esters, etc.). It may be something that has been done. Two or more kinds of such epoxy compounds (D) may be used.

Epoxy compounds (D) are selected from the viewpoints of antistatic properties, durability, and woody feel of molded products, such as bisphenol F diglycidyl ether, dicyclopentadienedimethanol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hexanediol diglycidyl ether. Glycidyl ether is preferred, and bisphenol F diglycidyl ether is more preferred.

The epoxy equivalent of the epoxy compound (D) is preferably from 70 to 2,000, more preferably from 100 to 1,000, and even more preferably from 150 to 600, from the viewpoint of antistatic properties, durability thereof, and wood texture of the molded product. preferable.

The polymer compound (E) of the present invention is a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2), and a compound having a hydroxyl group at both ends and having one or more ethyleneoxy groups ( It is obtained by reacting b) with an epoxy compound (D) having two or more epoxy groups, and is composed of a polyester block (A) composed of polyester (a) and compound (b). an epoxy compound having a hydroxyl group or a carboxyl group at the end of the polyester (a), a hydroxyl group at the end of the compound (b), and two or more epoxy groups. Products that have a structure in which the epoxy group or the hydroxyl group formed by the reaction of this epoxy group are bonded via an ester bond or an ether bond have antistatic properties and long-lasting properties. , is preferable in terms of the woody feel of the molded product.

Furthermore, the polymer compound (E) is composed of a polyester block (A) composed of polyester (a) and a compound (b), from the viewpoint of antistatic properties, its sustainability, and the wood texture of the molded product. A block polymer (C) having carboxyl groups at both ends, which is formed by repeatedly and alternately bonding polyether blocks (B) via ester bonds, and an epoxy compound (D) combine the carboxyl groups of the block polymer (C). and the epoxy group of the epoxy compound (D), preferably has a structure in which the epoxy group is bonded via an ester bond formed by the epoxy group, and further a hydroxyl group formed by ring opening of the epoxy group by reaction with a carboxyl group. It is also preferable that the compound has a structure in which the compound is bonded to the compound via an ester bond formed by a reaction with a carboxyl group.

The polyester (a) constituting the block of the polyester (A) according to the present invention may be one consisting of a diol (a1) and a dicarboxylic acid (a2), and has antistatic properties and durability, and wood of the molded product. From the viewpoint of texture, it preferably has a structure in which the residue of the diol (a1) excluding the hydroxyl group and the residue of the dicarboxylic acid (a2) excluding the carboxyl group are bonded via an ester bond.

Further, the polyester (a) preferably has a structure having carboxyl groups at both ends from the viewpoint of antistatic properties, durability thereof, and woody feel of the molded product. Further, the degree of polymerization of the polyester (a) is preferably in the range of 2 to 50 from the viewpoint of antistatic properties, durability thereof, and wood texture of the molded product.

Polyester (a) having carboxyl groups at both ends can be obtained by subjecting diol (a1) and dicarboxylic acid (a2) to an esterification reaction.

The dicarboxylic acid (a2) may be a derivative thereof (for example, an acid anhydride, an ester such as an alkyl ester, an alkali metal salt, an acid halide, etc.), and when a derivative is used to obtain the polyester (a), Finally, both ends may be treated to form carboxyl groups, and the polymer may be left as it is to proceed to the next reaction for obtaining a block polymer (C) having a structure having carboxyl groups at both ends.

Regarding the reaction ratio of dicarboxylic acid (a2) and diol (a1), it is preferable to use an excess of dicarboxylic acid (a2) so that both ends become carboxyl groups, and the molar ratio is It is preferable to use an excess of 1 molar amount. In the esterification reaction, a catalyst that promotes the esterification reaction may be used, and conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used.

In addition, when derivatives such as esters, alkali metal salts, acid halides, etc. are used instead of dicarboxylic acids, after reacting them with diols, both ends may be treated to form dicarboxylic acids, or they may be used as they are. Then, the reaction may proceed to the next reaction for obtaining a block polymer (C) having a structure having carboxyl groups at both ends.

Suitable polyester (a) consisting of diol (a1) and dicarboxylic acid (a2) and having carboxyl groups at both ends forms an ester bond by reacting with compound (b), resulting in the structure of block polymer (C). Preferably, the carboxyl groups at both ends may be protected or modified, or may be in the form of a precursor. Further, in order to suppress oxidation of the product during the reaction, an antioxidant such as a phenolic antioxidant may be added to the reaction system.

The compound (b) having one or more ethyleneoxy groups and hydroxyl groups at both ends is preferably reacted with the polyester (a) to form an ester bond or an ether bond, preferably an ester bond, and form a block polymer (C). The hydroxyl groups at both ends may be protected, modified, or in the form of a precursor.

The block polymer (C) having a structure having carboxyl groups at both ends of the polymer compound (E) according to the present invention is composed of a block (A) composed of the above polyester (a) and the above compound (b). It has a structure in which these blocks are repeatedly and alternately bonded via ester bonds formed by carboxyl groups and hydroxyl groups. An example of such a block polymer (C) is one having a structure represented by the following general formula (3).

In the general formula (3), (A) represents a block composed of the polyester (a) having carboxyl groups at both ends, and (B) represents a block composed of the compound (b) having hydroxyl groups at both ends. t is the number of repetitions of the repeating unit, and preferably represents a number from 1 to 10 from the viewpoint of antistatic properties, durability, and wood texture of the molded product. t is more preferably a number from 1 to 7, most preferably a number from 1 to 5.

The block polymer (C) having a structure having carboxyl groups at both ends is obtained by polycondensation reaction of a polyester (a) having carboxyl groups at both ends and a compound (b) having hydroxyl groups at both ends. However, the polyester (a) and the compound (b) have a structure equivalent to one in which the polyester (a) and the compound (b) are repeatedly and alternately bonded via ester bonds formed by carboxyl groups and hydroxyl groups. It is not necessarily necessary to synthesize the above-mentioned polyester (a) and the above-mentioned compound (b) as long as it is a compound.

If the reaction ratio of the polyester (a) and the compound (b) is adjusted so that the amount of the compound (b) is X+1 moles of the polyester (a), carboxyl groups are present at both ends. A block polymer (C) having the following can be preferably obtained.

In the reaction, after the synthesis reaction of the polyester (a) is completed, the compound (b) may be added to the reaction system without isolating the polyester (a), and the reaction may be allowed to proceed as it is.

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

The polymer compound (E) according to the present invention preferably contains a block polymer (C) having a structure having carboxyl groups at both ends, from the viewpoint of antistatic properties, its sustainability, and the woody feel of the molded product. It has a structure in which an epoxy compound (D) having three or more epoxy groups is bonded via an ester bond. The ester bond is an ester bond formed by the reaction between the terminal carboxyl group of the block polymer (C) and the epoxy group of the epoxy compound (D), and an ester bond formed by this reaction (reaction between the carboxyl group and the epoxy group). It may be either an ester bond formed by a reaction between a hydroxyl group and a carboxyl group, and the presence of both ester bonds is preferred from the viewpoints of antistatic properties, durability thereof, and woody feel of the molded product.

Further, the polymer compound (E) may further contain an ester bond formed by the carboxyl group of the polyester (a) and the epoxy group of the epoxy compound (D).

Furthermore, the polymer compound (E) may contain an ester bond formed by a hydroxyl group formed by the reaction between the carboxyl group of the polyester (a) and the epoxy group of the epoxy compound.

Furthermore, the polymer compound (E) further contains an ether bond formed by the hydroxyl group of the polyester (a) or the hydroxyl group of the compound (b) and the epoxy group of the epoxy compound (D). You can stay there.

In order to obtain a preferable polymer compound (E), the above block polymer (C) and the above epoxy compound (D) may be reacted. That is, the carboxyl group of the block polymer (C) may be reacted with the epoxy group of the epoxy compound (D). More preferably, a hydroxyl group formed from the reacted epoxy group and a carboxyl group may be reacted. The number of epoxy groups in the epoxy compound (D) is preferably 0.5 to 5 equivalents, more preferably 0.5 to 1.5 equivalents, of the number of carboxyl groups in the block polymer (C) to be reacted. Further, the above reaction may be carried out in various solvents or in a molten state.

