JP2017128682A - Antistatic halogen-containing resin composition and molded body formed by molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic halogen-containing resin composition capable of providing a molded product which has excellent antistatic properties and is excellently kept for a long period of time, and to provide a molded body formed by molding the same.SOLUTION: There is provided an antistatic halogen-containing resin composition which contains 2-40 pts.mass of a polymer compound (A) with respect to 100 pts.mass of a halogen-containing resin, where the polymer compound (A) has diol, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and one or more groups represented by the general formula (1), and a compound (C) having hydroxyl groups on both of terminal ends and a compound (D) having a reactive functional group are bonded to each other through an ester bond or the ester bond and an amide bond.SELECTED DRAWING: None

Description

  The present invention relates to an antistatic halogen-containing resin composition (hereinafter, also simply referred to as “resin composition”) and a molded article formed by molding the same, and more specifically, molding excellent in antistatic properties and its long-term maintenance. The present invention relates to an antistatic halogen-containing resin composition capable of providing a product and a molded article formed by molding the same.

  Halogen-containing resins such as polyvinyl chloride resin are soft products with a relatively large amount of plasticizer, or so-called semi-rigid products with a relatively small amount of plasticizer, various packaging films, containers, agricultural films, Widely used in building materials such as pipes, flooring materials, wall materials and window frame materials.

  These halogen-containing resins have excellent electrical insulation properties, but have a problem that static electricity is likely to accumulate due to friction. When the molded product is a building material such as a flooring material or a window frame material or an agricultural film, the appearance may be deteriorated by attracting dirt such as pollen or dust due to static electricity. In addition, when the molded product is an electronic product transport / protection case or a telecom communication device covering material, the electronic circuit of the product may not operate normally due to charging. In addition, there are problems caused by electric shock. Electric shock not only causes discomfort due to the generation of electric shock from the halogen-containing resin to the human body, but also may cause an explosion accident in the presence of flammable gas or dust.

  Nowadays, various methods have been proposed to prevent such an electrostatic failure, and a solution has been made by using an antistatic agent. Examples of such an antistatic agent include those used by spraying, dipping, coating, and the like on the resin molding surface, and kneading molds that are processed by being added to the polymer material as an additive. Most of those that are sprayed, dipped, or applied to the resin molding surface are water-soluble surfactants, and there is a problem that the antistatic effect is lost by wiping or washing. On the other hand, the kneading mold has a problem that the antistatic agent and the resin are decomposed and colored to impair the appearance of the molded product when the compatibility with the resin and the heat resistance against the molding processing temperature are poor.

  From such a viewpoint, an antistatic halogen-containing resin composition capable of exhibiting a sustained antistatic property is demanded. For example, Patent Documents 1 and 2 propose quaternary ammonium salt type antistatic agents. Patent Document 3 proposes that an ether alcohol ester and a nonionic antistatic agent are used in combination. Patent Document 4 proposes a fatty acid amide compound of aminoethylethanolamine. Patent Documents 5 and 6 propose polyether ester amide type antistatic agents. Patent Documents 7 to 9 propose various kneading type antistatic agents such as a block polymer having a structure in which an olefin block and a hydrophilic polymer block are alternately and repeatedly bonded. Patent Documents 8 and 9 propose an antistatic resin composition containing a polyether ester polymer type antistatic agent.

Japanese Patent Publication No. 40-7366 JP-A-2-233744 Japanese Examined Patent Publication No. 44-22616 JP 2011-256293 A JP 58-118838 A JP-A-3-290464 JP 2001-278985 A International Publication WO2014 / 115745 International publication WO2014 / 148454

  However, an antistatic agent made of polyetheresteramide cannot obtain sufficient antistatic performance unless it is added in a large amount to the resin. Moreover, although the antistatic agent of patent documents 1-7 is shown about the effect of antistatic property, it is not satisfactory, and the further improvement is calculated | required. In Patent Documents 8 and 9, an antistatic resin composition containing a polyether ester polymer type antistatic agent is proposed. However, since it does not contain an aromatic dicarboxylic acid, the antistatic resin composition of the present invention is antistatic. The structure is different from that of the polymer compound (A) used as the agent.

  Accordingly, an object of the present invention is to provide an antistatic halogen-containing resin composition capable of providing a molded product excellent in antistatic properties and its long-term maintenance, and a molded body formed by molding the same. .

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a polymer compound having a predetermined structure as an antistatic agent, and the present invention is completed. It came to.

で表される基を一つ以上有し、両末端に水酸基を有する化合物（Ｃ）、および、反応性官能基を有する化合物（Ｄ）が、エステル結合を介して、または、エステル結合およびアミド結合を介して結合してなる構造を有することを特徴とするものである。 That is, the antistatic halogen-containing resin composition of the present invention is an antistatic halogen-containing resin composition containing 2 to 40 parts by mass of the polymer compound (A) with respect to 100 parts by mass of the halogen-containing resin.
The polymer compound (A) is a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, the following general formula (1),

The compound (C) having one or more groups represented by the above and having a hydroxyl group at both ends and the compound (D) having a reactive functional group are bonded via an ester bond or an ester bond and an amide bond. It has the structure formed by connecting via.

  In the resin composition of the present invention, the polymer compound (A) includes a polyester (E) composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, the compound (C), and the compound ( D) is preferably bonded via an ester bond or via an ester bond and an amide bond.

  In the resin composition of the present invention, the polymer compound (A) includes a block composed of the polyester (E) and a block composed of the compound (C), which are alternately bonded via ester bonds. The block polymer (G) having carboxyl groups at both ends thus formed and the compound (D) have a structure formed by bonding via an ester bond or via an ester bond and an amide bond. preferable.

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

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

  In the resin composition of the present invention, the compound (D) is a polyhydric epoxy compound (D) -1 having two or more epoxy groups, a polyhydric alcohol compound (D) having three or more hydroxyl groups. -2, and at least one selected from the group consisting of polyvalent amine compounds (D) -3 having two or more amino groups.

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

  Furthermore, it is preferable that the resin composition of this invention contains 0.01-5 mass parts of 1 or more types of alkali metal salt (F) further.

  Moreover, in the resin composition of this invention, it is preferable to contain 0.01-15 mass parts of metal stabilizers (H) further.

  Furthermore, in the resin composition of this invention, it is preferable to contain 0.01-8 mass parts of (beta) -diketone compound (I) further.

  Furthermore, in the resin composition of this invention, it is preferable to contain 0.01-10 mass parts of lubricants (J) further.

  Moreover, in the resin composition of this invention, it is preferable to contain 0.01-6 mass parts of processing aids (K) further.

  The molded article of the present invention is characterized in that the resin composition of the present invention is molded.

  ADVANTAGE OF THE INVENTION According to this invention, the antistatic halogen-containing resin composition which can provide the molded article excellent in the antistatic property and its long-term maintenance, and the molded object formed by shape | molding it can be provided.

で表される基を一つ以上有し、両末端に水酸基を有する化合物（Ｃ）、および、反応性官能基を有する化合物（Ｄ）が、エステル結合を介して、または、エステル結合およびアミド結合を介して結合してなる構造を有している。 Hereinafter, the antistatic halogen-containing resin composition of the present invention and a molded article formed by molding the same will be described in detail. The resin composition of the present invention contains 2 to 40 parts by mass of the polymer compound (A) with respect to 100 parts by mass of the halogen-containing resin. In the resin composition of the present invention, the polymer compound (A) is a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, the following general formula (1),

The compound (C) having one or more groups represented by the above and having a hydroxyl group at both ends and the compound (D) having a reactive functional group are bonded via an ester bond or an ester bond and an amide bond. It has a structure formed by bonding via.

First, the halogen-containing resin used in the resin composition of the present invention will be described.
As the halogen-containing resin, there are no particular limitations on the polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like. For example, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyfluoride Vinylidene, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid Examples thereof include halogen-containing resins such as ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-cyclohexyl maleimide copolymers, and blends thereof. In the resin composition of the present invention, polyvinyl chloride is particularly preferable because the effect of the invention is remarkable.

  In the resin composition of this invention, you may add the thermoplastic resin which does not contain a halogen in the range which does not inhibit the effect of this invention. As such a thermoplastic resin, for example, petroleum resin, coumarone resin, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyphenylene sulfide, polyurethane, fibrous resin, polyimide resin, Thermoplastic resins such as polysulfone and liquid crystal polymer, and blends thereof can be used.

