JP6662646B2 - Antistatic thermoplastic resin composition and molded article obtained by molding the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to an antistatic thermoplastic resin composition (hereinafter, also simply referred to as “resin composition”) and a molded product obtained by molding the same. More specifically, the present invention has excellent antistatic durability and flame retardancy. TECHNICAL FIELD The present invention relates to an antistatic thermoplastic resin composition capable of providing a molded article obtained by the method, and a molded article obtained by molding the same.

  Thermoplastic resins are used in building materials, automotive materials, home appliance / electronic materials, textile materials, packaging materials, agricultural materials, home appliance housing materials, and living materials according to various physical properties such as moldability and low specific gravity. Widely used for various molded articles such as miscellaneous goods, films, sheets and structural parts.

  On the other hand, the thermoplastic resin has excellent insulating properties and has a property of being easily charged, and may attract dust and dirt to impair the appearance of the product. Further, when the molded product is an electronic product, the circuit may not operate normally due to charging. Further, an electric shock may be generated from the charged resin member, and when the electric shock is received, not only the user feels discomfort, but also where there is a flammable gas or dust, an explosion may be caused.

  Today, measures such as adding an antistatic agent to a thermoplastic resin have been taken in order to prevent charging of the resin member. Examples of such an antistatic agent include a coating type used by spraying, dipping, coating, or the like on a resin molding surface, and a kneading type, which is processed by adding an additive to a polymer material. In addition to the poor durability of the antistatic property, there is a problem that the antistatic agent is wiped off by touching the surface.

  In order to solve such a problem, Patent Documents 1 and 2 propose an antistatic resin composition containing a polyetherester polymer antistatic agent. On the other hand, since many thermoplastic resins are flammable substances, it is indispensable to make them flame-retardant depending on the use. As a method for flame retardation, for example, Patent Document 3 proposes a method of adding an inorganic hydroxide such as magnesium hydroxide, basic magnesium carbonate, hydrotalcite, or aluminum hydroxide to an ethylene copolymer. I have. Patent Document 4 proposes a flame-retardant polymer composition in which 80 to 300 parts by mass of an inorganic hydroxide flame retardant is blended with respect to 100 parts by weight of a copolymer of two kinds of ethylene-α-olefins. ing.

International Publication WO2014 / 115745 International Publication WO2014 / 148454 JP-A-8-316508 JP-A-9-137010

  However, as proposed in Patent Documents 3 and 4, in order to make a thermoplastic resin flame-retardant with an inorganic hydroxide, it is necessary to add a large amount of an inorganic hydroxide. There was a problem of impairing the moldability. In addition, since the inorganic hydroxide adsorbs or decomposes the antistatic agent, there is a problem that the antistatic performance and its durability are not sufficient. Patent Documents 1 and 2 disclose an antistatic resin composition containing a polyetherester polymer antistatic agent. However, since the composition does not contain an aromatic dicarboxylic acid, the present invention provides an antistatic resin composition. The structure is different from the polymer compound used as the agent.

  Therefore, an object of the present invention is to provide an antistatic thermoplastic resin composition capable of providing a molded article having excellent antistatic durability and flame retardancy, and a molded article obtained by molding the same. It is in.

  The present inventors have conducted intensive studies to solve the above problems, and found that the above problems can be solved by using an antistatic polymer compound having a specific structure and a flame retardant in combination. The invention has been completed.

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）と、反応性官能基を有する化合物（Ｄ）とが、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 thermoplastic resin composition of the present invention comprises 4 to 40 parts by mass of the polymer compound (A) and 1 to 80 parts by mass of the flame retardant (B) based on 100 parts by mass of the thermoplastic resin. In the containing antistatic thermoplastic resin composition,
A polyester (E) in which the polymer compound (A) is composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, and the following general formula (1):

The compound (C) having at least one group represented by the formula (I) and having a hydroxyl group at both terminals and the compound (D) having a reactive functional group are formed through an ester bond or an ester bond and an amide bond. Characterized by having a structure formed by bonding via

（式（２）中のｎは１〜１００の数を表し、Ｘ^１はアンモニアまたは下記一般式（３）、

（式（３）中のＺ^１およびＺ^２は、−ＮＲ^１Ｒ^２基、水酸基、メルカプト基、直鎖または分岐を有する炭素原子数１〜１０のアルキル基、直鎖または分岐を有する炭素原子数１〜１０のアルコキシ基、フェニル基、または、ビニル基を表し、Ｒ^１およびＲ^２は各々独立して、水素原子、直鎖または分岐を有する炭素原子数１〜６のアルキル基、または、メチロール基を表し、Ｚ^１およびＺ^２は同一でも異なっていてもよい。）で表されるトリアジン誘導体を表し、ｐは０＜ｐ≦ｎ＋２を満たす数を表す。）で表される（ポリ）リン酸塩化合物（Ｂ）−１成分と、下記一般式（４）、

（式（４）式中、ｒは１〜１００を表し、Ｙ^１は、〔Ｒ^３Ｒ^４Ｎ−（ＣＨ_２）_ｋ−ＮＲ^５Ｒ^６〕、ピペラジン、または、ピペラジン環を含むジアミンを表し、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は各々独立して、水素原子、直鎖または分岐を有する炭素原子数１〜５のアルキル基を表し、ｋは１〜１０の整数を表し、ｑは、０＜ｑ≦ｒ＋２を満たす数を表す。）で表される（ポリ）リン酸塩化合物（Ｂ）−２成分との混合物からなることが好ましい。 In the resin composition of the present invention, the flame retardant (B) is represented by the following general formula (2):

(N in the formula (2) represents a number of 1 to 100, and X ¹ is ammonia or the following general formula (3);

(Z ¹ and Z ² in the formula (3) ^each represent a —NR ¹ R ² group, a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched carbon atom. Wherein each of R ¹ and R ² independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or Represents a methylol group, and Z ¹ and Z ² may be the same or different.), And p represents a number satisfying 0 <p ≦ n + 2. (B) -1 component represented by the following general formula (4):

(In the formula (4), r represents 1 to 100, and Y ¹ represents [R ³ R ⁴ N— (CH ₂ ) _k —NR ⁵ R ⁶ ], piperazine, or a diamine containing a piperazine ring. , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, k represents an integer of 1 to 10, q Represents a number that satisfies 0 <q ≦ r + 2.) It is preferable to comprise a mixture with the (poly) phosphate compound (B) -2 component.

  Further, in the resin composition of the present invention, in the polymer compound (A), the block composed of the polyester (E) and the block composed of the compound (C) are repeatedly and alternately bonded via an ester bond. Has a structure in which the block polymer (G) having carboxyl groups at both ends and the compound (D) are bonded via an ester bond or via an ester bond and an amide bond. preferable.

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

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

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

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

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

  Furthermore, in the resin composition of the present invention, the thermoplastic resin is a group consisting of a polyolefin resin, a styrene resin, a polyester resin, a polyether resin, a polycarbonate resin, a polyamide resin, and a halogen-containing resin. It is preferably at least one selected from

  Further, the resin composition of the present invention contains, if necessary, one or more components selected from the group consisting of a metal oxide, an anti-drip agent, a silicone oil, a silane coupling agent, and a polyhydric alcohol compound. It is also preferable to make it.

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

  According to the present invention, an antistatic thermoplastic resin composition capable of providing a molded article having a sufficient antistatic property having long-lasting properties and long-term light stability, and a molded article obtained by molding the same. 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 thermoplastic resin composition of the present invention and a molded article obtained by molding the same will be described in detail. The resin composition of the present invention contains 4 to 40 parts by mass of the polymer compound (A) and 1 to 80 parts by mass of the flame retardant (B) based on 100 parts by mass of the thermoplastic resin. In the resin composition of the present invention, the polymer compound (A) includes a diol, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a compound represented by the following general formula (1),

The compound (C) having at least one group represented by the formula (I) and having a hydroxyl group at both terminals and the compound (D) having a reactive functional group are formed through an ester bond or an ester bond and an amide bond. Has a structure formed by bonding via

First, the thermoplastic resin used in the resin composition of the present invention will be described.
The resin that can be used in the resin composition of the present invention is not particularly limited as long as it is a thermoplastic resin.From the viewpoint of durability and moldability of antistatic performance, particularly, polyolefin-based resins, styrene-based resins, and polyester-based resins , Polyether resins, polycarbonate resins, polyamide resins, and halogen-containing resins are preferred.