The epoxy compound (D) having two or more epoxy groups to be reacted is preferably 0.1 to 2.0 equivalents, and 0.2 to 1.5 equivalents of the number of carboxyl groups in the block polymer (C) to be reacted. More preferred.

In the reaction, after the synthesis reaction of the block polymer (C) is completed, the epoxy compound (D) may be added to the reaction system without isolating the block polymer (C), and the reaction may be carried out as it is. In that case, the carboxyl group of the unreacted polyester (a) used in excess when synthesizing the block polymer (C) reacts with some epoxy groups of the epoxy compound (D) to form an ester bond. You may.

A preferred polymer compound (E) according to the present invention is a block polymer (C) having a structure having carboxyl groups at both ends, and an epoxy compound (D) having two or more epoxy groups, each of which has a carboxyl group and an epoxy group. It is not necessarily necessary to synthesize the above-mentioned block polymer (C) and the above-mentioned epoxy compound (D) as long as it has a structure equivalent to that having a structure bonded via an ester bond formed by a group. The ester bond formed by a carboxyl group and an epoxy group herein also includes an ester bond formed by a carboxyl group and a hydroxyl group formed from an epoxy group by reacting with the carboxyl group.

Moreover, the polymer compound (E) according to the present invention can be obtained by obtaining the polyester (a) from the diol (a1) and the dicarboxylic acid (a2), and then producing the compound (b) and/or without isolating the polyester (a). Alternatively, it may be reacted with an epoxy compound (D).

In the present invention, the number average molecular weight of the compound (b) constituting the block (B) composed of the compound (b) having hydroxyl groups at both ends in the polymer compound (E) is calculated from the measured value of the hydroxyl group value. However, from the viewpoint of antistatic property, its durability, and the wood texture of the molded product, it is preferably 400 to 10,000, more preferably 1,000 to 8,000, and still more preferably 2,000 to 8. ,000. The method for measuring the hydroxyl value and the method for calculating the number average molecular weight from the hydroxyl value are described below.

<How to calculate number average molecular weight from hydroxyl value>
The hydroxyl value was measured using the hydroxyl value measuring method described below, and the number average molecular weight (hereinafter also referred to as "Mn") was determined using the following formula.
Number average molecular weight = (56110 x 2) / hydroxyl value

<Hydroxyl value measurement method>
・Reagent A (acetylating agent)
(1) Triethyl phosphate 1560mL
(2) Acetic anhydride 193mL
(3) Perchloric acid (60%) 16g
The above reagents are mixed in the order of (1) → (2) → (3).
・Reagent B
Mix pyridine and pure water at a volume ratio of 3:1.
・Reagent C
Add 2 to 3 drops of phenolphthalein solution to 500 mL of isopropyl alcohol, and neutralize with 1N-KOH aqueous solution.

First, 2 g of a sample is weighed into a 200 mL Erlenmeyer flask, 10 mL of triethyl phosphate is added, and the sample is heated and dissolved. Add 15 mL of Reagent A, stopper and shake vigorously. Add 20 mL of Reagent B, stopper and shake vigorously. Add 50 mL of Reagent C. Titrate with 1N-KOH aqueous solution and calculate using the formula below.
Hydroxyl value [mgKOH/g]=56.11×f×(T-B)/S
f: factor of 1N-KOH aqueous solution
B: Blank test titer [mL]
T: Main test titer [mL]
S: Sample amount [g]

In addition, in the present invention, the number average molecular weight of the polyester (a) constituting the block (A) composed of polyester (a) in the polymer compound (E), in terms of polystyrene, is the antistatic property and its sustainability. , from the viewpoint of the wood texture of the molded article, preferably from 1,000 to 10,000, more preferably from 1,500 to 8,000, even more preferably from 2,500 to 7,500. If the number average molecular weight is less than 1,000, the storage stability may be poor; if it exceeds 10,000, the reaction to obtain the polymer compound (E) may take a long time, and the resulting polymer may be uneconomical. There is a risk that the molecular compound will become colored due to long-term reaction.

The method for measuring the number average molecular weight in terms of polystyrene is preferably gel permeation chromatography (GPC), and the method for this measurement is shown below.

<Method for measuring number average molecular weight in terms of polystyrene>
The number average molecular weight (hereinafter also referred to as "Mn") was measured by gel permeation chromatography (GPC). The conditions for measuring Mn are as follows.
Equipment: GPC device manufactured by JASCO Corporation Solvent: Chloroform reference material: Polystyrene detector: Differential refractometer (RI detector)
Column stationary phase: Shodex LF-804 manufactured by Showa Denko K.K.
Column temperature: 40℃
Sample concentration: 1mg/1mL
Flow rate: 0.8mL/min.
Injection volume: 100μL

Furthermore, in the polymer compound (E), the number average molecular weight of the block polymer (C) having a structure having carboxyl groups at both ends, in terms of polystyrene, is in terms of antistatic property, its sustainability, and the woody feel of the molded product. , preferably 5,000 to 50,000, more preferably 10,000 to 45,000, and still more preferably 15,000 to 40,000. If the number average molecular weight is less than 5,000, the storage stability may be poor, and if it exceeds 50,000, the reaction to obtain the polymer compound (E) may take a long time and be less economical, or the obtained polymer may be There is a risk that the molecular compound will become colored due to long-term reaction. The method for measuring the number average molecular weight in terms of polystyrene is preferably gel permeation chromatography (GPC), and the method for this measurement is as described above.

In the resin composition, the content of component (Y) is 1 to 60 parts by mass based on 100 parts by mass of the synthetic resin, and is preferably from the viewpoint of antistatic property and its sustainability, and the woody feel of the molded product. The amount is 5 to 50 parts by weight, more preferably 10 to 40 parts by weight. If it is less than 1 part by mass, sufficient antistatic properties may not be obtained, and if it exceeds 60 parts by mass, the physical properties of the molded article may be adversely affected.

The resin composition of the present invention has an antistatic property, its sustainability, and the woody texture of the molded product, and furthermore, it has at least one type selected from the group of alkali metal salts (F) and ionic liquids (G). It is preferable to contain.

Hereinafter, first, the alkali metal salt (F) will be explained. Examples of the alkali metal salt (F) include salts of organic acids or inorganic acids, and examples of the alkali metal include lithium, sodium, potassium, cesium, rubidium, 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, and lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, etc. Aliphatic dicarboxylic acids having 1 to 12 carbon atoms; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethane Examples include sulfonic acids having 1 to 20 carbon atoms such as sulfonic acid. 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 salts are preferred, and sodium is more preferred, from the standpoint of antistatic properties, durability, and safety for living organisms and the environment. In addition, from the viewpoint of antistatic properties and their durability, acetic acid salts, perchloric acid salts, p-toluenesulfonic acid salts, and dodecylbenzenesulfonic acid salts are preferable, and dodecylbenzenesulfonic acid salts are more preferable. Two or more types of alkali metal salts may be used.

Specific examples of the alkali metal salt (F) include lithium acetate, sodium acetate, potassium acetate, lithium chloride, sodium chloride, potassium chloride, lithium phosphate, sodium phosphate, potassium phosphate, lithium sulfate, and sodium sulfate. , lithium perchlorate, sodium perchlorate, potassium perchlorate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, dodecyl Examples include potassium benzenesulfonate. Among these, lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, and dodecylbenzenesulfone are preferable in terms of antistatic properties, durability, and safety for living organisms and the environment. The most preferred is sodium dodecylbenzenesulfonate.

In the resin composition of the present invention, the content of the alkali metal salt (F) is 0.01 to 0.01 to 100 parts by mass of the synthetic resin, from the viewpoint of antistatic properties, durability thereof, and wood texture of the molded product. It is preferably 15.0 parts by weight, more preferably 0.1 to 12.0 parts by weight, even more preferably 0.5 to 10.0 parts by weight, and even more preferably 1.0 to 8.0 parts by weight. 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 15.0 parts by mass, it may adversely affect the physical properties of the resin. There may be cases.