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

  In the resin composition of the present invention, the polymer compound (A) includes a polyester (E) composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, a compound (C), and a compound (D). Preferably have a structure formed by bonding via an ester bond or via an ester bond and an amide bond, and a block formed from a polyester (E) and a block formed from a compound (C) Block polymer (G) having a carboxyl group at both ends formed by alternately and alternately bonding via an ester bond and compound (D) via an ester bond or via an ester bond and an amide bond It is also preferable to have a structure formed by bonding.

  Polyester (E) should just consist of diol, aliphatic dicarboxylic acid, and aromatic dicarboxylic acid, and the residue except the hydroxyl group of diol, and the residue except the carboxyl group of aliphatic dicarboxylic acid, A structure having a structure that bonds via an ester bond, and a structure in which a residue that excludes a hydroxyl group of a diol and a residue that excludes a carboxyl group of an aromatic dicarboxylic acid are bonded via an ester bond Is preferred.

  In the resin composition of the present invention, the polyester (E) preferably has a structure having carboxyl groups at both ends, and the degree of polymerization of the polyester (E) is preferably in the range of 2-50.

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

  In addition, since it is preferable that aliphatic diol has hydrophobicity, polyethyleneglycol which has hydrophilic property among aliphatic diols is not preferable. However, this is not the case when used with other diols.

  Examples of the aromatic group-containing diol that can be used in the resin composition of the present invention include bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, and 1,4-benzene. Dimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, polyhydroxyethyl adduct of mononuclear dihydric phenol compounds such as 1,4-bis (2-hydroxyethoxy) benzene, resorcin, pyrocatechol Etc. Among these diols having an aromatic group, an ethylene oxide adduct of bisphenol A and 1,4-bis (β-hydroxyethoxy) benzene are preferable from the viewpoint of durability of antistatic performance.

  The aliphatic dicarboxylic acid that can be used in the resin composition of the present invention may be an aliphatic dicarboxylic acid derivative (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.). The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more.

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

  The aromatic dicarboxylic acid that can be used in the resin composition of the present invention may be an aromatic dicarboxylic acid derivative (eg, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.). Moreover, 2 or more types of mixtures may be sufficient as aromatic dicarboxylic acid and its derivative (s).

  The aromatic dicarboxylic acid is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms. For example, terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutar Acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate and 3-sulfoisophthalic acid Potassium etc. are mentioned.

Next, the compound (C) having one or more groups represented by the general formula (1) and having hydroxyl groups at both ends will be described.
The compound (C) is preferably a hydrophilic compound, more preferably a polyether having a group represented by the above general formula (1), and particularly preferably polyethylene glycol represented by the following general formula (2).

上記一般式（２）中、ｍは５〜２５０の整数を表す。ｍは、耐熱性や相溶性の点から、好ましくは２０〜１５０である。

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

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

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

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

  As glycol, C2-C20 aliphatic glycol, C5-C12 alicyclic glycol, C8-C26 aromatic glycol, etc. can be used.

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

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

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

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

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

  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 the number of carbon atoms. 8-14 aromatic secondary diamines and secondary alkanol diamines having 3 to 22 carbon atoms can be used.

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

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

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

  Examples of the aromatic secondary diamine include N, N′-dimethyl-phenylenediamine, N, N′-dimethyl-xylylenediamine, N, N′-dimethyl-diphenylmethanediamine, and N, N′-dimethyl-diphenyletherdiamine. , N, N′-dimethyl-benzidine and N, N′-dimethyl-1,4-naphthalenediamine.

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

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

  Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, methyl succinic acid, dimethyl malonic acid, β-methyl glutaric acid, ethyl succinic acid, isopropyl malonic acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanediic acid, tetradecanediic acid, hexadecanediic acid, octadecanediic acid and icosandiic acid.

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

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

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

Next, the compound (D) having a reactive functional group will be described.
In the present invention, the compound (D) having a reactive functional group may be any compound that can be bonded to a carboxyl group via an ester bond or can be bonded via an amide bond. The polyester (E) and the compound (C) ) Can be bonded via an ester bond or an amide bond, or a block composed of polyester (E) and a block composed of compound (C) are repeatedly bonded alternately via an ester bond. What is necessary is just to be able to couple | bond with the block polymer (G) which has a carboxyl group in the both terminal which becomes through an ester bond or an amide bond. Such functional groups include epoxy groups, hydroxyl groups, amino groups, and the like.

  In the present invention, the compound (D) having a reactive functional group is preferably a polyhydric epoxy compound (D) -1 having two or more epoxy groups, a polyhydric alcohol compound (D)-having three or more hydroxyl groups. A polyvalent amine compound (D) -3 having two and two or more amino groups is preferably used because of good reaction.

  The polyvalent epoxy compound (D) -1 is not particularly limited as long as it is a compound having two or more epoxy groups, and examples thereof include mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3 -Bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra ( 4-hi Roxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, polyglycidyl ether compounds of polynuclear polyphenols such as terpene phenol; ethylene Polyglycidyl ethers of polyols such as glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, Fumaric acid, itaconic acid, succinic acid, glu Phosphoric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as endomethylenetetrahydrophthalic acid and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N- Epoxy compounds having a glycidylamino group such as methyl-N-glycidylamino) phenyl) methane and diglycidylorthotoluidine; vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Epoxidized products of cyclic olefin compounds such as carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, Examples include epoxidized conjugated diene polymers such as epoxidized styrene-butadiene copolymer, heterocyclic compounds such as triglycidyl isocyanurate, and epoxidized soybean oil. In addition, these polyvalent epoxy compounds can be obtained by using those internally crosslinked by terminal isocyanate prepolymers or polyvalent active hydrogen compounds (polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphate esters, etc.). The molecular weight may be used. Two or more kinds of such polyvalent epoxy compounds may be used.

  The polyhydric alcohol compound (D) -2 is not particularly limited as long as it has three or more hydroxyl groups. For example, glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 2 -Methyl-1,2,3-propanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,3,5-pentanetriol, 2,3,4-pentanetriol, 2- Methyl-2,3,4-butanetriol, trimethylolethane, 2,3,4-hexanetriol, 2-ethyl-1,2,3-butanetriol, trimethylolpropane, 4-propyl-3,4,5 -Heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, triethanolamine, triisopropanolamine, 1,3,5-tri Trivalent alcohols such as (2-hydroxyethyl) isocyanurate; pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pen Tantetrol, 1,3,4,5-hexanetetrol, diglycerin, ditrimethylolpropane, sorbitan, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, Tetravalent alcohols such as N′-tetrakis (2-hydroxyethyl) ethylenediamine; pentavalent alcohols such as adonitol, arabitol, xylitol, triglycerin; dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, allose Hexavalent alcohol; Data erythritol, and the like. Moreover, there is no restriction | limiting in particular in the molecular weight of a polyol compound, High molecular weight polyols, such as polypentaerythritol and polyvinyl alcohol, can also be used, Polyester polyol etc. can also be used. Two or more kinds of such polyhydric alcohol compounds may be used.

  The polyvalent amine compound (D) -3 is not particularly limited as long as it has two or more primary amino groups and / or secondary amino groups. For example, ethylenediamine, trimethylenediamine, hexamethylene C2-C12 alkylene diamines such as diamine, heptamethylene diamine, octamethylene diamine, decamethylene diamine; aliphatic amines such as 2,2 ′, 2 ″ -triaminotriethylamine and bis (hexamethylene) triamine, diethylenetriamine A polyalkylene polyamine having 2 to 6 carbon atoms of an alkylene group such as 1,6,11-undecantriamine, 1,8-diamino-4-aminomethyloctane, 1,3,6- Alkanetriamines such as hexamethylenetriamine; melamine, piperazine; N- N-aminoalkylpiperazine having 2 to 6 carbon atoms in the alkylene group, such as minoethylpiperazine; heterocyclic polyamines such as heterocyclic polyamine described in JP-B No. 55-21044, isophoronediamine, bicycloheptane C4-C20 alicyclic polyamine such as triamine; carbon atoms such as phenyldiamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine, triphenylmethanetriamine Examples include aromatic polyamines of formula 6 to 20. Two or more kinds of such polyvalent amine compounds may be used.