  Examples of the polyolefin resin include polyethylene, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, cross-linked polyethylene, ultra-high-molecular-weight polyethylene, polypropylene, homopolypropylene, random copolymer polypropylene, block copolymer polypropylene, and isotactic polypropylene. , Syndiotactic polypropylene, hemiisotactic polypropylene, polybutene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1- Α-olefin polymers such as pentene, ethylene-propylene block or random copolymers, impact copolymer polypropylene, ethylene-methyl methacrylate Rate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, α-olefin copolymer such as ethylene-vinyl acetate copolymer, polyfluoroolefin, and more. Polyolefin-based thermoplastic elastomers may be mentioned, and copolymers of two or more of these may be used.

  Examples of the styrene resin include, for example, a vinyl group-containing aromatic hydrocarbon alone, and a vinyl group-containing aromatic hydrocarbon, and another monomer (for example, maleic anhydride, phenylmaleimide, (meth) acrylate, Butadiene, (meth) acrylonitrile, etc.), for example, polystyrene (PS) resin, impact-resistant polystyrene (HIPS), acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin , Methyl methacrylate-butadiene-styrene (MBS) resin, heat-resistant ABS resin, acrylonitrile-acrylate-styrene (AAS) resin, styrene-maleic anhydride (SMA) resin, methacrylate-styrene (MS) resin, styrene-isoprene-styrene (SIS) Resin, a Thermoplastic resins such as rilonitrile-ethylene propylene rubber-styrene (AES) resin, styrene-butadiene-butylene-styrene (SBBS) resin, and methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin, and those butadiene or isoprene. Styrene-ethylene-butylene-styrene (SEBS) resin with hydrogenated double bond, styrene-ethylene-propylene-styrene (SEPS) resin, styrene-ethylene-propylene (SEP) resin, styrene-ethylene-ethylene-propylene-styrene (SEEPS) resin and the like.

  Polyester resins include, for example, polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, and polycyclohexane dimethylene terephthalate; aromatic polyesters such as polyalkylene naphthalate such as polyethylene naphthalate and polybutylene naphthalate; polytetramethylene terephthalate Linear polyester such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, poly (2-oxetanone) and the like. Polyester and the like.

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

  Examples of the polycarbonate-based resin include polycarbonate, polycarbonate / ABS resin, and branched polycarbonate.

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

  Examples of the halogen-containing resin include polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chloride rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-chloride. Vinylidene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-cyclohexylmaleimide copolymer, and the like. Can be

  Further examples of the thermoplastic resin, for example, petroleum resin, cumarone resin, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyphenylene sulfide, polyurethane, cellulose resin, polyimide resin , Polysulfone, thermoplastic resins such as liquid crystal polymers, and blends thereof.

  Further, thermoplastic resins are isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluoro rubber, silicone rubber, polyester elastomer, nitrile elastomer, nylon elastomer, vinyl chloride elastomer, Elastomers such as polyamide-based elastomers and polyurethane-based elastomers may be used, or may be used in combination.

  In the resin composition of the present invention, these thermoplastic resins may be used alone or in combination of two or more. Further, it may be alloyed. These thermoplastic resins have a molecular weight, a degree of polymerization, a density, a softening point, a proportion of an insoluble portion in a solvent, a degree of stereoregularity, the presence or absence of a catalyst residue, a kind and a mixing ratio of a monomer as a raw material, a polymerization catalyst, (Eg, Ziegler catalyst, metallocene catalyst, etc.).

Next, the polymer compound (A) will be described.
The polymer compound (A) is blended for imparting 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 a hydroxyl group at both terminals. The compound (C) has a structure in which the compound (C) 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) comprises a polyester (E) composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, a compound (C), and a reactive functional group. The compound (D) preferably has a structure in which the compound (D) is bonded through an ester bond or through an ester bond and an amide bond, and further has a block composed of the polyester (E) and a compound (C). ), A block polymer (G) having carboxyl groups at both ends and a compound (D) having a reactive functional group, which is formed by alternately bonding the blocks constituted by ester bonds, via an ester bond. It is also preferable to have a structure formed by bonding through an ester bond and an amide bond.

  The polyester (E) may be composed of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and a residue obtained by removing a hydroxyl group of a diol and a residue obtained by removing a carboxyl group of an aliphatic dicarboxylic acid, Having a structure in which the residue excluding the hydroxyl group of the diol and the residue in which the carboxyl group of the aromatic dicarboxylic acid is removed through an ester bond have a structure in which the residue is removed through 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 to 50.

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

  In addition, since the aliphatic diol preferably has hydrophobicity, polyethylene glycol having hydrophilicity is not preferred among the aliphatic diols. However, when it is used together with other diols, it is not limited.

  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. Polyhydroxyethyl adducts of mononuclear dihydric phenol compounds such as dimethanol, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, 1,4-bis (2-hydroxyethoxy) benzene, resorcinol and pyrocatechol And the like. 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.

  Aliphatic dicarboxylic acids that can be used in the resin composition of the present invention may be derivatives of aliphatic dicarboxylic acids (eg, acid anhydrides, alkyl esters, alkali metal salts, acid halides, etc.). The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more.

  As the aliphatic dicarboxylic acid, preferably an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Sebacic acid, 1,10-decanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, maleic acid, fumaric acid and the like can be mentioned. Among these aliphatic dicarboxylic acids, from the viewpoint of melting point and heat resistance, aliphatic dicarboxylic acids having 4 to 16 carbon atoms are preferable, and aliphatic dicarboxylic acids having 6 to 12 carbon atoms are more preferable.

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

  Preferred aromatic dicarboxylic acids include aromatic dicarboxylic acids having 8 to 20 carbon atoms, such as terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, and β-phenylglutaric acid. 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 and the like.

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 compound having hydrophilicity, more preferably a polyether having a group represented by the above general formula (1), and particularly preferably a polyethylene glycol represented by the following general formula (5).

一般式（５）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 (5), m represents an integer of 5 to 250. m is preferably from 20 to 150 from the viewpoint of heat resistance and compatibility.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Next, the compound (D) having a reactive functional group will be described.
In the present invention, the compound (D) having a reactive functional group is not particularly limited as long as it 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) ) And a block composed of an ester bond or an amide bond, or a block composed of polyester (E) and a block composed of compound (C) are repeatedly and alternately coupled 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 at both ends by an ester bond or an amide bond. Examples of such a functional group include an epoxy group, a hydroxyl group, and an amino group.

  In the present invention, the compound (D) having a reactive functional group is preferably a polyvalent epoxy compound (D) -1 having two or more epoxy groups, a polyhydric alcohol compound (D)-having three or more hydroxyl groups. The polyvalent amine compound (D) -3 having two or 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 polyphenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds: dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3 -Bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra ( 4-H Roxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, polyglycidyl ether compounds of polynuclear polyphenol compounds 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, glue Lulic 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 diglycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Epoxides of cyclic olefin compounds such as carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, and 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. These polyepoxy compounds can be prepared by internally cross-linking with a prepolymer of terminal isocyanate or using a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). It may have a reduced molecular weight. Two or more polyepoxy compounds may be used.

  The polyhydric alcohol compound (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, -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-triol Trihydric alcohols such as (2-hydroxyethyl) isocyanurate; pentaerythritol, 1,2,3,4-pentane tetrol, 2,3,4,5-hexane tetrol, 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 ′, Quaternary alcohols such as N'-tetrakis (2-hydroxyethyl) ethylenediamine; pentavalent alcohols such as adonitol, arabitol, xylitol, triglycerin; dipentaerythritol, sorbitol, mannitol, iditol, inositol, darcitol, talose, allose, etc. Hexahydric alcohol; furthermore, tripe Data erythritol, and the like. The molecular weight of the polyol compound is not particularly limited, and high molecular weight polyols such as polypentaerythritol and polyvinyl alcohol can be used, and polyester polyols can also be used. Two or more 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 alkylenediamines such as diamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine; aliphatic amines such as 2,2 ', 2 "-triaminotriethylamine and bis (hexamethylene) triamine; diethylenetriamine A polyalkylene polyamine having 2 to 6 carbon atoms in the alkylene group and a degree of polymerization of 2 to 5; 1,6,11-undecanetriamine, 1,8-diamino-4-aminomethyloctane, 1,3,6- Alkanetriamines such as hexamethylenetriamine; melamine, piperazine; N-aminoalkylpiperazines having 2 to 6 carbon atoms in the alkylene group, such as minoethylpiperazine; heterocyclic polyamines such as heterocyclic polyamines described in JP-B-55-21044; dicyclohexylmethanediamine, isophoronediamine, bicycloheptane Alicyclic polyamines having 4 to 20 carbon atoms such as triamine; carbon atoms such as phenyldiamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine and triphenylmethanetriamine Examples thereof include aromatic polyamines of the formulas 6 to 20. Such polyamine compounds may be used in combination of two or more.