Next, the ionic liquid (G) will be explained.
Examples of the ionic liquid (G) include a liquid having a melting point of 100° C. or less, at least one of the cations or anions constituting the ionic liquid being an organic ion, and having an initial conductivity of 1 to 200 ms/cm, preferably is a room temperature molten salt having a velocity of 10 to 200 ms/cm, such as the room temperature molten salt described in International Publication No. 95/15572.

Examples of the cations constituting the ionic liquid (G) include cations selected from the group consisting of amidinium, pyridinium, pyrazolium, and guanidinium cations.

Among these, examples of amidinium cations include the following.
(1) Imidazolinium cation Examples include those having 5 to 15 carbon atoms, such as 1,2,3,4-tetramethylimidazolinium, 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 Examples include those having 6 to 15 carbon atoms, such as 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetra Methyl-1,4,5,6-tetrahydropyrimidinium;
(4) Dihydropyrimidinium cation Examples include those having 6 to 20 carbon atoms, such as 1,3-dimethyl-1,4-dihydropyrimidinium, 1,3-dimethyl-1,6-dihydropyrimidinium 8-methyl-1,8-diazabicyclo[5,4,0]-7,9-undecadienium, 8-methyl-1,8-diazabicyclo[5,4,0]-7,10-un Decadienium.

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

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

Examples of guanidinium cations include the following.
(1) Guanidinium cation having an imidazolinium skeleton Examples include those having 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3 ,4-trimethylimidazolinium;
(2) Guanidinium cation having an imidazolium skeleton Examples include those having 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4 -trimethylimidazolium;
(3) Guanidinium cation having a tetrahydropyrimidinium skeleton Examples include those having 10 to 20 carbon atoms, such as 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) Guanidinium cation having a dihydropyrimidinium skeleton Examples include those 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 cations may be used alone or in combination of two or more. Among these, from the viewpoint of antistatic properties and durability, amidinium cations are preferred, imidazolium cations are more preferred, and 1-ethyl-3-methylimidazolium cations and 1-ethyl-3methylimidazolium cations are particularly preferred. Lium dodecylbenzene sulfonate.

In the ionic liquid (G), examples of the organic acid or inorganic acid constituting the anion include the following. Examples of organic acids include carboxylic acids, sulfuric esters, sulfonic acids, and phosphoric esters; examples of inorganic acids include superstrong acids (e.g., fluoroboric acid, tetrafluoroboric acid, perchloric acid, phosphorus hexafluoride). phosphoric acid and boric acid). The above organic acids and inorganic acids may be used alone or in combination of two or more.

Among organic acids and inorganic acids, the ionic liquid (G) is preferable from the viewpoint of antistatic properties and its sustainability when the Hamett acidity function (-H0) of the anion constituting the ionic liquid (G) is 12 -100, a conjugate base of a super strong acid, an acid that forms an anion other than the conjugate base of a super strong acid, and mixtures thereof.

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

Superstrong acids also include those derived from protic acids and combinations of protic acids and Lewis acids, and mixtures thereof. Examples of protonic acids as superstrong acids include bis(trifluoromethylsulfonyl)imidic acid, bis(pentafluoroethylsulfonyl)imidic acid, tris(trifluoromethylsulfonyl)methane, perchloric acid, fluorosulfonic acid, and alkanes( 1-30 carbon atoms) sulfonic acids (e.g. methanesulfonic acid, dodecane sulfonic acid, etc.), poly(n=1-30) fluoroalkane (1-30 carbon atoms) sulfonic acids (e.g. trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboric acid. Among these, preferred from the viewpoint of ease of synthesis are borofluoric acid, trifluoromethanesulfonic acid, bis(trifluoromethanesulfonyl)imidic acid, and bis(pentafluoroethylsulfonyl)imidic acid.

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

Lewis acids include, for example, boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof. Among these, boron trifluoride and phosphorus pentafluoride are preferred from the viewpoint of the initial conductivity of the ionic liquid.

Although the combination of protonic acid and Lewis acid is arbitrary, examples of super strong acids made of these combinations include tetrafluoroboric acid, hexafluorophosphoric acid, tantalic acid hexafluoride, antimonic acid hexafluoride, and hexafluoroantimonic acid. Examples include chlorinated tantalum sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chlorotrifluoroboric acid, hexafluoroarsenic acid, and mixtures thereof.

Among these anions, conjugate bases of super strong acids (super strong acids consisting of protonic acids and super strong acids consisting of a combination of protonic acids and Lewis acids) are preferable from the viewpoint of the antistatic property of the ionic liquid and its sustainability. More preferred are a super strong acid consisting of a protic acid and a conjugate base of a super strong acid consisting of a protic acid and boron trifluoride and/or phosphorous pentafluoride.

Among the ionic liquids (G), preferred are ionic liquids having amidinium cations in terms of antistatic properties and their sustainability, and more preferred are ions having 1-ethyl-3-methylimidazolium cations. Particularly preferred is 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

In the resin composition of the present invention, the content of the ionic liquid (G) is 0.01 to 15 parts by mass based on 100 parts by mass of the synthetic resin, from the viewpoint of antistatic properties, durability thereof, and wood texture of the molded product. 0 parts by weight is preferred, 0.1 to 12.0 parts by weight is more preferred, 0.5 to 10.0 parts by weight is even more preferred, and 1.0 to 8.0 parts by mass is even more preferred. If the amount of ionic liquid (G) is less than 0.01 parts by mass, the effect of adding ionic liquid (G) may not be sufficient, and if it exceeds 15.0 parts by mass, it may have an adverse effect on the physical properties of the resin. There may be cases.

In the resin composition of the present invention, the alkali metal salt (F) and the ionic liquid (G) may be used together.

When the alkali metal salt (F) and ionic liquid (G) are blended into a synthetic resin, they may be directly blended, or the alkali metal salt (F) and ionic liquid (G) may be blended directly into the reaction system during the synthesis reaction of the polymer compound (E). One or more selected from the group of salts (F) and ionic liquids (G) may be added.

It is also preferable that the resin composition of the present invention contains a compatibilizer from the viewpoints of antistatic properties, durability thereof, and wood texture of the molded product. As the compatibilizing agent, one or more types of acid anhydride-modified polyolefins may be mentioned. Acid anhydride-modified polyolefin is a polymer obtained by grafting an acid anhydride such as maleic anhydride onto a polyolefin.

The polyolefin portion of the acid anhydride-modified polyolefin includes those obtained by polymerization or copolymerization of ethylene, propylene, α-olefin, or diene, and examples of the α-olefin include 1-butene, 4-methyl-1-pentene, etc. , 1-pentene, 1-octene, 1-decene, 1-dodecene and the like. Examples of the diene include butadiene, isoprene, cyclopentadiene, 1,11-dodecadiene and the like. Moreover, other copolymerization components may be included in addition to these. More specifically, polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/propylene/diene terpolymer, ethylene/1-butene copolymer, ethylene/vinyl acetate copolymer, and mixtures thereof, etc. can be mentioned. Among these, from the viewpoint of antistatic properties and durability, and the woody feel of the molded product, those obtained by polymerizing or copolymerizing ethylene, propylene, α-olefins having 4 to 12 carbon atoms, butadiene, and isoprene are preferred; , propylene, an α-olefin having 4 to 8 carbon atoms, and butadiene are more preferably polymerized or copolymerized, and ethylene, propylene, and butadiene are more preferably polymerized or copolymerized.

Examples of the acid anhydride include maleic anhydride and itaconic anhydride, with maleic anhydride being preferred from the viewpoint of antistatic properties, durability thereof, and wood texture of the molded article.

The acid anhydride-modified polyolefin is preferably maleic anhydride-modified polyolefin, and more preferably maleic anhydride-modified polypropylene, from the viewpoint of antistatic properties, durability thereof, and woody feel of the molded product. The acid anhydride-modified polyolefin can be obtained by grafting a polyolefin with an acid anhydride such as maleic anhydride by a conventionally known method, and various commercially available products may be used.

In the resin composition of the present invention, the content of the compatibilizer is 0.01 to 30.0 parts by mass based on 100 parts by mass of the synthetic resin, from the viewpoint of antistatic properties, durability thereof, and wood texture of the molded product. parts by weight, more preferably 0.1 to 20.0 parts by weight, and even more preferably 0.5 to 15.0 parts by weight. If it is less than 0.01 parts by mass, the effect of addition may not be sufficient, and if it exceeds 30.0 parts by mass, it may have an adverse effect on the physical properties of the resin.