Next, polyester (E) and block polymer (G) will be described.
As described above, in the resin composition of the present invention, from the viewpoint of antistatic performance, the polymer compound (A) is a polyester (E) composed of diol, aliphatic dicarboxylic acid and aromatic dicarboxylic acid, compound ( It is preferable that C) and the compound (D) having a reactive functional group have a structure formed by bonding via an ester bond or via an ester bond and an amide bond.

  Furthermore, from the viewpoint of antistatic properties, the polymer compound (A) is composed of a block composed of a polyester (E) composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and a compound (C). A block polymer (G) having a carboxyl group at both ends formed by repeating alternately and alternately bonded blocks via an ester bond and a compound (D) having a reactive functional group are bonded via an ester bond or It preferably has a structure formed by bonding via an ester bond and an amide bond.

  Polyester (E) can be obtained, for example, by subjecting an aliphatic dicarboxylic acid or derivative thereof, an aromatic dicarboxylic acid or derivative thereof, and a diol to a polycondensation reaction.

  As described above, the aliphatic dicarboxylic acid may be a derivative of an aliphatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.). If obtained, both ends may be finally treated to carboxyl groups, and the reaction for obtaining the next block polymer (G) having a structure having carboxyl groups at both ends is left as it is. You may go on. The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more.

  As described above, the aromatic dicarboxylic acid may also be a derivative of an aromatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.). If obtained, both ends may be finally treated to carboxyl groups, and the reaction for obtaining the next block polymer (G) having a structure having carboxyl groups at both ends is left as it is. You may go on. Moreover, 2 or more types of mixtures may be sufficient as aromatic dicarboxylic acid and its derivative (s).

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

  In the resin composition of the present invention, the polyester (E) is preferably a polyester having carboxyl groups at both ends, and the reaction ratio between the aliphatic dicarboxylic acid or derivative thereof and the aromatic dicarboxylic acid or derivative thereof and the diol is In addition, it is preferable to use an aliphatic dicarboxylic acid or a derivative thereof and an aromatic dicarboxylic acid or a derivative thereof in excess so that both ends are carboxyl groups, and to use a molar excess of the diol with respect to the diol. Is preferred.

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

  Further, depending on the blending ratio and reaction conditions, there are cases where a polyester composed only of a diol and an aliphatic dicarboxylic acid or a polyester composed only of a diol and an aromatic dicarboxylic acid may be produced. They may be mixed in E), or they may be reacted as they are with the compound (C) to obtain the block polymer (G).

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

  As described above, aliphatic dicarboxylic acids and aromatic dicarboxylic acids can be obtained by using diols, carboxylic acid esters, carboxylic acid metal salts, carboxylic acid halides or the like instead of dicarboxylic acids. After the reaction, both ends may be treated to form a dicarboxylic acid, and the reaction may proceed to the next reaction for obtaining a block polymer (G) having a structure having a carboxyl group at both ends as it is.

  Moreover, polyester (E) which consists of diol, aliphatic dicarboxylic acid, and aromatic dicarboxylic acid will form an ester bond by reacting with a compound (C), and if the structure of a block polymer (G) is formed. Good. Moreover, there may be a carboxyl group at both ends of the polyester (E), and the carboxyl group may be protected, modified, or in the form of a precursor. Moreover, in order to suppress the oxidation of a product at the time of reaction, you may add antioxidants, such as a phenolic antioxidant, to a reaction system.

  Furthermore, the compound (C) may be any compound that reacts with the polyester (E) to form an ester bond and form the structure of the block polymer (G), and the hydroxyl groups at both ends may be protected. It may be modified and may be in the form of a precursor.

Next, the block polymer (G) will be described.
The block polymer (G) having a carboxyl group at both ends according to the present invention has a block composed of a polyester (E) and a block composed of a compound (C). It has a structure formed by repeatedly and alternately bonding through ester bonds formed by carboxyl groups and hydroxyl groups. An example of such a block polymer (G) is, for example, one having a structure represented by the following general formula (3).

一般式（３）中、（Ｅ）は、両末端にカルボキシル基を有するポリエステル（Ｅ）から構成されたブロックを表し、（Ｃ）は、両末端に水酸基を有する化合物（Ｃ）から構成されたブロックを表し、ｔは繰り返し単位の繰り返しの数であり、好ましくは１〜１０の数を表す。ｔは、より好ましくは１〜７の数であり、最も好ましくは１〜５の数である。

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

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

  The block polymer (G) having a structure having carboxyl groups at both ends is obtained by polycondensation reaction between a polyester (E) having carboxyl groups at both ends and a compound (C) having hydroxyl groups at both ends. However, the polyester (E) and the compound (C) have a structure equivalent to that having a structure in which the polyester (E) and the compound (C) are alternately and repeatedly bonded via an ester bond formed by a carboxyl group and a hydroxyl group. If present, it is not always necessary to synthesize from the polyester (E) and the compound (C).

  If the reaction ratio of the polyester (E) and the compound (C) is adjusted so that the compound (C) is X mol and the polyester (E) is X + 1 mol, the block polymer having carboxyl groups at both ends (G) can be preferably obtained.

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

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

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

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

  The polymer compound (A) according to the present invention is an ester formed from a carboxyl group at the end of a block polymer (G) having a structure having a carboxyl group at both ends and a compound (D) having a reactive functional group Those having a structure through a bond or through an ester bond and an amide bond are preferred. Such a polymer compound (A) further includes an ester bond formed through an ester bond formed by the carboxyl group of the polyester (E) and the reactive functional group of the compound (D) having a reactive functional group. And a structure formed through an amide bond may be included.

  In order to obtain such a polymer compound (A), the carboxyl group of the block polymer (G), the epoxy group of the polyvalent epoxy compound (D) -1 of the compound (D), the polyhydric alcohol compound (D) -2 And the amino group of the polyvalent amine compound (D) -3 may be reacted.

  When the compound (D) is a polyvalent epoxy compound (D) -1 having two or more epoxy groups, the number of epoxy groups in the polyvalent epoxy compound is the number of carboxyl groups in the block polymer (G) to be reacted. 0.5 to 5 equivalents are preferable, and 0.5 to 1.5 equivalents are more preferable.

  The polyvalent epoxy compound (D) -1 having two or more epoxy groups to be reacted is preferably 0.1 to 2.0 equivalents of the carboxyl group of the block polymer (G) to be reacted, and 0.2 to 1. 5 equivalents are more preferred.

  When the compound (D) is a polyhydric alcohol compound (D) -2 having three or more hydroxyl groups, the number of hydroxyl groups of the polyhydric alcohol compound (D) -2 is the carboxyl group of the block polymer (G) to be reacted. 0.5 to 5 equivalents, and more preferably 0.5 to 1.5 equivalents.

  The polyhydric alcohol compound (D) -2 having three or more hydroxyl groups to be reacted is preferably 0.1 to 2.0 equivalents of the carboxyl group of the block polymer (G) to be reacted, 0.2 to 1.5 The equivalent is more preferable.

  When the compound (D) is a polyvalent amine compound (D) -3 having two or more amino groups, the number of amino groups of the polyvalent amine compound is the number of carboxyl groups of the block polymer (G) to be reacted. 0.5 to 5 equivalents are preferable, and 0.5 to 1.5 equivalents are more preferable.

  The polyvalent amine compound (D) -3 having two or more amino groups to be reacted is preferably 0.1 to 2.0 equivalents of the carboxyl group of the block polymer (G) to be reacted, and 0.2 to 1. 5 equivalents are more preferred.

  In the reaction, after completion of the synthesis reaction of the block polymer (G), the compound (D) may be added and reacted as it is without isolating the block polymer (G). In that case, the carboxyl group of the unreacted polyester (E) used excessively when synthesizing the block polymer (G) reacts with some reactive functional groups of the compound (D) to form an ester bond and An amide bond may be formed.

  In the preferred polymer compound (A) of the present invention, the block polymer (G) having a structure having a carboxyl group at both ends and the compound (D) are bonded via an ester bond or via an ester bond and an amide bond. As long as it has a structure equivalent to that having a bonded structure, it is not necessarily limited to the block polymer (G) and the compound (D).

  In the resin composition of the present invention, the number average molecular weight of the block composed of the polyester (E) in the polymer compound (A) is preferably 800 to 8,000, more preferably 1,000 in terms of polystyrene. 6,000 to 6,000, more preferably 2,000 to 4,000. Moreover, the number average molecular weight of the block comprised from the compound (C) which has a hydroxyl group in both ends in a high molecular compound (A) becomes like this. Preferably it is 400-6,000 in polystyrene conversion, More preferably, it is 1,000. It is -5,000, More preferably, it is 2,000-4,000.