Next, the polyester (E) and the block polymer (G) will be described.
As described above, in the resin composition of the present invention, from the viewpoint of antistatic properties, the polymer compound (A) comprises a polyester (E) comprising a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and a 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.

  Further, 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 composed of a compound (C). The block polymer (G) having carboxyl groups at both ends formed by repeating the blocks repeatedly and alternately via an ester bond, and the compound (D) having a reactive functional group are bonded via an ester bond, or It is preferred to have a structure formed by bonding through an ester bond and an amide bond.

  The polyester (E) can be obtained, for example, by subjecting an aliphatic dicarboxylic acid or a derivative thereof, an aromatic dicarboxylic acid or a 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, or the like). When it is obtained, both ends may be finally treated to form a carboxyl group. In the state as it is, a subsequent reaction for obtaining a block polymer (G) having a structure having a carboxyl group at both ends is carried out. You may proceed. Further, the aliphatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

  As described above, the aromatic dicarboxylic acid may be a derivative of the aromatic dicarboxylic acid (eg, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, or the like). When it is obtained, both ends may be finally treated to form a carboxyl group. In the state as it is, a subsequent reaction for obtaining a block polymer (G) having a structure having a carboxyl group at both ends is carried out. You may proceed. Further, the aromatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

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

  In the resin composition of the present invention, as the polyester (E), a polyester having a carboxyl group at both terminals is preferable, and the reaction ratio between an aliphatic dicarboxylic acid or a derivative thereof and an aromatic dicarboxylic acid or a derivative thereof and a diol is as follows. It is preferable to use an excess of an aliphatic dicarboxylic acid or a derivative thereof and an aromatic dicarboxylic acid or a derivative thereof such that both terminals are carboxyl groups. Is preferred.

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

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

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

  Note that, as described above, when aliphatic dicarboxylic acid and aromatic dicarboxylic acid are used instead of dicarboxylic acid, when a derivative such as a carboxylic acid ester, a carboxylic acid metal salt, or a carboxylic acid halide is used, the derivative of the diol with the diol is used. After the reaction, both ends may be treated to give a dicarboxylic acid, or the reaction may proceed as it is to obtain a block polymer (G) having a structure having a carboxyl group at both ends.

  Further, the polyester (E) comprising a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid may form an ester bond by reacting with the compound (C) and form a structure of the block polymer (G). Good. Further, the carboxyl group may be present at both ends of the polyester (E), and the carboxyl group may be protected, modified, or in the form of a precursor. Further, an antioxidant such as a phenolic antioxidant may be added to the reaction system in order to suppress oxidation of the product during the reaction.

  Further, the compound (C) may be any as long as it 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 terminals may be protected, It may be modified or in precursor form.

Next, the block polymer (G) will be described.
The block polymer (G) having a structure having carboxyl groups at both ends according to the present invention has a block composed of a polyester (E) and a block composed of a compound (C), and these blocks are: It has a structure that is repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group. As an example of such a block polymer (G), for example, a polymer having a structure represented by the following general formula (6) may be mentioned.

一般式（６）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 the general formula (6), (E) represents a block composed of a polyester (E) having carboxyl groups at both ends, and (C) is composed of a compound (C) having hydroxyl groups at both ends. Represents a block, and t is the number of repetitions of the repeating unit, and preferably represents a number of 1 to 10. t is more preferably a number from 1 to 7, and most preferably a number from 1 to 5.

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

  The block polymer (G) having a structure having carboxyl groups at both ends is obtained by subjecting a polyester (E) having carboxyl groups at both ends and a compound (C) having hydroxyl groups at both ends to a polycondensation reaction. A polyester (E) and a compound (C) having a structure equivalent to a structure in which a polyester (E) and a compound (C) are repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group. If so, 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 a carboxyl group at both terminals is obtained. (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 without isolating the polyester (E), and the reaction may be performed as it is.

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

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

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

  The polymer compound (A) according to the present invention is an ester formed by a terminal carboxyl group of a block polymer (G) having a structure having carboxyl groups at both ends and a compound (D) having a reactive functional group. Those having a structure formed through a bond or an ester bond and an amide bond are preferable. The polymer compound (A) further comprises an ester bond formed by a carboxyl group of the polyester (E) and a reactive functional group of the compound (D) having a reactive functional group, or And a structure formed via an amide bond.

  In order to obtain the polymer compound (A), the carboxyl group of the block polymer (G), the epoxy group of the polyhydric epoxy compound (D) -1 of the compound (D), and the polyhydric alcohol compound (D) -2 And the amino group of the polyamine compound (D) -3.

  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 (D) -1 depends on the number of the block polymer (G) to be reacted. The number of carboxyl groups is preferably 0.5 to 5 equivalents, more preferably 0.5 to 1.5 equivalents.

  The polyepoxy 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. Five 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 in the polyhydric alcohol compound (D) -2 depends on the number of carboxyl groups in the block polymer (G) to be reacted. Is preferably 0.5 to 5 equivalents, 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, and 0.2 to 1.5 equivalents. Equivalents are more preferred.

  When the compound (D) is a polyamine compound (D) -3 having two or more amino groups, the number of amino groups of the polyamine compound (D) -3 depends on the number of the block polymer (G) to be reacted. The number of carboxyl groups is preferably 0.5 to 5 equivalents, more preferably 0.5 to 1.5 equivalents.

  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. Five equivalents are more preferred.

  In the reaction, after completion of the synthesis reaction of the block polymer (G), the compound (D) may be added without isolating the block polymer (G), and the reaction may be performed as it is. In that case, the carboxyl group of the unreacted polyester (E) used excessively when synthesizing the block polymer (G) reacts with some of the 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 carboxyl groups at both ends and the compound (D) are formed through an ester bond or through an ester bond and an amide bond. The structure is not necessarily limited to the block polymer (G) and the compound (D) as long as the structure has the same structure as the structure having the bonded structure.

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

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

  In the polymer compound (A) according to the present invention, after obtaining a polyester (E) from a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, the compound (C) and the polyester (E) are isolated without isolating the polyester (E). And / or may be reacted with compound (D).

  The amount of the polymer compound (A) to be used is 4 to 40 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It is preferably from 35 to 35 parts by mass, more preferably from 7 to 30 parts by mass. If the amount is less than 4 parts by mass, sufficient antistatic properties may not be obtained, and if it exceeds 40 parts by mass, physical properties of a molded article may be adversely affected.

  Next, the flame retardant (B) used in the resin composition of the present invention will be described. In the resin composition of the present invention, the flame retardant (B) is not particularly limited, and a known flame retardant can be used. Among them, the (poly) phosphate compound (B) -1 component having a predetermined structure and the (poly) phosphate compound (B) -2 are preferable. Hereinafter, the (poly) phosphate compound (B) -1 component and the (poly) phosphate compound (B) -2 component will be described.

  The (poly) phosphate compound represented by the following general formula (2) used as the component (B) -1 in the resin composition of the present invention is phosphoric acid and ammonia or triazine represented by the following general formula (3) It is a salt with a derivative.

ここで、式（２）中のｎは１〜１００の数を表し、Ｘ^１はアンモニアまたは下記一般式（３）で表されるトリアジン誘導体を表し、ｐは０＜ｐ≦ｎ＋２を満たす数を表す。

Here, n in the formula (2) represents a number of 1 to 100, X ¹ represents ammonia or a triazine derivative represented by the following general formula (3), and p represents a number satisfying 0 <p ≦ n + 2. Represent.