The resin composition of the present invention may further contain a salt of a Group 2 element within a range that does not impair the effects of the present invention.

Examples of salts of Group 2 elements include salts of organic acids or inorganic acids, and 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, and lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, etc. Aliphatic dicarboxylic acids having 1 to 12 carbon atoms; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethane Examples include sulfonic acids having 1 to 20 carbon atoms such as sulfonic acid. 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.

Furthermore, the resin composition of the present invention may contain a surfactant within a range that does not impair the effects of the present invention. As surfactants, nonionic, anionic, cationic or amphoteric surfactants can be used.

Examples of nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; fatty acid esters of polyethylene oxide and glycerin. , pentaerythritol fatty acid ester, sorbitol or sorbitan fatty acid ester, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, and other polyhydric alcohol type nonionic surfactants.

Examples of anionic surfactants include carboxylates such as alkali metal salts of higher fatty acids; sulfate ester salts such as higher alcohol sulfate ester salts and higher alkyl ether sulfate ester salts; alkylbenzene sulfonates; alkyl sulfonates; Examples include sulfonate salts such as paraffin sulfonate; phosphate ester salts such as higher alcohol phosphate ester salts;

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

Examples of the amphoteric surfactants include amino acid type amphoteric surfactants such as higher alkylaminopropionates, betaine type amphoteric surfactants such as higher alkyl dimethyl betaines, higher alkyl dihydroxyethyl betaines, etc. These may be used alone or Two or more types can be used in combination.

When blending a surfactant, the blending amount is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 4 parts by mass, based on 100 parts by mass of the synthetic resin.

Furthermore, the resin composition of the present invention may contain a polymer type antistatic agent within a range that does not impair the effects of the present invention. As the polymer type antistatic agent, for example, a polymer type antistatic agent such as known polyether ester amide can be used. Examples include polyetheresteramides consisting of polyoxyalkylene adducts of bisphenol A described in . Further, a block polymer having a repeating structure of 2 to 50 bonding units between a polyolefin block and a hydrophilic polymer block can be used, and examples thereof include the block polymer described in US Pat. No. 6,552,131.

The amount of the polymer antistatic agent added is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the synthetic resin.

In addition, the resin composition of the present invention may contain phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, amine antioxidants, ultraviolet absorbers, hindered amines, within a range that does not impair the effects of the present invention. Various additives such as a light stabilizer can be further added, thereby stabilizing the resin composition of the present invention.

Examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, and 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'-oxamide-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-ethylhexyl -3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 2,2'-ethylenebis(4,6-di-tert-butylphenol), 3,5-di-tert -Butyl-4-hydroxy-benzenepropanoic acid and C13-15 alkyl ester, 2,5-di-tert-amylhydroquinone, hindered phenol polymer (trade name AO.OH.98, manufactured by Adeka Palmarol), 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]-dioxaphosphobine, hexamethylenebis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate, bis[monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate]calcium salt, 5,7-bis(1,1 -dimethylethyl)-3-hydroxy-2(3H)-benzofuranone and o-xylene reaction product, 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-hydroxybenzylthioacetate , 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-methyl phenol), 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-(3',5'-di-tert-butyl-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- 3-(3,5-dialkyl-4-hydroxyphenyl) such as butyl-4-hydroxyphenyl)propionic acid amide, lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide, etc. Propionic acid derivatives, N,N'-bis[2-"2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy"ethyl]oxamide, N,N'-(1,3- propanediyl)bis[3,5-di-tert-butyl-4-hydroxybenzenepropanamide], 1,6-hexanediolbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate , 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol, N,N'-bis[3-(4 -hydroxyphenyl)propanamide], bis[3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionic acid]thiobisethylene, N,N'-(1,6-hexanediyl)bis [3,5-di-tert-butyl-4-hydroxybenzenepropanamide], octyl 3-(4-hydroxy-3,5-diisopropylphenyl)propionate, calcium bis[3,5-di-tert-butyl- 4-hydroxybenzyl(ethoxy)phosphonate], 2,4-bis(octylthiomethyl)-6-methylphenol, 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltrimethyl) (decyl)-2H-1-benzopyran-6-ol and the like.

From the viewpoint of antistatic properties, durability, and wood texture of the molded product, a preferred phenolic antioxidant is 1,3,5-tris(3,5-di-tert-butyl-hydroxybenzyl)-1,3 ,5-triazine-2,4,6(1H,3H,5H)-trione, 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol) ), 6,6'-di-tert-butyl-4,4'-butylidene di-m-cresol, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy] -1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl )-2,4,6-trimethylbenzene, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate], N,N'-hexane-1,6-diylbis( 3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)), benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 Branched alkyl esters, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), hexa Examples include methylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).

The amount of these phenolic antioxidants added is preferably 0.001 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, per 100 parts by weight of the synthetic resin.

Next, examples of phosphorus antioxidants include bis(decyl)pentaerythritol diphosphite, bis(diisodecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, and bis(tridecyl)pentaerythritol. Diphosphite, bis(stearyl)pentaerythritol diphosphite, trilaurylthiophosphite heptakis(dipropylene glycol) triphosphite 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 poly(dipropylene glycol) phenyl phosphite, tetra(tridecyl) isopropylidene diphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidene bis(2-tert-butyl-5- methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl) [1,1-biphenyl]-4,4'-diylbisphosphonite, tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4'-biphenylidenephosphonite, tetra(C12- C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, alkyl (C10) bisphenol A phosphite, 4,4'-butylidene-bis(3-methyl-6-tert-butylphenylditridecyl) phosphite , 2,2'-methylenebis-4,6-di-tert-butylphenyl-2-butylphosphite, 2,2'-methylenebis-4,6-di-tert-butylphenyl-2-ethylhexylphosphite, 2 , 2'-methylenebis-4,6-di-tert-butylphenyl-2-decylphosphite, 2,2'-methylenebis-4,6-di-tert-butylphenyl-2-dodecylphosphite, 2,2 '-Methylenebis-4,6-di-tert-butylphenyl-2-octadecylphosphite, 2,2'-ethylenebis(4,6-di-tert-butylphenyl)fluorophosphite, 6-ethylhexyl-2, 4,8,10-tetra-tert-butyldibenzo [d. f][1,3,2]dioxaphosphepine, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert -Butyldibenzo [d. f][1,3,2]dioxaphosphepine (Sumilizer-GP), triethyl phosphite, tris(2-ethylhexyl) phosphite, tri(decyl) phosphite, triisodecyl phosphite, triisooctyl phosphite Phosphite, trilauryl phosphite, tris(tridecyl) phosphite, tristearyl phosphite, tris(dipropylene glycol) phosphite, trioleylphosphite, trisnonylphenyl phosphite, dioleyl hydrogen phosphite, diisooctylphenyl Phosphite, di(decyl)monophenylphosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylmonodecylphosphite, diphenylmono(tridecyl)phosphite, diphenyloctylphosphite, diphenylisooctylphosphite, diphenylisodecyl Phosphite, diphenyltridecyl phosphite, diisooctyl phosphite, bis(tridecyl) phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, tris[2-[(2 , 4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl]amine, tris(2,4-di-tert -butylphenyl) phosphite, tetraphenyldipropylglycol diphosphite, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, tetrakis(2, 4-di-tert-butylphenyl)biphenylene diphosphonite, hydrogenated bisphenol-A-pentaerythritol phosphite polymer (Johoku Chemical Co., Ltd. trade name JPH-3800), 2-hydroxyethyl methacrylate acid phosphate (Johoku Chemical Co., Ltd.) company's product name "JPA-514"), sten bisphenol-A phosphite polymer (Johoku Kagaku Kogyo Co., Ltd. product name HBP), and stearyl acid phosphate zinc salt (Johoku Kagaku Kogyo Co., Ltd. product name JP-518Zn).