  Furthermore, the number average molecular weight of the block composed of the block polymer (G) having a structure having a carboxyl group at both ends in the polymer compound (A) is preferably 5,000 to 25,000 in terms of polystyrene. More preferably, it is 7,000-17,000, More preferably, it is 9,000-13,000.

  In the polymer compound (A) according to the present invention, after obtaining the polyester (E) from the diol, the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid, the above compound (C) and It may also be reacted with compound (D).

  When the polymer compound (A) is blended with the halogen-containing resin, the polymer compound (A) is 2 to 40 parts by mass with respect to 100 parts by mass of the halogen-containing resin, and 5 to 20 masses from the viewpoint of antistatic properties. Part is preferable, and 7 to 15 parts by mass is more preferable. If the amount is less than 2 parts by mass, sufficient antistatic properties may not be obtained. If the amount exceeds 40 parts by mass, the physical properties of the molded product may be adversely affected.

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

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

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

  The blending amount of the alkali metal salt (F) is 0.01 to 5.0 parts by mass, and 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the halogen-containing resin from the viewpoint of antistatic properties. Preferably, 0.3-2.0 mass parts is more preferable. 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. There may be.

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

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

  In addition, the resin composition of the present invention contains a metal stabilizer (H), a β-diketone compound (I), a lubricant (J), and a processing aid (K) from the viewpoint of improving thermal stability and processability. It is preferable to contain.

  Examples of the metal stabilizer (H) include a lead stabilizer, an organic tin stabilizer, an organic acid metal salt, and a composite stabilizer thereof. However, when used in applications where low toxicity is important. A stabilizer containing no heavy metal is preferably used.

  Examples of lead-based stabilizers include lead white, basic lead silicate, basic lead sulfate, dibasic lead sulfate, tribasic lead sulfate, basic lead sulfite, dibasic lead phosphite, and silica gel coprecipitation. Lead silicate, dibasic lead phthalate, tribasic lead maleate, lead salicylate, lead stearate, basic lead stearate, dibasic lead stearate, lead laurate, lead octylate, 12-hydroxystearic acid Examples thereof include lead, lead behenate, and lead naphthenate.

  Examples of the organic tin stabilizer include methylstanoic acid, butylstanoic acid, octylstanoic acid, dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, dimethyltin sulfide, dibutyltin sulfide, and dioctyltin. Sulfide, monobutyltin oxide sulfide, methylthiostanoic acid, butylthiostanoic acid, octylthiostanoic acid, dibutyltin dilaurate, dibutyltin distearate, dioctyltin diolate, dibutyltin basic laurate, dibutyltin dicrotonate, Dibutyltin bis (butoxydiethylene glycol malate), dibutyltin methyl octyl neopentyl glycol malate, dibutyltin isooctyl-1,4-butanediol malate, dibuty Tin dimethacrylate, dibutyltin dicinnamate, dioctyltin bis (oleyl malate), dibutyltin bis (stearyl malate), dibutyltin itaconate, dioctyltin malate, dimethyltin dicrotonate, dioctyltin bis (butylmalate), dibutyltin dimethoxide, dibutyl Tin dilauroxide, dioctyl tin ethylene glycoxide, pentaerythritol dibutyl tin oxide condensate, dibutyl tin bis (lauryl mercaptide), dimethyl tin bis (stearyl mercaptide), monobutyl tin tris (lauryl mercaptide), dibutyl tin -Β-mercaptopropionate, dioctyltin-β-mercaptopropionate, dibutyltin mercaptoacetate, monobutyltin tris (isooctylmercaptoacetate) Monooctyltin tris (2-ethylhexyl mercaptoacetate), dibutyltin bis (isooctylmercaptoacetate), dioctyltin bis (isooctylmercaptoacetate), dioctyltin bis (2-ethylhexylmercaptoacetate), dimethyltinbis (isooctylmercapto) Acetate), dimethyltin bis (isooctylmercaptopropionate), monobutyltin tris (isooctylmercaptopropionate), bis [monobutyldi (isooctoxycarbonylmethylenethio) tin] sulfide, bis [dibutylmono (isooctoxycarbonyl) Methylenethio) tin] sulfide, monobutylmonochlorotin bis (isooctylmercaptopropionate), monobutylmonochlorotinbis (isooctylmerca) Toacetate), monobutylmonochlorotin bis (lauryl mercaptoide), butyltin bis (ethyl cersolobumarate), bis (dioctyltin butylmalate) malate, bis (methyltin diisooctylthioglycolate) disulfide, bis (Methyl / dimethyltin mono / diisooctylthioglycolate) disulfide, bis (methyltin diisooctylthioglycolate) trisulfide, bis (butyltin diisooctylthioglycolate) trisulfide, 2-butoxycarbonylethyl Tin tris (butyl thioglycolate) etc. are mentioned.

  Examples of organic acid metal salts include metal salts of carboxylic acids, phosphoric acids, and phenols. Examples of the metal constituting the metal salt of carboxylic acid, phosphoric acid, and phenol include lithium, potassium, sodium, calcium, magnesium, barium, aluminum, zinc, cadmium, and tin.

  Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, valeric acid, isobutanoic acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid Acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, 12-hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, nonadecyl acid, arachidic acid, heicosyl acid, behenic acid, tricosyl Acid, lignoceric acid, serotic acid, montanic acid, mellic acid, oleic acid, elaidic acid, linoleic acid, γ-linolenic acid, ricinoleic acid, erucic acid, nervonic acid, arachidonic acid, docosapentaenoic acid, linolenic acid, stearidonic acid , Eiko Pentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethyl Benzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, p-tert-octylsalicylic acid, thioglycolic acid, mercaptopropionic acid, Monovalent carboxylic acids such as octyl mercaptopropionic acid Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid , Chlorophthalic acid, aminophthalic acid, maleic acid, Divalent carboxylic acids such as fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid or their monoesters or monoamide compounds, butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid And di- or triester compounds of trivalent or tetravalent carboxylic acids such as merophanic acid and pyromellitic acid.

  Examples of phosphoric acids include mono- or dioctyl phosphoric acid, mono- or dododecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, mono- or dioctyl sublimate. Mention may be made of phosphoric acid, mono- or dioctadecyl phosphorous acid, and the like.

  Examples of the phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2-ethylhexylphenol. Tert-nonylphenol, decylphenol, tert-octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisofuxylphenol, methyl tert-octylphenol, and the like.

  The metal salts of carboxylic acid, phosphoric acid, and phenol are acidic salts, neutral salts, basic salts, or overbased complexes obtained by neutralizing part or all of the basic salt base with carbonic acid. Also good.

  0.01-15 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity of these metal type stabilizers (H), 0.03-13 mass parts is more preferable. When the amount of the metal stabilizer (H) is less than 0.01 parts by mass, the effect of adding the metal stabilizer (H) is not sufficient, and when it exceeds 15 parts by mass, the physical properties of the resin are affected. There is.

  Examples of the β-diketone compound (I) include acetylacetone, triacetylmethane, 2,4,6-heptatrione, stearoylbenzoylmethane, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylacetylmethane, and phenylacetyl. Acetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, bis (4-octylbenzoyl) methane, benzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, bis (4-carboxymethylbenzoyl) ) Methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, cyclohexane-1,3-dione, 3, - it can be exemplified dimethyl-2,4-dioxy cyclohexane -1-carboxylate, 2-acetyl cyclohexanone, dimedone, 2-benzoyl-cyclohexane, and the like. Also, metal salts of these β-diketone compounds can be used. Examples of metal species that can provide such β-diketone metal salts include alkali metals such as lithium, sodium and potassium; magnesium, calcium, strontium and Alkaline earth metals such as barium; zinc, aluminum, tin, alkyl tin, and the like can be given.

  0.01-8 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity of these (beta) -diketone compounds (I), 0.03-7 mass parts is more preferable. If the amount of the β-diketone compound (I) is less than 0.01 parts by mass, the effect of adding the β-diketone compound (I) may not be obtained, and if it exceeds 8 parts by mass, the molded product bleeds out. There is a case.