ここで、式（３）中のＺ^１およびＺ^２は、−ＮＲ^１Ｒ^２基、水酸基、メルカプト基、直鎖または分岐を有する炭素原子数１〜１０のアルキル基、直鎖または分岐を有する炭素原子数１〜１０のアルコキシ基、フェニル基、または、ビニル基を表し、Ｚ^１およびＺ^２は同一であっても異なるものであってもよい。また、Ｒ^１およびＲ^２は各々独立して、水素原子、直鎖または分岐を有する炭素原子数１〜６のアルキル基、または、メチロール基を表す。

Here, Z ¹ and Z ² in the formula (3) ^each have a —NR ¹ R ² group, a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched group. Represents an alkoxy group having 1 to 10 carbon atoms, a phenyl group, or a vinyl group, and Z ¹ and Z ² may be the same or different. R ¹ and R ² each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a methylol group.

Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by Z ¹ and Z ² in the general formula (3) include, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, Tributyl, isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, decyl, and the like.

Examples of the linear or branched alkoxy group having 1 to 10 carbon atoms represented by Z ¹ and Z ² in the general formula (3) include groups derived from the above-described alkyl groups.

Examples of the linear or branched alkyl group having 1 to 6 carbon atoms represented by R ¹ and R ² in the —NR ¹ R ² group which Z ¹ and Z ² can take are among the alkyl groups listed above. Those having 1 to 6 carbon atoms are exemplified.

  As the triazine derivative represented by the general formula (3), for example, melamine, acetoguanamine, benzoguanamine, acrylguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino- 6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, , 4-Diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,3 5-triazine, 2,4-diamino-6-mercapto-1,3,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine and the like can be mentioned.

  Among the (poly) phosphate compounds represented by the general formula (2), as a compound preferably used, for example, a salt of (poly) phosphoric acid and melamine or an (poly) ammonium phosphate compound can be mentioned. .

Examples of the salt of the above (poly) phosphoric acid and melamine include melamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, and the like. n is 2, p is 2, ^{X 1} is particularly preferably melamine pyrophosphate melamine.

  For example, in the case of melamine pyrophosphate, the salt of (poly) phosphoric acid and melamine is obtained by reacting sodium pyrophosphate and melamine by adding hydrochloric acid at an arbitrary reaction ratio and neutralizing with sodium hydroxide. be able to.

  The (poly) ammonium phosphate compound is a compound containing (poly) ammonium phosphate alone or (poly) ammonium phosphate as a main component. As the above-mentioned (poly) ammonium phosphate simple substance, "Exolit-422" and "Exolit-700" manufactured by Clariant, "Fossek-P / 30" and "Fossek-P / 40" manufactured by Monsanto, Sumitomo Examples include “Sumisafe-P” manufactured by Chemical Co., Ltd., and “Terage-S10” and “Terage-S20” manufactured by Chisso Corporation.

  Examples of the compound containing (poly) ammonium phosphate as a main component include, for example, those obtained by coating or microencapsulating (poly) ammonium phosphate with a thermosetting resin, melamine monomers, and other nitrogen-containing organic compounds. Examples thereof include those coated with a (poly) ammonium phosphate surface, those that have been treated with a surfactant and silicon, and those that have been made insoluble by adding melamine or the like in the process of producing (poly) ammonium phosphate. Examples of the compound containing (poly) ammonium phosphate as a main component include "Exolit-462" (trade name, manufactured by Clariant), "Sumisafe-PM" (trade name, manufactured by Sumitomo Chemical Co., Ltd.), and "Terage-C60" (trade name, manufactured by Chisso Corporation). , "Terage-C70", "Terage-C80" and the like.

Also, represented by (poly) phosphate compound in the resin composition of the present invention (B) the following formula for use as -2 component (4) is a diamine represented by (poly) phosphoric acid and Y ¹ Salt. Diamine represented by Y ^{1 _{is, R 3 R 4 N- (CH}} 2) k -NR 5 R 6, is a diamine containing a piperazine or piperazine ring.

ここで、式（４）式中、ｒは１〜１００を表し、Ｙ^１は、Ｒ^３Ｒ^４Ｎ−（ＣＨ_２）_ｋ−ＮＲ^５Ｒ^６、ピペラジン、または、ピペラジン環を含むジアミンを表し、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は各々独立して、水素原子、直鎖または分岐を有する炭素原子数１〜５のアルキル基を表し、ｋは１〜１０の整数を表し、ｑは、０＜ｑ≦ｒ＋２を満たす数を表す。

Here, in the formula (4), r represents 1 to 100, and Y ¹ represents R ³ R ⁴ N— (CH ₂ ) _k —NR ⁵ R ⁶ , piperazine, or a diamine containing a piperazine ring. , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, k represents an integer of 1 to 10, q Represents a number satisfying 0 <q ≦ r + 2.

Examples of the straight-chain or branched alkyl group having 1 to 5 carbon atoms represented by R ^{3 to} R ⁶ include, among those mentioned above as specific examples of the alkyl group represented by Z ¹ and Z ² Those having 1 to 5 carbon atoms are exemplified.

  Examples of the diamine containing a piperazine ring include, for example, a compound in which at least one of positions 2, 3, 5, and 6 of piperazine is substituted with an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms; Compounds in which the amino group at the 4-position is substituted with an alkyl group substituted with an amino group, preferably an alkyl group having 1 to 5 carbon atoms, are mentioned.

Specific examples of Y ¹ in the general formula (4) include, for example, N, N, N ′, N′-tetramethyldiaminomethane, ethylenediamine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N , N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-diethylethylenediamine, tetramethylenediamine, 1,2-propanediamine 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, piperazine, trans-2,5-dimethylpiperazine, 1,4-bis (2-amido Ethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, and the like.

Among the (poly) phosphate compounds represented by the general formula (4), as a compound preferably used, a salt of (poly) phosphoric acid and piperazine is exemplified, and piperazine orthophosphate, piperazine pyrophosphate, Piperazine polyphosphate is preferred. Among them, from the viewpoint of flame retardancy, piperazine polyphosphate in which q in the general formula (4) is 1 and Y ¹ is piperazine, particularly piperazine pyrophosphate, is preferable.

  For example, in the case of piperazine pyrophosphate, a salt of (poly) phosphoric acid and piperazine can be easily obtained as a hardly water-soluble precipitate by reacting piperazine with pyrophosphoric acid in water or an aqueous methanol solution. When piperazine polyphosphate is used, a salt obtained from piperazine and polyphosphoric acid composed of a mixture of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, and other polyphosphoric acids may be used. In this case, the configuration of the raw material (poly) phosphoric acid is not particularly limited.

  The content ratio (by mass) of the component (B) -1 and the component (B) -2, which can be suitably used as the flame retardant (B), is (B) -1 from the viewpoint of flame retardancy. / (B) -2 = 20/80 to 50/50 is preferable, (B) -1 / (B) -2 = 30/70 to 50/50 is more preferable, and (B) -1 / (B)- 2 = 35 / 65-45 / 55 is more preferable.

  In the resin composition of the present invention, the total content of the components (B) -1 and (B) -2, which are flame retardant components, is preferably from 1 to 80 parts by mass per 100 parts by mass of the thermoplastic resin. And more preferably from 20 to 70 parts by mass, and even more preferably from 30 to 60 parts by mass. If the amount is less than 1 part by mass, a sufficient flame retarding effect cannot be obtained, and if it exceeds 80 parts by mass, the properties of the resin may be deteriorated.

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

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

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

  The compounding amount of the alkali metal salt (F) is 0.01 to 5.0 parts by mass and 0.1 to 3.0 parts by mass based on 100 parts by mass of the thermoplastic resin from the viewpoint of antistatic properties. Preferably, 0.3 to 2.0 parts by mass is more preferable. If the amount of the alkali metal salt (F) is less than 0.01 part by mass, the effect of adding the alkali metal salt (F) may not be sufficient. If the amount exceeds 5.0 parts by mass, the physical properties of the resin are adversely affected. 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 the salt of the Group 2 element include salts of an organic acid or an inorganic acid, and examples of the Group 2 element include beryllium, magnesium, calcium, strontium, barium, and the like. Examples of the organic acid include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, and the like. Aliphatic carboxylic acids having 1 to 12 carbon atoms; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethane Examples thereof include sulfonic acids having 1 to 20 carbon atoms such as sulfonic acids. Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like.