From the viewpoints of antistatic properties, durability, and wood texture of the molded product, the preferred phosphorus antioxidant is 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane , 2,2'-methylenebis(4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra -C12-15-alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), 2-ethylhexyldiphenylphosphite, isodecyldiphenylphosphite, triisodecylphosphite, triphenylphosphite phyto, 3,9-bis[2,4-bis(1-methyl-1-phenylethyl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3, 9-bis[2,4-di-tert-butylphenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, tetrakis(2,4-di-tert-butylphenyl )-4,4'-bisphenyl diphosphonite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenylisodecyl phosphite, etc. can be mentioned.

The amount of these phosphorus antioxidants added is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the synthetic resin.

Next, examples of thioether antioxidants include 3,3'-thiodipropionic acid, alkyl (C12-14) thiopropionic acid, di(lauryl)-3,3'-thiodipropionate, di( tridecyl)-3,3'-thiodipropionate, di(myristyl)-3,3'-thiodipropionate, di(stearyl)-3,3'-thiodipropionate, di(octadecyl)-3, 3'-thiodipropionate, laurylstearylthiodipropionate, tetrakis[methylene-3-(dodecylthio)propionate]methane, thiobis(2-tert-butyl-5-methyl-4,1-phenylene)bis(3- (dodecylthio)propionate), 2,2'-thiodiethylenebis(3-aminobutenoate), 4,6-bis(octylthiomethyl)-o-cresol, 2,2'-thiodiethylenebis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2-ethylhexyl-(3,5-di-tert-butyl) -4-hydroxybenzyl)thioacetate, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(4-methyl-6-tert-butylphenol), 4,4' -[thiobis(methylene)]bis(2-tert-butyl-6-methyl-1-hydroxybenzyl), bis(4,6-di-tert-butylphenol-2-yl) sulfide, tridecyl-3,5-di -tert-butyl-4-hydroxybenzylthioacetate, 1,4-bis(octylthiomethyl)-6-methylphenol, 2,4-bis(dodecylthiomethyl)-6-methylphenol and the like.

From the viewpoint of antistatic property, its durability, and the wood texture of the molded product, a preferable thioether antioxidant is 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3 -diylbis[3-(dodecylthio)propionate], di(tridecyl)3,3'-thiodipropionate, bis[2-methyl-4-{3-n-dodecylthiopropionyloxy}-5-tert-butylphenyl ] Sulfide, 4-[4-hydroxy-3-tert-butyl-6-methylphenylthio]-2-tert-butyl-5-methylphenyl-3-dodecylthiopropanoate, bis[2-methyl-4- {3-n-alkyl (C12 or C14) thiopropionyloxy}-5-tert-butylphenyl] sulfide, didodecyl-3,3'-thiodipropionate, 3,3'-thiodipropionic acid dioctadecyl ester etc.

The amount of these thioether antioxidants added is preferably 0.001 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the synthetic resin.

Next, examples of amine antioxidants include dioctylmethylamine oxide, trioctylamine oxide, didecylmethylamine oxide, tridecylamine oxide, di(hydrogenated C12-14 alkyl)methylamine oxide, tri(hydrogenated C12-14 alkyl)methylamine oxide, hydrogenated C16-18 alkyl) amine oxide, di(hydrogenated C16-18 alkyl) methylamine oxide, tri(hydrogenated C16-18 alkyl) amine oxide, di(C20-22) alkylmethylamine oxide and tri(C20-22 ) amine oxide compounds such as amine oxide, N,N-dibenzylhydroxylamine, phenylnaphthylamine, 4,4'-dimethoxydiphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, 4-iso N,N-diarylhydroxylamine such as propoxydiphenylamine, N,N-alkylarylhydroxylamine, N,N-dicycloalkylhydroxylamine, diethylhydroxylamine, dioctylhydroxylamine, didodecylhydroxylamine, dioctadecylhydroxylamine, etc. N,N-dialkylhydroxylamine is mentioned.

Next, as the ultraviolet absorber, for example, 2-(2-hydroxy-5-methylphenyl)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'-methylenebis(4-ethylhydroxy-6-benzotriazolyl) polyethylene glycol ester of 2,2'-methylenebis(4-methyl-6-benzotriazolylphenol), 2-(2-hydroxy-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-butyl Phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxy) ethyl)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-hydroxy-4-(3-methacryloyloxy) 2-(2-hydroxyphenyl)benzotriazoles such as -2-hydroxypropyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole; 2-(4, 6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-( octyloxy)phenol, 2-(4,6-bis(4-butoxy-2-methylphenyl)-1,3,5-triazin-2-yl)-3,5-dibutoxyphenol, 2-(4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)phenol, 2-(4,6 -di([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-methylhexyl-2-(4,(4,6 - Phenol-containing triazines such as di([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-3-hydroxyphenoxy)propanoate; 2,2'-dihydroxy- 4,4'-dimethoxybenzophenone, 2,4-dihydroxybenzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone), 1,4-bis(4-benzoyl-3-hydroxyphenoxy)-butane, etc. 2-hydroxybenzophenones; 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-hydroxy)benzoate, Benzoates such as -butyl-4-hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, and behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2 -Substituted oxanilides such as ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-2-cyano-3,3-diphenylacrylate, 2'-ethylhexyl-2-cyano- 3,3-diphenylacrylate, ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, 4-(2-cyano-3-( 4-ethylphenoxy)-3-oxopropenyl)phenyl-4-propylcyclohexane-1-carboxylate, 4-(2-cyano-3-(4-ethylphenoxy)-3-oxopropenyl)phenyl-4-propylbenzoate , 4-butylphenyl-4-(2-cyano-3-oxo-3-(4-propylphenoxy)propenyl)benzoate, 4-(2-cyano-3-(4-cyanophenoxy)-3-oxopropenyl) Phenyl-4-pentylbenzoate, 4-(2-cyano-3-(4-fluorophenoxy)-3-oxopropenyl)phenyl-4-methylcyclohexane-1-carboxylate, 4-(2-cyano-3-( 4-Methoxyphenoxy)-3-oxopropenyl)phenyl-4-hexylcyclohexane-1-carboxylate, 4-(2-cyano-3-(4-ethoxyphenoxy)-3-oxopropenyl)phenyl-4-octylcyclohexane -1-carboxylate, 4-(2-cyano-3-oxo-3-(4-propoxyphenoxy)propenyl)phenyl-4-propylcyclohexane-1-carboxylate, 4-(2-cyano-3-oxo- 3-(4-pentylphenoxy)propenyl)phenyl-4-propylcyclohexane-1-carboxylate, 4-(2-cyano-3-(4-octylphenoxy)-3-oxopropenyl)-4-propylcyclohexane-1 -carboxylate, 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis-[[(2'-cyano-3',3'-diphenyl) cyanoacrylates such as acryloyl)oxy]methyl]propane; salicylic acids such as 4-tert-butylphenyl salicylate, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate) Examples include various metal salts or metal chelates, especially nickel and chromium salts or chelates.

A preferred UV absorber from the viewpoint of antistatic properties, durability, and wood texture of the molded product is 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl ) phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl) yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazole- 2-yl)-6-tert-butyl-4-methylphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy) )ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, [2-hydroxy-4-(octyloxy)phenyl]( phenyl)methanone.

The amount of these ultraviolet absorbers added is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 20 parts by mass, and even more preferably 0.03 to 10 parts by mass, per 100 parts by mass of the synthetic resin. Preferably, 0.05 to 5 parts by mass is even more preferable.

Next, examples of hindered amine light stabilizers include compounds having the structure of 2,2,6,6-tetramethylpiperidyl, and specifically, examples include, for example, 2,2,6,6-tetramethylpiperidyl. -4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6 -tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidyl) -4-yl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, butane-1,2,3,4-tetracarboxylic acid tetrakis (2,2,6,6- tetramethyl-4-piperidinyl), butane-1,2,3,4-tetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl), bis(2,2,6,6- Tetramethyl-4-piperidyl) di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) 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-tertiary octylamino-s-triazine polycondensate, 1-methyl-10-(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and bis Polycondensate of (2,2,6,6-tetramethyl-4-piperidyl)sebacate, butanetetracarboxylic acid tetramethyl ester, ester with spiroglycol and N-methylpiperidinol, butanetetracarboxylic acid, 3- Polycondensate of ester with hydroxy-2,2-dimatepentanal and N-methylpiperidinol, 1,2,3,4-butanetetracarboxylic acid tetramethyl ester, 2,2,6,6-tetra Polycondensate of methyl-4-piperidinol and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, 2,4 -dichloro-6-(1,1,3,3-tetramethylbutylamino)-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) Hexamethylene diamine polycondensate, 2,4-dichloro-6-(1,1,3,3-tetramethylbutylamino)-1,3,5-triazine, 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-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino) )-s-triazin-6-yl]aminoundecane, 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, Examples include 6,6-tetramethyl-1-undecyloxy)piperidyl)carbonate.