  The lubricant (J) is added for the purpose of lowering the melt viscosity of the resin at the time of molding, and imparting lubricity to the surface of the molded body to increase the effect of preventing damage. Specific examples of the lubricant include, for example, unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, stearic acid monoglyceride, and sorbitan monopal. Examples include micitate, sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearic acid amide, oleic acid amide, and ethylene bis-stearic acid amide. These may be used alone or in combination of two or more.

  0.001-10 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity of a lubricant (J), 0.01-7 mass parts is more preferable. If the blending amount of the lubricant (J) is less than 0.001 part by mass, the effect of adding the lubricant (J) may not be obtained, and if it exceeds 10 parts by mass, the resin may be affected.

  The processing aid (K) can be appropriately selected from known processing aids. For example, homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; And a copolymer of alkyl acrylate such as methyl acrylate, ethyl acrylate and butyl acrylate; a copolymer of the above alkyl methacrylate and an aromatic vinyl compound such as styrene, α-methyl styrene and vinyl toluene; And copolymers with vinylcyan compounds such as acrylonitrile and methacrylonitrile. These processing aids may be used alone or in combination of two or more.

  0.01-6 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity of a processing aid (K), 0.03-5 mass parts is more preferable. When the blending amount of the processing aid (K) is less than 0.01 parts by mass, the processability may be insufficient, and when it exceeds 6 parts by mass, there is a performance degradation such as a decrease in transparency.

  Moreover, you may mix | blend surfactant with the resin composition of this invention in the range which does not impair the effect of this invention. As the surfactant, nonionic, anionic, cationic or amphoteric surfactants can be used.

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

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

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

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

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

  Furthermore, you may mix | blend a polymeric antistatic agent with the resin composition of this invention in the range which does not impair the effect of this invention. As the polymer antistatic agent, for example, a polymer type antistatic agent such as a known polyether ester amide can be used, and examples of the known polyether ester amide include those described in JP-A-7-10989. And polyether ester amides comprising the polyoxyalkylene adducts of bisphenol A described. Moreover, the block polymer which has a repeating structure whose coupling unit of a polyolefin block and a hydrophilic polymer block is 2-50 can be used, For example, the block polymer of US Patent 6552131 can be mentioned.

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

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

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

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

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

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

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

  Furthermore, you may mix | blend a polymeric antistatic agent with the resin composition of this invention in the range which does not impair the effect of this invention. As the polymer antistatic agent, for example, a polymer type antistatic agent such as a known polyether ester amide can be used, and examples of the known polyether ester amide include those described in JP-A-7-10989. And polyether ester amides comprising the polyoxyalkylene adducts of bisphenol A described. Moreover, the block polymer which has a repeating structure whose coupling unit of a polyolefin block and a hydrophilic polymer block is 2-50 can be used, For example, the block polymer of US Patent 6552131 can be mentioned.

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

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

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

The following are mentioned as an amidinium cation.
(1) Imidazolinium cation Examples include those having 5 to 15 carbon atoms, such as 1,2,3,4-tetramethylimidazolinium and 1,3-dimethylimidazolinium;
(2) Imidazolium cation Examples include those having 5 to 15 carbon atoms, such as 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium;
(3) Tetrahydropyrimidinium cation One having 6 to 15 carbon atoms is exemplified, for example, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetra Methyl-1,4,5,6-tetrahydropyrimidinium;
(4) Dihydropyrimidinium cation A thing with 6-20 carbon atoms is mentioned, for example, 1,3-dimethyl-1,4-dihydropyrimidinium, 1,3-dimethyl-1,6-dihydropyrimidi Ni, 8-methyl-1,8-diazabicyclo [5,4,0] -7,9-undecadienium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,10-un Decadienium.

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

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

The following are mentioned as a guanidinium cation.
(1) Guanidinium cation having an imidazolinium skeleton One having 8 to 15 carbon atoms is exemplified, for example, 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3 , 4-trimethylimidazolinium;
(2) Guanidinium cation having an imidazolium skeleton, those having 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4 -Trimethylimidazolium;
(3) A guanidinium cation having a tetrahydropyrimidinium skeleton having 10 to 20 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydro Pyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium;
(4) A guanidinium cation having a dihydropyrimidinium skeleton having 10 to 20 carbon atoms, such as 2-dimethylamino-1,3,4-trimethyl-1,4-dihydropyrimidinium, 2-dimethylamino-1,3,4-trimethyl-1,6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4-dihydropyrimidinium, 2-diethylamino-1 , 3-Dimethyl-4-ethyl-1,6-dihydropyrimidinium.

  A cation may be used individually by 1 type, or may use 2 or more types together. Among these, from the viewpoint of antistatic properties, an amidinium cation is preferable, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

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

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

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

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

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

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

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

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

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

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

  Furthermore, the resin composition of the present invention may be blended with a compatibilizer, if necessary, within a range not impairing the effects of the present invention. By mix | blending a compatibilizing agent, the compatibility with an antistatic component, another component, and a resin component can be improved. Examples of the compatibilizer include a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and a polyoxyalkylene group. And the polymer described in JP-A-258850, the modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, or the block polymer having a polyolefin portion and an aromatic vinyl polymer portion. .

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

  Further, the resin composition of the present invention is a known resin additive (for example, a plasticizer, a heavy metal deactivator, a zeolite compound, an epoxy compound, a polyol compound, as needed) within a range not impairing the effects of the present invention. Foaming agents, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, other antioxidants, UV absorbers, hindered amine compounds, nucleating agents, flame retardants, flame retardant aids, fillers, metals Soap, hydrotalcite, pigments, dyes, and the like). The known resin additive may be mixed with the polymer compound (A) and then added to the halogen-containing resin, or may be separately added to the halogen-containing resin and molded.

  Examples of the plasticizer include phthalate esters such as diethyl phthalate, dimethoxyethyl phthalate, dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate, and the like. Phenyl phosphate, biphenylyl diphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri (butoxyethyl) phosphate, octyl diphenyl phosphate Phosphate esters such as Glycolic acid esters such as triacetin, tributyrin, butylphthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, adipates such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyl diglycol) adipate Plasticizers and polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5- Hexanediol, 1,6-hexanediol, neopentyl glycol, etc., and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelain , Plasticizers manufactured using sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and if necessary using a monohydric alcohol or monocarboxylic acid (acetic acid, aromatic acid, etc.) as a stopper, sebacic acid plasticizer , Stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer, pyromellitic acid plasticizer, biphenylene polycarboxylic acid plasticizer, polyhydric alcohol aromatic acid ester plasticizer (trimethylolpropane) Tribenzoate etc.).

  What is necessary is just to examine the usage-amount of a plasticizer suitably according to the characteristic of the desired molded article. For example, with respect to 100 parts by mass of the halogen-containing resin, 0 to 30 parts by mass, that is, no plasticizer is blended, or the blending amount is preferably 30 parts by mass or less, and 0 to 25 parts by mass is preferable. More preferred. If the amount of the plasticizer used exceeds 30 parts by mass, bleeding out from the surface of the molded product may occur.

  Examples of heavy metal deactivators include benzotriazole, salicylamide 1,2,4-triazol-3-yl, bissalicylic acid hydrazide, dodecandioyl bis (2- (2-hydroxybenzoyl) hydrazide), bis (3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid hydrazide and the like.

  When using the resin composition of this invention for a transparent material, it is preferable that the usage-amount of a heavy metal deactivator is 0.03 mass or less with respect to 100 mass parts of halogen-containing resin. When a heavy metal deactivator is blended, the halogen-containing resin is colored more. Therefore, it is more preferable not to blend a heavy metal deactivator.

  A zeolite compound is an aluminosilicate of an alkali or alkaline earth metal having a unique three-dimensional zeolite crystal structure, such as A-type, X-type, Y-type and P-type zeolite, monodenite, analsite, sodalite. Group aluminosilicate, clinobutyrolite, erionite and chabazite. These may be either a hydrate containing crystallization water of the zeolite compound (so-called zeolitic water) or an anhydride from which the crystallization water has been removed. In the vinyl chloride resin composition of the present invention, those having a particle size of 0.1 to 50 μm are preferred, and those having a particle size of 0.5 to 10 μm are more preferred.

  As for the compounding quantity in the case of mix | blending a zeolite compound, 0.01-10 mass parts is preferable with respect to 100 mass parts of halogen-containing resin.

  Examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil, and epoxidized stearin oil. Acid methyl, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, 3- (2-xenoxy) -1,2-epoxypropane, epoxidized polybutadiene, epoxy Tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, dicyclohexene diepoxide, 3,4-epoxy Hexyl-6-methyl-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexyl) adipate, and the like.

  When using an epoxy compound as a plasticizer, it mix | blends with respect to 100 mass parts of halogen-containing resin so that it may become 30 mass parts or less with the said plasticizer. When it mixes exceeding 30 mass parts, it may bleed out from a molded article.

  Examples of polyol compounds include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or stearic acid half ester of bis (dipentaerythritol) adipate, glycerin, tris (2-hydroxyethyl) isocyanurate and the like can be mentioned.

  0.01-10 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity in the case of mix | blending a polyol compound, 0.03-5 mass parts is more preferable.

  Examples of the blowing agent include decomposable organic blowing agents such as azodicarbonamide, azobisisobutyronitrile, p, p′-oxybisbenzenesulfonyl hydrazide, n, n′-toluenesulfonyl semicarbazide, trihydrazone triazine, Examples include decomposable inorganic foaming agents such as sodium carbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azide compounds, sodium borohydride and the like.

  0.01-10 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity in the case of mix | blending a foaming agent, 0.03-7 mass parts is more preferable.

  Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2′-methylenebis (4 -Ethyl-6-tert-butylphenol), 2,2'-thiobis- (6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2′-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, 2,2'-oxamido-bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2-ethylhexyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 2,2′-ethylenebis (4,6-di-tert-butylphenol), 3, Polymer of 5-di-tert-butyl-4-hydroxy-benzenepropanoic acid and C13-15 alkyl, 2,5-di-tert-amylhydroquinone, hindered phenol (trade name AO. Manufactured by Adeka Palmalol). OH. 98), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2-te t-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) Ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert- Butylbenz [d, f] [1,3,2] -dioxaphosphobin, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [monoethyl (3 5-Di-tert-butyl-4-hydroxybenzyl) phosphonate] calcium salt, 5,7-bis (1,1-dimethylethyl) -3-hydroxy-2 Reaction product of (3H) -benzofuranone and o-xylene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol DL-a-tocophenol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3,3-bis- (4′-hydroxy-3′-tert-butyl-) Phenyl) butanoic acid] glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-tert- Til-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-methylphenol), 2,2'-ethylidenebis (4,6-di-tert- Butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert) -Butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1 , 3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [Methylene-3- (3 ′, 5′-tert-tributyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl -5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8, 10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], stearyl-3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionic acid amide, palmityl-3- (3,5-di-tert-butyl-4-hydroxyphene) Nyl) propionic acid amide, myristyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Examples include 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as propionic acid amide.

  0.001-20 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity in the case of mix | blending a phenolic antioxidant, 0.01-5 are more preferable.

  Examples of phosphorus antioxidants include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, diphenyl Tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis (Tridecyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecyl phosphite, dinonylphenyl bi (Nonylphenyl) phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyldipropylene glycol diphosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris ( 2,4-di-tert-butyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl ] Phosphite, tri (decyl) phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite, a mixture of distearyl pentaerythritol and calcium stearate, alkyl (C 0) Bisphenol A phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) ) Pentaerythritol diphosphite, tetraphenyl-tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidenedipheno Rudiphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4- Hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, (1-methyl-1-propenyl-3-ylidene) tris (1,1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecyl phosphite, 2,2'-methylenebis (4 , 6-Di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methyle Bis (4,6-di-tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphite, 4,4′-butylidenebis (3- Methyl-6-tert-butylphenylditridecyl) phosphite, tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine Pin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphesspiro [5,5] undecane, 2 , 4,6-Tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4'-isopropylidenedipheno Le C12-15 alcohols phosphite, and the like.

  0.001-20 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity in the case of mix | blending phosphorus antioxidant, 0.01-5 mass parts is more preferable.

  Examples of the thioether-based antioxidant 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, lauryl stearyl thiodipropionate, 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), 2,2′-thiobis (6-tert-butyl-p-cresol), 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, distearyl-disulfide Bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl) sulfide and the like.

  0.001-20 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity in the case of mix | blending a thioether type | system | group antioxidant, 0.01-5 mass parts is more preferable.

  As other antioxidants, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α -Tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α Nitron compounds such as heptadecyl nitrone and N-octadecyl-α-heptadecyl nitrone, 3-arylbenzofuran-2 (3H) -one, 3- (alkoxyphenyl) benzofuran-2-one, 3- (acyloxyphenyl) benzofuran -2 (3H) -one, 5,7-di-tert-butyl- 3- (3,4-dimethylphenyl) -benzofuran-2 (3H) -one, 5,7-di-tert-butyl-3- (4-hydroxyphenyl) -benzofuran-2 (3H) -one, 5, 7-di-tert-butyl-3- {4- (2-hydroxyethoxy) phenyl} -benzofuran-2 (3H) -one, 6- (2- (4- (5,7-di-tert-2-) Oxo-2,3-dihydrobenzofuran-3-yl) phenoxy) ethoxy) -6-oxohexyl-6-((6-hydroxyhexanoyl) oxy) hexanoate, 5-di-tert-butyl-3- (4- And benzofuran compounds such as ((15-hydroxy-3,6,9,13-tetraoxapentadecyl) oxy) phenyl) benzofuran-2 (3H) one.

  0.001-20 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity in the case of mix | blending another antioxidant, 0.01-5 mass parts is more preferable.

  Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-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-hydroxy Polyethylene glycol ester of 3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy- 3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [ 2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2 -[2-hydroxy-3- ert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2- Hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [ 2- (2-hydroxy) such as 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole Phenyl) benzotriazoles; Phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate , Dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl-4) Benzoates such as -hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2 '-Ethoxyoxanilide, 2-ethoxy-4'-dodecy Substituted oxanilides such as oxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts; Alternatively, metal chelates, particularly nickel, chromium salts, chelates, and the like can be given.

  0.001-10 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity in the case of mix | blending a ultraviolet absorber, 0.01-0.5 mass part is more preferable.

  Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6- Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 , 4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6- Tetramethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperyl) L) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5 -Di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6 -Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6, 6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N- Butyl-N- (2 2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4 -Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-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- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate, TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals.

  0.001-5 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity in the case of mix | blending a hindered amine compound, 0.005-0.5 mass part is more preferable.

  Examples of the nucleating agent include sodium-2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, lithium-2,2′-methylenebis (4,6-di-tert-butylphenyl). Phosphate, aluminum hydroxybis [2,2′methylenebis (4,6-di-tert-butylphenyl) phosphate], sodium benzoate, 4-tert-butylaluminum benzoate, sodium adipate and disodium bicyclo [2. 2.1] Metal salt of carboxylic acid such as heptane-2,3-dicarboxylate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol , And bis (dimethyl Polyol derivatives such as benzylidene) sorbitol, N, N ′, N ″ -tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N ′, N ″ -tricyclohexyl-1,3,5 Examples include amide compounds such as -benzenetricarboxamide, N, N'-dicyclohexylnaphthalenedicarboxamide, and 1,3,5-tri (dimethylisopropoylamino) benzene.

  0.001-5 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity in the case of mix | blending a nucleating agent, 0.005-0.5 mass part is more preferable.

  Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis (diphenyl phosphate), (1-methylethylidene) -4,1-phenylenetetraphenyl diphosphate, 1,3-phenylenetetrakis (2,6-dimethylphenyl) phosphate, trade name ADEKA STAB FP-500 manufactured by ADEKA Corporation, trade name ADEKA STAB FP-600 manufactured by ADEKA Corporation, stock Company ADEKA product name Adeka Stub FP-800 aromatic phosphate ester, phenylphosphonic acid divinyl, phenylphosphonic acid diallyl, phenylphosphonic acid (1-butenyl) phosphonic acid ester, di Phosphinic acid esters such as phenyl phenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, bis (2-allylphenoxy) phosphazene, dicresyl phosphazene, etc. Phosphazene compounds, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing flame retardants such as phosphorus-containing vinylbenzyl compounds and red phosphorus, Metal hydroxide such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylene bis Pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene Ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, Examples thereof include pentabromobenzyl acrylate and brominated flame retardants such as brominated styrene. These flame retardants are preferably used in combination with anti-drip agents such as fluororesins and flame retardant aids such as polyols and hydrotalcites.

  1-50 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity in the case of mix | blending a flame retardant, 10-30 mass parts is more preferable.