  Further, the resin composition of the present invention preferably contains an anti-drip agent, if necessary. Examples of the anti-drip agent include fluorine-based anti-drip agents, silicone rubbers, and layered silicates. Among these, a fluorine-based anti-drip agent and a layered silicate are preferred.

  Examples of the fluorine-based drip inhibitor include fluorine-based resins such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene, sodium perfluoromethanesulfonate, potassium perfluoro-n-butanesulfonate, Perfluoroalkanesulfonic acid alkali metal salt compounds such as fluoro-t-butanesulfonic acid potassium salt, perfluorooctanesulfonic acid sodium salt, perfluoro-2-ethylhexanesulfonic acid calcium salt, and alkaline earth perfluoroalkanesulfonic acid compounds Metal salts and the like. Among these, polytetrafluoroethylene is particularly preferred from the viewpoint of anti-drip properties.

  Examples of the layered silicate include smectite-based clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, and nontronite, vermiculite, halloysite, swellable mica, and talc. Further, organic cations, quaternary ammonium cations, and phosphonium cations may be intercalated between the layers.

  The content of the anti-drip agent is preferably from 0.005 to 5 parts by mass, more preferably from 0.01 to 5 parts by mass, and even more preferably from 0.05 to 3 parts by mass, per 100 parts by mass of the flame retardant (B). Parts, more preferably 0.1 to 1 part by mass. When the amount is less than 0.005 parts by mass, the drip prevention effect is not sufficient, and when the amount exceeds 5 parts by mass, the properties of the resin may be reduced.

  Further, the resin composition of the present invention preferably contains a metal oxide which is a flame retardant aid, if necessary. Examples of the metal oxide include zinc oxide, titanium oxide, magnesium oxide, silicon oxide, and the like, and among them, zinc oxide is preferable. The metal oxide may be surface-treated. The addition amount of the metal oxide is preferably 0.01 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and more preferably 1.2 to 5 parts by mass, per 100 parts by mass of the flame retardant (B). It is. If the amount is less than 0.01 part by mass, the effect of the flame retardant aid is not sufficient, and if it exceeds 10 parts by mass, the properties of the resin may be deteriorated.

  Furthermore, it is preferable to add a silicone oil to the resin composition of the present invention, if necessary, in order to suppress secondary agglomeration during mixing and improve water resistance. Examples of the silicone oil include dimethyl silicone oil in which the side chains of polysiloxane and all terminals are methyl groups, methylphenyl silicone oil in which part of the side chains of polysiloxane are phenyl groups, and part of the side chains of polysiloxane And hydrogenated methyl hydrogen silicone oils, and copolymers thereof. In addition, an organic group is introduced into a part of a side chain and / or a terminal thereof, and is amine-modified, epoxy-modified, alicyclic epoxy-modified, Modified silicone oil modified by carboxyl, carbinol, mercapto, polyether, long chain alkyl, fluoroalkyl, higher fatty acid ester, higher fatty acid amide, silanol, diol, phenol and / or aralkyl May be used.

  Specific examples of silicone oils include dimethyl silicone oils such as KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-965 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-968 (manufactured by Shin-Etsu Chemical Co., Ltd.) Examples of methyl hydrogen silicone oil or silicone oil having a methyl hydrogen polysiloxane structure include KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-9901 (Shin-Etsu Chemical Co., Ltd.), and HMS-151 (Gelest). HMS-071 (manufactured by Gelest), HMS-301 (manufactured by Gelest), DMS-H21 (manufactured by Gelest), and the like. Examples of methylphenyl silicone oil include KF-50 (Shin-Etsu Chemical). KF-53 (Shin-Etsu Chemical Co., Ltd.), KF-54 (Shin-Etsu Chemical Co., Ltd.), KF-56 (Shin-Etsu Chemical Co., Ltd.) And epoxy-modified products such as X-22-343 (Shin-Etsu Chemical Co., Ltd.), X-22-2000 (Shin-Etsu Chemical Co., Ltd.), and KF- 101 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-102 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-1001 (manufactured by Shin-Etsu Chemical Co., Ltd.), and carboxyl-modified products include, for example, X-22-3701E (Shin-Etsu Chemical) Examples of the carbinol-modified product include X-22-4039 (Shin-Etsu Chemical Co., Ltd.) and X-22-4015 (Shin-Etsu Chemical Co., Ltd.). And KF-393 (manufactured by Shin-Etsu Chemical Co., Ltd.).

  In the resin composition of the present invention, the content of the silicone oil is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the flame retardant (B). Parts, more preferably 0.5 to 3 parts by mass. If the amount is less than 0.01 part by mass, the suppression of secondary aggregation and the water resistance may not be sufficient. If the amount exceeds 10 parts by mass, the properties of the resin may be reduced.

Furthermore, a silane coupling agent may be added to the resin composition of the present invention, if necessary. The silane coupling agent is a compound having a hydrolyzable group with an organic functional group, for example, represented by the general formula _{Q- (CH 2) s-Si} (OR 7) 3. Q is an organic functional group, s represents a number of 1 to 3, and R ⁷ represents a methyl group or an ethyl group. Examples of the organic functional group for Q include an epoxy group, a vinyl group, a methacryl group, an amino group, and a mercapto group. In the resin composition of the present invention, a silane coupling agent having an epoxy group is particularly preferable.

  In the resin composition of the present invention, the content of the silane coupling agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the flame retardant (B). It is 5 parts by mass, more preferably 0.5 to 3 parts by mass. If the amount is less than 0.01 part by mass, the suppression of secondary aggregation and the improvement in water resistance are not sufficient, and if it exceeds 10 parts by mass, the properties of the resin may be deteriorated.

  Further, the resin composition of the present invention may optionally contain a polyhydric alcohol compound. A polyhydric alcohol compound is a compound in which a plurality of hydroxyl groups are bonded, and may overlap with the above-mentioned polyhydric alcohol compound, but is a compound added as a flame retardant aid for improving flame retardancy. . Examples of the polyhydric alcohol compound of the flame retardant aid include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, 1,3,5-tris (2 -Hydroxyethyl) isocyanurate, polyethylene glycol, glycerin, diglycerin, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose (sucrose), trehalose, inositol, fructose, maltose, lactose and the like.

  In the resin composition of the present invention, pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, and the like, pentaerythritol, or a condensate of pentaerythritol is preferable, a condensate of pentaerythritol is more preferable, dipentaerythritol Erythritol is particularly preferred. Also, 1,3,5-tris (2-hydroxyethyl) isocyanurate and sorbitol can be suitably used.

  The condensate of pentaerythritol may be a mixture of a condensate of pentaerythritol and pentaerythritol (hereinafter, referred to as a “(poly) pentaerythritol mixture”). In terms of expression, it is preferable that the total content of pentaerythritol of n = 1 to 3 and its condensate is 5 to 40% by mass based on the total amount of the (poly) pentaerythritol mixture (where n = 1 to 3). Of pentaerythritol and a condensate thereof and a condensate of pentaerythritol with n ≧ 4 is 100% by mass.) Note that n = 1 is pentaerythritol and n = 2 is dipentaerythritol.

  When the degree of condensation of pentaerythritol is represented by n from the viewpoint of flame retardancy, the (poly) pentaerythritol mixture has a total content of pentaerythritol of n = 1 to 3 and its condensate with respect to the total amount of the mixture. Is preferably 10 to 30% by mass, the content of pentaerythritol with n = 1 is 0 to 10% by mass, and the total content of pentaerythritol with n = 1 to 3 and a condensate thereof is More preferably, the content of pentaerythritol of n = 1 is 0 to 5% by mass, and the total content of pentaerythritol of n = 1 to 3 and its condensate is 5 to 30% by mass. What is 10-30 mass% is especially preferable.

ここで、式（７）中のｔは１以上の整数である。 Examples of pentaerythritol and its condensate include a compound represented by the following general formula (7).

Here, t in the equation (7) is an integer of 1 or more.

  Examples of the (poly) pentaerythritol mixture include those in which a condensate of pentaerythritol represented by the general formula (7) is ether-bonded in a molecule, one in which an intermediate methylol group is ether-bonded to another molecule, and further, a network. And those in which the molecules are further connected to each other and become larger to form a macrocyclic ether structure at various places.