A preferred hindered amine light stabilizer from the viewpoint of antistatic properties, durability, and wood texture of the molded product is tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3 , 4-tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8-10-tetraoxospiro[5. 5] Mixed esterified product with undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol, and 3,9-bis(2-hydroxy-1, Mixed esterified product with 1-dimethylethyl)-2,4,8-10-tetraoxospiro[5.5]undecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis( 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6,- Pentamethyl-4-piperidyl methacrylate, 2,2,6,6,-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidini of C12-21 saturated fatty acid and C18 unsaturated fatty acid Examples include luesters.

The amount of these hindered amine light stabilizers added is preferably 0.001 to 30 parts by weight, more preferably 0.01 to 20 parts by weight, and 0.03 to 10 parts by weight based on 100 parts by weight of the synthetic resin. Even more preferred, and even more preferred is 0.05 to 5 parts by mass.

Furthermore, when a polyolefin resin is used as the synthetic resin, if necessary, a known neutralizing agent may be added to neutralize the residual catalyst in the polyolefin resin to the extent that the effects of the present invention are not impaired. It is preferable to add. Examples of the neutralizing agent include fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, or fatty acid amides such as ethylene bis(stearamide), ethylene bis(12-hydroxystearamide), and stearamide. These neutralizing agents may be used in combination.

The resin composition of the present invention may further contain other additives as necessary, such as aromatic carboxylic acid metal salts, alicyclic alkyl carboxylic acid metal salts, Crystal nucleating agents such as 3-butyl aluminum benzoate, aromatic phosphate metal salts, dibenzylidene sorbitol, metal soaps, hydrotalcites, triazine ring-containing compounds, metal hydroxides, phosphate ester flame retardants, condensed phosphorus Acid ester flame retardants, phosphate flame retardants, inorganic phosphorus flame retardants, (poly)phosphate flame retardants, halogen flame retardants, silicone flame retardants, antimony oxides such as antimony trioxide, and other inorganic retardants. Combustion aids, other organic flame retardant aids, neutralizers, anti-aging agents, fillers, pigments, lubricants, processing aids, plasticizers, reinforcing materials, pigments, dyes, and blowing agents may be added. .

Examples of the triazine ring-containing compounds include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, and trimethylene. Examples include dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimelamine, and the like.

Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kismer 5A (magnesium hydroxide, manufactured by Kyowa Chemical Industry Co., Ltd.), and the like.

Examples of the phosphate ester flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, Trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, tris-isopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis-(t-butylphenyl) phenyl phosphate, tris-(t-butyl) phenyl) phosphate, isopropylphenyl diphenyl phosphate, bis-(isopropylphenyl) diphenyl phosphate, tris-(isopropylphenyl) phosphate, and the like.

Examples of the condensed phosphate flame retardant include 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(dixylenyl phosphate), bisphenol A bis(diphenyl phosphate), and the like.

Examples of the above (poly)phosphate flame retardants include ammonium salts and amine salts of (poly)phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melamine pyrophosphate, and piperazine pyrophosphate. .

Examples of other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, and montmorillonite, and surface-treated products thereof.For example, TIPAQUE R-680 (oxidized Titanium: manufactured by Ishihara Sangyo Co., Ltd.), Kyowa Mag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), Alkamizer 4 (zinc modified hydrotal) Various commercially available products such as those manufactured by Kyowa Chemical Industry Co., Ltd. can be used. Furthermore, examples of other organic flame retardant aids include pentaerythritol.

Examples of the crystal nucleating agent include inorganic crystal nucleating agents and organic crystal nucleating agents. Specific examples of inorganic crystal nucleating agents include kaolinite, synthetic mica, clay, zeolite, silica, graphite, carbon black, Mention may be made of metal salts such as magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, neodymium oxide and phenylphosphonate. These inorganic crystal nucleating agents may be modified with an organic substance in order to improve their dispersibility in the composition.

Specific examples of organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, and calcium oxalate. , sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearic acid Metal organic carboxylates such as barium, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, and sodium cyclohexane carboxylate. Salts, organic sulfonates such as sodium p-toluenesulfonate and sodium sulfoisophthalate, stearamide, ethylene bislaurate amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris(t-butylamide) ), benzylidene sorbitol and its derivatives, phosphorus compound metal salts such as sodium-2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate, and 2,2-methylbis( Examples include sodium 4,6-di-t-butylphenyl.

The above neutralizing agent is added to neutralize the residual catalyst in the synthetic resin, and includes, for example, fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, or ethylene bis(stearamide). , ethylene bis(12-hydroxystearamide), stearic acid amide, and other fatty acid amide compounds.

The above lubricants include, for example, pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, microwax, synthetic paraffin, low molecular weight polyethylene, and polyethylene wax; halogenated hydrocarbon lubricants; fatty acid lubricants such as higher fatty acids and oxyfatty acids. Fatty acid amide lubricants such as fatty acid amide and bis fatty acid amide; Ester lubricants such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, and fatty alcohol esters of fatty acids (ester wax) Examples include metal soaps, fatty alcohols, polyhydric alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, partial ester-based lubricants of fatty acids and polyglycols and polyglycerols, silicone oils, mineral oils, and the like.

Examples of the processing aid include acrylic processing aids, and the acrylic processing aid may be one obtained by polymerizing one type of (meth)acrylic acid ester or copolymerizing two or more types of (meth)acrylic acid esters. Examples of (meth)acrylic acid esters to be polymerized or copolymerized include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, and isobutyl. Examples include (meth)acrylic acid esters such as acrylate, t-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and tridecyl methacrylate. In addition to the above, (meth)acrylic acid and (meth)acrylic acid ester containing a hydroxy group may also be mentioned.

Examples of the plasticizer include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, ether ester plasticizers, and epoxy plasticizers.

Examples of the above reinforcing materials include glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastenite, sepiolite, asbestos, and slag fiber. , inorganic fibrous reinforcement materials such as zonolite, elestadite, gypsum fiber, silica fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, and boron fiber, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, Acetate fibers, kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, Manila hemp, sugar cane, organic fibrous reinforcement materials such as wood pulp, waste paper, waste paper and wool, glass flakes, non-swellable mica, graphite , metal foil, ceramic beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, finely divided silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide , titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dawsonite, and white clay. These reinforcing materials may be coated or bundled with a thermoplastic resin such as ethylene/vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, and may be coated with a coupling agent such as aminosilane or epoxysilane. It may be processed.

Examples of the above-mentioned fillers include talc, calcium carbonate, magnesium sulfate fibers, silica, clay, kaolin, alumina, carbon black, and glass fibers, which have been subjected to treatments such as pulverization or micronization or surface treatment. Good too.

Examples of the above pigments include inorganic pigments, organic pigments, and metallic pigments. Examples of the inorganic pigments include titanium oxide, carbon black, titanium yellow, iron oxide pigments, ultramarine blue, cobalt blue, chromium oxide, spinel green, and chromium. Examples include acid lead pigments and cadmium pigments.

Examples of organic pigments include azo pigments such as azo lake pigments, benzimidazolone pigments, diallylide pigments, and condensed azo pigments, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, isoindolinone pigments, quinophthalone pigments, quinacridone pigments, and perylene pigments. Pigments, anthraquinone pigments, perinone pigments, condensed polycyclic pigments such as dioxazine violet, and the like.