  Examples of the filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, and dolomite. , Mica, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate, etc., and appropriately select and use the particle diameter (in the fibrous form, the fiber diameter, fiber length, and aspect ratio) Can do. Moreover, what was surface-treated as needed can be used for a filler.

  The blending amount in the case of blending the filler is preferably 0.01 to 80 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the halogen-containing resin.

  As the metal soap, metals such as magnesium, calcium, aluminum, and zinc and salts of saturated or unsaturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid are used.

  0.001-10 mass parts of metal soap is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity in the case of mix | blending metal soap, 0.01-5 mass parts is more preferable.

  Hydrotalcite is a complex salt compound consisting of magnesium, aluminum, hydroxyl group, carbonate group and any crystal water known as a natural product or synthetic product. Examples include those substituted with metal, hydroxyl groups, and carbonate groups substituted with other anionic groups. Specifically, for example, the hydrotalcite metal represented by the following general formula (4) is replaced with an alkali metal. The thing which was done is mentioned. In addition, as the Al—Li hydrotalcites, compounds represented by the following general formula (5) can also be used.

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

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

ここで、一般式（５）中、Ａ^ｑ−は、ｑ価のアニオンを表し、ｐは０または正の数を表す。

Here, in the general formula (5), A ^q− represents a q-valent anion, and p represents 0 or a positive number.

  Further, the carbonate anion in the hydrotalcite may be partially substituted with another anion.

  Hydrotalcite may be obtained by dehydrating crystallization water, higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal such as alkali metal dodecylbenzenesulfonate. It may be coated with a salt, higher fatty acid amide, higher fatty acid ester or wax.

  Hydrotalcites may be natural products or synthetic products. As the synthesis method of hydrotalcites, JP-B No. 46-2280, JP-B No. 50-30039, JP-B No. 51-29129, JP-B No. 3-36839, JP-A No. 61-174270 are disclosed. And publicly known methods described in JP-A-5-179052 and the like. Hydrotalcites can be used without being limited by their crystal structure, crystal particles, and the like.

  0.001-5 mass parts is preferable with respect to 100 mass parts of halogen-containing resin, and, as for the compounding quantity in the case of mix | blending hydrotalcite, 0.05-3 mass parts is more preferable.

  A commercially available pigment can also be used as the pigment. For example, Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71 Pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 1; 0, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

  As dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And dyes such as cyanine dyes, and a plurality of these may be used in combination.

  Furthermore, the resin composition of the present invention includes, as necessary, an impact resistance improver, a crosslinking agent, an antistatic agent, an antifogging agent, a plate-out preventing agent, a surface treatment agent, a brightening agent, a fluorescent agent, and an antifungal agent. Agents, bactericides, mold release agents, gelling aids, peroxidation scavengers, modifiers and other complexing agents of Lewis acids can be blended.

  The method for producing the resin composition of the present invention is not particularly limited, and the halogen-containing resin may be blended with the polymer compound (A), if necessary, an alkali metal salt (F) and other optional components. Any commonly used method can be used. For example, they may be mixed and kneaded by roll kneading, bumper kneading, an extruder, a kneader or the like.

  Moreover, although a high molecular compound (A) may be added as it is, you may add after impregnating a support | carrier as needed. In order to impregnate the carrier, it may be heated and mixed as it is, or if necessary, it may be diluted with an organic solvent, impregnated into the carrier, and then the solvent is removed.

  As such carriers, those known as halogen-containing resin fillers and fillers, or solid flame retardants and light stabilizers at room temperature can be used. For example, calcium silicate powder, silica powder, talc powder, alumina Examples thereof include powders, titanium oxide powders, those obtained by chemically modifying the surface of these carriers, and solids among the flame retardants and antioxidants listed below. Among these carriers, those obtained by chemically modifying the surface of the carrier are preferred, and those obtained by chemically modifying the surface of the silica powder are more preferred. These carriers preferably have an average particle size of 0.1 to 100 μm, and more preferably 0.5 to 50 μm.

  Furthermore, as a blending method of the polymer compound (A) to the halogen-containing resin, the block polymer (G) and the polymer compound (A) may be blended together or separately. .

  The polymer compound (A) may be blended by synthesizing the polymer compound (A) while kneading the block polymer (G) and the compound (D) having a reactive functional group into the resin component. At that time, the alkali metal salt (F) may be kneaded at the same time. Also, at the time of molding such as injection molding, the polymer compound (A), the alkali metal salt (F) and the resin component are mixed to obtain a molded product. You may mix | blend by the method, Furthermore, the masterbatch of said resin additive and / or alkali metal salt (F) and halogen-containing resin is manufactured, and this masterbatch may be mix | blended.

  Furthermore, the polymer compound (A) and the alkali metal salt (F) may be mixed in advance and then blended with the halogen-containing resin, and synthesized by adding the alkali metal salt (F) during the reaction. You may mix | blend a high molecular compound (A) with a halogen-containing resin.

Next, the molded product of the present invention will be described.
The molded article of the present invention is obtained by molding the resin composition of the present invention. By molding the resin composition of the present invention, a molded article having excellent antistatic properties and long-term maintenance can be produced. The molding method is not particularly limited, and secondary processing such as extrusion, calendaring, injection molding, roll, compression molding, grinding, sintering, spinning, extrusion blow molding, plastisol processing, etc. can also be performed. . Further, foam roll processing, melt rolling method, melt casting method, pressure molding processing, paste processing, powder molding processing, foam molding processing and the like can be exemplified.

  Usually, when an antistatic agent is blended, the physical properties are often lowered. However, the molded article of the present invention is excellent in excellent antistatic properties and its long-term maintenance, and has little deterioration in physical properties. In particular, it has antistatic resistance against wiping of the surface of the molded body.

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

  More specifically, the resin composition of the present invention and the molded product thereof are a film, a sheet, a wall material, a pillar material, an interior material, an exterior material, a window frame, a corrugated sheet, a rain gutter, a roofing material, a flooring material, and a siding material. (Siding materials), deck materials, slabs, building materials such as siding, terraces, balconies, materials for fences, frames and repetitive shapes, window and door shapes, soundproof plates, heat insulating plate pipes, and fittings Can do.

  Interior materials include, for example, handrails, staircase peripheral members such as headboards for staircases, construction materials such as baseboards and surrounding edges, door peripheral members such as door frames and other door frames, and middle parts of closets And storage furniture peripheral members such as drawers, wallpaper, wall coverings and the like.

  When using the resin composition of the present invention for a white window frame, it is preferable to contain titanium dioxide.

  The corrugated sheet can be used for, for example, a roof of a factory / warehouse, a side wall, a roof material of a temporary house, a terrace, a balcony, a carport, a storage, a snow enclosure of a snowy area, and the like.

  In addition to the above, the resin composition of the present invention includes telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic notebooks, cards, holders, stationery and other office supplies, TVs, VTRs, AV equipment such as video cameras, cassettes, tape recorders, mini-discs, CD players, speakers, liquid crystal displays, OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, kotatsu, and other home appliances , Food packaging film, pharmaceutical / medical wrap film, product packaging film, agricultural film, agricultural sheet, film material for greenhouse film, wall painting material, toys and other miscellaneous goods, equipment (fitting), sticker Marking film, office film, electrical equipment member, furniture, tube, hollow product (bottle), gasket, printer Electrical and electronic parts such as personal computers, word processors, keyboards, PDAs (small information terminals), connectors, relays, capacitors, switches, printed boards, coil bobbins, wire coating materials, cables, transformers, deflection yokes, distribution boards, watches, etc. And communication equipment, plate-making film, adhesive film, bottle, food container, seat (filling, dressing, etc.), belt, ceiling, compatible top, armrest, door trim, rear package tray, carpet, mat, sun visor, foil cover , Automobile parts such as mattress covers, airbags, suspension hands, suspension straps, wire covering materials, electrical insulation materials, paints, coating materials, upholstery materials, flooring materials, corner walls, carpets, window materials, etc. , Vehicles, ships, aircraft, buildings, housing and building materials and civil engineering materials, clothing, curtains Sheets, non-woven fabrics, plywood, synthetic fiber boards, carpets, doormats, sheets, buckets, hoses, containers, glasses, bags, cases, goggles, skis, rackets, tents, musical instruments, and other various uses such as sports equipment Can be widely used for.