  The (poly) pentaerythritol mixture is not particularly limited, and can be produced by a known method. For example, it can be produced by subjecting pentaerythritol and / or a condensate of pentaerythritol to a thermal dehydration condensation reaction as it is or in the presence of a suitable catalyst and a solvent.

  Examples of the catalyst used for producing the (poly) pentaerythritol mixture include an inorganic acid and an organic acid which are usually used in a dehydration condensation reaction of alcohol. Examples of the inorganic acid include: mineral acids such as phosphoric acid and sulfuric acid; acidic salts of these mineral acids; clay minerals (eg, montmorillonite); and solid acid catalysts such as silica-alumina and zeolite. Examples of the organic acid include formic acid and p-toluenesulfonic acid.

  The amount of the catalyst used is not particularly limited, but when a water-soluble acid catalyst is used, the amount may be such that the pH in the reaction system during the reaction can be maintained at less than 7, preferably 5 or less. When a solid acid catalyst is used, it is usually sufficient to use 0.1 to 100% by mass based on pentaerythritol.

  Examples of the solvent used for producing the (poly) pentaerythritol mixture include hydrocarbons such as benzene, xylene, decalin, and tetralin, dioxane, tetrahydrofuran, ethyl ether, anisole, phenyl ether, diglyme, tetraglyme, and 18-crown. Ethers such as -6, ketones such as methyl acetate, ethyl butyrate, methyl benzoate, and γ-butyrolactone; N-methylpyrrolidin-one; N, N-dimethylacetamide; N-methylpiperidone; hexamethylphosphoric triamide; N-substituted amides, tertiary amines such as N, N-diethylaniline, N-methylmorpholine, pyridine, quinoline, sulfones such as sulfolane, sulfoxides such as dimethyl sulfoxide, and 1,3-dimethyl- 2-imidazolidinone Urea derivatives, phosphine oxides such as tributylphosphine oxide, and silicone oil and the like, may be either water-containing product which was dehydrated.

  The reaction temperature of the thermal dehydration condensation in the production of the (poly) pentaerythritol mixture is usually about 100 to 280 ° C, and more preferably 150 to 240 ° C. If the temperature is lower than 100 ° C., the reaction may be slow, and if it is higher than 280 ° C., control of the condensation reaction may be difficult.

  In the resin composition of the present invention, when a polyhydric alcohol compound is added as a flame retardant auxiliary, the amount is preferably 0.5 to 15 parts by mass, and more preferably 2 to 12 parts by mass with respect to 100 parts by mass of the flame retardant (B). More preferably, it is more preferably 5 to 10 parts by mass.

  The timing at which the flame retardant aid, anti-drip agent, silane coupling agent, and polyhydric alcohol compound are blended with the antistatic thermoplastic resin is not particularly limited. The components may be blended with the resin, or each component may be blended with the thermoplastic resin. In the case of one-pack formation, each component may be ground and then mixed, or may be mixed and ground.

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

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

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

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

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

  When the surfactant is compounded, the amount is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 4 parts by mass, per 100 parts by mass of the thermoplastic resin.

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

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

  Further, 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 have a melting point below room temperature, at least one of the cations or anions constituting the ionic liquid is an organic ion, and the initial conductivity is preferably 1 to 200 ms / cm, more preferably A room-temperature molten salt of 10 to 200 ms / cm, for example, a room-temperature molten salt described in International Publication No. 95/15572.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  When the ionic liquid is compounded, the compounding amount is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

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

  The amount of the compatibilizer to be added is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the thermoplastic resin and the polymer compound (A).

  In addition, various additives such as a phenolic antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant can be further added to the resin composition of the present invention as long as the effects of the present invention are not impaired. Thereby, the resin composition of the present invention can be stabilized.

  Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-). (Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4′-thiobis (6-tert-butyl-m-cresol) 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl-phenol) m-cresol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4-sec-butyl-6-tert-butylpheno) 1,3,5-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butyl) 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, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycolbi [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [3,3 -Bis (4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) ) Phenyl) terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-} (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5,5] unde Can, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like. The addition amount of these phenolic antioxidants is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the thermoplastic resin.

  Examples of the phosphorus-based antioxidant include trisnonylphenyl phosphite and tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phospho. Phyte, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tributylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite Fight, bis (2,4-dicumylphenyl) pentae Thritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)- 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebis (4,6- Tert-butylphenyl) -octadecylphosphite, 2,2′-ethylidenebis (4,6 Di-tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl ) Oxy] ethyl) amine, phosphites of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol, and the like. The addition amount of these phosphorus antioxidants is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the thermoplastic resin.

  Examples of thioether-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (β-alkylthiopropionate) ester And the like. The addition amount of these thioether-based antioxidants is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the thermoplastic resin.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, and 2,2,6 , 6-Tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-tetramethyl-4-piperidyl) sebacate , Bis (1-octoxy-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-piperidyl) di (tridecyl) ) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl- 4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,2 6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Piperidylamino) he Sun / 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. The amount of the hindered amine light stabilizer to be added is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the thermoplastic resin.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzo Triazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octyl) Phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2 ′ 2- (2′-) such as methylenebis (4-tert-octyl-6- (benzotriazolyl) phenol) and 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3, Benzoates such as 5-di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4 ' Substituted oxanilides such as dodecyl oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate Cyanoacrylates such as methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-di Tert-butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl)- And triaryltriazines such as 4,6-bis (2,4-ditertbutylphenyl) -s-triazine. The addition amount of these ultraviolet absorbers is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the thermoplastic resin.

  Further, if necessary, a known neutralizing agent is preferably added to neutralize the residual catalyst in the antistatic thermoplastic resin. Examples of the neutralizing agent include fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, and fatty acid amides such as ethylene bis (stearamide), ethylene bis (12-hydroxystearamide), and stearamide. Compounds, and these neutralizing agents may be used as a mixture.

  Furthermore, the resin composition of the present invention may further contain, if necessary, a metal salt of an aromatic carboxylic acid, a metal salt of an alicyclic alkyl carboxylic acid, aluminum p-tert-butylbenzoate, dibenzylidene sorbitol, Nucleating agents such as phosphate metal salts, metal soaps, hydrotalcite, metal hydroxides, phosphate ester flame retardants, condensed phosphate ester flame retardants, inorganic phosphorus flame retardants, halogen flame retardants, silicon A flame retardant, antimony oxide such as antimony trioxide, other inorganic flame retardant aids, other organic flame retardant aids and the like may be added.

  Examples of the phosphate ester-based flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, and trikilic phosphate. Silenyl phosphate, octyl diphenyl phosphate, xyenyl diphenyl phosphate, tris isopropyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butyl phenyl diphenyl phosphate, bis- (t-butyl phenyl) phenyl phosphate, tris- (t-butyl phenyl) ) Phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropane) Pirufeniru) diphenyl phosphate, tris - (isopropylphenyl) phosphate, and the like.

  Examples of the condensed phosphate ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and naphthalene-2,5- Diyl-tetraphenyl bis (phosphate), [1,1′-biphenyl] -4,4′-diyl-tetraphenyl bis (phosphate), [1,1′-biphenyl] -4,4′-diyl-tetrakis ( 2,6-dimethylphenyl) bis (phosphate), tetraphenyl (thiobis (4,1-phenylene)) bis (phosphate), tetraphenyl (sulfonylbis (4,1-phenylene)) bis (phosphate) and the like. .

  Examples of other inorganic flame retardant aids include inorganic compounds such as hydrotalcite, talc, and montmorillonite, and surface-treated products thereof. For example, DHT-4A (hydrotalcite: Kyowa Chemical Industry Co., Ltd.) ) And Alkamizer 4 (zinc-modified hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.).

  In the resin composition of the present invention, if necessary, additives usually used for thermoplastic resins, for example, a crosslinking agent, an anti-fogging agent, a plate-out inhibitor, a surface treatment agent, a plasticizer, a lubricant, a fluorescent agent, An antifungal agent, a bactericide, a foaming agent, a metal deactivator, a release agent, a pigment, a dye, a processing aid, a filler, a foaming agent, and the like can be blended as long as the effects of the present invention are not impaired.

  The method for producing the resin composition of the present invention is not particularly limited, and the thermoplastic resin may be added to the polymer compound (A), the flame retardant (B) represented by the general formula (2), and if necessary, an alkali metal salt ( F) and other optional components may be blended, and the method may be any commonly used method. For example, they may be mixed by kneading with a roll, kneading with a bumper, an extruder, a kneader, or the like, and mixing.