Examples of metallic pigments include scale-like aluminum metallic pigments, spherical aluminum pigments used to improve weld appearance, mica powder for pearlescent metallic pigments, and other inorganic polyhedral particles such as glass. Examples include those coated with metal by plating or sputtering.

Examples of the above dyes include nitroso dyes, nitro dyes, azo dyes, stilbene azo dyes, ketoimine dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine/polymethine dyes, thiazole dyes, indamine/indophenol dyes. , azine dyes, oxazine dyes, thiazine dyes, sulfur dyes, aminoketone/oxyketone dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, and the like.

Examples of the above-mentioned blowing agents include thermally decomposable organic blowing agents and thermally decomposable inorganic blowing agents. Examples of thermally decomposable organic blowing agents include azodicarbonamide, azobisisobutylnitrile, and diazoaminobenzene. , diethyl azodicarboxylate, diisopropylazodicarboxylate, azo blowing agents such as azobis(hexahydrobenzonitrile), N,N'-dinitropentamethylenetetramine, N,N'-dimethyl-N,N'-dinitro Nitroso blowing agents such as terephthalamine, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, 3,3'-disulfonehydrazide phenylsulfone, toluenedisulfonylhydrazone, thiobis(benzenesulfonylhydrazide), toluenesulfonyl azide, toluenesulfonyl semicarbazide, Hydrazide blowing agents such as p,p'-bis(benzenesulfonylhydrazide) ether, carbazide blowing agents such as p-toluenesulfonyl semicarbazide, 4,4'-oxybiz(sulfonyl semicarbazide), trihydrazinotriazine, 1,3 Examples include triazine blowing agents such as -bis(o-biphenyltriazine). Examples of thermally decomposable inorganic blowing agents include sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azide compounds, and sodium borohydride.

In addition, the resin composition of the present invention may contain additives commonly used for synthetic resins, such as crosslinking agents, antifogging agents, plate-out inhibitors, surface treatment agents, fluorescent agents, and anti-mold agents, as necessary. , a bactericidal agent, an antibacterial agent, a metal deactivator, a mold release agent, etc., may be added within a range that does not impair the effects of the present invention.

The method for producing the resin composition of the present invention is not particularly limited, and a synthetic resin, particularly a thermoplastic resin, wood flour as the component (X), a polymer compound (E) as the component (Y), and an alkali metal as necessary. One or more of the salt (F) and the ionic liquid (G) and other optional components may be blended, and any commonly used method may be used. Examples include a method of dry blending using a blender, Henshil mixer, etc., and a method of melt blending using an extruder, Banbury mixer, kneader, etc.

The order of blending is also not particularly limited, and all components may be mixed simultaneously or in multiple stages. For example, there are methods in which all components except the polymer compound (E) of the component (Y) are first premixed and then the polymer compound (E) is mixed, or a method in which the wood flour of the component (X) and the polymer compound of the component (Y) are premixed. A method may be mentioned in which the molecular compound (E) and further optional additives are first premixed, and then the synthetic resin is mixed.

Furthermore, as a method for blending the polymer compound (E) of the component (Y) into a synthetic resin, especially a thermoplastic resin, the block polymer (C) and the epoxy compound (D) having two or more epoxy groups are mixed into a thermoplastic resin. The polymer compound (E) may be synthesized and blended while being kneaded together with the resin, and at that time, the wood flour of the component (X), and if necessary, the alkali metal salt (F) and the ionic liquid are added. One or more selected from the group (G) may be kneaded together, or the polymer compound (E) and a thermoplastic resin may be mixed together during molding such as injection molding to obtain a molded product. At that time, wood flour and, if necessary, one or more selected from the group of alkali metal salts (F) and ionic liquids (G) may be further blended. A masterbatch of the molecular compound (E) and the thermoplastic resin may be prepared in advance, and this masterbatch may be blended with wood flour, and if necessary, an alkali metal salt (F) and an ionic One or more types selected from the group of liquids (G) may be blended.

A molded article can be obtained by molding the resin composition of the present invention. The molding method is not particularly limited, and examples thereof include known molding methods such as extrusion molding, injection molding, compression molding, and lamination molding. Among these, extrusion molding is preferred from the viewpoint of antistatic properties, durability thereof, and woody feel of the molded product. Extrusion molding is carried out using an extruder. For example, the resin composition is supplied to the hopper of the extruder, mechanically melted and kneaded in the extruder, passed through a die, and then released into the air. A molded body is formed by being extruded. As the extruder, a well-known extruder equipped with a single screw or twin screws is used, and each component is kneaded and extruded with one extruder, which is easy to operate and has high productivity. It also has the advantage of being very expensive.

The molded article of the present invention has antistatic properties, long-lasting properties, and excellent wood texture.
When strength and rigidity are required using the molded product of the present invention (for example, building materials such as flooring materials), the molded product of the present invention can also be used by laminating it on an underlying resin base material. preferable. As the resin used as the resin base material, the above-mentioned synthetic resins, especially thermoplastic resins, can be used without restriction. From these, ABS resin, ASA resin, vinyl chloride resin, or a mixed resin thereof is suitable.

The molded product of the present invention has antistatic properties, its sustainability, and the wooden texture of the molded product, because the surface is uneven, so that the contact area is small and it is difficult for static charging to occur due to friction, and It is preferable because it has a large surface area and discharges easily. Furthermore, the unevenness provides a wood texture similar to that of natural wood, which is preferable.

The method of forming surface irregularities is not particularly limited, and specifically, chemical roughening methods in which the surface is treated with chemicals, physical roughening methods in which the surface is treated by laser irradiation, metal brushes, sandpaper, etc. Examples include a mechanical roughening method in which the surface is treated, and a molding method in which unevenness is provided on the surface of the skin layer of a mold of a molding machine simultaneously with extrusion. Among these, from the viewpoint of the operability of the treatment, the antistatic property and durability of the molded product, and the woody texture of the molded product, it is preferable that the molded product of the present invention be surface-treated with sandpaper or sanded. .

The antistatic resin composition of the present invention and its molded product have excellent antistatic properties and durability, and have an excellent wood texture, so they can be used in construction and building materials, such as floorboards, wall materials, frames, and recycled materials. Shapes, window and door profiles, shingles, roofing materials, siding, wall materials, residential interior materials, residential exterior materials, balconies, terraces, balconies, louvers, decking materials, flooring materials, fence materials, handrail materials, Siding materials, pipe materials, etc., or automotive materials such as vehicle interior materials, internal panels, rear shelves, side moldings, spare tire covers, etc., or civil engineering materials such as promenades, park equipment, docks, etc. It is suitably used for wooden paths, bridges, etc., or for consumer/industrial uses, such as picnic tables, benches, pallets, chairs, desks, furniture, handrails, etc.

EXAMPLES Hereinafter, the present invention will be explained in more detail using Examples, but the present invention is not limited thereto. In addition, in the following examples and the like, "%", "ppm", and "part" are based on mass unless otherwise specified.

According to the following production example, a polymer compound (E) which is the component (Y) of the resin composition of the present invention was produced. As the wood flour component (X), Eco Mills Super Feeder #100 manufactured by Sankyo Seifun Co., Ltd., which is a commercially available product, was used.

In addition, in the following production examples, the number average molecular weight of compound (b) is calculated according to the following <Method for calculating number average molecular weight from hydroxyl value>, and the number average molecular weight of compounds other than compound (b) is calculated according to the following <polystyrene conversion method>. The number average molecular weight was calculated using the following method.

<How to calculate number average molecular weight from hydroxyl value>
The hydroxyl value was measured using the hydroxyl value measurement method described below, and the number average molecular weight was determined using the following formula.
Number average molecular weight = (56110 x 2) / hydroxyl value

<Hydroxyl value measurement method>
・Reagent A (acetylating agent)
(1) Triethyl phosphate 1560mL
(2) Acetic anhydride 193mL
(3) Perchloric acid (60%) 16g
The above reagents are mixed in the order of (1) → (2) → (3).
・Reagent B
Mix pyridine and pure water at a volume ratio of 3:1.
・Reagent C
Add 2 to 3 drops of phenolphthalein solution to 500 mL of isopropyl alcohol, and neutralize with 1N-KOH aqueous solution.