Hereinafter, the present invention will be specifically described with reference to examples.
The polymer compound (A) was produced according to the following Production Examples 1 to 3. In the following production examples, the number average molecular weight was measured by the following method.

<Molecular weight measurement>
The number average molecular weight (hereinafter referred to as “Mn”) was measured by a gel permeation chromatography (GPC) method. The measurement conditions for Mn are as follows.
Apparatus: GPC apparatus manufactured by JASCO Corporation Solvent: Tetrahydrofuran Reference material: Polystyrene Detector: Differential refractometer (RI detector)
Column stationary phase: Shodex KF-804L manufactured by Showa Denko KK
Column temperature: 40 ° C
Sample concentration: 1 mg / 1 mL
Flow rate: 0.8mL / min
Injection volume: 100 μL

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

  Next, 600 g of the obtained polyester (E) -1 has one or more groups represented by the general formula (1), and has a number average molecular weight of 4,000 as a compound (C) having hydroxyl groups at both ends. Charge 300 g of polyethylene glycol (C) -1, 0.5 g of antioxidant (ADK STAB AO-60) and 0.8 g of zirconium octylate, and polymerize at 210 ° C. for 7 hours under reduced pressure. The block polymer (G) -1 having The acid value of this block polymer (G) -1 was 9, and the number average molecular weight Mn was 12,000 in terms of polystyrene.

  6 g of bisphenol F diglycidyl ether (D) -1 as a compound (D) having a reactive functional group of a polyvalent epoxy compound is added to 360 g of the obtained block polymer (G) -1 having a carboxyl group at both ends. The resultant was polymerized under reduced pressure at 240 ° C. for 3 hours to obtain a polymer compound (A) -1.

[Production Example 2] (Production of polymer compound (A) -2)
In a separable flask, 370 g (1.87 mol) of 1,4-bis (β-hydroxyethoxy) benzene as a diol, 289 g (1.98 mol) of adipic acid as an aliphatic dicarboxylic acid, aromatic dicarboxylic acid As an example, 8 g (0.05 mol) of isophthalic acid and 0.5 g of an antioxidant (ADK STAB AO-60) were charged, and polymerization was performed at normal pressure for 5 hours while gradually raising the temperature from 180 ° C to 220 ° C. Thereafter, 0.5 g of tetraisopropoxy titanate was charged and polymerized at 220 ° C. under reduced pressure for 5 hours to obtain polyester (E) -2. Polyester (E) -2 had an acid value of 56 and a number average molecular weight Mn of 4,900 in terms of polystyrene.

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

  300 g of the obtained block polymer (G) -2 was charged with 11 g of dicyclopentadienemethanol diglycidyl ether (D) -2 as a compound (D) having a reactive functional group of a polyvalent epoxy compound at 240 ° C. Polymerization was performed under reduced pressure for 4 hours to obtain a polymer compound (A) -2.

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

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

  Using the polymer compounds (A) -1 to (A) -3 obtained by the above production method, a sheet was produced by the following method and evaluated.

<Sheet preparation conditions>
The vinyl chloride resin composition shown in Table 1 below was pre-kneaded with a roll for 3 minutes at 190 ° C. and 30 rpm, and then pressed at 190 ° C. for 5 minutes to produce a sheet having a thickness of 1 mm.

<Method for measuring surface resistivity (SR value)>
Immediately after molding, the obtained sheet was stored for 1 day under the conditions of 30 ° C. and humidity 41% RH, and under the same atmosphere, using an R8340 resistance meter manufactured by Advantest Co., applied voltage 100 V, application time 1 The surface resistivity (Ω / □) was measured under the condition of minutes. The measurement was performed for 5 points, and the average value was obtained. These results are shown in Table 2 below.

<Color tone evaluation method>
YI (Yellowness Index) was measured for the obtained sheet | seat using Suga Test Co., Ltd. spectrocolorimeter SC-P. These results are shown in Table 2.

ＮａＤＢＳ；ドデシルベンゼンスルホン酸ナトリウム
ＬｉＯＴｓ；ｐ−トルエンスルホン酸リチウム
比較帯電防止剤−１；ポリエーテルエステルアミド型帯電防止剤，ＢＡＳＦ社製商品名「イルガスタットＰ−１８」
比較帯電防止剤−２；ポリエチレングリコール（分子量４，０００）

NaDBS; sodium dodecylbenzene sulfonate LiOTs; lithium p-toluenesulfonate comparative antistatic agent-1; polyether ester amide type antistatic agent, trade name “Irgastat P-18” manufactured by BASF
Comparative antistatic agent-2; polyethylene glycol (molecular weight 4,000)

  In addition, in Table 1, when 41 mass parts of (A) -1 was mix | blended as a high molecular compound (A), there were many adhesions to a plate-out or a roll, and the sheet | seat was not able to be produced.

  As shown in the above table, from Comparative Examples 3 to 5, when a compound different from the polymer compound (A) of the antistatic agent of the present invention was used, the antistatic property was poor and the color tone was sometimes poor. . Further, from comparison between Comparative Example 1 and Comparative Example 2, it is not possible to improve the antistatic property by using only the alkali metal salt (F), but from the comparison between Example 5 and Example 2, the antistatic agent according to the present invention can be improved. When the polymer compound (A) was used, the antistatic property was further improved by adding the alkali metal salt (F).

  Thus, from Examples 1-8, the sheet | seat which shape | molded the resin composition of this invention has the outstanding antistatic property, and is excellent in a color tone compared with the case where a polyetheresteramide type antistatic agent is mix | blended. Was confirmed.

Claims (13)

In the antistatic halogen-containing resin composition containing 2 to 40 parts by mass of the polymer compound (A) with respect to 100 parts by mass of the halogen-containing resin,
The polymer compound (A) is a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, the following general formula (1),

The compound (C) having one or more groups represented by the above and having a hydroxyl group at both ends and the compound (D) having a reactive functional group are bonded via an ester bond or an ester bond and an amide bond. An antistatic halogen-containing resin composition having a structure formed by bonding via   The polymer (A) is a polyester (E) composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, the compound (C), and the compound (D) via an ester bond. Or an antistatic halogen-containing resin composition according to claim 1, which is bonded via an ester bond and an amide bond.   The polymer compound (A) has a carboxyl group at both ends formed by alternately and alternately connecting a block composed of the polyester (E) and a block composed of the compound (C) via an ester bond. The antistatic halogen-containing resin composition according to claim 2, wherein the block polymer (G) and the compound (D) have a structure formed by bonding via an ester bond or an ester bond and an amide bond. object.   The number average molecular weight of the block composed of the polyester (E) is 800 to 8,000 in terms of polystyrene, and the number average molecular weight of the block composed of the compound (C) is 400 to 6,000 in terms of polystyrene. The antistatic halogen-containing resin composition according to claim 2 or 3, wherein the block polymer (G) has a number average molecular weight of 5,000 to 25,000 in terms of polystyrene.   The antistatic halogen-containing resin composition according to any one of claims 2 to 4, wherein the polyester (E) has a structure having carboxyl groups at both ends.   The compound (D) is a polyhydric epoxy compound (D) -1 having two or more epoxy groups, a polyhydric alcohol compound (D) -2 having three or more hydroxyl groups, and two or more amino groups. The antistatic halogen-containing resin composition according to claim 1, which is at least one selected from the group consisting of a polyvalent amine compound (D) -3.   The said compound (C) is polyethyleneglycol, The antistatic halogen-containing resin composition as described in any one of Claims 1-6.   Furthermore, the antistatic halogen-containing resin composition as described in any one of Claims 1-7 containing 0.01-5 mass parts of 1 or more types of alkali metal salt (F).   Furthermore, the antistatic halogen-containing resin composition as described in any one of Claims 1-8 containing 0.01-15 mass parts of 1 or more types of metal type stabilizer (H).   Furthermore, the antistatic halogen-containing resin composition as described in any one of Claims 1-9 containing 0.01-8 mass parts of 1 or more types of (beta) -diketone compound (I).   Furthermore, the antistatic halogen-containing resin composition as described in any one of Claims 1-10 containing 0.01-10 mass parts of 1 or more types of lubricants (J).   Furthermore, the antistatic halogen-containing resin composition as described in any one of Claims 1-11 containing 0.01-6 mass parts of 1 or more types of processing adjuvants (K).   A molded article, wherein the antistatic halogen-containing resin composition according to any one of claims 1 to 12 is molded.