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

  Further, as a method of blending the polymer compound (A) into the resin component, the polymer compound (A) is kneaded into the resin component while the block polymer (G) and the compound (D) having a reactive functional group are kneaded. The compound (C) and, if necessary, the alkali metal salt (F) may be kneaded together at the same time, or the polymer compound (A) and the compound (A) may be mixed during molding such as injection molding. (C), a resin component and, if necessary, an alkali metal salt (F) may be mixed to obtain a molded product, and the thermoplastic resin may be mixed with the thermoplastic resin in advance by the general formula (2). A masterbatch with the phosphoric acid ester compound (B) and, if necessary, the alkali metal salt (F) may be manufactured, and this masterbatch may be blended.

Next, the molded article 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, it is possible to produce a molded article having durability of antistatic property and excellent flame retardancy. The molding method is not particularly limited, and examples thereof include extrusion, calendering, injection molding, roll, compression molding, blow molding, rotational molding, and the like. Resin plates, sheets, films, bottles, fibers, irregular-shaped products And other various shapes.

  The molded article of the present invention has excellent antistatic properties and flame retardancy. Usually, when an antistatic agent is added, the physical properties often decrease, but the molded article of the present invention is excellent in antistatic performance and its durability, and the physical properties are hardly deteriorated. It also has resistance to wiping the surface of the molded body.

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

  More specifically, the resin composition of the present invention and a molded article thereof can be used for a printer, a personal computer, a word processor, a keyboard, a PDA (small information terminal), a telephone, a copying machine, a facsimile, and an ECR (electronic cash register). , Calculators, electronic organizers, cards, holders, stationery, etc., office equipment, OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, kotatsu and other home appliances, TVs, VTRs, video cameras, Audio-visual equipment such as boombox, tape recorder, mini disk, CD player, speaker, liquid crystal display, connector, relay, capacitor, switch, printed circuit board, coil bobbin, semiconductor encapsulation material, LED encapsulation material, electric wire, cable, transformer, deflection Electric and electronic parts and communications equipment such as yokes, distribution boards and watches, interior and exterior materials for automobiles, -Mediate bulk containers, artificial turf, plate making films, adhesive films, bottles, food containers, food packaging films, pharmaceutical and pharmaceutical wrap films, product packaging films, agricultural films, agricultural sheets, greenhouse films, etc. Used for applications.

  Further, the resin composition of the present invention and a molded article thereof are provided with a seat (filling, dress material, etc.), a belt, a ceiling covering, a compatible top, an armrest, a door trim, a rear package tray, a carpet, a mat, a sun visor, a foil cover, and a mattress cover. , Airbags, insulating materials, hanging hands, hanging straps, wire covering materials, electrical insulating materials, paints, coating materials, overlay materials, floor materials, corner walls, carpets, wallpapers, wall covering materials, exterior materials, interior materials , Roof materials, deck materials, wall materials, pillar materials, floorboards, fence materials, framing and profiles, window and door profiles, shingles, paneling, terraces, balconies, soundproofing boards, heat insulating boards, window materials, etc. Automobiles, vehicles, ships, aircraft, buildings, houses and construction materials and civil engineering materials, clothing, curtains, sheets, nonwovens, plywood, plywood, carpets, doormats, sheets, buckets, hoses, containers , It is possible to use glasses, bags, cases, goggles, skis, rackets, tents, household goods of musical instruments, etc., in various applications such as sporting goods.

Hereinafter, the present invention will be described specifically with reference to Examples.
According to the following production examples, polymer compound (A), (poly) phosphate compound (B) -1 and (poly) phosphate compound (B) -2 were produced. In the following Production Examples, the number average molecular weight was measured by the following method. Using the obtained test pieces, a measurement of a surface specific resistance value (SR value), a water wiping resistance test, and a flame retardancy UL-94V test were performed by the following methods.

(Molecular weight measurement)
The number average molecular weight (hereinafter, referred to as “Mn”) was measured by a gel permeation chromatography (GPC) method. The measuring conditions of Mn are as follows.
Apparatus: GPC apparatus manufactured by JASCO Corporation Solvent: tetrahydrofuran Reference substance: polystyrene Detector: Differential refractometer (RI detector)
Column stationary phase: Showex KF-804L manufactured by Showa Denko KK
Column temperature: 40 ° C
Sample concentration: 1mg / 1mL
Flow rate: 0.8 mL / 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 (4.85 mol) of adipic acid as an aliphatic dicarboxylic acid, and phthalic anhydride as an aromatic dicarboxylic acid 0.7 g (4.73 × 10 ⁻³ mol) of an antioxidant (tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane; trade name of ADEKA Corporation) 0.7 g of “ADK STAB AO-60”) was charged and polymerized at normal pressure for 5 hours while gradually raising the temperature from 160 ° C. to 210 ° C., and then polymerized at 210 ° C. under reduced pressure for 3 hours to obtain polyester (E) -1. Obtained. Polyester (E) -1 had an acid value of 28 and a number average molecular weight Mn of 5,400 in terms of polystyrene.

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

  To 360 g of the obtained block polymer (G) -1 having a carboxyl group at both ends, 6 g of bisphenol F diglycidyl ether (D) -1 as a compound (D) having a reactive functional group was charged, and heated at 240 ° C. Polymerization was performed under reduced pressure 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, and aromatic dicarboxylic acid Then, 8 g (0.05 mol) of isophthalic acid and 0.5 g of an antioxidant (ADEKA STAB AO-60) were charged, and polymerized at normal pressure for 5 hours while gradually raising the temperature from 180 ° C. to 220 ° C. Thereafter, 0.5 g of tetraisopropoxytitanate was charged and polymerized at 220 ° C. under reduced pressure for 5 hours to obtain a polyester (E) -2. Polyester (E) -2 had an acid value of 56 and a number average molecular weight Mn of 4,900 in terms of polystyrene.

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

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

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

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

(Production of flame retardant (B) -1)
Pyrophosphoric acid and melamine were reacted at a molar ratio of 1: 1 to obtain melamine pyrophosphate (B) -1-1 which is a (poly) phosphate compound.

(Production of flame retardant (B) -2)
Pyrophosphoric acid and piperazine were reacted at a molar ratio of 1: 1 to obtain piperazine pyrophosphate (B) -2-1 which is a (poly) phosphate compound.

[Examples 1 to 27, Comparative Examples 1 to 15]
0.1 parts by mass of a phenolic antioxidant (trade name "ADEKA STAB AO-60" manufactured by ADEKA Corporation), 0.05 parts by mass of a phosphorus antioxidant (trade name "ADEKA STAB 2112" manufactured by ADEKA CORPORATION), calcium stearate A test piece was obtained using the resin composition blended based on 0.05 mass and the blending amount (parts by mass) described in Tables 1 to 7 below according to the test piece preparation conditions shown below. Using the obtained test piece, the measurement of the surface specific resistance value (SR value), the water wiping resistance test, and the flame retardancy UL-94V test were performed as follows. * 1 to * 13 in the table are as follows.

* 1: Thermoplastic resin 1: homopolypropylene (melt flow rate = 8 g / 10 min)
* 2: Thermoplastic resin 2: impact-resistant polystyrene (melt flow rate = 2.7 g / 10 min), manufactured by Toyo Styrene Co., Ltd., trade name: E640N
* 3: Thermoplastic resin 3: ABS resin (melt flow rate = 23 g / 10 min), trade name “Techno ABS110” manufactured by Techno Polymer Co., Ltd.
* 4: NaDBS; sodium dodecylbenzenesulfonate * 5: LiOTs; lithium p-toluenesulfonate * 6: metal oxide; zinc oxide * 7: anti-drip agent: polytetrafluoroethylene, Mitsui-Dupont Fluorochemical Co., Ltd. Product name "PTFE-6J"
* 8: Silicone oil; methyl silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd. “KF-99”
* 9: silane coupling agent; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane * 10: polyhydric alcohol; dipentaerythritol * 11: comparative antistatic agent-1; glycerin monostearate * 12: comparative Antistatic agent-2; polyether polyolefin-based antistatic agent, manufactured by Sanyo Chemical Co., Ltd., trade name "Perestat 300"
* 13: Comparative antistatic agent-3; polyetheresteramide-based antistatic agent, manufactured by BASF, trade name "Ilgastat P-20"

[Comparative Example 16]
100 parts by mass of thermoplastic resin 1, 41 parts by mass of (A) -1 as polymer compound (A), 0.1 part by mass of phenolic antioxidant (trade name “ADEKA STAB AO-60” manufactured by ADEKA Corporation) 0.05 parts by mass of a phosphorus-based antioxidant (trade name “ADEKA STAB 2112” manufactured by ADEKA CORPORATION), 0.05 parts by mass of calcium stearate, and (B) -1- (as a (poly) phosphate compound (B) -1) 1 and 20 parts by mass, and (B) -2-1 as a (poly) phosphate compound (B) -2, a resin composition prepared by blending 30 parts by mass was produced according to the following test piece preparation conditions. However, a test piece could not be prepared due to poor molding workability.