First, 2 g of a sample is weighed into a 200 mL Erlenmeyer flask, 10 mL of triethyl phosphate is added, and the sample is heated and dissolved. Add 15 mL of Reagent A, stopper and shake vigorously. Add 20 mL of Reagent B, stopper and shake vigorously. Add 50 mL of Reagent C. Titrate with 1N-KOH aqueous solution and calculate using the formula below.
Hydroxyl value [mgKOH/g]=56.11×f×(T-B)/S
f: factor of 1N-KOH aqueous solution
B: Blank test titer [mL]
T: Main test titer [mL]
S: Sample amount [g]

<Method for measuring number average molecular weight in terms of polystyrene>
The number average molecular weight was measured by gel permeation chromatography (GPC) method. The conditions for measuring Mn are as follows.
Equipment: GPC device manufactured by JASCO Corporation Solvent: Chloroform reference material: Polystyrene detector: Differential refractometer (RI detector)
Column stationary phase: Shodex LF-804 manufactured by Showa Denko K.K.
Column temperature: 40℃
Sample concentration: 1mg/1mL
Flow rate: 0.8mL/min.
Injection volume: 100μL

[Manufacture example 1]
In a separable flask, in the presence of 0.2 g of an antioxidant (tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, ADEKA STAB AO-60 manufactured by ADEKA Co., Ltd.). Polyester ( a) -1 was obtained. The number average molecular weight of the obtained polyester (a)-1 was 3,000.

Next, 250 g of the obtained polyester (a)-1, and 160 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 as compound (b)-1 having hydroxyl groups at both ends. , 0.2 g of an antioxidant (ADK STAB AO-60) and 0.4 g of zirconium octylate were polymerized at 200°C for 3 hours under reduced pressure to obtain a block polymer (having a structure with carboxyl groups at both ends). 400g of C)-1 was obtained. The number average molecular weight Mn of block polymer (C)-1 having a structure having carboxyl groups at both ends was 16,500.

To 400 g of the obtained block polymer (C)-1 having a structure having carboxyl groups at both ends, bisphenol F diglycidyl ether (epoxy equivalent 170 g/ 3 g of eq) was charged and polymerized at 220° C. for 5 hours under reduced pressure to obtain a polymer compound (E)-1, which is the component (Y) of the resin composition of the present invention.

[Production example 2]
In a separable flask, add 656 g of 1,4-cyclohexanedimethanol, 708 g of adipic acid, 0.7 g of phthalic anhydride, and antioxidant (tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxymethyl]methane, 0.7 g of ADEKA STAB AO-60 manufactured by ADEKA Co., Ltd.) was charged, and the temperature was gradually raised from 160°C to 210°C for 4 hours at normal pressure, and then at 210°C for 3 hours under reduced pressure. Polyester was polymerized to obtain polyester (a)-2.

Next, 600 g of the obtained polyester (a)-2, 300 g of polyethylene glycol having a number average molecular weight of 4000 and the number of repeating units of ethyleneoxy group = 80 as compound (b)-2 having hydroxyl groups at both ends, and oxidation. 0.5 g of inhibitor (ADK STAB AO-60) and 0.8 g of zirconium octylate were charged and polymerized at 210°C for 7 hours under reduced pressure to obtain a block polymer (C) having a structure having carboxyl groups at both ends. I got -2. The number average molecular weight Mn of block polymer (C)-2 having a structure having carboxyl groups at both ends was 12,000.

To 360 g of the obtained block polymer (C)-2 having a structure having carboxyl groups at both ends, 6 g of bisphenol F diglycidyl ether (epoxy equivalent: 170 g/eq) was charged as the epoxy compound (D)-1, and the mixture was heated at 240°C. Polymerization was carried out under reduced pressure for 3 hours to obtain a polymer compound (E)-2, which is the component (Y) of the composition of the present invention.

[Examples 1 to 10 and Comparative Examples 1 to 4]
High-density polyethylene resin (HDPE resin) (melt flow rate = 8 g/10 min (ISO1133, 190°C x 2.16 kg)) as the thermoplastic resin, wood flour (manufactured by Sankyo Seiko Co., Ltd., Eco Mills) as the (X) component Super feeder #100), the polymer compound (E) obtained in the above production example was blended as the component (Y) in the amount (parts by mass) listed in Tables 1 and 2 below, and the resin composition of the present invention was prepared. I got something. The obtained resin composition was granulated using a twin-screw extruder (PCM 30, 60 mesh included) manufactured by Ikegai Co., Ltd. at 200° C. and 6 kg/hour to obtain pellets. The obtained pellets were molded using a horizontal injection molding machine (NEX80: manufactured by Nissei Jushi Kogyo Co., Ltd.) under processing conditions of a resin temperature of 200°C and a mold temperature of 40°C. 3 mm) was obtained. In addition, the surface of Test Piece-1 was sanded (polished) 20 times with #500 sandpaper (roughness) to obtain Test Piece-2.

Using the obtained test piece-1 and test piece-2, the surface resistivity (SR value) was measured according to the following, and the antistatic property and its durability were evaluated. Furthermore, using the obtained test piece-2, an evaluation test for the wood texture of the molded product was conducted in accordance with the following. These results are shown in Tables 1 and 2. In addition, the comparative resin compositions shown in Table 3 were evaluated in the same manner as in the examples. In the comparative example, a polyether ester amide type antistatic agent (manufactured by BASF, trade name "Irgastat P-18") was used as a comparative antistatic agent. The results are shown in Table 3.

<Surface resistivity (SR value) measurement method>
Immediately after the molding process, the obtained test piece-1 was stored under the conditions of a temperature of 25°C and a humidity of 50% RH, and after being stored for 1 and 30 days after the molding process, it was stored under the same atmosphere as R8340 manufactured by Advantest. The surface resistivity (Ω/□) was measured using a resistance meter under the conditions of an applied voltage of 100 V and an applied time of 1 minute. Measurements were performed on five test pieces at five points per piece, and the average value was calculated. Immediately after sanding, the obtained test piece-2 was stored under conditions of a temperature of 25°C and a humidity of 50% RH. The surface resistivity (Ω/□) was measured using a resistance meter under the conditions of an applied voltage of 100 V and an applied time of 1 minute. Measurements were performed on five test pieces at five points per piece, and the average value was calculated.

<Test method for evaluating the wood texture of molded objects>
The appearance of the obtained test piece-2 was visually observed and evaluated on a five-point scale from 1 to 5. Rating 1 is the appearance closest to natural wood, and the wood texture is the best, and as the value increases, the wood texture is inferior. Rating 5 is the lowest in wood feel.

From the above, it can be seen that the resin composition of the present invention can provide a molded article with excellent antistatic performance, durability, and wood texture.

Claims (6)

An antistatic resin composition containing 1 to 200 parts by mass of the following component (X) and 1 to 60 parts by mass of the following component (Y) based on 100 parts by mass of the synthetic resin.
(X) Ingredient: Wood flour.
(Y) component: polyester (a) obtained by reacting diol (a1) and dicarboxylic acid (a2), compound (b) having hydroxyl groups at both ends and having one or more ethyleneoxy groups, and epoxy group. One or more kinds of polymer compounds (E) obtained by reacting an epoxy compound (D) having two or more of the following. The polymer compound (E) has a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the compound (b), and the polyester Reaction between the hydroxyl group or carboxyl group at the terminal of (a), the hydroxyl group at the terminal of the compound (b), and the hydroxyl group formed by the reaction of the epoxy group or epoxy group of the epoxy compound (D). The antistatic resin composition according to claim 1, having a structure formed by bonding via an ester bond or an ether bond. A block polymer in which the polymer compound (E) has carboxyl groups at both ends, in which the polyester block (A) and the polyether block (B) are repeatedly and alternately bonded via ester bonds. The antistatic resin composition according to claim 2, having a structure in which (C) and the epoxy compound (D) are bonded via an ester bond. According to any one of claims 1 to 3, further comprising 0.01 to 15.0 parts by mass of one or more selected from the group consisting of an alkali metal salt (F) and an ionic liquid (G). antistatic resin composition. A molded article obtained from the antistatic resin composition according to any one of claims 1 to 3. A molded article obtained from the antistatic resin composition according to claim 4.