[Comparative Example 17]
100 parts by mass of thermoplastic resin 1, 20 parts by mass of (A) -1 as polymer compound (A), 0.1 part by mass of phenolic antioxidant (trade name “ADEKA STAB AO-60” manufactured by ADEKA Corporation) 0.05 parts by mass of a phosphorus-based antioxidant (trade name “ADEKA STAB 2112” manufactured by ADEKA CORPORATION), 0.05 parts by mass of calcium stearate, and (B) -1- (as a (poly) phosphate compound (B) -1) Using a resin composition obtained by blending 33 parts by mass of No. 1 and 49 parts by mass of (B) -2-1 as the (poly) phosphate compound (B) -2, it was produced according to the following test piece preparation conditions. However, a test piece could not be prepared due to poor molding workability.

<Test specimen preparation conditions>
Each resin composition was granulated under the conditions of 230 ° C. and 9 kg / hour using a twin screw extruder (with PCM 30, 60 mesh) manufactured by Ikegai Corporation to obtain pellets. The obtained pellets were molded using a horizontal injection molding machine (NEX80: manufactured by Nissei Plastics Industry Co., Ltd.) under the processing conditions of a resin temperature of 230 ° C. and a mold temperature of 50 ° C. (100 mm x 100 mm x 3 mm) and a flame-retardant UL-94V test specimen (127 mm x 12.7 mm x 1.6 mm) were obtained.

<Surface resistivity measurement method>
Immediately after molding, the obtained test piece for measuring surface specific resistance (100 mm × 100 mm × 3 mm) was stored under the conditions of a temperature of 25 ° C. and a humidity of 60% RH. Under the same atmosphere, the surface specific resistance (Ω / □) was measured using an R8340 resistance meter manufactured by Advantest Corporation under the conditions of an applied voltage of 500 V and an application time of 1 minute. The measurement was performed for five points, and the average value was obtained.

<Water resistance test>
After wiping the surface of the obtained test piece (100 mm × 100 mm × 3 mm) for 50 times with a running water rag, it was left in a thermo-hygrostat adjusted to 25 ° C. and 60% humidity for 24 hours. Then, the surface specific resistance value (Ω / □) was measured using an R8340 resistance meter manufactured by Advantest Corporation under the conditions of an applied voltage of 500 V and an application time of 1 minute. The measurement was performed at five points, and the average value was obtained.

<Flame retardant UL-94V test>
The obtained flame-retardant UL-94V test specimen (127 mm x 12.7 mm x 1.6 mm) was kept vertical, the flame was removed by indirectly burning a burner at the lower end for 10 seconds, and the flame was removed. The time for the ignited fire to extinguish was measured. Next, at the same time when the fire was extinguished, a second flame contact was performed for 10 seconds, and the time for extinguishing the fire was measured in the same manner as in the first time. In addition, whether or not the cotton under the test piece ignited due to the falling fire type was also evaluated at the same time. The burning rank was assigned according to the UL-94V standard from the first and second burning times, the presence or absence of cotton ignition, and the like. As for the combustion rank, V-0 has the highest flame retardancy, and the flame retardancy decreases as V-1 and V-2, and the NR is the lowest flame retardancy.

  From Comparative Examples 4 and 5, when glycerin monostearate, which is not a polymer compound, was used, the antistatic effect was obtained, but the antistatic property was impaired when a water wiping resistance test was performed.

  Further, from Comparative Example 6, Comparative Example 7, Comparative Example 11 and Comparative Example 12, a polymer compound (polyether polyolefin block copolymer or polyether ester amide block) different from polymer compound (A) according to the present invention. When using (copolymer), its antistatic property was not satisfactory.

On the other hand, from Examples 1 to 27, it was confirmed that the test pieces molded with the resin composition of the present invention had excellent antistatic properties, long-term maintenance thereof, and excellent flame retardancy.

Claims (13)

In an antistatic thermoplastic resin composition containing 4 to 40 parts by mass of a polymer compound (A) and 1 to 80 parts by mass of a flame retardant (B) based on 100 parts by mass of a thermoplastic resin,
A polyester (E) in which the polymer compound (A) is composed of a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, and the following general formula (1):

The compound (C) having at least one group represented by the formula (I) and having a hydroxyl group at both terminals and the compound (D) having a reactive functional group are formed through an ester bond or an ester bond and an amide bond. An antistatic thermoplastic resin composition having a structure formed by bonding via The flame retardant (B) is represented by the following general formula (2):

(N in the formula (2) represents a number of 1 to 100, and X ¹ is ammonia or the following general formula (3);

(Z ¹ and Z ² in the formula (3) ^each represent a —NR ¹ R ² group, a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched carbon atom. Wherein each of R ¹ and R ² independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or Represents a methylol group, and Z ¹ and Z ² may be the same or different.), And p represents a number satisfying 0 <p ≦ n + 2. (B) -1 component represented by the following general formula (4):

(In the formula (4 ) , r represents 1 to 100, Y ¹ represents [R ³ R ⁴ N— (CH ₂ ) _k —NR ⁵ R ⁶ ], piperazine, or a diamine containing a piperazine ring, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, k represents an integer of 1 to 10, and q represents , 0 <q ≦ r + 2.) The antistatic thermoplastic resin composition according to claim 1, comprising a mixture with a (poly) phosphate compound (B) -2 component represented by the following formula: The polymer compound (A) has carboxyl groups at both ends where a block composed of the polyester (E) and a block composed of the compound (C) are alternately bonded via an ester bond. The antistatic thermoplastic according to claim 1 or 2 , wherein the block polymer (G) and the compound (D) have a structure formed by bonding via an ester bond or via an ester bond and an amide bond. Resin composition. 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 thermoplastic resin composition according to claim 3 , wherein the number average molecular weight of the block polymer (G) is 5,000 to 25,000 in terms of polystyrene. The antistatic thermoplastic resin composition according to any one of claims 1 to 4 , wherein the polyester (E) has a structure having carboxyl groups at both ends. The compound (D) comprises 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 thermoplastic resin composition according to any one of claims 1 to 5 , which is at least one selected from the group consisting of polyamine compounds (D) -3. The antistatic thermoplastic resin composition according to any one of claims 1 to 6 , wherein the compound (C) is polyethylene glycol. The antistatic thermoplastic resin composition according to any one of claims 1 to 7 , further comprising 0.01 to 5 parts by mass of at least one alkali metal salt (F). The thermoplastic resin is, according to claim 8 is at least one selected from the group consisting of polyolefin resins, styrene resins, polyester resins, polyether resins, polycarbonate resins, polyamide resins, and halogen-containing resin The antistatic thermoplastic resin composition according to any one of the above. The antistatic thermoplastic according to any one of claims 1 to 9 , further comprising 0.005 to 5 parts by mass of at least one anti-drip agent based on 100 parts by mass of the flame retardant (B). Resin composition. Metal oxides, at least one kind of silicone oil and silane coupling agent, relative to the flame retardant (B) 100 parts by mass, either one of claims 1 to 10 containing from 0.01 to 10 parts by weight The antistatic thermoplastic resin composition according to claim 1. The antistatic thermoplastic according to any one of claims 1 to 11 , further comprising 0.5 to 15 parts by mass of at least one polyhydric alcohol compound based on 100 parts by mass of the flame retardant (B). Resin composition. A molded article obtained by molding the antistatic thermoplastic resin composition according to any one of claims 1 to 12 .